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At least 595 records · Page 33

Electronic structure, self-doping, and superconducting instability in the alternating single-layer trilayer stacking nickelates La 3 ⁢Ni 2 ⁢O 7

Motivated by the recently proposed alternating single-layer trilayer stacking structure for the nickelate La 3 ⁢Ni 2 ⁢O 7 , we comprehensively study this system using ab initio and random-phase approximation techniques. Here, our analysis unveils similarities between this novel La 3⁢ Ni 2 ⁢O 7 structure and other Ruddlesden-Popper nickelate superconductors, such as a similar charge-transfer gap value and orbital-selective behavior of the eg orbitals. Pressure primarily increases the bandwidths of the Ni e g bands, suggesting an enhancement of the itinerant properties of those e g states. By changing the cell volume ratio V/V 0 from 0.9 to 1.10, we found that the bilayer structure in La 3 ⁢Ni 2 ⁢O 7 always has lower energy than the single-layer trilayer stacking La 3 ⁢Ni 2 ⁢O 7 . In addition, we observe a “self-doping” effect (compared to the average 1.5 electrons per eg orbital per site of the entire structure) from the trilayer to the single-layer sublattices and this effect will be enhanced by overall electron doping. Moreover, we find a leading d x 2 -y 2 -wave pairing state that is restricted to the single layer. Because the effective coupling between the single layers is very weak, due to the nonsuperconducting trilayer in-between, this suggests that the superconducting transition temperature T c in this structure should be much lower than in the bilayer structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Designing Passivating, Carrier-Selective Contacts for Photovoltaic Devices

"The first step towards building a high-efficiency solar cell is to develop an absorber with few recombination-active defects. Many photovoltaic technologies have already achieved this (monocrystalline Si, III-V materials grown on lattice-matched substrates, perovskites, polycrystalline CdTe and CIGS); those that have not (a-Si:H, organics) have been limited to low open-circuit voltage. The second step is to develop contacts that both inhibit surface recombination and allow for low-resistance collection of either only electrons or only holes. For most photovoltaic technologies, this step is both more difficult and less explored than the first, and we are unaware of a prescribed methodology for selecting materials for contacts to solar cells. We elucidate a unified, conceptual understanding of contacts within which existing contacting schemes can be interpreted and future contacting schemes can be imagined. Whereas a split of the quasi-Fermi levels of holes and electrons is required in the absorber of any solar cell to generate a voltage, carriers are eventually collected through a metallic wire in which no such quasi-Fermi-level split exists. We define a contact to be all layers between the bulk of the absorber and the recombination-active interface through which carriers are extracted. The quasi-Fermi levels must necessarily collapse at this interface, and thus the transition between maximal quasi-Fermi-level splitting (in the absorber) and no splitting occurs entirely in the contact. Depending on the solar cell architecture, the contact will usually extend from the surface of the absorber to the surface of a metal or transparent conductive oxide layer, and may include deposited or diffused doped layers (e.g., as in crystalline and thin-film Si cells) and heterostructure buffer layers (e.g., the CdS layer in a CdTe device). We further define a passivating contact as one that enables high quasi-Fermi-level splitting in the absorber (large “internal” voltage), where “high” is relative to the splitting dictated by bulk recombination. Finally, we define a carrier-selective contact as one that enables a high “external” voltage measured across the contacts, where “high” is relative to the internal voltage. With these definitions, passivating contacts are those that allow only electrons, only holes, or neither electrons or holes to transport from the absorber to any position in the contact that has recombination-active defects. An excellent example of this is a SiNx layer on a Si wafer: the layer removes dangling bonds at the wafer surface (where there are both electrons and holes) and does not allow either carrier type to travel to its outermost surface, where there are undoubtedly defects. Carrier-selective contacts are then passivating contacts that also allow for low-impedance flow of either electrons or holes (but not both) to the recombination-active, extracting interface. The most common example is a heavily doped layer that establishes an electric field at the absorber surface, which then “filters” the carriers that may pass to the contact according to the sign of their charge.

