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Title: Formation Mechanism, Growth Kinetics, and Stability Limits of Graphene Adlayers in Metal-Catalyzed CVD Growth

Abstract

A new mechanism by which catalytic chemical vapor deposition of graphene spontaneously terminates at a single layer on Pt foils is discussed. This self-limited growth regime is identified by direct imaging of adlayer graphene evolution using in-situ environmental scanning electron microscopy. Two fundamentally different mechanisms for adlayer nucleation are revealed. Besides primary nucleation, which is the standard nucleation that occurs only at the onset of growth, a secondary nucleation of adlayers is observed near full coverage of the substrate. Direct observation reveals layer-dependent growth kinetics and the establishment of a dynamic equilibrium between the forward reaction of carbon incorporation and the reverse reaction of graphene etching. Increasing coverage of the active catalyst gives rise to a spontaneous reversal of adlayer evolution from growth to etching. The growth reversal has important practical benefits. It creates a self-limited growth regime in which all adlayer graphene is removed and it enables large-scale production of 100% single-layer graphene.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [5]
  1. Max Planck Society, Dahlem, Berlin (Germany). Fritz Haber Inst., Dept. of Inorganic Chemistry
  2. Inst. for Basic Science (IBS), Ulsan (Korea). Center for Multidimensional Carbon Materials (CMCM); Ulsan National Inst. of Science and Technology, Ulsan (Korea). School of Materials Science and Engineering
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  4. Max Planck Inst. of Colloids and Interfaces, Potsdam (Germany). Dept. of Colloid Chemistry
  5. Max Planck Society, Dahlem, Berlin (Germany). Fritz Haber Inst., Dept. of Inorganic Chemistry; Max Planck Inst. of Colloids and Interfaces, Potsdam (Germany). Dept. of Colloid Chemistry
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470869
Alternate Identifier(s):
OSTI ID: 1437060
Grant/Contract Number:  
[AC05-00OR22725]
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials Interfaces
Additional Journal Information:
[ Journal Volume: 5; Journal Issue: 14]; Journal ID: ISSN 2196-7350
Publisher:
Wiley-VCH
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Wang, Zhu-Jun, Ding, Feng, Eres, Gyula, Antonietti, Markus, Schloegl, Robert, and Willinger, Marc Georg. Formation Mechanism, Growth Kinetics, and Stability Limits of Graphene Adlayers in Metal-Catalyzed CVD Growth. United States: N. p., 2018. Web. doi:10.1002/admi.201800255.
Wang, Zhu-Jun, Ding, Feng, Eres, Gyula, Antonietti, Markus, Schloegl, Robert, & Willinger, Marc Georg. Formation Mechanism, Growth Kinetics, and Stability Limits of Graphene Adlayers in Metal-Catalyzed CVD Growth. United States. doi:10.1002/admi.201800255.
Wang, Zhu-Jun, Ding, Feng, Eres, Gyula, Antonietti, Markus, Schloegl, Robert, and Willinger, Marc Georg. Mon . "Formation Mechanism, Growth Kinetics, and Stability Limits of Graphene Adlayers in Metal-Catalyzed CVD Growth". United States. doi:10.1002/admi.201800255. https://www.osti.gov/servlets/purl/1470869.
@article{osti_1470869,
title = {Formation Mechanism, Growth Kinetics, and Stability Limits of Graphene Adlayers in Metal-Catalyzed CVD Growth},
author = {Wang, Zhu-Jun and Ding, Feng and Eres, Gyula and Antonietti, Markus and Schloegl, Robert and Willinger, Marc Georg},
abstractNote = {A new mechanism by which catalytic chemical vapor deposition of graphene spontaneously terminates at a single layer on Pt foils is discussed. This self-limited growth regime is identified by direct imaging of adlayer graphene evolution using in-situ environmental scanning electron microscopy. Two fundamentally different mechanisms for adlayer nucleation are revealed. Besides primary nucleation, which is the standard nucleation that occurs only at the onset of growth, a secondary nucleation of adlayers is observed near full coverage of the substrate. Direct observation reveals layer-dependent growth kinetics and the establishment of a dynamic equilibrium between the forward reaction of carbon incorporation and the reverse reaction of graphene etching. Increasing coverage of the active catalyst gives rise to a spontaneous reversal of adlayer evolution from growth to etching. The growth reversal has important practical benefits. It creates a self-limited growth regime in which all adlayer graphene is removed and it enables large-scale production of 100% single-layer graphene.},
doi = {10.1002/admi.201800255},
journal = {Advanced Materials Interfaces},
number = [14],
volume = [5],
place = {United States},
year = {2018},
month = {5}
}

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Cited by: 2 works
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Figures / Tables:

Figure 1 Figure 1: The early stages of adlayer growth: (a-d) Orthogonal views through an image stack recorded during the growth of a FLG at a Pt step edge (not visible). The yellow lines in (a), (b), and (c) indicate the cutting planes and position in the 3D stack, respectively. The timemore » axis runs from 0 sec to 2h. (d) shows a three-dimensional representation of the temporal evolution. (e) shows the evolution of the perimeter and area of the first (circle) and second (triangle) layer with time (see Supplementary Movie 3 and 4).« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.