Chalcogenoether complexes of Nb(V) thio- and seleno-halides as single source precursors for low pressure chemical vapour deposition of NbS2 and NbSe2 thin films

摘要

NbSCl3 was obtained via reaction of NbCl5 with S(SiMe3)2 in anhydrous CH2Cl2, whilst in MeCN solution the same reaction gives [NbSCl3(MeCN)2]. [NbSeCl3(MeCN)2] was obtained similarly from NbCl5 with Se(SiMe3)2. The chalcogenoether complexes, [NbSCl3(ER2)] (E = S: R = Me, nBu; E = Se: R = nBu), were obtained from reaction of NbCl5, ER2 and S(SiMe3)2 in CH2Cl2. The structure of the [Nb2S2Cl6(SMe2)2] reveals a Cl-bridged dimer with the SMe2 ligands disposed syn. The Cl bridges are highly asymmetric, with the long Nb–Cl bond trans Nb[double bond, length as m-dash]S. The complexes, [NbSCl3(L–L)] (L–L = MeSCH2CH2SMe, MeS(CH2)3SMe, iPrSCH2CH2SiPr, MeSe(CH2)3SeMe and nBuS(CH2)3SnBu), were obtained from reaction of L–L with preformed [NbSCl3(MeCN)2]. The structures of the Me-substituted complexes reveal distorted octahedral monomers with the neutral ligands trans to S/Cl. Solution 1H and 77Se{1H} NMR data showed that the neutral ligands are partially dissociated and undergoing fast exchange at ambient temperatures in CH2Cl2 solution, consistent with weak Lewis acidity for NbSCl3. The complexes containing nBu-substituted ligands have been used as single source precursors for low pressure chemical vapour deposition (CVD) of 3R-NbS2 thin films. 2H-NbSe2 thin films were also obtained via low pressure CVD using [NbSe2Cl3(SenBu2)]. The thin films were characterised by grazing incidence and in-plane XRD, pole figure analysis, scanning electron microscopy and energy dispersive X-ray analysis.