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Title: Cu diffusion in single-crystal and polycrystalline TiN barrier layers: A high-resolution experimental study supported by first-principles calculations

Abstract

Dense single-crystal and polycrystalline TiN/Cu stacks were prepared by unbalanced DC magnetron sputter deposition at a substrate temperature of 700 °C and a pulsed bias potential of −100 V. The microstructural variation was achieved by using two different substrate materials, MgO(001) and thermally oxidized Si(001), respectively. Subsequently, the stacks were subjected to isothermal annealing treatments at 900 °C for 1 h in high vacuum to induce the diffusion of Cu into the TiN. The performance of the TiN diffusion barrier layers was evaluated by cross-sectional transmission electron microscopy in combination with energy-dispersive X-ray spectrometry mapping and atom probe tomography. No Cu penetration was evident in the single-crystal stack up to annealing temperatures of 900 °C, due to the low density of line and planar defects in single-crystal TiN. However, at higher annealing temperatures when diffusion becomes more prominent, density-functional theory calculations predict a stoichiometry-dependent atomic diffusion mechanism of Cu in bulk TiN, with Cu diffusing on the N sublattice for the experimental N/Ti ratio. In comparison, localized diffusion of Cu along grain boundaries in the columnar polycrystalline TiN barriers was detected after the annealing treatment. The maximum observed diffusion length was approximately 30 nm, yielding a grain boundary diffusion coefficient of the order of 10{sup −16}more » cm{sup 2} s{sup −1} at 900 °C. This is 10 to 100 times less than for comparable underdense polycrystalline TiN coatings deposited without external substrate heating or bias potential. The combined numerical and experimental approach presented in this paper enables the contrasting juxtaposition of diffusion phenomena and mechanisms in two TiN coatings, which differ from each other only in the presence of grain boundaries.« less

Authors:
 [1];  [2];  [3];  [4]; ; ;  [1]; ; ; ;  [3];  [5];  [6]; ;  [7]
  1. Department of Physical Metallurgy and Materials Testing, Montanuniversität Leoben, Franz-Josef-Strasse 18, A-8700 Leoben (Austria)
  2. (IFM), Linköping University, S-581 83 Linköping (Sweden)
  3. Materials Center Leoben Forschung GmbH, Roseggerstrasse 12, A-8700 Leoben (Austria)
  4. (Austria)
  5. Institute of Physics, University of Graz, NAWI Graz, Universitätsplatz 5, A-8010 Graz (Austria)
  6. Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, Cyclotron Road 1, Berkeley, California 94720 (United States)
  7. Thin Film Physics Division, Department of Physics, Chemistry and Biology (IFM), Linköping University, S-581 83 Linköping (Sweden)
Publication Date:
OSTI Identifier:
22499256
Resource Type:
Journal Article
Journal Name:
Journal of Applied Physics
Additional Journal Information:
Journal Volume: 118; Journal Issue: 8; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-8979
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ANNEALING; COATINGS; COPPER; CRYSTAL DEFECTS; DENSITY FUNCTIONAL METHOD; DEPOSITION; DIFFUSION BARRIERS; DIFFUSION LENGTH; GRAIN BOUNDARIES; MAGNESIUM OXIDES; MAGNETRONS; MONOCRYSTALS; POLYCRYSTALS; PRESSURE RANGE MICRO PA; SPUTTERING; STOICHIOMETRY; TITANIUM NITRIDES; TOMOGRAPHY; TRANSMISSION ELECTRON MICROSCOPY; X-RAY SPECTROSCOPY

