0000000000370991
AUTHOR
Matthias Zorn
Liquid Crystalline Orientation of Semiconducting Nanorods in a Semiconducting Matrix
This paper describes the synthesis of narrowly distributed block copolymers consisting of a hole conducting triarylamine block and an anchor block via RAFT polymerization. The anchor block is thereby introduced via a reactive ester approach. Block copolymers with dopamine anchor groups bind to oxidic semiconductors like TiO 2 , SnO 2 , and ZnO. Thus, it becomes possible to cover inorganic electron conducting (acceptor) nanomaterials with a corona of an organic hole conducting (donor) polymer like poly(triphenylamine), giving new hybrid materials. The poly(triphenylamine) grafted to inorganic nanorods allows the preparation of stable nanorod dispersions in appropriate solvents. At higher con…
Quantum dot-block copolymer hybrids with improved properties and their application to quantum dot light-emitting devices.
To combine the optical properties of CdSe@ZnS quantum dots (QDs) with the electrical properties of semiconducting polymers, we prepared QD/polymer hybrids by grafting a block copolymer (BCP) containing thiol-anchoring moieties (poly(para-methyl triphenylamine-b-cysteamine acrylamide)) onto the surfaces of QDs through the ligand exchange procedure. The prepared QD/polymer hybrids possess improved processability such as enhanced solubility in various organic solvents as well as the film formation properties along with the improved colloidal stability derived from the grafted polymer shells. We also demonstrated light-emitting diodes based on QD/polymer hybrids, exhibiting the improved device …
Orientation and Dynamics of ZnO Nanorod Liquid Crystals in Electric Fields.
ZnO nanorod polymer hybrids (i.e., ZnO nanorods coated with a block copolymer with a short anchor block (dopamine) and a longer solubilizing block of polystyrene (PS)) form liquid crystalline (LC) phases if they are dispersed at high concentration e.g., in a PS oligomer matrix. Due to the high mobility of the low T(g)-matrix the nanorod polymer hybrids show a switching behavior under an applied AC electric field. Hence, the orientation of the nanorod mesogens can be changed from planar (parallel to the substrate) to homeotropic (perpendicular) in full analogy to the switching of low molecular liquid crystals in an electric field. Dielectric measurements show that such a switching is mainly …
Light induced charging of polymer functionalized nanorods.
ZnO nanorods were functionalized with new block copolymers containing a hole transporting moiety in one block and a dye and an anchor system in the second block. After functionalization, the ZnO nanorods are well dispersible in organic media and the fluorescence of the dye is quenched. Kelvin probe force microscopy was used to measure changes in electrical potential between the ZnO nanorod and the polymeric corona. Upon light irradiation, potential changes on the order of some tens of millivolts were observed on individual structures. This effect is attributed to light-induced charge separation between the ZnO nanorod and its hole transporting polymeric corona.
Characterization of quantum dot/conducting polymer hybrid films and their application to light-emitting diodes.
Quantum dot/conducting polymer hybrid films are used to prepare light-emitting diodes (LEDs). The hybrid films (CdSe@ZnS quantum dots excellently dispersed in a conducting polymer matrix, see figure) are readily prepared by various solution-based processes and are also easily micropatterned. The LEDs exhibit a turn-on voltage of 4 V, an external quantum efficiency greater than 1.5%, and almost pure-green quantum-dot electroluminescence.
Orientation of Polymer Functionalized Nanorods in Thin Films
A directed self assembly of anisotropic nanostructures offers a possibility to provide unique functional materials, which are e.g., important in optoelectronic devices. We use the liquid crystalline behavior of polymer functionalized TiO2 and ZnO nanorods to apply methods well known for low molecular liquid crystals to achieve oriented thin films. Convective forces in the meniscus on a structured substrate obtain thin layers of oriented nanoparticles with a ordering parameter of S = 0.7. As another method we present the orientation of polystyrene covered ZnO nanorods under an applied electric field. The method offers a perpendicular alignment of the rods to the surface.
Liquid Crystalline Ordering and Charge Transport in Semiconducting Materials
Organic semiconducting materials offer the advantage of solution processability into flexible films. In most cases, their drawback is based on their low charge carrier mobility, which is directly related to the packing of the molecules both on local (amorphous versus crystalline) and on macroscopic (grain boundaries) length scales. Liquid crystalline ordering offers the possibility of circumventing this problem. An advanced concept comprises: i) the application of materials with different liquid crystalline phases, ii) the orientation of a low viscosity high temperature phase, and, iii) the transfer of the macroscopic orientation during cooling to a highly ordered (at best, crystalline-like…
Liquid crystalline phases from polymer functionalised semiconducting nanorods
The orientation of semiconducting nanomaterials is a hot topic in optoelectronic applications. Liquid crystallinity offers the potential to orient inorganic anisotropic nanorods, if they can be solubilised sufficiently as realised by polymer functionalisation. In this work we functionalised TiO2, SnO2, ZnO and CdTe nanorods with PMMA, PS and PDEGMEMA (poly(diethylene glycol monomethyl ether) methacrylate) diblock copolymers containing anchor groupsvia grafting-to. The block copolymers were synthesised by RAFT polymerisation (PDI ≈ 1.2) via reactive ester diblock copolymers, which were functionalised later with anchor units polymer-analogously. The surface coverage of the nanorods (determine…
Reduced efficiency roll-off in light-emitting diodes enabled by quantum dot–conducting polymer nanohybrids
We demonstrate QLEDs implementing wider active layers (50 nm) based on QD–conducting polymer nanohybrids, which exhibit a stable operational device performance across a wide range of current densities and brightness. A comparative study reveals that the significant suppression of efficiency roll-off in the high current density regime is primarily attributed to a sufficient charge carrier distribution over the wider active layer and improved charge carrier balance within QDs enabled by the hybridization of QDs with conducting polymers. Utilization of this finding in future studies should greatly facilitate the development of high performance, stable QLEDs at high current density or luminance…