Aerosol‐Assisted CVD of Antimony Sulfide from Antimony Dithiocarbamates

Abstract

Asymmetric antimony dithiocarbamates, Sb[S2CN(Me)R]3 (R = Bu, Hex, Bz), can be thermally decomposed under a dynamic vacuum to yield high‐purity Sb2S3 rods. These precursors do not, however, have sufficient volatility for low‐pressure (LP) CVD, but are soluble in organic solvents and can be exploited in aerosol‐assisted (AA) CVD. Sb2S3 can be deposited using the latter procedure, but the film purity is dependent on substrate temperature. As temperature increases the films become more susceptible to oxidation, and the deposition of oxides and mixed oxide/sulfides becomes more prevalent.

Solution based CVD of main group materials

“…Thin films of Sb 2 S 3 have been deposited from [Sb(S 2 COR) 3 ] (R = Me, Et, i Pr) 118 which were shown to be superior precursors compared to the related antimony dithiocarbamates, [Sb(S 2 CNRR 0 ) 3 ], 119 which produced Sb 2 S 3 films prone to oxidation. Thin films of Sb 2 S 3 have been deposited from [Sb(S 2 COR) 3 ] (R = Me, Et, i Pr) 118 which were shown to be superior precursors compared to the related antimony dithiocarbamates, [Sb(S 2 CNRR 0 ) 3 ], 119 which produced Sb 2 S 3 films prone to oxidation.…”

Synthesis of Bi2−2xSb2xS3 (0 ≤ x ≤ 1) solid solutions from solventless thermolysis of metal xanthate precursors

“…19,20 These contrasts in the molar ratios of Bi/(Sb+Bi) have been ascribed to the operation of so-called semi-metal boiling, during which a sudden alteration in the Sb 2 S 3 /Bi 2 S 3 (Sb/Bi) ratio arises at a specific point along the flow path due to preferential volatilisation and loss of antimony from the ore fluid. [20][21][22] Numerous approaches have been employed for the preparation of Sb 2 S 3 and Bi 2 S 3 nanoparticles and thin films including solvothermal, 23,24 hydrothermal, 25,26 single-source routes, [27][28][29][30] colloidal methods; 16,31,32 melt thermolysis, 33 dip-dry techniques, 34 chemical bath deposition, 35,36 aerosol-assisted chemical vapour deposition (AA-CVD), 37 spray pyrolysis, 38,39 and successive ionic layer adsorption reactions (SILAR) have also been used. 40,41 Solventless thermolysis has advantages over other routes, as it is a simple method in which solid state decomposition of a precursor is achieved by thermal treatment under inert conditions.…”

“…This approach is simple, can produce high-quality materials with better control over composition, the potential for low-growth temperatures, and is highly suitable for mass production. 47 Indeed, great success has been achieved using the thermal decomposition of antimony/bismuth complexes of dithiocarbamates, 27,37,[48][49][50][51][52][53] dithiophosphates, 27,30,54 and thiourea, 55,56 as single-source precursors. The use of metal xanthate precursors for the preparation of Sb 2 S 3 27,57,58 and Bi 2 S 3 59-61 is promising owing to the low decomposition temperature of metal xanthate complexes (100-200 1C) and clean abstraction of volatile organic material from the crystal matrix by Chugaev elimination during thermolysis.…”

Colloidal Sb2S3nanocrystals: synthesis, characterization and fabrication of solid-state semiconductor sensitized solar cells

“…(AACVD) [32][33][34] and chemical bath deposition. 21 Oxygen contamination was a problem in most of the cases.…”