Orientation-Dependent Photoconductivity of Quasi-2D Nanocrystal Self-Assemblies: Face-Down, Edge-Up Versus Randomly Oriented Quantum Wells.

Here, strongly orientation-dependent lateral photoconductivity of a CdSe monolayer colloidal quantum wells (CQWs) possessing short-chain ligands is reported. A controlled liquid-air self-assembly technique is utilized to deliberately engineer the alignments of CQWs into either face-down (FO) or edge-up (EO) orientation on the substrate as opposed to randomly oriented (RO) CQWs prepared by spin-coating. Adapting planar configuration metal-semiconductor-metal (MSM) photodetectors, it is found that lateral conductivity spans ≈2 orders of magnitude depending on the orientation of CQWs in the film in the case of utilizing short ligands. The long native ligands of oleic acid (OA) are exchanged with short-chain ligands of 2-ethylhexane-1-thiol (EHT) to reduce the inter-platelet distance, which significantly improved the photoresponsivity from 4.16, 0.58, and 4.79 mA W-1 to 528.7, 6.17, and 94.2 mA W-1, for the MSM devices prepared with RO, FO, and EO, before and after ligands exchange, respectively. Such CQW orientation control profoundly impacts the photodetector performance also in terms of the detection speed (0.061 s/0.074 s for the FO, 0.048 s/0.060 s for the EO compared to 0.10 s/0.16 s for the RO, for the rise and decay time constants, respectively) and the detectivity (1.7 × 1010, 2.3 × 1011, and 7.5 × 1011 Jones for the FO, EO, and RO devices, respectively) which can be further tailored for the desired optoelectronic device applications. Attributed to charge transportation in colloidal films being proportional to the number of hopping steps, these findings indicate that the solution-processed orientation of CQWs provides the ability to tune the photoconductivity of CQWs with short ligands as another degree of freedom to exploit and engineer their absorptive devices.

Damage-Free Silica Coating for Colloidal Nanocrystals Through a Proactively Water-Generating Amidation Reaction at High Temperature.

Silica is a promising shell coating material for colloidal nanoparticles due to its excellent chemical inertness and optical transparency. To encapsulate high-quality colloidal nanocrystals with silica shells, the silane coupling hydrolysis is currently the most effective approach. However, this reaction requires water, which often adversely affects the intrinsic physicochemical properties of nanocrystals. Achieving a damage-free silica encapsulation process to nanocrystals by hydrolysis is a huge challenge. Here, a novel strategy is developed to coat colloidal nanocrystals with a denser silica shell via a proactively water-generating reaction at high temperature. In this work, water molecules are continuously and proactively released into the reaction system through the amidation reaction, followed by in situ hydrolysis of silane, completely avoiding the impacts of water on nanocrystals during the silica coating process. In this work, water sensitive perovskite nanocrystals (CsPbBr3) are selected as the typical colloidal nanocrystals for silica coating. Notably, this high-temperature in situ encapsulation technology greatly improves the optical properties of nanocrystals, and the silica shells exhibit a denser structure, providing nanocrystals with better protection. This method overcomes the challenge of the influence of water on nanocrystals during the hydrolysis process, and provides an important reference for the non-destructive encapsulation of colloidal nanocrystals.

Colloidal CsBr Nanocrystals Triggered Inorganic Cation and Anion Exchange Enables High-Performance Perovskite Solar Cells.

Achieving longitudinal doping of specific ions by surface treatment remains a challenge for perovskite solar cells, which are often limited by dopant and solvent compatibility. Here, with the flowing environment created by CsBr colloidal nanocrystals, ion exchange is induced on the surface of the perovskite film to enable the homogeneous distribution of Cs+ and gradient distribution of Br- simultaneously at whole depth of the film. Meanwhile, assisted by long-chain organic ligands, the excess PbI2 on the surface of perovskite film is converted to a more stable quasi-2D perovskite, which realizes effective passivation of defects on the surface. As a result, the unfavorable n-type doping on the top surface is suppressed, so that the energy level alignment between perovskite and hole transport layer is optimized. On the basis of co-modification of the surface and the bulk, the PCE of champion device reaches 23.22% with enhanced VOC of 1.12 V. Device maintains 97.12% of the initial PCE in dark ambient air at 1% RH after 1056 h without encapsulation, and 91.56% of the initial PCE under light illumination of 1 sun in N2 atmosphere for more than 200 h. The approach demonstrated here provides an effective strategy for the nondestructive introduction of inorganic ions in perovskite film.

