RESUMEN

Luminescence-encoded microbeads are important tools for many applications in the life and material sciences that utilize luminescence detection as well as multiplexing and barcoding strategies. The preparation of such beads often involves the staining of premanufactured beads with molecular luminophores using simple swelling procedures or surface functionalization with layer-by-layer (LbL) techniques. Alternatively, these luminophores are sterically incorporated during the polymerization reaction yielding the polymer beads. The favorable optical properties of semiconductor quantum dots (QDs), which present broadly excitable, size-tunable, narrow emission bands and low photobleaching sensitivity, triggered the preparation of beads stained with QDs. However, the colloidal nature and the surface chemistry of these QDs, which largely controls their luminescence properties, introduce new challenges to bead encoding that have been barely systematically assessed. To establish a straightforward approach for the bead encoding with QDs with minimized loss in luminescence, we systematically assessed the incorporation of oleic acid/oleylamine-stabilized CdSe/CdS-core/shell-QDs into 0.5-2.5 µm-sized polystyrene (PS) microspheres by a simple dispersion polymerization synthesis that was first optimized with the organic dye Nile Red. Parameters addressed for the preparation of luminophore-encoded beads include the use of a polymer-compatible ligand such as benzyldimethyloctadecylammonium chloride (OBDAC) for the QDs, and crosslinking to prevent luminophore leakage. The physico-chemical and optical properties of the resulting beads were investigated with electron microscopy, dynamic light scattering, optical spectroscopy, and fluorescence microscopy. Particle size distribution, fluorescence quantum yield of the encapsulated QDs, and QD leaking stability were used as measures for bead quality. The derived optimized bead encoding procedure enables the reproducible preparation of bright PS microbeads encoded with organic dyes as well as with CdSe/CdS-QDs. Although these beads show a reduced photoluminescence quantum yield compared to the initially very strongly luminescent QDs, with values of about 35%, their photoluminescence quantum yield is nevertheless still moderate.

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RESUMEN

The assembly of CdSe/CdS dot/rod nanocrystals (NCs) with variable length of ZnS tips into aerogel networks is presented. To this end, a partial region selective cation exchange procedure is performed replacing Cd by Zn starting at the NC tip. The produced aerogel networks are investigated structurally and optically. The networks of tip-to-tip connected NCs have an intricate band structure with holes confined to the CdSe cores while electrons are delocalized within the CdS also within connected building blocks. However, the ZnS tips act as a barrier of variable length and strength between the NC building blocks partly confining the electrons. This results in NC based aerogel networks with tunable strength of coupling between building blocks.

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Semiconductor nanoheterostructures (NHSs) are being increasingly used for the photocatalytic conversion of solar energy in which photo-induced charge separation is an essential step and hence it is necessary to understand the effect of various factors such as size, shape, and composition on the charge transfer dynamics. Ultrafast transient absorption spectroscopy is used to investigate the nature and dynamics of photo-induced charge transfer processes in ZnSe-CdS NHSs of different morphologies such as nanospheres (NSs), nanorods (NRs), and nanoplates (NPs). It demonstrates the fast separation of charge carriers and localization of both charges in adjacent semiconductors, resulting in the formation of a charge-separated (CS) state. The lifetime of the charge-separated state follows the order of NSs < NPs < NRs, emphasizing the effect of morphology on the enhancement of photo-induced charge separation and suppression of backward recombination. The separated charge carriers have been utilized in visible light driven hydrogen production and the hydrogen generation activity follows the same order as that for the lifetime of the CS state, underlining the role of charge separation efficiency. Therefore, the variation of the morphology of NHSs plays a significant role in their charge carrier dynamics and hence the photocatalytic hydrogen production activity.

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Employing nanocrystals (NCs) as building blocks of porous aerogel network structures allows the conversion of NC materials into macroscopic solid structures while conserving their unique nanoscopic properties. Understanding the interplay of the network formation and its influence on these properties like size-dependent emission is a key to apply techniques for the fabrication of novel nanocrystal aerogels. In this work, CdSe/CdS dot/rod NCs possessing two different CdSe core sizes were synthesized and converted into porous aerogel network structures. Temperature-dependent steady-state and time-resolved photoluminescence measurements were performed to expand the understanding of the optical and electronic properties of these network structures generated from these two different building blocks and correlate their optical with the structural properties. These investigations reveal the influence of network formation and aerogel production on the network-forming nanocrystals. Based on the two investigated NC building blocks and their aerogel networks, mixed network structures with various ratios of the two building blocks were produced and likewise optically characterized. Since the different building blocks show diverse optical response, this technique presents a straightforward way to color-tune the resulting networks simply by choosing the building block ratio in connection with their quantum yield.

