Self-assembly Of Colloidal Nanocrystals Research Articles

In Situ X-ray Scattering Reveals Coarsening Rates of Superlattices Self-Assembled from Electrostatically Stabilized Metal Nanocrystals Depend Nonmonotonically on Driving Force.

Self-assembly of colloidal nanocrystals (NCs) into superlattices (SLs) is an appealing strategy to design hierarchically organized materials with promising functionalities. Mechanistic studies are still needed to uncover the design principles for SL self-assembly, but such studies have been difficult to perform due to the fast time and short length scales of NC systems. To address this challenge, we developed an apparatus to directly measure the evolving phases in situ and in real time of an electrostatically stabilized Au NC solution before, during, and after it is quenched to form SLs using small-angle X-ray scattering. By developing a quantitative model, we fit the time-dependent scattering patterns to obtain the phase diagram of the system and the kinetics of the colloidal and SL phases as a function of varying quench conditions. The extracted phase diagram is consistent with particles whose interactions are short in range relative to their diameter. We find the degree of SL order is primarily determined by fast (subsecond) initial nucleation and growth kinetics, while coarsening at later times depends nonmonotonically on the driving force for self-assembly. We validate these results by direct comparison with simulations and use them to suggest dynamic design principles to optimize the crystallinity within a finite time window. The combination of this measurement methodology, quantitative analysis, and simulation should be generalizable to elucidate and better control the microscopic self-assembly pathways of a wide range of bottom-up assembled systems and architectures.

Waveguide-Integrated Colloidal Nanocrystal Supraparticle Lasers.

Supraparticle (SP) microlasers fabricated by the self-assembly of colloidal nanocrystals have great potential as coherent optical sources for integrated photonics. However, their deterministic placement for integration with other photonic elements remains an unsolved challenge. In this work, we demonstrate the manipulation and printing of individual SP microlasers, laying the foundation for their use in more complex photonic integrated circuits. We fabricate CdSxSe1-x/ZnS colloidal quantum dot (CQD) SPs with diameters from 4 to 20 μm and Q-factors of approximately 300 via an oil-in-water self-assembly process. Under a subnanosecond-pulse optical excitation at 532 nm, the laser threshold is reached at an average number of excitons per CQD of 2.6, with modes oscillating between 625 and 655 nm. Microtransfer printing is used to pick up individual CQD SPs from an initial substrate and move them to a different one without affecting their capability for lasing. As a proof of concept, a CQD SP is printed on the side of an SU-8 waveguide, and its modes are successfully coupled to the waveguide.

Self-Assembly of Colloidal Nanocrystals into 3D Binary Mesocrystals.

Biominerals are unique materials found in many living organisms that often display outstanding functionalities attributed to their mesocrystalline structure. Mesocrystals are nanocrystal superstructures with mutual crystallographic alignment of the building units. One could thus imagine these optimized evolutionary systems as archetypes to fabricate advanced materials. The main advantage of such systems relies on their ability to combine the features of the nanocrystals with those of single crystalline microscopic structures, yielding assemblies with directional, enhanced, and potentially emergent properties. Moreover, fueled by the promises of multifunctional materials with unprecedented and tunable properties, the rational design of mesocrystals assembled from two distinct colloidal nanocrystal ensembles has become a recent focus of research. However, the combination of dissimilar nanocrystals into ordered binary superstructures is still a major scientific challenge due to the nature of the coassembly process.We focus this Account on the growth of tridimensional (3D) binary mesocrystals and the understanding of the self-assembly of two colloidal nanocrystal ensembles with the ultimate goal to serve as a basis for more rational mesocrystal syntheses in the future. The formation of mesocrystals demands nanocrystals with defined surface faceting, the primary factor influencing their oriented self-assembly. Notably, such a process cannot be successfully afforded without functionalized nanocrystals with high and, in many cases, tunable colloidal stability. Besides, the nature and solvation degree of the surface ligand shell influences the effective shape of the nanocrystals and the kinetics of self-assembly. If the assembly is triggered by reducing the colloidal stability with nonsolvents, 3D single-component mesocrystals are often grown. Here, the different magnitude of the van der Waals attraction forces between nanocrystals with differing compositions, dimensions, and morphologies generally favors the segregation and growth of single component mesocrystals. This phenomenon was illustrated during the successful preparation of 3D binary mesocrystals composed of iron oxide and platinum nanocubes. Although the building blocks possessed comparable sizes and were stabilized by similar ligands, the amount of the second component could only be arbitrarily tuned up to some extent, even when the assembly conditions were rationally optimized to achieve 3D binary mesocrystals. Only a small amount of it was effectively incorporated into the matrix of the initial mesocrystal. The 3D binary mesocrystal growth process demands a delicate control over the size, shape, and surface chemistry of the nanocrystals, the solvent nature, and the self-assembly process. Hence, the improvement of our ability to control the synthesis of 3D binary mesocrystalline materials is critical to exploit their potential toward technological applications in catalysis, energy storage, or structural materials.

