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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 OSTI2022

Strategies for design and synthesis of porous liquids toward carbon capture and separation

Porous liquids (PLs) represent a promising category of sorbents in carbon capture and separation capable of integrating the advantages of flowing liquid and porous solid systems. Well-defined pores were engineered into liquid sorbents via liquifying molecules with stiff interior voids, dissolving rigid porous hosts in flowing liquids, or dispersing porous frameworks in high steric hindrance solvents, producing type I, II, or III PLs, respectively. Unique features of PLs have triggered broad interest in exploring their applications in carbon capture and separation, in which diverse design strategies, synthesis approaches, and enhanced performance have been reported. Here, in this minireview, recent progress in the design, synthesis, and structural engineering of PLs and efforts towards the optimization of their carbon capture and separation behavior will be summarized, including the comparison between PLs with varied types. Porosity engineering into liquid sorbents provides opportunities to resolve challenging issues in conventional sorption and separation systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Disjunctive linear separation conditions and mixed-integer formulations for aircraft conflict resolution

In this paper, we address the aircraft conflict resolution problem in air traffic control. We introduce new mixed-integer programming formulations for aircraft conflict resolution with speed, heading and altitude control which are based on disjunctive linear separation conditions. We first examine the two-dimensional aircraft conflict resolution problem with speed and heading control represented as continuous decision variables. We show that the proposed disjunctive linear separation conditions are equivalent to the classical nonlinear conditions for aircraft separation. Further, we characterise conflict-free trajectories based on aircraft velocity bounds and propose a simple pre-processing algorithm to identify aircraft pairs which are either always conflict-free, or which cannot be separated using speed and heading control only. We then incorporate altitude control and propose a lexicographic optimisation formulation that aims to minimise the number of flight level changes before resolving outstanding conflicts via two-dimensional velocity control. The proposed mixed-integer programming formulations are nonconvex, and we propose convex relaxations, decomposition methods and constraint generation algorithms to solve the two-dimensional and lexicographic optimisation formulations to guaranteed optimality. Numerical experiments on four types of conflict resolution benchmarking instances are conducted to test the performance of the proposed mixed-integer formulations. Further, the proposed method is compared against two benchmarks based on state-of-the-art approaches for the aircraft conflict resolution problem. Our numerical results show that the proposed method largely outperforms both benchmarks in terms of runtime and is able to solve significantly more instances to global optimality.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2026

Accelerating Laboratory-Based, All-Solid-State Battery Research and Development: Industrially Relevant Small-Batch Dry-Processing, Small and Low-Cost Test Fixtures, and Short-Tolerant Separators

This work presents improvements to mixing (for dry-processed electrodes), separator robustness, and cell testing jigs for all-solid-state batteries (ASSBs). These developments combine synergistically to enable rapid research and development of ASSB catholytes. A mechanical "kneader" is designed and built which emulates the mixing and fibrillation of poly-tetrafluoroethylene binder that occurs in industrially relevant twin-screw extruders. A modest improvement in the mixing and dispersion catholyte materials is observed using micro-resolution X-ray computed tomography (X-ray CT). Catholytes are paired with an In-metal anode and separated by a novel, dual-layer, polyaramid-fiber-supported, sulfide-solid electrolyte (Li6 PS5 Cl) separator. This separator achieves high short tolerance which enabled a 95% success rate across 20 attempted cells and to date over 100 successful cells have been built. ASSBs were tested in a 2032 coin-cell format. Simultaneous cycling of a large number of cells is further enabled by a compact and low cost (~ 38 USD per jig) pressure application jig of which 100 have been constructed to date. The utility of these advances is demonstrated through a brief study on the effect cathode-side conductive carbon and current collector type has on capacity and rate performance.

