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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 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Stepwise deprotonation of truxene: structures, metal complexation, and charge-dependent optical properties

As a planar subunit of C 60 -fullerene, truxene (C 27 H 18 ) represents a highly symmetrical rigid hydrocarbon with strong blue emission. Herein, we used truxene as a model to investigate the chemical reactivity of a fullerene fragment with alkali metals. Monoanion, dianion, and trianion products with different alkali metal counterions were crystallized and fully characterized, revealing the core curvature dependence on charge and alkali metal coordination. Moreover, a proton nuclear magnetic resonance study coupled with computational analysis demonstrated that deprotonation of the aliphatic CH 2 segments introduces aromaticity in the five-membered rings. Importantly, the UV-vis absorption and photoluminescence of truxenyl anions with different charges reveal intriguing charge-dependent optical properties, implying variation of the electronic structure based on the deprotonation process. An increase in aromaticity and π-conjugation yielded a red shift in the absorption and photoluminescent spectra; in particular, large Stokes shifts were observed in the truxenyl monoanion and dianion with high emission quantum yield and time of decay. Overall, stepwise deprotonation of truxene provides the first crystallographically characterized examples of truxenyl anions with three different charges and charge-dependent optical properties, pointing to their potential applications in carbon-based functional materials.

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

A divergent synthetic route to functional copolymer libraries via modular polymers

High-throughput polymer synthesis enables rapid exploration of chemical space but remains limited by batch-to-batch inconsistencies that can obscure structure–property relationship trends. To address this challenge, we developed a synthetic approach to produce multifunctional copolymers using post-polymerization modification of activated ester modular polymers with commercially available amines. Easily derivitized parent polymers—poly(tetrafluorophenyl acrylate) and poly(tetrafluorophenyl styrene sulfonate)—were synthesized by RAFT polymerization to yield single polymer batches containing highly reactive tetrafluorophenyl esters or sulfonate esters on each repeat unit. Tuning post-polymerization modification reaction conditions enabled the addition of sub-stoichiometric amounts of amines (relative to the repeat unit) to yield partially functionalized intermediates that could then be further derivatized. Reaction monitoring by 19 F NMR spectroscopy confirmed good control over these sequential post-polymerization modifications. This synthetic route produced a variety of copolymers with defined comonomer ratios while preserving the underlying polymer structure (degree of polymerization, dispersity, tacticity) for both the acrylate and styrene sulfonate backbones. We further applied this approach in a divergent manner to create a small library of structurally distinct copolymers from a single parent batch in three synthetic steps. This modular, divergent synthesis demonstrates a general route to structurally consistent copolymer libraries that enable systematic studies of structure–property relationships and can accelerate functional materials discovery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Cobalt–niobium co-doping of indium oxide: structural and adsorption/catalytic properties for CO 2 valorization

The co-doping of the indium oxide structure with cobalt and niobium is attempted using a microemulsion method to produce high-surface-area, mesoporous, functional materials. The co-doping leads to a major nanometric bixbyite oxide phase, with both cations occupying cation positions and affecting the size and shape of the oxide entities. For specific cobalt to niobium atomic ratios, the presence of a second surface phase is encountered. Such a surface phase corresponds to an ill-defined indium hydroxide-type phase. The coexistence of the two phases is a unique phenomenon associated with the presence of both cations, which play a decisive role in promoting the CO 2 adsorption capability of the solids, as well as the valorization of the molecule under dual heat–light excitation. The co-doping of indium oxide thus appears to be a unique way to intensify the analogous thermal (classical) catalytic process for the elimination/valorization of carbon dioxide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Vertically aligned biaxially textured molybdenum thin films

