Bismuth sulphide–polymer nanocomposites from a highly soluble bismuth xanthate precursor

Verena Kaltenhauser; Thomas Rath; Wernfried Haas; Ana Torvisco; Stefan K. Müller; Bettina Friedel; Birgit Kunert; Robert Saf; Ferdinand Hofer; Gregor Trimmel

doi:10.1039/C3TC31684J

Bismuth sulphide–polymer nanocomposites from a highly soluble bismuth xanthate precursor†

Verena Kaltenhauser,^ab Thomas Rath,*^ab Wernfried Haas,^bc Ana Torvisco,^d Stefan K. Müller,^d Bettina Friedel,^e Birgit Kunert,^e Robert Saf,^a Ferdinand Hofer^c and Gregor Trimmel^ab

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^a Institute for Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9, 8010 Graz, Austria
E-mail: thomas.rath@tugraz.at
Fax: +43 316-8731032331
Tel: +43 316-87332281

^b Christian Doppler Laboratory for Nanocomposite Solar Cells, Graz University of Technology, Stremayrgasse 9, 8010 Graz, Austria

^c Institute for Electron Microscopy and Nanoanalysis, Graz University of Technology, Steyrergasse 17, 8010 Graz, Austria

^d Institute of Inorganic Chemistry, Graz University of Technology, Stremayrgasse 9, 8010 Graz, Austria

^e Institute of Solid State Physics, Graz University of Technology, Petersgasse 16, 8010 Graz, Austria

Abstract

Bismuth sulphide nanocrystal–polymer hybrid layers are of interest for various optoelectronic, thermoelectric or sensing applications. In this work, we present a ligand-free in situ route for the formation of Bi₂S₃ nanorods directly within a polymer matrix. For this purpose, we introduce a novel bismuth xanthate (bismuth(III) O-3,3-dimethylbutan-2-yl dithiocarbonate), which is highly soluble in non-polar organic solvents. The analysis of the crystal structure revealed that the prepared bismuth xanthate crystallises in the monoclinic space group C2/c and forms dimers. The bismuth xanthate can be converted into nanocrystalline Bi₂S₃ with an orthorhombic crystal structure via a thermally induced solid state reaction at moderate temperatures below 200 °C. In combination with the high solubility in non-polar solvents this synthetic route for Bi₂S₃ is of particular interest for the preparation of Bi₂S₃–polymer nanocomposites as exemplarily investigated on Bi₂S₃–poly(methyl methacrylate) and Bi₂S₃–poly(3-hexylthiophene-2,5-diyl) (P3HT) nanocomposite layers. Atomic force and transmission electron microscopy revealed that Bi₂S₃ nanorods are dispersed in the polymer matrix. Photoluminescence experiments showed a quenching of the P3HT fluorescence with increasing Bi₂S₃ content in the hybrid layer.

Journal of Materials Chemistry C

Bismuth sulphide–polymer nanocomposites from a highly soluble bismuth xanthate precursor†

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