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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

A new approach to synthesize supported ruthenium phosphides for hydrodesulfurization

Highlights: • We bring out a new method to synthesize noble metal phosphides at low temperature. • Both RuP and Ru{sub 2}P were synthesized using triphenylphosphine as phosphorus sources. • Ru{sub 2}P was the better active phase for HDS than RuP and metal Ru. • RuP/SiO{sub 2} prepared by new method had better HDS activity to that by TPR method. - Abstract: Supported noble metal ruthenium phosphides were synthesized by one-step H{sub 2}-thermal treatment method using triphenylphosphine (TPP) as phosphorus sources at low temperatures. Two phosphides RuP and Ru{sub 2}P can be prepared by this method via varying the molar ratio of metal salt and TPP. The as-prepared phosphides were characterized by X-ray powder diffraction (XRD), low-temperature N{sub 2} adsorption, CO chemisorption and transmission electronic microscopy (TEM). The supported ruthenium phosphides prepared by new method and conventional method together with contradistinctive metallic ruthenium were evaluated in hydrodesulfurization (HDS) of dibenzothiophene (DBT). The catalytic results showed that metal-rich Ru{sub 2}P was the better active phase for HDS than RuP and metal Ru. Besides this, ruthenium phosphide catalyst prepared by new method exhibited superior HDS activity to that prepared by conventional method.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Effects of Phosphorous-doping and High Temperature Annealing on CVD grown 3C-SiC

The integrity and property behavior of the SiC layer of the Tri-isotropic (TRISO) coated particle (CP) for high temperature reactors (HTR) are very important as the SiC layer is the main barrier for gaseous and metallic fission product release. This study describes the work done on un-irradiated SiC samples prepared with varying phosphorus levels to simulate the presence of phosphorus due to transmutation. 30Si transmutes to phosphorous (31P) and other transmutation products during irradiation, which may affect the integrity of the SiC layer. The P-doping levels of the SiC samples used in this study cover the range from 1.1x1015 to 1.2x1019 at/cm3 and are therefore relevant to the PBMR operating conditions. Annealing from 1000 C to 2100 C was performed to study the possible changes in nanostructures and various properties due to temperature. Characterization results by X-ray diffraction (XRD), secondary ion mass spectrometry (SIMS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM), are reported in this article. As grain boundary diffusion is identified as a possible mechanism by which 110mAg, one of the fission activation products, might be released through intact SiC layer, grain size measurements is also included in this study. Temperature is evidently one of the factors/parameters amongst others known to influence the grain size of SiC and therefore it is important to investigate the effect of high temperature annealing on the SiC grain size. The ASTM E112 method as well as electron back scatter diffraction (EBSD) was used to determine the grain size of various commercial SiC samples and the SiC layer in experimental PBMR Coated Particles (CPs) after annealing at temperatures ranging from 1600 C to 2100 C. The HRTEM micrograph of the decomposition of SiC at 2100 C are shown and discussed. Nanotubes were not identified during the TEM and HRTEM analysis although graphitic structures were identified. The preliminary conclusion reached is that the P-content at these experimental levels (1.1x1015 - 1.2x1019 atom/cm3) does not have a significant influence on the nanostructure of SiC at high temperatures without irradiation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2018

Phosphate addition increases tropical forest soil respiration primarily by deconstraining microbial population growth

Tropical ecosystems are an important sink for atmospheric CO 2 ; however, plant growth is restricted by phosphorus (P) availability. Although soil microbiota facilitate organic P turnover and inorganic P mobilization, their role in carbon-phosphorus coupled processes remains poorly understood. To advance this topic, soils collected from four sites representing highly weathered tropical soils in the El Yunque National Forest, Puerto Rico were incubated with exogenous PO 4 3- under controlled laboratory conditions. P amendment increased CO 2 respiration by 14–23% relative to control incubations for soils sampled from all but the site with the greatest total and bioavailable soil P. Metatranscriptomics revealed an increase in the relative transcription of genes involved in cell growth and uptake of other nutrients in response to P amendment. A new methodology to normalize gene expression by population-level relative (DNA) abundance revealed that the pattern of increased transcription of cell growth and division genes with P amendment was community-wide. Soil communities responsive to P amendment possessed a greater relative abundance of α-glucosyl polysaccharide biosynthesis genes, suggestive of enhanced C storage under P-limiting conditions. Phosphorylase genes governing the degradation of α-glucosyl polysaccharides were also more abundant and increased in relative transcription with P amendment, indicating a shift from energy storage towards growth. Inversely, microbial communities in soils nonresponsive to P amendment were found to have metabolisms tuned for the phosphorolysis of labile plant-derived substrates, such as β-glucosyl polysaccharides. Accordingly, our results provided quantitative estimates of increased soil respiration upon alleviation of P constraints and elucidated several underlying ecological and molecular mechanisms involved in this response.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Phosphate amendment drives bloom of RNA viruses after soil wet-up