25 ENERGY STORAGE↗
DOE OSTI2026

In-situ observation of calcium chloride hexahydrate phase separation via neutron imaging

Inorganic salt hydrate offers a low-cost thermal energy storage solution with high energy density, but phase separation during thermal cycling poses a significant challenge, leading to irreversible performance degradation. In this research, neutron radiography was used to investigate phase separation in calcium chloride hexahydrate (CaCl₂·6H₂O, CCH) during thermal cycling to track its gradual accumulation into calcium chloride tetrahydrate (CaCl₂·4H₂O, CC4). Through in-situ visualization, phase separation and CC4 sedimentation were observed to occur during the cooling phase between 301.40 K and 304.80 K. CC4 accumulated linearly to 7.99 wt% after 10 thermal cycles. Crystallization and multi-cycle conversion models were developed to validate neutron imaging results of CC4 formation. The predicted CC4 content after 10 thermal cycles closely aligned with experimental observations. Neutron imaging offers a novel approach to investigate salt hydrate phase change materials (PCMs). It enables in-situ visualization of sub-hydrate (CC4) formation from original hydrate (CCH) in metastable phase change range (between 301.40 ± 0.66 K and 304.80 ± 0.60 K). Thereby, it provides a new insight of understanding the basis of phase separation mechanism and paves the way for future research of improving PCM thermal cycling performance.

Li, Yucen [The University of Tennessee, Knoxville]↗
DOE OSTI2016

Separable projection integrals for higher-order correlators of the cosmic microwave sky: Acceleration by factors exceeding 100

We present a case study describing efforts to optimise and modernise “Modal”, the simulation and analysis pipeline used by the Planck satellite experiment for constraining general non-Gaussian models of the early universe via the bispectrum (or three-point correlator) of the cosmic microwave background radiation. We focus on one particular element of the code: the projection of bispectra from the end of inflation to the spherical shell at decoupling, which defines the CMB we observe today. This code involves a three-dimensional inner product between two functions, one of which requires an integral, on a non-rectangular domain containing a sparse grid. We show that by employing separable methods this calculation can be reduced to a one-dimensional summation plus two integrations, reducing the overall dimensionality from four to three. The introduction of separable functions also solves the issue of the non-rectangular sparse grid. This separable method can become unstable in certain scenarios and so the slower non-separable integral must be calculated instead. We present a discussion of the optimisation of both approaches. We demonstrate significant speed-ups of ≈100×, arising from a combination of algorithmic improvements and architecture-aware optimisations targeted at improving thread and vectorisation behaviour. The resulting MPI/OpenMP hybrid code is capable of executing on clusters containing processors and/or coprocessors, with strong-scaling efficiency of 98.6% on up to 16 nodes. We find that a single coprocessor outperforms two processor sockets by a factor of 1.3× and that running the same code across a combination of both microarchitectures improves performance-per-node by a factor of 3.38×. By making bispectrum calculations competitive with those for the power spectrum (or two-point correlator) we are now able to consider joint analysis for cosmological science exploitation of new data.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Manufacturing Process Design of a Micro-Scale Liquid-Liquid Extractor and Multi-phase Separator

Advances in process innovation within the chemical process industry are impeded by the cost of producing new innovative components. In this paper, various manufacturing process routes were evaluated for scaling up a micro-scale liquid-liquid extractor and multi-phase separator capable of separating immiscible phases that are used for the extraction of a chemical product into a lower boiling point solvent to make downstream distillation easier. A manufacturing process design methodology was used to evaluate both photochemical machining and binder jetting as a means for producing the micropost arrays within the separator. Cost curves show that for a 0.3 mm deep micropost array, photochemical machining was found to be much cheaper than binder jetting. However, because binder jetting processes enable microposts with over 13 times higher depth-to-width aspect ratios, binder jetting was found to decrease the overall costs of the extractor/separator by more than half for a 500 barrel per day plant, with breakeven as low as 15 barrels per day. These economics were confirmed by building extractor/separator plates and characterizing them dimensionally and functionally. The binder jet plates were found to perform better than photochemical plates leading to the complete separation of the organic phase from water. The utilization of slower sintering cycles combined with surface grinding provided acceptable dimensional tolerances for the binder jet plates. Using pressurized air during depowdering improved the economics for the binder jetting process.

