Search NASA⌕ Search

SEARCH · Search NASA

Results for “Blend morphology”

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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Microphase Separation in Polyelectrolyte Blends: Weak Segregation Theory and Relation to Nuclear "Pasta".

We develop the weak segregation theory of micro phase separation in stoichiometric blends of oppositely and weakly charged polyelectrolytes, which would be immiscible in the absence of charged units. Short-range repulsions between polycation and polyanion monomers induce the formation of oppositely charged domains, the size of which is controlled by their excess Coulomb energy. The diagram of blend morphologies is constructed in the framework of Leibler's mean-field approach and to account for fluctuations within the Brazovskii-Fredrickson-Helfand approximation. Phase behavior of the polyelectrolyte blends is fully analogous to that of neutral diblock copolymers. The mean-field analysis predicts that the order-disorder transition (ODT) is second order for the symmetric blend. In asymmetric mixtures, an increasing incompatibility between polyelectrolytes triggers the usual cascade of first-order phase transitions, dis -> bcc -> hex -> lam. Fluctuations alter the phase diagram topology and allow the direct transitions from the disordered state (dis) to hex and lam microphases; for the symmetric blend, ODT becomes weakly first order. We also discuss that both microphase separation in polyelectrolyte blends and the formation of nuclear "pasta" phases within neutron stars are governed by similar physical principles, despite the 6 orders of magnitude difference in the periods of these structures.

Rumyantsev, Artem M.↗
DOE OSTI2020

Critical Role of Polymer Aggregation and Miscibility in Nonfullerene‐Based Organic Photovoltaics

Abstract Understanding the correlation between polymer aggregation, miscibility, and device performance is important to establish a set of chemistry design rules for donor polymers with nonfullerene acceptors (NFAs). Employing a donor polymer with strong temperature‐dependent aggregation, namely PffBT4T‐2OD [poly[(5,6‐difluoro‐2,1,3‐benzothiadiazol‐4,7‐diyl)‐ alt ‐(3,3″′‐di(2‐octyldodecyl)‐2,2′;5′,2″;5″,2″′‐quaterthiophen‐5,5‐diyl)], also known as PCE‐11 as a base polymer, five copolymer derivatives having a different thiophene linker composition are blended with the common NFA O‐IDTBR to investigate their photovoltaic performance. While the donor polymers have similar optoelectronic properties, it is found that the device power conversion efficiency changes drastically from 1.8% to 8.7% as a function of thiophene content in the donor polymer. Results of structural characterization show that polymer aggregation and miscibility with O‐IDTBR are a strong function of the chemical composition, leading to different donor–acceptor blend morphology. Polymers having a strong tendency to aggregate are found to undergo fast aggregation prior to liquid–liquid phase separation and have a higher miscibility with NFA. These properties result in smaller mixed donor–acceptor domains, stronger PL quenching, and more efficient exciton dissociation in the resulting cells. This work indicates the importance of both polymer aggregation and donor–acceptor interaction on the formation of bulk heterojunctions in polymer:NFA blends.

Yi, Xueping↗
DOE OSTI2024

Efficient and Photostable Organic Solar Cells Achieved by Alloyed Dimer Acceptors with Tailored Linker Structures

Abstract High power conversion efficiency (PCE) and long‐term stability are prerequisites for commercialization of organic solar cells (OSCs). Herein, two dimer acceptors (DYTVT and DYTCVT) are developed with different properties through linker engineering, and study their effects as alloy‐like acceptors on the photovoltaic performance and photostability of OSCs. These ternary OSCs effectively combine the advantages of both dimer acceptors. DYTVT, characterized by its high backbone planarity, ensures elevated electron mobility and high glass‐transition temperature (T g ), leading to efficient charge transport and enhanced photostability of OSCs. Conversely, DYTCVT, with its significant dipole moment and electrostatic potential, enhances compatibility of the alloy acceptors with donors and refines the blend morphology, facilitating efficient charge generation in OSCs. Consequently, D18:DYTVT:DYTCVT OSCs exhibit higher PCE (18.4%) compared to D18:MYT (monomer acceptor, PCE = 16.5%), D18:DYTVT (PCE = 17.4%), and D18:DYTCVT (PCE = 17.0%) OSCs. Furthermore, owing to higherT g of alloy acceptors (133 °C) than MYT (T g = 80 °C) and DYTCVT (T g = 120 °C), D18:DYTVT:DYTCVT OSCs have significantly higher photostability (t 80% lifetime = 4250 h under 1‐sun illumination) compared to D18:MYT (t 80% lifetime = 40 h) and D18:DYTCVT OSCs (t 80% lifetime = 2910 h).

