skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: In situ study of the electronic structure of atomic layer deposited oxide ultrathin films upon oxygen adsorption using ambient pressure XPS

Abstract

In this work, ambient pressure X-ray photoelectron spectroscopy (APXPS) was used to investigate the effect of oxygen adsorption on the band bending and electron affinity of Al 2O 3, ZnO and TiO 2 ultrathin films (~1 nm in thickness) deposited on a Si substrate by atomic layer deposition (ALD). Upon exposure to oxygen at room temperature (RT), upward band bending was observed on all three samples, and a decrease in electron affinity was observed on Al 2O 3 and ZnO ultrathin films at RT. At 80°C, the magnitude of the upward band bending decreased, and the change in the electron affinity vanished. These results indicate the existence of two surface oxygen species: a negatively charged species that is strongly adsorbed and responsible for the observed upward band bending, and a weakly adsorbed species that is polarized, lowering the electron affinity. Based on the extent of upward band bending on the three samples, the surface coverage of the strongly adsorbed species exhibits the following order: Al 2O 3 > ZnO > TiO 2. This finding is in stark contrast to the trend expected on the surface of these bulk oxides, and highlights the unique surface activity of ultrathin oxide films withmore » important implications, for example, in oxidation reactions taking place on these films or in catalyst systems where such oxides are used as a support material.« less

Authors:
 [1];  [2];  [3];  [3];  [4];  [5];  [6];  [7]
  1. Soochow Univ., Suzhou (China). Inst. of Functional Nano and Soft Materials (FUNSOM) and Jiangsu Key Lab. for Carbon-Based Functional Materials and Devices; Chinese Academy of Sciences (CAS), Shanghai (China). State Key Lab. of Functional Materials for Informatics and Shanghai Inst. of Microsystem and Information Technology; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division and Nanoscience and Technology Division; Yale Univ., New Haven, CT (United States). Dept. of Chemical and Environmental Engineering and School of Engineering and Applied Science; Univ. of Chicago, IL (United States). Inst. of Molecular Engineering
  5. Chinese Academy of Sciences (CAS), Shanghai (China). State Key Lab. of Functional Materials for Informatics and Shanghai Inst. of Microsystem and Information Technology; ShanghaiTech Univ., Shanghai (China). School of Physical Science and Technology
  6. Soochow Univ., Suzhou (China). Inst. of Functional Nano and Soft Materials (FUNSOM) and Jiangsu Key Lab. for Carbon-Based Functional Materials and Devices
  7. Chinese Academy of Sciences (CAS), Shanghai (China). State Key Lab. of Functional Materials for Informatics and Shanghai Inst. of Microsystem and Information Technology; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); ShanghaiTech Univ., Shanghai (China). School of Physical Science and Technology
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Materials Sciences and Engineering Division; National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1352564
Alternate Identifier(s):
OSTI ID: 1454449
Grant/Contract Number:  
AC02-06CH11357; AC02-05CH11231; 11227902; 61274019
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 6; Journal Issue: 18; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Mao, Bao-Hua, Crumlin, Ethan, Tyo, Eric C., Pellin, Michael J., Vajda, Stefan, Li, Yimin, Wang, Sui-Dong, and Liu, Zhi. In situ study of the electronic structure of atomic layer deposited oxide ultrathin films upon oxygen adsorption using ambient pressure XPS. United States: N. p., 2016. Web. doi:10.1039/c6cy00575f.
Mao, Bao-Hua, Crumlin, Ethan, Tyo, Eric C., Pellin, Michael J., Vajda, Stefan, Li, Yimin, Wang, Sui-Dong, & Liu, Zhi. In situ study of the electronic structure of atomic layer deposited oxide ultrathin films upon oxygen adsorption using ambient pressure XPS. United States. doi:10.1039/c6cy00575f.
Mao, Bao-Hua, Crumlin, Ethan, Tyo, Eric C., Pellin, Michael J., Vajda, Stefan, Li, Yimin, Wang, Sui-Dong, and Liu, Zhi. Thu . "In situ study of the electronic structure of atomic layer deposited oxide ultrathin films upon oxygen adsorption using ambient pressure XPS". United States. doi:10.1039/c6cy00575f. https://www.osti.gov/servlets/purl/1352564.
@article{osti_1352564,
title = {In situ study of the electronic structure of atomic layer deposited oxide ultrathin films upon oxygen adsorption using ambient pressure XPS},
author = {Mao, Bao-Hua and Crumlin, Ethan and Tyo, Eric C. and Pellin, Michael J. and Vajda, Stefan and Li, Yimin and Wang, Sui-Dong and Liu, Zhi},
abstractNote = {In this work, ambient pressure X-ray photoelectron spectroscopy (APXPS) was used to investigate the effect of oxygen adsorption on the band bending and electron affinity of Al2O3, ZnO and TiO2 ultrathin films (~1 nm in thickness) deposited on a Si substrate by atomic layer deposition (ALD). Upon exposure to oxygen at room temperature (RT), upward band bending was observed on all three samples, and a decrease in electron affinity was observed on Al2O3 and ZnO ultrathin films at RT. At 80°C, the magnitude of the upward band bending decreased, and the change in the electron affinity vanished. These results indicate the existence of two surface oxygen species: a negatively charged species that is strongly adsorbed and responsible for the observed upward band bending, and a weakly adsorbed species that is polarized, lowering the electron affinity. Based on the extent of upward band bending on the three samples, the surface coverage of the strongly adsorbed species exhibits the following order: Al2O3 > ZnO > TiO2. This finding is in stark contrast to the trend expected on the surface of these bulk oxides, and highlights the unique surface activity of ultrathin oxide films with important implications, for example, in oxidation reactions taking place on these films or in catalyst systems where such oxides are used as a support material.},
doi = {10.1039/c6cy00575f},
journal = {Catalysis Science and Technology},
number = 18,
volume = 6,
place = {United States},
year = {2016},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Save / Share:

Works referenced in this record:

A Single-Atom-Thick TiO 2 Nanomesh on an Insulating Oxide
journal, August 2015


Charge State of Gold Nanoparticles Supported on Titania under Oxygen Pressure
journal, February 2011

  • Porsgaard, Soeren; Jiang, Peng; Borondics, Ferenc
  • Angewandte Chemie International Edition, Vol. 50, Issue 10
  • DOI: 10.1002/anie.201005377

NO 2 Adsorption on Ultrathin θ-Al 2 O 3 Films:  Formation of Nitrite and Nitrate Species
journal, August 2005

  • Ozensoy, Emrah; Peden, Charles H. F.; Szanyi, János
  • The Journal of Physical Chemistry B, Vol. 109, Issue 33
  • DOI: 10.1021/jp052053e

Oxygen-Deficient Line Defects in an Ultrathin Aluminum Oxide Film
journal, July 2006


Increased Silver Activity for Direct Propylene Epoxidation via Subnanometer Size Effects
journal, April 2010


On the nature of trapping and desorption at high surface temperatures. Theory and experiments for the Ar–Pt(111) system
journal, January 1991

  • Head‐Gordon, Martin; Tully, John C.; Rettner, Charles T.
  • The Journal of Chemical Physics, Vol. 94, Issue 2
  • DOI: 10.1063/1.460695

Electronic structure and electrical properties of interfaces between metals and ?-conjugated molecular films
journal, October 2003

  • Kahn, Antoine; Koch, Norbert; Gao, Weiying
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 41, Issue 21
  • DOI: 10.1002/polb.10642

Gas Sensing Characteristics of Ultrathin TiO2-xFilms Investigated with XPS, TPD andIn SituResistance Measurements
journal, February 1997


Effect of Adsorbed Donor and Acceptor Molecules on Electron Stimulated Desorption: O 2 /TiO 2 (110)
journal, June 2010

  • Zhang, Zhen; Yates, John T.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 14
  • DOI: 10.1021/jz1007559

The termination of the α-Al2O3 (0001) surface: a LEED crystallography determination
journal, April 1998


Direct Work Function Measurement by Gas Phase Photoelectron Spectroscopy and Its Application on PbS Nanoparticles
journal, November 2013

  • Axnanda, Stephanus; Scheele, Marcus; Crumlin, Ethan
  • Nano Letters, Vol. 13, Issue 12
  • DOI: 10.1021/nl403524a

Low-Temperature Al2O3 Atomic Layer Deposition
journal, February 2004

  • Groner, M. D.; Fabreguette, F. H.; Elam, J. W.
  • Chemistry of Materials, Vol. 16, Issue 4, p. 639-645
  • DOI: 10.1021/cm0304546

Ultrathin films on copper(i) oxide water splitting photocathodes: a study on performance and stability
journal, January 2012

