skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Electronic structure of lanthanide scandates

Abstract

Here, x-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and density functional theory calculations were used to study the electronic structure of three lanthanide scandates: GdScO3, TbScO3, and DyScO3. X-ray photoelectron spectra simulated from first-principles calculations using a combination of on-site hybrid and GGA + U methods were found to be in good agreement with experimental x-ray photoelectron spectra. The hybrid method was used to model the ground state electronic structure and the GGA + U method accounted for the shift of valence state energies due to photoelectron emission via a Slater-Janak transition state approach. From these results, the lanthanide scandate valence bands were determined to be composed of Ln4f, O2p, and Sc3d states, in agreement with previous work. However, contrary to previous work the minority Ln4f states were found to be located closer to, and in some cases at, the valence band maximum. This suggests that minority Ln4f electrons may play a larger role in lanthanide scandate properties than previously thought.

Authors:
 [1];  [1];  [1]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1469191
Alternate Identifier(s):
OSTI ID: 1421303
Grant/Contract Number:  
FG02-01ER45945
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 2; Journal Issue: 2; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 74 ATOMIC AND MOLECULAR PHYSICS; density of states; electronic structure; insulators; oxides; strongly correlated systems; density functional theory; x-ray photoelectron spectroscopy

Citation Formats

Mizzi, Christopher A., Koirala, Pratik, and Marks, Laurence D. Electronic structure of lanthanide scandates. United States: N. p., 2018. Web. doi:10.1103/PhysRevMaterials.2.025001.
Mizzi, Christopher A., Koirala, Pratik, & Marks, Laurence D. Electronic structure of lanthanide scandates. United States. doi:10.1103/PhysRevMaterials.2.025001.
Mizzi, Christopher A., Koirala, Pratik, and Marks, Laurence D. Thu . "Electronic structure of lanthanide scandates". United States. doi:10.1103/PhysRevMaterials.2.025001. https://www.osti.gov/servlets/purl/1469191.
@article{osti_1469191,
title = {Electronic structure of lanthanide scandates},
author = {Mizzi, Christopher A. and Koirala, Pratik and Marks, Laurence D.},
abstractNote = {Here, x-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and density functional theory calculations were used to study the electronic structure of three lanthanide scandates: GdScO3, TbScO3, and DyScO3. X-ray photoelectron spectra simulated from first-principles calculations using a combination of on-site hybrid and GGA + U methods were found to be in good agreement with experimental x-ray photoelectron spectra. The hybrid method was used to model the ground state electronic structure and the GGA + U method accounted for the shift of valence state energies due to photoelectron emission via a Slater-Janak transition state approach. From these results, the lanthanide scandate valence bands were determined to be composed of Ln4f, O2p, and Sc3d states, in agreement with previous work. However, contrary to previous work the minority Ln4f states were found to be located closer to, and in some cases at, the valence band maximum. This suggests that minority Ln4f electrons may play a larger role in lanthanide scandate properties than previously thought.},
doi = {10.1103/PhysRevMaterials.2.025001},
journal = {Physical Review Materials},
number = 2,
volume = 2,
place = {United States},
year = {2018},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Figures / Tables:

FIG. 1. FIG. 1. : Experimental x-ray photoelectron spectra acquired with 1486.6 eV incident x rays for (a) GdScO3, (b) TbScO3, and (c) DyScO3 after origin correction. Each valence band spectrum extends from 0–15 eV and is qualitatively different for the three lanthanide scandates: it consists of two major features at 4more » and 8 eV in GdScO3, two major features at 2 and 9 eV in TbScO3, and three major features at 4, 6, and 9 eV in DyScO3. The features from 15–35 eV correspond to the Ln5p doublet (20 and 28 eV), O2$s$ (23 eV), and Sc3$p$ peaks (30.8 eV).« less

Save / Share:

Works referenced in this record:

Room-temperature ferroelectricity in strained SrTiO3
journal, August 2004

  • Haeni, J. H.; Irvin, P.; Chang, W.
  • Nature, Vol. 430, Issue 7001, p. 758-761
  • DOI: 10.1038/nature02773

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Validity of the Slater-Janak transition-state model within the LDA + U approach
journal, August 2008


Force calculation for orbital-dependent potentials with FP-(L)APW+lo basis sets
journal, December 2008

  • Tran, Fabien; Kuneš, Jan; Novák, Pavel
  • Computer Physics Communications, Vol. 179, Issue 11
  • DOI: 10.1016/j.cpc.2008.06.015

Exact exchange for correlated electrons
journal, March 2006


Atomic subshell photoionization cross sections and asymmetry parameters: 1 ⩽ Z ⩽ 103
journal, January 1985


