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At least 991 records · Page 55
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Excitonic Spin-Coherence Lifetimes in CdSe Nanoplatelets Increase Significantly with Core/Shell Morphology

Here, we report spin-polarized transient absorption for colloidal CdSe nanoplatelets as functions of thickness (2–6 monolayer thickness) and core/shell motif. Using electro-optical modulation of co- and cross-polarization pump–probe combinations, we sensitively observe spin-polarized transitions. Core-only nanoplatelets exhibit few-picosecond spin lifetimes that weakly increase with layer thickness. The spectral content of differenced spin-polarized signals indicate biexciton binding energies that decrease with increasing thickness and smaller values than previously reported. Shell growth of CdS with controlled thicknesses, which partially delocalize the electron from the hole, significantly increases the spin lifetime to ~49 ps at room temperature. Implementation of ZnS shells, which do not alter delocalization but do alter surface termination, increased spin lifetimes up to ~100 ps, bolstering the interpretation that surface termination heavily influences spin coherence, likely due to passivation of dangling bonds. Spin precession in magnetic fields both confirms long coherence lifetime at room temperature and yields the excitonic g factor.

2D semiconductor↗
DOE OSTI2023

Intrinsic Formamidinium Tin Iodide Nanocrystals by Suppressing the Sn(IV) Impurities

The long search for non-toxic alternatives to lead halide perovskites (LHPs) has shown that some compelling properties of LHPs, such as low effective masses of carriers, can only be attained in their closest Sn(II) and Ge(II) analogs, despite their tendency to oxidation. Judicious choice of chemistry allowed formamidinium tin iodide (FASnI 3 ) to reach a power conversion efficiency of 14.81% in photovoltaic devices. This progress motivated us to develop a synthesis of colloidal FASnI 3 NCs with a concentration of Sn(IV) reduced to an insignificant level and probe their intrinsic structural and optical properties. Intrinsic FASnI 3 NCs exhibit unusually low absorption coefficients of 4 x 10 3 cm -1 at the first excitonic transition, a 190 meV increase of the bandgap as compared to the bulk material, and a lack of excitonic resonances. These features are attributed to a highly disordered lattice, distinct from the bulk FASnI 3 as supported by structural characterizations and first-principles calculations.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Infrared Imaging Using Thermally Stable HgTe/CdS Nanocrystals

Transferring nanocrystals (NCs) from the laboratory environment toward practical applications has raised new challenges. HgTe appears as the most spectrally tunable infrared colloidal platform. Its low-temperature synthesis reduces the growth energy cost yet also favors sintering. Once coupled to a read-out circuit, the Joule effect aggregates the particles, leading to a poorly defined optical edge and large dark current. Here, in this study, we demonstrate that CdS shells bring the expected thermal stability (no redshift upon annealing, reduced tendency to form amalgams, and preservation of photoconduction after an atomic layer deposition process). The electronic structure of these confined particles is unveiled using k.p self-consistent simulations showing a significant exciton binding energy of ~ 200 meV. After shelling, the material displays a p-type behavior that favors the generation of photoconductive gain. The latter is then used to increase the external quantum efficiency of an infrared imager, which now reaches 40% while presenting long-term stability.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Quantifying Size Effects on Thermal Transport in CsPbBr 3 Nanocrystal Films

Colloidal lead halide perovskite nanocrystals (LHP NCs) are promising semiconductor materials for optoelectronic applications due to their strong quantum confinement, near-unity photoluminescence quantum yields, and tunable emission characteristics. However, their modest thermal stability remains a challenge, particularly at smaller core diameters due to enhanced phonon scattering at inorganic core-organic ligand interfaces. In this work, we directly quantify size-dependent thermal conductivity (κ) in lecithin-capped CsPbBr 3 NC thin films using a transducer-free, vibrational pump–visible probe (VPVP) spectroscopy technique. A mid-infrared pump thermally excites the ligand shell, while a broadband probe tracks transient reflectance change correlated to lattice temperature decay. Finite-element modeling of the decay dynamics yields κ values from 0.13 to 0.16 W·m –1 ·K –1 for NC films with sub-10 nm core diameter, significantly lower than those of its bulk counterpart. A steep κ suppression with decreasing NC size emphasizes the dominant role of ligand shells and boundary effects in thermal transport.