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Noble-metal-based electrocatalysts usually contain small nanoparticle building blocks to ensure a high specific surface area as the scene for the surface processes. Here, we show that relatively large noble-metal nanorods are also promising candidates to build up functional macrostructures with prominent electrocatalytic activity. After optimizing and upscaling the syntheses of gold nanorods and gold bipyramid-templated silver nanorods, cryoaerogels are fabricated on a conductive substrate via flash freezing and subsequent freeze drying. The versatile cryoaerogelation technique allows the formation of macrostructures with dendritic, open-pore structure facilitating the increase of the accessible nanorod surfaces. It is demonstrated via electrochemical oxidation and stripping test experiments that noble-metal surface sites are electrochemically active in redox reactions. Furthermore, gold nanorod cryoaerogels offer a platform for redox sensing, ethanol oxidation reaction, as well as glucose sensing. Compared to their simply drop-cast and dried counterparts, the noble-metal nanorod cryoaerogels offer enhanced activity due to the open porosity of the fabricated nanostructure while maintaining structural stability.

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Macroscopic materials with nanoscopic properties have recently been synthesized by self-assembling defined nanoparticles to form self-supported networks, so-called aerogels. Motivated by the promising properties of this class of materials, the search for versatile routes toward the controlled assembly of presynthesized nanoparticles into such ultralight macroscopic materials has become a great interest. Overcoating procedures of colloidal nanoparticles with polymers offer versatile means to produce aerogels from nanoparticles, regardless of their size, shape, or properties while retaining their original characteristics. Herein, we report on the surface modification and assembly of various building blocks: photoluminescent nanorods, magnetic nanospheres, and plasmonic nanocubes with particle sizes between 5 and 40 nm. The polymer employed for the coating was poly(isobutylene-alt-maleic anhydride) modified with 1-dodecylamine side chains. The amphiphilic character of the polymer facilitates the stability of the nanocrystals in aqueous media. Hydrogels are prepared via triggering the colloidally stable solutions, with aqueous cations acting as linkers between the functional groups of the polymer shell. Upon supercritical drying, the hydrogels are successfully converted into macroscopic aerogels with highly porous, open structure. Due to the noninvasive preparation method, the nanoscopic properties of the building blocks are retained in the monolithic aerogels, leading to the powerful transfer of these properties to the macroscale. The open pore system, the universality of the polymer-coating strategy, and the large accessibility of the network make these gel structures promising biosensing platforms. Functionalizing the polymer shell with biomolecules opens up the possibility to utilize the nanoscopic properties of the building blocks in fluorescent probing, magnetoresistive sensing, and plasmonic-driven thermal sensing.

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The impact of low-pressure treatment on the crystal structure, morphology, and chemical composition of ettringite, due to their major importance with respect to processability (i.a., drying conditions) and to the analysis of ettringite-containing samples, is examined utilizing X-ray diffraction, thermogravimetric analysis, Raman spectroscopy, and environmental scanning electron microscopy. Synthetic ettringite was treated for various durations (5 min up to 72 h) and at two different levels of low-pressure (4.0 mbar and 60 µbar). Evaluation showed a correlation between the procedural parameters (time and pressure), the chemical composition, and the morphology of ettringite. The experiments reveal that, when exposed to 4 mbar pressure, nearly no changes occur in the ettringite's morphology, whereas the crystals undergo swelling and slight deformations at very low pressures (60 µbar and 35.3 nbar), which is attributed to the loss of bound water and the partial transformation from ettringite to quicklime, anhydrite, and calcium aluminate. Furthermore, the strongly dehydrated ettringite shows the same morphology.

