Growth behavior of atomic-layer-deposited Pb(Zr,Ti)Ox thin films on planar substrate and three-dimensional hole structures

Takayuki Watanabe, Susanne Hoffmann-Eifert, Cheol Seong Hwang, Rainer Waser

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

Quaternary Pb(Zr,Ti)Ox (PZT) films were deposited at 240°C by a combination of liquid-injection atomic layer deposition (ALD) of binary PbO, TiOx, and ZrOx thin films. In preliminary work, binary ZrOx films were deposited at 240°C by ALD. Two solutions of Zr(C9H15O2)4[Zr(DIBM) 4] and Zr(C11H19O2)4 [Zr(DPM)4] dissolved in ethylcyclohexane (ECH) were prepared, and it was found that the Zr(DIBM)4 solution provides a three-times-higher deposition rate for the ZrOx films than the Zr(DPM)4 solution. We focused the study on the set of precursors which offers the highest degree of flexibility for adjusting the Zr(Zr+Ti) ratio in the PZT films: Pb(C11H19O2)2 [Pb(DPM)2], Ti[OCH(CH3)2]4 [Ti(Oi-Pr)4], and Zr(DIBM)4 dissolved in ECH, and water as the oxidant. This set of solutions contributed to increasing the Zr(Zr+Ti) ratio in the deposited PZT films to more than 0.2, which remained below 0.1 in the ALD-PZT using Pb(DPM)2, Ti(Oi-Pr)4, and Zr(DPM)4. The Zr(Zr+Ti) ratio was further increased to 0.5 by modifying the sequence of the discrete-source gas pulses. A polarization-voltage hysteresis loop was observed for a 70 nm thick PZT film deposited on a planar substrate after postannealing for crystallization. To assess the feasibility of ALD as a tool for coating three-dimensional (3D) structures uniformly, PZT films were deposited on submicrometer 3D structures. As-deposited amorphous PZT films as well as crystallized PZT films were both free of any gradient in the cation composition over the structure. The present work reports interesting interactions on stacking different binary-oxide layers by ALD and demonstrates why the multiprecursor ALD process is a promising approach for uniformly coating 3D nanostructures with complex oxide materials.

Original languageEnglish
JournalJournal of the Electrochemical Society
Volume155
Issue number11
DOIs
Publication statusPublished - Oct 1 2008

Fingerprint

Atomic layer deposition
Thin films
Substrates
Oxides
Coatings
Amorphous films
Hysteresis loops
Crystallization
Deposition rates
Oxidants
Thick films
Cations
Nanostructures
Gases
Positive ions
Polarization
Water
Liquids
Electric potential
Chemical analysis

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Renewable Energy, Sustainability and the Environment
  • Surfaces, Coatings and Films
  • Electrochemistry
  • Materials Chemistry

Cite this

Growth behavior of atomic-layer-deposited Pb(Zr,Ti)Ox thin films on planar substrate and three-dimensional hole structures. / Watanabe, Takayuki; Hoffmann-Eifert, Susanne; Hwang, Cheol Seong; Waser, Rainer.

In: Journal of the Electrochemical Society, Vol. 155, No. 11, 01.10.2008.

Research output: Contribution to journalArticle

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abstract = "Quaternary Pb(Zr,Ti)Ox (PZT) films were deposited at 240°C by a combination of liquid-injection atomic layer deposition (ALD) of binary PbO, TiOx, and ZrOx thin films. In preliminary work, binary ZrOx films were deposited at 240°C by ALD. Two solutions of Zr(C9H15O2)4[Zr(DIBM) 4] and Zr(C11H19O2)4 [Zr(DPM)4] dissolved in ethylcyclohexane (ECH) were prepared, and it was found that the Zr(DIBM)4 solution provides a three-times-higher deposition rate for the ZrOx films than the Zr(DPM)4 solution. We focused the study on the set of precursors which offers the highest degree of flexibility for adjusting the Zr(Zr+Ti) ratio in the PZT films: Pb(C11H19O2)2 [Pb(DPM)2], Ti[OCH(CH3)2]4 [Ti(Oi-Pr)4], and Zr(DIBM)4 dissolved in ECH, and water as the oxidant. This set of solutions contributed to increasing the Zr(Zr+Ti) ratio in the deposited PZT films to more than 0.2, which remained below 0.1 in the ALD-PZT using Pb(DPM)2, Ti(Oi-Pr)4, and Zr(DPM)4. The Zr(Zr+Ti) ratio was further increased to 0.5 by modifying the sequence of the discrete-source gas pulses. A polarization-voltage hysteresis loop was observed for a 70 nm thick PZT film deposited on a planar substrate after postannealing for crystallization. To assess the feasibility of ALD as a tool for coating three-dimensional (3D) structures uniformly, PZT films were deposited on submicrometer 3D structures. As-deposited amorphous PZT films as well as crystallized PZT films were both free of any gradient in the cation composition over the structure. The present work reports interesting interactions on stacking different binary-oxide layers by ALD and demonstrates why the multiprecursor ALD process is a promising approach for uniformly coating 3D nanostructures with complex oxide materials.",
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AU - Waser, Rainer

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