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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 289 records · Page 16

Colloidal InAs Quantum Dot-Based Infrared Optoelectronics Enabled by Universal Dual-Ligand Passivation

Solution-processed low-bandgap semiconductors are crucial to next-generation infrared (IR) detection for various applications, such as autonomous driving, virtual reality, recognitions, and quantum communications. In particular, III–V group colloidal quantum dots (CQDs) are interesting as nontoxic bandgap-tunable materials and suitable for IR absorbers; however, the device performance is still lower than that of Pb-based devices. Herein, a universal surface-passivation method of InAs CQDs enabled by intermediate phase transfer (IPT), a preliminary process that exchanges native ligands with aromatic ligands on the CQD surface is presented. IPT yields highly stable CQD ink. In particular, desirable surface ligands with various reactivities can be obtained by dispersing them in green solvents. Furthermore, CQD near-infrared (NIR) photodetectors are demonstrated using solution processes. Careful surface ligand control via IPT is revealed that enables the modulation of surface-mediated photomultiplication, resulting in a notable gain control up to ≈10 with a fast rise/fall response time (≈12/36 ns). Considering the figure of merit (FOM), EQE versus response time (or –3 dB bandwidth), the optimal CQD photodiode yields one of the highest FOMs among all previously reported solution-processed nontoxic semiconductors comprising organics, perovskites, and CQDs in the NIR wavelength range.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analyst-to-Analyst Variability in Simulation-Based Prediction

This report describes findings from the culminating experiment of the LDRD project entitled, "Analyst-to-Analyst Variability in Simulation-Based Prediction". For this experiment, volunteer participants solving a given test problem in engineering and statistics were interviewed at different points in their solution process. These interviews are used to trace differing solutions to differing solution processes, and differing processes to differences in reasoning, assumptions, and judgments. The issue that the experiment was designed to illuminate -- our paucity of understanding of the ways in which humans themselves have an impact on predictions derived from complex computational simulations -- is a challenging and open one. Although solution of the test problem by analyst participants in this experiment has taken much more time than originally anticipated, and is continuing past the end of this LDRD, this project has provided a rare opportunity to explore analyst-to-analyst variability in significant depth, from which we derive evidence-based insights to guide further explorations in this important area.

97 MATHEMATICS AND COMPUTING↗

SU-E-T-452: Identifying Inefficiencies in Radiation Oncology Workflow and Prioritizing Solutions for Process Improvement and Patient Safety

Purpose: Successful radiation therapy requires multi-step processes susceptible to unnecessary delays that can negatively impact clinic workflow, patient satisfaction, and safety. This project applied process improvement tools to assess workflow bottlenecks and identify solutions to barriers for effective implementation. Methods: We utilized the DMAIC (define, measure, analyze, improve, control) methodology, limiting our scope to the treatment planning process. From May through December of 2014, times and dates of each step from simulation to treatment were recorded for 507 cases. A value-stream map created from this dataset directed our selection of outcome measures (Y metrics). Critical goals (X metrics) that would accomplish the Y metrics were identified. Barriers to actions were binned into control-impact matrices, in order to stratify them into four groups: in/out of control and high/low impact. Solutions to each barrier were then categorized into benefit-effort matries to identify those of high benefit and low effort. Results: For 507 cases, the mean time from simulation to treatment was 235 total hours. The mean process and wait time were 60 and 132 hours, respectively. The Y metric was to increase the ratio of all non-emergent plans completed the business day prior to treatment from 47% to 75%. Project X metrics included increasing the number of IMRT QAs completed at least 24 hours prior to treatment from 19% to 80% and the number of non-IMRT plans approved at least 24 hours prior to treatment from 33% to 80%. Intervals from simulation to target contour and from initial plan completion to plan approval were identified as periods that could benefit from intervention. Barriers to actions were binned into control-impact matrices and solutions by benefit-effort matrices. Conclusion: The DMAIC method can be successfully applied in radiation therapy clinics to identify inefficiencies and prioritize solutions for the highest impact.

