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PHYSICS RESEARCH AND TECHNOLOGY
MICROFLUIDICS:
THEORY AND APPLICATIONS
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PHYSICS RESEARCH AND TECHNOLOGY
MICROFLUIDICS:
THEORY AND APPLICATIONS
IVAN A. KUZNETSOV
EDITOR
Nova Science Publishers, Inc.

New York
Copyright 2010 by Nova Science Publishers, Inc.

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Additional color graphics may be available in the e-book version of this book.
LIBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA
Microfluidics : theory and applications / editor, Ivan A. Kuznetsov.
p. cm.
Includes index.
ISBN 978-1-62100-034-1 (eBook)
1. Microfluidics. I. Kuznetsov, I. A. (Ivan Aleksandrovich), 1953TJ853.4.M53M545 2009
629.8'042--dc22
2010012217
Published by Nova Science Publishers, Inc. New York
CONTENTS
Preface
Chapter 1
Chapter 2
Chapter 3
Chapter 4
Chapter 5
vii
Microbiochips Monolithically Integrated
with Microfluidics, Micromechanics, Photonics, and
Electronics by 3D Femtosecond Laser Direct Writing
Ya Cheng, Koji Sugioka,
Katsumi Midorikawa and Zhizhan Xu
Electrokinetic Flows of Non-Newtonian
Fluids in Microfluidic Channels
Cunlu Zhao and Chun Yang
Microfluidic Electro- chemiluminescent Detection
Devices with Capillary Electrophoresis
K. M. Muzyka and M. M. Rozhitskii
Microfluidic Valves without Diaphragms:
Hydrogel Valves and PDMS-Based
Rotary Selection Valves
Steffen Howitz, Frank Baudisch,
Frank-Ulrich Gast, Andreas Richter,
Andreas Grodrian, Gunter Gastrock
and Josef Metze
Biocompatible and Mass Productive MEMS
Device for Localized Surface Plasmon Resonance
Xiaodong Zhou and Hong Liu
55
103
135
149
vi
Chapter 6
Index
Contents
Application to Adaptive Optics
and Laser Microfluidics
Jean-Pierre Delville, Alexis Casner,
Rgis Wunenburger and Iver Brevik
167
175
PREFACE
Microfluidics deals with the behavior, precise control and manipulation of
fluids that are geometrically constrained to a small, typically sub-millimeter
scale. It is a multidisciplinary field intersecting engineering, physics,
chemistry, microtechnology and biotechnology, with practical applications to
the design of systems in which such small volumes of fluids will be used. This
book presents topical data on microfluidics such as the application of
microfluidic principles for the creation of tandem capillary electrophoresis
chip devices with electrochemiluminscent detection techniques; microbiochips
monolithically integrated with microfluidics; analysis of the electroosmotic
flow of power-law fluids in a slit channel and microfluidic valves without
diaphragms.
Chapter 1 - Microbiochips such as lab-on-a-chip (LOC) devices and micro
total analysis systems (-TAS) can be regarded conceptually as a biological
equivalent of conventional silicon integrated circuits, which involve
miniaturization and integration of electronics. As its name implies, an ideal
LOC should have a very small footprint and yet still be capable of functioning
as a laboratory in which partial or complete chemical or biological analysis
can be performed automatically. A planar silicon chip that integrates only
microelectronics is clearly far from adequate for such a purpose, and other
functional components such as microfluidics, microoptics, and
micromechanics need to be incorporated into a chip with 3D configurations.
This poses a formidable challenge, because current mainstream
microfabrication technologies mostly rely on optical lithography, which is
essentially a surface structuring technology. Recently, femtosecond laser direct
writing has exhibited great potential for producing a variety of true 3D
microstructures in various transparent materials. This is enabled by the
viii
Ivan A. Kuznetsov
nonlinear interaction between the tightly focused femtosecond laser beam and
the material that is transparent to the laser beam, since the interaction can be
effectively confined to the vicinity of focal point where the laser intensity
exceeds the threshold for multiphoton absorption. In this chapter, we provide
an overview of 3D femtosecond laser direct writing technology and highlight
its potential for fabrication of complex smart microsystems by furnishing some
examples of fabrication and hybrid integration of microfluidics,
micromechanics, photonics, and electronics. In addition, application of some
of our microfluidic chips to biological research has resulted in new insights
into various biological behaviors such the dynamics and functions of
microorganisms. Possible solutions for overcoming remaining challenges are
discussed in the hope that this technology will provide a manufacturing
solution for the emerging LOC industry.
Chapter 2 - Advanced microfluidic devices can perform complete
biochemical analysis in a single fabricated chip. The generic microfluidic
systems involve buffer solutions and samples manipulations such as pumping,
valving, mixing, injection, dispensing, concentration etc. Fundamental
understanding of the liquid flow characteristics in microchannels is thus
essential to optimum design and precise control of microfluidic devices. In
general, liquid motion can be generated by either applying a pressure gradient
or imposing an electric field, leading to pressure-driven flow or
electrokinetically-driven flow, respectively. Traditionally, in large-sized
channels flow is often driven by pressure that is usually generated by
mechanical pumps. In microchannels however it becomes increasingly
difficult to utilize pressure-driven flow mode as the channel size shrinks,
especially down to micro-and submicron range. Moreover, some parts like
microvalves and micropumps with moving components are difficult to
fabricate, and they are prone to mechanical failure due to fatigue and
fabrication defects. Alternatively, electrokinetic flow enjoys numerous
advantages (over pressure-driven flow), including ease of fabrication and
control, no need for moving parts, high reliability, no noise etc. Specifically, a
plug-like velocity profile in electrokinetic flow can result in reduced
dispersion of sample species, making capillary electrophoresis become one of
most successful technologies for chemical and biomedical analyses. Most of
existing studies regarding electrokinetics flows focus on Newtonian fluids.
However, microfluidic devices are usually used to analyze biofluids which
may not be treated as Newtonian fluids. Thus, the more general Cauchy
momentum equation, instead of the Navier-Stokes equation should be used to
describe the flow characteristics of non-Newtonian fluids.
Preface
ix
This book chapter consists of two parts. In Part 1, electroosmotic flow of

power-law fluids in a slit channel is analyzed. The governing equations
including the linearized PoissonBoltzmann equation, the Cauchy momentum
equation and the continuity equation are solved to seek analytical expressions
for the shear stress, dynamic viscosity and velocity distribution. Particularly, a
counterpart for the classic Smoluchowski velocity is introduced by taking into
account contributions due to the finite thickness of the electric double layer
(EDL) and the flow behavior index of power-law fluids. In Part 2, the
pressure driven flow of power-law fluids in microchannels subject to
electrokinetic effects is addressed. The Cauchy momentum equation
together with the power-law fluid constitutive equation is used to
describe the power-law fluid flow in a slit microchannel with
consideration of a body force resulting from the interaction of the charge
density in the electrical double layer of the channel and the flow-induced
electrokinetic potential. The velocity profile, volumetric flow rate,
apparent viscosity and friction coefficient are analytically evaluated, and
the influencing factors including ionic concentration, wall zeta potential,
flow behavior index and pressure difference are investigated. It is found
that the pseudoplastic fluids are more susceptible to electrokinetic effects
than the dilatant fluids, and thus flow characteristics of the pseudoplastic
fluids are found to deviate drastically from those of Newtonian fluids.
Chapter 3 - The purpose of this chapter is to describe the applications of
microfluidic principles for creation of capillary electrophoresis (CE) chip
devices with electrochemiluminescent (ECL) detection and to discuss the
problems associated with their interfacing and the approaches that have been
developed to surmount them.
Basic methodology, instrumentation, unique features, and specific futures
of microfluidic ECL detection with CE are discussed. ECL assay detection
types, such as direct and indirect analysis, coreactant use including are
considered.
Publications data of scientific centers, involved in development of CE
chips with ECL detection from the start of microfluidic CE/ECL joint
technique are summarized. Basic tendencies of this direction future
developments are covered.
Chapter 4 - Microfluidic networks consisting of more than one channel
must often be controlled by valves. External valves are sturdy, but low dead
volumes require internal valves. Many present-day valves contain membranes
(that are, e.g., driven by air pressure) that become leaky by overpressure or
particles, and simple microfluidic valves control only a single channel at a
Ivan A. Kuznetsov
time. We describe here two different new approaches: a hydrogel valve, which
is robust, and a rotary valve, which is versatile. Both valves are pressurestable. The hydrogel valve contains a microfluidic chamber filled with
hydrogel particles that are swollen and thus close the valve at room
temperature (i.e. normally closed 2/2-way valve). Upon heating, the hydrogel
becomes dehydrated and opens reversibly in two to four seconds. This valve is
robust, autoclavable, and can retain cells without stressing them. The rotary
valve contains a valve seal cast from poly(dimethylsiloxane) (PDMS) with one
or more micromolded channels of extremely low dead volume; it can be
turned, in just 250 milliseconds, to a new position by air pressure or a
micromotor, thereby connecting new inlet and outlet holes. Many different
setups of a multiple-way selector/injector valves can be realized, and so it is
probably the most versatile and quick microfluidic valve available today. To
reduce swelling and abrasion and to allow thousands of cycles, the PDMS
rotor is metal-coated. These two valves represent attractive new ways to
control flows in microfluidic applications.
Chapter 5 - Localized surface plasmon resonance (LSPR) is the interaction
between the light and collective electrons of noble metal nanoparticles, which
exhibits as an extinction peak shift in the transmission spectrum of the
nanoparticles. LSPR is utilized to detect label free chemical or biological
samples, such as finding the kinetic coefficients between two kinds of
chemicals on the surface. To incorporate the noble metal nanoparticle chip into
a compact MEMS device will minimize the expensive biological samples
required, and will be able to make the LSPR biosensors into a large sensing
array for quick detections. The desired LSPR MEMS device should possess
the characteristics of nanofabrication compatible, biocompatible, highly
transparent, cost effective and mass productive.
This chapter introduces the design, fabrication and test of such a LSPR
MEMS device. Our MEMS device is based on a glass-silicon-glass sandwich
structure, it is biocompatible due to the stable nature of the glass and silicon
compared with other polymer based disposable MEMS devices. On the bottom
glass, gold nanostructures for LSPR are fabricated by nanosphere lithography.
The middle silicon layer forms the microfluidics channel and chamber of the
device, and also blocks the light from shedding onto the non-sensing areas.
The top glass is drilled with inlet and outlet for microfluidics. The three layers
are bonded together by UV cure epoxy. As the whole fabrication process
avoids the high temperature, high pressure and high stress, it is
nanofabrication compatible, that the gold nanostructures are intact even when
after the MEMS device is pried apart. The device is highly transparent with
Preface
xi
high signal-to-noise, because the glass surface was not damaged during the
process, and the light blockage of silicon greatly reduced the background of
the light. As the MEMS fabrication for theses three layers are prepared in
wafer level prior to epoxy bonding, the device is suitable for mass production
with low cost. The fabricated LSPR MEMS device is tested by UV-Vis
spectroscopy with bovine serum albumin sensing, and it demonstrates
satisfactory LSPR sensing function. Our experiments prove that such a design
has prominent advantages over the one without light blockage or with
polydimethylsiloxane (PDMS) polymer.
Chapter 6 - We already showed in Section V that linear interface
deformations could be used for soft lensing with large variations in accessible
focal distances. The nonlinear regime in deformation, particularly optically
driven liquid jetting, offers an even wider range of application since
hydrodynamics starts to couple with light propagation. One major point here is
that, contrary to electro-hydrodynamics where micrometric features are
difficult to implement, these are natural length scales in "optohydrodynamics".
In: Microfluidics: Theory and Applications

ISBN 978-1-61668-570-6
Editor: I. A. Kuznetsov, pp. 1-54
2010 Nova Science Publishers, Inc.
Chapter 1
MICROBIOCHIPS MONOLITHICALLY
INTEGRATED WITH MICROFLUIDICS,
MICROMECHANICS, PHOTONICS, AND
ELECTRONICS BY 3D FEMTOSECOND LASER
DIRECT WRITING
Ya Cheng1, Koji Sugioka2, Katsumi Midorikawa2, and
Zhizhan Xu1
1
State Key Laboratory of High Field Laser Physics, Shanghai Institute of

Optics and Fine Mechanics, Chinese Academy of Sciences,
P.O. Box 800-211, Shanghai 201800, China
2
RIKEN - Advanced Science Institute, Hirosawa 2-1,
Wako, Saitama 351-0198, Japan
ABSTRACT
Microbiochips such as lab-on-a-chip (LOC) devices and micro total
analysis systems (-TAS) can be regarded conceptually as a biological
equivalent of conventional silicon integrated circuits, which involve
miniaturization and integration of electronics. As its name implies, an
ideal LOC should have a very small footprint and yet still be capable of
functioning as a laboratory in which partial or complete chemical or
biological analysis can be performed automatically. A planar silicon chip
that integrates only microelectronics is clearly far from adequate for such
Ya Cheng, Koji Sugioka, Katsumi Midorikawa et al.

a purpose, and other functional components such as microfluidics,
microoptics, and micromechanics need to be incorporated into a chip with
3D configurations. This poses a formidable challenge, because current
mainstream microfabrication technologies mostly rely on optical
lithography, which is essentially a surface structuring technology.
Recently, femtosecond laser direct writing has exhibited great potential
for producing a variety of true 3D microstructures in various transparent
materials. This is enabled by the nonlinear interaction between the tightly
focused femtosecond laser beam and the material that is transparent to the
laser beam, since the interaction can be effectively confined to the
vicinity of focal point where the laser intensity exceeds the threshold for
multiphoton absorption. In this chapter, we provide an overview of 3D
femtosecond laser direct writing technology and highlight its potential for
fabrication of complex smart microsystems by furnishing some examples
of fabrication and hybrid integration of microfluidics, micromechanics,
photonics, and electronics. In addition, application of some of our
microfluidic chips to biological research has resulted in new insights into
various biological behaviors such the dynamics and functions of
microorganisms. Possible solutions for overcoming remaining challenges
are discussed in the hope that this technology will provide a
manufacturing solution for the emerging LOC industry.
Keywords: femtosecond laser direct writing, 3D microfabrication, lab-on-achip, microfluidics, micromechanics, photonics, electronics, integrated
microchip.
1. INTRODUCTION
The field of lab-on-a-chip (LOC) technology has experienced tremendous
growth over the last few years. A LOC device is a miniaturized system that
integrates one or more laboratory functions for chemical and biological
analyses. Because of its compact dimensions and high functionality, a LOC
device allows chemical and biological analyses to be performed easily with
low sample and reagent consumptions, low waste production, rapid analysis,
and high reproducibility due to standardization and automation [1,2]. Although
LOC technology has been used for a broad range of applications in a variety of
fields including medicine, healthcare, pharmaceutics, environmental
monitoring, and national security, it is not yet mature and it is still under active
development. One major problem is the lack of appropriate technology for
Microbiochips Monolithically Integrated with Microfluidics
fabricating LOC. For example, enclosed microfluidic structures such as

microfluidic channels and chambers are key elements in almost all LOC
devices; however, because of their inherently 3D nature, they cannot be
formed directly inside transparent substrates by 2D microfabrication
techniques. To overcome this problem, open microchannels and/or chambers
must be initially formed on the surfaces of substrates by photolithography or
soft lithography [35], and then stacking and bonding procedures must be used.
This leads to additional cost and complexity. On the other hand, unlike
semiconductor chips, which mostly consist of just integrated microelectronics,
LOC chips are hybrid integrated systems that incorporate elements having
different functions. Currently, a common way of achieving monolithic
integration of multifunctional components is to first separately fabricate the
different types of components and then assemble them onto a substrate using
microassembly techniques. However, because of the rapid development of
LOC technology, LOC systems are now becoming increasingly complex,
making assembly and packaging very difficult, if not impossible. Thus, new
fabrication processes need to be developed to tackle these problems.
In this chapter, we demonstrate that 3D femtosecond laser direct writing
has great potential for fabricating LOC devices [6,7]. On the one hand, it
allows for direct formation of hollow 3D microstructures embedded in
transparent materials without employing any stacking or bonding procedures;
such microstructures can serve as microfluidic, microoptical, and
micromechanical elements, etc. On the other hand, with this technique,
monolithic integration of multifunctional components into a single chip can be
realized after a single continuous laser writing process followed by chemical
treatments. Since the chemical treatments are batch processes, the increase in
the cost of individual LOC chips is insignificant and will not pose a major
problem [8].
This chapter is organized as follows: we begin by providing a brief
introduction to the basic concepts of 3D femtosecond laser direct writing in
Section 2. In Section 3, we show how to fabricate multifunctional structures
embedded in transparent materials with true 3D configurations. In Section 4,
we present a few examples of monolithically integrated, fully functional
microdevices. In Section 5, we demonstrate the use of microfluidic chips
fabricated by femtosecond laser micromachining for biological applications
such as dynamic observation of microorganisms. Finally, we summarize the
current major challenges of this technique and discuss possible solutions to
some of these problems in Section 6.
2. CONCEPT OF 3D DIRECT WRITING INSIDE

TRANSPARENT MATERIALS BY FEMTOSECOND LASER
Due to its ultrashort pulse duration, peak intensities of over 1014 W/cm2
can easily be attained by a tightly focused femtosecond laser beam even if the
pulse energy is only of the order of microjoules or millijoules. At such high
intensities, the electric field of the electromagnetic wave can significantly
distort the Coulomb potential of most neutral atoms, making the interaction
between the light and matter extremely nonlinear [9,10]. For this reason,
femtosecond laser microfabrication has several distinct advantages over
conventional laser microfabrication techniques that usually employ
nanosecond or continuous-wave lasers. The first advantage is that the
interaction between a femtosecond laser beam and a transparent material can
occur only in the vicinity of the focal point where the peak intensity is
sufficiently high to initiate the multiphoton process. This important property
lays the foundation for 3D direct writing inside transparent materials with
femtosecond laser pulses, because there is virtually no out-of-focus absorption
when a femtosecond laser beam is focused into a bulk material. The second
advantage is related to the fact that conventional laser microfabrication relies
on linear absorption of light. Because materials have complex electronic band
structures, lasers that operate at different wavelengths are required for
different materials. This is completely unnecessary for femtosecond laser
microfabrication because by gradually increasing the peak intensity, the
electric field of a femtosecond laser can always be increased to a level that is
not negligible compared with the binding field experienced by electrons in
transparent materials. The materials are then forced to absorb photons via
nonlinear absorption processes. Thus, a variety of materials can be processed
using a single femtosecond laser system by tuning the peak intensity. The third
advantage is also a result of the ultrashort pulse duration, namely thermal
effects in femtosecond laser fabrication are significantly suppressed,
particularly when the peak intensity of the laser is controlled to be near the
threshold of multiphoton absorption and the repetition rate is sufficiently low
(e.g., a few kilohertz or a few tens of kilohertz). Effective suppression of the
heat-affected zone permits fine structures with micrometer- or nanometer-scale
features to be fabricated by femtosecond lasers. The fourth advantage is that
the physical and chemical properties of materials can be finely tuned or even
completely altered in a spatially selective manner using femtosecond laser
pulses. Mainly as a result of this unique characteristic, 3D femtosecond laser

direct writing can integrate multiple functions on a single substrate.
Figure 1 shows a typical layout of the 3D femtosecond laser direct writing
systems used in our experiments [11]. In most of our experiments, the laser
wavelength is ~800 nm, the pulse width is ~150 fs, and the repetition rate is 1
kHz, although sometimes we used a laser with a wavelength of 800 nm, a
pulse width of ~50 fs, and a repetition rate of 1 kHz. To ensure a high beam
quality, the original size of the output laser beam is usually reduced to 3 mm
using a circular aperture placed before the focusing system. Microscope
objectives with numerical apertures (NA) in the range 0.20.8 are selected for
experiments requiring different fabrication resolutions and working distances,
and we typically use a long-working-distance, 20 objective lens with an NA
of 0.46, which can offer a spatial resolution of ~1 m and a working distance
of 1.8 mm. With this working distance, 3D microstructures can be fabricated
in a transparent sample at depths greater than 2 mm due to the refractive index
of the material being greater than unity. 3D microstructures are generally
formed by the direct writing technique by keeping the laser focal spot fixed
while translating the sample in 3D space using a precision XYZ stage. The
fabrication process is monitored using a charge coupled device (CCD) camera,
the output of which is displayed on a PC monitor.
Figure 1. Schematic of a typical system for 3D femtosecond laser direct writing.
In principle, 3D femtosecond laser direct writing can be performed inside

any material that is transparent to the incident beam [6]. However, to realize
multiple functions in a single substrate, most of our experiments were
performed with a photosensitive glass manufactured by Schott Corporation
and sold under the trade name Foturan [8,12]. The history of photosensitive
glass and its fabrication commenced half a century ago. Stooky at Corning
conducted the earliest work in developing this material in the 1950s [13]. The
photosensitive glass Foturan is lithium aluminosilicate doped with trace
amounts of silver and cerium. The cerium (Ce3+) ion functions as a
photosensitizer by absorbing a UV photon at a wavelength near 315 nm and
releasing an electron to become Ce4+. Some silver ions then capture some of
the free electrons and become silver atoms. In a subsequent heat treatment, the
silver atoms diffuse and agglomerate to form nanoclusters at about 500 C,
and then at about 600 C the crystalline phase of lithium metasilicate grows
around the silver clusters (which act as nuclei) in the amorphous glass matrix.
This crystalline phase of lithium metasilicate can be preferentially etched since
it has a much higher etching rate in dilute hydrofluoric acid than the glass
matrix. The conventional exposure procedure for 2D microfabrication on the
surface of Foturan glass is a UV lamp photography step. However, to fabricate
3D hollow microstructures in Foturan, it is necessary to focus the laser beam
into the sample. Since UV exposure is essentially a single-photon process, the
UV beam undergoes linear absorption as it propagates from the glass surface,
making internal modification very difficult. In addition, single-photon
processes intrinsically have poor fabrication resolutions in the laser beam
propagation direction. In contrast, an exposure procedure employing a
femtosecond laser can confine the absorption region to an area near the focal
spot by using a multiphoton process, improving the axial resolution, which is
vital for achieving true 3D microprocessing [14,15]. Our early investigations
revealed the photoreaction initiated by multiphoton excitation has a different
mechanism from that of single-photon excitation, because the interaction of
the high-intensity femtosecond laser with the glass matrix of Foturan generates
a large amount of free electrons. Consequently, it is not necessary to dope
Foturan glass with cerium for multiphoton processing [16].
In addition, using Foturan glass permits both the chemical etching rate and
the optical properties to be controlled. The hollow structures formed inside
Foturan usually have rough surfaces, but they can be greatly smoothened for
optical components (e.g., micromirrors and microoptical lenses) by applying a
postannealing process [17,18]. Furthermore, since the silver nanoparticles
produced by femtosecond laser irradiation exhibit the plasmonic effect, they
can be used to tune both the absorption and refractive index of Foturan
[19,20]. Thus, Foturan glass is an ideal material for fabricating optofluidic
devices, which integrate microfluidics and microoptics in a common substrate
[21,22].
3. FEMTOSECOND LASER FABRICATION OF 3D

