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At least 127 records · Page 7

Synthetic Ligand Selection Affects Stoichiometry, Carrier Dynamics, and Trapping in CuInSe 2 Nanocrystals

CuInSe 2 nanocrystals exhibit tunable near-infrared bandgaps that bolster utility in photovoltaic applications as well as offer potential as substitutes for more-toxic Cd- and Pb-based semiconductor compositions. However, they can present a variety of defect states as well as unusual photophysics. In this work, we examine the effects of ligand composition (oleylamine, diphenylphosphine, and tributylphosphine) on carrier dynamics in these materials. Via spectroscopic measurements such as photoluminescence and transient absorption, we find that ligands present during the synthesis of CuInSe 2 nanocrystals impart non-radiative electronic states which compete with radiative recombination and give rise to low photoluminescence quantum yields. We characterize the nature of these defect states (hole vs. electron traps) and investigate whether they exist at the surface or interior of the nanocrystals. Carrier lifetimes are highly dependent on ligand identity where oleylamine-capped nanocrystals exhibit rapid trapping (< 20 ps) followed by diphenylphosphine (< 500 ps) and finally tributylphosphine (> 2 ns). A majority of carrier population localizes at indium copper antisites (electrons), copper vacancies (holes), or surface traps (electrons and/or holes), all of which are non-emissive.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dual Atomic Coherence in the Self-Assembly of Patchy Heterostructural Nanocrystals

Advances in the synthesis and self-assembly of nanocrystals have enabled researchers to create a plethora of different nanoparticle superlattices. But while many super lattices with complex types of translational order have been realized, rotational order of nanoparticle building blocks within the lattice is more difficult to achieve. Self-assembled superstructures with atomically coherent nanocrystal lattices, which are desirable due to their exceptional electronic and optical properties, have been fabricated only for a few selected systems. Here, we combine experiments with molecular dynamics (MD) simulations to study the self-assembly of heterostructural nanocrystals (HNCs), consisting of a near-spherical quantum dot (QD) host decorated with a small number of epitaxially grown gold nanocrystal (Au NC) "patches ". Self-assembly of these HNCs results in face-centered-cubic (fcc) superlattices with well-defined orientational relationships between the atomic lattices of both QD hosts and Au patches. MD simulations indicate that the observed dual atomic coherence is linked to the number, size, and relative positions of gold patches. Here this study provides a strategy for the design and fabrication of NC superlattices with large structural complexity and delicate orientational order.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Resonant Multiple-Phonon Absorption Causes Efficient Anti-Stokes Photoluminescence in CsPbBr 3 Nanocrystals

Lead halide perovskite nanocrystals, such as CsPbBr 3 , exhibit efficient photoluminescence (PL) up-conversion, also referred to as anti-Stokes photoluminescence (ASPL). This is a phenomenon where irradiating nanocrystals up to 100 meV below gap results in higher energy band edge emission. Most surprising is that ASPL efficiencies approach unity and involve single-photon interactions with multiple phonons. This is unexpected given the statistically disfavored nature of multiple-phonon absorption. Here, in this study, we report and rationalize near-unity anti-Stokes photoluminescence efficiencies in CsPbBr 3 nanocrystals and attribute them to resonant multiple-phonon absorption by polarons. The theory explains paradoxically large efficiencies for intrinsically disfavored, multiple-phonon-assisted ASPL in nanocrystals. Moreover, the developed microscopic mechanism has immediate and important implications for applications of ASPL toward condensed phase optical refrigeration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Elucidating the Role of Halides and Iron during Radiolysis-Driven Oxidative Etching of Gold Nanocrystals Using Liquid Cell Transmission Electron Microscopy and Pulse Radiolysis

