Site-Selective Atomic Layer Deposition on Rutile TiO2: Selective Hydration as a Route to Target Point Defects

Kamphaus, Ethan P.; Jones, Jessica Catharine; Shan, Nannan; Martinson, Alex B. F.; Cheng, Lei

doi:10.1021/acs.jpcc.2c06992

Site-Selective Atomic Layer Deposition on Rutile TiO₂: Selective Hydration as a Route to Target Point Defects

Journal Article · Tue Jan 10 00:00:00 EST 2023 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.2c06992· OSTI ID:1969368

^[1]; ^[1]; Shan, Nannan ^[1]; ^[1]; ^[1]

Argonne National Lab. (ANL), Argonne, IL (United States)

Routes to area-and especially site-selective atomic layer deposition (ALD) remain an enticing challenge in precision surface science, despite the potentially game-changing capability for many energy applications. An unparalleled level of surface reaction control is required to direct ALD to select sites on the same nominal material, for example, targeted growth on distinct phases, facets, step-edges, and/or defects. However, as a sequential surface synthesis method, ALD is uniquely suited to these challenges, including the possibility of selective deposition at defective surface atom arrangements. Here, we computationally identify conditions for site-selective ALD through hydration of surface defects, including oxygen vacancies and titanium interstitials on low-index rutile TiO₂ facets. First-principles computation is used to predict, as a function of temperature, the hydroxylation of defects that are targeted by proton-exchange-mediated ALD processes. In situ ellipsometric measurements of ALD Al₂O₃ nucleation on TiO₂ (110) single crystals prepared with and without abundant oxygen vacancies demonstrate striking contrast, corroborating computational predictions and revealing a mechanistically clear path to site-selective ALD.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

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

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1969368

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 3 Vol. 127; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (66)