14 SOLAR ENERGY↗

Conduction band position tuning and Ga-doping in (Cd,Zn)S alloy thin films

In recent years, the number of novel photovoltaic absorber materials under exploration has rapidly increased. However, to reap the most benefit from these new absorbers, alternative device structures and components must also be considered. In particular, the choice of a heterojunction partner, or contact layer, is critical to device optimization. In this work, we explore alternative n-type contact layer candidates that could be widely applicable to a variety of new absorbers. We use theory to calculate the band edge tuning provided by a variety of II-VI alloy systems, and select the (Cd,Zn)S system as one that affords a wide range of conduction band tuning. The synthesis of (Cd,Zn)S alloys is explored using atomic layer deposition, which afforded precise compositional control and produced crystalline thin films. The predicted tuning of the band gap and conduction band minimum is confirmed through X-ray photoelectron spectroscopy and optical absorption measurements. In addition, we investigated Ga-doping in Cd 0.6 Zn 0.4 S films to decrease their series resistance when used as contact layers in photovoltaic devices. In conclusion, this study provides a framework for exploring and optimizing alternative contact layer materials, which will prove critical to the success of new PV absorbers.

14 SOLAR ENERGY↗

Synthesis of aviation biofuel precursors from biomass-derived ketones: Substrate adsorption configuration-catalytic activity

The production of aviation biofuel precursors from biomass-derived ketones by heterogeneous catalysis has been hindered by the low catalytic activity. Herein, a series of Cu-doped metal oxide catalysts were prepared for the conversion of biomass-derived ketones to aviation biofuel precursors. Solvent-free cyclopentanone conversion via aldol condensation reached 91.1 % over Cu/Al 2 O 3 with 100 % selectivity toward dimer and trimer oxygenated species, all of which are aviation biofuel precursors. This catalyst primarily contains Cu 2 O and Cu nanoparticles which are uniformly dispersed across the Al 2 O 3 surface. From in situ DRIFTS and DFT results, the incorporation of Cu species onto Al 2 O 3 not only increased the diversity of Lewis acidic sites, but also changed the adsorption of C = O groups, which lead to the increased aldol condensation activity of Cu/Al 2 O 3 . In conclusion, this study provides insight on the design of heterogeneous catalysts suitable for the solvent-free synthesis of aviation biofuel precursors from biomass-derived ketones.

Adsorption configuration↗

Microstructure and Cs Behavior of Ba-Doped Aluminosilicate Pollucite Irradiated with F+ Ions

Radionuclide 137Cs is one of the major fission products that dominate heat generation in spent fuels over the first 300 hundred years. A durable waste form for 137Cs that decays to 137Ba is needed to minimize its environmental impact. Aluminosilicate pollucite CsAlSi2O6 is selected as a model waste form to study the decay-induced structural effects. While Ba-containing precipitates are not present in charge-balanced Cs0.9Ba0.05AlSi2O6, they are found in Cs0.9Ba0.1AlSi2O6 and identified as monoclinic Ba2Si3O8. Pollucite is susceptible to electron irradiation induced amorphization. The threshold density of the electronic energy deposition for amorphization is determined to be ~235 keV/nm3. Pollucite can be readily amorphized under F+ ion irradiation at 673 K. A significant amount of Cs diffusion and release from the amorphized pollucite is observed during the irradiation. However, cesium is immobile in the crystalline structure under He+ ion irradiation at room temperature. The critical temperature for amorphization is not higher than 873 K under F+ ion irradiation. If kept at or above 873 K all the time, the pollucite structure is unlikely to be amorphized; Cs diffusion and release are improbable. A general discussion regarding pollucite as a potential waste form is provided in this report.

