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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
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 OSTI2023

IPL-Annealed Mixed-Cation Perovskites with Robust Coating Window toward Scalable Manufacturing of Commercial Perovskite Solar Cells

Perovskite solar cells (PSCs) are a promising alternative solar technology, but the technical challenges of (1) stability/durability, (2) efficiency at scale, and (3) manufacturability must be overcome to achieve widespread PSC commercialization. The challenge of balancing solution ink formulation and scalable manufacturing is often overlooked in the literature, where focus is on adopting inks from processes that will not scale. In this study, we apply a classical roll-to-roll manufacturing perspective, utilizing both compositional engineering and intense pulsed light (IPL) annealing, to develop a mixed-cation perovskite ink with a robust coating window that simultaneously solve issues of stability and manufacturability for PSCs. Our method resulted in blade-coated, flexible, mixed-cation PSCs on ITO-PET substrates with a champion power conversion efficiency (PCE) efficiency of 16.7% using IPL annealing of the absorber layer and, to our knowledge, is one of the fastest processing methods for the perovskite layer. This overall reduction in processing time with a stable ink represents an advance toward the scaled production of perovskite solar cells on flexible substrates.

flexible perovskite solar cells↗
DOE OSTI2023

Self-Patterning Tetrathiafulvalene Crystalline Films

Tetrathiafulvalene (TTF) crystals grown from the melt are organized as spherulites in which helicoidal fibrils growing radially from the nucleation center twist in concert with one another. Alternating bright and dark concentric bands are apparent when films are viewed between crossed polarizers, indicating an alternating pattern of crystallographic faces exposed at the film surface. Band-dependent reorganization of the TTF crystals was observed during exposure to methanol vapor. Crystalline growth appears on bright bands at the expense of the dark bands. After a 24 h period of exposure to methanol vapor, the original spherulites were completely restructured, and the films comprise isolated, concentric circles of crystallites whose orientations are determined by the initial TTF crystal fibril orientation. While the surface of these outgrowths appears faceted and smooth, cross-sectional SEM images revealed a semiporous inner structure, suggesting solvent-vapor-induced recrystallization. Collectively, these results show that crystal twisting can be used to rhythmically redistribute material. Crystal twisting is a common and often controllable phenomenon independent of molecular or crystal structure and therefore offers a generalizable path to spontaneous pattern formation in a wide range of materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Non-Covalent Interactions and Helical Packing in Thiophene-Phenylene Copolymers: Tuning Solid-State Ordering and Charge Transport for Organic Field-Effect Transistors

In this study, we introduce two thiophene-phenylene-thiophene (TPT) polymers designed to leverage noncovalent intramolecular interactions to regulate main-chain conformation and enhance solid-state ordering. By incorporating unsubstituted thiophene (T) or bithiophene (2T) units, we reveal striking divergence in the thermal, morphological, and optoelectronic properties of the resulting films, facilitated by these noncovalent interactions. Using a combination of computational and experimental approaches, we show that annealing yields remarkably different polymer conformations and, consequently, charge transport properties. TPT-T undergoes a significant structural transformation, adopting a more planar backbone conformation and a highly crystalline, edge-on molecular orientation. In contrast, the introduction of a single additional thiophene unit in TPT-2T leads to a more isotropic molecular orientation with a slight preference for face-on alignment, resulting in a heterogeneous film structure that hinders charge transport despite achieving tighter molecular packing. Remarkably, despite being composed of achiral components, TPT-2T develops chirality upon annealing, indicating the formation of a helical conformation. Organic field-effect transistor measurements reveal that the well-ordered alignment in annealed TPT-T films results in higher charge carrier mobility and a narrower distribution of mobility values than in TPT-2T. These findings provide critical insights into the structure−property relationships of conjugated polymers, offering guidance for optimizing molecular design and processing strategies for highperformance organic electronic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Evolution of Bonding and Magnetism via Changes in Valence Electron Count in CuFe 2– x Co x Ge 2