42 ENGINEERING↗
DOE OSTI2018

Nano-phase formation accompanying phase separation in undercooled CoCrCuFeNi-3 at.% Sn high entropy alloy

Highlights: • Undercooled multi-component CoCrCuFeNi-3 at.% Sn high-entropy alloy was studied. • Accompanying phase separation, the nano-precipitates were detected. • The effect of Sn on the microstructures and properties was clarified. • The microhardness increased markedly with the increase of undercooling. - Abstract: Highly undercooled multi-component CoCrCuFeNi-3 at.% Sn high-entropy alloy was studied by adopting molten glass purification combined with cycle superheating methods. Based on the critical undercooling ΔT{sup ⁎}, the characteristic of liquid-phase separation was researched at different undercoolings. Accompanying phase separation, two phases (CoCrFeNi-rich and CuNi-rich) and three kinds of nano-precipitates (CrCo-rich, CrSn-rich and Sn-rich nano-precipitates) were detected. The microhardness of undercooled CoCrCuFeNi-3 at.% Sn high-entropy alloys increased markedly with the increase of undercooling. The effect of Sn on the microstructure evolution and properties in the process of phase separation was clarified with the aid of nano-precipitates.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Robust natural nanocomposites realizing unprecedented ultrafast precise molecular separations

Synthetic polymer membranes can potentially reduce the large energy and carbon footprints that are typically associated with traditional chemical separation technologies. Unfortunately, current production protocols negate the green benefits of membrane separation. To address this bottleneck, here we report the use of natural materials monosaccharide – glucose and polydopamine and Zr-based metal organic frameworks (MOFs) to fabricate ultrathin nanocomposite membranes via interfacial polymerization reaction. The synergistic effect of these three materials on angstrom-scale molecular transport both in organic solvent and aqueous environment was elucidated using a series of complementary techniques. We demonstrate such nature-inspired nanocomposite membranes enable structural stability even in polar aprotic solvents, and unparalleled ultra-fast, low-pressure, precise separations in both nanofiltration modes, which easily surpass state-of-the-art membranes relying on unsustainable materials. Finally, the multi-functionality of saccharide nanocomposites was elegantly harnessed to impact separation applications that contribute towards a better living environment.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Amine-functionalized (Al) MIL-53/VTEC™ mixed-matrix membranes for H 2 /CO 2 mixture separations at high pressure and high temperature

In this report VTEC™ PI-1388 and 20 wt% (Al) NH 2 -MIL-53/VTEC™ PI-1388 mixed-matrix membranes (MMMs) with different thicknesses were tested for gas permeation of H2 and CO 2 from 5 to 30 bar and from 35 to 300 °C. 50/50 H 2 /CO 2 mixtures were also tested at 30 bar and 250 °C with stage cuts that ranged from 0.05 to 1. Gas permeation data show that the affinity of (Al) NH 2 -MIL-53 for VTEC™ PI-1388 is strong enough to perform gas separations under these conditions. At 30 bar and at temperatures above 200 °C, the performance of the MMMs for H 2 /CO 2 separation improved significantly with increasing temperature. Specifically, the H 2 permeability of the MMM at 300 °C increased by 70% with respect to that of VTEC™ PI-1388 (VTEC™ PI-1388: H 2 = 85 Barrer, H 2 /CO 2 = 4.0; MMM: H 2 = 144 Barrer, H 2 /CO 2 = 5.8). Gas mixture separations using VTEC™ PI-1388 and the MMM depended on the stage cut and reached a maximum H 2 /CO 2 separation of 7.2 for VTEC™ PI-1388 and 7.5 for the MMM at a stage cut of 0.05.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Atomic scale understanding of organic anion separations using ion-exchange resins

A combination of ab initio and classical molecular dynamic simulations was used to explore the adsorption/desorption and diffusion characteristics of ion-exchange resins for extraction of organic anions in electrically-driven separation processes. We considered two classes of carboxylate mixtures that are commonly encountered in bioprocessing separations: a short chain fatty acid mixture (acetate/butyrate) and an aromatic mixture (ferulate/coumarate). The suitability of several resin materials including PFC100E, IRC86, PFA444 and IRA67 was interrogated. The decomposition of the interaction energies by the symmetry-adapted perturbation theory and the classical molecular dynamic simulations of organic diffusion together reveal that the geometries of the organic anions and the functional groups of the resins, as well as their Columbic interactions, are the controlling factors in the diffusion process of the organic compounds in these resins. Additionally, classical simulations also show that modifying the functionality of resin beads, the magnitude of electric fields, and the ratio of organic mixtures may provide an effective way to control the diffusion rate and obtain selective separation of these organic mixtures. Finally, a general suggestion for favorable separation conditions is summarized.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Fabrication and accelerated long-term stability test of asymmetrical hollow fiber-supported thin film oxygen separation membrane

