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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Aqueous Processed All-Polymer Solar Cells with High Open-Circuit Voltage Based on Low-Cost Thiophene–Quinoxaline Polymers

Eco-friendly solution processing and the low-cost synthesis of photoactive materials are important requirements for the commercialization of organic solar cells (OSCs). Although varieties of aqueous-soluble acceptors have been developed, the availability of aqueous-processable polymer donors remains quite limited. In particular, the generally shallow highest occupied molecular orbital (HOMO) energy levels of existing polymer donors limit further increases in the power conversion efficiency (PCE). Here, we design and synthesize two water/alcohol-processable polymer donors, poly[(thiophene-2,5-diyl)-alt-(2-((13-(2,5,8,11-tetraoxadodecyl)-2,5,8,11-tetraoxatetradecan-14-yl)oxy)-6,7-difluoroquinoxaline-5,8-diyl)] (P(Qx8O-T)) and poly[(selenophene-2,5-diyl)-alt-(2-((13-(2,5,8,11-tetraoxadodecyl)-2,5,8,11-tetraoxatetradecan-14-yl)oxy)-6,7-difluoroquinoxaline-5,8-diyl)] (P(Qx8O-Se)) with oligo(ethylene glycol) (OEG) side chains, having deep HOMO energy levels (~–5.4 eV). The synthesis of the polymers is achieved in a few synthetic and purification steps at reduced cost. The theoretical calculations uncover that the dielectric environmental variations are responsible for the observed band gap lowering in OEG-based polymers compared to their alkylated counterparts. Notably, the aqueous-processed all-polymer solar cells (aq-APSCs) based on P(Qx8O-T) and poly[(N,N'-bis(3-(2-(2-(2-methoxyethoxy)-ethoxy)ethoxy)-2-((2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-methyl)propyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl)-alt-(2,5-thiophene)] (P(NDIDEG-T)) active layer exhibit a PCE of 2.27% and high open-circuit voltage (V OC ) approaching 0.8 V, which are among the highest values for aq-APSCs reported to date. This study provides important clues for the design of low-cost, aqueous-processable polymer donors and the fabrication of aqueous-processable OSCs with high V OC .

14 SOLAR ENERGY↗
DOE OSTI2020

Techno-Economic and Life Cycle Assessments for Sustainable Rare Earth Recovery from Coal Byproducts using Biosorption

Coal byproducts could be a promising feedstock to alleviate the supply risk of critical rare earth elements (REEs) due to their abundance and REE content. Herein, we investigated the economic and environmental potential of producing REEs from coal fly ash and lignite through an integrated process of leaching, biosorption, and oxalic precipitation on the basis of experimental data and modeling results. Two microbe immobilization systems (polyethylene glycol diacrylate (PEGDA) microbe beads and Si sol–gels) were examined for their efficiency in immobilizing Arthrobacter nicotianae to selectively recover REEs. Techno-economic analysis revealed that North Dakota lignite could be a profitable feedstock when Si sol–gel is used due to its high cell loading and REE adsorption capacity as well as high reuse cycles. Life cycle analysis revealed that Si sol–gel-based biosorption could be more environmental friendly than the prevailing REE production in China due to the use of less toxic chemicals. However, fly ash sourced from Powder River Basin coals was neither profitable nor environmentally sustainable, primarily due to low solubility of high-value scandium at an economical pulp density (100 g ash/L of acid solution). To further improve the proposed biotechnology, future research could focus on scandium recovery, leaching efficiency at a high pulp density, and reuse cycles of the immobilized microbes.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2025

Ionic liquids improve the long-term stability of perovskite solar cells

Achieving operational stability in halide perovskite solar cells remains a critical challenge for commercialization. Ionic liquids are promising bulk modifiers, yet their mechanistic role in perovskite crystallization is poorly understood. Here we engineered an ionic liquid, methoxyethoxymethyl-1-methylimidazole chloride (MEM-MIM-Cl), with an ethylene glycol ether side chain that regulates perovskite growth and stabilizes buried interfaces via synergistic interactions with NiO x . MEM-MIM-Cl induces a novel intermediate phase through chelation with undercoordinated Pb(II), suppressing defects and defect-induced degradation. Solar cells incorporating MEM-MIM-Cl achieved a power conversion efficiency of 25.9% and retained 90% of their initial performance after 1,500 h under continuous 1-sun illumination and 90 °C thermal stress—surpassing prior benchmarks under milder ageing conditions. Furthermore, diurnal cyclic ageing revealed unprecedented fatigue resistance, highlighting the dual role of MEM-MIM-Cl in simultaneously enhancing efficiency and operational resilience. In conclusion, this work elucidates design principles for functional ionic liquids while advancing perovskite photovoltaics towards industrial viability.

