Thin‐film solar cells consisting of earth‐abundant and non‐toxic materials were made from pulsed chemical vapor deposition (pulsed‐CVD) of SnS as the p‐type absorber layer and atomic layer deposition (ALD) of Zn(O,S) as the n‐type buffer layer. The effects of deposition temperature and annealing conditions of the SnS absorber layer were studied for solar cells with a structure of Mo/SnS/Zn(O,S)/ZnO/ITO. Solar cells were further optimized by varying the stoichiometry of Zn(O,S) and the annealing conditions of SnS. Post‐deposition annealing in pure hydrogen sulfide improved crystallinity and increased the carrier mobility by one order of magnitude, and a power conversion efficiency up to 2.9% was achieved. Copyright © 2014 John Wiley & Sons, Ltd.

Photovoltaic devices require p-type layers with high optical transparency and electrical conductivity. One promising material is cuprous iodide, CuI, thin films of which have hole mobilities in the 1−12 cm 2 /V•s range. However, despite adequate electrical properties in many CuI thin films, most deposition processes afford only rough films that have poor continuity and low optical transparency, hampering the final device performance. We now report an all-vapor method, amenable to large-scale processing, for preparation of CuI thin films with near record optical and electrical properties. In this process, thin films of Cu (2−x) S (x = 0− 0.1) or Cu 2 O grown by chemical vapor deposition from bis(N,N′-di-sec-butylacetamidinato)dicopper(I) in combination with hydrogen sulfide or water, respectively, were converted to γ-CuI upon exposure to dilute hydrogen iodide vapor. The rate of this iodide-for-chalcogenide anion exchange reaction is controlled by the concentration and delivery rate of HI. The nucleation rate of the nascent CuI may be modified by dosing with iodine vapor (for Cu (2−x) S) or with vapors of thiodiglycol or ethylene glycol (for Cu 2 O). By balancing the rates of nucleation and conversion, we are able to prepare smooth, continuous thin films possessing optical and electrical properties approaching those of the best native p-type CuI films. We believe that the underlying chemical and materials science reasoning leading to these high-quality films will prove instructive in other thin-film systems. Furthermore, based on the measured band positions and carrier mobilities we anticipate high utility for these smooth CuI films as hole-transport layers in Earth-abundant, inexpensive thin-film photovoltaics.

Thin films of Cu 2 S grown by pulsed-chemical vapor deposition of bis(N,N'-di-secbutylacetamidinato)dicopper(I) and hydrogen sulfide were converted to CuBr upon exposure to anhydrous hydrogen bromide. X-ray diffraction shows that the as-deposited films have a polycrystalline Cu 2 S structure. After exposure to HBr gas, the surface of the films is transformed to a γ-CuBr polycrystalline structure. Scanning electron microscopy and X-ray photoelectron spectroscopy reveal complete conversion of up to 100 nm of film. However, when the conversion to CuBr approaches the interface between as-2 deposited Cu 2 S and the SiO 2 substrate, the morphology of the film changes from continuous and nanocrystalline to sparse and microcrystalline.

Zinc oxysulfide, Zn(O,S), films grown by atomic layer deposition (ALD) were incorporated with aluminum to adjust the carrier concentration. The electron carrier concentration increased up to one order of magnitude from 10 19 to 10 20 cm -3 with aluminum incorporation and sulfur content in the range of 0 ≤ S/(Zn+Al) ≤ 0.16. However, the carrier concentration decreased by five orders of magnitude from 10 19 to 10 14 cm -3 for S/(Zn+Al) = 0.34, and decreased even further when S/(Zn+Al) > 0.34. Such tunable electrical properties are potentially useful for graded buffer layers in thin-film photovoltaic applications. Cu 2 ZnSn(Se,S) 4 (CZTS), [3][4][5] Compared to the conventional toxic CdS buffer material for CIGS and CZTS solar cells, Zn(O,S) is composed of earth-abundant and non-toxic elements. KeywordsThis ternary n-type buffer material also has the advantage of having the ability to adjust the band alignment through fine tuning of the stoichiometry, which is easily achieved by atomic layer deposition (ALD) through varying the precursor pulse ratios. [10][11][12] Increasing the sulfur content in Zn(O,S) raises the conduction band energy, which is critical in adjusting the conduction band offset (CBO) at the buffer/absorber interface to optimize the solar cell device performance, 13 as illustrated for SnS/Zn(O,S) heterojunctions in Fig. S1 (see Ref. 14). If the conduction band energy of the buffer layer is too low compared to that of the absorber layer, the negative CBO will induce recombination at the buffer/absorber interface via defects (Fig. S1a). 15 If the conduction band energy of the buffer layer is too high compared to that of the absorber layer, the positive CBO at the buffer/absorber interface creates a barrier that prevents electrons from flowing across the junction towards the transparent conducting oxide (TCO) layer ( Although it has been demonstrated that low electron carrier concentration of Zn(O,S) can improve SnS-based solar cells, this can increase contact resistance with the TCO layer by adding series resistance to the solar cell, which reduces the short-circuit current density (J SC ). While a low carrier concentration of Zn(O,S) can be beneficial for the portion of the buffer layer closer to the absorber layer to reduce possible recombination occurring at the absorber/buffer interface, a high carrier concentration of Zn(O,S) can be beneficial for the portion of the buffer layer closer to the TCO layer to reduce contact resistance. Aluminum is a well known dopant for increasing the electron carrier concentration of ZnO for TCO applications. 18,19 In this study, we report that the electron carrier concentration of ALD Zn(O,S) can be either increased or decreased by modifying the stoichiometry of the film with aluminum incorporation, which is potentially useful for graded buffer layers in thin-film solar cell applications.A custom-built hot-wall ALD reactor was used to grow Zn(O,S) and Al-incorporated Zn(O,S) films. Films were grown at a deposition temperature of 120°C in closed valve mode...

Zinc oxysulfide, Zn(O,S), films grown by atomic layer deposition (ALD) were annealed in oxygen to adjust the carrier concentration. The electron carrier concentration of Zn(O,S) can be reduced by several orders of magnitude from 10 19 to 10 15 cm -3 by post-deposition annealing in oxygen at temperatures from 200°C to 290°C. In the case of Zn(O,S) with S/Zn = 0.37, despite the considerable change in the electron carrier concentration, the bandgap energy decreased by onlỹ 0.1 eV, and the crystallinity did not change much after annealing. The oxygen/zinc ratio increased by 0.05 after annealing, but the stoichiometry remained uniform throughout the film.