Asymmetrical hollow fiber-supported thin film membrane may provide microstructural advantages for air separation and oxygen production. The fabrication of such a membrane is usually very difficult, particularly the sintering behaviors and thermal expansion coefficient (TEC) mismatch among multiple layers. This directly affects the reliability and long-term stability of the membrane. Here, in this research, the sintering behaviors of a set of simple oxides are systematically studied and ZnO is identified as a material component for composite substrate La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF)-ZnO. The LSCF-ZnO ratios are further optimized by trading off several factors, e.g., matching the sintering behaviors and TECs of the LSCF-ZnO composite with those of LSCF thin film separation layer while enhancing the substrate strength. With the identified LSCF-ZnO ratio, the LSCF-ZnO composite hollow fiber substrate precursor is formed through slurry spinning process with porous microstructure being formed via phase inversion process. The thin film LSCF dense separation layer is then dip-coated on the substrate followed by co-sintering process. A thin, porous PrBaCo(Fe 0.6 Zr 0.2 Y 0.2 )O 5+δ (PBCFZY) catalyst layer is fabricated on the dense LSCF separation layer with dip-coating and sintering process, forming an asymmetrical membrane device LSCF-ZnO/LSCF/PBCFZY. Oxygen permeation test of the device is systematically conducted, and the fundamental mechanisms are analyzed. An accelerated long-term stability test of the membrane is also conducted (~550h, 46 thermal cycling loads), demonstrating excellent robustness and durability. The device is characterized and analyzed before and after the test. By replacing a considerable amount of high cost LSCF with low cost ZnO in the substrate, it not only enhances the stability but also reduces the capital cost of the membrane for practical applications.

42 ENGINEERING↗
DOE OSTI2015

Traction–separation relationships for hydrogen induced grain boundary embrittlement in nickel via molecular dynamics simulations

A statistical approach combined with molecular dynamics simulations is used to study the influence of hydrogen on intergranular decohesion. This methodology is applied to a Ni Σ3(112)[11¯0] symmetric tilt grain boundary. Hydrogenated grain boundaries with different H concentrations are constructed using an energy minimization technique with initial H atom positions guided by Monte Carlo simulation results. Decohesion behavior is assessed through extraction of a traction–separation relationship during steady-state crack propagation in a statistically meaningful approach, building upon prior work employing atomistic cohesive zone volume elements (CZVEs). A sensitivity analysis is performed on the numerical approach used to extract the traction–separation relationships, clarifying the role of CZVE size, threshold parameters necessary to differentiate elastic and decohesion responses, and the numerical averaging technique. Results show that increasing H coverage at the Ni Σ3(112)[11¯0] grain boundary asymmetrically influences the crack tip velocity during propagation, leads to a general decrease in the work of separation required for crack propagation, and provides a reduction in the peak stress in the extracted traction–separation relationship. Furthermore the present framework offers a meaningful vehicle to pass atomistically derived interfacial behavior to higher length scale formulations for intergranular fracture.

36 MATERIALS SCIENCE↗
DOE OSTI2016

ASA-FTL: An adaptive separation aware flash translation layer for solid state drives

Here, the flash-memory based Solid State Drive (SSD) presents a promising storage solution for increasingly critical data-intensive applications due to its low latency (high throughput), high bandwidth, and low power consumption. Within an SSD, its Flash Translation Layer (FTL) is responsible for exposing the SSD’s flash memory storage to the computer system as a simple block device. The FTL design is one of the dominant factors determining an SSD’s lifespan and performance. To reduce the garbage collection overhead and deliver better performance, we propose a new, low-cost, adaptive separation-aware flash translation layer (ASA-FTL) that combines sampling, data clustering and selective caching of recency information to accurately identify and separate hot/cold data while incurring minimal overhead. We use sampling for light-weight identification of separation criteria, and our dedicated selective caching mechanism is designed to save the limited RAM resource in contemporary SSDs. Using simulations of ASA-FTL with both real-world and synthetic workloads, we have shown that our proposed approach reduces the garbage collection overhead by up to 28% and the overall response time by 15% compared to one of the most advanced existing FTLs. We find that the data clustering using a small sample size provides significant performance benefit while only incurring a very small computation and memory cost. In addition, our evaluation shows that ASA-FTL is able to adapt to the changes in the access pattern of workloads, which is a major advantage comparing to existing fixed data separation methods.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

