Toward Controllable Growth of Carbon Nanotubes

Honda Research Institute USA Inc. Toward Controllable Growth of Carbon Nanotubes Avetik R. Harutyunyan Materials Science Division, Columbus Ohio, USA (April 10, 2011) The 5 th Rice University/Air Force Research Laboratory/NASA Workshop on Nucleation and Growth Mechanisms of SWCNTs April 8-12, 2011, Guadalupe, Texas

Coauthors and collaborators Dr. Gugang Chen Dr. Elena Pigos Dr. Tereza Paronyan Prof. Eric A. Stach Dr. Dmitri Zakharov Honda Research Institute USA Inc. Brookhaven National Laboratory Brookhaven National Laboratory Dr. Seung Min Kim Purdue University Prof. Boris Yakobson Prof. Bruce Weisman Dr. Anton Naumov Prof. Millie Dresselhaus Prof. Jing Kong Rice University Rice University MIT Confidential 2009 Honda Research Institute USA, Inc. 2

Outline of the talk 1. Introduction: Highlighted "Key Questions" from previous Workshop 2. Thermodynamic aspects of carbon nanotube growth 3. Summary: Hints for selective growth 4. Preferential growth of metallic tubes: The origin of selectivity 5. Conclusion: control parameters 3

Introduction Ubiquitous applications of SWCNTs demand reasonably homogeneous material Controllable growth Growth mechanism Confidential 2009 Honda Research Institute USA, Inc. 4

"Key Questions" from previous Workshop State of catalyst - solid (crystal/disorder) vs liquid Diffusion path - surface vs bulk, sublayer diffusion Role of carbides - promote vs terminate the growth Confidential 2009 Honda Research Institute USA, Inc. 5

Why is so difficult to answer? 1. Definition of liquid Solid/liquid - lower symmetry, lower coordination, no elastic strain Same aspects for solid bulk /solid surface XRD, TEM - distinguish liquid vs disorder, surface melted layer 2. Bulk/surface diffusion Based on activation energy values (Arrhenius law) Growth of MWCNTs Detection of dissolved carbon - growth on diamonds 3. Carbides Based on ex-situ or in-situ analyses of TEM, SEM, X-Ray Confidential 2009 Honda Research Institute USA, Inc. 6

Established Synthesis methods High temperature Low temperature Arc discharge and laser ablation CCVD and derivatives What is a distinguish feature? Temperature! High or low, what is a criteria? Confidential 2009 Honda Research Institute USA, Inc. 7

Multiple roles of T related to "Key Questions" Liquid/solid = ƒ (T) Pressure Solid Liquid Metal Vapor Bulk and surface diffusion = E A (T) Temperature Stable, metastable, no carbides = E(T) Hidden common parameter - Carbon Hidden variable parameter - Catalyst composition - A Confidential 2009 Honda Research Institute USA, Inc. 8

Role of carbides Eutectic point A x B 1-x E T T α+β Isothermal line time A B Example of phase diagram infinite solubility in the liquid state and absence of solubility in the solid state. Insets shows typical cooling curve. Confidential 2009 Honda Research Institute USA, Inc. 9

Role of carbides T L α β α + β Solvus boundaries A Eutectic composition B Typical binary eutectic phase diagram that shows partial solid solubility. Confidential 2009 Honda Research Institute USA, 10 Inc.

Role of carbides Binary phase diagram of iron-iron carbide system. L CCVD T γ γ+fe 3 C S T α α+fe 3 C Fe Depends on temperature and composition Confidential C Arc discharge Laser ablation 2009 Honda Research Institute USA, Inc.

Key Questions F A =ƒ A (T,C) Confidential 2009 Honda Research Institute USA, 12 Inc.

Iron-carbon binary phase diagram Solid + Liquid states growth Solid state growth on Fe+Fe 3 C L T γ γ+fe 3 C S Solid state growth on Fe and Fe 3 C α α+fe 3 C T Fe PRL 37, 1433 91976) Confidential 2009 Honda Research Institute USA, 13 Inc. C D Fe ~10-8 cm 2 /s D Fe3C ~10-15 cm 2 /s

F A = ƒ A (T,C) Kinetics: Heating/cooling rates Carbon atoms dissolution/segregation rates F A = ƒ A [T(t),C(T,t)] Confidential 2009 Honda Research Institute USA, 14 Inc.

Assumption : The binary phase diagrams of nanoscale carbon-metal systems are same as for bulk?! Phys. Rev. Lett. 100, 195502 (2008) Phys. Rev. B 75, 205426 (2007) Confidential 2009 Honda Research Institute USA, 15 Inc.

