Chapter 1

CARBON: THE
NEXT SILICON?
CARBON: THE
NEXT SILICON?
Book 2 Applications
MARC J. MADOU,
VICTOR H. PEREZ-GONZALEZ, AND
BIDHAN PRAMANICK
MOMENTUM PRESS, LLC, NEW YORK
Carbon: The Next Silicon?: Book 2 Applications

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: 978-1-60650-883-1 (print)
ISBN-13: 978-1-60650-884-8 (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
Nuclear Magnetic Resonance (NMR) and Electron Spin Resonance (ESR)
spectroscopies are well-known characterization techniques that reveal the
molecular details of a sample non-invasively. We not only discuss how
NMR can provide useful information on the microstructure of carbon
and its surface properties, but also explain how C-MEMS/C-NEMS technology can be explored for building improved NMR microdevices. The
manipulation of fluids and particles by dielectrophoresis and the use of
carbon electrodes for dielectrophoresis in Lab-on-a-Chip applications is
also discussed. The use of these electrodes in sample preparation through
electrical polarization of a sample for identification, manipulation and
lysis of bioparticles is emphasized. A new generation of neural prosthetics based on glassy carbon micromachined electrode arrays is introduced.
The tuning of the electrical, electrochemical and mechanical properties of
these patternable electrodes for applications in bio-electrical signal recording and stimulation, and results from in-vivo testing of these glassy carbon
microelectrode arrays is reported, demonstrating a quantifiable superior
performance compared to metal electrodes. Also the merits of high aspect
ratio 3D C-MEMS/C-NEMS electrodes is made abundantly clear. When
using carbon Interdigitated Electrode Arrays (IDEAS) the lower limits of
detection (LODs) are often equivalent or better that those of the much
more complicated and expensive optical fluorescence sensing schemes.
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
Quick Overview of Book 2-Applications
Acknowledgments
1 Carbon MEMS for Magnetic Resonance
xi
xxiii
xxv
xxvii
xxxi
xxxiii
1
1.1Background
1
1.2Introduction to MR
2
1.3Characterization of Pyrolytic Carbon Using MR
5
1.4NMR for Key Carbon MEMS Applications andDevices
18
1.5Future Opportunities
25
1.6Conclusions
36
References37
2 Fluid and Particle Manipulation Using C-MEMS
53
2.1Introduction
53
2.2Solid-State Electric-Field-Driven Pumps
55
2.3Fully Functional AC Electroosmotic
Micropump Using C-MEMS
61
2.4An Alternative Method for Increasing Pumping E
fficiency:
Shaped 3D PlanarElectrodes
64
2.5Additional Flow Effects Induced by
Nonuniform AC Electric Fields
66
2.6Dielectrophoretic Particle Manipulation in C-MEMS
70
2.7Summary
74
References75
viii Contents
3 Carbon MEMS for Selected Lab-on-a-Chip Applications
79
3.1Introduction
79
3.2Background
81
3.3Fabrication
84
3.4Selected LOC Applications
86
3.5Perspective on a C-MEMS LOC
94
References95
4 Glassy Carbon Microelectrodes for
Neural Signal Sensing and Stimulation
101
4.1Introduction
101
4.2 Background in Neural Probes
104
4.3 Fabrication Process and Packaging
105
4.4 Electrode Characterizations
107
4.5Discussion
114
4.6Conclusions
116
References116
Terminology121
5 C-MEMS-Based on-Chip Microsupercapacitors
123
5.1Introduction
123
5.2 Basic Concepts
124
5.3 Fabrication Process
128
5.4 C-MEMS-Based Microsupercapacitors
130
5.5Conclusions
134
References136
6 Advanced Electroanalysis with C-MEMS
139
6.1Characteristics of Pyrolyzed Photoresist C

arbon
Electrodes139
6.2Trace Metal Ions Analysis with Pyrolyzed P
hotoresist
CarbonElectrodes
146
6.3Electroanalysis of Organic Analytes with Pyrolyzed
Photoresist Carbon Electrodes
153
6.4 Conclusions and Prospects
160
References162
7 C-MEMS-Based 3D Interdigitated Electrode
Arrays for Redox Amplification
7.1Introduction
7.2Background
7.3 Methods to IDEAs Fabrication
169
169
172
175
Contents ix
7.4State of the Art in C-MEMS-Based IDEAs

for Redox Amplification Applications
179
7.5 Concluding Remarks
186
References187
Index
191
List of Figures
Figure 1.1.Chemical shift range for 13C in NMR spectroscopy.
8
Figure 1.2.NMR spectra for various carbon films [56]: a-C,
softer carbon films without hydrogen usually formed
at low energy or higher temperature; a-C:H, softer
carbon films with hydrogen; DLC, diamondlike carbon;
and ta-C, tetrahedral amorphous carbon films with
high content of sp3 bonding and without hydrogen.
15
Figure 1.3.
Quantitative, direct-polarization 13C NMR spectra
of detonation nanodiamond and a heat-treated reference
sample. (a) Spectra of pristine nanodiamond (thin line)
and the 800 C heat-treated material (thick line), taken
at 14 kHz MAS. (b) Spectra after 800 C heat treatment,
expanded 34 times vertically, taken at 14 kHz MAS
(dashed line) and 6 kHz with TOSS (full line).
A broad CC band is clearly visible. (c) Same as (b) for
pristine nanodiamond (except higher spinning
frequency of 6.5 kHz for TOSS spectrum). ssb,
spinning sideband [21].
17
11
Figure 1.4.
(a) B MAS NMR spectra of BF4 in activated carbons
with specific surface area of 500 m2/g for impregnated,
charged, and discharged states as presented in [84];
(b) 11B MAS NMR spectra of BF4 in activated carbons
with specific surface area of 3,000 m2/g for impregnated,
charged, and discharged states. The sharp peaks
(A) have been assigned to free BF4 species, and the broad
peaks have been assigned to adsorbed BF4 species.
(Legend: Imp = impregnated; C/D +/ = charged/
discharged positive/negative polarization)
21
xii List of Figures

11
Figure 1.5.
B static NMR spectra taken in situ from a
supercapacitor at various voltages, as presented
in [86]: (a)spectra of the positive electrode charged
up to 2 V; (b) spectra of the negative electrode charged
up to 2 V; (c) chemical shift evolution for each
electrode as a function of the applied voltage; and
(d) integrated areas for each electrode spectra as a
function of the applied voltage.
22
Figure 1.6.(a) Schematic representation of frequency dependence
of the reflection coefficient. The quality factor Q can
be directly evaluated from the 3 dB bandwidth
around the resonance frequency 0. Mismatched
resonant circuits (matching capacitance CM) as well
as loss (depict by the equivalent resistance R) degrade
the resonance performance of the system. (b) Sketch
of a variety of planar MW resonators; (1) planar ohmshaped resonator [97], (2) split-ring resonator [98],
(3) half-wavelength resonator [99], and (4) surface
loop-gap resonator [100].
26
Figure 2.1.(a) Two-dimensional asymmetric planar electrode
array used to generate AC electroosmotic pumping,
consisting of large and narrow electrodes separated by
large and narrow gaps in a periodic manner along a
microfluidic channel. (b) The applied AC signal and
the ground return are applied alternately to successive
electrodes, resulting in induced electrical double layers
(EDLs) opposite in sign to the applied potential on each
electrode. The electric field simultaneously generated
by the applied potential difference, E, is nonuniform,
curving through the EDLs toward adjacent electrodes
and resulting in a tangential field component, Et. As a
result, there is a Coulomb force Fc acting across the
electrode surface and acting on the ions in the layers.
The resulting electroosmotic slip velocity across the
electrode surface has a nonzero time average because
the sign of the charge in the induced EDL is always
opposite to the applied potential and the Coulomb force
always points away from the electrode edge. (c) The
resulting continuous flow arising from the electroosmotic
slip on the surface of the electrodes. There are fluid
List of Figures xiii
rolls generated over each electrode edge: over the small

narrow electrode, the rolls are small and contained near
the surface; over the large electrode, one of the rolls
is large and fast and the other is small and slow. As
a result, the large roll is not balanced by the action of
the second and bulk unidirectional flow along the
array is produced [8, 15, 1618].
58
Figure 2.2.An extension of the asymmetric electrode array
shows an increase in the electrode surface area from
planar to 3D electrodes, but the channel volume
remains the same. Enclosed in a channel, electrodes
line the walls and top and bottom of the channel and
also fill the volume with pillars that all have the same
asymmetric configuration.
60
Figure 2.3.The AC electroosmotic micropump fabrication
process, constructing an electrically active solid-state
device only from SU-8. (a), (e) Asymmetric planar
electrodes patterned first on silicon wafer. (b),
(f) 3D HAR electrodes are built on the top of the planar
array. (c), (g) The electrodes are encapsulated with
a fluidic channel. (d), (h) the device is sealed with a
transparent lid.
61
Figure 2.4.Issues occurring during fabrication of HAR pillars.
(a) Looking from above, scanning electron microscopy
(SEM) images showing a comparison between 150 m
high HAR pillars before and after an optimization
process. The picture on the left shows HAR pillars
before optimization, where the corners of the pillars are
not sharp and the gaps between the large and small
pillars are not clear. After optimization of the
photolithography parameters, a good resolution, sharp
angles, 20 m clear gaps, and vertical walls of the pillars
were achieved (picture on the right). (b) The stiction
effect: pairs of large and small electrodes stuck together
due to the strong capillary action in the narrow gap
during solvent or developer evaporation or removal
(picture on the left). This effect is strongly dependent
onsolvent concentration or composition and
temperature, which in some cases produce an erratic
stiction (picture on the right).
63
xiv List of Figures
Figure 2.5.Completed electrode array, combining planar

electrodes and HAR conductive pillars on top.
Following all stages of the C-MEMS processing, a
good uniformity, resolution, and verticality were
achieved. The shrinkage in the electrode structures
that occurs during the pyrolysis stage results in a
distinctive shape for the asymmetric structure.
The two lower SEM images show the complete
3D ACEO micropump, including planar electrodes,
HAR conductive pillars, and fluidic channel.
As a result, the whole device was made only from
SU-8 photoresist [9].
65
Figure 2.6.Fluid flow velocity measurements versus the variation
in frequency in a channel with asymmetric planar
carbon electrodes with 20 and 100 m gaps. A fixed
applied voltage of 16 Vpp and 8-m diameter latex
tracer particles were used.
66
Figure 2.7.Illustration of the effect of changing the cross-sectional
profile of the electrodes on the motion and interaction
of the different components of the generated fluid flow
by (a) increasing the thickness of the electrodes and
(b)increasing the thickness of only part of the
electrodes and producing a stepped profile.
67
Figure 2.8.
(a) Fluid flow motion generated by C-MEMS
electrodes tracked using 500-nm diameter fluorescent
particles suspended in 0.1 mM phosphate buffered
saline. A steady and uniform fluid flow stream can be
clearly seen on top of the electrodes inside a 500-m
wide fluidic channel. C
omparison of fluid flow
velocity with applied voltage for (b) raised carbon
planar electrodes and (c) the same array with HAR pillar
electrodes [9]. For the 2D device, a slight reverse
pumping was noticed at low voltages. The planar array
had dimensions as follows: gap 60 m; electrode 60 m;
gap 20 m; electrode 20 m; with the 3D array having
50-m high p illars spaced at 74 m along the electrode
(acrossthe channel). Experiments were carried out
at a fixed frequency of 1 kHz and a voltage varying
between 1 Vpp and 19 Vpp.68
Figure 2.9.Fluid flow test using 8-m diameter latex beads on
asymmetric electrodes with 100-m wide electrodes
or gapsand 20 m for the narrow electrodes or gaps.
List of Figures xv
(a)Empty planar electrodes (before the injection of latex

beads). (b) Mass transportation of latex beads on the
top of the electrodes under the action of ACEO including
electrode end effects. (c) The generation of bubbles
and collection of beads at the exit of the array.
(d) Collection of beads at the ends of the large
electrodes.(e) Trapping of beads between the ends of
the narrow e lectrodes and the start of the wide ones.
69
Figure 2.10.SEM images of the C-MEMS fabrication process for
dielectrophoretic electrodes with planar electrode
structures on the top row and 3D pillar electrodes on
the bottom. For reference, the horizontal spacing of the
electrodes was 45 and 110 m in the vertical one.
The SU-8 structures were fabricated in a two-step
photolithography sequence (a, b) and were then
pyrolyzed to final carbon electrodes and connecting
leads (c, d). Connecting leads were protected and
isolated with a layer of SU-8 (e, f), with the device
sealed into an SU-8 fluidic channel (g, h).
72
2
Figure 2.11.3D surface plots depicting the magnitude of E in
various horizontal cross sections at different heights
above the channel floor for p lanar electrodes (top)
and pillar electrodes of the same size and cross section.
The dielectrophoretic force is proportional to the
gradient of this term, making these landscape plots
pseudo-gravity models of what a particle undergoing
DEP would do. For negative DEP, the particles would
roll down the slopes to the lowest points, and for
positive DEP, the particles would climb up the
slopes to the highest points. What is clear from these
plots is that for the pillar electrodes, there is little
change in value with height, whereas there is a rapid
decrease for the planar electrodes.
73
Figure 2.12.Retention efficiency in yeast cell samples as flow rate
increases for both planar and volumetric electrodes.
The sample conductivity was 51 mS/m and a 10 MHz,
10Vpp sinusoidal signal was applied between the
electrodes to perform DEP trapping of viable yeast
cells. The numbers of viable and nonviable yeast cells
at the output was determined by direct observation
for the same signal and increasing flow rate for a
fixed sample volume of 50 l.
74
xvi List of Figures
Figure 2.13.Cells focused into streamlines (red ellipses)

using positive DEP.
75
Figure 3.1.Fabrication process of carbon electrodes showing cross
sections at different steps. Choice of substrate includes
fused silica and silicon. See further details in the text. 84
Figure 3.2.PCR results demonstrating (a) the inability of
traditional PCR analysis to detect yeast cells when the
concentration of humic acids is above 10 g/ml and
(b)significant improvement obtained when using a
carbonDEP-based sample preparation module before
PCR analysis: humic acids concentrations of up to
75 g/ml are effectively removed from the sample to
enable yeast detection.
88
Figure 3.3.(a) The normalized percentage of intact and damaged
cells for each sample fraction. The control fraction refers
to the original sample, flowed through the chip without
polarizing the electrode array, (b) Intact and damaged cell
counts of the sequential fractions recovered during the
carbon DEP assay. The control fraction refers to the
original sample, flowed through the chip without
polarizing the electrode array.
90
Figure 3.4.(a) Fluorescence microscopy images showing
DNAconcentrated (red ellipse) on the surface of the
electrodes by pDEP (AC signal featuring frequency of
10kHz and magnitude 16 Vpp). (b) Characteristic
elution profile for a -DNA solution with and without
the application of a DEP force. Note the characteristic
peak obtained at a volume of 80 l, right after the
pDEPforce is turned off and the previously trapped
DNAis released.
91
Figure 3.5.Luminescence divided by the n umber of cells
illustrating the luciferase extracted from m
ammalian
cells during lysis. The control e xperiment was
performed without polarizing the e lectrode array.
Thetopdashed line corresponds to the chemical lysis,
whereas the bottom dashed line is the background
signal for living cells.
93
Figure 3.6.Schematic of a multistage carbonDEP device. A number
of electrode arrays are embedded in a channel. Each
array can be of different geometry and electrically
independent.
94
List of Figures xvii
Figure 4.1.(a) Lithography and pyrolysis process for fabricating