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3D nanoparticle assemblies offer a unique platform to enhance and extend the functionality and optical/electrical properties of individual nanoparticles. Especially, a self-supported, voluminous, and porous macroscopic material built up from interconnected semiconductor nanoparticles provides new possibilities in the field of sensing, optoelectronics, and photovoltaics. Herein, a method is demonstrated for assembling semiconductor nanoparticle systems containing building blocks possessing different composition, size, shape, and surface ligands. The method is based on the controlled destabilization of the particles triggered by trivalent cations (Y3+ , Yb3+ , and Al3+ ). The effect of the cations is investigated via X-ray photoelectron spectroscopy. The macroscopic, self-supported aerogels consist of the hyperbranched network of interconnected CdSe/CdS dot-in-rods, or CdSe/CdS as well as CdSe/CdTe core-crown nanoplatelets is used to demonstrate the versatility of the procedure. The non-oxidative assembly method takes place at room temperature without thermal activation in several hours and preserves the shape and the fluorescence of the building blocks. The assembled nanoparticle network provides longer exciton lifetimes with retained photoluminescence quantum yields, that make these nanostructured materials a perfect platform for novel multifunctional 3D networks in sensing. Various sets of photoelectrochemical measurements on the interconnected semiconductor nanorod structures also reveal the enhanced charge carrier separation.

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Over the past decades, cation exchange reactions applied to nanoparticles have opened up synthetic pathways to nanocrystals, which were not accessible by other means before. The limitation of cation exchange on the macroscopic scale of bulk materials is given by the limited ion diffusion within the crystal structure. Lyogels or aerogels are macroscopic, highly voluminous, porous materials composed of interconnected nanoscopic building blocks and hence represent a type of bridge between the macroscopic and the nanoscopic world. To demonstrate the feasibility of cation exchange on such macroscopic nanomaterials, the cation exchange on CdSe/CdS core/shell and CdS nanorod based lyogels to Cu2-xSe/Cu2-xS and Cu2-xS and the reversible exchange back to CdSe/CdS and CdS lyogels is presented. These copper-based lyogels can also be used as an intermediate state on the way to other metal chalcogenide-based macroscopic structures. By reversed cation exchange back to cadmium an additional proof is given, that the crystal structures remain unchanged. It is shown that cation exchange reactions can also be transferred to macroscopic objects like aerogels or lyogels. This procedure additionally allows the access of aerogels which cannot be synthesized via direct destabilization of the respective colloidal solutions.

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In this work we present the generation of new core-shell network nanostructures of macroscopic dimensionality by a two-step process analogous to the seeded-growth method in colloidal nanoparticle modification. The nanoparticle-based core network is assembled first and in a separate second step it is coated with a continuous metal oxide shell by sol-gel methods. The interparticle contact of the nanoparticles comprising the core network is kept intact throughout the process. By analyzing the local elemental distribution, the shells can be shown to be homogeneous over the macroscopic network monolith. The shell network can be used to considerably reinforce the mechanical strength of the final core-shell network structure.

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Nanoparticle-based voluminous 3D networks with low densities are a unique class of materials and are commonly known as aerogels. Due to the high surface-to-volume ratio, aerogels and xerogels might be suitable materials for applications in different fields, e.g. photocatalysis, catalysis, or sensing. One major difficulty in the handling of nanoparticle-based aerogels and xerogels is the defined patterning of these structures on different substrates and surfaces. The automated manufacturing of nanoparticle-based aerogel- or xerogel-coated electrodes can easily be realized via inkjet printing. The main focus of this work is the implementation of the standard nanoparticle-based gelation process in a commercial inkjet printing system. By simultaneously printing semiconductor nanoparticles and a destabilization agent, a 3D network on a conducting and transparent surface is obtained. First spectro-electrochemical measurements are recorded to investigate the charge-carrier mobility within these 3D semiconductor-based xerogel networks.

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The evolution of systems based on nanoparticles as the main component seems to be a self-accelerating process during the last five decades. Hence, an overview across this field gets more and more challenging. It is sometimes rewarding to focus on the fundamental physical phenomenon of the electronic interconnection between the different building blocks of the obtained devices. Therefore, the investigation of charge transport among the utilized particles and their substrate is one of the mandatory steps in the development of semiconductor nanoparticle based devices like e.g., sensors and LEDs. The investigation of the influence of tunneling barriers on the properties of nanoparticle-functionalized surfaces is a challenging task. The different basic influences on the charge transport dynamics are often difficult to separate from each other. Non-invasive and easily viable experiments are still required to resolve the charge distributing mechanisms in the systems. In the presented work, we want to focus on thin and transparent indium tin oxide (ITO) layers covered glass slides since this substrate is frequently utilized in nanoelectronics. CdSe/CdS nanorods (NRs) are applied as an optically addressable probe for the electronic surface states of the conductive glass. The presented experimental design provides the proof of electronic interconnections in ITO coated glass/linker/NR electrodes via easy reproducible functionalization and polishing experiments. UV/Vis absorption and photoluminescence (PL) lifetime measurements revealed changes in the optical properties caused by differences in the charge carrier dynamics between the system. Our work is focused on the modification of charge carrier dynamics due to the application of linker molecules with different functional groups like (3-mercaptopropyl)methoxysilane (MPTMS) and (3-aminopropyl)trimethoxysilane (APTMS). The presented observations are explained with a simple kinetic model.

