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Journal of Vacuum Science & Technology A / Volume 30 / Issue 1 / Atomic Layer Deposition (ALD)

J. Vac. Sci. Technol. A 30, 01A127 (2012); http://dx.doi.org/10.1116/1.3664090 (10 pages)

Reaction mechanisms for atomic layer deposition of aluminum oxide on semiconductor substrates

Annelies Delabie1, Sonja Sioncke1, Jens Rip1, Sven Van Elshocht1, Geoffrey Pourtois2, Matthias Mueller3, Burkhard Beckhoff3, and Kristine Pierloot4

1Imec, Kapeldreef 75, B-3001 Leuven, Belgium
2Imec, Kapeldreef 75, B-3001 Leuven, Belgium, Chemistry Department, and PLASMANT, University of Antwerp, Universiteitsplein 1, B-2610 Antwerp, Belgium
3Physikalisch-Technische Bundesanstalt (PTB), Abbestr. 2-12, 10587 Berlin, Germany
4Chemistry Departement, University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium

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(Published online 2 December 2011)

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In this work, we have studied the TMA/H2O (TMA = Al(CH3)3) atomic layer deposition (ALD) of Al2O3 on hydroxyl (OH) and thiol (SH) terminated semiconductor substrates. Total reflection x-ray fluorescence reveals a complex growth-per-cycle evolution during the early ALD reaction cycles. OH and SH terminated surfaces demonstrate growth inhibition from the second reaction cycle on. Theoretical calculations, based on density functional theory, are performed on cluster models to investigate the first TMA/H2O reaction cycle. Based on the theoretical results, we discuss possible mechanisms for the growth inhibition from the second reaction cycle on. In addition, our calculations show that AlCH3 groups are hydrolyzed by a H2O molecule adsorbed on a neighboring Al atom, independent of the type of backbonds (Si-O, Ge-O, or Ge-S) of AlCH3. The coordination of Al remains four-fold after the first TMA/H2O reaction cycle.

© 2012 American Vacuum Society

Article Outline

  1. INTRODUCTION
  2. EXPERIMENTAL DETAILS
  3. THEORETICAL DETAILS
  4. RESULTS
    1. Growth inhibition from the second reaction cycle
    2. TMA chemisorption versus ligand exchange reaction
    3. TMA chemisorption reactions with multiple surface sites
      1. TMA chemisorption reaction I
      2. TMA chemisorption reactions I, II versus III
      3. Chemisorption of two TMA molecules in close vicinity
    4. H 2 O reaction in the first TMA/H 2 O reaction cycle
      1. Hydrolysis of SiCH 3 or GeCH 3 surface species
      2. Hydrolysis of Si 7 H 8 O 4 (AlCH 3 ) 2 , Ge 7 H 8 O 4 (AlCH 3 ) 2 and Ge 7 H 8 S 4 (AlCH 3 ) 2
  5. DISCUSSION
  6. CONCLUSIONS

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KEYWORDS and PACS

Keywords

adsorption, aluminium compounds, atomic layer deposition, density functional theory, inhibitors, water, X-ray fluorescence analysis

PACS

  • 81.15.Gh

    Chemical vapor deposition (including plasma-enhanced CVD, MOCVD, ALD, etc.)

  • 82.30.-b

    Specific chemical reactions; reaction mechanisms

  • 82.80.Ej

    X-ray, Mössbauer, and other γ-ray spectroscopic analysis methods

  • 68.55.A-

    Nucleation and growth

  • 68.43.Mn

    Adsorption kinetics

  • 71.15.Mb

    Density functional theory, local density approximation, gradient and other corrections

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History
Received 12 August 2011
Accepted 31 October 2011
Published online 2 December 2011
Digital Object Identifier
http://dx.doi.org/10.1116/1.3664090

PUBLICATION DATA

ISSN

0734-2101 (print)  
1520-8559 (online)

Publisher

American Vacuum Society

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