GC electrodes from a negative tone photoresist. (b) final
hybrid structure with GC electrodes and metal traces. 105
Figure 4.2.Hybrid metal and glassy carbon electrode probes.
(a) SEM image of GC electrodes after pyrolysis,
(b) SEM image of GC-MEMS electrodes after pyrolysis
and depositing insulation layer, (c) bright-field
microscope image of final microelectrode array,
(d) front and back images of m
icroelectrodes.
106
Figure 4.3.
Details of a hybrid metal and glassy carbon electrode
probes. (a) Microelectrode structure after pyrolysis,
(b)complete ECoG device with carbon electrodes
connected to Hirose 40-pin connector and glued to
PCB for stability.
106
Figure 4.4.(a) Youngs modulus for a variety of pyrolysis
temperatures and (b) hardness of electrodes for a
variety of pyrolysis temperatures. Insets show both
types of pillars tested.
107
Figure 4.5.SEM images of cross section of glassy carbon pillars
pyrolyzed at different temperatures, 700, 800, 850, 900,
and 1,000C. At high pyrolysis temperatures, significant
pores are observed. The flow rate is kept constant for
alltemperatures.
108
Figure 4.6.Mapping of Youngs modulus of hybrid microelectrode
array. (a) Testing location on the electrode sets,
(b) mapping of Youngs Modulus on electrode set. This
demonstrates that the modulus of GC electrodes is not
substantially different from those of the polyimide
substrate itself.
108
Figure 4.7.(a) Impedance for a variety of pyrolysis temperatures
of electrodes at 100 Hz, (b) equivalent modified Randle
circuit for the in vitro electrochemical measurement
system. Rs=solution resistance, Rc = charge transfer
resistance (diameter of first semicircle), Ws = Warburg
coefficient, CPE = constant phase element at = 1.
109
Figure 4.8.(a) CIC for a variety of pyrolysis temperatures,
(b)Transient of CIC after plasma treatment for a
variety of pyrolysis temperatures (100 W for
60 seconds) showing a temporary effect.
110
Figure 4.9.Corrosion test in GC-MEMS electrodes involving
21 days of immersion in 300 mM H2O2 and PBS.
xviii List of Figures
(a) FTIR image shows that for p yrolysis temperature of

1,000C (both in PBS and H2O2), the amount of corrosion
by-products such as CO and C=O structures and phenyl
groups is substantially low as compared to electrodes
pyrolyzed at 700C. Note that 300 mM H2O2 is almost
10times the concentration typically seen in
inflammatory responses. (b) SEM images of surfaces
of electrodes after corrosion test.
111
Figure 4.10.(a) Location of implantation of both Au/Pt and Au/C
ECoG devices at motor cortex of rat model.
(b) Electrode map and locations of e licited
movements in anesthetized rat model.
112
Figure 4.11.Comparison of power spectra recordings by metal
and GC-MEMS microelectrodes on anesthetized rat.
Beta activity at 15 to 30 Hz band that is captured
better by GC-MEMS electrode is clearly visible.
TheECoG array shown in the inset had
4 4 GC-MEMS microelectrodes of 20 m height and
200 m diameter and was placed underneath the dura
in the motor cortex region. Locations where movements
were elicited through stimulation are alsoshown.
113
Figure 4.12.(a) Raw ECoG recording and power spectra between
twoelectrodes (i.e., differential recording) with wide
bandpass showing oscillations typical for an
anesthetizedrat. (b) Differential recordings
(i.e.,betweentwo electrodes) at two sites of evoked
potentials when the median nerve in the forearm of the
anesthetized rat is stimulated. The earlier peaks are
direct responses of sensory pathways to the stimulus;
the later peaks are p robably sensory responses to the
movement that was elicited by the s timulation.
114
Figure 5.1.The Ragone plot for different energy storage devices.
Note that electrochemical capacitors bridge the
gap between lithium-ion batteries and electrolytic
capacitors,with intermediate timeconstants.
127
Figure 5.2.Process flow of C-MEMS technology.
128
Figure 5.3.Schematic of ESD [15].
129
Figure 5.4.(a) Scanning electron microscope (SEM) images of
typical SU-8 structures generated using C-MEMS
processes [16]; (b) pyrolyzed C-MEMS structures
[16]; (c)C-MEMS-based three-dimensional posts
incorporatedwith CNTs [19]; (d) high-magnification
List of Figures xix
image of the c arbon post displaying the structure of

the PPY film [20].
130
Figure 5.5.(a) CV curves of the bare C-MEMS electrodes (dashed
lines) and CNT/C-MEMS composites for different
deposition times at a scan rate of 2mVs1 in 1M Na2SO4
electrolyte [19]; (b) chargedischarge cycle stability of
the pre- and post-oxygen plasma-treated C-MEMS
electrodes from cycle 1 to the cycle 1,000 [19]; (c) CVs
of nonactivated and 30-minute a ctivated samples at a
scan rate of 100 mVs1[16]; (d)chargedischarge curves
for activated C-MEMS samples for different current
densities [16]; (e) CVs of symmetric PPy/C-MEMS
microsupercapacitors with d ifferent polymerization times
[20]; (f) galvanostatic chargedischarge profile of a
PPy/C-MEMS symmetric microsupercapacitor [20]. 133
Figure 6.1.Cyclic voltammograms of 1 mM [Ru(NH3)6]3+/2+ in
1 M KCl on carbon films pyrolyzed at the indicated
temperatures. Scan rate: 200 mV s1.141
Figure 6.2.Voltammetry of dopamine on PPCE and HTGC.
141
Figure 6.3.Anodic and cathodic peaks potential difference (E)
of [Fe(CN)6]3-/4- in 0.1 M KCl at 25 mV s1 and ohmic
resistance for different film thicknesses, keeping other
dimensions constant.
143
Figure 6.4.(a) Background cyclic voltammogram recorded with a
PPCE at 25 mV s1 in 102 M HCl, pH 2.2; (b) in 102 M
phosphate buffer, pH 7.0 (dashed line), 102 M acetate
buffer, pH 4.5 (dotted line), 102 M HCl, pH 2.2
(solid line).
144
Figure 6.5.Cyclic voltammograms recorded in DMSO,
0.1 M TBABF4 at PPCE (full line) and GCE
(dashed line). Scanrate is 100 mV s1.145
Figure 6.6.Scheme of the PPC and electrode assembly.
148
Figure 6.7.(a) SW-ASV recorded at the in situ prepared
Bi-PPCE in 0.1 M acetate buffer (pH 4.5), 10 mg L1
Bi(III) in the absence (dotted line) and the presence
of increasing concentrations of Pb(II) and Cd(II), from
5to 30 g L1 (full lines). Deposition at 1.1 V for
300 s. Square wave voltammetry parameters: f requency
20 Hz, amplitude 50 mV, potential step of 5 mV.
(b)Corresponding calibration plots.
148
Figure 6.8.Cr(III)-PCVox is electroactive and adsorbed on the
electrode surface.
149
xx List of Figures
Figure 6.9.Cathodic reaction of Cr(III)PCVox that is reduced to

Cr(II)PCVox. In the presence of NO3-, a catalytic
cycle is active.
149
Figure 6.10.AdCSVs at the ex-situ prepared Bi-PPCE in the solution
of 5 g L1 of Cr(III) for increasing concentrations of
Cr(VI) in the range of 5 to 25 g L1, in acetate buffer
solution 0.01 mol L1 (pH 6) containing 0.1 mol L1
NaNO3 and 0.5 mmol L1 PCV. Inset: Corresponding
calibration plot.
150
Figure 6.11.(a) Square wave stripping voltammograms
(Estep = 10 mV, Epulse = 50 mV and frequency 50 Hz).
Dependence of current responses of bare Bi-PPCE on
concentration of target metals in 0.1 mol L1 acetate
buffer (pH 4.5); preconcentration at 1.3 V for 180 s;
concentration of Bi(III): 1 106 mol L1; calibration
plots inside. (b) Square wave stripping v oltammograms
(Estep = 10 mV, Epulse = 50 mV and frequency 50 Hz).
Dependence of current responses of Nafion-coated
BiFE on concentration of target metals in 0.1 mol L1
acetate buffer (pH 4.5); preconcentration at 1.3 V for
180s; concentration of Bi(III): 2106mol L1;
calibration plots inside.
151
Figure 6.12.Confocal microscopy image of the PPCE structure
used in the microfabrication of disk electrodes.
The dotted lines indicate the areas where the
profilometric data displayed in subfigures (a) and
(b) were collected. (a) The wavy profile and round
edges are the result of resist flow during pyrolysis.
152
Figure 6.13.Scheme of the spray-coater system with
coaxial nebulizer.
153
Figure 6.14.Cyclic voltammograms for the one-electron reduction
of O2 recorded in 0.1 M TBABF4, DMSO at a PPCE in
the presence of atmospheric oxygen at different BR
concentrations, namely, 0 (full line), 0.8 (dashed line),
and 4 mM (dotted line). Scan rate 50 mV s1.155
Figure 6.15.PPF microelectrode array. (a) SEM image taken of
the PPCE microelectrode array after dicing. Each
of the four electrodes is 10 m wide and 50 m long.
The white dots indicate the four electrodes, while the
arrow indicates the insulation layer. (b) Drawing of
the device (not scaled).
156
List of Figures xxi
Figure 6.16.Electrode geometry and microchip layout. (a) I llustration

of PPCE geometry. The electrode is 50 m wide at the
center working area. (b) Channel dimensions: 20 m
wide, 7 m deep, 7 mm from each sample (S), sample
waste (SW), and buffer (B) wells to the injection T,
effective separation length (Leff) varied.
157
Figure 6.17.Rapid separation of 5 M dopamine (1) and 250 M
ascorbic acid (2), first harmonic (3 Hz) time course.
Electrophoresis buffer 25 mM phosphate, 2 mM NaCl
(pH7.4); separation voltage, +750 V (440 V cm1)
with +405 V pull-back voltage; injection, +1 kV for 3s.
Effective separation length of channel is 1 cm.
SV d etection was accomplished by applying a 3-Hz
sine wave from 50 to 550 mV (vs Ag/AgCl).
158
Figure 6.18.Separation of 10 M dopamine (1), 25 M
epinephrine (2), 25 M isoproterenol (3), and 100 M
L-dopa (4) at the first harmonic (3 Hz).
Electrophoresis buffer 50 mM MES, 20 mM phosphate,
2mM KCl (pH 5.3); separation voltage, +1 kV
(180 V cm1) with +470 V pull-back voltage; injection,
+2kV for 2 s. Effective separation length of channel
is 4.8 cm. SV detection was accomplished by
applying a 3-Hz sine wave from 100 to 400 mV
(vs. AgAgCl).
159
Figure 6.19.Schematic diagram of different electrode alignments
formicrochip electrophoresis with EC detection:
(a) end-channel electrode alignment, (b) off-channel
electrode alignment, and (c) in-channel electrode
alignment. In-channel alignment is possible only
when using an electrically isolated potentiostat.
160
Figure 6.20.Schematic of the photolithographic fabrication
procedure used for the PPCEs (images not to scale).
1: alignment of electrode mask over p hotoresist-covered
glass plate; 2: photoresist patterned electrodes after
photolithography; 3: PPCE following pyrolysis;
4: pour and cure PDMS s eparation layer, align, and
reversibly seal to complete microchip device.
161
Figure 7.1.Schematic representation of the redox amplification
phenomenon in IDEAs. O: Oxidized species, R:
Reduced Species, G: Generator, C: Collector.
174
xxii List of Figures
Figure 7.2.Steps for C-MEMS process: (a) oxide grow over Si

wafer, (b) spin coating of photoresist, (c) soft baking,
(d) exposure to UV light, (e) postexposure bake,
(f) development, (g) pyrolysis, (h) final structure.
Figure 7.3.Scanning electron microscope (SEM) images of
IDEAs before and after pyrolysis [31].
Figure 7.4.Redox cycling behavior of carbon IDEAs as a function
of film thickness and interdigit gap, (a) Amplification
factor and (b) c ollection efficiency [31].
Figure 7.5.Amplification factor and collection efficiency as
function of potential sweep rate and (a) electrode
height, or (b) width-to-gap ratio.
Figure 7.6.Effect of sample flow in redox cycling [19].
Figure 7.7.Cyclic voltammograms of 0.02 mM dopamine (DA)
in the presence and absence of ascorbic acid (AA) in
1 PBS (7.4 pH). The solution contained 4 mM SDS.
Ig: Generator current, Ic: C
ollector current, s:
Single mode, d: Dual mode. Reproduced from [32].
177
180
181
183
184
185
List of Tables
Table 1.1.NMR relevant properties of 13C and 1H nuclei
Table 1.2.Various NMR experiment designs for carbon material