A series of solid solutions, CuFe 2–x Co x Ge 2 (x = 0, 0.2, 0.4, 0.8, and 1.0), have been synthesized by arc-melting and characterized by powder X-ray and neutron diffraction, magnetic measurements, Mössbauer spectroscopy, and electronic band structure calculations. All compounds crystallize in the CuFe 2 Ge 2 structure type, which can be considered as a three-dimensional framework built of fused MGe6 octahedra and MGe 5 trigonal bipyramids (M = Fe and Co), with channels filled by rows of Cu atoms. As the Co content (x) increases, the unit cell volume decreases in an anisotropic fashion: the b and c lattice parameters decrease while the a parameter increases. The changes in all the parameters are nearly linear, thus following Vegard’s law. CuFe 2 Ge 2 exhibits two successive antiferromagnetic (AFM) orderings, corresponding to the formation of a commensurate AFM structure, followed by an incommensurate AFM structure observed at lower temperatures. Additionally, as the Co content increases, the AFM ordering temperature (TN) gradually decreases, and only one AFM transition is observed for x ≥ 0.2. The magnetic behavior of unsubstituted CuFe 2 Ge 2 was found to be sensitive to the preparation method. The temperature-dependent zero-field 57 Fe Mössbauer spectra reveal two hyperfine split components that evolve in agreement with the two consecutive AFM orderings observed in magnetic measurements. In contrast, the field-dependent spectra obtained for fields ≥ 2 T reveal a parallel arrangement of the moments associated with the two crystallographically unique metal sites. Electronic band structure calculations and chemical bonding analysis reveal a mix of strong M–M antibonding and non-bonding states at the Fermi level, in support of the overall AFM ordering observed in zero field. The substitution of Co for Fe reduces the population of the M–M antibonding states and the overall density of states at the Fermi level, thus suppressing the T N value.

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

Toward a QUBO-Based Density Matrix Electronic Structure Method

Density matrix electronic structure theory is used in many quantum chemistry methods to “alleviate” the computational cost that arises from directly using wave functions. Although density matrix based methods are computationally more efficient than wave function based methods, significant computational effort is involved. Because the Schrödinger equation needs to be solved as an eigenvalue problem, the time-to-solution scales cubically with the system size in mean-field type approaches such as Hartree–Fock and density functional theory and is solved as many times in order to reach charge or field self-consistency. We hereby propose and study a method to compute the density matrix by using a quadratic unconstrained binary optimization (QUBO) solver. This method could be useful to solve the problem with quantum computers and, more specifically, quantum annealers. Our proposed approach is based on a direct construction of the density matrix using a QUBO eigensolver. We explore the main parameters of the algorithm focusing on precision and efficiency. We show that, while direct construction of the density matrix using a QUBO formulation is possible, the efficiency and precision have room for improvement. Moreover, calculations performed with quantum annealing on D-Wave’s new Advantage quantum computer are compared with results obtained with classical simulated annealing, further highlighting some problems of the proposed method. Finally, we also suggest alternative methods that could lead to a more efficient QUBO-based density matrix construction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Stable Glasses of Organic Semiconductor Resist Crystallization

The instability of glassy solids poses a key limitation to their use in several technological applications. Well-packed organic glasses, prepared by physical vapor deposition (PVD), have drawn attention recently because they can exhibit significantly higher thermal and chemical stability than glasses prepared from more traditional routes. We show here that PVD glasses can also show enhanced resistance to crystallization. By controlling the deposition temperature, resistance toward crystallization can be enhanced by at least a factor of ten in PVD glasses of the model organic semiconductor Alq3 (tris(8-hydroxyquinolinato) aluminum). PVD glasses of Alq3 first transform into a supercooled liquid before crystallizing. By controlling the deposition temperature, we increase the glass → liquid transformation time thereby also increasing the overall time for crystallization. Furthermore, we thus demonstrate a new strategy to stabilize glasses of organic semiconductors against crystallization, which is a common failure mechanism in organic light emitting diode devices.

