In situ observation of medium range ordering and crystallization of amorphous TiO2 ultrathin films grown by atomic layer deposition

Abbasi, Mehrdad; Dong, Yutao; Meng, Jun; Morgan, Dane; Wang, Xudong; Hwang, Jinwoo

doi:10.1063/5.0130918

In situ observation of medium range ordering and crystallization of amorphous TiO₂ ultrathin films grown by atomic layer deposition

Journal Article · Tue Jan 03 00:00:00 EST 2023 · APL Materials

DOI:https://doi.org/10.1063/5.0130918· OSTI ID:2279193

^[1]; ^[2]; ^[2]; ^[2]; ^[2]; ^[3]

Ohio State University, Columbus, OH (United States); University of Wisconsin-Madison Department of Materials Science and Engineering
University of Wisconsin, Madison, WI (United States)
Ohio State University, Columbus, OH (United States)

The evolution of medium range ordering (MRO) and crystallization behavior of amorphous TiO₂ films grown by atomic layer deposition (ALD) were studied using in situ four-dimensional scanning transmission electron microscopy. The films remain fully amorphous when grown at 120 °C or below, but they start showing crystallization of anatase phases when grown at 140 °C or above. The degree of MRO increases as a function of temperature and maximizes at 140 °C when crystallization starts to occur, which suggests that crystallization prerequires the development of nanoscale MRO that serves as the site of nucleation. In situ annealing of amorphous TiO₂ films grown at 80 °C shows enhancement of MRO but limited number of nucleation, which suggests that post-annealing develops only a small portion of MRO into crystal nuclei. The MRO regions that do not develop into crystals undergo structural relaxation instead, which provides insights into the critical size and degree of ordering and the stability of certain MRO types at different temperatures. In addition, crystallographic defects were observed within crystal phases, which likely negate corrosion resistance of the film. Our result highlights the importance of understanding and controlling MRO for optimizing ALD-grown amorphous films for next-generation functional devices and renewable energy applications.

View Accepted Manuscript (DOE)

Research Organization:: University of Wisconsin, Madison, WI (United States); University of Wisconsin-Madison, WI (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0020283

OSTI ID:: 2279193

Alternate ID(s):: OSTI ID: 2454975
OSTI ID: 1907485

Journal Information:: APL Materials, Journal Name: APL Materials Journal Issue: 1 Vol. 11; ISSN 2166-532X

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (63)

