High concentrations of defects are introduced into nanoscale ZnO through non‐equilibrium processes and resultant blue emissions are comprehensively analyzed, focusing on defect origins and broad controls. Some ZnO nanoparticles exhibit very strong blue emissions, the intensity of which first increase and then decrease with annealing. These visible emissions exhibit strong and interesting excitation dependences: 1) the optimal excitation energy for blue emissions is near the bandgap energy, but the effective excitation can obviously be lower, even 420 nm (2.95 eV < Eg = 3.26 eV); in contrast, green emissions can be excited only by energies larger than the bandgap energy; and, 2) there are several fixed emitting wavelengths at 415, 440, 455 and 488 nm in the blue wave band, which exhibit considerable stability in different excitation and annealing conditions. Mechanisms for blue emissions from ZnO are proposed with interstitial‐zinc‐related defect levels as initial states. EPR spectra reveal the predominance of interstitial zinc in as‐prepared samples, and the evolutions of coexisting interstitial zinc and oxygen vacancies with annealing. Furthermore, good controllability of visible emissions is achieved, including the co‐emission of blue and green emissions and peak adjustment from blue to yellow.
Laser ablation of solid targets in the liquid medium can be realized to fabricate nanostructures with various compositions (metals, alloys, oxides, carbides, hydroxides, etc.) and morphologies (nanoparticles, nanocubes, nanorods, nanocomposites, etc.). At the same time, the post laser irradiation of suspended nanomaterials can be applied to further modify their size, shape, and composition. Such fabrication and modification of nanomaterials in liquid based on laser irradiation has become a rapidly growing field. Compared to other, typically chemical, methods, laser ablation/irradiation in liquid (LAL) is a simple and “green” technique that normally operates in water or organic liquids under ambient conditions. Recently, the LAL has been elaborately developed to prepare a series of nanomaterials with special morphologies, microstructures and phases, and to achieve one‐step formation of various functionalized nanostructures in the pursuit of novel properties and applications in optics, display, detection, and biological fields. The formation mechanisms and synthetic strategies based on LAL are systematically analyzed and the reported nanostructures derived from the unique characteristics of LAL are highlighted along with a review of their applications and future challenges.
A weak acid selective etching strategy was put forward to fabricate oxide-based hollow nanoparticles (HNPs) using core/shell nanostructures of active metal/oxide nanoparticles as sacrificial templates. ZnO-based HNPs, including pure ZnO, Au/ZnO, Pt/ZnO, and Au/Pt/ZnO HNPs with diameter below 50 nm and shell thickness below 6 nm has been first achieved at low temperature. The diameter, thickness, and even sizes of ZnO and noble metal ultrafine crystals of HNPs can be well adjusted by the etching process. Synchronous with the formation of HNPs, the internal metal-semiconductor interfaces can be controllably eliminated (Zn-ZnO) and reconstructed (noble metal-ZnO). Excitingly, such microstructure manipulation has endued them with giant improvements in related performances, including the very strong blue luminescence with enhancement over 3 orders of magnitude for the pure ZnO HNPs and the greatly improved photocatalytic activity for the noble metal/ZnO HNPs. These give them strong potentials in relevant applications, such as blue light emitting devices, environment remediation, drug delivery and release, energy storage and conversion, and sensors. The designed fabrication procedure is simple, feasible, and universal for a series of oxide and noble metal/oxide HNPs with controlled microstructure and improved performances.
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