14 SOLAR ENERGY↗
DOE OSTI2024

ToF-SIMS evaluation of PEG-related mass peaks and applications in PEG detection in cosmetic products

Polyethylene glycols (PEGs) are used in industrial, medical, health care, and personal care applications. The cycling and disposal of synthetic polymers like PEGs pose significant environmental concerns. Detecting and monitoring PEGs in the real world calls for immediate attention. This study unveils the efficacy of time-of-flight secondary ion mass spectrometry (ToF-SIMS) as a reliable approach for precise analysis and identification of reference PEGs and PEGs used in cosmetic products. By comparing SIMS spectra, we show remarkable sensitivity in pinpointing distinctive ion peaks inherent to various PEG compounds. Moreover, the employment of principal component analysis effectively discriminates compositions among different samples. Notably, the application of SIMS two-dimensional image analysis visually portrays the spatial distribution of various PEGs as reference materials. The same is observed in authentic cosmetic products. The application of ToF-SIMS underscores its potential in distinguishing PEGs within intricate environmental context. ToF-SIMS provides an effective solution to studying emerging environmental challenges, offering straightforward sample preparation and superior detection of synthetic organics in mass spectral analysis. These features show that SIMS can serve as a promising alternative for evaluation and assessment of PEGs in terms of the source, emission, and transport of anthropogenic organics.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Isothermal Versus Sensible Cold Storage: A Model-Based Performance Comparison for Pumped Thermal Electricity Storage

Pumped-thermal energy storage (PTES) systems consume and produce electrical energy using thermal storage media as an intermediate stage. PTES lends itself to long-duration energy storage to facilitate high penetration of intermittent electricity generation. This study presents a model-based comparison of two thermal storage types within a PTES system: a conventional, single-phase, stratified water-glycol sensible storage system (SGS), and an ideal isothermal, two-phase heat exchanger that freezes a water reservoir (isothermal heat exchanger (IHEX)). The SGS thermal storage capacity is based on the liquid’s sensible heat change with temperature, whereas the capacity of the IHEX is based on the latent heat of isothermally freezing and melting water. The idealized IHEX modeled here undergoes steady-state melting and freezing (in contrast to transient rates, as observed with ice-on-coil storage). A computational model of a complete PTES system is presented and used to evaluate the PTES system-level performance with each type of cold storage. Compared to SGS-based PTES, under nominal operating conditions, the IHEX-based PTES increased electrical round-trip efficiency from 61% to 82% and increased energy density from 1.13 to 8.09 kWh/m 3 In conclusion, the performance of the PTES configured with IHEX storage was also analyzed under varying operating parameters.

25 ENERGY STORAGE↗
DOE OSTI2024

Development of 225Ac-doped biocompatible nanoparticles for targeted alpha therapy

Abstract Targeted alpha therapy (TAT) relies on chemical affinity or active targeting using radioimmunoconjugates as strategies to deliver α-emitting radionuclides to cancerous tissue. These strategies can be affected by transmetalation of the parent radionuclide by competing ions in vivo and the bond-breaking recoil energy of decay daughters. The retention of α-emitting radionuclides and the dose delivered to cancer cells are influenced by these processes. Encapsulating α-emitting radionuclides within nanoparticles can help overcome many of these challenges. Poly(lactic- co -glycolic acid) (PLGA) nanoparticles are a biodegradable and biocompatible delivery platform that has been used for drug delivery. In this study, PLGA nanoparticles are utilized for encapsulation and retention of actinium-225 ([ 225 Ac]Ac 3+ ). Encapsulation of [ 225 Ac]Ac 3+ within PLGA nanoparticles (Z ave = 155.3 nm) was achieved by adapting a double-emulsion solvent evaporation method. The encapsulation efficiency was affected by both the solvent conditions and the chelation of [ 225 Ac]Ac 3+ . Chelation of [ 225 Ac]Ac 3+ to a lipophilic 2,9-bis-lactam-1,10-phenanthroline ligand ([ 225 Ac]AcBLPhen) significantly decreased its release (< 2%) and that of its decay daughters (< 50%) from PLGA nanoparticles. PLGA nanoparticles encapsulating [ 225 Ac]AcBLPhen significantly increased the delivery of [ 225 Ac]Ac 3+ to murine (E0771) and human (MCF-7 and MDA-MB-231) breast cancer cells with a concomitant increase in cell death over free [ 225 Ac]Ac 3+ in solution. These results demonstrate that PLGA nanoparticles have potential as radionuclide delivery platforms for TAT to advance precision radiotherapy for cancer. In addition, this technology offers an alternative use for ligands with poor aqueous solubility, low stability, or low affinity, allowing them to be repurposed for TAT by encapsulation within PLGA nanoparticles. Graphical Abstract

