Molecular routes to CuZnSnS: A comparison of approaches to bulk and thin-film materials

A range of xanthates (R'P)CuSCOR [R' = Ph, R = Et (1), i-Pr (2), t-Bu (3), t-Amyl (4); R' = PhO, R = Et (5), R' = n-Bu, R = Et (6), Bu (7)], M(SCOR) [M = Sn R = Et (8); Zn, R = Et (10), i-Pr (11), n-Pr (12), n-Bu (13), n-Hex (14)], Sn(S COEt) (9), Zn(SCOEt).TMEDA (15) have been synthesised and their thermal decomposition profiles delineated by TGA.A parallel range of dithiocarbamates (R'P)CuS CN(Me)R [R' = Ph, R = Bu (16), Bz (17)], M[S CN(Me)R] [M = Sn, R = Bu (18), Bz (19); M = Zn, R = Bu (21), Bz (22)] has been similarly assessed.Although precursor combinations have been found from these systems that generate Cu ZnSnS (CZTS) from either a bulk decomposition (1, 8, 10 at 400 °C/Ar; CuZnSnS ), from a doctor-bladed film (7, 8, 13 at 400 °C/Ar; Cu ZnSnS), and as nanoparticles (7, 8, 13 in octadecane/oleic acid, 150 °C; Cu ZnSnS), attempts to deposit CZTS by aerosol-assisted CVD has proved more challenging and only successful from the dithiocarbamates 16, 18, 21 (350 °C; Cu ZnSn).As part of this work the crystal structures of 2-5, 8, 16, and the dithiocarbamate decomposition product {Sn[SCN(Me)Bu)]S} (20) have been determined.