Vertically aligned, biaxially textured molybdenum nanorods were deposited using dc magnetron sputtering with glancing flux incidence (alpha = 85 degrees with respect to the substrate normal) and a two-step substrate-rotation mode. These nanorods were identified with a body-centered cubic crystal structure. The formation of a vertically aligned biaxial texture with a [110] out-of-plane orientation was combined with a [-110] in-plane orientation. The kinetics of the growth process was found to be highly sensitive to an optimum rest time of 35 seconds for the two-step substrate rotation mode. At all other rest times, the nanorods possessed two separate biaxial textures each tilted toward one flux direction. While the in-plane texture for the vertical nanorods maintains maximum flux capture area, inclined Mo nanorods deposited at alpha = 85 degrees without substrate rotation display a [-1-1-4] in-plane texture that does not comply with the maximum flux capture area argument. Finally, an in situ capping film was deposited with normal flux incidence over the biaxially textured vertical nanorods resulting in a thin film over the porous nanorods. This capping film possessed the same biaxial texture as the nanorods and could serve as an effective substrate for the epitaxial growth of other functional materials.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Room-temperature thermally induced relaxation effect in a two-dimensional cyano-bridged Cu-Mo bimetal assembly and thermodynamic analysis of the relaxation process

We observed a photo-switching effect in [Cu{sup II}(1,4,8,11-tetraazacyclodecane)]{sub 2}[Mo{sup IV}(CN){sub 8}]{center_dot}10H{sub 2}O by irradiation with 410-nm light around room temperature using infrared spectroscopy. This photo-switching is caused by the photo-induced charge transfer from Mo{sup IV} to Cu{sup II}. The photo-induced phase thermally relaxed to the initial phase with a half-life time of 2.7 Multiplication-Sign 10{sup 1}, 6.9 Multiplication-Sign 10{sup 1}, and 1.7 Multiplication-Sign 10{sup 2} s at 293, 283, and 273 K, respectively. The relaxation process was analyzed using Hauser's equation, k=k{sub 0}exp[-(E{sub a}+E{sub a}{sup *}{gamma}) /k{sub B}T], where k is the rate constant of relaxation, k{sub 0} is the frequency factor, E{sub a} is the activation energy, E{sub a}{sup *} is the additional activation energy due to the cooperativity, and {gamma} is the fraction of the photo-induced phase. k{sub 0}, E{sub a}, and E{sub a}{sup *} were evaluated as 1.28 Multiplication-Sign 10{sup 7}{+-} 2.6 s{sup -1}, 4002 {+-} 188 cm{sup -1}, and 546 {+-} 318 cm{sup -1}, respectively. The value of E{sub a} is much larger than that of the relaxation process for the typical light-induced spin crossover effect (E{sub a} Almost-Equal-To 1000 cm{sup -1}). Room-temperature photo-switching is an important issue in the field of optical functional materials. The present system is useful for the demonstration of high-temperature photo-switching material.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Non-radiative relaxation and rectification behavior of metal/semiconductor tetrapod heterostructures

The metal-semiconductor hetero-structures have recently emerged as functional materials for their potential applications in the areas of photonic, optoelectronic, and other fields. Here, we discuss the structural characterization of Au/CdSe tetrapod hetero-structures by using high-resolution transmission electron microscope, high angle annular dark field-scanning transmission electron microscopic, and X-ray diffraction. The blue shifting of the plasmonic band and red shifting of the excitonic band suggest a strong surface plasmon-exciton interaction between Au and CdSe in Au/CdSe tetrapod heterostructure. A significant photoluminescence quenching (83.4%) of CdSe nanorod (NR) is observed in the presence of Au nanoparticle in Au/CdSe tetrapod heterostructure. The radiative and nonradiative decay rates of CdSe nanorods are found to be modified in Au/CdSe tetrapod structures and the nonradiative rate changes from 1.91 × 10{sup 7} s{sup −1} to 9.33 × 10{sup 9} s{sup −1} for CdSe NR to Au/CdSe tetrapod structure, respectively. Current-voltage characteristics of Au/CdSe heterostructure exhibit the rectification property with a threshold voltage of about 0.85 V and the rectifying ratio is 140 which can open up avenues for developing challenging devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Stranski-Krastanow islanding initiated on the stochastic rough surfaces of the epitaxially strained thin films

