High-yield growth kinetics and spatial mapping of single-walled carbon nanotube forests at wafer scale

Meshot, Eric R.; Park, Sei Jin; Buchsbaum, Steven F.; Jue, Melinda L.; Kuykendall, Tevye R.; Schaible, Eric; Bayu Aji, Leonardus Bimo; Kucheyev, Sergei O.; Wu, Kuang Jen J.; Fornasiero, Francesco

doi:10.1016/j.carbon.2019.12.023

High-yield growth kinetics and spatial mapping of single-walled carbon nanotube forests at wafer scale

Journal Article · Wed Apr 01 00:00:00 EDT 2020 · Carbon

DOI:https://doi.org/10.1016/j.carbon.2019.12.023· OSTI ID:1642502

^[1]; ^[1]; Buchsbaum, Steven F. ^[1]; Jue, Melinda L. ^[1]; Kuykendall, Tevye R. ^[1]; Schaible, Eric ^[2]; Bayu Aji, Leonardus Bimo ^[1]; Kucheyev, Sergei O. ^[1]; Wu, Kuang Jen J. ^[1]; ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

Emerging commercial applications of vertically aligned, single-walled carbon nanotube (SWCNT) “forests” require synthesis that minimizes nanotube diameter while maximizing number density across substrate areas exceeding centimeter scale. To address this need, we synthesized SWCNT forests on full silicon wafers with notable reproducibility and uniformity, and co-optimized growth for small diameters and high densities across large areas to access new territory in this 3D parameter space. We mapped the spatial uniformity of key structural features using Raman microscopy, synchrotron X-ray scattering, and Rutherford backscattering spectrometry. Low C₂H₂ flux over sub-nm Fe/Mo catalysts produced small-diameter SWCNTs (2.1 nm) at high number densities (2.26 × 10¹² cm^-2) on wafers up to 6 in. Although removing Mo resulted in larger SWCNT diameters and lower densities (<0.7 × 10¹² cm^-2), mass conversion rates from C₂H₂ to SWCNT product were high and remarkably invariant for catalyst compositions and densities (i.e., 47.7% or 1.30 × 10⁶% g-catalyst^-1 on 4-in. wafers). These carbon conversion efficiencies far exceed typical benchtop reactors and are on par with the best reported literature values. Our detailed elucidation of correlations among structural characteristics within this resource-efficient process is expected to guide future scale-up efforts of SWCNT forest growth beyond wafer scale.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC52-07NA27344

OSTI ID:: 1642502

Alternate ID(s):: OSTI ID: 1580312

Report Number(s):: LLNL-JRNL--778865; 972819

Journal Information:: Carbon, Journal Name: Carbon Journal Issue: na Vol. 159; ISSN 0008-6223

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (61)

