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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:
Journal Article: 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 = {Thu Jul 21 00:00:00 EDT 2016},
month = {Thu Jul 21 00:00:00 EDT 2016}
}

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Low-Temperature Al2O3 Atomic Layer Deposition
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