Application of ultrathin TiO ₂ layers in solar energy conversion devices Zhou, Chenyu; Xi, Zhaoyi; Stacchiola, Dario J. Energy Science & Engineering, Vol. 10, Issue 5 https://doi.org/10.1002/ese3.1142	journal	March 2022
Spectroscopy simulation and scattering, and the medium range order problem in glass Angell, C. A. Journal of Non-Crystalline Solids, Vol. 73, Issue 1-3 https://doi.org/10.1016/0022-3093(85)90334-5	journal	August 1985
Atomic layer deposition (ALD): from precursors to thin film structures Leskelä, Markku; Ritala, Mikko Thin Solid Films, Vol. 409, Issue 1, p. 138-146 https://doi.org/10.1016/S0040-6090(02)00117-7	journal	April 2002
TiO2 atomic layer deposition on ZrO2 particles using alternating exposures of TiCl4 and H2O Ferguson, J. D.; Yoder, A. R.; Weimer, A. W. Applied Surface Science, Vol. 226, Issue 4 https://doi.org/10.1016/j.apsusc.2003.10.053	journal	March 2004
A multi-method study of the transformation of the carbonaceous skeleton of a polymer-based nanoporous carbon along the activation pathway Hu, Cheng; Liu, Amelia C. Y.; Weyland, Matthew Carbon, Vol. 85 https://doi.org/10.1016/j.carbon.2014.12.051	journal	April 2015
Effect of Annealing Temperature on the Photocatalytic Activity of TiO2 Thin Films Lin, C. -P.; Chen, H.; Nakaruk, A. Energy Procedia, Vol. 34 https://doi.org/10.1016/j.egypro.2013.06.794	journal	January 2013
Direct determination of structural heterogeneity in metallic glasses using four-dimensional scanning transmission electron microscopy Im, Soohyun; Chen, Zhen; Johnson, Jared M. Ultramicroscopy, Vol. 195 https://doi.org/10.1016/j.ultramic.2018.09.005	journal	December 2018
Atomic-scale structure of amorphous TiO2 by electron, X-ray diffraction and reverse Monte Carlo simulations Petkov, V.; Holzhüter, G.; Tröge, U. Journal of Non-Crystalline Solids, Vol. 231, Issue 1-2 https://doi.org/10.1016/s0022-3093(98)00418-9	journal	July 1998
Atomic layer deposition of titanium dioxide from TiCl4 and H2O: investigation of growth mechanism Aarik, J.; Aidla, A.; Mändar, H. Applied Surface Science, Vol. 172, Issue 1-2 https://doi.org/10.1016/s0169-4332(00)00842-4	journal	March 2001
Atom pair persistence in disordered materials from fluctuation microscopy Gibson, J. M.; Treacy, M. M. J.; Voyles, P. M. Ultramicroscopy, Vol. 83, Issue 3-4 https://doi.org/10.1016/s0304-3991(00)00013-9	journal	June 2000
Electron nanodiffraction methods for measuring medium-range order Cowley, J. M. Ultramicroscopy, Vol. 90, Issue 2-3 https://doi.org/10.1016/s0304-3991(01)00130-9	journal	February 2002
Fluctuation microscopy in the STEM Voyles, P. M.; Muller, D. A. Ultramicroscopy, Vol. 93, Issue 2 https://doi.org/10.1016/s0304-3991(02)00155-9	journal	November 2002
Heat treatment on TiO2 nanoparticles prepared by vapor-phase hydrolysis Xia, Bin; Huang, Huizhong; Xie, Youchang Materials Science and Engineering: B, Vol. 57, Issue 2 https://doi.org/10.1016/s0921-5107(98)00322-5	journal	January 1999
Medium-range order in amorphous silicon measured by fluctuation electron microscopy Voyles, Paul M.; Abelson, John R. Solar Energy Materials and Solar Cells, Vol. 78, Issue 1-4 https://doi.org/10.1016/s0927-0248(02)00434-8	journal	July 2003
Variable Resolution Fluctuation Electron Microscopy on Cu-Zr Metallic Glass Using a Wide Range of Coherent STEM Probe Size Hwang, Jinwoo; Voyles, P. M. Microscopy and Microanalysis, Vol. 17, Issue 1 https://doi.org/10.1017/s1431927610094109	journal	December 2010
The Importance of Averaging to Interpret Electron Correlographs of Disordered Materials Sun, Tao; Treacy, Michael M. J.; Li, Tian Microscopy and Microanalysis, Vol. 20, Issue 2 https://doi.org/10.1017/s1431927613014116	journal	February 2014
High Dynamic Range Pixel Array Detector for Scanning Transmission Electron Microscopy Tate, Mark W.; Purohit, Prafull; Chamberlain, Darol Microscopy and Microanalysis, Vol. 22, Issue 1 https://doi.org/10.1017/s1431927615015664	journal	January 2016
