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

Title: Carbon-assisted catalyst pretreatment enables straightforward synthesis of high-density carbon nanotube forests

Abstract

In spite of extensive academic and commercial development, a comprehensive understanding of the principles necessary for high-yield production of carbon nanotubes (CNTs) is lacking, whether in oriented films, bulk powders, or other forms. In chemical vapor deposition growth of CNT films on substrates, trace contaminants of carbon, such as deposits on the reactor tube walls, are known to cause inconsistency in key production metrics, including CNT density and alignment. Here, we show that trace exposure of the catalyst to carbon during initial heating of the catalyst film is a critical determinant of CNT yield, and this carbon exposure accelerates catalyst nanoparticle formation via film dewetting and increases the probability of CNT nucleation and the resultant density of the CNT population. Through controlled exposure of the catalyst to a trace amount of carbon, we show up to a 4-fold increase in bulk mass density for a given forest height, an 8-fold increase in local CNT number density, and a 2-fold increase in the growth lifetime, relative to a reference condition. We discuss potential mechanisms to explain the role of carbon exposure on the probability of CNT nucleation from nanoparticle catalysts, supported by microscopy and gas analysis.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2];  [1];  [3];  [1];  [1];  [4];  [3]; ORCiD logo [5];  [1]; ORCiD logo [6];  [7];  [8];  [3]; ORCiD logo [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Swansea Univ. (United Kingdom)
  3. Yale Univ., New Haven, CT (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
  5. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Univ. of Pittsburgh, PA (United States)
  6. Brookhaven National Lab. (BNL), Upton, NY (United States); Air Force Research Lab. (AFRL), Wright-Patterson AFB, OH (United States)
  7. Air Force Research Lab. (AFRL), Wright-Patterson AFB, OH (United States)
  8. Brookhaven National Lab. (BNL), Upton, NY (United States); Univ. of Pennsylvania, Philadelphia, PA (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1581239
Report Number(s):
BNL-212500-2020-JAAM
Journal ID: ISSN 0008-6223; TRN: US2100869
Grant/Contract Number:  
SC0012704; SC0010795; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Carbon
Additional Journal Information:
Journal Volume: 153; Journal Issue: C; Journal ID: ISSN 0008-6223
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Dee, Nicholas T., Li, Jinjing, Orbaek White, Alvin, Jacob, Christine, Shi, Wenbo, Kidambi, Piran R., Cui, Kehang, Zakharov, Dmitri N., Janković, Nina Z., Bedewy, Mostafa, Chazot, Cécile A. C., Carpena-Núñez, Jennifer, Maruyama, Benji, Stach, Eric A., Plata, Desiree L., and Hart, A. John. Carbon-assisted catalyst pretreatment enables straightforward synthesis of high-density carbon nanotube forests. United States: N. p., 2019. Web. doi:10.1016/j.carbon.2019.06.083.
Dee, Nicholas T., Li, Jinjing, Orbaek White, Alvin, Jacob, Christine, Shi, Wenbo, Kidambi, Piran R., Cui, Kehang, Zakharov, Dmitri N., Janković, Nina Z., Bedewy, Mostafa, Chazot, Cécile A. C., Carpena-Núñez, Jennifer, Maruyama, Benji, Stach, Eric A., Plata, Desiree L., & Hart, A. John. Carbon-assisted catalyst pretreatment enables straightforward synthesis of high-density carbon nanotube forests. United States. https://doi.org/10.1016/j.carbon.2019.06.083
Dee, Nicholas T., Li, Jinjing, Orbaek White, Alvin, Jacob, Christine, Shi, Wenbo, Kidambi, Piran R., Cui, Kehang, Zakharov, Dmitri N., Janković, Nina Z., Bedewy, Mostafa, Chazot, Cécile A. C., Carpena-Núñez, Jennifer, Maruyama, Benji, Stach, Eric A., Plata, Desiree L., and Hart, A. John. 2019. "Carbon-assisted catalyst pretreatment enables straightforward synthesis of high-density carbon nanotube forests". United States. https://doi.org/10.1016/j.carbon.2019.06.083. https://www.osti.gov/servlets/purl/1581239.
@article{osti_1581239,
title = {Carbon-assisted catalyst pretreatment enables straightforward synthesis of high-density carbon nanotube forests},
author = {Dee, Nicholas T. and Li, Jinjing and Orbaek White, Alvin and Jacob, Christine and Shi, Wenbo and Kidambi, Piran R. and Cui, Kehang and Zakharov, Dmitri N. and Janković, Nina Z. and Bedewy, Mostafa and Chazot, Cécile A. C. and Carpena-Núñez, Jennifer and Maruyama, Benji and Stach, Eric A. and Plata, Desiree L. and Hart, A. John},
abstractNote = {In spite of extensive academic and commercial development, a comprehensive understanding of the principles necessary for high-yield production of carbon nanotubes (CNTs) is lacking, whether in oriented films, bulk powders, or other forms. In chemical vapor deposition growth of CNT films on substrates, trace contaminants of carbon, such as deposits on the reactor tube walls, are known to cause inconsistency in key production metrics, including CNT density and alignment. Here, we show that trace exposure of the catalyst to carbon during initial heating of the catalyst film is a critical determinant of CNT yield, and this carbon exposure accelerates catalyst nanoparticle formation via film dewetting and increases the probability of CNT nucleation and the resultant density of the CNT population. Through controlled exposure of the catalyst to a trace amount of carbon, we show up to a 4-fold increase in bulk mass density for a given forest height, an 8-fold increase in local CNT number density, and a 2-fold increase in the growth lifetime, relative to a reference condition. We discuss potential mechanisms to explain the role of carbon exposure on the probability of CNT nucleation from nanoparticle catalysts, supported by microscopy and gas analysis.},
doi = {10.1016/j.carbon.2019.06.083},
url = {https://www.osti.gov/biblio/1581239}, journal = {Carbon},
issn = {0008-6223},
number = C,
volume = 153,
place = {United States},
year = {Wed Jun 26 00:00:00 EDT 2019},
month = {Wed Jun 26 00:00:00 EDT 2019}
}