Chemistry↗
DOE OSTI2024

Impact of Linker Engineering in Core‐Linked Dimeric Acceptors for High‐Performance Organic Solar Cells

Abstract The dimerization of small molecule acceptors (SMAs) is a promising strategy for enhancing the long‐term stability and power conversion efficiency (PCE) of organic solar cells (OSCs). However, the reported DSMAs are primarily limited to end‐linked molecular configurations, highlighting the need for further exploration of various dimer architectures. Herein, the development of two distinct core‐linked dimerized SMAs (DYF‐V and DYF‐E) are reported with tailored linker structures (vinylene and ethynyl, respectively), achieving high‐performance OSCs (PCE = 18.53%). Interestingly, a subtle change in the linker structures results in markedly different molecular properties and photovoltaic performances of the dimer acceptors. DYF‐E with an ethynyl linker exhibits more twisted backbone conformation and mitigated aggregation property compared to DYF‐V, inducing desirable blend morphologies with a polymer donor including high crystallinity, face‐on oriented packing structures, and well‐intermixed domains. Thus, the DYF‐E‐based OSCs exhibit a high PCE (17.02%), which significantly outperforms the DYF‐V‐based OSCs (PCE = 9.98%). Furthermore, the ternary OSCs based on DYF‐E achieve a higher PCE of 18.53%. Thus, this study highlights the significance of selecting an appropriate linker in core‐linked dimerized SMAs for producing high‐performance OSCs.

Oh, Shinbee↗
DOE OSTI2025

Significant Efficiency Enhancements in Non‐Y Series Acceptors by the Addition of Outer Side Chains

Abstract Most current highly efficient organic solar cells utilize small molecules like Y6 and its derivatives as electron acceptors in the photoactive layer. In this work, a small molecule acceptor, SC8‐IT4F, is developed through outer side chain engineering on the terminal thiophene of a conjugated 6,12‐dihydro‐dithienoindeno[2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene (IDTT) central core. Compared to the reference molecule C8‐IT4F, which lacks outer side chains, SC8‐IT4F displays notable differences in molecule geometry (as shown by simulations), thermal behavior, single‐crystal packing, and film morphology. Blend films of SC8‐IT4F and the polymer donor PM6 exhibit larger carrier mobilities, longer carrier lifetimes, and reduced recombination compared to C8‐IT4F, resulting in improved device performance. Binary photovoltaic devices based on the PM6:SC8‐IT4F films reveal an optimal efficiency over 15%, which is one of the best values for non‐Y type small molecule acceptors (SMAs). The resultant devices also show better thermal and operational stability than the control PM6:L8‐BO devices. SC8‐IT4F and its blend exhibit a higher relative degree of crystallinity and π coherence length, compared to C8‐IT4F samples, beneficial for charge transport and device performance. The results indicate that outer side chain engineering on existing small electron acceptors can be a promising molecular design strategy for further pursuing high‐performance organic solar cells.

