Fabrication of ferroelectric Pb(ZrTi)O3 thin films with various Zr/Ti ratios by ink-jet printing

Ferroelectric Pb(Zr,Ti)O-3 (PZT) thin films with various Zr/Ti ratios were fabricated by ink-jet printing (UP). Two kinds of precursor solutions for PbTiO3 (PT) and PbZrO3 (PZ) were prepared from Pb(OCOCH3)(2) . 3H(2)O, Ti[OCH(CH3)(2)](4) and Zr(OC4H9)(4). Seven 1 x 1 cm(2) square patterns with mixing ratios PT : PZ = 6 : 0, 5 : 1, 4 : 2, 3 : 3, 2 : 4, 1 : 5 and 0 : 6 were formed on a 3-inch Pt/Ti/SiO2/Si substrate by overlapped printing. After printing, they were dried at 110degreesC for 10 min, calcined at 350degreesC for 10 min and finally sintered at 650degreesC for 30 min. The d-space corresponding to the (001) plane in the tetragonal phase estimated from X-ray diffraction (XRD) peaks first decreased, then increased and finally decreased again with increasing Zr-content, while the d-space corresponding to the (100) or (010) plane monotonically increased with increasing Zr-content. This suggests that the crystal structure of PZT thin films changed from tetragonal to rhombohedral to orthorhombic with increasing Zr-content.