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Semiconductor nanoparticle based porous 3D assemblies are interesting materials for various applications in the fields of photovoltaics, catalysis, or optical sensing. For use as photoelectrodes in photoelectrochemical sensors they need to be characterised by a high porosity, a good photostability, and a high charge carrier mobility. Our work reports on the preparation of cryoaerogel photoelectrodes based on CdSe nanoplatelets and their photoelectrochemical characterisation by means of linear sweep voltammetry (LSV) and intensity modulated photocurrent spectroscopy (IMPS). The obtained open-pored cryoaerogel films were observed to produce much higher photocurrents than comparable drop-cast films. By means of IMPS, the performance differences could be linked to the occurrence of charge carrier movement, which could solely be proven for the cryoaerogels. In a proof-of-principle experiment, the potential of the prepared photoelectrodes for application in photoelectrochemical sensing was moreover demonstrated.

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In this article, we demonstrate the fabrication of tailored multicomponent cryoaerogels from colloidal nanoparticles via the cryogelation method. With this method, it is possible to control the amount of components very precisely. Furthermore, the microscopic distribution of the different nanoparticle components in the resulting monolithic structure is shown to be adjustable by simply mixing calculated amounts of colloidal nanoparticle solutions with a suitable surface charge. We focus on titania cryoaerogels due to their potential for optical applications and investigate the properties of synthesized titania-gold cryoaerogels in dependency of the composition. In addition, titania-platinum cryoaerogels were tested for photocatalytic applications such as hydrogen evolution and showed a significant increase in performance and stability compared to their respective colloidal solutions. While showing comparable results for hydrogen evolution with aerogels as reported in literature, the fabrication is much faster and less complex and therefore might enable future industrial application.

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We address optical amplification properties of quantum nanoparticles of the cadmium selenide/cadmium sulfide (CdSe/CdS) material system with different dimensionality of spatial confinement. CdSe/CdS core/shell quantum dots (QDs), core/shell quantum rods (QRs) and 5 monolayer thick core/crown nanoplatelets (NPLs) at ambient temperature are considered, exhibiting 0D, 1D and 2D spatial confinement dimensionality of the electronic system, respectively. Continuous films of all these nanoparticles are synthesised, and amplified spontaneous emission (ASE) spectra are measured under femtosecond pumping at wavelengths of 400 nm and 800 nm, respectively. The lowest threshold is found for NPLs and the highest for QDs, demonstrating the influence of the rod-like and plate-like CdS structures. To emphasize this effect, ASE is demonstrated also in CdSe/CdS QRs and NPLs under nanosecond pumping at 355 nm in the same material films. The amplification has been achieved without use of any feedback structure, emphazising the efficiency of the antenna effect. The pumping threshold fluences for NPLs and QRs are observed to be similar, but no ASE is observed in QDs up to the damage threshold of the nanoparticle layers. The length variation investigation with nanosecond pumping resulted in the gain coefficients of 29 cm-1 and 37 cm-1 for QRs and NPLs, respectively.

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One of the most significant objectives in the field of nanotechnology is the transfer of specific properties of smaller nanoparticle building blocks into larger units. In this way, nanoscopic properties can be linked to the macroscopic addressability of larger systems. Such systems might find applications in fields like photoelectrochemical sensing or solar energy harvesting. Our work reports on the novel synthesis of hybrid semiconductor/polymer fibres, which are based on stacks of 4 monolayer (ML) thick CdSe nanoplatelets (NPLs) encapsulated into a polymer shell. The polymer encapsulation not only enables the water transfer of the NPL stacks but also allows the preparation of photoelectrodes by linking the fibres to surface modified indium tin oxide (ITO) glass slides. By applying electrochemical techniques like intensity modulated photocurrent spectroscopy (IMPS), it was possible to prove the motion of charge carriers inside the nanoplatelet stacks and by this the electronic addressibility of them.