Graphene liquid cell transmission electron microscopy (TEM) has enabled the observation of a variety of nanoscale transformations. Yet understanding the chemistry of the liquid cell solution and its impact on the observed transformations remains an important step toward translating insights from liquid cell TEM to benchtop chemistry. Gold nanocrystal etching can be used as a model system to probe the reactivity of the solution. FeCl 3 has been widely used to promote gold oxidation in bulk and liquid cell TEM studies, but the roles of the halide and iron species have not been fully elucidated. In this work, we observed the etching trajectories of gold nanocrystals in different iron halide solutions. We observed an increase in gold nanocrystal etch rate going from Cl - - to Br - - to I - -containing solutions. Furthermore, this is consistent with a mechanism in which the dominant role of halides is as complexation agents for oxidized gold species. Additionally, the mechanism through which FeCl 3 induces etching in liquid cell TEM remains unclear. Ground-state bleaching of the Fe(III) absorption band observed through pulse radiolysis indicates that iron may react with Cl 2 · - radicals to form an oxidized transient species under irradiation. Complete active space self-consistent field (CASSCF) calculations indicate that the FeCl 3 complex is oxidized to an Fe species with an OH radical ligand. Together our data indicate that an oxidized Fe species may be the active oxidant, while halides modulate the etch rate by tuning the reduction potential of gold nanocrystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Efficient up-conversion in CsPbBr 3 nanocrystals via phonon-driven exciton-polaron formation

Lead halide perovskite nanocrystals demonstrate efficient up-conversion, although the precise mechanism remains a subject of active research. This study utilizes steady-state and time-resolved spectroscopy methods to unravel the mechanism driving the up-conversion process in CsPbBr 3 nanocrystals. Employing above- and below-gap photoluminescence measurements, we extract a distinct phonon mode with an energy of ~7 meV and identify the Pb-Br-Pb bending mode as the phonon involved in the up-conversion process. This result was corroborated by Raman spectroscopy. We confirm an up-conversion efficiency reaching up to 75%. Transient absorption measurements under conditions of sub-gap excitation also unexpectedly reveal coherent phonons for the subset of nanocrystals undergoing up-conversion. This coherence implies that the up-conversion and subsequent relaxation is accompanied by a synchronized and phased lattice motion. This study reveals that efficient up-conversion in CsPbBr 3 nanocrystals is powered by a unique interplay between the soft lattice structure, phonons, and excited states dynamics.

Anti-Stokes Photoluminescence↗

Ligand structure and adsorption free energy of nanocrystals on solid substrates

In this paper, we present an investigation on the absorption of alkylthiolated nanocrystals on a solid substrate. We calculate adsorption free energies and report a number of effects induced by the substrate. Nearest neighbor distances and bonding free energies are significantly different than for a free floating case, there is a weakening of bonding free energies among nanocrystals, and the adsorption is manifestly anisotropic, i.e., stronger along certain directions of the nanocrystal core. We contend that this last result accounts for the Bain transition (fcc → bcc) observed in experimental results. We report the presence of vortices induced by the substrate, which explain the increased nearest neighbor distance among nanocrystals, which is in excellent quantitative agreement with experimental results and with the predictions of the Orbifold Topological Model. Implications for the assembly of nanostructures and future experiments are also discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Luminescence relaxation dynamics for planar and rolled-up CdSe nanocrystals in a photonic-crystal matrix

Samples of inverted photonic-crystal films, containing planar and rolled-up (in the form of scrolls) CdSe nanocrystals, are studied. The transmission spectra of these structures are recorded. These spectra (along with the change in colour) confirm the incorporation of nanocrystals into the films. The photoluminescence decay dynamics is investigated. It is shown that the photonic-crystal matrix affects significantly the luminescence kinetics of nanostructures. The differences in the decay curves measured for nanocrystals in a photonic-crystal matrix and for their ensemble on a glass substrate are explained by the influence of the photonic-crystal stop band and the orientational effect of crystalline matrix, which orients anisotropic nanocrystals and prevents them from aggregation. The results obtained may be important for potential applications in optoelectronic devices. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Device-quality, reconfigurable metamaterials from shape-directed nanocrystal assembly

Significance Colloidal nanocrystals with defined sizes and shapes are ideal building blocks for nanofabrication. However, the ability to arbitrarily arrange them on surfaces with control over their orientation remains elusive. Here we report a shallow-template-assisted DNA-mediated assembly strategy to precisely arrange colloidal nanocrystals on surfaces, with single-particle control across submillimeter areas. In addition, the oligonucleotide bonds between the nanocrystals and substrate can be reversibly expanded and contracted enabling postsynthetic tunability of the assembled structures. Using this approach, we synthesized a nanocrystal-based, dynamically tunable metasurface (an anomalous reflector), thereby illustrating the potential for unique device construction via DNA programmable assembly.