characterization11
Table 1.3.sp2 and sp3 NMR peak positions of carbon films [56]
14
Table 1.4.Susceptibility values of carbon allotropes
31
Table 5.1.A comparison between different C-MEMS platforms

for microsupercapacitors along with other reported
microsupercapacitors135
Table 7.1.Types of chemical sensors
170
Table 7.2.IDEAs dimensions before pyrolysis (bp) and after

pyrolysis (ap)
182
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,
xxvi 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
xxviiiForeword
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 sixties rock and roll (UC Irvine Professor Band-Second Law), Russian love b allads (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 xxix
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.
xxxForeword
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
Book2-Applications
In Chapter 1 of Book 2-Applications, Swati Sharma et al are introducing
perhaps a most unexpected application into the C-MEMS/C-NEMS community i.e., Magnetic Resonance (MR).
In this Chapter 1, this team discusses C-MEMS/C-NEMS for
Magnetic Resonance Applications. Nuclear Magnetic Resonance (NMR)
and Electron Spin Resonance (ESR) spectroscopies are well-known
characterization techniques that reveal the molecular details of a sample
non-invasively. These authors not only discuss how NMR can provide useful information on the microstructure of carbon and its surface properties,
but they also explain how C-MEMS/C-NEMS technology can be explored
for building improved NMR microdevices. In Chapter 2 Nicholas Green
and Hamza Rouabah, the team that pioneered the use of carbon electrodes for AC electroosmotic flow, are detailing an important C-MEMS/
C-NEMS application i.e., the manipulation of fluids and particles by dielectrophoresis. Along the same line Monsur Islam et al are tackling the use
of carbon electrodes for dielectrophoresis in Lab-on-a-Chip applications
in C
hapter3. They emphasize the use of these electrodes in sample preparation through electrical polarization of a sample for identification, manipulation and lysis of bioparticles. Of this team, Rodrigo Martinez was the
first to combine C-MEMS dielectrophoresis with compact disc (CD) based
microfluidics. In Chapter 4 Sam Kassegne and his team introduce a new
generation of neural prosthetics based on glassy carbon micromachined
electrode arrays. He reports on the tuning of the electrical, electrochemical and mechanical properties of these patternable electrodes for applications in bio-electrical signal recording and stimulation. Results from
in-vivo testing of these glassy carbon microelectrode arrays is reported,
demonstrating a quantifiable superior performance compared to metal
electrodes. We did briefly touch upon C-MEMS/C-NEMS supercapacitors
xxxii Quick Overview of Book2-Applications
in C
hapter1 of Book 1 but in Chapter 5 of Book 2, C
hunlei Wang delves
a couple of levels deeper into the topic of C-MEMS/C-NEMS on-chip
micro-supercapacitors. In Chapters 6 (Paolo Scopece et al) and 7 (Victor
Perez et al) the power of electrochemical analysis with C-MEMS/
C-NEMS electrodes is detailed. In Chapter 7 the merits of high aspect
ratio 3D C-MEMS/C-NEMS electrodes is made abundantly clear. When
using carbon Interdigitated Electrode Arrays (IDEAS) the lower limits of
detection (LODs) are often equivalent or better that those of the much
more complicated and expensive optical fluorescence sensing schemes.
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
xxxiv 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
Carbon MEMS for

Magnetic Resonance
Swati Sharma, Neil MacKinnon, Vlad Badilita,
LorenzoBordonali, Sebastian Z. Kiss, and Jan G. Korvink
Karlsruhe Institute of Technology, Germany
1.1BACKGROUND
The ability to form three-dimensional carbon micro- and nanostructures
that feature varying molecular morphology holds interesting potential for
magnetic resonance (MR) spectroscopy and instrumentation.
The first aspect that comes to mind is the ability to unravel the structure of these carbon molecular networks, so as to shed light on the fascinating material properties that are measured experimentally. Nuclear and
electronic spin spectroscopies are powerful tools that provide detailed
information on the molecular details of carbon. Nuclear magnetic resonance (NMR) spectroscopy is carried out for both 1H and 13C. During
13
C NMR, one needs to consider that it is a low-abundance isotope and
requires an optimum experimental design for a reliable investigation.
Second, structured carbon holds high potential for many applications, as
the other chapters of this volume conclusively demonstrate. These applications stand to benefit from MR analyses, especially the fairly recent
emergence of MR microscopy, which can shed light on chemical kinetics and ionic transport. Third, carbon also holds potential as a functional
material within MR microsystems. We explore and review these three
viewpoints.
We first offer a brief introduction to NMR and electron spin resonance (ESR, also known as electron paramagnetic resonance, EPR).
2 CARBON: THE NEXT SILICON?
A plethora of literature is available on these topics, and some excellent

general textbooks are recommended to the interested reader [1, 2]. The
introduction is followed by a literature review on MR characterization
techniques for investigating the underlying microstructure of carbon
materials. From this review, one acquires insights on how MR spectroscopy can be useful for determining the hybridization degree of carbon
atoms as well as the identity of surface functional groups that strongly
influence the electrochemical properties of the material. The subsequent
section details how advanced carbon microelectromechanical system
(C-MEMS) applications such as battery anodes can benefit from MR
spectroscopy, which is capable of providing real-time information on the
kinetics and ion transport of such devices. On the basis of our experience in both MR spectroscopy and the manufacture of carbon materials, we envision some new application areas, for example, using carbon
structures for the hyperpolarization of hydrogen and for the fabrication
of microwave (MW) resonators, with the latter integrating these two new
research areas. We hope that the information we provide on MR technology and our suggestions on possible future work will inspire carbon
scientists and engineers to use this powerful, noninvasive tool for the
characterization of carbon and to explore new ideas on how C-MEMS
and carbon nanoelectromechanical system (C-NEMS) technology can be
used to build improved MR microdevices.
1.2INTRODUCTION TO MR
MR encompasses a group of spectroscopic techniques exploiting the
quantum mechanical property of spin. Particles that possess spin (we are
concerned with nuclei and electrons) also possess spin angular momentum and when placed in an external magnetic field, a splitting of otherwise degenerate energy levels results. While not rigorously correct, one
may draw an analogy with the bar magnet of a compass aligning in the
direction of the Earths magnetic field, which is the energetically favorable configuration. Similarly, particles possessing spin angular momentum also have a magnetic moment, which aligns along the direction of an
applied magnetic field (typically defined as along the z-direction in Cartesian coordinates). The difference from the classical picture is that quantum
mechanics actually describes a superposition of states |I, m> in which the
magnetic momentum is aligned with and against the applied field. When a
measurement is performed, an alignment in one of these two directions is
observed. The energy of each state is given by
Carbon MEMS for Magnetic Resonance3
(1.1)
with the spin angular momentum

(1.2)
The magnitude of the applied magnetic field in the z-direction is Bz

(Tesla), is the spin angular momentum in the direction of the applied
field, and g is the gyromagnetic ratio, a constant for each particle (MHz/
Tesla). The spin angular momentum is dependent on the spin quantum
number of the particle (I = for 1H, 13C, and electrons), with values of m
ranging from I to +I in increments of 1. Thus for particles with I = , the
values of m = , which produces two states. This breaking of degeneracy of the energy levels is known as Zeeman splitting and may be probed
by external radiation, which typically falls in the megahertz (MHz; nuclei)
to gigahertz (GHz; electrons) range depending on the type of particle and
the strength of the external magnetic field.
There are important consequences resulting from the Zeeman splitting, which define MR as a spectroscopic technique. First, the energy
differences typically encountered at ambient conditions are comparable
to the thermal energy (kT), and thus population differences between the
energy states are exceedingly small. In order to obtain a signal, a relatively
large sample is required as compared to the alternative spectroscopic techniques (e.g., ultravioletvisible [UVVis] spectroscopy and Raman spectroscopy). There are benefits to the nearly equal population distributions,
the first being that relaxation rates from excited states are slow, commonly
on the order of seconds for nuclear species and micro- to nanoseconds
for electron spins. This permits the probing of spinspin coupling structures inherent to the system with sophisticated, multipulse experiments,
which is simply not possible in the optical spectroscopy domain (although
femtosecond [fs] laser pulses have been used for two-dimensional infrared
[2D IR] spectroscopy). Second, the linewidth of the detected resonances
can be exceptionally narrow (of the order of parts per billion [ppb] on a
megahertz scale for nuclear spins), which yields extremely detailed local
chemical and structural information.
The local interactions are determined by the local magnetic fields created by neighboring nuclei and electrons. These magnetic fields are typically orders of magnitude smaller than the strength of the external magnetic
field, and thus they are often treated as perturbations to the main field.
These interactions may be broadly defined as a chemical shift and dipolar
coupling (many interactions exist but are outside of the scope of this
chapter). In terms of Hamiltonians, the nuclear chemical shift is given by

(1.3)
which describes an orientation-dependent shift in the resonance frequency

of the given spin caused by the presence of local magnetic fields encapsulated in the chemical shift tensor, . These local fields are most often
caused by the electron density in the neighboring chemical bonds. The
electron g-factor is given by

(1.4)
which is dependent on the applied microwave frequency, ; Plancks constant, h; the Bohr magneton, B; and the magnetic field strength, Bz. A
value significantly different from that of a free electron (ge = 2.002319)
indicates a magnetic interaction with neighboring electrons and nuclei
and, therefore, contains chemical structure information. The dipolar coupling Hamiltonian is given by

(1.5)
which describes a shift in the resonance frequency inversely dependent

on the distance between two spins (denoted as I and S). The electron spin
possesses a hyperfine coupling Hamiltonian, which describes interactions
between nuclear and electron spins:

(1.6)
Without going into detail, the hyperfine coupling is dependent on

A describing two interactions including the Fermi contact, dependent on the electron wave function overlap with the nuclear position,
and the dipolar interaction, taking a form comparable to Equation 1.6.
In general, these interactions are anisotropic and solid samples yield
broad spectral lines attributable to the contribution of each orientation to the respective interaction. In the case of solution samples, in
which the molecules tumble isotropically, the broadening is reduced
to the isotropic chemical shift while the dipolar coupling averages to 0
and high-resolution s pectra are obtained. Solids can be made to act as
isotropic samples as well by mechanically rotating the solid sample at

an angle of 54.7 relative to the main magnetic field. Under these conditions (3cos21), a term that appears to first order in all anisotropic
interactions magically goes to zero and thus the technique is referred to
magic-angle spinning (MAS).
1.3CHARACTERIZATION OF PYROLYTIC
CARBON USING MR
C-MEMS and C-NEMS structures are fabricated by first patterning the
desired geometry into a high carbon-containing polymer and then pyrolyzing the patterned polymer precursor so as to obtain the desired carbon
shape. In the case of photopatterning photoresist precursors such as SU-8,
the process yields a glasslike carbon (commonly known as glassy carbon
or GC) whose microstructure features entangled graphite ribbonlike structures with <5 nm pores [3]. These pores are found to be smaller, or even
absent, depending on the nature of the starting material and the fabrication methodology [46]. Electronic, electrochemical, and surface properties of GC are strongly intertwined with its microstructure. Thus, for
the fabrication of GC-based electronic and electrochemical sensors (see
Chapters47) with optimal properties, it is extremely important that one
understands the chemical and morphological nature of the GC microstructure at the nano-length scale.
Carbon allotropes and carbon-containing compounds may either
feature pure sp, sp2, or sp3 hybridization or contain a mixture of them.
For example, diamond and graphite display pure sp3- and sp2-hybridized
carbon atoms, respectively, while fullerenes, carbon nanotubes (CNTs),
diamond-like carbon, and amorphous carbon possess a mixture of differently hybridized carbon [7]. The microstructure and resulting properties
of some of these carbon materials correlate with the ratio of the sp2- and
sp3-hybridized carbon in the matrix [7].
Common techniques for probing the graphitic content in a carbon
material such as GC are Raman spectroscopy, X-ray diffraction (XRD),
transmission electron microscopy (TEM), and, in some cases, electrical
property measurements. Raman spectroscopy and XRD measurements
are noninvasive techniques; however, the information one obtains on carbons crystallinity from these techniques is an average value of the crystallinity in a large area such as a circular spot with ~100 m diameter. In
case of GC, the D and G Raman bands and the characteristic 002 planes
of graphite in XRD tend to be broad owing to the fact that this material is
a mixture of sp2- and sp-hybridized carbon atoms, and sp carbons result

in a broad Raman peak. It is often difficult to draw any conclusion on
carbons atomic or molecular arrangements from these techniques, and
one needs to use supporting characterization techniques such as high-
resolution transmission electron microscopy (HR-TEM) imaging and
electron d iffraction patterning. HR-TEM analysis often requires powdered or focused ion beam milled samples that are only a few nanometers
thick, which may not be possible for all C-MEMS patterns. In summary,
none of these common techniques can directly provide quantitative information on the type of hybridization of the carbon atoms in a specific area
on a given sample.
MR is a noninvasive technique and is highly compatible with
C-MEMS patterns that can easily be placed into typical MR sample holders. Several examples of the application of NMR for carbon characterization are described in the literature, including, but not limited to, the
characterization of coal [810], charcoal [11, 12], graphite or graphite
oxide [8, 1315], graphene [16], diamond [8, 17], nanodiamond [1821],
nanohorns [22], nanotubes [23, 24], and amorphous hydrogenated carbon
[25]. In these studies, 13C is the most common probe of the molecular structure, which is often assisted by the presence of 1H in the sample. Several
material properties can be addressed using the combination of these two
nuclei: the presence and distribution of both domains and paramagnetic
centers and the content of carbon that is (i) sp3 versus sp2 hybridized,
(ii) CH or CH2 or CH3 or quaternary, (iii) nonprotonated, (iv) aromatic,
and (v) functionalized (COH, COC, C=O, etc.). In the case of ESR, a
nearly equivalent quantity of literature exists with applications including,
but not limited to, coal [2631], graphite or graphite oxide [3234], nanodiamond [19, 35, 36], nanohorns [37, 38], and nanotubes [3941]. The
principal spectral parameters that may be determined include the electron
g-value (dependent on the chemical environment), the signal line width
(dependent on spinspin couplings, paramagnetic gas exchange, etc.), signal line shape (differentiating localized and conducting electron signals),
hyperfine couplings (electronnucleus interactions), and paramagnetic
electron concentrations.
From the perspective of NMR, the first choice to study carbon materials would naturally be solid-state experiments based on 13C and, depending on the details of the material, 1H (see Table 1.1 for the NMR relevant
details of these nuclei).
The low natural abundance of 13C requires rather large sample
quantities but results in the absence of carboncarbon couplings, which
MR sensitive
isotope
13
C
1
H
Natural isotopic
abundance (%)
1.1
99.9
Spin quantum
number (I)
1/2
1/2
Table 1.1. NMR relevant properties of 13C and 1H nuclei