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

CdSe Magic-Size Clusters Deviate from Nanocrystal-Size Scalings for Ultrafast Intraband Relaxation and Auger Recombination

The cluster regime of colloidal semiconductor quantum dots (QDs) occupies an interesting space on the continuum from molecule to bulk material and allow the study of QD properties at extreme quantum confinement limits. For typical QDs, several size-dependent property trends are well established including intraband relaxation rates and universal scaling of Auger recombination with particle volume. Advances in synthesis now allow isolation of atomically precise semiconductor magic-size clusters (MCs), which offer experimental insight regarding how electronic structure changes with particle size in the ultrasmall limit. Here, we report intraband cooling and Auger recombination for several stable CdSe MCs as a function of particle size and observe deviation from QD response in the cluster regime. We additionally show optical signatures ascribed to transient disordering 2 that appear in the single exciton regime for MCs, which point to complexities regarding their implementation.

Auger recombination↗
DOE OSTI2025

Automated Nanocrystal Synthesis: Lessons from 25 Years of Robots, Microfluidics, and Machine Learning

Here, this perspective highlights the evolution of techniques for automating the synthesis of colloidal nanocrystals. Over the past 25 years, microfluidic reactors and robotic workflows have been developed to enhance the reproducibility of nanocrystal synthesis, facilitate rapid screening of reaction conditions, optimize material properties, and perform multistep syntheses of high-quality nanoparticles with complex heterostructures. Modern automated systems are now valued for their ability to generate robust data sets for validating physical models, supporting chemical mechanisms, training machine learning models, and for directing autonomous experimentation. We discuss the early challenges and limitations of these technologies and present key lessons for effectively utilizing automated and ML-guided tools to accelerate nanocrystal discovery for the next 25 years.

Nanocrystals↗
DOE OSTI2026

Nanorod Pair Complexes Manipulated via Magnetic Casimir Forces

Here, we demonstrate a route to modulate Casmir–Lifshitz interactions between anisotropic nanoparticles and magnetic fluids. By semiclassical quantum electrodynamics, we study ground state dispersion forces for cylindrical dielectric nanorods made of polystyrene (PS) and zinc oxide (ZnO) embedded in toluene-based host media with gold-coated magnetite nanoparticles and also predict magnetic contributions to the fully retarded excited state interaction. The variation in magnetic permeability enables tuning between repulsive and attractive interactions, and measurable magnetic Casimir traps are predicted between a pair of ZnO–PS nanoparticles whose equilibrium position can be modulated over an order of magnitude with a small variation in the size of the magnetite nanoparticle. This provides an alternative magnetic Casimir-effect pathway to reversibly tune quantum electromagnetic forces at the nanoscale for the assembly and enhancement of colloidal stability.

Excited-state interaction↗
DOE OSTI2021

Phase-Controlled Synthesis of Pd–Sn Nanocrystal Catalysts of Defined Size and Shape

Bimetallic Pd-based nanoparticles (NPs) are of interest as electrocatalysts for formic acid electrooxidation (FAEO) because of their higher initial catalytic activity and CO tolerance when compared to Pt. Intermetallic NPs (i-NPs) with specific geometric and electronic structures generally exhibit superior catalytic activity, selectivity, and durability when compared to their disordered (random alloy) counterparts; however, the colloidal synthesis of i-NPs remains a challenge. Here, a one-pot method was demonstrated as a facile route to obtain monodisperse Pd–Sn NPs with phase control, including intermetallic hexagonal Pd 3 Sn 2 (P6 3 /mmc), intermetallic orthorhombic Pd 2 Sn (Pnma), and alloy cubic Pd 3 Sn (FCC, Fm 3 ¯m) as size-controlled NPs with quasi-spherical shapes. Initial metal precursor ratios and reaction temperature were critical parameters to achieving phase control. Also, slight modifications of synthetic conditions resulted in either Pd 2 Sn nanorhombohedra or nanorods with tunable aspect ratios. A systematic evaluation of the Pd–Sn NPs for FAEO showed that most presented higher specific activities when compared to commercial Pd/C, in which Pd 2 Sn quasi-spheres and nanorhombohedra showed the highest catalytic activity for FAEO. Furthermore, these results highlight the benefits of phase-controlled Pd-based nanocatalysts with defined nanocrystal size and shape, with use of trioctylphospine (TOP) and oleic acid (OA) central to shape and size control.

