Measurement of the Dewetting, Nucleation, and Deactivation Kinetics of Carbon Nanotube Population Growth by Environmental Transmission Electron Microscopy

Bedewy, Mostafa; Viswanath, B.; Meshot, Eric R.; Zakharov, Dmitri N.; Stach, Eric A.; Hart, A. John

doi:10.1021/acs.chemmater.6b00798

Measurement of the Dewetting, Nucleation, and Deactivation Kinetics of Carbon Nanotube Population Growth by Environmental Transmission Electron Microscopy

Journal Article · Mon May 23 00:00:00 EDT 2016 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.6b00798· OSTI ID:1336127

Bedewy, Mostafa ^[1]; Viswanath, B. ^[2]; Meshot, Eric R. ^[3]; Zakharov, Dmitri N. ^[4]; Stach, Eric A. ^[4]; Hart, A. John ^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Univ. of Michigan, Ann Arbor, MI (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Sciences Directorate
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials

Understanding the collective growth of carbon nanotube (CNT) populations is key to tailoring their properties for many applications. During the initial stages of CNT growth by chemical vapor deposition, catalyst nanoparticle formation by thin-film dewetting and the subsequent CNT nucleation processes dictate the CNT diameter distribution, areal density, and alignment. Here, in this study, we use in situ environmental transmission electron microscopy (E-TEM) to observe the catalyst annealing, growth, and deactivation stages for a population of CNTs grown from a thin-film catalyst. Complementary in situ electron diffraction and TEM imaging show that, during the annealing step in hydrogen, reduction of the iron oxide catalyst is concomitant with changes in the thin-film morphology; complete dewetting and the formation of a population of nanoparticles is only achieved upon the introduction of the carbon source, acetylene. The dewetting kinetics, i.e., the appearance of distinct nanoparticles, exhibits a sigmoidal (autocatalytic) curve with 95% of all nanoparticles appearing within 6 s. After nanoparticles form, they either nucleate CNTs or remain inactive, with incubation times measured to be as small as 3.5 s. Via E-TEM we also directly observe the crowding and self-alignment of CNTs after dewetting and nucleation. In addition, in situ electron energy loss spectroscopy reveals that the collective rate of carbon accumulation decays exponentially. We conclude that the kinetics of catalyst formation and CNT nucleation must both be addressed in order to achieve uniform and high CNT density, and their transient behavior may be a primary cause of the well-known nonuniform density of CNT forests.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials; Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC52-07NA27344; SC0004927

OSTI ID:: 1336127

Alternate ID(s):: OSTI ID: 1959600

Report Number(s):: BNL--112593-2016-JA; LLNL-JRNL-683473

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 11 Vol. 28; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Measurement of the Dewetting, Nucleation, and Deactivation Kinetics of Carbon Nanotube Population Growth by Environmental Transmission Electron Microscopy

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