Probing the Interfacial Chemistry of Ultrathin ALD-Grown TiO ₂ Films: An In-Line XPS Study Bronneberg, Aafke C.; Höhn, Christian; van de Krol, Roel The Journal of Physical Chemistry C, Vol. 121, Issue 10 https://doi.org/10.1021/acs.jpcc.6b09468	journal	March 2017
Similarity Between Amorphous and Crystalline Phases: The Case of TiO ₂ Mavračić, Juraj; Mocanu, Felix C.; Deringer, Volker L. The Journal of Physical Chemistry Letters, Vol. 9, Issue 11 https://doi.org/10.1021/acs.jpclett.8b01067	journal	May 2018
Oxidatively Stable Nanoporous Silicon Photocathodes with Enhanced Onset Voltage for Photoelectrochemical Proton Reduction Zhao, Y.; Anderson, N. C.; Zhu, K. Nano Letters, Vol. 15, Issue 4 https://doi.org/10.1021/acs.nanolett.5b00086	journal	March 2015
Metastable Intermediates in Amorphous Titanium Oxide: A Hidden Role Leading to Ultra-Stable Photoanode Protection Yu, Yanhao; Sun, Congli; Yin, Xin Nano Letters, Vol. 18, Issue 8 https://doi.org/10.1021/acs.nanolett.8b02559	journal	July 2018
Laser Selective Photoactivation of Amorphous TiO₂ Films to Anatase and/or Rutile Crystalline Phases Benavides, Jaime A.; Trudeau, Charles P.; Gerlein, Luis F. ACS Applied Energy Materials, Vol. 1, Issue 8 https://doi.org/10.1021/acsaem.8b00171	journal	July 2018
Insight into the Degradation Mechanisms of Atomic Layer Deposited TiO ₂ as Photoanode Protective Layer Ros, Carles; Carretero, Nina M.; David, Jeremy ACS Applied Materials & Interfaces, Vol. 11, Issue 33 https://doi.org/10.1021/acsami.9b05724	journal	July 2019
Kinetics of Crystallization and Crystal Growth of Nanocrystalline Anatase in Nanometer-Sized Amorphous Titania Zhang, Hengzhong; Banfield, Jillian F. Chemistry of Materials, Vol. 14, Issue 10 https://doi.org/10.1021/cm020072k	journal	October 2002
Solar Water Splitting Cells Walter, Michael G.; Warren, Emily L.; McKone, James R. Chemical Reviews, Vol. 110, Issue 11, p. 6446-6473 https://doi.org/10.1021/cr1002326	journal	November 2010
Design of semiconductor photoelectrochemical systems for solar energy conversion Bard, Allen J. The Journal of Physical Chemistry, Vol. 86, Issue 2 https://doi.org/10.1021/j100391a008	journal	January 1982
Understanding Polymorphic Phase Transformation Behavior during Growth of Nanocrystalline Aggregates: Insights from TiO ₂ Zhang, Hengzhong; Banfield, Jillian F. The Journal of Physical Chemistry B, Vol. 104, Issue 15 https://doi.org/10.1021/jp000499j	journal	April 2000
Initial Surface Reactions of TiO₂ Atomic Layer Deposition onto SiO₂ Surfaces: Density Functional Theory Calculations Hu, Zheng; Turner, C. Heath The Journal of Physical Chemistry B, Vol. 110, Issue 16 https://doi.org/10.1021/jp060367b	journal	April 2006
Enhancing Water Splitting Activity and Chemical Stability of Zinc Oxide Nanowire Photoanodes with Ultrathin Titania Shells Liu, Mingzhao; Nam, Chang-Yong; Black, Charles T. The Journal of Physical Chemistry C, Vol. 117, Issue 26 https://doi.org/10.1021/jp404032p	journal	June 2013
Role of Water in the Atomic Layer Deposition of TiO₂ on SiO₂ Gu, Wei; Tripp, Carl P. Langmuir, Vol. 21, Issue 1 https://doi.org/10.1021/la047811r	journal	December 2004
Metal Oxide Composite Enabled Nanotextured Si Photoanode for Efficient Solar Driven Water Oxidation Sun, Ke; Pang, Xiaolu; Shen, Shaohua Nano Letters, Vol. 13, Issue 5 https://doi.org/10.1021/nl400343a	journal	April 2013
Electron Microscopy Observation of TiO ₂ Nanocrystal Evolution in High-Temperature Atomic Layer Deposition Shi, Jian; Li, Zhaodong; Kvit, Alexander Nano Letters, Vol. 13, Issue 11 https://doi.org/10.1021/nl403566u	journal	October 2013
Electrochemical Photolysis of Water at a Semiconductor Electrode Fujishima, Akira; Honda, Kenichi Nature, Vol. 238, Issue 5358, p. 37-38 https://doi.org/10.1038/238037a0	journal	July 1972