Towards chiral-selective synthesis What potential control parameters do we have currently? 1.Catalyst diameter-on some level controls the diameter of tubes 2.Catalyst structure - may correlate with the tube structure How to exploit these features of catalyst? Ensure that catalyst is in solid state Confidential 2009 Honda Research Institute USA, 16 Inc.

Selective synthesis S. M. Bachilo,, D. Resasco JACS 125 (2003) CVD Growth of SWCNTs with narrow chirality distribution Li et al., Nano Lett. 4, 317 (2004) Preferential growth by a plasma enhanced CVD method ~90 % semiconducting tubes Qu, et al., Nano Lett. 8, 2682 (2008) Fast heating combined with plasma enhanced CVD ~ 96% semiconducting tubes Origin of selectivity is not known W. H. Chiang, R. M. Sankaran Nature Mat., 8, 882, 2009 Exploiting atmospheric-pressure microplasma technique Conclusion: Epitaxial relationship between SWCNTs chirality and the catalyst structure Confidential 2009 Honda Research Institute USA, 17 Inc.

Proposed models for selectivity 18 S. Reich, L. Li, J. Robertson Chem. Phys. Lett., 421, 469, (2006) Control the chirality of carbon nanotubes by epitaxial growth Lattice -matched caps and tubes are more stable O. Yazyev, A. Pasquaerello Phys. Rev. Lett, September 2008 Binding of the CNT through the armchair edges is favorable, but stability varies among the metals

Our results By varying the noble gas ambient He and Ar during Fe catalyst conditioning in the presence of H 2 and H 2 O species, we altered fraction of tubes with metallic conductivity from 1/3 up to a max of 90%. Science 326, 116 (2009) Confidential 2009 Honda Research Institute USA, 19 Inc.

20 CCVD Synthesis of SWCNT thin films CH 4, Ar/He, H 2, H 2 O Water bubbler Dew point probe (1ppb v level) Si/SiO 2 (~300 nm) substrate Typical conditions: Vacuum level: ~10-9 atm Catalyst precursor - Fe(NO 3 ) 3 9H 2 O in IPA with ratio 0.02-20mg Catalyst conditioning ambient: Ar/H 2 or He/H 2 at T= 500 860 o C ~3.5 mtorr of H 2 O Carbon source: CH 4, synthesis temperature T= 830-860 o C All gases 99.9999% or 99.999% of purity Synthesis duration 1-5min.

Variation of catalyst ambient and annealing time He/H 2 O 200nm 200nm Ar/H 2 O 200nm R= I(met.)/I(sem.)= 0.34 20.2 100 Metallic% = ηref 1+ η Sample N N s m Krupke et al., Science 301, 344, (2003) Confidential 2009 Honda Research Institute USA, 21 Inc.

22 Preparation of samples for chirality assignment based on individual SWCNTs Raman (632nm)

(a) (b) E Laser (c) Fig. 1 (a) Optical transition energy E ii (ev) vs. radial breathing mode frequency (ω RBM ) for metallic (M), type I (S I) and type II (S II) semiconducting SWNTs based on ref [PRB 2004]. Crosses (x) are experimental data. (b) Small version of the Kataura plot around the laser excitation (E Laser =1.96eV) (c) Raman spectra of our typical (S#1, 18% metal) and highest metallic tube enriched (S#8, 91% metal) SWNTs in the low frequency range. 23

24 Combined electrical characterization (FET) & Raman analysis (λ=632.8 nm) Ar ambient: 32 devices: 24% met. (18% based on Raman) He ambient: 72 devices: 57% met. (50% based on Raman) 1µm R 710KΩ R 47KΩ

Results of Electrical Characterizations Under Ar: (H 2 O/ H 2 )=9:1 ambient ~20% metallic & ~80% semiconducting 2-unsure Under He: (H 2 O/H 2 )=9:1 ambient ~60% metallic & ~40% semiconducting 2-unsure Under He: (H 2 O/H 2 )=8:2 ambient ~ 85% metallic & 15% semiconducting 3-unsure Science, 326, p116 (2009) 25

Quantifying the Semiconducting Fraction in SWCNTs Samples through comapartive AF and photoluminescence 26 Nano Letters 9, 3203 (2009)

Determined chiralities (15, 0); (14,2); (13,4); (12,6); (11,8); (10,10) (9,9); (13,7); (14,5); (15,3) 27

Origin of preferential growth? 28

29 In situ TEM studies Pressure of He, Ar - 550 mtorr, H 2 O ~3.5mTorr at 500 o C for 1h All Fe particles preliminarily have been reduced under H 2 for 1 h at T= 500 o C Fe catalyst coarsening under different ambient He/H 2 O 200nm Ar/H 2 O 200nm 200nm

Catalyst morphology dynamic reconstruction under different ambient: In situ ETEM studies Reconstruction of Fe nanocatalyst under He/H 2 O and Ar/H 2 O ambient (0.5 Torr) at 550C Confidential 2009 Honda Research Institute USA, 30 Inc.