60 APPLIED LIFE SCIENCES↗

Decentralized Signal Processing and Distributed Control of Collaborative Autonomous Networks (17-ERD-101 LDRD Final Report)

Intelligent autonomous sensor networks, often comprised of large numbers of sensors, must be capable of jointly exploiting data collected at each agent in the network, and using that data to optimize their future actions towards multiple mission objectives. Centralized signal processing and optimization solutions process all data and determine all future actions at a single agent, and the resulting information and commands are disseminated back to the network. The communications bandwidth this requires and the single point of failure the central agent represents often make these solutions untenable for national security applications. In this project, several fundamental algorithms for solving both the decentralized signal processing and network optimization were developed, as well as simulation software to validate the results of these algorithms at scale. Specifically, novel algorithms for Bayesian decentralized estimation and decentralized detection and optimization based on the alternating direction method of multipliers (ADMM) were developed for autonomous sensor networks and published in the literature. The first large scale simulation of autonomous sensor networks (1000 agents) was conducted on this project, validating the performance of the developed algorithms. These algorithms and simulation tools are critical components of any decentralized autonomous network and have current and future national security applications, including distributed sensor networks for detection, estimation, and tracking problems, and large decentralized cyber-physical infrastructure such as the power grid.

42 ENGINEERING↗

Cofacial Versus Coplanar Arrangement in Centrosymmetric Packing Dimers of Dipolar Small Molecules: Structural Effects on the Crystallization Behaviors and Optoelectronic Characteristics

Two D-π–A-A molecules ( MIDTP and TIDTP ) composed of an electron-rich ditolylamino group (D) and an electron-deficient 5-dicyanovinylenylpyrimidine (A-A) fragment bridged together with indeno[1,2- b ]thiophene (IDT) were synthesized. These molecules provide an opportunity to examine in-depth the impact of side-chain variations (methyl vs p -tolyl) on the crystallization behaviors, solid-state morphology, physical properties, and optoelectronic characteristics relevant for practical applications. X-ray analyses on single-crystal structures indicate that methyl-substituted MIDTP forms “coplanar antiparallel dimers” via C–H···S interactions and organizes into an ordered slip-staircase arrays. In contrast, p -tolyl-bearing TIDTP shows “cofacial centrosymmetric dimers” via π–π interactions and packs into a less-ordered layered structures. The X-ray diffraction analyses upon thermal treatment are consistent with a superior crystallinity of MIDTP , as compared to that of TIDTP . This difference indicates a greater propensity to organization by introduction of the smaller methyl group versus the bulkier p -tolyl group. The increased propensity for order by MIDTP facilitates the crystallization of MIDTP in both solution-processed and vacuum-deposited thin films. MIDTP forms solution-processed single-crystal arrays that deliver OFET hole mobility of 6.56 × 10 –4 cm 2 V –1 s –1 , whereas TIDTP only forms amorhpous films that gave lower hole mobility of 1.34 × 10 –5 cm 2 V –1 s –1 . MIDTP and TIDTP were utilized to serve as donors together with C 70 as acceptor in the fabrication of small-molecule organic solar cells (SMOSCs) with planar heterojunction (PHJ) or planar-mixed heterojunction (PMHJ) device architectures. OPV devices based on higher crystalline MIDTP delivered power conversion efficiencies (PCEs) of 2.5% and 4.3% for PHJ and PMHJ device, respectively, which are higher than those of TIDTP -based cells. Finally, the improved PCEs of MIDTP -based devices are attributed to better hole-transport character.

36 MATERIALS SCIENCE↗

Selective Isolation of Surface Grain Boundaries by Oxide Dielectrics Improves Cd(Se,Te) Device Performance