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

Conversion of Formic Acid on Single- and Nano-Crystalline Anatase TiO 2 (101)

Understanding thermochemical transformations of formic acid (FA) on metal oxide surfaces is important for many catalytical reactions. Here we study thermally induced reactions of FA on a single-crystalline and nanocrystalline anatase TiO 2 (101). We employ a combination of scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), infrared reflection absorption spectroscopy (IRAS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and density functional theory (DFT) to follow the FA surface intermediates and reaction products above room temperature. We find that the primary reaction products desorbing at about 300, 480, and 515 K are molecular water, carbon monoxide, and formaldehyde, respectively. Bidentate (BD) formate and bridging hydroxyl (HO b ) are identified as central intermediates in the FA transformations. Bridging oxygen vacancies (V O ) are also likely participants despite their low stability at the surface. In conclusion, the parallel studies on single crystals and faceted TiO 2 (101) nanoparticles reveal the spectroscopic commonalities of surface species and of the thermal conversion of molecular and deprotonated forms of FA.

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

AlCl 3 -Dosed Si(100)-2 × 1: Adsorbates, Chlorinated Al Chains, and Incorporated Al

The adsorption of AlCl 3 on Si(100) and the effect of annealing the AlCl 3 -dosed substrate were studied to reveal key surface processes for the development of atomic-precision, acceptor-doping techniques. This investigation was performed via scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. At room temperature, AlCl 3 readily adsorbed to the Si substrate dimers and dissociated to form a variety of species. Annealing the AlCl 3 -dosed substrate at temperatures below 450 °C produced unique chlorinated aluminum chains (CACs) elongated along the Si(100) dimer row direction. An atomic model for the chains is proposed with supporting DFT calculations. Al was incorporated into the Si substrate upon annealing at 450 °C and above, and Cl desorption was observed for temperatures beyond 450 °C. Al-incorporated samples were encapsulated in Si and characterized by secondary ion mass spectrometry (SIMS) depth profiling to quantify the Al atom concentration, which was found to be in excess of 10 20 cm –3 across a ~2.7 nm-thick δ-doped region. Here, the Al concentration achieved here and the processing parameters utilized promote AlCl 3 as a viable gaseous precursor for novel acceptor-doped Si materials and devices for quantum computing.

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

Efficient Free Triplet Generation Follows Singlet Fission in Diketopyrrolopyrrole Polymorphs with Goldilocks Coupling

Microcrystal electron diffraction, grazing incidence wide-angle scattering, and UV–vis spectroscopy were used to determine the unit-cell structure and the relative composition of dimethylated diketopyrrolopyrrole H- and J-polymorphs within thin films subjected to vapor solvent annealing (VSA) for different times. The electronic structure and excited-state deactivation pathways of the different polymorphs were examined by transient absorption spectroscopy, conductive probe atomic force microscopy, and molecular modeling. We find that VSA initially converts amorphous films into mixtures of H- and J-polymorphs and promotes further conversion from H to J with longer VSA times. Here, though both polymorphs exhibit efficient SF to form coupled triplets, free triplet yields are higher in J-polymorph films compared to mixed films because coupling in J-aggregates is lower and, in turn, more favorable for triplet decoupling.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Electronic Conductivity of Nanoporous Indium Oxide Derived from Sequential Infiltration Synthesis

Sequential infiltration synthesis (SIS) is a vapor phase synthetic method that enables the selective nucleation and growth of metal oxides within polymer volumes. The expanding palette of SIS materials and process designs enables tunability of the resulting material properties. We derive porous indium oxide thin films from the SIS of indium oxide using trimethyl indium and H 2 O 2 in polymethyl methacrylate films and observe the strong effect of SIS and post-deposition processing, which affords 7 orders of magnitude of tunability in electrical resistivity. While as-deposited hybrid nanocomposites show no measurable conductivity, high-temperature treatment in O 2 removes the polymer matrix and creates a porous nanocrystalline In 2 O 3 film with resistivities ranging from 10 3 to 10 5 Ω*cm, with lower resistivity correlated to larger grain sizes. Subsequent annealing in H 2 decreases the resistivity of films to less than 10 –2 Ω*cm. A clear correlation between increasing In 2 O 3 volume fraction, grain size, and carrier mobility is observed, which arises from increased percolation pathways, path length, and contact area in nanocrystalline In 2 O 3 films. Furthermore, this wide tunability demonstrates the importance of understanding growth mechanisms and processing conditions for functional materials development.

