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. Our findings promote a facile route toward further creation of soft materials, nanorobotics, and out-of-equilibrium assemblies based on nanocrystal building blocks.

Type-I CdS/ZnS Core/Shell Quantum Dot-Gold Heterostructural Nanocrystals for Enhanced Photocatalytic Hydrogen Generation.

Developing Type-I core/shell quantum dots is of great importance toward fabricating stable and sustainable photocatalysts. However, the application of Type-I systems has been limited due to the strongly confined photogenerated charges by the energy barrier originating from the wide-bandgap shell material. In this project, we found that through the decoration of Au satellite-type domains on the surface of Type-I CdS/ZnS core/shell quantum dots, such an energy barrier can be effectively overcome and an over 400-fold enhancement of photocatalytic H2 evolution rate was achieved compared to bare CdS/ZnS quantum dots. Transient absorption spectroscopic studies indicated that the charges can be effectively extracted and subsequently transferred to surrounding molecular substrates in a subpicosecond time scale in such hybrid nanocrystals. Based on density functional theory calculations, the ultrafast charge separation rates were ascribed to the formation of intermediate Au2S layer at the semiconductor-metal interface, which can successfully offset the energy confinement introduced by the ZnS shell. Our findings not only provide insightful understandings on charge carrier dynamics in semiconductor-metal heterostructural materials but also pave the way for the future design of quantum dot-based hybrid photocatalytic systems.

Nanocrystals with metastable high-pressure phases under ambient conditions.

The ambient metastability of the rock-salt phase in well-defined model systems comprising nanospheres or nanorods of cadmium selenide, cadmium sulfide, or both was investigated as a function of composition, initial crystal phase, particle structure, shape, surface functionalization, and ordering level of their assemblies. Our experiments show that these nanocrystal systems exhibit ligand-tailorable reversibility in the rock salt-to-zinc blende solid-phase transformation. Interparticle sintering was used to engineer kinetic barriers in the phase transformation to produce ambient-pressure metastable rock-salt structures in a controllable manner. Interconnected nanocrystal networks were identified as an essential structure that hosted metastable high-energy phases at ambient conditions. These findings suggest general rules for transformation-barrier engineering that are useful in the rational design of next-generation materials.

Three-dimensional atomic packing in amorphous solids with liquid-like structure.

Liquids and solids are two fundamental states of matter. However, our understanding of their three-dimensional atomic structure is mostly based on physical models. Here we use atomic electron tomography to experimentally determine the three-dimensional atomic positions of monatomic amorphous solids, namely a Ta thin film and two Pd nanoparticles. We observe that pentagonal bipyramids are the most abundant atomic motifs in these amorphous materials. Instead of forming icosahedra, the majority of pentagonal bipyramids arrange into pentagonal bipyramid networks with medium-range order. Molecular dynamics simulations further reveal that pentagonal bipyramid networks are prevalent in monatomic metallic liquids, which rapidly grow in size and form more icosahedra during the quench from the liquid to the glass state. These results expand our understanding of the atomic structures of amorphous solids and will encourage future studies on amorphous-crystalline phase and glass transitions in non-crystalline materials with three-dimensional atomic resolution.

Mn2+/Yb3+ Codoped CsPbCl3 Perovskite Nanocrystals with Triple-Wavelength Emission for Luminescent Solar Concentrators.

Doping metal ions into lead halide perovskite nanocrystals (NCs) has attracted great attention over the past few years due to the emergence of novel properties relevant to optoelectronic applications. Here, the synthesis of Mn2+/Yb3+ codoped CsPbCl3 NCs through a hot-injection technique is reported. The resulting NCs show a unique triple-wavelength emission covering ultraviolet/blue, visible, and near-infrared regions. By optimizing the dopant concentrations, the total photoluminescence quantum yield (PL QY) of the codoped NCs can reach ≈125.3% due to quantum cutting effects. Mechanism studies reveal the efficient energy transfer processes from host NCs to Mn2+ and Yb3+ dopant ions, as well as a possible inter-dopant energy transfer from Mn2+ to Yb3+ ion centers. Owing to the high PL QYs and minimal reabsorption loss, the codoped perovskite NCs are demonstrated to be used as efficient emitters in luminescent solar concentrators, with greatly enhanced external optical efficiency compared to that of using solely Mn2+ doped CsPbCl3 NCs. This study presents a new model system for enriching doping chemistry studies and future applications of perovskite NCs.

