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Understanding the Effects of Cd and Ag Doping in Cu2znsns4 Solar Cells

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Understanding the Effects of Cd and Ag Doping in Cu2znsns4 Solar Cells Article Cite This: Chem. Mater. 2018, 30, 4543−4555 pubs.acs.org/cm ff Understanding the E ects of Cd and Ag Doping in Cu2ZnSnS4 Solar Cells Gopalakrishnan Sai Gautam,† Thomas P. Senftle,†,§ and Emily A. Carter*,‡ † ‡ Department of Mechanical and Aerospace Engineering and School of Engineering and Applied Science, Princeton University, Princeton, New Jersey 08544-5263, United States *S Supporting Information ABSTRACT: Cu2ZnSnS4-based solar cells, which constitute an inex- pensive, beyond-Si photovoltaic technology, often suffer from low open- circuit voltage and efficiency. This drawback is often attributed to disorder in the Cu−Zn sublattice of the kesterite structure. While previous experiments have reported improved performances with isovalent substitution of Cd and Ag for Cu and Zn, respectively, the fundamental driving force for such improvements remains unclear. Here, we use density functional theory to study bulk stability, defect, and surface energetics, as fi well as the electronic structure of these dopants in Cu2ZnSnS4.We nd that Cd and Ag can increase efficiencies, depending on the dopant concentration and Cu content used during synthesis. Most importantly, we find that a low level of Cd doping can suppress disorder in the kesterite phase across all Cu concentrations, while a low level of Ag doping can do so only when Zn- and Sn-rich conditions are employed. A higher Ag content is beneficial as it stabilizes the kesterite structure, whereas a higher Cd content is detrimental as it stabilizes the lower- fi fl gap stannite structure. Cd does not signi cantly in uence the surface energetics of kesterite Cu2ZnSnS4. Ag, on the other hand, decreases the surface energies significantly, which would favor smaller particle sizes. We thus attribute the coarsening of particle size and changes in morphology observed during Cu2ZnSnS4 synthesis to annealing conditions during sulfurization and selenization, instead of any effect of Cd or Ag. Finally, we suggest the exploration of abundant, nontoxic, isovalent dopants, i.e., ff di erent from the attributes of Cd and Ag, to improve the performance of Cu2ZnSnS4. ■ INTRODUCTION cheap to process, and has an ideal single-junction band gap − 10,11 Photovoltaic (PV) technology, which converts solar irradiation (1.4 1.6 eV). Typically, Cu2ZnSnS4 is selenized, i.e., Se is introduced into the S sublattice, allowing the band gap of directly into usable electricity, is an important source of clean 12 Cu2ZnSnS4 to be tuned to improve the power conversion and sustainable electricity. Commercially, multicrystalline ffi 13,14 ff ffi ∼ 1,2 e ciency. Despite its ideal band gap, Cu2ZnSnS4 su ers silicon (Si) PVs, with e ciencies of 20%, constitute the ffi ∼ Downloaded via INDIAN INST OF SCIENCE on August 16, 2020 at 11:05:24 (UTC). from poor e ciencies (a maximum of 12.6% in Se-doped state of the art, because of the abundance of Si and highly 15 fi ≥ optimized fabrication methods. However, Si PVs suffer from cells ) that are signi cantly lower than the 20% observed in 2 ffi See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles. poor light absorption arising from the indirect band gap of Cu(In,Ga)(S,Se)2-, CdTe-, and Si-based cells. Poor e ciency crystalline Si and consequently require thick Si layers that then caused by band-gap narrowing has been attributed to the near- increase the cost, amount of material used, and energy of degeneracy of the kesterite and stannite polymorphs, which 3 fi 4 leads to disorder in the Cu and Zn sublattices (i.e., formation production. Thin- lm, beyond-Si technologies, which rely on 16−22 direct band gap semiconductors such as GaAs,5 CdTe,6 of CuZn and ZnCu antisite defects, respectively). Previous 7 − work has shown that Cu vacancies (Vac ), which are more Cu(In,Ga)(S,Se)2, and organic inorganic hybrid perov- Cu skites,8 have been developed to overcome the limitation likely to form under Zn-rich conditions, can improve ffi 23,24 imposed by the intrinsic properties of Si. However, these e ciencies. Thus, Cu2ZnSnS4 is ideally synthesized compound semiconductor materials are made of rare (such as under both Cu-poor and Zn-rich conditions to achieve high ffi 20,24−26 Ga) or toxic elements (such as Cd, Pb, or As), which inhibits e ciency. − their potential as commercial PV technologies.9 Developers of One strategy for reducing disorder on the Cu Zn sublattice ffi beyond-Si solar cells therefore are still searching for materials (and thereby improving e ciency) is to use isovalent dopants 27,28 that have high efficiency and are cheap, abundant, and that destabilize CuZn and ZnCu antisite defects. In general, nontoxic. Among various beyond-Si candidates, Cu2ZnSnS4-based Received: February 13, 2018 cells display promise because the light-absorbing component Revised: June 16, 2018 is comprised of abundant, environmentally friendly elements, is Published: June 18, 2018 © 2018 American Chemical Society 4543 DOI: 10.1021/acs.chemmater.8b00677 Chem. Mater. 