Sp2 Carbon Nanomaterials

Graphene Analogues

Dr. Abraham Cano

SNI I, CONACYT researcher at
CIMAV Campus Monterrey
Background
Education
2014 2014 Postdoc, Penn State University, 2D Center for Advanced Materials - USA
2010 2012 Postdoc, Departamento de Fsica, Universidade Federal de Minas Gerais, Belo
Horizonte, Brasil
2007 2010 D. Sc., Nanomaterials, Instituto Potosino de Investigacin Cientfica y Tecnolgica
(IPICYT), San Luis Potos
2003 2006 M. Sc., Electrochemistry UASLP, Mxico
1999 2002 B. Sc., Chemistry, Facultad de Ciencias Qumicas, Universidad Autnoma de San Luis
Potos (UASLP), Mxico

Interests
Chemistry of carbon nanomaterials
Electronically conducting polymers, industrial polymers
Applications of Raman spectroscopy
Artificial muscles, fuel cells, photovoltaic cells, FETs, water purification, metal recovery
Non-academic: family, mountain biking, photo, collecting minerals, vintage computers, Japan

2
Outline
1. There and back again

2. Polymer-based carbon nanocomposites & Carbon Nanoribbons

3. Modification of AFM tips & Raman Spectroscopy

4. Low-pressure CVD synthesis of hexagonal boron nitride

5. New trends in Conducting Polymers and Carbon Nanomaterials

3
There and Back Again

(4) 550 km
Apodaca
Ctedras
CONACYT

(3) 3300 km State College, PA

Posdoc CONACYT
(2) 8000 km, Belo Horizonte, MG
Posdoc CNPq CAPES
(1) 180 km
UASLP & IPICYT, CONACYT

4
Raman
Spectro Electro
scopy Chemistry Rare
Coupling reactions Earth
Archaeology Mining
Nanostructured
Carbon

Condensation
electronically
Nano- conducting
materials/ polymers:
Composites PAni, PPY,
PEDOT

Non-
conventional
Organic Suzuki,
Polymers:
Chemistry Friedel-
polyphos-
Crafts
Energy phazenes
Water

Flexible electronics, thermoelectrics

Rechargeable batteries, photovoltaic cells,
electrochromic devices, fuel cells
5

1. Polymeric Composites
from polyanilines
Electrochimica Acta 52 (2007) 52945303
2. Exfoliated Carbon Nanotubes (ExMWNTs)
and 2D boron nitride
Nano Lett., 2009, 9 (4), pp 15271533
DOI: 10.1021/nl803585s
3. Modified AFM/SNOM tips
Scientific Reports | 5:10408 | DOI: 10.1038/srep10408
POLYMER-BASED CARBON
NANOCOMPOSITES &
Carbon Nanoribbons
IPICYT, San Luis Potos, Mxico
 Carbon Nanotubes & Polymer Composites

Main problem: Poor interaction between CNTs and the polymer matrix, with lack
of effective stress transfer and pull-out effects, along with bundling and poor
dispersion of CNTs.

[2]

Telescopic effect

[1] [3]
Pull-out Dispersion
1 D. Qian et al. Appl. Phys Lett. 76 (2000) 2868-2870 3 Z. Yao et al. JACS. 125 (2003) 16015-
2 Z. Xia, W. A. Curtin. Phys. Rev. B 69 (2004) 233408 16024
8
 Carbon Nanotubes & Polymer Composites
What is a composite?
Composites from carbon nanotubes and polymers
Applications: reinforcing materials, actuators, EMI shielding, sensors, paints,
catalysts, electronic devices.
Production methods: mixing from powders, melts, solutions, electrostatic self-
assembly, functionalization, etc.

Carbon nanotubes Polymers

Unique physical and electronic Versatility: compositions, uses,
properties: high aspect-ratio. properties
Young's modulus (~1.4 Tpa, vs steel
Lightweight
200 Gpa), current density 109 Acm-2.
Tensile strength MWNTs: 63 GPa Easy processing/mfg
Low loads can improve properties of Youngs modulus ~MPa
composites (0.1 1 wt% CNTs)
K. Balasubramanian, M. Burghard. Small 1 (2005) 180-192 Y. Liu, S. Kumar. Appl. Mater. & Interfaces 6 (2014) 6069-6087
M-F. Yu et al. Science 287 (2000) 637-640 R. Khare, S. Bose. JMMCE 4 (2005) 31-46
9
 Why functionalization?

