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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 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
DOE OSTI2011

Management of the baseline shift using a new and simple method for respiratory-gated radiation therapy: Detectability and effectiveness of a flexible monitoring system

Purpose: In respiratory-gated radiation therapy, a baseline shift decreases the accuracy of target coverage and organs at risk (OAR) sparing. The effectiveness of audio-feedback and audio-visual feedback in correcting the baseline shift in the breathing pattern of the patient has been demonstrated previously. However, the baseline shift derived from the intrafraction motion of the patient's body cannot be corrected by these methods. In the present study, the authors designed and developed a simple and flexible system. Methods: The system consisted of a web camera and a computer running our in-house software. The in-house software was adapted to template matching and also to no preimage processing. The system was capable of monitoring the baseline shift in the intrafraction motion of the patient's body. Another marker box was used to monitor the baseline shift due to the flexible setups required of a marker box for gated signals. The system accuracy was evaluated by employing a respiratory motion phantom and was found to be within AAPM Task Group 142 tolerance (positional accuracy <2 mm and temporal accuracy <100 ms) for respiratory-gated radiation therapy. Additionally, the effectiveness of this flexible and independent system in gated treatment was investigated in healthy volunteers, in terms of the results from the differences in the baseline shift detectable between the marker positions, which the authors evaluated statistically. Results: The movement of the marker on the sternum [1.599 {+-} 0.622 mm (1 SD)] was substantially decreased as compared with the abdomen [6.547 {+-} 0.962 mm (1 SD)]. Additionally, in all of the volunteers, the baseline shifts for the sternum [-0.136 {+-} 0.868 (2 SD)] were in better agreement with the nominal baseline shifts than was the case for the abdomen [-0.722 {+-} 1.56 mm (2 SD)]. The baseline shifts could be accurately measured and detected using the monitoring system, which could acquire the movement of the marker on the sternum. The baseline shift-monitoring system with the displacement-based methods for highly accurate respiratory-gated treatments should be used to make most of the displacement-based gating methods. Conclusions: The advent of intensity modulated radiation therapy and volumetric modulated radiation therapy facilitates margin reduction for the planning target volumes and the OARs, but highly accurate irradiation is needed to achieve target coverage and OAR sparing with a small margin. The baseline shifts can affect treatment not only with the respiratory gating system but also without the system. Our system can manage the baseline shift and also enables treatment irradiation to be undertaken with high accuracy.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2020

Adiabatic frequency shifting in epsilon-near-zero materials: the role of group velocity

The conversion of a photon’s frequency has long been a key application area of nonlinear optics. It has been discussed how a slow temporal variation of a material’s refractive index can lead to the adiabatic frequency shift (AFS) of a pulse spectrum. Such a rigid spectral change has relevant technological implications, for example, in ultrafast signal processing. Here, we investigate the AFS process in epsilon-near-zero (ENZ) materials and show that the frequency shift can be achieved in a shorter length if operating in the vicinity of R e { ε <#comment/> r } = 0 . We also predict that, if the refractive index is induced by an intense optical pulse, the frequency shift is more efficient for a pump at the ENZ wavelength. Remarkably, we show that these effects are a consequence of the slow propagation speed of pulses at the ENZ wavelength. Our theoretical predictions are validated by experiments obtained for the AFS of optical pulses incident upon aluminum zinc oxide thin films at ENZ. Our results indicate that transparent metal oxides operating near the ENZ point are good candidates for future frequency conversion schemes.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Deconvolution by finite-size-source effects of x-ray phase-contrast images