General Syntheses of High-Performance Thermoelectric Nanostructured Solids without Post-Synthetic Ligand Stripping.

Ligand-assisted wet chemical synthesis is a versatile methodology to produce controllable nanocrystals (NCs). The post-treatment of ligands is significant for the performance of functional devices. Herein, a method that retains ligands of colloidal-synthesized nanomaterials to produce thermoelectric nanomaterials is proposed, which differs from the conventional methods that strip ligands using multistep cumbersome processes. The ligand-retention method can control the size and dispersity of nanocrystals during the consolidation of the NCs into dense pellets, in which retained ligands are transformed into organic carbon within the inorganic matrices, establishing clear organic-inorganic interfaces. Characterizations of the nonstripped and stripped samples confirm that this strategy can affect electric transport slightly but reduce the thermal conductivity largely. As a result, the materials (e.g., SnSe, Cu2-xS, AgBiSe2, and Cu2ZnSnSe4) with ligands retained achieve higher peak zT and better mechanical properties. This method can be applied to other colloidal thermoelectric NCs and functional materials.

Remarkable Electrical Conductivity Increase and Pure Metallic Properties from Semiconducting Colloidal Nanocrystals by Cation Exchange for Solution-Processable Optoelectronic Applications.

The authors report a strategic approach to achieve metallic properties from semiconducting CuFeS colloidal nanocrystal (NC) solids through cation exchange method. An unprecedentedly high electrical conductivity is realized by the efficient generation of charge carriers onto a semiconducting CuS NC template via minimal Fe exchange. An electrical conductivity exceeding 10 500 S cm-1 (13 400 S cm-1 at 2 K) and a sheet resistance of 17 Ω/sq at room temperature, which are among the highest values for solution-processable semiconducting NCs, are achieved successfully from bornite-phase CuFeS NC films possessing 10% Fe atom. The temperature dependence of the corresponding films exhibits pure metallic characteristics. Highly conducting NCs are demonstrated for a thermoelectric layer exhibiting a high power factor over 1.2 mW m-1 K-2 at room temperature, electrical wires for switching on light emitting diods (LEDs), and source-drain electrodes for p- and n-type organic field-effect transistors. Ambient stability, eco-friendly composition, and solution-processability further validate their sustainable and practical applicability. The present study provides a simple but very effective method for significantly increasing charge carrier concentrations in semiconducting colloidal NCs to achieve metallic properties, which is applicable to various optoelectronic devices.

Surface-Stabilized CsPbI3 Nanocrystals with Tailored Organic Polymer Ligand Binding.

Perovskite nanocrystals (NCs) exhibit attractive photophysical properties by combining the excellent optoelectronic properties of bulk perovskites with the strong quantum confinement effect at the nanoscale. However, CsPbI3 NCs easily transform into a non-perovskite phase because of the ionic lattice and dynamic ligand binding. Herein, stable black-phase CsPbI3 NCs capped with a new organic ligand, HO-PS-N3 (HOPS), which consists of a polystyrene segment with hydroxyl and azide end groups, are reported. This organic polymer ligand passivated the surface defects and enhanced the stability of CsPbI3 NCs by exposing the linking hydrophobic polystyrene segment. Consequently, the optimized CsPbI3 NCs exhibit significantly improved resistance to moisture or light and maintained 70 % of the original luminous intensity after immersion in water for two months. The theoretical results revealed that the binding energy of the HOPS ligand on the surface of the CsPbI3 NCs is higher than that of the commonly used oleic acid, alleviating the defects-induced degradation during purification. Thus, surface-stabilized CsPbI3 NCs are beneficial for a broad range of optoelectronic applications.

