Spectroscopic characterization of the plasmas formed during the deposition of ZnO and Al-doped ZnO films by plasma-assisted pulsed laser deposition

Abstract

An oxygen-zinc plasma and an oxygen-zinc-aluminum plasma are formed by pulsed laser ablation of a Zn target or pulsed laser co-ablation of a Zn target and an Al target in an electron cyclotron resonance (ECR) discharge-generated oxygen plasma for the deposition of ZnO and Al-doped ZnO (AZO) films. The plasmas are characterized spectroscopically by time-integrated and time-resolved optical emission spectroscopy. Both the oxygen-zinc plasma and the oxygen-zinc-aluminum plasma contain excited species originally present in the working O2 gas and energetic species ablated from the targets. The optical emission of the oxygen-zinc-aluminum plasma is abundant in the emission bands of oxygen molecular ions and the emission lines of mono-atomic oxygen, zinc and aluminum atoms and atomic ions. The time-integrated spectra as well as the time-resolved spectra of the plasma emission indicate that the oxygen species in the ECR oxygen plasma experience additional excitation by the expanding ablation plumes, and the ablated species are excited frequently when traveling accompanying the plume expansion in the oxygen plasma, making the formed plasma highly excited and very reactive, which plays an important role in the reactive growth of ZnO matrix and the in-situ doping of Al into the growing ZnO matrix. The deposited ZnO and AZO films were evaluated for composition analysis by energy dispersive X-ray spectroscopy, structure characterization by X-ray diffraction and optical transmission measurement. The deposited ZnO is slightly rich in O. The Al concentration of the AZO films can be controlled and varied simply by changing the repetition rate of the laser used for Al target ablation. Both the ZnO and the AZO films are featured with hexagonal wurtzite crystal structure and exhibit high optical transparency in a wide spectral region. Al doping results in an improvement in the ultraviolet transparency, a blue shift in the absorption edge and a widening of the band gap.