Quantum dots (QD) have discrete energy spectrum, which can be adjusted over a wide range by tuning composition, density, size, lattice strain, and morphology. These features make quantum dots attractive for the design and fabrication of novel electronic, magnetic and photonic devices and other functional materials used in cutting-edge applications. The formation of QD on epitaxially strained thin film surfaces, known as Stranski-Krastanow (SK) islands, has attracted great attention due to their unique electronic properties. Here, we present a systematic dynamical simulation study for the spontaneous evolution of the SK islands on the stochastically rough surfaces (nucleationless growth). During the development of SK islands through the mass accumulation at randomly selected regions of the film via surface drift-diffusion (induced by the capillary and mismatch stresses) with and/or without growth, one also observes the formation of an extremely thin wetting layer having a thickness of a few Angstroms. Above a certain threshold level of the mismatch strain and/or the size of the patch, the formation of multiple islands separated by shallow wetting layers is also observed as metastable states such as doublets even multiplets. These islands are converted into a distinct SK islands after long annealing times by coalescence through the long range surface diffusion. Extensive computer simulation studies demonstrated that after an initial transient regime, there is a strong quadratic relationship between the height of the SK singlet and the intensity of the lattice mismatch strain (in a wide range of stresses up to 8.5 GPa for germanium thin crystalline films), with the exception at those critical points where the morphological (shape change with necking) transition takes place.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Chlorine doped graphene quantum dots: Preparation, properties, and photovoltaic detectors

Graphene quantum dots (GQDs) are becoming one of the hottest advanced functional materials because of the opening of the bandgap due to quantum confinement effect, which shows unique optical and electrical properties. The chlorine doped GQDs (Cl-GQDs) have been fabricated by chemical exfoliation of HCl treated carbon fibers (CFs), which were prepared from degreasing cotton through an annealing process at 1000 °C for 30 min. Raman study shows that both G and 2D peaks of GQDs may be redshifted (softened) by chlorine doping, leading to an n-type doping. The first vertical (Cl)-GQDs based photovoltaic detectors have been demonstrated, both the light absorbing and electron-accepting roles for (Cl)-GQDs in photodetection have been found, resulting in an exceptionally big ratio of photocurrent to dark current as high as ∼10{sup 5} at room temperature using a 405 nm laser irradiation under the reverse bias voltage. The study expands the application of (Cl)-GQDs to the important optoelectronic detection devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Theory of melt polyelectrolyte blends and block copolymers: Phase behavior, surface tension, and microphase periodicity

Polymer mixtures such as blends or block copolymers are of great interest in energy applications and functional materials, and often, one or more of these species contain charges. The traditional fashion in which such materials are studied uses Self-Consistent Field Theory (SCFT) methods that incorporate electrostatics using Poisson-Boltzmann (PB) theory. We adapt a new and rigorous approach that does not rely on the mean-field assumptions inherent in the PB theory and instead uses Liquid State (LS) integral equation theory to articulate charge correlations that are completely neglected in PB. We use this theory to calculate phase diagrams for both blends and block copolyelectrolytes using SCFT-LS and demonstrate how their phase behavior is highly dependent on chain length, charge fraction, charge size, and the strength of Coulombic interactions. Beyond providing phase behavior of blends and block copolyelectrolytes, we can use this theory to investigate the interfacial properties such as surface tension and block copolyelectrolyte lamellar spacing. Lamellar spacing provides a way to directly compare the SCFT-LS theory to the results of experiments. SCFT-LS will provide conceptual and mathematical clarification of the role of charge correlations in these systems and aid in the design of materials based on charge polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Spontaneous decoration of Au nanoparticles on micro-patterned reduced graphene oxide shaped by focused laser beam

We report a facile, two-step method for the micro-landscaping of Au nanoparticles(NPs) on reduced graphene oxide (rGO) film en route to micro-patterned Au(NPs)-rGO hybrid functional materials. This method employs a focused laser beam to first locally convert GO to rGO before immersing the micro-patterned GO-rGO film into HAuCl{sub 4} solution. The rGO micro-pattern, shaped by the focused laser beam, serves as nucleation sites for the reduction of Au ions. The reduction mechanism that governs the decoration of Au NPs on rGO films is akin to electroless deposition process. In this instance, surface charges that are formed during laser reduction of GO to rGO provide active nucleation sites for Au{sup 3+} ions to form Au NPs when HAuCl{sub 4} solution is introduced. The number density, the size, and size distribution of the Au NPs can thus be directly tuned and preferentially anchored onto the rGO micro-pattern by varying the incident laser power, the scanning speed of the laser, or the concentration of HAuCl{sub 4}. The resulting hybrid materials can be used as a substrate for Surface Enhanced Raman Spectroscopy (SERS). Using Rhodamine 6G as the test subject, we found an improvement of SERS enhancement over bare rGO of up to four times, depending on the size of the Au NPs.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Facile construction of vertically aligned EuS-ZnO hybrid core shell nanorod arrays for visible light driven photocatalytic properties

