CdSe nanoplatelets (NPLs) are promising 2D semiconductors for optoelectronic applications, in which efficient charge transport properties are desirable. It is reported that thermal annealing constitutes an effective strategy to control the optical absorption and electrical properties of CdSe NPLs by tuning the inter-NPL distance. Combining optical absorption, transmission electron microscopy, and thermogravimetric analysis, it is revealed that the thermal decomposition of ligands (e.g., cadmium myristate) governs the inter-NPL distance and thus the inter-NPL electronic coupling strength. Employing ultrafast terahertz spectroscopy, it is shown that this enhanced electronic coupling increases both the free carrier generation efficiency and the short-range mobility in NPL solids. The results show a straightforward method of controlling the interfacial electronic coupling strength for developing functional optoelectronic devices through thermal treatments.

The steric stability of inorganic colloidal particles in an apolar solvent is usually described in terms of the balance between three contributions: the van der Waals attraction, the free energy of mixing, and the ligand compression. However, in the case of nanoparticles, the discrete nature of the ligand shell and the solvent has to be taken into account. Cadmium selenide nanoplatelets are a special case. They combine a weak van der Waals attraction and a large facet to particle size ratio. We use coarse grained molecular dynamics simulations of nanoplatelets in octane to demonstrate that solvation forces are strong enough to induce the formation of nanoplatelet stacks, and by that have a crucial impact on the steric stability. In particular, we demonstrate that for sufficiently large nanoplatelets, solvation forces are proportional to the interacting facet area, and their strength is intrinsically tied to the softness of the ligand shell.

The development of new two-photon fluorescent probes is desirable for imaging in biosystems. Semiconductor CdSe nanoplatelets are promising candidates for this purpose due to their large absorption cross sections, extremely narrow photolumines-cence emission, and high spectral brightness. Herein, we obtained water dispersible nanoplatelets (poly-NPLs) and explored their potential for intracellular imaging using commercially available Qdot 655 CdSe-based quantum dots as a control. Comparison was carried out for one- and two-photon imaging. The emission of poly-NPLs was found to be consistently higher than the one of Qdot 655at equal particle concentrations as well as at equal cadmium concentrations for both one-photon and two-photon excitations. In particular, poly-NPLs can show up to 3 orders of magnitude higher fluorescence brightness compared to Qdot 655 when excited with two-photons, which makes them interesting candidates for multiphoton imaging and single molecule detection applications

We synthesized indium phosphide (InP) nanoparticles of different shapes and sizes, utilizing triphenyl phosphite (TPOP) as the phosphorus source. We show that this reaction proceeds via the formation of in situ formed In2O3 nanoparticles followed by subsequent transformation with triphenyl TPOP acting as the phosphorus source. Our findings open up new synthetic possibilities utilizing a cost-effective, non-pyrophoric and non-toxic phosphorus precursor. The large surface area of hyperbranched InP NCs might be ideally suited for surface-driven processes such as catalysis and energy storage.

Monoclinic α‐Ag 2 S is an intriguing member of transition metal sulfides with great potential for all‐inorganic flexible optoelectronics and thermoelectrics. Fabrication of large‐area, high‐quality α‐Ag 2 S thin films and understanding their charge transport properties are critical for device operations yet have remained largely unexplored. Here, a novel two‐step, the solution‐processed approach is reported to produce wafer‐sized, highly crystalline α‐Ag 2 S thin films. Ultrafast terahertz (THz) conductivity measurements reveal that photogenerated charge carriers undergo efficient band transport, with room‐temperature mobility of ≈ 150 cm 2 V ‐1 s ‐1 and a diffusion length exceeding 500 nm. Furthermore, introducing poly(vinyl alcohol) (PVA) as the rigid component into the aqueous silver thiolate precursor enables the synthesis of free‐standing α‐Ag 2 S thin films with a mobility of ≈ 35 cm 2 V ‐1 s ‐1 , demonstrating their potential for flexible optoelectronics. This study provides a facile synthesis route for high‐quality, large‐area α‐Ag 2 S thin films with good charge transport properties, relevant for their integration into optoelectronics and wearable electronics.

