Tin monosulfide (SnS) is a promising semiconductor material for low-cost conversion of solar energy, playing the role of absorber layer in photovoltaic devices. SnS is, due to its high optical damping, also an excellent semiconductor candidate for the realization of ultrathin (nanoscale thickness) plasmonic solar cells [1].

Here, we present an important step to further control and understand SnS film properties produced using low temperature ALD with Sn(acac)2 and H2S as precursors. We show that the SnS film properties vary over a rather wide range depending on substrate temperature and reaction conditions, and that this is connected to the growth of cubic (π-SnS) and orthorhombic SnS phases. The optical properties of the two polymorphs differ significantly, as demonstrated by spectroscopic ellipsometry [2].

1. C. Hägglund, G. Zeltzer, R. Ruiz, A. Wangperawong, K. E. Roelofs, S. F. Bent, ACS Photonics 3 (3) (2016) 456–463.

2. O. V. Bilousov, Y. Ren, T. Törndahl, O. Donzel-Gargand , T. Ericson, C. Platzer-Björkman, M. Edoff, and C. Hägglund, ACS Chemistry of Materials  29 (7) (2017) 2969–2978.

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.

Herein, we study the native point defect equilibrium in Cu2ZnSnS4 (CZTS) by applying a statistical thermodynamic model. The stable chemical- potential space (SCPS) of CZTS at an elevated temperature was estimated directly, on the basis of deviations from stoichiometry calculated for the different combinations of chemical potential of the components. We show that the SCPS is narrow due to high concentration of (V-Cu(-) Zn-Cu(+)) complex which is dominant over other complexes and isolated defects. The CZTS was found to have p-type conductivity for both stoichiometric and Cu-poor/Zn-rich composition. It is established that the reason for this is that the majority of donor-like Zn-Cu(+) antisites are involved in the formation of (V-Cu(-) Zn-Cu(+)) complex making Cu-Zn dominant and providing p- type conductivity even for Cu-poor/Zn-rich composition. However, our calculation reveals that the hole concentration is almost insensitive to the variation of the chemical composition within the composition region of the single-phase CZTS due to nearly constant concentration of dominant charged defects. The calculations for the full equilibrium and quenching indicate that hole concentration is strongly dependent on the annealing temperature and decreases substantially after the drastic cooling. This means that the precise control of annealing temperature and post-annealing cooling rate are critical for tuning the electrical properties of CZTS.

TiN thin films have previously been used as intermediate barrier layers on Mo back contacts in CZTS(e) solar cells to suppress excessive reaction of the Mo in the annealing step. In this work, TiN films with various thickness (20, 50 and 200 nm) were prepared with reactive DC magnetron sputtering on Mo/SLG substrates and annealed, without CZTS(e) layers, in either S or Se atmospheres. The as-deposited references and the annealed samples were characterized with X-ray Photoelectron Spectroscopy, X-ray Diffraction, Time-of-Flight-Elastic Recoil Detection Analysis, Time-of-Flight-Medium-Energy Ion Scattering, Scanning Electron Microscopy and Scanning Transmission Electron Microscopy – Electron Energy Loss Spectroscopy. It was found that the as-deposited TiN layers below 50 nm show discontinuities, which could be related to the surface roughness of the Mo. Upon annealing, TiN layers dramatically reduced the formation of MoS(e)2, but did not prevent the sulfurization or selenization of Mo. The MoS(e)2 had formed near the discontinuities, both below and above the TiN layers. Another unexpected finding was that the thicker TiN layer increased the amount of Na diffused to the surface after anneal, and we suggest that this effect is related to the Na affinity of the TiN layers and the MoS(e)2 thickness.

Chalcogen-based materials like Cu2ZnSnS4 (CZTS) have attracted extensive attention for applications such as photovoltaics and water splitting. However, an inability to monitor the sulfur partial pressure (P-S2) during the non equilibrium annealing process at high temperatures complicates the synthesis of CZTS with controlled optoelectronic properties. Here we demonstrate that P-S2 can be monitored by investigating the Sn-S phase transformation. We showed that P-S2 drops considerably over the annealing time, causing gradual alterations in CZTS: (i) a change in defect type and (ii) evolution of ZnS and SnxSy phases. With additional ordering treatment, we observed that the low room-temperature photoluminescence energy usually seen in CZTS can result from insufficient P-S2 during annealing. It is proven that remarkable V-oc beyond 700 mV for solar cells with nonoptimal CdS buffer can be repeatedly achieved when CZTS is prepared under a sufficiently high P-S2. An ordering treatment before CdS deposition can further improve V-oc to 783 mV.

