CARBON: THE

NEXT SILICON?

CARBON: THE
NEXT SILICON?
Book 1 Fundamentals

MARC J. MADOU,
VICTOR H. PEREZ-GONZALEZ, AND
BIDHAN PRAMANICK

MOMENTUM PRESS, LLC, NEW YORK

Carbon: The Next Silicon?: Book 1 Fundamentals

Copyright Momentum Press, LLC, 2016.
All rights reserved. No part of this publication may be reproduced, stored
in a retrieval system, or transmitted in any form or by any means
electronic, mechanical, photocopy, recording, or any otherexcept for
brief quotations, not to exceed 400 words, without the prior permission
of the publisher.
First published by Momentum Press, LLC
222 East 46th Street, New York, NY 10017
www.momentumpress.net
ISBN-13: 978-1-60650-723-0 (print)
ISBN-13: 978-1-60650-724-7 (e-book)
Momentum Press Micro Electronic Mechanical Devices Collection
Cover and interior design by Exeter Premedia Services Private Ltd.,
Chennai, India
10 9 8 7 6 5 4 3 2 1
Printed in the United States of America

Abstract
This book provides an introduction to the state-of-the art in C-MEMS/
C-NEMS with an emphasis on lithographically patterned photo-
polymers, carbonized in an inert atmosphere. It is obvious that we can
expand our perspective considerably by learning from the traditional
carbon manufacturing community where researchers deal with a much
wider variety of carbon feed stocks such as coal, coconut shell, wood,
agricultural wastes and industrial wastes to make all types of useful
carbons. In addition to their expertise in choosing the right catalysts to end
up with the desired carbon nanomaterials from any of these feedstocks,
these carbon scientists works with dry and wet pyrolysis processes. Wet
pyrolysis process is also known as hydrothermal carbonization, a process
new to the C-MEMS/C-NEMS community.
The new concepts are introduced by discussing carbon nanomaterials
synthesis aided with catalysts and chemistry and detailing the micro
structure of the resulting nanocarbons.
The performance of carbon materials is determined to a large extent
by their surface and interfacial properties. The methods to tailor the
surface activity of different carbon structures, how to characterize them
and the potential applications derived from the modifications achieved are
also discussed.

KEYWORDS
Carbon allotropes catalysis electrochemistry surface modification MEMS
and NEMS super capacitors energy storage devices CNTs glassy carbon
NMR electrospinning redox amplification AC/DC electrokinetics pyrolysis
electroanalysis

Contents
List of Figures
List of Tables
About the Contributors
Foreword

ix
xxi
xxiii
xxv

Quick Overview of Book 1-Fundamentals

xxix

Acknowledgments

xxxi

1 C-MEMS and C-NEMS Introduction

1.1 Purpose of Chapter 1

1
1.2 C-MEMS and C-NEMS: What Is It? 
2
1.3In C-MEMS and C-NEMS the Manufacturing Method
Determines the Carbon Microstructure
10
1.4Current and Projected Applications of C-MEMS
and C-NEMS
18
References27
2 The Beautiful World of Carbon

39

2.1Introduction
39
2.2 Carbon Materials
39
2.3 Applications of Carbon Materials
56
2.4Challenges and Opportunities in Designing
Nanostructured Carbon
65
References67
3 Synthesis of Nanocarbons and Tuning of Their Properties
3.1Introduction
3.2 Carbon Materials

77
77
78

viii Contents

3.3 Functionalization of Nanocarbons

96
3.4Conclusions
99
References100
4 Historical Overview of Carbon Nanowire
Fabrication Methods

109

4.1Objective
109
4.2CNWs Compared with CNTs
110
4.3Background of Carbon Nanowire Fabrication Processes
111
4.4Conclusions
144
References145
5 Carbon Nanowire Fabrication: C-MEMS

151

5.1Objective
151
5.2Fabrication of Supporting Structures for CNWs
152
5.3Electrospinning
155
5.4 Electro-Mechanical Spinning
163
5.5Conclusions
167
References168
6 Organic Xerogel-Based C-MEMS

171

6.1Introduction to Organic and Carbon Xerogel

171
6.2 Importance of Carbon Xerogels
174
6.3Synthesis of Various Morphologies in Carbon Xerogels
175
6.4Fabrication of Three-Dimensional C-MEMS Structures
Using RF-Derived Carbon Xerogel
185
6.5Electrochemical Performance of RF-Derived
Carbon Xerogels
188
6.6Summary
192
References194
7 Surface Modification of Carbon Materials

199

7.1 Purpose of Chapter 7

199
7.2Surface Modification of Carbon Materials:
An Introduction
200
7.3 Plasma Modification
201
7.4Surface Modification of Carbonaceous Materials
206
7.5 Concluding Remarks
219
References220
Index

231

List of Figures
Figure 1.1.An illustration of one type of C-MEMS:
photolithographic patterning of a polymer precursor
(SU-8 photoresist) and pyrolysis (see text for
details) [9].
Figure 1.2.SEM images of (a) and (b) SU-8 post arrays before
pyrolysis and (c) and (d) carbon post arrays after
pyrolysis (left panel) [9]. SEM images of three-level
C-MEMS: a three-level C-MEMS structure with two
levels in good alignment but with a third-level out
of alignment (right panel) [9, 21].
Figure 1.3.Typical SEM images of suspended (a) carbon plates
(carbon microtable), (b) carbon bridge, (c) carbon
networks, (d) carbon ribbons, (e) carbon fibers (wash
cloth lines), and (f) self-assembled C-MEMS (also
carbon flowers) [21].
Figure 1.4.Typical SEM images of (a) a photoresist post
obtained from modified SU-8 before pyrolysis, (b) a
carbon post after pyrolysis, (c) a carbon post surface
under high magnification, (d) a broken piece of a carbon
post with embedded carbon fibers, and (e) an embedded
cavity under high magnification [24, 25].
Figure 1.5.Typical SEM images of C-MEMS posts fabricated
with a final SU-8 carbonization temperature of 900C.
Temperature ramp rate of 15C/min (left) to 90C/min
(right) [29].
Figure 1.6.SEM of C-MEMS surface after plasma
treatment [29].
Figure 1.7.Schematic of the SU-8 photoresist pyrolysis
process [36].

7
8
9

x List of Figures

Figure 1.8.(a) Young modulus versus pyrolysis temperature for

SU8 carbon intermediate materials [36], (b) electrical
properties of polyacrylonitrile (PAN)carbon
intermediates [37].
9
Figure 1.9.Microstructure of glassy carbon proposed by Haris [10],
Jenkins and Kawamura [11], and Jenkins [12].
10
Figure 1.10.(a) Comparison of FFES and NFES and
(b) FFES setup.
11
Figure 1.11.SEM images of arrays of patterned fibrous carbon
structures: (a, b) lines, (c, d) 3D pillars, and (e, f)
connecting squares. Images (b) and (d) are m
agnified
views of images (a) and (c), respectively, and
higher-magnification images of (b) and (d) are
shown as insets. Images (a)(d) are on Si wafer
substrates, and images (e) and (f) are on a plasmatreated SU-8-derived carbon film on a Si wafer [41]. 12
Figure 1.12.FFES with a rotating drum target (left) and
Si substrate with SU-8 contact pads perpendicular
to the nanowire direction (right) [53].
13
Figure 1.13.Single CNW across suspending carbon walls (left).
Schematic of C-MEMS and C-NEMS structure used
to collect nanowires (a dense array is shown here)
(middle). HR-TEM image of electrospun SU-8-derived
CNF: tube-like graphitic CNW with glassy carbon core
and graphite shell (right) [53].
13
Figure 1.14.(a) Model of the molecular chain orientation according
to Ji et al. [54]: (A) thin fiberpolymer chains oriented
throughout the entire fiber; (B) thick fiberpolymer
chain orientation starts at the surface and propagates
into the bulk. Rg is the polymer gyration radius.
(b)HR-TEM images of nanowire graphitic all the way
to the core (top) and tube-like graphitic CNW with
glassy carbon core and graphite shell (bottom) [55].
14
Figure 1.15.FFES (a, c) compared with EMS (b, d). The fibers in
Figure 1.15c and 1.15d, when using the correct ink
formulation, can subsequently be carbonized,
thinning them even further [59].
16
Figure 1.16.Patterned CNWs made by carbonization of nanofiber
array of 70 parallel fibers made by continuous EMS.
The measured average distance between carbon
fibers was 18.6 4.8 m. Inset: Fibers are cut with
a FIB to form cantilever beams [62].
17

List of Figures xi

Figure 1.17.EulerBernoulli beam theory results for CNWs.

At 200 nm, Youngs modulus is already up to 400 GPa
(CNTs are between 270 and 950 GPa [1 TPa]) [62].
17
Figure 1.18.Carbon: the next Si? [9].
18
Figure 1.19.Smart Li-ion battery. Typical two-level carbon-based
MEMS electrodes with carbon contacts underneath. The
inset image shows enlarged SU-8 two-level structure [9]. 20
Figure 1.20.IDEAs consist of a pair of comb-shaped electrodes
one of which works as a generator and the other as a
collector (left panel). S
chematic view of redox cycling of
oxidized (O) and reduced (R) species in an IDEA: (i) plane
electrodes, (ii) 3D electrodes (right panel) [109113].
21
Figure 1.21.(a) Shows the actual 3D carbon IDEA sensor. WE1
and WE2 are contact pads for the generator and the
collector, respectively. C and R are counter and
reference electrodes, r espectively; (b) shows the final
device with p olydimethylsiloxane flow channels. The
reference electrode is coated with Ag or AgCl ink,
and contact pads are coated with silver paste for better
electrical connection. (c and e) SEM images (tilted view
60) under 10,000 magnification of SU-8 IDEA
patterning before pyrolysis; height= 0.6 and 2.1 m,
respectively. (d and f) Carbon IDEA after p yrolysis;
height = 0.22 and 0.59 m, respectively [71, 115].
23
Figure 1.22.We compare the suspended nanowire (left) with a wash
cloth line (right). By derivatizing the CNW surface
with a monolayer of sensor molecules, say proteins or
DNA (the clothes on the wash cloth line), these
nanowires can be turned into nano-immuno or
nano-DNA sensors. The binding of the
complementary protein or DNA strands changes
the impedance of the nanowire.
24
Figure 1.23.(a) SEM images of a 358-nm thick CNW with WO3
deposited on its surface by selected area CVD,
(b) a high-magnification image of the granular surface
of WO3. Inset: schematic of the local CVD process
on a suspended nanowire [36].
25
Figure 1.24.SEM images of a 28.3-m long, 220.5-nm diameter CNW
showing breakage due to overheating at its center. The
entire CNW with thinning taking place approximately halfway is shown in the panel on the left and the central region
of the CNW is illustrated in the panel on the right [36]. 27

xii List of Figures

Figure 2.1.The structure of hexagonal graphite with trigonal

geometry from sp2 hybridization [20].
41
Figure 2.2.Simplified classification of carbon materials based
on the hybridization of carbon atoms.
42
Figure 2.3.Examples of three generation of nanocarbon materials. 43
Figure 2.4.(Super) structure representations of (a) SWCNT and
(b) MWCNT, with TEM images of the actual structure
(c) and (d).
45
Figure 2.5.A sheet of graphene rolled to show formation of
different types of SWCNTs. The space group symmetry
operation, R = (y/t), is also shown, in which y denotes
the angle of rotation around the nanotube axis and t is
the translation in the direction of T as specified by the
symmetry vector R.46
Figure 2.6.The schematic construction of SWCNT from a graphene
sheet. (a) Ch, depicts chiral vector, and a1 and a2,
represent the unit cell vectors of the hexagonal cell. The
chiral angle () is the angle between zigzag axis and
chiral vector (Ch) and can be represented by = tan1
(m3/m + 2n). (b) R
epresentation of the integer values
(n, m), which decide among zigzag, armchair, and
chiral SWCNTs.
47
Figure 2.7.Top views of MWCNTs: (a) cylindrically curved Russian
inset doll model, (b) coaxial polygon, and (c) graphene
sheets scroll (according to Amelinckx et al. [34]). The
figure (d) reports instead a scheme representing the
structure of an encapsulate kink in an MWCNT.
47
Figure 2.8.Family of fullerene carbon materials.
49
Figure 2.9.Fullerene-like soot deriving from a diesel engine.
50
Figure 2.10.(a) Atomic-resolution image of a graphene sheet,
with an indication of the carboncarbon bond length
of about 0.142 nm. (b)Honeycomb lattice structure of
graphene exhibiting a basis with two c arbon atoms, A
and B, per unit cell [43]. (c) Idealized Brillouin zone
(graphene p-band) with a zoom to the K-point, where
the bands cross at the Fermi level forming a Dirac cone. 51
Figure 2.11.Schematic diagram depicting single-layer pristine
graphene with various types of defects, functional
groups and heteroatoms.
52
Figure 2.12.Strategies for covalent functionalization of CNTs
(A: direct sidewall functionalization; B: defect
functionalization).60

List of Figures xiii

Figure 2.13.Scheme of a CNT-based device for gas sensing.

61
Figure 2.14.(a) Schematics of the bottom-up and top-down hybrid
method to fabricate 3D CNT complex structures on a
single wafer. (b) SEM image of silicon pillars with CNT
sheets and CNT beams suspended on them. Scale bar
1 mm. (c) SEM images of suspended CNT cantilevers
on silicon wafer with p re-etched trenches. Scale bar
2 mm. (d) SEM images of 3D CNT cantilevers. Scale
bar 10 mm.62
Figure 3.1.Currently available CNT synthesis methods.
78
Figure 3.2.The three steps involved in the VLS mechanism:
(a)decomposition of the carbon-containing precursor
on the surface of the catalyst particle; (b) diffusion of
carbon atoms through the particle as a solid solution;
and (c) precipitation of carbon at the metalsupport
interface and formation of a nanofiber or a nanotube.
In an alternative mechanism, carbon species diffuse
only on the surface of the catalyst particle (de).
80
Figure 3.3.Top: HRTEM images of FeCo and SBA-15 catalyst, with
HRTEM images of the larger (c) and smaller (d) CNTs
obtained from FeCo nanoparticles located outside and
inside the SBA-15 mesoporous channel, respectively. 82
Figure 3.4.Simplified scheme of the synthesis of aligned CNT
(CNTs carpet) by CCVD with scanning electron
microscopy (SEM) images of the samples obtained.
84
Figure 3.5.Possible structures of carbon nanofilaments, with
HRTEM images on the bottom of the different
nanostructure, in particular of the terminating graphitic
planes on the surface.
85
Figure 3.6.Schematic drawing of the CCVD growth mechanism of
cup-stacked and platelet CNFs with relative HRTEM,
images.87
Figure 3.7.(a) HRTEM and (b) SEM images of commercial
Pyrograf P
roducts PR24.
89
Figure 3.8.Carbon nanofilaments grown on the surface of
carbon fibers.
91
Figure 3.9.Chemical modification of nanotubes through thermal
oxidation, followed by subsequent esterification or
amidization of the carboxyl group.
97
Figure 3.10.Oxygen functionalities created by oxidation treatment
with HNO3 (or other oxidants) in a graphene sheet at
the edges (a) or at defect sites (b).
97

xiv List of Figures

Figure 4.1.(a) Bright-field TEM image of CNWs and SAED pattern

of a single nanowire (inset), and (b) TEM image
of metallic catalysts on the tips of the nanowires [6]. 111
Figure 4.2.(a)(f) PEDAL process flow [10].
113
Figure 4.3. Various nanowire routing of PEDAL process [10].
114
Figure 4.4.(a) Generation of conducting nanowires. (b) C
onducting
AFM measurement of nanowires. (c) Conducting AFM
image of irradiated fullerene thin film. The vertical
bars represent the current flowing through individual
nanowires [11].
115
Figure 4.5.The conductivity versus annealing temperature
graph [13].
117
Figure 4.6.(a) Polycrystalline CVD diamond film substrate with two
500 m CNW structures. (b) A fragment of one of the
500m structures showing individual nanowires [13]. 118
Figure 4.7.Response of the sensor to the droplets of the different
liquids rapidly brought to a distance of 1 cm to the
sensor and then rapidly retracted [13].
118
Figure 4.8.SEM images of CNTs (a) before and (b) after ion beam
irradiation [14].
119
Figure 4.9.(a) TEM image of a single a-CNW deposited on W tip.
(b) HRTEM image showing amorphous nature [15]. 120
Figure 4.10.TEM images. (a) The a-CNW (the lower part) was
controlled to make contact with a Fe filled MWCNT
(the upper part), with the arrow indicating the direction
of the current, (b) Almost all Fe particles had been
introduced into the a-CNW [15].
121
Figure 4.11.(a) TEM images of filamentary structures. Inset, SAED
pattern showing three rings corresponding to 002, 111,
and 200 graphite diffraction reflections. (b) HRTEM
image of selected area of filamentary structure [16].
123
Figure 4.12. Schematic of CNWs fabrication process [17].
124
Figure 4.13. SEM images of CNWs [17].
124
Figure 4.14.Schematic setup of the e xperimental process:
(1) c ooling-regurgitated pipe, (2) DC electric power
supply, (3) graphite e lectrodes, (4) silicon chip
coated with Fe film, and (5) gas diffuser [18].
125
Figure 4.15.EM images of CNTs and CNWs synthesized with
different H2O contents (a) in pure ethanol, (b) in ethanol
with 2percent H2O, (c) in ethanol with 5 percent H2O,
and (d) in ethanol with 8 percent H2O [18].
126

List of Figures xv

Figure 4.16.Schematic growth steps of CNWs, CNTs, or

graphene[18].
Figure 4.17.TEM images of silicon chip surface during the
experiments [18].
Figure 4.18.CNWs synthesized in pure ethanol with the top
capped by a Fe particle. The top right corner image
is the energy dispersive X-ray s pectroscopy image
of the synthesized CNWs [18].
Figure 4.19. Schematic drawing of the experimental settings [19].
Figure 4.20.SEM images of the CNWs grown on the
Si (100) in (a) NH3/C2H2 ambient and (b) N/2C2H2
ambient [19].
Figure 4.21.(a) TEM and (b) HRTEM images of SWCNT
CNWs [20].
Figure 4.22.(a) Experimental setup for corona-discharge-assisted
TCVD. (b) Schematic of the device (cross-sectional
and top view) [21].
Figure 4.23.SEM images of corona-discharge-assisted TCVD
growth of CNW at (a) 500C, (b) 600C, and
(c) 700C [21].
Figure 4.24.First reported C-MEMS structures [22].
Figure 4.25.Fabrication process steps of carbon nanostructures:
(a) SU8 spin coating, (b) patterning by EBL, (c) PR
development, (d) pyrolysis process, and (e) carbon
nanostructure [23].
Figure 4.26.SEM image of suspended CNW on 3D carbon
post [24].
Figure 4.27.SEM images of single suspended nanowire: (a) Su8
derived and (b) PAN derived. (c) IV curve for the
both cases [24].
Figure 4.28.Fabrication steps of a group of nanoelectrode set in a
microchannel [26].
Figure 4.29.SEM images of nanoelectrode set [26].
Figure 4.30.Fabrication steps of a suspended nanowire
structure [27].
Figure 4.31.SEM images of photoresist and suspended nanowire
structure [27].
Figure 4.32.HRTEM images of Su8-derived CNWs: (a) tubelike
graphitic CNW with glassy carbon core and graphite
shell and (b) glassy carbon trapped between graphite
walls in a CNW [29].

