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BaCe$_{0.25}$Mn$_{0.75}$O$_{3-\delta}$ (BCM), a non-stoichiometric oxide closely resembling a perovskite crystal structure, has recently emerged as a prospective contender for application in renewable energy harvesting by solar thermochemical hydrogen generation. Using solar energy, oxygen-vacancies can be created in BCM and the reduced crystal so obtained can, in turn, produce H2 by stripping oxygen from H2O. Therefore, a first step toward understanding the working mechanism and optimizing the performance of BCM, is a thorough and comparative analysis of the electronic structure of the pristine and the reduced material. In this paper, we probe the electronic structure of BCM using the combined effort of first-principles calculations and experimental O K-edge x-ray absorption spectroscopy (XAS). The computed projected density-of-states (PDOS) and orbital-plots are used to propose a simplified model for orbital-mixing between the oxygen and the ligand atoms. With the help of state-of-the-art simulations, we are able to find the origins of the XAS peaks and to categorize them on the basis of contribution from Ce and Mn. For the reduced crystal, the calculations show that, as a consequence of dielectric screening, the change in electron-density resulting from the reduction is strongly localized around the oxygen vacancy. Our experimental studies reveal a marked lowering of the first O K-edge peak in the reduced crystal which is shown to result from a diminished O-2p contribution to the frontier unoccupied orbitals, in accordance with the tight-binding scheme. Our study paves the way for investigation of the working-mechanism of BCM and for computational and experimental efforts aimed at design and discovery of efficient water-splitting oxides.

Solar thermochemical hydrogen production (STCH) via redox-active metal oxides is an approach for direct solar-driven hydrogen generation typically using a high-temperature redox cycle involving refractory oxides and steam. Typical cycles involve high-temperature reduction of oxides to form oxygen vacancies, followed by lower temperature reaction between oxygen vacancies and steam where the oxide is re-oxidized and the steam is reduced to hydrogen. Only a few materials have demonstrated reversible cycling under the typically harsh STCH conditions (e.g. 1500°C reduction, 900°C re-oxidation) and critical questions remain on the true reversibility of non-stoichiometric multi-cation oxide systems, significantly hampered by the lack of single-phase samples for these material systems. To date, most STCH processes have relied on CeO2 as a benchmark active material, but more recently, the 12R phase of BaCe0.25Mn0.75O3 (BCM) has demonstrated greater hydrogen-generation potential at lower peak temperatures. However, previous reports of 12R-BCM have included large fractions, > 10 wt%, of secondary phases, which complicate analysis of the stability and performance. A comprehensive understanding of the redox mechanism and reversibility of the process in BCM can only be achieved with nearly single-phase samples which, to date, have been difficult to produce. Here two approaches to BCM synthesis are reported: solid state and sol–gel-based routes. It is demonstrated that both routes can be tuned to produce the 12R structure with > 97 wt% yield when annealed ≥1450°C. Herein synchrotron-based diffraction measurements of rhombohedral 12R-BCM enabled characterization of the anisotropy between thermal expansion along the c-axis and within the ab plane. The impact of high-temperature redox cycling on the stability and phase fraction of the 12R-BCM polytype was also investigated. These results offer two viable routes for synthesis of high-purity 12R-BCM critically needed for evaluating the efficacy of BCM as a STCH material and validate its ability to split water at lower temperatures over extended numbers of redox cycles.

Manganese oxides have enabled a wide range of technologies including oxygen evolution catalysts, lithium ion batteries, and thermochemical water splitting. However, the variable oxidation state and rich polymorphism of manganese oxides make it difficult to find the processing conditions to target a particular phase of manganese oxide. Targeted synthesis requires a more complete understanding of the phase space and the impact of multiple processing variables on phase formation. Here, we demonstrate the impact of substrate temperature, total deposition pressure, partial pressure of oxygen, and target composition on the phase formation of manganese oxides grown using combinatorial pulsed laser deposition (PLD). Thin films were deposited from a MnO, Mn2O3 or MnO2 target onto amorphous glass substrates with a continuously varied temperature provided by a combinatorial heater. A combination of X-ray diffraction, Rutherford backscattering spectroscopy, and Raman and Fourier transform infrared (FTIR) spectroscopies were used to determine the phases present in the samples. The oxygen partial pressure was found to be the critical factor determining phase formation, while the total pressure, target composition, and substrate temperature have smaller and more complex effects on phase formation. Comparing the results of this work to the published temperature–pressure phase diagrams shows that the PLD thin films vary significantly from the expected equilibrium phases of either the bulk materials or nanoparticles. These results suggest that PLD provides a route to capture phases of manganese oxides at lower temperatures or higher oxygen pressures than those required for bulk synthesis or solution processing.

