Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Blending”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Influence of Added Salt on Chain Conformations in Poly(ethylene oxide) Melts: SANS Analysis with Complications

Poly(ethylene oxide) (PEO)-based electrolytes have gained increasing attention in both the rechargeable battery industry and fundamental research, but any influence of the ions on the polymer conformation is not fully understood. Small-angle neutron scattering (SANS) is a powerful means to determine single-polymer chain conformations. We conducted SANS experiments on 50:50 blends of perdeuterated PEO (dPEO) and hydrogenous PEO (hPEO) of two different molecular weights (20 and 40 kDa) doped with two different salts (LiTFSI and LiClO 4 ) at various concentrations. An additional measurement with LiI is also reported. The scattering profiles of salt-doped dPEO/hPEO blends were measured, and the incoherent scattering from dPEO and hPEO doped with salt was measured separately. A strong low q upturn was observed in some of the blends and in the pure dPEO homopolymers. The statistical segment lengths of PEO–salt mixtures were derived using a Kratky analysis. The segment length decreases modestly with increasing amounts of LiTFSI but apparently first increases then decreases with added LiClO 4 . At the highest salt concentration examined (r = [Li+]/[EO] = 0.125), a roughly 10% decrease in the statistical segment length was observed in both LiTFSI and LiClO 4 -doped PEOs, for both molecular weights. This work confirms that added salt causes a contraction of the PEO chain dimensions, but the effect appears slightly weaker than reported recently. Certain difficulties in data analysis are also discussed, including the unexplained low q scattering even in pure deuterated polymers, uncertainties in background subtraction, and inappropriate application of the Debye function.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Simulations of Glass Transition and Mechanical Behavior of Off-Stoichiometric Crosslinked Polymers

Here, this work explores the influence of blend composition, network architecture, and hydrogen bonding on the material properties of crosslinked epoxy networks, focusing on the glass transition temperature (T g ) and Young’s modulus (Y). We used coarse-grained molecular dynamics simulations to simulate varying compositions of stiff and flexible components in epoxy monomer blends with varying excess of curative. We find that, without hydrogen bonding, networks of any composition show a monotonically increasing T g with decreasing excess curative, consistent with theory. In contrast, we find that when hydrogen bonding is introduced, the binary blend networks show significant enhancement in T g for lightly crosslinked systems. This result contributes to an explanation of the anomalous T g behavior observed experimentally in these systems. We further find that Y is generally enhanced by hydrogen bonds, especially below T g , demonstrating that hydrogen bonding has a significant influence on mechanical properties and can allow access to other desirable dynamic behavior, especially self-healing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Understanding the Influence of Chain Architecture on the Transport Quantities of Polymer Electrolytes with Covalently Bonded Anions

Here, we use a combination of experiments and coarse-grained molecular dynamics simulations to elucidate the structure–property relationships in polymer electrolytes obtained by the copolymerization of poly(vinyl ethylene carbonate─lithium styrene bis(trifluoromethanesulfonyl)imide) or p(VEC-LiSTFSI). Experiments show that the conductivity reduces with increasing anion (i.e., STFSI) fraction on the chain, and the cation transference number (t + ) is found to be dependent on the anion fraction. Furthermore, a significant fraction of unpolymerized VEC monomers are observed. Since it is inherently difficult to experimentally control the chain architecture and the amount of unpolymerized VEC in these systems, we perform coarse-grained molecular dynamics simulations on model polymer systems with different chain architectures to mimic the plausible experimental systems. Specifically, we look at the differences in transference numbers arising from (i) a random copolymer of VEC and STFSI monomers; (ii) a blend of VEC-STFSI copolymer with VEC monomers; and (iii) a ternary blend of the VEC homopolymer, STFSI homopolymers, and VEC monomers. The ternary blend model demonstrates the closest resemblance with the experimental transference numbers and diffusivities. The lithium diffusivity obtained from the coarse-grained models with VEC monomers (plasticizers) is about 1.5 times that of the model without VEC monomers, showing that the plasticizing effect of VEC monomers is modest. We rationalize the experimental observations based on aggregate and cluster analyses obtained from molecular simulations. This work reveals that polymer electrolyte chain architecture and plasticizers can critically influence the transport properties, and these parameters should be considered when designing single ion conducting polymeric electrolytes.

cluster distribution↗
DOE OSTI2020

Comparison of Fused-Ring Electron Acceptors with One- and Multidimensional Conformations