Improvement of
dispersion
Strong interaction
with polymer
matrix
Applications

[1,2]

1
P. M. Ajayan, J. M. Tour. Nature 447 (2007) 1066-1068
2
S. Banerjee et al. Adv. Mater. 17 (2005) 17-29
10
 Conjugated Polymers
Polyacetylene

Synthesis: chemical/electrochemical oxidation

Properties: conjugated bonds, stability, electrochromism, electrocatalysis,
conductivity modulation by doping
Disadvantages: brittleness, redox activity may decay upon cycling

H2N
H H H H

N N N N

Cl- -
Cl
n
Polyaniline (PAni)
Aniline PROTONATED EMERALDINE SALT - HIGHLY CONDUCTING

1 A. G. Mac Diarmid. Angew. Chem. Int. Ed. 40 (2001) 2581-2590

2
J. Liu, et al. Langmuir 21 (2005) 5596-5599
3 T. V. Vernitskaya, O. N. Efimov. Russ. Chem. Rev. 66 (1997) 443-457

11
Nanotubes salts Reductive alkylation

Li NH , liquid Li+ + e-(solv)

3

- Li +
+ Li+ + e-(solv)

Carbon nanotube
salt (nucleophile)
F. Liang et al. Chem. Mater. 18 (2006) 4764-4767
J. Chattopadhyay et al. J. Phys. Chem. C 111 (2007) 17928-17932
A. Pnicaud et al. J. Am. Chem. Soc. 127 (2005) 8-9 12
1 J. Chattopadhyay et al. Chem. Mater. 18 (2006) 5864-5868
2 J. Stephenson et al. Chem. Mater. 18 (2006) 4658-4661
3 F. Liang et al. J. Am. Chem. Soc. 127 (2005) 13941-13948
4 J. Chattopadhyay et al. Org. Lett. 7 (2005) 4067-4069
5 A. Mukherjee et al. Chem. Mater. 20 (2008) 7339-7343
6 J. Chattopadhyay. JPC C 111 (2007) 17928-17932
7 F. Liang et al. Chem. Mater. 18 (2006) 4764-4767
13
8 C. G. Espinosa-Gonzlez et al. J. Mater. Res. 28 (2013) 1087-1096
Nanotubes salts - Experimental setup

(1) NH3
(2) Li
(3) Nanotubes
(4) Monomer

14
Nanotubes salts - Experimental setup

Intercalated MWNTs-polymer
composite

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 MWNTs-PAni composites

SEM images: (A) MWNTs; (BF) MWNTs-SPAni nanocomposites. MWNTs:monomer ratio (w/w)

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MWNTs-PAni composites

MWNTs-PAni nanocomposites from different MWNTs:aniline ratios (wt./wt.)

17
Exfoliation of MWNTs in composites

Unzipped MWNTs (Ex-MWNTs)

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Functionalization

Raman Spectroscopy FTIR

= 514
nm

D G

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20
Modification of AFM tips &
Raman Spectroscopy
Universidade Federal de Minas Gerais,
Belo Horizonte, MG, Brasil
Raman spectroscopy/AFM
Scan head

XY STAGE
60x
Oil Objective

NA 1.4
iDUS
SAMPLE+561 CCD
f1 f2 Maxi-line Shutter
Expansor Collimator
Filter
lens lens 561.4 nm
SAMPLE
f1 = 6 cm Flip
mirror f4 = 30 cm
f2 = 25 cm f3 = 30 cm

XY Andor
Collimator Spectro
stage
lens
meter USB cable
to workstation

Avalanche
Photodiode
on xyz
stage
BNC1 to RHK
22
 Importance of TERS
TERS of a SWNT (a);
far-field Raman
spectrum of the same
tube (b); TERS of
amorphous carbon (c);
topography image and
AFM profile of isolated
SWNTs

P. Verna, Y. Inouye, S. Kawata. Tip-enhanced near-field Raman scattering: fundamentals and new aspects for
molecular nanoanalyis/identification in Surface-enhanced Raman Scattering Physics and Applications,
Topics Appl. Phys. 103, 241-260 (2006) Springer-Verlag Berlin Heidelberg 2006
23
Modification of Au tips with CNCs

Quanta FIB 3D GIS Pt source

Au tip

Si waffer
bearing
cone/disks
sample
Cyanoacrylic glue
(Loctite)/Silver ink
coating

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 Carbon nanocones - MPCVD

= 19.2 = 38.9 = 60.0

= 84.6 = 112.9

Arc-plasma carbon generator, heavy oil, 2-3 bar, 50-150 kg/h, 2000C
A. Krishnan et al. Nature 388 (1997) 451-454 Images a-f, scale: 200 nm 25
Modification of Au tips with CNCs

Encapsulation of a gold nanotip with a carbon nanocone. (A) cone on Si substrate. (B-D)
Approaching and soldering on a gold tip. (E, F) The Au nanotip on a larger scale. In (F) the
nanocone is no longer seen.

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First AFM of SWNTs bundles

Atomic force microscopy (AFM) with

the gold/carbon nanotip. (A) SEM image
of an Au/cone tip glued on a tuning fork for
SPM measurements. (B) AFM topography
image of single wall carbon nanotubes on a
glass cover slip. (C) Height profile at the blue
line shown in (B).