127
128

129
129

130
131

132

133
134

135
135

136
137
138
139
139

140

xvi List of Figures

Figure 4.33.(a) FIB cutting for extra CNWs and (b) IV curve
for a single suspended CNW [29].
Figure 4.34.Fabrication process steps [44].
Figure 4.35.SEM images of fabricated results (a) before and
(b) after pyrolysis [44].
Figure 4.36.TEM images of the formation of CNTCNW junction
under strong electric field, (a) capped CNT, (b)
nucleation of the CNW at the tube tip, (c) the growth
of nanowire, and (d) high-resolution image of
the CNW depicts amorphous nature [45].
Figure 5.1.Typical C-MEMS fabrication process steps [8]:
(a) spin-coating photoresist, (b) UV exposure,
(c) developing, and (d) pyrolysis.
Figure 5.2. MEMS structures before and after UV exposure [8].
Figure 5.3. Schematic of traditional electrospinning setup [8].
Figure 5.4. Schematic of the path of the fiber jet.
Figure 5.5.Taylor cone formation and polymer jet discharge
during electrospinning process [24].
Figure 5.6.Model of a rectilinear segment of the electrospinning
jet represented as a viscoelastic d umbbell [8].
Figure 5.7.Photographs of UCI BioMEMS lab electrospinning
setup [8].
Figure 5.8.Schematic of an FFES system with rotating drum and
commercially available electrospinning setup [8].
Figure 5.9. Schematic of EMS setup [8].
Figure 5.10.Photographs of voltage supply, syringe, and grounded
substrate of EMS setup [8].
Figure 5.11.SEM images of suspended nanowires on carbon posts
(a) six carbon post connected to each other by
nanowires, (b) and individual nanowire [8].
Figure 5.12.SEM image of a single suspended CNW between two
carbon electrodes.
Figure 6.1.Schematic illustrating the mechanism of
polymerization of r esorcinol and formaldehyde [10].
Figure 6.2.Schematic showing inverse emulsification of RF sol in
organic phase (cyclohexane) to form RFX particles.
Figure 6.3.Optical micrographs showing the transition to
nonspherical shapes of RF-derived carbon xerogel
microparticles with a change in dilution ratio:
(a) R/W = 0.037; (b) R/W = 0.0037. Other conditions
for both cases are R/C = 25, surfactant
concentration = 1% (v/v), and stirring time = 5 h.

141
142
143

144

154
154
156
157
159
160
162
163
164
165

166
167
172
175

176

List of Figures xvii

Figure 6.4.Field emission scanning electron m

icroscopy (FESEM)
images showing aggregation and coalescence of RFbased carbon microspheres at a span-80 concentration of
1% (v/v) (a) R/C = 10, stirring time = 5 h; (b) R/C = 10,
stirring time = 24 h; (c) R/C = 25, stirring time = 24 h;
(d) R/C = 500, stirring time = 24 h.
177
Figure 6.5. Optical micrographs of the RF-based carbon m
icrospheres
obtained at R/C = 25, 1% (v/v) span-80 concentration
with different stirring times: (a) 2 h; (b) 5 h; (c) 7 h.
178
Figure 6.6.Optical micrographs showing the effect of surfactant
concentration on particle size at R/C = 25, stirring time
of 5 h in low surfactant concentration region
(a) 1% (v/v) span-80; (b) 4% (v/v) span-80.
179
Figure 6.7.FESEM images of carbon bushes and flowers type
fractal-like structures obtained at high surfactant
concentrations: (a) 16 percent span-80, 2 h stirring;
(b) 16 percent span-80, 5 h stirring; (c) 33 percent
span-80, 1 h stirring; (d) 33 percent span-80, 2 h stirring;
(e) high magnification image of (d); (f) 50 percent
span-80, 1 h stirring; (g) 50 percent span-80, 2 h stirring.
Images (a)(g) are obtained using the surfactant from
Loba Chemie at R/C = 25. Images (h) and (j) are
obtained using the surfactant from Sigma Aldrich at
R/C = 10, 2 h stirring with 33 and 50 percent span-80,
respectively. Images (i), (k), and (l) are obtained using the
surfactant from SD Fine Chemicals with other conditions
such as 33 percent span-80, 2 h stirring with R/C = 10
and 25, respectively, for image (i) and (k) and
50percent span-80, 2 h stirring, R/C = 25 for image (l).180
Figure 6.8.Schematic showing the various steps of synthesis of
RF-derived carbon xerogel nanoparticles using
repetitive inverse e mulsification.
181
Figure 6.9.Low- and high-magnification FESEM images of carbon
xerogel nanoparticles network: (ab) sample collected from
sediment after 12 h sedimentation of first cycle; (cd)
sample collected after 12 h sedimentation of second cycle.181
Figure 6.10.(a) Schematic of electrospraying setup; (b) scanning
electron microscope image of carbon nanoparticles;
(c) magnified image of (b).
183
Figure 6.11.(a) X-ray diffraction pattern; (b) Raman spectra;
(c) high-resolution transmission electron microscopy
image of RF-derived carbon xerogel nanoparticles.
184

xviii List of Figures

Figure 6.12.Schematic diagram of replica molding to fabricate

three-dimensional microposts arrays in RFX.
185
Figure 6.13.(a) High aspect ratio (HAR) 3D cylindrical posts in
SU-8 used as master pattern; (b) PDMS replica showing
holes; (c) RFX-based cylindrical posts; (d) RFX-derived
cylindrical nonporous carbon posts; (e) HAR 3D posts
with cross-shaped design in SU-8; (f) PDMS replica
showing holes; (g)(h) RFX-derived 3D cross-shaped
nonporous carbon posts.
187
Figure 6.14.Schematic for fabricating hierarchical C-MEMS
structures by combining electrospraying with
lithographically fabricated master stamp.
188
Figure 6.15.(a) An array of RFX-derived cross-shaped carbon
posts integrated by electrosprayed SU-8-derived
submicrometer-sized carbon spheres; (b) magnified
side view of a post; (c) magnified top view of one of the
posts showing a conformal deposition of
submicrometer-sized carbon spheres; (d) an array of
RFX-derived cross-shaped carbon posts integrated by
electrosprayed RFX-derived carbon nanospheres;
(e) magnified side view of a post; (f) magnified top
view of one of the posts showing a conformal
deposition of carbon nanospheres; (g) an array of
RFX-derived cylindrical carbon posts integrated by
electrosprayed SU-8-derived submicrometer-sized
carbon spheres; (h) magnified side view of such a
hierarchical post; (i) magnified top view of one of
the cylindrical posts showing a dense conformal
deposition of submicrometer-sized carbon spheres.
189
Figure 6.16.Cyclic voltammogram of RF-derived c arbon xerogel
nanoparticles at a scan rate of 0.1 mV/s.
190
Figure 6.17.(a) Galvanostatic charge or discharge cycle behavior of
RF-gel-derived carbon film for first six cycles;
(b) comparison of gravimetric capacity of RFX-derived
carbon with SU-8-derived carbon; (c) comparison of
specific capacity of RFX-derived carbon with SU-8derived carbon. The reported values for capacities in
(b) and (c) are after 20 cycles.
191
Figure 6.18. Cycling performance of carbon xerogel nanoparticles. 192

List of Figures xix

Figure 7.1.Raman spectra of unmodified CB and after AA

deposition by cold plasma.
Figure 7.2.Scheme of the main groups formed on a polymeric
surface (polystyrene) after nitrogen and oxygen
plasma treatments.
Figure 7.3.Reaction of azomethine ylides on C60 fullerenes as
suggested in reference [120].

208

214
218

List of Tables

Table 2.1.Comparison of mechanical properties of CNTs with

stainless steel

56

Table 2.2.Examples of CNT-based materials in C-MEMS and

C-NEMS applications

63

Table 2.3.Examples of graphene-based materials in C-MEMS

and C-NEMS applications

64

Table 3.1.Overview of graphene synthesis processes

94

Table 6.1.Characteristic sizes of RF-derived carbon xerogel

particles synthesized at different R/W ratios with 5 h of
stirring time and 1% (v/v) span-80 concentration

176

Table 6.2.Characteristic sizes of RF-derived carbon xerogel

particles synthesized at different R/C ratios with 5 h of
stirring time and 1% (v/v) span-80 concentration

178

Table 6.3.Summary of electrochemical performance of previously

reported carbon gel materials and a comparison with
present work [39]

193

Table 7.1.Internal and external parameters for cold plasma

characterization204
Table 7.2.Surface energy for unmodified CB and after AA
deposition209

About the Contributors

Dr. Marc J. Madou, before joining UCI as the Chancellors Professor
in Mechanical and Aerospace Engineering (MEA), Dr. Madou was Vice
President of Advanced Technology at Nanogen in San Diego, California.
He specializes in the application of miniaturization technology to chemical and biological problems (BIO-MEMS). He is the author of several
books in this burgeoning field he helped pioneer both in Academia and in
Industry. He founded several micromachining companies and has been on
the board of many more.
Many of his colleagues became well know in their own right in academia and through successful MEMS start-ups. Madou was the founder
of the SRI Internationals Microsensor Department, founder and President
of Teknekron Sensor Development Corporation (TSDC), Visiting Miller
Professor at UC Berkeley and Endowed Chair at the Ohio State University (Professor in Chemistry and Materials Science and Engineering). The
third edition of Fundamentals of Microfabrication, an introduction to
MEMS and NEMS, which has become known as the bible of micromachining, was published in July of last year (http://fundamentalsofmicrofabrication.wordpress.com/).
Some of Dr. Madous current research work involves a compact
disc-based fluidic platform and carbon MEMS, the two latter fields were
pioneered by Dr. Madou. To find out more about those recent research
projects, visit www.biomems.net.
Dr. Victor H. Perez-Gonzalez, received the BS degree in Electronics and
Communications Engineering (honors) from Universidad Autonoma de
Nuevo Leon, Mexico, in 2006; and the MS in Electronics Engineering and
PhD in Information Technologies and Communications from Tecnologico
de Monterrey, Mexico, in 2008 and 2013, respectively. He has held a visiting research position at the University of California Irvine. For the past
2 years he has been a Research Associate at Tecnologico de Monterrey,

xxiv About the Contributors

Mexico. In 2015 he was awarded with the National Researcher Level

1 distinction by the Sistema Nacional de Investigadores, Mexico, and
became a member of the IEEE Eta Kappa Nu Honor Society. His research
has been supported by CONACYT and UC-MEXUS.
Dr. Perez-Gonzalezs research interests are focused in the multidisciplinary area of Micro-/Nano- Electro-Mechanical Systems (MEMS/
NEMS). From this broad research field, where he has published several
papers in international journals and conference proceedings, his efforts
are strongly aligned in the development of the sensing or actuating stages
of Lab on a Chip devices and their integration with microelectronic
elements. For the development of such stages he uses a broad range of
materials, including: carbon, metals, electroconductive polymers, PDMS,
and glass, among others. His current research projects deal with (1) the
application of electrokinetic and mechanical forces for the manipulation,
separation, or characterization of particles (e.g., microalgae, proteins, and
bacteria) or fluids; (2) the development of highly sensitive amperometric
sensors with Carbon-MEMS/NEMS; and (3) the development of novel
micro/nano fabrication processes. Research efforts integrate mathematical
modeling with experimental work for extending the practical applications
of these technologies.
Dr. Bidhan Pramanick, received PhD Degree from Indian Institute of
Technology (IIT) Kharagpur, India, in 2012 after completing B. Tech
and M. Tech courses in Electronics and Communication Engineering
from Kalyani Government Engineering College, India, in 2005 and 2007,
respectively. He worked more than 2 years as Assistant Professor in
Indian Institute of Space Science and Technology (IIST), an Institute of
ISRO (Indian Space Research Organization) family. Dr. Pramanick joined
Tecnologico de Monterrey, Mexico as Postdoctoral Research Investigator
in January, 2015 in collaboration with University of California Irvine, CA,
U.S. He was a recipient of the CSIR SRF Fellowship (India) for his PhD
Programme and UGC grant for his Masters Programme.
He has authored or co-authored more than 16 papers in international
journals and conference proceedings, two book chapters and one book. He
was also one of the editors of two books on C-MEMS. He was a JPO in
ISRO-sponsored project and he has successfully developed MEMS-based
Microvalve and Micropump for space applications.
His current research interests include Carbon MEMS/NEMS especially Carbon Nanowire based sensors. He is also interested in the area of
Micropropulsion and RFMEMS.

Foreword

UC Irvine, Sept 1416, 2014. Chair: Dr. Marc Madou

Co-Chairs: Dr. Chunlei Wang, Dr. Rodrigo Martinez-Duarte and
Mr. Jacob Moebius
Dear reader, two books: Carbon: The Next Silicon? Book 1-Fundamentals
and Carbon: The Next Silicon? Book 2-Applications came about as
a follow-up to the 1st International Conference on Carbon Micro and
Nano Electromechanical Systems (C-MEMS /C-NEMS) held September
1416, 2014 on the UC Irvine campus (see conference LOGO above).
This was an invitation only event with delegates from the US, Italy,
Spain, M
alaysia, Mexico, Denmark, Germany, Switzerland and India.
The group was limited to 6070 researchers currently working in the
field and expected to contribute to breakthroughs in this field and interested in international collaborations. Indeed research funding is weak
globally and by leveraging efforts internationally we still have a chance
to remain p roductive scientists regardless of politicians irresponsibility.
The pictures below are from some of the C-MEMS/C-NEMS team at the
2014 conference.
At the conference we had presentations on the latest C-MEMS and
C-NEMS results, suggested future directions and discussed what each
country is offering in terms of funding for international collaborations
and formed several motivated proposal teams. We identified opportunities
for students to be part of this international C-MEMS/C-NEMS research

xxviForeword

ring and to be able to work in any one laboratory that is part of this
ring to faster produce science breakthroughs and in the process become
broader-thinking global citizens.
The format of the conference was a new and exciting experiment in
itself. Over the last decade we have developed serious doubts about the
effectiveness of huge, profit driven conferences so instead we brought
together a small group of researchers in an intimate setting and made
this an occasion where there was plenty of time to talk and make friends
and make plans over drinks and food. Besides the science sessions we
had several cultural events, including a class on Ancient Indian History: Aryan Invasion: Myth or Reality? (Prof. A. Ghosh) and a Malay
board game: Congkak (Prof. Fatimah Ibrahim). We also had exhibits of
paintings and photography and plenty of music [from Persian classical
music to s ixties rock and roll (UC Irvine Professor Band-Second Law),
Russian love ballads (Dr. Lawrence Kulinsky) and Frank Sinatra (Prof.
Jan Korvink)] we even had a yoga class (Prof. Regina Ragan) all by and
for the invited C-MEMS/C-NEMS researchers. Art and science have a
lot in common, in both one must create de-novo, not accept any preconceived notion of what the best science/art might be or where it will
lead and in both cases, if good enough, one can transcend even the most
miserable of times.

Part of the C-MEMS/C-NEMS team at the 1st C-MEMS

International Conference. Sept 1416, 2014. Location: Lobby
CalIT2 on the UC Irvine Campus.