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

Coaxial Ceramic Direct Ink Writing on Heterogenous and Rough Surfaces: Investigation of Core–Shell Interactions

In this work, coaxial conductor–ceramic direct ink writing enables the printing of sensitive or encapsulated materials onto heterogeneous and rough substrates. While encasing the core fluid within a stiff ceramic shell, continuity may be maintained, even while printing onto conventionally challenging substrates. Here, we report the development of a coaxial ceramic direct ink writing suite and explore coflow interrelationships based on microfluidic principles. A coaxial nozzle is designed to facilitate the coextrusion of an alumina shell, whereas indium–tin-oxide inks constitute the core. In this manner, a core–shell ceramic element may be printed onto rough substrates for future high-temperature applications. Colloidal inks are engineered to provide the required rheological and sintering performance. Moreover, flow simulations in conjunction with microfluidic coflow principles are used to explore the coaxial printing processing space, thus controlling the core–shell architectures. Physical modeling is further used to analyze core deformations and eccentricity. As a result, simulations are validated experimentally, and the analyses are used to deposit coaxial ceramic features onto heterogeneous, high-temperature ceramic substrates.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2022

One-Step Ligand-Exchange Method to Produce Quantum Dot–DNA Conjugates for DNA-Directed Self-Assembly

To address the current challenges in making bright, stable, and small DNA-functionalized quantum dots (QDs), we have developed a one-step ligand-exchange method to produce QD–DNA conjugates from commonly available hydrophobic QDs. We show that by systematically adjusting the reaction conditions such as ligand-to-nanoparticle molar ratio, pH, and solvent composition, stable and highly photoluminescent water-soluble QD–DNA conjugates with relatively high ligand loadings can be produced. Moreover, by site specifically binding these QD–DNA conjugates to a DNA origami template, we demonstrate that these bioconjugates have sufficient colloidal stability for DNA-directed self-assembly. Fluorescence quenching by an adjacent gold nanoparticle (AuNP) was demonstrated. Such QD–AuNP dimers may serve as biosensors with improved sensitivity and reproducibility. Furthermore, our simple method can facilitate the assembly of QDs into more complex superlattices and discrete clusters that may enable novel photophysical properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Ultrastable Gold Nanostars via Bottlebrush-like Block Copolymers

Gold (Au) nanostars are plasmonic nanostructures possessing potentials for small molecule detection, photocatalytic activities, and photothermal therapy. However, Au nanostars synthesized in the traditional way are often plagued by poor photo, thermal, and chemical stabilities. Here, we report an unconventional route to the synthesis of ultrastable colloidal Au nanostars enabled by bottlebrush-like block copolymers (BBCPs), dispensing with the need for Au seeds. Crafting of Au nanostars using BBCPs is rendered by bridging the latter with Au 3+ ions as cross-linkers that have multiple coordination sites. Notably, the presence of a covalently tethered polymer shell on the surface of Au nanostars (i.e., polymer-ligated Au nanostars) imparts remarkably high stability under high temperature and laser excitation over conventional cetyltrimethylammonium bromide (CTAB)-mediated Au nanostars. Due to enhanced laser stability, plasmonic fields near Au nanostars can be visualized under high laser fluence by ultrafast electron microscopy (UEM) without morphological degradation. Notably, the presence of insulating polystyrene chains does not compromise the plasmonic field distribution, with the highest field intensity observed along the star arms. In conclusion, the greatly improved long-term photo, thermal, and chemical stabilities make Au nanostars a prospective noble metal nanomaterial for a range of sensing applications.

Cellulose↗
DOE OSTI2025

Sensitized Near-Infrared Emission of SiGe Nanocrystals via Heterostructuring with Quasi Two-Dimensional Perovskite

The near-infrared (NIR) emission of silicon–germanium alloy nanocrystals (SiGe NCs) was sensitized by heterostructuring with a quasi two-dimensional (Q-2D) perovskite (CsPbBr 3 blended with butylammonium bromide (BABr)). Colloidal SiGe NCs were synthesized by using a nonthermal plasma method with chloride precursors. As-synthesized SiGe NCs showed no detectable photoluminescence (PL). Embedding the SiGe NCs within the perovskite matrix via spin coating led to a heterostructure exhibiting dual emissions: green emission at 520 nm from the perovskite and NIR emission at 1035 nm from the SiGe NCs. Time-integrated and resolved PL measurements and transient absorption spectroscopy revealed energy transfer from the perovskite to the SiGe NCs, which sensitized the NIR emission from the SiGe NCs and quenched the green PL for the perovskite. These results demonstrate that Ge alloying can effectively tune the bandgap of Si NCs and highlight the feasibility of heterostructuring perovskites and photoluminescent NCs to enhance or activate their PL. In conclusion, this approach broadens their potential applications in the NIR region.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Pathways of CdS Quantum Dot Degradation during Photocatalysis: Implications for Enhancing Stability and Efficiency for Organic Synthesis

