Over 13% Efficient, Ambient Air‐Processed CuIn(S,Se)₂ Solar Cells via Compositional Engineering of Molecular Inks

Abstract

A dimethylformamide (DMF) and thiourea (TU)‐based ink deposition route is used to fabricate narrow bandgap (≈1.0 eV) CuIn(S,Se)2 (CISSe) films with Cu‐poor ([Cu]/[In] = 0.85), stoichiometric ([Cu]/[In] = 1.0), and Cu‐rich ([Cu]/[In] = 1.15) compositions for photovoltaic applications. Characterization of KCN‐ or (NH4)2S‐treated Cu‐rich absorber films using X‐ray diffraction and scanning electron microscopy confirms the removal of copper‐selenide phases from the film surface, while electron backscatter diffraction measurements and depth‐dependent energy‐dispersive X‐ray spectroscopy indicate remnant copper‐selenides in the absorber layer bulk. Contrary to best practice for vacuum‐processed cells, optimum [Cu]/[In] ratios appear to be stoichiometric, rather than Cu‐poor, in DMF–TU‐based CISSe devices. Accordingly, stoichiometric film compositions yield large‐grained (≈2 μm) absorber layers with smooth absorber surfaces (root mean square roughness <20 nm) and active area device efficiencies of 13.2% (without antireflective coating). Notably, these devices reach 70.0% of the Shockley–Queisser limit open‐circuit voltage (i.e., 526 mV at Eg of 1.01 eV), which is among the highest for ink‐based CISSe devices.