Three fused-ring electron acceptors (FXIC-1, FXIC-2, and FXIC-3) were designed and synthesized. This FXIC series has similar electron-rich central units and the same electron-poor termini. Due to the different steric structures of fluorene, bifluorenylidene, and spirobifluorene, FXIC-1 is a one-dimensional (1D) crystal, while FXIC-2 and FXIC-3 are multidimensional (MD) amorphous materials. The conformations of the FXIC series have a slight impact on their absorption and energy levels. FXIC-1 has higher electron mobility than FXIC-2 and FXIC-3. When blending with different polymer donors (PTB7-Th, J71, and PM7), the FXIC-1-based organic solar cells have efficiencies higher than those of the FXIC-2/FXIC-3-based cells. Finally, the ternary-blend cells based on PTB7-Th:F8IC with FXIC-1, FXIC-2, and FXIC-3 show similar efficiencies, which are all better than those of the binary-blend devices.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Correlation of the Structure with Performance in MEH-PPV/dPS Thin Films Illuminated during Processing

Thin films containing conjugated polymers have been used in a wide array of optoelectronic devices, and much research has focused on the conformation of the conjugated polymer as a key aspect to tuning the performance of the resulting devices. White light exposure has been studied as a post-processing method to alter the film’s morphology and photoluminescence (PL) in systems composed of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and polystyrene (PS). To date, there have been few studies that correlate the changes in the depth profile with the PL performance of MEH-PPV/PS films. This study is designed to address this gap in knowledge. Thin films of MEH-PPV/dPS annealed above the glass transition temperatures (T g ) in an illuminated environment led to lower PL than that found in annealed samples that are not illuminated. However, at higher MEH-PPV loading in the blend film, the extent of variation of PL with illumination diminished. Additionally, time-of-flight secondary ion mass spectrometry and small-angle neutron scattering document the three-dimensional morphology of the films under illumination conditions, which are correlated with the changes in PL. Illumination during annealing compressed MEH-PPV-rich layers in the thin film blends at low loadings of MEH-PPV (below 10 wt %) but resulted in significant in-plane phase separation at higher loadings (above 15 wt %). Both changes increase interchain interactions and lower the PL of the illuminated samples. The changes in the depth profile significantly alter the PL of the films, while the in-plane phase separation affected the optoelectronic properties to a lesser degree. This work, therefore, provides insights into how illumination and film composition can be utilized to predictably alter the structure and optoelectronic performance of conjugated polymer blend films.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Warpage-Resistant, Under-Extrusion-Free, High-Surface-Quality Additive Manufacturing Process for Polyethylene-Based Composite Radiation Shielding Material

Polyethylene (PE) is one of the best shielding materials for primary space radiation due to its high hydrogen content. For effective secondary neutron shielding, boron-rich fillers are incorporated to enhance performance. The semicrystalline nature and high thermal expansion coefficient of PE impede its adoption for in situ additive manufacture in space via the fused deposition modeling (FDM) 3D printing. Here, we developed an optimized PE blend to mitigate the effects of under-extrusion and warpage. Guided by studies on extrusion and warpage, we developed an optimal set of printing parameters for the proposed PE blend. The optimum PE blend─both in its pure form and when doped with fillers─has been tested on different FDM printers. The printed structures exhibit high and uniform density, smooth surfaces, no warpage, and competitive mechanical properties. The FDM-printed plates demonstrate efficient shielding from thermal neutrons, predicted via modeling and confirmed experimentally using extended Q-range small-angle neutron scattering.

additive manufacturing↗
DOE OSTI2025

Electrolyte Immersion Increases Photoconductivity in a Model Polymer Photocathode

Immersing polymer solar cells in aqueous electrolyte for photoelectrochemical (PEC) hydrogen production is likely to cause photophysical changes that could present both challenges and opportunities for engineering functional and durable devices. Herein we study the bulk heterojunction blend poly(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)-alt-(2-(((2-ethylhexyl)oxy)carbonyl)-3-fluorothieno[3,4-b]thiophene-4,6-diyl):poly(N,N'-di(2-octyldodecyl)naphthalene-1,8:4,5-bis(dicarboximide)-2,6-diyl)-alt-(2,2-bithiophene-5,5'-diyl) (PTB7-Th:N2200) excited-state dynamics in electrolyte from femtosecond to millisecond time scales using pump-probe microwave conductivity and absorption spectroscopy. While the blend swells very little, electrolyte exposure increases the microwave-frequency mobility and possibly the yield of photogenerated charges while also decreasing crystallinity. These results indicate an enhancement in key performance metrics, implying that any limitations on the performance of PEC test devices do not arise from active layer-electrolyte interactions. For the PTB7-Th:N2200 blend or similar photocathode systems, our results indicate that improving the interfacial kinetics and/or the carrier lifetime should be prioritized, not protecting the active layer from the electrolyte. Since this observation may not be universal to all polymer systems, future research should focus on identifying their limiting photophysical processes. electrolyte.

