Inter-diffusion across a direct p-n heterojunction of Li-doped NiO and Al-doped ZnO

We herein report inter-diffusion across the interface between p-type Ni0.98Li0.02O and n-type Zn0.98Al0.02O for various applications including p-n-heterojunction diodes and oxide thermoelectrics. Diffusion couples were made of polished surfaces of ceramic samples pre-sintered at 1250 and 1350 degrees C for Ni0.98Li0.02O and Zn0.98Al0.02O, respectively. The inter-diffusion couples were annealed at 900-1200 degrees C for 160 h in ambient air. Electron Probe Micro Analysis (EPMA) was used to acquire diffusion profiles, followed by fitting to Fick's second law and Whipple-Le Claire's models for bulk and grain-boundary diffusion calculation, respectively. Zn2+ diffused into Ni0.98Li0.02O mainly by bulk diffusion with an activation energy of 250 +/- 10 kJ/mol, whereas Ni2+ diffused into Zn0.98Al0.02O by both bulk and enhanced grain boundary diffusion with activation energies of 320 +/- 120 kJ/mol and 245 +/- 50 kJ/mol, respectively. The amount of Al3+ diffused from the Al-doped ZnO into the NiO phase was too small for a corresponding diffusion coefficient to be calculated. Li-ion distribution and diffusivity were not determined due to lack of analyzer sensitivity for Li. The bulk and effective diffusivities of Zn2+ and Ni2+ into NiO and ZnO enable prediction of inter-diffusion lengths as a function of time and temperature, allowing estimates of device performance, stability, and lifetimes at different operation temperatures.