Dynamic Nanocrystal Superlattices with Thermally Triggerable Lubricating Ligands.

The size-dependent and collective physical properties of nanocrystals (NCs) and their self-assembled superlattices (SLs) enable the study of mesoscale phenomena and the design of metamaterials for a broad range of applications. However, the limited mobility of NC building blocks in dried NCSLs often hampers the potential for employing postdeposition methods to produce high-quality NCSLs. In this study, we present tailored promesogenic ligands that exhibit a lubricating property akin to thermotropic liquid crystals. The lubricating ability of ligands is thermally triggerable, allowing the dry solid NC aggregates deposited on the substrates with poor ordering to be transformed into NCSLs with high crystallinity and preferred orientations. The interplay between the dynamic behavior of NCSLs and the molecular structure of the ligands is elucidated through a comprehensive analysis of their lubricating efficacy using both experimental and simulation approaches. Coarse-grained molecular dynamic modeling suggests that a shielding layer from mesogens prevents the interdigitation of ligand tails, facilitating the sliding between outer shells and consequently enhancing the mobility of NC building blocks. The dynamic organization of NCSLs can also be triggered with high spatial resolution by laser illumination. The principles, kinetics, and utility of lubricating ligands could be generalized to unlock stimuli-responsive metamaterials from NCSLs and contribute to the fabrication of NCSLs.

Thermally Reconfigurable, 3D Chiral Optical Metamaterials: Building with Colloidal Nanoparticle Assemblies.

The three-dimensional, geometric handedness of chiral optical metamaterials allows for the rotation of linearly polarized light and creates a differential interaction with right and left circularly polarized light, known as circular dichroism. These three-dimensional metamaterials enable polarization control of optical and spin excitation and detection, and their stimuli-responsive, dynamic switching widens applications in chiral molecular sensing and imaging and spintronics; however, there are few reconfigurable solid-state implementations. Here, we report all-solid-state, thermally reconfigurable chiroptical metamaterials composed of arrays of three-dimensional nanoparticle/metal bilayer heterostructures fabricated from coassemblies of phase change VO2 and metallic Au colloidal nanoparticles and thin films of Ni. These metamaterials show dynamic switching in the mid-infrared as VO2 is thermally cycled through an insulator-metal phase transition. The spectral range of operation is tailored in breadth by controlling the periodicity of the arrays and thus the hybridization of optical modes and in position through the mixing of VO2 and Au nanoparticles.

Surface Engineering of Metal and Semiconductor Nanocrystal Assemblies and Their Optical and Electronic Devices.

ConspectusColloidal nanocrystals (NCs) are composed of inorganic cores and organic or inorganic ligand shells and serve as building blocks of NC assemblies. Metal and semiconductor NCs are well known for the size-dependent physical properties of their cores. The large NC surface-to-volume ratio and the space between NCs in assemblies places significant importance on the composition of the NC surface and ligand shell. Nonaqueous colloidal NC syntheses use relatively long organic ligands to control NC size and uniformity during growth and to prepare stable NC dispersions. However, these ligands create large interparticle distances that dilute the metal and semiconductor NC properties of their assemblies. In this Account, we describe postsynthesis chemical treatments to engineer the NC surface and design the optical and electronic properties of NC assemblies. In metal NC assemblies, compact ligand exchange reduces the interparticle distance and drives an insulator-to-metal transition tuning the dc resistivity over a 1010 range and the real part of the optical dielectric function from positive to negative across the visible-to-IR region. Juxtaposing NC and bulk metal thin films in bilayers allows the differential chemical and thermal addressability of the NC surface to be exploited in device fabrication. Ligand exchange and thermal annealing densifies the NC layer, creating interfacial misfit strain that triggers folding of the bilayers and is used to fabricate, with only one lithography step, large-area 3D chiral metamaterials. In semiconductor NC assemblies, chemical treatments such as ligand exchange, doping, and cation exchange control the interparticle distance and composition to add impurities, tailor stoichiometry, or make entirely new compounds. These treatments are employed in longer studied II-VI and IV-VI materials and are being developed as interest in III-V and I-III-VI2 NC materials grows. NC surface engineering is used to design NC assemblies with tailored carrier energy, type, concentration, mobility, and lifetime. Compact ligand exchange increases the coupling between NCs but can introduce intragap states that scatter and reduce the lifetime of carriers. Hybrid ligand exchange with two different chemistries can enhance the mobility-lifetime product. Doping increases carrier concentration, shifts the Fermi energy, and increases carrier mobility, creating n- and p-type building blocks for optoelectronic and electronic devices and circuits. Surface engineering of semiconductor NC assemblies is also important to modify device interfaces to allow the stacking and patterning of NC layers and to realize excellent device performance. It is used to construct NC-integrated circuits, exploiting the library of metal, semiconductor, and insulator NCs, to achieve all-NC, solution-fabricated transistors.