We demonstrated the development of coupled semiconductor in the form of hybrid heterostructures for significant advancement in catalytic functional materials. In this article, we report the preparation of vertically aligned core shell ZnO-EuS nanorod photocatalyst arrays by a simple chemical solution process followed by sulfudation process. The XRD pattern confirmed formation of the hexagonal wurtzite structure of ZnO and cubic nature of the EuS. Cross sectional FESEM images show vertical rod array structure, and the size of the nanorods ranges from 80 to 120 nm. UV-Vis DRS spectra showed that the optical absorption of ZnO was significantly enhanced to the visible region by modification with EuS surfaces. TEM study confirmed that the surface of ZnO was drastically improved by the modification with EuS nanoparticle. The catalytic activity of EuS−ZnO core shell nanorod arrays were evaluated by the photodegradation of Methylene Blue (MB) dye under visible irradiation. The results revealed that the photocatalytic activity of EuS−ZnO was much higher than that of ZnO under natural sunlight. EuS−ZnO was found to be stable and reusable without appreciable loss of catalytic activity up to four consecutive cycles.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Characterization of individual molecular adsorption geometries by atomic force microscopy: Cu-TCPP on rutile TiO{sub 2} (110)

Functionalized materials consisting of inorganic substrates with organic adsorbates play an increasing role in emerging technologies like molecular electronics or hybrid photovoltaics. For such applications, the adsorption geometry of the molecules under operating conditions, e.g., ambient temperature, is crucial because it influences the electronic properties of the interface, which in turn determine the device performance. So far detailed experimental characterization of adsorbates at room temperature has mainly been done using a combination of complementary methods like photoelectron spectroscopy together with scanning tunneling microscopy. However, this approach is limited to ensembles of adsorbates. In this paper, we show that the characterization of individual molecules at room temperature, comprising the determination of the adsorption configuration and the electrostatic interaction with the surface, can be achieved experimentally by atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM). We demonstrate this by identifying two different adsorption configurations of isolated copper(II) meso-tetra (4-carboxyphenyl) porphyrin (Cu-TCPP) on rutile TiO{sub 2} (110) in ultra-high vacuum. The local contact potential difference measured by KPFM indicates an interfacial dipole due to electron transfer from the Cu-TCPP to the TiO{sub 2}. The experimental results are verified by state-of-the-art first principles calculations. We note that the improvement of the AFM resolution, achieved in this work, is crucial for such accurate calculations. Therefore, high resolution AFM at room temperature is promising for significantly promoting the understanding of molecular adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Porous silicon-VO{sub 2} based hybrids as possible optical temperature sensor: Wavelength-dependent optical switching from visible to near-infrared range

Morphological properties of thermochromic VO{sub 2}—porous silicon based hybrids reveal the growth of well-crystalized nanometer-scale features of VO{sub 2} as compared with typical submicron granular structure obtained in thin films deposited on flat substrates. Structural characterization performed as a function of temperature via grazing incidence X-ray diffraction and micro-Raman demonstrate reversible semiconductor-metal transition of the hybrid, changing from a low-temperature monoclinic VO{sub 2}(M) to a high-temperature tetragonal rutile VO{sub 2}(R) crystalline structure, coupled with a decrease in phase transition temperature. Effective optical response studied in terms of red/blue shift of the reflectance spectra results in a wavelength-dependent optical switching with temperature. As compared to VO{sub 2} film over crystalline silicon substrate, the hybrid structure is found to demonstrate up to 3-fold increase in the change of reflectivity with temperature, an enlarged hysteresis loop and a wider operational window for its potential application as an optical temperature sensor. Such silicon based hybrids represent an exciting class of functional materials to display thermally triggered optical switching culminated by the characteristics of each of the constituent blocks as well as device compatibility with standard integrated circuit technology.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Size effects of 109° domain walls in rhombohedral barium titanate single crystals—A molecular statics analysis