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Raman spectroscopy of carbon nanocones

Raman spectra from

carbon nanocones sitting on
silicon (A); placed on a gold
tip (B); (C) from the N-TEC
sample consisting of 70 wt%
carbon nanodisks, 20% wt
MWCNCs, and 10% wt
impurities; (D) from graphite
for comparison.
= 561.4 nm

28
 Raman spectroscopy of carbon nanocones
3000
1602
Set point 0.7
2500 E-PLL 1.4/1.3
Knob 5.35

-C=C-
2000
Raman intensity

stretching
Out-of-plane vibrations?
1500 Au/cone tip
carbon-hydrogen ?
in contact with glass
1557
1000 or -C-C
C-C sp3
826 1310
1400
500 1141
C-C sp3

0
250 500 750 1000 1250 1500 1750 2000 2250 2500 2750
29
Raman shift (cm-1)
MWCNCs Raman spectra
2.5 m2 Raman spectra of a multiwalled carbon microcone
G G* G' 2G''

23

20

12

Raman intensity (a.u.)

10

8
5

1000 1500 2000 2500 3000 3500

Raman shift (cm-1)

30
Raman shifts for MWCNCs

* Higher shifts due to LO modes 31

 Multiwalled carbon microdisks
5 m2, 002
Forward scan
Backward scan

Low laser power at source < 5mW

128x128, 20 ms, 40 m/s

32
ND 1+0.1
Multiwalled carbon microdisks
Representative spectra
D G G* G' 2G''

35

Raman intensity (a.u.)

31

16

10

05
03

500 1000 1500 2000 2500 3000 3500

-1
Raman shift (cm )
33
Multiwalled carbon microdisks

34
Low pressure CVDsynthesis
of hexagonal boron nitride
Penn State University, State College, PA, USA
 Properties of hBN
0.1446 nm Covalent
bonds

VDW
interactions

0.6661 nm

Electronic Gap: 6 eV 0.2504 nm

A. K. Geim, I. K. Griegoreva. Nature 499 (2013) 419-425

Pakdel, A. et al. Materials Today 15 (2012) 256-265
Nagashima, A. et al. Phys. Rev. Lett. 75 (1995) 3918-3921
36
Schematics LPCVD system for hBN

37
CVD: h-BN
Ceramic boat (inverted)
(1)
upside

downside

Copper foil
Alfa Aesar 99.998% (2) (3)
electrochemically
polished

Center of furnace
(hottest zone)
38
CVD hBN/Cu morphologies

150 mW, 488 nm

Coating
(Wrinkles)

3x105
D

Coating on different
copper grains
CPS

O 1s
N 1s
B 1s
C 1s

0
700 600 500 400 300 200 100 0
Binding Energy (eV) 39
CVD hBN/Cu morphologies

A B

40
 CVD hBN/Cu morphologies

A B

Ribbons

2D nanostructure formation limited by reactant diffusion, partial vapor pressure,

density of nucleation sites, G energy (substrate). Tube formation could be
induced by type of substrate (Si<111>).
41
CVD hBN/Si morphologies

A B

TEM images
by Kazunori Fujisawa
at Penn State

42
New trends in
Conducting polymers and
carbon nanomaterials
CIMAV Unidad Monterrey, Apodaca
 Electrochemical Station
PARSTAT 4000+ & Seiko EQCM

44
Electrochemical quartz crystal microbalance

Counter Reference
electrode Potentiostat Computer

Work

Oscillator Freq. Meter

Detection order : nanograms

f = - Cfm f frequency change due to mass addition per area
m added mass
Cf sensitivity constant = 1.0707 ng for each Hertz
45
 EQCM Example. Sulfonated Polyaniline
+E
dE
Upper m= =
dt
limit

Origin
t (s)
0.5 M HCl 0.5 M HCS
M /ng I /A M /ng
I /A I
1000 700 900 800
I
800 600 700
700
II 500 600
600
400 500 II 500
400
300 300 400
200 300
200
0 100 200
100
-200 0 -100 100
-400 -100 0
II' -300
-600 -200 I' -100
I' II'
-800 -300 -500 -200
-300 -150 0 150 300 450 600 750 900 -400 -200 0 200 400 600 800 1000
E /mV E/mV vs Ag|AgCl|NaCl 3M E /mV
E/mV vs Ag|AgCl|NaCl 3M

Anions are little or no involved at all (similar CVs)

V = 50 mVs-1. A.G. = 0.1963 cm2
DM reversible
Anion independent 46
Summary of research lines 2017

1. Chemical/electrochemical synthesis of hierarchical nanostructures

based on carbon nanomaterials and intrinsically electroactive
conducting polymers. Graphene oxide/conducting polymer coatings
for thermoelectric devices (2 year project).

2. Novel applications: flexible organoelectronics, selective heavy ion

recovery, rechargeable batteries, thermoelectric devices.

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