Trade-offs between Translational and Orientational Order in 2D Superlattices of Polygonal Nanocrystals with Differing Edge Count.

The goal of this work is to identify factors which modulate structural order in 2D self-assembled superlattices of polygon-shaped colloidal nanocrystals. Using combined experimental and simulation techniques, we quantify order in superlattices of hexagonal prism-shaped CdSe/CdS nanocrystals and cube-shaped CsPbBr3 nanocrystals. Superlattices derived from cube-shaped nanocrystals display less translational order compared to hexagonal prism-shaped nanocrystals both experimentally and in simulations. This effect can be attributed to geometric considerations inherent to the combined rotational and translational symmetries of different polygonal shapes and their superlattices. Cubes form a simple cubic lattice where nanocrystals can slide without steric overlap, whereas hexagonal prisms interlock, preventing translation. Regarding orientational order, cube assemblies display a narrower orientation distribution. Intuitively, hexagonal prisms are a more "spherical" shape compared to cubes. The results presented here outline a conceptual framework for identifying superlattice structures which favor translationally and orientationally ordered self-assembled superlattices.

Alloying Bi-Doped Cs2Ag1-xNaxInCl6 Nanocrystals with K+ Cations Modulates Surface Ligands Density and Photoluminescence Efficiency.

We show how, in the synthesis of yellow-emissive Bi-doped Cs2Ag1-xNaxInCl6 double perovskite nanocrystals (NCs), preventing the transient formation of Ag0 particles increases the photoluminescence quantum yield (PLQY) of the NCs from ∼30% to ∼60%. Calculations indicate that the presence of even a single Ag0 species on the surface of a NC introduces deep trap states. The PL efficiency of these NCs is further increased to ∼70% by partial replacement of Na+ with K+ ions, up to a 7% K content, due to a lattice expansion that promotes a more favorable ligands packing on the NC surface, hence better surface passivation. A further increase in K+ lowers the PLQY, due to both the activation of nonradiative quenching channels and a lower oscillator strength of the BiCl6→AgCl6 transition (through which PL emission occurs). The work indicates how a deeper understanding of parameters influencing carrier trapping/relaxation can boost the PLQY of double perovskites NCs.

Surface Sites and Ligation in Amine-capped CdSe Nanocrystals.

Converting colloidal nanocrystals (NCs) into devices for various applications is facilitated by designing and controlling their surface properties. One key strategy for tailoring surface properties is thus to choose tailored surface ligands. In that context, amines have been universally used, with the goal to improve NCs synthesis, processing and performances. However, understanding the nature of surface sites in amine-capped NCs remains challenging, due to the complex surface compositions as well as surface ligands dynamic. Here, we investigate both surface sites and amine ligation in CdSe NCs by combining advanced NMR spectroscopy and computational modelling. Notably, dynamic nuclear polarization (DNP) enhanced 113 Cd and 77 Se 1D NMR helps to identify both bulk and surface sites of NCs, while 113 Cd 2D NMR spectroscopy enables to resolve amines terminated sites on both Se-rich and nonpolar surfaces. In addition to directly bonding to surface sites, amines are shown to also interact through hydrogen-bonding with absorbed water as revealed by 15 N NMR, augmented with computations. The characterization methodology developed for this work provides unique molecular-level insight into the surface sites of a range of amine-capped CdSe NCs, and paves the way to identify structure-function relationships and rational approaches towards colloidal NCs with tailored properties.

Entropy-Driven Unconventional Crystallization of Spherical Colloidal Nanocrystals Confined in Wide Cylinders.