A Short History of Atomic Layer Deposition: Tuomo Suntola's Atomic Layer Epitaxy: A Short History of Atomic Layer Puurunen, Riikka L. Chemical Vapor Deposition, Vol. 20, Issue 10-11-12 https://doi.org/10.1002/cvde.201402012	journal	October 2014
Hubbard-corrected DFT energy functionals: The LDA+U description of correlated systems Himmetoglu, Burak; Floris, Andrea; de Gironcoli, Stefano International Journal of Quantum Chemistry, Vol. 114, Issue 1 https://doi.org/10.1002/qua.24521	journal	July 2013
Structure and properties of TiO 2 surfaces: a brief review Diebold, U. Applied Physics A: Materials Science & Processing, Vol. 76, Issue 5 https://doi.org/10.1007/s00339-002-2004-5	journal	March 2003
Dissociation of liquid water on defective rutile TiO2 (110) surfaces using ab initio molecular dynamics simulations Wang, Hui-Li; Hu, Zhen-Peng; Li, Hui Frontiers of Physics, Vol. 13, Issue 3 https://doi.org/10.1007/s11467-018-0763-5	journal	June 2018
Low energy electron diffraction and electron spectroscopy studies of the clean (110) and (100) titanium dioxide (rutile) crystal surfaces Chung, Y. W.; Lo, W. J.; Somorjai, G. A. Surface Science, Vol. 64, Issue 2 https://doi.org/10.1016/0039-6028(77)90064-4	journal	May 1977
Titanium and reduced titania overlayers on titanium dioxide(110) Mayer, J. T.; Diebold, U.; Madey, T. E. Journal of Electron Spectroscopy and Related Phenomena, Vol. 73, Issue 1 https://doi.org/10.1016/0368-2048(94)02258-5	journal	May 1995
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Interface and material characterization of thin Al2O3 layers deposited by ALD using TMA/H2O Gosset, L. G.; Damlencourt, J. -F.; Renault, O. Journal of Non-Crystalline Solids, Vol. 303, Issue 1 https://doi.org/10.1016/S0022-3093(02)00958-4	journal	May 2002
Organic functionalization of group IV semiconductor surfaces: principles, examples, applications, and prospects Bent, Stacey F. Surface Science, Vol. 500, Issue 1-3 https://doi.org/10.1016/S0039-6028(01)01553-9	journal	March 2002
An NEXAFS investigation of the reduction and reoxidation of TiO2(001) Lusvardi, V. S.; Barteau, M. A.; Chen, J. G. Surface Science, Vol. 397, Issue 1-3 https://doi.org/10.1016/S0039-6028(97)00740-1	journal	February 1998
A surface perspective on self-diffusion in rutile TiO2 Henderson, Michael A. Surface Science, Vol. 419, Issue 2-3 https://doi.org/10.1016/S0039-6028(98)00778-X	journal	January 1999
Density functionals from LDA to GGA Ziesche, Paul; Kurth, Stefan; Perdew, John P. Computational Materials Science, Vol. 11, Issue 2 https://doi.org/10.1016/S0927-0256(97)00206-1	journal	April 1998
Prediction of high-temperature point defect formation in TiO2 from combined ab initio and thermodynamic calculations He, J.; Behera, R. K.; Finnis, M. W. Acta Materialia, Vol. 55, Issue 13 https://doi.org/10.1016/j.actamat.2007.04.005	journal	August 2007
Digging Ti interstitials at the r-TiO2(1 1 0) surface: Mechanism of porphyrin Ti sequestration by iminic N nucleophilic attack Kremer, Markus K.; Forrer, Daniel; Rogero, Celia Applied Surface Science, Vol. 564 https://doi.org/10.1016/j.apsusc.2021.150403	journal	October 2021
Detailed investigation of the surface mechanisms and their interplay with transport phenomena in alumina atomic layer deposition from TMA and water Gakis, Georgios P.; Vergnes, Hugues; Scheid, Emmanuel Chemical Engineering Science, Vol. 195 https://doi.org/10.1016/j.ces.2018.09.037	journal	February 2019
Defects at the (1 1 0) surface of rutile TiO2 from ab initio calculations Bjørheim, Tor S.; Kuwabara, Akihide; Mohn, Chris E. International Journal of Hydrogen Energy, Vol. 37, Issue 9 https://doi.org/10.1016/j.ijhydene.2011.12.165	journal	May 2012
A brief review of atomic layer deposition: from fundamentals to applications Johnson, Richard W.; Hultqvist, Adam; Bent, Stacey F. Materials Today, Vol. 17, Issue 5 https://doi.org/10.1016/j.mattod.2014.04.026	journal	June 2014