Foreword xxvii

Dr. Swati Sharma (Karlsruhe Institute of Technology, Germany)

on C-MEMS and EPR (Left panel). Sharifah Bee Binti O.A Abd
Hamid on carbon and nano catalysis (Right panel). At the 1st
C-MEMS International Conference. UC Irvine, Sept 1416, 2014

A mixed-media sketch by Ashutosh Sharma (Indian Institute of

Technology Kanpur) (Left panel). A Malay board game called
Congkak I kid you not! (Right panel). At the 1st C-MEMS
International Conference. UC Irvine, Sept 1416, 2014.

xxviiiForeword

Prof. Jan Korvink (Karlsruhe Institute of Technology, Germany)

singing Frank Sinatras I did it my way at the 1st C-MEMS
International Conference. UC Irvine, Sept 1416, 2014.

Quick Overview of
Book1-Fundamentals
In Book 1-Fundamentals, Chapters 1 to 7, we cover the theoretical aspects
of carbon and the manufacture of carbon based devices. In Chapter 1,
Marc Madou provides an introduction to the state-of-the art in C-MEMS/
C-NEMS with an emphasis on lithographically patterned photo-polymers,
carbonized in an inert atmosphere. The most prevalent allotrope covered
in this first chapter is glassy carbon and we show that by choosing another
manufacturing approach electrospinning (ES) instead of spin-coating the
polymer precursor - the material can be rendered more graphitic. It is obvious that we can expand our perspective considerably by learning from the
traditional carbon manufacturing community where researchers deal with
a much wider variety of carbon feed stocks such as coal, coconut shell,
wood, agricultural wastes and industrial wastes to make all types of useful
carbons. In addition to their expertise in choosing the right catalysts to end
up with the desired carbon nanomaterials from any of these feedstocks,
these carbon scientists works with dry and wet pyrolysis processes. Wet
pyrolysis process is also known as hydrothermal carbonization, a process
new to the C-MEMS/C-NEMS community. In Chapters 2 and 3 Sharifah
Bee Abd Hamid and team introduce these new concepts to the C-MEMS/
C-NEMS community by discussing carbon nanomaterials synthesis aided
with catalysts and chemistry and detail the microstructure of the resulting
nanocarbons. The carbon nanowires discussed in Chapter 1 were made
by carbonization of electrospun polymer precursors only (either far field
electrospinning or electromechanical spinning). Bidhan Pramanick, in
Chapter 4, is surveying all the options that are available for the fabrication of carbon nanowires. In Chapter 5 Bidhan Pramanick et al are digging
deeper into the theory and application of electrospinning to come up with
yet other ways to impact C-MEMS/C-NEMS. We barely touched upon
xerogels for C-MEMS/C-NEMS in Chapter 1 but in Chapter 6 Chandra

xxx Quick Overview of Book1-Fundamentals

Sharma and Manohar Kakunuri take on the challenge of integration of

organic xerogels more firmly into the C-MEMS/C-NEMS arsenal of tools.
In Chapter 7 Salvador Borros et al are turning our attention to the details of
C-MEMS/C-NEMS surfaces in terms of their chemical composition and
microstructure. They point out that the performance of carbon materials
is determined to a large extent by their surface and interfacial properties.
This team describes the methods to tailor the surface activity of different
carbon structures, how to characterize them and the potential applications
derived from the modifications achieved.

Acknowledgments
1. Acknowledgments for C-MEMS/C-NEMS Introduction: NSF
grant.1449397
2. Acknowledgments for The Beautiful World of Carbon: Financial supports from Malaysian Ministry of Higher Education HIR
F00032, TRGS TR002B-2014B, and University of Malaya grant
UMRG (RP022-2012A) are acknowledged.
3. Acknowledgments for Synthesis of Nanocarbons and Tuning of
Their Properties: Financial support from the University Malaya
UMRG (RP022-2012A), Ministry of Higher Education (MOHE)
Transdisciplinary Research Grant Scheme (TR002A-2014B),
Ministry of Science Technology and Innovation (MOSTI) Science
Fund (SF-020-2014), and University of Malaya Flagship Grant
(FL001-14AET) for the Carbon NEMS research are acknowledged.
4. Acknowledgments for Historical Overview of Carbon Nanowire
Fabrication Methods: The financial support from UC-Mexus
grant UCM-104728 and CONACYT Ciencia Basica CB-2014-01241458.
5. Acknowledgments for Carbon Nanowire Fabrication: C-MEMS:
Financial support from CONACYT Ciencia Basica CB-2014-01241458, Ministry of Higher Education (MOHE) Transdisciplinary
Research Grant Scheme (TR002A-2014B), Ministry of Science
Technology and Innovation (MOSTI) Science Fund (SF-020-2014),
and University of Malaya Flagship Grant (FL001-14AET) for
the Carbon NEMS research, University Malaya UMRG (RP0222012A) are acknowledged.
6. Acknowledgments for C-MEMS based On-Chip Microsupercapacitors: This article was supported financially by the National
Science Foundation (NSF), (Award number 1506640) and NSF
ASSIST center seed funding. Richa Agrawal acknowledges

xxxii Acknowledgments

niversity Graduate School (UGS) at Florida International

U
University for support through a Doctoral Evidence Acquisition
(DEA) Fellowship. The previous works summarized in this c hapter
were funded by the US Defense Advanced Research Projects
Agency (DARPA), Young Faculty Award program (Project No.
HR0011-08-1-0036), NSF (MRI program CMMI-0821582) and
the American Chemical Society Petroleum Research Fund (493010N110).
7. Acknowledgments for Glassy Carbon Microelectrodes for Neural
Signal Sensing and Stimulation: The project described was
supported by Award NumberEEC-1028725from the National
Science Foundation. The content is solely theresponsibility ofthe
authors and does not necessarily represent the official views of the
NationalScienceFoundation.
8. Acknowledgments for Advanced Electroanalysis with C-MEMS:
Financial support by MIUR-PRIN 2010AXENJ8 and Veneto
Region Project RESMIA is acknowledged.
9. Acknowledgments for Carbon MEMS for Magnetic Resonance:
The financial support from the European Research Council through
the senior grant 290586 NMCEL.
10. Acknowledgments for C-MEMS-Based 3D Interdigitated Electrode Arrays for Redox Amplification: The financial support from
UC-Mexus grant UCM-104728 and CONACYT Ciencia Basica
CB-2014-01-241458.

CHAPTER 1

C-MEMS and
C-NEMS Introduction
Marc J. Madou
University of California Irvine, USA

Courtesy of Dr. Samira Hosseini.

1.1 PURPOSE OF CHAPTER 1

The purpose of this chapter is to explain what the most prominent carbon
microelectromechanical system (C-MEMS) and carbon nanoelectromechanical system (C-NEMS) fabrication processes are, to illustrate how the

2 CARBON: THE NEXT SILICON?

details of the fabrication process enable one to obtain different carbon

microstructures, to introduce important current and to discuss anticipated
applications.

1.2 C-MEMS AND C-NEMS: WHAT IS IT?

Shaping of most carbon allotropes into micro- or nanodevices with mechanical machining techniques is not a straightforward task because the material
is usually hard and brittle. Integrated Circuit (IC) processing technologies,
such as focused ion beam (FIB) milling [1] and reactive ion etching [2]
of carbon, are more up to the task but are often too time consuming and
too expensive because of the need for sophisticated equipment involving
vacuum systems. Low feature resolution and poor repeatability of the carbon composition limit the application of the less sophisticated and, therefore, less expensive screen-printing technique of carbon inks [3]. As we
just noted, carbon, because it is brittle and hard, is a difficult material to
machine directly. Polymers, on the other hand, can be machined easily in a
wide variety of machine tools and then converted to carbon devices through
pyrolysis, resulting in shapes that are often impossible to make in carbon by
any other means. Simply stated, the underlying p rinciple of C-MEMS and
C-NEMS is to choose an easy to work with polymer precursor, machine, or
photopattern this precursor material (in the case of a photoresist) and then
convert it to carbon by pyrolysis [46]. The words MEMS and NEMS stand
for microelectromechanical system and nanoelectromechanical systems,
respectively [7]. These used to be made almost exclusively from Si but with
C-MEMS and C-NEMS, the 3D (three-dimensional) building materials are
any of the many carbon a llotropes instead [8, 9].
In one embodiment of the C-MEMS and C-NEMS process, a photoresist is patterned by photolithography and is subsequently pyrolyzed at high
temperatures in an oxygen-free environment. By changing the lithography

C-MEMS AND C-NEMS INTRODUCTION3

conditions, soft and hard baking times and temperatures, resist additives
(e.g., a catalyst), pyrolysis time, temperature, and e nvironment, C-MEMS
and C-NEMS permit a wide variety of interesting new applications that
use structures having a wide variety of shapes, resistivities, mechanical
properties, and other physicochemical properties.
An example of photolithography process (using SU-8, an epoxy-based
negative photoresist) to make C-MEMS and C-NEMS structures is
illustrated in Figure 1.1. The process includes spin coating, soft bake (not
shown), near-ultraviolet (UV) exposure, postbake (also not shown), and
development. After the photolithography steps, C-MEMS and C-NEMS
architectures are obtained in a two-step pyrolysis process. The latter may
be carried out in an open-ended quartz-tube furnace, where the samples
are postbaked in an N2 atmosphere at 300C for about 40 minutes first and
then heated in an N2 atmosphere (2,000 sccm) up to 900C. At this point,
the N2 gas is shut off and forming gas [H2(5%)/N2] is introduced (2,000
sccm) for 1 hour and then the heater is turned off and the samples are
cooled down again in an N2 atmosphere to room temperature. The heating
rate is about 10C/min, and the total cooling time is about 10 hours [9].
The resulting microstructure of the carbon material from the process detailed previously was found to be that of glassy carbon (not to be
confused with amorphous carbon because it has no dangling bonds and
is made up by 2D (two-dimensional) structural elements) [5]. The exact
nature of the glassy carbon (also vitreous carbon) microstructure is still
a subject of debate, but it is generally agreed to have a fullerene-related
microstructure (see also Figure 1.9) that leads to a great variety of unique
material properties [1014]. Glassy carbon is one of the favored electrode
materials for electrochemists. Other manufacturing approaches that can
lead to other carbon microstructures are discussed in the next section.
UV light
Pyrolisis

Photoresist layer on Standard photolithography. Photopatterned resist. Carbon structures. Planar

or volumetric,
Negative resist case.
Planer or volumetric
Si or SiO2 substrate.
structures.
isometric shrinkage

Figure 1.1. An illustration of one type of C-MEMS: photolithographic

patterning of a polymer precursor (SU-8 photoresist) and pyrolysis (see text
for details) [9].

4 CARBON: THE NEXT SILICON?

Initial work that qualifies as C-MEMS and C-NEMS was carried out
by Lyons, Wilkins, and Robbins [15]. This team prepared carbon films
by the thermal decomposition of photo-defined novolac resist (HPR-206)
patterns and observed that the electrical resistivity decreased over 18
orders of magnitude as the pyrolysis temperature was increased to 1050C.
Sometime later, Scheuller et al. used soft lithography to fabricate glassy
carbon microstructures [16, 17]. In the latter approach, micromolding
of a resin (not a photoresist in this case) such as poly (furfuryl alcohol)
in an
elastomeric mold yielded polymeric microstructures and the
polymeric microstructures were then converted to free-standing carbon
by carbonization. In these works, only low aspect ratio (flat) carbon
structures were fashioned and involved IC-related applications such as
capacitors and masking.
This author and his team optimized the photoresist process from
Lyons [18] and Lyons, Wilkins, and Robbins [15]; Lyons, Hale, and
Wilkins [19]; Lyons, Wilkins, and Robbins [20] and were the first to
make high aspect ratio micro- and nanocarbon microstructures, dope the
polymer precursors, create multilevel devices, introduce different carbon
microstructures into the arsenal, and explore a wide variety of applications
of these novel structures (see Application section) [9].
An example of early work from the UCI C-MEMS and C-NEMS
group is shown in Figure 1.2. The average height of the SU-8 posts shown
in typical scanning electron microscope (SEM) images (Figure 1.2a and
1.2b, left panel) is around 300 m. As shown in Figure 1.2c and 1.2d, after
pyrolysis, the overall shape of the cylindrical posts is largely retained, and
a typical aspect ratio of the carbon post achieved is around 10:1 [9,21].
To construct yet higher aspect ratio C-MEMS features (up to 40:1),
we developed a multilevel C-MEMS process. Here each layer of SU-8
a)

b)

c)

d)
3rd level
2nd level
1st level

Figure 1.2. SEM images of (a) and (b) SU-8 post arrays before pyrolysis
and (c) and (d) carbon post arrays after pyrolysis (left panel) [9]. SEM
images of three-level C-MEMS: a three-level C-MEMS structure with
two levels in good alignment but with a third-level out of alignment (right
panel) [9, 21].

C-MEMS AND C-NEMS INTRODUCTION5

p hotoresist is exposed and baked separately and then the whole a ssembly
is developed in a last step. SEM images of a three-level C-MEMS device
are shown in Figure 1.2 (right panel); in this three-level C-MEMS
structure, the first two exposures were in good alignment but the third was
out of alignment [9, 21]. This multilevel C-MEMS microfabrication process has its analogy in the multilevel polysilicon surface micromachining
process [22].
As alluded to earlier, by tightly controlling the various lithography
and carbonization process parameters, a wide range of 3D C-MEMS
structures, such as suspended carbon wires (wash cloth lines), bridges,
plates (carbon microtable, see also the inset in the heading of this c hapter),
and self-organized posts (carbon flowers, again see the inset in the heading
of this chapter) and ribbons (networks) can be microfabricated. Some
examples are shown in Figure 1.3. These intricate 3D structures shown
here are fabricated using nontraditional lithography and resist process
recipes, such as overexposure, underdevelopment, photoresist additives
(a)

(b)

(c)

(d)

(e)

(f)

Figure 1.3. Typical SEM images of suspended (a) carbon plates

(carbon microtable), (b) carbon bridge, (c) carbon networks,
(d) carbon ribbons, (e) carbon fibers (wash cloth lines), and
(f)self-assembled C-MEMS (also carbon flowers) [21].

6 CARBON: THE NEXT SILICON?

(e.g., catalysts), directed flow of the developer, and exploitation of surface

tension in the developing photoresist patterns [21].
It should be noted that upon pyrolysis, the polymer nanofibers with
diameters in the several hundreds of nanometer range shrink to fibers with
diameters below 100 nm, revealing yet another benefit of this type of
nanofabrication approach. In the next section, we return to the controlled
manufacture of suspended carbon nanowires (CNWs) (see Figure 1.3e).
The suspended wires and other overhanging features illustrated in Figure
1.3 are a result of SU-8 polymer T-topping [23] connecting SU-8 posts,
these wires and other overhangs are converted into carbon in the p yrolysis
step together with the suspending posts. The T-topping p henomenon is
hard to render into a controllable process, however, and we shall see
that by electrospinning (ES) of polymer precursor wires onto the SU-8
polymer posts, suspended CNWs can be manufactured in a much more
controlled manner.
In Figure 1.4, we show the effect of adding a catalyst to the polymer
precursor. Carbon nanofibers (CNFs) (<1 percent weight) with the
Fe catalyst nanoparticles still embedded in them were mixed in SU-8
photoresist. In Figure 1.4a, we see an SEM image of a CNF-doped

photoresist post before pyrolysis, and in Figure 1.4b and c, we show

the same post after pyrolysis. Clearly, the amount of nanofibers on the
(a)

(b)

(e)

(c)

(d)

Figure 1.4. Typical SEM images of (a) a photoresist post

obtained from modified SU-8 before pyrolysis, (b) a carbon
post after pyrolysis, (c) a carbon post surface under high
magnification, (d) a broken piece of a carbon post with
embedded carbon fibers, and (e) an embedded cavity under
high magnification [24, 25].

C-MEMS AND C-NEMS INTRODUCTION7

posts has increased dramatically. Figure 1.4d and e reveals that there
are nanofibers in the post too and that the post has some voids also. It is
believed that this nanofiber growth during pyrolysis is a chemical vapor
deposition (CVD) process with the pyrolyzing polymer matrix providing
the hydrocarbon source to redeposit on the original CNWs, which is the
reason for the tremendous increase of the amount of CNWs after pyrolysis
[24, 25].
As is the case of the lithography process, the carbonization process can
be carried out in many different ways as well: changing the heating ramp
rate, for example, can produce microporous carbon if carried out fast (say
above 10C/min) [26] and changing the gas composition (e.g., to include
some H2) can lead to a nanoporous carbon amenable to super capacitor
manufacturing [27, 28]. In Figure 1.5, we show that when changing the
heating ramp rate to reach the final temperature of 900C from around
15C/min to 90C/min the size of the pores is dramatically increased [from
a couple of microns (Figure 1.5, left panel) to 10 to 15 m (Figure 1.5, right
panel)]. Sharma, Kamath, and Madou studied the impact on the interfacial
capacitance and electrochemical behavior for these types of porous carbons
[26]. With a slow ramp rate of 2C/min, the resulting C-MEMS is nonporous even under Scanning Tunneling Microscopy (STM) observation.
During the pyrolysis step, the photoresist transforms into carbon by replacing the carbon chemical bonds with nitrogen, oxygen, and hydrogen with
all c arboncarbon bonds. When the pyrolysis rate is very fast, the pyrolysis
gaseous products are not yet annealed out and porosity results [29].
Hsia et al. demonstrated that the pyrolysis of SPR-220 photoresist, in
an ambient consisting of Ar at 900C followed by an anneal in an H2/Ar
mixture, results in a high-surface-area porous carbon, applicable to on-Si
chip super capacitor fabrication [27]. In this case, a reaction of hydrogen

Figure 1.5. Typical SEM images of C-MEMS posts fabricated with a final
SU-8 carbonization temperature of 900C. Temperature ramp rate of 15C/
min (left) to 90C/min (right) [29].

