Effect of pH on the properties of electrochemically prepared ZnO thin films

Zinc Oxide (ZnO) thin films have been electrochemically deposited on fluorine doped tin oxide (FTO) coated glass substrates from an aqueous electrolyte. Deposition potential −0.96 V was optimized by cyclic voltammetry experiment for slow scan rate 5 mV/s with moderate agitation of electrolyte. The effect of pH on the electrodeposition of ZnO is studied by cyclic voltammetry, X-ray diffraction (XRD), scanning electron microscopy (SEM), optical spectroscopy and photoelectrochemical I-t transient characteristics. It is revealed that the pH of the electrolyte has significant influence on the surface morphology and structural properties. Highly crystalline ZnO layers with hexagonal crystal structure deposited for all pH of the solutions. A systematic shift observed in the reflections (002) and (101) is correlated with an effective tensile strain developed in the crystal lattice. A remarkable improvement in the crystallinity was noticed in the as-deposited ZnO samples with increasing pH and upon heat treatment. Optical direct band gap ~ 3.26-3.33 eV and transmittance ~70 −80% was measured by optical spectroscopy. PL measurement showed the band edge emission at 375-382 nm and a visible light emission at 410-550 nm. The intensities of emission peaks are found to be affected by the pH of bath. The compact, densely packed and well adherent thin films of ZnO electrodeposited in zinc nitrate bath for pH 2.0, 3.5 and 6.0. The surface morphology has been changed from granular to disc shaped and finally a large hexagonal sheets were obtained with an increase in the pH of bath. Nearly stoichiometric ZnO thin films are electrodeposited at −0.96 V versus Ag/AgCl reference electrode for pH 6.0. The photoelectrochemical (PEC) measurement (I-t transient curve) shows the enhancement in photocurrent with increasing the pH of zinc nitrate solution. After heat treatment the photocurrent is increased by 54%, 98% and 130% in the samples deposited from 2.0, 3.5 and 6.0 pH of the bath. I-V measurements were further confirmed the current enhancement in all samples after heat treatment.