Purpose: In the hard x-ray region, the cross sections for the phase shift of low-Z elements are about 1000 times larger than the absorption ones. As a consequence, phase contrast is detectable even when absorption contrast is minimal or absent. Therefore, phase-contrast imaging could become a valid alternative to absorption contrast without delivering high dose to tissue/human body parts. Methods: To enhance the quality of phase-contrast images without increasing the dose, a possible approach could be the partial deconvolution of the finite source size effects by experimental phase-contrast images. The deconvolution procedure, the authors propose, employs the acquisition of two images on a suitable well-known test sample, one in contact and the other in phase-contrast conditions. Both acquired images are used along with a simulated phase-contrast image (obtained from the test sample in ideal conditions of pointlike source illumination) to correctly retrieve the experimental source distribution function. This information allows a generic experimental phase-contrast image, acquired in the same conditions, to be partially deconvolved by finite source size effects. Results: The performed experimental tests indicate that deconvolved images are equivalent to those which would be obtained with a source 40% smaller than the actual size. In turn, this finding is equivalent to an increase of the ''effective'' lateral spatial coherence length. The corresponding quality improvement of the phase-contrast imaging is directly deducible by the presence of many Fresnel fringes, much better visible with respect to the original experimental phase-contrast images. Conclusions: The use of a test standard sample, always possible in every experimental setup, to partially deconvolve the finite-size-source blurring effects shows that higher quality phase-contrast images could be readily available, making easier diagnoses and tissue/sample analyses. The method could give, in the future, the possibility to further lower the delivered dose to patients, organs, and tissues when compact room-sized and brilliant microfocus x-ray sources will be available for clinical applications in hospitals.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Ecological acclimation: A framework to integrate fast and slow responses to climate change

Ecological responses to climate change occur across vastly different time-scales, from minutes for physiological plasticity to decades or centuries for community turnover and evolutionary adaptation. Accurately predicting the range of ecosystem trajectories will require models that incorporate both fast processes that may keep pace with climate change and slower ones likely to lag behind and generate disequilibrium dynamics. However, the knowledge necessary for this integration is currently fragmented across disciplines. We develop ‘ecological acclimation’ as a unifying framework to emphasize the similarity of dynamics driven by processes operating on dramatically different time-scales and levels of biological organization. The framework focuses on ecoclimate sensitivities, measured as the change in an ecological response variable per unit of climate change. Acclimation processes acting at different time-scales cause these sensitivities to shift in magnitude and even direction over time. We highlight shifting ecoclimate sensitivities in case studies from diverse ecosystems, including terrestrial plant communities, coral reefs and soil microbiomes. Models predicting future ecosystem states inevitably make assumptions about acclimation processes; these assumptions must be explicit for users to evaluate whether a model is appropriate for a given forecast horizon. Similarly, decision frameworks that clearly account for multiple acclimation processes and their distinct time-scales will help natural resource managers plan for ecological impacts of climate change from years to many decades into the future. We outline a synthetic research programme focused on the time-scales of ecological acclimation to reduce uncertainty in ecological forecasts.

climate adaptation↗
DOE OSTI2022

Ablating Ion Velocity Distributions in Short-Pulse-Heated Solids via X-Ray Doppler Shifts

Solids ablate under laser irradiation, but experiments have not previously characterized the initiation of this process at ultrarelativistic laser intensities. Here, we present first measurements of bulk ion velocity distributions as ablation begins, captured as a function of depth via Doppler-shifted x-ray line emission from two viewing angles. Bayesian analysis indicates that bulk ions are either nearly stationary or flowing outward at the plasma sound speed. The measurements quantitatively constrain the laser-plasma ablation mechanism, suggesting that a steplike electrostatic potential structure drives solid disassembly.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2012

ACTIVE REGION MOSS: DOPPLER SHIFTS FROM HINODE/EXTREME-ULTRAVIOLET IMAGING SPECTROMETER OBSERVATIONS

Studying the Doppler shifts and the temperature dependence of Doppler shifts in moss regions can help us understand the heating processes in the core of the active regions. In this paper, we have used an active region observation recorded by the Extreme-ultraviolet Imaging Spectrometer (EIS) on board Hinode on 2007 December 12 to measure the Doppler shifts in the moss regions. We have distinguished the moss regions from the rest of the active region by defining a low-density cutoff as derived by Tripathi et al. in 2010. We have carried out a very careful analysis of the EIS wavelength calibration based on the method described by Young et al. in 2012. For spectral lines having maximum sensitivity between log T = 5.85 and log T = 6.25 K, we find that the velocity distribution peaks at around 0 km s{sup -1} with an estimated error of 4-5 km s{sup -1}. The width of the distribution decreases with temperature. The mean of the distribution shows a blueshift which increases with increasing temperature and the distribution also shows asymmetries toward blueshift. Comparing these results with observables predicted from different coronal heating models, we find that these results are consistent with both steady and impulsive heating scenarios. However, the fact that there are a significant number of pixels showing velocity amplitudes that exceed the uncertainty of 5 km s{sup -1} is suggestive of impulsive heating. Clearly, further observational constraints are needed to distinguish between these two heating scenarios.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1987

Velocity measurements in the plume of an arcjet engine

A nonintrusive technique has been used to conduct a radial survey in the flow field of an arcjet engine plume. The technique measures the Doppler shift of an optically thin line resulting from recombination and relaxation processes in the high Mach number stream, in order to determine flow velocities. Atom temperature can also be calculated from the same Doppler-broadened line widths, when these shifts are measured with a scanning Fabry-Perot spectrometer whose design is presented in detail.

