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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
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Amplitude-mode spectroscopy of chemically injected and photogenerated charge carriers in semiconducting single-walled carbon nanotubes

In one-dimensional semiconductors such as conjugated polymers and semiconducting single-walled carbon nanotubes (s-SWCNTs), injected charge carriers (electrons or holes) can have profound impacts on both electronic conductivity and optical spectra, even at low carrier densities. Understanding charge-related spectral features is a key fundamental challenge with important technological implications. Here, we employ a systematic suite of experimental and theoretical tools to understand the mid-infrared charge signatures of heavily p-type doped polymer-wrapped s-SWCNTs. Across a broad range of nanotube diameters, we find that hole charge carriers induce strong Fano anti-resonances in mid-infrared transmission spectra that correspond to defect-related (D-band) and in-plane tangential (G-band) Raman-active vibrational modes, along with anti-resonances arising from infrared (IR)-active polymer and SWCNT modes. We employ 13C isotope-labeled s-SWCNTs and a removable wrapping polymer to clarify the relative intensities, energies, and sources of all observed anti-resonances. Simulations performed with the "amplitude mode model" are used to quantitatively reproduce Raman spectra and also help to explain the outsized intensity of the D-band anti-resonance, relative to the G-band, observed for both moderately and degenerately doped s-SWCNTs. Here, the results provide a framework for future studies of ground- and excited-state charge carriers in s-SWCNTs and a variety of low-dimensional materials.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Investigation of poly(phenylacetylene) derivatives for carbon precursor with high carbon yield and good solubility

This paper investigates a family of poly(phenylacetylene) derivatives with a p-electrons conjugated polymer backbone and side groups containing only sp 2 and sp carbons. The objective is to identify the suitable carbon precursor that is processible and can be transformed to carbonaceous material with high carbon yield by a simple (one-step) thermal transformation process (without any external reagent). Poly(phenylacetylene) with para-substituted acetylene group poly(PA-A) shows an exceptionally high C-yield (~90%) in one-step heating from ambient temperature to 1000 °C under N 2 atmosphere. Unfortunately, this poly(PA-A) polymer is quite sensitive to heat and light with very limited solubility. On the other hand, poly(phenylacetylene) with para-substituted phenylacetylene group, i.e. poly(PA-PA), offers a relatively high C-yield (~80%) and also good solubility in common organic solvents, such as toluene and tetrahydrofuran (THF). Several uniform dark-red poly(PA-PA) fibers with smooth surface and fiber diameter in the range of 3–6 μm were prepared from 30 wt% poly(PA-PA)/THF solution using electrospinning technique. Furthermore, the resulting precursor fibers were converted to the corresponding carbon structure in a one-step thermal heating process under N 2 atmosphere. Both X-ray and Raman spectra show the polymorphous carbon morphology with the graphene crystalline domains.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Green solvent-processable poly(3-hexylthiophene) derivative maintains high hole mobility in diodes

The development of environmentally sustainable fabrication methods for organic solar cells (OSCs) is critical to enable their large-scale adoption. Conventional solution-processed OSCs often rely on halogenated, toxic solvents that pose health and environmental risks, limiting their scalability. This is because π-conjugated polymers tend to have a low solubility in non-halogenated solvents. A common strategy to enhance solubility in alternative solvents is through the incorporation of polar solubilizing groups, often on every repeat unit of at least one monomer. However, too many polar side chains tend to disrupt favorable morphology and decrease charge transport properties. In this study, we demonstrate that a minimal degree of side chain functionalization can improve green solvent processability while preserving electrical performance. We tested this hypothesis using our previously reported random copolymer derivative of poly(3-hexylthiophene) (P3HT) where ∼10 mol% of the side chains are 6-pentanoatehexyl side chains. We find that this low-level functionalization significantly broadens the solvents that can be used to process P3HT to less toxic solvents such as o-xylene and anisole. Furthermore, the copolymer processed from greener solvents showed high hole mobilities (∼10⁻ 3 cm 2 /Vs by the Space-Charge Limiting Current method in diodes), comparable to P3HT films cast from toxic chloroform. These findings suggest that minimal side-chain modification is a viable strategy for expanding green solvent compatibility while preserving electrical performance, paving the way toward more sustainable organic semiconductor designs.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Quantifying Charge Carrier Localization in PBTTT Using Thermoelectric and Spectroscopic Techniques

