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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 1,477 records · Page 82
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Crystalline oligo(ethylene sulfide) domains define highly stable supramolecular block copolymer assemblies.

With proper control over copolymer design and solvation conditions, self-assembled materials display impressive morphological variety that encompasses nanoscale colloids as well as bulk three-dimensional architectures. Here we take advantage of both hydrophobicity and crystallinity to mediate supra-molecular self-assembly of spherical micellar, linear fibrillar, or hydrogel structures by a family of highly asymmetric poly(ethylene glycol)-b-oligo(ethylene sulfide) (PEG-OES) copolymers. Assembly structural polymorphism was achieved with modification of PEG-OES topology (linear versus multiarm) and with precise, monomer-by-monomer control of OES length. Notably, all three morphologies were accessed utilizing OES oligomers with degrees of polymerization as short as three. These exceptionally small assembly forming blocks represent the first application of ethylene sulfide oligomers in supramolecular materials. While the assemblies demonstrated robust aqueous stability over time, oxidation by hydrogen peroxide progressively converted ethylene sulfide residues to increasingly hydrophilic and amorphous sulfoxides and sulfones, causing morphological changes and permanent disassembly. We utilized complementary microscopic and spectroscopic techniques to confirm this chemical stimulus-responsive behavior in self-assembled PEG-OES colloidal dispersions and physical gels. In addition to inherent stimulus-responsive behavior, fibrillar assemblies demonstrated biologically relevant molecular delivery, as confirmed by the dose-dependent activation of murine bone marrow-derived dendritic cells following fibril-mediated delivery of the immunological adjuvant monophosphoryl lipid A. In physical gels composed of either linear or multiarm PEG-OES precursors, rheologic analysis also identified mechanical stimulus-responsive shear thinning behavior. Thanks to the facile preparation, user-defined morphology, aqueous stability, carrier functionality, and stimuli-responsive behaviors of PEG-OES supramolecular assemblies, our findings support a future role for these materials as injectable or implantable biomaterials.

cylindrical micelle↗
DOE OSTI2015

Plasmon–Exciton Interactions Probed Using Spatial Coentrapment of Nanoparticles by Topological Singularities

We study plasmon-exciton interaction by using topological singularities to spatially confine, selectively deliver, cotrap and optically probe colloidal semiconductor and plasmonic nanoparticles. The interaction is monitored in a single quantum system in the bulk of a liquid crystal medium where nanoparticles are manipulated and nanoconfined far from dielectric interfaces using laser tweezers and topological configurations containing singularities. When quantum dot-in-a-rod particles are spatially colocated with a plasmonic gold nanoburst particle in a topological singularity core, its fluorescence increases because blinking is significantly suppressed and the radiative decay rate increases by nearly an order of magnitude owing to the Purcell effect. We argue that the blinking suppression is the result of the radiative rate change that mitigates Auger recombination and quantum dot ionization, consequently reducing nonradiative recombination. Our work demonstrates that topological singularities are an effective platform for studying and controlling plasmon-exciton interactions.

14 SOLAR ENERGY↗
DOE OSTI2016

Quantum Yield Heterogeneity among Single Nonblinking Quantum Dots Revealed by Atomic Structure-Quantum Optics Correlation

Physical variations in colloidal nanostructures give rise to heterogeneity in expressed optical behavior. This correlation between nanoscale structure and function demands interrogation of both atomic structure and photophysics at the level of single nanostructures to be fully understood. In this paper, by conducting detailed analyses of fine atomic structure, chemical composition, and time-resolved single-photon photoluminescence data for the same individual nanocrystals, we reveal inhomogeneity in the quantum yields of single nonblinking “giant” CdSe/CdS core/shell quantum dots (g-QDs). We find that each g-QD possesses distinctive single exciton and biexciton quantum yields that result mainly from variations in the degree of charging, rather than from volume or structure inhomogeneity. We further establish that there is a very limited nonemissive “dark” fraction (<2%) among the studied g-QDs and present direct evidence that the g-QD core must lack inorganic passivation for the g-QD to be “dark”. Finally and therefore, in contrast to conventional QDs, ensemble photoluminescence quantum yield is principally defined by charging processes rather than the existence of dark g-QDs.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Understanding the Role of Solvation Forces on the Preferential Attachment of Nanoparticles in Liquid

