Exploring Doping Mechanisms and Modulating Carrier Concentration in Copper Iodide: Applications in Thermoelectric Materials

Due to its small hole-effective mass, flexibility, and transparency, copper iodide (CuI) has emerged as a promising p-type alternative to the predominantly used n-type metal oxide semiconductors. However, the lack of effective doping methods hinders the utility of CuI in various applications. Sulfur (S)-doping through liquid iodination is previously reported to significantly enhance electrical conductivity up to 511 S cm⁻¹. In this paper, the underlying doping mechanism with various S-dopants is explored, and suggested a method for controlling electrical conductivity, which is important to various applications, especially thermoelectric (TE) materials. Subsequently, electric and TE properties are systematically controlled by adjusting the carrier concentration from 3.0 × 10¹⁹ to 4.5 × 10²⁰ cm⁻³, and accurately measured thermal conductivity with respect to carrier concentration and film thickness. Sulfur-doped CuI (CuI:S) thin films exhibited a maximum power factor of 5.76 µW cm⁻¹ K⁻² at a carrier concentration of 1.3 × 10²⁰ cm⁻³, and a TE figure of merit (ZT) of 0.25. Furthermore, a transparent and flexible TE power generator is developed, with an impressive output power density of 43 nW cm⁻² at a temperature differential of 30 K. Mechanical durability tests validated the potential of CuI:S films in transparent and flexible TE applications.