Shape-Directed Co-Assembly of Lead Halide Perovskite Nanocubes with Dielectric Nanodisks into Binary Nanocrystal Superlattices.

Self-assembly of colloidal nanocrystals (NCs) holds great promise in the multiscale engineering of solid-state materials, whereby atomically engineered NC building blocks are arranged into long-range ordered structures—superlattices (SLs)—with synergistic physical and chemical properties. Thus far, the reports have by far focused on single-component and binary systems of spherical NCs, yielding SLs isostructural with the known atomic lattices. Far greater structural space, beyond the realm of known lattices, is anticipated from combining NCs of various shapes. Here, we report on the co-assembly of steric-stabilized CsPbBr3 nanocubes (5.3 nm) with disk-shaped LaF3 NCs (9.2–28.4 nm in diameter, 1.6 nm in thickness) into binary SLs, yielding six columnar structures with AB, AB2, AB4, and AB6 stoichiometry, not observed before and in our reference experiments with NC systems comprising spheres and disks. This striking effect of the cubic shape is rationalized herein using packing-density calculations. Furthermore, in the systems with comparable dimensions of nanocubes (8.6 nm) and nanodisks (6.5 nm, 9.0 nm, 12.5 nm), other, noncolumnar structures are observed, such as ReO3-type SL, featuring intimate intermixing and face-to-face alignment of disks and cubes, face-centered cubic or simple cubic sublattice of nanocubes, and two or three disks per one lattice site. Lamellar and ReO3-type SLs, employing large 8.6 nm CsPbBr3 NCs, exhibit characteristic features of the collective ultrafast light emission—superfluorescence—originating from the coherent coupling of emission dipoles in the excited state.

Multicomponent perovskite superlattices

Multicomponent perovskite superlattices

Nanoparticles exploring the macroscopic world

Nanoparticles exploring the macroscopic world

Reversible isomerization of metal nanoclusters induced by intermolecular interaction

Reversible isomerization of metal nanoclusters induced by intermolecular interaction

Structural-property correlations of all-inorganic CsPbBr3 perovskites via synergetic controls by PbBr2, 2-mercapto-3-methyl-4-thiazoleacetic acid and water

The low resistance to moisture will be the main obstacle for the perovskites used in device package and solar cell application. Most of literatures refer to the route that the quantum dots should be incorporated into a wide variety of stabilized hosts. However, the generation of protecting layers requires complicated treatments and decreases solubility or dispersity. Moreover, morphological control of perovskite nanocrystals with the assistance of covering substrate is a big challenge. Self-assembly of colloidal nanocrystals into ordered architectures has caused considerable interests and enabled new ways to manipulate the physicochemical properties for targeted applications. Herein, we describe how inorganic halide perovskites (CsPbBr3) with five different shapes (cubic, dot, sheet, ring and complex-coated) are formed by adjusting the sequence of PbBr2, 2-mercapto-3-methyl-4-thiazoleacetic acid (MMTA) and water. Realization of long-term stability and high efficiency requires innovative designs in both internal chemical structure and external interface engineering. PbBr2 improves the ionic nature of CsPbBr3 due to its cation supplement strategy. MMTA plays an important role in cross-linking process and the hydrogen bond/coordination interactions can passivate the interfacial surface for optimizing the microstructure. Water is not always detrimental in producing irreversible degradation. The shape evolution from the individual particles into much extended structure leads to the formation of complex-coated- CsPbBr3 (CC- CsPbBr3). It can retain 40% of its original emission intensity in water for 36 h, whereas the typical cubic CsPbBr3 exhibits poor performance during water tolerance experiments and has been completely quenched within 12 h. A wide color gamut system with 153% of National Television System Committee (NTSC) space is developed for CC- CsPbBr3.