aluminosilicate pollucite↗

Predictions of delafossite-hosted honeycomb and kagome phases

Delafossites, typically denoted by the formula ABO 2 , are a class of layered materials that exhibit a wide range of electronic and optical properties. Recently, the idea of modifying these delafossites into ordered kagome or honeycomb phases via strategic doping has emerged as a potential way to tailor these properties. In this study, we use high-throughput density functional theory calculations to explore many possible candidate kagome and honeycomb phases by considering dopants selected from the parent compounds of known ternary delafossite oxides from the inorganic crystal structure database. Here our results indicate that while A-site in existing delafossites can host a limited range of elemental specifies, and display a low propensity for mixing or ordering, the oxide sub-units in the BO 2 much more readily admit guest species. Our study identifies four candidate B-site kagome and fifteen candidate B-site honeycombs with a formation energy more than 50 meV f.u. −1 below other competing phases. The ability to predict and control the formation of these unique structures offers exciting opportunities in materials design, where innovative properties can be engineered through the selection of specific dopants. A number of these constitute novel correlated metals, which may be of interest for subsequent efforts in synthesis. These novel correlated metals may have significant implications for quantum computing, spintronics, and high-temperature superconductivity, thus inspiring future experimental synthesis and characterization of these proposed materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

First-principles electronic structure and formation energies of group V and VII impurities in the α-Fe{sub 2}O{sub 3} alloys

Based on density functional theory, the electronic structures, formation energy, and transition level of the selected group V and VII impurities in α-Fe{sub 2}O{sub 3} are investigated by means of first-principles methods. Numerical results show that the group V and VII atoms-doped α-Fe{sub 2}O{sub 3} can be energetically favorable under the Fe-rich condition. Group V atom substituting O atom can induce the acceptor impurity level, while the deep donor impurity states are formed inside the band gap when group VII atom substitute O atom in the α-Fe{sub 2}O{sub 3}. Moreover, our results show that halogen atom F substituting O atom should be very easy in the α-Fe{sub 2}O{sub 3}. In addition, our results also show that for both group V and VII atom-doped α-Fe{sub 2}O{sub 3}, the upper sides of valence band are modified obviously, while the conduction band edge does not change.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Threshold switching behavior of Ag-Si based selector device and hydrogen doping effect on its characteristics

The effect of hydrogen treatment on the threshold switching property in a Ag/amorphous Si based programmable metallization cells was investigated for selector device applications. Using the Ag filament formed during motion of Ag ions, a steep-slope (5 mV/dec.) for threshold switching with higher selectivity (∼10{sup 5}) could be achieved. Because of the faster diffusivity of Ag atoms, which are inside solid-electrolytes, the resulting Ag filament could easily be dissolved under low current regime, where the Ag filament possesses weak stability. We found that the dissolution process could be further enhanced by hydrogen treatment that facilitated the movement of the Ag atoms.

36 MATERIALS SCIENCE↗

MO-F-CAMPUS-T-05: Design of An Innovative Beam Monitor for Particle Therapy for the Simultaneous Measurement of Beam Fluence and Energy

Purpose: Monitoring the prescribed dose in particle therapy is typically carried out by using parallel plate ionization chambers working in transmission mode. The use of gas detectors has several drawbacks: they need to be calibrated daily against standard dosimeters and their dependence on beam quality factors need to be fully characterized and controlled with high accuracy. A detector capable of single particle counting is proposed which would overcome all these limitations. Combined with a gas ionization chamber, it will allow determining the average particle stopping power, thus providing an effective method for the online verification of the selected particle energy and range. Methods: Low-Gain Avalanche Detectors (LGADs) are innovative n-in-p silicon sensors with moderate internal charge multiplication occurring in the strong field generated by an additional p+ doping layer implanted at a depth of a few µm in the bulk of the sensor. The increased signal-to-noise ratio allows designing very thin, few tens of microns, segmented LGADs, called Ultra Fast Silicon Detectors (UFSD), optimized for very fast signal, which would be suitable for charged particle counting at high rates. A prototype UFSD is being designed for this purpose. Results: Different LGAD diodes have been characterized both in laboratory and beam tests, and the results compared both with those obtained with similar diodes without the gain layer and with a program simulating the signal in the sensors. The signal is found to be enhanced in LGADs, while the leakage current and the noise is not affected by the gain. Possible alternative designs and implementations are also presented and discussed. Conclusion: Thanks to their excellent counting capabilities, UFSD detectors are a promising technology for future beam monitor devices in hadron-therapy applications. Studies are ongoing to better understand their properties and optimize the design in view of this application.