Open and Close-Packed, Shape-Engineered Polygonal Nanoparticle Metamolecules with Tailorable Fano Resonances.

A top-down lithographic patterning and deposition process is reported for producing nanoparticles (NPs) with well-defined sizes, shapes, and compositions that are often not accessible by wet-chemical synthetic methods. These NPs are ligated and harvested from the substrate surface to prepare colloidal NP dispersions. Using a template-assisted assembly technique, fabricated NPs are driven by capillary forces to assemble into size- and shape-engineered templates and organize into open or close-packed multi-NP structures or NP metamolecules. The sizes and shapes of the NPs and of the templates control the NP number, coordination, interparticle gap size, disorder, and location of defects such as voids in the NP metamolecules. The plasmonic resonances of polygonal-shaped Au NPs are exploited to correlate the structure and optical properties of assembled NP metamolecules. Comparing open and close-packed architectures highlights that introduction of a center NP to form close-packed assemblies supports collective interactions, altering magnetic optical modes and multipolar interactions in Fano resonances. Decreasing the distance between NPs strengthens the plasmonic coupling, and the structural symmetries of the NP metamolecules determine the orientation-dependent scattering response.

Three-Dimensionally Complex Phase Behavior and Collective Phenomena in Mixtures of Acoustically Powered Chiral Microspinners.

The process of dynamic self-organization of small building blocks is fundamental to the emergent function of living systems and is characteristic of their out-of-equilibrium homeostasis. The ability to control the interactions of synthetic particles in large groups could lead to the realization of analogous macroscopic robotic systems with microscopic complexity. Rotationally induced self-organization has been observed in biological systems and modeled theoretically, but studies of fast, autonomously moving synthetic rotors remain rare. Here, we report switchable, out-of-equilibrium hydrodynamic assembly and phase separation in suspensions of acoustically powered chiral microspinners. Semiquantitative modeling suggests that three-dimensionally (3D) complex spinners interact through viscous and weakly inertial (streaming) flows. The interactions between spinners were studied over a range of densities to construct a phase diagram, which included gaseous dimer pairing at low density, collective rotation and multiphase separation at intermediate densities, and ultimately jamming at high density. The 3D chirality of the spinners leads to self-organization in parallel planes, forming a three-dimensionally hierarchical system that goes beyond the 2D systems that have so far been modeled computationally. Dense mixtures of spinners and passive tracer particles also show active-passive phase separation. These observations are consistent with recent theoretical predictions of the hydrodynamic coupling between rotlets generated by autonomous spinners and provide an exciting experimental window to the study of colloidal active matter and microrobotic systems.

Self-Assembly of Atomically Aligned Nanoparticle Superlattices from Pt-Fe3O4 Heterodimer Nanoparticles.

Multicomponent nanoparticle superlattices (SLs) promise the integration of nanoparticles (NPs) with remarkable electronic, magnetic, and optical properties into a single structure. Here, we demonstrate that heterodimers consisting of two conjoined NPs can self-assemble into novel multicomponent SLs with a high degree of alignment between the atomic lattices of individual NPs, which has been theorized to lead to a wide variety of remarkable properties. Specifically, by using simulations and experiments, we show that heterodimers composed of larger Fe3O4 domains decorated with a Pt domain at one vertex can self-assemble into an SL with long-range atomic alignment between the Fe3O4 domains of different NPs across the SL. The SLs show an unanticipated decreased coercivity relative to nonassembled NPs. In situ scattering of the self-assembly reveals a two-stage mechanism of self-assembly: translational ordering between NPs develops before atomic alignment. Our experiments and simulation indicate that atomic alignment requires selective epitaxial growth of the smaller domain during heterodimer synthesis and specific size ratios of the heterodimer domains as opposed to specific chemical composition. This composition independence makes the self-assembly principles elucidated here applicable to the future preparation of multicomponent materials with fine structural control.

Red Emission from Copper-Vacancy Color Centers in Zinc Sulfide Colloidal Nanocrystals.

