In this work, we have demonstrated the extreme radiation hardness of thin film CZTSSe solar cells. Thin film solar cells with CZTSSe, CZTS and CIGS absorber layers were irradiated with 3 MeV protons. No degradation in device parameters was observed until a displacement damage dose of 2 x 10(10) MeV/g for CZTS and CZTSSe. CIGS solar cells degraded by 13% at the same dose. For the highest proton dose both the CZTSSe and CZTS degraded by 16% while CIGS suffered from 34% degradation in efficiency. The degradation in efficiency maybe attributed to the reduction in the minority carrier lifetime due to radiation induced lattice defects. Comparisons with previously available literature show that our CZTS technology has superior radiation hardness by about two orders of magnitude compared to existing state of the art Si and GaAs technology.

Cu2ZnSn(S,Se)(4) precursors are fabricated by compound cosputtering from metal sulfide and selenide targets, and annealed in mixed argon, sulfur, and selenium atmosphere at temperatures between 540 and 580 degrees C and at pressures between 24 and 47 kPa. We produce solar cell devices from these absorbers that range from 2.0% to 9.0% power conversion efficiency. We extensively characterize the morphology and elemental composition of the absorbers, and are able to closely relate the annealing conditions, precursor sulfur-selenium content, device performance, and absorber quality. We develop a qualitative model which relates the sulfur-selenium distribution in the precursor and the relative partial pressures of sulfur and selenium during the annealing process to the absorber properties. We show that selenium inclusion in the precursor allows more rapid recrystallization of the absorber at lower temperature. Alternating stacking of sulfur and selenium containing precursor material leads to differential rates of recrystallization, which allows some control over the morphology of the annealed absorber and Zn(S,Se) secondary phase segregation in that absorber. We further show that selenium containing precursors can be used to fabricate the superior devices relative to sulfur-only precursors, when the annealing phase space is subject to severe practical restrictions.

It is investigated if the performance of Cu(In,Ga)Se-2 (CIGSe) solar cells produced by co-evaporation can be improved by surface sulfurization in a postdeposition treatment. The expected benefit would be the formation of a sulfur/selenium gradient resulting in reduced interface recombination and increased open-circuit voltage. In the conditions used here it was, however, found that the reaction of the CIGSe layer in a sulfur environment results in the formation of a CuInS2 (CIS) surface phase containing no or very little selenium and gallium. At the same time, a significant pile up of gallium was observed at the CIGSe/CIS boundary. This surface structure was formed for a wide range of annealing conditions investigated in this paper. Increasing the temperature or extending the time of the dwell stage had a similar effect on the material. The gallium enrichment and CIS surface layer widens the surface bandgap and therefore increases the open-circuit voltage. At the same time, the fill factor is reduced, since the interface layer acts as an electron barrier. Due to the balance of these effects, the conversion efficiency could not be improved.

Cu-Zn disorder in Cu₂ZnSnS₄ (CZTS) may be responsible for the large open circuit voltage deficit in CZTS based solar cells. In this study, it was investigated how composition-dependent defect complexes influence the order-disorder transition. A combinatorial CZTS thin film sample was produced with a cation composition gradient across the sample area. The graded sample was exposed to various temperature treatments and the degree of order was analyzed with resonant Raman spectroscopy for various compositions ranging from E- and A-type to B-, F-, and C-type CZTS. We observe that the composition has no influence on the critical temperature of the order-disorder transition, but strongly affects the activation energy. Reduced activation energy is achieved with compositions with Cu/Sn > 2 or Cu/Sn < 1.8 suggesting an acceleration of the cation ordering in the presence of vacancies or interstitials. This is rationalized with reference to the effect of point defects on exchange mechanisms. The implications for reducing disorder in CZTS thin films are discussed in light of the new findings.

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.