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

Preparation and Characterization of Model Homotopic Catalysts: Rh Adatoms, Nanoparticles, and Mixed Oxide Surfaces on Fe 3 O 4 (001)

The atomic-level characterization of active sites is essential to understanding the mechanisms behind catalytic reactions. In this study, using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS), we follow the morphological changes of a model Rh catalysts supported on Fe 3 O 4 (001) as a function of temperature and Rh coverage. Here, we identify the preparation conditions leading to model catalysts containing homotopic or nearly homotopic Rh species bound as adatoms, small clusters, substitutional within the Fe 3 O 4 (001), and nanoparticles. Adsorbates such as CO and CO 2 are further subsequently used to characterize the properties of different Rh sites. Using temperature programmed desorption (TPD), we demonstrate that adatoms, clusters, and nanoparticles exhibit high-temperature CO desorption (250-600 K). Strong binding on such sites further allows for CO oxidation to CO 2 via the Mars-van-Krevelen mechanism. In contrast, CO 2 was found to interact weakly with all Rh sites. Differences in desorption temperature enable the use of CO and CO 2 as titration methods for nanoparticles and Fe 3 O 4 (001), respectively. A small quantity of CO 2 was found to be reduced to CO on Rh adatoms and clusters.

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

Tuning Strong Metal–Support Interaction Kinetics on Pt-Loaded TiO 2 (110) by Choosing the Pressure: A Combined Ultrahigh Vacuum/Near-Ambient Pressure XPS Study

Pt catalyst particles on reducible oxide supports often change their activity significantly at elevated temperatures due to the strong metal–support interaction (SMSI), which induces the formation of an encapsulation layer around the noble metal particles. However, the impact of oxidizing and reducing treatments at elevated pressures on this encapsulation layer remains controversial, partly due to the “pressure gap” between surface science studies and applied catalysis. In the present work, we employ synchrotron-based near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) to study the effect of O 2 and H 2 on the SMSI-state of well-defined Pt/TiO 2 (110) catalysts at pressures of up to 0.1 Torr. Further, by tuning the O 2 pressure, we can either selectively oxidize the TiO 2 support or both the support and the Pt particles. Catalyzed by metallic Pt, the encapsulating oxide overlayer grows rapidly in 1 × 10 –5 Torr O 2 , but orders of magnitude less effectively at higher O 2 pressures, where Pt is in an oxidic state. While the oxidation/reduction of Pt particles is reversible, they remain embedded in the support once encapsulation has occurred.

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

Annealing Controls Ultrafast Dynamics of Carrier Production in Organic Photovoltaics Incorporating a Nonfullerene Acceptor

Nonfullerene acceptors have emerged as leading candidates in organic photovoltaics pushing past some of the limitations of their fullerene counterparts with absorption extending in the visible and NIR, decreased air-sensitivity, and tunable energy levels. Significant progress has been made in demonstrating the potential of nonfullerene acceptor-based devices to reach high efficiencies; however, a photophysical and mechanistic understanding of charge generation in these nonfullerene acceptors lags behind. In particular, the effects of annealing on carrier production have not been previously examined. Here, we use transient absorption spectroscopy and atomic force microscopy to examine the effect of solvent vapor annealing on a perylene diimide-based nonfullerene acceptor, PDI-DPP-PDI. We find that when mixed with the donor PTB7-Th, the effect of solvent vapor annealing on PDI-DPP-PDI is to reduce geminate recombination, leading to balanced exciton generation and charge separation.