He, Qiao [Department of Chemistry and Centre for P↗
DOE OSTI2023

Linking Phase Behavior to Performance Parameters in Non-Fullerene Acceptor Solar Cells

Performance of nonfullerene-based organic solar cells is largely dependent on the donor:acceptor blend morphology, which is initially tuned by composition. However, morphological design rules are difficult to identify due to the complex relationship between composition-dependent phase behavior and performance properties. In this study, the authors are able to establish a direct link between PM6:Y6 film morphology and device properties by combining grazing-incidence wide-angle X-ray scattering with highly sensitive Fourier transform photocurrent spectroscopy. By analyzing properties across the full composition range, interfacial microstructure and the corresponding charge transfer (CT) states are identified and direct structure–property relationships are established. Here the results indicate that open-circuit voltage is controlled by the CT state at amorphous-PM6:crystalline-Y6 interfaces. Crystalline Y6 is found to increase both transport and non-radiative recombination, suggesting that morphological tradeoffs may be necessary for overall device optimization.

14 SOLAR ENERGY↗
DOE OSTI2020

Vacuum-Free, All-Solution, and All-Air Processed Organic Photovoltaics with over 11% Efficiency and Promoted Stability Using Layer-by-Layer Codoped Polymeric Electrodes

Nonfullerene organic photovoltaics (OPVs) have achieved a breakthrough in pushing the efficiency beyond 15%. Although this sheds light on OPV commercialization, the high cost associated with the scalable device fabrications remains a giant challenge. Herein, a vacuum-free, all-solution and all-air processed OPV is reported that yields 11.12% efficiency with a fill factor of 0.725, due to the usages of high-merit polymeric electrodes and modified active blends. The design principle toward the high-merit electrodes is to induce heavy acid doping into the matrices for a raised carrier concentration and mobility, make a large removal of insulating components in the whole matrices rather than surfaces, and restrain the formation of large-domain aggregates. A unique layer-by-layer doping is developed to enable the polymeric electrodes with record-high trade-offs between optical transmittance and electrical conductivity. Moreover, solvent vapor annealing is proposed to boost device efficiency and it has the advantages of finely adjusting the active blend morphology and raising the electron mobility. The resulting devices are highly efficient and most (≈91%) of the initial efficiency are maintained in 30 day storage. Finally, this work indicates bright future for making cost-effective all-solution processed OPVs in air.

14 SOLAR ENERGY↗
DOE OSTI2022

Lowly Fused Non-Fullerene Acceptors Towards Efficient Organic Solar Cells Enabled by Isomerization

Here two lowly fused non-fullerene acceptors (NFAs) with isomeric structures, named as BTP-out-4F and BTP-in-4F, were developed by tailoring the fused 7-ring central core of Y6 into a lowly fused 5-ring linked with two octyloxythiophene bridges. BTP-out-4F with octyloxy side chains away from the central core exhibited large steric hindrance that restrained the rotational freedom between the thiophene bridge and end group but maintained free rotation between the central core and the thiophene bridge. In contrast, BTP-in-4F with octyloxy side chains close to the central core had much lower rotation freedom due to the non-covalent S … O interactions locked the central core, thiophene bridge and end group simultaneously, making BTP-in-4F have higher molecular crystallinity. On the other hand, the optical properties, energy levels and the blend morphology properties were significantly influenced, leading to distinctive photovoltaic performances. BTP-out-4F formed favorable energy level alignment and morphology when matching with PBDB-T donor, thus its device realized a much higher PCE of 13.32%, which was over 13 times than that of BTP-in-4F based device (PCE=0.97%).

36 MATERIALS SCIENCE↗
DOE OSTI2021

Optimized molecular aggregation via incorporating fluorinated unit in the polymer donor for 17.3% efficiency organic solar cells