Pivirotto, T. J.↗
DOE OSTI2025

Machine‐Learning‐Driven Exploration of Surface Reconstructions of Reduced Rutile TiO 2

Titanium dioxide (TiO 2 ) is widely used as a catalyst support due to its stability, tunable electronic properties, and surface oxygen vacancies, which are crucial for catalytic processes such as the reverse water-gas shift (RWGS) reaction. Reduced TiO 2 surfaces undergo complex surface reconstructions that endow unique properties but are computationally challenging to describe. In this study, we utilize machine-learning interatomic potentials (MLIPs) integrated with an active-learning workflow to efficiently explore reduced rutile TiO 2 surfaces. This approach enabled the prediction of a phase diagram as a function of oxygen chemical potential, revealing a variety of reconstructed phases, including a previously unreported subsurface shear plane structure. We further investigate the electronic properties of these surfaces and validate our results by comparing experimental and theoretical high-resolution transmission electron microscopy (HRTEM). Our findings provide new insights into how extreme surface reductions influence the structural and electronic properties of TiO 2 , with potential implications for catalyst design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Hierarchically Structured Catalysts Toward Sustainable Hydrogen Economy: Electro‐ and Thermo‐Chemical Pathways

Abstract Hydrogen, as an important clean energy source, plays a more and more crucial role in decarbonizing the planet and meeting the global climate challenge due to its high energy density and zero‐emission. The demand for sustainable hydrogen is increasing drastically worldwide as driven by the global shift towards low‐carbon energy solutions. Thermochemical catalysis process dominates hydrogen production at scale given its relatively mature technology and commercialization status, as well as the established manufacturing infrastructure. While due to its environmentally friendly nature and growing abundant sources of renewable electricity, the electrochemical path for hydrogen production is rising as a major alternative to the thermochemical means. Nevertheless, hierarchically structured catalysts and devices have gradually taken the center stage toward replacing the traditional counterparts, especially with the rapid advancement of the design and manufacture of such ordered nanostructure assemblies toward high activity, efficient mass transport, and superb stability. In this review, the latest progress of the hierarchically structured catalysts for hydrogen production have been surveyed on electro‐ and thermo‐ chemical pathways comparatively. It covers the structure designs of atomic dispersion, nanoscale surfaces and interfaces for achieving highly active and durable catalysts, components, and devices. Both electrochemical and thermochemical approaches are reviewed in terms of the vast design details, engineered benefits, and understandings of various Pt‐group metal (PGM) and non‐PGM based transition metal catalysts for hydrogen production. As the growing trend, brief discussions are also presented toward the high‐level assembly and manufacture of complexly structured components and devices at scale in the electrochemical and thermochemical energy systems.

Deng, Chenxin↗
DOE OSTI2022

Dynamic Material Flow Analysis of Silicon Photovoltaic Modules to Support a Circular Economy Transition

Solar photovoltaics (PV) are the fastest growing renewable energy technologies for clean, cheap, and sustainable electricity generation. To prepare for rapid scale-up, the PV industry needs to project material requirements to build out all aspects of the supply chain appropriately and plan to handle large volumes of module waste. Impacts of deploying different material circularity strategies to reduce waste and conserve primary resources need to be quantified to inform sustainable material management. Here, we introduce the photovoltaic dynamic material flow analysis (PV DMFA) model based on PV electricity generation. The model quantifies material flows and stocks in the cradle-to-cradle life cycles of utility-scale c-Si PV systems in the United States through 2100. We present case studies for solar flat glass and aluminum frame materials under various scenarios to project the impacts of PV performance, reliability, and processing parameters, material circularity strategies, and module design shifts. In the absence of circularity measures, ~100 million MT of flat glass and ~12 million MT of aluminum would be needed for PV installations by 2100 to meet projected growth in domestic utility PV demand to nearly 1000 TWh in 2100. With optimistic but feasible improvements in efficiency, reliability, and circularity, material intensity and waste could be reduced by nearly 50%. Efficient module collection, minimally intrusive recycling, and careful scrap handling and cleaning could improve material circularity in the PV value chain. This model serves as a sustainability data support tool that may aid in the circular economy transition for PV systems.