14 SOLAR ENERGY↗
DOE OSTI2022

Radical Polymer-Based Organic Electrochemical Transistors

Organic electrochemical transistors (OECTs) are an emerging platform for bioelectronic applications. Significant effort has been placed in designing advanced polymers that simultaneously transport both charge and ions (i.e., macromolecules that are mixed conductors). Furthermore, the considerations for mixed organic conductors are often different from the established principles that are well-known in the solid-state organic electronics field; thus, the discovery of new OECT macromolecular systems is highly desired. Here, we demonstrate a new materials system by blending a radical polymer (i.e., a macromolecule with a nonconjugated backbone and with stable open-shell sites at its pendant group) with a frequently used conjugated polymer. Specifically, poly(4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl) (PTEO) was blended with poly(3-hexylthiophene) (P 3 HT) to create thin films with distinct closed-shell and open-shell domains. Importantly, the sharp and unique oxidation–reduction (redox) potential associated with the radical moieties of the PTEO chain provided a distinct actuation feature to the blended films that modulated the ionic transport of the OECT devices. In turn, this led to controlled regulation of the doping of the P 3 HT phase in the composite film. By decoupling the ionic and electronic transport into two distinct phases and by using an ion transport phase with well-controlled redox activity, never-before-seen performance for a P3HT-based OECT was observed. That is, at loadings as low as 5% PTEO (by weight) OECTs achieved figure-of-merit (i.e., μC*) values >150 F V –1 cm –1 s –1 , which place the performance on the same order as state-of-the-art conjugated polymers despite the relatively common conjugated macromolecular moiety implemented. As such, this effort presents a design platform by which to readily create a tailored OECT response through strategic macromolecular selection and polymer processing.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Symmetry-Breaking and Self-Sorting in Block Copolymer-Based Multicomponent Nanocomposites

Co-assembly of inorganic nanoparticles (NPs) and nanostructured polymer matrix represents an intricate interplay of enthalpic or entropic forces. Particle size largely affects the phase behavior of the nanocomposite. Theoretical studies indicate that new morphologies would emerge when the particles become comparable to the soft matrix's size, but this has rarely been supported experimentally. By designing a multicomponent blend composed of NPs, block copolymer-based supramolecules, and small molecules, a 3-D ordered lattice beyond the native BCP's morphology was recently reported when the particle is larger than the microdomain of BCP. The blend can accommodate various formulation variables. In this work, when the particle size equals the microdomain size, a symmetry-broken phase appears in a narrow range of particle sizes and compositions, which we named the "train track" structure. In this phase, the NPs aligned into a 3-D hexagonal lattice and packed asymmetrically along the c axis, making the projection of the ac and the bc plane resemble train tracks. Computational studies show that the broken symmetry reduces the polymer chain deformation and stabilizes the metastable hexagonally perforated lamellar morphology. Given the mobility of the multicomponent blend, the system shows a self-sorting behavior: segregating into two macroscopic phases with different nanostructures based on only a few nanometers NP size differences. Smaller NPs form "train track" morphology, while larger NPs form a "simple hexagon" structure, where the NPs take a symmetric hexagonal arrangement. Detailed structural evolution and simulation studies confirm the systematic-wide cooperativity across different components, indicating the strong self-regulation of the multicomponent system.