Gyromagnetic
ratio (MHz/T)
10.7
42.7
Relative
sensitivity
0.02
1
Chemical shift
range (ppm)
250
10

O
C C R
R2C = CH2
R - CO2R
RHC = CHR
R2C = O R - CO2H
200
R2C = CH2
C - Ar
C - OR
Aromatics
150
CCR
C-C=C
C - OH
100
C-H
50
C Chemical Shift (ppm)
13
Figure 1.1. Chemical shift range for 13C in NMR spectroscopy.
greatly simplifies the resulting spectrum and analysis. The 13C chemical
shift range, that is, the spread over which the resonance frequencies are
detected, is 25 times larger than that of 1H (Figure 1.1).
This implies that the resonance frequency response to chemical environment is much more sensitive and indeed 13C NMR can be used to distinguish hybridization states and functionalization (see Figure 1.1). While
1
H NMR is also sensitive to the same chemical information, the large natural abundance and gyromagnetic ratio combined with the narrow chemical shift dispersion typically result in spectra with broad resonance line
shapes, especially in solid-state NMR, complicating data analysis. The
benefit of the presence of 1H in the same sample is the possibility to transfer magnetization from the highly abundant, highly sensitive 1H to the
low abundance, insensitive 13C using a technique known as cross polarization magic-angle spinning (CPMAS). This technique has the potential to
enhance 13C signals by a factor of 4 (the ratio of the gyromagnetic ratios).
Accessing these material properties required the development of
sophisticated NMR experiments capable of exploiting the various nuclear
interactions. For a better perspective, graphite was first studied by 13C
NMR spectroscopy in 1958, just over a decade after the discovery of
NMR [42], and because of the broad spectral lines observed with the first
spectrometers, very little structural or chemical information was obtained.
Some early studies explicitly aimed at the determination of chemical
composition of carbon materials were carried out in the 1970s [8, 43]
with the investigation of graphite, coal, and diamond. With the development of MAS [44, 45] and cross polarization (CP) [4648], unprecedented structural detail could suddenly be accessed. S
tate-of-the-art work
(as of 2015) uses a variety of NMR experiments based on careful control of various nuclear interactions to truly approach atomic-level detail
about the molecular structure. MAS is such a ubiquitous technique that,

in describing all further experiments, it should be assumed that the sample was spinning.
In the most straightforward case, the 13C spectrum of carbon materials will contain contributions from each carbon species comprising the
sample. This spectrum is referred to as the direct polarization (DP) or
Bloch decay spectrum because it is produced by exciting all 13C nuclei
without bias. From the DP spectrum, hints about chemical composition
are revealed, including the presence of sp3, sp2, or functionalized carbon
(purely based on the differences in chemical shift). Gaining further insight
into the chemical structure of the material relies on the ability to edit
the DP spectrum for particular features of interest. Features that may be
exploited in solid-state NMR for spectral editing include relaxation times
(spinlattice T1 and spinspin T2), number of attached hydrogen atoms,
mobility of the functional group (e.g., methyl group rotation), and distance
to nonbonded hydrogen. The remainder of this section will briefly examine some of the common NMR experiments that are performed and how
their results relate to chemical structure.
The first strategy commonly used is CP. This technique takes advantage of the 1H nuclei present in the sample and aims to transfer the large 1H
polarization to the less-abundant, less-sensitive 13C nuclei, resulting in 13C
signal enhancement. The polarization transfer is permitted only when the
Zeeman energy levels of the two nuclei are equal. This is accomplished
by applying a spin-lock radiofrequency (RF) pulse simultaneously to both
nuclei with the condition that the field strength is the same on both channels. Polarization is then transferred as a function of the contact time, that
is, the period in which the spin-lock pulse is applied. One might expect that
long contact times will greatly enhance the 13C signal; however, one is also
competing with relaxation mechanisms that deplete the total polarization,
and thus there is an optimal contact time that maximizes the 13C enhancement. It is important to note that the nuclear interaction Hamiltonian
responsible for the polarization transfer is the dipolar coupling between
the 1H and 13C. One example of spectral editing then becomes clearonly
13
C nuclei in the proximity of 1H will be enhanced. The contact time offers
another alternative for spectral editing and exploits the strength of the
dipolar coupling. By choosing a globally suboptimal, short contact time
(SCT), only those 13C nuclei with strongly dipolar coupled 1H nuclei will
be enhanced, often permitting the distinction of bonded versus nonbonded
hydrogen.
A second strategy that uses the strength of the dipolar coupling interaction is dipolar dephasing (DD), also referred to as gated decoupling
[49, 50]. This technique requires the selective introduction of the dipolar
coupling, which is otherwise suppressed with appropriate decoupling RF
pulse sequences. By turning on the dipolar coupling for a short period
(~40 s), strongly coupled 13C will lose coherence and, therefore, will not
contribute to the detected signal. When combined with DP or CP spectroscopy, the resulting spectrum will be edited to highlight nonprotonated and
mobile 13C nuclei.
A third strategy for spectral editing takes advantage of differential
relaxation rates of the 13C (or 1H) nuclei. The relaxation mechanisms may
be complicated, but it is sufficient to note that different domains within
the material may possess different relaxation rates (e.g., aliphatic versus
aromatic domains) [25]. By carefully timing the delays in the NMR pulse
sequence, it is possible to eliminate contributions from the quickly relaxing population relative to the slowly relaxing population.
A fourth strategy aims to directly map the correlations between the
13
C and 1H. These are 2D NMR techniques, which aim to correlate 13C
chemical shifts with bonded or neighboring 1H chemical shifts (heteronuclear correlation, HetCor [51]) or 1H linewidths (wideline separation,
WISE [52, 53]). These spectra offer insight into chemical shift assignment
(via chemical shift correlations), proximity of functional groups [14], and
mobility (via 1H line widths).
With a careful choice of the appropriate experiments, it becomes possible to uncover structural details of the carbon material (see Table1.2).
Straightforward application of the techniques described will reveal proximity to 1H, while maintaining the chemical environment information
encoded in the chemical shift. Further detail is gained by taking spectral differences of two experimentsfor example, CH signals may be
obtained by taking the difference between a CP spectrum (all 13C near 1H)
and a CP or DD spectrum (13C near 1H but not bonded) [21].
A powerful application involving control of the dipolar coupling is
in determining domain structures. There are several cases where this is
important: in determining aliphatic domain sizes, in determining fused
aromatic domain sizes, and in the determination of nanoparticle surface
signals versus core signals. The key to determining aliphatic domain sizes
is in the ability to monitor polarization (i.e., signal) loss as it flows through
a dipolar-coupled network. One must create channels through which
polarization is allowed to flow in the form of multiple quantum (MQ)
coherences. These coherences are allowed only in the case of multiple
spin couplings, and they may be described by an MQ order dictated by
the number of coupled spins. Therefore, by monitoring signal intensity as
a function of the type of MQ coherence that is accessed, and how long it
DEPT (MQ)
HetCor
C13C correlations
1
H spectral pattern at each
resolved 13C
1
H13C chemical shift
correlation
13
CH and quaternary
RFDR
WISE
13
Details revealed
All C
13
C near 1H
Domain features
Domain features
Mobile and np 13C
Mobile and np 13C
Quaternary and p 13C
Quaternary and mobile 13C
13
Experiment
DP
CP
Relaxation Edit
MQMAS
DP or DD
CP or DD
SCT-CP
SCT-CP or DD
C distant from 1H
CH2 groups
13
Rigid 13CH groups

Rigid 13CH groups
13
C distant from 1H (>3 bonds)
13
C distant from 1H, rigid 13CH
groups
-
13
Details concealed
Table 1.2. Various NMR experiment designs for carbon material characterization
[20]
[10, 20]
[14]
[19, 20]
(Continued)
Example refs
Standard
Standard
[25]
[25]
[10, 12, 20, 21, 55]
[10, 12, 13, 20, 21, 25, 55]
[12, 13, 20, 55]
[12, 20, 55]
Details revealed
Quaternary 13C
Domain features
(p versus np)
p 13C and residual np 13C
p 13C
Domain and particle size
sp3 13C (alkyl)
sp2 and sp 13C
Details concealed
CH2 and rigid 13CH groups
13
[20]
[20]
[20]
[10, 12, 53, 55]
[20]
[10, 12, 20, 54, 55]
Example refs
DP, direct polarization; CP, cross polarization; MQMAS, multiple quantum magic angle spinning; DD, dipolar dephasing;
SCT, short contact time; RFDR, radio frequency driven recoupling; WISE, wideline separation; HetCor, heteronuclear correlation; DEPT, distortionless enhancement by polarization transfer; LR, long range; DIPSHIFT, dipolar and chemical shift
(correlation); HARDSHIP, heteronuclear recoupling with dephasing by strong homonuclear interactions of protons; CSA,
chemical shift anisotropy; np, non-protonated; p, protonated.
DIPSHIFT
DIPSHIFT or DD
HARDSHIP
CSA filtering
Experiment
DETP(MQ) or DD
LR-REDOR
Table 1.2. Various NMR experiment designs for carbon material characterization (Continued)
is allowed to exist (all controlled by the RF pulse sequence), it is possible

to determine the number of correlated spins. This experiment was used
by Jaeger et al. to probe the nanostructure of amorphous hydrogenated
carbon [25]. By including relaxation time editing, the authors were able
to reveal the heterogeneous nanostructure of the material, concluding with
the existence of small sp3 CH2 domains (approximately five CH2 groups)
separated by nonhydrogenated olefinic sp2 carbons among a statistical distribution of olefinic sp2 and sp3 CH groups.
A second technique reliant on the decay of signal as a function of
proximity to 1H has been used to measure the size of fused aromatic
domains. The principle of the experiment is based on DD with a modification to include long-range couplings [54]. With short DD times, the
long-range couplings permit the observation of 13C signals originating
from within fused aromatic systems. As the DD time increases, these signals are destroyed quickly for small domains and persist for longer DD
times for large domains. This technique has been used to identify surface
versus interior carbons in nanodiamonds [15] and to study fused aromatic
systems in coals [10, 12] and charcoal [55].
1.3.1NMR FOR INVESTIGATING CARBON HYBRIDIZATION
In the case of glasslike carbons as obtained in the C-MEMS process, the
NMR analysis can shed light on the extent of graphitization as well as
on the presence of H impurities. The sp2 and sp3 peaks resulting from
the different types of amorphous carbon exhibit slight variations in their
chemical shifts, which makes NMR a particularly useful characterization
tool. In Table 1.3, the sp2 and sp3 NMR peak positions as observed in
various carbon film samples are summarized [56]. One can determine the
presence of differently hybridized atoms in a carbon material based on the
number and the area of the peaks that are present at their respective values
in parts per million. It is also reported that NMR can be used as a standard
method to calibrate the sp2-to-sp3 ratio derived from other methods [57].
An illustration of typical NMR spectrum of various carbon samples is
shown in Figure 1.2.
This technique can also be very useful for detecting the presence of
H in the given carbon, for example, in carbon materials obtained from
low-temperature pyrolysis. The low-temperature pyrolysis materials have
fascinating properties and are a research topic for scientists studying the
mechanism of the pyrolysis process [64].
The second MR spectroscopic technique, ESR, is dependent on the
presence of unpaired electrons in the material. From the perspective of
39
40
40
40
50
62
40
130
130
130
140
130 + 5
130
140
sp3 Peak position (ppm)

36 + 2
50
sp2 Peak position (ppm)

120
135
140
0.55, 0.34, 0.19
1.44
2.35, 1.85, 1.25
1.63
14.6
0.16, 0.25, 1.00,
1.25, 1.63
-
sp2/sp3
~0/100
100/0
1.51.7
a-C:H and a-C denote amorphous carbon films with and without H, respectively.
a-C:H
Film type
Diamond powder
Graphite
Diamond-like
carbon
a-C:H
a-C:H
a-C:H
a-C:H
a-C
a-C:H
Table 1.3.sp2 and sp3 NMR peak positions of carbon films [56]
0.35
0.34, 0.40, 0.42
<0.15
0.61, 0.58, 0.47,
0.31, 0.35
-
0
0.3-0.4
H (at%)
[63]
[57]
[25]
[59]
[60]
[61]
[62]
Reference
[17]
[8]
[58]