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

Solubility Testing to Support the Addition of Sodium Reactor Experiment Material to Sludge Batch 10

The Savannah River Site H-Canyon Facility is planning to discard dissolved Sodium Reactor Experiment (SRE) material into Tank 51 prior to Sludge Batch 10 (SB10). SB10 with the SRE material will be processed in the Defense Waste Processing Facility (DWPF) using the Nitric-Glycolic Acid (NGA) flowsheet. The DWPF Nuclear Criticality Safety Evaluation (NCSE) protects a 14:1 mass ratio of manganese to equivalent uranium-235 in both the solid and liquid phases during processing by requiring a 70:1 mass ratio in the feed. A concern was raised that freshly precipitated manganese in the SRE material will behave differently from the manganese in sludge during DWPF processing and potentially invalidate the criticality control. To mitigate risks to the DWPF criticality controls, the Savannah River National Laboratory (SRNL) performed a metals solubility test applicable to recently precipitated manganese and uranium, as would be expected with SRE transfers to SB10. The objective of this analysis is the tracking of partitioning of the primary fissile component (uranium-235) with the credited poison (manganese) between the aqueous and insoluble phases.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Thermal Management for a Novel Non-Heavy Rare-Earth Interior Permanent Magnet Machine

The work presents a thermal management solution for a novel non-heavy rare-earth permanent magnet machine being developed at Oak Ridge National Laboratory. The motor has been designed to minimize losses while maximizing performance for a range of speeds and power ratings. The novel motor design reduces rare-earth magnet usage, thereby avoiding supply chain issues. The motor component heat losses are established for operating windows and desired performance. These heat losses, along with windage losses, are being used to develop cooling solutions for different components of this machine. A novel thermal management solution for stators and rotors has been developed, and progress is presented in this paper. The stator cooling is achieved with the help of water-ethylene glycol flowing over the finned aluminum stator jacket, and rotor cooling with automatic transmission fluid passing through novel channels designed in the rotor laminations. The attempt is to establish effective cooling of the stator winding, laminations, and rotor magnets. A 3D conjugate heat transfer model has been developed for overall thermal analysis to establish a down- selected thermal management solution for the machine. The model, in addition to estimated component heat losses, includes windage losses and its impact on rotor and stator cooling. Overall, the work presents a workable thermal solution for the interior permanent magnet machine with potential for further improvements. Future work will involve establishing end winding and refinement of other end parts of the machine with the aim of establishing a robust thermal management solution. The work will also focus on different shapes (e.g., round, non-round, presence of wedges) of rotor-stator gaps and investigate windage losses and their impact on thermal management for higher rotational speeds for the machine.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Transcriptome Analysis of Drought-Resistant and Drought-Sensitive Sorghum ( Sorghum bicolor ) Genotypes in Response to PEG-Induced Drought Stress

Drought is a major limiting factor of crop yields. In response to drought, plants reprogram their gene expression, which ultimately regulates a multitude of biochemical and physiological processes. The timing of this reprogramming and the nature of the drought-regulated genes in different genotypes are thought to confer differential tolerance to drought stress. Sorghum is a highly drought-tolerant crop and has been increasingly used as a model cereal to identify genes that confer tolerance. Also, there is considerable natural variation in resistance to drought in different sorghum genotypes. Here, we evaluated drought resistance in four genotypes to polyethylene glycol (PEG)-induced drought stress at the seedling stage and performed transcriptome analysis in seedlings of sorghum genotypes that are either drought-resistant or drought-sensitive to identify drought-regulated changes in gene expression that are unique to drought-resistant genotypes of sorghum. Our analysis revealed that about 180 genes are differentially regulated in response to drought stress only in drought-resistant genotypes and most of these (over 70%) are up-regulated in response to drought. Among these, about 70 genes are novel with no known function and the remaining are transcription factors, signaling and stress-related proteins implicated in drought tolerance in other crops. This study revealed a set of drought-regulated genes, including many genes encoding uncharacterized proteins that are associated with drought tolerance at the seedling stage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2002