Band gaps and electronic structure of transition-metal compounds
journal, July 1985


Si-compatible candidates for high- κ dielectrics with the P b n m perovskite structure
journal, August 2010


Low temperature magnetism in the perovskite substrate DyScO3
journal, April 2009

  • Ke, X.; Adamo, C.; Schlom, D. G.
  • Applied Physics Letters, Vol. 94, Issue 15
  • DOI: 10.1063/1.3117190

The influence of the Hubbard U parameter in simulating the catalytic behaviour of cerium oxide
journal, January 2014

  • Bennett, Liam James; Jones, Glenn
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 39
  • DOI: 10.1039/C4CP00928B

A simple effective potential for exchange
journal, June 2006

  • Becke, Axel D.; Johnson, Erin R.
  • The Journal of Chemical Physics, Vol. 124, Issue 22
  • DOI: 10.1063/1.2213970

Theory of dielectric screening and electron energy loss spectroscopy at surfaces
journal, July 2009


Electronic and magnetic structure of R ScO 3 ( R = Sm ,Gd,Dy) from x-ray spectroscopies and first-principles calculations
journal, March 2009


Polar phonon anomalies in single-crystalline TbScO 3
journal, February 2013


Single Crystal Rare-earth Scandate Perovskites Analyzed Using X-ray Photoelectron Spectroscopy: 5. DyScO 3 (110)
journal, December 2014

  • Haasch, Richard T.; Martin, Lane W.; Breckenfeld, Eric
  • Surface Science Spectra, Vol. 21, Issue 1
  • DOI: 10.1116/11.20140910

Crystal chemistry of GdScO3, DyScO3, SmScO3 and NdScO3
journal, January 2007

  • Veličkov, Boža; Kahlenberg, Volker; Bertram, Rainer
  • Zeitschrift für Kristallographie, Vol. 222, Issue 9
  • DOI: 10.1524/zkri.2007.222.9.466

Fixed-Point Optimization of Atoms and Density in DFT
journal, May 2013

  • Marks, L. D.
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 6
  • DOI: 10.1021/ct4001685

Band theory and Mott insulators: Hubbard U instead of Stoner I
journal, July 1991

  • Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K.
  • Physical Review B, Vol. 44, Issue 3, p. 943-954
  • DOI: 10.1103/PhysRevB.44.943

Proof that E n i = ε in density-functional theory
journal, December 1978


Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008


Numerical investigation of the validity of the Slater-Janak transition-state model in metallic systems
journal, October 2005


Properties of rare-earth scandate single crystals (Re=Nd−Dy)
journal, May 2008


Electronic structure of the α and δ phases of Bi 2 O 3 : A combined ab initio and x-ray spectroscopy study
journal, June 2006


Band alignment between (100)Si and complex rare earth∕transition metal oxides
journal, December 2004

  • Afanas’ev, V. V.; Stesmans, A.; Zhao, C.
  • Applied Physics Letters, Vol. 85, Issue 24
  • DOI: 10.1063/1.1829781

Single Crystal Rare-earth Scandate Perovskites Analyzed Using X-ray Photoelectron Spectroscopy: 4. TbScO 3 (110)
journal, December 2014

  • Haasch, Richard T.; Martin, Lane W.; Breckenfeld, Eric
  • Surface Science Spectra, Vol. 21, Issue 1
  • DOI: 10.1116/11.20140909

Single Crystal Rare-earth Scandate Perovskites Analyzed Using X-ray Photoelectron Spectroscopy: 3. GdScO 3 (110)
journal, December 2014

  • Haasch, Richard T.; Martin, Lane W.; Breckenfeld, Eric
  • Surface Science Spectra, Vol. 21, Issue 1
  • DOI: 10.1116/11.20140908

Study of the 4f and valence band density of states in rare-earth metals. II. Experiment and results
journal, January 1981


Rationale for mixing exact exchange with density functional approximations
journal, December 1996

  • Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
  • The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
  • DOI: 10.1063/1.472933

Band-gap variation in R ScO 3 ( R = Pr , Nd, Sm, Eu, Gd, Tb, and Dy): X-ray absorption and O K -edge x-ray emission spectroscopies
journal, October 2012


NIST databases with electron elastic-scattering cross sections, inelastic mean free paths, and effective attenuation lengths
journal, January 2005

  • Powell, C. J.; Jablonski, A.; Salvat, F.
  • Surface and Interface Analysis, Vol. 37, Issue 11
  • DOI: 10.1002/sia.2098

New perspectives for Rashba spin–orbit coupling
journal, August 2015

  • Manchon, A.; Koo, H. C.; Nitta, J.
  • Nature Materials, Vol. 14, Issue 9
  • DOI: 10.1038/nmat4360

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.