Polycrystalline graphite
Diamond
a-C
a-C:H
DLC
sp3
sp2
400
300
200
ta-C
100
-100
-200
Chemical shift (ppm)
Figure 1.2. NMR spectra for various carbon films [56]:

a-C, softer carbon films without hydrogen usually formed
at low energy or higher temperature; a-C:H, softer carbon
films with hydrogen; DLC, diamondlike carbon; and ta-C,
tetrahedral amorphous carbon films with high content of
sp3 bonding and without hydrogen.
c arbon materials, an ESR signal typically arises from broken carbon

carbon bonds (dangling bonds) or transition metal impurities. If impurities are excluded, then ESR is a technique that primarily uses the g-value
to identify the chemical environment of the electron. As summarized by
Petrakis et al., characteristic g-values are known for aromatic hyrdocarbons
of various ring sizes, aliphatic hydrocarbons, oxygen-containing radicals
(e.g., quinones and ethers), and nitrogen- or sulfur-containing radicals [29],
which by comparison reveal hints as to the environment of the electron in
the carbon material. From the linewidth of the ESR signal, details about
chemical environment distributions may be inferred. The linewidth is also
strongly affected by adsorbed oxygen (a paramagnetic molecule), and thus
investigations into signal linewidth as a function of oxygen partial pressure

reveal details such as material porosity. If the material is conductive, then
the transition from a symmetric dispersive to an asymmetric dispersive
ESR signal may be used to differentiate localized and conduction electrons,
respectively. Recent advances in pulsed ESR techniques have allowed
even further details to be uncovered, including hyperfine interactions hidden within the broad ESR signal (electron-spin-echo envelope modulation
[ESEEM], hyperfine sublevel correlation [HYSCORE] [40]), and direct
measurement of nuclear-electron interactions electron nuclear double resonance (ENDOR [36]). In a landmark report, nanodiamond samples with
nitrogen defects have been used to detect a single electron spin [65].
1.3.2NMR FOR CARBON SURFACES
NMR spectroscopy can also serve as an important tool for electrochemists
who wish to quantify C=O and C=C functional groups on carbon electrode surfaces. Electrochemical devices such as supercapacitors and battery anodes are some of the most researched application areas of GC and
C-MEMS technology. The performance of such electrochemical devices
depends on establishing charge-storage processes on high surface area
electrodes and is strongly influenced by carbons surface properties. Highsurface-area carbons are known to have complicated kinetics because
of the presence of various surface functional groups [66]. These surface
groups may contain functionalities such as quinoid, quinhydrone, phenolic, carboxyl, carbonyl, or lactone depending on the fabrication technique
used for manufacturing the electrodes. NMR has the unique ability to
quantitatively analyze the surface composition of carbon materials and
this can be very useful in C-MEMS electrochemical technology.
In a recent report, 13C NMR was used to detect and quantify very
small amounts of sp2-hybridized carbon on the surface of nanodiamond
particles of ~5 nm diameter [21]. The authors were also able to determine
whether or not the carbon atoms were protonated, that is, if there is any
H impurity in detonation nanodiamonds (also known as ultradispersed
diamonds). Typical NMR spectra for the nanodiamond material prepared
using different heat treatments are shown in Figure 1.3.
In their analysis of the surface functional groups present in detonation nanodiamonds, the authors used MAS and TOSS (total suppression of
spinning sidebands) techniques and quantitatively determined the presence
of CH, COH, C=O, and CC groups, which, in this case, accounts for
12 to 14 percent of all carbon. Clearly, in addition to the characterization

Pristine nanodiamond
ssb
ssb
(c)
C=O
sp2-C
sp3-C
x 34
C=C
200
150
100
Treated ssb
at 800C
sp2-C
(b)
ssb
C=C
ssb
50
ppm
x 34
ssb
200
(a)
200
150
100
50
Pristine nanodiamond
Treated at 800C
COH
ssb
Alkyl C
150
100
50
ppm
ppm
Figure 1.3. Quantitative, direct-polarization

13
C NMR spectra of detonation nanodiamond
and a heat-treated reference sample. (a) Spectra
of pristine nanodiamond (thin line) and the
800C heat-treated material (thick line), taken
at 14 kHz MAS. (b) Spectra after 800C heat
treatment, expanded 34 times vertically, taken
at 14 kHz MAS (dashed line) and 6 kHz with
TOSS (full line). A broad CC band is clearly
visible. (c) Same as (b) for pristine nanodiamond (except higher spinning frequency of
6.5 kHz for TOSS spectrum). ssb, spinning
sideband [21].
of carbons atomic arrangements and hybridization, the potential of NMR

for investigating the presence and extent of similar functional groups on
the surface of C-MEMS electrodes could be a very interesting area for
further research.
1.4NMR FOR KEY CARBON MEMS

APPLICATIONS AND DEVICES
Small foot print batteries and supercapacitors are two types of electrical
energy storage devices that have been developed during the past three
decades to meet the dramatically increased energy demand in portable
electronic devices. Batteries exhibit remarkably high energy densities;
however, they suffer from a rather limited cycle life [67]. On the other
hand, supercapacitors, also known as electrochemical double-layer capacitors (EDLCs), in spite of a relatively lower energy density, show essentially unlimited cycle lives and very fast charge or discharge rates (also see
Volume 2, Chapter 5) [68].
There is a wide range of graphitic carbon materials that meet the
requirements of conductivity, porosity, and electrochemical stability for
use in supercapacitors: carbon onions [69] and nanohorns [70]; activated,
templated, and carbide-derived carbons [71]; and CNTs [72]. Activated
carbons are the most widely used materials nowadays in the fabrication
of supercapacitors because of their high surface area and high electronic
conductivity, along with low cost. The key characteristic to achieve high
surface area is the porosity of this class of materials, which is tunable in
the synthesis process. Activated carbons are derived from organic precursors such as wood, coconut shells, or coal, and a porous network is created
upon activation in the bulk of the carbon particles. The mean pore size
is tuned by means of temperature and activation time (longer activation
time or higher temperatures lead to larger mean pore size [68]): micropores (<2nm in size), mesopores (250nm), and macropores (>50nm).
The small pore sizes are typically slightly larger than the solvated electrolyte ions [73]. The storage mechanism in supercapacitors is based on the
formation of an electrical double layer at the interface between the solid
porous electrode and the liquid electrolyte solution. In order to provide
an in-depth understanding of the associated processes taking place during
the charge or discharge cycles and to investigate the behavior of ions
inside the nanopores, a wide variety of experimental methods and theoretical studies have been used. Changes in the concentration of electrolyte
ions inside the pores versus the applied potential have been assessed by
small-angle neutron scattering. Ion diffusion inside mesoporous carbon
electrodes has been investigated for different charge states by neutron
diffraction [74]. Other experimental techniques include in situ electrochemical quartz crystal microbalance methodologies [75] and in situ IR
spectroscopy [76]. In parallel with the experimental efforts, a significant
amount of theoretical work has been dedicated to the understanding of the
storage mechanism in supercapacitors. The anomalous increase in capacitance in nanoporous supercapacitors has been explained by a mean field
theoretical model [77], further extended to take into account the dynamics of charging [78]. Molecular dynamics simulations have also successfully predicted the anomalous enhancement of capacitance experimentally
observed in micropores [7981].
In spite of all the efforts presented earlier, an investigation methodology capable of direct observation and quantitative measurement
of the evolution of ion environments in supercapacitors is still needed.
MR-based investigation methods have been attracting a lot of attention in
the past several years and are more and more used in the study of batteries
and supercapacitors. The versatility of NMR as an investigation method
comes from the weak coupling between the nuclear spin states and the
surrounding environment, making it extremely sensitive to the local environment. NMR is therefore a perfect tool for the study of electrochemical
interfaces, in particular for the investigation of supercapacitors and batteries, offering quantitative and element-selective information at the molecular level about the structure and dynamics of the ions in the electrolyte and
at the electrodeelectrolyte interface.
As NMR spectroscopy enables direct observation of the adsorbed
atomic species storing the electrical charge in the carbon-based matrix, the
most straightforward and convenient experimental arrangement is ex situ
NMR investigation [82, 83]. This usually means that the device, supercapacitor or battery, is disassembled at different charge or discharge states, and an
NMR spectrum or image is acquired from the carbon electrode soaked with
electrolyte. Ex situ NMR is capitalizing on the opportunity of using MAS
spectroscopy, therefore, taking advantage of higher spectral resolution to
gain exquisite information about changes in the immediate neighborhood of
the intercalating ions. However, ex situ NMR brings along a series of inherent disadvantages such as uncertainties about modifying the charge state of
the device by ion desorption during the disassembly procedure as well as the
obvious evaporation of the solvent (usually acetonitrile [ACN]), which may
trigger changes in binding and even cause electrolyte solidification.
In situ NMR circumvents the physical and chemical changes that
occur on disassembling the cells and before actual measurements are
being recorded. Taking advantage of NMR being a noninvasive technique,
in situ NMR investigation enables real-time monitoring of interactions
and distributions of anions and cations separately in the carbon electrodes
offering a more realistic picture of the behavior of working devices. The
price to be paid is a significant decrease in spectral resolution because of
the inherent incompatibility between in situ NMR and MAS.
1.4.1NMR FOR EDLCs

A large number of C-MEMS-based EDLCs are based on high surface
area porous carbons. Solid-state NMR constitutes a powerful means
of discrimination for species that have been adsorbed inside the porous
carbon matrix. This is especially the case of very small pore sizes with
a high trapping efficiency, where liquid-state NMR is not able to provide enough information because of the limited ion mobility. Solid-state
NMR has been used to observe and study ex situ the electrolyte organization in nanoporous-activated carbon supercapacitor electrodes [83], as
the adsorbed molecules within the graphene layers yield NMR signals that
are shifted by approximately 6 ppm relative to the free molecules. In this
study, natural abundance 13C MAS NMR was used to investigate the degree
of structural disorder of the nanoporous-activated carbon electrodes, the
results being confirmed by Raman spectroscopy. Together with 13C spectra,
11
B MAS NMR spectra were used to quantify the amounts of electrolyte
moleculesACN and tetraethylammonium tetrafluoroborate (TEA+ and
BF4)either outside or trapped inside the nanoporous carbon matrix, for
uncharged and charged supercapacitors [83]. Moreover, 2D exchange spectra performed on both 11B and natural abundance 13C provide information
about the dynamics of the electrolyte species as well as about the chemical
exchange between the adsorption sites and the free state of the electrolyte.
In the case of EDLCs, a number of other nuclei found in the organic
electrolyte are used to characterize activated carbon electrodes using
NMR spectroscopy techniques. A typical example exploits the 11B and 19F
species found in the organic electrolyte tetraethylammonium-tetrafluoroborate (Et4NBF4). Lee et al. [84] used solid-state 11B NMR to study two
different activated carbons used as electrode material in EDLCs: M500
activated carbon and M3000 activated carbon exhibiting medium (500
m2/g) and high (3,000 m2/g) surface area, respectively (Figure1.4). 11B
MAS NMR spectra recorded for each of the two types of electrodes allow
for the identification of two BF4 species that differ through the localization of the ions in the matrix of the activated carbons. The MAS spectra
for M500 electrodes show that a larger amount of electrolyte is left on the
external surface of the activated carbon matrix (A-peaks) compared to
the electrolyte solution, which has been adsorbed within the small, pore
volume (B-peaks). For the high surface area (M3000) electrodes, 11B MAS
spectra show a reversed tendency as more BF4 ions are localized inside
the large pores compared to what is left at the outer surface. T1 (spin
lattice relaxation times) have been estimated for both cases using the saturation recovery method [1]. This allows for a common ground to compare

Free(A)
Adsorb(B)
Adsorb(B)
Free(A)
D(-)
C(-)
D(+)
Intensity
D(+)
D(-)
C(-)
C(+)
C(+)
Imp
Imp
10
-10
/ppm
(a)
-20
10
-20
0
-10
Chemical shift (ppm)
(b)
Figure 1.4. (a) 11B MAS NMR spectra of BF4 in activated carbons with
specific surface area of 500 m2/g for impregnated, charged, and discharged
states as presented in [84]; (b) 11B MAS NMR spectra of BF4 in activated
carbons with specific surface area of 3,000 m2/g for impregnated, charged,
and discharged states. The sharp peaks (A) have been assigned to free BF4
species, and the broad peaks have been assigned to adsorbed BF4 species.
(Legend: Imp = impregnated; C/D +/ = charged/discharged positive/negative polarization)
the mobility of various ionic species within the same activated carbon, as
well as between the two samples under consideration.
Along the same line of characterizing the matrix of activated carbons
in EDLCs, liquid-state NMR has been performed on the fluorine in atom
in the
anion [85], exploiting the fact that 19F is a spin nucleus with
100 percent natural abundance, therefore, constituting a precious NMR
investigation instrument. However, the characterization is rather limited
to the interaction of the BF4 with the surface of the activated carbon electrode, as liquid-state NMR cannot capture the information from the ions
trapped inside the small pores, which have very limited mobility.
Grey et al. [86] have implemented in situ NMR to investigate the
migration of electrolyte ions between the supercapacitor carbon electrodes
in real time, as well as their interaction within the porous electrode matrix
itself (Figure 1.5). The authors have proposed a special supercapacitor
2V
1.5 V
1V
0.5 V
0V
(a)
10
0
-10
-20
Chemical shift (PPM)
(b)
10
-2 V
-1.5 V
-1 V
-0.5 V
-0 V
0
-10
-20
(c)
-2 V
-1.5V
-1 V
-0.5V
0V
0 .5 V
1V
1.5V
2V
10
(d)
Integrated area
80103
70
60
50
40
30
0
-10
-20
20
-2.0
-1.0
0.0
1.0
Voltage (V)
2.0
Figure 1.5. 11B static NMR spectra taken

in situ from a supercapacitor at various
voltages, as presented in [86]: (a)spectra
of the positive electrode charged up to 2
V; (b) spectra of the negative electrode
charged up to 2 V; (c) chemical shift
evolution for each electrode as a function
of the applied voltage; and (d) integrated
areas for each electrode spectra as a
function of the applied voltage.
design with the electrodes spatially shifted with respect to each other,
which allows one to separate the resonances associated with each electrode, as only one electrode can be placed inside the NMR coil detector
at a time. 11B NMR spectra were acquired in situ as a function of the
supercapacitor state of charge as controlled with an external charger, and
the dynamics and binding of ions within the supercapacitor were followed
this way. NMR experiments have also revealed a significant decrease in
the T1 relaxation times from 2.1 to 0.3 s when the voltage was increased
from 2 to 2 V [86], one potential cause for this trend is attributed to an
increased interaction between the anions and the carbon matrix at positive
potentials.
A follow-up work from the same group uses in situ NMR spectroscopy to gain insight into the charge storage mechanism in EDLCs [87].
This is achieved by NMR spectra collected in real time for direct observation of the changes in the amount of charge storing species (adsorbed
species) on the applied voltage and for differentiating various charge storage regimes.
In situ NMR investigation of EDLCs has been recently pushed one
step forward when the first magnetic resonance imaging (MRI) results
were published [88], yielding spatially resolved chemical information
related to the electrolyte ions. Chemical shift information data is acquired
fast enough to provide real-time snapshots of the nonequilibrium states
of the supercapacitor during electrochemical cycling, thus differentiating
the specific charge storage mechanisms during charging and discharging,
respectively. 1H NMR information was used to characterize the cation
(
), as the ACN solvent used here was deuterated, while 11B NMR
information was used to characterize the anion (
). Multinuclear imag1
11
ing on H and B nuclei allows for capturing information from each type of
ions occupying each electrode of the cell during electrochemical cycling.
1.4.2NMR FOR BATTERIES
As described in Chapter 5, graphite and GC are very suitable electrode
materials to study the mechanism of lithium intercalation in lithium-ion
batteries. Graphite and GC are preferred over other carbon materials
because of their higher volumetric energy density and lower cost. During
charging and discharging cycles, lithium ions intercalate into and deintercalate out of the graphitic layers, processes that are associated with significant changes in the electrode volume [89]. Another process profoundly
affecting the subsequent battery performance is the formation of passive
films on the graphite electrodes because of the decomposition reactions of
the battery electrolyte, especially when using propylene carbonate (PC)