Lead-Free Cs4CuSb2Cl12 Layered Double Perovskite Nanocrystals.

Concerns about the toxicity of lead-based perovskites have aroused great interest for the development of alternative lead-free perovskite-type materials. Recently, theoretical calculations predict that Pb2+ cations can be substituted by a combination of Cu2+ and Sb3+ cations to form a vacancy-ordered layered double perovskite structure with superior optoelectronic properties. However, accessibilities to this class of perovskite-type materials remain inadequate, hindering their practical implementations in various applications. Here, we report the first colloidal synthesis of Cs4CuSb2Cl12 perovskite-type nanocrystals (NCs). The resulting NCs exhibit a layered double perovskite structure with ordered vacancies and a direct band gap of 1.79 eV. A composition-structure-property relationship has been established by investigating a series of Cs4CuxAg2-2xSb2Cl12 perovskite-type NCs (0 ≤ x ≤ 1). The composition induced crystal structure transformation, and thus, the electronic band gap evolution has been explored by experimental observations and further confirmed by theoretical calculations. Taking advantage of both the unique electronic structure and solution processability, we demonstrate that the Cs4CuSb2Cl12 NCs can be solution-processed as high-speed photodetectors with ultrafast photoresponse and narrow bandwidth. We anticipate that our study will prompt future research to design and fabricate novel and high-performance lead-free perovskite-type NCs for a range of applications.

Reversible Photo-Switching of Dual-Color Fluorescent Mn-Doped CdS-ZnS Quantum Dots Modulated by Diarylethene Molecules.

Dynamic materials have been given an increased amount of attention in recent years with an expectation that they may exhibit properties on demand. Especially, the combination of fluorescent quantum dots (QDs) and light-responsive organic switches can generate novel photo-switchable materials for diverse applications. In this work, a highly reversible dynamic hybrid system is established by mixing dual-color emitting Mn-doped CdS-ZnS quantum dots (QDs) with photo-switchable diarylethene molecules. We show that the diarylethene 1,2-bis(5-(3,5-bis(trifluoromethyl)phenyl)-2-methylthiophen-3-yl)cyclopent-1-ene (switch molecule 1) performs fabulous photo-switching property (between its open, 1o and closed, 1c forms), and high fatigue resistance in this hybrid system. The emission color switching between blue and pink of the system can be induced mainly by selective quenching/recovering of the Mn- photoluminescence (PL) of the QDs due to the switchable absorbance of the molecule 1. Mechanistic studies show that quenching of QD emission following UV illumination was caused by both Förster resonance energy transfer (FRET) and reabsorption by surrounding 1c molecules in the case of the Mn-PL, and solely by reabsorption in the case of badngap- (BG-)PL. This photo-switchable system could be potentially used in applications ranging from self-erasing paper to super-resolution fluorescence imaging.

Yb- and Mn-Doped Lead-Free Double Perovskite Cs2AgBiX6 (X = Cl-, Br-) Nanocrystals.

Lead-free double perovskite nanocrystals (NCs) have emerged as a new category of materials that hold the potential for overcoming the instability and toxicity issues of lead-based counterparts. Doping chemistry represents a unique avenue toward tuning and optimizing the intrinsic optical and electronic properties of semiconductor materials. In this study, we report the first example of doping Yb3+ ions into lead-free double perovskite Cs2AgBiX6 (X = Cl-, Br-) NCs via a hot injection method. The doping of Yb3+ endows the double perovskite NCs with a newly emerged near-infrared emission band (sensitized from the NC hosts) in addition to their intrinsic trap-related visible photoluminescence. By controlling the Yb-doping concentration, the dual emission profiles and photon relaxation dynamics of the double perovskite NCs can be systematically tuned. Furthermore, we have successfully inserted divalent Mn2+ ions in Cs2AgBiCl6 NCs and observed emergence of dopant emission. Our work illustrates an effective and facile route toward modifying and optimizing optical properties of double perovskite Cs2AgBiX6 (X = Cl-, Br-) NCs with an indirect bandgap nature, which can broaden a range of their potential applications in optoelectronic devices.

Controlling Nanoparticle Orientations in the Self-Assembly of Patchy Quantum Dot-Gold Heterostructural Nanocrystals.