8 CARBON: THE NEXT SILICON?

with the carbon results in nanopores rather than the micropores observed
in the case of Figure 1.5 that form because of the escaping pyrolysis
gases. Porosity in C-MEMS structures was also studied by Wang et al.
who produced porous carbon micropillars using the block copolymer
Pluronic F127 composed of (polyethyleneoxide)(polypropyleneoxide)
(polyethyleneoxide) [(PEO)-(PPO)-(PEO)] as a porogen [30]. Sharma et
al. made a variety of carbon structures by the inverse emulsification of
resorcinolformaldehyde sol in cyclohexane with the nonionic surfactant
Span-80, followed by pyrolysis at 900C in nitrogen. Carbon xerogel
microspheres and folded fractal-like structures were demonstrated, and by
varying the reaction conditions, the porosity could be modulated [3133].
From the preceding, we recognize that there are at least four different
methods to make porous C-MEMS and C-NEMS with different pore size,
density, and distribution.
While fast pyrolysis results in microporous high aspect ratio C-MEMS
structures (see Figure 1.5), treatment with oxygen plasma can texture the
carbon surface on the submicrometer scale. Surface roughening may
be achieved by subjecting the pyrolyzed samples to an oxygen plasma
environment. Using a moderate power of 300 W and 200 mT of oxygen,
4 minutes is enough to dramatically change the texture of C-MEMS surfaces. Two types of indentations were observed as a result of the plasma
treatment: larger indentations around 2 m in size and smaller ridges
around 200 nm in width (see Figure 1.6) [29, 34]. Plasma treatment of

Figure 1.6. SEM of C-MEMS surface after plasma treatment

[29].

C-MEMS AND C-NEMS INTRODUCTION9

C-MEMS surfaces has been shown to enhance electrochemical reactivity

and interfacial capacitance [16, 26, 35].
It is clear to this author that plenty of opportunities for new C-MEMS
and C-NEMS discoveries remain. A prime example with almost untapped
potential involves the polymercarbon intermediates that form during
the carbonization of polymer precursors with or without additives (see
Figure1.7 in case of SU-8 carbonization). During pyrolysis, electrically,
one goes from an insulating material to a good conductor and m
echanically,
one transitions from a low Youngs modulus polymer to a hard and brittle
carbon. Those intermediate materials have hardly been characterized at all.
In some initial work along this line, Sharma [36] found that the Youngs
modulus for a photopatterned SU-8 film as a function of temperature (as
shown in Figure 1.8a) features a dip: the material is softest, even softer
than the starting SU-8, between 600C and 700C, and hardness increases
again after 700C.
This interesting observation can be explained based on the poroelasticity regime of the material between 600C and 700C; in this region,
mostly gaseous pyrolysis reaction products are generated, and this results
in a porous matrix [36].

UV

Starting material

Pyrolysis
After crosslinking

After carbonization

12
10
8
6
4
2
0

500

1000

Pyrolysis temperature (C)

(a)

Resistance (10 M)

Young's modulus (GPa)

Figure 1.7. Schematic of the SU-8 photoresist pyrolysis process [36].

80
70
60
50
40
30
20
10
0
200

400

600

800

1000

Pyrolysis temperature (C)

(b)

Figure 1.8. (a) Young modulus versus pyrolysis temperature for SU8 carbon
intermediate materials [36], (b) electrical properties of polyacrylonitrile
(PAN)carbon intermediates [37].

10 CARBON: THE NEXT SILICON?

The pyrolysis temperature regime where most carbonization gases are

formed is also the regime where the resistance of the material changes the
most dramatically. This is shown in Figure 1.8b for the pyrolysis of PAN
[37].

1.3IN C-MEMS AND C-NEMS THE

MANUFACTURING METHOD DETERMINES
THE CARBON MICROSTRUCTURE
In all the C-MEMS and C-NEMS examples presented so far, the r esulting
carbon microstructure obtained is that of glassy carbon [1012] (see
Figure 1.9). But carbon also comes in other allotropes such as diamond,
graphite, fullerene, nanotube, amorphous, and diamond like. Based on the
details of their microstructure, these allotropes are used in widely differing
physical, chemical, mechanical, thermal, and electrical applications (see
the Applications section). In this section, we demonstrate how one can
obtain a different carbon microstructure by using different manufacturing
techniques and how one can even afford the building of hybrid C-MEMS
and C-NEMS devices that incorporate components with differing carbon
microstructures by combining different manufacturing methods [13, 38,
39].
When the polymer precursor for C-MEMS and C-NEMS is d eposited
by ES instead of spin coating (as in photolithography), the carbon
obtained is much more graphitic. To understand the reason behind this,
we have to look somewhat deeper into the physics of the ES process
[40]. ES is a simple, versatile, and widely used method for producing all
types of polymer fibers, and it comes in three principal flavors, known as

La

Lo

Figure 1.9. Microstructure of glassy

carbon proposed by Haris [10], Jenkins and
Kawamura [11], and Jenkins [12].

C-MEMS AND C-NEMS INTRODUCTION11

far-field electrospinning (FFES), near-field electrospinning (NFES), and

electromechanical spinning (EMS).
FFES involves the application of a high voltage (1015 kV) to bias a
polymer solution in a syringe against a substrate of the opposite polarity
with the syringe tip separated 10 to 15 cm from that substrate (also target
or collector) (see Figure 1.10a). When the electrostatic field overcomes
the surface tension that keeps a droplet of polymer solution at the syringe
tip, a Taylor cone forms and if the polymer dissolved in the solution is at a
high enough concentration, a fiber is drawn from it. In the air-gap between
the nozzle and the collector, the polymer solution jet undergoes a whipping process wherein the solvent evaporates, leaving behind a charged
polymer fiber, which lays itself randomly on the grounded collector.
In a C-MEMS and C-NEMS application of FFES, our team electrospun
mats of SU-8 [41]. Next, this nanofibrous mat was micropatterned using
photolithography, and finally, pyrolysis produced ordered arrays of microdomains containing CNFs. With lithography features in the microdomain
and fibers with diameters in the hundreds to tens of nanometers range, this
approach enables the fabrication of multiscale hierarchal assemblies such
as fractal-like electrodes where a high external surface area is coupled with
a minimized internal resistance, which is a feature of great utility, in batteries and fuel cells [4244]. An example of this c ombination of lithography
with ES to create structured C-MEMS and C-NEMS arrays is shown in
Figure 1.11 [41]. Interesting as well is that these arrays of SU-8-derived
carbon fibers were found to be very hydrophobic (water contact angle,
130) [41]. The biocompatibility of SU-8-derived carbon [45, 46] provides
further motivation for the development of multiscale hierarchal scaffolds
[47] for tissue engineering and in vivo biosensors [48, 49].
However, FFES is hard to control because of the electric field
instabilities that are inherent in the ES process [50]. Despite the whipping
of the nanofibers, even with FFES, some alignment along the preferred

Spinneret
Spinning tip

Taylor cone

Nanofiber
jet

Syringe pump

+ or - kv

Near
field

Target

Far
field

(a)

High voltage
power supply

Collector

(b)

Figure 1.10. (a) Comparison of FFES and NFES and (b) FFES setup.

Taylor
cone
1 mm

12 CARBON: THE NEXT SILICON?

100mm

a 20mm

100mm

c 50mm

50mm

e 50mm

Figure 1.11. SEM images of arrays of patterned fibrous carbon s tructures:

(a, b) lines, (c, d) 3D pillars, and (e, f) connecting squares. Images (b)
and (d) are magnified views of images (a) and (c), respectively, and
higher-magnification images of (b) and (d) are shown as insets. Images
(a)(d) are on Si wafer substrates, and images (e) and (f) are on a
plasma-treated SU-8-derived carbon film on a Si wafer [41].

direction can be achieved by using a rotating drum collector [51] or

electrical field manipulation [52]. Using a rotating target drum equipped
with Si samples featuring SU-8 contact pads (Figure 1.12), our team
deposited polymer nanofibers perpendicular to the suspending SU-8 walls
of the contact pad structure [53]. These hybrid contact or nanowire assemblies were then carbonized to yield CNWs suspended between carbon
electrodes. A contact pad with CNWs deposited on it is shown in Figure
1.13 (left) and 1.13 (middle). To be able to study single-suspended CNWs,
extraneous wires were cut using FIB milling. It was found that these
CNWs are better conductors than bulk glassy carbon. The high-resolution
transition electron microscope (HR-TEM) images of these electrospun
SU-8-derived CNFs revealed high-quality graphitic wire (for the thinnest

C-MEMS AND C-NEMS INTRODUCTION13

Polymer source
Fiber jet
Rotating
drum

Voltage applied:
1030 kV
1020 cm

Sheath solution

Rotating collector

Nanofibers

Figure 1.12. FFES with a rotating drum target (left) and Si substrate with
SU-8 contact pads perpendicular to the nanowire direction (right) [53].

42 nm
30 m

Figure 1.13. Single CNW across suspending carbon walls (left). Schematic
of C-MEMS and C-NEMS structure used to collect nanowires (a dense array
is shown here) (middle). HR-TEM image of electrospun SU-8-derived CNF:
tube-like graphitic CNW with glassy carbon core and graphite shell (right)
[53].

ones) and tube-like graphitic CNWs with a glassy carbon core and a graphite shell for the slightly thicker ones (see Figure 1.13 [right], in which we
show a tube-like CNW and Figure 1.14 in which we show both types).
These results can be explained with reference to the work by Ji
etal. [54] who convincingly demonstrated that the Youngs modulus of
electrospun polymer fibers increases significantly with a decrease of the
fibers diameter.
This is due to the orientation of the polymer chains in the ES process.
The large shear imposed during the ES process orients the chains in the
outermost regions of the fiber (see Figure 1.14a).
The smaller the diameter of the fiber, the easier it is for chains to orient
themselves along the fibers length throughout the entire fiber thickness, which
results in a larger modulus. Ji et al. speculated and confirmed experimentally

14 CARBON: THE NEXT SILICON?

5 mm
Rg
Rg

5 mm

(a)

(b)

Figure 1.14. (a) Model of the molecular chain orientation according

to Ji et al. [54]: (A) thin fiberpolymer chains oriented throughout
the entire fiber; (B) thick fiberpolymer chain orientation starts at
the surface and propagates into the bulk. Rg is the polymer gyration
radius. (b) HR-TEM images of nanowire graphitic all the way to the
core (top) and tube-like graphitic CNW with glassy carbon core and
graphite shell (bottom) [55].

that the phenomenon scales with R/Rg, where R is the fiber radius and Rg
the polymer radius of gyration rather than scaling with the absolute fiber
diameter. The effect can propagate radially into the fiber for large distances
(20 Rg) [54]. Our C-MEMS and C-NEMS results depicted in Figure 1.14b
nicely validate Ji et al.s work. Indeed the degree of polymer chain orientation
is reflected in the resulting carbon microstructure: carbon fibers are more
graphitic when the c orresponding p olymer region consists of more oriented
polymer chains and they are more glassy when corresponding with regions
of more random chain orientation. Also in agreement with Ji et al., we found
from HR-TEM images that the thinnest CNWs were more graphitic all the
way to the core and thicker wires were tubelike with a glassy carbon core and
a graphite shell (see Figure 1.14b). The microstructure of the contact pad is
mostly glassy carbon, the suspended nanowire, on the other hand, because of
the mechanical forces involved in ES, the pulling by the spinning drum, and
yet further pulling because of shrinkage during carbonization, all conspire to
yield a much more graphitic suspended wire component.

C-MEMS AND C-NEMS INTRODUCTION15

Current voltage (I/V) plots of the suspended carbon wires are linear,
clear evidence for the ohmicity of the carbon-to-carbon contacts [53].
For CNWs with diameters in the 42 to 113 nm range, the average value
for the electrical conductivity was 6.13 104 S/m, which is almost twice
that of glassy carbon (2.8 104 S/m). The reported electrical conductivity values for graphite range from 2.4 104 S/m to 1.02 105 S/m
parallel and perpendicular to the C-axis, respectively. The experimental
conductivity values are lower than that of graphite but higher than that of
glassy carbon but not as dramatic a change as we had expected, given the
amount of graphitization observed in HR-TEM images. In the following,
we demonstrate that the Youngs modulus of CNWs fabricated using EMS
also increases dramatically as the CNF diameter decreases (Figure 1.17).
Despite the efforts with rotating drums and electrical field manipulation, generally speaking, FFES fails to deliver precise, inexpensive, fast,
and continuous nanofiber patterning capability. The problem of random
nanofiber whipping was addressed by reducing the distance between the
nozzle and the substrate to less than a few millimeters, so that fibers land
on the substrate before the onset of whipping (see Figure 1.10a) [56].
In this approach, voltages are as low as 600 Vconsiderably reducing
electric-field-induced instabilities. But with low voltages such as this,
the surface of the polymer droplet must be artificially disrupted (e.g., by
poking with a sharp glass tip) to create a localized region of a very high
electric field on the droplets surface initiating the ES process [56, 57].
This configuration, known as NFES, was suggested relatively recently
[57]. Our group has found that production of yet thinner stable fibers
necessitates operation at a yet lower voltage, and the results demonstrate
that even nanofibers of sub-20-nm diameter are possible at a bias as low
as 300 to 200 V when using superelastic viscoelastic polymers and by
moving the stage or working with a rotating drum to mechanically pull
and thus thin the wires [5861]. We call this technique EMS as the moving stage or rotating drum mechanically pull on the viscoelastic fibers
to further thin them. The polymers viscoelasticity ensures that the fibers
do not break while pulling. The viscoelastic nature of the polymer ink
enables continuous ES at a very low voltage of 200 V, considerably lower
than that in NFES, thereby reducing bending instabilities and increasing the control of the resulting polymer jet even further. The resulting
jet is stable and can be easily and precisely targeted onto a stationary
or moving substrate. By controlling the applied voltage and the relative
stage speed of the substrate with respect to the nozzle, EMS results in
superior nanowire deposition control. In Figure 1.15, we compare FFES
with EMS [59].

16 CARBON: THE NEXT SILICON?

a)

b)

Polymer

Dispensing
electrode
nozzle
Polymer
droplet

High voltage
power supply

Power
supply
V

Taylor cone
1 mm

Electrospinning jet

Substrate
Collector
c)

d)

Figure 1.15. FFES (a, c) compared with EMS (b, d). The fibers in
Figure 1.15c and 1.15d, when using the correct ink formulation, can
subsequently be carbonized, thinning them even further [59].

Now we can combine the photopatterning of SU-8 for making contacts

pads with EMS for the suspended nanowires as shown in Figure1.15d.
With the right formulation of the polymer solution, these suspended
polymer nanowires can be carbonized, thinning them even further, and
glassy carbon contacts can thus be wired together with graphitic EMS
electrospun nanofibers.
Such a hybrid microstructure construct is also illustrated in Figure 1.16
in which we show a set of carbonized EMS fibers (graphitic) suspended
over a carbon support structure (glassy) that was used to establish the
Youngs modulus (E) of the CNWs. As shown in the inset of Figure 1.16,
these carbon fibers were cut with an FIB to form cantilever beams [62].
A laser Doppler vibrometer was used to measure the natural frequency
of the FIB cut nanowires, and using the EulerBernoulli beam theory,
the Youngs modulus as a function of nanowire diameter was derived as
shown in Figure 1.17. Just as predicted from the model of Ji et al. [54],
the Youngs modulus increases very fast as the wire diameter shrinks. At
200 nm, Youngs modulus is already up to 400 GPathis is eight times
higher than that for a 1-m diameter nanowire (carbon nanotubes [CNTs]
are between 270 and 950 GPa [1 TPa]). This is a very promising result as

C-MEMS AND C-NEMS INTRODUCTION17

Probing pads
Carbon walls

Carbon wall
Suspended fibers

Carbon wall

20m

Youngs modulus (GPa)

Figure 1.16. Patterned CNWs made by carbonization of nanofiber array

of 70 parallel fibers made by continuous EMS. The measured average
distance between carbon fibers was 18.6 4.8 m. Inset: Fibers are cut
with a FIB to form cantilever beams [62].
500
450
400
350
300
250
200
150
100
50
0

0.5

1
1.5
Diameter (mm)

2.5

Figure 1.17. EulerBernoulli beam theory results for CNWs. At 200 nm,
Youngs modulus is already up to 400 GPa (CNTs are between 270 and 950
GPa [1 TPa]) [62].

it suggests that CNWs could reach the mechanical performance level of

CNTs! As we can make our CNWs very long, this EMS combined with
carbonization constitutes a plausible alternative to CNTs that are much
harder to make into long cables. The maximum conductivity for the same
wires is 7 104 S/m [62], only a bit more than twice the glassy carbon
value (the value of wires obtained with FFESsee earlier information
was very s imilar at 6.13 104 S/m).