Cd(Se,Te) photovoltaics (PV) are the most widely deployed thin-film solar technology globally, yet continued efficiency improvements are stymied by challenges at the device hole contacts. The inclusion of solution-processed oxide layers such as AlGaO x in the contact stack has yielded improved device open-circuit voltages (V OC ) and fill factors (FF). However, contradictory mechanisms by which these layers improve the device properties have been proposed by the research community. We demonstrate in this work that an underappreciated property of such spin-coated layers is the preferential deposition at grain boundaries, a process that isolates the grain boundaries during contact metallization. The effects of grain-boundary isolation are probed by varying the coverage of solution-processed AlGaO x “barrier” layers on the Cd(Se,Te) surface, quantified by scanning Auger microscopy. Examining coverage-dependent V OC and FF, it was observed that isolating the grain boundaries during metallization is sufficient to prevent damage to the absorber that occurs in devices lacking a barrier layer, while additional coverage contributes to the increased series resistance. Such an effect is agnostic to the material used as a barrier layer, as long as the material does not itself damage the absorber. Spin-coated SiO x was used in place of AlGaO x for an equally beneficial effect. This grain-boundary isolation phenomenon is also observed during Mo deposition and in absorbers that have been contacted with a nitrogen-doped ZnTe layer. The mechanisms by which metallization may degrade the absorber are discussed, as are contact design strategies leveraging barrier layers, which may lead to improved device efficiencies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid Stoichiometry Control in Cu 2 Se Thin Films for Room-Temperature Power Factor Improvement

Cu 2 Se thin films provide a promising route toward relatively safe, sustainable and solution processed thermoelectric (TE) modules in contrast to more expensive and toxic materials currently on the market such as Bi2Te3. Cu 2 Se is known in the TE community for its high performance at high temperature and has recently attracted attention from its large theoretically predicted figure of merit at room temperature. Unfortunately, one of the main limitations encountered so far in Cu 2 Se thin films is that the carrier concentrations are not optimized for TE operation after solution processing. In this work, we conduct a comprehensive study of the structural, optical, and TE properties of Cu 2 Se thin films and demonstrate that nonoptimized carrier concentrations in these films lead to observations of poor performance at room temperature. Through a simple soaking procedure in a Cu+ ion solution for only a few minutes, we demonstrate a 200-300% increase in power factor. This soaking process pushes the carrier concentration of the Cu 2 Se thin film toward its optimal value for TE operation and marks the highest TE performance for any solution processed Cu 2 Se thin film at room temperature thus far. If the performance can be further optimized at room temperature, Cu 2 Se thin films will be the material of choice to utilize in TE modules for powering miniature electronics and sensors, which has been an increasingly popular and rapidly expanding market.

36 MATERIALS SCIENCE↗

Interface Engineering using Vapor Transport Deposited Perovskite Films for Solar Cells

The overarching goal of this project was to demonstrate the viability of vapor transport deposition (VTD) for the fabrication of efficient and stable metal-halide perovskite solar cells. VTD is a solvent-free alternative to conventional solution-processing of the light-absorbing, perovskite active layer. Since solution-processing frequently requires the use of toxic solvents, transition to a dry-processing approach has the potential to remove an obstacle to facile and economically meaningful commercialization. Further, VTD bears similarity to existing industrially-relevant processing approaches used for the production of thin-film CdTe solar modules, suggesting the potential for rapid adoption and transition to industry. The results described within this report offer design rules for the processing of metal-halide perovskites via VTD and new insights into the design of deposition systems to inform future applications.

14 SOLAR ENERGY↗

Self-Assembling Tripodal Small-Molecule Donors for Bulk Heterojunction Solar Cells

The power conversion efficiency of organic solar cells (OSCs) could benefit from systematic studies to improve bulk heterojunction (BHJ) morphology by modifying donor compounds. Supramolecular self-assembly is an attractive strategy to combine the beneficial properties of polymeric donors, such as a well-controlled morphology, with the homogeneous composition of small molecule donors for OSCs. We report here on two tripodal “star-shaped” small-molecule donor compounds based on diketopyrrolopyrrole (DPP) side chains for solution-processed BHJ OSCs. The tripod molecules were found not to aggregate in solution or form crystalline domains in thin films when a branched alkyl chain (2-ethylhexyl) substituent was used, whereas linear (docedecyl) alkyl chains promote the formation of one-dimensional (1D) nanowires and more crystalline domains in the solid state. Here, we demonstrate that the 1D self-assembly of these tripods enhances the performance of the corresponding solution-processed OSCs by 50%, which is attributed to the significant increase in the fill factor of devices resulting from a reduction of trap states.