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

Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: CNT growth procedure with “carbon preload”. (a) Photo of custom CVD reactor that allows for rapid insertion and removal of a quartz boat (inset) carrying the substrate into the furnace. (b) Schematic sequence of process steps (1e5) for CNT forest synthesis according to the carbon preload recipe, whichmore » has sequential gas compositions for each step as noted in the accompanying table; note the carbon preload step is shaded in pink. The transfer arm moves inward from left to right. Red and gray colors on the furnace indicate the furnace is turned on and off, respectively. Further details are in the Supplementary Material.« less

Save / Share:

Works referenced in this record:

Enhanced thermal transport at covalently functionalized carbon nanotube array interfaces
journal, January 2014


Denser and taller carbon nanotube arrays on Cu foils useable as thermal interface materials
journal, August 2015


Integration and electrical characterization of carbon nanotube via interconnects
journal, May 2011


Carbon nanotube growth for through silicon via application
journal, March 2013


Programmable transdermal drug delivery of nicotine using carbon nanotube membranes
journal, June 2010


Ultrabreathable and Protective Membranes with Sub-5 nm Carbon Nanotube Pores
journal, May 2016


In-situ X-ray Photoelectron Spectroscopy Study of Catalyst−Support Interactions and Growth of Carbon Nanotube Forests
journal, July 2008


Evolution in Catalyst Morphology Leads to Carbon Nanotube Growth Termination
journal, February 2010


Effect of the Metal−Substrate Interaction Strength on the Growth of Single-Walled Carbon Nanotubes
journal, March 2011


Atomic scale simulation of carbon nanotube nucleation from hydrocarbon precursors
journal, December 2015


Model for Self-Assembly of Carbon Nanotubes from Acetylene Based on Real-Time Studies of Vertically Aligned Growth Kinetics
journal, August 2009


High-Speed in Situ X-ray Scattering of Carbon Nanotube Film Nucleation and Self-Organization
journal, May 2012


Population Growth Dynamics of Carbon Nanotubes
journal, October 2011


In situ measurements and modeling of carbon nanotube array growth kinetics during chemical vapor deposition
journal, July 2005


Mechanism and Kinetics of Growth Termination in Controlled Chemical Vapor Deposition Growth of Multiwall Carbon Nanotube Arrays
journal, February 2009


Self-Deactivation of Single-Walled Carbon Nanotube Growth Studied by in Situ Raman Measurements
journal, February 2009


Site-Specific Fabrication of Fe Particles for Carbon Nanotube Growth
journal, February 2009


State of Transition Metal Catalysts During Carbon Nanotube Growth
journal, January 2009


Direct evidence of active and inactive phases of Fe catalyst nanoparticles for carbon nanotube formation
journal, November 2014


Analysis of Fe Catalyst during Carbon Nanotube Synthesis by Mössbauer Spectroscopy
journal, October 2009


Growth of Ultrahigh Density Single-Walled Carbon Nanotube Forests by Improved Catalyst Design
journal, March 2012


Growth of Ultrahigh Density Vertically Aligned Carbon Nanotube Forests for Interconnects
journal, December 2010


Kinetics of Water-Assisted Single-Walled Carbon Nanotube Synthesis Revealed by a Time-Evolution Analysis
journal, July 2005


Highly Consistent Atmospheric Pressure Synthesis of Carbon Nanotube Forests by Mitigation of Moisture Transients
journal, May 2016


In Situ Mechanochemical Modulation of Carbon Nanotube Forest Growth
journal, December 2018


Wet-chemical catalyst deposition for scalable synthesis of vertical aligned carbon nanotubes on metal substrates
journal, August 2011


Evaluation of thermal resistance of carbon nanotube film fabricated using an improved slope control of temperature profile growth
journal, March 2015


One hundred fold increase in current carrying capacity in a carbon nanotube–copper composite
journal, July 2013


84% Catalyst Activity of Water-Assisted Growth of Single Walled Carbon Nanotube Forest Characterization by a Statistical and Macroscopic Approach
journal, April 2006


Quantitative assessment of the effect of purity on the properties of single wall carbon nanotubes
journal, January 2015


Effects of atomic hydrogen and active carbon species in 1mm vertically aligned single-walled carbon nanotube growth
journal, September 2006


Synthesis of High Aspect-Ratio Carbon Nanotube “Flying Carpets” from Nanostructured Flake Substrates
journal, June 2008


Rapid and Scalable Reduction of Dense Surface-Supported Metal-Oxide Catalyst with Hydrazine Vapor
journal, June 2009


Multiple Alkynes React with Ethylene To Enhance Carbon Nanotube Synthesis, Suggesting a Polymerization-like Formation Mechanism
journal, November 2010


Extraction of metals from ores
journal, January 1943


In Situ Study of Iron Catalysts for Carbon Nanotube Growth Using X-Ray Diffraction Analysis
journal, March 2004


Thermodynamics behind Carbon Nanotube Growth via Endothermic Catalytic Decomposition Reaction
journal, January 2009


Structural ( n , m ) Determination of Isolated Single-Wall Carbon Nanotubes by Resonant Raman Scattering
journal, February 2001


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