circular economy↗
DOE OSTI2017

Carbazole Substituted BODIPYs: Synthesis, Computational, Electrochemical and DSSC Studies

Carbazole and p-anisyl substituted BODIPY dyes with a cyanoacetic acid anchoring group have been prepared and their spectral, electrochemical properties and photosensitizing potential in DSSC have been evaluated. X-ray structure of N-phenylcarbazole substituted BODIPY revealed lower torsion angle between BODIPY plane and carbazole plane, suggesting increased communication between the two units. DFT studies indicated effective electronic interactions between the BODIPY unit and carbazole substituents. The N-butylcarbazole and N-phenylcarbazole substituted BODIPYs showed anodic shifts in their reduction potentials, indicating facile reduction process. The predicted HOMO–LUMO gaps are in agreement with the electrochemical result and the lower band gap was observed for the carbazole substituted BODIPYs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Influence of Molybdenum on Rapid Solidification Microstructure and Microsegregation in Primary Ferrite Solidified Stainless Steel

Due to the widespread use and familiarity of austenitic stainless steels in many industries these alloys are often the first materials used when adapting new processing techniques. The rapid cooling and solidification rates that occur during fusion based additive manufacturing processes like powder bed fusion cause a fundamental shift in the solidification behavior of the material. While the effects that Cr and Ni have on the microstructure have been fairly well documented across a range of solidification conditions, the impact of alloying elements like Mo are not as well understood at rapid solidification rates. For this study, four custom stainless steel alloy feedstocks were made with targeted modification of the Cr and Mo concentrations to maintain a constant Cr/Ni eq ratio of ~1.7. Two-piston splat quenching was used to produce rapidly solidified samples and the solidification mode, phase, and cell size were investigated. Solidification rates were estimated to be between 0.4 and 1.5m/s. A comparison of the microsegregation and partitioning behavior of Cr, Ni and Mo in ferrite solidified material was also performed for the different alloy compositions. Variations of the Mo concentration between each feedstock showed no measurable influence on the solidification/cooling rates, solidification morphology, or the partitioning of Mo. Furthermore, higher concentrations of Mo were found to significantly increase the amount of ferrite phase in the microstructure by suppressing the ferrite to austenite massive transformation.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Synthesis and properties of (Yb, N)-TiO{sub 2} photocatalyst for degradation of methylene blue (MB) under visible light irradiation

Highlights: • The (Yb, N)-TiO{sub 2} nanoparticles were prepared and characterized. • The spectrum absorption region of (Yb, N)-TiO{sub 2} is red-shifted to visible light. • The recombination of the photo-generated electron–hole pairs of (Yb, N)-TiO{sub 2} is suppressed. • The photocatalytic activity of (Yb, N)-TiO{sub 2} is more higher than that of TiO{sub 2}-P25, N-TiO{sub 2} and the Yb-TiO{sub 2}. - Abstract: (Yb, N)-TiO{sub 2} photocatalyst has been synthesized by sol–gel method combined with microwave chemical synthesis. Also, the efficiency of the (Yb, N)-TiO{sub 2} as a photocatalyst for the degradation of methylene blue (MB) using visible light irradiation has been evaluated. The prepared samples were characterized by XRD, TEM, XPS, UV–vis-DRS and PL. The results show that the (Yb, N)-TiO{sub 2} photocatalyst has the anatase TiO{sub 2} crystalline phase. The TEM micrograph demonstrated that the average particle size of the sample was about 12 nm. The band-gap energy absorption edge shifted to longer wavelength as compared to commercial TiO{sub 2}-P25, N-TiO{sub 2} and the Yb-TiO{sub 2} prepared by our group. Results of degradation revealed that the (Yb, N)-TiO{sub 2} has shown much more higher photocatalytic activity than that of the TiO{sub 2}-P25, the N-TiO{sub 2} and the Yb-TiO{sub 2} under the visible light.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Effect of electrode rinse solutions on the electrodialysis of concentrated salts