Copper-doped zinc sulfide (ZnS:Cu) exhibits down-conversion luminescence in the UV, visible, and IR regions of the electromagnetic spectrum; the visible red, green, and blue emission is referred to as R-Cu, G-Cu, and B-Cu, respectively. The sub-bandgap emission arises from optical transitions between localized electronic states created by point defects, making ZnS:Cu a prolific phosphor material and an intriguing candidate material for quantum information science, where point defects excel as single-photon sources and spin qubits. Colloidal nanocrystals (NCs) of ZnS:Cu are particularly interesting as hosts for the creation, isolation, and measurement of quantum defects, since their size, composition, and surface chemistry can be precisely tailored for biosensing and optoelectronic applications. Here, we present a method for synthesizing colloidal ZnS:Cu NCs that emit primarily R-Cu, which has been proposed to arise from the CuZn-VS complex, an impurity-vacancy point defect structure analogous to well-known quantum defects in other materials that produce favorable optical and spin dynamics. First-principles calculations confirm the thermodynamic stability and electronic structure of CuZn-VS. Temperature- and time-dependent optical properties of ZnS:Cu NCs show blueshifting luminescence and an anomalous plateau in the intensity dependence as temperature is increased from 19 K to 290 K, for which we propose an empirical dynamical model based on thermally activated coupling between two manifolds of states inside the ZnS bandgap. Understanding of R-Cu emission dynamics, combined with a controlled synthesis method for obtaining R-Cu centers in colloidal NC hosts, will greatly facilitate the development of CuZn-VS and related complexes as quantum point defects in ZnS.

Frequency Stabilization and Optically Tunable Lasing in Colloidal Quantum Dot Superparticles.

Self-assembled superparticles composed of colloidal quantum dots establish microsphere cavities that support optically pumped lasing from whispering gallery modes. Here, we report on the time- and excitation fluence-dependent lasing properties of CdSe/CdS quantum dot superparticles. Spectra collected under constant photoexcitation reveal that the lasing modes are not temporally stable but instead blue-shift by more than 30 meV over 15 min. To counter this effect, we establish a high-fluence light-soaking protocol that reduces this blue-shift by more than an order of magnitude to 1.7 ± 0.5 meV, with champion superparticles displaying mode blue-shifts of <0.5 meV. Increasing the pump fluence allows for optically controlled, reversible, color-tunable red-to-green lasing. Combining these two paradigms suggests that quantum dot superparticles could serve in applications as low-cost, robust, solution-processable, tunable microlasers.

Deterministic Quantum Light Arrays from Giant Silica-Shelled Quantum Dots.

Colloidal quantum dots (QDs) are promising candidates for single-photon sources with applications in photonic quantum information technologies. Developing practical photonic quantum devices with colloidal materials, however, requires scalable deterministic placement of stable single QD emitters. In this work, we describe a method to exploit QD size to facilitate deterministic positioning of single QDs into large arrays while maintaining their photostability and single-photon emission properties. CdSe/CdS core/shell QDs were encapsulated in silica to both increase their physical size without perturbing their quantum-confined emission and enhance their photostability. These giant QDs were then precisely positioned into ordered arrays using template-assisted self-assembly with a 75% yield for single QDs. We show that the QDs before and after assembly exhibit antibunching behavior at room temperature and their optical properties are retained after an extended period of time. Together, this bottom-up synthetic approach via silica shelling and the robust template-assisted self-assembly offer a unique strategy to produce scalable quantum photonics platforms using colloidal QDs as single-photon emitters.

Chemical and Physical Properties of Photonic Noble-Metal Nanomaterials.

Colloidal noble metal nanoparticles (NPs) are composed of metal cores and organic or inorganic ligand shells. These NPs support size- and shape-dependent plasmonic resonances. They can be assembled from dispersions into artificial metamolecules which have collective plasmonic resonances originating from coupled bright and dark optical electric and magnetic modes that form depending on the size and shape of the constituent NPs and their number, arrangement, and interparticle distance. NPs can also be assembled into extended 2D and 3D metamaterials that are glassy thin films or ordered thin films or crystals, also known as superlattices and supercrystals. The metamaterials have tunable optical properties that depend on the size, shape, and composition of the NPs, and on the number of NP layers and their interparticle distance. Interestingly, strong light-matter interactions in superlattices form plasmon polaritons. Tunable interparticle distances allow designer materials with dielectric functions tailorable from that characteristic of an insulator to that of a metal, and serve as strong optical absorbers or scatterers, respectively. In combination with lithography techniques, these extended assemblies can be patterned to create subwavelength NP superstructures and form large-area 2D and 3D metamaterials that manipulate the amplitude, phase, and polarization of transmitted or reflected light.

Large Exciton Polaron Formation in 2D Hybrid Perovskites via Time-Resolved Photoluminescence.