Self-assembly of nanocrystals is a promising route for creating macroscale materials that derive function from the properties of their nanoscale building blocks. While much progress has been made assembling nanocrystals into different superlattices, controlling the relative orientations of nanocrystals in those lattices remains a challenge. Here, we combine experiments with computer simulations to study the self-assembly of patchy heterostructural nanocrystals (HNCs), consisting of near-spherical quantum dots decorated with regular arrangements of small gold satellites, into close-packed superlattices with pronounced orientational alignment of HNCs. Our simulations indicate that the orientational alignment is caused by van der Waals interactions between gold patches and is sensitive to the interparticle distance in the superlattice. We demonstrate experimentally that the degree and type of orientational alignment can be controlled by changing ligand populations on HNCs. This study provides guidance for the design and fabrication of nanocrystal superlattices with enhanced structural control.

Single-component quasicrystalline nanocrystal superlattices through flexible polygon tiling rule.

Quasicrystalline superlattices (QC-SLs) generated from single-component colloidal building blocks have been predicted by computer simulations but are challenging to reproduce experimentally. We discovered that 10-fold QC-SLs could self-organize from truncated tetrahedral quantum dots with anisotropic patchiness. Transmission electron microscopy and tomography measurements allow structural reconstruction of the QC-SL from the nanoscale packing to the atomic-scale orientation alignments. The unique QC order leads to a tiling concept, the "flexible polygon tiling rule," that replicates the experimental observations. The keys for the single-component QC-SL formation were identified to be the anisotropic shape and patchiness of the building blocks and the assembly microscopic environment. Our discovery may spur the creation of various superstructures using anisotropic objects through an enthalpy-driven route.

Superstructures generated from truncated tetrahedral quantum dots.

The assembly of uniform nanocrystal building blocks into well ordered superstructures is a fundamental strategy for the generation of meso- and macroscale metamaterials with emergent nanoscopic functionalities1-10. The packing of spherical nanocrystals, which frequently adopt dense, face-centred-cubic or hexagonal-close-packed arrangements at thermodynamic equilibrium, has been much more widely studied than that of non-spherical, polyhedral nanocrystals, despite the fact that the latter have intriguing anisotropic properties resulting from the shapes of the building blocks11-13. Here we report the packing of truncated tetrahedral quantum dot nanocrystals into three distinct superstructures-one-dimensional chiral tetrahelices, two-dimensional quasicrystal-approximant superlattices and three-dimensional cluster-based body-centred-cubic single supercrystals-by controlling the assembly conditions. Using techniques in real and reciprocal spaces, we successfully characterized the superstructures from their nanocrystal translational orderings down to the atomic-orientation alignments of individual quantum dots. Our packing models showed that formation of the nanocrystal superstructures is dominated by the selective facet-to-facet contact induced by the anisotropic patchiness of the tetrahedra. This study provides information about the packing of non-spherical nanocrystals into complex superstructures, and may enhance the potential of self-assembled nanocrystal metamaterials in practical applications.

Regulating Multiple Variables To Understand the Nucleation and Growth and Transformation of PbS Nanocrystal Superlattices.

Nanocrystals (NCs) can self-assemble into ordered superlattices with collective properties, but the ability for controlling NC assembly remains poorly understandable toward achievement of desired superlattice. This work regulates several key variables of PbS NC assembly (e.g., NC concentration and solubility, solvent type, evaporation rate, seed mediation and thermal treatment), and thoroughly exploits the nucleation and growth as well as subsequent superlattice transformation of NC assembles and underneath mechanisms. PbS NCs in toluene self-assemble into a single face-centered-cubic (fcc) and body-centered-cubic (bcc) superlattice, respectively, at concentrations ≤17.5 and ≥70 mg/mL, but an intermediate concentration between them causes the coexistence of the two superlattices. Differently, NCs in hexane or chloroform self-assemble into only a single bcc superlattice. Distinct controls of NC assembly in solvent with variable concentrations confirm the NC concentration/solubility mediated nucleation and growth of superlattice, in which an evaporation-induced local gradient of NC concentration causes simultaneous nucleation of the two superlattices. The observation for the dense packing planes of NCs in fast growing fcc rather than bcc reveals the difference of entropic driving forces responsible for the two distinct superlattices. Decelerating the solvent evaporation does not amend the superlattice symmetry, but improves the superlattice crystallinity. In addition to shrinking the superlattice volume, thermal treatment also transforms the bcc to an fcc superlattice at 175 °C. Through a seed-meditated growth, the concentration-dependent superlattice does not change lattice symmetry over the course of continuous growth, whereas the newly nucleated secondary small nuclei through a concentration change have relatively higher surface energy and quickly dissolve in solution, providing additional NC sources for the ripening of the primarily nucleated larger and stable seeds. The observations under multiple controls of assembly parameters not only provide insights into the nucleation and growth as well as transformation of various superlattice polymorphs but also lay foundation for controlled fabrication of desired superlattice with tailored property.

