Luminescence tuning of MOFs via ligand to metal and metal to metal energy transfer by co-doping of 2∞[Gd2Cl6(bipy)3]*2bipy with europium and terbium

The series of anhydrous lanthanide chlorides LnCl3, Ln=Pr–Tb, and 4,4'-bipyridine (bipy) constitute isotypic MOFs of the formula 2∞[Ln2Cl6(bipy)3]*2bipy. The europium and terbium containing compounds both exhibit luminescence of the referring trivalent lanthanide ions, giving a red luminescence for Eu3+ and a green luminescence for Tb3+ triggered by an efficient antenna effect of the 4,4'-bipyridine linkers. Mixing of different lanthanides in one MOF structure was undertaken to investigate the potential of this MOF system for colour tuning of the luminescence. Based on the gadolinium containing compound, co-doping with different amounts of europium and terbium proves successful and yields solid solutions of the formula 2∞[Gd2-x-yEuxTbyCl6(bipy)3]*2bipy (1–8), 0≤x, y≤0.5. The series of MOFs exhibits the opportunity of tuning the emission colour in-between green and red. Depending on the atomic ratio Gd:Eu:Tb, the yellow region was covered for the first time for an oxygen/carboxylate-free MOF system. In addition to a ligand to metal energy transfer (LMET) from the lowest ligand-centered triplet state of 4,4'-bipyridine, a metal to metal energy transfer (MMET) between 4f-levels from Tb3+ to Eu3+ is as well vital for the emission colour. However, no involvement of Gd3+ in energy transfers is observed rendering it a suitable host lattice ion and connectivity centre for diluting the other two rare earth ions in the solid state. The materials retain their luminescence during activation of the MOFs for microporosity

Tuneable interfacial surfactant aggregates mimic lyotropic phases and facilitate large scale nanopatterning.

It is shown that the air-liquid interface can be made to display the same rich curvature phenomena as common lyotropic liquid crystal systems. Through mixing an insoluble, naturally occurring, branched fatty acid, with an unbranched fatty acid of the same length, systematic variation in the packing constraints at the air-water interface could be obtained. The combination of atomic force microscopy and neutron reflectometry is used to demonstrate that the water surface exhibits significant tuneable topography. By systematic variation of the two fatty acid proportions, ordered arrays of monodisperse spherical caps, cylindrical sections, and a mesh phase are all observed, as well as the expected lamellar structure. The tuneable deformability of the air-water interface permits this hitherto unexplored topological diversity, which is analogous to the phase elaboration displayed by amphiphiles in solution. It offers a wealth of novel possibilities for the tailoring of nanostructure

Molecularly imprinted conductive polymers for controlled trafficking of neurotransmitters at solid–liquid interfaces

We realize a molecularly imprinted polymer (MIP) which is imprinted with the retinal neurotransmitter glutamate. The films prepared by electrochemical deposition have a smooth surface with a granular morphology as observed using an atomic force microscope. Multiple reflection attenuated total reflection infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) are used to chemically confirm the imprint of a neurotransmitter in the MIP at the solid–liquid and the solid–air interface, respectively. Fluorescence spectroscopy using the dye fluorescamine is used to monitor the changes in neurotransmitter concentration in various solvents induced by application of voltage to the MIP. By controlling neurotransmitter trafficking across a solid–liquid interface with voltage, we suggest the possibility of using such a neurotransmitter imprinted MIP for chemical stimulation of retinal neurons. The current state of the art approach to restore sight in certain cases of blindness is the replacement of damaged photoreceptors by a subretinal implant consisting of light-sensitive photodiodes. Thus a future perspective of our work would be to chemically stimulate the neurons by replacing the photodiodes in the subretinal implant by the neurotransmitter imprinted polymer film

