Insight of the doping mechanism of F and Al co-doped ZnO transparent conductive films

Transparent conductive oxide (TCO) films, as transparent electrodes, are widely used in thin-film solar cells. The performance of TCO film has a significant influence on the conversion efficiency of the film solar cell fabricated byusing it. Although the conductivity can be improved by increasing the carrier concentration, the transmittance in the long wave will be sacrificed. Therefore, the only feasible method is to increase the carrier mobility within a certain carrier concentration range, rather than increase the mobility by reducing carrier concentration. In this paper, the F and Al co-doped ZnO (FAZO) films are deposited on glass substrates (Corning XG) by an RF magnetron sputtering technique with using a small amount of ZnF₂ (1 wt.%) and Al₂O₃ (1 wt.%) dopant. The influences of sputtering pressure on the structure, morphology and photoelectric characteristics of the films are respectively investigated by X-ray diffraction analysis, scanning electron microscope, Hall effect measurement, and ultraviolet–visible–near infrared spectrophotometry. All the thin films show typical wurtzite structure with the <i>c</i> axis preferentially oriented perpendicular to the substrate. With the increase of sputtering pressure, the deposition rate of FAZO film decreases, the crystallization quality is deteriorated, surface topography changes gradually from “crater-like” to co-existent “crater-like” and “granular-like”, and the surface roughness increases. The FAZO film deposited at 0.5 Pa presents the optimal performance with a mobility of 40.03 cm²/V·s, carrier concentration of 3.92 × 10²⁰ cm^–3, resistivity of 3.98 × 10^–4 Ω·cm, and about 90% average transmittance in a range of 380－1200 nm. The theoretical result shows that the co-doping of F and Al takes the advantages of single F and Al doped ZnO films, and overcomes the shortcoming of metal elements doping, which donates the carriers just from doped metal elements. Furthermore, the co-doping of F and Al not only increases the carriers but also reduces the scatterings caused by the inter-orbital interaction of doped atoms. The doped F 2p electron orbitals repel the O 2p and Zn 4s electron orbitals, making them move down and donate electrons. At the same time, the orbitals of Al 3s and Al 3p also make a contribution to the conductivity. After co-doping of F and Al, both the carrier concentration and conductivity increase significantly.