Indium oxide is a major component of many technologically important thin films, most notably the transparent conductor indium tin oxide (ITO). Despite being pyrophoric, homoleptic indium(III) alkyls do not allow atomic layer deposition (ALD) of In O using water as a co-precursor at substrate temperatures below 200 °C. Several alternative indium sources have been developed, but none allows ALD at lower temperatures except in the presence of oxidants such as O or O , which are not compatible with some substrates or alloying processes. We have synthesized a new indium precursor, tris(N,N'-diisopropylformamidinato)indium(III), compound 1, which allows ALD of pure, carbon-free In O films using H O as the only co-reactant, on substrates in the temperature range 150-275 °C. In contrast, replacing just the H of the anionic iPrNC(H)NiPr ligand with a methyl group (affording the known tris(N,N'-diisopropylacetamidinato)indium(III), compound 2) results in a considerably higher and narrower ALD window in the analogous reaction with H O (225-300 °C). Kinetic studies demonstrate that a higher rate of surface reactions in both parts of the ALD cycle gives rise to this difference in the ALD windows.

The oxide and sulfide of divalent tin show considerable promise for sustainable thin-film optoelectronics, as transparent conducting and light absorbing p-type layers, respectively. Chemical vapor deposition (CVD) and atomic layer deposition (ALD) provide attractive routes to these layers. The literature on volatile tin(II) compounds used as CVD or ALD precursors shows that new compounds can provide different growth rates, film morphologies, preferred crystallographic orientations, and other material properties. We report here the synthesis and characterization of a new liquid tin(II) precursor, bis(N, N′-diisopropylformamidinato)tin(II) (1), which is effective in ALD of SnS in combination with H2S between 65 and 180 °C. Like other highly reactive tin(II) precursors, the growth per cycle linearly decreases from 0.82 Å/cycle at 65 °C to 0.4 Å/cycle at 180 °C. This is obviously different from the case of previously reported SnS ALD using bis(2,4pentanedionato)tin(II), Sn(acac)2, and H2S; films grow at 0.22-0.24 Å/cycle almost independent of the substrate temperature (125-225 °C, J. Phys. Chem. C 2010, 114, 17597). Quartz crystal microbalance (QCM) experiments for SnS ALD using 1 at 80, 120, and 160 °C were carried out to study the linear decrease of the growth per cycle with increasing substrate temperature. Based on these QCM studies, although the mechanism of chemisorption-loss of one ligand or two-can be manipulated by changing the exposure of 1, the purging time, or the temperature, only the temperature changes the growth per cycle. We therefore attribute the decreasing growth per cycle with increasing temperature to a decreasing surface thiol density. Photovoltaic devices prepared from 1-derived SnS have similar performance to the best devices prepared from other precursors, and the device yield and replicability of J-V properties are substantially increased by using 1.

Tin germanium oxide, (Sn,Ge)O2, films were prepared using atomic layer deposition and tailored to a SnS absorber layer by incorporating various amounts of germanium into tin oxide to adjust band alignments at the interfaces of SnS/(Sn,Ge)O2 photovoltaic devices. Carrier concentrations of (Sn,Ge)O2 were suppressed from 1020 to 1018 cm−3 with germanium incorporation, with nitrogen doping further reducing carrier concentrations by another order of magnitude. Excellent tunability of both band energy levels and carrier concentrations of (Sn,Ge)O2 allowed optimizing SnS-based solar cells. SnS/(Sn,Ge)O2:N devices were demonstrated, with an open-circuit voltage as high as 400 mV, due to the effective mitigation of interfacial recombination of photogenerated carriers at the SnS/(Sn,Ge)O2:N absorber-buffer heterojunction interface.

We have prepared two new CaII amidinates, which comprise a new class of ALD precursors. The syntheses proceed by a direct reaction between Ca metal and the amidine ligands in the presence of ammonia. Bis(N,N′‐diisopropylformamidinato)calcium(II) (1) and bis(N,N′‐diisopropylacetamidinato)calcium(II) (2) adopt dimeric structures in solution and in the solid state. X‐ray crystallography revealed asymmetry in one of the bridging ligands to afford the structure [(η2‐L)Ca(μ‐η2:η2‐L)(μ‐η2:η1‐L)Ca(η2‐L)]. These amidinate complexes showed unprecedentedly high volatility as compared to the widely employed and commercially available CaII precursor, [Ca3(tmhd)6]. In CaS ALD with 1 and H2S, the ALD window was approximately two times wider and lower in temperature by about 150 °C than previously reported with [Ca3(tmhd)6] and H2S. Complexes 1 and 2, with their excellent volatility and thermal stability (up to at least 350 °C), are the first homoleptic CaII amidinates suitable for use as ALD precursors.

Thin film solar cells were fabricated using cuprous oxide (Cu2O) absorber layers grown by chemical vapor deposition (CVD) and gallium oxide (Ga2O3) buffer layers grown by atomic layer deposition (ALD) on the cuprous oxide CVD films. The in-situ formation of heterojunction in the same deposition system without exposure to oxygen-rich ambient was found to be effective in mitigating the creation of detrimental cupric oxide (CuO) at the interface, resulting in a pristine photovoltaic junction capable of delivering an enhanced open-circuit voltage of 1.78 V. Numerical device simulations of a novel two-layer absorber architecture (CVD-Cu2O on ECD-Cu2O) showed promising possibilities (theoretical 13.2 % efficiency) for a solar cell combining in-situ junction formation with electrochemical deposition of the absorber layer.