Rapid and Simultaneous Characterization of Drug Conjugation in Heavy and Light Chains of a Monoclonal Antibody Revealed by High-Resolution Ion Mobility Separations in SLIM

Antibody-drug conjugates (ADCs) have recently gained traction in the biomedical community due to their promise for human therapeutics and an alternative to chemotherapy for cancer. Crucial metrics for ADC efficacy, safety, and selectivity are their drug-antibody ratios (DARs). However, DAR characterization (i.e., determining the average number of conjugated drugs on the antibody) through analytical methods remains challenging due to the heterogeneity of drug conjugation as well as the numerous post-translational modifications possible in the monoclonal antibody. In this work, we report on the use of high-resolution ion mobility spectrometry separations in our structures for lossless ion manipulations coupled to mass spectrometry (SLIM IMS-MS) platform for the rapid and simultaneous characterization of the drug load profile (i.e., stoichiometric distribution of the number of conjugated drugs present on the mAb), determination of the weighted average DAR in both the heavy and light chains of a model antibody-drug conjugate, and calculation of the overall DAR of the ADC. After chemical reduction of the ADC and a subsequent 31.5 meter SLIM IMS separation the various drug bound antibody species could be well resolved for both chains. Furthermore, we also show that higher resolution separations were possible with SLIM IMS as compared to ones performed on a commercially available (~1 meter) drift tube IMS-MS platform. Interestingly, additional gas-phase substructures become evident with longer path length SLIM IMS, potentially providing insight related to how drug conjugation may alter the structural properties of a monoclonal antibody and thus affect its overall potency and/or selectivity for a given antigen. We expect high-resolution SLIM IMS separations will augment the existing toolbox for ADC characterization, particularly for structural confirmation to enable the rapid optimization of DAR for a given ADC and thus better understand its potential toxicity and potency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

The Conformational Change in Elongation Factor Tu Involves Separation of Its Domains

Elongation factor Tu (EF-Tu) is a highly conserved GTPase that is responsible for supplying the aminoacylated tRNA to the ribosome. Upon binding to the ribosome, EF-Tu undergoes GTP hydrolysis, which drives a major conformational change, triggering the release of aminoacylated tRNA to the ribosome. Using a combination of molecular simulation techniques, we studied the transition between the pre- and post-hydrolysis structures through two distinct pathways. Here, we show that the transition free energy is minimal along a non-intuitive pathway that involves “separation” of the GTP binding domain (domain 1) from the OB folds (domains 2 and 3), followed by domain 1 rotation, and, eventually, locking the EF-Tu conformation in the post-hydrolysis state. The domain separation also leads to a slight extension of the linker connecting domain 1 to domain 2. Using docking tools and correlation-based analysis, we identified and characterized the EF-Tu conformations that release the tRNA. These calculations suggest that EF-Tu can release the tRNA before the domains separate and after domain 1 rotates by 25°. Lastly, we also examined the EF-Tu conformations in the context of the ribosome. Given the high degrees of sequence similarity with other translational GTPases, we predict a similar separation mechanism is followed.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Review of Multifunctional Separators: Stabilizing the Cathode and the Anode for Alkali (Li, Na, and K) Metal–Sulfur and Selenium Batteries

Alkali metal batteries based on lithium, sodium, and potassium anodes and sulfur-based cathodes are regarded as key for next-generation energy storage due to their high theoretical energy and potential cost effectiveness. However, metal–sulfur batteries remain challenged by several factors, including polysulfides’ (PSs) dissolution, sluggish sulfur redox kinetics at the cathode, and metallic dendrite growth at the anode. Functional separators and interlayers are an innovative approach to remedying these drawbacks. Here we critically review the state-of-the-art in separators/interlayers for cathode and anode protection, covering the Li–S and the emerging Na–S and K–S systems. The approaches for improving electrochemical performance may be categorized as one or a combination of the following: Immobilization of polysulfides (cathode); catalyzing sulfur redox kinetics (cathode); introduction of protective layers to serve as an artificial solid electrolyte interphase (SEI) (anode); and combined improvement in electrolyte wetting and homogenization of ion flux (anode and cathode). It is demonstrated that while the advances in Li–S are relatively mature, less progress has been made with Na–S and K–S due to the more challenging redox chemistry at the cathode and increased electrochemical instability at the anode. Throughout these sections there is a complementary discussion of functional separators for emerging alkali metal systems based on metal–selenium and the metal–selenium sulfide. The focus then shifts to interlayers and artificial SEI/cathode electrolyte interphase (CEI) layers employed to stabilize solid-state electrolytes (SSEs) in metal–sulfur solid-state batteries (SSBs). The discussion of SSEs focuses on inorganic electrolytes based on Li- and Na-based oxides and sulfides but also touches on some hybrid systems with an inorganic matrix and a minority polymer phase. The review then moves to practical considerations for functional separators, including scaleup issues and Li–S technoeconomics. The review concludes with an outlook section, where we discuss emerging mechanics, spectroscopy, and advanced electron microscopy (e.g. cryo-transmission electron microscopy (cryo-TEM) and cryo-focused ion beam (cryo-FIB))-based approaches for analysis of functional separator structure–battery electrochemical performance interrelations. Finally, throughout the review we identify the outstanding open scientific and technological questions while providing recommendations for future research topics.