2018, 30, 4543−4555 Chemistry of Materials Article fi antisite defect formation is facilitated if the cations forming the signi cant particle coarsening observed during Cu2ZnSnS4 antisites have similar ionic radii,21 such as ∼0.6 Å for both Cu+ synthesis experimentally is not caused by either Cd or Ag and Zn2+ in tetrahedral coordination.29 Thus, ions that are doping but rather may be attributed to selenization conditions. isovalent with Cu+ or Zn2+ with ionic radii significantly Our results indicate that a careful tuning of both the chemical different compared to those of Cu+ or Zn2+ are doping conditions during synthesis and the extent of doping are candidates that can potentially inhibit the formation of required to maximize performance. Previous theoretical − antisites. For example, Cd2+ (with an ionic radius of 0.78 Å studies20,27,28,37 39 have calculated the antisite formation vs an ionic radius of 0.6 Å for Zn2+) and Ag+ (1 Å vs 0.6 Å for energies, but they have done so only at dilute Cd and Ag Cu+) are promising candidates.29 Indeed, experiments have doping levels, signifying the depth and importance of our demonstrated a significant improvement in efficiencies of current study. 2+ + 30−33 Cu2ZnSnS4 cells that are doped with either Cd or Ag . Interestingly, both Cd2+ and Ag+ exhibit a peak in the open- ■ METHODS ffi circuit voltage (Voc) and e ciency as a function of doping content.30,31 For example, Cd2+-doped cells achieve a peak V We calculated the bulk, defect, and surface energetics of Cu2ZnSnS4 oc in this work using spin-polarized DFT, as implemented in the Vienna and an efficiency of ∼0.438 V and 8%, respectively, at 5% Cd 40,41 30 ab initio simulation package (VASP), and employing the doping in selenized Cu2ZnSnS4 cells. Analogously, a peak projector-augmented-wave (PAW)42 theory. We use a kinetic energy efficiency of ∼11% at 40% Cd doping has been reported in cutoff of 520 eV for the plane wave basis. The orbitals are sampled on 34 + Cu2ZnxCd1−xSnS4 cells. Similarly, Ag -doped cells exhibit a a well-converged k-point mesh (energy converged within <0.05 meV/ ∼ ffi ∼ maximum Voc of 0.422 V and a peak e ciency of 9.8% at atom) with a density of at least 1728 k-points per reciprocal atom 31 43 3−5% Ag doping. Note that 5% Ag doping refers to a (where ki is the number of k-points in the ith direction). We began substitution of 5% for all Cu sites with Ag, which corresponds by using the strongly constrained and appropriately normed (SCAN)44,45 functional for describing the electronic exchange- to a Ag concentration (xAg) of 0.025 per S. Similarly, 5% Cd fl ∼ correlation (XC) for all bulk and defect calculations, because SCAN doping re ects a Cd concentration (xCd)of 0.0125 per S. fi 2+ + satis es all 17 known constraints for the behavior of an XC functional, Also, both Cd doping and Ag doping cause an increase in unlike the generalized gradient approximation (GGA).46 We also the particle size of the synthesized Cu2ZnSnS4 during the high- benchmarked the SCAN-predicted formation enthalpies of binary Cu, 30,31 temperature selenization process. It therefore is unclear Zn, Sn, Cd, and Ag sulfides (Figure S1) and the lattice parameters of whether Cd and Ag doping improves performance via layered SnS2 and kesterite Cu2ZnSnS4 (Table S1)against destabilizing antisites in the bulk or via stabilizing certain experimental values and found fair agreement between SCAN- surface facets and enhancing grain growth, which could predicted and experimental quantities. decrease the number of charge-carrier trap sites at grain Notably, our benchmarking indicates that SCAN does not predict band gaps of semiconductors accurately, with calculated eigenvalue boundaries. ∼ ∼ In this work, we evaluate the formation energy of various gaps of 0.13 and 0.05 eV for kesterite and stannite Cu2ZnSnS4, respectively (Figure S2e,f). These values are significantly lower than neutral and charged antisite defects in pure Cu2ZnSnS4,at ∼ − 47,48 ∼ those reported experimentally ( 1.4 1.6 eV ) and theoretical dilute Cd and Ag doping levels (xCd and xAg 0.015 per S), values employing advanced many-body methods (1.33−1.64 eV49). ∼ and at high concentrations of Ag and Cd (xCd 0.125 per S, Indeed, the performance of SCAN is of similar quality to that of GGA, ∼ and xAg 0.25 per S) using a variety of density functional which is well-known for underestimating band gaps of semi- 35,36 50 theory (DFT) -based calculations. We consider the conductors for the case of kesterite and stannite Cu2ZnSnS4 (Figure formation of neutral antisites under three distinct chemical S2c,d).
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