"train track" morphology↗
DOE OSTI2021

Deconstruction of Woody Biomass via Protic and Aprotic Ionic Liquid Pretreatment for Ethanol Production

Ionic liquids (ILs) have emerged as important solvents for conversion of lignocellulosic feedstocks to fuels and chemicals due to their ability to enable efficient biomass deconstruction and fractionation. Woody biomass derived from forest and agricultural residues has the potential to be used for production of biofuels and its removal from forests can help mitigate disastrous wildfires in fire-prone states like California. This study evaluated woody biomass types (pine, almond, walnut, and fir) from California as potential biofuel feedstocks. The feedstocks were pretreated with the ILs cholinium lysinate ([Ch][Lys]) and ethanolamine acetate ([EOA][OAc]), followed by enzymatic hydrolysis and fermentation of lignocellulosic sugars to produce ethanol. Under optimal conditions, [EOA][OAc] pretreatment and enzymatic hydrolysis generated glucose and xylose yields in the range of 24-82 and 14-80%, respectively, while glucose and xylose yields for the [Ch][Lys] ranged between 28-83 and 23-80%, respectively. Maximum fermentable sugar was released from almond wood, and the lowest amount was from pine and fir. Further, blends of feedstocks were also explored, and a blend with a mass ratio of 2/2/1 (almond/walnut/pine) resulted in maximum glucose and xylose (>90%) yields using [Ch][Lys]. Fermentation of this hydrolysate using a C5-utilizing strain of Saccharomyces cerevisiae resulted in a maximum ethanol concentration of 17.9 g/L for mixture biomass hydrolysate, corresponding to 60.8% fermentation efficiency. This study represents the first demonstration of the use of these ILs for pretreatment of woody biomass blends that resulted in a high overall conversion efficiency for ethanol production.

09 BIOMASS FUELS↗
DOE OSTI2023

Auxiliary sequential deposition enables 19%-efficiency organic solar cells processed from halogen-free solvents

High-efficiency organic solar cells are often achieved using toxic halogenated solvents and additives that are constrained in organic solar cells industry. Therefore, it is important to develop materials or processing methods that enabled highly efficient organic solar cells processed by halogen free solvents. In this paper, we report an innovative processing method named auxiliary sequential deposition that enables 19%-efficiency organic solar cells processed by halogen free solvents. Our auxiliary sequential deposition method is different from the conventional blend casting or sequential deposition methods in that it involves an additional casting of dithieno[3,2-b:2’,3’-d]thiophene between the sequential depositions of the donor (D18-Cl) and acceptor (L8-BO) layers. The auxiliary sequential deposition method enables dramatic performance enhancement from 15% to over 18% compared to the blend casting and sequential deposition methods. Furthermore, by incorporating a branched-chain-engineered acceptor called L8-BO-X, device performance can be boosted to over 19% due to increased intermolecular packing, representing top-tier values for green-solvent processed organic solar cells. Comprehensive morphological and time-resolved characterizations reveal that the superior blend morphology achieved through the auxiliary sequential deposition method promotes charge generation while simultaneously suppressing charge recombination. This research underscores the potential of the auxiliary sequential deposition method for fabricating highly efficient organic solar cells using environmentally friendly solvents.

14 SOLAR ENERGY↗
DOE OSTI2020

Elucidating the differences in oxidation of high-performance α- and β- diisobutylene biofuels via Synchrotron photoionization mass spectrometry

Abstract Biofuels are a promising ecologically viable and renewable alternative to petroleum fuels, with the potential to reduce net greenhouse gas emissions. However, biomass sourced fuels are often produced as blends of hydrocarbons and their oxygenates. Such blending complicates the implementation of these fuels in combustion applications. Variations in a biofuel’s composition will dictate combustion properties such as auto ignition temperature, reaction delay time, and reaction pathways. A handful of novel drop-in replacement biofuels for conventional transportation fuels have recently been down selected from a list of over 10,000 potential candidates as part of the U.S. Department of Energy’s (DOE) Co-Optimization of Fuels and Engines (Co-Optima) initiative. Diisobutylene (DIB) is one such high-performing hydrocarbon which can readily be produced from the dehydration and dimerization of isobutanol, produced from the fermentation of biomass-derived sugars. The two most common isomers realized, from this process, are 2,4,4-trimethyl-1-pentene (α-DIB) and 2,4,4-trimethyl-2-pentene (β-DIB). Due to a difference in olefinic bond location, the α- and β- isomer exhibit dramatically different ignition temperatures at constant pressure and equivalence ratio. This may be attributed to different fragmentation pathways enabled by allylic versus vinylic carbons. For optimal implementation of these biofuel candidates, explicit identification of the intermediates formed during the combustion of each of the isomers is needed. To investigate the combustion pathways of these molecules, tunable vacuum ultraviolet (VUV) light (in the range 8.1–11.0 eV) available at the Lawrence Berkeley National Laboratory’s Advanced Light Source (ALS) has been used in conjunction with a jet stirred reactor (JSR) and time-of-flight mass spectrometry to probe intermediates formed. Relative intensity curves for intermediate mass fragments produced during this process were obtained. Several important unique intermediates were identified at the lowest observable combustion temperature with static pressure of 93,325 Pa and for 1.5 s residence time. As this relatively short residence time is just after ignition, this study is targeted at the fuels’ ignition events. Ignition characteristics for both isomers were found to be strongly dependent on the kinetics of C 4 and C 7 fragment production and decomposition, with the tert-butyl radical as a key intermediate species. However, the ignition of α-DIB exhibited larger concentrations of C 4 compounds over C 7 , while the reverse was true for β-DIB. These identified species will allow for enhanced engineering modeling of fuel blending and engine design.