[90]. This process is irreversible and diminishes the cycling efficiency of
graphite electrodes leading to a large capacity loss in lithium-ion batteries
after the first cycle.
Kim et al. [91] have concomitantly used 7Li and 13C NMR together
with electrochemical impedance spectroscopy in order to study the intercalation or deintercalation mechanisms of lithium ions into graphite layers as well as the association of the lithium ion with various solvents.
Chemical shifts in the 7Li NMR spectra are expected to reveal whether
solvent molecules are intercalated together with Li ions inside the electrode graphite lattice. These results are being cross-checked with 13C
NMR spectra of charged graphite electrodes in electrolyte solutions that
should exhibit signals corresponding to the solvents if these are present
in the graphite structure. Kim et al. have shown that using crown ethers,
these ethers indeed cointercalate with lithium ions in the graphite structure slowing down the passivation reaction. However, this occurs at the
expense of a lower charge-transfer rate in the battery [91].
A well-known issue in lithium-metal [ion] batteries is the formation of metallic lithium dendrites on the lithium-metal anode during the
charging process. The strategy that emerged to alleviate this problem
was the development of graphite negative electrodes in lithium-ion batteries. The latter come with the compromise that the discharge capacity
of a graphite electrode is smaller than the discharge capacity of metallic
lithium. The discharge capacity of the graphite electrode can be improved
by doping the graphite with boron, taking advantage of the fact that the
boron atomic size is comparable to that of carbon; therefore, it does not
introduce significant distortion of the carbon lattice. However, the discharge capacity of a graphite electrode doped with boron is a function of
the percentage of dissolved boron and the maximum solubility of boron in
graphite is only about 2.35 percent even at 2,350C [92]. It is, therefore,
important to precisely characterize the structural states of boron atoms in
the carbon lattice, and besides classical methods such as Raman or Auger
electron spectroscopy, NMR has the capability to decipher the chemical
environments of the boron atoms.
Lee et al. [93] have successfully characterized the structural states of
boron in boron-doped graphite obtained by mixing graphite with various
percentages (1, 2.5, 5, and 7 wt.%) of boron carbide during the graphitization process by solid-state 11B NMR spectroscopy. The results show that,
for low concentrations, all boron atoms are replacing carbon atoms in the
graphite lattice. However, excess boron diffuses fast between the graphite
planes, it being a light mass atom, eventually forming graphite carbide and
preventing the free movement of the actual charge carriers [93], therefore
affecting the ultimate performance of the battery.
While graphite and lithium easily form intercalation compounds [94],
this is not the case between graphite and sodium when Na+ is being electrochemically reduced at a carbon electrode. Gotoh et al. [95] have used
MAS and static NMR to analyze the state of the 23Na nucleus inserted in
hard carbon electrodes and to compare sodium with lithium intercalation
in the carbon matrix. The authors observed a significantly different behavior of sodium spectra compared to 7Li NMR in hard carbon. At ambient
temperature, very different from the lithium, the sodium signal does not
shift as a function of sodium content, whereas at low temperature, the
lineshapes of MAS and static NMR spectra did not change and the peaks
did not exhibit any splitting [95]. Gotoh et al. concluded that the behavior
of sodium with respect to hard carbon electrodes is qualitatively different
from that of lithium with the exchange of sodium between different carbon
matrix sites happening at a slow rate relative to the NMR time scale. At the
same time, NMR experiments show that sodium does not form metallic
clusters in the closed nanopores of hard carbon [95].
Gerald et al. [96] have demonstrated an NMR platform for the in
situ investigation of 7Li ions in carbon electrode materials. Similar to the
case of supercapacitors, in situ battery NMR allows for the observation
of ongoing electrochemical processes during battery cycling, as opposed
to disassembling the battery after a certain number of charge or discharge
cycles. This advantage comes with the drawback of the incompatibility
between MAS and in situ NMR spectroscopy, with the associated resolution loss. Gerald et al. developed a device, which integrates an electrochemical cell and an NMR detector, identifying the signatures of several
lithium species within the same spectrum: lithium in the electrolyte, intercalated lithium, and inorganic lithium in the solidelectrolyte interphase.
With in situ NMR, the evolution of each species during multiple charge or
discharge cycles can be followed.
1.5FUTURE OPPORTUNITIES
1.5.1CARBON MEMS FOR MR-RELATED RF AND MW
APPLICATIONS
In this section, we explore new possible applications of photoresist-derived carbon as a functional material for MR experiments. We are well
aware of the fact that some of the concepts presented may not be so readily
applicable to current NMR hardware design, but carbon MEMS is still a

very young technology which we believe has great potential to influence
in one way or other way even such seemingly disparate disciplines as MR
hardware engineering.
The performance of an MR detector relies heavily on the quality of
the RF resonances. As shown in Figure 1.6, a standard resonant circuit
comprises an inductor (NMR probe) and two capacitors for frequency
tuning and impedance matching. The energy inside the system is stored
periodically in the form of electric and magnetic fields inside the capacitors and the inductor, respectively. A commonly used figure of merit and
measure of the effectiveness of a resonating system to store energy is the
quality factor Q = 2 (maximum energy stored per cycle)/(average energy
loss per cycle).
For RF and MW resonators, losses have at least four causes: dielectric, conduction, radiation, and external losses. In Figure 1.6, the effect
of loss on the resonance linewidth and thus the Q-factor is schematically
illustrated. For MR detector design, it is highly desirable to efficiently
translate a given amount of current into a confined magnetic field that is
stimulating the sample. Hence, it is important to try to minimize all potential loss mechanisms that might obscure or degrade the actual MR signal to
be detected from the sample. For example, the signal-to-noise ratio (SNR)
for metal-based inductive detectors is directly proportional to R1/2 with
R being the equivalent ohmic resistance of the electrical conductor [101].
Log scale
0dB
-3dB
Reference level
CM
(3)
R
CT
(4)
(a)
0
Frequency
(1)
(2)
(b)
Figure 1.6. (a) Schematic representation of frequency dependence of the

reflection coefficient. The quality factor Q can be directly evaluated from
the 3 dB bandwidth around the resonance frequency 0. Mismatched
resonant circuits (matching capacitance CM) as well as loss (depict by the
equivalent resistance R) degrade the resonance performance of the system.
(b) Sketch of a variety of planar MW resonators; (1) planar ohm-shaped
resonator [97], (2) split-ring resonator [98], (3) half-wavelength resonator
[99], and (4) surface loop-gap resonator [100].
Among the emerging but still rather exotic optical and force-based
MR detection principles, Faraday induction is by far the most prevalent
and is an industry standard. The archetype of inductive detectors is a
solenoid made of metal wire. However, a vast variety of surface resonators (spirals [102, 103], microstrip lines [104], slot lines [105], loop gaps
[100]) and volume resonator types (Helmholtz pairs [106], bird cage coils,
metal cavities [107], or loop-gap resonators [108, 109]) have been used,
each motivated by a particular application. Material-wise, metals of high
electric conductivity and matched magnetic susceptibility are typically
used. For ESR experiments that operate at exceedingly higher frequencies
compared to NMR (fESR 28 GHz/T vs. fNMR 42 MHz/T), dielectric
materials have been used for years as a low loss complement to metal
cavity resonators [110]. Upon the advent of high field NMR (>10 T) and
MRI (>7 T) experiments, dielectrics became an interesting alternative as
a material for high-frequency MR probes [111]. Dielectric materials relevant for MR are essentially electric insulators with relative permittivities
r that range from 10 to several hundreds to thousands. Typically, these
materials (e.g., ceramics such as barium titanate and zirconium oxides)
show a low dielectric loss tangent (tan 10-5) and low temperature coefficients ( 15 to 15 ppm/K) and are formed into cylindrical or ring-type
resonant structures, which effectively act as field concentrators or storage
for a narrow range of frequencies. The resonance frequency of a resonator
is determined by the permittivity of the material and its near surroundings, as well as its overall physical dimensions. Owing to their potentially
high permittivity, the electromagnetic (EM) fields are well confined to the
structure, which decreases radiation loss. Even more interesting for miniaturized MEMS-based devices, higher r is also connected to a decreased
wavelength inside the material and shrinks the overall resonator size proportional to 1/(r)1/2 [112].
The material properties discussed earlier are a function of frequency,
which must be known for rational RF or MW engineering decisions. However, there is only limited literature available on the dielectric properties of
suitable GC films in the RF or MW regimes. In contrast, composite materials
made from carbon-based fillers such as CNTs or carbon black mixed into
polymer matrixes are being actively characterized and are established as
dielectric electromagnetic interference (EMI) sheets or foam absorbers
[113115]. Apart from free space and transmission line techniques (e.g.,
planar lines [116] and open ended lines [117]), resonant methods provide
a highly accurate and sensitive way to characterize MW material properties at a particular frequency or a discrete set of frequencies. Therefore,
the perturbation in the response (phase, magnitude of s-parameters) of a
resonator of known performance is measured on sample loading. The perturbation because of the interaction of the sample under test with the electric field results in a resonant frequency peak shift as well as a decreased
loaded Q-factor of the known probing resonator. The loaded Q-factor QL is
obtained by the measured resonant frequency f and the half power (3db)
bandwidth f of the mode resonance: QL = f/f. Especially, planar resonators, such as ring [118] or microstripline [119] resonators, seem to be a
reasonable choice to investigate carbon MEMS thin films as produced by
standard UV lithography. The reliable assessment of the C-MEMS material
permittivity as a function of frequency is a crucial requirement for further
investigations leading to interesting RF or MW applications.
The specific resistivity of photoresist-derived carbon can vary by
orders of magnitude depending on annealing, ranging between that of
semimetals and semiconductors [120]. For C-MEMS films to be considered as a suitable RF or MW dielectric, its dielectric losses are most probably too high. On the other hand, its semimetallic character is not reaching
the high electric performance standard of metals such as silver or copper.
Hence, modifications of the material should aim for one of the two goals,
namely, to render it more metal-like (i.e., higher electric conductivity) and
to improve its dielectric properties (e.g., reduce conduction loss).
We envision three possible routes to approach this challenge that all
take advantage of the tailorability of carbon: (1) tuned process and preparation conditions, (2) the use of fillers, and (3) galvanic metal reinforcement:
1. Park et al. [120] confirmed the remarkable dependence of the electrical conductivity on the carbonization temperature. Park et al. and
Singh et al. [120, 121] suggested that a further increase in carbonization temperature (beyond 1,000C) will also lead to a further
increase in conductivity, denser structures, and nucleation of small
graphitic nanocrystallites (graphitization completion at 2,700C).
This route seems to be promising; however, besides higher machine
complexity, the glass-transition temperature of the utilized substrate will naturally limit at some point the maximal applicable temperature. Other process parameters such as gas pressure and type
might influence the physical properties of the achieved structures.
The concept of donor or acceptor gasses can be exploited, whereas
increased process pressure might enhance the tendency of the material to form graphitic domains.
2. There is an opportunity to tailor the dielectric RF or MW performance of the carbon film matrix by forming mixtures of two
materials of different r, Q, and so on. The photoresist precursor
can be readily mixed with dielectric fillers such as calcium titanate (CaTiO3) or barium titanate (BaTiO3) powders, so that the
permittivity as well as the dielectric loss can be varied in the given
range of start or end values as a function of the mass fraction of
the two materials [112]. The carbonization or sintering temperature represents a further parameter with which to adjust the material properties. Interestingly, many technical ceramics exhibit
sintering temperatures (starting at approximately 900C) that are
covered by the carbonization process used for photoresist-derived
carbon. As the resist becomes successively more opaque as the
filler concentration increases, a major issue is the decreased performance of the UV lithography resulting in degraded conformity
and resolution of the resist patterns. As shown by Rashidian et
al. [122], a feasible alternative to UV lithography for patterning polymer matrixes with high solid filler content is casting the
solution into prepatterned forms followed by baking and hard UV
or X-ray exposure.
3. Galvanization leaves the carbonized structure itself unchanged
but improves its electrical conductivity by reinforcing it with a
thin layer of highly conductive metal by means of electroplating. Particularly for higher frequencies (MHz to several GHz),
the skin effect is very pronounced with the current density highest
near the surface or skin of the conductor, and as a consequence,
most of the resistive losses occur there. For example, a conductor
made from copper features a skin depth of 63 m at 1 MHz but
only 2m at 1 GHz. For electrical applications, typically, copper
or gold electroplating baths or electroless plating solutions are
used to change the surface properties of an object. The metal plating process should be optimized in order to yield smooth metal
surfaces as well as high structural conformity by, for example,
avoiding nonuniform electroplating current distributions. In a
study from Reijerse et al. [123], a CW ESR or ENDOR resonator
was manufactured from high density graphite, which was electroplated with 10 to 15 m gold. For ESR or ENDOR experiments,
a high-frequency (typically MW) ESR resonator excites electrons
inside a sample, while a second low-frequency signal (typically
RF) modulation field is simultaneously applied. In this case, the
graphite offers the advantage of being suitable for plating and can
be used to geometrically define the MW cavity while offering at
the same time a low enough specific resistance to prevent excessive damping of the RF modulation field.
A useful feature of photoresist-derived carbon structures is that

numerous units can be reproducibly fabricated on a single substrate or
wafer, in parallel and with high precision. Another aspect is the potential
to pattern the photoresist not only in 2D but also in 3D. With the advent of
3D laser lithography, which allows direct writing of precise and arbitrary
3D patterns into a photosensitive resin, hollow structures, spirals, ring
resonators, or spherical objects can be readily fabricated at microscale
dimensions. Given that losses could be overcome or substantially reduced,
3D micro NMR detectors made from photoresist-derived carbon would
offer superior sensitivity (e.g., for coil detectors the SNR is proportional
to d1 where d is the outer diameter) per unit volume as stronger magnetic
fields can be generated.
Similar to polymer composites filled with, for example, carbonaceous
particles, photoresist-derived carbon might also play a role in integrated
MW absorbing coatings and for developing antielectrostatic measures
with increased chemical resistance [124]. This includes, for example, the
reduction of backradiation of microstrip resonators or reduced EMI among
electrical components and circuits [113]. The work of Kuzhir et al. [115]
demonstrated that even nanometrically thin pyrolytic carbon (PyC) films
produced via chemical vapor deposition offer reasonably high EM attenuation. The authors proposed that the semitransparent PyC films might
emerge as a promising material for manufacturing ultrathin microwave
filters and shields.
1.5.2CARBON FOR SHIMMING
The ability to form a material with tunable magnetic susceptibility has
important consequences for MR engineering. Carbon in its many forms
displays magnetic susceptibilities varying from 3.5 107 emu/g for C60
all the way to 3 105 emu/g for graphite perpendicular to the 002 plane,
a span of almost two orders of magnitude (see also Table 1.4). In case
of pyrolytic carbon, the susceptibility values depend on the nature of the
starting material as well as the pyrolysis temperature. One can, therefore,
tune the susceptibility of the material to suit the desired application.
Even small susceptibility differences (in ppm) between material layers along the field lines cause variations in magnetic field strengths. As
this type of variance is three orders of magnitude larger than that tolerable
for the measurement of NMR signals (required resolution: parts-per-billion range), one of the maxims of conventional NMR engineering is the
parallel arrangement of materials with respect to the strong B0 magnetic
Table 1.4. Susceptibility values of carbon allotropes

