The doctoral dissertations of the former Helsinki University of Technology (TKK) and Aalto University Schools of Technology (CHEM, ELEC, ENG, SCI) published in electronic format are available in the electronic publications archive of Aalto University - Aaltodoc.
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Atomic Layer Deposition of Binary and Ternary Lead and Bismuth Oxide Thin Films

Jenni Harjuoja

Dissertation for the degree of Doctor of Science in Technology to be presented with due permission of the Department of Chemical Technology for public examination and debate in Auditorium KE2 at Helsinki University of Technology (Espoo, Finland) on the 27th of April, 2007, at 12 noon.

Overview in PDF format (ISBN 978-951-22-8703-1)   [1255 KB]
Dissertation is also available in print (ISBN 978-951-22-8702-4)

Abstract

This thesis describes the deposition of binary lead oxide and ternary lead titanate, lead zirconate, bismuth silicate, and bismuth titanate films by atomic layer deposition (ALD) and characterization of structural, compositional and surface properties of the films. The first part of the thesis reviews the principles of the ALD technique and the relevant literature on perovskite oxides and films and the deposition of lead and bismuth films by ALD, and the second part summarizes the experimental work reported in the five appended publications.

On the basis of the binary lead oxide depositions, the Ph4Pb/O3 process was chosen for the ternary oxide studies. Careful optimization of the pulsing ratio of the binary oxides allowed processing of stoichiometric perovskite PbTiO3 and PbZrO3 thin films. Crystalline PbTiO3 on Si(100) was detected after annealing at 600 °C. In the case of lead zirconate, the perovskite phase (PbZrO3) was obtained on SrTiO3(100) after annealing at 600 °C. In both cases, a slight excess of lead enhanced the crystallinity. Roughness values were nevertheless higher than values obtained in binary processes.

A new bimetallic precursor Bi(CH2SiMe3)3 was introduced for the deposition of bismuth silicate. With ozone as oxidizing agent, ALD-window for Bi-Si-O thin film growth was found at 250-350 °C. The Si to Bi atomic ratio in this region was about 2. Addition of a second bismuth precursor, BiPh3, increased the bismuth content. Combination of the BiPh3/O3 process and the Ti(O-i-Pr)4/H2O process allowed successful deposition of bismuth titanate. Good control of the film stoichiometry was achieved at the deposition temperature of 250 °C.

Both as-deposited ternary bismuth oxides were amorphous. After annealing at 600 °C, the a-axis-oriented Bi2SiO5 phase was detected. Higher annealing temperatures were necessary for bismuth titanate. The most textured film of Bi4Ti3O12 was obtained in N2 atmosphere at annealing temperature of 1000 °C. Roughness values of the thin films were reasonable, being in the range of 0.3-1.3 nm.

This thesis consists of an overview and of the following 5 publications:

  1. Harjuoja, J., Putkonen, M., and Niinistö, L., Exploiting volatile lead compounds as precursors for the atomic layer deposition of lead dioxide thin films, Thin Solid Films 497 (2006) 77-82. © 2006 Elsevier Science. By permission.
  2. Harjuoja, J., Kosola, A., Putkonen, M., and Niinistö, L., Atomic layer deposition and post-deposition annealing of PbTiO3 thin films, Thin Solid Films 496 (2006) 346-352. © 2006 Elsevier Science. By permission.
  3. Harjuoja, J., Väyrynen, S., Putkonen, M., Niinistö, L., and Rauhala, E., Atomic layer deposition of PbZrO3 thin films, Applied Surface Science 253 (2007) 5228-5232. © 2007 Elsevier Science. By permission.
  4. Harjuoja, J., Hatanpää, T., Vehkamäki, M., Väyrynen, S., Putkonen, M., Niinistö, L., Ritala, M., Leskelä, M., and Rauhala, E., New approach to the ALD of bismuth silicates: Bi(CH2SiMe3)3 acting as a precursor for both bismuth and silicon, Chemical Vapor Deposition 11 (2005) 362-367.
  5. Harjuoja, J., Väyrynen, S., Putkonen, M., Niinistö, L., and Rauhala, E., Crystallization of bismuth titanate and bismuth silicate grown as thin films by atomic layer deposition, Journal of Crystal Growth 286 (2006) 376-383. © 2006 Elsevier Science. By permission.

Errata of publication 5

Keywords: ALD, atomic layer deposition, oxides, thin films, lead oxides, bismuth oxides

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© 2007 Helsinki University of Technology

Last update 2011-05-26