We find evidence for the formation and relaxation of large exciton polarons in 2D organic-inorganic hybrid perovskites. Using ps-scale time-resolved photoluminescence within the phenethylammonium lead iodide family of compounds, we identify a red shifting of emission that we associate with exciton polaron formation time scales of 3-10 ps. Atomic substitutions of the phenethylammonium cation allow local control over the structure of the inorganic lattice, and we show that the structural differences among materials strongly influence the exciton polaron relaxation process, revealing a polaron binding energy that grows larger (up to 15 meV) in more strongly distorted compounds.

Magnetic Field Alignment and Optical Anisotropy of MoS2 Nanosheets Dispersed in a Liquid Crystal Polymer.

Molybdenum disulfide (MoS2) nanosheets exhibit anisotropic optical and electronic properties, stemming from their shape and electronic structure. Unveiling this anisotropy for study and usage in materials and devices requires the ability to control the orientation of dispersed nanosheets, but to date this has proved a challenging proposition. Here, we demonstrate magnetic field driven alignment of MoS2 nanosheets in a liquid crystal (LC) polymer and unveil the optical properties of the resulting anisotropic assembly. Nanosheet optical anisotropy is observed spectroscopically by Raman and direction-dependent photoluminescence (PL) measurements. Resulting data indicate significantly lower PL emission due to optical excitation with electric field oscillation out of plane, parallel to the MoS2 c-axis, than that associated with perpendicular excitation, with the dichroic ratio Iperp/Ipar = 3. The approach developed here provides a useful route to elucidate anisotropic optical properties of MoS2 nanosheets and to utilize such properties in new materials and devices.

Nanocrystal Superparticles with Whispering-Gallery Modes Tunable through Chemical and Optical Triggers.

Whispering-gallery microresonators have the potential to become the building blocks for optical circuits. However, encoding information in an optical signal requires on-demand tuning of optical resonances. Tuning is achieved by modifying the cavity length or the refractive index of the microresonator. Due to their solid, nondeformable structure, conventional microresonators based on bulk materials are inherently difficult to tune. In this work, we fabricate irreversibly tunable optical microresonators by using semiconductor nanocrystals. These nanocrystals are first assembled into colloidal spherical superparticles featuring whispering-gallery modes. Exposing the superparticles to shorter ligands changes the nanocrystal surface chemistry, decreasing the cavity length of the microresonator by 20% and increasing the refractive index by 8.2%. Illuminating the superparticles with ultraviolet light initiates nanocrystal photo-oxidation, providing an orthogonal channel to decrease the refractive index of the microresonator in a continuous fashion. Through these approaches, we demonstrate optical microresonators tunable by several times their free spectral range.

Dynamic magnetic field alignment and polarized emission of semiconductor nanoplatelets in a liquid crystal polymer.

Reconfigurable arrays of 2D nanomaterials are essential for the realization of switchable and intelligent material systems. Using liquid crystals (LCs) as a medium represents a promising approach, in principle, to enable such control. In practice, however, this approach is hampered by the difficulty of achieving stable dispersions of nanomaterials. Here, we report on good dispersions of pristine CdSe nanoplatelets (NPLs) in LCs, and reversible, rapid control of their alignment and associated anisotropic photoluminescence, using a magnetic field. We reveal that dispersion stability is greatly enhanced using polymeric, rather than small molecule, LCs and is considerably greater in the smectic phases of the resulting systems relative to the nematic phases. Aligned composites exhibit highly polarized emission that is readily manipulated by field-realignment. Such dynamic alignment of optically-active 2D nanomaterials may enable the development of programmable materials for photonic applications and the methodology can guide designs for anisotropic nanomaterial composites for a broad set of related nanomaterials.

Photophysics of Two-Dimensional Semiconducting Organic-Inorganic Metal-Halide Perovskites.

Two-dimensional organic-inorganic hybrid perovskites (2DHPs) consist of alternating anionic metal-halide and cationic organic layers. They have widely tunable structural and optical properties. We review the role of the organic cation in defining the structural and optical properties of 2DHPs through the example of lead iodide 2DHPs. Even though excitons reside in the metal-halide layers, the organic and inorganic frameworks cannot be separated-they must be considered as a single unit to fully understand the photophysics of 2DHPs. We correlate cation-induced distortion and disorder in the inorganic lattice with the resulting optical properties. We also discuss the role of the cation in creating and altering the discrete excitonic structure that appears at cryogenic temperatures in some 2DHPs, including the cation-dependent presence of hot-exciton photoluminescence. We conclude our review with an outlook for 2DHPs, highlighting existing gaps in fundamental knowledge as well as potential future applications.