Carbon allotrope
Diamond
Graphite parallel to plane
Graphite perpendicular to
plane
C60
C70
Pyrolytic (glassy)
carbon obtained from
polyvinylchloride between
1,000C2,000C
Pyrolytic (glassy)
carbon obtained from
polyvinylidene chloride at
3,000C
Susceptibility in [emu/g]
4.9 107
5 107
3 105
Reference
[125]
[125]
[125]
3.5 107
5.9 107
Range: 0 to 6.0 106
[125]
[125]
[126]
4.7 106
[126]
field, thus avoiding susceptibility jumps close to the measurement volume.

As susceptibility jumps are undesirable, NMR systems contain multiple
shimming magnets that are intended to compensate for such effects. With
continued progress in miniaturization and integration, and because designs
do not follow necessarily the design rules of traditional macroscopic NMR
hardware, shimming becomes much more complicated. One remedy is
to perform the so-called structural preshimming through the addition of
regions of materials of given susceptibility that help to compensate for
these shifts in magnetic field strength in the active region of the NMR
detection system.
In essence, the concept is straightforward. Jumps in susceptibilities
are the reason for field shifts, that is, the differential jump strength along
the field direction for a directed area element. So a surface element dA
with unit normal n is measured in (1 2)dA(Bn)/|B|, and can be considered a source term (in the sense that charge is the source for electric
fields) for the field shifts that penetrate the surrounding medium. Hence,
by distributing additional bounding shapes of materials of particular susceptibility j, we can directly shim a region of interest. In Jia et al. [127],
it is shown how this can be achieved through the addition of materials
with positive or negative susceptibility using topology optimization
here mainly for an MRI application of interventional surgical devices.
Ryanetal. [128] suggested that a similar shimming effect can be achieved

by creating specially shaped air holes surrounding the functional part of
a lab-on-a-chip device for an application in NMR, using a Monte-Carlo
simulation method. We speculate that resist-derived, patterned, carbon
films are an excellent source for structural shimming. As the susceptibility
of pyrolytic carbon can be widely varied according to processing conditions, this suggests the ability to tune the degree of passive shimming
depending on NMR sample needs.
1.5.3PYROLYTIC CARBON FOR ON-DEMAND

HYPERPOLARIZATION
Hydrogen is widely considered a promising clean energy alternative to
fossil fuels. In a hydrogen-centered energy economy, the biggest market
would be represented by fuel cells, to generate electricity at high efficiency. Particular efforts are being put into the design and characterization
of fuel cells, and NMR is contributing by enabling investigations into the
H2 adsorption characteristics of hydrogen storage materials. However, the
energy sector is not the only one that is currently driving general interest of
NMR researchers toward hydrogen: The need for on-demand H2 production, and in particular parahydrogen (pH2) production, has been growing
since the 1990s, thanks to the advances in NMR technology. Specifically,
parahydrogen-induced hyperpolarization, or PHIP [129, 130], is a wellknown and established technique for NMR signal enhancement in analytical chemistry, medical imaging [131133], metabolomics [134137], and
gas and fluid analytics [138140]. NMR detector miniaturization and integration in portable and multipurpose analytical devices would also benefit
significantly from a signal-boosting technique such as PHIP.
Parahydrogen is one of the two spin isomers of the H2 molecule, having an antiparallel nuclear spin configuration; orthohydrogen, the parallel-spin isomer, has a much higher state density than parahydrogen so that,
at room temperature and 1 bar pressure, H2 gas is naturally found as a 3:1
mixture of ortho- and parahydrogen. The relevance of parahydrogen in
NMR stems from the availability of NMR signal enhancement techniques
(hyperpolarization) that exploit the very large reservoir of spin order represented by pH2; indeed, PHIP offers enhancement factors of more than
105-fold [130].
Parahydrogen production relies on the slow-rate conversion mechanism of the ortho-H2 fraction at very low temperatures at which the para
state is the low lying energy state [141]. Conversion from a triplet ortho
state (S = 1) to the singlet para state (S = 0) is prohibited by the angular

momentum conservation principle, thus a catalytic action from an agent,
such as an iron oxide substrate or an activated carbon substrate, is usually
necessary to enable and boost the conversion. Parahydrogen mixtures as
pure as 98 percent pH2 content can be achieved, for example, by driving
the conversion at T < 14K. The need for catalytic op conversion in the
hydrogen production industry originates from the necessity to deal with
the release of heat upon spontaneous op H2 conversion, which is responsible for the evaporation of more than 60 percent of the liquefied H2.
The established large-scale hydrogen production route is based on
fossil fuel and natural gas reforming. Common feedstocks for hydrogen
production are methanol, ethanol, and ammonia. Aqueous-phase reforming of biomass and bio-produced H2 (i.e., fermentative H2) are two production strategies that are also gaining momentum [142]. Efforts have been
put into the miniaturization of hydrogen production and storage devices
to achieve a higher energy density in fuel cells or to alleviate the problems associated with storing a large quantity of either liquid or gaseous
hydrogen [143].
Carbon-based materials, and potentially C-MEMS, enter the PHIP picture from two aspects: On the one hand, carbon is currently being explored
as a catalyst for H2 production via an electrocatalytic reaction route and as
a catalyst-supporting material for aqueous phase reforming reactions. On
the other hand, activated forms of carbon are also required as parahydrogen
conversion catalysts in pH2 converters. It is possible to envision a scenario
where C-MEMS devices are streamlining both the production and conversion processes at the micro level and could thus meet the on-demand need
for H2 and pH2 gas, for example, in hyperpolarized NMR. We will now
explore the potential of carbon in the context of these two applications.
Traditionally, the development of H2 microgenerators has stemmed
from the need for on-demand H2 production for fuel cells: The storing of
small volumes of hydrogen for small fuel cells (e.g., portable fuel cells)
has proved to be very challenging, if not impossible. As an alternative to
compressed gas and liquid hydrogen, hydrogen-packed chemicals, such as
hydrides, have gained attention as hydrogen storage materials, providing
high hydrogen densities at room temperature and ambient pressure.
The feasibility of hydrogen microgenerators has been demonstrated a
number of times; here we report on just a few inspiring examples. A good
amount of experimentation has been dedicated to the fabrication of methanol
reforming hydrogen microgenerators [144]. Gervasio et al. [145] fabricated
a room-temperature-operated microfluidic device for heterogeneous catalytic hydrolysis of aqueous alkaline borohydride solution. Kim [146] and
Hoeppner [147] proposed two different microreactors for hydrogen generation from sodium borohydride as a convenient room-temperature solutions
to the H2 production problem. More recently, Zhu et al. [148] proposed an
on-demand microfluidic hydrogen generator with self-regulated gas generation, and Um et al. [149] reported on a micro-TPV (microscale-thermophotovoltaic) device integrated with a microreformer for hydrogen (H2)
production by burning and reforming ammonia (NH3).
Electrocatalytic hydrogen production from water, commonly known
as hydrogen evolution reaction (HER), is also an option that still needs
to be fully exploited in the context of MEMS. The most commonly used
metal catalyst for HER devices is Pd, although the very fact that Pd is a rare
earth element has pushed the research toward finding viable alternatives,
such as Mo, Ni, Co, and Fe. Although cheaper, transition metals are prone
to oxidation and corrosion, two factors that ultimately impact the long-term
durability and catalytic effectiveness. Carbon is a recent addition to the
list of possible HER catalysts: The high tunability of molecular topology,
the large material availability, and the marked chemical resistance render
carbon-based materials quite advantageous for metal-free catalytic hydrogen production. In several instances, carbon-based materials have attracted
much attention as suitable catalyst support for HER reactions: Structured
carbon devices supporting noble metal catalysts have been evaluated for
both oxygen reduction reactions (ORR) and HER, leading to promising
results (see, e.g., [150] and references therein). FeN4-containing CNTs have
been investigated for electrocatalytic activity [151] and have been found
stable toward the ORR in an acidic electrolyte. Li et al. [152] reported
an oxygen reduction electrocatalyst based on CNTgraphene complexes
showing high catalytic activity, as well as superior stability in comparison
to other nonprecious metal catalysts, in both acidic and alkaline solutions.
Gong et al. [153] investigated the possibility of using nitrogen-containing CNTs for ORR, reporting an impressive 4.1 mA/cm2 output current
density if compared to platinumcarbon electrodes (1.1 mA/cm2). Dubey
etal. [154] reported a significant rate of electrolytic hydrogen production
at anodic voltages as low as 1 V using CNT electrodes as the anode. More
recently, Zheng et al. [155, 156] demonstrated a P- and N-doped graphene
catalyst for HER, featuring highly efficient electrocatalytic activity because
of the promotion of both proton absorption and reduction kinetics.
Microbial electrolysis cells (MEC) are attractive and scalable alternate possibilities for hydrogen production. These bioelectrochemical
devices exploit the metabolic action of living microorganisms to produce
hydrogen. The appeal of such devices is the very-low-voltage requirement
and the possibility to operate at room temperatures.
The operating principle of an MEC is a variant of the microbial fuel

cell (MFC). In an MFC, organic matter is oxidized by a bacterial colony
(e.g., Pseudomonas spp. or Shewanella spp.), producing carbon dioxide
as a waste product, while releasing protons to the liquid medium and
electrons that are collected at the anode. Spontaneous current generation
ensues when oxygen is reduced at the cathode. However, under anaerobic
conditions, and forcing a small positive voltage across the anode and the
cathode (as little as +0.2 V), hydrogen gas is produced at the cathode.
Thus an MEC is different from an MFC in that an MEC is equivalent to
an electrolytic cell that produces hydrogen (i.e., the systems Gibbs Free
energy is positive, G > 0), while an MFC is analogous to a galvanic
current generator (G < 0).
Carbon-based materials in the form of carbon cloth, carbon paper,
graphite felt, graphite granules, and graphite brushes are ideal for the
anode in an MEC, offering a favorable growth substrate for bacteria to
thrive on [157]. In this instance, an MEC capable of supporting a bacterial population on carbon-based scaffolds would make for a sustainable
hydrogen generator with extremely low energy requirements. We speculate that the easy patternability of carbon-based materials and the low
voltage requirements for conventional or microbial electrolysis would
make C-MEMS technology very appealing for the design of on-demand
hydrogen generators.
We will now briefly discuss the opportunities offered by carbon-based
materials to the conversion of ortho-rich to para-rich hydrogen. The main
requirements for successful ortho-to-parahydrogen (op) conversion are
(i) low temperatures and (ii) the presence of a suitable catalyst to trigger
the spin flip transition from triplet to singlet nuclear spin state. Thus, a
catalytic converter is usually composed of three elements: a refrigerator
stage, a conversion chamber, and a gas collection system. In this context,
the catalyst is usually a material containing paramagnetic defects, and the
spin flip is caused by the hydrogen molecule coming in close proximity to
such defects [158].
As for requirement (i), technology for localized in situ cryogenics is
already in place, with steady advances each year. Notable mentions from
the recent literature are, for example, low-cost microthermoelectric coolers [159], a Stirling microcooler [160], and a JouleThomson cryocooler
[12], where the cooling fluid itself is hydrogen gas.
Carbon could play a major role as the material to fulfill requirement (ii),
namely, as an ortho-to-parahydrogen conversion catalyst. Commonly used
conversion catalysts to rapidly convert from ortho- to para-H2 are iron oxide
and hydrous ferric oxide, nickel sulfate and nickel silicate, chromic oxide,
ruthenium metal and ruthenium alloys, and activated charcoal (see Ref.
[161] for a review). The conversion chamber is usually designed as a storage
space for a large quantity of catalyst and with an inlet and the outlet for H2
gas and pH2-rich gas mixtures. The geometry of the chamber is optimized
for the largest possible contact surface between H2 gas and the catalyst.
Although the op conversion phenomenon has been intensely investigated and theoretically explained [162], this is not true for most allotropes
of carbon that feature paramagnetic properties and as such theoretically
viable for op conversion. This knowledge gap offers an opportunity for
research on a form of carbon that is suited to perform the op conversion
at high efficiency and easily fabricated in a C-MEMS manner at the same
time. Catalytic activity in the case of the op conversion is essentially tied
to the presence of paramagnetic centers and the rates of H2 adsorption and
desorption; pyrolitic carbon, for instance, could represent a solution to
decouple the paramagnetism problem, which is a tunable bulk property of
carbon, from H2 adsorption, which is mostly a surface-related problem and
can be solved by cleverly patterning the sacrificial polymer. We thus propose that existing parahydrogen converter designs might be miniaturized
by exploiting the potentialities of carbon as an MEMS building material,
for example, in the shape of consolidated solutions such as packed-bed
microreactors or flow-through cell microreactors.
1.6CONCLUSIONS
The potential of MR spectroscopy for the characterization of carbon materials and C-MEMS devices has not yet been fully recognized. There are
several, but unconnected, scattered studies where MR technology has
been implemented to unravel the molecular arrangement and properties
of a variety of carbon materials. Here we have summarized a number of
such reports to inspire the C-MEMS community for making use of this
widespread powerful technology. NMR and ESR are excellent tools for
probing carbons microstructure and its surface and to characterize the
performance of a variety of C-MEMS devices.
Additionally, C-MEMS is not yet an established technology for applications in NMR or ESR. Nevertheless, the potential for a number of such
applications has been identified, which range from catalysis to shimming,
and we foresee concrete applications emerging in the near future. It is
especially the ability to prepattern the precursor polymers in a variety of
ways, through electrospinning and lithography with subsequent pyrolysis,
which presents a real opportunity to combine carbon structures with other
system components at the microscale.
Many applications depend on having carbon structures of predefined