Optimization of colloidal nanoparticle synthesis techniques requires an understanding of underlying particle growth mechanisms. Non-classical growth mechanisms are particularly important as they affect nanoparticle size and shape distributions which in turn influence functional properties. For example, preferential attachment of nanoparticles is known to lead to the formation of mesocrystals, although the formation mechanism is currently not well understood. Here we employ in situ liquid cell scanning transmission electron microscopy (STEM) and steered molecular dynamics (SMD) simulations to demonstrate that the experimentally observed preference for end-to-end attachment of silver nanorods is a result of weaker solvation forces occurring at rod ends. SMD reveals that when the side of a nanorod approaches another rod, perturbation in the surface bound water at the nanorod surface creates significant energy barriers to attachment. Additionally, rod morphology (i.e. facet shape) effects can explain the majority of the side attachment effects that are observed experimentally.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2025

Design of Zn Chalcogenide Shells for Emissive Ga-Rich In 1– X Ga X As Quantum Dots Synthesized in Molten Salts

Colloidal quantum dots (QDs) have seen expanded applications in optoelectronics from visible to near-infrared (NIR) wavelengths. However, the options for QDs with bright and size-tunable emission in the NIR region are mostly limited to heavy-metal-based (Pb, Cd, Hg) semiconductors. Here, Ga-rich In 1–X Ga X As QDs with zinc chalcogenide shells are demonstrated as candidates for NIR emitters. Based on new developments in inorganic molten salt chemistry, we synthesized colloidal In 1–X Ga X As QDs containing up to 85% gallium with high crystallinity based on Raman and XRD analyses. Zinc selenide and sulfide shells with different morphologies were grown on In 1–X Ga X As QDs by controlling the Zn precursor chemistry. Despite the nominally reduced lattice mismatch in the In 1–X Ga X As/ZnSe heterostructure, a ZnS shell was found to be a much more effective passivation material: In 1–X Ga X As/ZnS core–shell QDs show a photoluminescence quantum yield (PL QY) of about 30% versus 11% for ZnSe shells. In conclusion, based on the analysis of PL decay and transient absorption (TA) dynamics, we surmise that electron trapping is the major reason for efficiency loss, providing a clear heterostructure design principle for realizing efficient NIR-emitting In 1–X Ga X As QDs.

Electron trapping↗
DOE OSTI2017

Speed Limit for Triplet-Exciton Transfer in Solid-State PbS Nanocrystal-Sensitized Photon Upconversion

Hybrid interfaces combining inorganic and organic materials underpin the operation of many optoelectronic and photocatalytic systems and allow for innovative approaches to photon up- and down-conversion. However, the mechanism of exchange-mediated energy transfer of spin-triplet excitons across these interfaces remains obscure, particularly when both the macroscopic donor and acceptor are composed of many separately interacting nanoscopic moieties. Here, we study the transfer of excitons from colloidal lead sulfide (PbS) nanocrystals to the spin-triplet state of rubrene molecules. By reducing the length of the carboxylic acid ligands on the nanocrystal surface from 18 to 4 carbon atoms, thinning the effective ligand shell from 13 to 6 Å, we are able to increase the characteristic transfer rate by an order of magnitude. However, we observe that the energy transfer rate asymptotes for shorter separation distances (≤10 Å) which we attribute to the reduced Dexter coupling brought on by the increased effective dielectric constant of these solid-state devices when the aliphatic ligands are short. This implies that the shortest ligands, which hinder long-term colloidal stability, offer little advantage for energy transfer. Indeed, we find that hexanoic acid ligands are already sufficient for near-unity transfer efficiency. Using nanocrystals with these optimal-length ligands in an improved solid-state device structure, we obtain an upconversion efficiency of (7 ± 1)% with excitation at λ = 808 nm.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Infrared Quantum Dots: Progress, Challenges, and Opportunities

Infrared technologies provide tremendous value to our modern-day society. The need for easy-to-fabricate, solution-processable, tunable infrared active optoelectronic materials has driven the development of infrared colloidal quantum dots, whose band gaps can readily be tuned by dimensional constraints due to the quantum confinement effect. In this Perspective, we summarize recent progress in the development of infrared quantum dots both as infrared light emitters (e.g., in light-emitting diodes, biological imaging, etc.) as well as infrared absorbers (e.g., in photovoltaics, solar fuels, photon up-conversion, etc.), focusing on how fundamental breakthroughs in synthesis, surface chemistry, and characterization techniques are facilitating the implementation of these nanostructures into exploratory device architectures as well as in emerging applications. We discuss the ongoing challenges and opportunities associated with infrared colloidal quantum dots.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Enhancing Lignin Dispersion and Bioconversion by Eliminating Thermal Sterilization