CdS quantum dots (QDs) are widely employed as photocatalysts for reactions such as hydrogen evolution, and their degradation under aerobic aqueous conditions is well understood. However, despite evidence of aggregation and precipitation of CdS QD photocatalysts under anaerobic conditions, catalyst speciation and degradation under such conditions are underexplored. In this work, we demonstrate that during a reductive dehalogenation reaction, CdS QDs undergo surface ligand etching, which leads to a loss of colloidal stability and the formation of microcrystalline cadmium metal deposits. We hypothesize that this results from the accumulation of electrons on the QD surface. In addition, we demonstrate mild surface sulfur oxidation and the formation of an ammonium salt byproduct of a commonly used hole quencher. Furthermore, this work adds to our atomic-level understanding of the reactions occurring at the QD surface during photocatalysis, so that we can design more stable and efficient photocatalysts for organic synthesis.

cadmium sulfide↗
DOE OSTI2024

Single-Step Nonthermal Plasma Synthesis of Water-Soluble and Near-Infrared-Emitting Si Quantum Dots for Bioimaging Applications

Here, we present a single-step nonthermal plasma method for the synthesis of near-infrared (NIR)-emitting and water-soluble Si quantum dots (QDs) for bioimaging applications. Oxygen gas and water vapor were introduced together with acrylic acid (AA) into the afterglow region of the synthesis plasma leading to the surface functionalization of the upstream synthesized Si QDs. The simultaneous surface oxidation and ligand grafting enabled solubility and colloidal stability of the Si QDs in water, as evidenced by strongly reduced hydrodynamic diameters. Aged Si QDs in water emitted NIR photoluminescence (PL) at around 830 nm. The PL quantum yield of the Si QDs in water increased over time from initially undetectable to ~30% after 8 days. Cell viability tests showed that >70% of 3T3 cells survived for 24 h at a concentration of 200 μg/mL of oxidized AA grafted Si QDs. The water solubility, NIR emission with a high quantum yield, and cell viability make the Si QDs promising for bioimaging applications.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Self-Assembly Interactions in Magnetite-Coated Cellulose Nanocrystals: Implications for Magnetic Hyperthermia Applications

Magnetic cellulose nanocrystal (MCNC) nanocomposites are promising sustainable and biocompatible platforms for magnetic hyperthermia; however, the molecular mechanisms governing Fe 3 O 4 adsorption and deposition onto CNCs remain poorly understood. Here, sulfated (S-CNC) and TEMPO-oxidized CNCs (T-CNC) were used to prepare nanocomposites at 1:2 and 1:4 CNC:Fe 3 O 4 mass ratios, enabling a systematic evaluation of how surface chemistry and nanoparticle loading dictate interfacial interactions and magneto-colloidal behavior. Bare magnetite nanoparticles were 21 ± 5 nm by TEM but grew to 144 ± 18 in the DLS measurement at pH 7. The S-CNC nanocomposites had hydrodynamic sizes between 144 and 210 nm, not much larger than the 140 nm long CNC rods, suggesting an enhanced dispersion stability compared to Fe3O4 alone. X-ray photoelectron spectroscopy combined with density functional theory revealed that −OH and −COOH groups drive electrostatic adsorption with charge transfer from Fe 3 O 4 to the CNC surface, while T-CNCs showed more favorable adsorption energies and evidence of covalent Fe−O bonding. Vibrating sample magnetometry demonstrated superparamagnetic behavior for all samples, with S-CNC/Fe 3 O 4 1:4 and 1:2 displaying saturation magnetizations of 78 and 77 emu/g-Fe 3 O 4 , close to the 83 emu/g of bare magnetite. The T-CNC composites showed lower (60 and 66 emu/g-Fe3O4) saturation magnetizations. Zero-field-cooled/field-cooled measurements resulted in a blocking temperature of 112 K for all samples, except T-CNC/Fe 3 O 4 1:2 (100 K). Magnetic hyperthermia studies revealed that specific absorption rate (SAR) increased with field strength and Fe 3 O 4 content; however, S-CNC/Fe 3 O 4 (1:2) achieved the highest intrinsic SAR per gram of Fe 3 O 4 (649 W/g-Fe 3 O 4 ) likely due to its anisotropy and fast magnetic relaxation. Cytotoxicity assays confirmed that all nanocomposites were nontoxic toward mammalian cells. These results establish quantitative structure−property relationships between CNC surface chemistry, interfacial bonding mechanisms, and magnetic heating performance, providing a foundation for rational design of biocompatible magnetic nanocomposites for hyperthermia and related applications.