molecular morphology. Here, especially ESR is an important tool with
which to probe the electronic structure of the resultant carbon samples,
with the ability to reveal the extent to which the amorphous and polycrystalline material matrix consists of unpaired electrons. On the other hand,
NMR can reveal intimate structural details, especially in conjunction with
chemical bonds formed with other compounds.
With its stronger sensitivity to protons and other electrochemically
active species, NMR microscopy is predestined to become a method of
choice with which to spatially analyze and discriminate dynamic molecular processes, to reveal, for example, the degradation mechanisms that
confront electrochemical energy storage and energy conversion devices.
Through hyphenation with other techniques, such as optical excitation and
detection, we expect to see numerous advances that build on the impressive capabilities already available today. We, therefore, expect the trio
consisting of carbon in general, C-MEMS as a specific embodiment, and
MR both as a method of investigation and targeted application, to be a
fruitful combination of techniques in the short to medium term.
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Index
A
AC electroosmosis (ACEO)
2D to 3D electrodes, 5861
fully functional, 6164
physics of, 5758
solid-state electric-field-driven
pumps, 5557
ACEO. See AC electroosmosis
AC impedance, 115
Adsorptive stripping voltammetry
(AdSV), 146
AdSV. See Adsorptive stripping
voltammetry
Amperometric sensors, 172173
Anodic stripping voltammetry
(ASV), 146
ASV. See Anodic stripping
voltammetry
B
Bacterial persistence, LOC
applications, 8990
Batteries, NMR applications,
2325
Bio-MEMS, 54
Bismuth-modified pyrolyzed
photoresist carbon electrodes,
147
Bloch decay spectrum, 9
C
Carbon microelectromechanical
systems (C-MEMS)
dielectrophoresis, 7172
3D Interdigitated electrode
arrays, 176179
electrochemically activated
microsupercapacitors, 130131
lab-on-a-chip perspectives,
9495
microsupercapacitors, 128129,
132134
polypyrrole-based
Carbon-nanotubes-integrated
Cathodic stripping voltammetry
(CSV), 146
Cell lysis, 83
CEs. See Counter electrodes
Charge storage mechanism,
125126
Chemical sensors, 170
Chemical shift, 35
C-MEMS. See Carbon
microelectromechanical
systems
C-MEMS-based 3D interdigitated
electrode arrays
description, 176
development, 178
dopamine detection, 184186
electrochemical sensing,
179181
oxide growth, 176177
postexposure bake, 178
192Index
pyrolysis, 179
redox amplification, 181184
soft baking, 177178
spin coat, 177
UV exposure, 178
Corrosion tests, 109111
Counter electrodes (CEs), 170171
CSV. See Cathodic stripping
voltammetry
D
DD. See Dipolar dephasing
DEP. See Dielectrophoresis
Dielectrophoresis (DEP)
applications, 7274
C-MEMS electrodes, 7172
lab-on-a-chip applications,
8082
principles of, 7071
Dipolar coupling, 34
Dipolar coupling Hamiltonian, 4
Dipolar dephasing (DD), 910
Direct electroanalysis of organics,
153154
Direct polarization (DP) spectrum,
9
Dopamine detection, IDEAs,
184186
E
ECs. See Electrochemical
capacitors
EDLCs. See Electrochemical
double-layer capacitors
Electrical characterization, glassy
carbon, 108109
Electrical lysis, 8384
Electrochemical capacitors (ECs)
advantages, 123
charge storage mechanism,
125126
fundamentals of, 124125
Electrochemical characterization,
glassy carbon, 109111
Electrochemical double-layer
capacitors (EDLCs), 1823,
125126
Electrochemically activated
C-MEMS-based
Electrochemical sensing, IDEAs,
179181
Electrochemical sensors, 170
Electrodes, 170171
Electron g-factor, 4
Electropermeabilization, 83
Electroporation, 83
Electrostatic spray deposition
(ESD), 129
Electrothermal effect, 6869
Equivalent series resistance (ESR),
125
ESR. See Equivalent series
resistance
Evoked muscular movements,
113114
F
Faradaic capacitors, 126
Fully functional AC
electroosmosis micropumps
complete, 64
fabrication process, 6162
lithography parameters, 62
residual electrical resistance,
6364
stiction effect, 6263
G
GC. See Glassy carbon
Glassy carbon (GC)
corrosion tests, 109111
description, 102104
difficulties of, 103
electrical characterization,
108109
electrochemical characterization,
109111
Index 193
evoked muscular movements,

113114
fabrication process, 105106
impedance, 114116
mechanical characterization,
107108
properties of, 103
rat in vivo stimulation and
recording, 112113
Gyromagnetic ratio, 3
H
Helmholtz double layer, 126
HER. See Hydrogen evolution
reaction
Hybrid electrochemical capacitor,
126
Hydrogen evolution reaction
(HER), 34
Hyperfine coupling Hamiltonian, 4
I
IDEAs. See Interdigitated
electrode arrays
Interdigitated electrode arrays
(IDEAs)
C-MEMS-based 3D, 176179
metallic, 175176
redox amplification, 173175
Interdigitated electrodes, 127128
L
Lab-on-a-chip (LOC)
advantages, 7980
bacterial persistence, 8990
cell lysis, 9294
concept of, 80
definition, 79
dielectrophoresis, 8082
electrical lysis, 8384
fabrication, carbon electrodes,
8485
lambda DNA trapping, 9192
natural contaminants, PCR-based
protocols, 8689
perspectives on C-MEMS, 9495
Lambda DNA trapping, 9192
Limit of detection (LOD), 87
Lithography parameters, 62
Loaded Q-factor, 28
LOD. See Limit of detection
M
Magic-angle spinning (MAS), 5
Magnetic resonance (MR)
description, 12
nuclear. See Nuclear magnetic
resonance (NMR)
overview of, 25
pyrolytic carbon characterization,
513
MAS. See Magic-angle spinning
MEC. See Microbial electrolysis
cells
Mechanical characterization,
glassy carbon, 107108
Mechanical micropumps, 55
Membrane potential, 8384
Metallic interdigitated electrode
arrays, 175176
MFC. See Microbial fuel cell
Microbial electrolysis cells
(MEC), 3435
Microbial fuel cell (MFC), 35
Microelectrodes, amperometric
sensors, 172173
Micropumps, 55
Microsupercapacitors
advantages, 127128
carbon microelectromechanical
systems, 128129, 132134
carbon-nanotubes-integrated,
131132
comparative study, 135
definition, 126127
electrochemically activated
C-MEMS-based, 130131
electrostatic spray deposition, 129
194Index
polypyrrole-based, 132134
Miniaturized electrochemical
capacitors. See
Microsupercapacitors
MR. See Magnetic resonance
Multiple quantum (MQ)
coherences, 10, 13
N
Neural probes, 104
Nonmechanical micropumps, 55
Nonuniform AC electric fields,
6668
Nuclear chemical shift, 4
Nuclear magnetic resonance
(NMR)
batteries, 2325
carbon hybridization, 1316
carbon surfaces, 1617
electrochemical double-layer
capacitors, 1823
on-demand hyperpolarization,
3236
radiofrequency and microwave
applications, 2530
shimming, 3032
O
ORR. See Oxygen reduction
reaction
Ortho-to-parahydrogen (op)
conversion, 3536
Oxygen reduction reactions
(ORR), 34
P
Parahydrogen, 32
Parahydrogen-induced
hyperpolarization (PHIP), 32
Parallel plate capacitor, 124
PEB. See Postexposure bake
PHIP. See Parahydrogen-induced
hyperpolarization
Photoresist-derived carbon, 2830

Photoresists, 124
Polymerase chain reaction
(PCR)-based protocols, 8689
Polypyrrole-based
Postexposure bake (PEB), 178
Power, 125
PPCE. See Pyrolyzed photoresist
carbon electrodes
Pseudocapacitors, 126
Pumping efficiency, 6466
Pyrolysis, 179
Pyrolytic carbon
characterization, 513
on-demand hyperpolarization,
3236
Pyrolyzed photoresist carbon
electrodes (PPCE)
bismuth-modified, 147
characteristics of, 139146
cyclic voltammogram, 141,
144145
direct electroanalysis of organics,
153154
electrochemical properties, 140,
143
photolithographic fabrication
procedure, 162
physicochemical
characterization, 142
trace metal ions analysis,
146152
in vivo and flow analysis,
154160
R
Redox amplification
C-MEMS-based 3D
interdigitated electrode arrays,
181184
interdigitated electrode arrays,
173175
Index 195
Redox capacitors, 126

Reference electrodes (REs),
170171
REs. See Reference electrodes
Residual electrical resistance,
6364
S
Shaped 3D planar electrodes,
6466
Shimming, 3032
Soft baking, 177178
Solid-state electric-field-driven
pumps
AC electroosmosis, 5557
ACEO pumps, 5758
2D to 3D electrodes, 5861
fluid flow generation, 5557
Stiction effect, 6263
Stripping voltammetry, 146
Supercapacitors. See
Electrochemical capacitors
(ECs)
T
Trace metal ions analysis, 146152
Transmembrane potential, 83
U
Ultracapacitors. See
Electrochemical capacitors
(ECs)
Ultradispersed diamonds, 16
W
WEs. See Working electrodes
Working electrodes (WEs),
170171
Z
Zeeman splitting, 3

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CARBON: THE

MOMENTUM PRESS, LLC, NEW YORK

Carbon: The Next Silicon?: Book 2 Applications

3 Carbon MEMS for Selected Lab-on-a-Chip Applications

6.1Characteristics of Pyrolyzed Photoresist C

7.4State of the Art in C-MEMS-Based IDEAs

xii List of Figures

List of Figures xiii

rolls generated over each electrode edge: over the small

xiv List of Figures

Figure 2.5.Completed electrode array, combining planar

(a)Empty planar electrodes (before the injection of latex

xvi List of Figures

Figure 2.13.Cells focused into streamlines (red ellipses)

List of Figures xvii

Figure 4.1.(a) Lithography and pyrolysis process for fabricating

xviii List of Figures

(a) FTIR image shows that for p yrolysis temperature of

List of Figures xix

image of the c arbon post displaying the structure of

Figure 6.9.Cathodic reaction of Cr(III)PCVox that is reduced to

List of Figures xxi

Figure 6.16.Electrode geometry and microchip layout. (a) I llustration

xxii List of Figures

Figure 7.2.Steps for C-MEMS process: (a) oxide grow over Si

Table 1.2.Various NMR experiment designs for carbon material

Table 1.4.Susceptibility values of carbon allotropes

Table 5.1.A comparison between different C-MEMS platforms

Table 7.2.IDEAs dimensions before pyrolysis (bp) and after

About the Contributors

xxvi About the Contributors

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

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

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

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

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

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

xxxii Quick Overview of Book2-Applications

niversity Graduate School (UGS) at Florida International

Carbon MEMS for

2 CARBON: THE NEXT SILICON?

A plethora of literature is available on these topics, and some excellent

Carbon MEMS for Magnetic Resonance3

with the spin angular momentum

The magnitude of the applied magnetic field in the z-direction is Bz

4 CARBON: THE NEXT SILICON?

which describes an orientation-dependent shift in the resonance frequency

which describes a shift in the resonance frequency inversely dependent

Without going into detail, the hyperfine coupling is dependent on

Carbon MEMS for Magnetic Resonance5

isotropic samples as well by mechanically rotating the solid sample at

6 CARBON: THE NEXT SILICON?

a mixture of sp2- and sp-hybridized carbon atoms, and sp carbons result

Table 1.1. NMR relevant properties of 13C and 1H nuclei

Carbon MEMS for Magnetic Resonance7

8 CARBON: THE NEXT SILICON?

C Chemical Shift (ppm)

Figure 1.1. Chemical shift range for 13C in NMR spectroscopy.

Carbon MEMS for Magnetic Resonance9

about the molecular structure. MAS is such a ubiquitous technique that,

3 Carbon MEMS for Selected Lab-on-a-Chip Applications

6.1Characteristics of Pyrolyzed Photoresist C

7.4State of the Art in C-MEMS-Based IDEAs

Figure 2.5.Completed electrode array, combining planar

Figure 2.13.Cells focused into streamlines (red ellipses)

Figure 4.1.(a) Lithography and pyrolysis process for fabricating

Figure 6.9.Cathodic reaction of Cr(III)PCVox that is reduced to

Figure 6.16.Electrode geometry and microchip layout. (a) I llustration

Figure 7.2.Steps for C-MEMS process: (a) oxide grow over Si

Table 1.2.Various NMR experiment designs for carbon material

Table 1.4.Susceptibility values of carbon allotropes

Table 5.1.A comparison between different C-MEMS platforms

Table 7.2.IDEAs dimensions before pyrolysis (bp) and after

1.4NMR FOR KEY CARBON MEMS

1.4.1NMR FOR EDLCs

1.5.3PYROLYTIC CARBON FOR ON-DEMAND