Cadmium-free Cu(In,Ga)Se-2 (CIGS) solar cells are fabricated on stainless steel substrate using an industrial, inline vacuum, all sputtering process. The absorber layer is deposited from compound CIGS targets and crystallized simultaneously by high temperature processing. In-depth compositional and structural characterization of the chalcopyrite material is conducted and a Solar Cell Capacitance Simulator (SCAPS) model for the complete device is set-up. Ga-grading of the absorber through the successive use of different CIGS target compositions and resulting in solar cell performance enhancement is shown. At the research and development scale, efficiency values of 15.1% and 13.2% are reported for 1 cm(2) and 225 cm(2) total area solar cells, respectively. Successful transfer to production is also demonstrated. A series of a hundred 225 cm(2) solar cells produced following an optimized process including the Ga grading studied in the present contribution average at 14.8% total area efficiency.

Kesterite Cu2ZnSnS4 (CZTS), having only earth abundant elements, is a promising solar cell material. Nevertheless, the impact of the SnS secondary phase, which often forms alongside CZTS synthesis at high annealing temperature, on CZTS solar cells is poorly studied. We confirm, by means of X-ray diffraction, Raman scattering, and energy dispersive X-ray spectroscopy mapping, that this phase tends to segregate at both the surface and the back side of annealed CZTS films with Cu-poor and Zn-rich composition. Using electron beam-induced current measurements, it is further demonstrated that the formation of SnS on the CZTS surface is harmful for solar cells, whereas the SnS phase can be beneficial for solar cells when it segregates on the CZTS rear. This positive contribution of SnS could stem from a passivation effect at the CZTS/SnS rear interface. This work opens new possibilities for an alternative interface development for kesterite-based photovoltaic technology.

Thin film solar cells based on Cu2ZnSn(S, Se)(4), "CZTS", are attractive by combining high light absorption and high abundance of constituent elements. The efficiency of CZTS solar cells developed rapidly during the last decades, but significant improvements are still needed to reach commercially viable levels. This review covers the most recent trends in CZTS research; (i) alloying with new elements, (ii) exchange of CdS buffer layer with alternative materials, (iii) back contact engineering and (iv) defect studies as a function of compositional variations and annealing. Better understanding of the material and device limitations is expected to emerge from this research. In the perspective of large scale use of CZTS modules, non-toxicity and earth-abundance cannot be compromised in the view of competition with commercially mature CdTe and CIGS technologies. Large band gap kesterite derivatives for stable top cells in tandem solar cells is an interesting and less explored field meriting more attention.

The capacitance-voltage (C-V) method is frequently used to evaluate the net doping of thin-film solar cells, an important parameter for the function of solar cells. However, complex materials such as kesterites are challenging to characterize. To minimize ambiguity when determining the apparent doping concentration (N-A) of Cu2ZnSnS4 (CZTS), we fabricated and investigated different structures: CZTS/ZnS metal-insulator-semiconductor (MIS) device, stand-alone CZTS and ZnS metal-sandwich structures, and CZTS solar cells. Characterization was carried out by means of admittance spectroscopy (AS) and C-V measurements. ZnS exhibits excellent intrinsic properties, and with the high-quality MIS sample we managed to successfully isolate the capacitive response of the CZTS itself. N-A, as extracted from the MIS structure, is found to be more reliable and four times higher compared with the solar cell, impacting any estimated collection efficiency substantially. Data herein presented also show that CZTS has a substantial low-frequency dispersive capacitance and the extraction of N-A depends on the chosen measurement frequency, symptoms of presence of deep defects. Furthermore, the CZTS/ZnS MIS structure is strongly resilient to leakage currents at both forward and reverse voltage bias where contribution from deep defects is minimized and maximized, respectively.

Dielectric functions of Cu2ZnSn(SxSe1-x)(4) thin film absorbers with varied x were determined by spectroscopic ellipsometry and ab initio calculations. From the combination of experimental and theoretical studies, the fundamental interband transition energy E-0 (similar to 1-1.5 eV) and the next following transition energy E-1 (similar to 2-3 eV) were identified and found to blue-shift with increasing sulfur anion content, while keeping the energy separation E-1 - E-0 almost constant, similar to 1.4 eV from experiments, and 1 eV from theory. In addition, the average dielectric responses were found to decrease with sulfur anion content from both theoretical and experimental results. The Tauc optical bandgap value E-g determined on samples prepared on Mo and soda lime glass substrate showed a positive linear relationship between x and bandgap E-g. The bandgap bowing factor determined from the theoretical data is 0.09 eV. (C) 2017 Author(s).