Thermal sterilization is widely applied in fermentation to ensure a pure culture. In this study, a facile and energy-efficient strategy by eliminating thermal sterilization (ETS) was unveiled for upgrading lignin bioconversion. Through alkaline solubilization and neutralization, lignin dispersion in aqueous fermentation media was significantly enhanced by ETS. Small-angle X-ray scattering and dynamic light scattering analyses indicated that the lignin colloid size was dramatically reduced. Compared to 20.5 wt % lignin precipitation during the conventional thermal sterilization, precipitated lignin was not observed within the ETS medium. 31P NMR characterization demonstrated an 11.7% increase of phenolic OH in ETS lignin. Ionization of phenolic OH presented more negatively charged groups, strengthening electrostatic repulsion, resulting in smaller colloidal particles. Interestingly, the pure culture of Rhodococcus opacus PD630 was achieved within the ETS medium due to the lack of lignin degradation ability with most natural microbes. R. opacus PD630 cell amount, lignin degradation, and lipid production by ETS increased by 330, 16.6, and 20.7%, respectively. Overall, an energy-efficient ETS strategy that promoted lignin dispersion and bioconversion significantly is reported in this study.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Epitaxial Growth of Three-Dimensionally Mesostructured Single-Crystalline Cu 2 O via Templated Electrodeposition

Significant efforts have been made over the past few decades to realize functional three-dimensional photonic crystal devices including zero-threshold lasers, waveguides, light-emitting diodes (LEDs), and solar cells; however, progress has been limited because of difficulties in creating three-dimensional photonic crystals from single-crystal materials. Most have been formed from polycrystalline materials and thus have generally exhibited poor electronic properties. Realization of materials containing complex three-dimensional mesostructures, in single-crystal form, remains a significant challenge. Furthermore, we demonstrate the epitaxial growth of three-dimensionally mesostructured Cu 2 O by bottom-up electrodeposition through a 3D silica colloidal template. Not only is the templated Cu 2 O single crystal, but when the electrodeposition continues past the colloidal template, the crystallinity of the overlying solid Cu 2 O appears to be improved because the template blocks threading dislocations, resulting in substantial reductions in the dislocation density of the overlying solid Cu 2 O.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Nanoparticle Superlattices through Template-Encoded DNA Dendrimers

The chemical interactions that lead to the emergence of hierarchical structures are often highly complex and difficult to program. In this paper, the synthesis of a series of superlattices based upon 30 different structurally reconfigurable DNA dendrimers is reported, each of which presents a well-defined number of single-stranded oligonucleotides (i.e., sticky ends) on its surface. Such building blocks assemble with complementary DNA-functionalized gold nanoparticles (AuNPs) to yield five distinct crystal structures, depending upon choice of dendrimer and defined by phase symmetry. These DNA dendrimers can associate to form micelle-dendrimers, whereby the extent of association can be modulated based upon surfactant concentration and dendrimer length to produce a low-symmetry Ti5Ga4-type phase that has yet to be reported in the field of colloidal crystal engineering. Taken together, colloidal crystals that feature three different types of particle bonding interactions.template-dendron, dendrimer-dendrimer, and DNA-modified AuNP-dendrimer.are reported, illustrating how sequence-defined recognition and dynamic association can be combined to yield complex hierarchical materials.

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

Ethanol-Induced Condensation and Decondensation in DNA-Linked Nanoparticles: A Nucleosome-like Model for the Condensed State

Inspired by the conventional use of ethanol to induce DNA precipitation, ethanol condensation has been applied as a routine method to dynamically tune “bond” lengths (i.e., the surface-to-surface distances between adjacent nanoparticles that are linked by DNA) and thermal stabilities of colloidal crystals involving DNA-linked nanoparticles. However, the underlying mechanism of how the DNA bond that links gold nanoparticles changes in this class of colloidal crystals in response to ethanol remains unclear. Here, we conducted a series of all-atom molecular dynamic (MD) simulations to explore the free energy landscape for DNA condensation and decondensation. Our simulations confirm that DNA condensation is energetically much more favorable under 80% ethanol conditions than in pure water, as a result of ethanol’s role in enhancing electrostatic interactions between oppositely charged species. Moreover, the condensed DNA adopts B-form in pure water and A-form in 80% ethanol, which indicates that the higher-order transition does not affect DNA’s conformational preferences. We further propose a nucleosome-like supercoiled model for the DNA condensed state, and we show that the DNA end-to-end distance derived from this model matches the experimentally measured DNA bond length of about 3 nm in the fully condensed state for DNA where the measured length is 16 nm in water. Altogether, this study provides an atomistic understanding of the mechanism underlying ethanol-induced condensation and water-induced decondensation, while our proposed nucleosome-like model allows the design of new strategies for interpreting experimental studies of DNA condensation.