Tough Nano-Architectured Conductive Textile Made by Capillary Splicing of Carbon Nanotubes : Tough Nano-Architectured Conductive Textile… Liang, Yue; Sias, David; Chen, Ping Ju Advanced Engineering Materials, Vol. 19, Issue 7 https://doi.org/10.1002/adem.201600845	journal	April 2017
A Pyrenylpropyl Phosphonic Acid Surface Modifier for Mitigating the Thermal Resistance of Carbon Nanotube Contacts Taphouse, John H.; Smith, O'Neil L.; Marder, Seth R. Advanced Functional Materials, Vol. 24, Issue 4 https://doi.org/10.1002/adfm.201301714	journal	September 2013
Superaligned Carbon Nanotube Arrays, Films, and Yarns: A Road to Applications Jiang, Kaili; Wang, Jiaping; Li, Qunqing Advanced Materials, Vol. 23, Issue 9 https://doi.org/10.1002/adma.201003989	journal	January 2011
Density Variant Carbon Nanotube Interconnected Solids Ozden, Sehmus; Tiwary, Chandra Sekhar; Hart, Amelia H. C. Advanced Materials, Vol. 27, Issue 11 https://doi.org/10.1002/adma.201404995	journal	February 2015
Ultrabreathable and Protective Membranes with Sub-5 nm Carbon Nanotube Pores Bui, Ngoc; Meshot, Eric R.; Kim, Sangil Advanced Materials, Vol. 28, Issue 28 https://doi.org/10.1002/adma.201600740	journal	May 2016
Wafer Scale Mapping and Statistical Analysis of Radio Frequency Characteristics in Highly Uniform CVD Graphene Transistors Tian, Mengchuan; Hu, Ben; Yang, Haifang Advanced Electronic Materials, Vol. 5, Issue 4 https://doi.org/10.1002/aelm.201800711	journal	February 2019
Diameter and Density Control of Single-Walled Carbon Nanotube Forests by Modulating Ostwald Ripening through Decoupling the Catalyst Formation and Growth Processes Sakurai, Shunsuke; Inaguma, Masayasu; Futaba, Don N. Small, Vol. 9, Issue 21 https://doi.org/10.1002/smll.201300223	journal	April 2013
Algorithms for the rapid simulation of Rutherford backscattering spectra Doolittle, Lawrence R. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 9, Issue 3 https://doi.org/10.1016/0168-583X(85)90762-1	journal	June 1985
Gas analysis of the CVD process for high yield growth of carbon nanotubes over metal-supported catalysts Ago, Hiroki; Uehara, Naoyasu; Yoshihara, Naoki Carbon, Vol. 44, Issue 14 https://doi.org/10.1016/j.carbon.2006.05.049	journal	November 2006
Sub-millimeter-long carbon nanotubes repeatedly grown on and separated from ceramic beads in a single fluidized bed reactor Kim, Dong Young; Sugime, Hisashi; Hasegawa, Kei Carbon, Vol. 49, Issue 6 https://doi.org/10.1016/j.carbon.2011.01.022	journal	May 2011
Fluidized-bed synthesis of sub-millimeter-long single walled carbon nanotube arrays Kim, Dong Young; Sugime, Hisashi; Hasegawa, Kei Carbon, Vol. 50, Issue 4 https://doi.org/10.1016/j.carbon.2011.11.032	journal	April 2012
Diameter-dependent kinetics of activation and deactivation in carbon nanotube population growth Bedewy, Mostafa; Meshot, Eric R.; Hart, A. John Carbon, Vol. 50, Issue 14 https://doi.org/10.1016/j.carbon.2012.06.051	journal	November 2012
High density carbon nanotube growth using a plasma pretreated catalyst Zhang, C.; Xie, R.; Chen, B. Carbon, Vol. 53 https://doi.org/10.1016/j.carbon.2012.11.020	journal	March 2013
Temperature gradient chemical vapor deposition of vertically aligned carbon nanotubes Youn, Seul Ki; Frouzakis, Christos E.; Gopi, Baskar Pagadala Carbon, Vol. 54 https://doi.org/10.1016/j.carbon.2012.11.046	journal	April 2013
Over 99.6 wt%-pure, sub-millimeter-long carbon nanotubes realized by fluidized-bed with careful control of the catalyst and carbon feeds Chen, Zhongming; Kim, Dong Young; Hasegawa, Kei Carbon, Vol. 80 https://doi.org/10.1016/j.carbon.2014.08.072	journal	December 2014
