Pushing the Limits of Capillary Assembly for the Arbitrary Positioning of Sub-50nm Nanocubes in Printable Plasmonic Surfaces.

The fabrication of high quality nanophotonic surfaces for integration in optoelectronic devices remains a challenge because of the complexity and cost of top-down nanofabrication strategies. Combining colloidal synthesis with templated self-assembly emerged as an appealing low-cost solution. However, it still faces several obstacles before integration in devices can become a reality. This is mostly due to the difficulty in assembling small nanoparticles (<50 nm) in complex nanopatterns with a high yield. In this study, a reliable methodology is proposed to fabricate printable nanopatterns with an aspect ratio varying from 1 to 10 and a lateral resolution of 30 nm via nanocube assembly and epitaxy. Investigating templated assembly via capillary forces, a new regime was identified that was used to assemble 30-40 nm nanocubes in a patterned polydimethylsiloxane template with a high yield for both Au and Ag with multiple particles per trap. This new method relies on the generation and control of an accumulation zone at the contact line that is thin as opposed to dense, displaying higher versatility. This is in contrast with conventional wisdom, identifying a dense accumulation zone as a requirement for high-yield assembly. In addition, different formulations are proposed that can be used for the colloidal dispersion, showing that the standard water-surfactant solutions can be replaced by surfactant-free ethanol solutions, with good assembly yield. This allows to minimize the presence of surfactants that can affect electronic properties. Finally, it is shown that the obtained nanocube arrays can be transformed into continuous monocrystalline nanopatterns via nanocube epitaxy at near ambient temperature, and transferred to different substrates via contact printing. This approach opens new doors to the templated assembly of small colloids and could find potential applications in various optoelectronic devices ranging from solar cells to light-emitting diodes and displays.

Nanoparticle Imprint Lithography: From Nanoscale Metrology to Printable Metallic Grids.

Large scale and low-cost nanopatterning of materials is of tremendous interest for optoelectronic devices. Nanoimprint lithography has emerged in recent years as a nanofabrication strategy that is high-throughput and has a resolution comparable to that of electron-beam lithography (EBL). It is enabled by pattern replication of an EBL master into polydimethylsiloxane (PDMS), that is then used to pattern a resist for further processing, or a sol-gel that could be calcinated into a solid material. Although the sol-gel chemistry offers a wide spectrum of material compositions, metals are still difficult to achieve. This gap could be bridged by using colloidal nanoparticles as resist, but deep understanding of the key parameters is still lacking. Here, we use supported metallic nanocubes as a model resist to gain fundamental insights into nanoparticle imprinting. We uncover the major role played by the surfactant layer trapped between nanocubes and substrate, and measure its thickness with subnanometer resolution by using gap plasmon spectroscopy as a metrology platform. This enables us to quantify the van der Waals (VDW) interactions responsible for the friction opposing the nanocube motion, and we find that these are almost in quantitative agreement with the Stokes drag acting on the nanocubes during nanoimprint, that is estimated with a simplified fluid mechanics model. These results reveal that a minimum thickness of surfactant is required, acting as a spacer layer mitigating van der Waals forces between nanocubes and the substrate. In the light of these findings we propose a general method for resist preparation to achieve optimal nanoparticle mobility and show the assembly of printable Ag and Au nanocube grids, that could enable the fabrication of low-cost transparent electrodes of high material quality upon nanocube epitaxy.

Nanocube Epitaxy for the Realization of Printable Monocrystalline Nanophotonic Surfaces.

Plasmonic nanoparticles of the highest quality can be obtained via colloidal synthesis at low-cost. Despite the strong potential for integration in nanophotonic devices, the geometry of colloidal plasmonic nanoparticles is mostly limited to that of platonic solids. This is in stark contrast to nanostructures obtained by top-down methods that offer unlimited capability for plasmon resonance engineering, but present poor material quality and have doubtful perspectives for scalability. Here, an approach that combines the best of the two worlds by transforming assemblies of single-crystal gold nanocube building blocks into continuous monocrystalline plasmonic nanostructures with an arbitrary shape, via epitaxy in solution at near ambient temperature, is introduced. Nanocube dimers are used as a nanoreactor model system to investigate the mechanism in operando, revealing competitive redox processes of oxidative etching at the nanocube corners and simultaneous heterogeneous nucleation at their surface, that ensure filling of the sub-nanometer gap in a self-limited manner. Applying this procedure to nanocube arrays assembled in a patterned poly(dimethylsiloxane) (PDMS) substrate, it is able to obtain printable monocrystalline nanoantenna arrays that can be swiftly integrated in devices. This may lead to the implementation of low-cost nanophotonic surfaces of the highest quality in industrial products.

Monocrystalline Methylammonium Lead Halide Perovskite Materials for Photovoltaics.

Lead halide perovskite solar cells have been gaining more and more interest. In only a decade, huge research efforts from interdisciplinary communities enabled enormous scientific advances that rapidly led to energy conversion efficiency near that of record silicon solar cells, at an unprecedented pace. However, while for most materials the best solar cells were achieved with single crystals (SC), for perovskite the best cells have been so far achieved with polycrystalline (PC) thin films, despite the optoelectronic properties of perovskite SC are undoubtedly superior. Here, by taking as example monocrystalline methylammonium lead halide, the authors elaborate the literature from material synthesis and characterization to device fabrication and testing, to provide with plausible explanations for the relatively low efficiency, despite the superior optoelectronics performance. In particular, the authors focus on how solar cell performance is affected by anisotropy, crystal orientation, surface termination, interfaces, and device architecture. It is argued that, to unleash the full potential of monocrystalline perovskite, a holistic approach is needed in the design of next-generation device architecture. This would unquestionably lead to power conversion efficiency higher than those of PC perovskites and silicon solar cells, with tremendous impact on the swift deployment of renewable energy on a large scale.