36 MATERIALS SCIENCE↗

Direct electron beam patterning of electro-optically active PEDOT:PSS

The optical and electronic tunability of the conductive polymer poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) has enabled emerging applications as diverse as bioelectronics, flexible electronics, and micro- and nano-photonics. High-resolution spatial patterning of PEDOT:PSS opens up opportunities for novel active devices in a range of fields. However, typical lithographic processes require tedious indirect patterning and dry etch processes, while solution-processing methods such as ink-jet printing have limited spatial resolution. Here, we report a method for direct write nano-patterning of commercially available PEDOT:PSS through electron-beam induced solubility modulation. The written structures are water stable and maintain the conductivity as well as electrochemical and optical properties of PEDOT:PSS, highlighting the broad utility of our method. We demonstrate the potential of our strategy by preparing prototypical nano-wire structures with feature sizes down to 250 nm, an order of magnitude finer than previously reported direct write methods, opening the possibility of writing chip-scale microelectronic and optical devices. We finally use the high-resolution writing capabilities to fabricate electrically-switchable optical diffraction gratings. We show active switching in this archetypal system with >95 % contrast at CMOS-compatible voltages of +2 V and -3 V, offering a route towards highly-miniaturized dynamic optoelectronic devices.

42 ENGINEERING↗

Microfluidic-Based Robotic Sampling System for Radioactive Solutions

A novel microfluidic based robotic sampling system has been developed for sampling and analysis of liquid solutions in nuclear processes. This system couples the use of a microfluidic sample chip with a robotic system designed to allow remote, automated sampling of process solutions in-cell and facilitates direct coupling of the microfluidic sample chip with analytical instrumentation. This system provides the capability for near real time analysis, reduces analytical waste, and minimizes the potential for personnel exposure associated with traditional sampling methods. A prototype sampling system was designed, built and tested. System testing demonstrated operability of the microfluidic based sample system and identified system modifications to optimize performance.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

High Photoluminescence Quantum Yield in Band Gap Tunable Bromide Containing Mixed Halide Perovskites

Hybrid organic-inorganic halide perovskite based semiconductor materials are attractive for use in a wide range of optoelectronic devices because they combine the advantages of suitable optoelectronic attributes and simultaneously low-cost solution processability. Here, we present a two-step low-pressure vapor-assisted solution process to grow high quality homogeneous CH 3 NH 3 PbI 3-x Br x perovskite films over the full band gap range of 1.6-2.3 eV. Photoluminescence light-in versus light-out characterization techniques are used to provide new insights into the optoelectronic properties of Br-containing hybrid organic-inorganic perovskites as a function of optical carrier injection by employing pump-powers over a 6 orders of magnitude dynamic range. The internal luminescence quantum yield of wide band gap perovskites reaches impressive values up to 30%. This high quantum yield translates into substantial quasi-Fermi level splitting and high "luminescence or optically implied" open-circuit voltage. Most importantly, both attributes, high internal quantum yield and high optically implied open-circuit voltage, are demonstrated over the entire band gap range (1.6 eV ≤ E g ≤ 2.3 eV). These results establish the versatility of Br-containing perovskite semiconductors for a variety of applications and especially for the use as high-quality top cell in tandem photovoltaic devices in combination with industry dominant Si bottom cells. (Figure Presented).

36 MATERIALS SCIENCE↗

Trajectory Design Employing Convex Optimization for Landing on Irregularly Shaped Asteroids