The densest packings of identical spherical colloidal nanocrystals in a thin cylinder generally give rise to confinement-induced chiral ordering. Here, we demonstrate that entropy can invalidate Pauling's packing rules for the nanocrystals confined in wide cylinders and novel ordered phases, where chiral ordering is broken, emerge. The nucleation and growth of spherical colloidal nanocrystals in the wide cylinders exhibit unique mechanisms which are distinctly different from that of thin ones. Furthermore, theoretical models which capture the essential physics of the ordering transitions are developed to reproduce the achiral ordering and reveal that the ordered phases are thermodynamically stable and stabilized through confinement-mediated entropic effect. These findings demonstrate that entropy arising from thermal motion can invalidate Pauling's packing rules of spherical colloidal nanocrystals confined in cylinders, which provides new insights into confinement physics of colloidal particles and might inspire nonintuitive design rules for the fabrication of novel ordered phases through confinement.

Surface Chemistry Impact on the Light Absorption by Colloidal Quantum Dots.

At the size scale at which quantum confinement effects arise in inorganic semiconductors, the materials' surface-to-volume ratio is intrinsically high. This consideration sets surface chemistry as a powerful tool to exert further control on the electronic structure of the inorganic semiconductors. Among the materials that experience the quantum confinement regime, those prepared via colloidal synthetic procedures (the colloidal quantum dots - and wires and wells, too -) are prone to undergo surface reactions in the solution phase and thus represent an ideal framework to study the ensemble impact of surface chemistry on the materials' electronic structure. It is here discussed such an impact at the ground state by using the absorption spectrum of the colloidal quantum dots as a descriptor. The experiments show that the chemical species (the ligands) at the colloidal quantum dot surface induce changes to the optical band gap, the absorption coefficient at all wavelengths, and the ionization potential. These evidences point to a description of the colloidal quantum dot (the ligand/core adduct) as an indecomposable species, in which the orbitals localized on the ligands and the core mix in each other's electric field. This description goes beyond conventional models that conceive the ligands on the basis of pure electrostatic arguments (i. e., either as a dielectric shell or as electric dipoles) or as a mere potential energy barrier at the core boundaries.

Colloidal upconversion nanocrystals enable low-temperature-grown GaAs photoconductive switch operating atλ = 1.55µm.

Microwave photoconductive switches, allowing an optical control on the magnitude and phase of the microwave signals to be transmitted, are important components for many optoelectronic applications. In recent years, there are significant demands to develop photoconductive switches functional in the short-wave-infrared spectrum window (e.g.λ = 1.3-1.55µm) but most state-of-the-art semiconductors for photoconductive switches cannot achieve this goal. In this work, we propose a novel approach, by the use of solution-processed colloidal upconversion nanocrystals deposited directly onto low-temperature-grown gallium arsenide (LT-GaAs), to achieve microwave photoconductive switches functional atλ = 1.55µm illumination. Hybrid upconversion Er3+-doped NaYF4nanocrystal/LT-GaAs photoconductive switch was fabricated. Under a continuous waveλ = 1.55µm laser illumination (power density âˆ¼ 12.9 mWµm-2), thanks to the upconversion energy transfer from the nanocrystals, a more than 2-fold larger value in decibel was measured for the ON/OFF ratio on the hybrid nanocrystal/LT-GaAs device by comparison to the control device without upconversion nanoparticles. A maximum ON/OFF ratio reaching 20.6 dB was measured on the nanocrystal/LT-GaAs hybrid device at an input signal frequency of 20 MHz.

Let There Be Order, in Films of Colloidal CdSe 2D Nanocrystals.

Progression from random orientation of 2D CdSe nanoplatelets to ordered close-packed thin films enables us to exploit the in-plane dipole moment of the band-edge transition on a macroscopic scale and gain control over the direction of charge and energy transport within the film. Momper et al. show how this can be achieved by tuning the solvent evaporation rate during deposition. They are able to switch from thermodynamically to kinetically controlled conditions for the film formation, resulting in ordered films with either face-down or edge-up alignment of the 2D nanoplatelets.

Facile in situ Synthesis of Ag-Doped CdSe Supra-Quantum Dots and their Characterization.

