For a crystal to exhibit nonlinear optical (NLO) activity such as second-harmonic generation (SHG), it must belong to a noncentrosymmetric (NCS) space group. Moreover, for these nonlinear optical (NLO) materials to be suitable for practical uses, the synthesized crystals should be phase-matchable (PM). Previous synthetic research into SHG-active crystals has centered on (i) how to create NCS compounds and/or (ii) how to obtain NCS compounds with high SHG efficiencies. With these tactics, one can synthesize a material with a high SHG efficiency, but the material could be unusable if the material was nonphase-matchable (non-PM). To probe the origin of phase matchability of NCS structures, we present two new chemically similar hybrid compounds within one composition space: (I) [Hdpa]2NbOF5·2H2O and (II) HdpaNbOF4 (dpa = 2,2'-dipyridylamine). Both compounds are NCS and chemically similar, but (I) is non-PM while (II) is PM. Our results indicate--consistent with organic crystallography--the arrangement of the organic molecule within hybrid materials dictates whether the material is PM or non-PM.
Additive manufacturing (AM) of complex three‐dimensional (3D) metal oxides at the micro‐ and nanoscales has attracted considerable attention in recent years. State‐of‐the‐art techniques that use slurry‐based or organic–inorganic photoresins are often hampered by challenges in resin preparation and synthesis, and/or by the limited resolution of patterned features. A facile process for fabricating 3D‐architected metal oxides via the use of an aqueous metal‐ion‐containing photoresin is presented. The efficacy of this process, which is termed photopolymer complex synthesis, is demonstrated by creating nanoarchitected zinc oxide (ZnO) architectures with feature sizes of 250 nm, by first patterning a zinc‐ion‐containing aqueous photoresin using two‐photon lithography and subsequently calcining them at 500 ºC. Transmission electron microscopy (TEM) analysis reveals their microstructure to be nanocrystalline ZnO with grain sizes of 5.1 ± 1.6 nm. In situ compression experiments conducted in a scanning electron microscope show an emergent electromechanical response: a 200 nm mechanical compression of an architected ZnO structure results in a voltage drop of 0.52 mV. This photopolymer complex synthesis provides a pathway to easily create arbitrarily shaped 3D metal oxides that could enable previously impossible devices and smart materials.
Additive manufacturing at small scales enables advances in micro-and nanoelectromechanical systems, micro-optics, and medical devices. Materials that lend themselves to AM at the nano-scale, especially for optical applications, are limited. State-of-the-art AM processes for high refractive index materials typically suffer from high porosity, poor repeatability, and require complex experimental procedures. We developed an AM process to fabricate complex 3D architectures out of fully dense titanium dioxide (TiO 2) with a refractive index of 2.3 and nano-sized critical dimensions. Transmission Electron Microscopy (TEM) analysis proves this material to be rutile phase of nanocrystalline TiO 2 , with an average grain size of 110 nm and <1% porosity. Proof-ofconcept woodpile architectures with 300-600 nm beam dimensions exhibit a full photonic bandgap centered at 1.8-2.9 μm, revealed by Fourier-transform Infrared Spectroscopy (FTIR) and supported by Plane Wave Expansion simulations. The developed AM process enables advances in 3D MEMS, micro-optics, and prototyping of 3D dielectric PhCs.
In order to determine a material's hydrogen storage potential, capacity measurements must be robust, reproducible, and accurate. Commonly, research reports focus on the gravimetric capacity, and often times the volumetric capacity is not reported. Determining volumetric capacities is not as straight‐forward, especially for amorphous materials. This is the first study to compare measurement reproducibility across laboratories for excess and total volumetric hydrogen sorption capacities based on the packing volume. The use of consistent measurement protocols, common analysis, and figure of merits for reporting data in this study, enable the comparison of the results for two different materials. Importantly, the results show good agreement for excess gravimetric capacities amongst the laboratories. Irreproducibility for excess and total volumetric capacities is attributed to real differences in the measured packing volume of the material.
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