Phase diagrams of simple models of colloidal nanocrystals in two dimensions

The self-assembly of colloidal nanocrystals at interfaces provides a bottom-up approach to create functional materials for developing next-generation flexible optoelectronic devices and sensors. In this work, we report phase diagrams of simple models of colloidal nanocrystals confined at a flat interface. By performing extensive computer simulations we elucidate the mesoscale organization that takes place as different parameters are varied. Our simulation results uncover rich phase diagrams where hexagonal, rhomboid, honeycomb and stripe phases as well as hierarchical self-assembly are found. Our results could serve as a guideline for experimentalists to design colloidal nanocrystal arrangements to target specific applications.

Micro-scale 2D quasi-nanosheets formed by 0D nanocrystals: from single to multicomponent building blocks

Self-assembly of colloidal nanocrystals (NCs) into large-scale superlattices with complex and controllable structures has attracted extensive attention due to their collective properties and promising device applications. Plasmonic NCs are very popular for long-range ordered superstructures by virtue of their collective nanogaps for electromagnetic field enhancement, in particular bulk-scale single-layer assembly. Large-area two-dimensional (2D) quasinanosheets (QNSs) composed of mono-component Au NCs or multi-component Au@ZnS core-shell hetero-nanocrystals (HNCs) were successfully prepared, via careful solvent evaporation-induced interfacial self-assembly. The entire self-assembly process was carried out on the liquid-air surface and mediated simply by tuning the operating temperatures and concentrations of the NCs. Specifically, monolayer and double-layer 2D QNSs in tens of micrometers scale with different stacking models were fabricated by precisely controlling the solvent evaporation rate and colloidal concentration.

1-nm-Wide Hydrated Dipole Arrays Regulate AuNW Assembly on Striped Monolayers in Nonpolar Solvent

Summary We show that striped phases of horizontally oriented phospholipids presenting 1-nm-wide orientable dipole arrays can order and straighten flexible 2-nm-diameter gold nanowires (AuNWs) with lengths (up to 1 μm) that greatly exceed the template pitch (∼7.5 nm). AuNW ordering can extend over areas > 100 μm2. Whereas wires bundle in solution, with contact between ligand shells, wires adsorbing to the template separate to much larger center-to-center distances (e.g., 12–30 nm) near multiples of the template pitch, consistent with repulsive interactions between wires emerging during interactions with dipole arrays in the template. AuNW assembly was carried out in cyclohexane, a nonpolar solvent. Interestingly, we found that wire ordering was contingent on the extent of phospholipid headgroup hydration and the presence of excess oleylamine, which assembled into hemicylindrical micelles around the hydrated headgroups. Together, these components generated a protected polar environment that enabled the phospholipid headgroups to function collectively to regulate AuNW assembly.

Controlled Self-Assembly and Tuning of Large PbS Nanoparticle Supercrystals

Self-assembly of colloidal nanocrystals (NCs) into ordered superlattices (SLs) and supercrystals (SCs) enables new artificial NC solids for nanoelectronic and nanophotonic applications, which requires critical control of nucleation and growth conditions. Herein large SCs of PbS NCs up to ∼100 μm size were synthesized by two controlled self-assembly methods from NC solutions. Both translational symmetry and orientational ordering of the nanocrystals in the SCs were readily tuned by excess oleic acid ligands and antisolvents. Slow evaporation and the counterdiffusion method of solvents resulted in the formation of single SCs with two different SLs from the same PbS NCs: a face-centered cubic SL with weak yet complex orientational order or a body-centered cubic SL with strong and uniform particle orientation, respectively. The translational ordering was mainly determined by the effective shape of the NCs while the difference in orientational order was a result of the balance between ligand–ligand attraction and rotational entropy. The ease of the growth of large SC solids could lead to diverse NC systems and facilitate essential investigation of nanoparticle interactions and coupling based nanoelectronic and nanophotonic properties.

