Preparation and characterization of lead lanthanum titanate thin films by metalorganic decomposition

There is a critical need for materials with very high dielectric constant to be integrated in the next generation of 64- and 256-Mb ULSI DRAMs. Materials in the Pb-based perovskite family have high relative permittivities and have consequently attracted a world wide attention. Cubic Lead Lanthanum Titanate (PLT) is one of the prime candidates in this respect and its structure and properties in the thin film form were investigated in the present study, for potential application in the ULSI DRAMs.

Thin films of Lead Lanthanum Titanate corresponding to 28 atomic percentage of lanthanum were prepared by metalorganic decomposition (MOD) process. Solutions were prepared from lead acetate, lanthanum acetate and titanium iso-propoxide and thin films were then spin-coated from these solutions on PtlTilSi0₂/Si and sapphire substrates. The films were fabricated from two solutions of different compositions. The composition of the first solution was determined assuming that the incorporation of La³⁺ in the PbTi0₃ structure gives rise to A-site or Pb vacancies whereas for the composition of the other solution the creation of B-site or Ti vacancies was assumed. The effect of excess lead on the structure and the properties was also studied for 0% to 20% of excess PbO. The x-ray diffraction patterns of all films at room temperature indicated a cubic structure with lattice constant of 3.92 A. Optical and electrical measurements showed that the films made assuming B-site vacancies had better properties. In general, excess PbO was found to improve the optical as well as the electrical properties of films. However, in films with Bsite vacancies this improvement occurred only up to 5-10% of excess PbO, while higher PbO additions had a deleterious effect. The films had high resistivity, good relative permittivity, low loss, very low leakage current density, and high charge storage density. A type-B film with 10 % excess Pb had a permittivity of 1336 at 100 kHz. It also had a charge storage density at room temperature of around 16.1 μC/cm² at a field of 200 kV/cm and no sign of polarization loss or breakdown was observed up to 10¹⁰ cycles under the accelerated degradation breakdown test.