Germanium Compounds Containing Ge═E Double Bonds (E = S, Se, Te) as Single-Source Precursors for Germanium Chalcogenide Materials

Abstract

New germanium chalcogenide precursors, S═Ge(dmamp) (3), S═Ge(dmampS) (4), Se═Ge(dmamp) (5), Se═Ge(dmampS) (6), Te═Ge(dmamp) (7), and Te═Ge(dmampS) (8), were synthesized from Ge(dmamp) (1) and Ge(dmampS) (2) using sulfur, selenium, and tellurium powders (dmamp = 1-dimethylamino-2-methyl-2-propanolate, dmampS = 1-dimethylamino-2-methylpropane-2-thiolate). Complexes 1 and 2 were synthesized from metathesis reactions of GeCl·dioxane with 2 equiv of aminoalkoxide or aminothiolate ligands. Thermogravimetric analysis of complex 1 displayed good thermal stability and volatility. The molecular structures of complexes 2-8 from X-ray single crystallography showed distorted trigonal bipyramidal geometry at the germanium centers. Germanium chalcogenide materials (GeSe and GeTe) were obtained from the thermal decomposition of complexes 5, 6, and 8 in hexadecane. X-ray diffraction patterns exhibited that GeSe and GeTe had orthorhombic and rhombohedral phases, respectively. This study affords a facile method to easily prepare germanium chalcogenide materials using well-designed and stable complexes by thermal decomposition of single-source precursors in solution.

Stable N‐Heterocyclic Germylenes of the Type [Fe{(η5‐C5H4)NR}2Ge] and Their Oxidation Reactions with Sulfur, Selenium, and Diphenyl Diselenide

“…As a caveat we note that 77 Se NMR chemical shifts of the comparatively much more abundant germaneselones with four‐ or five‐coordinated Ge IV lie in the broad range between ca. –464 and 1116 ppm, with no clear trend being apparent , . In fact, small structural changes may cause massive chemical shift differences, as is illustrated by a comparison of two homologous germaneselones of the type [(Me 3 Si)(2‐pyridyl) R C] 2 GeSe with pentacoordinate Ge IV : The 77 Se NMR signal is located at δ = –97.6 ppm for R = SiMe 3 and at δ = 1097.1 ppm for R = Ph.…”

“…In fact, small structural changes may cause massive chemical shift differences, as is illustrated by a comparison of two homologous germaneselones of the type [(Me 3 Si)(2‐pyridyl) R C] 2 GeSe with pentacoordinate Ge IV : The 77 Se NMR signal is located at δ = –97.6 ppm for R = SiMe 3 and at δ = 1097.1 ppm for R = Ph. [19e], [19g] A significant dissociation of [ 1Pr* Ge(μ‐Se)] 2 into the monomeric germaneselone 1Pr* GeSe in benzene solution was ruled out by the result of a molecular weight determination by cryoscopy in benzene.…”

[Ge(TenBu)4] – a single source precursor for the chemical vapour deposition of germanium telluride thin films

“…Gupta et al synthesised (R 2 GeTe) 3 (R = Et, Bu) (1) from the reaction of Li 2 Te and R 2 GeCl 2 , and thermal decomposition of the precursor in trioctylphosphine at 300°C resulted in rhombohedral GeTe, 38 while Kim et al showed that thermal decomposition of [Te = Ge(dmampS) 2 ] (2) in hexadecane at 270°C produced Te-rich rhombohedral Ge 40 Te 57 . 39 There is just one previous example of a single source CVD precursor for the deposition of GeTe thin films. Using [Ge{N(SiMe 2 CH 2 CH 2 Me 2 Si)} 2 ( i Pr)(Te i Pr)] (3) in NH 3 , Chen et al reported that GeTe film growth occurs between 280 and 400°C.…”

Synthesis of Ferrocenyl-Substituted Organochalcogenyldichlorogermanes

“…Germanium chalcogenides are interesting chemical species for optoelectronic modules due to the appropriate combination between the electron-accepting element Ge and an electron-donating element, such as Se or Te, because the size and energy levels of frontier orbitals should be close to each other (4p and 4p/5p) [1,2]. Therefore, organogermanium species that bear a chalcogen (Ch) moiety should be able to serve as building blocks for organic-inorganic hybrid materials that contain a Ge-Ch bond.…”