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Obtaining single-phase tin monosulfide (SnS) films at low temperatures is challenging since cubic (π-SnS) and orthorhombic (α-SnS) polymorphs have similar energies of formation and grow under similar conditions. Here, we show that in atomic layer deposition (ALD) of polycrystalline SnS using tin(II) acetylacetonate and H2S precursors, the substrate surface greatly influences the SnS phase evolution. For example, a silicon (100) substrate, with a highly hydroxylated surface, favors the growth of α-SnS. Meanwhile, ozone treatment or preannealing of the same substrate leads to mainly π-SnS. Just a few ALD cycles of another oxide or sulfide can even more substantially alter the outcome. Substrates that favor α-SnS growth typically produce initially enhanced growth rates, while those promoting π-SnS are partially surface-poisoned by the acetylacetonate precursor ligands. Growth of either polymorph is self-sustained after its initiation, and the sustaining factor appears to be the surface–ligand interaction; π-SnS preferentially evolves on substrates and π-SnS surfaces that are rich in highly reactive dangling bonds, while chemically inert substrates and α-SnS surfaces promote α-SnS. While lattice matching is less central, the role of ligand bonding in SnS ALD also helps explain the previously reported phase dependence on growth temperature and H2S precursor dose and shows promise for area-selective ALD of SnS.

Tin monosulfide can be grown in cubic (pi-SnS) and orthorhombic (alpha-SnS) polymorphs by low-temperature atomic layer deposition (ALD). The optical properties of these polymorphs make them attractive for the realization of plasmonic solar cells with ultrathin absorber layers down to 10 nm in thickness. SnS is also an earth-abundant and nontoxic compound semiconductor of high interest for regular thin-film photovoltaics. To better understand the behavior of the two SnS polymorphs in ultrathin solar cell configurations, we here fabricate, characterize, and analyze a range of such devices. ALD is used to grow SnS and form heterojunctions with zinc oxysulfide [Zn(O,S)], acting as a buffer layer with a composition-tunable bandgap. Apart from the roles of the SnS polymorph and Zn(O,S) composition, the effects of the back contact material and thicknesses of buffer and absorber layers are investigated. Devices using pi-SnS and pure ZnO buffers yield the highest photocurrents (3.1 mA/cm(2)) and higher open circuit voltage (159 mV) than similar alpha-SnS-based devices. Analysis of the equivalent-circuit parameters suggests that interface recombination limits the voltage for these devices. While Zn(O,S) with a higher sulfur content provides chemical passivation of the SnS interface and excessive open circuit voltages above 600 mV, it also exhibits a too high conduction band offset, which hampers current collection. A growth delay during the ALD of Zn(O,S) on SnS initially amplifies the known sulfur-oxygen exchange reaction, such that a sulfur-rich Zn(O,S) region forms next to the SnS interface. This causes a thin ZnS-like barrier to form already for low cycle fractions of the H2S precursor in the ALD super-cycle. Voltage and fill factor trends suggest an optimal SnS absorber layer thickness in the range of 15-35 nm, presenting an opportunity for plasmonic absorption enhancement. Devices with pi-SnS show most promise, but interface recombination versus current-blocking is a di

This contribution evaluates a sequential post‐deposition treatment of Cu(In,Ga)Se2 (CIGS) films, consisting of 1) a post‐sulfurization in elemental S‐atmosphere and 2) a subsequent treatment by heavy alkali fluorides (Alk‐PDT). First, the effect of the sulfurization step on the corresponding solar cell performance is investigated and optimum process parameters, leading to an efficiency improvement, are identified. Losses in carrier collection observed after S‐incorporation are attributed to an increased grain boundary (GB) recombination. It is found that the corresponding reduction in short‐circuit current density can be mitigated by a RbF‐ or KF‐PDT, supposedly by depleting GBs in Cu. However, in strong contrast to non‐sulfurized CIGS, the Alk‐PDT results in a lower open‐circuit voltage and distortions in the current–voltage (I –V ) characteristics for sulfurized absorbers. Possible explanations are the absence of a wide‐gap surface phase and/or air exposure between the post‐treatment steps. It is further proposed that a back contact barrier may be responsible for the distortions in I–V.

Herein, the effect of the initial copper content of co‐evaporated Cu(In1−x,Gax)Se2 (CIGS) absorber films on the impact of a post‐annealing step in elemental sulfur atmosphere is studied. The Cu concentration is varied over a wide range ([Cu]/[III] = CGI = 0.57–1.23), allowing to identify composition‐dependent trends in phase formation, chemical rearrangements, and solar cell performance after sulfurization. For all samples, a ternary CuInS2 layer forms at the surface. In addition, sulfur 1) is incorporated in randomly distributed CuIn(S,Se)2 mixed crystals underneath CuInS2; 2) diffuses into multidimensional defects (e.g., dislocations and grain boundaries); and 3) is bound in Na–In–S surface plates. It is found that Cu‐poor absorber composition (CGI ≤ 0.82) favors CuInS2 growth as compared with close‐stoichiometric CIGS films, driven by a faster diffusion of Cu toward the surface. For Cu‐rich absorbers (CGI > 1), Se—S exchange is significantly accelerated, presumably by the presence of Cu2−xSe phases reacting to Cu2−xS and eventually catalyzing CuInS2 formation. Finally, open‐circuit voltage (VOC), fill factor (FF), and efficiency (η) of corresponding solar cells increase after sulfurization with increasing CGI until stoichiometry is reached. The result is explained by a mitigated Cu depletion of the absorber bulk after sulfurization for close‐stoichiometric CIGS.

Tin monosulfide (SnS) is a promising light-absorbing material with weak environmental constraints for application in thin film solar cells. In this paper, we present low-temperature atomic layer deposition (ALD) of high-purity SnS of both cubic and orthorhombic phases. Using tin(II) 2,4-pentanedionate [Sn(acac)(2)] and hydrogen sulfide (H2S) as precursors, controlled growth of the two polymorphs is achieved. Quartz crystal microbalance measurements are used to establish saturated conditions and show that the SnS ALD is self-limiting over temperatures from at least 80 to 160 degrees C. In this temperature window, a stable mass gain of 19 ng cm(-2) cycle(-1) is observed. The SnS thin film crystal structure and morphology undergo significant changes depending on the conditions. High-resolution transmission electron microscopy and X-ray diffraction demonstrate that fully saturated growth requires a large H2S dose and results in the cubic phase. Smaller H2S doses and higher temperatures favor the orthorhombic phase. The optical properties of the two polymorphs differ significantly, as demonstrated by spectroscopic ellipsometry. The orthorhombic phase displays a wide (0.3-0.4 eV) Urbach tail in the near-infrared region, ascribed to its nanoscale structural disorder and/or to sulfur vacancy-induced gap states. In contrast, the cubic phase is smooth and void-free and shows a well-defined, direct forbidden-type bandgap of 1.64 eV.