09 BIOMASS FUELS↗
DOE OSTI2021

Lower limits for non-radiative recombination loss in organic donor/acceptor complexes

Understanding the factors controlling radiative and non-radiative transition rates for charge transfer states in organic systems is important for applications ranging from organic photovoltaics (OPV) to lasers and LEDs. Here we explore the role of charge-transfer (CT) energetics, lifetimes, and photovoltaic properties in the limit of very slow non-radiative rates by using a model donor/acceptor system with photoluminescence dominated by thermally activated delayed fluorescence (TADF). This blend exhibits an extremely high photoluminescence quantum efficiency (PLQY = ~22%) and comparatively long PL lifetime, while simultaneously yielding appreciable amounts of free charge generation (photocurrent external quantum efficiency EQE of 24%). In solar cells, this blend exhibits non-radiative voltage losses of only ~0.1 V, among the lowest reported for an organic system. Notably, we find that the non-radiative decay rate, k nr , is on the order of 10 5 s -1 , approximately 4–5 orders of magnitude slower than typical OPV blends, thereby confirming that high radiative efficiency and low non-radiative voltage losses are achievable by reducing k nr . Furthermore, despite the high radiative efficiency and already comparatively slow k nr , we find that k nr is nevertheless much faster than predicted by Marcus–Levich–Jortner two-state theory and we conclude that CT-local exciton (LE) hybridization is present. Our findings highlight that it is crucial to evaluate how radiative and non-radiative rates of the LE states individually influence the PLQY of charge-transfer states, rather than solely focusing on the PLQY of the LE. This conclusion will guide material selection in achieving low non-radiative voltage loss in organic solar cells and high luminescence efficiency in organic LEDs.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Spontaneous carrier generation and low recombination in high-efficiency non-fullerene solar cells

The current research reveals the unique photo physical properties and carrier generation mechanisms of high efficiency non-fullerene acceptor-based organic photovoltaic blends. The analysis of device performance, morphology, and photo physics reveals that the interface carrier generation cannot support the device's current output. It is seen that primary photon excitons can dissociate into charge carriers in Y6, which displays a time scale of ∼0.3 ps with polaron yields above 28% in neat and blended thin films. This characteristic in combination with a large exciton diffusion length enables high morphology tolerance in Y6-overloaded blends. The carrier generation process is also combined with recombination studies. The recombination rate quantified by flux-dependent transient absorption measurements yields less than 5% total recombination and nearly 0% geminate recombination. Furthermore, these results define the advantages of the Y6 non-fullerene acceptor (NFA) and reveal the fundamental importance of developing new NFA materials with superior photo physical properties.

14 SOLAR ENERGY↗
DOE OSTI2025

Dynamic disulfide bond networks enable self-healable and mechanically resilient intrinsically stretchable organic solar cells

A dynamic disulfide network introduced into donor/acceptor blends enables room-temperature self-healing and mechanical resilience in intrinsically stretchable organic solar cells, achieving performance recovery after high mechanical strain. The development of intrinsically stretchable organic solar cells (IS-OSCs) faces significant challenges in balancing mechanical durability and optoelectronic performance. Conventional π-conjugated polymer-based donor/acceptor blend films often exhibit limited stretchability and irreversible performance degradation under mechanical strain. To address these limitations, we propose a novel self-healable donor/acceptor blended film with a dual-network morphology, achieved by incorporating a dynamic disulfide bond-based crosslinked network into the bulk-heterojunction film. The resulting thin films demonstrate a power conversion efficiency (PCE) of 16.39% in rigid OSC devices and a fracture strain of 15.6%. Remarkably, the IS-OSCs retain 80% of their initial PCE under 30% strain and exhibit performance recovery after multiple stretch-release cycles at 40% strain through a room-temperature self-healing process. This work provides a proof-of-concept for highly stretchable and durable IS-OSCs, offering valuable insights for advancing the field of wearable energy systems, adaptive solar textiles, and sustainable electronics.

