A p-type ZnO was prepared on a sapphire substrate using P2O5 as a phosphorus dopant. As-grown n-type ZnO films doped with phosphorus showed electron concentrations of 1016–1017/cm3 and these films were converted to p-type ZnO by a thermal annealing process at a temperature above 800 °C under a N2 ambient. The electrical properties of the p-type ZnO showed a hole concentration of 1.0×1017–1.7×1019/cm3, a mobility of 0.53–3.51 cm2/V s, and a low resistivity of 0.59–4.4 Ω cm. The phosphorus-doped ZnO thin films showed a strong photoluminescence peak at 3.35 eV at 10 K, which is closely related to neutral acceptor bound excitons of the p-type ZnO. This thermal activation process was very reproducible and effective in producing phosphorus-doped p-type ZnO thin films, and the produced p-type ZnO was very stable.

ZnO has attracted considerable attention for optical device applications because of several potential advantages over GaN, such as commercial availability of bulk single crystals and a larger exciton binding energy (~60 meV compared with ~25 meV for GaN). Recent improvements in the control of background conductivity of ZnO and demonstrations of p-type doping have intensified interest in this material for applications in light-emitting diodes (LEDs). In this paper, we summarize recent progress in ZnO-based LEDs. Physical and electrical properties, bandgap engineering, and growth of n- and p-type ZnO thin films are also reviewed.

We report on the characteristics of a ZnO light-emitting diode (LED) comprised of a heterostructure of $p$ -ZnO/$n$ -GaN. The LED structure consisted of a phosphorus doped $p$ -ZnO film with a hole concentration of $6.68\times {10}^{17}{\mathrm{cm}}^{-3}$ and a Si-doped $n$ -GaN film with an electron concentration of $1.1\times {10}^{18}{\mathrm{cm}}^{-3}$ . The $I\text{–}V$ of the LED showed a threshold voltage of 5.4 V and an electroluminescence (EL) emission of 409 nm at room temperature. The EL emission peak at 409 nm was attributed to the band gap of $p$ -ZnO which was reduced as the result of the band offset at the interface of $p$ -ZnO and $n$ -GaN.

Using an appropriate SeS₂/Se weight ratio, band gap grading was realized. By increasing the value ofV_OCthrough band gap grading in the depletion region, a recordV_OCdeficit of 0.576 V and an efficiency of 12.3% were obtained.

We fabricated CZTSSe thin films using optimized SLG-Mo/Zn/Cu/Sn (MZCT) as a stacked structure and described the phenomenon of Zn elemental volatilization using the MZCT stacked structure. We introduced H₂S gas to effectively control the S/(S + Se) ratio of the film in the sulfo-selenization process and to suppress Zn volatilization. Unlike during the selenization process, a stable ZnSSe thin film was formed on the precursor surface during the sulfo-selenization process. The formation of the ZnSSe thin film inhibited Zn volatilization, which facilitated control of the thin film stoichiometry and played an important role in crystal growth. In addition, the sulfo-selenization process using H₂S forms a grading of the S/(S + Se) ratio in the depth direction in the ZnSSe layer. The ZnSSe layer with this property causes the band gap grading in the CZTSSe absorption layer. Finally, through our optimized annealing process, we realized a world record CZTSSe solar cell with a certified power conversion efficiency of 12.62% and a centimetre-scale (1.1761 cm²) efficiency of 11.28%.