Regulating molecular aggregation state via chemical modification of photovoltaic materials to optimize the blend morphology is an effective and challenging strategy to improve the photovoltaic performance of organic solar cells (OSCs). Here, in this work, we demonstrate a random terpolymerization strategy by incorporating 1,3-bis(5-bromo-4-fluorothiophen-2-yl)-5,7-bis(2-ethylhexyl)-4H,8H-benzo[1,2-c:4,5-c']bisthiophene-4,8-dione (BFT, 30 mol%) unit with fluorinated π-bridges into the molecular backbone of PM6 and develop a terpolymer PF1. Benefiting from the strong electronegativity of fluorine atom and noncovalent interaction of F---S, the energy levels, molecular ordering, and aggregation properties of the polymer donors are precisely regulated. Notably, in the active layer film based on PF1: Y6, the π-π stacking distance can reduce to 3.51 Å, which is significantly smaller than that of PM6:Y6 (3.65 Å) and boosts the effective exciton dissociation and charge transport, thereby effectively optimize the photovoltaic properties of the related devices. As a result, the PF1:Y6-based OSCs achieved a power conversion efficiency (PCE) of up to 17.3%, which is much higher than that of the controlled OSCs based on PM6:Y6 (PCE = 16.2%). These results demonstrate high-efficiency OSCs enabled by regulating molecular aggregation via terpolymerization strategy.

14 SOLAR ENERGY↗
DOE OSTI2024

The role of interfacial donor–acceptor percolation in efficient and stable all-polymer solar cells

Polymerization of Y6-type acceptor molecules leads to bulk-heterojunction organic solar cells with both high power-conversion efficiency and device stability, but the underlying mechanism remains unclear. Here we show that the exciton recombination dynamics of polymerized Y6-type acceptors (Y6-PAs) strongly depends on the degree of aggregation. While the fast exciton recombination rate in aggregated Y6-PA competes with electron-hole separation at the donor–acceptor (D–A) interface, the much-suppressed exciton recombination rate in dispersed Y6-PA is sufficient to allow efficient free charge generation. Indeed, our experimental results and theoretical simulations reveal that Y6-PAs have larger miscibility with the donor polymer than Y6-type small molecular acceptors, leading to D–A percolation that effectively prevents the formation of Y6-PA aggregates at the interface. Besides enabling high charge generation efficiency, the interfacial D–A percolation also improves the thermodynamic stability of the blend morphology, as evident by the reduced device “burn-in” loss upon solar illumination.

14 SOLAR ENERGY↗
DOE OSTI2023

Air-stable ternary organic solar cells achieved by using fullerene additives in non-fullerene acceptor-polymer donor blends

Organic solar cells (OSCs) based on donor–acceptor blends have shown a rapid improvement in power conversion efficiency (PCE) now approaching, for small cells, those of the state-of-the art commercial solar modules. However, performance degradation remains one of the most critical impediments for OSC technology commercialization. Ternary solar cells where a third component, for instance an acceptor, is added to a non-fullerene acceptor–polymer donor blend are an effective approach for improving both OSC efficiency and long-term stability. Here, in this work, we study the role of two fullerene acceptors, ET18 and PCBM, as the third component in P D :Y6 blends. These fullerene derivatives significantly enhance the cell stability, which retained >90% of their initial PCEs (13–14%) even after storage in air for 6 months, compared to only ~20% retention for the binary devices. GIWAXS, AFM, in situ impedance spectroscopy and femtosecond transient absorption spectroscopy measurements reveal that the enhanced stability of the ternary devices results from a more robust blend morphology reducing charge recombination in the ternary devices during aging.

14 SOLAR ENERGY↗
DOE OSTI2021

Controlling the Morphology of PEDOT:PSS Blend Films with Pre-Deposition Solution Composition and Deposition Technique

Understanding the relationships between morphology, fabrication processes, and thermoelectric performance in conducting polymers is essential to the development of high- efficiency organic thermoelectrics as an alternative to commonly used rare metals. Altering the film fabrication process of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) with the addition of high boiling solvents to the precast solution improves the electrical conductivity and significantly increases its Seebeck value. Neutron scattering monitors the changes in the atomic, nanoscale, and mesoscale morphologies of PEDOT:PSS thin films with the addition of dimethyl sulfoxide (DMSO) to the aqueous solution prior to film formation and with varying fabrication procedures. The neutron scattering results show a decrease in the deuterated PSS domain size along with systematic variations in PEDOT fibril assemblies in the final blend film with the addition of DMSO to the pre-deposition solution. These structural modifications indicate that the increase in conductivity of PEDOT:PSS blends with addition of DMSO reported in the literature can be ascribed to the disruption of solvated PEDOT assemblies by the DMSO, forming smaller PSS domains in the pre-deposition solution and allowing smoother film formation. These improvements are observed significantly with the addition of just 1% DMSO but continue to modestly improve with the addition of up to 5% DMSO to the PEDOT:PSS blend pre-deposition solution. The fact that the variations in the measured morphology are independent of whether the films were deposited by spin or ultrasonic spray casting methods emphasizes the crucial importance of the structure of the blend in the pre-deposition solution in determining the final thin film blend morphology.

