Tuning Bandgap of p-Type Cu2Zn(Sn, Ge)(S, Se)4 Semiconductor Thin Films via Aqueous Polymer-Assisted Deposition.

Bandgap engineering of kesterite Cu2Zn(Sn, Ge)(S, Se)4 with well-controlled stoichiometric composition plays a critical role in sustainable inorganic photovoltaics. Herein, a cost-effective and reproducible aqueous solution-based polymer-assisted deposition approach is developed to grow p-type Cu2Zn(Sn, Ge)(S, Se)4 thin films with tunable bandgap. The bandgap of Cu2Zn(Sn, Ge)(S, Se)4 thin films can be tuned within the range 1.05-1.95 eV using the aqueous polymer-assisted deposition by accurately controlling the elemental compositions. One of the as-grown Cu2Zn(Sn, Ge)(S, Se)4 thin films exhibits a hall coefficient of +137 cm3/C. The resistivity, concentration and carrier mobility of the Cu2ZnSn(S, Se)4 thin film are 3.17 ohm·cm, 4.5 × 1016 cm-3, and 43 cm2/(V·S) at room temperature, respectively. Moreover, the Cu2ZnSn(S, Se)4 thin film when used as an active layer in a solar cell leads to a power conversion efficiency of 3.55%. The facile growth of Cu2Zn(Sn, Ge)(S, Se)4 thin films in an aqueous system, instead of organic solvents, provides great promise as an environmental-friendly platform to fabricate a variety of single/multi metal chalcogenides for the thin film industry and solution-processed photovoltaic devices.