Chemically doped poly[2,5-bis(3-alkylthiophen-2-yl)thieno[3,2- b ]thiophene] (PBTTT) shows promise for many organic electronic applications, but rationalizing its charge transport properties is challenging because conjugated polymers are inhomogeneous, with convoluted optical and solid-state transport properties. Herein, we use the semilocalized transport (SLoT) model to quantify how the charge transport properties of PBTTT change as a function of iron(III) chloride (FeCl 3 ) doping level. We use the SLoT model to calculate fundamental transport parameters, including the carrier density needed for metal-like electrical conductivities and the position of the Fermi energy level with respect to the transport edge. We then contextualize these parameters with other polymer-dopant systems and previous PBTTT reports. Additionally, we use grazing incidence wide-angle X-ray scattering and spectroscopic ellipsometry techniques to better characterize inhomogeneity in PBTTT. Our analyses indicate that PBTTT obtains high electrical conductivities due to its quickly rising reduced Fermi energy level, and this rise is afforded by its locally high carrier densities in highly ordered microdomains. Ultimately, this report sets a benchmark for comparing transport properties across polymer-dopant-processing systems.

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

Manipulating Photoconduction in Cu–Pyrene 1-D Coordination Nanosheets by Modulating Interlayer π–π Stacking

2D conductive metal organic frameworks (MOFs) have become promising candidates for applications in electronic and photoelectronic devices. However, the lack of a fundamental understanding of the charge transport mechanism and synthetic design to alter their conductivity limits their potential applications. In this work, we report the design and synthesis of two 1D Cu–pyrene coordination nanosheets, Cu–pyrene-4,5,9,10 tetrathiol (Cu-PTT) and Cu–2,7-di-tert-butylpyrene-4,5,9,10-tetrathiol (Cu– tBu PTT), as models of 2D conductive MOFs, where the introduction of two different functional groups (H and tert-butyl groups) at the 2 and 7 positions of the PTT ligands is used to tune the interlayer distance and π–π stacking of MOFs. Using optical pump terahertz probe spectroscopy, we show that both nanosheets exhibit appreciable photoconduction, but the photoconduction in Cu– tBu PTT is reduced with respect to that in Cu–PTT, which can be attributed to the larger interlayer distance in the former leading to the decoupling of the interlayer charge transport pathway. Furthermore, these results demonstrate a unique strategy to investigate the impact of out-of-plane extended conjugation on photoconduction in conductive conjugated polymers, MOFs, or coordination nanosheets through adjusting their interlayer spacing.

14 SOLAR ENERGY↗
DOE OSTI2021

Nucleobase-Functionalized Poly(alkylthiophene)s: One-Pot, Sequential Direct Arylation Polymerization and Deprotection, and Surface Modification for Oil–Water Separations

Direct arylation polymerization (DArP) has emerged as an environmentally friendly, atom efficient method of synthesizing a variety of conjugated polymers. In this work, we report a one-pot approach consisting of DArP followed by Boc deprotection to synthesize a functional, surface-active adenine-containing poly(alkylthiophene). Careful control over the polymerization temperature enables the one-pot polymerization and deprotection strategy for synthesis, with quantitative (>99%) Boc deprotection achieved in 24 h. This temperature-controlled synthesis method reduces extra purification and isolation steps, which makes the total synthesis more efficient and practical, and allows higher molecular weight polymer to be made. We quantify the hydrogen bonding ability of the resulting adenine-containing polythiophene, T Ad -tT 4h , by 1 H NMR host–guest titration studies and analyze the results with the Benesi–Hildebrand model, yielding an association constant of 18.7 M –1 between alkylated thymine and T Ad -tT 4h . We demonstrate that T Ad -tT 4h robustly modifies the surface of cellulosic filter paper (CFP), and the modified cellulosic filter paper, CFP-T Ad -tT 4h , is an effective oil–water separatory filter with superhydrophobic properties (water contact angle (CA) ~151°). The utility of hydrogen bonding interactions between adenine and cellulose highlights the importance of side-chain engineering for creating functional materials.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Oligoether-Functionalized PEDOT: Combining an EDOT Backbone with Polar Side Chains for Solution Processability and High Electrical Conductivity

