Ferroelectric surface chemistry: First-principles study of the PbTiO<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:msub><mml:mrow /><mml:mn>3</mml:mn></mml:msub></mml:math>surface

Garrity, Kevin F.; Kakekhani, Arvin; Kolpak, Alexie M.; Ismail‐Beigi, Sohrab

doi:10.1103/physrevb.88.045401

Cited by 91 publications

(82 citation statements)

References 33 publications

(34 reference statements)

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“…The partial removal of surface adsorbates during such a process has been previously shown to affect screening 28 and lead to polarization reversal simply by varying the environmental conditions at moderate temperatures. 30,33,34 Moreover, even at low-to-moderate temperatures extremely oxygen-rich or oxygen-poor environments can lead to the formation of a surface "skin layer" with very different vacancy densities from the bulk. 29 Finally, oxygen vacancy mobility depends very strongly on temperature, with residence times varying from 10 000 s at 0 C down to 0.0001 s at 150 C. 35 We therefore posit that during the annealing process, the changes in the depolarizing field resulting from the partial removal of surface adsorbates and the accompanying polarization reversal are compensated by the rapid redistribution of oxygen vacancies, as schematically illustrated in Fig.…”

Section: )O 3 Thin Filmsmentioning

confidence: 99%

Towards reversible control of domain wall conduction in Pb(Zr0.2Ti0.8)O3 thin films

Gaponenko

Tückmantel

Karthik

et al. 2015

Applied Physics Letters

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Section: )O 3 Thin Filmsmentioning

confidence: 99%

Towards reversible control of domain wall conduction in Pb(Zr0.2Ti0.8)O3 thin films

Gaponenko

Tückmantel

Karthik

et al. 2015

Applied Physics Letters

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“…In addition, there is interest in and need for ferroelectrics with improved functionality for various applications, including magnetoelectrics, Pb-free piezoelectrics, room temperature multiferroics, solar energy converters, silicon compatible ferroelectrics, ferroelectric catalysts, etc. [15][16][17][18][19][20] High-throughput first principles density functional theory (DFT) calculations have been used increasingly in recent years as a tool for materials discovery and screening [21][22][23][24][25][26]. DFT calculations using semilocal functionals are generally reliable tools for computing ground state properties and the energy differences between closely related phases, which is the primary screening tool needed to identify ferroelectrics.…”

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confidence: 99%

High-throughput first-principles search for new ferroelectrics

Garrity

2018

Phys. Rev. B

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We use a combination of symmetry analysis and high-throughput density functional theory calculations to search for new ferroelectric materials. We use two search strategies to identify candidate materials. In the first strategy, we start with non-polar materials and look for unrecognized energylowering polar distortions. In the second strategy, we consider polar materials and look for related higher symmetry structures. In both cases, if we find new structures with the correct symmetries that are also close in energy to experimentally known structures, then the material is likely to be switchable in an external electric field, making it a candidate ferroelectric. We find sixteen candidate materials, with variety of properties that are rare in typical ferroelectrics, including large polarization, hyperferroelectricity, antiferroelectricity, and multiferroism.Ferroelectrics, which are materials that have a ground state polar phase that can be switched to a symmetryequivalent structure by the application of an external electric field, have been studied and used in applications for many years. Much of the attention on ferroelectrics has focused on prototypical examples from the perovskite oxides, like PbTiO 3 and BiFeO 3 . However, in recent years, there has been a renewed theoretical and experimental interest in discovering and understanding the properties of new ferroelectric materials [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. These new materials have shown a variety of new or rare behaviors, including hybrid improper ferroelectricity, hyperferroelectricity, topological defects/domain walls, etc. In addition, there is interest in and need for ferroelectrics with improved functionality for various applications, including magnetoelectrics, Pb-free piezoelectrics, room temperature multiferroics, solar energy converters, silicon compatible ferroelectrics, ferroelectric catalysts, etc. [15][16][17][18][19][20] High-throughput first principles density functional theory (DFT) calculations have been used increasingly in recent years as a tool for materials discovery and screening [21][22][23][24][25][26]. DFT calculations using semilocal functionals are generally reliable tools for computing ground state properties and the energy differences between closely related phases, which is the primary screening tool needed to identify ferroelectrics. The main obstacle to finding new ferroelectric materials computationally is identifying the relevant polar and non-polar structures to consider. Any insulator known experimentally to have both a polar and a non-polar phase has likely already been recognized as a potential ferroelectric, necessitating a search for new structures of known compounds. However, systematically searching all insulating compounds for possible new phases is too computationally demanding to attempt systematically.In this work, we employ two strategies to identify new ferroelectrics, which we apply to a much larger range of materials than related previous searches [1,10,14,[27][28][29][30][31][32][33][34...