18 CARBON: THE NEXT SILICON?

1.4CURRENT AND PROJECTED APPLICATIONS

OF C-MEMS AND C-NEMS
Although silicon, humans foremost technological material, is abundant
in silicate minerals, carbon is the key to life. It can be argued that carbon,
especially with the recent (somewhat frantic) research efforts on CNTs and
graphene, is also becoming a more and more important material in human
technology. Neither single crystalline nor polycrystalline Si encompasses
that wide a range of shapes and microstructures. Some key advantages of
carbon compared with Si are summarized in Figure 1.18 [9].
Much has been made of the myriad of applications of just two of
the currently most popular carbon allotropes, that is, CNTs [6369] and
graphene [65, 70]. Here we promote the idea that C-MEMS and C-NEMS
could eventually, depending on the manufacturing process, incorporate all
of the carbon allotropes. In this more holistic view of a world with carbon
as the most important technological material, one tailors one allotrope or
a combination of allotropes to suit each application.
Some recent examples of C-MEMS and C-NEMS applications
include electrochemical sensors [49, 71, 72], substrate for molecular
electronics [7375], batteries [4244, 7679], fuel cells [8083], dielectrophoresis electrodes [8486], capacitors [27, 35, 87], scaffolds [45, 47],
nanoconstrictions [88], hot nanowires for local CVD [36], molds for bulk
metallic glasses [89], and gas sensors [90]. Several of these applications
Polymerizes better than Si (see inset 1 below)
Takes all types of forms: amorphous, graphite, nanotubes, etc. (see inset 2 below)
Has a wide electrochemical stability window
Exhibits biocompatibility
Has a low cost
Is chemically inert
Is easy to derivatize
Is well known for its battery and sensor application
Carbon nanotubes connect via carbon-based microelectromechanical system
Is natures builiding block for living things
H
H H H H H H H H
C C C C C C C C
H H H H H H H H
Mer unit
(a)

0.2

No
film

[CH2]n

0.8

0.4

0.6

0.6
Diamond
C

(b)

Csp

Figure 1.18. Carbon: the next Si? [9].

Inset 2

[CH]n

Hard a-C:H
0.8
ta.C
0.2

Pre-graphitic
carbon

0.4

0.4

0.2

0.6

Hard a-C
Inset 1

Soft a-C:H

0.8
Soft a-C

Graphite
Csp

C-MEMS AND C-NEMS INTRODUCTION19

were also alluded to in the preceding text, and we will single out some of
them for more scrutiny in the current section and in subsequent chapters
of this book.
Here we limit ourselves to short descriptions of the following three
emerging C-MEMS and C-NEMS applications: (i) C-MEMS smart Li-ion
batteries, (ii) redox amplifications with carbon interdigitated electrode
arrays (IDEAs), and (iii) carbon hot nanowires to make nanogas sensors
with local CVD, nanoconstrictions, and nanogaps.
1.4.1 C-MEMS LI-ION BATTERIES
The electrochemical characteristics of carbon produced by pyrolysis
of photoresists have been studied to some extent [5]. It is found that
electrochemical reactions on pyrolyzed photoresist exhibit kinetics

very similar to those on glassy carbon. Glassy carbon electrodes are the
gold standard for electrochemists because of their wide electrochemical
stability window, low background, and low cost [91]. Also graphite and
hard carbons are well known for their utility in Li-ion battery applications
because of their Li intercalation or deintercalation capacity [9295]. Our
team established that glassy carbon electrodes produced by carbonization
do not only show the same fast kinetics for surface reactions as commercial
glassy carbon electrodes [96] but also that they can be intercalated and
deintercalated with lithium ions as fast and with as high a capacity as
other carbon anodes in commercial Li-ion batteries [31, 78, 97, 98]. The
latter observation did set the stage for the introduction of Li-ion batteries
based on C-MEMS [99]. The multilevel C-MEMS process described in
Figure 1.2 (right panel) was used for making the two-level Li-ion-based
C-MEMS battery shown in Figure 1.19 [100]. In the C-MEMS battery
depicted here, one layer of carbon constitutes the current collector (20 m
thick) for the rows of anode and cathode posts (250 m high) made in the
second C-MEMS layer. This type of C-MEMS battery holds the promise
of changing the battery world in three significant ways [9, 77, 100]:
1. Smarter batteries: C-MEMS batteries contain a multitude of anodes
and cathodes (baxels, by analogy to pixels) that are interconnected to
provide the optimal current or voltage depending on the a pplication
need. This way in-battery smart load leveling is enabled;
2. Faster charging batteries: In charging the C-MEMS battery, Li ions
only need to intercalate into the thin individual carbon posts rather
than intercalating into one big chunk of carbon;

20 CARBON: THE NEXT SILICON?

1.00 mm
Madou 0.5 kV 12.8mmx250 2/10/04

200 um

Figure 1.19. Smart Li-ion battery. Typical two-level carbon-based MEMS

electrodes with carbon contacts underneath. The inset image shows enlarged
SU-8 two-level structure [9].

3. Theoretically, the capacity of the C-MEMS batteries, depending

on the aspect ratio of the posts and the thickness of the electrolyte, can be significantly higher than that of current Li-ion batteries
[77, 101].
Recently, carbon anodes for Li-ion batteries are combined in clever
ways with Si that has yet a higher capacity than carbon but is irreversible
[102104]. By combining these two elements in the correct way, a superior
battery that remains reversible can be built, maintaining all the advantages
listed earlier and featuring an even higher capacity than when using carbon alone.
1.4.2REDOX AMPLIFICATION WITH CARBON
INTERDIGITATED ELECTRODE ARRAYS
A second recent application of C-MEMS and C-NEMS we are illustrating
here is its use in the fabrication of ultramicroelectrodes (UM). UM
have become an important tool in electrochemical analysis because the
electrochemical signal is determined almost exclusively by diffusion with
no or little effect of convection and because the steady-state currents are

C-MEMS AND C-NEMS INTRODUCTION21

achieved very fast owing to the nonlinear diffusion effects that make
for more effective mass transport [105]. Most importantly, in UMs, the
signal can be amplified through a clever electrode arrangement involving
interdigitated working electrodes (generator and collector separated by a

narrow gap) (see Figure 1.20). By applying a different potential on the two
working electrodes in an IDEA, redox species can be recycled between
the electrodes before diffusing away into the bulk of the solution. This
recycling results in current amplification. If the electrode gap is small,
and especially when the electrodes are high (nonplanar), the redox species
may experience multiple redox cycles before diffusing away into the bulk
of the solution [106108]. Better current amplification can be achieved
by reducing the electrode gap to the nanometer level by implementing
high aspect ratio 3D IDEA electrodes and with a combination of both. To
make submicrometer nanogaps, expensive processes such as FIB milling,
e-beam lithography, and nanoimprinting are required. However, 3D IDEA
electrodes can achieve comparable or better current amplification using
more conventional microfabrication technology, which is better for batch
fabrication of less expensive commercial sensors. The redox amplification improves the lower limit of detection (LOD) of a simple, inexpensive
electrochemical sensor dramatically so much so that it might become competitive with widely used and more expensive and cumbersome optical
techniques such as fluorescence sensing.
Today, IDEAs are typically made from noble metals such as thin
films of Pt or Au on a Si substrate (see Figure 1.20b [106108, 114].
(i)

Generator

e
Generator

e
Collector

R
e
Generator

(ii)

Collector

e
e e

e
e e

e
e e

Generator

Collector

Generator

Figure 1.20. IDEAs consist of a pair of comb-shaped electrodes one

of which works as a generator and the other as a collector (left panel).
Schematic view of redox cycling of oxidized (O) and reduced (R) species
in an IDEA: (i) plane electrodes, (ii) 3D electrodes (right panel) [109113].

22 CARBON: THE NEXT SILICON?

These IDEAs require the deposition of a thin layer of a metal adhesion

layer (e.g., Cr or Ti) followed by the noble metal layer. The patterning of
the noble metal layer requires the use of a cumbersome lift-off process. As
two different metals are used, corrosion potentials are hard to avoid. While
metal electrodes exhibit a lower electrical resistance than that of carbon,
they come with all types of unwanted electrochemical side reactions even
at low potentials, while glassy carbon electrodes are stable and come with
a wider stability window than any noble metal. C-MEMS and C-NEMS
IDEAs are not only much simpler to make (one step process), carbon
also is easier to make into a 3D structure (high aspect ratio that benefits
redox amplificationsee preceding information). As an added benefit,
one avoids the corrosion issue by dealing with one material only. Moreover, metal electrodes have lower biocompatibility and a higher fouling
propensity compared to c arbon electrodes. High aspect ratio metal electrodes, on the other hand, are difficult and expensive to fabricate, especially if nanometer gaps are required. C-MEMS and C-NEMS techniques,
on the other hand, excel at reaching both the nanometer dimensions and
highaspect ratios.
Three-dimensional (3D) carbon IDEAs were fabricated in our group
by using inexpensive, conventional, UV photolithography of SU-8 with
slightly modified exposure and postexposure bake settings followed
by pyrolysis in an inert environment (see Figure 1.21) [71]. The redox
amplification of sensors made this way was investigated as a function of
both the IDEA digit width-to-gap ratio and digit height as a function of
potential sweep rate and under flow and no flow conditions. A gradual
increase in redox amplification with an increase in the IDEA digit width-togap ratio was demonstrated. A maximum amplification of 37 was obtained
for a width-to-gap ratio of 1.58 and for an electrode height of 1.1 m.
Redox amplification significantly increased with an increase in the IDEA
height, from a factor of 9 at a 0.22 m digit height to a factor of 37 at a
1.1 m height. As the sweep rate was decreased from 50 mV/s to 5 mV/s,
the collection efficiency increased from 0.92 to 0.97, whereas the amplification increased from 7 to 25. Under flow conditions, the amplification
decreases substantially as the cycling of the redox species is impeded by
convection. The highest amplification of 37 dropped to 4 at a flow rate of
500 nL/s. Under flow conditions, redox amplification increased with an
increase in the IDEA height [71, 115]. This can be understood by the fact
that between the electrodes the diffusion paths of cycling redox species are
linear and little disturbed by flow, whereas above the electrodes, the diffusion is elliptical and very sensitive to flow (see right panel in Figure1.20).

C-MEMS AND C-NEMS INTRODUCTION23

4 m
e

3 m
f

5m

5.0m

Figure 1.21. (a) Shows the actual 3D carbon IDEA sensor. WE1
and WE2 are contact pads for the generator and the c ollector,
respectively. C and R are counter and reference electrodes,
respectively; (b) shows the final device with p olydimethylsiloxane
flow channels. The reference electrode is coated with Ag or
AgCl ink, and contact pads are coated with silver paste for better
electrical connection. (c and e) SEM images (tilted view 60) under
10,000 magnification of SU-8 IDEA patterning before pyrolysis;
height= 0.6 and 2.1 m, respectively. (d and f) Carbon IDEA after
pyrolysis; height = 0.22 and 0.59 m, respectively [71, 115].

To make the redox amplification even less sensitive to flow, the C-MEMS
walls can be made much higher (in the example, walls were only 1.1 m
high).
Voldman et al. experimented with thicker microfabricated
nonplanar gold electrode arrays (paired microelectrodes that were 3 m
thick and spaced 10 m apart) for dielectrophoretic single cell trapping
[116, 117]. To fashion the 3D gold electrodes, they used gold electroplating in an SU-8 mold to plate up the thin underlying Au film. These
3D arrangements produce more uniform electrical fields compared
to conventional planar microelectrodes and are more efficient at cell
trapping just as our 3D IDEAs are more efficient at redox cycling The
underlying reason is the same, that is, a higher aspect ratio. But electroplating is cumbersome and expensive compared to the 3D C-MEMS
approach, and 3D C-MEMS is now also used in the dielectrophoresis
application [86, 118].

24 CARBON: THE NEXT SILICON?

1.4.3CARBON HOT NANOWIRES TO MAKE NANOGAS

SENSORS WITH LOCAL CVD, NANOCONSTRICTIONS,
AND NANOGAPS
As nanowires are almost all surface and because sensing is usually a s urface
phenomenon, sensing induced changes on a nanowire has a larger effect
on the overall resistivity or impedance of a nanowire than that in the case
of a bulk wire and this leads to an improved lower LOD [9]. Suspended
CNWs as shown in Figures 1.13 and 1.15 have several f urther advantages.
Suspended nanowires are removed from the supporting substrate, and this
leads to significant advantages over other nanowire-based sensors typically
embedded on a solid substrate. The suspension a rrangement avoids deleterious substrate influences such as contamination and charge shunting. The
LOD also further increases because of higher mass transport because of
the nonlinear diffusion effects and because the wire can be approached by
analyte molecules from all directions. We call this principle wash cloth line
sensors, and by derivatizing the CNW s urface with a monolayer of sensor
molecules (the clothes on the wash line), say p rotein or DNA molecules,
the nanowires can be turned nano-immuno or nano-DNA sensors by monitoring how the binding of the complementary molecules modulates the
nanowiress impedance (see Figure 1.22). When coating the CNWs with
metal oxide semiconductors (MOS), they can also be turned into nanogas
sensors [90, 119124]. It is the nanogas sensor application we will detail a
bit further here, and this brings us to the topic of carbon nano hot wires [36].

9/1/2010 Spot HV
mag
WD
10:24:00 AM 4.5 5.00 kV 1500 x 10.0 mm

40 m

Figure 1.22. We compare the suspended nanowire (left) with a wash cloth
line (right). By derivatizing the CNW surface with a monolayer of sensor
molecules, say proteins or DNA (the clothes on the wash cloth line), these
nanowires can be turned into nano-immuno or nano-DNA sensors. The binding
of the complementary protein or DNA strands changes the impedance of the
nanowire.

C-MEMS AND C-NEMS INTRODUCTION25

In principle, when direct current is applied to a suspended CNW as

shown in Figure 1.22 (left panel), the high resistance of the CNW compared to the bulkier supporting C-MEMS contacting electrodes allows for
its selective heating, which initiates local CVD on the wires but not on the
supporting contact electrodes from any suitable precursor. Local CVD for
depositing a metal oxide material for gas sensor applications was first used
on CMOS micro hot plates by Semancik et al. [125128]. However, as
the heated area is reduced from the micro to the nano regime, and as one
moves from a plate (2D) to a wire (1D), Joule heating becomes much more
complicated because of the huge temperature gradient along the wire and
the rapid cooling of the nanostructure material [36]. While the suspended
CNW remains at a temperature close to that of the contacting electrodes at
the contact points (often referred to as cold points), its center reaches a much
higher temperature and a parabolic temperature profile results [36] (for references discussing Joule heating of metal nanowires consult [129131]).
As an example of MOS deposition that can be used for the f abrication of
a NOx nanogas sensor, we have demonstrated the local CVD on CNWs
by depositing a tungsten oxide (WO3) film from tungsten hexacarbonyl
[W(CO)6] as the precursor [36]. WO3 is a well-known s ensitive and selective NOx sensor material (ammonia and methane are also detected depending on catalyst and temperature used) [132, 133]. SEM images of a 358-nm
thick, 30-m long CNW after WO3 deposition by local CVD of W(CO)6
are shown in Figure 1.23a and b. The thickness of the deposit follows the
temperature profile expected for a heated nanowire with the center being

Heated CNW
Electrodes

Figure 1.23. (a) SEM images of a 358-nm thick CNW with

WO3 deposited on its surface by selected area CVD, (b) a
high-magnification image of the granular surface of WO3.
Inset: schematic of the local CVD process on a suspended
nanowire [36].