We used high-throughput experimental screening methods to unveil the physical and chemical properties of Mn1-x Zn x O wurtzite alloys and identify their appropriate composition for effective water splitting application. The Mn1-x Zn x O thin films were synthesized using combinatorial pulsed laser deposition, permitting for characterization of a wide range of compositions with x varying from 0 to 1. The solubility limit of ZnO in MnO was determined using the disappearing phase method from X-ray diffraction and X-ray fluorescence data and found to increase with decreasing substrate temperature due to kinetic limitations of the thin-film growth at relatively low temperature. Optical measurements indicate the strong reduction of the optical band gap down to 2.1 eV at x = 0.5 associated with the rock salt-to-wurtzite structural transition in Mn1-x Zn x O alloys. Transmission electron microscopy results show evidence of a homogeneous wurtzite alloy system for a broad range of Mn1-x Zn x O compositions above x = 0.4. The wurtzite Mn1-x ZnxO samples with the 0.4 < x < 0.6 range were studied as anodes for photoelectrochemical water splitting, with a maximum current density of 340 μA cm-2 for 673 nm-thick films. These Mn1-x Zn x O films were stable in pH = 10, showing no evidence of photocorrosion or degradation after 24 h under water oxidation conditions. Doping Mn1-x Zn x O materials with Ga dramatically increases the electrical conductivity of Mn1-x Zn x O up to ∼1.9 S/cm for x = 0.48, but these doped samples are not active in water splitting. Mott-Schottky and UPS/XPS measurements show that the presence of dopant atoms reduces the space charge region and increases the number of mid-gap surface states. Overall, this study demonstrates that Mn1-x Zn x O alloys hold promise for photoelectrochemical water splitting, which could be enhanced with further tailoring of their electronic properties.

A wide variety of brookite TiO2 synthesis methods have been published over the past several decades, but few studies discuss the underlying mechanism that stabilizes brookite over its stable counterparts, rutile and anatase. Here, we investigate of the effect of pulsed laser deposition parameters on the as-deposited amorphous precursor titania thin films, which subsequently crystallize into stable and metastable TiO2 polymorphs upon annealing. We find that oxygen pressure in the deposition chamber strongly influences the non-equilibrium state of the amorphous precursor, which ultimately allows for selective polymorph formation. Rutile forms as the dominant phase at low pO2 5 mTorr. Brookite forms primarily at intermediate pO2 (0.5–1.0 mTorr). Controlling the amorphous structure (i.e. Ti—O bonding and polyhedral arrangement) of the precursors via oxygen deficiency is therefore likely for the selective formation of crystalline TiO2 polymorphs from sub-stoichiometric amorphous precursors. Directing phase selectivity by manipulating the structure and internal energy of the precursor amorphous state may have tremendous potential for synthesis of metastable crystalline phases that exhibit more desirable properties in comparison to their stable counterparts.

In this work, we present the design, construction, and experimental results of a prototype latent heat thermal energy storage system. The prototype consists of a thermal storage tank with 100 kg of the aluminum-silicon eutectic as a phase change material, a valved thermosyphon that controls heat flow from the thermal storage tank to the power block, and thermoelectric generators for conversion of heat to electricity. We tested the prototype over four simulated days, where each day consisted of four phases of operation: charging, discharging, simultaneous charging and discharging, and storage. Our results show three major conclusions. First, the thermal energy storage system was able to receive and distribute heat with small temperature gradients – less than 5 °C throughout the thermal storage tank. Second, the valved thermosyphon was able to effectively control heat transfer, demonstrating an on/off thermal conductance ratio of 430. Third, the interfaces between subsystems had small temperature drops: of the ∼ 560 °C temperature drop from the thermal storage tank to the heat rejection system, ∼ 525 °C occurred across the power block. This work overcomes the challenges of integrating previously-developed subsystems together, providing a proof-of-concept of this system.