Hubbard U calculations on optical properties of 3d transition metal oxide TiO2 Samat, M. H.; Ali, A. M. M.; Taib, M. F. M. Results in Physics, Vol. 6 https://doi.org/10.1016/j.rinp.2016.11.006	journal	January 2016
Energetics of oxygen vacancies at rutile TiO2(110) surface Pabisiak, T.; Kiejna, A. Solid State Communications, Vol. 144, Issue 7-8 https://doi.org/10.1016/j.ssc.2007.08.043	journal	November 2007
Oxygen vacancies in transition metal and rare earth oxides: Current state of understanding and remaining challenges Ganduglia-Pirovano, M. Verónica; Hofmann, Alexander; Sauer, Joachim Surface Science Reports, Vol. 62, Issue 6 https://doi.org/10.1016/j.surfrep.2007.03.002	journal	June 2007
Atomic layer deposition—Sequential self-limiting surface reactions for advanced catalyst “bottom-up” synthesis Lu, Junling; Elam, Jeffrey W.; Stair, Peter C. Surface Science Reports, Vol. 71, Issue 2 https://doi.org/10.1016/j.surfrep.2016.03.003	journal	June 2016
Dissociative and molecular oxygen chemisorption channels on reduced rutile TiO2(110): An STM and TPD study Lira, Estephania; Hansen, Jonas Ø.; Huo, Peipei Surface Science, Vol. 604, Issue 21-22 https://doi.org/10.1016/j.susc.2010.08.004	journal	October 2010
A Selective Toolbox for Nanofabrication Lee, Han-Bo-Ram; Bent, Stacey F. Chemistry of Materials, Vol. 32, Issue 8 https://doi.org/10.1021/acs.chemmater.0c00838	journal	April 2020
Direct Measurements of Half-Cycle Reaction Heats during Atomic Layer Deposition by Calorimetry Lownsbury, James M.; Gladden, James A.; Campbell, Charles T. Chemistry of Materials, Vol. 29, Issue 20 https://doi.org/10.1021/acs.chemmater.7b01491	journal	October 2017
Area-Selective Atomic Layer Deposition Assisted by Self-Assembled Monolayers: A Comparison of Cu, Co, W, and Ru Bobb-Semple, Dara; Nardi, Katie Lynn; Draeger, Nerissa Chemistry of Materials, Vol. 31, Issue 5 https://doi.org/10.1021/acs.chemmater.8b04926	journal	February 2019
Selective Hydroxylation of In₂O₃ as A Route to Site-Selective Atomic Layer Deposition Shan, Nannan; Jones, Jessica Catharine; Luo, Chunxin The Journal of Physical Chemistry C, Vol. 126, Issue 25 https://doi.org/10.1021/acs.jpcc.2c01311	journal	June 2022
Stability of Excess Electrons Introduced by Ti Interstitial in Rutile TiO ₂ (110) Surface Morita, Kazuki; Shibuya, Taizo; Yasuoka, Kenji The Journal of Physical Chemistry C, Vol. 121, Issue 3 https://doi.org/10.1021/acs.jpcc.6b09669	journal	January 2017
Selective Hydration of Rutile TiO₂ as a Strategy for Site-Selective Atomic Layer Deposition Kamphaus, Ethan P.; Shan, Nannan; Jones, Jessica Catharine ACS Applied Materials & Interfaces, Vol. 14, Issue 18 https://doi.org/10.1021/acsami.1c24807	journal	April 2022
Structure of Clean and Adsorbate-Covered Single-Crystal Rutile TiO ₂ Surfaces Pang, Chi Lun; Lindsay, Robert; Thornton, Geoff Chemical Reviews, Vol. 113, Issue 6 https://doi.org/10.1021/cr300409r	journal	December 2012
Atomic Layer Deposition: An Overview George, Steven M. Chemical Reviews, Vol. 110, Issue 1, p. 111-131 https://doi.org/10.1021/cr900056b	journal	January 2010
CO Oxidation at Rutile TiO ₂ (110): Role of Oxygen Vacancies and Titanium Interstitials Yu, Yan-Yan; Gong, Xue-Qing ACS Catalysis, Vol. 5, Issue 4 https://doi.org/10.1021/cs501900q	journal	February 2015
Infrared studies of the reactions between silica and trimethylaluminum Yates, David J. C.; Dembinski, G. W.; Kroll, W. R. The Journal of Physical Chemistry, Vol. 73, Issue 4 https://doi.org/10.1021/j100724a026	journal	April 1969
IR and NMR Study of the Chemisorption of Ammonia on Trimethylaluminum-Modified Silica Puurunen, Riikka L.; Root, Andrew; Haukka, Suvi The Journal of Physical Chemistry B, Vol. 104, Issue 28 https://doi.org/10.1021/jp000454i	journal	June 2000