25 ENERGY STORAGE↗
DOE OSTI2019

Superhydrophobic or Hydrophilic Porous Metallic/Ceramic Tubular Membranes for Continuous Separations of Biodiesel–Water W/O and O/W Emulsions

This study reports the effective surface effect of porous inorganic membranes on improving the emulsion separations (i.e., perm-selective extraction of either oil phase or aqueous phase from the emulsions). A novel tubular form of superwetting, porous, stainless steel/ceramic membranes were demonstrated for enabling continuous separations of oil–water emulsions, extracting either oil phase or aqueous phase from the flowing emulsions. The superhydrophobic membranes consist of macroporous (4 μm) stainless-steel SS434 tube with inner wall surface modified with superhydrophobicity (>150° contact angle) via perfluoro-silane grafting functionalization. The (super)hydrophilic membranes consist of 4-μm porous stainless-steel SS434 tube without/with inner wall coated with nanoporous alumina (6 nm average pore size), the surface of which was further modified with superhydrophilicity via Hydrophil-S solution deposition. With the cross-flow membrane filtration setup, the surface-engineered tubular membranes were studied for perm-selective extraction of aqueous or oil phase from oil–water emulsions (water-in-oil W/O and oil-in-water O/W) that are relevant to a real industrial biodiesel (FAME) production process. The superhydrophobic membrane (4 μm pore size) has demonstrated capability of extracting nearly 100% pure oil while rejecting water phase when either W/O or O/W emulsions were tested as feed. The superhydrophobic membrane showed distinct advantage of 2-orders-of-magnitude-higher flux extraction of oil at 100 times higher “break-through” pressures. On the other hand, the super/hydrophilic nanoporous membranes (6 nm) have shown selective water permeation (separation factor up to 35) when biodiesel-relevant W/O emulsions were tested. Finally, the membrane function is discussed from the perspective of improving industrial biodiesel processing yield by overcoming equilibrium limitations during the biodiesel formation reactions. Future work on in situ reaction–separation experiments are envisioned.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Ultrafast Triplet Pair Separation and Triplet Trapping following Singlet Fission in Amorphous Pentacene Films

In this work, ultrafast infrared and electronic spectroscopy are used to examine the dynamics of triplet pair separation following singlet fission in amorphous and crystalline films of the model singlet fission chromophore, 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-Pn). Direct probing of correlated triplet pair intermediates through their unique vibrational frequencies, infrared electronic transitions, and indirectly through their visible triplet absorptions reveals that triplet pair separation occurs on similar picosecond timescales in both amorphous and crystalline films despite their markedly different average intermolecular coupling strengths. Although triplet pair separation occurs on similar timescales in both environments, measurements of diffusion-controlled triplet-triplet annihilation reveal that the diffusivity of triplet excited states is an order of magnitude lower in amorphous films. The data reveal the presence of sparse triplet traps in the amorphous environment that inhibit the transport of triplet excitons in comparison to crystalline films. These observations inform recent efforts to develop disordered and polymeric singlet fission sensitizers that contain amorphous regions. In particular, the data suggest that it may be possible to nanostructure amorphous or polymeric singlet fission sensitizers to allow ultrafast triplet pair separation and harvesting in photovoltaic and light emitting applications despite their low triplet exciton diffusivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