Electrochemically deposited molybdenum disulfide surfaces enable polymer adsorption studies using quartz crystal microbalance with dissipation monitoring (QCM-D).

Polymer and small molecules are often used to modify the wettability of mineral surfaces which facilitates the separation of valuable minerals such as molybdenum disulfide (MoS2) from gangue material through the process of froth flotation. By design, traditional methods used in the field for evaluating the separation efficacy of these additives fail to give proper access to adsorption kinetics and molecule conformation, crucial aspects of flotation where contact times may not allow for full thermodynamic equilibrium. Thus, there is a need for alternative methods for evaluating additives that accurately capture these features during the adsorption of additives at the solid/liquid interface. Here, we present a novel method for preparing MoS2 films on quartz crystals used for Quartz Crystal Microbalance with Dissipation (QCM-D) measurements through an electrochemical deposition process. The resulting films exhibit well-controlled structure, composition, and thickness and therefore are ideal for quantifying polymer adsorption. After deposition, the sensors can be annealed without damaging the quartz crystal, resulting in a phase transition of the MoS2 from the as-deposited, amorphous phase to the 2H semiconducting phase. Furthermore, we demonstrate the application of these sensors to study the interactions of additives at the solid/liquid interface by investigating the adsorption of a model polymer, dextran, onto both the amorphous and crystalline MoS2 surfaces. We find that the adsorption rate of dextran onto the amorphous surface is approximately twice as fast as the adsorption onto the annealed surface. These studies demonstrate the ability to gain insight into the short-term kinetics of interaction between molecules and mineral surface, behavior that is key to designing additives with superior separation efficiency.

Sub-5 nm Anisotropic Pattern Transfer via Colloidal Lithography of a Self-Assembled GdF3 Nanocrystal Monolayer.

Patterning materials with nanoscale features opens many research opportunities ranging from fundamental science to technological applications. However, current nanofabrication methods are ill-suited for sub-5 nm patterning and pattern transfer. We demonstrate the use of colloidal lithography to transfer an anisotropic pattern of discrete features into substrates with a critical dimension below 5 nm. The assembly of monodisperse, anisotropic nanocrystals (NCs) with a rhombic-plate morphology spaced by dendrimer ligands results in a well-ordered monolayer that serves as a 2D anisotropic hard mask pattern. This pattern is transferred into the underlying substrate using dry etching followed by removal of the NC mask. We exemplify this approach by fabricating an array of pillars with a rhombic cross-section and edge-to-edge spacing of 4.4 ± 1.1 nm. The fabrication approach enables broader access to patterning materials at the deep nanoscale by implementing innovative processes into well-established fabrication methods while minimizing process complexity.

Template-Assisted Self-Assembly of Fluorescent Nanodiamonds for Scalable Quantum Technologies.

Milled nanodiamonds containing nitrogen-vacancy (NV) centers are nanoscale quantum sensors that form colloidal dispersions. However, variations in their size, shape, and surface chemistry limit the ability to position individual nanodiamonds and statistically study properties that affect their optical and quantum characteristics. Here, we present a scalable strategy to form ordered arrays of nanodiamonds using capillary-driven, template-assisted self-assembly. We demonstrate the precise spatial arrangement of isolated nanodiamonds with diameters below 50 nm across millimeter-scale areas. Measurements of over 200 assembled nanodiamonds yield a statistical understanding of their structural, optical, and quantum properties. The NV centers' spin and charge properties are uncorrelated with nanodiamond size but rather are consistent with heterogeneity in their nanoscale environment.

Ink-Lithography for Property Engineering and Patterning of Nanocrystal Thin Films.

Next-generation devices and systems require the development and integration of advanced materials, the realization of which inevitably requires two separate processes: property engineering and patterning. Here, we report a one-step, ink-lithography technique to pattern and engineer the properties of thin films of colloidal nanocrystals that exploits their chemically addressable surface. Colloidal nanocrystals are deposited by solution-based methods to form thin films and a local chemical treatment is applied using an ink-printing technique to simultaneously modify (i) the chemical nature of the nanocrystal surface to allow thin-film patterning and (ii) the physical electronic, optical, thermal, and mechanical properties of the nanocrystal thin films. The ink-lithography technique is applied to the library of colloidal nanocrystals to engineer thin films of metals, semiconductors, and insulators on both rigid and flexible substrates and demonstrate their application in high-resolution image replications, anticounterfeit devices, multicolor filters, thin-film transistors and circuits, photoconductors, and wearable multisensors.