Surface termination control of charge transfer and band alignment across a semiconductor–crystalline-oxide heterojunction

Chrysler, Matthew; Gabel, Judith; Lee, Tien-Lin; Zhu, Zihua; Kaspar, Tiffany C.; Bowden, Mark; Sushko, Peter V.; Chambers, Scott A.; Ngai, Joseph H.

doi:10.1103/physrevmaterials.7.084604

Title: Surface termination control of charge transfer and band alignment across a semiconductor–crystalline-oxide heterojunction

Journal Article · 16 August 2023 · Physical Review Materials

DOI: https://doi.org/10.1103/physrevmaterials.7.084604 · OSTI ID:2263359

Chrysler, Matthew ^[1];

^[2]; Lee, Tien-Lin ^[2]; Zhu, Zihua ^[3];

^[4]; Bowden, Mark ^[4];

^[4]; Chambers, Scott A. ^[4]; Ngai, Joseph H. ^[1]

Univ. of Texas, Arlington, TX (United States)
Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Diamond Light Source, Ltd.
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Charge redistribution across heterojunctions has long been utilized to induce functional response in materials systems. Here we examine how the composition of the terminating surface affects charge transfer across a heterojunction consisting of Si and the crystalline complex oxide SrTiO₃. Itinerant electrons in Si migrate across the interface toward the surface of SrTiO₃ due to surface depletion. The electron transfer in turn creates an electric field across the interface that modifies the interfacial dipole associated with bonding between SrTiO₃ and Si. The modification in the dipole leads to a change in band alignment, in which the conduction band of SrTiO₃ moves from being above the valence band of Si in energy, to below it. By capping the SrTiO₃ surface with ultrathin (≤ 1 nm) layers of BaO, SrO or TiO₂, charge transfer across the interface can be weakened or inhibited. Ab initio modeling implicates the adsorption of oxygen associated with exposure to ambient conditions as driving the surface depletion in SrTiO₃. In conclusion, the electronic coupling between the surface and buried interface expands the functionality of semiconductor-crystalline oxide heterojunctions.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: AC02-05CH11231; AC05-76RL01830

OSTI ID:: 2263359

Report Number(s):: PNNL-SA-183613

Journal Information:: Physical Review Materials, Journal Name: Physical Review Materials Journal Issue: 8 Vol. 7; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

References (27)