59 BASIC BIOLOGICAL SCIENCES↗

Intermediate Bandgap (IB) Cu 3 VS x Se 4−x Nanocrystals as a New Class of Light Absorbing Semiconductors

A new family of highly uniform, cubic-shaped Cu 3 VS x Se 4−x (CVSSe; 0 ≤ x ≤ 4) nanocrystals based on earth-abundant materials with intermediate bandgaps (IB) in the visible range is reported, synthesized via a hot-injection method. The IB transitions and optical band gap of the novel CVSSe nanocrystals are investigated using ultraviolet-visible spectroscopy, revealing tunable band gaps that span the visible and near-infrared regimes. The composition-dependent relationships among the crystal phase, optical band gap, and photoluminescence properties of the novel IB semiconductors with progressive substitution of Se by S are examined in detail. High-resolution transmission electron microscopy and scanning electron microscopy characterization confirm the high crystallinity and uniform size (~19.7 nm × 17.2 nm for Cu 3 VS 4 ) of the cubic-shaped nanocrystals. Density functional theory (DFT) calculations based on virtual crystal approximation support the experimental findings, showing good agreement in lattice parameters and band gaps across the CVSSe series and lending confidence that the targeted phases and compositions have been successfully realized. A current conversion efficiency, i.e., incident photon-to-current efficiency, of 14.7% was achieved with the p-type IB semiconductor Cu 3 VS 4 . These novel p-type IB semiconductor nanocrystals hold promise for enabling thin film solar cells with efficiencies beyond the Shockley–Queisser limit by allowing sub-band-gap photon absorption through intermediate-band transitions, in addition to the conventional direct-band-gap transition.

Cu3VSxSe4−x↗

Facile Synthesis of Rhodium‐Based Nanocrystals in a Metastable Phase and Evaluation of Their Thermal and Catalytic Properties

Abstract Controlling the polymorphism of metal nanocrystals is a promising strategy for enhancing properties and discovering new phenomena. However, previous studies on Rh nanocrystals have focused on their thermodynamically stable face‐centered‐cubic (fcc) phase. Herein, a facile synthesis of Rh‐based nanocrystals featuring the metastable hexagonal close‐packed (hcp) phase is reported by using Ru seeds in their native hcp phase to template the deposition of Rh atoms. The success of such phase‐controlled synthesis relies on the templating effect promoted by the small lattice mismatch between Ru and Rh and the slow dropwise titration of the precursor at an elevated temperature, ensuring the layer‐by‐layer growth mode and thus the formation of a conformal hcp‐Rh shell. Faster injection rate of Rh(III) precursor leads to the formation of a rough Rh shell in the conventional fcc phase due to accelerated reaction kinetics. Considering both thermodynamic and kinetic aspects of this system, the hcp‐Rh phase is favored when the low surface energy from smooth overlayers balances the high bulk energy of the metastable phase, achieved through tight control of reaction rates and deposition patterns. These Ru hcp @Rh hcp core–shell nanocrystals demonstrate thermal stability up to 400 °C, while exhibiting higher catalytic activity toward ethanol oxidation reaction compared to Ru hcp @Rh fcc counterparts.