26 CARBON: THE NEXT SILICON?

considerably thicker (diameter of ~1.8 m) compared to the ends of the

CNW (358 nm). The diameter at the center of the wire after deposition as
well as the granular nature of the deposited material can be observed in
Figure 1.23b, which is a high-magnification micrograph of a central segment of the CNW. The composition of the deposited film was confirmed by
Energy Dispersive X-Ray Analysis (EDX) spectroscopy and by evaluating
the photoresistive behavior of the deposited material.
The local CVD phenomenon illustrated here is not limited to WO3
deposition; it can be used to obtain nanowires of any desired material by
heating the appropriate precursor gas, volatile liquid, or solid onto a hot
CNW. This fabrication technique is compatible with batch manufacturing
and offers scalability at low cost that renders it suitable for both research
and industrial applications. Joule heating for local CVD on CNWs has
the potential to become a useful tool for thermal deposition for the
manufacture of all types of nanosensor and nanoelectronics devices.
Controlled Joule heating of suspended nanowires is also intrinsically
capable of creating nanoconstrictions and nanogaps. Controlled thinning
of CNWs at their center by inducing carbon sublimation might eventually
allow one to study the transition from diffusional electron conduction to
ballistic conduction as the wire is thinned down to the couple of nanometer range [36, 62, 88]. This way one can manufacture quantum mechanical
nanoconstrictions without the need for expensive equipment. The thinning
(nanoconstriction) and eventual breakage (nanogaps) of the CNW can be
understood as follows. At the beginning of a Joule heating experiment, a
central region of the CNW attains the highest temperature, high enough to
sublimate some carbon from its surface. If a constant current is imposed,
this thinner segment attains the sublimation temperature even faster, as
it offers a yet higher resistance, which will lead to yet faster thinning at
its center. Finally, when the center cannot withstand further thinning the
nanowire breaks. Figure 1.24 shows that the breakage point is not always
exactly at the center in the CNW; this is only true for a completely uniform
CNW; any imperfection or nick in the carbon wire might have the thinning
occur there.
The thinner and shorter the CNW wire, the higher is the temperature
gradient and the smaller is the nanogap in its center can be made. N
anogaps
(with a dimension of less than 10 nm) in a CNW as described here might
have great utility as a building block for molecular electronics, based on
molecular interactions in a carbonmoleculecarbon (C-M-C) structure
[134136]. In a C-M-C system, the electronic function will be the property
of the molecular structure in the C-M-C chain and can be characterized
through I/V measurements. Such a system has the ability to measure and

C-MEMS AND C-NEMS INTRODUCTION27

Figure 1.24. SEM images of a 28.3-m long, 220.5-nm diameter CNW

showing breakage due to overheating at its center. The entire CNW with
thinning taking place approximately half-way is shown in the panel on the
left and the central region of the CNW is illustrated in the panel on the right
[36].

to transduce events of specific molecules into useful electrical signals.

There are a lot of techniques for obtaining nanogaps, but a process to
totally control the gap size has not been found yet.
So far, to use Joule heating of a nanowire to make nanoconstrictions
and nanogaps has proven to be difficult; once the thinning process starts,
it is difficult to control, and if a constant current is used, the breakage of
the CNW takes place very rapidly. Our team is currently developing an
electronic control system to control the wire thickness in the center to
any desired radius (nanoconstriction) and to make nanogaps of any size.
For the fabrication of nanoconstrictions and nanogaps using the n anowire
thinning method described here, two requirements must thus be met: (1)
exquisite control of the carbon sublimation, which can be achieved by
introducing a sophisticated control system in our setup that allows for
switching between current and voltage, and (2) creating as short a sublimation zone at the nanowire center as possible, which can be done by
tuning the initial CNW length and thickness.

REFERENCES
[1]Youn, S.W., M. Takahashi, H. Goto, and R. Maeda. 2006. Microstructuring
of Glassy Carbon Mold for Glass EmbossingComparison of Focused Ion
Beam, Nano/Femtosecond-Pulsed Laser and Mechanical Machining.
Microelectronic Engineering 83, no. 11, pp. 248292. doi: http://dx.doi.
org/10.1016/j.mee.2006.05.007

28 CARBON: THE NEXT SILICON?

[2]Hans, L.E., K. Prater, C. Kilchoer, T. Scharf, H.P. Herzig, and A. Hermerschmidt. 2014. Conference on Advanced Fabrication Technologies for
Micro/Nano Optics and Photonics VII. San Francisco, CA.
[3]Wang, J., B. Tian, V.B. Nascimento, and L. Angnes. 1998. Performance of
Screen-Printed Carbon Electrodes Fabricated from Different Carbon Inks.
Electrochimica Acta 43, no. 23, pp. 345965. doi: http://dx.doi.org/10.1016/
s0013-4686(98)00092-9
[4]Madou, M., A. Lai, G. Schmidt, X. Songc, K. Kinoshitac, M. Fendorf, A.
Zettl, and R. White. 1997. Carbon Micromachining (C-Mems). In Chemical and Biological Sensors and Analytical Electrochemical Methods:
Proceedings of the Symposium on Chemical and Biological Sensors and
Analytical Electrochemical Methods, p. 1961.
[5]Ranganathan, S., R. McCreery, S.M. Majji, and M. Madou. 2000. PhotoresistDerived Carbon for Microelectromechanical Systems and Electrochemical
Applications. Journal of the Electrochemical Society 147, no. 1, pp. 27782.
doi: http://dx.doi.org/10.1149/1.1393188
[6]Wang, C.L., G.Y. Jia, L.H. Taherabadi, and M.J. Madou. 2005. A Novel
Method for the Fabrication of High-Aspect Ratio C-MEMS Structures.
Journal of Microelectromechanical Systems 14, no. 2, pp. 34858. doi: http://
dx.doi.org/10.1109/jmems.2004.839312
[7]Madou, M.J. 2002. Fundamentals of Microfabrication: The Science of
Miniaturization, Second Edition. Boca Raton, FL: CRC Press.
[8]Madou, M.J. 2011. Manufacturing Techniques for Microfabrication and
Nanotechnology. Boca Raton, FL: CRC Press.
[9]Madou, M.J. 2011. From MEMS to Bio-MEMS and Bio-NEMS:
Manufacturing Techniques and Applications. Boca Raton, FL: CRC Press.
[10]Harris, P.J.F. 2004. Fullerene-Related Structure of Commercial Glassy
Carbons. Philosophical Magazine 84, no. 29, pp. 315967. doi: http://dx.
doi.org/10.1080/14786430410001720363
[11]Jenkins, G.M., and K. Kawamura. 1971. Structure of Glassy Carbon.
Nature 231, no. 5299, pp. 17576. doi: http://dx.doi.org/10.1038/231175a0
[12]Jenkins, G.M. 1976. Polymeric CarbonsCarbon Fibre, Glass and Char.
Cambridge, New York: Cambridge University Press.
[13]Franklin, R.E. 1951. The Structure of Graphitic Carbons. Acta Crystallographica
4, no. 3, pp. 25361. doi: http://dx.doi.org/10.1107/s0365110x51000842
[14]
Franklin, R.E. 1951. Crystallite Growth in Graphitizing and Non-
Graphitizing Carbons. Proceedings of the Royal Society A: Mathematical,
Physical and Engineering Sciences 209, no. 1097, pp. 196218. doi: http://
dx.doi.org/10.1098/rspa.1951.0197
[15]Lyons, A.M., C.W. Wilkins, and M. Robbins. 1983. Thin Pinhole-Free
Carbon Films. Thin Solid Films 103, no. 4, pp. 33341. doi: http://dx.doi.
org/10.1016/0040-6090(83)90589-8
[16]Schueller, O.J.A., S.T. Brittain, and G.M. Whitesides. 1997. Fabrication of
Glassy Carbon Microstructures by Pyrolysis of Microfabricated Polymeric

C-MEMS AND C-NEMS INTRODUCTION29

Precursors. Advanced Materials 9, no. 6, pp. 47780. doi: http://dx.doi.
org/10.1002/adma.19970090604
[17]Schueller, O.J.A., S.T. Brittain, C. Marzolin, and G.M. Whitesides. 1997.
Fabrication and Characterization of Glassy Carbon MEMS. C
hemistry
of Materials 9, no. 6, pp. 1399406. doi: http://dx.doi.org/10.1021/
cm960639v
[18]Lyons, A.M. 1985. Photodefinable Carbon Films: Electrical Properties.
Journal of Non-Crystalline Solids 70, no. 1, pp. 99109. doi: http://dx.doi.
org/10.1016/0022-3093(85)90097-3
[19]Lyons, A.M., L.P. Hale, and C.W. Wilkins. 1985. Photodefinable Carbon
Films: Control of Image Quality. Journal of Vacuum Science & Technology
B 3, no. 1, pp. 44752. doi: http://dx.doi.org/10.1116/1.583284
[20]Lyons, A.M., C.W. Wilkins, and M. Robbins. 1984. 308. Carbon Films
Prepared from a Phenol Formaldehyde Polymer Precursor. Carbon 22,
no.2, p. 239. doi: http://dx.doi.org/10.1016/0008-6223(84)90525-6
[21]Wang, C., and M. Madou. 2005. From MEMS to NEMS with Carbon.
Biosensors and Bioelectronics 20, no. 10, pp. 2181187. doi: http://dx.doi.
org/10.1016/j.bios.2004.09.034
[22]Ki Bang, L., and L. Liwei. 2003. Surface Micromachined Glass and Polysilicon Microchannels Using MUMPs. In Micro Electro Mechanical Systems,
2003.MEMS-03 Kyoto.IEEE The Sixteenth Annual International Conference, January 1923, pp. 57881.
[23]Lee, S.J., W. Shi, P. Maciel, and S.W. Cha. 2003. University/Government/
Industry Microelectronics Symposium, 2003. In Proceedings of the 15th
Biennial, pp. 38990.
[24]Wang, C., L. Taherabadi, K. Malladi, and M. Madou. 2005. C, Ni and Si
Nanowires Formation by Local CVD and SLS Mechanisms. Nanotech 2005,
Anaheim, CA.
[25]Wang, C., R. Zaouk, and M. Madou. 2006. Local Chemical Vapor D
eposition
of Carbon Nanofibers from Photoresist. Carbon 44, no. 14, pp. 307377.
doi: http://dx.doi.org/10.1016/j.carbon.2006.05.007
[26]Sharma, S., R. Kamath, and M. Madou. 2014. Porous Glassy Carbon Formed
by Rapid Pyrolysis of Phenol-Formaldehyde Resins and Its P
erformance as
Electrode Material for Electrochemical Double Layer Capacitors. J ournal
of Analytical and Applied Pyrolysis 108, pp. 1218. doi: http://dx.doi.
org/10.1016/j.jaap.2014.05.025
[27]Hsia, B., M.S. Kim, M. Vincent, C. Carraro, and R. Maboudian. 2013.
Photoresist-Derived Porous Carbon for On-Chip Micro-Supercapacitors.
Carbon 57, pp. 395400. doi: http://dx.doi.org/10.1016/j.carbon.2013.01.089
[28]Wang, S., B. Hsia, C. Carraro, and R. Maboudian. 2014. High-Performance
All Solid-State Micro-Supercapacitor Based on Patterned Photoresist-Derived
Porous Carbon Electrodes and an Ionogel Electrolyte. Journal of M
aterials
Chemistry A 2, no. 21, pp. 79978002. doi: http://dx.doi.org/10.1039/
c4ta00570h

30 CARBON: THE NEXT SILICON?

[29] Zaouk, R.B. 2008. Mechanical and Aerospace Engineering. UC Irvine.
[30]Penmatsa, V., J.H. Yang, Y. Yu, and C. Wang. 2010. Fabrication of Porous
Carbon Micropillars Using a Block Copolymer as Porogen. Carbon 48,
no.14, pp. 410915. doi: http://dx.doi.org/10.1016/j.carbon.2010.07.019
[31]Sharma, C.S., H. Katepalli, A. Sharma, G.T. Teixidor, and M. Madou. March
25, 2014. Fabrication of Resorcinol-Formaldehyde Xerogel Based High
Aspect Ratio 3-D Hierarchical C-MEMS Structures. ECS Transactions 61,
no. 7, pp. 4554. doi: http://dx.doi.org/10.1149/06107.0045ecst.
[32]Sharma, C.S., M.M. Kulkarni, A. Sharma, and M. Madou. 2009. Synthesis
of Carbon Xerogel Particles and Fractal-Like Structures. Chemical
Engineering Science 64, no. 7, pp. 153643. doi: http://dx.doi.org/10.1016/
j.ces.2008.12.013
[33]Sharma, C.S., S. Patil, S. Saurabh, A. Sharma, and R. Venkataraghavan.
2009. Resorcinol-Formaldehyde Based Carbon Nanospheres by Electrospraying. Bulletin of Materials Science 32, no. 3, pp. 23946. doi: http://
dx.doi.org/10.1007/s12034-009-0036-6
[34]Teixidor, G.T., R.A. Gorkin, III, P.P. Tripathi, G.S. Bisht, M. Kulkarni,
T.K. Maiti, T.K. Battacharyya, J.R. Subramaniam, A. Sharma, B.Y. Park, and
M. Madou. 2008. Carbon Microelectromechanical Systems as a Substratum
for Cell Growth. Biomedical Materials 3, no. 3, p. 034116. doi: http://dx.
doi.org/10.1088/1748-6041/3/3/034116
[35]Kavaliauskas, Z., L. Marcinauskas, and V. Valincius. 2014. Influence
of the Oxygen Plasma Treatment on Carbon Electrode and Capacity of
Supercapacitors. Acta Physica Polonica A 125, no. 6, pp. 131619. doi:
http://dx.doi.org/10.12693/aphyspola.125.1316
[36]Sharma, S. 2013. Microstructural Tuning of Glassy Carbon for Electrical
and Electrochemical Sensor Applications [dissertation]. University of
California, Irvine, CA.
[37]
Monsur Islam, R.B., S. Sharma, and M.J. Madou. 2013. Early Career
Technical Conference 2013, pp. 4652. Birmingham, AL.
[38]
Kipling, J.J., J.N. Sherwood, P.V. Shooter, and N.R. Thompson. 1964.
Factors Influencing the Graphitization of Polymer Carbons. Carbon 1,
no.3, pp. 31520. doi: http://dx.doi.org/10.1016/0008-6223(64)90285-4
[39]Oberlin, A. 1984. Carbonization and Graphitization. Carbon 22, no. 6,
pp.52141. doi: http://dx.doi.org/10.1016/0008-6223(84)90086-1
[40]Wendorff, J.H., S. Agarwal, and A. Greiner. 2012. Nanofiber Properties. In
Electrospinning, 69104. Wiley-VCH Verlag GmbH & Co. KGaA.
[41]
Sharma, C.S., A. Sharma, and M. Madou. 2010. Multiscale Carbon
Structures Fabricated by Direct Micropatterning of Electrospun Mats of
SU-8 Photoresist Nanofibers. Langmuir 26, no. 4, pp. 221822. doi: http://
dx.doi.org/10.1021/la904078r
[42]Teixidor, G.T., P. Mukherjee, B. Park, and M. Madou. 2009. Theoretical Evaluation of Fractal-Like Electrode Characteristics for Litium-Ion Batteries.
Meeting Abstracts, no. 4, pp. 25959.

C-MEMS AND C-NEMS INTRODUCTION31

[43]
Teixidor, G.T., P.P. Mukherjee, and M. Madou. 2008. Modeling of
Fractal Electrodes in Lithium-Ion Batteries. Meeting Abstracts, no. 12,
pp. 116767.
[44]Teixidor, G.T., R.B. Zaouk, B.Y. Park, and M.J. Madou. 2008. Fabrication and
Characterization of Three-Dimensional Carbon Electrodes for Lithium-Ion
Batteries. Journal of Power Sources 183, no. 2, pp. 73040. doi: http://
dx.doi.org/10.1016/j.jpowsour.2008.05.065
[45]Mitra, J., S. Jain, A. Sharma, and B. Basu. 2013. Patterned Growth and
Differentiation of Neural Cells on Polymer Derived Carbon Substrates with
Micro/Nano Structures in Vitro. Carbon 65, pp. 14055. doi: http://dx.doi.
org/10.1016/j.carbon.2013.08.008
[46]Teixidor, G.T., R.A. Gorkin, P.P. Tripathi, G.S. Bisht, M. Kulkarni, T.K.
Maiti, T. K. Battacharyya, J.R. Subramaniam, A. Sharma, B.Y. Park, and
M.Madou. 2008. Biomedical Materials (Bristol, England) 3, no. 3, p.
034116. doi: http://dx.doi.org/10.1088/1748-6041/3/3/034116
[47]Amato, L., A. Heiskanen, C. Caviglia, F. Shah, K. Zor, M. Skolimowski,
M.Madou, L. Gammelgaard, R. Hansen, E.G. Seiz, M. Ramos, T. Moreno,
A. Martnez-Serrano, S.S. Keller, and J. Emnus. 2014. Pyrolysed 3D
Carbon Scaffolds Induce Spontaneous Differentiation of Human Neural

Stem Cells and Facilitate Real-Time Dopamine Detection. Advanced Functional Materials 24, no. 44, pp. 704252. doi: http://dx.doi.org/10.1002/
adfm.201400812
[48]
Xu, H., K. Malladi, C. Wang, L. Kulinsky, M. Song, and M. Madou.
2008. Carbon Post-Microarrays for Glucose Sensors. Biosensors and
Bioelectronics 23, no. 11, pp. 163744. doi: http://dx.doi.org/10.1016/j.
bios.2008.01.031
[49]Njagi, J., M.M. Chernov, J.C. Leiter, and S. Andreescu. 2010. Amperometric
Detection of Dopamine in Vivo with an Enzyme Based Carbon Fiber Microbiosensor. Analytical Chemistry 82, no. 3, pp. 98996. doi: http://dx.doi.
org/10.1021/ac9022605
[50]Dogan, M., and O. Karatay. 2011. Modelling of Electrospinning Process at
Various Electric Fields. Micro & Nano Letters 6, no. 10, pp. 85862. doi:
http://dx.doi.org/10.1049/mnl.2011.0440
[51]Salifu, A.A., B.D. Nury, and C. Lekakou. 2011. Electrospinning of Nanocomposite Fibrillar Tubular and Flat Scaffolds with Controlled Fiber
Orientation. Annals of Biomedical Engineering 39, no. 10, pp. 251020.
doi: http://dx.doi.org/10.1007/s10439-011-0350-1
[52]Viswanadam, G., and G.G. Chase. 2013. Modified Electric Fields to Control
the Direction of Electrospinning Jets. Polymer 54, no. 4 pp. 1397404. doi:
http://dx.doi.org/10.1016/j.polymer.2012.12.082
[53]
Sharma, S., A. Sharma, Y.K. Cho, and M. Madou. 2012. Increased
Graphitization in Electrospun Single Suspended Carbon Nanowires I ntegrated
with Carbon-MEMS and Carbon-NEMS Platforms. ACS Applied Materials
& Interfaces 4, no. 1, pp. 3439. doi: http://dx.doi.org/10.1021/am2014376

