N‐Type Surface Design for p‐Type CZTSSe Thin Film to Attain High Efficiency

As a low-cost substitute that uses no expensive rare-earth elements for the high-efficiency Cu(In,Ga)(S,Se)₂ solar cell, the Cu₂ ZnSn(S,Se)₄ (CZTSSe) solar cell has borrowed optimization strategies used for its predecessor to improve its device performance, including a profiled band gap and surface inversion. Indeed, there have been few reports of constructing CZTSSe absorber layers with surface inversion to improve efficiency. Here, a strategy that designs the CZTSSe absorber to attain surface modification by using n-type Ag₂ ZnSnS₄ is demonstrated. It has been discovered that Ag plays two major roles in the kesterite thin film devices: surface inversion and front gradient distribution. It has not only an excellent carrier transport effect and reduced probability of electron-hole recombination but also results in increased carrier separation by increasing the width of the depletion region, leading to much improved V_OC and J_SC . Finally, a champion CZTSSe solar cell renders efficiency as high as 12.55%, one of the highest for its type, with the open-circuit voltage deficit reduced to as low as 0.306 V (63.2% Shockley-Queisser limit). The band engineering for surface modification of the absorber and high efficiency achieved here shine a new light on the future of the CZTSSe solar cell.