[Ag{S₂CNR(C₂H₄OH)}] as Single‐Source Precursor for Ag₂S – Synthesis, Decomposition Mechanism, and Deposition Studies

Abstract

Silver(I) dithiocarbamates [Ag{S2CNR(C2H4OH)}] (3a, R = Me; 3b, R = Bu) were accessible by the reaction of AgNO3 with K{S2CNR(C2H4OH)} (2a, R = Me; 2b, R = Bu). Alternatively, 3b could be prepared by the condensation of CS2 and Ag2O with NHBu(C2H4OH) (1b). The thermal behavior of 3 was studied by thermogravimetric (TG) analysis. A two‐step decomposition process leads to the formation of α‐Ag2S, as evidenced by X‐ray powder diffraction studies. A decomposition mechanism of 3a to form Ag2S through the release of 3‐methyloxazolidine‐2‐thione is discussed based on TG–MS, GC–MS, and NMR experiments. Because of the better solubility of 3b, this complex was tested for Ag2S spin‐coating deposition studies on different substrates (SiO2/Si, TiN/SiO2/Si, glass) with subsequent annealing at 450 °C under a N2 atmosphere. Film thickness, composition, and morphology of the as‐deposited films were determined by XRD, SEM, energy‐dispersive X‐ray spectroscopy, and X‐ray photoelectron spectroscopy, which showed the formation of 200 nm thick, conformal, adherent, monoclinic α‐Ag2S layers.

Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S2CN(iPr)CH2CH2OH]2

“…The reason for this structural difference is not immediately clear but the bridging bond formed by S2 has shortened to 2.5545(11) Å. The oxazolidine molecule is known to be a decomposition/cyclization product derived from the ¯S2CN(iPr)CH2CH2OH anion [95], a phenomenon reported for related species [96,97], and its molecular structure [95] matches closely that observed in 3 as seen the overlay diagram in Fig. 9.…”

Dithiocarbamate copper(I) and silver(I) complexes: Synthesis, structure and thermal behavior

“…chalcocite with x = 1.96; 6b: b-chalcocite with x = 2). This discrepancy between 6a,b and 6c,d from the TG as well as the XRPD experiments can likely be explained by the proposed decomposition mechanism of (b-hydroxyethyl)-methyldithiocarbamates as recently published by Nomura et al [19] and our group [20] (Scheme 2). The influence of the number n of the PBu 3 ligands present in the complex on the thermal induced decomposition is shown in Fig.…”

“…Complexes [Cu(PBu 3 ) n Cl] and [Ag(PBu 3 ) n (NO 3 )] [22] (n = 1, 2, 3), K[S 2 CNRR 0 ] [9,20] (R = R 0 = CH 2 CH@CH 2 , (CH 2 ) 4 , C 2 H 4 OH; R = Me, R 0 = C 2 H 4 OH; R = Bu, R 0 = C 2 H 4 OH), [Ag(S 2 CN(CH 2 CH@CH 2 ) 2 )], [23] [Ag(S 2 CNMe(C 2 H 4 OH))] and [Ag(S 2 CNBu(C 2 H 4 OH))] [20] were prepared by published procedures. All other chemicals were purchased by commercial suppliers and were used as received.…”

Binding of Gold(III) from Solutions by the [Ag6{S2CN(CH2)6}6] Cluster: Synthesis, Thermal Behavior, and Self-Organization of the Supramolecular Structure of the Double Complex [Au{S2CN(CH2)6}2]2[AgCl2]Cl·2CHCl3 (Role of Secondary Au⋅⋅⋅Cl, Ag⋅⋅⋅S, and Cl⋅⋅⋅Cl Interactions)

“…Silver(I) dithiocarbamate (Dtc) complexes are convenient precursors for the preparation of both acanthite (α-Ag 2 S) films and nanopowders [1][2][3][4] and Janus nanoparticles Ag 2 S/Ag 0 (including a combination of the metal and metal sulfide) [5,6], which are of practical interest for microelectronics. Since Ag 2 S is characterized by low toxicity and high stability in biological media, it is promising to use it in medicine for manufacturing biocompatible nanoprobes [7,8].…”