Electrochemical synthesis of flat-[Ga_13−xIn_x(μ₃-OH)₆(μ-OH)₁₈(H₂O)₂₄(NO₃)₁₅] clusters as aqueous precursors for solution-processed semiconductors

Abstract

Electrochemical reduction is used to synthesize indium-gallium-hydroxide-nitrate nanoclusters which are shown to be promising precursors for thin-film transistors.

Synthetic routes to a nanoscale inorganic cluster [Ga13(μ3-OH)6(μ2-OH)18(H2O)](NO3)15 evaluated by solid-state 71Ga NMR

“…Side view Figure 1: Representation of the "Ga 13 " structure, [Ga 13 (µ 3 -OH) 6 (µ 2 -OH) 18 (H 2 O)](NO 3 ) 15 as a ball-and-stick structure and as space-filling polyhedra. The core gallium, middle ring, and outer ring gallium sites are colored green, orange, and blue, respectively.…”

“…octahedra, while the outer ring atoms are in corner sharing octahedral sites. The possible routes for the synthesis of the Ga 13 cluster includes the dibutylnitrosamine (DBNA) addition method, [8] electrochemical reduction method, [17,18] and zinc reduction method. [13] We recently detailed the solid-state 69 Ga and 71 Ga NMR characterization of Ga 13 .…”

“…Solid-state NMR is a powerful technique in the characterization of metal-oxide clusters as it is nucleus specific and can provide a wealth of information regarding structure. Here, 71 Ga NMR was used to deconvolute the experimental NMR spectra of the [Ga 13 (µ 3 -OH) 6 (µ 2 -OH) 18 (H 2 O)](NO 3 ) 15 "Ga 13 " clusters made by multiple synthetic methods. Gallium has two NMR-active isotopes, 69 Ga and 71 Ga, both of which are quadrupolar and have a nuclear spin quantum number of I = 3/2.…”

“…For the purpose of our study, we focused on the [Ga 13 (µ 3 -OH) 6 (µ 2 -OH) 18 (H 2 O)](NO 3 ) 15 species, which we refer to as "Ga 13 ." The cluster contains 13 six-coordinate gallium species with three types of sites: the core, the middle ring, and the outer ring.…”

Heat capacities and thermodynamics of formation of flat-Al13 nitrate – [Al13(OH)24(H2O)24](NO3)15·11H2O

“…[4,[12][13][14]. Since recent advances in their synthesis, several reports have demonstrated their use as a greener and more economic route towards fabricating aluminum oxide based materials, specifically thin film transistors (TFTs) [6,10,[15][16][17]. Thus understanding their formation and persistence in solution under varying conditions is essential for understanding the underlying dehydration reactions which produce such thin films and other solid materials.…”