Formation of three-dimensional cell/polymer constructs for bone tissue engineering in a spinner flask and a rotating wall vessel bioreactor

The aim of this study is to investigate the effect of the cell culture conditions of three-dimensional polymer scaffolds seeded with rat marrow stromal cells (MSCs) cultured in different bioreactors concerning the ability of these cells to proliferate, differentiate towards the osteoblastic lineage, and generate mineralized extracellular matrix. MSCs harvested from male Sprague-Dawley rats were culture expanded, seeded on three-dimensional porous 75:25 poly(D,L-lactic-co-glycolic acid) biodegradable scaffolds, and cultured for 21 days under static conditions or in two model bioreactors (a spinner flask and a rotating wall vessel) that enhance mixing of the media and provide better nutrient transport to the seeded cells. The spinner flask culture demonstrated a 60% enhanced proliferation at the end of the first week when compared to static culture. On day 14, all cell/polymer constructs exhibited their maximum alkaline phosphatase activity (AP). Cell/polymer constructs cultured in the spinner flask had 2.4 times higher AP activity than constructs cultured under static conditions on day 14. The total osteocalcin (OC) secretion in the spinner flask culture was 3.5 times higher than the static culture, with a peak OC secretion occurring on day 18. No considerable AP activity and OC secretion were detected in the rotating wall vessel culture throughout the 21-day culture period. The spinner flask culture had the highest calcium content at day 14. On day 21, the calcium deposition in the spinner flask culture was 6.6 times higher than the static cultured constructs and over 30 times higher than the rotating wall vessel culture. Histological sections showed concentration of cells and mineralization at the exterior of the foams at day 21. This phenomenon may arise from the potential existence of nutrient concentration gradients at the interior of the scaffolds. The better mixing provided in the spinner flask, external to the outer surface of the scaffolds, may explain the accelerated proliferation and differentiation of marrow stromal osteoblasts, and the localization of the enhanced mineralization on the external surface of the scaffolds. Copyright 2002 Wiley Periodicals, Inc.

NASA Discipline Cell Biology↗
NASA NTRS1999

Crystallization and preliminary X-ray diffraction analysis of restriction endonuclease EcoRII

Crystals of the restriction endonuclease EcoRII have been obtained by the vapor-diffusion technique in the presence of ammonium sulfate or polyethylene glycol. The best crystals were grown with ammonium sulfate as a precipitant. Crystals with dimensions of up to 0.6 x 0. 6 x 0.6 mm have been observed. The crystals diffract to about 4.0 A resolution at a cryo-temperature of 100 K using a rotating-anode X-ray source and a Rigaku R-AXIS IV imaging-plate detector. The space group has been determined to be either I23 or I2(1)3, with unit-cell parameters a = b = c = 160.3 A, alpha = beta = gamma = 90 degrees. The crystal asymmetric unit contains two protein molecules, and self-rotation function analysis shows a pseudo-twofold symmetry relating the two monomers. Attempts to improve the resolution of crystal diffraction and to search for heavy-atom derivatives are under way.

Deoxyribonucleases, Type II Site-Specific/chemistr↗
NASA NTRSDate not supplied

Thermal Cycle and Capacitance Testing of Mezzo Industries Phase Change Material Heat Capacitor

A phase change material heat capacitor prototype, designed and built under a NASA Small Business Innovation Research grant by Mezzo Technologies, was tested through coolant thermal cycling within the expected flow rates and temperature range of the Orion spacecraft’s propylene glycol-water mixture coolant system. Testing was performed with the phase change material contained under sealed conditions after a degassing procedure and exposed to atmosphere without prior degassing. The useful heat storage capacitance was measured and compared to Orion spacecraft requirements and theoretical N-Pentadecane storage capacity.