Conjugated polymers functionalized with oligoether (OE)-based side chains are a key class of materials for various organic electronic applications, including transparent electrodes, thermoelectrics, electrochromic displays, and electrochemical transistors. Herein, we report a highly soluble OE-functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) homopolymer, prepared by direct (hetero)arylation polymerization, which allows solution processing to yield films with comparable redox properties to oxidatively polymerized PEDOT. This polymer, PEDOT(OE3), when optimally oxidatively doped, reaches among the highest electrical conductivities of any OE-functionalized polymer and is comparable to more synthetically complex OE-functionalized polymers. X-ray scattering and spectroscopy were utilized to rationalize the transport properties resulting from varying the doping level. Comparison of PEDOT(OE3) to a series of OE-functionalized dioxythiophenes with varying amounts of 3,4-ethylenedioxythiophene units allows for a deeper understanding of structure–property relationships through charge-transport models. Ultimately, PEDOT(OE3) is shown to be a material with exceptional charge-transport properties and is promising for various applications.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Revealing the Full Potential of Glycolated Mixed Ionic-Electronic Semiconductors – Symmetric Monomer Polymerization to Boost Electrochemical Transistor Performance

Organic electrochemical transistors (OECTs) enable the transduction of ionic signals into electronic outputs, positioning them as ideal candidates for next-generation sensing and (bio)signal processing applications. Recent years have witnessed the development of various OECT channel materials, affording insights into structural fine-tuning to achieve optimal performance and/or stability. However, homocouplings, commonly present in alternating conjugated polymers, have largely been overlooked. This study investigates the effect of homocoupling on OECT materials by employing two synthesis methods – standard Stille polymerization and an alternative symmetric approach – to create the p-type enhancement-mode benchmark polymer pgBTTT. The impact of homocoupling, and its absence, is studied by comparing the bulk properties of the two polymers and evaluating their respective OECT metrics. The new, homocoupling-free polymer exhibits a notably improved OECT performance ( μC *), mainly due to an average 3-fold increase in electronic mobility (μ).

defects↗
DOE OSTI2021

Computing inelastic neutron scattering spectra from molecular dynamics trajectories

Abstract Inelastic neutron scattering (INS) provides a weighted density of phonon modes. Currently, INS spectra can only be interpreted for perfectly crystalline materials because of high computational cost for electronic simulations. INS has the potential to provide detailed morphological information if sufficiently large volumes and appropriate structural variety are simulated. Here, we propose a method that allows direct comparison between INS data with molecular dynamics simulations, a simulation method that is frequently used to simulate semicrystalline/amorphous materials. We illustrate the technique by analyzing spectra of a well-studied conjugated polymer, poly(3-hexylthiophene-2,5-diyl) (P3HT) and conclude that our technique provides improved volume and structural variety, but that the classical force field requires improvement before the morphology can be accurately interpreted.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Amine-functionalized porous organic polymers for carbon dioxide capture

Recent developments in CO 2 capture using porous organic polymers (POPs) have received accrescent attention due to their sorbent properties such as high CO 2 uptake capacity and selectivity, tunable chemical structure and permanent porosity. POPs are constructed using two and/or three-dimensional organic monomers (building blocks) linked to each other through covalent bonding, creating high porosity. The pore structure in POPs is exceptionally stable, which leads to their cyclable CO 2 adsorption performance. However, POPs generally suffer from low CO 2 uptake and selectivity due to their interaction with CO 2 in physisorption limits (20–40 kJ mol -1 ). Similar to that in other physisorbents, the CO 2 uptake capacity of POPs further decreases under humid conditions. Pursuant to these limitations, amine functionalization in POPs has resulted in enhanced CO 2 uptake performance with improved CO 2 selectivity over non-polar gases such as N 2 . More importantly, several types of amine-functionalized POPs showed that the CO 2 uptake could remain intact under humid conditions such as in post-combustion flue gas. This review article covers recent developments in amine-functionalized porous organic polymers. Three main categories of amine functionalization, such as direct amine synthesis, amine impregnation and amine grafting, were investigated in detail by considering the effect of amines on the sorbent properties and CO 2 capture performance of POPs. The recent findings in amine-functionalized POPs were investigated including porous polymeric networks (PPNs), covalent organic frameworks (COFs), amine linked POPs, hyper-crosslinked polymers (HCPs), conjugated microporous polymers (CMPs), benzimidazole linked polymers (BILPs), porous aromatic frameworks (PAFs) and polymers of intrinsic microporosity (PIMs).