Ferroelectric functional materials are of great interest in science and technology due to their electromechanically coupled material properties. Therefore, ferroelectrics, such as barium titanate, are modeled and simulated at the continuum scale as well as at the atomistic scale. Due to recent advancements in related manufacturing technologies the modeling and simulation of smart materials at the nanometer length scale is getting more important not only to predict but also fundamentally understand the complex material behavior of such materials. In this study, we analyze the size effects of 109° nanodomain walls in ferroelectric barium titanate single crystals in the rhombohedral phase using a recently proposed extended molecular statics algorithm. We study the impact of domain thicknesses on the spontaneous polarization, the coercive field, and the lattice constants. Moreover, we discuss how the electromechanical coupling of an applied electric field and the introduced strain in the converse piezoelectric effect is affected by the thickness of nanodomains.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Geometry of electromechanically active structures in Gadolinium - doped Cerium oxides

Local distortions from average structure are important in many functional materials, such as electrostrictors or piezoelectrics, and contain clues about their mechanism of work. However, the geometric attributes of these distortions are exceedingly difficult to measure, leading to a gap in knowledge regarding their roles in electromechanical response. This task is particularly challenging in the case of recently reported non-classical electrostriction in Cerium-Gadolinium oxides (CGO), where only a small population of Ce-O bonds that are located near oxygen ion vacancies responds to external electric field. We used high-energy resolution fluorescence detection (HERFD) technique to collect X-ray absorption spectra in CGO in situ, with and without an external electric field, coupled with theoretical modeling to characterize three-dimensional geometry of electromechanically active units.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Current status of BL-2B at photon factory

A new soft x-ray beamline BL-2B at Photon Factory of High Energy Accelerator Research Organization (KEK-PF) covers energy range from vacuum ultraviolet (30 eV) to soft x-ray (4000 eV). This wide energy range could be achieved by employing two undulators and two monochromators. Two different energy range undulators were installed tandem to a 9-meter straight section of PF storage ring. The 1{sup st} undulator is for VUV (30 eV) to SX (280 eV), while the other one is for SX (280 eV) to HX (4000 eV). It is also necessary to be equipped with two different monochrometors for energy above and under 2000 eV; grating monochrometor and double crystal monochrometor. One of the main purposes of this bemaline is spectroscopic study of light elements contained in several functional materials. The beamline is designed for photoemission spectroscopy (PES), X-ray absorption fine structure (XAFS) and other types of experiments. The performance of the new beamline is reported and typical examples of its application to material science are demonstrated.

43 PARTICLE ACCELERATORS↗
DOE OSTI2016

The polar 2e/12c bond in phenalenyl-azaphenalenyl hetero-dimers: Stronger stacking interaction and fascinating interlayer charge transfer

An increasing number of chemists have focused on the two-electron/multicenter bond (2e/mc) that was first introduced to interpret the bonding mechanism of radical dimers. Herein, we report the polar two-electron/twelve center (2e/12c) bonding character in a series of phenalenyl-azaphenalenyl radical hetero-dimers. Interestingly, the bonding energy of weaker polar hetero-dimer (P-TAP) is dominated by the overlap of the two different singly occupied molecular orbital of radicals, while that of stronger polar hetero-dimer (P-HAP) is dominated by the electrostatic attraction. Results show that the difference between the electronegativity of the monomers plays a prominent role in the essential attribution of the polar 2e/12c bond. Correspondingly, a stronger stacking interaction in the hetero-dimer could be effectively achieved by increasing the difference of nitrogen atoms number between the monomers. It is worthy of note that an interesting interlayer charge transfer character is induced in the polar hetero-dimers, which is dependent on the difference between the electronegativity of the monomers. It is our expectation that the new knowledge about the bonding nature of radical hetero-dimers might provide important information for designing radical based functional materials with various applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