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

Title: Atomic layer oxidation on graphene sheets for tuning their oxidation levels, electrical conductivities, and band gaps

Abstract

Graphene sheets that can exhibit electrical conducting and semiconducting properties are highly desirable and have potential applications in fiber communications, photodetectors, solar cells, semiconductors, and broadband modulators. However, there is currently no efficient method that is able to tune the band gap of graphene sheets. This paper adopts an efficient atomic layer oxidation (ALO) technique to cyclically increase the oxidation level of graphene sheets, thus, tuning their electrical conductance, band-gap structure, and photoluminescence (PL) response. The O/C atomic ratio as an increasing function of the ALO cycle number reflects two linear regions: 0.23% per cm 2 per cycle (0–15 cycles) and 0.054% per cm 2 per cycle (15–100 cycles). The excellent correlation coefficients reveal that the ALO process follows a self-limiting route to step-by-step oxidize graphene layers. The interlayer distance of ALO-graphene sheets shows an obvious increase after the ALO treatment, proved by X-ray diffraction. As analyzed by X-ray photon spectroscopy, the hydroxyl or epoxy group acts as a major contributor to the interlayer spacing distance and oxidation extent in the initial ALO stage, as compared to carbonyl and carboxyl groups. The ALO mechanism, based on Langmuir–Hinshelwood and Eley–Rideal models, is proposed to clarify the formation of oxygen functionalities andmore » structural transformation from pristine graphene sheets to oxidized ones during the ALO cycle. With a tunable oxidation level, the electrical resistivity, semiconductor character, and PL response of ALO-graphene samples can be systematically controlled for desired applications. Finally, the ALO approach is capable of offering a straightforward route to tune the oxidation level of graphene sheets or other carbons.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [3];  [4]; ORCiD logo [5]; ORCiD logo [6]
  1. Xiamen Univ. of Technology (China). Fujian Provincial Key Lab. of Functional Materials and Applications. Inst. of Material Preparation and Applied Technology. School of Materials Science and Engineering
  2. Yuan Ze Univ., Taoyuan (Taiwan). Dept. of Chemical Engineering and Materials Science; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Mechanical, Aerospace, and Biomedical Engineering
  3. Yuan Ze Univ., Taoyuan (Taiwan). Dept. of Chemical Engineering and Materials Science
  4. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Mechanical, Aerospace, and Biomedical Engineering
  5. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Nuclear Science and Engineering. Dept. of Materials Science and Engineering; National Chiao Tung Univ., Hsinchu (Taiwan). Dept. of Materials Science and Engineering
  6. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Energy and Transportation Science Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Yuan Ze Univ., Taoyuan (Taiwan); National Chiao Tung Univ., Hsinchu (Taiwan)
Sponsoring Org.:
USDOE; Ministry of Science and Technology of Taiwan
OSTI Identifier:
1468151
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Nanoscale
Additional Journal Information:
Journal Volume: 10; Journal Issue: 33; Journal ID: ISSN 2040-3364
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Gu, Siyong, Hsieh, Chien-Te, Lin, Tzu-Wei, Yuan, Chun-Yao, Ashraf Gandomi, Yasser, Chang, Jeng-Kuei, and Li, Jianlin. Atomic layer oxidation on graphene sheets for tuning their oxidation levels, electrical conductivities, and band gaps. United States: N. p., 2018. Web. doi:10.1039/C8NR04013C.
Gu, Siyong, Hsieh, Chien-Te, Lin, Tzu-Wei, Yuan, Chun-Yao, Ashraf Gandomi, Yasser, Chang, Jeng-Kuei, & Li, Jianlin. Atomic layer oxidation on graphene sheets for tuning their oxidation levels, electrical conductivities, and band gaps. United States. doi:10.1039/C8NR04013C.
Gu, Siyong, Hsieh, Chien-Te, Lin, Tzu-Wei, Yuan, Chun-Yao, Ashraf Gandomi, Yasser, Chang, Jeng-Kuei, and Li, Jianlin. Tue . "Atomic layer oxidation on graphene sheets for tuning their oxidation levels, electrical conductivities, and band gaps". United States. doi:10.1039/C8NR04013C. https://www.osti.gov/servlets/purl/1468151.
@article{osti_1468151,
title = {Atomic layer oxidation on graphene sheets for tuning their oxidation levels, electrical conductivities, and band gaps},
author = {Gu, Siyong and Hsieh, Chien-Te and Lin, Tzu-Wei and Yuan, Chun-Yao and Ashraf Gandomi, Yasser and Chang, Jeng-Kuei and Li, Jianlin},
abstractNote = {Graphene sheets that can exhibit electrical conducting and semiconducting properties are highly desirable and have potential applications in fiber communications, photodetectors, solar cells, semiconductors, and broadband modulators. However, there is currently no efficient method that is able to tune the band gap of graphene sheets. This paper adopts an efficient atomic layer oxidation (ALO) technique to cyclically increase the oxidation level of graphene sheets, thus, tuning their electrical conductance, band-gap structure, and photoluminescence (PL) response. The O/C atomic ratio as an increasing function of the ALO cycle number reflects two linear regions: 0.23% per cm2 per cycle (0–15 cycles) and 0.054% per cm2 per cycle (15–100 cycles). The excellent correlation coefficients reveal that the ALO process follows a self-limiting route to step-by-step oxidize graphene layers. The interlayer distance of ALO-graphene sheets shows an obvious increase after the ALO treatment, proved by X-ray diffraction. As analyzed by X-ray photon spectroscopy, the hydroxyl or epoxy group acts as a major contributor to the interlayer spacing distance and oxidation extent in the initial ALO stage, as compared to carbonyl and carboxyl groups. The ALO mechanism, based on Langmuir–Hinshelwood and Eley–Rideal models, is proposed to clarify the formation of oxygen functionalities and structural transformation from pristine graphene sheets to oxidized ones during the ALO cycle. With a tunable oxidation level, the electrical resistivity, semiconductor character, and PL response of ALO-graphene samples can be systematically controlled for desired applications. Finally, the ALO approach is capable of offering a straightforward route to tune the oxidation level of graphene sheets or other carbons.},
doi = {10.1039/C8NR04013C},
journal = {Nanoscale},
number = 33,
volume = 10,
place = {United States},
year = {2018},
month = {7}
}