Shock formation and rate effects in impacted carbon nanotube foams Thevamaran, Ramathasan; Meshot, Eric R.; Daraio, Chiara Carbon, Vol. 84 https://doi.org/10.1016/j.carbon.2014.12.006	journal	April 2015
In situ time resolved wide angle X-ray diffraction study of nanotube carpet growth: Nature of catalyst particles and progressive nanotube alignment Landois, Périne; Pinault, Mathieu; Rouzière, Stéphan Carbon, Vol. 87 https://doi.org/10.1016/j.carbon.2015.01.046	journal	June 2015
Growth of high quality, high density single-walled carbon nanotube forests on copper foils Zhong, Guofang; Yang, Junwei; Sugime, Hisashi Carbon, Vol. 98 https://doi.org/10.1016/j.carbon.2015.11.047	journal	March 2016
Integration and electrical characterization of carbon nanotube via interconnects Chiodarelli, Nicolo’; Li, Yunlong; Cott, Daire J. Microelectronic Engineering, Vol. 88, Issue 5 https://doi.org/10.1016/j.mee.2010.06.017	journal	May 2011
Data Analytics Enables Significant Improvement of Robustness in Chemical Vapor Deposition of Carbon Nanotubes Based on Vacuum Baking Lee, Jaegeun; Abdulhafez, Moataz; Bedewy, Mostafa Industrial & Engineering Chemistry Research, Vol. 58, Issue 27 https://doi.org/10.1021/acs.iecr.9b01725	journal	June 2019
Highly Consistent Atmospheric Pressure Synthesis of Carbon Nanotube Forests by Mitigation of Moisture Transients Li, Jinjing; Bedewy, Mostafa; White, Alvin Orbaek The Journal of Physical Chemistry C, Vol. 120, Issue 20 https://doi.org/10.1021/acs.jpcc.6b02878	journal	May 2016
Generation of Terahertz Radiation by Optical Excitation of Aligned Carbon Nanotubes Titova, Lyubov V.; Pint, Cary L.; Zhang, Qi Nano Letters, Vol. 15, Issue 5 https://doi.org/10.1021/acs.nanolett.5b00494	journal	April 2015
Photon-Impenetrable, Electron-Permeable: The Carbon Nanotube Forest as a Medium for Multiphoton Thermal-Photoemission Vahdani Moghaddam, Mehran; Yaghoobi, Parham; Sawatzky, George A. ACS Nano, Vol. 9, Issue 4 https://doi.org/10.1021/acsnano.5b00115	journal	February 2015
Quantifying the Hierarchical Order in Self-Aligned Carbon Nanotubes from Atomic to Micrometer Scale Meshot, Eric R.; Zwissler, Darwin W.; Bui, Ngoc ACS Nano, Vol. 11, Issue 6 https://doi.org/10.1021/acsnano.6b08042	journal	April 2017
Water-Assisted Growth of Uniform 100 mm Diameter SWCNT Arrays Wyss, Roman M.; Klare, Jennifer E.; Park, Hyung Gyu ACS Applied Materials & Interfaces, Vol. 6, Issue 23 https://doi.org/10.1021/am505692a	journal	November 2014
Morphological Evolution of Fe–Mo Bimetallic Catalysts for Diameter and Density Modulation of Vertically Aligned Carbon Nanotubes Youn, Seul Ki; Park, Hyung Gyu The Journal of Physical Chemistry C, Vol. 117, Issue 36 https://doi.org/10.1021/jp402941u	journal	August 2013
Orientation Distribution of Vertically Aligned Multiwalled Carbon Nanotubes Vainio, Ulla; Schnoor, Thea I. W.; Koyiloth Vayalil, Sarathlal The Journal of Physical Chemistry C, Vol. 118, Issue 18 https://doi.org/10.1021/jp501060s	journal	April 2014
Study of Single-Walled Carbon Nanotubes Growth via the Catalyst Lifetime Mora, Elena; Harutyunyan, Avetik R. The Journal of Physical Chemistry C, Vol. 112, Issue 13 https://doi.org/10.1021/jp710064k	journal	March 2008
In-situ X-ray Photoelectron Spectroscopy Study of Catalyst−Support Interactions and Growth of Carbon Nanotube Forests Mattevi, Cecilia; Wirth, Christoph Tobias; Hofmann, Stephan The Journal of Physical Chemistry C, Vol. 112, Issue 32 https://doi.org/10.1021/jp802474g	journal	July 2008
Temperature and Gas Pressure Effects in Vertically Aligned Carbon Nanotube Growth from Fe−Mo Catalyst Pint, Cary L.; Nicholas, Nolan; Pheasant, Sean T. The Journal of Physical Chemistry C, Vol. 112, Issue 36 https://doi.org/10.1021/jp8025539	journal	August 2008