36 MATERIALS SCIENCE↗
DOE OSTI2025

Annihilation-limited long-range exciton transport in high-mobility conjugated copolymer films

A combination of ultrafast, long-range, and low-loss excitation energy transfer from the photoreceptor location to a functionally active site is essential for cost-effective polymeric semiconductors. Delocalized electronic wavefunctions along π-conjugated polymer (CP) backbone can enable efficient intrachain transport, while interchain transport is generally thought slow and lossy due to weak chain–chain interactions. In contrast to the conventional strategy of mitigating structural disorder, amorphous layers of rigid CPs, exemplified by highly planar poly(indacenodithiophene-co-benzothiadiazole) (IDT-BT) donor-accepter copolymer, exhibit trap-free transistor performance and charge-carrier mobilities similar to amorphous silicon. Here, we report long-range exciton transport in HJ -aggregated IDTBT thin-film, in which the competing exciton transport and exciton–exciton annihilation (EEA) dynamics are spectroscopically separated using a phase-cycling-based scheme and shown to depart from the classical diffusion-limited and strong-coupling regime. In the thin film, we find an annihilation-limited mechanism with ≪100% per-encounter annihilation probability, facilitating the minimization of EEA-induced excitation losses. In contrast, excitons on isolated IDTBT chains diffuse over 350 nm with 0.56 cm 2 s −1 diffusivity, before eventually annihilating with unit probability on first contact. We complement the pump–probe studies with temperature-dependent photocurrent and EEA measurements from 295 K to 77 K and find a remarkable correspondence of annihilation rate and photocurrent activation energies in the 140 K to 295 K temperature range.

Shi, Yuping (ORCID:0000000318289415)↗
DOE OSTI2023

Nanomechanics and Electronic Structure of Organic Photovoltaics in Real Application Conditions by Advanced Scanning Probe Microscopy (Final Technical Report for Project DE-SC0018041)

This project report consists of the following three sections: A.) Investigation of Charge Transport Properties in Semiconducting Conjugated Polymer Blends Using Computational Chemistry and Experiments: This section provides unpublished but valuable research results that correlate the electronic structure of PCBM:PCDTBT organic photovoltaic systems with their current-voltage characteristics. The presentation is structured in the form of a scientific publication. B.) Scanning Probe Microscopy Methodology Development Efforts for Organic Photovoltaic Materials: This section summarizes various published works focusing on advancements in scanning probe microscopy methods. Each sub-section corresponds to a scientific publication for which the abstract and citation are provided. C.) Other Publications Supported by the Project: This section lists additional published works partially supported by the project, which are not included in the previous two sections.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Photoluminescence of Cis-Polyacetylene Semiconductor Material

Photoluminescence (PL) is one of the key experimental characterizations of optoelectronic materials, including conjugated polymers (CPs). In this study, a simplified model of an undoped cis-polyacetylene (cis-PA) oligomer was selected and used to explain the mechanism of photoluminescence (PL) of the CPs. Using a combination of the ab initio electronic structure and a time-dependent density matrix methodology, the photo-induced time-dependent excited state dynamics were computed. We explored the phonon-induced relaxation of the photoexcited state for a single oligomer of cis-PA. Here, the dissipative Redfield equation of the motion was used to compute the dissipative excited state dynamics of electronic degrees of freedom. This equation used the nonadiabatic couplings as parameters. The computed excited state dynamics showed that the relaxation rate of the electron is faster than the relaxation rate of the hole. The dissipative excited-state dynamics were combined with radiative recombination channels to predict the PL spectrum. The simulated results showed that the absorption and emission spectra both have a similar transition. The main result is that the computed PL spectrum demonstrates two mechanisms of light emission originating from (i) the inter-band transitions, corresponding to the same range of transition energies as the absorption spectrum and (ii) intra-band transitions not available in the absorption spectra. However, the dissipative Redfield equation of the motion was used to compute the electronic degrees of freedom of the nonadiabatic couplings, which helped to process the time propagation of the excited dynamic state. This excited dynamic state shows that the relaxation rate of the electron is faster than the relaxation rate of the hole, which can be used for improving organic semiconductor materials for photovoltaic and LED applications.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Fluorogenic Biosensing with Tunable Polydiacetylene Vesicles