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

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Continuous and ultrathin platinum films on graphene using atomic layer deposition: a combined computational and experimental study
journal, January 2016

  • Karasulu, Bora; Vervuurt, René H. J.; Kessels, Wilhelmus M. M.
  • Nanoscale, Vol. 8, Issue 47
  • DOI: 10.1039/C6NR07483A

Advantages of Mobile Liquid-Crystal Phase of AIE Luminogens for Effective Solid-State Emission
journal, November 2016

  • Bui, Hoa Thi; Kim, Jinhee; Kim, Ho-Joong
  • The Journal of Physical Chemistry C, Vol. 120, Issue 47
  • DOI: 10.1021/acs.jpcc.6b10026

Electrochemical Capacitors Based on Graphene Oxide Sheets Using Different Aqueous Electrolytes
journal, June 2011

  • Hsieh, Chien-Te; Hsu, Shu-Min; Lin, Jia-Yi
  • The Journal of Physical Chemistry C, Vol. 115, Issue 25
  • DOI: 10.1021/jp2032687

Facile Synthetic Method for Pristine Graphene Quantum Dots and Graphene Oxide Quantum Dots: Origin of Blue and Green Luminescence
journal, May 2013


Elucidating Quantum Confinement in Graphene Oxide Dots Based On Excitation-Wavelength-Independent Photoluminescence
journal, May 2016

  • Yeh, Te-Fu; Huang, Wei-Lun; Chung, Chung-Jen
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 11
  • DOI: 10.1021/acs.jpclett.6b00752

High-Yield Synthesis of Few-Layer Graphene Flakes through Electrochemical Expansion of Graphite in Propylene Carbonate Electrolyte
journal, June 2011

  • Wang, Junzhong; Manga, Kiran Kumar; Bao, Qiaoliang
  • Journal of the American Chemical Society, Vol. 133, Issue 23
  • DOI: 10.1021/ja203725d

Size-controlled platinum nanoparticles prepared by modified-version atomic layer deposition for ethanol oxidation
journal, February 2015


Blue Photoluminescence from Chemically Derived Graphene Oxide
journal, January 2010

  • Eda, Goki; Lin, Yun-Yue; Mattevi, Cecilia
  • Advanced Materials, Vol. 22, Issue 4, p. 505-509
  • DOI: 10.1002/adma.200901996

Atomic Layer Deposition of Platinum Nanoparticles on Carbon Nanotubes for Application in Proton‐Exchange Membrane Fuel Cells
journal, June 2009


In Situ Synthesis of Metal Nanoparticles on Single-Layer Graphene Oxide and Reduced Graphene Oxide Surfaces
journal, May 2009

  • Zhou, Xiaozhu; Huang, Xiao; Qi, Xiaoying
  • The Journal of Physical Chemistry C, Vol. 113, Issue 25
  • DOI: 10.1021/jp903821n

Atomic layer deposition for nanomaterial synthesis and functionalization in energy technology
journal, January 2017

  • Meng, Xiangbo; Wang, Xinwei; Geng, Dongsheng
  • Materials Horizons, Vol. 4, Issue 2
  • DOI: 10.1039/C6MH00521G

Graphene−Metal Particle Nanocomposites
journal, November 2008

  • Xu, Chao; Wang, Xin; Zhu, Junwu
  • The Journal of Physical Chemistry C, Vol. 112, Issue 50
  • DOI: 10.1021/jp807989b

Decorating Graphene Sheets with Gold Nanoparticles
journal, March 2008

  • Muszynski, Ryan; Seger, Brian; Kamat, Prashant V.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 14, p. 5263-5266
  • DOI: 10.1021/jp800977b

The reduction of graphene oxide
journal, August 2012


One- and two-dimensional carbon nanomaterials as counter electrodes for dye-sensitized solar cells
journal, August 2011


Surface analysis of carbon black waste materials from tire residues
journal, March 1999