This article addresses the challenges presented by photoelectrochemical solar fuels technology in a discussion that begins with a functioning device and proceeds to the more fundamental science of its component parts. In this flow of discussion issues are addressed that frame the discussion for the next, increasingly more fundamental topic. The analysis begins with a discussion of the need for an analytical facility for confirmation of reported efficiencies of solar fuels device prototypes and then progressively narrows its scope to prototype design, the discovery of novel materials and the design of durable interfacial structures for fuels evolution. Molecular hydrogen will be considered first as the target fuel since many of the challenges with hydrogen production are general and applicable to the more complex CO2 reduction, which will be treated as a supplementary subject.

This chapter covers the integrated analysis component of the program, which provided a critical resource to help define the optimal research agenda. This work includes assessing the solar resource across the various climate zones in India and a coupling of this to the technology roadmaps in India and the United States. The analysis was coupled with mapping optimal site selections for diverse applications of photovoltaics (PV) and concentrated solar power (CSP) from village power to national grid. The results were backed up by detailed tech-to-market and techno-economic analysis that helped to define the detailed research roadmap for both PV and CSP. Various potential scenarios were defined for the manufacture of silicon solar cells in India, revitalizing this manufacturing sector. Overall, this work led to clearly defining the bankability of solar across different deployment length scales. This analysis helped investors and governmental entities develop specific policies to meet solar deployment goals. Part of this work included developing online tools specific to India to assess the resource and technology/deployment scenarios; one example is the System Advisor Model tool specific to India.

This chapter highlights the multiscale concentrated solar power thrust, which focused on developing new low-cost manufacturable technologies for both high- and moderate-temperature thermal cycles. In the high-temperature range, the focus was on the supercritical carbon dioxide (s-CO2) Brayton cycle. Research involved developing low-cost heliostats coupled with novel bladed receivers and a novel CO2 test loop. A key focus was developing a functional testbed to evaluate and optimize the Brayton cycle as a cost-shared effort with the Indian Institute of Science. The project also investigated developing a novel helical receiver to heat the CO2. Extensive computational modeling of the thermal flow and gradients was conducted to develop the novel CO2 cycle. The program also pursued developing low-cost mirrors, absorbers, and troughs for Rankine cycle solar thermal parabolic trough technology. A new small-scale, positive-displacement organic Rankine cycle expander was developed and tested. Solution-based approaches were considered that promise low-cost manufacturing. Coupled with the heat-collection work were investigations of thermal storage approaches. Specifically, new molten salts were developed capable of much higher-temperature performance with improved thermal conductivity, and a new system was developed for low-temperature Rankine systems.

In this paper, we present performance simulations and techno-economic analysis of a modular dispatchable solar power tower. Using a heliostat field and power block three orders of magnitude smaller than conventional solar power towers, our unique configuration locates thermal storage and a power block directly on a tower receiver. To make the system dispatchable, a valved thermosyphon controls heat flow from a latent heat thermal storage tank to a Stirling engine. The modular design results in minimal balance of system costs and enables high deployment rates with a rapid realization of economies of scale. In this new analysis, we combine performance simulations with techno-economic analysis to evaluate levelized cost of electricity, and find that the system has potential for cost-competitiveness with natural gas peaking plants and alternative dispatchable renewables.

