Mn-Based Nanostructured Building Blocks: Synthesis, Characterization and Applications
Beltran Huarac, Juan
Morell, Gerardo (Consejero)
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The quest for smaller functional elements of devices has stimulated increased interest in charge-transfer phenomena at the nanoscale. Mn-based nanostructured building blocks are particularly appealing given that the excited states of high-spin Mn2+ ions induce unusual d-d energy transfer processes, which is critical for better understanding the performance of electronic and spintronic devices. These nanostructures also exhibit unique properties superior to those of common Fe- and Co-based nanomaterials, including: excellent structural flexibility, enhanced electrochemical energy storage, effective ion-exchange dynamics, more comprehensive transport mechanisms, strong quantum yield, and they act as effective luminescent centers for more efficient visible light emitters. Moreover, Mn-based nanostructures (MBNs) are crucial for the design and assembly of inexpensive nanodevices in diluted magnetic semiconductors (DMS), optoelectronics, magneto-optics, and field-effect transistors, owing to the great abundance and low-cost of Mn. Nonetheless, the paucity of original methods and techniques to fabricate new multifunctional MBNs that fulfill industrial demands limits the sustainable development of innovative technology in materials sciences. In order to meet this critical need, in this thesis we develop and implement novel methods and techniques to fabricate zero- and one-dimensional highly-crystalline new-generation MBNs conducive to the generation of new technology, and provide alternative and feasible miniaturization strategies to control and devise at nanometric precision their size, shape, structure and composition. Herein, we also establish the experimental conditions to grow Mn-based nanowires (NWs), nanotubes (NTs), nanoribbons (NRs), nanosaws (NSs), nanoparticles (NPs) and nanocomposites (NCs) via chemical/physical deposition and co-precipitation chemical routes, and determine the pertinent arrangements to our experimental schemes in order to extend our bottom-up approaches towards the fabrication of different types of functional MBNs. Likewise, strategic procedures that advance the facile integration of these self-assembled nanostructures with carbon-based and magnetic/optical materials, chalcogenides, oxides, and ferroics are widely analyzed and discussed. Furthermore, we present the attractive peculiarities of three versatile MBN systems (bridging the gap between their advantageous properties and the lack of methods for their fabrication): single-crystal saw-like MnS NRs, and single-crystal MnS NWs conformally coated with carbon; doped rare-earth manganite NCs, and carbon NTs conformally coated with doped rare-earth manganite; and ZnS:Mn NPs, and Fe3O4/ZnS:Mn NCs. Concerning the applicative significance, the main features of these three systems obtained by our method are suitable to advance direct applications in nanotechnology. In this regard, this work represents a step ahead in the following areas: i) alternative anode materials to enhance the capacity and cycling performance of lowdrain, long-life, low-cost, high-energy density light-weight and safer lithium-ion batteries; ii) promising luminescent materials to improve the optoelectronic performance of visible light emitters; iii) new elements for field-effect transistors that outperform the transport properties of conventional carbon-based channels; iv) bifunctional materials exhibiting optical response sensitive to external magnetic fields vital for DMS; v) novel types of nanocantilevers useful for nanosensors and nanotweezers; vi) unique multiferroics materials that exhibit magnetoelectric coupling at room temperature for spintronics; vii) potential core-shell materials showing stress-free and protective carbon shells for shock-resistance semiconductors; and viii) high-quality ceramics useful as starting materials to deposit films by pulsed laser deposition, sputtering and thermal evaporation techniques.