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Tin Guanidinato Complexes: Oxidative Control of Sn, SnS, SnSe and SnTe Thin Film Deposition


A family of tin(II) guanidinate complexes of the general form [{RNC(NMe2)NR}i2Sn] (R = iPr (6), Cy (7), Tol (9) and Dipp (10) and [{tBuNC(NMe2)NtBu}Sn{NMe2}] (8) have been synthesized and isolated from the reaction of tin(II) bis-dimethylamide and a series of carbodiimides (1-5). The cyclic poly-chalcogenide compounds [{CyNC(NMe2)NCy}2Sn{Chx}] (Ch = S, x = 4 (11), Ch = Se x = 4 (12), and Ch = S, x = 6 (13)) with {SnChx} rings were prepared by the oxidative addition of elemental sulfur and selenium, to the heteroleptic stannylene complex [{CyNC(NMe2)NCy}2Sn] (7) in THF at room temperature. Similarly, reaction of compounds 6 and 7 with an equimolar amount of the chalcogen transfer reagents (SC3H6 and Se=PEt3 respectively) led to the formation of the chalcogenide tin(IV) complexes [{RNC(NMe2)NR}Sn(Ch)] (R = Cy: Ch = S (14); R = iPr, Ch = Se (15); R = Cy, Ch = Se (16)) with terminal Sn=Ch (14 & 16) and dimeric bridged seleno-tin {Sn2Se2} rings (15), respectively. The mono telluro-compounds [{RNC(NMe2)NR}Sn(Te)] (R = iPr (17); R = Cy (18)) were similarly prepared by the oxidative addition of elemental tellurium to 7 and 8 respectively. All the tin containing compounds have been investigated by multinuclear NMR (1H, 13C 119Sn and 77Se /125Te, where possible), elemental analysis and single crystal X-ray structural analysis (7, 8, 10-13, 15-18). Thermogravimetric analysis (TGA) was used to probe the possible utility of complexes 6-8, 11-12 and 14-18 as single source Sn and SnCh precursors. The Sn(II) compounds 6 and 7 have been utilized in the growth of thin films by aerosol-assisted chemical vapor deposition (AACVD) at both 300 and 400 °C. The thin films have been analysed by pXRD, EDS, SEM and AFM and shown to be Sn metal. Subsequent studies provided film growth at temperatures as low as 200 °C. Similarly, the mono-chalcogenide systems 14, 16 and 18 have been utilised in the AACVD of thin films. These latter studies provided films, grown at 300 and 400 °C, which have also been analyzed by pXRD, Raman spectroscopy, XPS, AFM, and SEM and are shown to comprise of phase pure SnS, SnSe and SnTe, respectively. These preliminary results demonstrate the potential of such simple guanidinate complexes to act as single source precursors with a high degree of oxidative control over the deposited thin films.

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Publication details

The article was accepted on 05 Mar 2018 and first published on 07 Mar 2018

Article type: Paper
DOI: 10.1039/C8DT00773J
Citation: Dalton Trans., 2018, Accepted Manuscript
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    Tin Guanidinato Complexes: Oxidative Control of Sn, SnS, SnSe and SnTe Thin Film Deposition

    A. L. Johnson, I. Y. Ahmet, M. S. Hill and P. R. Raithby, Dalton Trans., 2018, Accepted Manuscript , DOI: 10.1039/C8DT00773J

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