  • Paracchino, Adriana; Mathews, Nripan; Hisatomi, Takashi
  • Energy & Environmental Science, Vol. 5, Issue 9
  • DOI: 10.1039/c2ee22063f

Silicon protected with atomic layer deposited TiO2: durability studies of photocathodic H2 evolution
journal, January 2013

  • Seger, Brian; Tilley, David S.; Pedersen, Thomas
  • RSC Advances, Vol. 3, Issue 48
  • DOI: 10.1039/c3ra45966g

Oxidative Decomposition of Methanol on Subnanometer Palladium Clusters: The Effect of Catalyst Size and Support Composition
journal, May 2010

  • Lee, Sungsik; Lee, Byeongdu; Mehmood, Faisal
  • The Journal of Physical Chemistry C, Vol. 114, Issue 23
  • DOI: 10.1021/jp912220w

Electron theory of thin-film gas sensors
journal, November 1993


Influence of ambient air exposure on surface chemistry and electronic properties of thin copper phthalocyanine sensing layers
journal, January 2011


Tuning the Electronic Structure of Graphene by an Organic Molecule
journal, January 2009

  • Lu, Y. H.; Chen, W.; Feng, Y. P.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 1
  • DOI: 10.1021/jp806905e

Physical Chemistry of Semiconductor−Liquid Interfaces
journal, January 1996

  • Nozik, Arthur J.; Memming, Rüdiger
  • The Journal of Physical Chemistry, Vol. 100, Issue 31
  • DOI: 10.1021/jp953720e

Basics of oxygen and SnO2 interaction; work function change and conductivity measurements
journal, October 2006


Band bending measurement of HfO2/SiO2/Si capacitor with ultra-thin La2O3 insertion by XPS
journal, July 2008


Atomic Layer Deposition: An Overview
journal, January 2010

  • George, Steven M.
  • Chemical Reviews, Vol. 110, Issue 1, p. 111-131
  • DOI: 10.1021/cr900056b

Surface Transfer p-Type Doping of Epitaxial Graphene
journal, August 2007

  • Chen, Wei; Chen, Shi; Qi, Dong Chen
  • Journal of the American Chemical Society, Vol. 129, Issue 34
  • DOI: 10.1021/ja071658g

ZnO:Al Thin Film Gas Sensor for Detection of Ethanol Vapor
journal, October 2006

  • Chou, Shih; Teoh, Lay; Lai, Wei
  • Sensors, Vol. 6, Issue 10
  • DOI: 10.3390/s6101420

Amorphous gallium indium zinc oxide thin film transistors: Sensitive to oxygen molecules
journal, May 2007

  • Kang, Donghun; Lim, Hyuck; Kim, Changjung
  • Applied Physics Letters, Vol. 90, Issue 19
  • DOI: 10.1063/1.2723543

Compositional and structural analysis of aluminum oxide films prepared by plasma-enhanced chemical vapor deposition
journal, January 1994


New ambient pressure photoemission endstation at Advanced Light Source beamline 9.3.2
journal, May 2010

  • Grass, Michael E.; Karlsson, Patrik G.; Aksoy, Funda
  • Review of Scientific Instruments, Vol. 81, Issue 5
  • DOI: 10.1063/1.3427218

A near ambient pressure XPS study of subnanometer silver clusters on Al 2 O 3 and TiO 2 ultrathin film supports
journal, January 2014

  • Mao, Bao-Hua; Chang, Rui; Shi, Lei
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 48
  • DOI: 10.1039/C4CP02325K

Ozone-Induced Band Bending on Metal-Oxide Surfaces Studied under Environmental Conditions
journal, June 2013

  • Lampimäki, Markus; Zelenay, Veronika; Křepelová, Adéla
  • ChemPhysChem, Vol. 14, Issue 11
  • DOI: 10.1002/cphc.201300418

Work Function, Band Bending, and Microwave Conductivity Studies on the Selective Alkane Oxidation Catalyst MoVTeNb Oxide (Orthorhombic M1 Phase) under Operation Conditions
journal, December 2013

  • Heine, Christian; Hävecker, Michael; Sanchez-Sanchez, Maricruz
  • The Journal of Physical Chemistry C, Vol. 117, Issue 51
  • DOI: 10.1021/jp409601h

Surface transfer doping of semiconductors
journal, September 2009


Energy Level Alignment and Interfacial Electronic Structures at Organic/Metal and Organic/Organic Interfaces
journal, June 1999