FUNCTIONAL COMPONENTS
3.1. Microfluidic Components and Controlling the Aspect Ratio
of Microchannels
Initially, our research was mainly focused on establishing a technique for
directly forming a variety of microfluidic components within glass [14,23,24].
The fabrication process consists of three main steps: (1) 3D direct writing of
latent images in the sample using a femtosecond laser beam tightly focused by
an objective lens, (2) baking the sample in a programmable furnace for the
formation of modified regions, and (3) etching the sample in a 10% aqueous
solution of hydrofluoric (HF) acid in an ultrasonic bath to selectively remove
the modified regions. Figure 2(a) shows X-shaped microfluidic channels
formed at a depth of 300 m below the sample surface with a channel length
of ~2800 m and a width of ~45 m. The channels appear to be uniform,
which is probably a result of using a relatively high concentration of HF acid
(10% in our case compared with 5% HF for UV exposure by H. Helvajian et
al. [8]) and a high-intensity ultrasonic bath. We find that using an ultrasonic
bath is critical for fabricating uniform structures by chemical etching because
it greatly enhances the supply of fresh HF acid and reactant in the narrow
channels and tiny chambers during etching. Moreover, a chemical
microreactor was fabricated by forming microchannels and microchambers
with true 3D configurations inside Foturan glass, as shown in Figure 3 [23]. It
is noteworthy that all these structures are directly formed in a glass coupon
without using any multistep procedures such as stacking and bonding, greatly
reducing the cost by enabling high-throughput manufacturing.
A frequent problem in 3D laser microprocessing is that the vertical
resolution (i.e., parallel to the laser beam) is always inferior to the lateral
resolution due to the focal spot being elongated in the propagation direction of
the laser beam (i.e., the axial direction). Consequently, the cross-sections of
fabricated microfluidic channels have high aspect ratios (i.e., the height to
width ratio). The cross-section of the Y-branched microfluidic channel in
Figure 4 has an aspect ratio of ~4.2 [14]. To overcome this problem, we
inserted a narrow slit above the objective lens to tailor the focal spot shape, as
illustrated in Figure 5(a). The slit functions as a diffraction aperture and allows
the shape of the focal spot and hence the aspect ratio of fabricated channels to
be controlled [17]. This is because that the slits causes the laser beam to be
loosely focused in the direction perpendicular to the slit, which laterally

expands the focal spot; meanwhile, the laser beam will still be tightly focused
in the direction parallel to the slit to ensure a high axial resolution. Figure 5(c)
shows the cross-section of a microfluidic channel fabricated with a
combination of an objective lens with an NA of 0.46 and a 500 m (width)
3000 m (length) slit; it shows that the slit reduces the aspect ratio of the
cross-section from ~3 to ~1.6. This technique is now also widely used for
writing optical waveguides in glasses [2527]. Using an objective lens with an
NA of 0.8 and a slit with dimensions 200 m (width) 3000 m (length)
produced waveguides with a completely circular cross-sections (diameter: ~9
m) that can be used as single-mode waveguides [28].
Figure 2. A large-scale crossed-channel buried in Foturan glass.
Figure 3. A chemical microreactor with a vertical configuration.
Figure 4. (a) A horizontal Y-branched microchannel structure embedded 300 m

below the sample surface. (b) Cross-section of the microchannel. The cutting point is
indicated in Figure 4(a).
10
Figure 5. (a) Close-up view of a focusing system with a slit for controlling the
microfluidic channel aspect ratio. (b) Side view and cross-section of a bridge-like
microstructure fabricated without a slit. (c) Side view and cross-section of the same
structure fabricated with a 0.5-mm-wide slit.
11
Although using a slit to shape the beam can achieve symmetrical crosssections when fabricating microfluidic channels, it is not the only solution to
the problem. In fact, after being shaped by the narrow slit, the focal spot will
not be truly spherical in 3D space, but instead it be compressed in the direction
parallel to the slit. Compression of the focal spot in the direction parallel to the
slit should not be a problem when fabricating 1D microstructures, such as
microfluidic channels or optical waveguides, because it can be compensated
by reducing the laser scanning speed in the sample; however, an anisotropic
focal spot is undesirable in many applications (e.g., 3D data storage in glass
using femtosecond laser generated microvoids). In such cases, a threedimensionally isotropic focal spot is preferable. This can be achieved by using
a novel focusing geometry in which two focused femtosecond laser beams are
perpendicular to each other [29].
Figure 6(a) shows a schematic view of the crossed-beam irradiation
system; the combined optical fields of the two beams results in an isotropic
energy distribution in the central region of the focal spot (the area enclosed by
the dashed red circle in Figure 6(b)). To ensure an isotropic illumination
volume, the foci of the two beams in the crossed-beam system must
spatiotemporally overlap throughout the entire period of laser scanning. This is
impossible to fulfill if we scan the glass in air due to the mismatch in the
refractive indices of Foturan glass (n~1.52) and air (n~1). To overcome this
problem, we designed a special XYZ stage which translates the glass sample
in a refractive index matching liquid, as shown in Figure 6(a). The liquid is a
mixture of -bromnaphtalene (n~1.66) and paraffin (n~1.48); thus, an
identical refractive index to that of Foturan glass can be achieved by mixing
the two liquids in the appropriate ratio. Since translating the glass sample in a
fixed glass cell containing the refractive index matching liquid will not alter
the optical paths of the two orthogonal beams, two foci that are initially
aligned will continue to spatiotemporally overlap each other over the entire
scanning step. Before we started to scan the sample, the two objective lenses
were aligned by observing femtosecond-laser-induced fluorescence in the
glass sample. That is, when two high-intensity femtosecond laser beams were
simultaneously sent into the two objective lenses with a crossed-beam
focusing system, two lines of fluorescence were simultaneously observed on
the PC monitor connected to a CCD camera. The CCD camera was installed
with its optical axis perpendicular to the plane defined by the two crossed
beams. We carefully adjusted the positions of the objective lenses using a
computer-controlled translation stage to make the centers of the two
fluorescence lines spatially overlap. We then adjusted the time delay between
12
the two beams by varying the optical path length using another translation
stage until the fluorescence in the overlapping region of the two fluorescence
lines was maximized. When this alignment procedure was completed, the
crossed-beam irradiation system was able to create microstructures inside
glass with isotropic 3D resolution.
Figure 6. (a) Schematic view of crossed-beam irradiation system. (b) The energy
distribution in the focal spot synthesized by the two perpendicular beams.
13
To demonstrate the effectiveness of the crossed-beam irradiation

geometry, we fabricated several microfluidic channels by both single-beam
and crossed-beam irradiation methods, and scanned the samples in different
directions. Figures 7(a) and (b) clearly show that with single-beam irradiation,
the fabricated channel has an elliptical cross-section. In contrast, when the
crossed-beam irradiation method was adopted, the cross-sections of the
fabricated microchannels were circular regardless of the scanning direction
(see Figures 7(c)(f)). The circular cross-section generated at arbitrary
scanning directions is clear evidence that a nearly spherical focal spot was
generated inside the Foturan glass sample. We believe that this will be very
useful in a broad range of applications, including 3D data storage and photonic
crystal fabrication by two-photon polymerization [30].
Figure 7. Optical micrographs of the cross-sectional shapes of the microfluidic hollow

channels fabricated by (a) single-beam irradiation, (b) crossed-beam irradiation with
the laser scanning direction perpendicular to the plane defined by the two beams, and
(c) crossed-beam irradiation with the laser scanning direction along the axis of one of
the two crossed beams. The scanning geometries for fabricating the structures in
(a)(c) are presented in (d)(f), respectively.
14
3.2. Micromechanics
Micromechanical structures such as micropumps and active microvalves
are important elements for realizing microfluidic routing and switching in
LOC applications [14,31,32]. The 3D femtosecond laser direct writing
technique allows direct fabrication of mechanical elements encapsulated in a
microfluidic cavity. As an example, we first demonstrated the fabrication of a
freely movable microplate in a microfluidic chamber that serves as a
microvalve (see Figure 8) [14].
Figure 8 shows the exposure scheme in Foturan glass used to fabricate the
freely movable microplate. After scanning the femtosecond laser beam at a
velocity of 2 mm/s and a laser fluence of 170 mJ/cm2 in the dark regions in
Figure 8(a), the above-mentioned postannealing was performed to form
modified regions of lithium metasilicate crystallites. To obtain a high spatial
resolution, the irradiation conditions were set slightly above the threshold
fluence above which the photosensitive glass was modified but below which it
was not modified at all [14]. The modified regions were completely removed
in the subsequent chemical wet etching so that hollow structures (indicated by
the white regions in Figure 8(b)) were formed in the glass. A movable glass
plate was left in the hollow structure, which can serve as a microfluidic
chamber. The fabricated movable microplate can function as a microvalve in
the microfluidic network, as illustrated in Figure 9. This device was
manufactured by stacking three Foturan glass substrates, each with a thickness
of 2 mm (the thickest substrate available). A syringe was used as an air
compressor to drive the microplate motion. The top layer contains three inlet
cells; the center cell is an opening for adding the reagents while the left and
right cells are openings attached to silicon tubes for infusing compressed air
from the syringes. In the middle layer, a movable microplate was embedded in
a rectangular hollow chamber connected to five microchannels to the cells in
the top and bottom plates. The microplate was fabricated by the exposure
scheme shown in Figure 8. In the bottom layer, two cells were installed in the
glass as outlets for the reagents. Each structure was fabricated by the same
procedure using the femtosecond laser. The microplate was driven to the right
when compressed air was infused from the left opening in the top layer. In this
case, the flow channel of the reagents to the right outlet was switched off so
that the reagents could flow only to the left outlet (Figure 9(a)). When the
compressed air infusion was changed to the right opening, the microplate was
driven to the left. As a result, the reagent flow was switched to the right outlet
15
(Figure 9(b)). Thus, this microplate can switch the flow direction of the
reagent like a microvalve.
Figure 8. Schematic illustration of the femtosecond laser exposure for fabricating a

freely movable microplate embedded in glass. (a) The dark regions are scanned by the
focused femtosecond laser beam. (b) The dark regions are completely removed after
postannealing and subsequent chemical etching in an HF solution. The movable glass
plate is left in the hollow chamber buried in the glass (the white regions).
Figure 9. Schematic illustration of the microplate functioning as a microvalve in a

microreactor.
16
Figure 10 shows two photographs of the fabricated sample. It is clear that

the microplate moves from one side to another when the infusion direction of
the compressed air is switched. We confirmed that the microvalve can switch
the flow direction of microfluids by injecting a liquid into the microdevice.
More recently, a freely movable micromechanical needle was integrated into a
microfluidic biochip to elucidate the information transmission process in
Pleurosira laevis [32].
Figure 10. Photographs of a fabricated microreactor in which a freely movable

microplate is embedded. (a) When compressed air was infused from the left opening in
the top layer, the microplate moved to the right side. (b) When the infusion of the
compressed air was changed to the right opening, the microplate moved to the left side.
3.3. Microoptics
Since chemical and biological analyses frequently employ optical
detection methods, integration of microoptics into LOC chips has advantages
such as low cost, robustness, stability, and ease of operation [33]. The
microstructuring of Foturan glass by a femtosecond laser is essentially nonablative processing that results in smooth and debris-free internal surfaces;
thus, both 3D microfluidic components and 3D microoptics can be
simultaneously fabricated inside the glass. For example, Figure 11(a) shows a
45 micromirror embedded in Foturan glass [17]. To fabricate this structure,
we scanned parallel lines layer by layer from the top surface to the bottom of
the sample. The interval between two adjacent lines in the Foturan glass was
set at ~15 m. Thus, since the total sample thickness was 2000 m, we
17
scanned 140 parallel lines to form a plane structure vertically embedded in

glass. The laser pulse energy was 700 nJ and the scanning speed was 500
m/s. After laser irradiation, the sample was subjected to heat treatment and
then to chemical etching. In this case, chemical etching was performed for
about ~1 h. Finally, we rinsed the sample in distilled water and dried it with
nitrogen gas flow.
To examine the optical properties of the micromirror, we polished the four
sidewalls of the glass sample. We then examined the beam spot produced by
reflecting a heliumneon (HeNe) laser beam from the etched internal surface.
An incident angle of 45 resulted in total reflection. The two arrows in Figure
11(a) indicate the optical path. A receiving screen was placed 10 mm from the
end of the Foturan glass. The arrow head in Figure 11(b) indicates the
reflected beam spot on this screen. The beam spot was significantly larger than
the incident laser beam, indicating that the reflected beam is highly divergent.
Since the lithium metasilicate crystallites developed by postannealing must
grow to a certain size (a few microns) to form an etchable network, etching of
the crystallites naturally leaves a rough surface. This high roughness causes
strong scattering and consequently the reflected light beam is highly divergent
and has a high loss. Therefore, it is essential to reduce the surface roughness
for microoptical applications.
18
Figure 11. (a) Top view of the 3D micromirror fabricated inside Foturan glass with its
optical path indicated by arrows. Beam spots reflected from the sample (b) before and
(c) after the additional annealing.
We overcame this problem by including an additional annealing process.

After chemical etching, we baked the Foturan glass sample again. The
19
temperature of this additional annealing was lower than that used to crystallize
lithium metasilicate. In this annealing process, the sample was heated to 570
C at 5 C/min, it was held at this temperature for 5 h, and then cooled to 370
C at 1 C/min. After the sample cooled to room temperature, we reexamined
its optical properties. The results are shown in Figure 11(c). The reflected
beam spot is clearly much smaller than that from the sample that was not
subjected to the additional annealing, which demonstrates that the divergence
of reflected beam has been reduced. Figures 12(a) and (b) show the
morphologies of etched surfaces that had not and had been subjected to the
additional annealing, respectively. Figure 12(b) reveals that after the additional
annealing, the smoothness of surface is comparable to that of a polished glass
surface (although there are still a few irregular nanodots on the surface). The
average surface roughness before the additional annealing was measured to be
~81 nm, whereas after the annealing it was only ~0.8 nm. Consequently, both
the divergence angle and the optical loss of the reflected beam can be reduced.
In addition to microoptical structures with plane surfaces, microlenses
with curved surfaces can be produced using this technique [18]. Microlenses
are important elements for optical biosensors, and they are used as collimators,
focusers, and imaging elements [34]. Figures 13(a) and (b) show respectively a
microoptical cylindrical lens and a hemispherical lens fabricated on Foturan
glass by 3D femtosecond laser direct writing; the focal spots produced by
these lenses are shown on the right. These microlenses were fabricated by
gouging them out from the Foturan matrix, but they can be also formed inside
the glass chip by the present technique for fabricating hollow microstructures
[35]. The fabricated hollow structures have openings at one or both ends in a
Foturan glass chip and one of the internal sidewalls of the hollow structure is
spherical in shape, (i.e., it has a plano-concave hollow structure), as shown in
Figure 14. The curvature of the spherical surface corresponds exactly to the
designed optical microlens curvature so that the curved surface can function as
a plano-convex lens. Thus, a microoptical lens can be fabricated inside a glass
chip. Figure 14 also shows optical microscope images of a plano-convex
microlens fabricated inside a glass chip with a thickness of 2 mm, a radius of
curvature R of 0.75 mm (designed value), and a focal length of 1.5 mm
(calculated using the formula: 1/f = (n1)(1/R), n=1.5 (refractive index of
photosensitive glass)). The figure shows that one of the sidewalls of the buried
hollow structure is spherical in shape with a smooth surface, although a small
bump is visible on the lens surface. To examine the focusing performance of
the microlens, we irradiated a HeNe laser beam such that it passed through
the microlens inside the glass, and the focused laser beam was projected onto a
20
CCD camera by a 20 objective lens with an NA of 0.35. The focal spot size
was approximately 30 m in diameter for an incident HeNe laser beam of
1.51.8 mm. Furthermore, we roughly estimated the focal length
experimentally and found that it was about 1.7 mm. This focal length is
slightly longer than the designed value of 1.5 mm. Reflection at the airglass
interface is probably responsible for the longer focal length; in other words,
the laser beam is reflected by the flat internal wall of the hollow structure after
the lens. Another cause for the longer focal length may be somewhat imperfect
fabrication precision. The efficiency of the fabricated microlens was evaluated
to be more than 80%. The optical loss is considered to be mainly due to four
Fresnel reflections at the airglass interfaces (two glass chip sidewalls and two
lens surfaces). Subtracting the loss of the four Fresnel reflections (4% for
each), the net loss is estimated to be ~6%. However, the focusing results and
the efficiency evaluation indicate that the smooth spherical surface of the
buried hollow structure is suitable for optical applications.
By using 3D femtosecond laser direct writing, microoptical and photonic
components have now been fabricated in various transparent materials by
modifying their refractive indices [6,20,36]. Changes in the refractive index
can be induced in Foturan glass by femtosecond laser irradiation followed by
annealing at 520 C [20]. This results in silver nanoparticles being selectively
precipitated in the irradiated region, which changes the refractive index by as
much as ~0.4%. Since the process involves only a photochemical reaction, the
pulse energy for such processing was as low as 70 nJ/pulse for an objective
lens with an NA of 0.8. Such a low pulse energy induced little thermal effects,
resulting in a high spatial resolution. Figure 15 shows a 5-m-pitch
micrograting together with its diffraction pattern obtained using a HeNe laser
beam. Using the same principle, optical waveguides can be fabricated inside
Foturan glass; guided beams in these waveguides have a single-mode profile
because the beam was shaped using a slit during waveguide writing [28]. Very
recently, a volume optical grating has been formed inside Foturan glass by
focusing a femtosecond laser beam using a pair of cylindrical lenses [37].
Each cylindrical lens focuses the beam in one dimension, so that each
femtosecond laser beam pulse forms a vertical plane at the focus. This enables
the volume grating to be fabricated by simply translating the sample
perpendicular to the cylindrical lens at a constant speed while the laser beam is
periodically switched on and off using a programmable shutter. This technique
significantly reduces the time required to fabricate a volume grating because
21
there is no need to scan the laser beam along the direction parallel to the
cylindrical lens.
Figure 12. AFM images of the surface of Foturan glass after the irradiation by the
femtosecond laser beam and chemical etching (a) before and (b) after the additional
annealing.
22
Figure 13. SEM images of microoptical (a) cylindrical and (b) hemispherical lenses.
The focal spots produced both lenses are presented in the right panel.
23
Figure 14. Schematic illustration and optical microscope images of a plano-convex

microlens buried in Foturan glass.
Figure 15. A 5-m-pitch microoptical grating (upper) embedded in Foturan glass and
its diffraction pattern (lower).
24
Even femtosecond laser direct writing without postannealing can increase

the refractive index in Foturan glass [38,39]. This process is based on
photophysical and/or photothermal reactions such as compaction and direct
bond breaking, so it requires much higher pulse energies (12 J/pulse) are
required than femtosecond laser direct writing in Foturan followed by
annealing. However, optical waveguides written by this process have higher
transmission efficiencies, especially in the visible region, since silver
nanoparticles are not precipitated. The propagation loss at 632.8 nm was
evaluated by fabricating three waveguides of different lengths under the same
conditions in coupons cut out from the same substrate. Figure 16 shows the
optical loss as a function of waveguide length for three different scanning
speeds. The data were fit with linear equations; the slope of the linear fit
represents the propagation loss in decibels per centimeter and the y-axis
intercept gives the coupling loss from both facets of the waveguide. The
coupling loss is clearly caused by a size mismatch or misalignment between
the waveguide and the focused HeNe laser beam. However, the values
obtained under the different conditions in this experiment are quite similar to
each other, being in the range 1.5 to 1.6 dB. The propagation loss is around 0.5
dB/cm for all samples under the conditions investigated. This propagation loss
is within acceptable limits for biophotonic microchip applications.
Since the physical properties of the photosensitive glass in unirradiated
regions did not change markedly even after multiple thermal treatments, we
were able to write optical waveguides inside the glass by femtosecond-laserinduced refractive index modification after fabricating 3D hollow structures.
Thus, 3D integration of waveguides with microoptics, such as micromirrors
and microlenses with hollow structures, can be realized in a single glass chip.
Figure 17 shows an optical microscope image of a microoptical circuit in
which two waveguides were integrated by a micromirror and a microlens in a
single glass chip. In the fabricated structures, a 5-mm-long waveguide
(waveguide I) is connected to a micromirror at an angle of 45 and it is also
connected to a 4-mm-long waveguide (waveguide II) at an angle of 90. The
writing of waveguide II was terminated 2 mm before the plano-convex
microlens so as to obtain a focused beam output. In order to characterize the
3D integrated microoptical device, we coupled a HeNe laser beam into
waveguide I and placed a 20 objective lens outside the glass chip to capture
images of the focused beam spot (indicated by the red arrow in Figure 17)
using a CCD camera. In this manner, the near-field focal spot profile was
observed. As seen in Figure 17, the output spot size (dark blue spot) was about
7 m in diameter. Thus, the combination of a microlens with a waveguide is
25
highly effective for laser beam transmission. As mentioned above, the

propagation loss of the optical waveguide was 0.5 dB/cm and the net loss of
the microlens was ~6%. In addition, the bending loss at the micromirror was
evaluated to be less than 0.3 dB at a wavelength of 632.8 nm [38]. One of the
biggest advantages of this structure is that it can bend a light beam in a small
area with a small bending loss. From a practical point of view, a light beam
guided by a waveguide often needs to be bent when it is integrated into optical
and microfluidic devices. A curved waveguide is commonly used to bend a
beam, but its bending loss is significant and cannot be disregarded. To
minimize the bending loss, the curvature of a curved waveguide should be
greater than several millimeters (e.g., 56 mm), but this causes an undesirable
increase in the device size. Thus, 3D integration of waveguides with a
microlens and a micromirror should enable efficient transmission of a light
beam in biophotonic microchip devices.
Figure 16. Dependence of optical loss on the length of waveguides written at different
laser energies and scanning speeds. Linear fit equations give the propagation loss in
dB/cm (slope) and the coupling loss in dB (y-axis intercept).
26
Figure 17. Optical microscope image and characterization of 3D integration of two

waveguides with a micromirror and an optical plano-convex microlens in a single glass
chip. Solid gray lines indicate the invisible waveguides in the glass.
3.4. Microelectronics
Fabrication of microelectronic components by femtosecond laser direct
writing is certainly desirable for developing monolithic and compact LOC
systems [4045]. Selective metallization of the surfaces of some glass
materials (e.g., Foturan and microscope slide glass) has been achieved by
direct femtosecond laser ablation followed by electroless copper plating, but
this technique cannot be applied to other glass materials such as fused silica
[40]. The process requires a certain degree of surface roughness for the socalled anchor effect to operate, which enables the deposited metal film to
adhesion strongly to the glass surface. Figure 18 shows optical microscope
images of fine metal lines deposited on a Foturan surface after electroless
plating. The laser power was varied from 1.2 to 3 mW and the laser scanning
speed was 50 m/s. As an application of this selective metallization technique,
Figure 19 shows a microheater that was fabricated on a Foturan glass chip.
The microheater temperature is a linear function of the electric power applied
to it [40].
27
Figure 18. Optical microscope images of (a) as ablated and (b) copper-plated glass
after ablation. The laser power is varied from 1.2 to 3 mW. The laser scanning speed is
50 m/s.
With the purpose of realizing selective metallization on surfaces of

dielectric materials other than Foturan and microscope slide glass, a modified
femtosecond laser direct writing was developed [4245]. As illustrated in
Figure 20, the fabrication process consists of four main steps: (1) formation of
silver nitrate thin films on insulator substrates by dip coating, (2) selective
modification of insulator surfaces by femtosecond laser direct writing, (3)
removal of unirradiated silver nitrate film by acetone, and (4) selective copper
coating by electroless plating.
28
Figure 19. (a) Schematic diagram of a microheater; (b) microscope image of the
microheater; (c) enlarged image of the left-hand end of the microheater; (d)
experimental setup for measuring the temperature of the microheater.
Figure 20. Schematic illustration of the fabrication process for the selective
metallization of insulators: (1) formation of silver nitrate thin films on insulator
substrates; (2) modification of insulator surfaces by femtosecond laser direct writing;
(3) removal of unirradiated silver nitrate films by acetone; (4) copper coating by
selective electroless plating.
29
In our experiment, a 3-mm-thick lithium niobate (LiNbO3) crystal was

used as the insulator substrate because of its potential application to electrooptic integration [42]. Figures 21(a) and (b) show top and end view images of
electrodes embedded in a crystal, respectively. Two 10-m-wide grooves with
a 16 m center-to-center interval between them were ablated using a tightly
focused femtosecond laser beam with an average power of 10 mW and a
scanning speed of 200 m/s. The micrograph of the V-shaped cross-section of
the electrodes shown in Figure 21(b) reveals that the two ~10-m-deep
grooves have been filled with deposited copper after electroless plating for 120
min. Since optical waveguides can also be directly written inside a LiNbO3
crystal using femtosecond laser pulses [46], the embedded microelectrodes can
thus be easily integrated with the buried optical waveguides, opening up the
potential to fabricate 3D micro-electro-optical devices such as optical switches
and optical modulators.
Figure 21. Optical micrographs of microelectrodes embedded in a LiNbO3 crystal: (a)

top view and (b) end view.
30
Although selective metallization of insulators using nanosecond lasers has

been reported [47,48], the use of femtosecond lasers has several critical
advantages. One advantage is that, as Figure 21(b) clearly shows, the
microelectrodes are embedded deep within the insulator, which is a desirable
characteristic for many novel microdevices requiring 3D configurations.
Another advantage is that when the femtosecond laser intensity is well
controlled near the ablation threshold, selective metallization of glass can be
realized with a nanometer-scale spatial resolution, as demonstrated by the fact
that tiny nanostructures (i.e., nanometer-sized holes and grooves) have been
reliably produced in dielectrics using a femtosecond laser [49]. A further
advantage of this technique is that it offers the ability to directly incorporate
microelectrical elements into microoptical and/or microfluidic circuits in a
single glass chip. Future development of this technique holds great promise for
rapid, flexible, and cost-effective fabrication of monolithic 3D micro-electroopto-fluidic devices.
4. MONOLITHIC INTEGRATION OF MICROFLUIDICS,

PHOTONICS, AND ELECTRONICS
4.1. Microfluidic Dye Laser
With the establishment of the above-mentioned capabilities, microoptics
and microfluidics can be readily integrated into a single glass chip by 3D
femtosecond laser direct writing for fabricating hybrid devices. In particular,
we are interested in a microfluidic dye laser which is a useful light source for
optical analyses such as fluorescence detection or photoabsorption
spectroscopy in LOC systems [22]. Figure 22(a) shows a micrograph of the
top view of a fabricated microfluidic laser that has an optical microcavity
composed of four 45 micromirrors vertically buried in glass, a horizontal
microfluidic chamber embedded ~400 m beneath the glass surface, and a
microfluidic through channel that passes through the center of the
microchamber. Figure 22(b) shows a micrograph of the side view of a
fabricated microfluidic laser, showing the microchannel that has an average
diameter of ~80 m and the microchamber that is ~200 m thick. Figure 22(c)
depicts the optical path of the microfluidic laser. The optical cavity is
composed of a pair of corner mirrors, which are formed by two micromirrors
on the left-hand side and two micromirrors on the right-hand side. Light
31
bounces back and forth in the optical cavity by total internal reflection. Lasing
can occur if the microchamber is filled with a gain medium laser dye
rhodamine 6G (Rh6G) and then pumped by a frequency-doubled Nd:yttrium
aluminum garnet (Nd:YAG) laser. Since the surfaces of the micromirrors
could not be fabricated perfectly smooth, and also the angle between any two
micromirrors could not be exactly 90 due to the limited fabrication precision,
a small amount of light will eventually leak out of the optical cavity and be
emitted tangentially from the internal surfaces of the micromirrors. Light
emission from the side of the cavity has been frequently observed in many
experiments with microcavity lasers [50,51].
Figure 22. (a) Optical micrographs of the top-view of the microfluidic laser and (b) of
the side view of the microfluidic chamber and through channel. (c) The light path in
the microfluidic laser.
We carried out lasing experiments to demonstrate the function of the

microfluidic laser. A syringe needle was used to fill the microfluidic chamber
with laser dye Rh6G dissolved in ethanol (~0.02 mol/L). The microfluidic
laser was then attached to an optical alignment stage and pumped by a pulsed,
frequency-doubled Nd:YAG laser with a pulse duration of 5 ns and a
32
repetition rate of 15 Hz. When the pumping power was increased above the
lasing threshold, light emission could be clearly observed from the output end
of the dye microlaser, as shown in Figure 23(a). We then placed a receiving
screen approximately 8 mm from the output end of the structure to take a
photograph of the far-field pattern of the emission, as shown in Figure 23(b).
Two laser beams emitted tangentially from the internal surfaces of the two 45
mirrors were simultaneously observed on the screen, with one propagating
upward and the other downward. The laser beams were well confined in the
direction perpendicular to the plane of the optical cavity.
Figure 23. Digital camera images of (a) laser emission from glass sample and (b) farfield pattern of the laser beam on a receiving screen.
We measured the emission spectra of the microfluidic laser at different

pumping energies. The detector head of the spectrometer (USB2000, Ocean
Optics, Inc.) was placed near the output end of the microfluidic laser to collect
the light from the beam that propagated downward. After measuring each
spectrum, a power meter (Lasermate, Coherent, Inc.) was used to measure the
average power of the pumping laser. When a low pumping pulse fluence of
0.46 mJ/cm2 was applied, only spontaneous emission with a broad spectrum
was observed. Lasing commenced near a pumping fluence of 1.66 mJ/cm2.
Further increasing the pumping fluence greatly increased the output power of
the microfluidic laser and narrowed its bandwidth. A typical emission
spectrum of the microfluidic laser with a center wavelength of ~578 nm under
a high pumping energy of 4.49 mJ/cm2 was obtained with a bandwidth of
approximately 5 nm. The output power of the microfluidic laser was evaluated
at this pumping energy; the measured average power of one beam reached ~10
33
W at a repetition rate of 15 Hz. Thus, a conservative estimate of the total

pulse energy of both beams emitted from the microfluidic laser is
approximately 1 J.
Using the same technique, a dual-wavelength microfluidic dye laser was
fabricated in Foturan in which two microfluidic chambers were embedded at
different depths in the glass [52]. By designing two microfluidic chambers
serially stacked in the glass, we built a dual-wavelength microfluidic laser that
produces two laser emissions with different wavelengths using a single
pumping laser. Figures 24(a) and (b) show that the fabricated microfluidic
laser has two horizontal microchambers, which share a common optical ring
cavity. The dual-wavelength laser spectrum is presented in Figure 25; one
peak is centered at ~568 nm and the other at ~618 nm, corresponding
respectively to the stimulated emissions of Rh6G and Rh640 dyes used in this
experiment. A different approach for achieving multiwavelength output from
microfluidic dyes is to produce a mixed gain medium by dissolving several
different kinds of laser dyes into the solution; a dual-wavelength dye laser
produced in this manner has been reported by Q. Kou et al. [53].
Figure 24. Optical micrographs of (a) top view of the dual-wavelength microfluidic
laser and of (b) the side view of the two microfluidic chambers serially embedded in
glass with a center-to-center distance of ~1000 mm.
34
Figure 25. The spectrum of the dual-wavelength microfluidic laser. The peaks centered
at 532, 568, and 618 nm correspond to scattered light from the pump laser, the Rh6G
dye laser, and the rhodamine 640 dye laser, respectively.
4.2. Optofluidic Integration

