Plasmonic and semiconductor nanoparticles interfere with stereolithographic 3D printing

Two-photon polymerization stereolithographic three-dimensional (3D) printing is used for manufacturing a variety of structures ranging from microdevices to refractive optics. Incorporation of nanoparticles in 3D printing offers huge potential to create even more functional nanocomposite structures. However, this is difficult to achieve since the agglomeration of the nanoparticles can occur. Agglomeration not only leads to an uneven distribution of nanoparticles in the photoresin but also induces scattering of the excitation beam and altered absorption profiles due to interparticle coupling. Thus, it is crucial to ensure that the nanoparticles do not agglomerate during any stage of the process. To achieve noninteracting and well-dispersed nanoparticles on the 3D printing process, first, the stabilization of nanoparticles in the 3D printing resin is indispensable. We achieve this by functionalizing the nanoparticles with surface-bound ligands that are chemically similar to the photoresin that allows increased nanoparticle loadings without inducing agglomeration. By systematically studying the effect of different nanomaterials (Au nanoparticles, Ag nanoparticles, and CdSe/CdZnS nanoplatelets) in the resin on the 3D printing process, we observe that both, material-specific (absorption profiles) and unspecific (radical quenching at nanoparticle surfaces) pathways co-exist by which the photopolymerization procedure is altered. This can be exploited to increase the printing resolution leading to a reduction of the minimum feature size.