Nguyen, Quynh N.↗

X-ray diffraction and in situ pressurization of dentine apatite reveals nanocrystal modulus stiffening upon carbonate removal

Bone-like materials comprise carbonated-hydroxyapatite nanocrystals (c-Ap) embedding a fibrillar collagen matrix. The mineral particles stiffen the nanocomposite by tight attachment to the protein fibrils creating a high strength and toughness material. The nanometer dimensions of c-Ap crystals make it very challenging to measure their mechanical properties. Mineral in bony tissues such as dentine contains 2~6 wt.% carbonate with possibly different elastic properties as compared with crystalline hydroxyapatite. Here we determine strain in biogenic apatite nanocrystals by directly measuring atomic deformation in pig dentine before and after removing carbonate. Transmission electron microscopy revealed the platy 3D morphology while atom probe tomography revealed carbon inside the calcium rich domains. High-energy X-ray diffraction in combination with in situ hydrostatic pressurization quantified reversible c-Ap deformations. Additionally, crystal strains differed between annealed and ashed (decarbonated) samples, following 1 or 10 h heating at 250 °C or 550 °C respectively. Measured bulk moduli (K) and a-/c-lattice deformation ratios (η) were used to generate synthetic K syn and ηsyn identifying the most likely elastic constants C 33 and C 13 for c-Ap. These were then used to calculate the nanoparticle elastic moduli. For ashed samples, we find an average E 11 =107 GPa and E 33 =128 GPa corresponding to ~5% and ~17% stiffening of the a-/c-axes of the nanocrystals as compared with the biogenic nanocrystals in annealed samples. Ashed samples exhibit ~10% lower Poisson's ratios as compared with the 0.25~0.36 range of carbonated apatite. Carbonate in c-Ap may therefore serve for tuning local deformability within bony tissues.

36 MATERIALS SCIENCE↗

Nanocrystal Geometry Governs Phase Transformation Pathways in Palladium Hydride

Pathways and structural dynamics of phase transformations impact performance of materials in energy and information storage technologies. Palladium hydride (PdH x ) nanocrystals are an ideal model system for studying solute-induced phase transformations, where elastic energy from lattice mismatch between α-PdH x and β-PdH x phases is often considered a key to determining the transformation pathways. α/β-PdH x interfacial elastic energy is affected by the confined geometry of a nanocrystal. However, how nanocrystal geometry influences phase transformation pathways is largely unknown. Using in situ liquid phase transmission electron microscopy, we directly visualize hydrogenation in Pd nanocrystals with two geometries, a nanocube and a hexagonal nanoplate. Both follow similar sequences of an initially curved nucleus, interface flattening, and reverse-stage nucleation; however, their evolving α/β-PdH x interfaces exhibit geometry-dependent crystallographic alignments. In nanocubes, {100}-aligned configurations conform to static elastic energy ordering, representing a pathway that maintains a local mechanical equilibrium, whereas nanoplates display both {110}- and {211}-aligned interfaces. Theoretical simulations show that geometry determines the accessibility of alternative phase transformation pathways as the system is driven far from equilibrium during hydrogenation. In conclusion, these findings identify geometry as a fundamental parameter for directing phase transformation pathways, offering design principles for accessing atypical configurations and improving properties of intercalation-based devices.

Lee, Daewon [Lawrence Berkeley National Laboratory↗

Ferroelectric Polarization in BaTiO 3 Nanocrystals Controls Photoelectrochemical Water Oxidation and Photocatalytic Hydrogen Evolution

Ferroelectric (FE) semiconductors such as BaTiO 3 support a remnant polarization after the application of an electric field that can promote the separation of photogenerated charge carriers. Here, we demonstrate FE-enhanced photocatalytic hydrogen evolution and photoelectrochemical water oxidation with barium titanate nanocrystals for the first time. Nanocrystals of the ferroelectric tetragonal structure type were obtained by a hydrothermal synthesis from TiO 2 and barium hydroxide in 63% yield. BaTiO 3 nanocrystal films on tantalum substrates exhibit water oxidation photocurrents of 0.141 mA cm –2 at 1.23 V RHE under UV light (60 mW cm –2 ) illumination. Electric polarization at 52.8 kV cm –1 normal to the film plane increases the photocurrent by a factor of 2 or decreases it by a factor of 3.5, depending on the field polarity. It also shifts the onset potential by –0.15 or +0.09 V and it modifies the surface photovoltage signal. Lastly, exposure to an electric field increases the H 2 evolution rate of Pt/BaTiO 3 by a factor of ~1.5, and it raises the selectivity of photodeposition of silver onto the (001) facets of the nanocrystal. All FE enhancements can be removed by heating samples above the Curie temperature of BaTiO 3 . Furthermore, these findings can be explained by FE dipole-induced changes to the potential drop across the space charge layer of the material. The ability to use the ferroelectric effect to enhance hydrogen evolution and water oxidation is of potential interest for the development of improved solar energy for fuel conversion systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic Transformation of High-Architectural Nanocrystal Superlattices upon Solvent Molecule Exposure