Pressure-Enabled Synthesis of Hetero-Dimers and Hetero-Rods through Intraparticle Coalescence and Interparticle Fusion of Quantum-Dot-Au Satellite Nanocrystals.

This report presents the fabrication and pressure-driven processing of heterostructural nanocrystal superlattices (HNC-SLs) self-assembled from quantum-dot-Au (QD-Au) satellite-type HNCs. In situ small/wide-angle X-ray scattering and electron microscopic measurements showed that the HNC-SLs underwent structural transformation at both atomic- and mesoscales during the pressure processing. Upon deviatoric stress-driven orientational migration, the intraparticle coalescence of Au satellites at QD surfaces transforms individual HNCs into heterodimers, whereas the interparticle fusion drives assembled HNCs into ordered heterorod arrays. These results demonstrate high-pressure-processing as a clean and fast means for conversion of HNCs into novel heteromaterials that are difficult to achieve through conventional synthetic routes.

Nanocube Superlattices of Cesium Lead Bromide Perovskites and Pressure-Induced Phase Transformations at Atomic and Mesoscale Levels.

Lead halide perovskites are promising materials for a range of applications owing to their unique crystal structure and optoelectronic properties. Understanding the relationship between the atomic/mesostructures and the associated properties of perovskite materials is crucial to their application performances. Herein, the detailed pressure processing of CsPbBr3 perovskite nanocube superlattices (NC-SLs) is reported for the first time. By using in situ synchrotron-based small/wide angle X-ray scattering and photoluminescence (PL) probes, the NC-SL structural transformations are correlated at both atomic and mesoscale levels with the band-gap evolution through a pressure cycle of 0 ↔ 17.5 GPa. After the pressurization, the individual CsPbBr3 NCs fuse into 2D nanoplatelets (NPLs) with a uniform thickness. The pressure-synthesized perovskite NPLs exhibit a single cubic crystal structure, a 1.6-fold enhanced photoluminescence quantum yield, and a longer emission lifetime than the starting NCs. This study demonstrates that pressure processing can serve as a novel approach for the rapid conversion of lead halide perovskites into structures with enhanced properties.

Surface characteristics and electrical properties of PMMA chips for incubation-type planar-patch-clamp biosensors.

Polymethylmethacrylate (PMMA) plates were successfully applied as sensor chips in an incubation-type planar patch clamp (IPPC). Hot embossing both sides formed the PMMA plates, and a focused ion beam realized micropores. The low seal resistance of the IPPC was investigated by analyzing the surface roughness of the chips. Atomic force microscopy (AFM) showed that the chip surface had a roughness of several nanometers due to the molding process. Coating the molded surface with an anti-adhesive compound further increased the surface roughness of the PMMA chip because the anti-adhesive compound itself had a large roughness and in some case, the compound partially peeled off while detaching the mold. Similarly, coating a chip with extracellular matrix (ECM) poly-l-lysine (PLL) also increased the surface roughness. The measured seal resistance of the PMMA chip for an HEK293 cell was in the range of 4-15 MΩ. The low seal resistance was attributed to the sharp-edge structure of the micropore and the surface roughness of the chip. Nevertheless, the whole cell current was successfully recorded from HEK293 cells expressing channel rhodopsin wide receiver (ChRWR) using salt-bridge-type stable Ag/AgCl electrodes. Another advantage of the PMMA sensor chip was the small parasitic capacitance.

Structural control of nanocrystal superlattices using organic guest molecules.

We report a host-guest chemistry approach to controlling the structures of nanocrystal superlattices through a molecular inclusion process. Upon addition of an appropriate amount of guest molecules such as squalane, polyisoprene, and 4-cyano-4'-pentylbiphenyl into a nanocrystal suspension, the resulting nanocrystal superlattices adopted non-close-packed structures (e.g., from face-centered cubic to body-centered cubic) and changed their morphologies to form superparticles. Our mechanistic studies revealed that these guest molecules can strongly tailor the kinetic process in superlattice formation, resulting in the formation of non-close-packed nanocrystal superlattices. The insights gained in this study are not only important for making nanocrystal superlattices with desirable architectures but also open a new way of synthesizing novel organic/inorganic composite materials.