Conventional concentrated solar power (CSP) is a reliable alternative energy source that uses the sun’s heat to drive a heat engine to produce electrical power. An advantage of CSP is its ability to store thermal energy for use during off-sun hours which is typically done by storing sensible heat in molten salts. Alternatively, thermal energy may be stored as latent heat in a phase-change material (PCM), which stores large quantities of thermal energy in an isothermal process. On-sun, the PCM melts, storing energy. Off-sun, the latent heat is extracted to produce dispatchable electrical power. This paper presents the design of a thermosyphon-based device with sodium working fluid that is able to extract heat from a source as demand requires. A prototype has been designed to transfer 37 kW of thermal energy from a 600 °C molten PCM tank to an array of 9% efficient thermoelectric generators (TEGs) to produce 3 kW of usable electrical energy for 5 h. This “thermal valve” design incorporates a funnel to collect condensate and a central shut-off valve to control condensate gravity return to the evaporator. Three circumferential tubes allow vapour transport up to the condenser. Pressure and a thermal resistance models were developed to predict the performance of the thermal valve. The pressure model predicts that the thermal valve will function as designed. The thermal resistance model predicts a 5500× difference in total thermal resistance between “on” and “off” states. The evaporator and condenser walls comprise 96% of the “on” thermal resistance, while the small parasitic heat transfer in the “off” state is primarily (77%) due to radiation losses. This simple and effective technology can have a strong impact on the feasibility, scalability, and dispatchability of CSP latent storage. In addition, other industrial and commercial applications can benefit from this thermal valve concept.

Beta-gallium oxide (β-Ga2O3) is an ultrawide bandgap semiconductor that has potential for power electronic applications and devices operating at high temperatures. Particularly important for these applications are its 4.9 eV bandgap, facile electron doping, and the ability to grow β-Ga2O3 crystals from the melt. In this work, vertical β-Ga2O3 Schottky barrier diodes were fabricated using Pt Schottky and Ti-based Ohmic contacts and Au contact pads on unintentionally doped n-type, ( 2 ¯ 01)-oriented single crystal substrates. The diode’s temperature-dependent electrical properties up to 400 °C were investigated, and the Pt/Ga2O3 Schottky barrier height was determined to be close to 1.2 eV. The degradation of the contacts over multiple cycles up to 400 °C was observed, resulting in a significant increase in series resistance of the diodes by 1000× at ambient temperature after they were cycled. According to electron microscopy measurements, this degradation is likely due in part to the migration and oxidation of Ti at the top surface of the Au contact pads. This degradation highlights the need for further research and development to ensure stable Ohmic and Schottky contacts to Ga2O3 at temperatures above 400 °C.

Beta-gallium oxide (β-Ga2O3) is of increasing interest to the optoelectronic community for transparent conductor and power electronic applications. Considerable variability exists in the literature on the growth and doping of Ga2O3 films, especially as a function of growth approach, temperature, and oxygen partial pressure. Here pulsed laser deposition (PLD) was used to grow high-quality β-Ga2O3 films on (0001) sapphire and (−201) Ga2O3 single crystals and to explore the growth, stability, and dopability of these films as function of temperature and oxygen partial pressure. There is a strong temperature dependence to the phase formation, morphology, and electronic properties of β-Ga2O3 from 350 to 550 °C.

The International Symposium on Transparent Oxide Thin Films for Electronics and Optics (TOEO) has been held every two years since 1997. The 10th TOEO conference (TOEO‐10), whose name was changed to ...

We demonstrate a ferroelectric response in MAPbI3 single crystals that can modulate the electronic response and increase stability., Methylammonium lead iodide (MAPbI3) exhibits exceptional photovoltaic performance, but there remains substantial controversy over the existence and impact of ferroelectricity on the photovoltaic response. We confirm ferroelectricity in MAPbI3 single crystals and demonstrate mediation of the electronic response by ferroelectric domain engineering. The ferroelectric response sharply declines above 57°C, consistent with the tetragonal-to-cubic phase transition. Concurrent band excitation piezoresponse force microscopy–contact Kelvin probe force microscopy shows that the measured response is not dominated by spurious electrostatic interactions. Large signal poling (>16 V/cm) orients the permanent polarization into large domains, which show stabilization over weeks. X-ray photoemission spectroscopy results indicate a shift of 400 meV in the binding energy of the iodine core level peaks upon poling, which is reflected in the carrier concentration results from scanning microwave impedance microscopy. The ability to control the ferroelectric response provides routes to increase device stability and photovoltaic performance through domain engineering.

