ABSTRACT
Water-processable organic semiconductor nanoparticles (NPs) are considered promising materials for the next-generation of optoelectronic applications due to their controlled size, internal structure, and environmentally friendly processing. Reasonably, the controllable assembly of donor:acceptor (D:A) NPs on large areas, quality, and packing density of deposited films, as well as layer morphology, will influence the effectiveness of charge transfer at an interface and the final performance of designed optoelectronic devices.This work represents an easy and effective approach for designing self-assembled monolayers of D:A NPs. In this self-assembly procedure, the NP arrays are prepared on a large scale (2 × 2 cm2 ) at the air/water interface with controlled packing density and morphology. Due to the unique structure of individual D:A Janus particles and their assembled arrays, the Janus nanoparticle (JNP)-based device exhibits an 80% improvement of electron mobility and more balanced charge extraction compared to the conventional core-shell NP-based device. An outstanding performance of polymer solar cells with over 5% efficiency is achieved after post-annealing treatment of assembled arrays, representing one of the best results for NP-based organic photovoltaics. Ultimately, this work provides a new protocol for processing water-processable organic semiconductor colloids and future optoelectronic fabrication.
ABSTRACT
Cation exchange emerged as a versatile tool to obtain a variety of nanocrystals not yet available via a direct synthesis. Reduced reaction times and moderate temperatures make the method compatible with anisotropic nanoplatelets (NPLs). However, the subtle thermodynamic and kinetic factors governing the exchange require careful control over the reaction parameters to prevent unwanted restructuring. Here, we capitalize on the research success of CdSe NPLs by transforming them into PbSe NPLs suitable for optoelectronic applications. In a two-phase mixture of hexane/N-methylformamide, the oleate-capped CdSe NPLs simultaneously undergo a ligand exchange to NH4I and a cation exchange reaction to PbSe. Their morphology and crystal structure are well-preserved as evidenced by electron microscopy and powder X-ray diffraction. We demonstrate the successful ligand exchange and associated electronic coupling of individual NPLs by fabricating a simple photodetector via spray-coating on a commercial substrate. Its optoelectronic characterization reveals a fast light response at low operational voltages.
ABSTRACT
In this work, we present a new synthetic approach to colloidal PbS nanoplatelets (NPLs) utilizing a cation exchange (CE) strategy starting from CuS NPLs synthesized via the hot-injection method. Whereas the thickness of the resulting CuS NPLs was fixed at approx. 5 nm, the lateral size could be tuned by varying the reaction conditions, such as time from 6 to 16 h, the reaction temperature (120 °C, 140 °C), and the amount of copper precursor. In a second step, Cu+ cations were replaced with Pb2+ ions within the crystal lattice via CE. While the shape and the size of parental CuS platelets were preserved, the crystal structure was rearranged from hexagonal covellite to PbS galena, accompanied by the fragmentation of the monocrystalline phase into polycrystalline one. Afterwards a halide mediated ligand exchange (LE) was carried out in order to remove insulating oleic acid residues from the PbS NPL surface and to form stable dispersions in polar organic solvents enabling thin-film fabrication. Both CE and LE processes were monitored by several characterization techniques. Furthermore, we measured the electrical conductivity of the resulting PbS NPL-based films before and after LE and compared the processing in ambient to inert atmosphere. Finally, we fabricated field-effect transistors with an on/off ratio of up to 60 and linear charge carrier mobility for holes of 0.02 cm2 V-1 s-1.