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

SI-PET-RAFT Polymerization via Electrodeposited Macroinitiator Thin Films: Toward Biomedical and Sensing Applications

Surface-initiated photoinduced electron transfer-reversible addition–fragmentation chain transfer (SI-PET-RAFT) polymerization has been preferentially used for preparing thin polymeric film coatings due to its simple execution under ambient conditions (e.g., in air) and visible light requirement. In this study, we demonstrate the preparation of polymer brushes by SI-PET-RAFT polymerization on a thin macroinitiator film electrodeposited on electrically conductive indium tin oxide and gold surfaces. An electrochemically active carbazole-containing chain transfer agent as macroinitiator was shown to be not only effective in mediating SI-PET-RAFT polymerization for various monomers but also capable of forming block copolymers. Additionally, the fabricated polymer brush films were able to encapsulate colloidal gold nanoparticles, thereby demonstrating potential use for biomedical and sensing applications.

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

Facet Impact of CuMn 2 O 4 Spinel Nanocatalysts on Enhancement of the Oxygen Reduction Reaction in Alkaline Media

Surface-structure engineering represents an attractive strategy to optimize the energy conversion performance of nanocatalysts using their deliberately controlled exposed facets. To further exploit the potential of non-PGM-based spinel catalysts for alkaline oxygen reduction reaction (ORR), a cathodic fuel cell reaction, we hereby report a strategy of ORR improvement by controlling the crystallographic facets of ultra-small CuMn 2 O 4 spinel nanocatalysts through a developed colloidal synthesis approach. The synthesis of CuMn 2 O 4 nanocrystals with morphological control relies on the design and selection of the Cu-/Mn-precursors with striking discrepancies in reaction kinetics. Following carbon loading and an annealing post-treatment of the as-synthesized nanocatalysts, the exclusively {101} facet-exposed CuMn 2 O 4 spinel nano-octahedra exhibit improved electrocatalytic activity toward ORR in 1 M KOH, when compared to their spherical counterparts, exhibiting a mass activity (MA) of 37.6 A/g at 0.85 V. After 10,000 cycles of ORR durability test, the nano-octahedra still retain an MA of 24.5 A/g, which is twice that of the CuMn 2 O 4 spinel nanospheres. Structural characterizations after durability testing indicate that the MA decay is likely associated with a decrease in the Mn 3+ fraction and the emergence of Cu + on CuMn 2 O 4 nano-octahedral surfaces. Finally, as a paradigm, this synthesis approach could be extended to other Mn-based spinel nanocatalysts with precise shape control, enabling us to understand and establish the relationship between the surface lattice/valence state and electrocatalytic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Hydrogen Dissociation Controls 1-Hexyne Selective Hydrogenation on Dilute Pd-in-Au Catalysts

Increasing the selectivity of the catalytic hydrogenation of alkynes to alkenes is of major importance for the processing of petrochemicals and the production of fine chemicals. Achieving high selectivity for alkene formation at high conversions, however, remains a long-standing challenge in heterogeneous catalysis. Here, the mechanism and origin of the high selectivity of dilute Pd-in-Au catalysts has been studied by a combination of first-principles calculations, microkinetic simulations, and isotopic exchange hydrogenation experiments using Pd 0.04 Au 0.96 nanoparticles embedded in raspberry colloid-templated silica. The Pd is predominantly in the form of isolated atoms, only surrounded by Au atoms, based on prior studies. The simulations indicate that the rate-limiting process for 1-hexyne hydrogenation on Pd monomers in Au(111) is H 2 dissociation, which has a large free energy barrier of 0.86 eV at 363 K and 0.2 bar of H 2 . The C–H bond formation steps, on the other hand, proceed with lower barriers, which contrasts with previous studies of extended Pd catalysts. The microkinetic simulations identify the sizable H 2 dissociation barrier and the small barrier for the hydrogenation of 1-hexyne as key factors that lead to a high selectivity for the production of 1-hexene from 1-hexyne, even at high conversion. The unconventional H 2 dissociation limiting process in combination with the low coverage of weakly bound hydrocarbon intermediates explains the near-zero order of 1-hexyne found experimentally. Furthermore, the partial hydrogenation of 1-hexyne to form 1-hexene is shown to be an irreversible process from our isotopic exchange hydrogenation experiments and is explained by the strongly exothermic nature of the reaction. Diluting active species, like Pd, in a less active host metal, like Au, hence appears promising as a means of tuning the binding energy of reactants and altering reaction profiles, leading to distinct kinetic behavior for an optimal catalytic activity and selectivity. Furthermore, the combination of microkinetic modeling, density functional theory calculations, and isotopic exchange experiments is thus demonstrated to be an effective approach to modeling important catalytic phenomena.

1-hexyne↗