32 CARBON: THE NEXT SILICON?

[54]Ji, Y., C. Li, G. Wang, J. Koo, S. Ge, B. Li, J. Jiang, B. Herzberg, T. Klein,
S. Chen, J.C. Sokolov, and M.H. Rafailovich. 2008. Confinement-Induced
Super Strong PS/MWNT Composite Nanofibers. EPL (Europhysics Letters)
84, no. 5, p. 56002. doi: http://dx.doi.org/10.1209/0295-5075/84/56002
[55]Sharma Swati, Y.K.C., and M. Madou. 2010. Nano-Bio-Tech Montreux.
Montreux 2010.
[56]Chang, C., K. Limkrailassiri, and L. Lin. 2008. Continuous Near-Field
Electrospinning for Large Area Deposition of Orderly Nanofiber Patterns. Applied Physics Letters 93, no. 12, p. 123111. doi: http://dx.doi.
org/10.1063/1.2975834
[57]Sun, D., C. Chang, S. Li, and L. Lin. 2006. Near-Field Electrospinning.
Nano Letters 6, no. 4, pp. 83942. doi: http://dx.doi.org/10.1021/nl0602701
[58]Bisht, G., G. Canton, A. Mirsepassi, D. Dunn-Rankin, L. Kulinsky, M.Madou.
2011. In Proceedings of Technologies for Future Micro-Nano Manufacturing.
Napa, CA.
[59]
Bisht, G., S. Nesterenko, L. Kulinsky, and M. Madou. 2012. A

Computer-Controlled Near-Field Electrospinning Setup and Its Graphic User

Interface for Precision Patterning of Functional Nanofibers on 2D and 3D
Substrates. Journal of Laboratory Automation 17, no. 4, pp. 30208. doi:
http://dx.doi.org/10.1177/2211068212446372
[60]Bisht, G.S., G. Canton, M. Madou, A. Mirsepassi, and D. Dunn-rankin. 2012.
Low Voltage Near-Field Electrospinning Method and Device.
[61]Bisht, G.S., G. Canton, A. Mirsepassi, L. Kulinsky, S. Oh, D. Dunn-Rankin,
and M.J. Madou. 2011. Controlled Continuous Patterning of Polymeric
Nanofibers on Three-Dimensional Substrates Using Low-Voltage Near-Field
Electrospinning. Nano Letters 11, no.4, pp. 183137. doi: http://dx.doi.
org/10.1021/nl2006164
[62]Canton, G. 2014. Development of Electro-Mechanical Spinning for Controlled Deposition of Carbon Nanofibers [PhDThesis]. Irvine, CA: Mechanical and Aerospace Engineering, University of California.
[63]Harrison, B.S., and A. Atala. 2007. Carbon Nanotube Applications for Tissue Engineering. Biomaterials 28, no. 2, pp. 34453. doi: http://dx.doi.
org/10.1016/j.biomaterials.2006.07.044
[64]
He, H., L.A. Pham-Huy, P. Dramou, D. Xiao, P. Zuo, and C. PhamHuy. 2013. Carbon Nanotubes: Applications in Pharmacy and Medicine. BioMed Research International 2013, p. 12. doi: http://dx.doi.
org/10.1155/2013/578290
[65]Liang, F., and B. Chen. 2010. A Review on Biomedical Applications of
Single-Walled Carbon Nanotubes. Current Medicinal Chemistry 17, no. 1,
pp. 1024. doi: http://dx.doi.org/10.2174/092986710789957742
[66]Yang, W., P. Thordarson, J.J. Gooding, S.P. Ringer, and F. Braet. 2007.
Carbon Nanotubes for Biological and Biomedical Applications. Nanotechnology 18, no. 41, p. 412001. doi: http://dx.doi.org/10.1088/0957-4484/18/41/
412001

C-MEMS AND C-NEMS INTRODUCTION33

[67]Rao, S.S., A. Stesmans, D.V. Kosynkin, A. Higginbotham, and J.M. Tour.
2011. Paramagnetic Centers in Graphene Nanoribbons Prepared from
Longitudinal Unzipping of Carbon Nanotubes. New Journal of Physics 13,
no. 11, p. 113004. doi: http://dx.doi.org/10.1088/1367-2630/13/11/113004
[68]Sulong, A.B., N. Muhamad, J. Sahari, R. Ramli, M.D. Baba, and J. Park. 2009.
Electrical Conductivity Behaviour of Chemical Functionalized MWCNTs
Epoxy Nanocomposites. European Journal of Scientific Research 29, no.1,
pp. 1321.
[69]De Volder, M.F.L., S.H. Tawfick, R.H. Baughman, and A.J. Hart. 2013.
Carbon Nanotubes: Present and Future Commercial Applications. Science
339, no. 6119, pp. 53539. doi: http://dx.doi.org/10.1126/science.1222453
[70]Randviir, E.P., D.A.C. Brownson, and C.E. Banks. 2014. A Decade of
Graphene Research: Production, Applications and Outlook. Materials Today
17, no. 9, pp. 42632. doi: http://dx.doi.org/10.1016/j.mattod.2014.06.001
[71]Kamath, R.R., M.J. Madou. 2014. Three-Dimensional Carbon Interdigitated Electrode Arrays for Redox-Amplification. Analytical Chemistry 86,
no. 6, pp. 296371. doi: http://dx.doi.org/10.1021/ac4033356
[72]Mardegan, A., R. Kamath, S. Sharma, P. Scopece, P. Ugo, and M. Madou.
2013. Optimization of Carbon Electrodes Derived from Epoxy-based
Photoresist. Journal of the Electrochemical Society 160, no. 8, B13237.
doi: http://dx.doi.org/10.1149/2.107308jes
[73]Anariba, F., and R.L. McCreery. 2002. Electronic Conductance Behavior
of Carbon-Based Molecular Junctions with Conjugated Structures. The
Journal of Physical Chemistry B 106, no. 40, pp. 1035562. doi: http://dx.
doi.org/10.1021/jp026285e
[74]Ranganathan, S., I. Steidel, F. Anariba, and R.L. McCreery. 2001. Covalently
Bonded Organic Monolayers on a Carbon Substrate: A New Paradigm for
Molecular Electronics. Nano Letters 1, no. 9, pp. 49194. doi: http://dx.doi.
org/10.1021/nl015566f
[75]
Solak, A.O., S. Ranganathan, T. Itoh, and R.L. McCreery. 2002. A
Mechanism for Conductance Switching in Carbon-Based Molecular

Electronic Junctions. Electrochemical and Solid-State Letters 5, no. 8,

pp.E4346. doi: http://dx.doi.org/10.1149/1.1490716
[76]
Galobardes, F., C. Wang, and M. Madou. 2006. Investigation on the
Solid Electrolyte Interface Formed on Pyrolyzed Photoresist Carbon
Anodes for C-MEMS Lithium-Ion Batteries. Diamond and Related
Materials 15, no.1112, pp. 193034. doi: http://dx.doi.org/10.1016/
j.diamond.2006.08.015
[77]Long, J.W., B. Dunn, D.R. Rolison, and H.S. White. 2004. Three-Dimensional
Battery Architectures. Chemical Reviews 104, no. 10, pp.446392. doi:
http://dx.doi.org/10.1021/cr020740l
[78]Sharma, S., A. Khalajhedayati, T.J. Rupert, and M.J. Madou. 2014. SU8
Derived Glassy Carbon for Lithium Ion Batteries. ECS Transactions 61,
no.7, pp. 7584. doi: http://dx.doi.org/10.1149/06107.0075ecst

34 CARBON: THE NEXT SILICON?

[79]Turon Teixidor, G., B.Y. Park, P.P. Mukherjee, Q. Kang, and M.J. Madou.
2009. Modeling Fractal Electrodes for Li-Ion Batteries. E
lectrochimica
Acta 54, no. 24, pp. 592836. doi: http://dx.doi.org/10.1016/j.electacta.2009.05.060
[80]Wang, Y., K.S. Chen, J. Mishler, S.C. Cho, and X.C. Adroher. 2011. A
Review of Polymer Electrolyte Membrane Fuel Cells: Technology, Applications, and Needs on Fundamental Research. Applied Energy 88, no. 4,
pp.9811007. doi: http://dx.doi.org/10.1016/j.apenergy.2010.09.030
[81]
Wang, Y., L. Pham, G.P.S.de. Vasconcellos, and M. Madou. 2010.
Fabrication and Characterization of Micro PEM Fuel Cells Using Pyrolyzed
Carbon Current Collector Plates. Journal of Power Sources 195, no. 15,
pp.4796803. doi: http://dx.doi.org/10.1016/j.jpowsour.2010.02.050
[82]Park, B.Y., and M.J. Madou. 2006. Design, Fabrication, and Initial Testing
of a Miniature PEM Fuel Cell with Micro-Scale Pyrolyzed Carbon Fluidic
Plates. Journal of power sources 162, no. 1, pp. 36979. doi: http://dx.doi.
org/10.1016/j.jpowsour.2006.06.077
[83]Park, B.Y., and M.J. Madou. 2006. The Sixth International Workshop on
Micro and Nanotechnology for Power Generation and Energy Conversion
Applications. University of California, Berkeley, CA.
[84]Rouabah, H. A., B.Y. Park, R.B. Zaouk, M.J. Madou, and N.G. Green. 2008.
Producing Fluid Flow Using 3D Carbon Electrodes. Journal of Physics:
Conference Series 142, no. 1, p. 012072. doi: http://dx.doi.org/10.1088/17426596/142/1/012072
[85]Martinez-Duarte, R., R.A. Gorkin Iii, K. Abi-Samra, and M.J. Madou. 2010.
The Integration of 3D Carbon-Electrode Dielectrophoresis on a CD-Like
Centrifugal Microfluidic Platform. Lab on a Chip 10, no. 8, pp. 103043.
doi: http://dx.doi.org/10.1039/b925456k
[86]Martinez-Duarte, R., P. Renaud, and M.J. Madou. 2011. A Novel Approach
to Dielectrophoresis Using Carbon Electrodes. Electrophoresis 32, no. 17,
pp. 238592. doi: http://dx.doi.org/10.1002/elps.201100059
[87]Beidaghi, M., W. Chen, and C. Wang. 2011. Electrochemically Activated
Carbon Micro-Electrode Arrays for Electrochemical Micro-Capacitors.
Journal of Power Sources 196, no. 4, pp. 240309. doi: http://dx.doi.
org/10.1016/j.jpowsour.2010.09.050
[88]Mendoza-Buenrostro, C. 2013. Development and Characterization of Suspended Carbon Fiber Nanoconstriction, Nanogap, Incandescence, and
Deformation Effects Induced by Electric Currents [PhDThesis]. Monterrey,
NL, Mexico: Electric and Computer Engineering, Tecnologico de Monterrey.
[89]Schroers, J., G. Kumar, M. Madou, and R. Martinez-Duarte. 2010. Carbon
Molds for Use in the Fabrication of Bulk Metallic Glass Parts and Molds.
Google Patents.
[90]
Sharma, S., and M. Madou. A New Approach to Gas Sensing with
Nanotechnology. Philosophical Transactions of the Royal Society A:
Mathematical, Physical and Engineering Sciences 370, no. 1967, pp. 244873.
doi: http://dx.doi.org/10.1098/rsta.2011.0506

C-MEMS AND C-NEMS INTRODUCTION35

[91]Pocard, N.L., D.C. Alsmeyer, R.L. McCreery, T.X. Neenan, and M.R., Callstrom. 1992. Feature Articles. Doped Glassy Carbon: A New Material for
Electrocatalysis. Journal of Materials Chemistry 2, no. 8, pp. 77184. doi:
http://dx.doi.org/10.1039/jm9920200771
[92]Fong, R., U.von Sacken, and J.R. Dahn. 1990. Studies of Lithium Intercalation into Carbons Using Nonaqueous Electrochemical Cells. Journal
of The Electrochemical Society 137, no. 7, pp. 200913. doi: http://dx.doi.
org/10.1149/1.2086855
[93]Guerard, D., and A. Herold. 1975. Intercalation of Lithium into G
raphite
and Other Carbons. Carbon 13, no. 4, pp. 33745. doi: http://dx.doi.
org/10.1016/0008-6223(75)90040-8
[94]Kostecki, R., and F. McLarnon. 2003. Microprobe study of the Effect of Li
Intercalation on the Structure of Graphite. Journal of Power Sources 119
121, pp. 55054. doi: http://dx.doi.org/10.1016/s0378-7753(03)00287-8
[95]Shu, Z.X., R.S. McMillan, and J.J. Murray. 1993. Electrochemical Intercalation of Lithium into Graphite. Journal of The Electrochemical Society
140, no. 4, pp. 92227. doi: http://dx.doi.org/10.1149/1.2056228
[96]
Ranganathan, S., R. McCreery, S.M. Majji, and M. Madou. 2000.

Photoresist-Derived Carbon for Microelectromechanical Systems and

Electrochemical Applications. Journal of the Electrochemical Society 147,
no. 1, pp. 27782. doi: http://dx.doi.org/10.1149/1.1393188
[97]Kinoshita, K., X. Song, J. Kim, and M. Inaba. 1999. Development of a
Carbon-Based Lithium Microbattery. Journal of Power Sources 8182,
pp. 17075. doi: http://dx.doi.org/10.1016/s0378-7753(99)00189-5
[98]Turon-Teixidor, G., C. Wang, and M. Madou. 2006. Fabrication of 3D Carbon Microelectrodes for Li-Ion Battery Applications. In Proceedings of the
NSTI 2006 Conference. Boston, MA.
[99]Min, H.-S., B.Y. Park, L. Taherabadi, C. Wang, Y. Yeh, R. Zaouk, M. Madou,
and B. Dunn. 2008. Fabrication and Properties of a Carbon/Polypyrrole
Three-Dimensional Microbattery. Journal of Power Sources 178, no. 2,
pp. 795800. doi: http://dx.doi.org/10.1016/j.jpowsour.2007.10.003
[100]Wang, C., L. Taherabadi, G. Jia, M. Madou, Y. Yeh, and B. Dunn. 2004.
C-MEMS for the Manufacture of 3D Microbatteries. E
lectrochemical
and Solid-State Letters 7, no. 11, p. A435. doi: http://dx.doi.
org/10.1149/1.1798151
[101]Wang, C., F.G. Jornet, G.T. Teixidor, R. Zaouk, and M. Madou. June 30,
2006. C-MEMS for on-Chip Miniaturized Energy Source. Meeting
Abstracts, vol. MA2006-02, p. 1202.
[102]Yoshio, M., H. Wang, K. Fukuda, T. Umeno, N. Dimov, and Z. Ogumi. 2002.
Carbon-Coated Si as a Lithium-Ion Battery Anode Material. Journal of
The Electrochemical Society 149, no. 12, pp. A1598603. doi: http://dx.doi.
org/10.1149/1.1518988
[103]Cui, L.F., Y. Yang, C.M. Hsu, and Y. Cui. 2009. CarbonSilicon Core
Shell Nanowires as High Capacity Electrode for Lithium Ion Batteries.
Nano Letters 9, no. 9, pp. 337074. doi: http://dx.doi.org/10.1021/nl901670t

36 CARBON: THE NEXT SILICON?

[104]Bridel, J.S., T. Azas, M. Morcrette, J.M. Tarascon, and D. Larcher. 2010.
Key Parameters Governing the Reversibility of Si/Carbon/CMC Electrodes
for Li-Ion Batteries Chemistry of Materials 22, no. 3, pp. 122941. doi:
http://dx.doi.org/10.1021/cm902688w
[105]Heinze, J. 1993. Ultramicroelectrodes in Electrochemistry. Angewandte
Chemie International Edition in English 32, no. 9, pp. 126888. doi: http://
dx.doi.org/10.1002/anie.199312681
[106]
Lewis, P.M., L.B. Sheridan, R.E. Gawley, I. Fritsch. 2010. Signal
Amplification in a Microchannel from Redox Cycling with Varied
Electroactive Configurations of an Individually Addressable Microband
Electrode Array. Analytical Chemistry 82, no. 5, pp. 165968. doi: http://
dx.doi.org/10.1021/ac901066p
[107]
Takahashi, S., M. Futagawa, M. Ishida, K. Sawada. 2013. Proposition
and Fabrication of Amplified Redox Sensor (ARS) for High Sensitive
Chemical Analysis. In Solid-State Sensors, Actuators and Microsystems
(TRANSDUCERS & EUROSENSORS XXVII), 2013 Transducers &
Eurosensors XXVII: The 17th International Conference.
[108]Takahashi, S., M. Futagawa, M. Ishida, and K. Sawada. 2014. Directly
Amplified Redox Sensor for On-Chip Chemical Analysis. Japanese
Journal of Applied Physics 53, no. 3, p. 036702. doi: http://dx.doi.