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

Phase Behavior and Ionic Conductivity of Blended, Ion-Condensed Electrolytes with Ordered Morphologies

In this study, the amphiphilic salt lithium trifluoromethanesulfonylimide octadecane (C18LiTFSI) was used as a basis to investigate the effects of anion density and cation coordination sites within blended electrolytes with strong ionic aggregation. C18LiTFSI was previously reported as a single-component, ion-condensed electrolyte with a wide layered liquid crystalline phase regime. Three additive molecules with varyingly sized polar sulfonyl groups attached to an octodecane-tail were synthesized and mixed with C18LiTFSI. The thermal properties, morphology, and ionic conductivity of the blended electrolytes were characterized. It was found that the blended electrolytes exhibited layered liquid crystalline morphology over a narrower temperature range than the pure salt, and the ionic conductivity of the blended liquid crystalline electrolytes were generally lower than that of the pure salt. Surprising, the additives were found to have the greatest effect on the bulk ionic conductivity of the semicrystalline phase of the electrolytes. Addition of minor fractions of methylsulfonyloctadecane to C18LiTFSI resulted in increases in conductivity of over two orders of magnitude at room temperature, while addition of ethylsulfonyloctadecane or isopropylsulfonyloctadecane with the larger head group resulted in decreased ionic conductivity over the entire composition space and temperature range investigated.

Collins, Hannah (ORCID:0000000338858136)↗
DOE OSTI2020

Bimolecular crystal instability and morphology of bulk heterojunction blends in organic and perovskite solar cells

The performance of polymer:fullerene bulk heterojunction (BHJ) solar cells is significantly influenced by the morphology of electron donor and acceptor blends under the premise that electronic structure is complimentary regarding donor and acceptor materials. There are many cases where intimate mixing of donor and acceptor perturbs the electronic structure, which fundamentally changes the transport and photovoltaic characteristics. In this work, we present the bimolecular crystal packing of polymers and fullerenes, and investigate the correlation between device performance and structural details. We find that bimolecular crystallization can reorganize polymer chain packing, leading to poor electron transport and device performance. The size compatibility and the passivation of entropy penalty led to cocrystallization instability, which was clearly seen by in situ GIWAXS data. PC 61 BM is found to intercalate into side chains of PQT by reorganizing both PQT and PC 61 BM, forming stable, highly ordered bimolecular crystals. The poor electron transport in bimolecular crystal domain could account for the poor device performance in both perovskite and organic solar cells. Bis-PC 61 BM, on the other hand, only forms loosely packed aggregates in solution, and then rapidly phase separated into large domains with an edge-on interfacial orientation and performed poorly in solar cells.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Morphology of poly-3-hexyl-thiophene blends with styrene–isoprene–styrene block-copolymer elastomers from X-ray and neutron scattering