A wide range of optoelectronic devices depend critically on transparent conducting contacts. The range of these applications is increasing due to higher performance and flexible photovoltaic devices; large-area displays and touch screens; and new, flexible, optoelectronic devices based on hybrid materials, including organic, biological, and inorganic materials at the macroscale, mesoscale, and nanoscale. The ability to combine highly conductive, anisotropic nanomaterials such as silver, carbon, and oxide nanowires in an oxide or organic matrix has produced a new class of highly conductive and transparent contacts that can be used in a diverse range of devices and environmental conditions. These solution-depositable contacts can transform large-area devices such as photovoltaics and displays. This chapter summarizes the current state of the art for hybrid nanowire contacts with specific emphasis on their applicability to current and emerging PV technology.

In this work, we present the design and experimental results of a prototype latent heat thermal energy storage system. This prototype used 100 kg of aluminum-silicon as a phase change material with embedded heat pipes for effective heat transfer, a valved thermosyphon to control heat flow out of the thermal storage system, and a Stirling engine to convert heat to electricity. We tested this system for 11 simulated days of operation; each day included charging of the thermal storage tank, simultaneous electricity generation with heat input, and electricity generation from stored heat alone. On each simulated day, we set the engine to a different power level, allowing us to investigate the response of heat pipes and our valved thermosyphon to part-load conditions. The prototype demonstrated a maximum efficiency of 18.5% in converting stored heat to electricity, at a maximum power output of over 1 kW e . Extending these results to a commercial scale system with solar heat input, our modeling indicates that a discharge efficiency of over 30% and an annual efficiency of 18% could be achieved. This performance represents an advancement in established efficiency for any system that combines latent heat storage with electricity generation, and demonstrates that this system has potential for future commercial development.

The Solar Energy Research Institute for India and the United States (SERIIUS - http://www.seriius.org) is dedicated to creating a bi-national network of its 40 partners with members from academia, national laboratories, non-profit organizations, and industry to foster new ideas and collaborations to expedite a sustainable solar industry in the US and in India. SERIIUS is developing disruptive technologies through foundational research in sustainable photovoltaics (PV), multi-scale concentrating solar power (CSP) and coupled to an analysis activity to address the critical barriers for solar energy development in India that intersect the grand challenges for solar energy in the U.S. The consortium has published over 330 papers and conference proceedings of which 45 are joint between India and the US. SERIIUS has engaged overs 200 graduate students and had 30 binational intern exchanges.

Many technologically critical materials are metastable under ambient conditions, yet the understanding of how to rationally design and guide the synthesis of these materials is limited. This work presents an integrated approach that targets a metastable lead-free piezoelectric polymorph of SrHfO3 . First-principles calculations predict that the previous experimentally unrealized, metastable P4mm phase of SrHfO3 should exhibit a direct piezoelectric response (d33 ) of 36.9 pC N-1 (compared to d33 = 0 for the ground state). Combining computationally optimized substrate selection and synthesis conditions lead to the epitaxial stabilization of the polar P4mm phase of SrHfO3 on SrTiO3 . The films are structurally consistent with the theory predictions. A ferroelectric-induced large signal effective converse piezoelectric response of 5.2 pm V-1 for a 35 nm film is observed, indicating the ability to predict and target multifunctionality. This illustrates a coupled theory-experimental approach to the discovery and realization of new multifunctional polymorphs.

For concentrated solar power (CSP) to be an effective replacement for power generation by fossil fuels, the thermal energy must be stored and then released for when demand exceeds production, such as during off-sun hours. Until now, there has been limited methods to reliably and efficiently release and control the extraction of thermal energy from a material containing stored sensible or latent heat. Due to their isothermal property, phase change materials (PCMs) storing latent heat are an ideal choice for storage, though it has proven challenging to reliably extract and utilize that heat. To solve this problem, the geometry of a thermosyphon was rearranged to create a thermal valve that is able to turn the flow of thermal energy from a PCM “on” and “off”. A stainless steel thermal valve using sodium as the working fluid was designed, fabricated, assessed, and found to effectively and selectively extract heat from a 577°C molten aluminum PCM. It is expected that thermal valves will significantly contribute to more widespread implementation of CSP as a stored energy source from distributed generation to utility-scale power production.