In fact, the above-mentioned microfluidic dye laser is just one example of
the general concept of optofluidic integration [54,55]. Toward this end, optical
waveguides have been buried in Foturan glass by modifying its refractive
index using femtosecond laser pulses, as described in Section 3.3 [38,39].
Additionally, optical waveguides and other microoptics such as microlenses
and microfluidics can be easily integrated in a single glass chip by a single
ultrafast laser system for manufacturing microchips for biochemical analysis
and medical inspection. Such integrated microchips are often called
optofluidics. Figure 26 shows a schematic illustration of a 3D integrated
optofluidic system for photonic biosensing, in which one 6-mm-long optical
waveguide is connected to a microfluidic chamber with dimensions of 1.0 mm
1.0 mm 1.0 mm, and two microlenses with a radius of curvature of 0.75
mm are separately arranged on the left side of the microchamber for
fluorescence measurements and on the opposite side from the optical
waveguide across the microchamber for absorption measurements with a
distance of 300 m. The inset shows an optical microscope image of the
fabricated microchip. Experimental demonstration of photonic biosensing
using the integrated microchip revealed that fluorescence analysis and
35
absorption measurement of liquid samples can be performed with efficiencies

enhanced by factors of 8 and 3, respectively [56].
(a)
(b)
Figure 26. Schematic configuration of optofluidics in which microoptics, such as
microoptical plano-convex lenses and an optical waveguide, are integrated with a
microfluidic chamber in a single glass chip. An optical microscope image of the top
view of the fabricated microchip is shown in the upper left corner.
36
In the above examples, the waveguides have to be written into the Foturan
glass after fabricating micromirrors and microlenses, because the refractive
index changes induced by femtosecond laser irradiation cannot withstand the
high temperature applied to the Foturan sample during postannealing. This
problem can easily be resolved by fabricating freestanding optical fibers rather
than buried optical waveguides [57].
A freestanding fiber was fabricated by scanning the area surrounding the
fiber in a glass chip and then baking and etching the glass sample as described
above. Figure 27(a) shows a structure composed of a freestanding fiber
integrated with a 45 micromirror at the entrance of the fiber in the glass. The
arrows in Figure 27(a) indicate the optical path of the coupling scheme. The
45 micromirror allows us to couple the light into the fiber from the side of the
sample. Figure 27(b) shows the optical micrograph of the micromirror and
entrance of the fiber. The inset of Figure 27(b) (upper right corner) shows the
cross-sectional shape of the fabricated fiber, which has approximate
dimensions of 100 m (width) 80 m (height). Light was coupled into the
fiber by focusing a HeNe laser beam on the micromirror using an objective
lens with an NA of 0.46, as shown in Figure 27(c). The guided light was
clearly observed at exit of the fiber. The total length of the fiber in Figure
27(c) is 8 mm, which is sufficiently long for many microchip applications.
Fabricating longer fibers is not technically challenging, but it requires longer
fabrication times. The measured loss for the freestanding fibers was
approximately 1.3 dB/cm.
The freestanding fibers were then incorporated into a microfluidic circuit
for on-chip biophotonic applications. Figure 28(a) illustrates a 3D schematic
view of the integrated structure, which is a biosensor composed of two series
of freestanding fibers intercepted by a microwell fabricated on a glass chip.
Figure 28(b) shows an optical micrograph of part of the fabricated
microstructure, showing the fibers and the microwell on the glass surface. To
demonstrate that the light exiting from the first fiber can be effectively coupled
into the second fiber, we focused the HeNe laser beam onto the entrance
facet of the first fiber using a 20 objective lens. As shown in Figure 28(c),
both scattering light at the microwell and the exiting light at the end of the
second fiber can clearly be observed. The coupling loss between the two fibers
intercepted by the microwell was approximately 1 dB. We ascribe such a low
coupling loss between the two fibers to two main factors: (1) the relatively
large diameter of the fiber permits light beams with large mode areas to
propagate in the fiber, thereby reducing the divergence angle of the exiting
37
light, and (2) the inner walls of the microchannel between the two fibers are
smooth and fabricated nearly perpendicular to the fibers, preventing the
wavefront for the beam exiting the first fiber and entering the second fiber
from tilting.
A freestanding fiber fabricated on a Foturan glass chip has many potential
applications besides functioning as a waveguiding element. For example, the
fiber could be fabricated inside a microfluidic channel and immersed in the
sample solution. By measuring the optical loss of the beam propagating in the
fiber, high-sensitivity photoabsorption measurements could be conducted.
Moreover, because of the large refractive index difference between the
freestanding fiber and the surrounding air, curved fibers can be fabricated with
tight bends without significant optical losses. Recently, it has been pointed out
that the curved freestanding fibers may find applications in astrophotonics
(e.g., 3D mode converters in giant telescopes) [58].
Figure 27. (a) 3D schematic drawing of a freestanding optical fiber integrated with a
micromirror fabricated on a glass chip. Red arrows indicate the optical path of the
coupling scheme. (b) Optical micrograph of the top view of the freestanding fiber and
the micromirror. The inset (upper right corner) shows the cross-section of the
fabricated fiber. (c) Digital-camera image of the side coupling of a HeNe laser beam
into the freestanding fiber through the micromirror.
38
Figure 28. (a) Schematic 3D diagram of two freestanding optical fibers intercepted by
a microwell fabricated on a glass chip. (b) Optical micrograph of the structure. (c)
Image of the guiding HeNe light through the entire structure. Scattering light at
microwell and the guided light at the exit facet of the second fiber are indicated by
arrows.
Besides integrating individual fluidic and optical components in a single

microchip, optofluidic chips can also be produced by employing microfluids
as tunable optical media. One example of this is a microfluidic waveguide uses
a liquid as the waveguide cores [5962]. Microfluidic waveguides can easily
be fabricated by filling a microfluidic channel formed on a glass surface by
femtosecond laser ablation with a liquid that has an adjustable refractive index
[59]. Figure 29(a) shows a digital camera image of a 90 arc-shaped
microchannel with a radius of curvature of 5 mm fabricated on a glass plate. A
cross-sectional view of the waveguide is shown in the inset; it shows a Vshaped channel with a width of ~7 m at the opening and a depth of ~10 m.
Figure 29(b) shows a top view of the microfluidic optical waveguide carrying
a HeNe laser beam. Figure 30 shows end views of microfluidic waveguides
carrying a HeNe laser beam. It can be seen that using the same microfluidic
channel, the waveguide can be switched between multimode (Figure 30(a))
and single-mode operation (Figure 30(b)). This was achieved by using a
mixture of two liquids (paraffin, n=1.474, and -bromnaphtalene, n=1.658)
with different refractive indices so that the refractive index can be
continuously tuned by varying the mixing ratio of the two liquids. In Figure
30(a), the refractive index of the liquid core was set to 1.658, which resulted in
a multimode waveguide. When the refractive index was reduced to 1.527,
39
which led to the formation of a single-mode waveguide as shown in Figure

30(b). Figure 30(c) shows that the single-mode beam has a diameter of ~5 m.
Figure 29. (a) Digital camera captured image of a 90 arc-shaped microchannel with a
radius of curvature of 5 mm fabricated on a glass plate. Inset: cross-sectional view of
the waveguide. (b) CCD camera image of the microfluidic optical waveguide carrying
a HeNe laser beam.
40
Figure 30. Near-field patterns of (a) multimode and (b) single-mode beams. (c) Beam
profile of the single-mode beam.
4.3. Electro-Optic Integration

Although optofluidic integration by femtosecond laser direct writing is
currently under intense investigation [6365], electro-optic (EO) integration
41
by the same approach has not been widely demonstrated to date. EO

integration in transparent materials can be achieved by combining selective
metallization and waveguide writing by focused femtosecond laser beam
irradiation [45]. An excellent material for demonstrating EO integration is a
lithium niobate (LiNbO3) crystal, which is one of the most widely used
nonlinear optical materials in integrated optics. Figure 31 shows a schematic
diagram of a MachZehnder interferometer (MZI) EO modulator.
Commercially available MgO-doped x-cut LiNbO3 crystals were used in the
experiment. To produce thermally stable waveguides in the low repetition rate
regime, we wrote two parallel lines with a close separation, which produced a
guiding region between the two lines [66]. Unlike waveguides formed in the
focal volume, a waveguide between the two tracks of the laser modified areas
can preserve the nonlinearity of the bulk crystal [67]. Three embedded
electrodes were integrated into the LiNbO3 crystal, as illustrated in Figure 31.
In addition, three metallic pads and connecting lines, which allow the
modulator to be connected to an external electrical source, were fabricated
together with the microelectrodes by the same technique.
Figure 31. Schematic layout of the EO modulator.
The device was examined using a 633-nm HeNe laser polarized in the
extraordinary (Z) direction by applying a varying dc voltage to the electrodes,
and we simultaneously captured images of the near-field mode at the output
42
end of the MZI using a CCD camera. The results are shown in Figure 32. The
measured extinction ratio was ~9.2 dB. A higher extinction ratio is expected if
the two arms of the MZI can be fabricated more symmetrically by improving
the translation precision of the XYZ stage. The voltage required to completely
switch the modulator on and off was measured to be ~19 V, indicating an
excellent EO overlap integral of ~0.95 [68].
Figure 32. Near-field intensity distribution measured at the exit of EO modulator at dc

voltages of (a) 0 V and (b) 19 V.
The examples listed in this section demonstrate the potential of 3D

femtosecond laser direct writing to integrate several fundamentally different
functions in a single substrate. To our knowledge, there is currently no other
continuous processing technique that offers the same capability.
5. NANOAQUARIUM FOR DYNAMIC OBSERVATION

OF MICROORGANISMS
5.1. Concept of Nanoaquarium
One important application of microfluidic structures embedded in Foturan
glass fabricated by the present technique is the dynamic observation of
microorganisms. A large variety of microorganisms live on the earth. Some of
them move extremely rapidly, which is unusual in the macro-scale world in
which we live, and exhibit unique 3D movement that goes against gravity.
Most of them are single cells. It is very important to investigate their dynamic
movement and physiological energy generation mechanisms to gain a better
understanding of the potential ability and function of single cells that make up
more complex organisms such as humans. The results will also be useful for
43
developing biomotors. Consequently, observing microorganisms is currently

important for cell biologists.
Optical microscopes equipped with high-speed cameras are commonly
used by cell biologists to observe microorganisms [6972]. In conventional
observation systems, a glass slide with a coverslip or a Petri dish is generally
used. However, the high-NA objective lens typically used for these
observations limits the field of view to several hundred micrometers and it also
restricts the depth of focus to several hundred micrometers, making it difficult
to capture images of rapidly moving microorganisms. Consequently, it takes a
very long time to obtain clear images of moving microorganisms. Reduced
observation times are urgently needed by biologists not only in the interests of
cost and time effectiveness, but also because of limited computer memory,
which becomes problematic when acquiring movies using high-speed cameras.
To solve these problems, we propose using microchips with 3D microfluidic
structures for observing microorganisms [32]. The microchip reduces the size
of observation area; that is, it can three-dimensionally encapsulate
microorganisms in a limited area. But it still provides sufficient space for them
to move, making it much easier to capture images of their movement, as
shown in Figure 33. Using a microchip in which microfluidics are threedimensionally confined in glass has an additional advantage of enabling
microorganisms to remain highly active for a long time, since such a structure
prevents evaporation and leakage of water.
Figure 33. Concept of nanoaquarium for dynamic observation of microorganisms.
44
One advantage of our technique for fabricating 3D hollow microstructures

is that a wide variety of structures can easily be fabricated by the same
procedure, because of its ability to manufacture rapidly. The ability to rapidly
manufacture various microchips with different structures and functions is
needed by biologists to enable them to observe different kinds of
microorganisms [7376]. In addition, micromechanical components such as
microvalves can be integrated in the microfluidics, as described in Section 3.2.
Such functional microcomponents need to be integrated into microchips
for some kinds of microorganisms (e.g., to stimulate a cell using a
micromechanical component). Such functional microcomponents can be easily
integrated by our technique. We refer to such microchips for observing
microorganisms as nanoaquariums, because they are far smaller than
conventional aquariums (although the microchannel widths in the microchips
are of the order of several tens of microns). In addition, the volume of liquids
used in such microchips is of the order of a nanoliter.
5.2. Nanoaquarium for Observing the Motion of Euglena gracilis

Euglena gracilis is a single-celled organism that lives in fresh water. It has
a flagellum that emerges from the anterior end of the cell and it whips its
flagellum rapidly to swim in water. Many biologists have used microscopes to
investigate the continuous flagellum movement for both biomotor applications
and to determine the origins of this functionality. However, only the thrusting
movement of the flagellum has been investigated in previous research [77,78]
and its detailed mechanism still remains unknown due to difficulties in
capturing continuous high-speed images of the flagellum.
To enable clear and efficient observation of flagellum movement, we
fabricated a microchannel in photosensitive glass, as depicted schematically in
Figure 33. One Euglena gracilis is about 100 m long and 40 m wide and it
generally propels itself forward by whipping its flagellum around its body.
Therefore, we fabricated a microstructure with a 1-mm-long channel and with
a cross-section of 150 m 150 m embedded 150 m below the glass
surface. At both ends of the channel, two open reservoirs with dimensions of
500 m 500 m were connected to allow the introduction of Euglena
gracilis in water. The most important constraint in fabricating this microchip is
that the distance between the glass surface and the upper wall of the
microchannel needs to be between 130 and 170 m, as determined by the
working distance of the objective lens used for the observation. In this
45
experiment, this distance was designed to be 150 m. Furthermore, the etched

glass surface must be smooth and the upper wall of the channel must be flat
and parallel to the glass surface to obtain clear images. For observations, a
Euglena gracilis is introduced into one of the reservoirs using an injection
syringe filled with water. The microchannel is immediately filled with water
and the Euglena gracilis swims into the microchannel by itself since there is
no water flow in the microchannel. In the microchannel, the Euglena gracilis
is confined in a limited area enabling dynamic observations of the flagellum
movement to be performed easily using a microscope above the glass surface,
as shown in Figure 33.
For microchip fabrication, the laser beam was translated in the glass
sample line-by-line with a pitch of 5 m and layer-by-layer with a pitch of 10
m. After etching for 30 min in a 10% HF solution, additional heat treatment
was performed to smooth the etched surface. This smoothing process is
essential for obtaining clear images of Euglena gracilis in microscopic
observations. Figure 34(a) shows optical micrographs of the top view of the
microchip, and Figure 34(b) shows the side view of the microchannel when
cutting the microchip along the dashed line indicated in Figure 34(a). As
Figure 34(a) shows, a 1-mm-long microchannel with an almost constant width
of 150 m was fabricated. Figure 34(b) reveals that the microchannel has a
rectangular cross-section and is embedded 150 m below the glass surface,
which satisfies the requirements for observations. In addition, the top internal
wall of the microchannel is flat and smooth and is parallel to the glass surface.
Such an internal wall was fabricated by multiple scanning of the laser beam
with lateral shifts and additional annealing.
Figure 34. Optical microscope images of (a) the top view and (b) the side view of the
microchip used for observing the motion of Euglena gracilis.
46
Figure 35(a) shows an optical microscope image of Euglena gracilis

swimming in the embedded microchannel using the scheme shown in Figure
33. We also succeeded in recording movies, and Figure 35(b) shows enlarged
sequential images of an advancing Euglena gracilis obtained from a movie. It
shows that the Euglena gracilis coils its flagellum around its body and rotates
very rapidly to swim in a straight line.
Figure 35. Microscope images of (a) encapsulated Euglena gracilis swimming in the
microchannel and (b) sequential pictures of advancing Euglena gracilis.
Using this microchannel, we could stimulate the Euglena gracilis by

irradiating light from any direction, and by this means we could easily control
its motion. Figure 36(a) shows sequential pictures of a rotating Euglena
gracilis when white light was irradiated from the bottom of the microchip, as
shown in Figure 36(b). The Euglena gracilis turns its body to get away from
the light since it is very sensitive to strong light. Interestingly, the Euglena
gracilis thrust its flagellum forward to turn its body, unlike when it swims in a
straight line (see Figure 36(b)). Furthermore, it has been impossible to observe
Euglena gracilis from the front using conventional methods, although such
observations are highly desirable for biologists to enable more detailed
analysis of the flagellum movement. The microchip we developed enables
such observations using the scheme shown in Figure 37(a). Figure 37(b)
shows, for the first time, a front view of Euglena gracilis swimming upward in
the reservoir, which is a part of a movie.
Using the microchip, the observation time can be reduced by a factor of
more than 10 compared to the conventional method that uses a Petri dish. In
47
addition, water in the embedded channel does not evaporate or leak, unlike
when using a Petri dish, bonded glass, or polymer microchips. Consequently,
quantitative analysis of the flagellum movement could be easily carried out
using the fabricated microchip. We have also succeeded in fabricating some
other kinds of nanoaquariums with different structures and functionalities for
various applications, including determining the information transmission
process in Pleurosira laevis, observing the high-speed motion of
Cryptomonas, and attaching Phormidium to seedling roots to promote the
growth of Komatsuna.
Figure 36. (a) Sequential pictures of rotating Euglena gracilis stimulated by light and
(b) schematic illustration of the light stimulation of Euglena gracilis in the microchip.
48
Figure 37. (a) Schematic illustration of the scheme for observing Euglena gracilis from
the front and (b) microscopic image of the front view of Euglena gracilis swimming
upward in the reservoir.
6. CONCLUSIONS AND OUTLOOK

As we have demonstrated above, we are currently able to obtain functions
such as microfluidics, microoptics, photonics, micromechanics, and
microelectronics in various transparent materials by 3D femtosecond laser
direct writing. These functions can also be integrated into microchips to
construct hybrid microdevices. A few integrated microfluidic biochips have
been successfully used in biological research and they have important
advantages over conventional techniques. All these facts clearly indicate that
this technique has great potential to become an important tool for
manufacturing LOC devices.
Although the examples given above make it appear straightforward to
integrate functional components by 3D femtosecond laser direct writing, this is
often not the case. The major difficulties that we currently face are as follows:
1. Creation of embedded microfluidic channels and chambers inevitably
requires chemical wet etching, while a limited contrast ratio in etching
49
rates between modified and unmodified regions results in

inhomogeneity in the microstructures (they are usually wider at
openings and narrower in the middle). This problem becomes
particularly severe when the channels are long. Thus, the lengths of
most microfluidic structures produced by femtosecond laser direct
writing followed by chemical etching are limited to a few millimeters
or less, which is not sufficiently long for some LOC applications.
2. The optical properties of microoptical components are still relatively
poor compared to those of finely polished optical components
fabricated by conventional techniques. For example, although over a
small area (i.e., 20 m 20 m), the average roughness on an optical
surface created by femtosecond laser direct writing can be as low as
~0.8 nm, the surface is still slightly wavy over a larger scale (e.g., a
few hundred microns). As a result, a microlens fabricated by
femtosecond laser direct writing followed by chemical etching and
postannealing creates a significantly larger focal spot than the
diffraction-limited one. This aspect certainly needs to be improved.
3. The compatibility of the fabrication procedures for different
functional components requires further optimization, because it
determines the ability to integrate certain elements. For example, in
the fabrication of Foturan glass, postannealing after laser irradiation is
required to develop a chemically etchable phase in the glass matrix.
This will be unacceptable if it is desired to write an optical waveguide
in glass by inducing refractive index changes in glass while
simultaneously writing hollow structures. To overcome this problem,
a waveguide can be written after forming all the hollow structures, but
this solution means that fabrication is no longer a single continuous
process.
4. Because of the chemical etching procedure involved, the spatial
resolution of this technique is of the order of micrometers. This
urgently requires improvement. This is particularly important for
microdevices integrated with microoptics. As is well known, for
optical applications such as imaging or beam focusing, the positioning
precision of lens should be on the wavelength scale or even better. It
is very difficult to meet this requirement because of the uncertainty in
removing glass material in the chemical etching process. Fortunately,
optofluidic components are usually tunable so that this problem can
be overcome by exploiting tunability.
50
Although the above-mentioned difficulties exist, we are optimistic that

they can all be overcome by technical advances in the near future. At this
stage, only microdevices integrated with a small number of elements have
been successfully fabricated, such as the microfluidic laser, the nanoaquarium,
and the microoptical modulator. However, we have started to fabricate more
complex microdevices by femtosecond laser direct writing, which may
eventually replace expensive and bulky equipment such as optical
microscopes. The integration of microfluidics, microoptics, and
microelectronics in a single glass chip may lead to active devices for
applications in both biotechnology and information technology. Finally, we
believe that close collaboration between physicists and biologists will lead to
innovative devices that have never been previously fabricated being produced
by 3D femtosecond laser direct writing.
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ISBN 978-1-61668-570-6
Editor: I. A. Kuznetsov, pp. 55-101
2010 Nova Science Publishers, Inc.
Chapter 2
ELECTROKINETIC FLOWS OF NONNEWTONIAN FLUIDS IN

MICROFLUIDIC CHANNELS
Cunlu Zhao and Chun Yang*
School of Mechanical and Aerospace Engineering
Nanyang Technological University, Singapore 639798,
Republic of Singapore
ABSTRACT
Advanced microfluidic devices can perform complete biochemical
analysis in a single fabricated chip. The generic microfluidic systems
involve buffer solutions and samples manipulations such as pumping,
valving, mixing, injection, dispensing, concentration etc. Fundamental
understanding of the liquid flow characteristics in microchannels is thus
essential to optimum design and precise control of microfluidic devices.
In general, liquid motion can be generated by either applying a pressure
gradient or imposing an electric field, leading to pressure-driven flow or
electrokinetically-driven flow, respectively. Traditionally, in large-sized
channels flow is often driven by pressure that is usually generated by
mechanical pumps. In microchannels however it becomes increasingly
difficult to utilize pressure-driven flow mode as the channel size shrinks,
* To whom the correspondence should be addressed.
Tel: (+65) 6790-4883; Fax: (65) 6792-4062
E-mail: mcyang@ntu.edu.sg.
56

especially down to micro-and submicron range. Moreover, some parts
like microvalves and micropumps with moving components are difficult
to fabricate, and they are prone to mechanical failure due to fatigue and
fabrication defects. Alternatively, electrokinetic flow enjoys numerous
advantages (over pressure-driven flow), including ease of fabrication and
control, no need for moving parts, high reliability, no noise etc.
Specifically, a plug-like velocity profile in electrokinetic flow can result
in reduced dispersion of sample species, making capillary electrophoresis
become one of most successful technologies for chemical and biomedical
analyses. Most of existing studies regarding electrokinetics flows focus
on Newtonian fluids. However, microfluidic devices are usually used to
analyze biofluids which may not be treated as Newtonian fluids. Thus,
the more general Cauchy momentum equation, instead of the NavierStokes equation should be used to describe the flow characteristics of
non-Newtonian fluids.
This book chapter consists of two parts. In Part 1, electroosmotic
flow of power-law fluids in a slit channel is analyzed. The governing
equations including the linearized PoissonBoltzmann equation, the
Cauchy momentum equation and the continuity equation are solved to
seek analytical expressions for the shear stress, dynamic viscosity and
velocity distribution. Particularly, a counterpart for the classic
Smoluchowski velocity is introduced by taking into account contributions
due to the finite thickness of the electric double layer (EDL) and the flow
behavior index of power-law fluids. In Part 2, the pressure driven flow
of power-law fluids in microchannels subject to electrokinetic
effects is addressed. The Cauchy momentum equation together with
the power-law fluid constitutive equation is used to describe the
power-law fluid flow in a slit microchannel with consideration of a
body force resulting from the interaction of the charge density in the
electrical double layer of the channel and the flow-induced
electrokinetic potential. The velocity profile, volumetric flow rate,
apparent viscosity and friction coefficient are analytically evaluated,
and the influencing factors including ionic concentration, wall zeta
potential, flow behavior index and pressure difference are
investigated. It is found that the pseudoplastic fluids are more
susceptible to electrokinetic effects than the dilatant fluids, and thus
flow characteristics of the pseudoplastic fluids are found to deviate
drastically from those of Newtonian fluids.
Electrokinetic Flows of Non-Newtonian Fluids
57
1. ELECTROOSMOTIC FLOW OF POWER-LAW FLUIDS IN A