The cluster-based body-centered-cubic superlattice (cBCC SL) represents one of the most complicated structures among reported nanocrystal assemblies, comprised of 72 truncated tetrahedral quantum dots per unit cell. Our previous report revealed that truncated tetrahedral quantum dots within cBCC SLs possessed highly controlled translational and orientational order owing to an unusual energetic landscape based on the balancing of entropic and enthalpic contributions during the assembly process. However, the cBCC SL’s structural transformability and mechanical properties, uniquely originating from such complicated nanostructures, have yet to be investigated. Herein, we report that cBCC SLs can undergo dynamic transformation to face-centered-cubic SLs in response to post-assembly molecular exposure. We monitored the dynamic transformation process using in situ synchrotron-based small-angle X-ray scattering, revealing a dynamic transformation involving multiple steps underpinned by interactions between incoming molecules and TTQDs’ surface ligands. Furthermore, our mechanistic study demonstrated that the precise configuration of TTQDs’ ligand molecules in cBCC SLs was key to their high structural transformability and unique jelly-like soft mechanical properties. While ligand molecular configurations in nanocrystal SLs are often considered minor features, our findings emphasize their significance in controlling weak van der Waals interactions between nanocrystals within assembled SLs, leading to previously unremarked superstructural transformability and unique mechanical properties. Finally, our findings promote a facile route toward further creation of soft materials, nanorobotics, and out-of-equilibrium assemblies based on nanocrystal building blocks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Seed-Mediated Colloidal Synthesis of Multimetallic and High-Entropy Alloy Nanocrystal Libraries with Enhanced Catalytic Performance

Engineering colloidally stable multimetallic nanocrystals offers many benefits in a wide range of applications and allows manipulation of physical, chemical, and electronic properties of materials at the nanoscale. Synthesis routes are challenged by the chemical complexity required to temporally and spatially coordinate the reduction and alloying of multiple metal species, which has hampered the development of tunable libraries of colloidal materials to date. Here, in this work, we demonstrate a seed-mediated synthesis method to incorporate five or more metal elements into uniform, colloidally stable nanocrystals. By integrating machine learning-accelerated simulations, the synthesis of shortlisted high-entropy alloy nanocrystals was demonstrated. Multiple seed materials can be used, leading to a library of multimetallic nanocrystals with tunable electronic, physical, and alloy structures. The advantage of this synthetic protocol is highlighted in the preparation of catalytic materials that showed 2 orders of magnitude higher reaction rates than monometallic catalysts and outstanding thermal stability, thus highlighting the promise of this approach for high-performance materials in many areas.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Heteroepitaxial chemistry of zinc chalcogenides on InP nanocrystals for defect-free interfaces with atomic uniformity

Heteroepitaxy on colloidal semiconductor nanocrystals is an essential strategy for manipulating their optoelectronic functionalities. However, their practical synthesis typically leads to scattered and unexpected outcomes due to the intervention of multiple reaction pathways associated with complicated side products of reactants. Here, the heteroepitaxy mechanism of zinc chalcogenide initiated on indium phosphide (InP) colloidal nanocrystals is elucidated using the precursors, zinc carboxylate and trialkylphosphine selenide. The high magnetic receptivity of 77 Se and the characteristic longitudinal optical phonon mode of ZnSe allowed for monitoring the sequence of epilayer formation at the molecular level. The investigation revealed the sterically hindered acyloxytrialkylphosphonium and diacyloxytrialkylphosphorane to be main intermediates in the surface reaction, which retards the metal ion adsorption by a large steric hindrance. The transformation of adsorbates to the crystalline epilayer was disturbed by surface oxides. Raman scattering disclosed the pathway of secondary surface oxidation triggered by carboxylate ligands migrated from zinc carboxylate. The surface-initiated heteroepitaxy protocol is proposed to fabricate core/shell heterostructured nanocrystals with atomic-scale uniformity of epilayers. Despite the large lattice mismatch of ZnS to InP, we realised a uniform and interface defect-free ZnS epilayer (~0.3 nm thickness) on InP nanocrystals, as evidenced by a high photoluminescence quantum yield of 97.3%.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Enamel nanocrystal misorientation increased with meat-eating and agriculture

