Hexagonal nanoporous germanium through surfactant-driven self-assembly of Zintl clusters.

Surfactant templating is a method that has successfully been used to produce nanoporous inorganic structures from a wide range of oxide-based material. Co-assembly of inorganic precursor molecules with amphiphilic organic molecules is followed first by inorganic condensation to produce rigid amorphous frameworks and then, by template removal, to produce mesoporous solids. A range of periodic surfactant/semiconductor and surfactant/metal composites have also been produced by similar methods, but for virtually all the non-oxide semiconducting phases, the surfactant unfortunately cannot be removed to generate porous materials. Here we show that it is possible to use surfactant-driven self-organization of soluble Zintl clusters to produce periodic, nanoporous versions of classic semiconductors such as amorphous Ge or Ge/Si alloys. Specifically, we use derivatives of the anionic Ge9(4-) cluster, a compound whose use in the synthesis of nanoscale materials is established. Moreover, because of the small size, high surface area, and flexible chemistry of these materials, we can tune optical properties in these nanoporous semiconductors through quantum confinement, by adsorption of surface species, or by altering the elemental composition of the inorganic framework. Because the semiconductor surface is exposed and accessible in these materials, they have the potential to interact with a range of species in ways that could eventually lead to new types of sensors or other novel nanostructured devices.

Chemical tuning of the electronic properties in a periodic surfactant-templated nanostructured semiconductor.

In this work, we report the synthesis and characterization of a series of hexagonal nanostructured platinum/tin/tellurium inorganic/surfactant composites. The composites are formed through solution-phase self-assembly of SnTe4(4-) Zintl clusters, which are cross-linked with platinum salts in the presence of a cetyltriethylammonium cationic structure directing agent. The cross-linking utilizes various combinations of Pt(II) and Pt(IV) salts. Low-angle X-ray diffraction indicates that all composites form hexagonal honeycomb (p6mm) structures. A combination of elemental analysis and XANES is used to describe the composition and oxidation states within the composites. We find that the extent of tin telluride self-oligomerization and the platinum:tin telluride ratio both vary, indicating that the composite compensates for different platinum oxidation states by tuning the inorganic composition. Near-IR/visible reflectance spectroscopy and UPS can be used to measure both band gaps and absolute band energies. The results show that while moving from all Pt(II) to all Pt(IV) increases the band gap from 0.6 to 0.8 eV, it increases the absolute valence and conduction band energies by almost a full electronvolt. AC impedance spectroscopy further reveals that the conductivities of the materials can be tuned from 0.009 to 0.003 Omega(-1).cm(-1). Additionally, a capacitance arising from the periodic nanoscale organic domains was observed. The conductivity and band gap were used to estimate carrier mobilities in these composites. Chemical tuning of the electronic properties within related nanostructured composites is a useful tool for designing applications that exploit the properties of nanostructured semiconductors.