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“…1). As usual, below STO three Pt(001) layers are included to screen the dipole moments of STO [24,25]. We use a (2 × 1) surface cell, with a 2 × 4 × 1 mesh to sample k space.…”

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confidence: 99%

TiO2 /Ferroelectric Heterostructures as Dynamic Polarization-Promoted Catalysts for Photochemical and Electrochemical Oxidation of Water

Lee

Selloni

2014

Phys. Rev. Lett.

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Using first-principles density functional theory calculations, we explore the chemical activity of epitaxial heterostructures of TiO 2 anatase on strained polar SrTiO 3 films focusing on the oxygen evolution reaction (OER), the bottleneck of water splitting. Our results show that the reactivity of the TiO 2 surface is tuned by electric dipoles dynamically induced by the adsorbed species during the intermediate steps of the reaction while the initial and final steps remain unaffected. Compared to the OER on unsupported TiO 2 , the combined effects of the dynamically induced dipoles and epitaxial strain strongly reduce rate-limiting thermodynamic barriers and significantly improve the efficiency of the reaction. DOI: 10.1103/PhysRevLett.112.196102 PACS numbers: 82.45.Jn, 82.45.Un, 82.50.−m, 77.55.fp Titanium dioxide (TiO 2 ) is widely used in photocatalysis and solar energy conversion due to its many favorable properties, like stability against photocorrosion and proper band alignment relative to the water redox potentials [1][2][3]. However, the efficiency of TiO 2 is notoriously low, and efforts at improving it through modifications such as doping [4] or synthesis of (nano)crystals exposing highly reactive facets [5] have encountered only limited success. Among the possible alternatives to TiO 2 , polar materials have recently attracted significant interest because their surface dipoles can react easily with charged species and supply built-in electric potentials to increase the carrier mobility [6,7]. However, control of the surface reactivity of these materials is difficult [8], e.g., because exposed surface dipoles often cause undesired atomic or electronic reconstructions and unexpected adsorption of charged species which can interfere with the reaction of interest [9][10][11]. Less well known than TiO 2 and polar semiconductors are heterostructures composed of stable TiO 2 thin films supported by a ferroelectric substrate [12,13]. Experimental studies have shown that the surface reactivity of TiO 2 is directly influenced and improved by the underlying ferroelectric domain structure, an effect that has been attributed to the combined efficient absorption and charge separation in the ferroelectric substrate and transport across the TiO 2 =substrate interface [12,13]. Despite some encouraging results [13,14], however, the interest in such TiO 2 =ferroeletric heterostructures has remained limited. In particular, their physical properties are largely unexplored and an atomic-scale understanding of their reactivity is missing.We present here a first-principles density functional theory (DFT) study of TiO 2 =ferroelectric heterostructures, which provides evidence that these composite materials can have a substantially enhanced reactivity relative to TiO 2 . We focus on model heterostructures composed of a TiO 2 (001) film of anatase (the TiO 2 polymorph most efficient for photocatalysis [15]) supported by a nearly ferroelectric SrTiO 3 (STO) substrate that can easily acquire a macroscopic polarization in the p...

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Ferroelectric surface chemistry: First-principles study of the PbTiO3surface

Cited by 91 publications

References 33 publications

Towards reversible control of domain wall conduction in Pb(Zr0.2Ti0.8)O3 thin films

Towards reversible control of domain wall conduction in Pb(Zr0.2Ti0.8)O3 thin films

High-throughput first-principles search for new ferroelectrics

TiO2 /Ferroelectric Heterostructures as Dynamic Polarization-Promoted Catalysts for Photochemical and Electrochemical Oxidation of Water

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