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.

Enhanced Carrier Transport in Strongly Coupled, Epitaxially Fused CdSe Nanocrystal Solids.

Strongly coupled, epitaxially fused colloidal nanocrystal (NC) solids are promising solution-processable semiconductors to realize optoelectronic devices with high carrier mobilities. Here, we demonstrate sequential, solid-state cation exchange reactions to transform epitaxially connected PbSe NC thin films into Cu2Se nanostructured thin-film intermediates and then successfully to achieve zinc-blende, CdSe NC solids with wide epitaxial necking along {100} facets. Transient photoconductivity measurements probe carrier transport at nanometer length scales and show a photoconductance of 0.28(1) cm2 V-1 s-1, the highest among CdSe NC solids reported. Atomic-layer deposition of a thin Al2O3 layer infiltrates and protects the structure from fusing into a polycrystalline thin film during annealing and further improves the photoconductance to 1.71(5) cm2 V-1 s-1 and the diffusion length to 760 nm. We fabricate field-effect transistors to study carrier transport at micron length scales and realize high electron mobilities of 35(3) cm2 V-1 s-1 with on-off ratios of 106 after doping.

Chemo- and Thermomechanically Configurable 3D Optical Metamaterials Constructed from Colloidal Nanocrystal Assemblies.

Nanofabrication has limited most optical metamaterials to 2D or, often with multiple patterning steps, simple 3D meta-atoms that typically have limited built-in tunability. Here, with a one-step scalable patterning process, we exploit the chemical addressability and structural adaptability of colloidal Au nanocrystal assemblies to transform 2D nanocrystal/Ti bilayers into complex, 3D-structured meta-atoms and to thermally direct their shape morphing and alter their optical properties. By tailoring the length, number, and curvature of 3D helical structures in each meta-atom, we create large-area metamaterials with chiroptical responses of as high as ∼40% transmission difference between left-hand (LCP) and right-hand (RCP) circularly polarized light (ΔT = TRCP - TLCP) that are suitable for broadband circular polarizers and, upon thermally configuring their shape, switch the polarity of polarization rotation. These 3D optical metamaterials provide prototypes for low-cost, large-scale fabrication of optical metamaterials for ultrathin lenses, polarizers, and waveplates.

Designing Strong Optical Absorbers via Continuous Tuning of Interparticle Interaction in Colloidal Gold Nanocrystal Assemblies.

We program the optical properties of colloidal Au nanocrystal (NC) assemblies via an unconventional ligand hybridization (LH) strategy to precisely engineer interparticle interactions and design materials with optical properties difficult or impossible to achieve in bulk form. Long-chain hydrocarbon ligands used in NC synthesis are partially exchanged, from 0% to 100%, with compact thiocyanate ligands by controlling the reaction time for exchange. The resulting NC assemblies show transmittance, reflectance, optical permittivity, and direct-current (DC) resistivity that continuously traverse a dielectric-metal transition, providing analog tuning of their physical properties, unlike the digital control realized by complete exchange with ligands of varying length. Exploiting this LH strategy, we create Au NC assemblies that are strong, ultrathin film optical absorbers, as seen by a 6× increase in the extinction of infrared light compared to that in bulk Au thin films and by a temperature rise of 20 °C upon illumination with 808 nm light. Our LH strategy may be applied to the design of materials constructed from NCs of different size, shape, and composition for specific applications.

Air-Stable CuInSe2 Nanocrystal Transistors and Circuits via Post-Deposition Cation Exchange.

Colloidal semiconductor nanocrystals (NCs) are a promising materials class for solution-processable, next-generation electronic devices. However, most high-performance devices and circuits have been achieved using NCs containing toxic elements, which may limit their further device development. We fabricate high mobility CuInSe2 NC field-effect transistors (FETs) using a solution-based, post-deposition, sequential cation exchange process that starts with electronically coupled, thiocyanate (SCN)-capped CdSe NC thin films. First Cu+ is substituted for Cd2+ transforming CdSe NCs to Cu-rich Cu2Se NC films. Next, Cu2Se NC films are dipped into a Na2Se solution to Se-enrich the NCs, thus compensating the Cu-rich surface, promoting fusion of the Cu2Se NCs, and providing sites for subsequent In-dopants. The liquid-coordination-complex trioctylphosphine-indium chloride (TOP-InCl3) is used as a source of In3+ to partially exchange and n-dope CuInSe2 NC films. We demonstrate Al2O3-encapsulated, air-stable CuInSe2 NC FETs with linear (saturation) electron mobilities of 8.2 ± 1.8 cm2/(V s) (10.5 ± 2.4 cm2/(V s)) and with current modulation of 105, comparable to that for high-performance Cd-, Pb-, and As-based NC FETs. The CuInSe2 NC FETs are used as building blocks of integrated inverters to demonstrate their promise for low-cost, low-toxicity NC circuits.

Ultrasensitive, Mechanically Responsive Optical Metasurfaces via Strain Amplification.