Propylene Glycol Water↗
DOE OSTI2020

Novel Foaming Solutions for High Level Waste (HLW) Processing - 20195

Foaming occurs during treatment of high level waste (HLW) at Savannah River Site's Defense Waste Processing Facility (DWPF) in the Chemical Process Cell (CPC) due to high gas generation from process steam and chemical offgas products [1]. The presence of amphiphilic particles in the waste slurry stabilizes the foam [2], [3]. Efficient processing of HLW requires foam control, as foam-overs lead to lower productivity and potential radioactive contamination of condensate streams. DWPF currently employs Siovation Antifoam 747, a surfactant produced by Momentive Performance Materials, as an antifoaming agent during waste treatment. Despite its ability to control foam generation, processing issues have arisen from its use [4]. During DWPF chemical processing, a chemical antifoam agent must be effective at temperatures up to 103 deg. C between pH 3-13. Antifoam 747 is effective at pH 7 but degrades as pH deviates [5]. Antifoam 747 is 90% by weight Momentive{sup TM} L77 and 10% by weight Momentive{sup TM} Y-17580. These ingredients are trisiloxane products, which are especially vulnerable to attack in acidic and caustic environments. Since Antifoam 747 readily degrades, periodic addition is required. Several processing concerns related to Antifoam 747 have affected DWPF operation. Its overuse warranted concern of potential flammable melter offgas under upset conditions due to the generation of carbon dioxide and hydrogen. As a result, a Potential Inadequacy in the Safety Analysis (PISA) was declared [6]. Antifoam contribution has been included in the melter offgas flammability strategy and the quantity of antifoam is monitored to ensure limits are not exceeded. Testing at Savannah River National Laboratory (SRNL) determined that propanal, tri-methylsilanol, and hexamethyldisiloxane are generated as Antifoam 747 degrades, leading to a second PISA [7]. The formation of these byproducts poses additional flammability risks. Furthermore, the methyl and ethyl groups of these compounds may be responsible for the formation of the methyl and ethyl mercury discovered in DWPF [8], [9]. The formation of organomercury has specifically been called out by DOE as a need for increased research. The effectiveness of non-chemical methods for foam control and the efficiency of alternative antifoam agents were evaluated as part of an effort to improve HLW treatment operations at DWPF and to reduce, or eliminate, the flammability hazards associated with Antifoam 747 currently in use. Foaming of high-level waste (HLW) slurries is an issue at the Defense Waste Processing Facility (DWPF) Chemical Process Cell (CPC) which is currently mitigated with a chemical antifoam agent. The effectiveness of non-chemical methods for foam control and the efficiency of alternative antifoams were examined to improve HLW treatment at DWPF and to eliminate the flammability hazards associated with Siovation Antifoam 747 currently in use. Non-chemical foam control methods were deemed unviable for chemical processing at DWPF, as the spray/mist technique requires too much water and space limitations make installation and implementation of headspace agitators unfeasible. The use of ultrasonic energy thickened and further stabilized the foam. Two suitable alternative defoaming agents, Momentive{sup TM} Y- 17112 and Evonik Surfynol{sup R} MD-20, were identified. Both defoamers control foam over a pH range of 4- 13 at boiling, with no flammable degradation products, and only minimal quantities (100-200 mg/kg) are required under glycolic acid conditions. In order to validate the effectiveness of these defoaming agents, SRNL recommends irradiation testing and laboratory scale SRAT/SME experiments with actual radioactive waste. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Balancing Ionic and Electronic Conduction for High‐Performance Organic Electrochemical Transistors

Abstract Conjugated polymers that support mixed (electronic and ionic) conduction are in demand for applications spanning from bioelectronics to energy harvesting and storage. To design polymer mixed conductors for high‐performance electrochemical devices, relationships between the chemical structure, charge transport, and morphology must be established. A polymer series bearing the same p‐type conjugated backbone with increasing percentage of hydrophilic, ethylene glycol side chains is synthesized, and their performance in aqueous electrolyte gated organic electrochemical transistors (OECTs) is studied. By using device physics principles and electrochemical analyses, a direct relationship is found between the OECT performance and the balanced mixed conduction. While hydrophilic side chains are required to facilitate ion transport—thus enabling OECT operation—swelling of the polymer is not de facto beneficial for balancing mixed conduction. It is shown that heterogeneous water uptake disrupts the electronic conductivity of the film, leading to OECTs with lower transconductance and slower response times. The combination of in situ electrochemical and structural techniques shown here contributes to the establishment of the structure–property relations necessary to improve the performance of polymer mixed conductors and subsequently of OECTs.