Solvent-Assisted Self-Assembly of CsPbBr3 Perovskite Nanocrystals into One-Dimensional Superlattice

The self-assembly of colloidal nanocrystals into ordered architectures has attracted significant interest enabling innovative methods of manipulating physicochemical properties for targeted applications. This study reports the self-assembly of CsPbBr3 perovskite nanocrystals (NCs) in one-dimensional (1D) superlattice chains mediated by ligand–solvent interactions. CsPbBr3 NCs synthesized at ≥170 °C and purified in a nonpolar solvent, hexane, self-assembled into 1D chains, whereas those purified in polar solvents, including toluene and ethyl acetate, were disordered or formed short-range two-dimensional (2D) assemblies. The NCs assembled into 1D chains showed red shifts in both the absorbance and photoluminescence spectra relative to those of disordered NCs purified in a 50/50 hexane/ethyl acetate mixture. Microscopy and X-ray diffraction results confirmed the formation of polymeric nanostrands in hexane followed by organization of the NCs into 1D chains along the nanostrands. Our results suggest that excess aliphatic ligands remaining after purification of the NCs complex with ionic Cs+ and Br– species through a hydrophobic effect; further, the alkyl chains of these ligands interlace with each other through van der Waals forces. Collectively, these interactions give rise to the nanostrands and subsequent self-assembly of CsPbBr3 into 1D chains. In polar solvents, the minimization of repulsive forces between the solvent and the ligands drives proximal CsPbBr3 NCs together into short-range 2D assemblies or disordered clusters. Our solvent-assisted self-assembly approach provides a general strategy for designing 1D superlattice chains of nanocrystals of any geometry, dimension, and composition by simply tuning the ligand–solvent interactions.

Self-Assembly of Colloidal Nanocrystals: From Intricate Structures to Functional Materials.

Chemical methods developed over the past two decades enable preparation of colloidal nanocrystals with uniform size and shape. These Brownian objects readily order into superlattices. Recently, the range of accessible inorganic cores and tunable surface chemistries dramatically increased, expanding the set of nanocrystal arrangements experimentally attainable. In this review, we discuss efforts to create next-generation materials via bottom-up organization of nanocrystals with preprogrammed functionality and self-assembly instructions. This process is often driven by both interparticle interactions and the influence of the assembly environment. The introduction provides the reader with a practical overview of nanocrystal synthesis, self-assembly, and superlattice characterization. We then summarize the theory of nanocrystal interactions and examine fundamental principles governing nanocrystal self-assembly from hard and soft particle perspectives borrowed from the comparatively established fields of micrometer colloids and block copolymer assembly. We outline the extensive catalog of superlattices prepared to date using hydrocarbon-capped nanocrystals with spherical, polyhedral, rod, plate, and branched inorganic core shapes, as well as those obtained by mixing combinations thereof. We also provide an overview of structural defects in nanocrystal superlattices. We then explore the unique possibilities offered by leveraging nontraditional surface chemistries and assembly environments to control superlattice structure and produce nonbulk assemblies. We end with a discussion of the unique optical, magnetic, electronic, and catalytic properties of ordered nanocrystal superlattices, and the coming advances required to make use of this new class of solids.

Polycatenar Ligand Control of the Synthesis and Self-Assembly of Colloidal Nanocrystals.

Hydrophobic colloidal nanocrystals are typically synthesized and manipulated with commercially available ligands, and surface functionalization is therefore typically limited to a small number of molecules. Here, we report the use of polycatenar ligands derived from polyalkylbenzoates for the direct synthesis of metallic, chalcogenide, pnictide, and oxide nanocrystals. Polycatenar molecules, branched structures bearing diverging chains in which the terminal substitution pattern, functionality, and binding group can be independently modified, offer a modular platform for the development of ligands with targeted properties. Not only are these ligands used for the direct synthesis of monodisperse nanocrystals, but nanocrystals coated with polycatenar ligands self-assemble into softer bcc superlattices that deviate from conventional harder close-packed structures (fcc or hcp) formed by the same nanocrystals coated with commercial ligands. Self-assembly experiments demonstrate that the molecular structure of polycatenar ligands encodes interparticle spacings and attractions, engineering self-assembly, which is tunable from hard sphere to soft sphere behavior.

ChemInform Abstract: Self‐Assembly of Colloidal One‐Dimensional Nanocrystals

AbstractReview: 222 refs.