Upscaling of integrated photoelectrochemical water-splitting devices to large areas Turan, Bugra; Becker, Jan-Philipp; Urbain, Félix Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12681	journal	September 2016
Identifying champion nanostructures for solar water-splitting Warren, Scott C.; Voïtchovsky, Kislon; Dotan, Hen Nature Materials, Vol. 12, Issue 9 https://doi.org/10.1038/nmat3684	journal	July 2013
An 18.2%-efficient black-silicon solar cell achieved through control of carrier recombination in nanostructures Oh, Jihun; Yuan, Hao-Chih; Branz, Howard M. Nature Nanotechnology, Vol. 7, Issue 11 https://doi.org/10.1038/nnano.2012.166	journal	September 2012
Controllable fabrication of nanostructured materials for photoelectrochemical water splitting via atomic layer deposition Wang, Tuo; Luo, Zhibin; Li, Chengcheng Chem. Soc. Rev., Vol. 43, Issue 22 https://doi.org/10.1039/c3cs60370a	journal	January 2014
Morphology and crystallization kinetics in HfO2 thin films grown by atomic layer deposition Ho, M. -Y.; Gong, H.; Wilk, G. D. Journal of Applied Physics, Vol. 93, Issue 3 https://doi.org/10.1063/1.1534381	journal	February 2003
Increasing medium-range order in amorphous silicon with low-energy ion bombardment Gerbi, J. E.; Voyles, P. M.; Treacy, M. M. J. Applied Physics Letters, Vol. 82, Issue 21 https://doi.org/10.1063/1.1578164	journal	May 2003
Free‐Volume Model of the Amorphous Phase: Glass Transition Turnbull, David; Cohen, Morrel H. The Journal of Chemical Physics, Vol. 34, Issue 1 https://doi.org/10.1063/1.1731549	journal	January 1961
Relaxation and flow mechanisms in ‘‘fragile’’ glass‐forming liquids Stillinger, Frank H. The Journal of Chemical Physics, Vol. 89, Issue 10 https://doi.org/10.1063/1.455365	journal	November 1988
New insights into the atomic structure of amorphous TiO ₂ using tight-binding molecular dynamics Yang, Kai; Kachmar, Ali; Wang, Bu The Journal of Chemical Physics, Vol. 149, Issue 9 https://doi.org/10.1063/1.5042783	journal	September 2018
Powering the planet: Chemical challenges in solar energy utilization Lewis, N. S.; Nocera, D. G. Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735 https://doi.org/10.1073/pnas.0603395103	journal	October 2006
X-ray cross correlation analysis uncovers hidden local symmetries in disordered matter Wochner, Peter; Gutt, Christian; Autenrieth, Tina Proceedings of the National Academy of Sciences, Vol. 106, Issue 28 https://doi.org/10.1073/pnas.0905337106	journal	June 2009
Fluctuation microscopy: a probe of medium range order Treacy, M. M. J.; Gibson, J. M.; Fan, L. Reports on Progress in Physics, Vol. 68, Issue 12 https://doi.org/10.1088/0034-4885/68/12/r06	journal	October 2005
Fluctuation electron microscopy study of crystal nucleation in TiO₂–SiO₂ glass with heat treatment Rezikyan, Aram; Moore, Galan G. Journal of Physics: Condensed Matter, Vol. 32, Issue 48 https://doi.org/10.1088/1361-648X/abae19	journal	September 2020
Statistical measures of angular correlations in amorphous materials from electron nano-diffraction in the scanning/transmission electron microscope Bøjesen, E. D.; Petersen, T. C.; Martin, A. V. Journal of Physics: Materials, Vol. 3, Issue 4 https://doi.org/10.1088/2515-7639/aba820	journal	August 2020
Systematic Mapping of Icosahedral Short-Range Order in a Melt-Spun Zr 36 Cu 64 Metallic Glass Liu, A. C. Y.; Neish, M. J.; Stokol, G. Physical Review Letters, Vol. 110, Issue 20 https://doi.org/10.1103/PhysRevLett.110.205505	journal	May 2013
X-ray cross-correlation analysis and local symmetries of disordered systems: General theory Altarelli, M.; Kurta, R. P.; Vartanyants, I. A. Physical Review B, Vol. 82, Issue 10 https://doi.org/10.1103/physrevb.82.104207	journal	September 2010