Soil rewetting after a dry period results in a surge of activity and succession in both microbial and DNA virus communities. Less is known about the response of RNA viruses to soil rewetting—while they are highly diverse and widely distributed in soil, they remain understudied. We hypothesized that RNA viruses would show temporal succession following rewetting and that phosphate amendment would influence their trajectory, as viral proliferation may cause phosphorus limitation. Using 39 time-resolved metatranscriptomes and amplicon data, 2190 RNA viral populations were identified across five phyla, with 26 % of these predicted to infect bacteria, and 11 % fungi. Only 1.2 % of viral populations had annotated capsid genes, suggesting most persist via intracellular replication without a free virion phase. Phosphate amendment altered RNA viral community composition within the first week and amended vs. unamended communities remained distinguishable for up to three weeks. While the overall host community remained stable, certain bacterial populations showed reduced abundance in phosphate-amended soils, likely due to increased viral lysis, as RNA bacteriophages proliferated significantly. Notably, 60 % of the viruses with increased abundance under phosphate amendment belonged to basal Lenarviricota clades rather than well-known groups like Leviviricetes. We estimate RNA bacteriophage infections may affect 10 7 –10 9 bacteria per gram of soil, aligning with the total bacterial population (10 7 –10 10 g -1 soil), suggesting that RNA phages significantly influence bacterial communities post-wet-up, with phosphorus availability modulating this effect.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Oxidation-Induced Polymerization of InP Surface and Implications for Optoelectronic Applications

InP is among the most studied materials for energy-conversion applications including optoelectronics and photoelectrochemical devices. One of the long-standing challenges with this material, and III–V semiconductors more generally, is to understand and control surface oxide formation, which critically impacts device functionality, performance, and durability. In this work, we integrate advanced in situ ambient pressure X-ray photoelectron spectroscopy (APXPS) and ab initio simulations to reveal the mechanism of the oxidation process on the InP(001) surface. By interpreting the APXPS results through direct ab initio spectroscopic calculations of surface models, and by comparing calculated and measured work functions, we provide an unbiased picture of the chemical evolution of the thermal oxide. Furthermore, at low temperatures (<573 K), O 2 exposure leads to predominant formation of cross-linked PO x units dispersed with submonolayer thickness, which grow into an amorphous two-dimensional (2D) film that is kinetically limited to the surface layer. Increased temperature (>573 K) leads to the polymerization of PO x units and the formation of a complex, inhomogeneous 3D network of surface oxide that is progressively indium rich and phosphorus poor toward the surface. Finally, accelerated phosphorus loss via a hitherto unreported coupled charge-transfer isomer transformation mechanism leads to the formation of a thick, amorphous In 2 O 3 -like oxide at 773 K with very different optoelectronic and hot carrier transportation properties. In addition to unraveling complex mechanisms of surface oxidation, our results suggest the possibility of deliberately tuning oxide composition by leveraging competition between thermodynamic and kinetic factors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

First-Principles Surface Characterization and Water Adsorption of Fe 3 P Schreibersite

We report the meteoritic mineral schreibersite, e.g., Fe 3 P, is a proposed abiotic source of phosphorus for phosphate ion (PO 4 – ) production, needed for nucleobases, phospholipids, and other life building materials. Schreibersite could have acted as both a source of elemental phosphorus and as a catalyst, and the hostile conditions on early Earth could have accelerated its degradation in different environments. Here, we present results from quantum calculations of bulk schreibersite and of its low Miller index surfaces. We also investigate water surface adsorption and identify possible dissociation pathways on the most stable facet. Our calculations provide useful chemical insights into schreibersite interactions in aqueous environments, paving the way for further detailed investigation on more reactive surfaces. Our results help provide a “bottom-up” understanding for phosphorylated organic synthesis on the primitive planet and its role in producing life building molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2011