A supra-quantum dot (SQD) is a three-dimensionally assembled QD structure composed of several hundreds to thousands of QDs connected through oriented attachments. Owing to their three-dimensional interconnected structures and relatively large volumes, impurity atoms are thermodynamically more stable in SQDs than in conventional QDs. Herein, we report the facile in-situ synthesis of colloidal Ag-doped CdSe SQDs. Ag dopants were efficiently incorporated into CdSe SQDs through the three-dimensional interconnection of Ag-doped primary CdSe QDs, as confirmed by elemental analysis combined with chemical etching. Photoelectron spectroscopic studies revealed that the Ag-doped CdSe SQDs exhibit n-type doping behavior, since the valence electrons from the interstitial Ag atoms are directly donated to the lattice.

In Situ X-ray Scattering Guides the Synthesis of Uniform PtSn Nanocrystals.

Compared to monometallic nanocrystals (NCs), bimetallic ones often exhibit superior properties due to their wide tunability in structure and composition. A detailed understanding of their synthesis at the atomic scale provides crucial knowledge for their rational design. Here, exploring the Pt-Sn bimetallic system as an example, we study in detail the synthesis of PtSn NCs using in situ synchrotron X-ray scattering. We show that when Pt(II) and Sn(IV) precursors are used, in contrast to a typical simultaneous reduction mechanism, the PtSn NCs are formed through an initial reduction of Pt(II) to form Pt NCs, followed by the chemical transformation from Pt to PtSn. The kinetics derived from the in situ measurements shows fast diffusion of Sn into the Pt lattice accompanied by reordering of these atoms into intermetallic PtSn structure within 300 s at the reaction temperature (∼280 °C). This crucial mechanistic understanding enables the synthesis of well-defined PtSn NCs with controlled structure and composition via a seed-mediated approach. This type of in situ characterization can be extended to other multicomponent nanostructures to advance their rational synthesis for practical applications.

Self-Assembly of Quantum Dot-Gold Heterodimer Nanocrystals with Orientational Order.

The self-assembly of nanocrystals into ordered superlattices is a powerful strategy for the production of functional nanomaterials. The assembly of well-ordered target structures, however, requires control over the building blocks' size and shape as well as their interactions. While nanocrystals with homogeneous composition are now routinely synthesized with high precision and assembled into various ordered structures, high-quality multicomponent nanocrystals and their ordered assemblies are rarely reported. In this paper, we demonstrate the synthesis of quantum dot-gold (QD-Au) heterodimers. These heterodimers possess a uniform shape and narrow size distribution and are capped with oleylamine and dodecyltrimethylammonium bromide (DTAB). Assembly of the heterodimers results in a superlattice with long-range orientational alignment of dimers. Using synchrotron-based X-ray measurements, we characterize the complex superstructure formed from the dimers. Molecular dynamics simulations of a coarse-grained model suggest that anisotropic interactions between the quantum dot and gold components of the dimer drive superlattice formation. The high degree of orientational order demonstrated in this work is a potential route to nanomaterials with useful optoelectronic properties.

Stable, Ultralow Threshold Amplified Spontaneous Emission from CsPbBr3 Nanoparticles Exhibiting Trion Gain.

Wet-chemically synthesized cesium lead halide nanoparticles have many attractive properties that make them promising as optical gain media, but generally suffer from poor stability under ambient conditions and an optical gain threshold that is widely believed to be dictated by the need for biexcitons. These conditions make it impractical for such particles to be utilized as gain media given the need to undergo repeated stimulated emission processes at above-threshold pump intensities over long periods of time. We demonstrate that the surface treatment of CsPbBr3 nanoparticles with a mixture of PbBr2, oleic acid, and oleylamine not only raises their fluorescence quantum yield to nearly unity and prolongs their stability in air from days to months, but it also dramatically increases their trion photoluminescence lifetime from ∼0.9 to ∼1.6 ns. Via a combination of time-resolved photoluminescence and transient absorption spectroscopy, we provide evidence for trion gain at sufficiently low pump intensities in which the likelihood of predominantly biexciton-based gain is small. We then show that, in line with theoretical prediction, the amplified spontaneous emission (ASE) threshold of a thin film of surface-treated CsPbBr3 nanoparticles reduces to a record low of ∼1.2 µJ/cm2 with a corresponding average exciton occupancy per nanoparticle of 0.62. The ultralow pump threshold and increased stability allow for stable ASE over millions of laser shots, paving the way for the deployment of these nanoparticles as viable solution-processed optical gain media.