Savva, Achilleas↗
DOE OSTI2021

Head on Comparison of Self- and Nano-Assemblies of Gamma Peptide Nucleic Acid Amphiphiles

Peptide nucleic acids (PNAs) are nucleic acid analogs with hybridization properties and enzymatic stability superior to that of DNA. In addition to gene targeting applications, PNAs have garnered significant attention as bio-polymers due to the Watson–Crick-based molecular recognition and flexibility of synthesis. Here, in this work, PNA amphiphiles are engineered using chemically modified gamma PNA (8 mer in length) containing hydrophilic diethylene glycol units at the gamma position and covalently conjugated lauric acid (C12) as a hydrophobic moiety. Gamma PNA ($\gamma$PNA) amphiphiles self-assemble into spherical vesicles. Further, nano-assemblies (NA) are formulated using the amphiphilic $\gamma$PNA as a polymer via ethanol injection-based protocols. Comprehensive head-on comparison of the physicochemical and cellular uptake properties of PNA derived self- and NA is performed. Small-angle neutron and X-ray scattering analysis reveal ellipsoidal morphology of $\gamma$PNA NA that results in superior cellular delivery compate to the spherical self-assembly. Next, the functional activities of $\gamma$PNA self-and NA in lymphoma cells via multiple endpoints, including gene expression, cell viability, and apoptosis-based assays are compared. Overall, it is established that $\gamma$PNA amphiphile is a functionally active bio-polymer to formulate NA for a wide range of biomedical applications.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

In-situ Investigations on Gold Nanoparticles Stabilization Mechanisms in Biological Environments Containing HSA

Nanoparticles (NPs) developments advance innovative biomedical applications. However, complex interactions and the low colloidal stability of NPs in biological media restrict their widespread utilization. The influence of NPs properties on the colloidal stability for gold NPs with 5 and 40 nm in diameter with two surface modifications, methoxy-polyethylene glycol-sulfhydryl (PEG) and citrate, in NaCl and human serum albumin (HSA) protein solution, is investigated. This study is based on small-angle X-ray scattering (SAXS) methods allowing the in-situ monitoring of interactions in physiological conditions. The PEG coating provides high colloidal stability for NPs of both sizes. For 5 nm NPs in NaCl solution, a stable 3D self-assembled body-centered cubic (BCC) arrangement is detected with an interparticle distance of 20.7 ± 0.1 nm. In protein solution, this distance increases to 21.9 ± 0.1 nm by protein penetration inside the ordered structure. For citrate-capped NPs, a different mechanism is observed. The protein particles attach to the NPs surfaces, and an appropriate concentration of proteins results in a stable suspension. Cryogenic transmission electron microscopy (Cryo-TEM), UV–visible spectroscopy, and dynamic light scattering (DLS) support the SAXS results. The findings will pave the way to design and synthesize NPs with controlled behaviors in biomedical applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Double Doping of Semiconducting Polymers Using Ion-Exchange with a Dianion

The interactions between counterions and electronic carriers in electrically doped semiconducting polymers are important for delocalization of charge carriers, electronic conductivity, and thermal stability. The introduction of a dianions in semiconducting polymers leads to double doping where there is one counterion for two charge carriers. Double doping minimizes structural distortions, but changes the electrostatic interactions between the carriers and counterions. Polymeric ionic liquids (PIL) with croconate dianions are helpful to investigate the role of the counterion in p-type semiconducting polymers. PILs prevent diffusion of the cation into the semiconducting polymers during ion exchange. The redox-active croconate dianions undergo ion exchange with doped semiconducting polymers depending on their ionization energy. Croconate dianions are found to reduce doped films of poly(3-hexyl thiophene), but undergo ion exchange with a polythiophene with tetraethylene glycol side chains, P(g 4 2T-T), that has a lower ionization energy. The croconate dianion maintains crystalline order in P(g 4 2T-T) and leads to a lower activation energy for the electrical conductivity than PF 6 – counterions. The control of the doping level with croconate allows optimization of the thermoelectric performance of the semiconducting polymer. Finally, the thermal stability of the doped films of P(g 4 2T-T) is found to depend strongly on the nature of the counterion.

36 MATERIALS SCIENCE↗