The nano- and micron scale morphology of poly(3-hexylthiophene) (P3HT) and polystyrene-block-polyisoprene-block-polystyrene (PS–PI–PS) elastomeric blends is investigated through the use of ultra-small and small angle X-ray and neutron scattering (USAXS, SAXS, SANS). It is demonstrated that loading P3HT into elastomer matrices is possible with little distortion of the elastomeric structure up to a loading of ~5 wt%. Increased loadings of conjugated polymer is found to significantly distort the matrix structure. Changes in processing conditions are also found to affect the blend morphology with especially strong dependence on processing temperature. Processing temperatures above the glass transition temperature (T g ) of polystyrene and the melting temperature (T m ) of the conjugated polymer additive (P3HT) creates significantly more organized mesophase domains. P3HT blends with PS–PI–PS can also be flow-aligned through processing, which results in an anisotropic structure that could be useful for the generation of anisotropic properties (e.g. conductivity). Moreover, the extent of flow alignment is significantly affected by the P3HT loading in the PS–PI–PS matrix. The work adds insight to the morphological understanding of a complex P3HT and PS–PI–PS polymer blend as conjugated polymer is added to the system. Here, we also provide studies isolating the effect of processing changes aiding in the understanding of the structural changes in this elastomeric conjugated polymer blend.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Enhance the performance of organic solar cells by nonfused ring electron acceptors bearing a pendent perylenediimide group

A new nonfused ring electron acceptor PDI-DO-2F is designed and synthesized by attaching perylenediimide (PDI) unit as a pendent group to the central donor core. Compared with the control molecule DO-2F, the introduction of PDI lateral substituent can greatly enhance the solubility and decrease the crystallinity of the resulted acceptor. The PBDB-T:PDI-DO-2F blend film exhibits a much better morphology with higher and more balanced carrier mobility in contrast to PBDB-T:DO-2F one. PDI-DO-2F based organic solar cells (OSCs) give a power conversion efficiency (PCE) of 11.78%, higher than DO-2F based ones (9.82%). Furthermore, PDI-DO-2F based OSCs shows a ΔE non-rad value of 0.23 eV, which is significantly lower than the DO-2F based ones (0.28 eV). More importantly, the addition of PDI-DO-2F as the third component to the PBDB-T:DO-2F binary system can optimize the morphology of blend films and improve the shelf stability of devices. Finally, the PBDB-T:DO-2F:PDI-DO-2F based ternary OSCs achieve a higher PCE of 13.82%.

14 SOLAR ENERGY↗
DOE OSTI2022

Chain Redistribution Stabilizes Coexistence Phases in Block Copolymer Blends

The nanoscale morphologies of block copolymer (BCP) thin films are determined by chain architecture. Experimental studies of thin film blends of different BCP chain types have demonstrated that blending can stabilize new motifs, such as coexistence phases. Here, we deploy coarsegrained molecular dynamics (MD) simulations in order to better understand the self-assembly behavior of BCP blend thin films. Here, we consider blends of lamella- and cylinder-forming BCP chains, studying their morphological makeup, the chain distribution within the morphology, and the underlying polymer chain conformations. Our simulations show that there are local concentration deviations at the scale of the morphological objects that dictate the local structure, and that BCP chains redistribute within the morphology so as to stabilize the structure. Underlying these effects are measurable distortions in the BCP chain conformations. The conformational freedom afforded by BCP blending stabilizes defects and allows coexistence phases to appear, while also leading to kinetic trapping effects. These results highlight the power of blending in designing the morphology that forms.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The Crystalline Behavior and Device Function of Nonfullerene Acceptors in Organic Solar Cells

The current research investigates the structure features and intermolecular interactions of nonfullerene acceptors (NFAs) in single crystal and thin films, as well as their solar cell applications. Guiding parameters and key intermolecular forces that lead to 2D brickwork or 3D web packing are identified. The atomic modification is shown as the key to induce hydrogen bonding or π–π stacking column, which results in different crystalline packing. The molecular assembly in thin film is initiated by hydrogen bonding and completed by π–π stacking reorganization. The packing energy is seen as a guiding parameter that dictates the NFA crystalline morphology in blended thin films. The crystalline packing motif is not directly related with device efficiency. However, the crystalline morphology is the key parameter to influence exciton/carrier dynamics and device performance. In conclusion, a broader picture on the scaling behavior of organic semiconductor crystals ranging from oligoacenes to NFAs is established.

14 SOLAR ENERGY↗