Yang, Wenyu↗
DOE OSTI2020

Impact of particle arrays on phase separation composition patterns

We examine the symmetry-breaking effect of fixed constellations of particles on the surface-directed spinodal decomposition of binary blends in the presence of particles whose surfaces have a preferential affinity for one of the components. Our phase-field simulations indicate that the phase separation morphology in the presence of particle arrays can be tuned to have a continuous, droplet, lamellar, or hybrid morphology depending on the interparticle spacing, blend composition, and time. In particular, when the interparticle spacing is large compared to the spinodal wavelength, a transient target pattern composed of alternate rings of preferred and non-preferred phases emerges at early times, tending to adopt the symmetry of the particle configuration. We reveal that such target patterns stabilize for certain characteristic length, time, and composition scales characteristic of the pure phase-separating mixture. To illustrate the general range of phenomena exhibited by mixture-particle systems, we simulate the effects of single-particle, multi-particle, and cluster–particle systems having multiple geometrical configurations of the particle characteristic of pattern substrates on phase separation. Our simulations show that tailoring the particle configuration, or substrate pattern configuration, a relative fluid-particle composition should allow the desirable control of the phase separation morphology as in block copolymer materials, but where the scales accessible to this approach of organizing phase-separated fluids usually are significantly larger. Limited experiments confirm the trends observed in our simulations, which should provide some guidance in engineering patterned blend and other mixtures of technological interest.

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

Effects of interaction strength of associating groups on linear and star polymer dynamics

A small number of associating groups incorporated onto a polymer backbone have dramatic effects on the mobility and viscoelastic response of the macromolecules in melts. These associating groups assemble, driving the formation of clusters, whose lifetime affects the properties of the polymers. In this study, we probe the effects of the interaction strength on the structure and dynamics of two topologies, linear and star polymer melts, and further investigate blends of associative and non-associating polymers using molecular dynamics simulations. Polymer chains of approximately one entanglement length are described by a bead–spring model, and the associating groups are incorporated in the form of interacting beads with an interaction strength between them that is varied from 1 to 20 k B T. We find that, for all melts and blends, interaction of a few k B T between the associating groups drives cluster formation, where the size of the clusters increases with increasing interaction strength. These clusters act as physical crosslinkers, which slow the chain mobility. Blends of chains with and without associating groups macroscopically phase separate for interaction strength between the associating groups of a few k B T and above. For weakly interacting associating groups, the static structure function S(q) is well fit by functional form predicted by the random phase approximation where a clear deviation occurs as phase segregation takes place, providing a quantitative assessment of phase segregation.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Interactions between nonfullerene acceptors lead to unstable ternary organic photovoltaic cells

For organic photovoltaic (OPV) devices to achieve consistent performance and long operational lifetimes, organic semiconductors must be processed with precise control over their purity, composition, and structure. This is particularly important for high volume solar cell manufacturing where control of materials quality has a direct impact on yield and cost. Ternary-blend OPVs containing two acceptor–donor–acceptor (A–D–A)-type nonfullerene acceptors (NFAs) and a donor have proven to be an effective strategy to improve solar spectral coverage and reduce energy losses beyond that of binary-blend OPVs. Here, we show that the purity of such a ternary is compromised during blending to form a homogeneously mixed bulk heterojunction thin film. We find that the impurities originate from end-capping C=C/C=C exchange reactions of A–D–A-type NFAs, and that their presence influences both device reproducibility and long-term reliability. The end-capping exchange results in generation of up to four impurity constituents with strong dipolar character that interfere with the photoinduced charge transfer process, leading to reduced charge generation efficiency, morphological instabilities, and an increased vulnerability to photodegradation. As a consequence, the OPV efficiency falls to less than 65% of its initial value within 265 h when exposed to up to 10 suns intensity illumination. We propose potential molecular design strategies critical to enhancing the reproducibility as well as reliability of ternary OPVs by avoiding end-capping reactions.

14 SOLAR ENERGY↗