Morphology reconstruction of Fe nanocluster dependence on ambient gases (He/H 2 O -- Ar/H 2 O) 31

32 In -situ TEM under Ar/H 2 O and He/H 2 O Under He/H 2 O ambient Fe catalyst is more faceted and (111) facet is stable

Reversible shape changes of Cu nanocrystal on ZnO substrate Under H 2 at 1.5 mbar Under H 2 /H 2 O (3:1) at 1.5 mbar (total pressure) Under H 2 at 1.5 mbar Presence of H 2 O molecules on cluster surfaces causes its reconstruction P.L. Hansen et al., Science 295, 2053 (2002) Confidential 2009 Honda Research Institute USA, 33 Inc.

Morphology reconstruction of nanocatalyst under adgas (Wulff Construction) FCC particle γ 111 = 1.97 J/m 2 γ 100 = 2.2 J/m 2 γ 110 = 2.1 J/m 2 (111) (100) (110) γ 111 = 1.5 J/m 2 γ 100 = 2.2 J/m 2 γ 110 = 2.1 J/m 2 γ 111 = 1.97 J/m 2 γ 100 = 1.5 J/m 2 γ 110 = 2.1 J/m 2 γ 111 = 1.97 J/m 2 γ 100 = 2.2 J/m 2 γ 110 = 1.7 J/m 2 IC-2/55 lecture -6 21-10-2004 34 34

What is a mechanism of selectivity? Is there epitaxial relationship between metal catalyst structure and grown nanotube chirality? 35

Experimental Clues 36 Co catalyst H. Zhu et al., J. Cryst. Growth. 310, 5473 (2008) The nanotube chirality could be associated with the angle of the step edge on (111) plane of the catalyst with respect to the growth direction of CNT

(a) (-2 1 1) (b) Step edge (0 1-1) (1 1 1) C h α α Step edge Carbon atom Iron surface atom (a) Structural correlation between the unrolled honeycomb lattice of a nanotube and the underlying FCC Fe (1 1 1) surface, and (b) schematic diagram illustrates how nanotube chirality forms at the step edge. C h represents the nanotube chiral vector as determined by the step edge, which is directly related to the chiral angle α and tube diameter d (d=c h /2π).

(n, m) (Diameter, Chiral angle) The Best matches for each SWCNT structures with Low-indexes facets of Fe catalyst at 860 C Fe (1 1 1) (Diameter, Chiral angle) D/D, θ/θ Fe (1 0 0) (Diameter, Chiral angle) D/D, θ/θ Fe (1 1 0) (Diameter, Chiral angle) D/D, θ/θ (15, 0) (1.182nm, 0 ) (1.173, 0 ) D/D=-0.761%, θ/θ=0% (1.198, 0 ) D/D=1.354%, θ/θ=0% (1.173, 0 ) D/D=-0.761%, θ/θ=0% (14, 2) (1.190nm, 6.587 ) (1.113, 5.818 ) D/D=-6.471%, θ/θ=- 11.675% (1.394, 7.595 ) D/D=17.143%, θ/θ=15.303% (1.246, 6.371 ) D/D=4.706%, θ/θ=-3.279% (13, 4) (1.213nm, 13.004 ) (1.067, 12.218 ) D/D=-12.036%, θ/θ=- 6.044% (1.229, 12.995 ) D/D=1.319%, θ/θ=-0.069% (1.205, 13.263 ) D/D=-0.660%, θ/θ=1.992% (12, 6) (1.251nm, 19.107 ) (1.257, 21.054 ) D/D=0.480%, θ/θ=10.190% (1.370, 19.654 ) D/D=9.512%, θ/θ=2.863% (1.306, 18.519 ) D/D=4.396%, θ/θ=-3.077% (11, 8) (1.302nm, 24.791 ) (1.361, 24.507 ) D/D=4.531%, θ/θ=-1.146% (1.319, 24.775 ) D/D=1.306%, θ/θ=-0.065% (1.297, 25.240 ) D/D=-0.384%, θ/θ=1.811% (10, 10) (1.365nm, 30 ) (1.354, 30.003 ) D/D=-0.806%, θ/θ=0.01% (1.407, 31.608 ) D/D=3.077%, θ/θ=5.360% (1.418, 29.173 ) D/D=3.883%, θ/θ=-2.757%

Summary There is definite correlation between catalyst facet structures and grown SWCNT chiralities So, problem of selective growth of SWCNTs became a problem of our capability to make nanocatalysts with preferable facets How to solve this problem at elevated temperatures? Confidential 2009 Honda Research Institute USA, 40 Inc.