Adsorption Reactions of Dimethylaluminum Isopropoxide and Water on the H/Si(100)-2 × 1 Surface: Initial Reactions for Atomic Layer Deposition of Al₂O₃ Ghosh, Manik Kumer; Choi, Cheol Ho The Journal of Physical Chemistry B, Vol. 110, Issue 23 https://doi.org/10.1021/jp060342c	journal	May 2006
Electrical Properties and Defect Chemistry of TiO ₂ Single Crystal. I. Electrical Conductivity ^† Nowotny, M. K.; Bak, T.; Nowotny, J. The Journal of Physical Chemistry B, Vol. 110, Issue 33 https://doi.org/10.1021/jp0606210	journal	August 2006
Comparison of DFT Methods for Molecular Orbital Eigenvalue Calculations Zhang, Gang; Musgrave, Charles B. The Journal of Physical Chemistry A, Vol. 111, Issue 8 https://doi.org/10.1021/jp061633o	journal	March 2007
Defect Chemistry of Rutile TiO ₂ from First Principles Calculations Bjørheim, Tor S.; Kuwabara, Akihide; Norby, Truls The Journal of Physical Chemistry C, Vol. 117, Issue 11 https://doi.org/10.1021/jp304146e	journal	March 2013
Reactivity of the Defective Rutile TiO ₂ (110) Surfaces with Two Bridging-Oxygen Vacancies: Water Molecule as a Probe Shi, Hui; Liu, Ying-Chun; Zhao, Zhi-Jian The Journal of Physical Chemistry C, Vol. 118, Issue 35 https://doi.org/10.1021/jp500721z	journal	August 2014
Nature of Ti Interstitials in Reduced Bulk Anatase and Rutile TiO ₂ Finazzi, Emanuele; Di Valentin, Cristiana; Pacchioni, Gianfranco The Journal of Physical Chemistry C, Vol. 113, Issue 9 https://doi.org/10.1021/jp8111793	journal	February 2009
Unraveling the Diffusion of Bulk Ti Interstitials in Rutile TiO ₂ (110) by Monitoring Their Reaction with O Adatoms Zhang, Zhen; Lee, Junseok; Yates, John T. The Journal of Physical Chemistry C, Vol. 114, Issue 7 https://doi.org/10.1021/jp910358w	journal	January 2010
Self-reduction of the native TiO2 (110) surface during cooling after thermal annealing – in-operando investigations Rogala, M.; Bihlmayer, G.; Dabrowski, P. Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-019-48837-3	journal	August 2019
Successive reactions of gaseous trimethylaluminium and ammonia on porous alumina Puurunen, Riikka L.; Lindblad, Marina; Root, Andew Physical Chemistry Chemical Physics, Vol. 3, Issue 6 https://doi.org/10.1039/b007249o	journal	January 2001
Simulating the atomic layer deposition of alumina from first principles Elliott, Simon D.; Greer, James C. Journal of Materials Chemistry, Vol. 14, Issue 21 https://doi.org/10.1039/b405776g	journal	January 2004
Extending the reliability and applicability of B3LYP Zhang, Igor Ying; Wu, Jianming; Xu, Xin Chemical Communications, Vol. 46, Issue 18 https://doi.org/10.1039/c000677g	journal	January 2010
Quantum chemical study of the mechanism of aluminum oxide atomic layer deposition Widjaja, Yuniarto; Musgrave, Charles B. Applied Physics Letters, Vol. 80, Issue 18 https://doi.org/10.1063/1.1473237	journal	May 2002
Achieving area-selective atomic layer deposition on patterned substrates by selective surface modification Chen, Rong; Kim, Hyoungsub; McIntyre, Paul C. Applied Physics Letters, Vol. 86, Issue 19 https://doi.org/10.1063/1.1922076	journal	May 2005
DFT+U study of defects in bulk rutile TiO2 Stausholm-Møller, Jess; Kristoffersen, Henrik H.; Hinnemann, Berit The Journal of Chemical Physics, Vol. 133, Issue 14 https://doi.org/10.1063/1.3492449	journal	October 2010
Density-functional expansion methods: Evaluation of LDA, GGA, and meta-GGA functionals and different integral approximations Giese, Timothy J.; York, Darrin M. The Journal of Chemical Physics, Vol. 133, Issue 24 https://doi.org/10.1063/1.3515479	journal	December 2010
A new mixing of Hartree–Fock and local density‐functional theories Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 2 https://doi.org/10.1063/1.464304	journal	January 1993