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

Laser-Induced Enhancement of Acoustic Mode Quality Factor Revealed by Correlated Single-Particle Optical and Electron Microscopy

Acoustic modes in plasmonic nanostructures provide fundamental insights into their optomechanical behavior at the nanoscale, enabling emerging applications in plasmon-enhanced optomechanics, ultrasensitive sensing, and nanoscale energy transduction. Here we explore the modulation of acoustic phonon dynamics in lithographically fabricated gold nanodisks via laser-induced photothermal annealing. Using a correlated approach that utilizes both single-particle transient extinction spectroscopy and advanced electron microscopy, we directly link nanoscale structural transformations to changes in mechanical properties as probed through the coherence of the excited acoustic modes. Specifically, ultrafast pump–probe microscopy reveals an enhancement in the acoustic mode quality factor of annealed gold nanodisks, indicative of reduced damping and improved vibrational coherence. Structural characterization via scanning electron microscopy and electron backscatter diffraction confirms that photoinduced annealing results in smoother surface morphology and overall enhanced crystallinity. The improved crystalline order reduces defect and crystal boundary scattering, which we suggest as the reason underlying the lower quality factor before annealing. Furthermore, these findings demonstrate that targeted structural engineering at the nanoscale offers a powerful strategy for optimizing the optomechanical performance of plasmonic nanostructures, with broad implications for the design of next-generation nanophotonic and optomechanical systems.

Annealing (metallurgy)↗
DOE OSTI2020

Imaging Supramolecular Morphogenesis with Confocal Laser Scanning Microscopy at Elevated Temperatures

The morphogenesis of supramolecular assemblies is a highly dynamic process that has only recently been recognized, and our understanding of this phenomenon will require imaging techniques capable of crossing scales. Shape transformations depend both on the complex energy landscapes of supramolecular systems and the kinetically controlled pathways that define their structures and functions. We report here the use of confocal laser scanning microscopy coupled with a custom-designed variable-temperature sample stage that enables in situ observation of such shape changes. The submicrometer resolution of this technique allows for real-time observation of the nanostructures in the native liquid environments in which they transform with thermal energy. We use this technique to study the temperature-dependent morphogenic behavior of peptide amphiphile nanofibers and photocatalytic chromophore amphiphile nanoribbons. Furthermore, the variable-temperature confocal microscopy technique demonstrated in this work can sample a large volume and provides real-time information on thermally induced morphological changes in the solution.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Mild-Annealed Molecular Layer Deposition (MLD) Tincone Thin Film as Photoelectrochemically Stable and Efficient Electron Transport Layer for Si Photocathodes

Metalcone thin films, composed of inorganic–organic hybrids, are synthesized using molecular layer deposition (MLD) through reactions between organometallic precursors (e.g., Sn, Al, and Ti) and organic reactants (e.g., ethylene glycol and glycerol). Despite their unique properties, metalcones exhibit significant vulnerability to water due to their organic components, limiting their potential in electrochemical applications. This study focuses on enhancing the photoelectrochemical stability of tincone thin films in aqueous electrolyte while preserving their hybrid characteristics through mild annealing in air at 250 °C. As-deposited and vacuum-annealed tincone thin films exhibited significant degradation under these conditions, while high-temperature-annealed (500 °C) tincone thin films offered improved stability with a significant decline in charge transfer efficiency. In contrast, mild annealing in air maintained the C–O bond at half level and improved the stability and charge transport without compromising the unique characteristics of tincone. This was confirmed by ellipsometry, X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR). Mild-annealed tincone deposited on a lightly doped p-type silicon (p-Si) photocathode produced a 20-fold increase in CO volume compared to high-temperature annealed tincone in a CO 2 -saturated potassium bicarbonate (KHCO 3 ) electrolyte with dispersed graphene oxide–cobalt phthalocyanine (GO-CoPc) under 1 sun illumination at 0.9 V vs reversible hydrogen electrode (RHE), while maintaining the faradaic efficiency for CO and H 2 . These results suggest that mild-annealed tincone thin films hold significant potential as protective charge transport layers on silicon photocathodes for the aqueous CO 2 reduction reaction (CO 2 RR).

Annealing (metallurgy)↗