Modern electric grids that use intermittent renewables require energy storage to maintain reliability. Many potential solutions exist, but latent heat thermal energy storage shows particularly high potential for low cost grid scale energy storage. In this paper, we present the design and initial experimental results for a lab-scale prototype of a novel latent heat thermal storage system. This version of our prototype used 50 kg of aluminum-silicon alloy as a phase change material, and a novel valved thermosyphon concept to control heat flow from a thermal storage tank to thermoelectric generators for dispatchable electricity production. Our results validate the system: the thermal storage system was able to receive heat input, evenly distribute heat to and from the phase change material with small temperature gradients, and controllably dispatch heat to a heat engine for electricity generation on demand. With the basic principle of this technology demonstrated, our next step will be to evaluate and improve system efficiency.

Location selection is an important factor for the effectiveness and cost of a solar electricity generation system. Latitude and weather impact efficiency and availability, and local labor rates have a further influence on cost. To explore the impact of these effects, we performed techno-economic analysis of a small-scale solar power tower concept in six different locations in the United States, Australia, and India. The specific configuration we considered has a nominal power rating of 100 kWe and 5 hours of thermal energy storage. Further, we considered two deployment strategies: a single stand-alone 100 kWe tower, and a 20 MWe cluster of many towers. For each scenario, we used a probabilistic analysis method to evaluate levelized cost of electricity. We found that this configuration has potential for cost-competitive electricity generation and the ability to improve grid flexibility for integration of intermittent renewables. In addition, solar resource, latitude, and local labor rates all have an impact on the levelized cost of electricity of the system.

The dominant point defect mechanism of amorphous (a-) indium zinc oxide (IZO) was probed through in situ electrical characterization of sputtered a-IZO thin films in response to changes in oxygen partial pressure (pO2) at 300∘C. The results yielded a power law dependence of conductivity (σ) versus pO2 of ∼−1/6. This experimental method, known as Brouwer analysis, confirms doubly-charged oxygen vacancies as the dominant defect species in a-IZO. The success of this study suggests that Brouwer analysis is a viable method for studying the defect mechanisms of amorphous oxides.

An organometallic ink based on the nickel formate–ethylenediamine (Ni(O2CH)2(en)2) complex forms high performance NiOx thin film hole transport layers (HTL) in organic photovoltaic (OPV) devices. Improved understanding of these HTLs functionality can be gained from temperature-dependent decomposition/oxidation chemistries during film formation and corresponding chemical structure-function relationships for energetics, charge selectivity, and transport in photovoltaic platforms. Investigations of as-cast films annealed in air (at 150 °C–350 °C), with and without subsequent O2-plasma treatment, were performed using thermogravimetric analysis, Fourier transform infrared spectroscopy, ultraviolet and X-ray photoelectron spectroscopy, and spectroscopic ellipsometry to elucidate the decomposition and oxidation of the complex to NiOx. Regardless of the anneal temperature, after exposure to O2-plasma, these HTLs exhibit work functions greater than the ionization potential of a prototype donor polymer poly(N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole) (PCDTBT), thereby meeting a primary requirement of energy level alignment. Thus, bulk-heterojunction (BHJ), OPV solar cells made on this series of NiOx HTLs all exhibit similar open circuit voltages (Voc). In contrast, the short circuit currents increase significantly from 1.7 to 11.2 mA cm−2 upon increasing the anneal temperature from 150 °C to 250 °C. Concomitantly, increased conductivity and electrical homogeneity of NiOx thin films are observed at the nanoscale using conductive tip-AFM. Similar Voc observed for all the O2-plasma treated NiOx interlayers and variations to nanoscale conductivity suggest that the HTLs all form charge selective contacts and that their carrier extraction efficiency is determined by the amount of precursor conversion to NiOx. The separation of these two properties: selectivity and conductivity, sheds further light on charge selective interlayer functionality.

