TY - JOUR
T1 - Deep and Shallow Gap States in Reduced and n-Type Doped m-ZrO2
AU - Lee, Taehun
AU - Selloni, Annabella
N1 - Funding Information:
The authors acknowledge the support of DOE BES, CSGB Division under Award DESC0007347. They also acknowledge support from the Computational Chemical Center: Chemistry in Solution and at Interfaces, funded by the DoE under Award DESC0019394. The authors used resources of the National Energy Research Scientific Computing Center (DoE No. DE-AC02-05cH11231) and the TIGRESS high-performance computer center at Princeton University.
Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/7/20
Y1 - 2023/7/20
N2 - Monoclinic zirconium dioxide (m-ZrO2) is a wide-band-gap functional oxide with many applications. Understanding the role of intrinsic defects and dopants is important for improving the properties of m-ZrO2 relevant to its applications. In this work, we characterize the electronic states and energy levels of oxygen vacancies (VO’s) and n-type Nb, Ta, Rb, H, and F dopants in the bulk and at the majority (1̅11) surface of m-ZrO2, using accurate dielectric-dependent hybrid functional calculations. Our results show that VO’s generally behave as deep donors with the excess electrons localized at the vacant O sites in the form of F centers, in agreement with previous studies. In contrast, surface VO’s at two-fold coordinated oxygen sites show a rather shallow (1+/0) transition level. Shallow levels are also obtained for adsorbed hydrogen (Hads) and fluorine substituting an oxygen atom (FO) either in the bulk or at the surface, whereas Nb and Ta form deep levels.
AB - Monoclinic zirconium dioxide (m-ZrO2) is a wide-band-gap functional oxide with many applications. Understanding the role of intrinsic defects and dopants is important for improving the properties of m-ZrO2 relevant to its applications. In this work, we characterize the electronic states and energy levels of oxygen vacancies (VO’s) and n-type Nb, Ta, Rb, H, and F dopants in the bulk and at the majority (1̅11) surface of m-ZrO2, using accurate dielectric-dependent hybrid functional calculations. Our results show that VO’s generally behave as deep donors with the excess electrons localized at the vacant O sites in the form of F centers, in agreement with previous studies. In contrast, surface VO’s at two-fold coordinated oxygen sites show a rather shallow (1+/0) transition level. Shallow levels are also obtained for adsorbed hydrogen (Hads) and fluorine substituting an oxygen atom (FO) either in the bulk or at the surface, whereas Nb and Ta form deep levels.
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U2 - 10.1021/acs.jpcc.3c02833
DO - 10.1021/acs.jpcc.3c02833
M3 - Article
AN - SCOPUS:85165921299
SN - 1932-7447
VL - 127
SP - 13936
EP - 13944
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 28
ER -