Nanoscale Structure and Structural Relaxation in Zr 50 Cu 45 Al 5 Bulk Metallic Glass Hwang, Jinwoo; Melgarejo, Z. H.; Kalay, Y. E. Physical Review Letters, Vol. 108, Issue 19 https://doi.org/10.1103/physrevlett.108.195505	journal	May 2012
Diminished Medium-Range Order Observed in Annealed Amorphous Germanium Gibson, J. M.; Treacy, M. M. J. Physical Review Letters, Vol. 78, Issue 6 https://doi.org/10.1103/physrevlett.78.1074	journal	February 1997
Medium-range ordering, structural heterogeneity, and their influence on properties of Zr-Cu-Co-Al metallic glasses Im, Soohyun; Wang, Yuchi; Zhao, Pengyang Physical Review Materials, Vol. 5, Issue 11 https://doi.org/10.1103/physrevmaterials.5.115604	journal	November 2021
Observation of the Role of Subcritical Nuclei in Crystallization of a Glassy Solid Lee, B. -S.; Burr, G. W.; Shelby, R. M. Science, Vol. 326, Issue 5955 https://doi.org/10.1126/science.1177483	journal	November 2009
The Local Structure of Amorphous Silicon Treacy, M. M. J.; Borisenko, K. B. Science, Vol. 335, Issue 6071 https://doi.org/10.1126/science.1214780	journal	February 2012
Amorphous TiO2 coatings stabilize Si, GaAs, and GaP photoanodes for efficient water oxidation Hu, S.; Shaner, M. R.; Beardslee, J. A. Science, Vol. 344, Issue 6187 https://doi.org/10.1126/science.1251428	journal	May 2014
Photoelectrochemistry Bard, A. J. Science, Vol. 207, Issue 4427 https://doi.org/10.1126/science.207.4427.139	journal	January 1980
Research opportunities to advance solar energy utilization Lewis, N. S. Science, Vol. 351, Issue 6271 https://doi.org/10.1126/science.aad1920	journal	January 2016
Substrate Materials and Deposition Temperature Dependent Growth Characteristics and Photocatalytic Properties of ALD TiO[sub 2] Films Cheng, Hsyi-En; Hsu, Ching-Ming; Chen, Yi-Chih Journal of The Electrochemical Society, Vol. 156, Issue 8 https://doi.org/10.1149/1.3138723	journal	January 2009
Refinement of the structure of anatase at several temperatures* Horn, M.; Schwerdtfeger, C. F.; Meagher, E. P. Zeitschrift für Kristallographie, Vol. 136, Issue 3-4 https://doi.org/10.1524/zkri.1972.136.3-4.273	journal	November 1972
The crystal structure of rutile as a function of temperature up to 1600° C Sugiyama, Kazumasa; Takéuchi, Yoshio Zeitschrift für Kristallographie - Crystalline Materials, Vol. 194, Issue 1-4 https://doi.org/10.1524/zkri.1991.194.14.305	journal	August 1991
Observations of structural order in ion-implanted amorphous silicon Cheng, Ju-Yin; Gibson, J. M.; Jacobson, D. C. Journal of Materials Research, Vol. 16, Issue 11 https://doi.org/10.1557/jmr.2001.0416	journal	November 2001
Reverse Monte Carlo structural model for a zirconium-based metallic glass incorporating fluctuation microscopy medium-range order data Hwang, Jinwoo; Clausen, Anna M.; Cao, Hongbo Journal of Materials Research, Vol. 24, Issue 10 https://doi.org/10.1557/jmr.2009.0386	journal	October 2009
Role of HCl in Atomic Layer Deposition of TiO₂Thin Films from Titanium Tetrachloride and Water Leem, Jina; Park, Inhye; Li, Yinshi Bulletin of the Korean Chemical Society, Vol. 35, Issue 4 https://doi.org/10.5012/bkcs.2014.35.4.1195	journal	April 2014

Similar Records

Utilizing TiO₂ amorphous precursors for polymorph selection: An in situ TEM study of phase formation and kinetics

Journal Article · Thu Dec 19 19:00:00 EST 2019 · Journal of the American Ceramic Society · OSTI ID:1598127

Related Subjects

36 MATERIALS SCIENCE
4D-STEM
Amorphous TiO2
Amorphous materials
Atomic layer deposition
Crystallization
Crystallographic defects
Electron diffraction
MRO
Renewable energy
Thin films
Transmission electron microscopy

In situ observation of medium range ordering and crystallization of amorphous TiO2 ultrathin films grown by atomic layer deposition

Citation Formats

References (63)

Similar Records

Related Subjects

In situ observation of medium range ordering and crystallization of amorphous TiO₂ ultrathin films grown by atomic layer deposition