SLIT MICROCHANNEL
1.1. Introduction
Advanced microfluidic devices can perform complete biochemical
analysis in a single fabricated chip. The generic microfluidic systems involve
buffer fluid and sample manipulations such as pumping, valving, mixing,
injection, dispensing, etc [1-3]. Fundamental understanding of the liquid flow
characteristics in microchannels is thus essential to optimum design and
precise control of microfluidic devices.
In general, liquid motion can be generated by either applying a pressure
gradient or imposing an electric field, leading to respective pressure-driven
flow or electrokinetically-driven flow. Traditionally, in large-sized channels
flow is often driven by pressure that is usually generated by mechanical
pumps. In microchannels however it becomes increasingly difficult to utilize
pressure-driven flow mode as the channel size shrinks, especially down to
micro-and submicron range. Moreover, some parts like microvalves and
micropumps with moving components are difficult to fabricate, and they are
prone to mechanical failure due to fatigue and fabrication defects.
Alternatively, electroosmotic flow enjoys numerous advantages (over
pressure-driven flow), including ease of fabrication and control, no need for
moving parts, high reliability, no noise etc. Specifically, a plug-like velocity
profile in electroosmotic flow can result in reduced dispersion of sample
species, making capillary electrophoresis become one of most successful
technologies for chemical and biomedical analyses [4] .
Extensive studies of electroosmotic flow in microcapillaries have been
reported in the literature. Rice and Whitehead [5] analyzed electroosmotic
flow in a narrow cylindrical capillary within the framework of the Debye
Hckel approximation. Following the method proposed by Philip and
Wooding [6] for solving the nonlinear Poisson-Boltzmann equation , Levine et
al. [7]extended Rice and Whiteheads model to high zeta potentials for the
electrokinetic flow in the same geometry. Using the slip velocity approach,
Minor et al. [8] performed an analysis of dynamic aspects of electroosmosis
and electrophoresis, and Santiago [9] studied the effects of fluid inertia and
pressure on transient electroosmotic flows in a two-parallel plate. The slip
velocity model was first proposed by Overbeek [10] who showed that for
58
microchannels with relatively thin EDL thickness, the flow field outside the
EDL is an irrotational flow with a slip velocity boundary condition determined
by the well-known Smoluchowski equation. Kang et al. [11] presented an
analytical scheme to solve the PoissonBoltzmann equation for arbitrary zetapotentials, and analyzed the dynamic electroosmotic flow in a cylindrical
capillary. In Xuan and Lis work [12], the electroosmotic flow was analyzed
for microchannels with arbitrary cross-section and heterogeneous potential.
Yan et al. [13] presented a model to analyze the finite reservoir effects on EOF
in a rectangular microchannel, and performed a micro-PIV experiment to
validate the proposed model. Other than analytical and experimental
investigations, numerical simulations of the electroosmotic flow in complex
geometry of microchannel networks have been reported [14-18].
All the aforementioned studies are concerned with Newtonian fluids.
However, microfluidic devices are usually used to analyze biofluids which
may not be treated as Newtonian fluids. Thus, the more general Cauchy
momentum equation, instead of the Navier-Stokes equation should be used to
describe the flow characteristics of non-Newtonian fluids provided that proper
constitutive equations are available. The aim of constructing constitutive
equations for non-Newtonian fluids is to find correlations between dynamic
viscosity and shear rate. The Power-law model [19], Carreau model [20],
Moldflow first-order model [21], and Bingham model [22] have been
successfully developed to analyze non-Newtonian fluid flow and heat/mass
transfer. As for electroosmotic flow of non-Newtonian fluids, however there
are few studies reported in the literature. Zimmerman et al. [20] presented a
two-dimensional finite element simulation of electrokinetic flow in a
microchannel T-junction for fluid with a Carreau-type nonlinear viscosity.
They claimed that the fluid experiences a range of shear rate as it turns around
the corner, and the flow field is shown to be sensitive to the non-Newtonian
characteristics of the Carreau-type. Otevel and Kleprnk [23] derived the
exact solutions for electroosmotic flow in a capillary channel filled with
polymer electrolytes having a varying viscosity, and the steady-state velocity
profile was calculated by assuming that the viscosity decreases exponentially
in the radial direction (i.e., from the capillary wall to the centerline). To our
best knowledge, the only relevant study that we could locate is by Das and
Chakraborty [24] who analyzed the electroosmotic flow of a Non-Newtonian
fluid in microchannels. However, Das and Chakrabortys analyses were based
on an approximation of the hyperbolic sine function, and such approximation
can lead to large errors when the electrokinetic parameter H is small, e.g.,
the case of overlapped double layers. Moreover, their velocity derivation
59
cannot be reduced to the well-known velocity expression for the Newtonian

fluids when the flow behavior index is equal to unit one.
This study reports analyses of the electroosmotic flow of power-law fluids
in a slit microchannel. Exact solutions of the velocity distributions are found
for several special values of the flow behavior index. For arbitrary values of
the flow behavior index, approximate solutions of the velocity distributions are
obtained by using an approximate scheme for the hyperbolic sine function.
The approximate solutions are found to be in good agreement with the exact
solutions and the numerical solutions. In addition, a general Smoluchowski
velocity is proposed for power-law fluids. Parametric studies are performed to
examine effects of the dimensionless electrokinetic parameter, H , flow
behavior index, double layer thickness, and applied electric field on the shear
stress, dynamic viscosity and velocity distributions of the electroosmotic flow
of power-law fluids.
1.2. Power-Law Fluids and Governing Equations

The difference between non-Newtonian and Newtonian fluids lies in that
the viscous stress is not a linear function of the rate of strain tensor. A number
of empirical expressions have been used to describe variations in the apparent
viscosity with the rate of strain. A scalar measure of the rate of strain suitable
for such expression, is the magnitude of the rate of strain tensor, which is
defined as [25]
( : )
2
1/ 2
(1)
where is the rate of strain tensor and is its magnitude. The fluid viscosity
then can be expressed as a function of , namely
( ) . In the present work,
a special non-Newtonian fluid termed as the power-law fluid is assumed, and

its dynamic viscosity, is given by [25]
= m ( 2 )
n 1
(2)
60
where m is the flow consistency index, and n is the flow behavior index which
represents an apparent or effective viscosity being a function of the shear rate.
Shear-thinning (also termed as pseudoplastic) behavior is obtained for n < 1,
and it indicates that the fluid viscosity decreases with increasing the rate of
shear. Pseudoplasticity can be demonstrated by shaking a bottle of ketchup
such that the ketchup undergoes an unpredictable change in its viscosity.
Newtonian behavior is obtained for n = 1 . Shear-thickening (also termed as
dilatant) behavior is obtained for n > 1 , and it shows that the fluid viscosity
increases with the rate of shear. The dilatant effect can readily be seen with a
mixture of cornstarch and water, which acts in counter-intuitive ways when
struck or thrown against a surface.
The flow field of the power-law fluids is governed by the continuity
equation and the Cauthy momentum equation. For an incompressible fluid, the
continuity equation can be written as [25]
v = 0
(3)
where v is the velocity vector. Using a general relationship between the

viscous stress tensor and the rate of strain tensor, given by Eq. (4),
T
= 2 ( ) = ( ) v + ( v )
(4)
One can readily show that the Cauchy monmentum equation is expressed
as [25]
Dv
T
= P + F + ( ) v + ( v )
Dt
(5)
where is the density, P is the pressure, F is the body force vector, v is

the velocity gradient tensor and ( v )
gradient tensor.
is the transpose of the velocity
61
1.3. Exact Solutions of Electroosmosis of Power-Law Fluids in a

Slit Microchannel
Figure 1 shows a two-dimensional slit microchannel of height 2H. The
channel is filled with a liquid electrolyte of dielectric constant, . It is
assumed that the slit wall is uniformly charged with a zeta-potential, w , and
the liquid solution behaves as power-law fluid with a flow consistency index m,
and a flow behavior index n. When an external electric field E0 is imposed
along x direction, the liquid sets in motion due to electroosmosis, and the flow
field is governed by Eq. (5). Because of symmetry, the analysis is restricted in
the upper half domain of the slit microchannel.
Figure 1. The sketch of a two-dimensional slit channel.
For a steady, fully-developed flow, the velocity components satisfy
vx = vx ( y ) and v y = vz = 0 . Therefore, the material derivative of v with

respect to time vanishes and the continuity equation is automatically satisfied.
Furthermore, for electroosmotic flow, no pressure is applied and gravitational
body force is negligible, and thus the only driving force is due to the
interaction of the applied electrical field E0 and the net charge density in the
electric double layer (EDL) of the channel wall. Such force acts only along x
direction, and is expressed by [4]
Fx = E0 e
(6)
62
According to the theory of electrostatics, the net charge density e in the

diffuse layer of the wall EDL is given by the Poisson equation, which takes the
form [4]
d 2
= e
dy 2
(7)
With the assumptions of the Boltzmann distribution and small zeta

potentials, the electrical potential profile in the EDL is governed by the
linearized PoissonBoltzmann equation expressed by [4]
d 2
= 2
dy 2
(8)
which is subject to the following boundary conditions:
y=H
d
dy
= w
(9a)
=0
(9b)
y =0
1 is called the Debye length, and is defined as 1 = ( k BT / 2e 2 z 2 n ) ,

1/ 2
where n and z are the bulk number concentration and the valence of ions,
respectively, e is the fundamental charge, kB is the Boltzmann constant, and T
is the absolute temperature.
The solution for the electrical potential distribution is of the following
form
( y) = w
cosh ( y )
cosh ( H )
(10)
63
Then the net charge density e can be expressed as a function of the EDL
potential,
e ( y ) = 2
(11)
Recalling that the magnitude of the rate of strain tensor defined in Eq. (1),
in this case is given by = (1/ 2 ) dvx / dy , the viscosity defined in Eq. (2)
can be expressed in terms of the velocity gradient as follows
= m ( 2 )
n 1
dv
=m x
dy
n 1
dv
= m x
dy
n 1
(12)
Here the negative sign is chosen because the velocity decreases with
increasing y.
Therefore, one can show that the Cauchy momentum equation (i.e., Eq.
(5)) can be considerably simplified to
d dvx
m
dy dy
n 1
dvx
2 E0 = 0
dy
(13)
This equation constrained by the following boundary conditions:
vx
y=H
dvx
dy
=0
=0
(14a)
(14b)
y =0
gives the electroosmotic flow field of power-law fluids in a slit microchannel.

Equation (13) is equivalent to
64
n
2 E0
d dvx

=
dy dy
m
(15)
Integrating this equation from 0 to y with consideration of the boundary

condition given by Eq. (14b) and the electrical potential distribution expressed
by Eq. (10) leads to
n
dvx
E0 w sinh( y )
=
m cosh ( H )
dy
(16)
Consequently, the shear stress distribution can be obtained as
yx = E0 w
sinh( y )
cosh ( H )
(17)
From Eq. (16), the velocity gradient can be expressed as

1
dvx
E0 w n
=
dy
m
sinh( y ) n
cosh ( H )
(18)
Substituting Eq. (18) into Eq. (12) gives the expression for the viscosity of
the power-law fluids,
dvx
dy
= m
n 1
=m
1
n
( E0 w )
n 1
n
sinh( y )
cosh ( H )
n 1
n
(19)
Introducing
ws = E w
1
n
ws = m ( E0 w )
(20a)
n 1
n
(20b)
65
which under the liming case of H are respectively the shear stress
and the dynamic viscosity on the channel wall according to Eqs.(17) and (19).
Therefore, the shear stress distribution yx and the viscosity of the power-law
, respectively given by Eq. (17) and Eq. (19), can be rewritten in

terms of ws and w s as the following forms,
fluids
yx = ws
sinh( y )
cosh ( H )
sinh( y )
cosh ( H )
= ws
(21)
n 1
n
(22)
Finally, integrating Eq. (18) from y to H with boundary condition given by

Eq. (14a) taken into account can lead to the velocity distribution,
vx ( y ) =
1 n
n
w E0
1
n
( )
sinh n ( y ' )d y '

cosh
1
n
(23)
( H )
Examination of Eq. (23) suggests that the integration can be analytically

carried out only for specific values of the flow behavior index, n such as 1,
and
1
etc.
3
The case of n = 1 corresponds to a Newtonian fluid where
1
2
= m , and
thus Eq. (23) can be evaluated as
vx ( y ) =
cosh ( y )
1
cosh ( H )
w E0
m
(24)
66
which is the same as the velocity distribution shown in [4] using the
Newtonian fluids hypothesis. When n = 1/ 2 , one can have that
cosh ( H )
1
and show that
E0 w sinh( y )
= m2
1 E [sinh(2kH ) sinh(2ky ) 2(kH ky ) ]

vx ( y ) = w 0
m
2
2 cosh 2 (kH )
2
(25)
cosh 2 ( H )
1
1
3
Similarly, for n = , one can get = m
2
3
E0 w sinh ( y )
2
and show that

3
1 E sinh(3 H ) sin(3 y ) + 9sinh ( kH ) 9sinh ( ky ) (26)
vx ( y ) = 2 w 0
3
4cosh 3 ( kH )
m
1.4. Approximate Analytical Solutions of Electroosmosis of

Power-Law Fluids in a Slit Microchannel
As the integral in Eq. (23) can be analytically evaluated only under certain
circumstances, in the following we will present an approximate approach to
obtain the velocity distributions from Eq. (23). Mathematically, the hyperbolic
sine function can be approximated as
sinh ( y ) 1 y
2 e
0 < y 1
y >1
(27)
Such approximation was successfully used by Philip and Wooding [6] in

their study to obtain the electrical potential distribution outside a charged
cylindrical particle immersed in an electrolyte. Substituting Eq. (27) into Eq.
(23), one can analytically obtain the velocity distributions with consideration
of two different cases, H > 1 and 0 < H 1 .
67
Case I, H > 1
(a) In this case, if 0 y 1 , Eq. (23) can be integrated piecewise with
the above approximation adopted, and thus an analytical expression
for the velocity distribution can be obtained as,
1
1
1
H 1 ( y ' ) n
' n
'
y d y + e d y'
1 ky
1
1 n
2
E n
vx ( y ) = n w 0
1
m
cosh n ( H )
( ) ( )
( )
H
1
1
1+ n
1 n
n
n
y
e
e
1
( ) 1
1 n
n +1

n
n
E
2
(28)
= n n w 0
1
m
n
cosh ( H )
If y > 1 , Eq. (23) can be evaluated as
(b)
vx ( y ) =
1 n
n
w E0 n
1 ( y ' ) n
'
2 e d y
( )
cosh n ( H )
H
y
1 n
e e n
1
1
1 n
E n n
= n n w 0 2
1
m
cosh n ( H )
(29)
Average velocity can be obtained from Eqs. (28) and (29) using the
following definition
V=
1
H
vx dy
Therefore, the average velocity is
(30)
68
1
n
1
1
1
1 n
E n n
V = n n w 0 2
m
H
n
cosh
1
n 1 n
1
e +
H H (1 + 2n )
1
n
(31)
( H )
The volumetric flow rate can also be found as
Q = 2V H = nk
1 n
n
Furthermore, if
w E0
m
1
n
n 1
n
H
1
n n n 1 n
2
e +
H e +
1
2n )
+
cosh
1
n
(32)
( H )
H >> 1 it can be shown that

1
e kH n
cosh ( H )
2
1
n
(33)
In this case, Eq. (31) is thus reduced to
V = Vs = n
1 n
n
w E0 n
(34)
Equation (34) shows that for Newtonian fluids the average velocity is linearly
proportional to external electric field strength and wall zeta potential, but
independent of EDL thickness. However, for the power-law fluids whose flow
behavior index is not equal to unit one, the dependence of the velocity on
external electric field strength, wall potential, and EDL thickness becomes
nonlinear. In addition, it is interesting to note that the Smoluchowski velocity
can be recovered from Eq. (34) when n=1. We thus can term Vs as the
generalized Smoluchowski velocity for power-law fluids. In Section 1.5,
without otherwise specified, the generalized Smoluchowski velocity, Vs , will
be used as a reference velocity to obtain dimensionless velocity. It is noted that
this generalized Smoluchowski velocity is only valide for solid surfaces with
small zeta potentials.In the more recent work [26], a more general
Smoluchowski velocity for arbitrary zeta potentials is presented.
69
The velocity distribution hence can be further rewritten in terms of the

average velocity as
vx ( y ) =
kH
1
1+ n
2n
n
n
n
ky
e
e
1
(
)
n +1

n
1
H
H
n
y
nH
e e n
n
1
H
H
n
0 ky 1
1
n 1 n
2n
e +
+
H H (1 + 2n )
(35)
ky > 1
2n
n 1 n
e +
+
H H (1 + 2n )
1
It should be pointed out here that although the approximation given in Eq.
(27) leads to discontinuity at y=1, the velocity distribution expressed in Eq.
(35) is continuous at y=1.
Case II, 0 < H 1

The integration of Eq. (23) gives
1+ n
1+ n
1
n ( y ) n
H
(
)
1 n
E n + 1
vx ( y ) = n n w 0
1
m
cosh n ( H )
1
n
(36)
Likewise, the average velocity, the volumetric flow rate, and the velocity
distribution can be obtained respectively as
V = nk
1 n
n
1+ n
1
H) n
(
w E0 1 + 2n
m
1
cosh n ( H )
1
n
(37)
70

1+ n
1+ 2 n
2
nH n
1 n
n
+
1
2
w 0
n
Q = 2V H = nk
1
m
cosh n ( H )
(38)
1+ n
2n + 1 y n
vx ( y ) =
V 1
n +1 H
(39)
1
n
1.5. Results and Discussion

In calculations, the following parameters and constants are used: the
relative permittivity, r =80, the vacuum, 0 = 8.85 10 12 F/m , the absolute
temperature, T=300K, the valence of ions, z=1, the wall zeta potential,l
w = 50 mV , and the flow consistency index, m = 0.90 103 Pa s n .

1.5.1. Comparison of the Exact and Approximate Solutions with the
Numerical Simulations
In order to verify the approximate solutions presented in Section 1.4, we
consider a special case of Newtonian fluids, namely n=1; in this case the exact
solution for the velocity distribution is given by Eq. (24), numerical
integration of Eq. (23) can be performed using the Romberg method with a
specified accuracy of 10-6, and the approximate solution for the velocity
distribution is either given by Eqs. (28) and (29) when H >1 or by Eq. (36)
when H 1 .
Comparison of the Newtonian fluid velocity distributions obtained from
the approximate solutions, the exact solution, and the numerical solution is
shown in Figure 2A (when H > 1 ) and in Figure 2B (when H < 1 ). It is
observed that the flow exhibits a plug like profile when H is large, say
H 50 . Decrease in H (e.g., H 3 ) causes the overlapped wall
EDLs, which in turn not only reduces the maximum velocity at the channel
centerline, but also makes the velocity distribution exhibit a parabolic like
profile. It also can be seen that the velocity distributions predicted by the exact
solution and the numerical solution are indistinguishable. The approximate
solutions can provide a good estimation of the velocity field for either
71
relatively large H values (e.g., H 3 ) or relatively small H values

(e.g., H 0.7 ). Since the cause of the deviation of the approximation
solutions from the exact and the numerical solutions results from the
approximate scheme in Eq. (27), it is expected that the maximum error
induced by the approximate solution occurs when H = 1 . Therefore, as for
microfluidic applications concerned where H is usually very large, Eqs.
(28) and (29) are more appropriate.
1.0
vx/Vs
0.8
H=10
0.6
H=50
H=2
H=3
0.4
0.2
0.0
0.0
exact solution
approximate solution
numerical solution
0.2
0.4
y/H
0.6
0.8
1.0
0.8
1.0
(A)
0.20
H=0.7
vx/Vs
0.16
H=0.5
0.12
0.08
0.04
0.00
0.0
exact solution
approximate solution
numerical solution
0.2
0.4
y/H
0.6
(B)
Figure 2. (A) Comparison of the exact solution, approximate and numerical solutions
for the velocity distributions of Newtonian fluids (i.e., n=1) when the electrokinetic
parameter H > 1 . (B) Comparison of the exact, approximate and numerical solutions
for the velocity distributions of Newtonian fluids (i.e., n=1) when the electrokinetic
parameter H < 1
72
1.5.2. Characteristics of Electroosmotic Flow of Power-Law Fluids

Figure 3 shows the normalized shear stress distributions (evaluated using
Eq. (21) with the shear stress on the channel wall given by Eq. (20a) as the
reference shear stress) for different values of H . The shear stress is
independent of the fluid behavior index, n, and is zero at the channel centerline
due to the symmetry. While for H > 1 , the shear stress distribution exhibits
nonlinear. As H increases, the magnitude of the dimensionless shear stress
on the channel wall approaches to unit one. In the limiting case where
H , the shear stress remains zero almost in the entire portion of the
channel except for the channel wall where the shear stress rapidly jumps to
unit one. The features shown by Figure 3 can be understood as follows: when
H is small (e.g., H<1), the EDL occupies the entire channel, which induces a
relatively uniform body force to drive liquid fluid. It can be expected that the
flow pattern resembles that of the pressure driven flow. Hence, the shear stress
linearly grows along y direction, but it cannot reach the magnitude of the wall
shear stress, ws (= E0 w ) which is defined in Eq. (20a) for large values of
H. However, for the large H, the EDL only exists near the channel wall
region, and so does the driving force. Consequently the shear stress changes
slowly in the middle portion of the channel (i.e., outside the EDL region), but
quickly surpasses the shear stress for the small H and finally reaches the
magnitude of the wall shear stress, ws on the channel wall.
1.0
yx/ws
0.8
0.6
H=0.7
H=1.0
H=3.0
H=10.0
0.4
0.2
0.0
0.0
0.2
0.4
y/H
0.6
0.8
1.0
Figure 3. Normalized shear stress distributions yx / ws (evaluated using Eq. (21) with
the shear stress on the channel wall given by Eq. (20a) as the reference shear stress) for
various values of H
73
Figure 4 shows the dimensionless dynamic viscosities / ws calculated

from Eq. (22) for different values of the fluid behavior index, n while keeping
H=10. For pseudoelastic fluids, namely n < 1 , the dimensionless dynamic
viscosity monotonically decreases from the channel centerline to the channel
wall. It should be pointed out that Eq. (22) fails to predict the dynamic
viscosity at the channel centerline, because it produces an infinite value there.
For dilatant fluids, namely n > 1 , the fluids exhibit inviscid at the channel
centerline, and thus the viscosity increases gradually. At the channel wall, the
dimensionless viscosity approaches to unit one regardless of the values of the
fluid behavior index, n. For Newtonian fluids, namely n = 1 , the
dismensionless viscosity is equal to unit one.
20
18
n=0.8
n=0.9
n=1.1
n=1.2
16
/ws
14
12
10
8
6
n=1.0
4
2
0
0
10
Figure 4. Dimensionless dynamic viscosity / ws (calculated from Eq. (22) with the
dynamic viscosity on the channel wall given by Eq. (20b) as the reference viscosity)
for various values of the fluid behavior index, n while keeping H = 10
The dynamic viscosity on the channel wall, ws calculated using Eq.

(20b) is shown in Figure 5A (for various Debye lengths/EDL thicknesses) and
in Figure 5B (for various applied electric field strengths). In Figures 5A and
5B, the Newtonian fluid viscosity 0 is chosen as the reference viscosity, and
is indicated at point (1.0, 1.0). It can be noted that different from Newtonian
fluids, whose dynamic viscosity is constant, the wall dynamic viscosity of
power-law fluids not only depends on the flow behavior index, n, but also
depends on both the EDL thickness and the applied external electric field. For
74
dilatant liquids, n > 1 , thinner EDL thickness or higher electric field strength
will result in higher wall dynamic viscosity. Whereas, for pseudoplastic
liquids, n < 1 , the dependence of the wall dynamic viscosity on the EDL
thickness and the external electric field is insignificant.
14
5
12
E0=2x10 V/m
1
-2
-3
-4
ws/0
=1nm (C=9.5x10 M)
10
=5nm (C=3.8x10 M)
=10nm (C=9.5x10 M)
6
4
2
0
0.80
0.85
0.90
0.95
1.00
1.05
1.10
1.15
1.20
1.05
1.10
1.15
1.20
(A)
14
12
ws/0
10
-3
=8nm(C=1.5x10 M)
5
E0=1.0 10 V/m
5
E0=5.0 10 V/m
E0=1.0 10 V/m
4
2
0
0.80
0.85
0.90
0.95
1.00
(B)
Figure 5. (A) Effect of the EDL thickness on the dynamic viscosity at the channel wall,
ws (calculated using Eq. (20b)) normalized with the Newtonian fluid viscosity 0 . (B)
Effect of the applied electric field on the dynamic viscosity at the channel wall, ws
(calculated using Eq. (20b)) normalized with the Newtonian fluid viscosity 0
75
Figure 6 shows the dimensionless velocity distributions vx / Vs (evaluated

from Eqs. (28) and (29)) for various values of the fluid behavior index, n while
keeping H=10. The dimensionless velocity was obtained using the
generalized Smoluchowski velocity given by Eq. (34) as the reference
velocity. It can be seen that irrespective of the value of the fluid behavior
index, the velocity near the center portion of the channel approaches to the
generalized Smoluchowski velocity. The velocity profile becomes more pluglike as the fluid behavior index decreases, thereby selecting Smoluchowski
velocity as the slip velocity is more appropriate for characterizing
electroosmotic flow of power fluids with lower flow behavior index.
1.0
vx/Vs
0.8
n=1.5
n=1.2
n=1.0
n=0.8
n=0.5
0.6
0.4
0.2
0.0
0
10
Figure 6. Dimensionless velocity distributions vx / Vs (evaluated from Eqs. (28) and

(29)) normalized with the generalized Smoluchowski velocity (given by Eq. (34)) for
various values of the fluid behavior index, n while keeping H = 10
In certain practical applications, constant flow rate/average velocity is

purposefully maintained. Figure 7 shows the velocity distributions normalized
by the average velocity given by Eq. (31) for various values of the fluid
behavior index, n while keeping H = 10 . In the channel center region, the
velocity increases with increasing flow behavior index; while near the channel
wall, it shows an opposite trend. However, the geometric area under each
curve is same so as to ensure the same flow rate.
76
1.2
1.0
vx/V
0.8
0.6
n=1.5
n=1.2
n=1.0
n=0.8
n=0.5
0.4
0.2
0.0
0
10
Figure 7. Dimensionless velocity distributions (evaluated from Eqs. (28) and (29))
normalized by the average velocity (given by Eq. (31)) for various values of the fluid
behavior index, n while keeping H = 10
Figure 8 depicts the ratio of the average velocity (calculated using Eq.
(31)) to the generalized Smoluchowski velocity versus the flow behavior
index, n for various values of H . The difference between the average
velocity and the Smoluchowski velocity reduces with increasing H or
decreasing the flow behavior index. As H , the ratio becomes unit one,
indicating that in this case the average velocity is the same as the
Smoluchowski velocity regardless of change of the flow behavior index.
Figure 9 shows the generalized Smoluchowski velocity Vs (for power-law
fluids) normalized by the conventional Smoluchowski velocity
( Vs 0 = E0 w / 0 for Newtonian fluids) versus the flow behavior index, n for
various EDL thicknesses. It is noted that all the three curves pass through a
unique point (1, 1). This indicates at such point, the Smoluchowski velocity is
independent of the EDL thickness, and is corresponding to the Newtonian
fluids. In general, the Smoluchowski velocity monotonically decreases when
increasing the flow behavior index. For pseudoplastic liquids, n < 1 , the effect
of the EDL thickness on the Smoluchowski velocity is more pronounced than
that for dilatant liquids, n > 1 . Interestingly, it is found that for small flow
behavior index, say n = 0.9 , the generalized Smoluchowski velocity can be
several times larger than the conventional Smoluchowski velocity. This
suggests a possible method of increasing the electrokinetic flow velocity in
microfluidic devices by adjusting the flow behavior index while keeping other
77
parameters unchanged such as applied electric field, zeta potential, dielectric

constant etc.
1.0
V/Vs
0.9
0.8
0.7
H=3
H=5
H=10
H=50
0.6
0.5
0.4
0.0
0.4
0.8
1.2
1.6
2.0
Figure 8. The ratio of the average velocity (calculated using Eq. (31)) to the
generalized Smoluchowski velocity (given by Eq. (34)) versus the flow behavior
index, n for various values of H
40
5
E0=2.0x10 V/m
Vs/Vs0
-2
-3
=1nm (C=9.5x10 M)
30
=5nm (C=3.8x10 M)
1
-4
=10nm (C=9.5x10 M)
20
10
0
0.80
0.85
0.90
0.95
1.00
1.05
1.10
1.15
1.20
Figure 9. The generalized Smoluchowski velocity Vs (for power-law fluids)

normalized with the conventional Smoluchowski velocity ( Vs 0 = E0 w / 0 for
Newtonian fluids) versus the flow behavior index, n for various EDL thicknesses
Figure 10 shows the normalized volumetric flow rate versus the flow
behavior index, n, for various electric field strengths while keeping a constant
78
microchannel height of H = 5 m . The volumetric flow rate, Q0 is evaluated

from Eq. (32) and the reference flow rate is chosen as
Q0 =
E0 w
2H
0
(40)
which is corresponding to the flow rate of Newtonian fluids when H >> 1 .