Citation Formats

Mühlbacher, Marlene, E-mail: marlene.muehlbacher@unileoben.ac.at, Thin Film Physics Division, Department of Physics, Chemistry and Biology, Bochkarev, Anton S., Institute of Physics, University of Graz, NAWI Graz, Universitätsplatz 5, A-8010 Graz, Mendez-Martin, Francisca, Schalk, Nina, Mitterer, Christian, Sartory, Bernhard, Chitu, Livia, Popov, Maxim N., Spitaler, Jürgen, Puschnig, Peter, Ding, Hong, Lu, Jun, and Hultman, Lars. Cu diffusion in single-crystal and polycrystalline TiN barrier layers: A high-resolution experimental study supported by first-principles calculations. United States: N. p., 2015. Web. doi:10.1063/1.4929446.
Mühlbacher, Marlene, E-mail: marlene.muehlbacher@unileoben.ac.at, Thin Film Physics Division, Department of Physics, Chemistry and Biology, Bochkarev, Anton S., Institute of Physics, University of Graz, NAWI Graz, Universitätsplatz 5, A-8010 Graz, Mendez-Martin, Francisca, Schalk, Nina, Mitterer, Christian, Sartory, Bernhard, Chitu, Livia, Popov, Maxim N., Spitaler, Jürgen, Puschnig, Peter, Ding, Hong, Lu, Jun, & Hultman, Lars. Cu diffusion in single-crystal and polycrystalline TiN barrier layers: A high-resolution experimental study supported by first-principles calculations. United States. doi:10.1063/1.4929446.
Mühlbacher, Marlene, E-mail: marlene.muehlbacher@unileoben.ac.at, Thin Film Physics Division, Department of Physics, Chemistry and Biology, Bochkarev, Anton S., Institute of Physics, University of Graz, NAWI Graz, Universitätsplatz 5, A-8010 Graz, Mendez-Martin, Francisca, Schalk, Nina, Mitterer, Christian, Sartory, Bernhard, Chitu, Livia, Popov, Maxim N., Spitaler, Jürgen, Puschnig, Peter, Ding, Hong, Lu, Jun, and Hultman, Lars. Fri . "Cu diffusion in single-crystal and polycrystalline TiN barrier layers: A high-resolution experimental study supported by first-principles calculations". United States. doi:10.1063/1.4929446.
@article{osti_22499256,
title = {Cu diffusion in single-crystal and polycrystalline TiN barrier layers: A high-resolution experimental study supported by first-principles calculations},
author = {Mühlbacher, Marlene, E-mail: marlene.muehlbacher@unileoben.ac.at and Thin Film Physics Division, Department of Physics, Chemistry and Biology and Bochkarev, Anton S. and Institute of Physics, University of Graz, NAWI Graz, Universitätsplatz 5, A-8010 Graz and Mendez-Martin, Francisca and Schalk, Nina and Mitterer, Christian and Sartory, Bernhard and Chitu, Livia and Popov, Maxim N. and Spitaler, Jürgen and Puschnig, Peter and Ding, Hong and Lu, Jun and Hultman, Lars},
abstractNote = {Dense single-crystal and polycrystalline TiN/Cu stacks were prepared by unbalanced DC magnetron sputter deposition at a substrate temperature of 700 °C and a pulsed bias potential of −100 V. The microstructural variation was achieved by using two different substrate materials, MgO(001) and thermally oxidized Si(001), respectively. Subsequently, the stacks were subjected to isothermal annealing treatments at 900 °C for 1 h in high vacuum to induce the diffusion of Cu into the TiN. The performance of the TiN diffusion barrier layers was evaluated by cross-sectional transmission electron microscopy in combination with energy-dispersive X-ray spectrometry mapping and atom probe tomography. No Cu penetration was evident in the single-crystal stack up to annealing temperatures of 900 °C, due to the low density of line and planar defects in single-crystal TiN. However, at higher annealing temperatures when diffusion becomes more prominent, density-functional theory calculations predict a stoichiometry-dependent atomic diffusion mechanism of Cu in bulk TiN, with Cu diffusing on the N sublattice for the experimental N/Ti ratio. In comparison, localized diffusion of Cu along grain boundaries in the columnar polycrystalline TiN barriers was detected after the annealing treatment. The maximum observed diffusion length was approximately 30 nm, yielding a grain boundary diffusion coefficient of the order of 10{sup −16} cm{sup 2} s{sup −1} at 900 °C. This is 10 to 100 times less than for comparable underdense polycrystalline TiN coatings deposited without external substrate heating or bias potential. The combined numerical and experimental approach presented in this paper enables the contrasting juxtaposition of diffusion phenomena and mechanisms in two TiN coatings, which differ from each other only in the presence of grain boundaries.},
doi = {10.1063/1.4929446},
journal = {Journal of Applied Physics},
issn = {0021-8979},
number = 8,
volume = 118,
place = {United States},
year = {2015},
month = {8}
}