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Results for “Molecular packing”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Surface equilibration mechanism controls the molecular packing of glassy molecular semiconductors at organic interfaces

Significance Because glasses are nonequilibrium materials, even a single-component system has an enormous number of distinct glass structures. Physical vapor deposition (PVD) is an important tool for preparing a wide range of these glasses. While the substrate can influence structure for hundreds of nanometers for crystalline and liquid crystalline systems, little is known about the structure of PVD glasses near an underlying substrate. This is important for organic electronics, as layers of PVD glasses as thin as 10 nm are used as active elements in organic light-emitting diodes, and molecular packing is vital to performance. We show that the free surface controls molecular packing of PVD glasses near a buried interface rather than the substrate, in sharp contrast with crystalline systems.

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

Enhancing Organic Semiconductor Molecular Packing Using Perovskite Interfaces to Improve Singlet Fission

Singlet fission, a process by which one singlet exciton is converted into two lower energy triplet excitons, is sensitive to the degree of electronic coupling within a molecular packing structure. Variations in molecular packing can be detrimental to triplet formation and triplet–triplet separation, ultimately affecting the harvesting of triplets for electricity in organic photovoltaic devices. Here, six phase-pure molecular packing structures of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) with varying optoelectronic properties are isolated using 2D lead halide perovskites as tunable, crystalline surfaces for crystallization. Transient absorption spectroscopy reveals that while triplet formation is fast (<100 fs) regardless of template structure, the increased ordering in perovskite-templated samples speeds up triplet–triplet separation and recombination, providing evidence that the benefits of phase-purity offset minor variations in molecular packing. Molecular dynamics modeling of the interface reveals that perovskite-templating allows for closer packing of TIPS-pentacene molecules for all perovskite templates. With an extensive number of organic molecule-perovskite pairings, this work provides a methodology to use ordered, periodic surfaces to elucidate structure–property relationships of small organic molecules in order to adjust structural or optoelectronic responses, such as molecular packing and singlet fission.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Molecular packing modulation enabling optimized blend morphology and efficient all small molecule organic solar cells

The molecular planarity of a small molecule donor is one of the key factors affecting its molecular packing behavior, the morphology of the related active blend and thus the photovoltaic properties of all small molecule organic solar cells (ASM-OSCs). Here, a series of new benzodithiophene (BDT)-based A-π-D-π-A type small molecules were developed, namely SD1, SD2 and SD3, by combining the chemical modification of side chain (sulfuration), π-bridge (alkoxy groups introducing) and end group (different type or different alkyl chain). The sulfuration of the BDT side chains and introducing alkoxy group to the π-bridge could induce intermolecular S … S and intramolecular S … O non-covalent interactions for higher planarity of these small molecules. The rhodanine and cyanoacetate end groups showed less effect on the optical and electronic properties but significantly affected the molecular packing behavior and blend morphology. From SD1:Y6-T to SD2:Y6-T and SD3:Y6-T, the face-to-face packing was gradually reduced, while the face-to-edge packing was increased, which resulted in lowered exciton dissociation efficiency, further decreased the device performance. SD1:Y6-T blend exhibited more favorable face-to-face packing and ideal morphology for efficient charge dissociation and transport, contributing to a champion PCE of 10.12%. This work provided a deep insight of the donor and acceptor packing behavior effect on the photovoltaic property by molecular design.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Regiospecific N -alkyl substitution tunes the molecular packing of high-performance non-fullerene acceptors

The rapid development of non-fullerene acceptors (NFAs) with strong near-infrared absorption has led to remarkably enhanced short-circuit current density (J sc ) values in organic solar cells (OSCs). NFAs based on the benzotriazole (Bz) fused-ring π-core have great potential in delivering both high J sc and decent open-circuit voltage values due to their strong intramolecular charge transfer with reasonably low energy loss. Here in this work, we have designed and synthesized a series of Bz-based NFAs, PN6SBO-4F, AN6SBO-4F and EHN6SEH-4F, via regiospecific N-alkyl engineering based on the high-performance NFA mBzS-4F that was reported previously. The molecular packing of mBzS-4F, AN6SBO-4F, and EHN6SEH-4F single crystals was analyzed using X-ray crystallography in order to provide a comprehensive understanding of the correlation between the molecular structure, the charge-transporting properties, and the solar cell performance. Compared with the typical honeycomb single-crystal structure of Y6 derivatives, these NFAs exhibit distinctly different molecular packing patterns. The strong interactions of terminal indanone groups in mBzS-4F and the J-aggregate-like packing in EHN6SEH-4F lead to the formation of ordered 3D networks in single-crystals with channels for efficient charge transport. Consequently, OSCs based on mBzS-4F and EHN6SEH-4F show efficient photon-to-current conversions, achieving the highest power conversion efficiency of 17.48% with a Jsc of 28.83 mA cm -2 .

