Li-doped ZnO nanorods with single-crystal quality - non-classical crystallization and self-assembly into mesoporous materials

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.The benefits and promise of nanoscale dimensions for the properties of (ceramic) semiconductors are widely known. 1-D nanostructures in particular have proven to be of extraordinary relevance due to their applicability in future electronic and optoelectronic devices. Key to successful technological implementation of semiconductor nanostructures is the control of their electronic properties via doping. Despite its tremendous importance, precise chemical doping of defined nano-objects has been addressed rarely so far. Frequent problems are the creation of secondary defects and related undesired property changes by incorporation of hetero-elements, and the difficulty in ensuring a uniform and precise positioning of the dopant in the nanocrystal lattice. Here, we present the synthesis of Li-doped zinc oxide nanorods, which possess excellent (single-crystal) quality. The method is based on a novel non-classical crystallization mechanism, comprising an unusually oriented disassembly step. Afterwards, the nanorods are incorporated into mesoporous layers using colloidal self-assembly. Proof-of-principle gas sensing measurements with these novel materials demonstrate the beneficial role of Li-doping, indicating not only better conductivity but also the occurrence of catalytic effects

Uniform Large-Area Free-Standing Silver Nanowire Arrays on Transparent Conducting Substrates

Arrays of silver nanowires have received increasing attention in a variety of applications such as surface-enhanced Raman scattering (SERS), plasmonic biosensing and electrode for photoelectric devices. However, until now, large scale fabrication of device-suitable silver nanowire arrays on supporting substrates has seen very limited success. Here we show the synthesis of free-standing silver nanowire arrays on indium-tin oxide (ITO) coated glass by pulsed electrodeposition into anodic aluminum oxide (AAO) templates. We use an in situ oxygen plasma cleaning process and a sputtered Ti layer to enhance the adhesion between the template and ITO glass. An ultrathin gold layer (2 nm) is deposited as a nucleation layer for the electrodeposition of silver. An unprecedented high level of uniformity and control of the nanowire diameter, spacing and length has been achieved. The absorption measurements show that the free-standing silver nanowire arrays possess tunable plasmonic resonances.publishe

Nanoparticle shape anisotropy and photoluminescence properties : Europium containing ZnO as a model case

The precise control over electronic and optical properties of semiconductor (SC) materials is pivotal for a number of important applications like in optoelectronics, photocatalysis or in medicine. It is well known that the incorporation of heteroelements (doping as a classical case) is a powerful method for adjusting and enhancing the functionality of semiconductors. Independent from that, there already has been a tremendous progress regarding the synthesis of differently sized and shaped SC nanoparticles, and quantum-size effects are well documented experimentally and theoretically. Whereas size and shape control of nanoparticles work fairly well for the pure compounds, the presence of a heteroelement is problematic because the impurities interfere strongly with bottom up approaches applied for the synthesis of such particles, and effects are even stronger, when the heteroelement is aimed to be incorporated into the target lattice for chemical doping. Therefore, realizing coincident shape control of nanoparticle colloids and their doping still pose major difficulties. Due to a special mechanism of the emulsion based synthesis method presented here, involving a gelation of emulsion droplets prior to crystallization of shape-anisotropic ZnO nanoparticles, heteroelements can be effectively entrapped inside the lattice. Different nanocrystal shapes such as nanorods, -prisms, -plates, and -spheres can be obtained, determined by the use of certain emulsification agents. The degree of morphologic alterations depends on the type of incorporated heteroelement M, concentration, and it seems that some shapes are more tolerant against doping than others. Focus was then set on the incorporation of Eu³⁺ inside the ZnO particles, and it was shown that nanocrystal shape and aspect ratios could be adjusted while maintaining a fixed dopant level. Special PL properties could be observed implying energy transfer from ZnO excited near its band-gap (3.3 eV) to the Eu³⁺ states mediated by defect luminescence of the nanoparticles. Indications for an influence of shape on photoluminescence (PL) properties were found. Finally, rod-like Eu@ZnO colloids were used as tracers to investigate their uptake into biological samples like HeLa cells. The PL was sufficient for identifying green and red emission under visible light excitation

Morphologiekontrolle von dotierten und undotierten Halbleiter-Metalloxid-Nanopartikeln mit Hilfe von „Bottom-Up“-Synthesemethoden

publishe

Nanoparticle shape anisotropy and photoluminescence properties : Europium containing ZnO as a model case