Tin nitride, Sn3N4, is a semiconductor composed of common elements with a band gap in the visible range, making it a candidate for optical and electronic applications. In this work, the semiconducting properties of tin nitride are explored by thin-film experiments and first-principles theory to evaluate the prospects of this material for optoelectronic applications. Calculations of related group IV nitride polymorphs provide additional insight into the properties and challenges associated with this class of semiconductors. Experimentally, in Sn3N4 polycrystalline thin films the electron concentration was found to be 1018 cm−3 with Hall mobility of ∼1 cm2 V−1 s−1 and a minority carrier (holes) diffusion length of 50–100 nm. The optical absorption onset was determined at 1.6 eV and an ionization potential was measured at 5.9–6.0 eV. From theory, a direct band gap of 1.54 eV was determined with weak dipole-forbidden lowest energy transitions and the ionization potential was determined to be 6.5 eV, both in reasonable agreement with the experiments. Calculations also predict an exceptionally small electron effective mass (0.18 m0) and a large hole effective mass (12.9 m0), which may be in part responsible for the short hole diffusion length. To elucidate the origin of the heavy holes in Sn3N4, elemental and crystallographic trends in electronic structure and thermochemical properties are calculated in the IV3N4 polymorphs. It was found that hole effective masses generally increase down the period and are structure-dependent, while electron effective masses decrease down the period and show no strong structural trends. These results suggest that changing composition in the group-IV nitride alloys will have a large impact on the fundamental semiconductor properties such as carrier effective masses, and provide other insight into the materials chemistry of Sn3N4 and the IV3N4 family.

Site-specific preparation of specimens using focused ion beam instruments for transmission electron microscopy is at the forefront of targeting regions of interest for nanoscale characterization. Typical methods of pinpointing desired features include electron backscatter diffraction for differentiating crystal structures and energy-dispersive X-Ray spectroscopy for probing compositional variations. Yet there are situations, notably in the titanium dioxide system, where these techniques can fail. Differentiating between the brookite and anatase polymorphs of titania is either excessively laborious or impossible with the aforementioned techniques. However, due to differences in bonding structure, Raman spectroscopy serves as an ideal candidate for polymorph differentiation. In this work, a correlative approach utilizing Raman spectroscopy for targeted focused ion beam specimen preparation was employed. Dark field imaging and diffraction in the transmission electron microscope confirmed the region of interest located via Raman spectroscopy and demonstrated the validity of this new method. Correlative Raman spectroscopy, scanning electron microscopy, and focused ion beam is shown to be a promising new technique for identifying site-specific preparation of nanoscale specimens in cases where conventional approaches do not suffice.

Theoretically predicted metastable phases are realized in thin-film synthesis of Mn1−xZnxO and Sn1−xCaxS alloys., Structure and composition control the behavior of materials. Isostructural alloying is historically an extremely successful approach for tuning materials properties, but it is often limited by binodal and spinodal decomposition, which correspond to the thermodynamic solubility limit and the stability against composition fluctuations, respectively. We show that heterostructural alloys can exhibit a markedly increased range of metastable alloy compositions between the binodal and spinodal lines, thereby opening up a vast phase space for novel homogeneous single-phase alloys. We distinguish two types of heterostructural alloys, that is, those between commensurate and incommensurate phases. Because of the structural transition around the critical composition, the properties change in a highly nonlinear or even discontinuous fashion, providing a mechanism for materials design that does not exist in conventional isostructural alloys. The novel phase diagram behavior follows from standard alloy models using mixing enthalpies from first-principles calculations. Thin-film deposition demonstrates the viability of the synthesis of these metastable single-phase domains and validates the computationally predicted phase separation mechanism above the upper temperature bound of the nonequilibrium single-phase region.