Deviatoric stress driven formation of large single-crystal PbS nanosheet from nanoparticles and in situ monitoring of oriented attachment.

Two-dimensional single-crystal PbS nanosheets were synthesized by deviatoric stress-driven orientation and attachment of nanoparticles (NPs). In situ small- and wide-angle synchrotron X-ray scattering measurements on the same spot of the sample under pressure coupled with transmission electron microscopy enable reconstruction of the nucleation route showing how enhanced deviatoric stress causes ordering NPs into single-crystal nanosheets with a lamellar mesostructure. At the same time that deviatoric stress drives SC(110) orientation in a face-centered-cubic supercrystal (SC), rocksalt (RS) NPs rotate and align their RS(200) and RS(220) planes within the SC(110) plane. When NPs approach each other along the compression axis, enhanced deviatoric stress drives soft ligands passivated at RS(200) and RS(220) surfaces to reorient from a group of SC(110) in-planes to the interspace of SC[110]-normal planes. While the internal NP structure starts a rocksalt-to-orthorhombic transition at 7.1 GPa, NPs become aligned on RS(220) and RS(200) and thus become attached at those faces. The transition-catalyzed surface atoms accelerate the inter-NP coalescing process and the formation of low-energy structure nanosheet. Above 11.6 GPa, the nucleated single-crystal nanosheets stack into a lamellar mesostructure that has a domain size comparable to the starting supercrystal.

Formation of heterodimer nanocrystals: UO2/In2O3 and FePt/In2O3.

This Article reports a mechanistic study on the formation of colloidal UO(2)/In(2)O(3) and FePt/In(2)O(3) heterodimer nanocrystals. These dimer nanocrystals were synthesized via the growth of In(2)O(3) as the epitaxial material onto the seed nanocrystals of UO(2) or FePt. The resulting dimer nanocrystals were characterized using X-ray powder diffraction (XRD), energy dispersion spectroscopy, transmission electron microscopy (TEM), scanning transmission electron microscopy, and high-resolution TEM (HRTEM). The results from XRD and HRTEM clearly show that lattice strains exist in both of these dimer nanocrystals. Interestingly, the lattice of In(2)O(3) expands in UO(2)/In(2)O(3) dimers, whereas FePt/In(2)O(3) dimers exhibit compressed In(2)O(3) lattices. Using HRTEM and nanocrystal structure simulations, we have identified the crystallographic orientation of the attachment of the two segments in these two types of dimers. An unconventional Miller index was introduced to describe the crystallographic orientation of these heterodimer nanocrystals. On the basis of the results herein as well as those from other researchers, we propose an empirical law for the determination of the crystallographic attachment orientation in heterodimers: instead of growth on the facet of the seed nanocrystals where lattice mismatch is minimized, the growth of an epitaxial material often chooses the crystal facets where the first atomic monolayer of this material has the strongest affinity for the seed nanocrystals.

Ratiometric bioluminescence indicators for monitoring cyclic adenosine 3',5'-monophosphate in live cells based on luciferase-fragment complementation.

Bioluminescent indicators for cyclic 3',5'-monophosphate AMP (cAMP) are powerful tools for noninvasive detection with high sensitivity. However, the absolute photon counts are affected substantially by adenosine 5'-triphosphate (ATP) and d-luciferin concentrations, limiting temporal analysis in live cells. This report describes a genetically encoded bioluminescent indicator for detecting intracellular cAMP based on complementation of split fragments of two-color luciferase mutants originated from click beetles. A cAMP binding domain of protein kinase A was connected with an engineered carboxy-terminal fragment of luciferase, of which ends were connected with amino-terminal fragments of green luciferase and red luciferase. We demonstrated that the ratio of green to red bioluminescence intensities was less influenced by the changes of ATP and d-luciferin concentrations. We also showed an applicability of the bioluminescent indicator for time-course and quantitative assessments of intracellular cAMP in living cells and mice. The bioluminescent indicator will enable quantitative analysis and imaging of spatiotemporal dynamics of cAMP in opaque and autofluorescent living subjects.