3D nanoprinting of semiconductor quantum dots by photoexcitation-induced chemical bonding

Three-dimensional (3D) laser nanoprinting allows maskless manufacturing of diverse nanostructures with nanoscale resolution. However, 3D manufacturing of inorganic nanostructures typically requires nanomaterial-polymer composites and is limited by a photopolymerization mechanism, resulting in a reduction of material purity and degradation of intrinsic properties. We developed a polymerization-independent, laser direct writing technique called photoexcitation-induced chemical bonding. Without any additives, the holes excited inside semiconductor quantum dots are transferred to the nanocrystal surface and improve their chemical reactivity, leading to interparticle chemical bonding. As a proof of concept, we printed arbitrary 3D quantum dot architectures at a resolution beyond the diffraction limit. Our strategy will enable the manufacturing of free-form quantum dot optoelectronic devices such as light-emitting devices or photodetectors. Nanoparticle assembly often requires tailored selection of the ligands so that they can selectively bond, as with complementary DNA strands. Alternately, they can be linked together at specified locations using photopolymerization to connect ligands at desired places. However, this process adds to the complexity of making the nanoparticles and is limited by the fidelity of the ligand attachment. Liu et al . show that light can be used to desorb surface thiolate ligands from cadmium selenide/zinc sulfide core shell quantum dots (see the Perspective by Pan and Talapin). The resulting trapped holes drive bonding between the particles through the remaining surface ligands. The authors reveal photoprinting of arbitrary three-dimensional architectures at a resolution beyond the diffraction limit and for a range of nanocrystals. Printing can be optically selected based on the size and/or bandgap of the quantum dots. —MSL Photoexcitation-induced chemical bonding enables high-resolution three-dimensional printing of semiconductor quantum dots.