Polydiacetylenes (PDAs) are conjugated polymers that are well known for their colorimetric transition from blue to red with the application of energetic stimulus. Sensing platforms based on polymerized diacetylene surfactant vesicles and other structures have been widely demonstrated for various colorimetric biosensing applications. Although less studied and utilized, the transition also results in a change from a non-fluorescent to a highly fluorescent state, making polydiacetylenes useful for both colorimetric and fluorogenic sensing applications. Here, we focus on the characterization and optimization of polydiacetylene vesicles to tune their sensitivity for fluorogenic sensing applications. Particularly, we look at how the structure of the diacetylene (DA) hydrocarbon tail and headgroup affect the self-assembled vesicle size and stability, polymerization kinetics, and the fluorogenic, blue to red phase transition. Longer DA acyl tails generally resulted in smaller and more stable vesicles. The polymerization kinetics and the blue to red transition were a function of both the DA acyl tail length and structure of the headgroup. Decreasing the acyl tail length generally led to vesicles that were more sensitive to energetic stimuli. Headgroup modifications had different effects depending on the structure of the headgroup. Ethanolamine headgroups resulted in vesicles with potentially increased stimuli responsivity. The lower energy stimulus to induce the chromatic transition was attributed to an increase in headgroup hydrogen bonding and polymer backbone strain. Boronic-acid headgroup functionalization led to vesicles that were generally unstable, only weakly polymerized, and unable to fully transform to the red phase due to strong polar, aromatic headgroup interactions. This work presents the design of PDA vesicles in the context of biosensing platforms and includes a discussion of the past, present, and future of PDA biosensing.

Chemistry↗
NASA NTRS1993

Prediction of nonlinear optical properties of organic materials. General theoretical considerations

The prediction of nonlinear optical properties of organic materials is geared to assist materials scientists in the selection of good candidate molecules. A brief summary of the quantum mechanical methods used for estimating hyperpolarizabilities will be presented. The advantages and limitations of each technique will be discussed. Particular attention will be given to the finite-field method for calculating first and second order hyperpolarizabilities, since this method is better suited for large molecules. Corrections for dynamic fields and bulk effects will be discussed in detail, focusing on solvent effects, conformational isomerization, core effects, dispersion, and hydrogen bonding. Several results will be compared with data obtained from third-harmonic-generation (THG) and dc-induced second harmonic generation (EFISH) measurements. These comparisons will demonstrate the qualitative ability of the method to predict the relative strengths of hyperpolarizabilities of a class of compounds. The future application of molecular mechanics, as well as other techniques, in the study of bulk properties and solid state defects will be addressed. The relationship between large values for nonlinear optical properties and large conjugation lengths is well known, and is particularly important for third-order processes. For this reason, the materials with the largest observed nonresonant third-order properties are conjugated polymers. An example of this type of polymer is polydiacetylene. One of the problems in dealing with polydiacetylene is that substituents which may enhance its nonlinear properties may ultimately prevent it from polymerizing. A model which attempts to predict the likelihood of solid-state polymerization is considered, along with the implications of the assumptions that are used. Calculations of the third-order optical properties and their relationship to first-order properties and energy gaps will be discussed. The relationship between monomeric and polymeric third-order optical properties will also be considered.

Cardelino, B.↗
NASA NTRS1994

Photodeposition of Thin Polydiacetylene Films from Solution that Exhibit Large Third-Order Optical Nonlinearities

One promising class of organic compounds for applications in the field of nonlinear optics (NLO) are polydiacetylenes, which are of interest because they are highly conjugated polymers capable of exhibiting very large optical nonlinearities with fast response times. During the course of crystal growth studies in anticipation of a space experiment, we discovered a novel, simple method for the formation of polydiacetylene thin films by photodeposition from monomer solutions onto quartz or glass substrates. Characterization of these PDAMNA films is not trivial; they are not soluble in common organic solvents, which makes the standard solution-based methods of polymer analysis useless.

Paley, M. S.↗