Toward Functionalized Ultrathin Oxide Films: The Impact of Surface Apical Oxygen Gabel, Judith; Pickem, Matthias; Scheiderer, Philipp Advanced Electronic Materials, Vol. 8, Issue 4 https://doi.org/10.1002/aelm.202101006	journal	December 2021
Adsorption of O2 on the SrTiO3 (100)−(1 × 1) surface Bermudez, Victor M.; Ritz, Victor H. Chemical Physics Letters, Vol. 73, Issue 1 https://doi.org/10.1016/0009-2614(80)85226-2	journal	July 1980
Photoemission study of the metallic state of lightly electron-doped SrTiO3 Aiura, Y.; Hase, I.; Bando, H. Surface Science, Vol. 515, Issue 1 https://doi.org/10.1016/S0039-6028(02)01784-3	journal	August 2002
A silicon-based photocathode for water reduction with an epitaxial SrTiO3 protection layer and a nanostructured catalyst Ji, Li; McDaniel, Martin D.; Wang, Shijun Nature Nanotechnology, Vol. 10, Issue 1 https://doi.org/10.1038/nnano.2014.277	journal	December 2014
Extracting band edge profiles at semiconductor heterostructures from hard-x-ray core-level photoelectron spectra Sushko, Peter V.; Chambers, Scott A. Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-69658-9	journal	August 2020
Solar hydrogen production using epitaxial SrTiO ₃ on a GaAs photovoltaic Kornblum, L.; Fenning, D. P.; Faucher, J. Energy & Environmental Science, Vol. 10, Issue 1 https://doi.org/10.1039/C6EE03170F	journal	January 2017
Band-gap energies of sol-gel-derived SrTiO3 thin films Bao, Dinghua; Yao, Xi; Wakiya, Naoki Applied Physics Letters, Vol. 79, Issue 23 https://doi.org/10.1063/1.1423788	journal	December 2001
Surface depletion in doped SrTiO3 thin films Ohtomo, A.; Hwang, H. Y. Applied Physics Letters, Vol. 84, Issue 10 https://doi.org/10.1063/1.1668329	journal	March 2004
Oxygen precipitation in silicon Borghesi, A.; Pivac, B.; Sassella, A. Journal of Applied Physics, Vol. 77, Issue 9 https://doi.org/10.1063/1.359479	journal	May 1995
Interfacial structure in epitaxial perovskite oxides on (001) Ge crystal Shen, Xuan; Ahmadi-Majlan, K.; Ngai, Joseph H. Applied Physics Letters, Vol. 106, Issue 3 https://doi.org/10.1063/1.4906430	journal	January 2015
Band gap tuning of epitaxial SrTiO3-δ/Si(001) thin films through strain engineering Cottier, Ryan J.; Steinle, Nathan A.; Currie, Daniel A. Applied Physics Letters, Vol. 107, Issue 22 https://doi.org/10.1063/1.4936608	journal	November 2015
Oxygen partial pressure dependence of surface space charge formation in donor-doped SrTiO ₃ Andrä, Michael; Dvořák, Filip; Vorokhta, Mykhailo APL Materials, Vol. 5, Issue 5 https://doi.org/10.1063/1.4983618	journal	May 2017
A grid-based Bader analysis algorithm without lattice bias Tang, W.; Sanville, E.; Henkelman, G. Journal of Physics: Condensed Matter, Vol. 21, Issue 8 https://doi.org/10.1088/0953-8984/21/8/084204	journal	January 2009
Atoms in Molecules Bader, Richard F. W. https://doi.org/10.1093/oso/9780198551683.001.0001	book	December 1990
Surface defects and the electronic structure of SrTi O 3 surfaces Henrich, Victor E.; Dresselhaus, G.; Zeiger, H. J. Physical Review B, Vol. 17, Issue 12 https://doi.org/10.1103/PhysRevB.17.4908	journal	June 1978
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I. Physical Review Letters, Vol. 100, Issue 13 https://doi.org/10.1103/PhysRevLett.100.136406	journal	April 2008
Profiling the Interface Electron Gas of LaAlO 3 / SrTiO 3 Heterostructures with Hard X-Ray Photoelectron Spectroscopy Sing, M.; Berner, G.; Goß, K. Physical Review Letters, Vol. 102, Issue 17 https://doi.org/10.1103/PhysRevLett.102.176805	journal	April 2009
Charge Transfer and Built-in Electric Fields between a Crystalline Oxide and Silicon Lim, Z. H.; Quackenbush, N. F.; Penn, A. N. Physical Review Letters, Vol. 123, Issue 2 https://doi.org/10.1103/PhysRevLett.123.026805	journal	July 2019
Crystalline Oxides on Silicon: The First Five Monolayers McKee, R. A.; Walker, F. J.; Chisholm, M. F. Physical Review Letters, Vol. 81, Issue 14 https://doi.org/10.1103/PhysRevLett.81.3014	journal	October 1998
Tuning band alignment at a semiconductor-crystalline oxide heterojunction via electrostatic modulation of the interfacial dipole Chrysler, M.; Gabel, J.; Lee, T. -L. Physical Review Materials, Vol. 5, Issue 10 https://doi.org/10.1103/PhysRevMaterials.5.104603	journal	October 2021
Transient electron scavengers modulate carrier density at a polar/nonpolar perovskite oxide heterojunction Samarakoon, Widitha S.; Sushko, Peter V.; Lee, Dooyong Physical Review Materials, Vol. 6, Issue 10 https://doi.org/10.1103/PhysRevMaterials.6.103405	journal	October 2022
Chemisorbed phases of O2 on TiO2 and SrTiO3 Henrich, Victor E.; Dresselhaus, G.; Zeiger, H. J. Journal of Vacuum Science and Technology, Vol. 15, Issue 2 https://doi.org/10.1116/1.569464	journal	March 1978
Experimental determination of electron attenuation lengths in complex materials by means of epitaxial film growth: Advantages and challenges Chambers, Scott A.; Du, Yingge Journal of Vacuum Science & Technology A, Vol. 38, Issue 4 https://doi.org/10.1116/6.0000291	journal	July 2020
The Interface Phase and the Schottky Barrier for a Crystalline Dielectric on Silicon McKee, R. A. Science, Vol. 300, Issue 5626 https://doi.org/10.1126/science.1083894	journal	June 2003