The data presented indicate that modest attention to the chemistry of the electrode rinse solution can yield as much as 56% improvement in process efficiency. When operating electrodialysis (ED) with salt concentrations greater than 10,000 mg/l (as NaCl) the amperage can be relatively high even at low voltages. To maximize the overall rate of ion transport from diluate to concentrate, there is a need to minimize resistances in the electrode cells since these can represent as much as 30% of the total resistances in the entire process and in this particular ED unit, represented resistance roughly equivalent to that within the membrane stack. This work describes the performance of a 10-cell pair, 200 cm 2 (0.02 m 2 ) per membrane, pilot ED unit operated in batch mode at 5 V potential. The feedstock to the stack was varied from 0.5% to 6% NaCl. Results from Volt-amp profiles (2.0–15 V) were used as the rationale for choosing the preferred electrode rinse solution, 90 g/l (kg/m 3 ) disodium sulfate at pH 12.5. The recommended solution of 30 g/l (kg/m 3 ) disodium sulfate at neutral pH was tested against stronger solutions (60, 90, and 120 g/l (kg/m 3 ) disodium sulfate) at neutral pH and with 1 g/l (kg/m 3 ) sodium hydroxide added to yield solutions at pH 12.5. There were stark differences in the performance of the ED unit between the solutions at pH 7 and those at pH 12.5. The slopes of the Volt-amp profiles improved indicating less resistance to ion flow at pH 12.5. Most of the difference can be attributed to the greater conductivity of sodium hydroxide compared to disodium sulfate, where even a modest addition of 1 g/l (kg/m 3 ) sodium hydroxide increased the conductivity of the solution between 8 and 20% depending on the concentration of disodium sulfate. Most notably, the initiation voltage was 2.39 ± 0.08 V with solutions at pH 7 and 1.99 V ± 0.04 V when the rinse solutions were around pH 12.5, a difference of around 0.42 V. Since the full batch runs were performed at 5.0 V, this 0.42 V differential represented a loss of 8% in process efficiency. A series of tests showed a shift in initiation voltage occurred between pH 11.5 and 12.5. Nernst equations for water electrolysis are coupled with a simple flux model that estimates the concentration of hydroxide and hydronium ions at the electrode surfaces. This model indicates that the potential demanded by the electrodes is directly linked to the current. Furthermore, there is a steep drop in the potential demanded by the anode when there is sufficient hydroxide available to generate oxygen from hydroxide as opposed to generation from water. The voltage demand is minimal at pH 12.5 and reflective of the reference standard voltage (just over 1.23 V predicted at 0.1 amps). However, the flux model predicts that the voltage demanded by the electrodes at pH 7 is 1.61 V at 0.1 amps (the lowest amperage measurable with the power pack). In conclusion, comparing this result to the reference standard (E 0 = -1.23 V) yields a satisfactory explanation for the observed difference below reference standard of 0.42 V.

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

Flow-Assisted Selective Mineral Extraction from Seawater

The sustainable production of critical materials from natural sources requires a paradigm shift away from currently used resource-intensive processes. In this paper, we report a single-step, laminar co-flow method (LCM) that leverages non-equilibrium conditions to selectively extract pure Mg(OH) 2 from natural seawater. Conventional seawater-based Mg extraction involves adding individual or a combination of precipitants to obtain Mg(OH) 2 , but the co-existence of Ca 2+ unavoidably results in CaCO 3 impurities requiring additional purification steps. Here we show that the non-equilibrium conditions in LCM achieved using a microfluidics device and by simply co-injecting a NaOH solution with seawater can result in improved selectivity for Mg(OH) 2 unlike in conventional bulk mixing method. The resulting precipitates are characterized for composition and the process yield and purity are optimized through systematic variations of the reaction time and the concentration of NaOH. This is the first demonstration of LCM for selective separation, and as a one-step process that does not rely on novel sorbents, membranes, or external stimuli, it is easy to scale-up. LCM has the potential to be broadly relevant to selective separations from complex feed streams and diverse chemistries—enabling more sustainable materials extraction and processing.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

The [M 6 (S 2 C 2 Ph 2 ) 6 ] (M = Ni, Pd, Pt) Series: Multielectron Reservoirs That Sustain Ligand-Based Oxidations and Metal-Based Reductions