An X-ray Absorption Spectroscopy Study of the Cathodic Discharge of Ag2VO2PO4: Geometric and Electronic Structure Characterization of Intermediate Phases and Mechanistic Insights

Bimetallic phosphorus oxides have emerged as attractive candidates for use as cathode materials in the next generation of lithium-based batteries owing to the operation of multielectron transfer processes and thermochemical stabilities conferred by the incorporation of phosphate groups. In particular silver vanadium phosphorus oxide, Ag{sub 2}VO{sub 2}PO{sub 4}, shows a much desired in situ conductivity enhancement upon discharge resulting in inherently high power capability with minimal conductive additives needed. However, the amorphization of Ag{sub 2}VO{sub 2}PO{sub 4} during electrochemical discharge precludes the use of standard diffraction tools to monitor changes in the local electronic and geometric structure. Here, we have utilized a combination of V K-, V L-, Ag K-, and O K-edge X-ray absorption fine structure spectroscopy to determine the local vanadium and silver oxidation states, local coordination geometry, and stoichiometry for Ag{sub 2}VO{sub 2}PO{sub 4} samples with varying extents of electrochemical lithiation. Soft X-ray V L- and O K-edge measurements provide a detailed orbital-specific picture of changes in vanadium electronic structure upon discharge.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Characterization and Geological Implications of Precambrian Calcite-Hosted Phosphate

Constraints on marine phosphate availability and cycling directly inform our understanding of long-term biological evolution. However, early Earth phosphate records are sparse, biased toward siliciclastic samples, and susceptible to post-depositional modification. Well-preserved shallow marine inorganic carbonate precipitates provide a complementary yet understudied record of phosphate cycling. We combined micro-X ray fluorescence mapping, X-ray absorption, and Nuclear Magnetic Resonance spectroscopy on samples of Precambrian syndepositional herringbone calcite (HBC) and microspar to characterize phosphorus speciation and distribution in these carbonate fabrics. Phosphorus spectroscopy from synthetic calcite, HBC, and microspar, is qualitatively consistent with a disordered distribution of phosphate. These characteristics are diagnostic of calcite-hosted phosphate, which is pervasive at low concentrations in HBC and microspar. This study provides evidence that ancient, well-preserved carbonate fabrics retain phosphate sourced from seawater and highlights the potential for an unaltered archive of marine phosphate concentration over geologic time.

58 GEOSCIENCES↗
DOE OSTI2026

Opportunities and challenges for the expansion of LFP battery supply chains

Global markets for energy storage are growing rapidly, with some applications transitioning from traditional LiNi x Mn y Co 1−x−y O 2 (NMC) toward LiFePO 4 (LFP) due to cost, safety, and performance advantages. Battery growth has seeded interest in critical material supplies such as high-purity lithium precursors. In contrast, challenges in securing high-purity iron and phosphorus, historically not considered critical materials, are often overlooked. Precursors must remain inexpensive to maintain LFP's current cost advantage, which leverages the low-cost (∼$\$100$ per t) FeSO 4 byproduct from titanium dioxide manufacturing and will not be available as LFP manufacturing expands. As an alternative, iron is mined primarily for steel manufacturing, for which the existing supply chain and beneficiation process is optimized. LFP batteries require small iron volumes compared to steel (0.11%), but profit margins associated with existing low-cost iron ores and high costs (∼$27 000 per t) associated with low volume high-purity iron oxides may limit interest in manufacturing small volumes of high-purity, specialized iron battery precursors. The complementary LFP precursor, phosphoric acid (H 3 PO 4 ), is primarily utilized in fertilizers. Of the current phosphate ore demand for fertilizers, 4–22.8% would be required to meet projected 2045 LFP H 3 PO 4 demand, suggesting significant supply chain planning is needed to achieve projected demand. If only higher-grade material is considered, demand jumps to 15–77% of current world production. While lithium precursor purity requirements have been evaluated (Li 2 CO 3 is commonly defined as ≥99.5%), “battery grade” iron and phosphorus precursors remain poorly defined, with no internationally accessible and widely adopted standard, further challenging expanding industry by creating manufacturing uncertainty and increasing potential costs.