Semiconductor nanoplatelets can possess desirable optical properties. For example, CdSe nanoplatelets show a high fluorescence quantum yield, a large one- and two-photon absorption cross section, and the ability to emit polarized light. However, their usage in devices requires control over their self-assembly, particularly the formation of stacks. The interplay of the various forces leading to stack formation in experiments remains unclear. Here, we use coarse grained molecular dynamics simulations of nanoplatelets in octane solvent to investigate the role of solvation forces in nanoplatelet interactions. We demonstrate that solvation forces resulting from solvent layering are sufficiently strong to stabilize nanoplatelet stacks. We examine the dependence of solvation forces on the nanoplatelets' ligand shell, size, and other parameters. In particular, we demonstrate that for sufficiently large nanoplatelets, solvation forces are proportional to the interacting facet area, and their strength is intrinsically tied to the softness of the ligand shell. The solvation forces exhibit an oscillatory nature; increases in their strength leads to a stronger attraction between close nanoplatelet facets and in addition to an increase in the kinetic barriers.

This work analyzes the intracellular fate of protein-based nanocarriers along their endolysosomal pathway by means of correlative light and electron microscopy methods. To unambiguously identify the nanocarriers and their degradation remnants in the cellular environment, they are labeled with fluorescent, inorganic nanoplatelets. This allows tracking the nanocarriers on their intracellular pathway by means of electron microscopy imaging. From the present data, it is possible to identify different cell compartments in which the nanocarriers are processed. Finally, three different terminal routes for the intracellular destiny of the nanocarriers are presented. These findings are important to reveal the degradation process of protein nanocapsules and contribute to the understanding of the therapeutic success of an encapsulated drug.

Magic-sized clusters (MSCs) of semiconductor are typically defined as specific molecular-scale arrangements of atoms that exhibit enhanced stability. They often grow in discrete jumps, creating a series of crystallites, without the appearance of intermediate sizes. However, despite their long history, the mechanism behind their special stability and growth remains poorly understood. This is particularly true considering experiments that have shown discrete evolution of MSCs to sizes well beyond the “cluster” regime and into the size range of colloidal quantum dots. Here, we study the growth of these larger magic-sized CdSe nanocrystals to unravel the underlying growth mechanism. We first introduce a synthetic protocol that yields a series of nine magic-sized nanocrystals of increasing size. By investigating these crystallites, we obtain important clues about the mechanism. We then develop a microscopic model that uses classical nucleation theory to determine kinetic barriers and simulate the growth. We show that magic-sized nanocrystals are consistent with a series of zinc-blende crystallites that grow layer by layer under surface-reaction-limited conditions. They have a tetrahedral shape, which is preserved when a monolayer is added to any of its four identical facets, leading to a series of discrete nanocrystals with special stability. Our analysis also identifies strong similarities with the growth of semiconductor nanoplatelets, which we then exploit to increase further the size range of our magic-sized nanocrystals. Although we focus here on CdSe, these results reveal a fundamental growth mechanism that can provide a different approach to nearly monodisperse nanocrystals.

Lamellar silver thiolates (Ag-MPA) possess reversible temperature dependent blue-to-near infrared optical transitions resulting from metallophilic interactions in the layers and conformational stabilization of the ligands.

Supraparticles are large clusters of much smaller colloidal particles. Controlling the shape and anisotropy of supraparticles can enhance their functionality, enabling applications in fields such as optics, magnetics, and medicine. The evaporation of self-lubricating colloidal ouzo droplets is an easy and efficient strategy to create supraparticles, overcoming the problem of the "coffee-stain effect" during drop evaporation. Yet, the parameters that control the shape of the supraparticles formed in such evaporating droplets are not fully understood. Here, we show that the size of the colloidal particles determines the shape of the supraparticle. We compared the shape of the supraparticles made of seven different sizes of spherical silica particles, namely from 20 to 1000 nm, and of the mixtures of small and large colloidal particles at different mixing ratios. Specifically, our in situ measurements revealed that the supraparticle formation proceeds via the formation of a flexible shell of colloidal particles at the rapidly moving interfaces of the evaporating droplet. The time tc0 when the shell ceases to shrink and loses its flexibility is closely related to the size of particles. A lower tc0, as observed for smaller colloidal particles, leads to a flat pancake-like supraparticle, in contrast to a more curved American football-like supraparticle from larger colloidal particles. Furthermore, using a mixture of large and small colloidal particles, we obtained supraparticles that display a spatial variation in particle distribution, with small colloids forming the outer surface of the supraparticle. Our findings provide a guideline for controlling the supraparticle shape and the spatial distribution of the colloidal particles in supraparticles by simply self-lubricating ternary drops filled with colloidal particles.