We are developing a novel concentrating solar electricity-generating technology that is both modular and dispatchable. Solar ThermoElectricity via Advanced Latent heat Storage (STEALS) uses concentrated solar flux to generate high-temperature thermal energy, which directly converts to electricity via thermoelectric generators (TEGs), stored within a phase-change material (PCM) for electricity generation at a later time, or both allowing for simultaneous charging of the PCM and electricity generation. STEALS has inherent features that drive its cost-competitive scale to be much smaller than current commercial concentrating solar power (CSP) plants. Most obvious is modularity of the solid-state TEG, which favors smaller scales in the kilowatt range as compared to CSP steam turbines, which are minimally 50 MWe for commercial power plants. Here, we present techno-economic and market analyses that show STEALS can be a cost-effective electricity-generating technology with particular appeal to small-scale microgrid applications. We evaluated levelized cost of energy (LCOE) for STEALS and for a comparable photovoltaic (PV) system with battery storage. For STEALS, we estimated capital costs and the LCOE as functions of the type of PCM including the use of recycled aluminum alloys, and evaluated the cost tradeoffs between plasma spray coatings and solution-based boron coatings that are applied to the wetted surfaces of the PCM subsystem. We developed a probabilistic cost model that accounts for uncertainties in the cost and performance inputs to the LCOE estimation. Our probabilistic model estimated LCOE for a 100-kWe STEALS system that had 5 hours of thermal storage and 8–10 hours of total daily power generation. For these cases, the solar multiple for the heliostat field varied between 1.12 and 1.5. We identified microgrids as a likely market for the STEALS system. We characterized microgrid markets in terms of nominal power, dispatchability, geographic location, and customer type, and specified additional features for STEALS that are needed to meet the needs of this growing power market.

As the world’s demand for energy grows, the search for cost competitive and earth abundant thin film photovoltaic absorbers is becoming increasingly important. A promising approach to tackle this challenge is through thin film photovoltaics made of elements that are abundant in the Earth’s crust. In this work, we focus on Cu2SnS3, a promising earth abundant absorber material. Recent publications have presented 3% and 6% device efficiencies using Cu2SnS3-based absorber materials and alloys, respectively. However, little is understood about the fundamental defect and doping physics of this material, which is needed for further improvements in device performance. Here, we identify the origins of the changes in doping in sputtered cubic Cu2SnS3 thin films using combinatorial experiments and first-principles theory. Experimentally, we find that the cubic Cu2SnS3 has a large phase width and that the electrical conductivity increases with increasing Cu and S content in the films, which cannot be fully explained ...

The influence of backbone composition on the physical properties of donor-acceptor (D-A) copolymers composed of varying amounts of benzodithiophene (BDT) donor with the thienoisoindoledione (TID) acceptor is investigated. First, the synthesis of bis- and tris-BDT monomers is reported; these monomers are subsequently used in Stille copolymerizations to create well-defined alternating polymer structures with repeating (D-A), (D-D-A), and (D-D-D-A) units. For comparison, five semi-random D-A copolymers with a D:A ratio of 1.5, 2, 3, 4, and 7 were synthesized by reacting trimethyltin-functionalized BDT with various ratios of iodinated BDT and brominated TID. While the HOMO levels of all the resultant polymers are very similar, a systematic red shift in the absorbance spectra onset of the D-A copolymer films from 687 to 883 nm is observed with increasing acceptor content, suggesting the LUMO can be fine-tuned over a range of 0.4 eV. When the solid-state absorbance spectra of well-defined alternating copolymers are compared to those of semi-random copolymers with analogous D:A ratios, the spectra of the alternating copolymers are significantly more red-shifted. Organic photovoltaic device efficiencies show that the semi-random materials all outperform the well-defined alternating copolymers, and an optimal D:A ratio of 2 produces the highest efficiency. Additional considerations concerning fine-tuning the lifetimes of the photoconductance transients of copolymer:fullerene films measured by time-resolved microwave conductivity are discussed. Overall, the results of this work indicate that the semi-random approach is a powerful synthetic strategy for fine-tuning the optoelectronic and photophysical properties of D-A materials for a number of systematic studies, especially given the ease with which the D:A ratios in the semi-random copolymers can be tuned.

The electronic structure of the hybrid interface between ZnO and the prototypical organic semiconductor PTCDI is investigated via a combination of ultraviolet and X-ray photoelectron spectroscopy (UPS/XPS) and density functional theory (DFT) calculations. The interfacial electronic interactions lead to a large interface dipole due to substantial charge transfer from ZnO to 3,4,9,10-perylenetetracarboxylicdiimide (PTCDI), which can be properly described only when accounting for surface defects that confer ZnO its n-type properties.