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Title: A comprehensive study on the structural evolution of HfO 2 thin films doped with various dopants

Abstract

The origin of the unexpected ferroelectricity in doped HfO 2 thin films is now considered to be the formation of a non-centrosymmetric Pca2 1 orthorhombic phase. Due to the polycrystalline nature of the films as well as their extremely small thickness (~10 nm) and mixed orientation and phase composition, structural analysis of doped HfO 2 thin films remains a challenging task. As a further complication, the structural similarities of the orthorhombic and tetragonal phase are difficult to distinguish by typical structural analysis techniques such as X-ray diffraction. To resolve this issue, the changes in the grazing incidence X-ray diffraction (GIXRD) patterns of HfO 2 films doped with Si, Al, and Gd are systematically examined. For all dopants, the shift of o111/ t101 diffraction peak is observed with increasing atomic layer deposition (ALD) cycle ratio, and this shift is thought to originate from the orthorhombic to P4 2/ nmc tetragonal phase transition with decreasing aspect ratio (2 a/(b + c) for orthorhombic and c/a for the tetragonal phase). For quantitative phase analysis, Rietveld refinement is applied to the GIXRD patterns. A progressive phase transition from P2 1/c monoclinic to orthorhombic to tetragonal is confirmed for all dopants, and a strong relationshipmore » between orthorhombic phase fraction and remanent polarization value is uniquely demonstrated. The concentration range for the ferroelectric properties was the narrowest for the Si-doped HfO 2 films. As a result, the dopant size is believed to strongly affect the concentration range for the ferroelectric phase stabilization, since small dopants can strongly decrease the free energy of the tetragonal phase due to their shorter metal–oxygen bonds.« less

Authors:
 [1];  [1];  [2];  [3];  [3];  [1];  [3];  [3];  [1];  [1]
  1. NaMLab gGmbH, Dresden (Germany)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. North Carolina State Univ., Raleigh, NC (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1357985
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Materials Chemistry C
Additional Journal Information:
Journal Volume: 5; Journal Issue: 19; Journal ID: ISSN 2050-7526
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Park, Min Hyuk, Schenk, Tony, Fancher, Christopher M., Grimley, Everett D., Zhou, Chuanzhen, Richter, Claudia, LeBeau, James M., Jones, Jacob L., Mikolajick, Thomas, and Schroeder, Uwe. A comprehensive study on the structural evolution of HfO2 thin films doped with various dopants. United States: N. p., 2017. Web. doi:10.1039/C7TC01200D.
Park, Min Hyuk, Schenk, Tony, Fancher, Christopher M., Grimley, Everett D., Zhou, Chuanzhen, Richter, Claudia, LeBeau, James M., Jones, Jacob L., Mikolajick, Thomas, & Schroeder, Uwe. A comprehensive study on the structural evolution of HfO2 thin films doped with various dopants. United States. doi:10.1039/C7TC01200D.
Park, Min Hyuk, Schenk, Tony, Fancher, Christopher M., Grimley, Everett D., Zhou, Chuanzhen, Richter, Claudia, LeBeau, James M., Jones, Jacob L., Mikolajick, Thomas, and Schroeder, Uwe. Wed . "A comprehensive study on the structural evolution of HfO2 thin films doped with various dopants". United States. doi:10.1039/C7TC01200D. https://www.osti.gov/servlets/purl/1357985.
@article{osti_1357985,
title = {A comprehensive study on the structural evolution of HfO2 thin films doped with various dopants},
author = {Park, Min Hyuk and Schenk, Tony and Fancher, Christopher M. and Grimley, Everett D. and Zhou, Chuanzhen and Richter, Claudia and LeBeau, James M. and Jones, Jacob L. and Mikolajick, Thomas and Schroeder, Uwe},
abstractNote = {The origin of the unexpected ferroelectricity in doped HfO2 thin films is now considered to be the formation of a non-centrosymmetric Pca21 orthorhombic phase. Due to the polycrystalline nature of the films as well as their extremely small thickness (~10 nm) and mixed orientation and phase composition, structural analysis of doped HfO2 thin films remains a challenging task. As a further complication, the structural similarities of the orthorhombic and tetragonal phase are difficult to distinguish by typical structural analysis techniques such as X-ray diffraction. To resolve this issue, the changes in the grazing incidence X-ray diffraction (GIXRD) patterns of HfO2 films doped with Si, Al, and Gd are systematically examined. For all dopants, the shift of o111/t101 diffraction peak is observed with increasing atomic layer deposition (ALD) cycle ratio, and this shift is thought to originate from the orthorhombic to P42/nmc tetragonal phase transition with decreasing aspect ratio (2a/(b + c) for orthorhombic and c/a for the tetragonal phase). For quantitative phase analysis, Rietveld refinement is applied to the GIXRD patterns. A progressive phase transition from P21/c monoclinic to orthorhombic to tetragonal is confirmed for all dopants, and a strong relationship between orthorhombic phase fraction and remanent polarization value is uniquely demonstrated. The concentration range for the ferroelectric properties was the narrowest for the Si-doped HfO2 films. As a result, the dopant size is believed to strongly affect the concentration range for the ferroelectric phase stabilization, since small dopants can strongly decrease the free energy of the tetragonal phase due to their shorter metal–oxygen bonds.},
doi = {10.1039/C7TC01200D},
journal = {Journal of Materials Chemistry C},
number = 19,
volume = 5,
place = {United States},
year = {Wed Apr 19 00:00:00 EDT 2017},
month = {Wed Apr 19 00:00:00 EDT 2017}
}

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