In this work, we unravel the role of surface properties of colloidal particles on the formation of supraparticles (clusters of colloidal particles) in a colloidal Ouzo droplet. Self-lubricating colloidal Ouzo droplets are an efficient and simple approach to form supraparticles, overcoming the challenge of the coffee stain effect in situ. Supraparticles are an efficient route to high-performance materials in various fields, from catalysis to carriers for therapeutics. Yet, the role of the surface of colloidal particles in the formation of supraparticles using Ouzo droplets remains unknown. Therefore, we used silica particles as a model system and compared sterically stabilized versus electrostatically stabilized silica particles-positively and negatively charged. Additionally, we studied the effect of hydration. Hydrated negatively charged silica particles and sterically stabilized silica particles form supraparticles. Conversely, dehydrated negatively charged silica particles and positively charged amine-coated particles form flat film-like deposits. Notably, the assembly process is different for all the four types of particles. The surface modifications alter (a) the contact line motion of the Ouzo droplet and (b) the particle-oil and particle-substrate interactions. These alterations modify the particle accumulation at the various interfaces, which ultimately determines the shape of the final deposit. Thus, by modulating the surface properties of the colloidal particles, we can tune the shape of the final deposit, from a spheroidal supraparticle to a flat deposit. In the future, this approach can be used to tailor the supraparticles for applications such as optics and catalysis, where the shape affects the functionality.

Combining excellent optoelectronic properties with the benefits of solution processability, metal-halide perovskites are promising materials for photovoltaic and light-emitting technologies. To facilitate the integration of perovskite thin films into optoelectronic devices, a need exists for simple and efficient fabrication methods. Here, we present a template-stripping technique to produce ultraflat and flexible perovskite thin films. We apply a one-step spin-coating procedure to produce high-quality CH3NH3PbBr3 perovskite thin films on top of ultraflat silicon templates. These films can be mechanically cleaved from the template using a polymer adhesive to reveal the ultraflat perovskite surfaces. We demonstrate how the flatness and flexibility of the template-stripped films enable new processing strategies based on dry interfacing, by interfacing them with plasmonic hole arrays. Moreover, we show that by using prepatterned silicon templates, structured perovskite surfaces can be produced with feature sizes down to a micrometer.

Sensitization of organic molecules by semiconductor nanocrystals is a promising way to boost the absorption of the former, important for applications in fluorescence labeling and photocatalysis. Semiconductor nanoplatelets provide the opportunity of increasing the absorption cross section by increasing the lateral dimension without inducing changes to the band gap. However, the lateral size dependence of FRET in nanoplatelet small-molecule conjugates is unknown. Our FRET study supports the view that excitons in nanoplatelets are localized in a small area and spatially distributed in a stochastic fashion. In larger nanoplatelets, the likelihood of an offset between the position of the exciton and the acceptor increases. Although this could be mitigated by increasing the number of fluorophores, excessive coverage of the nanoplatelets with the fluorophores leads to severe self-quenching. Based on these results, we predict that using few fluorophores on nanoplatelets with edge lengths of similar to 9 nm would optimize the delicate balance between maximizing the absorption cross section of the nanoplatelets and minimizing the likelihood of exciton-fluorophore offset and self-quenching simultaneously, thus leading to optimal FRET conditions.

Colloidal semiconductor nanoplatelets are rectangular, quasi-two-dimensional crystallites that are only a few atomic layers thick. In the most heavily studied systems (such as CdE with E = S, Se, o...

Semiconductor nanoplatelets exhibit spectrally pure, directional fluorescence. To make polarized light emission accessible and the charge transport effective, nanoplatelets have to be collectively oriented in the solid state. We discovered that the collective nanoplatelets orientation in monolayers can be controlled kinetically by exploiting the solvent evaporation rate in self-assembly at liquid interfaces. Our method avoids insulating additives such as surfactants, making it ideally suited for optoelectronics. The monolayer films with controlled nanoplatelets orientation (edge-up or face-down) exhibit long-range ordering of transition dipole moments and macroscopically polarized light emission. Furthermore, we unveil that the substantial in-plane electronic coupling between nanoplatelets enables charge transport through a single nanoplatelets monolayer, with an efficiency that strongly depends on the orientation of the nanoplatelets. The ability to kinetically control the assembly of nanoplatelets into ordered monolayers with tunable optical and electronic properties paves the way for new applications in optoelectronic devices.