Preferential growth of specific facets by using proper adgas along with hydrocarbon source (e.g. CO/CH 4, CO 2 /CH 4, H 2 O/CH 4, CH 4 /C 2 H 4, ) (100) γ 111 = 1.97 J/m 2 γ 100 = 2.2 J/m 2 γ 110 = 2.1 J/m 2 (111) (110) γ 111 = 1.5 J/m 2 γ 100 = 2.2 J/m 2 γ 110 = 2.1 J/m 2 γ 111 = 1.97 J/m 2 γ 100 = 1.5 J/m 2 γ 110 = 2.1 J/m 2 Confidential γ 111 = 1.97 J/m 2 γ 100 = 2.2 J/m 2 γ 110 = 1.7 J/m 2 41 2009 Honda Research Institute USA, Inc.

Substrate effect FCC particle with (100) facet up (100) γ 111 = 1.97 J/m 2 γ 100 = 2.2 J/m 2 γ 110 = 2.1 J/m 2 (no interaction) (110) (111) A weak interaction Some interaction Strong interaction IC-2/55 lecture -6 21-10-2004 Confidential 2009 Honda Research Institute USA, 42 Inc.

Adsorption and support H. Graoui et al., Surface Science 417, 350 (1998) Along (110) axis) Pd particle on MgO annealed in UHV (T=550 o C) Pd particle on MgO annealed in O 2 (10-3 Torr at 550 o C) Light drawings correspond to unsupported particles. Confidential 2009 Honda Research Institute USA, 43 Inc.

Conclusion 1. Catalyst particles with narrow diameter distribution 2. Low temperature synthesis (by proper choice of catalyst and carbon source) that ensure solid state of catalyst. 3. Possible low concentration of dissolved C - ensure solid state 4. New control parameter: Formation of dominant facet with desirable structure (before hydrocarbon introduction). How? - one way is by adsorption induced reconstruction of catalyst morphology or substrate induced reconstruction. Confidential 2009 Honda Research Institute USA, 44 Inc.

Thank you! HRI USA seeks qualified candidate for research position to begin immediately. The position is open for a two years appointment, with possible extension at company discretion. Areas of interest include synthesis and processing of carbon nanostructures and characterizations. 45

Ni reshaping upon C adsorption: first-principles (210) (111) (110) (320) (210) (111) (100) (100) Nano Lett. 2008 Homma and coauthors Yakobson, Harutyunyan unpublished

Diffusion path - surface, sublayer, bulk PHYSICAL REVIEW B 71, 045402 (2005) Minimum energy path of C diffusion into Fe(110) and the structures for the initial, transition, and final states. Fe atoms are in gray and C in white. Minimum energy path of C diffusion into Fe(100) and several structures along the path. Fe atoms are in gray and C in white. Depends on synthesis temperature Confidential 2009 Honda Research Institute USA, 47 Inc.

Liquid or solid Pressure-temperature phase diagram of pure metal Peculiarities for nano Gibbs-Thompson effect 1500 T (bulk) Liquid Pressure Solid Metal Vapor 1000 Temperature 500 1 10 100 Particle radius (nm) Depends on synthesis temperature Confidential 2009 Honda Research Institute USA, 48 Inc.

Search for right conditioning adgas Pure inert, -515 ε = 0.0001 ev Impurity, ε = 0.2 ev Pure inert, ε = 0.0001 ev -520 T = 800 K P = 1 atm 147 Fe atoms Energy/ev Initial structure -525-530 -535 0 2 4 6 8 Time/ns Long MD demonstrates reversible change in cluster state/shape! Yakobson, Harutyunyan (unpublished) Time/ns Confidential 2009 Honda Research Institute USA, 49 Inc.

Important information Ni in carburizing atmosphere Pure Ni, T=1200 C Ni exposed to C J.-S. Hong et al., Phil. Mag. 89, 2989 (2009) Confidential 2009 Honda Research Institute USA, 50 Inc.

Possible Structures with Close Energies of Icosahedrons for 14-104 atoms J.P. K. Doye et al., J. Chem.116 (2002) 51 Confidential 2009 Honda Research Institute USA, 51 Inc.

Modeling of epitaxial relationship Carbon Nanotube In-situ observations of CNT nucleation Correlating the epitaxial relationships

53 Requirement: Nanobeam Diffraction From Jian-Min Zuo at UIUC; Science, 300, 1419, 2003 Nanotube is illuminated with parallel coherent electrons Example image of a SWNT illuminated by a coherent nanoprobe Diffraction pattern from a doublewalled nanotube. The layer lines spacing and spot spacing with in the lines yields indices n,m

54 TEM measurements of as grown SWCNTs Catalyst Nanotube

55 Raman studies S#8 Si S#1 The Raman spectra of the samples S#1 and S#8 for λ=532nm laser excitation wavelength.