The precise control over electronic and optical properties of semiconductor (SC) materials is pivotal for a number of important applications like in optoelectronics, photocatalysis or in medicine. It is well known that the incorporation of heteroelements (doping as a classical case) is a powerful method for adjusting and enhancing the functionality of semiconductors. Independent from that, there already has been a tremendous progress regarding the synthesis of differently sized and shaped SC nanoparticles, and quantum-size effects are well documented experimentally and theoretically. Whereas size and shape control of nanoparticles work fairly well for the pure compounds, the presence of a heteroelement is problematic because the impurities interfere strongly with bottom up approaches applied for the synthesis of such particles, and effects are even stronger, when the heteroelement is aimed to be incorporated into the target lattice for chemical doping. Therefore, realizing coincident shape control of nanoparticle colloids and their doping still pose major difficulties. Due to a special mechanism of the emulsion based synthesis method presented here, involving a gelation of emulsion droplets prior to crystallization of shape-anisotropic ZnO nanoparticles, heteroelements can be effectively entrapped inside the lattice. Different nanocrystal shapes such as nanorods, -prisms, -plates, and -spheres can be obtained, determined by the use of certain emulsification agents. The degree of morphologic alterations depends on the type of incorporated heteroelement M, concentration, and it seems that some shapes are more tolerant against doping than others. Focus was then set on the incorporation of Eu³⁺ inside the ZnO particles, and it was shown that nanocrystal shape and aspect ratios could be adjusted while maintaining a fixed dopant level. Special PL properties could be observed implying energy transfer from ZnO excited near its band-gap (3.3 eV) to the Eu³⁺ states mediated by defect luminescence of the nanoparticles. Indications for an influence of shape on photoluminescence (PL) properties were found. Finally, rod-like Eu@ZnO colloids were used as tracers to investigate their uptake into biological samples like HeLa cells. The PL was sufficient for identifying green and red emission under visible light excitation

Uniform Large-Area Free-Standing Silver Nanowire Arrays on Transparent Conducting Substrates

Arrays of silver nanowires have received increasing attention in a variety of applications such as surface-enhanced Raman scattering (SERS), plasmonic biosensing and electrode for photoelectric devices. However, until now, large scale fabrication of device-suitable silver nanowire arrays on supporting substrates has seen very limited success. Here we show the synthesis of free-standing silver nanowire arrays on indium-tin oxide (ITO) coated glass by pulsed electrodeposition into anodic aluminum oxide (AAO) templates. We use an in situ oxygen plasma cleaning process and a sputtered Ti layer to enhance the adhesion between the template and ITO glass. An ultrathin gold layer (2 nm) is deposited as a nucleation layer for the electrodeposition of silver. An unprecedented high level of uniformity and control of the nanowire diameter, spacing and length has been achieved. The absorption measurements show that the free-standing silver nanowire arrays possess tunable plasmonic resonances.publishe

Magneto-Adaptive Surfactants Showing Anti-Curie Behavior and Tunable Surface Tension as Porogens for Mesoporous Particles with 12-Fold Symmetry

Gaining external control over self-organization is of vital importance for future smart materials. Surfactants are extremely valuable for the synthesis of diverse nanomaterials. Their self-assembly is dictated by microphase separation, the hydrophobic effect, and head-group repulsion. It is desirable to supplement surfactants with an added mode of long-range and directional interaction. Magnetic forces are ideal, as they are not shielded in water. We report on surfactants with heads containing tightly bound transition-metal centers. The magnetic moment of the head was varied systematically while keeping shape and charge constant. Changes in the magnetic moment of the head led to notable differences in surface tension, aggregate size, and contact angle, which could also be altered by an external magnetic field. The most astonishing result was that the use of magnetic surfactants as structure-directing agents enabled the formation of porous solids with 12-fold rotational symmetry.publishe

Presence of gustatory and olfactory dysfunction in the time of the COVID-19 pandemic

Background!#!The unexpected outbreak of the novel severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) caused more than 49 million cases and an estimated 2,000,000 associated deaths worldwide. In Germany, there are currently more than 2,000,000 laboratory-confirmed coronavirus disease 2019 (COVID-19) cases including 51,800 deaths. However, regional differences also became apparent and with the second wave of infections, the detailed characterization of COVID-19 patients is crucial to early diagnosis and disruption of chains of infections.!##!Methods!#!Handing out detailed questionnaires to all individuals tested for COVID-19, we evaluated the clinical characteristics of negative and positive tested individuals. Expression of symptoms, symptom duration and association between predictor variables (i.e. age, gender) and a binary outcome (olfactory and gustatory dysfunction) were assessed.!##!Results!#!Overall, the most common symptoms among individuals who tested positive for SARS-CoV-2 were fatigue, headache, and cough. Olfactory and gustatory dysfunction were also reported by many SARS-CoV-2 negative individuals, more than 20% of SARS-CoV-2 negative tested individuals in our study reported olfactory and gustatory dysfunction. Independent of SARS-CoV-2 status, more females displayed symptoms of gustatory (29.8%, p = 0.0041) and olfactory dysfunction (22.9%, p = 0.0174) compared to men.!##!Conclusions!#!Bringing early SARS-CoV-2 tests to the populations at risk must be a main focus for the upcoming months. The reliability of olfactory and gustatory dysfunction in COVID-19 negative tested individuals requires deeper investigation in the future