Crystallization of Nanocrystals in Spherical Confinement Probed by in Situ X-ray Scattering.

We studied the formation of supraparticles from nanocrystals confined in slowly evaporating oil droplets in an oil-in-water emulsion. The nanocrystals consist of an FeO core, a CoFe2O4 shell, and oleate capping ligands, with an overall diameter of 12.5 nm. We performed in situ small- and wide-angle X-ray scattering experiments during the entire period of solvent evaporation and colloidal crystallization. We observed a slow increase in the volume fraction of nanocrystals inside the oil droplets up to 20%, at which a sudden crystallization occurs. Our computer simulations show that crystallization at such a low volume fraction is only possible if attractive interactions between colloidal nanocrystals are taken into account in the model as well. The spherical supraparticles have a diameter of about 700 nm and consist of a few crystalline face-centered cubic domains. Nanocrystal supraparticles bear importance for magnetic and optoelectronic applications, such as color tunable biolabels, color tunable phosphors in LEDs, and miniaturized lasers.

Extremely Small Pyrrhotite Fe7 S8 Nanocrystals with Simultaneous Carbon-Encapsulation for High-Performance Na-Ion Batteries.

Na/FeSx batteries have remarkable potential applicability due to their high theoretical capacity and cost-effectiveness. However, realization of high power-capability and long-term cyclability remains a major challenge. Herein, ultrafine Fe7 S8 @C nanocrystals (NCs) as a promising anode material for a Na-ion battery that addresses the above two issues simultaneously is reported. An Fe7 S8 core with quantum size (≈10 nm) overcomes the kinetic and thermodynamic constraints of the Na-S conversion reaction. In addition, the high degree of interconnection through carbon shells improves the electronic transport along the structure. As a result, the Fe7 S8 @C NCs electrode achieves excellent power capability of 550 mA h g-1 (≈79% retention of its theoretical capacity) at a current rate of 2700 mA g-1 . Furthermore, a conformal carbon shell acts as a buffer layer to prevent severe volume change, which provides outstanding cyclability of ≈447 mA h g-1 after 1000 cycles (≈71% retention of the initial charge capacity).

Colloid-Interface-Assisted Laser Irradiation of Nanocrystals Superlattices to be Scalable Plasmonic Superstructures with Novel Activities.

High-efficient charge and energy transfer between nanocrystals (NCs) in a bottom-up assembly are hard to achieve, resulting in an obstacle in application. Instead of the ligands exchange strategies, the advantage of a continuous laser is taken with optimal wavelength and power to irradiate the film-scale NCs superlattices at solid-liquid interfaces. Owing to the Au-based NCs' surface plasmon resonance (SPR) effect, the gentle laser irradiation leads the Au NCs or Au@CdS core/shell NCs to attach each other with controlled pattern at the interfaces between solid NCs phase and liquid ethanol/ethylene glycol. A continuous wave 532 nm laser (6.68-13.37 W cm-2 ), to control Au-based superlattices, is used to form the monolayer with uniformly reduced interparticle distance followed by welded superstructures. Considering the size effect to Au NCs' melting, when decreasing the Au NCs size to ≈5 nm, stronger welding nanostructures are obtained with diverse unprecedented shapes which cannot be achieved by normal colloidal synthesis. With the help of facile scale-up and formation at solid-liquid interfaces, and a good connection of crystalline between NCs, the obtained plasmonic superstructured films that could be facilely transferred onto different substrates exhibit broad SPR absorption in the visible and near-infrared regime, enhanced electric conductivities, and wide applications as surface enhanced Raman scattering (SERS)-active substrates.