Enamel covers teeth, is the hardest tissue in the vertebrate body and has a complex multiscale structure from nanometres to millimetres. The structure comprises thin, long hydroxyapatite (Ca 5 (PO 4 ) 3 OH) nanocrystals, 50–70 nm wide, many micrometres long, parallel and bundled into approximately 5-µm-wide rods. The rods undulate and cross into a microscale ‘decussation pattern’ that toughens enamel by deflecting cracks. However, the crystallographic orientation of enamel nanocrystals is poorly understood. Here we show that the misorientation angle of adjacent nanocrystals varies markedly across 12 primate teeth spanning 9 species, 17.8 million years of evolution and diverse diets. Using a method called Polarization Enabled Large Input of Crystal Angles at the Nanoscale (PELICAN), we compare nanocrystals in the same (pre)molar locations and show that misorientation increases with food hardness in extant and fossil non-human apes and monkeys. We compare misorientation across three major dietary shifts in human evolution: the transition to meat-eating about 2.0–1.5 million years before present, to agriculture (about 12,000 years before present), and the Industrial Revolution (about 250 years before present). We show that over the past 1.6 million years, in the human lineage misorientation increased with time, especially when meat and stone-ground grains were introduced into human diets, but not with the Industrial Revolution. Thus, besides macro-changes, teeth adapted to dietary change at the nanoscale and crystallographically. This observation suggests that misorientation may contribute to enamel’s resilience; thus, bioinspired materials may consider small misorientation angles for added resilience.

biomaterials↗

Alkali triel chalcogenide nanocrystals: a molecular reactivity approach to ternary phase selectivity

Alkali-metal-based materials are promising building blocks for energy conversion and storage technologies. Here, we use a molecular reactivity-based solution-phase approach to selectively synthesize multiple phases and specific polymorphs of lithium- and sodium-containing triel chalcogenide nanocrystals, LiTrCh 2 , NaTrCh 2 , and NaTr 3 Ch 5 , where Tr = Ga and In and Ch = S, Se, and Te. Analogous to the case of binary II–VI and III–V tetrahedral semiconductors, where the two commonly isolated zinc blende and wurtzite polymorphs are separated by only 1–50 meV f.u. −1 , we find that LiTrCh 2 nanocrystals easily adopt tetragonal (chalcopyrite) and orthorhombic polymorphs separated by only 2.7–6.2 meV f.u. −1 Because of this small energy difference, soft colloidal synthesis succeeds in accessing either one of these polymorphs, depending on the specific dichalcogenide precursor used. Highly reactive diethyl diselenide favors the thermodynamically more stable tetragonal I$\bar{4}2$d phase, whereas mildly reactive diphenyl diselenide favors the kinetic, metastable orthorhombic Pna2 1 phase. Density functional theory calculations confirm the relative energies among multiple LiTrCh 2 polymorphs and also model the observed powder X-ray diffraction pattern of a new C2 NaIn 3 Te 5 phase. 7 Li, 69 Ga, and 77 Se solid-state NMR spectra are consistent with phase-pure ternary LiGaSe 2 nanocrystals. A majority of the nanocrystal compositions are visible-light emitters. This work opens the door to new Li/Na-based ternary triel chalcogenide nanostructures for energy storage and conversion applications.

Pavel, Md Riad Sarkar [Iowa State Univ., Ames, IA ↗