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

Growth of Nanocrystal Superlattices from Liquid Crystals

The growth of superlattices (SLs) made from self-assembled nanocrystals (NCs) is a powerful method for creating new materials and gaining insight into fundamental molecular dynamics. Previous explorations of NCSL syntheses have mostly compared them to crystallization. However, NCSL synthesis has not broadly shown cooling crystallization from saturated solutions as a reversible crystallization–dissolution process. We demonstrate the reversible growth of NCSLs by dispersing NCs in liquid crystal (LC) “smart solvents,” and harnessing the transitions between the isotropic and nematic phases of the LCs. The growth mode and morphology can be tuned. Furthernore, this process is a model platform for studying crystallization and demonstrates great potential in manufacturing NCSLs as colloidal crystals through liquid-phase epitaxy or colloidal synthesis.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2015

Direct Aqueous-Phase Synthesis of Sub-10 nm “Luminous Pearls” with Enhanced in vivo Renewable Near-Infrared persistent luminescence

Near-infrared persistent luminescence nanoparticles (PLNPs) possess unique near-infrared persistent luminescence properties. They have recently been emerging as important materials for a wide variety of applications in chemistry and biology. Yet, they must endure high-temperature solid-state annealing reactions and subsequent complicated physical post-treatments. Herein, we report on a first direct aqueous-phase chemical synthesis route of NIR PLNPs and present their enhanced in vivo renewable near-infrared persistent luminescence. Our method leads to monodisperse PL nanoparticles as small as ca. 8 nm. More importantly, such sub-10 nm nanocrystals are readily dispersed, functionalized as well as form stable colloidal solutions in aqueous solution and cell culture medium for biological applications. Under bio-tissue penetrable red-light excitation, we found that such nanocrystals possess superior renewable PL photoluminescence in vitro and in vivo than current larger counterparts made by existing methods. We believe that this solid-state-reaction-free chemical approach overcomes the current key roadblock in regard to PLNP development, and thus will pave the way to broad use of these advanced miniature “luminous pearls” in photonics and biophotonics.

Luminous Pearls, Near-Infrared persistent luminesc↗
DOE OSTI2015

Shape-Controlled Narrow-Gap SnTe Nanostructures: From Nanocubes to Nanorods and Nanowires

The rational design and synthesis of narrow-gap colloidal semiconductor nanocrystals (NCs) is an important step toward the next generation of solution-processable photovoltaics, photodetectors, and thermoelectric devices. SnTe NCs are particularly attractive as a Pb-free alternative to NCs of narrow-gap lead chalcogenides. Previous synthetic efforts on SnTe NCs have focused on spherical nanoparticles. Here we report new strategies for synthesis of SnTe NCs with shapes tunable from highly monodisperse nanocubes, to nanorods (NRs) with variable aspect ratios, and finally to long, straight nanowires (NWs). Reaction at high temperature quickly forms thermodynamically favored nanocubes, but low temperatures lead to elongated particles. Transmission electron microscopy studies of reaction products at various stages of the synthesis reveal that the growth and shape-focusing of monodisperse SnTe nanocubes likely involves interparticle ripening, while directional growth of NRs and NWs may be initiated by particle dimerization via oriented attachment.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Band Gap Engineering and Metastable Phase Discovery in Cu 2 BaSnS 4– x Se x Nanocrystals via Topotactic Anion Exchange

Earth-abundant multinary inorganic chalcogenides, such as Cu 2 BaSnS 4–x Se x (CBTSSe), have emerged as promising absorbers for next-generation solar cells. However, accessing colloidal CBTSSe nanocrystals, including metastable polymorphs with more favorable optoelectronic properties, remains a critical synthetic challenge. Herein, we report the first use of topotactic anion exchange to access metastable crystal structures in soft chemistry syntheses. By varying the stoichiometry of selenium precursors, we directly synthesize Cu 2 BaSnS 4–x Se x (0 ≤ x ≤ 4) nanocrystals with a broad band gap tunability of 1.51–2.04 eV. At x = 4, a new metastable trigonal phase of Cu 2 BaSnSe 4 is isolated. This phase arises via an in-situ topotactic anion exchange from sulfur-rich Cu 2 BaSnS 4–x Se x intermediates, while retaining both the cation sublattice and overall nanocrystal morphology. The trigonal Cu 2 BaSnSe 4 exhibits a nearly direct band gap that is 280 meV lower than its thermodynamically stable orthorhombic counterpart, aligning more closely with the optimal band gap for single-junction solar cells. In contrast, a post-synthetic anion exchange route leads to the thermodynamically preferred orthorhombic polymorph, pointing to the critical nature of the in-situ transformation. Our findings open a versatile pathway for both polymorphic and morphological control in colloidal nanocrystals, expanding the synthetic design space for new optoelectronic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