Mission proposals that land on asteroids are becoming popular. However, in order to have a successful mission the spacecraft must reliably and softly land at the intended landing site. The problem under investigation is how to design a fuel-optimal powered descent trajectory that can be quickly computed on- board the spacecraft, without interaction from ground control. An optimal trajectory designed immediately prior to the descent burn has many advantages. These advantages include the ability to use the actual vehicle starting state as the initial condition in the trajectory design and the ease of updating the landing target site if the original landing site is no longer viable. For long trajectories, the trajectory can be updated periodically by a redesign of the optimal trajectory based on current vehicle conditions to improve the guidance performance. One of the key drivers for being completely autonomous is the infrequent and delayed communication between ground control and the vehicle. Challenges that arise from designing an asteroid powered descent trajectory include complicated nonlinear gravity fields, small rotating bodies and low thrust vehicles. There are two previous studies that form the background to the current investigation. The first set looked in-depth at applying convex optimization to a powered descent trajectory on Mars with promising results.1, 2 This showed that the powered descent equations of motion can be relaxed and formed into a convex optimization problem and that the optimal solution of the relaxed problem is indeed a feasible solution to the original problem. This analysis used a constant gravity field. The second area applied a successive solution process to formulate a second order cone program that designs rendezvous and proximity operations trajectories.3, 4 These trajectories included a Newtonian gravity model. The equivalence of the solutions between the relaxed and the original problem is theoretically established. The proposed solution for designing the asteroid powered descent trajectory is to use convex optimization, a gravity model with higher fidelity than Newtonian, and an iterative solution process to design the fuel optimal trajectory. The solution to the convex optimization problem is the thrust profile, magnitude and direction, that will yield the minimum fuel trajectory for a soft landing at the target site, subject to various mission and operational constraints. The equations of motion are formulated in a rotating coordinate system and includes a high fidelity gravity model. The vehicle's thrust magnitude can vary between maximum and minimum bounds during the burn. Also, constraints are included to ensure that the vehicle does not run out of propellant, or go below the asteroid's surface, and any vehicle pointing requirements. The equations of motion are discretized and propagated with the trapezoidal rule in order to produce equality constraints for the optimization problem. These equality constraints allow the optimization algorithm to solve the entire problem, without including a propagator inside the optimization algorithm.

Pinson, Robin M.↗

Silyl Hot-Injection Versus Thiocyanate Heat-Up Synthesis of Chalcohalides: Pushing the Size and Composition Envelope

Chalcohalide semiconductors are rapidly gaining traction as stable, biocompatible materials for energy conversion applications. While the solid-state synthesis of bulk chalcohalides is relatively well-developed, the colloidal chemistry of these materials is still in its early stages. Colloidal semiconductors are often advantageous in device fabrication due to the cost effectiveness of solution processing. Thus, we aim to increase the utility of chalcohalides in device fabrication by establishing solution phase chemistry of promising compositions. We show that silyl hot-injection is a versatile and effective method of making colloidal PnChI (Pn = Sb, Bi; Ch = S, Se) and Sn 2 PnS 2 I 3 (Pn = Sb, Bi) chalcohalides of tunable sizes and compositions. Furthermore, we demonstrate the preparation of mixed-pnictide chalcohalides through direct hot-injection and/or postsynthetic cation exchange, the latter being one of the few reported instances in chalcohalides. Additionally, we use the thiocyanate heat-up approach in combination with density functional theory to study halide mixing in quaternary tin chalcohalides. By pushing the limits of each synthetic technique, we have designed more soluble chalcohalides with tunable compositions while also gaining a better understanding of the efficacy of each procedure in respect to thin film and subsequent device fabrication. In addition to size and composition tuning, silyl hot-injection can help facilitate the future development and wide-scale application of chalcohalide-based devices by expanding the selection of solution-processable chalcohalides.

halogens↗

Lead-Free Cs 4 CuSb 2 Cl 12 Layered Double Perovskite Nanocrystals

Concerns about the toxicity of lead-based perovskites have aroused great interest for the development of alternative lead-free perovskite-type materials. Recently, theoretical calculations predict that Pb 2+ cations can be substituted by a combination of Cu 2+ and Sb 3+ cations to form a vacancy-ordered layered double perovskite structure with superior optoelectronic properties. However, accessibilities to this class of perovskite-type materials remain inadequate, hindering their practical implementations in various applications. Here, we report the first colloidal synthesis of Cs 4 CuSb 2 Cl 12 perovskite-type nanocrystals (NCs). The resulting NCs exhibit a layered double perovskite structure with ordered vacancies and a direct bandgap of 1.79 eV. A composition-structure-property relationship has been established by investigating a series of Cs 4 Cu x Ag 2-2x Sb 2 Cl 12 perovskite-type NCs (0 ≤ x ≤ 1). The composition-induced crystal structure transformation, thus the electronic bandgap evolution has been explored by experimental observations and further confirmed by theoretical calculations. Taking advantages of both the unique electronic structure and solution processability, we demonstrate that the Cs 4 CuSb 2 Cl 12 NCs can be solution-processed as high-speed photodetectors with ultrafast photo-response and narrow bandwidth. We anticipate that our study will prompt future research to design and fabricate novel and high-performance lead-free perovskite-type NCs for a range of applications.