25 ENERGY STORAGE↗
DOE OSTI2011

Microwave Annealing of Ion Implanted 4H-SiC

Ultra-fast high-temperature microwave annealing at temperatures as high as 2050 deg. C for 30 s has been performed on phosphorus ion-implanted 4H-SiC for phosphorus doping concentrations in the range 5x10{sup 19} cm{sup -3}-8x10{sup 20} cm{sup -3}. For comparison, inductive heating furnace anneals were performed at 1800 deg. C-1950 deg. C for 5 min. Electrical resistivity of the P{sup +}-implanted samples decreased with increasing annealing temperature reaching a minimum value of 6.8x10{sup -4} {Omega}cm for 2050 deg. C/30 s microwave annealing and a slightly higher value for 1950 deg. C/5 min inductive heating furnace annealing. X-ray rocking curve measurements showed that the microwave annealing not only removed the lattice damage introduced by the ion-implantation process, but also the defects present in the original virgin sample as well.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Near-infrared free carrier absorption in heavily doped silicon

Free carrier absorption in heavily doped silicon can have a significant impact on devices operating in the infrared. In the near infrared, the free carrier absorption process can compete with band to band absorption processes, thereby reducing the number of available photons to optoelectronic devices such as solar cells. In this work, we fabricate 18 heavily doped regions by phosphorus and boron diffusion into planar polished silicon wafers; the simple sample structure facilitates accurate and precise measurement of the free carrier absorptance. We measure and model reflectance and transmittance dispersion to arrive at a parameterisation for the free carrier absorption coefficient that applies in the wavelength range between 1000 and 1500 nm, and the range of dopant densities between ∼10{sup 18} and 3 × 10{sup 20} cm{sup −3}. Our measurements indicate that previously published parameterisations underestimate the free carrier absorptance in phosphorus diffusions. On the other hand, published parameterisations are generally consistent with our measurements and model for boron diffusions. Our new model is the first to be assigned uncertainty and is well-suited to routine device analysis.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Edge effects on the electronic properties of phosphorene nanoribbons

Two dimensional few-layer black phosphorus crystal structures have recently been fabricated and have demonstrated great potential in electronic applications. In this work, we employed first principles density functional theory calculations to study the edge and quantum confinement effects on the electronic properties of the phosphorene nanoribbons (PNR). Different edge functionalization groups, such as H, F, Cl, OH, O, S, and Se, in addition to a pristine case were studied for a series of ribbon widths up to 3.5 nm. It was found that the armchair-PNRs (APNRs) are semiconductors for all edge groups considered in this work. However, the zigzag-PNRs (ZPNRs) show either semiconductor or metallic behavior in dependence on their edge chemical species. Family 1 edges (i.e., H, F, Cl, OH) form saturated bonds with P atoms in the APNRs and ZPNRs, and the edge states keep far away from the band gap. However, Family 2 edges (pristine, O, S, Se) form weak unsaturated bonds with the p{sub z} orbital of the phosphorus atoms and bring edge states within the band gap of the ribbons. For the ZPNRs, the edge states of Family 2 are present around the Fermi level within the band gap, which close up the band gap of the ZPNRs. For the APNRs, these edge states are located at the bottom of the conduction band and result in a reduced band gap.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

Probing the limits of Si:P δ -doped devices patterned by a scanning tunneling microscope in a field-emission mode

Recently, a single atom transistor was deterministically fabricated using phosphorus in Si by H-desorption lithography with a scanning tunneling microscope (STM). This milestone in precision, achieved by operating the STM in the conventional tunneling mode, typically utilizes slow (∼102 nm2/s) patterning speeds. By contrast, using the STM in a high-voltage (>10 V) field-emission mode, patterning speeds can be increased by orders of magnitude to ≳104 nm2/s. We show that the rapid patterning negligibly affects the functionality of relatively large micron-sized features, which act as contacting pads for these devices. For nanoscale structures, we show that the resulting electrical transport is consistent with the donor incorporation chemistry constraining the electrical dimensions to a scale of 10 nm even though the pattering spot size is 40 nm.