Solvent content in thin spin-coated polystyrene homopolymer films

The solvent content of thin polystyrene (PS) films, spin-coated from protonated and deuterated toluene onto silicon substrates, is investigated. Neutron reflectometry (NR) is used to probe the total remaining solvent inside the PS films in a nondestructive and noninvasive way. In freshly prepared films, the investigated parameters are the molecular weight of PS and the total film thickness. Moreover, the effect of postproduction treatment by annealing at temperatures below and above the glass transition of PS as well as long-term storage over 2 years are examined to deduce the reduction of the remaining solvent. The remaining solvent content increases with increasing molecular weight and with increasing film thickness. An enrichment of toluene at the Si/polymer interface is found. Under the different annealing and storage conditions tested, the remaining solvent is not totally removed. The observed behavior is discussed in the framework of polymer thin films and compared with results obtained by alternative experimental approaches

A closer look into two-step perovskite conversion with X-ray scattering

Recently, hybrid perovskites have gathered much interest as alternative materials for the fabrication of highly efficient and cost-competitive solar cells; however, many questions regarding perovskite crystal formation and deposition methods remain. Here we have applied a two-step protocol where a crystalline PbI2 precursor film is converted to MAPbI3–xClx perovskite upon immersion in a mixed solution of methylammonium iodide and methylammonium chloride. We have investigated both films with grazing incidence small-angle X-ray scattering to probe the inner film morphology. Our results demonstrate a strong link between lateral crystal sizes in the films before and after conversion, which we attribute to laterally confined crystal growth. Additionally, we observe an accumulation of smaller grains within the bulk in contrast with the surface. Thus, our results help to elucidate the crystallization process of perovskite films deposited via a two-step technique that is crucial for controlled film formation, improved reproducibility, and high photovoltaic performance

Metal-Organic Framework MIL-68(In)-NH2_{2} on the Membrane Test Bench for Dye Removal and Carbon Capture

The metal-organic framework (MOF) MIL-68(In)-NH$_{2}$ was tested for dye removal from wastewater and carbon capture gas separation. MIL-68(In)-NH$_{2}$ was synthesized as a neat, supported MOF thin film membrane and as spherical particles using pyridine as a modulator to shape the morphology. The neat MIL-68(In)-NH$_{2}$ membranes were employed for dye removal in cross-flow geometry, demonstrating strong molecular sieving. MIL-68(In)-NH$_{2}$ particles were used for electrospinning of poylethersulfone mixed-matrix membranes, applied in dead-end filtration with unprecedented adsorption values. Additionally, the neat MOF membranes were used for H$_{2}$/CO$_{2}$ and CO$_{2}$/CH$_{4}$ separation

Real time investigations during sputter deposition for tailoring optical properties of metal-polymer interfaces

Poster presented at the 16th International Conference on Small-Angle Scattering, held on 13-18th September, 2015, Berlin (Germany).Tailoring optoelectronic properties of metal-polymer interfaces using self-assembly of nanoparticles is of crucial importance in organic electronics and organic photovoltaics [1]. In particular, metal sputter deposition on block-co-polymers is one widely used method to fabricate nanostructured metal layers on a large scale exploiting the selective wetting and doping of metals on polystyrene domains [2,3]. In order to obtain full control over the nanostructural evolution at the metal-polymer interface and its impact on optoelectronic properties, we employed a combination of in situ time-resolved microfocus Grazing Incidence Small Angle X-ray Scattering (μGISAXS) with in situ UV/Vis Specular Reflectance Spectroscopy (SRS) during sputter deposition of gold (Au) on thin polystyrene films (PS). We monitored the evolution of the metallic layer morphology according to changes in the key scattering features by geometrical modeling [4] and correlate the nanostructural development to optical properties. The changes of optoelectronic properties induced by metal nanoparticle growth during the sputter deposition process were exemplarily monitored using SRS. The morphological characterization is complemented by X-ray reflectivity and electron microscopy. This enables us to identify the different growth regimes including their specific thresholds and permits better understanding of the growth kinetics of gold clusters and their self-organization into complex nanostructures on polymer substrates. Thus, our findings are of great interest for applications in organic photovoltaics [5] and organic electronics, which benefit from tailored metal-polymer interfaces