61 RADIATION PROTECTION AND DOSIMETRY↗

Revealing the role of redox reaction selectivity and mass transfer in current–voltage predictions for ensembles of photocatalysts

Photocatalysts are conceptually simple reaction units where nanoscale semiconductors integrated with catalysts drive a pair of redox reactions on illumination. However, the proximity of reaction sites performing cathodic and anodic reactions poses dire challenges to realize large light-to-fuel conversion efficiencies. In this study, a powerful, yet straightforward, equivalent-circuit detail-balance modeling framework is developed and applied to evaluate the performance of photocatalytic systems featuring multiple light absorbers. Specifically, low bandgap iridium-doped strontium titanate is modeled as a Z-scheme photocatalyst to achieve desirable hydrogen evolution and iron-based redox shuttle oxidation reactions. Our model has unique capabilities to simulate competing redox reactions and address mass-transfer limitations. In a significant departure from state-of-the-art circuit models, our study develops tools to perform load-line analyses by incorporating a net electrochemical load curve that includes both desired and competing redox reactions. Consequently, reaction selectivity is predicted from equivalent circuit models for photocatalytic and photoelectrochemical systems. Our investigation into ensembles comprised of multiple, semi-transparent light absorbers reveals their potential to outperform a single, optically thick light absorber, particularly when operated under mass-transfer-limited conditions. However, this outcome hinges on minimizing mass-transfer rates of select redox species to prevent undesired reactions of hydrogen oxidation and/or redox shuttle reduction. Our findings demonstrate that reaction selectivity can be achieved by tuning asymmetry in redox species mass-transfer even with perfectly symmetric electrocatalytic charge-transfer coefficients. The influences of various kinetic, mass-transfer, and thermodynamic parameters are explored to offer crucial insights for synthesis of the next-generation of photocatalysts and selective coatings, and reactor designs.

25 ENERGY STORAGE↗

Sputtering yields and surface chemical modification of tin-doped indium oxide in hydrocarbon-based plasma etching

Sputtering yields and surface chemical compositions of tin-doped indium oxide (or indium tin oxide, ITO) by CH{sup +}, CH{sub 3}{sup +}, and inert-gas ion (He{sup +}, Ne{sup +}, and Ar{sup +}) incidence have been obtained experimentally with the use of a mass-selected ion beam system and in-situ x-ray photoelectron spectroscopy. It has been found that etching of ITO is chemically enhanced by energetic incidence of hydrocarbon (CH{sub x}{sup +}) ions. At high incident energy incidence, it appears that carbon of incident ions predominantly reduce indium (In) of ITO and the ITO sputtering yields by CH{sup +} and CH{sub 3}{sup +} ions are found to be essentially equal. At lower incident energy (less than 500 eV or so), however, a hydrogen effect on ITO reduction is more pronounced and the ITO surface is more reduced by CH{sub 3}{sup +} ions than CH{sup +} ions. Although the surface is covered more with metallic In by low-energy incident CH{sub 3}{sup +} ions than CH{sup +} ions and metallic In is in general less resistant against physical sputtering than its oxide, the ITO sputtering yield by incident CH{sub 3}{sup +} ions is found to be lower than that by incident CH{sup +} ions in this energy range. A postulation to account for the relation between the observed sputtering yield and reduction of the ITO surface is also presented. The results presented here offer a better understanding of elementary surface reactions observed in reactive ion etching processes of ITO by hydrocarbon plasmas.