36 MATERIALS SCIENCE↗
DOE OSTI2025

Fused-ring isomerism modulates molecular packing and device performance in non-halogenated organic solar cells

Subtle changes in molecular backbone geometry impact intermolecular interactions and performance of organic solar cells. Here, three isomeric small-molecule acceptors (NaO1, NaO2, and NaO3) are investigated to reveal how different fused-ring configurations control molecular packing, electronic coupling, and film formation. Structural and spectroscopic analyses show that the linearly fused NaO1 forms a compact three-dimensional packing network with large and balanced electronic couplings (>24 meV) across multiple directions, while the more curved analogues exhibit excessive crystallization and phase segregation. In-situ optical measurements demonstrate that NaO1 promotes fast and continuous structural evolution during film formation, resulting in smooth morphology and homogeneous phase distribution. These structural and dynamic advantages facilitate efficient charge generation and transport, accompanied by reduced non-radiative energy loss, ultimately achieving an efficiency of 20.07% for non-halogenated ternary devices. Our findings highlight how fused-ring isomerism decisively governs structure–packing–performance relationships in organic solar cells.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Resonant Tender X-ray Diffraction for Disclosing the Molecular Packing of Paracrystalline Conjugated Polymer Films

The performance of optoelectronic devices based on conjugated polymers is critically dependent upon molecular packing; however, the paracrystalline nature of these materials limits the amount of information that can be extracted from conventional X-ray diffraction. Resonant diffraction (also known as anomalous diffraction) occurs when the X-ray energy used coincides with an X-ray absorption edge in one of the constituent elements in the sample. The rapid changes in diffraction intensity that occur as the X-ray energy is varied across an absorption edge provide additional information that is lost in a conventional nonresonant experiment. Taking advantage of the fact that many conjugated polymers contain sulfur as heteroatoms, here we reveal pronounced resonant diffraction effects at the sulfur K-edge with a particular focus on the well-studied electron transporting polymer poly([N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)), P(NDI2OD-T2). The observed behavior is found to be consistent with the theory of resonant diffraction, and by simulating the energy-dependent peak intensity based on proposed crystal structures for P(NDI2OD-T2), we find that resonant diffraction can discriminate between different crystalline packing structures. The utilization of resonant diffraction opens up a new way to unlock important microstructural information about conjugated polymers for which only a handful of diffraction peaks are typically available.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Probing Molecular Packing of Amorphous Pharmaceutical Solids Using X-ray Atomic Pair Distribution Function and Solid-State NMR

The structural investigation of amorphous pharmaceuticals is of paramount importance in comprehending their physicochemical stability. However, it has remained a relatively underexplored realm primarily due to the limited availability of high-resolution analytical tools. Here in this study, we utilized the combined power of X-ray pair distribution functions (PDFs) and solid-state nuclear magnetic resonance (ssNMR) techniques to probe the molecular packing of amorphous posaconazole and its amorphous solid dispersion at the molecular level. Leveraging synchrotron X-ray PDF data and employing the empirical potential structure refinement (EPSR) methodology, we unraveled the existence of a rigid conformation and discerned short-range intermolecular C–F contacts within amorphous posaconazole. Encouragingly, our ssNMR 19 F– 13 C distance measurements offered corroborative evidence supporting these findings. Furthermore, employing principal component analysis on the X-ray PDF and ssNMR data sets enabled us to gain invaluable insights into the chemical nature of the intermolecular interactions governing the drug–polymer interplay. These outcomes not only furnish crucial structural insights facilitating the comprehension of the underlying mechanisms governing the physicochemical stability but also underscore the efficacy of synergistically harnessing X-ray PDF and ssNMR techniques, complemented by robust modeling strategies, to achieve a high-resolution exploration of amorphous structures.

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

Generic Behavior of Ultrastability and Anisotropic Molecular Packing in Codeposited Organic Semiconductor Glass Mixtures

Vapor-deposited glass mixtures of organic semiconductors commonly serve as active layers in organic electronic devices, whose lifetime and performance are strongly influenced by the stability and structure of these mixed glasses. Here, we study the stability and anisotropic molecular packing of six co-deposited organic semiconductor glass mixtures with 50:50 weight ratio, by differential scanning calorimetry and spectroscopic ellipsometry. We also find that all six binary systems exhibit high kinetic stability and significantly reduced enthalpy relative to the corresponding liquid-cooled glassy mixtures (ultrastable behavior), even for systems where the glass transition temperatures of the components differ by more than 90 K. Furthermore, we demonstrate that the birefringence of a co-deposited glass mixture, a measure of its anisotropic packing, can be predicted from the birefringence of glasses of the two pure components. These results for stability and structure are expected to be applicable to other co-deposited organic semiconductor glass mixtures, so long as the two components mix well in the glass and individually can form ultrastable glasses. Therefore, our findings are significant for designing novel electronic devices with enhanced device lifetime and increased operational efficiency.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Thermodynamic Properties and Molecular Packing Explain Performance and Processing Procedures of Three D18:NFA Organic Solar Cells