Hubbard-Uband-structure methods Albers, R. C.; Christensen, N. E.; Svane, A. Journal of Physics: Condensed Matter, Vol. 21, Issue 34 https://doi.org/10.1088/0953-8984/21/34/343201	journal	August 2009
TiO ₂ —a prototypical memristive material Szot, K.; Rogala, M.; Speier, W. Nanotechnology, Vol. 22, Issue 25 https://doi.org/10.1088/0957-4484/22/25/254001	journal	May 2011
Visualization and analysis of atomistic simulation data with OVITO–the Open Visualization Tool Stukowski, Alexander Modelling and Simulation in Materials Science and Engineering, Vol. 18, Issue 1 https://doi.org/10.1088/0965-0393/18/1/015012	journal	December 2009
Point defects in ZnO: an approach from first principles Oba, Fumiyasu; Choi, Minseok; Togo, Atsushi Science and Technology of Advanced Materials, Vol. 12, Issue 3 https://doi.org/10.1088/1468-6996/12/3/034302	journal	June 2011
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation Perdew, John P.; Chevary, J. A.; Vosko, S. H. Physical Review B, Vol. 46, Issue 11 https://doi.org/10.1103/PhysRevB.46.6671	journal	September 1992
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Theory of the crystal structures of selenium and tellurium: The effect of generalized-gradient corrections to the local-density approximation Kresse, G.; Furthmüller, J.; Hafner, J. Physical Review B, Vol. 50, Issue 18 https://doi.org/10.1103/PhysRevB.50.13181	journal	November 1994
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
Calculations of Hubbard U from first-principles Aryasetiawan, F.; Karlsson, K.; Jepsen, O. Physical Review B, Vol. 74, Issue 12 https://doi.org/10.1103/PhysRevB.74.125106	journal	September 2006
Composition, structure, and stability of the rutile TiO 2 ( 110 ) surface: Oxygen depletion, hydroxylation, hydrogen migration, and water adsorption Kowalski, Piotr M.; Meyer, Bernd; Marx, Dominik Physical Review B, Vol. 79, Issue 11 https://doi.org/10.1103/PhysRevB.79.115410	journal	March 2009
Inapplicability of exact constraints and a minimal two-parameter generalization to the DFT+ U based correction of self-interaction error Moynihan, Glenn; Teobaldi, Gilberto; O'Regan, David D. Physical Review B, Vol. 94, Issue 22 https://doi.org/10.1103/PhysRevB.94.220104	journal	December 2016
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Density Functional Theory in Transition-Metal Chemistry: A Self-Consistent Hubbard U Approach Kulik, Heather J.; Cococcioni, Matteo; Scherlis, Damian A. Physical Review Letters, Vol. 97, Issue 10 https://doi.org/10.1103/PhysRevLett.97.103001	journal	September 2006
Atomic layer deposition of Al2O3 thin films using dimethylaluminum isopropoxide and water Cho, Wontae; Sung, Kiwhan; An, Ki-Seok Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 21, Issue 4 https://doi.org/10.1116/1.1562184	journal	July 2003
The Role of Interstitial Sites in the Ti3d Defect State in the Band Gap of Titania Wendt, S.; Sprunger, P. T.; Lira, E. Science, Vol. 320, Issue 5884 https://doi.org/10.1126/science.1159846	journal	June 2008
First-Principles Calculation of Point Defects in Uranium Dioxide Iwasawa, Misako; Chen, Ying; Kaneta, Yasunori MATERIALS TRANSACTIONS, Vol. 47, Issue 11 https://doi.org/10.2320/matertrans.47.2651	journal	January 2006
The DFT+U: Approaches, Accuracy, and Applications Tolba, Sarah A.; Gameel, Kareem M.; Ali, Basant A. Density Functional Calculations - Recent Progresses of Theory and Application https://doi.org/10.5772/intechopen.72020	book	May 2018

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ALD
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nucleation
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r-TiO2
site selective
surface chemistry

Site-Selective Atomic Layer Deposition on Rutile TiO2: Selective Hydration as a Route to Target Point Defects

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