Abstract
The large area scalable fabrication of supported porous metal and metal oxide nanomaterials is acknowledged as one of the greatest challenges for their eventual implementation in on-device applications. In this work, we will present a comprehensive revision and the latest results regarding the pioneering use of commercially available metal phthalocyanines and porphyrins as solid precursors for the plasma-assisted deposition of porous metal and metal oxide films and three-dimensional nanostructures (hierarchical nanowires and nanotubes). The most advanced features of this method relay on its ample general character from the point of view of the porous material composition and microstructure, mild deposition and processing temperature and energy constrictions and, finally, its straightforward compatibility with the direct deposition of the porous nanomaterials on processable substrates and device-architectures. Thus, taking advantage of the variety in the composition of commercially available metal porphyrins and phthalocyanines, we present the development of metal and metal oxides layers including Pt, CuO, Fe2O3, TiO2, and ZnO with morphologies ranging from nanoparticles to nanocolumnar films. In addition, we combine this method with the fabrication by low-pressure vapor transport of single-crystalline organic nanowires for the formation of hierarchical hybrid organic@metal/metal-oxide and @metal/metal-oxide nanotubes. We carry out a thorough characterization of the films and nanowires using SEM, TEM, FIB 3D, and electron tomography. The latest two techniques are revealed as critical for the elucidation of the inner porosity of the layers.
Highlights
The synthesis of nanostructured porous metal and metal oxide nanomaterials has become imperative to the development of functional and catalytic applications because of their tunable physical and chemical properties, high surface area and advantageous use as the host material in the novel hybrid and heterostructured systems (Morris and Wheatley, 2008; Shiju and Guliants, 2009; Kim and Nair, 2013; Zhu et al, 2015; Wang et al, 2017; Jin and Maduraiveeran, 2019)
The remote plasma-assisted vacuum deposition process (RPAVD) method consists of the thermal evaporation of the precursor molecules in the afterglow region of a microwave plasma supported by electron cyclotron resonance (ECR), i.e., in a downstream configuration
We have developed a general protocol for the formation of hybrid and porous metal oxides by a vacuum process in combination with oxygen plasma etching by extending the remote plasma assisted method to the use of commercially available metal phthalocyanines and porphyrins
Summary
The synthesis of nanostructured porous metal and metal oxide nanomaterials has become imperative to the development of functional and catalytic applications because of their tunable physical and chemical properties, high surface area and advantageous use as the host material in the novel hybrid and heterostructured systems (Morris and Wheatley, 2008; Shiju and Guliants, 2009; Kim and Nair, 2013; Zhu et al, 2015; Wang et al, 2017; Jin and Maduraiveeran, 2019). In the case of vacuum phase approaches, the methodologies previously developed for the synthesis of highly compact films, such as thermal, electronbeam or ion-assisted evaporation, magnetron sputtering, atomic layer deposition (ALD), and plasma enhanced chemical vapor deposition (PECVD) have been thoroughly modified and expanded to produce microporous and mesoporous layers (Romero-Gómez et al, 2010; Sánchez-Valencia et al, 2010; Borras et al, 2012; Barranco et al, 2016; Coll and Napari, 2019; Coll et al, 2019) Strategies, such as deposition in glancing angle conditions (Barranco et al, 2016) or the use of sacrificial soft and hard templates (Pal and Bhaumik, 2013; Lee and Park, 2014; Sun and Xu, 2014; Malgras et al, 2015) have allowed the fabrication of metal and metal oxide layers endowed with underdesign porosity, microstructure and structure as well as with strict control on the chemical bulk and surface composition, and functionalization. We used FIB-3D for the analysis of a supported nanoporous oxide thin film and electron tomography for the 3D reconstruction of an isolated TiO2 porous
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