36 MATERIALS SCIENCE↗

Polymorphism controls the degree of charge transfer in a molecularly doped semiconducting polymer

When an organic semiconductor (OSC) is blended with an electron acceptor molecule that can act as a p-type dopant, there should ideally be complete (integer) transfer of charge from the OSC to the dopant. However, some dopant–OSC blends instead form charge transfer complexes (CTCs), characterized by fractional charge transfer (CT) and strong orbital hybridization between the two molecules. Fractional CT doping does not efficiently generate free charge carriers, but it is unclear what conditions lead to incomplete charge transfer. Here we show that by modifying film processing conditions in the semiconductor–dopant couple poly(3-hexylthiophene):2,3,5,6-tetrafluoro-7,7,8,8,-tetracyanoquinodimethane (P3HT:F4TCNQ), we can selectively obtain nearly pure integer or fractional CT phases. Fractional CT films show electrical conductivities approximately 2 orders of magnitude lower than corresponding integer CT films, and remarkably different optical absorption spectra. Grazing incidence wide-angle X-ray diffraction (GIXD) reveals that fractional CT films display an unusually dense and well-ordered crystal structure. These films show lower paracrystallinity and shorter lamellar and π-stacking distances than undoped films processed under similar conditions. Using plane-wave DFT we obtain a structure with unit cell parameters closely matching those observed by GIXD. This first-ever observation of both fractional and integer CT in a single OSC–dopant system demonstrates the importance of structural effects on OSC doping and opens the door to further studies.

36 MATERIALS SCIENCE↗

Evaluation of fuel-borne sodium effects on a DOC-DPF-SCR heavy-duty engine emission control system: Simulation of full-useful life

Here we report that for renewable fuels to displace petroleum, they must be compatible with emissions control devices. Pure biodiesel contains up to 5 ppm Na + K and 5 ppm Ca + Mg metals, which have the potential to degrade diesel emissions control systems. This study aims to address these concerns, identify deactivation mechanisms, and determine if a lower limit is needed. Accelerated aging of a production exhaust system was conducted on an engine test stand over 1001 h using 20% biodiesel blended into ultra-low sulfur diesel (B20) doped with 14 ppm Na. This Na level is equivalent to exposure to Na at the uppermost expected B100 value in a B20 blend for the system full-useful life. During the study, NOx emissions exceeded the engine certification limit of 0.33 g/bhp-hr before the 435,000-mile requirement. Replacing aged diesel oxidation catalyst (DOC), diesel particulate filter (DPF), and selective catalytic reduction (SCR) devices with new degreened parts showed that each device contributed equally to the NOx increase. Following this systems-based evaluation, a detailed investigation of the individual components was completed. Na was determined to have minimal impact on DOC activity. For this system, it is estimated that B20-Na resulted in 50% more ash into the DPF. However, the Na did not diffuse into the cordierite DPF nor degrade its mechanical properties. The SCR degradation was found to be caused by a small amount of precious group metals (PGM) contamination that increased NH3 oxidation, and lowered NOx reduction. Therefore, we determined that the primary effect of Na in this study is through increased ash in the DPF rather than deactivation of the catalytic activity.

42 ENGINEERING↗

Polycrystalline indium phosphide on silicon by indium assisted growth in hydride vapor phase epitaxy

Polycrystalline InP was grown on Si(001) and Si(111) substrates by using indium (In) metal as a starting material in hydride vapor phase epitaxy (HVPE) reactor. In metal was deposited on silicon substrates by thermal evaporation technique. The deposited In resulted in islands of different size and was found to be polycrystalline in nature. Different growth experiments of growing InP were performed, and the growth mechanism was investigated. Atomic force microscopy and scanning electron microscopy for morphological investigation, Scanning Auger microscopy for surface and compositional analyses, powder X-ray diffraction for crystallinity, and micro photoluminescence for optical quality assessment were conducted. It is shown that the growth starts first by phosphidisation of the In islands to InP followed by subsequent selective deposition of InP in HVPE regardless of the Si substrate orientation. Polycrystalline InP of large grain size is achieved and the growth rate as high as 21 μm/h is obtained on both substrates. Sulfur doping of the polycrystalline InP was investigated by growing alternating layers of sulfur doped and unintentionally doped InP for equal interval of time. These layers could be delineated by stain etching showing that enough amount of sulfur can be incorporated. Grains of large lateral dimension up to 3 μm polycrystalline InP on Si with good morphological and optical quality is obtained. The process is generic and it can also be applied for the growth of other polycrystalline III–V semiconductor layers on low cost and flexible substrates for solar cell applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Phase-change Reconfigurable Optical WavEfront Synthesis System (PROWESS)