25 ENERGY STORAGE↗

Development of quantum dot materials for infrared cameras (Final CRADA Report)

The aim of this project was to develop scalable methods to produce infrared (IR) mercury telluride (HgTe) colloidal quantum dot (CQD) thin films and demonstrate their utility in a proof-of-concept monolithic SWIR focal plane array (FPA). These objectives were accomplished by scaling up the HgTe CQD synthesis, characterizing physical and electrical properties of HgTe CQDs, evaluating solution-processed coating methods for quality and efficiency, and developing a process flow to integrate HgTe CQDs with commercial-off-the-shelf silicon CMOS readout circuits by solution-processed coating to produce monolithic FPAs. The FPA is the image sensor in an infrared imaging system responsible for detecting and processing reflected or emitted light into an infrared image of the scene under observation. The quality of the image is determined by the sensitivity and resolution of the image sensor in the system. Higher resolution IR FPAs enable higher throughput in manufacturing quality assurance, wider field of view for autonomous navigation, and longer range surveillance for defense.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A Three-Phase Microgrid Restoration Model Considering Unbalanced Operation of Distributed Generation

Recent severe outages highlight the urgency of improving grid resiliency in the U.S. Microgrid formation schemes are proposed to restore critical loads after outages occur. Most distribution networks have unbalanced configurations that are not represented in sufficient detail by single-phase models. This study provides a microgrid formation plan that adopts a three-phase network model to represent unbalanced distribution networks. The problem formulation has a quadratic objective function with mixed-integer linear constraints. The three-phase network model enables us to examine the three-phase power outputs of distributed generators (DGs), preventing unbalanced operation that might trip DGs. Because the DG unbalanced operation constraint is non-convex, an iterative process is presented that checks whether the unbalanced operation limits for DGs are satisfied after each iteration of optimization. We also develop a relatively conservative linear approximation on the unbalanced operation constraint to handle larger networks. Compared with the iterative solution process, the conservative linear approximation is able to accelerate the solution process at the cost of sacrificing optimality to a limited extent. Simulation in the IEEE 34 node and IEEE 123 test feeders indicate that the proposed method yields more practical microgrid formations results. In addition, this paper explores the coordinated operation of DGs and energy storage (ES) installations. The unbalanced three-phase outputs of ESs combined with the relatively balanced outputs of DGs could supply unbalanced loads. In conclusion, the case study also validates the DG-ES coordination.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Dimensional Control in Phase-Pure Coevaporated Quasi-2D Ruddlesden–Popper Structures

Fast, uncontrolled crystallization with several competing pathways makes solution-processing of phase-pure quasi-two-dimensional (quasi-2D) metal halide Ruddlesden–Popper thin films challenging. Typically, solution-processing results in the formation of different structural phases with varying dimensionality ranging from 2D, to quasi-2D, and 3D, introducing bandgap disorder and inhibiting charge transport. In this work, we eliminate interactions between precursor salts and solvents by using controlled thermal coevaporation to grow quasi-2D thin films that show high phase purity and narrow phase distribution. We study the structural landscape using synchrotron-based X-ray scattering and charge-carrier dynamics using ultrafast pump–probe spectroscopy. We then demonstrate a strategy to control the crystallographic phase of the film through phosphonic acid-based surface modification. We use density functional theory to study the interactions between propylphosphonic acid and the organic precursors and find that the interactions of loosely bound phosphonic acid molecules with evaporated precursors, followed by the migration of phosphonic acids through the deposited thin film, dictate the film structure between 2D and quasi-2D phases. These findings introduce new solvent-free methods for the fabrication of phase-pure quasi-2D Ruddlesden–Popper thin films and control phase selectivity across different dimensional (2D and quasi-2D) structures.

36 MATERIALS SCIENCE↗