A complete [M 6 (S 2 C 2 R 2 ) 6 ] series (M = Ni (1), Pd (2), Pt (3); R = Ph), the rarest variety among homoleptic dithiolene transition-metal compounds, has been prepared by reaction between [M(S 2 C 2 Ph 2 ) 2 ] and a M 0 source. The platinum member of this set is the first of its type. Diffraction-quality crystals, grown with high reproducibility by evaporation from PhNO 2 solutions, reveal fully reduced [Ph 2 C 2 S 2 ] 2– dianions and an octahedral M 6 core that is reduced to C 2 symmetry by the fusion of a mononuclear D 2h [M(S 2 C 2 Ph 2 ) 2 ] fragment upon a C 4 -symmetric base. The [Ni 6 (S 2 C 2 Ph 2 ) 2 ] 1– monoanion, prepared by Cp* 2 Co reduction, shows only modest structural differences from its neutral counterpart. In CH 2 Cl 2 , 1 and 2 can undergo two reductions and an oxidation, while 3 sustains two reductions and two oxidations. In benzonitrile, 1 sustains three reversible oxidations at potentials that are shifted appreciably to less positive values. The cathodic processes are shown by density functional theory (DFT) calculations to involve an MO largely of metal–sulfur composition that has contributions throughout the C 4 -symmetric pentametallic base of the assembly, while the oxidations are largely ligand-based and confined to the monometallic [M(S 2 C 2 Ph 2 ) 2 ] cap. The absorption spectra are marked by multiple overlapping bands that produce a continuous, tapering absorption profile of unresolved shoulders and swells.

Ligands↗
DOE OSTI2017

Persistent anomalies of the extratropical Northern Hemisphere wintertime circulation as an initiator of El Niño/Southern Oscillation events

Climates across both hemispheres are strongly influenced by tropical Pacific variability associated with the El Niño/Southern Oscillation (ENSO). Conversely, extratropical variability also can affect the tropics. In particular, seasonal-mean alterations of near-surface winds associated with the North Pacific Oscillation (NPO) serve as a significant extratropical forcing agent of ENSO. However, it is still unclear what dynamical processes give rise to year-to-year shifts in these long-lived NPO anomalies. Here in this paper we show that intraseasonal variability in boreal winter pressure patterns over the Central North Pacific (CNP) imparts a significant signature upon the seasonal-mean circulations characteristic of the NPO. Further we show that the seasonal-mean signature results in part from year-to-year variations in persistent, quasi-stationary low-pressure intrusions into the subtropics of the CNP, accompanied by the establishment of persistent, quasi-stationary high-pressure anomalies over high latitudes of the CNP. Overall, we find that the frequency of these persistent extratropical anomalies (PEAs) during a given winter serves as a key modulator of intraseasonal variability in extratropical North Pacific circulations and, through their influence on the seasonal-mean circulations in and around the southern lobe of the NPO, the state of the equatorial Pacific 9–12 months later.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Manipulation of intramolecular hydrogen bonds in conjugated pseudoladder polymer for semiconductivity and solution-processability

The conformational coplanarity and local rigidity of π-conjugated backbones are critical for the semiconducting performance of organic electronic materials. The conformational coplanarity and local rigidity of π-conjugated backbones are critical for the semiconducting performance of organic electronic materials. While fusing the aromatic system into a ladder-type structure effectively enhances these properties, it also often results in poor solution processability and hence limits their transition to device application. To address this challenge, an intramolecularly hydrogen-bonded pseudoladder polymer (HPLP) system based on alternating hydrogen bond donating benzobisimidazole (BBI) and hydrogen bond accepting benzodifuran (BDF) units, is designed and synthesized. A Boc-protected precursor of HPLP allows for feasible solution processing of the polymer into thin films. Subsequently, in situ thermal Boc-deprotection generates the HPLP polymer, in which intramolecular hydrogen bonds form between each pair of neighboring repeating units, inducing coplanarity and rigidity throughout the entire backbone. This process is accompanied by a significant red-shift of the absorption spectrum, reduced bandgap, and enhanced rigidity, as confirmed by NMR, UV-Vis, and density functional theory analyses. HPLP films exhibit a three-order-of-magnitude enhancement in charge carrier mobility compared to the Boc-protected precursor and demonstrate excellent solvent resistance in organic thin-film transistors.

Miranda, Octavio↗