Two-photon polymerization stereolithographic three-dimensional (3D) printing is used for manufacturing a variety of structures ranging from microdevices to refractive optics. Incorporation of nanoparticles in 3D printing offers huge potential to create even more functional nanocomposite structures. However, this is difficult to achieve since the agglomeration of the nanoparticles can occur. Agglomeration not only leads to an uneven distribution of nanoparticles in the photoresin but also induces scattering of the excitation beam and altered absorption profiles due to interparticle coupling. Thus, it is crucial to ensure that the nanoparticles do not agglomerate during any stage of the process. To achieve noninteracting and well-dispersed nanoparticles on the 3D printing process, first, the stabilization of nanoparticles in the 3D printing resin is indispensable. We achieve this by functionalizing the nanoparticles with surface-bound ligands that are chemically similar to the photoresin that allows increased nanoparticle loadings without inducing agglomeration. By systematically studying the effect of different nanomaterials (Au nanoparticles, Ag nanoparticles, and CdSe/CdZnS nanoplatelets) in the resin on the 3D printing process, we observe that both, material-specific (absorption profiles) and unspecific (radical quenching at nanoparticle surfaces) pathways co-exist by which the photopolymerization procedure is altered. This can be exploited to increase the printing resolution leading to a reduction of the minimum feature size.

Quasi-two dimensional semiconductor nanoplatelets (NPLs) exhibit high spectral brightness and large absorption cross sections, making them promising for various applications including bioimaging. However, the synthesis of NPLs takes place in organic solvents, therefore they require phase transfer in order to use them in aqueous environments. The phase transfer of NPLs has so far been challenging with few examples in literature. This is likely due to the facile agglomeration of materials with plate-like geometries during the coating procedure. Here we demonstrate how to overcome agglomeration and transfer NPLs, individually coated with amphiphilic polymer chains, to aqueous phase. Upon one and two-photon excitation the water transferred NPLs exhibit more than two fold higher fluorescent brightness relative to commercially available quantum dots. Additionally, the polymer coating increase the stability of nanoparticles in physiological conditions (pH 4.5-7.4, [NaCl] 5.8-11.7 g L-1, and in human serum). Our experiments with NPL labeled RAW264.7 cells demonstrate the capabilities of NPLs as next generation ultra-bright fluorescent labels for bioimaging.

In the synthesis of CdSe nanoplatelets, the selenium-to-selenide reduction pathway is unknown. We study solvent-free growth of CdSe nanoplatelets and identify bis(acyl) selenides as key reactive intermediates. Based on our findings, we prepare a series of bis(acyl) selenides that provide useful precursors with tailored reactivity for liquid-phase syntheses of nanoplatelets.

Ostwald ripening describes how the size distribution of colloidal particles evolves with time due to thermodynamic driving forces. Typically, small particles shrink and provide material to larger particles, which leads to size defocusing. Semiconductor nanoplatelets, thin quasi-two-dimensional (2D) particles with thicknesses of only a few atomic layers but larger lateral dimensions, offer a unique system to investigate this phenomenon. Experiments show that the distribution of nanoplatelet thicknesses does not defocus during ripening, but instead jumps sequentially from m to (m + 1) monolayers, allowing precise thickness control. We investigate how this counterintuitive process occurs in CdSe nanoplatelets. We develop a microscopic model that treats the kinetics and thermodynamics of attachment and detachment of monomers as a function of their concentration. We then simulate the growth process from nucleation through ripening. For a given thickness, we observe Ostwald ripening in the lateral direction, but none perpendicular. Thicker populations arise instead from nuclei that capture material from thinner nanoplatelets as they dissolve laterally. Optical experiments that attempt to track the thickness and lateral extent of nanoplatelets during ripening appear consistent with these conclusions. Understanding such effects can lead to better synthetic control, enabling further exploration of quasi-2D nanomaterials.