Optical metasurfaces promise ultrathin, lightweight, miniaturized optical components with outstanding capabilities to manipulate the amplitude, phase, and polarization of light compared to conventional, bulk optics. The emergence of reconfigurable metasurfaces further integrates dynamic tunability with optical functionalities. Here, we report a structurally reconfigurable, optical metasurface constructed by integrating a plasmonic lattice array in the gap between a pair of symmetric microrods that serve to locally amplify the strain created on an elastomeric substrate by an external mechanical stimulus. The strain on the metasurface is amplified by a factor of 1.5-15.9 relative to the external strain by tailoring the microrod geometry. For the highest strain amplification geometry, the mechano-sensitivity of the optical responses of the plasmonic lattice array is a factor of 10 greater than that of state-of-the-art stretchable plasmonic resonator arrays. The spatial arrangement and therefore the optical response of the plasmonic lattice array are reversible, showing little hysteresis.

3D Nanofabrication via Chemo-Mechanical Transformation of Nanocrystal/Bulk Heterostructures.

Planar nanocrystal/bulk heterostructures are transformed into 3D architectures by taking advantage of the different chemical and mechanical properties of nanocrystal and bulk thin films. Nanocrystal/bulk heterostructures are fabricated via bottom-up assembly and top-down fabrication. The nanocrystals are capped by long ligands introduced in their synthesis, and therefore their surfaces are chemically addressable, and their assemblies are mechanically "soft," in contrast to the bulk films. Chemical modification of the nanocrystal surface, exchanging the long ligands for more compact chemistries, triggers large volume shrinkage of the nanocrystal layer and drives bending of the nanocrystal/bulk heterostructures. Exploiting the differential chemo-mechanical properties of nanocrystal and bulk materials, the scalable fabrication of designed 3D, cell-sized nanocrystal/bulk superstructures is demonstrated, which possess unique functions derived from nanocrystal building blocks.

The Effect of Dielectric Environment on Doping Efficiency in Colloidal PbSe Nanostructures.

Doping, as a central strategy to control free carrier type and concentration in semiconductor materials, suffers from low efficiency at the nanoscale, especially in systems having high permittivity (ϵ) and large Bohr radii, such as lead chalcogenide nanocrystals (NCs) and nanowires (NWs). Here, we study dielectric confinement effects on the doping efficiency of lead chalcogenides nanostructures by integrating PbSe NWs in the platform of field effect transistors (FETs). Elemental Pb or In or elemental Se is deposited by thermal evaporation to remotely n- or p-dope the NWs. Polymeric and oxide materials of varying ϵ are subsequently deposited to control the dielectric environment surrounding the NWs. Analyzing the device characteristics, we extract the change of carrier concentration introduced by tailoring the dielectric environment. The calculated doping efficiency for n-type (Pb/In) and p-type (Se) dopants increases as the ϵ of the surrounding medium increases. Using a high-ϵ material, such as HfO2 for encapsulation, the doping efficiency can be enhanced by >10-fold. A theoretical model is built to describe the doping efficiency in PbSe NWs embedded in different dielectric environments, which agrees with our experimental data for both NW array and single NW devices. As dielectric confinement affects all low-dimensional materials, engineering the dielectric environment is a promising general approach to enhance doping concentrations, without introducing excess impurities that may scatter carriers, and is suitable for various device applications.

High-strength magnetically switchable plasmonic nanorods assembled from a binary nanocrystal mixture.

Next-generation 'smart' nanoparticle systems should be precisely engineered in size, shape and composition to introduce multiple functionalities, unattainable from a single material. Bottom-up chemical methods are prized for the synthesis of crystalline nanoparticles, that is, nanocrystals, with size- and shape-dependent physical properties, but they are less successful in achieving multifunctionality. Top-down lithographic methods can produce multifunctional nanoparticles with precise size and shape control, yet this becomes increasingly difficult at sizes of ∼10 nm. Here, we report the fabrication of multifunctional, smart nanoparticle systems by combining top-down fabrication and bottom-up self-assembly methods. Particularly, we template nanorods from a mixture of superparamagnetic Zn0.2Fe2.8O4 and plasmonic Au nanocrystals. The superparamagnetism of Zn0.2Fe2.8O4 prevents these nanorods from spontaneous magnetic-dipole-induced aggregation, while their magnetic anisotropy makes them responsive to an external field. Ligand exchange drives Au nanocrystal fusion and forms a porous network, imparting the nanorods with high mechanical strength and polarization-dependent infrared surface plasmon resonances. The combined superparamagnetic and plasmonic functions enable switching of the infrared transmission of a hybrid nanorod suspension using an external magnetic field.

Advanced Architecture for Colloidal PbS Quantum Dot Solar Cells Exploiting a CdSe Quantum Dot Buffer Layer.

Advanced architectures are required to further improve the performance of colloidal PbS heterojunction quantum dot solar cells. Here, we introduce a CdI2-treated CdSe quantum dot buffer layer at the junction between ZnO nanoparticles and PbS quantum dots in the solar cells. We exploit the surface- and size-tunable electronic properties of the CdSe quantum dots to optimize its carrier concentration and energy band alignment in the heterojunction. We combine optical, electrical, and analytical measurements to show that the CdSe quantum dot buffer layer suppresses interface recombination and contributes additional photogenerated carriers, increasing the open-circuit voltage and short-circuit current of PbS quantum dot solar cells, leading to a 25% increase in solar power conversion efficiency.