Synthesis and development of lead zirconate titanate inks for direct writing

Abstract

The work presented in this thesis is focused on the development of a novel low processing temperature PZT (lead zirconate titanate) ink for direct writing of functional microsystems. The work examines both the synthesis of PZT powder for use in the ink as well as the formulation of the ink. Two different routes were investigated for the powder synthesis: electro hydrodynamic atomisation (EHDA) and molten salt synthesis (MSS). EHDA is a technique that leads to the formation of small and spherical droplets that, after drying, result in solid particles. Several process parameters were investigated in order to determine their influence on particle size. PZT sols with concentrations up to 0.6 M were electrosprayed under different conditions: the flow rate was varied from 0.2 to 0.6 ml h1 and the distance between the needle and the bottom electrode was increased from 20 to 40 mm. The solvent was dried by the use of a focused lamp with temperature between 200 and 680oC. It was determined that, in order to reduce the size of the PZT particles, low concentration and low flow rate were needed. The needle-electrode distance was found not to have a strong effect on size. However an increase in the focus temperature to a threshold of 520oC led to a reduction of the particle diameter. A further increase of the degree of heating led to the formation of big and irregular particles. Small PZT particles with diameter of 260 nm were obtained under the following conditions: flow rate of 0.2 ml h1, sol concentration of 0.2 M, needle-electrode distance of 30 mm and drying temperature of 520oC. The synthesised powder was spherical in shape, that made it suitable for IJP, but the yield was very low. In order to overcome the problem associated with the low yield of EHDA, MSS was investigated. Also in this case process parameters were studied with the purpose to reduce particle size. The optimum synthesis conditions were found to be 1 hour at 850oC, with a ramp rate of 3.3oC min1. Under these circumstances, PZT particles with a mean diameter of 340 nm were synthesised. From the investigation it came to light that long times and higher temperatures led to an increase in particle size due to coarsening process. Short times and low temperatures led instead to an incomplete reaction between the starting oxides. A reaction mechanism for the formation of PZT is also proposed: fully dissolved Pb reacts with the insoluble TiO2 to form PbTiO3. Then ZrO2 reacts with PT and the remaining Pb to form PZT. Composite inks were formulated from the powders synthesised by both the routes. In the case of EHDA however the formulation was hampered due to a low amount of powder available. This resulted in a quick powder sedimentation that led to nozzle clogging during printing. Inks composed of MSS powder were formulated with different solid loadings to identify under which conditions the nozzles were clogging. Two different patterns were printed on the substrate: a 20x20 drops for the identification of the ink behaviour on the wafer, and a line array pattern to determine in which conditions printing quality was enhanced.