Beiträge zur Chemie des Germaniums. XX. Über das Germaniummonochlorid und das Digermaniumhexachlorid

Abstract

Durch thermische Spaltung von Germaniumtetrachlorid im Abschreckrohr gelang es, ein Germaniummonochlorid der Formel (GeCl)x darzustellen. Sein Existenzbereich wurde ermittelt. Thermische Zersetzung dieses Monochlorids führt je nach Art der Reaktionsbedingungen neben Germaniumtetrachlorid zu kristallinem Germaniumdichlorid, höheren Germaniumchloriden und metallischem Germanium. — Es konnte ein Digermaniumhexachlorid der Formel Ge2Cl6 dargestellt werden.

Atomic Layer Deposition of GeTe and Ge–Sb–Te Films Using HGeCl3, Sb(OC2H5)3, and {(CH3)3Si}2Te and Their Reaction Mechanisms

“…The deposition of GeTe films was conducted through direct reaction between HGeCl 3 and ((CH 3 ) 3 Si) 2 Te based on the following suggested ALD mechanism. HGeCl 3 is known to be easily cleaved into dichlorogermylene and hydrogen chloride, as shown in eq . , Therefore, it is proposed that the GeCl 2 from eq reacted with the Te precursor to make stoichiometric GeTe through the reaction . …”

“…HGeCl 3 is known to be easily cleaved into dichlorogermylene and hydrogen chloride, as shown in eq 1. 22,27 Therefore, it is proposed that the GeCl 2 from eq 1 reacted with the Te precursor to make stoichiometric GeTe through the reaction 2. (1)…”

“…Regarding the chemical equilibrium of eq 1, it was reported that its equilibrium point shifted toward the GeCl 2 + HCl side at a low temperature, and that even pure GeCl 2 can be obtained under suction at −30 °C. 27,28 In this study, the canister temperature of the Ge precursor was maintained at 3 °C, and thus, the drawn vapor may contain GeCl 2 , HCl, and HGeCl 3 . To confirm the chemical reactivity between the Ge and the Te precursors, film deposition was attempted using the typical ALD sequence shown in Figure 1a, and the growth behavior during each pulse and purge can be seen in Figures 1b−e.…”

Halides of the Heavier Group 14 Homologues Germanium, Tin, and Lead—A Journey through Unusual Compounds and Oxidation States

“…The most common Ge IV halide is GeCl 4 , which is synthesized by the reaction of germanium dioxide with hydrochloric acid . Additionally, the hexachlorodigermane Ge 2 Cl 6 is known; it was first synthesized in 1954 by the reaction of elemental germanium and GeCl 4 at high pressure and temperature . Hexachlorodigermane decomposes to give Ge 5 Cl 12 ⋅GeCl 4 with a neopentyl‐like Ge 5 skeleton among other species .…”

“…[8] Additionally,t he hexachlorodigermane Ge 2 Cl 6 is known; it was first synthesized in 1954 by the reactiono fe lemental germanium and GeCl 4 at high pressure and temperature. [9] Hexachlorodigermane decomposes to give Ge 5 Cl 12 ·GeCl 4 with an eopentyl-like Ge 5 skeleton among other species. [10] In 1989 Sakurai and co-workerss howedt hat GeCl 4 can be ap recursor for generating clusterc ompounds by reacting it with bis(trimethylsilyl)methylmagnesium chloride to get (Me 3 Si) 2 CHGeCl 3 ,w hich is further reductively coupled with elemental lithium to give the first hexagermaprismane [{(Me 3 Si) 2 CHGe} 6 ] ( Figure 1a).…”