We report the design, fabrication, and testing of electrically tunable metasurface k-space filters based on the low-loss, high-contrast phase-change material GSST and a transparent Si electrode heating architecture. A 10x10 array of PCM elements integrated with Si heaters was fabricated via foundry processes, and used to actively control the crystallinity of a metasurface consisting of GSST nano antennae. By selectively varying the structural state of individual PCM elements, specific k-vectors of transmitted light can effectively be filtered out, resulting in improved imaging quality by reducing the scattered light that reaches a detector. Optimized doping profiles in the Si heaters allow for uniform, low power, reliable and repeatable switching of the GSST state. Compared to other k-space filters, this new architecture is completely transparent to the wavelength of interest and can be actively reconfigured in real time with high performance, low power consumption and a small footprint. The 10x10 array device is a proof-of-concept demonstration that can enable high-resolution arbitrary wavefront synthesis and correction in the future, with key applications in optical communications, beam steering, remote sensing, and adaptive optics.

phase change material↗

A general strategy and a consolidated mechanism for low-methane hydrogenolysis of polyethylene over ruthenium

Polyethylene (PE) is one of the most environment-threatening plastic waste. Its Ru-catalyzed hydrogenolysis is rapid but produces too much methane. Here, in this study, low-density PE hydrogenolysis is performed at mild conditions and short times over Ru-doped zirconia catalysts (Ru-XZr, X = Ti, Nb, Ce, W, V, Mo, Fe) to determine low-methane catalysts. Methane is produced via direct terminal C-C scission and surface cascade of consecutive C-C scissions, with the latter sensitive to hydrogen availability and dominant in hydrogen-lean conditions. Reactivity studies, characterization and theory reveal that the most effective dopant oxides (W, V, and Mo) are intermediately reducible, as they store and supply extra hydrogen to Ru via reverse hydrogen spillover. This hydrogen readily hydrogenates and desorbs long alkyl surface intermediates that would otherwise produce cascade methane. Our proposed mechanism reconciles the low methane production achieved by increasing the hydrogen pressure or reducing the particle size and exposes the key selectivity descriptors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Super-Resolution Photothermal Patterning in Conductive Polymers Enabled by Thermally Activated Solubility

Doping induced solubility control (DISC) patterning is a recently developed technique which uses the change in polymer solubility upon doping, along with an optical dedoping process, to achieve high resolution optical patterning. DISC patterning is remarkable because the process resolution exceeds the linear Abbe’s diffraction limit, however, no mechanism has been proposed to explain such high resolution. Here, we use diffraction to spatially modulate the light intensity and determine the dissolution rate, revealing a superlinear dependence on light intensity, which yields features that are sharper than the profile of the writing photomask. This rate law is independent of wavelength, indicating that patterning resolution is not dominated by an optical dedoping reaction, as was previously proposed. Instead we show here that the optical patterning mechanism is primarily controlled by the thermal profile generated by the laser. To quantify this effect, the thermal profile and dissolution rate are modeled using a finite-element model and compared against patterned line cross sections as a function of wavelength, laser intensity, and dwell time. Our model reveals that although the laser-generated thermal profile is broadened considerably beyond the lasers resolution, the highly temperature dependent dissolution rate results in selective dissolution near the peak of the thermal profile. Therefore, the key factor in achieving super-resolution patterning is a strongly temperature dependent dissolution rate|a common feature of many polymers. In addition to suggesting several routes to improved resolution, our model also demonstrates that doping is not required for optical patterning of conjugated polymers, as was previously believed. Instead, we demonstrate that superlinear resolution optical patterning is attainable in any conjugated polymer simply by tuning the solvent quality during patterning, thus extending the applicability of our method to a wide class of materials. Here, we demonstrate the generality of photothermal patterning by writing sub-400 nm features into undoped Pff-BT4T-2OD.

36 MATERIALS SCIENCE↗