Abstract
The archetypal silica- and aluminosilicate-based zeolite-type materials are renowned for wide-ranging applications in heterogeneous catalysis, gas-separation and ion-exchange. Their compositional space can be expanded to include nanoporous metal chalcogenides, exemplified by germanium and tin sulfides and selenides. By comparison with the properties of bulk metal dichalcogenides and their 2D derivatives, these open-framework analogues may be viewed as three-dimensional semiconductors filled with nanometer voids. Applications exist in a range of molecule size and shape discriminating devices. However, what is the electronic structure of nanoporous metal chalcogenides? Herein, materials modeling is used to describe the properties of a homologous series of nanoporous metal chalcogenides denoted np-MX2, where M = Si, Ge, Sn, Pb, and X = O, S, Se, Te, with Sodalite, LTA and aluminum chromium phosphate-1 structure types. Depending on the choice of metal and anion their properties can be tuned from insulators to semiconductors to metals with additional modification achieved through doping, solid solutions, and inclusion (with fullerene, quantum dots, and hole transport materials). These systems form the basis of a new branch of semiconductor nanochemistry in three dimensions.
Highlights
The concept of reconstructing a bulk semiconductor through chemical synthesis into a semiconductor containing a periodic array of nanopores was introduced in 1992.1 The vision was a new genre of semiconductor device with electronic, optoelectronic, and optical properties that were sensitive to the size and shape of molecules adsorbed within the nanopores
We report the electronic properties of nanoporous metal chalcogenides exemplified by the sodalite (SOD), Linde Type A (LTA) and aluminum chromium phosphate-1 (ACO) structures and compare these properties with those of the bulk forms (MX2)
We have demonstrated the thermodynamic feasibility of electroactive porous chalcogenide frameworks, and recent work in the field of infiltrated carbon nanotubes[57] and electro-activated MOFs58 already demonstrates the wide array of novel technologies made possible by such strategies
Summary
The concept of reconstructing a bulk semiconductor through chemical synthesis into a semiconductor containing a periodic array of nanopores was introduced in 1992.1 The vision was a new genre of semiconductor device with electronic, optoelectronic, and optical properties that were sensitive to the size and shape of molecules adsorbed within the nanopores The archetypes of this class of zeolitic semiconductors (ZSs) were based on germanium and tin sulfide and selenide compositions. The results allow insights into how the structure and composition of nanoporous metal chalcogenides determine their electrical and optical properties, and provide a robust platform for developing “inverse quantum dot” nanoporous semiconductors
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