The volumetric flow rate is reduced as increasing the flow behavior index.
Under the conditions considered, for certain dilatant liquids, for example
n 1.3 , imposing high electric field does not necessarily increase the
electrokinetic flow rate. However, for pseudoplastic liquids, n < 1 , the
electrokinetic flow rate can be significantly higher than that for Newtonian
fluids.
36
30
H=5m
1
-6
=250nm (C=1.5x10 M)
Q/Q0
24
E0=1.0x10 V/m
5
18
E0=5.0x10 V/m
6
E0=1.0x10 V/m
12
6
0
0.9
1.0
1.1
1.2
1.3
1.4
1.5
Figure 10. Dimensionless volumetric flow rate versus the flow behavior index, n, for
various electric field strengths while keeping a constant microchannel height of
H = 5 m . The volumetric flow rate Q is evaluated from Eq. (32) and the reference
flow rate is chosen as Q0 = 2 H E0 w / 0 .
1.6. Summary for Electroosmotic Flow of Power-Law Fluids

This study presents a mathematical model for describing the
electroosmotic flow of power-law fluids in a slit microchannel. Within the
79
framework of the linearized Poisson-Boltzmann theory, exact solutions of the

velocity distribution are found for several special values of the flow behavior
index. Furthermore, by utilizing an approximate scheme for the hyperbolic
cosine function, approximate solutions of the velocity distribution are also
obtained. The approximate solutions are validated by comparing with
numerical solutions. A generalized Smoluchowski velocity is introduced by
taking into account contributions due to the finite EDL thickness and the flow
behavior index of power-law fluids.
The calculations show that the shear stress is independent of the fluid
behavior index. For pseudoplastic fluids, n < 1 , the dimensionless dynamic
viscosity monotonically decreases from the channel centerline to the channel
wall. For dilatant fluids, n > 1 , the fluids exhibit inviscid at the channel
centerline, and then the viscosity increases gradually. At the channel wall, the
dimensionless viscosity approaches to unit one regardless of the values of the
fluid behavior index, n. Irrespective of the value of the fluid behavior index,
the velocity near the center portion of the channel approaches to the
generalized Smoluchowski velocity. The velocity profile becomes more plug
like as the fluid behavior index decreases, suggesting that the Smoluchowski
velocity is more appropriate as the slip velocity for electroosmotic flow of
power fluids with low flow behavior index. The generalized Smoluchowski
velocity monotonically decreases when increasing the flow behavior index.
For pseudoplastic liquids, n < 1 , the effect of the EDL thickness on the
Smoluchowski velocity is more pronounced than that for dilatant liquids,
n > 1 . It is also found that for pseudoplastic liquids, n < 1 , the generalized
Smoluchowski velocity can be several times of the conventional
Smoluchowski velocity, and thus the electrokinetic flow rate can be
significantly higher than that for Newtonian fluids.
2. PRESSURE DRIVEN FLOW OF POWER-LAW FLUIDS IN A

MICROCHANNEL WITH ELECTROKINETIC EFFECTS
2.1. Introduction
Liquid flow through microchannels has found its applications in
microfluidic devices, ranging from pH and temperature sensors, to fluid
actuators, such as pumps, mixers, and valves [27], as well as Lab-on-a-Chip
80
systems for drug delivery, chemical analysis, and biomedical diagnosis [3].
Understanding of flow physics in microchannels is of great importance to the
successful and optimal design and precise control of microfluidic devices.
However, the existing theories cannot be scaled down to describe completely
the flow in microchannels, where some surface phenomena such as capillary,
wetting, electrokinetic effects, can cause the flow characteristics to deviate
from those in large-sized channels.
In the literature, numerous theoretical studies were reported to explain the
deviation of microscale flow characteristics; the micro-polar fluid theory [28],
the micro-moment theory [29], and the electrokinetics [5] are a few to name.
In this study, the electrokinetic effects are considered. It is known that most
solid surfaces acquire electrostatic charges, i.e., an electrical surface potential.
The presence of such charges would cause the redistribution ions in the
neighborhood of the charged surface, leading to the development of a so-called
electrical double layer (EDL). An EDL consists of an immobile compact layer
and a mobile diffuse layer where there are more counter-ions than co-ions and
hence the net charge density is not zero. When a liquid is forced through a
microchannel under an applied hydrostatic pressure, more counter-ions in the
diffuse layer are carried towards the downstream to form a streaming current,
along the direction of the liquid flow. Meanwhile, the accumulation of
counter-ions in the downstream end builds up an electric field with a streaming
potential which in turn generates a conduction current, in the opposite
direction of the flow. When the conduction current equals the streaming
current, a steady state is reached. It is easy to comprehend that the streaming
potential would exert electrostatic resistant force on the net charge density in
the diffuse layer, thereby hinder the pressure-driven flow, which is also termed
as the electroviscous effects. The electrokinetic electroviscous effects become
significant for liquid flow in a microchannel where the thickness of the EDL is
often comparable with the channel dimension.
The electrokinetic effects on microchannel flow have been
experimentally studied by Mala et al.[30], Ren et al.[31], Kulinsky et al.
[32] and Brutin and Tadrist [33]. Their results showed that depending on
the channel height and the electrical properties of the channel surface, the
measured flow rate of the distilled water can be 80% lower than that predicted
from the classical Poiseuille flow equation. The electroviscous effects have
also been theoretically studied for slit-like channels (Mala et al.[34], Chun and
Kwak [35]) and for rectangular channels (Yang and Li [36, 37], Yang et
al.[38] ). In these studies, the electrokinetic effects on velocity distribution,
friction coefficient, apparent viscosity, and heat transfer were examined. Their
81
analyses predicted that the electrokinetic effects can result in a higher friction
coefficient, a larger apparent viscosity, and a reduced Nusselt number.
However few studies have been reported for the flow of non-Newtonian fluids
in microchannels. Das and Chakraborty [24] considered the electroosmotic
flow of power-law fluids in a slit. Zimmerman et al.[20] studied the
electrokinetic flow of Carreau fluids in a T-shaped microchannel. Berli and
Olivares [39] analyzed the wall depletion effect on flow of non-Newtonian
fluids by extending the general force-flux relations for simple fluids to nonNewtonian fluids. More recently, Zhao et al. [40] derived a generalized
Smoluchowski slip velocity for electroosmotic flow of power-law fluids.
In this work, the electrokinetic effects on pressure driven flow of powerlaw fluids in a microchannel are studied. The flow field of power-law fluids is
governed by the general Cauchy momentum equation with consideration of a
body force originating from the interaction of the net charge density in the
channel EDL and the induced electrokinetic streaming potential. Analytical
expressions are obtained for the velocity distribution, volumetric flow rate,
apparent viscosity and friction coefficient. Parametric studies of the
electrokinetic effects on flow of power-law fluids in a microchannel under the
influence of the ionic concentration, wall zeta potential, flow behavior
index and pressure difference are performed.
2.2. Pressure Driven Flow Field of Power-Law Fluids in a Slit

Microchannel with Electrokinetic Effects
Consider a slit microchannel of height 2H and length L as illustrated in
Figure 11. The channel is filled with an incompressible, power-law electrolyte
of constant dielectric constant , flow consistency index m, and flow behavior
index n. The slit wall is assumed to be uniformly charged with a zeta potential
w . Because of geometric symmetry, the analysis is restricted in the upper

half domain of the slit microchannel.
When a pressure difference is applied along the microchannel, the liquid flow
is governed by the Cauchy momentum Eq. (5). For a steady, fully developed
flow, the components of v satisfy vx = vx ( y ) and v y = vz = 0 . The
hydraulic pressure gradient is a constant. Therefore, the material derivative of
v with respect to time vanishes and the continuity equation is automatically
satisfied.
82
Figure 11. Schematic configuration of a microchannel slit with height of 2H and length
of L, and with a uniformly zeta potential of w.
Furthermore, with negligible gravitational force, the only body force

considered here is due to the interaction of the net charge density in the
channel EDL
e and the induced streaming potential Ex . Such force acts only
along x direction, and is given by
Fx = Ex e
(41)
When the wall zeta potential w is small, the net charge density
e can
be expressed as a function of the EDL potential [4]
e ( y ) = 2
(42)
1 is termed as the Debye length, and is defined as

1 = ( k BT / 2e 2 z 2 n )1/ 2 (here n and z are the bulk number
where
concentration and the valence of ions, respectively, e is the fundamental

charge, kB is the Boltzmann constant, and T is the absolute temperature). An
expression for the EDL potential distribution is of the following form [4]
( y) = w
cosh( y )
cosh( H )
(43)
Defining the dimensionless groups: K=H, Y=y/H and =ze/kbT, we can

nondimensionalize Eq. (43) as
(Y ) = w
83
cosh( KY )
cosh ( K )
(44)
Recalling that the magnitude of the rate of strain tensor in this case is
expressed as = (1/ 2) dvx / dy , we can obtain an expression for the viscosity
using Eq. (2),
= m(
d vx n 1
)
dy
(45)
where the negative sign is chosen because the velocity decreases with
increasing y in the channel.
Therefore, we can show that the Cauchy momentum Eq. (5) can be
simplified to
dv
dv
dp d
+
[m ( x ) n 1 x ] 2 Ex = 0
dx dy
dy
dy
(46)
By introducing the following dimensionless parameters,
v=
vx
V
Px =
H dp
V 2 dx
Ex =
Ex H
G1 =
2zen 0
V 2
n 1 dp n nn+1
V=
H
n + 1 m dx
(47)
we can obtain Eq. (48) that gives the dimensionless form of Eq. (46),
n +1 n d
dv n
n +1 n
)
[(
) ] (
) ( Px ) 1 G1 E x = 0
n
dY
dY
n
(48)
where V is the centerline velocity without consideration of the EDL effect and
0 is a reference electrical potential. Eq. (48) can be solved using the following
boundary conditions
84
v Y =1 = 0
dv
dY
=0
(49)
Y =0
An analytical solution of Eq. (48) can be obtained as
v(Y ) =
1
G E sinh( KY ' ) 1n '
n +1
( P ) n [( Px )Y ' 1 x w
] dY
Y
cosh( K )
n
K
(50)
Eq. (50) shows that the flow is retarded due to the induced streaming
potential. The integral can be carried out analytically only for specific values
of the flow behavior index n, such as 1, 1/ 2 and 1/ 3 etc.
Specific Cases
The case of n = 1 corresponds to Newtonian fluids where m = , and
Eq. (50) can be evaluated as
v (Y ) = (1 Y 2 ) 2( Px ) 1 G1 w Ex
cosh ( K ) cosh ( KY )
K 2 cosh ( K )
(51)
When n = 1/ 2 , we can show that the dimensionless velocity can be

expressed as
[sinh(2 K ) sinh(2 KY )] 2( K KY )
4 K 3 cosh 2 ( K )
2{[ K cosh( K ) KY cosh( KY )] [sinh( K ) sinh( KY )]}
3( Px ) 1 G1 w E x
K 3 cosh ( K )
(52)
v (Y ) = (1 Y 3 ) + 3( Px ) 2 (G1 w Ex ) 2
Approximate Analytical Solution

As the integral in Eq. (50) can be analytically evaluated only under certain
circumstances, in the following we will present an approximate approach to
obtain the velocity distributions from Eq. (50). It is assumed that in Eq. (50)
the actuating pressure force term is much larger than the induced electrostatic
body force term due to electrokinetic effects, and thus we have the following
assumption
G1 w Ex sinh( KY ' )
K
cosh( K )
1
( Px )Y '
85
(53)
Using Taylors series for |x| 1 and an arbitrary real number , we have
(1 + x )
1+ x +
( 1)
2
x 2 + ......
Therefore, Eq. (50) can be

approximations in Eqs. (53) and (54),
v (Y) =
analytically
(54)
integrated
using
the
1
1
1
1
2 2 2
2
1 sinh(KY ') 1 n G E
2 sinh (KY ')
1
n +1
1 GE
+ 2 1 x2 w (PY
(Px ) n [(PY
')n 1 x w (PY
')n
')n
]dY'
x
x
x
Y
n
n K
K
cosh(K) 2n
cosh2 (K)
n+1
= (1Y n )
n +1
F (n, K) F(n, KY) 1 n2
H(n, K) H(n, KY)
+ 3 (Px )2 G122wEx2
(Px )1G1wEx
n+1
n+1
2
n
n
2
K n cosh(K)
K n cosh2 (K)
(55)
where the two auxiliary functions, i.e., F(n, x) and H(n, x), are defined in
Appendix. Likewise, all other auxiliary functions, including F1 (n, x), F2 (n, x),
F3 (n, x), H1 (n, x) and H2 (n, x), used in the following are also defined in
Appendix without otherwise specified, and the detailed formulation of these
functions can also be found in [41].
In case no electrokinetic effects, the second term and third term on the
right hand side of Eq. (55) vanish. Eq. (55) reduces to
v0 (Y ) = 1 Y
n +1
n
(56)
which is the well-known pressure-driven flow velocity profile of power-law

fluids through a parallel-plate channel.
Using Eqs. (55) and (56), we can show that the mean velocity with and
without the consideration of the electrokinetic effects respectively are
86
1
Vav = v ( Y ) dY =
0
KF ( n, K ) F1 ( n, K ) F1 ( n, 0 )
1
n +1 n +1
2 ( Px ) G1 w Ex
2 n +1
2n + 1 n
K n cosh( K )
KH ( n, K ) H1 ( n, K ) H1 ( n, 0 )
2
1 n2
Px ) G12 2w Ex2
2 n +1
3 (
2n
K n cosh 2 ( K )
(57)
and
1
Vav 0 = v0 (Y ) dY =
0
n +1
2n + 1
(58)
Hence, the non-dimensional volumetric flow rate through the slit

microchannel, defined by Q =Q/(2HV0), is given by
Q=
V
Vav
V0
(59)
Here another constant reference velocity V0 is adopted instead of using the

reference velocity V introduced earlier. The reason is that we usually want to
examine the effects of pressure gradient and flow behavior index on the flow
rate, but the reference velocity V already includes the pressure gradient and
flow behavior index. Correspondingly, in the absence of the electrokinetic
effects, the non-dimensional volumetric flow rate is expressed as
Q0 =
V
Vav 0
V0
(60)
2.3. Streaming Potential

As seen from Eqs. (55) and (57), the local and mean velocity can be
evaluated only when the induced streaming potential Ex is known. As
explained previously, under a steady-state condition, the conduction current Ic
is equal to the streaming current Is, and the net electrical current I should be
zero
I = I s + Ic = 0
87
(61)
Due to symmetry of the microchannel, the electrical streaming current Is is

defined as
H
I s = 2 vx ( y ) e dy = 4ezn HV v (Y )dY
(62)
The electrical conduction current Ic in the microchannel consist of two

parts: one is due to the conductance of the bulk liquid; the other is due to the
surface conductance of the compact layer of the EDL. The electrical
conductance current can be expressed as
I c = I bc + I sc = t Ex Ac = 2t 0 Ex
(63)
where I bc , I sc represent the bulk and surface conductance current respectively.
t is the total electrical conductivity and it can be calculated by t=b+ sPs/Ac.

Here Ps and Ac are the wetting perimeter and the cross-sectional area of the
channel, respectively. b is the bulk conductivity of the solution, and s is the
surface conductivity, which may be determined by experiment.
From Eqs. (61), (62) and (63), we can obtain an expression for the
streaming potential
1
Ex = G2 v (Y )dY
0
(64)
Here we introduce a dimensionless parameter, G2 = 2 zen HV /(t 0 ) .

Using the velocity distribution (i.e., Eq. (55)) and the EDL potential
profile (i.e., Eq. (44)), we can show that the streaming potential satisfies the
following quadratic equation
an Ex2 (1 + bn ) Ex + cn = 0
where three constant coefficients an , bn , and cn are given by
(65)
88
an =
sinh( K ) H ( K , n) [ H 2 (n, K ) H 2 (n, 0)]

1 n2
G1G2 ( Px ) 2 3w
2 n +1
3
2n
K n cosh 3 ( K )
bn =
sinh( K ) F ( K , n) [ F2 (n, K ) F2 (n, 0)]

n +1
G1G2 ( Px )1 2w
2 n +1
n2
K n cosh 2 ( K )
cn = G2 w
n +1
n
sinh( K ) [ F3 ( n, K ) F3 ( n, 0)]
K
2 n +1
n
(66a)
(66b)
(66c)
cosh ( K )
Then the dimensionless streaming potential can be determined by using

Eq. (67)
1+ b
n)
(
Ex =
cn
1 + b
n
(1 + bn )
2an
4an cn
n 1
(67)
n =1
Recall that in the previous section, the exact solutions of the velocity
distributions are already obtained for the flow index, n=1 and 1/ 2 . Therefore,
the exact solutions of the streaming potential for these two cases can also be
found. For Newtonian fluids when n=1, substituting Eqs. (51) and (44) into
Eq. (64), we can show that the streaming potential satisfies a linear equation as
follow
(b1 + 1) Ex + c1 = 0
(68)
where
b1 = G1G2 ( Px ) 1 2w
cosh ( K ) sinh( K ) K
K 3 cosh 2 ( K )
(69a)
c1 = 2G2 w
K cosh ( K ) sinh ( K )
K 3 cosh ( K )
89
(69b)
The exact solution of the streaming potential can be readily evaluated

from Eq. (68)
Ex =
c1
b1 + 1
(70)
Likewise, for n =
1
, it can be shown that by substituting Eqs. (52) and
2
(44) into Eq. (64), we can have the following quadric equation,
a1/ 2 Ex2 (b1/ 2 + 1) Ex + c1/ 2 = 0
(71)
where
a1/ 2
1
5
8
sinh (2 K ) sinh ( K ) cosh (3K ) cosh ( K ) +
6
2
3
= 3G1G2 ( Px )
4 K 4 cosh 3 ( K )
2
3
w
b1/ 2 = 3G1G2 ( Px ) 1 2w
c1/ 2 = 3G2 w
K sinh (2 K ) sinh 2 ( K ) K 2
2( K ) 4 cosh 2 ( K )
K 2 cosh ( K ) 2 K sinh ( K ) + 2 cosh ( K ) 2

K 4 cosh ( K )
(72a)
(72b)
(72c)
From Eq. (71), the exact solution of the streaming potential is determined
from Eq. (73),
Ex =
(1 + b1/ 2 ) (1 + b1/ 2 ) 2 4a1/ 2 c1/ 2

2a1/ 2
(73)
90
One can readily verify that the two exact results given by Eqs. (70) and (73)
can be recovered from the general solution (Eq. (67)) as special cases when n
respectively equals 1 and 1 / 2 .
2.4. Apparent Viscosity and Electroviscous Effects

In analogy to the expression for the volumetric flow rate of the classical
Poiseuille flow, we define an apparent viscosity a to express the volumetric
flow rate as
Qp =
2 H 3 dp
( )
3 a
dx
(74)
Eq. (74) can be nondimensionalized to
Qp =
1 V VH
( Px )
3 V0 a
(75)
Substituting Eq. (59) and Eq. (60) respectively into Eq. (75), we can
obtain the apparent viscosities of power-law fluids
a =
VH V Px with consideration of the electrokinetic effects
a 0 =
VH V Px without consideration of the electrokinetic effects (77)
3 V0 Q
(76)
3 V0 Q0
Then the ratio of the apparent viscosity with electrokinetic effects to that
without electrokinetic effects is
a Q0
=
a 0 Q
(78)
Eq. (78) can be used to characterize the electroviscous effect. From a

physics viewpoint, this ratio should be always larger than unit one.
91
2.5. Friction Coefficient

The friction factor for the flow through a channel is defined as
f =
dP
Dh / 4
P
dx
= 2 2x
2
Vav
Vav / 2
(79)
where Dh is the hydrodynamic diameter and Dh =4H for the present

microchannel slit. Therefore, the friction coefficient, i.e., the product of the
friction factor f and Reynolds number, is given by
C f = f Re = 2(
n +1 4 n
)
n Vav
(80)
where the Reynolds number is defined as Re = Vav Dh / m .

2 n
2.6. Results and Discussion

Examination of the afore-derived analytical expressions reveals that the
characteristics of power-law fluids flow in a microchannel slit are determined
by the four dimensionless parameters: K, Px , G1 and G2 . Physically, the nondimensional electrokinetic diameter, K=H, represents the ratio of half channel
height to the thickness of the EDL. By definition, the non-dimensional
H dp 1
pressure gradient, Px =
/ V 2 , can be interpreted as the ratio of the
2 dx 2
pressure energy to the kinetic energy. G1 = 2 zen / V 2 characterizes the ratio of
the electrical energy of the solution to the mechanical kinetic energy.
G2 = 2 zen HV / t 0 represents the ratio of the streaming current to the
conduction current[36-38].
In calculation, without other specifications the following parameters and
constants are used: the slit channel height 2H=20 m and length L=2 cm, the
relative permittivity r = 80 , the absolute temperature T=300 K, the valence
92
of ions z+ = z = z = 1 , the wall zeta potential w = 70 mV, the ionic

number concentration, 6.0221020/m3, the fluid consistency index
m=0.9010-3 Pasn, and the pressure difference p = 20 kPa.
It should be pointed out that from the definitions of all the auxiliary
functions in Appendix, they all have a singular point at x = 0 . Therefore, in
the calculations the limit values when x approaches to zero are used to
evaluate their values at x = 0 .
2.6.1. Velocity Distribution

Figure 12 shows the dimensionless velocity distributions (valuated using
Eq. (55) with the centerline velocity in the absence of the EDL effects as the
reference velocity given in Eq. (47)) for three different flow behavior index of
power-law fluids. In Figures 12(A)-(C), the dimensionless velocity
distributions of power-law fluids without the electrokinetic effects are also
plotted in dotted lines for comparison. As seen from the figures, the EDL
exhibits stronger effects on the velocity distributions with lower flow behavior
index than that with higher fluid behavior index. For a small fluid behavior
index in Figure 12(A), the velocity distribution is distorted and the flow
velocity approaches zero in the neighborhood of the channel wall region due to
the action of the EDL field and the induced streaming potential.
1.0
0.8
0.6
0.4
n=0.8
With EDL effects

Without EDL effects
0.2
0.0
0.0
0.2
0.4
(A)
0.6
0.8
1.0
93
1.0
0.8
0.6
0.4
n=1.0
With EDL effects
Without EDL effects
0.2
0.0
0.0
0.2
0.4
0.6
0.8
1.0
(B)
1.0
0.8
0.6
0.4
0.2
n=1.2
With EDL effects

Without EDL effects
0.0
0.0
0.2
0.4
0.6
0.8
1.0
(C)
Figure 12. Non-dimensional Velocity distributions for three different flow behavior
index (A) n=0.8; (B) n=1.0; and (C) n=1.2. The solid lines represent with EDL effects
and the dotted line denote without EDL effects. Other parameters are the wall zeta
potential w=-70mV, the ionic concentration n= 6.022 1020 / m3 , and the applied
pressure difference p=10kPa.
Meanwhile, the velocity at the channel centerline is significantly reduced.