org/10.7567/jjap.53.036702
[109]Heo, J.-I., Y. Lim, B. Lee, M. Madou, and H. Shin. 2012. Development
of a Carbon Microchannel Integrated with a Horizontal Carbon Sandwich
Electrode Pair for Ultra Sensitive Electrochemical/Bio Sensors. In 16th
International Conference on Miniaturized Systems for Chemistry and Life
Sciences, pp. 124042. Okinawa, Japan.
[110]Jeong-II, H., L. Yeongjin, M. Madou, and S. Heungjoo. 2012. Scalable
Suspended Carbon Nanowire Meshes as Ultrasensitive Electrochemical
Sensing Platforms. In Micro Electro Mechanical Systems (MEMS), IEEE
25th International Conference, January 29February 2, pp. 87881.
[111]Heo, J.-I., M. Madou, and H. Shin. 2011. Scalable Monolithic Suspended
Carbon Nanowire Array Systems as Ultrasensitive Electrochemical Sensing
Platforms. In 15th International Conference on Miniaturized Systems for
Chemistry and Life Sciences, pp. 197173. Seattle, Washington, USA.
[112]
Heo, J.-I., D.-S. Shim, R. Martinez-Duarte, M. Madou, and H. Shin.
2010. 3-D Carbon Interdigitated Array Nanoelectrodes for Highly Sensitive Sensing of Neurotransmitters. In 14th International Conference on
Miniaturized Systems for Chemistry and Life Sciences, MicroTAS 2010,
pp. 197678. Groningen, Netherlands.
[113]Heo, J.I., D.S. Shim, G.T. Teixidor, S. Oh, M.J. Madou, and H. Shin.
2011. Carbon Interdigitated Array Nanoelectrodes for Electrochemical
Applications. Journal of the Electrochemical Society 158, no. 3, pp. J76
80. doi: http://dx.doi.org/10.1149/1.3531952
[114]Wollenberger, U., M. Paeschke, and R. Hintsche, 1994. Interdigitated Array
Microelectrodes for the Determination of Enzyme Activities. A
nalyst 119,
no. 6, pp. 124549. doi: http://dx.doi.org/10.1039/an9941901245

C-MEMS AND C-NEMS INTRODUCTION37

[115]Kamath, R.R., and M.J. Madou. 2014. Selective Detection of D
opamine
Against Ascorbic Acid Interference Using 3D Carbon Interdigitated
Electrode Arrays. ECS Transactions 61, no. 7, pp. 6573. doi: http://dx.
doi.org/10.1149/06107.0065ecst
[116]Voldman, J. 2007. Dielectrophoretic Traps for Cell Manipulation. In
BioMEMS and Biomedical Nanotechnology, eds. M. Ferrari, R. Bashir, and
S. Wereley, 15986. Springer US.
[117]Voldman, J., M.L. Gray, M. Toner, and M.A. Schmidt. 2002. A Microfabrication-Based Dynamic Array Cytometer. Analytical Chemistry 74, no. 16,
pp. 398490.doi: http://dx.doi.org/10.1021/ac0256235
[118]Martinez-Duarte, R., R.A. Gorkin Iii, K. Abi-Samra, and M.J. Madou, 2010.
The Integration of 3D Carbon-Electrode Dielectrophoresis on a CD-Like
Centrifugal Microfluidic Platform. Lab on a Chip 10, no. 8, p.103043.
doi: http://dx.doi.org/10.1039/b925456k
[119]Barsan, N., and U. Weimar. 2001. Conduction Model of Metal Oxide Gas
Sensors. Journal of Electroceramics 7, no. 3, pp. 14367. doi: http://dx.
doi.org/10.1023/a:1014405811371
[120]
Barsan, N., and U. Weimar. 2003. Understanding the
Fundamental
Principles of Metal Oxide Based Gas Sensors; the Example of CO
Sensing with SnO 2 Sensors in the Presence of Humidity. Journal of
Physics: Condensed Matter 15, no. 20, pp. R81339. doi: http://dx.doi.
org/10.1088/0953-8984/15/20/201
[121]Basu, S., and P.K. Basu. 2009. Nanocrystalline Metal Oxides for Methane
Sensors: Role of Noble Metals. Journal of Sensors 2009, no. 1, pp. 120.
doi: http://dx.doi.org/10.1155/2009/861968
[122]Simon, I., N. Brsan, M. Bauer, and U. Weimar. 2001. Micromachined
Metal Oxide Gas Sensors: Opportunities to Improve Sensor Performance.
Sensors and Actuators B: Chemical 73, no. 1, pp. 126. doi: http://dx.doi.
org/10.1016/s0925-4005(00)00639-0
[123]Wang, C., L. Yin, L. Zhang, D. Xiang, and R. Gao. 2010. Metal Oxide
Gas Sensors: Sensitivity and Influencing Factors. Sensors 10, no. 3,
pp.2088106. doi: http://dx.doi.org/10.3390/s100302088
[124]
Wang, X., W.P. Carey, and S.S. Yee. 1995. Monolithic Thin-Film
Metal-Oxide Gas-Sensor Arrays with Application to Monitoring of Organic
Vapors. Sensors and Actuators B: Chemical 28, no. 1, pp. 6370. doi:
http://dx.doi.org/10.1016/0925-4005(94)01531-l
[125]
Semancik, S., R.E. Cavicchi, K.G. Kreider, J.S. Suehle, and
P.Chaparala. 1996. Selected-Area Deposition of Multiple Active
Films for
Conductometric Microsensor Arrays. Sensors and Actuators B: Chemical 34, no. 13, pp.20912. doi: http://dx.doi.org/10.1016
/s0925-4005(96)01823-0
[126]Semancik, S., R.E. Cavicchi, M.C. Wheeler, J.E. Tiffany, G.E. Poirier,
R.M. Walton, J.S. Suehle, B. Panchapakesan, and D.L. DeVoe. 2001.

Microhotplate Platforms for Chemical Sensor Research. Sensors

and Actuators B: Chemical 77, no. 12, pp. 57991. doi: http://dx.doi.
org/10.1016/s0925-4005(01)00695-5

38 CARBON: THE NEXT SILICON?

[127]Benkstein, K.D., C.J. Martinez, G. Li, D.C. Meier, C.B. Montgomery, and
S. Semancik. 2006. Integration of Nanostructured Materials with MEMS
Microhotplate Platforms to Enhance Chemical Sensor Performance.
Journal of Nanoparticle Research 8, no. 6, pp. 80922. doi: http://dx.doi.
org/10.1007/s11051-005-9019-8
[128]Cavicchi, R.E., S. Semancik, R.M. Walton, B. Panchapakesan, D.L. DeVoe,
M.I. Aquino-Class, J.D. Allen, and J.S. Suehle.1999. Microhotplate Gas
Sensor Arrays. In Proc. SPIE 3857, Chemical Microsensors and Applications II, pp. 3849.
[129]Fangohr, H., D.S. Chernyshenko, M. Franchin, T. Fischbacher, and G.
Meier. 2011. Joule Heating in Nanowires. Physical Review B 84, no. 5.
doi: http://dx.doi.org/10.1103/physrevb.84.054437
[130]Tohmyoh, H., and S. Fukui. 2012. Manipulation and Joule Heat Welding
of Ag Nanowires Prepared by Atomic Migration. Journal of Nanoparticle
Research 14, no. 9. doi: http://dx.doi.org/10.1007/s11051-012-1116-x
[131]Leonard, F. 2011. Reduced Joule Heating in Nanowires. Applied Physics
Letters 98, no. 10, p. 103101. doi: http://dx.doi.org/10.1063/1.3561772
[132]
Ashraf, S., C.S. Blackman, S.C. Naisbitt, and I.P. Parkin. 2008. The
Gas-Sensing Properties of WO 3 x Thin Films Deposited via the Atmospheric Pressure Chemical Vapour Deposition (APCVD) of WCl 6 with
Ethanol. Measurement Science and Technology 19, no. 2, p. 025203. doi:
http://dx.doi.org/10.1088/0957-0233/19/2/025203
[133]Zhao, Y.M., and Y.Q. Zhu. 2009. Room Temperature Ammonia Sensing
Properties of W18O49 Nanowires. Sensors and Actuators B: Chemical
137, no. 1, pp. 2731. doi: http://dx.doi.org/10.1016/j.snb.2009.01.004
[134]Fischbein, M.D., and M. Drndi. 2006. Nanogaps by Direct Lithography
for High-Resolution Imaging and Electronic Characterization of Nanostructures. Applied Physics Letters 88, no. 6, p. 193106. doi: http://dx.doi.
org/10.1063/1.2172292
[135]Motto, P., A. Dimonte, I. Rattalino, D. Demarchi, G. Piccinini, and P. Civera.
2012. Nanogap Structures for Molecular Nanoelectronics. Nanoscale
Research Letters 7, no. 1, pp. 19. doi: http://dx.doi.org/10.1186/1556276x-7-113
[136]Tang, Q., Y. Tong, T. Jain, T. Hassenkam, Q. Wan, K. Moth-Poulsen, and
T.Bjrnholm. 2009. Self-Assembled Nanogaps for Molecular Electronics.
Nanotechnology 20, no. 24, p. 245205. doi: http://dx.doi.org/10.1088/09574484/20/24/245205

Index
A
Ablation, 203
Aerogel. See Organic aerogels;
Supercritical drying
B
Buckypapers, 219
C
Carbonaceous materials, surface
modification
carbon surface nitrogen
enrichment, 213214
carbon surface oxidation,
210213
description, 206
functionalization of, 209219
grafting deposition, 206209
other treatments, 214215
polymer deposition, 206209
specific surface treatments,
CNTs, 215219
Carbon materials. See also
Nanocarbon materials
carbon nanofibers, 8488
carbon nanofilaments, impurities,
8892
as catalysts, 5658
challenges and opportunities,
6567
in C-MEMS, 5965
in C-NEMS, 5965
in composites, 5658

graphene synthesis, 9296

nanotube growth methods, 7884
Carbon microelectromechanical
system (C-MEMS)
carbon hot nanowires, 2427
carbon microstructure
determination, 1017
carbon nanowires fabrication,
132142
CNT-based materials, 5964
description, 23
electromechanical spinning,
1117
far-field electrospinning, 1117
graphene-based materials, 6465
near-field electrospinning, 1117
photolithography process, 310
redox amplification, carbon
interdigitated electrode arrays,
2023
smart Li-ion batteries, 1920
three-dimensional structures,
185188
Carbon nanoelectromechanical
system (C-NEMS)
carbon hot nanowires, 2427
carbon microstructure
determination, 1017
CNT-based materials, 5964
description, 23
electromechanical spinning,
1117
far-field electrospinning, 1117

232Index

graphene-based materials, 6465

near-field electrospinning, 1117
photolithography process, 310
redox amplification, carbon
interdigitated electrode arrays,
2023
smart Li-ion batteries, 1920
Carbon nanofibers (CNFs), 8488
Carbon nanofilaments, impurities,
8892
Carbon nanotubes (CNTs)
vs. carbon nanowires, 110
liquid-phase oxidation of, 96
multiwalled. See Multiwalled
carbon nanotubes (MWCNTs)
as reinforcing bars, 99
single-walled. See Single-walled
carbon nanotubes (SWCNTs)
specific surface treatments,
215219
Carbon nanowires (CNWs)
carbon microelectromechanical
system, 2427, 132142
carbon nanoelectromechanical
system, 2427
carbon nanotubes vs., 110
catalytic chemical liquid
deposition, 124130
catalytic growth, 121122
chemical vapor deposition,
128130
DC arc discharge method,
130132
electrospinning. See
Electrospinning
Euler-Bernoulli beam theory,
1617
ion and electron beam processes,
114121
Langmuir-Blodgett films,
122124
other fabrication methods,
142144
photolithography process,
153154

planar edge defined alternate

layer process, 112114
pyrolysis process, 154155
reactive ion etching, 122124
Carbon surface nitrogen
enrichment, 213214
Carbon xerogels
electrospraying, 182184
importance of, 174175
inverse emulsification method,
175181
Catalysts, as carbon materials,
5658
Catalytic chemical liquid
deposition (CCLD), 124130
Catalytic growth method, 121122
CCLD. See Catalytic chemical
liquid deposition
Chemical vapor deposition (CVD),
128130
Chiral vector, 44
C-MEMS. See Carbon
microelectromechanical system
C-NEMS. See Carbon
nanoelectromechanical system
CNFs. See Carbon nanofibers
CNWs. See Carbon nanowires
Cold plasma
characterization, 204
definition, 202
Cold points, 25
Composites, carbon materials,
5658
Cryogel. See Freeze drying
Cup-stacked CNFs, 86
CVD. See Chemical vapor
deposition
D
DC arc discharge method,
130132
Droplet formation, 156158
E
Electro-mechanical spinning (EMS)

Index 233

carbon nanoelectromechanical
system, 1117
materials and methods, 165166
mechanical stretching control,
166167
set up description, 164165
voltage effects, 166
Electron beam CNWs process,
114121
Electron transport, 5354
Electrospinning
droplet formation, 156158
elongation of straight segment,
159160
far-field, 162163
launching jet, 158159
nanowire dimensions, 161162
solidification into nanowires, 161
Taylor cone formation, 158
traditional set up, 155156
whipping instability, 160161
Electrospraying, 182184
EMS. See Electro-mechanical
spinning
Equilibrium plasmas, 202
Etching, 203
Euler-Bernoulli beam theory,
1617
F
Far-field electrospinning (FFES)
carbon nanoelectromechanical
system, 1117
challenges, 162163
FFES. See Far-field
electrospinning
Freeze drying, 173
Fullerene carbon materials, 4852
G
GC. See Glassy carbon
Glassy carbon (GC), 152153
Grafting deposition method,
206209
Graphene

C-MEMS applications, 6465

C-NEMS applications, 6465
nanocarbon materials, 5052
synthesis, 9296
Graphite, 4041
H
Heat transport, 5354
Hybrid materials, 9899
I
IDEAs. See Interdigitated
electrode arrays
Impurities, carbon nanofilaments,
8892
Interdigitated electrode arrays
(IDEAs), 2023
Inverse emulsification method,
175181
Ion beam CNWs process, 114121
L
Langmuir-Blodgett (LB) films,
122124
Low-pressure plasma, 203205
M
Mechanical stretching control,
166167
Molecular chain orientation model,
14
Multiwalled carbon nanotubes
(MWCNTs)
chiral vector, 44
formulation of, 4546
Russian inset doll model, 4647
schematic construction, 47
structure representations, 4445
translation vector, 44
MWCNTs. See Multiwalled
carbon nanotubes
N
Nanocarbon materials. See also
Carbon materials

234Index

electron transport, 5354

first generation of, 4243
functionalization of, 9697
heat transport, 5354
hybrid materials, 9899
mechanical and other properties,
5456
pore structure, 53
second generation of, 43
stiction, 56
surface area, 53
third generation of, 43
Nanotube growth methods, 7884
Nanowires
dimensions of, 161162
solidification into, 161
Near-field electrospinning (NFES),
1117, 163
NFES. See Near-field
electrospinning
Nonequilibrium plasmas, 202
O
Organic aerogels. See Resorcinolformaldehyde (RF)-based
organic aerogels
P
Photolithography process, 310,
153154
Planar edge defined alternate layer
(PEDAL) process, 112114
Plasma
cold, 202204
deposition, 203
equilibrium, 202
etching/ablation, 203
functionalization, 203
low-pressure plasma, 203205
nonequilibrium, 202
thermal, 202
Platelet CNFs, 86
Polymer deposition method,
206209
Pore structure, 53
Pyrolysis process, 154155

R
Reactive ion etching method,
122124
Redox amplification, IDEAs,
2023
Reinforcing bars, 99
Resorcinol-formaldehyde
(RF)-based organic aerogels
freeze drying, 173
physicochemical properties, 172
preparation of, 171172
subcritical drying, 173
supercritical drying, 173
Resorcinol-formaldehyde
(RF)-derived carbon xerogels
electrochemical performance of,
188194
three-dimensional C-MEMS
structures, 185188
Russian inset doll model, 4647
S
Single-walled carbon nanotubes
(SWCNTs)
chiral vector, 44
formulation of, 4546
schematic construction, 47
structure representations, 4445
translation vector, 44
Smart Li-ion batteries, 1920
Solidification, 161
Stiction, 56
Subcritical drying, 173
Supercritical drying, 173
Surface area, 53
Surface modification
carbon surface nitrogen
enrichment, 213214
carbon surface oxidation,
210213
description, 200201, 206
functionalization of, 209219
grafting deposition, 206209
other treatments, 214215
plasma. See Plasma
polymer deposition, 206209

Index 235

specific surface treatments,

CNTs, 215219
SWCNTs. See Single-walled
carbon nanotubes
T
Taylor cone formation, 158
Thermal plasmas, 202
Three-dimensional (3D) carbon
IDEAs, 22
Three-dimensional C-MEMS
structures, 185188
Translation vector, 44

U
Ultramicroelectrodes (UM), 2021
UM. See Ultramicroelectrodes
V
Voltage effects, 166
W
Whipping instability, 160161
X
Xerogel. See Carbon xerogels;
Subcritical drying