Rudolph, M.↗
DOE OSTI2015

Electron transport behaviors through donor-induced quantum dot array in heavily n-doped junctionless nanowire transistors

We investigated single electron tunneling through a phosphorus donor-induced quantum dot array in heavily n-doped junctionless nanowire transistor. Seven subpeaks splitting in current oscillations are clearly observed due to the coupling of quantum dot array under the bias voltage below 1.0 mV at the temperature of 6 K. The conduction system can be well described by a two-band Hubbard model. The activation energy of phosphorus donors is tuned by the gate voltage to be 7.0 meV for the lower Hubbard band and 4.4 meV for the upper Hubbard band due to the localization effects below threshold voltage. The evolution of electron behaviors in the quantum dots is identified by adjusting the gate voltage from quantum-dot regime to one-dimensional regime.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2015

Sensitivity of CoSi{sub 2} precipitation in silicon to extra-low dopant concentrations. I. Experiment

We demonstrate that the precipitation of cobalt disilicide phase in silicon during high-temperature (500 °C and 650 °C) implantation is noticeably affected by impurities of phosphorus and boron. Measurements of B-type CoSi{sub 2} cluster sizes and number densities as a function of implantation dose indicate that the number density of clusters progressively increases as the phosphorus concentration increases from 7 × 10{sup 11} to 8 × 10{sup 13 }cm{sup −3}. A tentative explanation of these observations is proposed based on the previously suggested mechanism of precipitate nucleation, and on the results of first principles calculations summarized in Paper II, published as a follow-up paper. The results imply that utmost care is to be taken when dealing with transition metal precipitation during ion implantation into silicon because variations in the dopant content can affect the reproducibility of results even at extremely low dopant concentrations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Silicon-nitride photonic circuits interfaced with monolayer MoS 2

Herein we report integration of monolayer molybdenum disulphide with silicon nitride microresonators assembled by visco-elastic layer transfer techniques. Evanescent coupling from the resonator mode to the monolayer is confirmed through measurements of cavity transmission. The absorption of the monolayer semiconductor flakes in this geometry is determined to be 850 dB/cm, which is larger than that of graphene and black phosphorus with the same thickness. This technique can be applied to diverse monolayer semiconductors for assembling hybrid optoelectronic devices such as photodetectors and modulators operating over a wide spectrum range.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Suppression of transient enhanced diffusion in sub-micron patterned silicon template by dislocation loops formation

We investigate the evolution of two dimensional transient enhanced diffusion (TED) of phosphorus in sub-micron scale patterned silicon template. Samples doped with low dose phosphorus with and without high dose silicon self-implantation, were annealed for various durations. Dopant diffusion is probed with plane-view scanning capacitance microscopy. The measurement revealed two phases of TED. Significant suppression in the second phase TED is observed for samples with high dose self-implantation. Transmission electron microscopy suggests the suppressed TED is related to the evolution of end of range defect formed around ion implantation sidewalls.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Alkali metal ion storage properties of sulphur and phosphorous molecules encapsulated in nanometer size carbon cylindrical pores

We investigated the physical and chemical stabilities of sulfur and phosphorus molecules encapsulated in a mesoporous carbon (MPC) and two kinds of single-walled carbon nanotubes (SWCNTs) having different cylindrical pore diameters. The sublimation temperatures of sulfur molecules encapsulated in MPC and the two kinds of SWCNTs were measured by thermo-gravimetric measurements. It was found that the sublimation temperature of sulfur molecules encapsulated in SWCNTs having mean tube diameter of 1.5 nm is much higher than any other molecules encapsulated in larger pores. It was also found that the capacity fading of lithium-sulfur battery can be diminished by encapsulation of sulfur molecules in SWCNTs. We also investigated the electrochemical properties of phosphorus molecules encapsulated in SWCNTs (P@SWCNTs). It was shown that P@SWCNT can adsorb and desorb both Li and Na ions reversibly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