As the fluid behavior index is increased (e.g., Figure 12(B)), the distortion
becomes smaller. In Figure 12(C) where the fluid behavior index is n=1.2, the
difference of the velocity distributions with and without consideration of the
electrokinetic effects become indistinguishable, indicating negligible
electrokinetic effects in this case. In addition, as revealed by Figure 12(A) and
94
12(B), changing flow behavior index from 1 to 0.8 can increase one order of
magnitude of the velocity, suggesting that the magnitude of velocity for
pseudoplastic fluids (i.e., n<1) is very sensitive to the flow behavior index.
Hence this feature may be able to be used as an effective way to adjust the
flow rate in practical applications.
2.6.2. Non-Dimensional Induced Streaming Potential

Figure 13 which shows the non-dimensional induced streaming potential
(calculated from Eq. (67)) versus the flow behavior index for three different
pressure differences. As elaborated earlier, in pressure-driven flow a streaming
potential is induced along the channel axial direction due to the presence of the
channel EDL. Therefore, a larger pressure difference can cause a larger
amount of fluid transport and hence more ions are carried to the downstream
end of the channel, giving rise to a stronger (more negative) induced
electrokinetic potential. Also, it is shown that under the same pressure
difference, the streaming potential is larger for the pseudoplastic fluids than
for the dilatants fluids (i.e., n>1). Once the fluid behavior index is very large,
say n>1.3 in this case, no streaming potential is generated regardless of the
difference in applied pressure.
0.0
1
-0.5
1 p=10kPa
2 p=20kPa
3 p=40kPa
Ex
-1.0
-1.5
-2.0
-2.5
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
Figure 13. Non-dimensional streaming potential versus flow behavior index for three
different pressure differences p=10kPa, 20kPa, and 40kPa. Other parameters are the
wall zeta potential w=-70mV and the ionic concentration n= 6.022 1020 / m3 .
2.6.3. Volumetric Flow Rate

In Figure 14, the non-dimensional volumetric flow rate is plotted as a
function of the flow behavior index for two different wall zeta potentials and
95
pressure differences. As expected, the volumetric flow rate decreases with

increasing the flow behavior index. For large flow behavior index of dilatants
fluids, e.g., n>1.3, the fluids become so viscous so that no flow occurs under
such applied pressures. Also, the electrokinetic effects are observed only in the
pseudoplastic fluids, i.e., n<1. The consequence of electrokinetic effects is a
reduction of flow rate, and such electrokinetic effects are stronger for a larger
applied pressure difference or/and higher channel zeta potential.
2.6.4. Apparent Viscosity (Electroviscous Effects)

The ratio of the apparent viscosity (defined by Eq. (78)) with the EDL
effects to that without consideration of the EDL effects is presented in Figure
15 which shows this ratio versus the flow behavior index for four different
electrokinetic parameters. For a small electrokinetic parameters of K=10, it is
noticeable that the electroviscous effect is present in almost the entire range of
the flow behavior index range studied here. Specifically, the apparent viscosity
ratio can be 2.5 times for a pseudoplastic fluid of n=0.6. As K increases, the
range of fluids (characterized by the flow behavior index) where
electroviscous effects are present shrinks significantly. Since increasing K
either means an increase of the EDL thinness or a decrease of the channel
height, both reduce the predominance of the EDL in the flow domain, resulting
in weaker electroviscous effects. In a limiting case of K=100, the ratio a/ a0
becomes unity one, indicating that no electroviscous effects can be observed
irrespective of the flow behavior index.
0 .8
0 .7
1 p=40kPa
2 p=10kPa
0 .6
0 .5
Q, Q
W ith o u t E D L e ffe c ts
w = -3 0 m V
w = -7 0 m V
0 .4
0 .3
0 .2
0 .1
0 .0
0 .8
2
0 .9
1 .0
1 .1
1 .2
1 .3
Figure 14. Non-dimensional volumetric flow rate versus flow behavior index for two
different pressure differences (p=10kPa and 40kPa) and two zeta potentials (w=-30mV
and -70mV).
96
2.6
2.4
2.2
a/a0
2.0
K=10
1.8
1.6
1.4
1.2
1.0
0.8
0.6
K=20
K=50
K=100
0.7
0.8
0.9
1.0
1.1
1.2
1.3
Figure 15. Variation of a/a0 with flow behavior index for four different electrokinetic
parameters K with an applied pressure difference p =20kP and a wall potential w=70mV.
2.6.5. Friction Coefficient

Figure 16 depicts variation of the friction coefficient, expressed by Eq.
(80) with the flow behavior index for three different bulk ionic number
concentrations. The general trend is that the friction coefficient increases with
increasing the flow behavior index. Also, a well-known friction coefficient of
24 for Newtonian fluids without electrokinetic effects is retrieved in this
figure. All these coincide with our expectations.
Figure 16 shows that the friction coefficient with EDL effects is always
larger than that without EDL effects. The electrokinetic effects intensify as the
ionic concentration decreases. However, for a concentrated solution of
n=6.0221023/m3, the electrokinetic effects vanish. As shown in the definition
of 1 = ( k BT / 2e 2 z 2 n )1/ 2 , a decrease of ionic concentration leads to a
thicker EDL, and thus the EDL exhibits stronger effects. Moreover, decreasing
ionic concentration elevates the friction coefficient in the pseudoplastic
domain more remarkably than that in the dilatant domain. This feature can also
be ascribed to the fact that the pseudoplastic fluids are more sensitive to the
hindrance of electroviscous effects.
97
50
40
Without EDL effects

20
3
n=6.02210 /m
21
23
Cf
n=6.02210 /m
n=6.02210 /m
30
20
10
0.7
0.8
0.9
1.0
1.1
1.2
1.3
Figure 16. Variation of friction coefficient with flow behavior index for three different
bulk ionic concentrations n = 6.022 1020 / m3 , 6.022 1021 / m3 and 6.022 10 23 / m3
with an applied pressure difference p=20kPa and a wall zeta potential w=-70mV.
2.7. Summary for Pressure Driven Flow of Power-Law Fluids

with Electrokinetic Effects
The electrokinetic effects on the liquid flow of power-law fluids through a
microchannel slit are studied analytically. An electrostatic body force is
considered in the Cauchy momentum equation governing the flow behavior of
power-law fluids to account for the electrokinetic effects caused by the
interaction of the channel wall EDL field and the induced streaming potential.
The analytical solutions to the Cauchy momentum equation is obtained by
using an approximate scheme. The expressions for the streaming potential,
velocity distribution, volumetric flow rate, apparent viscosity and friction
coefficient are derived. The computational results show that the electrokinetic
effects result in the velocity distribution distortion, and thus cause stronger
retarded flow of power-law fluids with smaller behavior index. Small
dimensionless electrokinetic diameters or dilute ionic concentrations can leads
to stronger electrokinetic effects, giving rise to larger apparent viscosity ratio
and higher friction coefficient. Overall, the electrokinetic effects in the
pseudoplastic domain are more remarkable than in the dilatant domain.
98
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99
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APPENDIX
In the following, we will define several auxiliary functions which
facilitate the analytical evaluation of the pertinent expressions in the second
100
part of present work. All these functions are obtained through integrations and
are found to have a combination of the incomplete Gamma function.
F ( n, x ) = x
1+
1
n
sinh ( x ) dx
1 1
1
1
1
= [ ( , x) ( x) n x n ( , x)]
2
n
n
(A1)
F1 ( n, x) = F ( n, x) dx
1
1
1 1+ 1
1
1
1
1
= [ x n (1 + , x)( x ) n (1 + , x) + x( , x) ( x) 1/ n x1+1/ n ( , x)]
2
n
n
n
n
(A2)
F2 ( n, x) = F ( n, x) cosh ( x) dx
n +1
n
1
1
( x) 1/ n {x n ( , 2 x) +
n
1
1
1
1
1
1+
1
1
1
+ ( x ) n ( , 2 x)2 n [ n( x 2 ) n x n ( , x) sinh ( x) + ( x) n ( , x) sinh ( x)]}
n
n
n
=2
(A3)
1+
F3 (n, x) = x
1
n
cosh ( x) dx
1 1
1
1
1
= {( x) n x n (2 + , x) + (2 + , x)}
2
n
n
H ( n, x) = x
2 +
1
n
(A4)
sinh 2 ( x) dx
1+
1 nx n
1
1
= [
+ 21/ n ( x) 1/ n x1/ n ( 1 + , 2 x) 21/ n ( 1 + , 2 x)]
2 1 + n
n
n
(A5)
101
H1 (n, x) = H (n, x) dx
1
1
1 1
= {21/ n ( x) 1/ n x1/ n [ x(1 + , 2 x) + ( , 2 x)]
n
2
2 n
n 2 x1/ n
1
1 1
21/ n [ x(1 + , 2 x) ( , 2 x)] +
}
n
n 1
2 n
(A6)
H 2 (n, x ) = H (n, x ) cosh ( x )dx

1+ n
1
+2
1
1
1
1
= {( x )1/ n x1/ n [(1 + , x ) 3 n (1 + , 3x ) + 2 n (1 + , 2 x ) sinh ( x )]
8
n
n
n
1
1+ n
+2
1
1
1
[ (1 + , x ) + 3 n (1 + ,3x ) + 2 n (1 + , 2 x )sinh ( x )] +
n
n
n
1
2n
1
1
[( x )1/ n x n ( , x ) ( , x )]}
+
( 1 + n )
n
n
(A7)
where ( , ) is the incomplete Gamma function.

ISBN 978-1-61668-570-6
Editor: I. A. Kuznetsov, pp. 103-134 2010 Nova Science Publishers, Inc.
Chapter 3
MICROFLUIDIC ELECTROCHEMILUMINESCENT DETECTION DEVICES

WITH CAPILLARY ELECTROPHORESIS
K. M. Muzyka1 and M. M. Rozhitskii2
Kharkiv National University of Raio Electronics, Laboratory of Analytical
Optochemotronics, Departament of Biomedical Electronic Apparatus and
Systems, Kharkiv, Ukraine
ABSTRACT
The purpose of this chapter is to describe the applications of
microfluidic principles for creation of capillary electrophoresis (CE) chip
devices with electrochemiluminescent (ECL) detection and to discuss the
problems associated with their interfacing and the approaches that have
been developed to surmount them.
Basic methodology, instrumentation, unique features, and specific
futures of microfluidic ECL detection with CE are discussed. ECL assay
detection types, such as direct and indirect analysis, coreactant use
including are considered.
Publications data of scientific centers, involved in development of
CE chips with ECL detection from the start of microfluidic CE/ECL joint
1
2
Email: mkm@kture.kharkov.ua
Email: rzh@kture.kharkov.ua
104

technique are summarized. Basic tendencies of this direction future
developments are covered.
ABBREVIATION
Auxiliary electrode
2-(2-aminoethyl)-1methylpyrrolidine
capillary electrophoresis
chemiluminescence
electrochemiluminescence
electrochemistry
electroosmotic flow
fluorescence
indium tin oxide
limit of detection
microfluidic chip
nanoparticles
printed circuit board
photomultiplier tube
polydimethylsiloxane
pulse electrolysis
quantum dots
reference electrode
signal-to-noise ratio
spectroscopic
tri-n-propylamin
tris(bipyridil)ruthenium (II)
working electrode
(AE)
(AEMP)
(CE)
(CL)
(ECL)
(EC)
(EOF)
(FL)
(ITO)
(LOD)
(MFC)
(NPs)
(PCB)
(PMT)
(PDMS)
(PE)
(QDs)
(RE)
(S/N)
(SP)
(TPrA)
(BR)
(WE)
INTRODUCTION
The important features in many areas of human activity are definition of
substances with low and trace concentration (medicine, ecology, food industry
etc.). Successful execution of such assays is possible using novel methods and
technologies, which have very low limit of detection (LOD), high selectivity,
Microfluidic Electro-chemiluminescent Detection Devices
105
very small dimensions and price such as lab-on-a-chip technologies and

devices.
Capillary electrophoresis (CE) technologies [1] in microfluidic chips
(MFC) have received considerable interest in analytical and bioanalytical
applications recently due to their promising features such as efficient
separation capabilities, high selectivity, short analysis time, very small
consumption of samples and reagents, portability, low assay and instruments
cost. On the other hand, the low sample consumption requires very sensitive
detection systems to be used. In general CE with fluorescent (FL),
electrochemical (EC), spectroscopic (SP) and chemiluminescent (CL)
detectors is well-known. However from the middle of this decade the efforts of
many researches are directed to implementation of electrochemiluminescent
(ECL) techniques in microchip CE devices [2-7].
ECL is a type of CL in which the light-emitting process is initiated by
electrochemical reactions. The electrochemically generated reactants undergo
subsequent electron transfer reactions with production of excited molecules,
which emit light.
In comparison with the most widespread EC, luminescent (especially FL)
and spectroscopic analytical methods ECL have very low LOD [8].
Interest to combine ECL analysis with separation methods appeared lately.
Notwithstanding that the term electrochemiluminescence was born in 1929,
the first papers devotes to ECL phenomena in CE devices in chip format have
appeared at the beginning of 2000. In contrast to microanalytical systems with
FL, CL, EC, SP detection [9-13], microfluidic ECL devices are on a stage of
development (Figure 1.).
Figure 1. The diagram of microfluidic devices with FL, SP, EC, CL and ECL detectors
since 2000 till 2010.
106
UNIQUE FEATURES OF ECL

The analytical characterization of the detection methods included the
evaluation of the following parameters: sensitivity, linear concentration range,
LOD, specificity and selectivity, response time, stability and reproducibility.
Among the top analytical features sensitivity, specificity and selectivity are the
most important in microfluidic applications. That is caused by a very low
amount at analyte concentration in submililiters MFD sample volume.
Sensitivity as analytical property can be ascribed as the ability to detect
(qualitative analysis) or determine (quantitative analysis) of small amounts of
an analyte in a sample. Sensitivity is defined by several parameters that
establish the minimum concentration that can be detect or determinated. Thus,
the LOD is the analyte concentration which produces a signal that can be
statistically distinguished from the blank signal.
Analytical method is selective if it can determine simultaneously several
components independently from each other. On the other hand, an analytical
method is specific if only one component (species) can be determined
independently from all the other components which give no analytical signal
in this case.
As an analytical technique, ECL possesses several advantages over other
most widespread methods (see Table 1). The ECL technique is very sensitive,
since very low light levels can be measured (e.g., by single photon counting
methods). ECL in comparison with photoexcitation has the advantage that a
excitation light source is not used, so scattered excitation light and
interferences by luminescent impurities emission are not the problems. This
results in low limits of detection in ECL assays as well as excellent selectivity
in comparison with FL detection.
ECL prosesses are much selective and possibilitics to computerization
(automation) than other chemiluminescent methods, since the electrochemical
excitation allows temporal and spatial control over light-emitting reactions.
ECL can be used to detect either the emitting species (which often serve as
labels) or a coreactant (see later) that ameliorate specificity [8].
Notice that selectivity and spesificity in various detecting methods can be
improved by different ways. So, the basic manner of selection in EC analysis
are electrolysis mode and potential change, in FL and spectroscopy change
of optical radiation wave length; in CL change of reagents and media.
Table 1. Competitive matrix of ECL and widespread detection methods on a microfluidic chip
TYPES OF TRANSDUSERS
ATTENDANT PROBLEMS AND CHARACTERISTICS OF DETECTIONS METHODS
ECL
CL
FL
SP
EC
Analytical
signal time
control
Varying
electrode
potentials
possibility
Background
currents of
electrolysis
Scattered
excitation
light and
luminescent
impurities
Analytical
signal
position
control
Light source
Optical
filters
Photodetector
sensitivity
Improving
sensitivity
Selectivity
increasing
Sensitivity
decreasing
Sensitivity
decreasing
Multianalyteanalysis
Cost and
dimensions
increasing
Cost and
dimensions
increasing
Necessity
of
registration
of faint and
superfaint
light flux
Yes
Difficult
Yes
Yes
Yes
Yes
No
No
No
Yes
No
No
No
No
Yes
No
No
Yes
Yes
No
Yes
No
Yes
Yes
Yes
No
No
Yes
Yes
No
No
No
Yes
Yes
No
Yes
Yes
No
No
No
Disadvantages
Advantages
Tables color scheme (dark corresponds to disadvantage, light advantage) indicated

unique characteristics of ECL analysis in comparison with related detecting methods
108
ECL ANALYSIS TYPES

The Direct and Indirect ECL Analysis
In the first case the objects of detection are substances (analytes), which
possess its own ECL, in the second one all substances that can influence
ECL of reactants substances [14-17]. Direct analysis has some specific issues,
such us:
own ECL (sufficient quantum efficiency of luminescence);

EC activity of the determined components;
presence in solution or on the electrode surface electrone donors
or acceptors which in electron transfer reactions with the
electrooxidized or electroreduced analyte create electron-excited
molecules.
These requirements satisfy significant numbers of electrochemilumiphores

of various chemical classes [8, 18, 19]. Tris(bipuridil)ruthenium(II)
(Ru(bpy)32+) (BR) complex and its derivatives [20] are the most used due to
rather high (in comparison with luminol) selectivity with a high ECL emitters
output in reactions with determined components.
ECL with Creactant

Due to high energy of annihilation, narrow working potentials window for
conventional metal electrodes and poor solubility in water of organic
compounds method of classical ECL excitation known for aprotic solutions
can not in general be utilized in water and bioliquids assays due to narrow
working potential range in water.
Among possible solution of mentioned problem is using so called
coreactants. They can produce highly reducing or oxidizing radicals species
that can react with an oxidized or reduced ECL luminophore to generate
excited states. Unlike ion annihilation ECL, in which electrolytic generation of
both the oxidized and reduced ECL precursors is required, ECL with
coreactants can be generated with one direction potential scan of an electrode
in a solution containing luminophore species (emitter). To be a good ECL
coreactant, a number of criteria need to be met, namely [21]:
109
solubility,
electrochemical activity,
reactions participation,
absence of background ECL, etc.
Among those the reduction/oxidation properties of the coreactant play

important role. The coreactant should be easily oxidized or reduced either at
electrode processes or by the luminophore species near the electrode and
undergo a rapid chemical reactions to form an intermediate with subsequent
productions luminophore excited state [14].
The most widespread reactant for ECL emission are oxalates and
tertiary amines [14, 21, 22]. The TBR/tri-n-propylamin (TPrA) ECL system, a
good example of an oxidativereductive system, has been extensively studied
[23].
BASIC METHODOLOGY OF CE/ECL ANALYSIS

IN MICROFLUIDICS
The majority of CE/ECL MFC embodies two essential stages. On the first
one the substances of interest are isolated from the matrix of the sample by
separation; on the second one identification and quantitatively determination
of analytes are taking place. Whereas CE realized in central body structure of
MFC with the microscale channels which define the selectivity of analytes
determination, detection element of MFC characterizes sensitivity of analysis.
Capillary electrophoresis is the motion of charged particles relative to the
surrounding liquid due to an imposed external electric field. In contrast,
electroosmosis is the electrically driven motion of a liquid relative to the walls
of the solid borders. Separation in electrophoresis is based on differences in
solute mobility that is the cause of probes dividing on individual zones. The
efficiency of this separation process can be described, by analogy with
chromatography, in terms of the number of theoretical plates. The difference
necessary to resolve two zones is dependent on the zone length; the latter is
strongly dependent on the dispersive processes. Dispersion should be
controlled because it increases zone length and the mobility difference
necessary to achieve separation. Dispersion, or spreading of the solute zone,
result from differences in solute velocity within that zone, and can be defined
as the baseline peak width.
110
The velocity of migration, u, of particular ionic species in buffer solution

is given by:
u = a E ,
(1)
where
a = e + eof the apparent solute mobility, (m2.V-1.s-1);

e, eof electrophoretic and electrosmotic mobilities accordingly;
E applied electric field, V/m.
Thus, due to difference in electrophoretic particles mobility probes zones

reach detection zone at different time. The received peaks sequence presents
so called electrophoregramme.
The typical MFC contains two microchannels that crossed at an
intersection while the ends of the microchannels are connected with reservoirs
(Figure2).
Chemical analysis can be divided into steps of sampling, sample
preparation, separation, detection, and data processing.
Because of the minute sample volumes and masses used in microfluidic
CE, LOD are often relatively poor. However, by using preconcentration
techniques, improved concentration LOD and separation properties can be
realized for biological analytes.
Generally, MFC operations can be divided onto the following stages.
During the first stages the sample is injected by applying high voltage between
reservoirs 3 and 4 (Figure 2, a). A very small plug (of pl volumes) can be
introduced, with dimensions approximately the same as the channel width
(Figure 2, b). For electrophoresis, the second stage, the reactant is injected
electrophoretically into the intersection resulting in a sample plug shiffing.
The separation is performed by applying a voltage between reservoirs 1 and 2.
The sample plug then moved into another reservoir 2 through detection zone
(Figure 2, c). At this zone, ECL is emitted and is detection is performed as the
third stages.
There are analytical characteristics of ECL analysis such as spectral and
integral intensity linked by certain dependence to analyte concentration,
providing possibility to define it by measurement of light intensity.
Microfluidicc Electro-chem
miluminescent Detection Deevices
1
111
(A)
(B)
(C)
Figure 2. MFC design (Reservoirs:
(
1 buffer solutionn, 2 sample inj
njection waste, 3
sample, and 4 waste) and electrophorresis procedures, (b) schematicc representationn of
sample injection (doublle-T structure foor sample injecttion), (c) pullingg back to form a
p
and (d) sepparation. The caationic analyte (1) has the highhest mobility
sample plug,
followedd by the neutralss (n) and two annionic analytes (2, 3).
112
ECL INSTRUMENTATION
An ECL system often includes two sub-units [8]: optical part for
luminescence detection and electrochemical one that initiates the ECL
reaction.
Optical Part of ECL Mode

An efficient and accurate light detection is a common need to all
analytical luminescence methods. The size of the required photosensitive area
of the detector varies depending on the application. Usually high detection
sensitivity of photodetector is required, but the detector must also be able to
register many orders of magnitude higher light fluxes than those corresponding
to LOD of the analytes in question [24].
Photomultiplier Tube
The photomultiplier tube (PMT) is the most popular device adopted for
collection of the luminescence signal for its high sensitivity.
Channel Photomultipliers
Channel photomultipliers (or microchannel plate photomultipliers) are
performing better than ordinary PMTs. In these devices, electrons from the
photocathode pass through a narrow semi-conductive channel. Multiple
secondary electrons are emitted each time the electrons on their way to the
anode hit the inner wall of the curved channel. This effect occurs multiple
times along the path, leading to an avalanche effect with a gain exceeding 108.
These detectors also have extremely low dark current (much lower than the
traditional PMTs), but they require special high voltage sources due to the
needed very high operating voltage of 24003000V.
Diode array
Relatively large and rather costly PMT detection system which also
requires high voltage to achieve maximum sensitivity is mainly suitable for
laboratory analysis. To overcome the size and cost limitations of PMTs, in
some of the ECL set-ups PMT are replaced with small device, such as a silicon
PIN diode that could be operated at low voltages. Semiconductor
113
photosensitive devices can occasionally be used when sensitivity is not the

first consideration [25].
Electrochemical Part of ECL Mode

Having the character of an EC method, ECL detection has great potential
for miniaturization the electrode can be directly formed on the chip by a
thin-film photolithographic procedures. The well developed micro-electronics
industry makes it possible to effectively produce integrated microfluidic-ECL
systems with high reproducibility at rather low cost.
ECL detector cell typically consists of three electrodes the working,
auxiliary, and reference placed in electrolyte solution. ECL assay is
controlled by application of the desired potential to the working electrode.
Types and characteristics of ECL electrodes are shown in table 2.
Table 2. Types and characteristics of ECL electrodes
TYPE OF
ELECTRODES
Working (WE)
Reference (RE)
Auxiliary
(counter) (AE)
CHARACTERISTICS
WE is the electrode in an EC/ECL system on which the

reaction of interest is occurring, therefore electric current
flow through this electrode and subsequent ECL emission
constitute the analytical signals. The minimum
requirements are reasonable degrees of electrochemical
inertness and electrical conductivity, optical transparency
and minimal rate quenching of excited states near
electrode surface
RE is an electrode which has a stable and well-known
electrode potential in a given electrolyzed solution. The
high stability of the electrode potential is usually reached
by employing a redox system with constant (buffered or
saturated, e.g. saturated calomel, Ag/AgCl, etc.)
concentrations of each participants of the redox reactions
AE is needed to provide a current path that closes the
electrical circuit
114
The chemical composition/structure of the WE can vary considerably, and

a proper selection is often critical to achieving success in a given application.
Wide-spread WE include metals, such as Pt, Au, or Hg, semiconductors
(indium tin oxide (ITO)), carbon. Notice that the optical transparency property
makes ITO electrodes an ideal electrode material for ECL analysis. In
addition, the surface of these electrode materials can also be modified
chemically by a number of different approaches in order to optimize
performance for a specific EC and ECL process [26]. For example, the charge,
polarity, porosity, and specific chemical and biochemical reactivity can be
adjusted by the addition of appropriate functional groups, self-assembled
mono- and multilayers, and polymer coatings [27].
A representative three-electrode ECL detection configuration and a
simplified potentiostat circuit are shown in Figure 3. The WE and RE are
placed in the amplifier feedback loops so that the voltage difference between
them must match an adjustable external voltage source. Because the
composition of the RE is designed to maintain its potential at a constant value,
the WE potential is just the external voltage compared to or versus the
specific RE. The RE is connected to a high input impedance buffer amplifier,
which serves to limit the current flow through it to a negligible level, which in
turn serves to keep RE composition unchanged and its potential at its starting
value. The oxidation or reduction reactions occurred when an electroactive
analyte at the WE produces current flow that is then converted into ECL signal
trough appropriate sequence of reactions.
Figure 3. Scheme of EC part of microfluidic ECL mode.
115
The three-electrode systems are generally used, but for simple applications
the two-electrode system can be utilize also. At that AE function is combine
with RE and lead to design simplicity. However two-electrode systems have
not full potential control possibility. In the simple EC system it is not a
problem, but for high precision analysis three-electrodes systems will be
needed. If two-electrodes systems is been used then several criteria ought to be
accomplished, such as electrodes surfaces ratio, its geometry etc. [8].
Working Electrode Placement in CE/ECL Detection

There are many diverse separating procedures and many different
identifying instruments, and each particular combination demands a unique
interface. CE/ECL combination is difficult but, nevertheless, can be
successfully achieved by the use of some cleverly designed interfaces. In the
microfluidic system, the separation electric field has profound effects on EC
detection as well as the conventional CE. Three different approaches have
been developed for this purpose and are depicted in Figure 4. These
approaches are termed end-channel, in-channel, and off-channel detection [28,
29].
Figure 4. Four configurations for aligning the WE in EC as well as ECL detection that
facilitate isolation of the detector from the separation voltage. Reprint from ref. [28]
with modification.
As well as in electrochemical mode, the placement of the WE in CE/ECL

detection systems can be divided into three different categories, off-channel,
end-channel and in-channel detection (see table 3).
116
Table 3. Special set-up and characteristics of three modes of CE/ECL

detection systems
Set-up
Characteristics
END-CHANNEL
Potential shifts at the WE due to the
Set-up with precise electrode
remaining separation field;
positioning (just beyond the end of
band-broadening and decreasing
the separation channel in the CE
detector response due to diffusion;
buffer reservoir) is needed;
higher background currents and less
the WE is positioned tens of
sensitivity than the other detection
micrometers from the exit of the
modes;
separation channel;
decreasing separation efficiency due to
the separation voltage could be
grounded through the potentiostat to the analyte diffusion that occurs in the
area between the exit of the separation
prevent electronics damaging
channel and the WE;
suitable for single-use, disposable
microchips.
OFF-CHANNEL
The decoupler effectively shunts the
Placing the WE directly within the
separation voltage to ground;
separation channel;
Electroosmotic flow (EOF)generated
an additional decoupler is needed,
before the decoupler;
e.g. electrically conducting
decoupler can absorb hydrogen evolved
fracture and thin crack, opening
on the capillary electrophoretic ground
or hole created in the capillary,
electrode;
channel wall is in a short distance
technical difficulties to implement.
from the exit.
IN-CHANNEL
Limitation due to bubble generation in
Placing the WE directly within the
the channel;
separation channel;
decreasing the electrochemical signalan electrically isolated potentiostat
to-noise (S/N) ratio;
is needed.
background current generated at the
surface of the WE;
elimination of the band-broadening.
117
MICROFLUIDIC DEVICES PROBLEMS

It should be notice that LOD reduction in joint CE/ECL devices can be
reached not only by improving detection, but also by peaks broadening
reduction.
The Major Factors Loss of Separation Efficiency

The major factors bringing loss of separation efficiency (peaks
broadening) as follows [30]).
(1) Radial diffusion. In contrast to high-pressure liquid chromatography
where diffusion has three components, in CE only longitudinal
diffusion is taking place.
(2) Dispersion due to Joule heating, At worst Joule heating could result
in convective overturning that obliterates all bands or production of
microbubbles, resulting in complete blockage of EOF and current
(vapor lock). In modern CE systems with capillary diameters less
than 100 m, such failures are rare; however, Joule heating can be a
significant source of band broadening [31].
Elimination of these effects is possible by changing of a capillary
diameter and concentration of the buffer reducing and/or applying the
buffer with low ionic conductivity and, also, capillary cooling.
(3) An electric dispersion (electric field local infringement). The
phenomenon is caused by the big distinction of conductivity in the
buffer and in a zone of test, heterogeneity of zeta-potential [31, 32]
(because of a roughness of a surface of the channel, heterogeneity of
the channel material, absorption on walls, a variation of buffers
values) [33]. Undesirable effects are eliminated, using special
coverings and high concentrated buffers and also providing the
minimal roughness and the maximal uniformity of the channel [34].
Electric field local infringement is possible due to bubbles
formation (H2 and O2) as a result of the electrolysis. This effect can be
suppressed partly by all solution filtration, WE positioning concerning
the separation channel end, change of [35].
(4) Dispersion due to channel curvature [30]. This can be observed, for
example, using of the serpentine channel (this is frequently done for
the chip contraction).
118

(5) Probes zone passive transport due to great EOF values [30].
Adjusting buffer pH and channel surface properties leads to EOF
suppressing.
Precise design and operational control of the liquid matrix separation

process are keys to performance of microfluidic CE analysis. In a typical
separation experiment there are a number of parameters affecting the system
performance. These can be broadly categorized as parameters determined by
the chemical peculiarities such as mobility of ions, diffusion coefficients,
sample concentration and EOF mobility; detector controlled parameters such
as width of the detector, sensitivity and noise level; and some other parameters
such as width of the sample plug, distance to the detector, electric field
intensity. In general the designer has little control over the first set of these and
the second are typically limited by the equipment available.
One example from the engineering point of view the fluid flow
mechanism occurring in CE separation channel was analyzed in [36]. Onedimensional model of electrokinetic sample motion was developed to simulate
the separation process of sample with aminoacids (tryptophan, tyrosine,
proline, methionine) that migrate in buffer solution through straight
polymethylmethacrylate separation channel within microfluidic chip under
different conditions [36]. On this basis optimal channel size, chip material,
applied voltage and pH dependencies on separation efficiency were predicted.
This is important to know before chip fabrications and assay conducting.
CE/ECL Key Specific Futures