Abstract Organic solar cells (OSCs) based on D18:Y6 have recently exhibited a record power conversion efficiency of over 18%. The initial work is extended and the device performance of D18‐based OSCs is compared with three non‐fullerene acceptors, Y6, IT‐4F, and IEICO‐4Cl, and their molecular packing characteristics and miscibility are studied. The D18 polymer shows unusually strong chain extension and excellent backbone ordering in all films, which likely contributes to the excellent hole‐transporting properties. Thermodynamic characterization indicates a room‐temperature miscibility for D18:Y6 and D18:IT‐4F near the percolation threshold. This corresponds to an ideal quench depth and explains the use of solvent vapor annealing rather than thermal annealing. In contrast, D18:IEICO‐4Cl is a low‐miscibility system with a deep quench depth during casting and poor morphology control and low performance. A failure of ternary blends with PC 71 BM is likely due to the near‐ideal miscibility of Y6 to begin with and indicates that strategies for developing successful ternary or quaternary solar cells are likely very different for D18 than for other high‐performing donors. This work reveals several unique property–performance relations of D18‐based photovoltaic devices and helps guide design or fabrication of yet higher efficiency OSCs.

Wang, Zhen↗
DOE OSTI2020

Hierarchical supramolecular assembly of a single peptoid polymer into a planar nanobrush with two distinct molecular packing motifs

Significance The preparation of hierarchical biomimetic nanostructures remains a challenging task. Bioinspired peptoid polymers offer a promising opportunity to encode assembly information within the component chains. Here, we report a one-pot preparation of planar nanobrush structures from poly(ethyleneglycol)- block -poly( N -octylglycine) based on tuning the interplay of crystallization and solvophobicity. Each nanobrush assembly is composed of two distinct structural domains, which form sequentially by control of the solution temperature, and contain distinct molecular packing motifs. Micellar intermediates first assemble into linear arrays at elevated temperature in a mesophase state, followed by lateral, crystallization-driven growth in a living manner upon cooling. Precise control over the nanobrush dimensions could be achieved. The structural tunability and excellent biocompatibility of polypeptoids offer great potential for nanomaterials inaccessible previously.

36 MATERIALS SCIENCE↗
DOE OSTI2021

High Miscibility Compatible with Ordered Molecular Packing Enables an Excellent Efficiency of 16.2% in All-Small-Molecule Organic Solar Cells

In all-small-molecule organic solar cells (ASM-OSCs), a high short-circuit current (Jsc) usually needs a small phase separation, while a high fill factor (FF) is generally realized in a highly ordered packing system. However, small domain and ordered packing always conflicted each other in ASM-OSCs, leading to a mutually restricted J sc and FF. Here, in this study, alleviation of the previous dilemma by the strategy of obtaining simultaneous good miscibility and ordered packing through modulating homo- and heteromolecular interactions is proposed. By moving the alkyl-thiolation side chains from the para- to the meta-position in the small-molecule donor, the surface tension and molecular planarity are synchronously enhanced, resulting in compatible properties of good miscibility with acceptor BTP-eC9 and strong self-assembly ability. As a result, an optimized morphology with multi-length-scale domains and highly ordered packing is realized. The device exhibits a long carrier lifetime (39.8 μs) and fast charge collection (15.5 ns). A record efficiency of 16.2% with a high FF of 75.6% and a J sc of 25.4 mA cm –2 in the ASM-OSCs is obtained. These results demonstrate that the strategy of simultaneously obtaining good miscibility with high crystallinity could be an efficient photovoltaic material design principle for high-performance ASM-OSCs.

14 SOLAR ENERGY↗
DOE OSTI2025

Enhanced Ion Transport and Molecular Packing Stability in Asymmetric 2D Nanostructured π‐Conjugated Thieno[3,2‐b]Thiophene‐Based Liquid Crystal

Organic semiconductors based on liquid crystal (LC) molecules have attracted increasing interest. Here, in this work, two linear LCs based on 2,5‐bis(thien‐2‐yl)thieno[3,2‐b]thiophene (BTTT) mesogen are designed and synthesized, including BTTT/dEO3 with two symmetrically attached tri(ethylene oxide) groups and BTTT/mEO6 with one asymmetrically attached hexa(ethylene oxide) group. These two molecules have comparable functional‐group compositions but different molecular geometries, leading to their moderately different material performances. Both LCs show smectic mesophases with relatively low transition temperatures as confirmed by differential scanning calorimetry and polarized optical microscopy. A combination of experimental grazing incidence wide‐angle X‐ray scattering and molecular dynamics (MD) simulations reveals a herringbone packing motif of BTTT segments in both LCs while a smaller molecular tilt angle in BTTT/mEO6. Ionic conductivities are measured by doping LCs with different amounts of ionic dopants, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). BTTT/mEO6 shows better smectic phase stability to higher LiTFSI doping ratios. Both LCs exhibit similar ionic conductivities in the smectic phases, but BTTT/mEO6 outperforms BTTT/dEO3 by a factor of three in the amorphous phase at higher temperatures. MD simulations, performed to examine the ion solvation environment, reveal that BTTT/mEO6 is more efficient in coordinating Li‐ions and screening their interactions with TFSI‐ions which further promote ionic transport.

grazing incidence wide-angle X-ray scattering↗