Self-Assembly of Colloidal Hexagonal Bipyramid- and Bifrustum-Shaped ZnS Nanocrystals into Two-Dimensional Superstructures

We present a combined experimental, theoretical, and simulation study on the self-assembly of colloidal hexagonal bipyramid- and hexagonal bifrustum-shaped ZnS nanocrystals (NCs) into two-dimensional superlattices. The simulated NC superstructures are in good agreement with the experimental ones. This shows that the self-assembly process is primarily driven by minimization of the interfacial free-energies and maximization of the packing density. Our study shows that a small truncation of the hexagonal bipyramids is sufficient to change the symmetry of the resulting superlattice from hexagonal to tetragonal, highlighting the crucial importance of precise shape control in the fabrication of functional metamaterials by self-assembly of colloidal NCs.

Self-assembly of colloidal one-dimensional nanocrystals

The ability of nanoscopic materials to self-organize into large-scale assembly structures that exhibit unique collective properties has opened up new and exciting opportunities in the field of nanotechnology. Although earlier work on nanoscale self-assembly has focused on colloidal spherical nanocrystals as building blocks, there has been significant interest in recent years in the self-assembly of colloidal nanocrystals having well-defined facets or anisotropic shapes. In this review, particular attention is drawn to anisotropic one-dimensional (1D) nanocrystals, notably nanorods and nanowires, which can be arranged into a multitude of higher-order assembly structures. Different strategies have been developed to realize self-assembly of colloidal 1D nanocrystals and these are highlighted in the first part of this review. Self-assembly can take place (1) on substrates through evaporation control, external field facilitation and template use; (2) at interfaces, such as the liquid-liquid and the gas-liquid interface; and (3) in solutions via chemical bonding, depletion attraction forces and linker-mediated interactions. The choice of a self-assembly approach is pivotal to achieving the desired assembly configuration with properties that can be exploited for functional device applications. In the subsequent sections, the various assembly structures that have been created through 1D nanocrystal self-assembly are presented. These organized structures are broadly categorized into non-close-packed and close-packed configurations, and are further classified based on the different types of 1D nanocrystal alignment (side-by-side and end-to-end), orientation (horizontal and vertical) and ordering (nematic and smectic), and depending on the dimensionality of the structure (2D and 3D). The conditions under which different types of arrangements are achieved are also discussed.

Interface-Induced Nucleation, Orientational Alignment and Symmetry Transformations in Nanocube Superlattices

The self-assembly of colloidal nanocrystals into ordered superstructures depends critically on the shape of the nanocrystal building blocks. We investigated the self-assembly of cubic PbSe nanocrystals from colloidal suspensions in real-time using in situ synchrotron-based X-ray scattering. We combined small-angle and wide-angle scattering to investigate the translational ordering of nanocrystals and their orientational ordering in the lattice sites, respectively. We found that cubic PbSe nanocrystals assembled into a face-up (i.e., [100] normal to the interface) configuration at the liquid/substrate interface whereas nanocubes at the liquid/air interface assume a corner-up (i.e., [111] normal to the interface) configuration. The latter nanocrystal superlattice displays polymorphism as a function inter-NC separation distance. We explain the observed superlattice structure polymorphs in terms of the interactions directing the self-assembly. Insights into the directed self-assembly of superlattices gained from this study have important implication on the future development of nanocrystals as building blocks in artificial solids.

Evaluation of Ordering in Single-Component and Binary Nanocrystal Superlattices by Analysis of Their Autocorrelation Functions

Self-assembly of colloidal nanocrystals and other nanosized building blocks has led to numerous large-scale and well-ordered superstructures. To quantify the superlattice quality we present a simple and efficient method, based on analysis of the autocorrelation function to determine characteristic order parameters for short-range and long-range ordering. This provides a feedback for further improvements of deposition techniques and self-assembly processes. To show the power of this method, it is applied to various two-dimensional ordered single component and binary nanocrystal assemblies. A quantitative comparison of the normalized long-range order parameter for various colloidal or epitaxially grown superlattice structures evidences that the long-range ordering in monodisperse colloidal superlattices by far supersedes that obtained at best by epitaxially grown quantum dots. Astonishingly, for selected binary nanocrystal superlattices the long-range ordering parameter reaches almost the same values as for single component superlattices. Besides the high sensitivity of the introduced quantification method to lattice imperfections our analysis also reveals any anisotropy in the ordering of the superlattices, which again can be quantified, for example, to identify the areas of highest quality within one specific sample.