In CE/ECL technology combination of two complex measuring systems
must be achieved with neither influencing upon the other.
For CE as well as ECL detection some problems that have affected
analytical mode are peculiar. The main problem for CE is the large numbers
effect that results in enhanced dispersion, which limits the efficiency of
separation.
There are also hardships for ECL with respect to right choose of ECL
excitation modes.
Linear sweep voltammetry is a voltammetric method where the current at
a WE is measured while the potential between the WE and a RE is swept
linearly in time. Oxidation or reduction of species is registered as a peak or
trough in the current signal at the potential at which the species begins to be
119
oxidized or reduced. The main disadvantage of this technique is the rapid

electrode fouling. For example, after the oxidation process, some analytes will
form a thin layer on the electrode, decreasing the effective area and
therefore, the signal. Coating or mechanical treatment the electrodes can solve
this problem, however, they require disassembly of flow cells and lengthen
time between runs. Therefore, the use of pulse electrolysis (PE) is a way to
overcome problems associated with electrode fouling (see Table 4).
PE can be considered as a derivative of linear sweep voltammetry, with a
series of regular voltage pulses superimposed on the potential linear sweep or
stair steps. The system for this measurement is usually the same as that for the
standard voltammetry. The potential of WE is repeated for about 5 to 100
milliseconds, changing the final potential, and a constant difference is kept
between the initial and the interlevel potential.
PE is an excellent method for detection of analytes that can foul
electrodes, espessially in microfluidic applications at water and bioliquids
assay. WE cleaning and reactivation potentials can be identified by performing
cyclic voltammogram and looking for the electrode oxidation and reduction
potentials. It is worth noting that the electrode requires the possibility of being
oxidized and reduced without significant loss of its material. For this reason,
gold and platinum have been extensively used in a variety of media [37],
unlike electrodes with diamond-like films (see later).
In PE, the WE electrode is first cleaned at a high potential, then
reactivated at a opposite potential dissolving the surface contaminant, and
finally used to determinate the analyte at a moderate positive potential.
Moreover, in MFD with ECL detection PE using is very promosing
because of the following two features:
(1) in these measurements, the effect of the charging (non faradic) current
can be minimized, so higher assay efficiency can be achieved;
(2) faradaic current can be extracted, so electrode reactions can be studied
more precisely.
Due to the advantages and versatility of PE, many different variations of
the detection waveform is be described [37].
However, two problems are still present. First by, specific (and sometimes
more expensive) instrumentation is required. Second by, there are more
variables to adjust than using linear sweep voltammetry, so longer
optimization time than simple electrochemical techniques is required.
For CE/ECL systems, however, there are key specific issues that must be
taking into account. The main features are presented in Table 4 [21].
120
Table 4. Specific futures of ECL microfluidic detection

PROBLEMS
Redox potential change

of the analyte species
due to its affect on
electrical current under
high electric field
Poor sensitivity and
reproducibility
(e.g. too short distance
would block the ECL
reactant diffusion and
too long one would
lower the analyte
concentration at the WE)
Band broadening at short
length (e.g., a few
centimeters) of detection
capillary
ECL excitation mode
right choose
LOD LOWERING
FACTORS
The elimination or
reduction of the CE
current from the
Faradic current of
analyte/reactant species
DECISION
Use of CE decoupler
The distance between

the end of the capillary
and the WE needs to be
optimized
Necessary high
precision of the
alignment or
arrangement of the
WE against the
detection zone and
the photodetector
should be rached
Rising pressure in the

capillary due to electric
field gradient absence
in the detection zone
Length of the
detection zone should
be optimized
WE fouling during
electrolysis
PE mode or
disposable electrodes
should be used
KEY RESEARCH FINDINGS

CE/ECL microdevice concept was first demonstrated by Manz et al. in
2001 [38]. In their article, a microfabricated glass device was characterized for
micellar electrokinetic chromatography of Ru(bpy)33+ and Ru(phen)33+. In this
design the legs of a U-shaped Pt electrode placed across the separation
channel act as the WE and AE. The required potential difference for the ECL
reaction is supplied by the electrophoretic electric field. Indirect detection of
three amino acids (proline, valine, and phenylalanine) was also reported. Later,
Crooks group reported one- [39], two- [40], and three-channel microfluidic
sensors [41] that could detect redox reactions indirectly using anodic
coreactant ECL [i.e., TBR/TPrA system].
121
As shown on Figure 5, a [41], a one-channel microfluidic device,

incorporating either one or two electrodes, is able to detect electrochemical
processes at the cathode and provide information about them via light
emission at the anode.
(A)
(B)
(C)
Reprinted from [41].
Figure 5. Scheme of microfluidic devices.
Similarly, a two-electrode, two-channel microfluidic device (Figure 5, b)

can be used in the same manner, but with complete chemical separation of the
detection and reporting (light-emission) functions. The one- and two-channel
methods, however, permit detection only of analytes that can be reduced when
the Ru(bpy)32+/TPrA system is used. This problem was overcome by using a
multichannel approach, such as the three-channel configuration (Figure 5, c).
In this case, channel 1 houses the cathode and a flowing solution of an
electroactive molecules [e.g., Ru(NH3)63+] that can be easily reduced. A
solution containing Ru(bpy)32+/TPrA flows in channel 2 and the oxidizable
analyte of interest is present in channel 3. Both of these channels share a
common anode. When a sufficiently large potential is applied between the
122
cathode and anode, Ru(NH3)63+ is reduced to Ru(NH3)62+, whereas Ru(bpy)32+

and TPrA are oxidized. In the absence of a redox-active analyte in channel 3,
maximum light emission is observed at the anode. However, when an
oxidizable analyte is present in channel 3, it competes with the ECL reactions
in channel 2 to provide electrons for the cathodic reduction in channel 1. This
results in a decrease in light intensity from the electrode in channel 2,
indicating the presence of the target analyte. Reducible analytes can be
detected also with this three-channel method. For example, if only buffer is
present in channel 3 and the analyte is present in channel 1, then the device is
essentially identical to the two-channel device shown in Figure 5, b. All three
proposed schemes are based on charge balance between the anode and
cathode. In other words, the cathode current must be equal to the anode one.
Accordingly, there is a correspondence between the number of electrons
consumed at the cathode and the ECL photons emitting at the anode.
An integrated ITO electrode-based Ru(bpy)32+ ECL detector for a
polydimethylsiloxane (PDMS) microchip CE device (Figure 6) was first
reported by Wangs group in 2003 [42]. The microchip CE-ECL system
described in this article consists of the PDMS layer containing separation and
injection channels and an electrode plate with an ITO electrode fabricated by a
photolithographic method. The PDMS layer was reversibly bound to the ITO
electrode plate, which greatly simplified the alignment of the separation
channel with the WE and enhanced the photon-capturing efficiency.
Moreover, the high separation electric field had no significant influence on the
ECL detector, and decouplers for isolating the separation electric field in the
microchip CE-ECL system were not needed. Proline was selected to test the
microchip device with a LOD of 1.2 M (S/N = 3) and a linear range from 5 to
600 M.
Reprinted from ref [43].

Figure 6. Schematic of the detection region enlargement in microchip CE-ECL device.
Distance between the separation channel outlet and the ITO electrode is 30 m.
123
The transparency of the ITO material makes these electrodes superior to

the more widely used platinum-based electrodes, because of sufficient
diminishing of ECL quanta losses.
This microchip CE-ECL system can be used for the rapid analysis of
lincomycin. Under the optimized conditions, the linear range was obtained
from 5 to 100 M with correlation coefficient of 0.998. The LOD of 3.1 M
was obtained for lincomycin in the standard solution. This method was used
for determination of lincomycin in the urine matrix without pretreatment. The
LOD of 9.0 M was obtained.
In dual detection scheme TBR was used as an ECL reagent as well as a
precursor (in the formation of Ru(bpy)33+) for the EC detection [4]. In the
Ru(bpy)32+-ECL process, Ru(bpy)33+ was generated and then reacted with
analytes resulting in an ECL emission and a great current enhancement in EC
detection due to the catalysis of Ru(bpy)33+. In the experiments, dopamine and
three kinds of pharmaceuticals, anisodamine, ofloxacin, and lidocaine, were
selected to validate this dual detection strategy. Typically, for the EC detection
of dopamine with the presence of Ru(bpy)32+, an approximately 5 times higher
S/N can be achieved than that without Ru(bpy)32+ during the simultaneous EC
and ECL detection of a mixture of dopamine and lidocaine using CE
separation. The results indicated that this dual EC and ECL detection strategy
could provide a simple and convenient detection method for analysis of more
types of analytes in CE separation than in the sole EC or ECL detection alone.
Additionally more information about detected analytes could be achieved
using this assay mode.
The solid-state ECL detector was fabricated by immobilizing TBR into an
Eastman AQ55D-silica-carbon nanotube composite thin film on an ITO
electrode [44]. After being made by a photolithographic method, the surface of
the ITO electrode was coated with a thin composite film through a
micromolding in capillary technique using a PDMS microchannel with the
same pattern as an ITO electrode. Then the TBR was immobilized via ion
exchange by immersing the ITO electrode containing the thin film in TBR
aqueous solution. The whole system was built by reversibly sealing the TBRmodified ITO electrode plate with a PDMS layer containing electrophoresis
microchannels. The results indicated that the present solid-state ECL detector
displayed good durability and stability in the microchip CE-ECL system.
Proline was selected to test the microchip device with a LOD of 2 M (S/N=3)
and a linear range from 25 to 1000 M. In comparison with the CE-ECL of
TBR in aqueous solution, while the CE microchip with solid-state ECL
124
detector system had the same assay sensitivity, a much lower TBR
consumption and a high integration of the whole system were obtained.
The microchip CE/ECL system utilizes tertiary amine derivative, 2-(2aminoethyl)-1-methylpyrrolidine (AEMP) determination [45]. The system was
characterized by the interaction between biotin and avidin. A 4.5 cm
microchannel was used to separate the mixture of AEMP and biotinylated
AEMP. The results indicated that AEMP has a good reactivity to the analytes
containing carboxyl group with a similar ECL efficiency to TPA. Under
optimal condition, the LOD (based on 3 S/N) of AEMP was 2.7 M. The
system was also validated by the reaction between biotin and avidin. The
calculated binding ratio between avidin and biotin based on the present
method was 4.4 [45].
Printed circuit board (PCB) based technology to integrate ECL analysis in
microfluidic systems was used in [46]. PCB gold macro- (10 mm2) and micro(0.09 mm2) electrodes and two ECL microfluidic devices were designed,
fabricated and tested with luminol ECL detection. Potential modulation was
performed between 0.7 and 0 V vs. Ag/AgCl for luminol oxidation, thus
giving rise to on/off ECL responses in the presence of hydrogen peroxide.
Synchronous detection was adopted to allow weak ECL signal recovery at a
very low S/N ratio. The LOD obtained with the two ECL microfluidic devices
was 50 nM and 100 nM H2O2 for macroelectrodes and microelectrodes,
respectively. Similar results were published in [47, 48].
The Japanese researchers have developed ECL microfluidic system for
amino acids determination [49, 50]. The ECL chip for mercury ions definition
with LOD of 66 n at a current 1.85 p is created [51]. There are also other
publications on microfluidics ECL systems [52, 53].
A microfluidic cell designed to transport and mix two different solutions
on the chip and generate ECL using TBR as luminophor and amino acids as
coreactants was presented recently by Hosono et al. [54]. The fabricated
system consisted of the PDMS substrate with a flow channel structure and
three-electrode systems formed on a glass substrate that resulted in the
microfluidic transport and the ECL emission. An amino acid and a reagent
solution containing TBR were transported by electrowetting by applying a
negative potential to gold WEs formed along the flow channels. The two
solutions were then mixed in the mixing channel using an additional gold WE
formed between the electrodes for transport. ECL was generated by applying a
potential to a platinum WE formed in the mixing channel. The ECL from lproline, l-lysine, l-leucine, l-valine, and l-histidine was registered.
125
Solid state ECL detectors coupled with microchip CE by immobilizing

TBR into either Eastman AQ55Dsilica carbon nanotube composite thin film
on a patterned ITO electrode or zirconia-Nafion composite on a glassy carbone
disk electrode have been constructed and used for the detection of proline and
pharmaceuticals of tramadol, lidocaine, and ofloxacin [55]. Detailed
fabrication of the other solid state ECL detector can be found in ref [56].
GEOGRAPHY OF SCIENTIFIC CENTRES

Scientific centers engaged in research and application of ECL
phenomenon in a combination with CE are concentrated in East Asia,
basically, in China. In the first turn it is Prof. E. Wangs group (Lab. of
Electroanalytical Chemistry, Changchun Institute of Applied Chemistry of the
Chinese Academy of Sciences), but development and applications of
microfluidic ECL devices are done in France, Great Britain, Canada, USA and
some other countries. The basic centers on these subjects are summarized in
table 5.
POSSIBLE FUTURE DEVELOPMENTS (BASIC TENDENCIES)

At present CE/ECL systems have been developed. Unification of
separation and ECL detecting techniques are obvious aspects of this
phenomenon. Further improving of CE/ECL system and its miniaturization are
possible by using of micro- and nanotechnologies opportunities.
ECL analytical characteristics can be improved by development and use of
new electrode materials. Electrodes covered by diamond-like films exhibit
enhanced sensitivity compared to a commonly used thick-film carbon detector.
Their advantages in the ECL analysis in comparison with electrodes from
carbon or platinum are caused by stability, reproducibility of surface condition
(frequently without regular recycling processing), wide area of ideal
polarization, low size of electrolysis background currents. Electrode stability is
caused by inertness to adsorption of reagents and products of reaction, and
also by tolerance to dissolved oxygen in water solutions (both alkaline and
acid). The first articles on the given subjects have appeared in 2003 [57-59]
though electrochemical research of doped diamond began about twenty years
ago by Yu. Pleskov [60]. Doped diamond electrodes are promising candidates
126
as the electrode material for ECL chip devices with a wide ECL potential
region and high stability [60-63].
Table 5. Scientific centers involved in development of CE chips
with ECL detection
Scientific centers
Dalian University of Technology: Laboratory of Precision and
Non-Traditional Machining Technology.
Key Laboratory for Micro/Nano Technology and System of
Liaoning Province.
Chinese Academy of Sciences State (Changchun): Key
Laboratory of Electroanalytical Chemistry, Changchun Institute
of Applied Chemistry
Korea University (Seoul): Departments of Biomicrosystem
Technology. South Korea
University of Tsukuba: Graduate School of Pure and Applied
Sciences
Universit Claude Bernard (Lyon): Institut des
Nanotechnologies de Lyon (INL), CNRS;
Institut de Chimie et Biochimie Molculaires et
Supramolculaires (ICBMS), Laboratoire de Gnie
Enzymatique et Biomolculaire (LGEB),
Institut des Nanotechnologies de Lyon (INL), CNRS.
Univ. Sci./Technol. (Lille), CNRS
Universit de Montral Institute for Microstructural Sciences,
National Research Council Canada, Dpartement de Chimie
University of Manchester School of Chemical Engineering
and Analytical Science.
Institute of Research in the Applied Natural Sciences
(Luton)
University of Neuchatel: Institute of Microtechnology,
Sensors, Actuators and Microsystems Laboratory
Petroleum University of Technology
University of Athens: Laboratory of Analytical Chemistry,
Department of Chemistry
Cornell University (Ithaca): Department of Biological and
Environmental Engineering.
Innovative Biotechnologies International, Inc., Grand Island
Countries
China
Korea
Japan
France
Canada
Great
Britain
Switzerland
Iran
Greece
USA
127
It is necessary to remember that new electrode materials use will demand

new fabrication technique development, resolving the problems of studying
materials properties and their application.
Another possible tendency is electrochemilluminophore immobilization
on electrodes surface (creation of solid-state devices). It allows to save
expensive reagents, to use electrodes repeatedly, to simplify the system design
and miniaturized it, to expand analytes range due to possibility of use
insoluble in water electrochemiluminophores [27]. The first article on TBR
immobilization was published in 1980 [64], works in this direction continue to
be published until now [65-67], and development of micro- and
nanotechnologies contributes to "solid-state" detectors tendency strengthening.
Scientific and technology progress of this direction can be achieved in
matrixes, new electrochemiluminophore-reagents, and also immobilization
techniques development [68-72].
Nanodimension
materials,
as
alternative
to
traditional
electrochemiluminophores one more step in improvement of analytical
characteristics of chip-using ECL detectiong. Semiconductor nanocrystals or
quantum dots (QDs) are bright and photostable materials with broad excitation
spectra but narrow Gaussion type emission spectra superior in comparison to
conventional organic fluorescent dyes. Furthermore, their emission positions
are tunable in a wide emission range from ultraviolet to near infrared
depending on QDs radius due to the quantum confined effect.
ECL study of semiconductor nanoparticles (NPs) (also known as
nanocrystals, QDs) was first reported in 2002 for Si NPs, where ECL was
generated from both annihilation and coreactant oxalate and persulfate systems
in MeCN [73]. Moreover, the increasing numbers of publications indicate a
growing interest to this direction, and its wide analytical perspectives.
CONCLUSION
In spite of the fact that microfluidic principles with ECL detection yet
have not so widespread in comparison, for example, with fluorescent methods
(see Figure 1), their numerous positive characteristics allow to solve difficult
analytical tasks quite simple and effectively. The opportunity of decrease in
LOD, increase in sensitivity of the analysis with the help of new types of
electrodes and luminophores also raises interest to this area [74].
Despite the obvious CE/ECL potential advantages, presence of
experimental samples yet has not led to commercial products creation.
128
However it is connected most probably not to the analytical reasons, but to

technical, organizational and information one. It is reasonable to suggest, that
the stage of industrial samples creation and their active use in practice now
begins; there is no doubts in the broadest opportunities of ECL applications.
That is why in the nearest future the commercialization of ECL
microfluidic-chips and their wide utilization will be more and more obvious.
ACKNOWLEDGMENT
We express our sincere appreciation for financial support from Scientific
and Technology Centre in Ukraine (Projects ## GE 77, 4180, 4495).
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ISBN 978-1-61668-570-6
Chapter 4
MICROFLUIDIC VALVES WITHOUT

DIAPHRAGMS: HYDROGEL VALVES AND
PDMS-BASED ROTARY SELECTION VALVES
Steffen Howitz1, Frank Baudisch1, Frank-Ulrich Gast1,
Andreas Richter2, Andreas Grodrian3, Gunter Gastrock3,
and Josef Metze3
1
GeSiM mbH, 01454 Grosserkmannsdorf, Germany

Technische Universitt Dresden, Institute of Semiconductors and
Microsystems, 01069 Dresden, Germany
3
Institut fr Bioprozess- und Analysenmesstechnik e. V., 37308 Heilbad
Heiligenstadt, Germany
2
ABSTRACT
Microfluidic networks consisting of more than one channel must
often be controlled by valves. External valves are sturdy, but low dead
volumes require internal valves. Many present-day valves contain
membranes (that are, e.g., driven by air pressure) that become leaky by
overpressure or particles, and simple microfluidic valves control only a
single channel at a time. We describe here two different new approaches:
a hydrogel valve, which is robust, and a rotary valve, which is versatile.
Both valves are pressure-stable. The hydrogel valve contains a
microfluidic chamber filled with hydrogel particles that are swollen and
thus close the valve at room temperature (i.e. normally closed 2/2-way
136
Steffen Howitz, Frank Baudisch, Frank-Ulrich Gast et al.

valve). Upon heating, the hydrogel becomes dehydrated and opens
reversibly in two to four seconds. This valve is robust, autoclavable, and
can retain cells without stressing them. The rotary valve contains a valve
seal cast from poly(dimethylsiloxane) (PDMS) with one or more
micromolded channels of extremely low dead volume; it can be turned, in
just 250 milliseconds, to a new position by air pressure or a micromotor,
thereby connecting new inlet and outlet holes. Many different setups of a
multiple-way selector/injector valves can be realized, and so it is
probably the most versatile and quick microfluidic valve available today.
To reduce swelling and abrasion and to allow thousands of cycles, the
PDMS rotor is metal-coated. These two valves represent attractive new
ways to control flows in microfluidic applications.
INTRODUCTION
Around 1990, a novel concept, micro total analysis system or TAS,
emerged [1-3], in which chemical sensors were placed in small channels that
were fabricated with methods used in microelectronics. Since then, this
concept has matured into systems suited for such diverse tasks as chemical
synthesis [4], chemical sensing, or processing and analysis of biological
material [1,2]. Whereas the first systems were controlled by constantly driven
syringe pumps and so contained mostly simple branches to mix and separate
fluids, the growing complexity, e.g. for the preparation of biological samples,
required the integration of actuator systems such as mechanical microvalves.
Today a multitude of valve designs exists [5].
Many valves are based on a membrane or diaphragm [5-10, further
citations in 11 and 17] that is either actively actuated using different methods
or passively driven by the fluid, e.g. in a check valve. (Such microvalves that
are not actively driven, e.g. those on gyrating discs, shall not be discussed
here.) The idea of a diaphragm was also applied in the field of soft lithography
that came up in the late 1990s [11-16]. Here, a channel structure is replicated
in an elastomeric material such as PDMS by casting the gelous material on a
negatively structured master, followed by crosslinking of the gel. Its charm is
the easy handling and its cost-effectiveness, making this technology available
to standard laboratories. One of the first attempts to create a monolithic PDMS
valve was taken by the Quake group in 2000 [14], which led to diverse
variants and their integration into complicated microreactor networks
[examples: 11,15,17].
Microfluidic Valves without Diaphragms
137
Generally, membrane-based valves suffer from a complicated design and

the problem of leakage, especially when particles are present in the fluid.
PDMS channels, on the other hand, can collapse when the geometry is not
optimized [11], and their pneumatic control is complex. Moreover, membrane
valves can only be opened or closed and so represent the equivalent of a 2/2
valve in the macroscopic world, 2/2 meaning two inlets/outlets and two
valve positions (i.e. open and closed). More complicated switching regimes,
like in valves with single input and multiple output (distribution or selection
valves) or in HPLC injection valves, are unattainable by this design or can
only be realized by combining several 2/2 valves, resulting in a larger size and
more control inputs.
We looked for alternative switching modes and came up with two novel
concepts, both of which allow small dead volumes: a sturdy, normally closed,
2/2-type hydrogel valve that, due to its soft actuator material, has excellent
sealing properties, and a rotary valve with PDMS rotor disc that is flexible and
uses marginal space.
HYDROGEL VALVE
Originally, hydrogel actuators were used in chemomechanical devices that
are sensitive to pH, temperature, and alcohol concentration [18-21]. The
functional principle of pH- and temperature-dependent hydrogels and their use
in chemical sensors and valves are discussed in [22,23]. We were among the
first to employ the thermally induced swelling of a hydrogel for displacementfree valve actuation, practically without moving parts [24-26]. Others,
applying the same idea, photopolymerized a monolithic block of poly(Nisopropylacrylamide) (PNIPAAm) inside a microchannel to create a hydrogel
microvalve in situ [27]. We, on the other hand, have devised a particle actuator
in an etched silicon chamber. A block of PNIPAAm is polymerized from Nisopropylacrylamide in the presence of N,N-methylenebisacrylamide as
crosslinker [25]. The chamber space is then filled to about 50% with hydrogel
particles that were ground from the dry PNIPAAm block and sieved. Use of
particles significantly reduces switching time, as the volume change is
diffusion-limited [26]. The volume phase transition temperature (Tt) of
PNIPAAm, at which the volume increases or decreases by about one order of
magnitude, is approximately 34 C and thus biocompatible. At room
temperature, the hydrogel is completely hydrated and the valve thus normally
closed [23,25,26] whereas at higher temperature the weak hydrogen bonds
138
between polar solvent (water) and slightly hydrophobic hydrogel break down,
leading to a collapse of the polymer chains [22]. Addition of polar solvents
(methanol, ethanol, 1- and 2-propanol, acetone) or salt leads to a decrease of Tt
[28], which allows measurement of their concentrations, higher solvent
concentrations even to complete loss of the volume increase [28], but this is
generally reversible. Interestingly, hydrogel swelling returns to normal for
short-chain alcohols above concentrations of 80% (v/v) (data not shown).
The actuator chamber is manufactured by methods of microsystem
technology. Swelling of the hydrogel particles is induced by filling the valve
with a pH-neutral, water-based liquid; the valve is ready for operation after a
few swelling/shrinking cycles [22,26] and very durable as long as no salts are
trapped within [23,28]. Manufacturing of a separate device (as opposed to
photopolymerization of a gel plug in a microchannel [25,27]) has the
advantage that it can be individually controlled and tested before using it in a
complicated channel system.
In the first designs, the actuator chamber (version number PV5: 500 m x
500 m x 200 m) was placed in a horizontal flow channel [25,26] and closed
by a glued-on Pyrex glass cover containing a microstructured thin-film heater;
anodic bonding of glass and silicon would destroy the hydrogel. Loss of
hydrogel particles was avoided by barriers surrounding the actuator chamber
so that the space between silicon and glass became very narrow. Inlets and
outlets of the valve channel were through-etched on the bottom layer, so to
mount tubes to the front side, a second, anodically bonded silicon/glass
manifold was glued onto the rear of the chip, which was therefore not
autoclavable. This valve was placed in a PEEK housing that allowed the
connection of tubes via UNF (Unified National Fine Thread) fittings (data not
shown). Its larger size limits its use in small microsystems, but it can be also
directly attached to microfluidic manifolds. A more compact design (PV6) was
realized by directing the flow vertically through the chip [28]; this is currently
the system of choice and commercially available (Figures 1-2). Direct
photopatterning of hydrogel pads in microchannels [24,25,27] is currently not
offered to customers.
To manufacture the 500 m x 500 m x 300 m large actuator chamber,
bottom and the cover are thinned by a two-side process on 4-inch silicon
wafers: wet etching with KOH followed by through-etching of 25 to 40 m
wide pores via deep reactive ion etching (RIE) using the classical ASE-Bosch
process [29]. Platinum heater and sensor (Figure 1A,C) are structured via liftoff technology [25]. Filling of the chamber with dry hydrogel powder (particle
size 12525 m; Figure 1A) is done manually; an automatic method using an
139
XYZ robotics (GeSiM Nano-Plotter 2.1) with a newly developed small