Collective Mechanism for the Evolution and Self-Termination of Vertically Aligned Carbon Nanotube Growth Bedewy, Mostafa; Meshot, Eric R.; Guo, Haicheng The Journal of Physical Chemistry C, Vol. 113, Issue 48 https://doi.org/10.1021/jp904152v	journal	October 2009
Broadband Terahertz Polarizers with Ideal Performance Based on Aligned Carbon Nanotube Stacks Ren, Lei; Pint, Cary L.; Arikawa, Takashi Nano Letters, Vol. 12, Issue 2 https://doi.org/10.1021/nl203783q	journal	January 2012
Carbon Nanotube Terahertz Detector He, Xiaowei; Fujimura, Naoki; Lloyd, J. Meagan Nano Letters, Vol. 14, Issue 7 https://doi.org/10.1021/nl5012678	journal	June 2014
Role of Water in Super Growth of Single-Walled Carbon Nanotube Carpets Amama, Placidus B.; Pint, Cary L.; McJilton, Laura Nano Letters, Vol. 9, Issue 1 https://doi.org/10.1021/nl801876h	journal	January 2009
Mechanism and Kinetics of Growth Termination in Controlled Chemical Vapor Deposition Growth of Multiwall Carbon Nanotube Arrays Stadermann, Michael; Sherlock, Sarah P.; In, Jung-Bin Nano Letters, Vol. 9, Issue 2 https://doi.org/10.1021/nl803277g	journal	February 2009
Atomic-Scale Analysis on the Role of Molybdenum in Iron-Catalyzed Carbon Nanotube Growth Yoshida, Hideto; Shimizu, Takuma; Uchiyama, Tetsuya Nano Letters, Vol. 9, Issue 11 https://doi.org/10.1021/nl9019903	journal	November 2009
Millimeter-Tall Single-Walled Carbon Nanotubes Rapidly Grown with and without Water Hasegawa, Kei; Noda, Suguru ACS Nano, Vol. 5, Issue 2 https://doi.org/10.1021/nn102380j	journal	January 2011
Growth of Ultrahigh Density Vertically Aligned Carbon Nanotube Forests for Interconnects Esconjauregui, Santiago; Fouquet, Martin; Bayer, Bernhard C. ACS Nano, Vol. 4, Issue 12 https://doi.org/10.1021/nn1025675	journal	December 2010
Millimeter-Long Carbon Nanotubes: Outstanding Electron-Emitting Sources Perea-López, Néstor; Rebollo-Plata, Bernabé; Briones-León, Juan Antonio ACS Nano, Vol. 5, Issue 6 https://doi.org/10.1021/nn201149y	journal	May 2011
Growth of Ultrahigh Density Single-Walled Carbon Nanotube Forests by Improved Catalyst Design Zhong, Guofang; Warner, Jamie H.; Fouquet, Martin ACS Nano, Vol. 6, Issue 4 https://doi.org/10.1021/nn203035x	journal	March 2012
Population Growth Dynamics of Carbon Nanotubes Bedewy, Mostafa; Meshot, Eric R.; Reinker, Michael J. ACS Nano, Vol. 5, Issue 11 https://doi.org/10.1021/nn203144f	journal	October 2011
High-Speed in Situ X-ray Scattering of Carbon Nanotube Film Nucleation and Self-Organization Meshot, Eric R.; Verploegen, Eric; Bedewy, Mostafa ACS Nano, Vol. 6, Issue 6 https://doi.org/10.1021/nn300758f	journal	May 2012
Statistical Analysis of Variation in Laboratory Growth of Carbon Nanotube Forests and Recommendations for Improved Consistency Oliver, C. Ryan; Polsen, Erik S.; Meshot, Eric R. ACS Nano, Vol. 7, Issue 4 https://doi.org/10.1021/nn400507y	journal	March 2013
Improved and Large Area Single-Walled Carbon Nanotube Forest Growth by Controlling the Gas Flow Direction Yasuda, Satoshi; Futaba, Don N.; Yamada, Takeo ACS Nano, Vol. 3, Issue 12 https://doi.org/10.1021/nn9007302	journal	November 2009
Influence of Alumina Type on the Evolution and Activity of Alumina-Supported Fe Catalysts in Single-Walled Carbon Nanotube Carpet Growth Amama, Placidus B.; Pint, Cary L.; Kim, Seung Min ACS Nano, Vol. 4, Issue 2 https://doi.org/10.1021/nn901700u	journal	January 2010
Electrophoretically induced aqueous flow through single-walled carbon nanotube membranes Wu, Ji; Gerstandt, Karen; Zhang, Hongbo Nature Nanotechnology, Vol. 7, Issue 2 https://doi.org/10.1038/nnano.2011.240	journal	January 2012