Electrochemical Properties of Graphene Paper Electrodes Used in Lithium Batteries
journal, July 2009

  • Wang, Caiyun; Li, Dan; Too, Chee O.
  • Chemistry of Materials, Vol. 21, Issue 13
  • DOI: 10.1021/cm900764n

Efficient Process for Direct Atomic Layer Deposition of Metallic Cu Thin Films Based on an Organic Reductant
journal, January 2017


Nanoengineering Energy Conversion and Storage Devices via Atomic Layer Deposition
journal, July 2016

  • Wen, Liaoyong; Zhou, Min; Wang, Chengliang
  • Advanced Energy Materials, Vol. 6, Issue 23
  • DOI: 10.1002/aenm.201600468

Silver nanorods attached to graphene sheets as anode materials for lithium-ion batteries
journal, October 2013


Density Functional Theory Study of the Interaction of Arginine-Glycine-Aspartic Acid with Graphene, Defective Graphene, and Graphene Oxide
journal, March 2013

  • Guo, Ya-nan; Lu, Xiong; Weng, Jie
  • The Journal of Physical Chemistry C, Vol. 117, Issue 11
  • DOI: 10.1021/jp310088e

Ultralow Loading Pt Nanocatalysts Prepared by Atomic Layer Deposition on Carbon Aerogels
journal, August 2008

  • King, Jeffrey S.; Wittstock, Arne; Biener, Juergen
  • Nano Letters, Vol. 8, Issue 8, p. 2405-2409
  • DOI: 10.1021/nl801299z

Vapor adsorption on coal- and wood-based chemically activated carbons
journal, January 1999


Atomic layer deposition for perovskite solar cells: research status, opportunities and challenges
journal, January 2017

  • Zardetto, V.; Williams, B. L.; Perrotta, A.
  • Sustainable Energy & Fuels, Vol. 1, Issue 1
  • DOI: 10.1039/C6SE00076B

Thermal transport in stereo carbon framework using graphite nanospheres and graphene nanosheets
journal, September 2016


Atomic Layer Deposition Route To Tailor Nanoalloys of Noble and Non-noble Metals
journal, September 2016

  • Ramachandran, Ranjith K.; Dendooven, Jolien; Filez, Matthias
  • ACS Nano, Vol. 10, Issue 9
  • DOI: 10.1021/acsnano.6b04464

Atomic Layer Deposition of Platinum Nanocatalysts onto Three-Dimensional Carbon Nanotube/Graphene Hybrid
journal, December 2012

  • Hsieh, Chien-Te; Liu, Yung-Ying; Tzou, Dong-Ying
  • The Journal of Physical Chemistry C, Vol. 116, Issue 51
  • DOI: 10.1021/jp303552j

Field Emission of Single-Layer Graphene Films Prepared by Electrophoretic Deposition
journal, May 2009

  • Wu, Zhong-Shuai; Pei, Songfeng; Ren, Wencai
  • Advanced Materials, Vol. 21, Issue 17
  • DOI: 10.1002/adma.200802560

Semiconducting nature of the oxygen-adsorbed graphene sheet
journal, June 2008

  • Ito, Jun; Nakamura, Jun; Natori, Akiko
  • Journal of Applied Physics, Vol. 103, Issue 11
  • DOI: 10.1063/1.2939270

Surface Chemistry Routes to Modulate the Photoluminescence of Graphene Quantum Dots: From Fluorescence Mechanism to Up-Conversion Bioimaging Applications
journal, July 2012

  • Zhu, Shoujun; Zhang, Junhu; Tang, Shijia
  • Advanced Functional Materials, Vol. 22, Issue 22
  • DOI: 10.1002/adfm.201201499

Design and synthesis of model and practical palladium catalysts using atomic layer deposition
journal, January 2016

  • Lu, Zheng; Kizilkaya, Orhan; Kropf, A. Jeremy
  • Catalysis Science & Technology, Vol. 6, Issue 18
  • DOI: 10.1039/C6CY00682E

Graphene Oxide: Preparation, Functionalization, and Electrochemical Applications
journal, August 2012

  • Chen, Da; Feng, Hongbin; Li, Jinghong
  • Chemical Reviews, Vol. 112, Issue 11
  • DOI: 10.1021/cr300115g

Applications of Graphene Electrophoretic Deposition. A Review
journal, November 2012

  • Chavez-Valdez, A.; Shaffer, M. S. P.; Boccaccini, A. R.
  • The Journal of Physical Chemistry B, Vol. 117, Issue 6
  • DOI: 10.1021/jp3064917

A Novel Approach to Create a Highly Ordered Monolayer Film of Graphene Nanosheets at the Liquid−Liquid Interface
journal, January 2009

  • Biswas, Sanjib; Drzal, Lawrence T.
  • Nano Letters, Vol. 9, Issue 1
  • DOI: 10.1021/nl802724f

Facile preparation and upconversion luminescence of graphene quantum dots
journal, January 2011

  • Shen, Jianhua; Zhu, Yihua; Chen, Cheng
  • Chem. Commun., Vol. 47, Issue 9
  • DOI: 10.1039/C0CC04812G