DNA-Encoded Protein Janus Nanoparticles

Asymmetric functionality and directional interactions, which are characteristic of noncentrosymmetric particles, such as Janus particles, present an opportunity to encode particles with properties, but also a great synthetic challenge. Here, we exploit the chemical anisotropy of proteins, and the versatile chemistry of DNA to synthesize a protein-based Janus nanoparticle comprised of two proteins encoded with sequence-specific nucleic acid domains, tethered together by an interprotein “DNA bond”. We use these novel nanoparticles to realize a new class of three-dimensional superlattice, only possible when two sides of the particle are modified with orthogonal oligonucleotide sequences. The low symmetry, intrinsic to Janus particles, enables the realization of unprecedented multicomponent nanoparticle superlattices with unique, hexagonal layered architectures. In addition, the interprotein “DNA bond” can be modulated to selectively expand the lattice in a single direction. The results presented herein not only emphasize the power of rationally designing nanoscale building blocks to create highly engineered colloidal crystals, but also establish a precedent for applications of multidomain DNA-encoded nanoparticles, especially in the field of colloidal crystallization.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Atomically Thin Metal Sulfides

We developed a method to colloidally synthesize atomically thin metal sulfides (ATMS). Unlike conventional 2D systems such as MoS 2 and graphene, none of the systems developed here are inherently layered compounds nor have known layered polymorphs in their bulk forms. The synthesis proceeds via a cation-exchange reaction starting from single- and multi-layer Ag 2 S and going to various metal sulfides. The synthesized ATMS retain their size and shape during the cation-exchange reaction and are either single-layer or a few-layer, depending on the starting Ag 2 S samples. They have lateral dimensions on the order of 5-10 nm and are colloidally stabilized by Z- and L-type ligands. Here, we demonstrate the synthesis of single-layer and a few-layer ZnS, CdS, CoS 2 , and PbS. We find that the optical properties of these ATMS are quite distinct from the platelet or quantum-dot versions of the same metal sulfides.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Near-Infrared Photoluminescence Enhancement in Ge/CdS and Ge/ZnS Core/Shell Nanocrystals: Utilizing IV/II-VI Semiconductor Epitaxy

Ge nanocrystals have a large Bohr radius and a small, size-tunable band gap that may engender direct character via strain or doping. Colloidal Ge nanocrystals are particularly interesting in the development of near-infrared materials for applications in bioimaging, telecommunications and energy conversion. Epitaxial growth of a passivating shell is a common strategy employed in the synthesis of highly luminescent II–VI, III–V and IV–VI semiconductor quantum dots. Here, we use relatively unexplored IV/II–VI epitaxy as a way to enhance the photoluminescence and improve the optical stability of colloidal Ge nanocrystals. Selected on the basis of their relatively small lattice mismatch compared with crystalline Ge, we explore the growth of epitaxial CdS and ZnS shells using the successive ion layer adsorption and reaction method. Powder X-ray diffraction and electron microscopy techniques, including energy dispersive X-ray spectroscopy and selected area electron diffraction, clearly show the controllable growth of as many as 20 epitaxial monolayers of CdS atop Ge cores. In contrast, Ge etching and/or replacement by ZnS result in relatively small Ge/ZnS nanocrystals. The presence of an epitaxial II–VI shell greatly enhances the near-infrared photoluminescence and improves the photoluminescence stability of Ge. Ge/II–VI nanocrystals are reproducibly 1–3 orders of magnitude brighter than the brightest Ge cores. Ge/4.9CdS core/shells show the highest photoluminescence quantum yield and longest radiative recombination lifetime. Thiol ligand exchange easily results in near-infrared active, water-soluble Ge/II–VI nanocrystals. We expect this synthetic IV/II–VI epitaxial approach will lead to further studies into the optoelectronic behavior and practical applications of Si and Ge-based nanomaterials.

36 MATERIALS SCIENCE↗