A carbon nanotube optical rectenna Sharma, Asha; Singh, Virendra; Bougher, Thomas L. Nature Nanotechnology, Vol. 10, Issue 12 https://doi.org/10.1038/nnano.2015.220	journal	September 2015
Synthesis of subnanometer-diameter vertically aligned single-walled carbon nanotubes with copper-anchored cobalt catalysts Cui, Kehang; Kumamoto, Akihito; Xiang, Rong Nanoscale, Vol. 8, Issue 3 https://doi.org/10.1039/C5NR06007A	journal	January 2016
The carbon nanotube formation parameter space: data mining and mechanistic understanding for efficient resource use Shi, Wenbo; Xue, Ke; Meshot, Eric R. Green Chemistry, Vol. 19, Issue 16 https://doi.org/10.1039/C7GC01421J	journal	January 2017
Measuring the lengthening kinetics of aligned nanostructures by spatiotemporal correlation of height and orientation Meshot, Eric R.; Bedewy, Mostafa; Lyons, Kevin M. Nanoscale, Vol. 2, Issue 6 https://doi.org/10.1039/b9nr00343f	journal	January 2010
Abrupt self-termination of vertically aligned carbon nanotube growth Meshot, Eric R.; Hart, A. John Applied Physics Letters, Vol. 92, Issue 11 https://doi.org/10.1063/1.2889497	journal	March 2008
Measurement of area density of vertically aligned carbon nanotube forests by the weight-gain method Esconjauregui, Santiago; Xie, Rongsie; Fouquet, Martin Journal of Applied Physics, Vol. 113, Issue 14 https://doi.org/10.1063/1.4799417	journal	April 2013
Ion exclusion by sub-2-nm carbon nanotube pores Fornasiero, F.; Park, H. G.; Holt, J. K. Proceedings of the National Academy of Sciences, Vol. 105, Issue 45 https://doi.org/10.1073/pnas.0710437105	journal	June 2008
Programmable transdermal drug delivery of nicotine using carbon nanotube membranes Wu, J.; Paudel, K. S.; Strasinger, C. Proceedings of the National Academy of Sciences, Vol. 107, Issue 26 https://doi.org/10.1073/pnas.1004714107	journal	June 2010
Carbon nanotube growth for through silicon via application Xie, R.; Zhang, C.; van der Veen, M. H. Nanotechnology, Vol. 24, Issue 12 https://doi.org/10.1088/0957-4484/24/12/125603	journal	March 2013
A SAXS/WAXS/GISAXS Beamline with Multilayer Monochromator Hexemer, Alexander; Bras, Wim; Glossinger, James Journal of Physics: Conference Series, Vol. 247 https://doi.org/10.1088/1742-6596/247/1/012007	journal	October 2010
Nature of the constant factor in the relation between radial breathing mode frequency and tube diameter for single-wall carbon nanotubes Araujo, P. T.; Maciel, I. O.; Pesce, P. B. C. Physical Review B, Vol. 77, Issue 24 https://doi.org/10.1103/PhysRevB.77.241403	journal	June 2008
Influence of Mo on the Fe:Mo:C nanocatalyst thermodynamics for single-walled carbon nanotube growth Curtarolo, Stefano; Awasthi, Neha; Setyawan, Wahyu Physical Review B, Vol. 78, Issue 5 https://doi.org/10.1103/PhysRevB.78.054105	journal	August 2008
Correlation between density and hydrogen content in vertically aligned carbon nanotube forests by ion beam analysis Girshevitz, Olga; Richter, Vova; Avraham, Efrat Shawat Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 35, Issue 6 https://doi.org/10.1116/1.4999774	journal	November 2017
The partial space qualification of a vertically aligned carbon nanotube coating on aluminium substrates for EO applications Theocharous, Evangelos; Chunnilall, Christopher J.; Mole, Ryan Optics Express, Vol. 22, Issue 6 https://doi.org/10.1364/OE.22.007290	journal	January 2014
Confocal Microscopy for Process Monitoring and Wide-Area Height Determination of Vertically-Aligned Carbon Nanotube Forests Piwko, Markus; Althues, Holger; Schumm, Benjamin Coatings, Vol. 5, Issue 3 https://doi.org/10.3390/coatings5030477	journal	August 2015

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