Ba substituted Pb(ZrxTi1-x)O3 thin films grown by MOCVD

High quality Pb(Zr,Ti)O3 [PZT] and (Pb1-xBax)(ZryTi1-y)O3 (x ≤ 0.15, 0.25 ≤ y ≤ 0.50) [PBZT] thin films were grown on Pt (111) and Ir (111) coated silicon substrates by means of a pulsed liquid injection metal organic chemical vapor deposition (MOCVD) technique. The precursor solutions of Pb(DPM)2, Ba(DPM)2, Zr(IBPM)4, and Ti(OiPr)2(DPM)2 dissolved in butylacetate were separately injected into an AIX-200 reactor using a TriJet™ vaporizer. Stoichiometric films (0.98 ≤ A/B ≤ 1.06) with thickness between 80 nm and 150 nm were deposited at a susceptor temperature of 615 °C to 660 °C. Pure PZT films grown on platinum coated substrates show a randomly oriented perovskite structure accompanied with formation of a PbPtx alloy at the PZT/Pt interface. On the Ir(111) coated substrates the pure PZT films also exhibit a random orientation possibly due to oxidation of the Ir surface layer during the deposition process. Ferroelectric properties of Pr = 35 µC/cm2 and Ec = 90 kV/cm were obtained for a PZT (30/70) film of 150 nm thickness grown on Ir/Si. In contrast, PBZT films with a Ba content of about 5 to 15% show lower tendency for formation of a PbPtx interfacial layer, and a preferred (111) texture was observed for PBZT films grown on the Ir (111) substrates under optimized process conditions. Tetragonal and rhombohedral PBZT films with 15% Ba and a Zr-content of about 0.35 and 0.50, respectively, show an orientation dependence of the ferroelectric properties in the way that Ec is highest for <111> textured films in comparison to Ec determined for <110> textured films. The remanent polarization of 85 nm thick tetragonal PBZT films changes from 17 µC/cm2 for <111> orientation to 13.5 µC/cm2 for <110> texture. The relative permittivity changes in the same way from 600 to 540, respectively. The rhombohedral films exhibit a nearly independent Pr value of about 11 µC/cm2 while the switching field changes from 75 kV/cm for an <111> textured film to 46 kV/cm for an (110) textured one. The relative permittivity values of both films are 890 and 715 for the (110) and the (111) textured films, respectively. The trends observed for the textured PBZT films grown on Si substrates reflect the behaviour reported for epitaxial films [2]