Multilayer thin films consisting of anionic α-zirconium phosphate (α- ZrP) sheets, tetrameric zirconium hydroxide cations [Zr4(OH)8(H2O)16]8+ (Zr48+), and alkanediylbis(phosphonic acid) (C(n)BPA) have been grown on silicon and gold surfaces by sequential adsorption reactions. The thin films were characterized by ellipsometry, X- ray diffraction, reflectance infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). Alternately dipping cationic substrates into exfoliated α-ZrP-containing suspensions, aqueous zirconium oxychloride, and ethanolic C16BPA solutions generates a mixed ionic/covalent multilayer structure. The tetrameric Zr48+ cation adsorbs onto the α-ZrP surface, providing a covalent anchoring point for the growth of the C16BPA layer. Adsorbing a second layer of zirconium ions onto the C16BPA layer allows one to continue the layer growth sequence using either covalent (metal/phosphonate) or ionic (α-ZrP/polycation) interlayer connections. A multilayer film with a repeating α- ZrP/Zr48+/C16BPA/Zr48+ sequence is sufficiently well-ordered in the stacking direction to give a Bragg peak in the diffraction pattern. The intensities of infrared absorbances in the symmetric and asymmetric C-H stretching regions, which arise from C16BPA, are linear with the C16BPA layer number. This 'mix and match' approach provides a versatile means of assembling multilayer heterostructures from both ionic and covalent building blocks, with essentially any desired sequence of layers.
All Science Journal Classification (ASJC) codes
- General Chemistry
- Colloid and Surface Chemistry