powder dispenser and camera-aided target finding is under development. The
chamber is closed by flip-chip gluing of top and bottom silicon layers,
followed by wire bonding of heater and temperature sensor to a printed circuit
board (PCB) as shown in Figure 1B. A scanning electron micrograph of the
actuator chamber is presented in Figure 1C. Loss of hydrogel material is
prevented by making the pore size about three times smaller than the particle
size [28] and avoiding pressures larger than 4105 Pa (4 bar), although the
valve can withstand pressures in water of at least 6105 Pa. If the pressure limit
is not exceeded, no leakage occurs, even if dust particles are trapped in the
valve, due to the softness of the hydrogel [23,26].
Figure 1. Small hydrogel microvalve, PV6, with 500 m x 500 m x 300 m large
actuator chamber and an overall chip size of 5 mm x 5 mm. (A) The picture shows the
top sieve plate with meandering temperature sensor (left) and the bottom sieve plate
filled with hydrogel particles and Pt heater (right). (B) PV6, glued together and wirebonded to a PCB. The socket to connect the device to external control electronics is not
yet soldered on the chip. (C) Scanning electron micrograph of a cut hydrogel valve
showing the KOH-etched actuator chamber, RIE-etched vertical sieve pores (diameter
35 m, length 80 m), and dehydrated hydrogel particles. (D) Eight PV6 valves glued
to a microfluidic manifold with PCB. The variation of the direction of the flow through
the central cuvette over 360 by combining different inlets and outlets is used for
hydrodynamic experiments in which elongated molecules like DNA are aligned in the
flow field. The hydrogel valves are cooled by a heat sink placed at their top (not
shown).
140
The microvalve is connected to an external microcontroller-based

electronics (Figure 2A) with I2C bus via a small socket soldered on the PCB.
To heat and thus to open the valve, a voltage of 3.5 V DC at 150 mW is
applied. To avoid overheating and hence long closing times, the temperature is
continuously measured by the integrated T-sensor and the heating power is
adjusted via pulse-width modulation to values down to 50 mW. Closing of the
valve is passive by switching off the heater and thus depends on the ambient
temperature. Such valves exhibit opening times of around one second and
closing times of a few seconds [26]. Active cooling by a Peltier element can
further decrease the shut-off time, but the effect is too small to justify the
effort. Direct attachment of hydrogel microvalves to a microfluidic system is
shown in Figure 1D.
The small size of the hydrogel valve makes it possible to place it inside a
UNF fitting as a microfluidic control element, e.g. in GeSiMs modular PDMS
microflow cell for microscopes, MicCell (Figure 2A). The rationale behind the
MicCell [30] is a reusable microscope chip holder with constant, softwarecontrolled fluidic periphery and standardized chip-to-world interface, while
the microfluidic channel system can be arbitrary: it is molded in a special
casting station on the surface of a customized silicon master chip. The
microchannel layer is then taken out, capped with a coverslip and immediately
ready to use. A hydrogel valve in a fitting screwed into an opening of a Tbranch system controls the loading of test substances into the main channel.
Normally, buffer or medium is aspirated from a reservoir through the other
branch of the T-junction. Test compounds are filled into the small cavity at the
top of the valve fitting (Figure 2A), and to inject them, the flow is stopped, the
main inlet blocked by an external valve, and the substance sucked into the
channel after opening the hydrogel valve. To clean the dead volume in the
bore downstream of the valve, a cleaning solution can be applied to the
opening of the valve and sucked through an extra channel that bypasses the
main microfluidic channel (K-type channel setup) [30]. Injection of fluids can
also be achieved by connecting the hydrogel valve with a tube (Figure 2B).
Due to the attachment to a PCB and socket, PV6 cannot be autoclaved.
We have therefore devised PV7 whose platinum heater and sensor films are
directly contacted without intermediary PCB (Figure 2B). Six of these valves
were built into a six-well plate in which hybridoma cells were grown on the
milliliter scale to overexpress monoclonal antibodies. The valves controlled
the automatic withdrawal of microliter amounts of sample to measure protein
expression and hence optimize growth conditions [31], which requires an
autoclavable system. As the cells were maintained at 37 C, the hydrogel valve
141
had to be cooled by a heat sink chilled by either a Peltier element or cooling

water to maintain it in its normally closed position.
Figure 2. Small hydrogel microvalve in a UNF 1-4/28 fitting. Sealing is achieved by an

O-ring. (A) PV6 assembled in a MicCell [30] with 22 mm x 22 mm large fluid system,
resting in a blue metal support that is placed in an inverted microscope. The valve is
marked by the arrow. The flow control unit is in the background; it contains a syringe
pump operating in suction mode (left), hydrogel control electronics and external 2/2
valve (middle), and 4 in / 1 out selection (turning) valve to switch between fluids and
stopping the flow (right). (B) PV7 in fitting, disassembled. The four electrical pins
contact the actuator chip without intermediary PCB, hence this microvalve is
autoclavable (> 10 times for 20 min at 125 C / 2 bar).
142
ROTARY VALVE
More complicated valves with several inlets and outlets exist in the
macroworld. The hydrogel valve is a simple on/off (2/2) valve, so such a valve
must be built into each fluidic channel to be controlled, much like the many
valves in a soft lithography rotary micropump [32]. A 2/3 valve, with one inlet
and two outlets between which the flow switches, already needs two hydrogel
valves; if all two-out-of-three combinations should be available, all three
channels must be controlled. A rotary (turning) valve would be such a
solution, as not only many pipes can be hooked up, but inlet and outlet
channels can also be interconnected in a flexible way, e.g. as in a
distribution/selection valve (one input, many outputs or vice versa). Generally,
such a valve consists of a stator containing all fluidic inlets and outlets and a
rotor containing one or more channels that bridge individual channels in
different ways upon rotation (Figure 3). The rotor face must be in sealing
contact with the stator surface. Like the hydrogel valve, rotary valves such as
HPLC injection valves can switch flows with very little fluid displacement.
A microfluidic rotary valve consisting of micromachined parts has been
proposed, but its design is complicated [33]. Our experience in silicon master
micromachining and PDMS molding [30] led us to propose that the rotor
material should be PDMS [11-17], as this material is easy to form by simple
gel casting and curing, durable, biocompatible, and elastomeric, i.e. it can be
used not only as rotor, but also as sealing surface.
Our first attempt to turn the valve used a pneumatic drive (Figure 4A), but
better control is obtained with a encoder-controlled, brushless electrical gear
micromotor (Dr. Fritz Faulhaber GmbH & Co. KG, Schnaich, Germany) with
an outer diameter of 6.5 mm, a switching power of 1 W, and a switching time
of 250 milliseconds (Figure 4D). The PDMS rotor has a diameter of 3.5 mm
and is mounted on a shaped piece (Figure 4B) for force transmission. Due to
outside contacts, the overall space required for the valve is about 10 mm x 13
mm. We soon found out that the rotor material becomes swollen (see also
[34]), thus reducing its durability due to friction between PDMS and silicon.
Sputtering with Cr 5 nm/Au 20 nm (Figure 4C) increased the lifetime of the
rotor from about 1000 to 3000 cycles. If the rotor is worn out, it can be
replaced by casting a new one and coating it with metal, all other parts are
reused. The stator can be of any material, as long as it is plane; we have used
stators of PMMA (Figure 4A) and silicon (Figure 5).
143
Figure 3. Examples of a rotary valve layout, with channels in black, through-etched

holes in grey, and rotor in orange. The rotor channel in the first motor position is
depicted as solid red line, alternative positions after turning the valve are shown as
dashed red lines.
Figure 4. PDMS rotary valve. (A) Pressure-driven valve in a PMMA manifold. (B) Tip
of the actuator mechanics in a fitting that is screwed into a tapped hole with O-ring
sealing. (C) PDMS rotor, metal-coated with Cr/Au, with single channel (length 1400
m, width 500 m, depth 300 m), used. (D) CAD sketch of the electric motor drive.
144
A patent has been applied for this new valve type, which is rather new so
that only few applications exist. As an example, Figure 5 shows a chip to
automatically culture cells in a microsystem. Cells are grown on a silicon sieve
plate with ~ 25 m through-etched holes through which medium is passed; the
sieve is placed in a holder attached to the microchannel via two holes (Figure
5A, arrow). The rotary valves (Figure 5B) allow to change between different
media and to clean the channel, in the forward and backward direction.
Figure 5. Experimental setup with three rotary valves for cell culturing in a
flowthrough system. (A) Silicon/glass fluidic channels, seen through the glass cover.
Each of the through-etched triple holes in the stator regions is contacted by a PDMS
valve rotor on the rear. Single holes on the chip margins are inlets and outlets,
connected to reservoirs containing medium. (B) Ready to use setup, with servo motors
at the bottom and microfluidic system at the top.
145
CONCLUSION
We have outlined here two different concepts for microfluidic valves.
Which valve to use depends on the application: if a sturdy, pressure-resistant
and particle-tolerant 2/2 valve is required that is practically displacement-free
(as the gel material simply takes up the surrounding process medium) and may
even be autoclaved, use the hydrogel valve. Its drawback is its somewhat slow
switching time and that the hydrogel comes in contact with the liquid, thus
possibly adsorbing solutes. Nevertheless, blocking of live cell suspensions
without harming the cells has been successfully demonstrated (data not
shown). If complicated switching processes (such as a selector or an HPCL
injection valve), high flexibility, and short opening and closing times need to
be realized on a small footprint of approx. two square centimeters, use the
PDMS rotary valve. We expect both valves to be valuable for microfluidics,
biotechnology, and chemical and medical engineering.
It has come to our attention that turning valves similar to ours, but using
different material, have also been developed at the Institut fr Mikrotechnik
Mainz (IMM), Germany.
ACKNOWLEGDMENTS
We are grateful to Prof. Dirk Kuckling, Universitt Paderborn, who was
involved in the initial experiments with the hydrogel valve. This work has
been supported by grants from the German Ministry of Education, Science and
Technology (BMBF), projects Protein Processing Platform (3P) (FKZ
16SV1832, Frderkonzept Mikrosystemtechnik 2000+, 2003 - 2006), and
CryoLab (FKZ 16SV2382, Rahmenprogramm Mikrosysteme, 2006 2010).
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ISBN 978-1-61668-570-6
Chapter 5
BIOCOMPATIBLE AND MASS PRODUCTIVE

MEMS DEVICE FOR LOCALIZED SURFACE
PLASMON RESONANCE
Institute of Materials Research and Engineering, A*STAR (Agency for
Science, Technology and Research), 3 Research Link, Singapore 117602
ABSTRACT
Localized surface plasmon resonance (LSPR) is the interaction
between the light and collective electrons of noble metal nanoparticles,
which exhibits as an extinction peak shift in the transmission spectrum of
the nanoparticles. LSPR is utilized to detect label free chemical or
biological samples, such as finding the kinetic coefficients between two
kinds of chemicals on the surface. To incorporate the noble metal
nanoparticle chip into a compact MEMS device will minimize the
expensive biological samples required, and will be able to make the
LSPR biosensors into a large sensing array for quick detections. The
desired LSPR MEMS device should possess the characteristics of
nanofabrication compatible, biocompatible, highly transparent, cost
effective and mass productive.
This chapter introduces the design, fabrication and test of such a
LSPR MEMS device. Our MEMS device is based on a glass-silicon-glass
sandwich structure, it is biocompatible due to the stable nature of the
glass and silicon compared with other polymer based disposable MEMS
devices. On the bottom glass, gold nanostructures for LSPR are fabricated
150

by nanosphere lithography. The middle silicon layer forms the
microfluidics channel and chamber of the device, and also blocks the
light from shedding onto the non-sensing areas. The top glass is drilled
with inlet and outlet for microfluidics. The three layers are bonded
together by UV cure epoxy. As the whole fabrication process avoids the
high temperature, high pressure and high stress, it is nanofabrication
compatible, that the gold nanostructures are intact even when after the
MEMS device is pried apart. The device is highly transparent with high
signal-to-noise, because the glass surface was not damaged during the
process, and the light blockage of silicon greatly reduced the background
of the light. As the MEMS fabrication for theses three layers are prepared
in wafer level prior to epoxy bonding, the device is suitable for mass
production with low cost. The fabricated LSPR MEMS device is tested
by UV-Vis spectroscopy with bovine serum albumin sensing, and it
demonstrates satisfactory LSPR sensing function. Our experiments prove
that such a design has prominent advantages over the one without light
blockage or with polydimethylsiloxane (PDMS) polymer.
1. INTRODUCTION
Biosensors have been exploited by researchers for many years in the areas
of diagnosis and monitoring of diseases, drug discovery, proteomics and
environmental monitoring. Fundamentally, biosensor is an analytical device
which converts biological response into a detectable electrical or optical
signal. Much biosensor research effort has been devoted to the evaluation of
the relative merits of various signal transduction methods in optics,
radiochemistry, electrochemistry, piezoelectricity, magnetoelectricity and
micromechanics, and two or more mechanisms might be combined or
multiplexed in a sensor or sensor array.
Recently, biological applications upon the localized surface plasmon
resonance (LSPR) spectroscopy have been demonstrated by several research
groups. Noble metal nanoparticles exhibit a strong UV-visible absorption band
that is absent in the spectrum of the bulk noble metal. This absorption results
when the incident photon frequency resonates with the collective oscillation of
the conduction electrons in the metal nanoparticles, which is known as
localized surface plasmon resonance (LSPR) [1-7]. Since the LSPR extinction
wavelength depends on the refractive index of the media adjacent to the metal
nanoparticles, LSPR is employed as a sensitive, real-time and label-free
sensing mechanism revealing the surface interactions of analytes. Detecting a
biomarker by LSPR starts from bonding a ligand/anchor of the biomarker onto
Biocompatible and Mass Productive MEMS Device
151
the gold nanoparticles; subsequently these functionalized nanoparticles are

rinsed (sometimes incubated) with the serum or buffer with biomarkers; and
the existence, concentration, or the binding dynamics of the biomarkers can be
extrapolated from the wavelength shift of the LSPRs extinction peak. Similar
to surface plasmon resonance (SPR) [8, 9], which is a well established
technology and has been applied for the detections of hundreds of analytes,
LSPR is also an effective tool to characterize the biological interfaces in realtime, and it has ten times higher sensitivity than SPR within its
electromagnetic decay length of 5 15 nm, which is very suitable for
monolayer molecular or short-chain DNA detections.
Compared with SPR which has a noble metal film and needs some optical
structures (either prism, or grating, or waveguide) to enhance the momentum
of the light so as to excite SPR, the occurrence condition of LSPR is much
relaxed, LSPR happens whenever the light irradiates onto the metal
nanostructures, thus LSPR eliminates the bulky optical setup of SPR, and it
can be miniaturized into a glass chip and easily be measured through a
conventional UV-vis-near-IR spectroscopy, by taking the absorption spectrum
of a glass substrate fabricated with noble metal (silver or gold) nanostructures.
The peak of the LSPR spectrum is also tunable according to the size, shape,
interval, material and surrounding medium of the metal nanostructures, which
provides the convenience of enhancing the signals through the surface
plasmon polariton wavelength matching. Moreover, when LSPR chip is
fabricated into a microfluidics device or microarray, it can characterize the
biological samples with an ultra-small amount, renders much shorter
measurement time and multiple sample measurements. It has been
demonstrated that a bio-chip with up to 300 of sensing spots can be realized by
using the LSPR chip combined with microfluidic channels fabricated by
polydimethylsiloxane (PDMS) [6, 7], a polymer that can form microfluidic
channels quickly by molding and can be covered on a glass chip to form
microfluidics.
However, PDMS has the problems of swelling and dissolution of PDMS
oligomers in solvent, it is preferred that silicon or glass materials, which are
more stable and durable in chemicals, can be used for LSPR micro-electromechanical systems (MEMS). LSPR MEMS is actually a challenging task to
fulfill. In order to realize it, the MEMS fabrication must be nanofabrication
compatible and biocompatible, and it should be robust, cost-effective,
transparent with minimum light scatterings, and preferably can be fabricated
through mass production. These requirements eliminate a lot of conventional
MEMS fabrication process, for instance, anodic bonding at high temperature
152
will damage the gold nanostructures, glass etching will roughen the surface of
the glass wafers and cause optical scatterings in LSPR. Combining all of the
above requirements in our design, we have developed a cost-effective LSPR
MEMS prototype that consists of a glass-silicon-glass sandwich structure, with
successful design and fabrication, the application of this LSPR MEMS on
bovine serum albumin (BSA) test is demonstrated. We also prove that 3 mm
thick PDMS layer obviously widens the LSPR spectrum, so it should be
avoided in LSPR MEMS device in terms of both spectral broadening and
biological absorptions.
2. DEVICE DESIGN AND FABRICATION

The proposed microfluidic biosensor is made of commonly-used
semiconductor materials, i.e., silicon and Pyrex 7740 glass through MEMS
fabrication technology, as illustrated in Figure 1. In Figure 1, the bottom glass
layer is with gold nanostructures fabricated for LSPR sensing, the middle layer
is with silicon to form the microfluidic channels, and the top layer is glass with
holes drilled for inlet and outlet of the device.
Figure 1. The cross-section view of the fabricated microfluidic LSPR biosensor.
Prior to MEMS fabrication, a layer of gold nanostructures was fabricated

on the bottom Pyrex 7740 glass chip through dispersed nanosphere lithography
(NSL). NSL is a powerful technique to inexpensively fabricate gold
nanostructures on the glass substrate with controlled shape, size and
153
interparticle spacing, and its fabricated nanostructures are suitable for LSPR
sensing because of their tunability and varieties. In our sensing device, the
gold nanostructures on the glass substrate were fabricated as following. First a
4 Pyrex 7740 glass wafer was implanted with silicon ions in a Varian EHP200 ion implanter at an energy of 5 keV and a dose of 1E14/cm2, this step is to
modify the surface of the glass in order to disperse the nanospheres. Then the
glass wafer was diced into a 20 mm 10 mm chip. After cleaning, the glass
substrate was dip coated with a 1:5 diluted poly(diallyldimethyl ammonium
chloride) (PDDA) solution for 30 sec, PDDA was purchased from Sigma
Aldrich as a 20 wt% solution in water. After rinsing and drying, the glass
substrate was drop coated with 1 mL 10 times diluted solution of polystyrene
nanospheres bought from Duke Scientific Ltd. The positive charges in PDDA
cancelled out the negative charges of the nanospheres as well as the charges of
the silicon ion implanted glass surface, thus the nanospheres were dispersed on
the glass surface. Finally, 50 nm of gold was evaporated onto the nanospheres
at 70 (see Figure 5). Under these fabrication conditions, the gold on the
nanospheres attaches to the gold on the glass substrate and forms nonconformal 3D gold nanostructures [10], which yield a LSPR extinction peak
when light passing through these nanostructures. The wavelength redshift of
the LSPR peak reflects the reflective index increment of adjacent medium, or
the bonding of analyte onto the gold nanostructures.
The fabrication process for the silicon layer started from a standard RCA
cleaning of a 4 silicon wafer (100) with a thickness of 400 m. Then, a 1 m
thick silicon dioxide layer was deposited by PECVD on both sides of the
wafer. After that, the silicon wafer was spin coated with a layer of AZ4620
photoresist on both sides. The silicon wafer was subsequently exposed at 7
mW/cm2 for 13 s and developed with AZ developer for 45 s to open the
windows of inlet, outlet and light path. The silicon dioxide was etched by
buffered oxide etch solution (7:1) at an etch rate of 850 /min, as shown in
Figure 2(a). A microchannel of 100 m wide was patterned on the other side
of the wafer by photoresist coating, exposure, developing and oxide removal
as shown in Figure 2(b). Figure 2(c) presents that a channel depth of 50 m
was achieved using DRIE. Then the inlet, outlet and light path were etched
through by DRIE to connect with the fluid path of the microchannel as shown
in Figure 2(d). This silicon wafer was diced into 20 mm 10 mm chips for the
following bonding process.
A Pyrex 7740 glass wafer was diced into chips with the same size of
silicon chips. These glass chips serve as the top covers of the microfluidics and
are regarded as top glass chips. Inlet and outlet were drilled in the top glass
154
chip and Loctitte 3301 UV curable epoxy with a refractive index of 1.48 was
spin coated on the top glass chip. After aligning properly, the silicon chip and
top glass chip were bonded together and exposed under UV light at 7 mW/cm2
(365 nm wavelength) for 5 min to cure the epoxy and form the bonding
strongly, which is shown in Figure 2(e). A layer of Loctite 3301 UV curable
epoxy was spin coated on the silicon surface of the previously bonded Si-glass
structure, which was then carefully aligned to the bottom glass chip with gold
nanostructures fabricated to bond them together. After UV exposure, the glasssilicon-glass sandwich structure device was completed as shown in Figure
2(f).
Figure 2. The MEMS fabrication process of the microfluidic LSPR biosensor.
155
Figure 3. The schematic of the assembly for LSPR measurements (a) and the photo of
the packaged device (b).
156
Figure 4. 3D demonstration for the fabrication and assembly of the LSPR MEMS. (a)
shows the fabricated gold nanostructures on glass substrate, (b) shows the silicon
microfluidic layer on the substrate, (c) shows the glass-silicon-glass structured LSPR
chip, (d) shows the fabricated chip in the bottom part of the package, with gaskets and
ferrules affixed, (e) and (f) are respectively the top and side views of the packaged
device.
For demonstration and testing purpose, a plastic jig was fabricated to

assemble the prototype with commercially available microfluidic connections
including a pair of tubing, fittings, ferrules and gaskets. Figure 3(a) illustrates
the schematic of the assembly for testing, and Figure 3(b) is the photo of the
packaged device in the size of 36 mm 20 mm 10 mm. The fabrication and
assembly process shown in Figure 4 gives a more authentic relative size
comparison of the sensing area, the chip and the package.
In order to make sure that the MEMS fabrication process did not affect the
fabricated gold nanostructures on the bottom of the device, one of the devices
was pried apart, and the discrete nanostructures on the bottom layer of the
157
glass substrate were observed under a scanning electron microscope (SEM).

As presented in Figure 5, the structural integrity of the gold nanostructures did
not adversely change after carrying out the fabrication steps to make the
microfluidic sensor chip, which indicates that the performance of the LSPR
will not degrade when the fabricated microfluidic chamber is used.
Figure 5. SEM pictures of the gold nanostructures in the fabricated device, which
proves that the gold nanostructures kept intact at the bottom glass substrate. (a) was
observed in an area of 46.7 m 35 m, and (b) is with 9.2 magnification of (a).
158
3. UNIQUENESS OF THE DEVICE

The uniqueness of the device is that it is mass productive, because prior to
the epoxy bonding, the process is in wafer level. At the same time, it gets rid
of PDMS, and the light blockage of the silicon layer increases the signal-tonoise ratio of the device.
1. Comparison to the Device With PDMS

The LSPR spectra of the device were measured with an Ocean Optics
spectrometer at the wavelength range of 400 - 900 nm and an optical
resolution of 0.35 - 0.36 nm, as plotted in Figure 6. Figure 6a shows the LSPR
spectrum for a glass-silicon-glass structure when the adjacent media of the
gold nanostructures were air and water. It can be seen that when the adjacent
medium changed from air to water (i.e., the refractive index changes from 1 to
1.33), the extinction peak of the LSPR spectra shifted from 642.16 nm to
677.35 nm, which is equivalent to a LSPR sensitivity of 106 nm/RIU, RIU is
the unit of the refractive index. It should be noted that this sensitivity depends
on the size, shape and material of the nanostructures, and is not related with
the microfluidic design. Gold nanostructures used in the experiments were
fabricated as described in Section 2, and they looked similar to the ones
photographed in Figure 5. Since the angle and thickness of the gold deposition
might be different for each sample, the LSPR sensitivity also differs a little.
Figure 6(b) compares the LSPR spectra when a layer of 3 mm thick
PDMS was added on the top of the LSPR MEMS device. PDMS is transparent
and allows light to be transmitted to the nanostructures. There is a slight
spectrum broadening due to the addition of PDMS. From the experimental
results provided in Figure 6(b), it can be seen that PDMS may still be used for
LSPR MEMS, however, the LSPR signal is more superior when glass is being
used as the transparent layer. Moreover, PDMS is a porous material and it is
not suitable for long term use in detecting biological samples because it tends
to absorb some biological samples. For multiple use of a device, it is believed
that the residue in PDMS may also influence the accuracy of LSPR
measurements adversely. In conclusion, silica and glass based microfluidic
device for LSPR application is most desirable in terms of durability, stability,
reliability, repeatability and high optical transparency.
159
(a)
(b)
Figure 6. LSPR spectra of the LSPR MEMS device measured with an Ocean Optics
spectrometer. (a) shows the LSPR spectrum for a glass-silicon-glass structure when the
adjacent media of the gold nanostructures were air and water, (b) shows the LSPR
spectrum for the same structure with a 3 mm thick layer of PDMS added, when the
nanostructures adjacent medium was water.
2. Signal Enhancement by Light Blockage

Our experiments also prove that the silicon layer in the device can
effectively block the light and increase the signal-to-noise ratio of the device.
160
The experimental process was as following: the gold nanostructures were

fabricated on the substrate of the LSPR MEMS device, and the LSPR
spectrum was taken (marked as without block in air in Figure 8, with the
diagram drawn in Figure 7(a)); then this chip was bonded with the silicon
layer with microfluidics and the top glass layer to form the MEMS device to
measure the LSPR spectra (marked as with block in air in Figure 8, with the
diagram drawn in Figure 7(b)). Four samples were measured in total as
presented in Figure 8, and the results show that the light blockage improved
the shapes of LSPR spectra, due to the fact that the gold nanostructures were
more evenly distributed in a smaller MEMS sensing area (less than 1 mm in
diameter) than a large area of the whole light spot (about 5 mm in diameter).
(a)
(b)
Figure 7. The diagram of the LSPR measurement for comparing the effect of the light
blockage in LSPR MEMS device. Pink rectangle is the glass substrate, the red circle
indicates the size of the light spot of our spectrometer (about 5 mm in diameter), and
the yellow spots represent gold nanostructures. (a) is without light blockage before
MEMS fabrication; (b) is with light blockage in the MEMS structure.

0.7
without block in air

with block in air
Extinction
0.6
0.5
0.4
0.3
0.2
400
500
600
700
800
900
800
900
Wavelength / nm
(a)
0.38

with block in air
0.36
0.34
Extinction
0.32
0.30
0.28
0.26
0.24
0.22
0.20
0.18
400
500
600
700
Wavelength / nm
(b)
161
162
0.60

with block in air
0.55
Extinction
0.50
0.45
0.40
0.35
0.30
0.25
0.20
400
500
600
700
800
900
Wavelength/ nm
(c)
0.40

with block in air
0.36
Extinction
0.32
0.28
0.24
0.20
0.16
0.12
0.08
400
500
600
700
800
900
Wavelength / nm
(d)
Figure 8. (a)-(d) LSPR spectra taken when with and without light blockage for 4 LSPR
MEMS devices, the adjacent medium of the nanostructures was air.
163
4. LSPR SENSING
To demonstrate that such a device is suitable for biological test, a LSPR
chip with the gold nanostructures fabricated as in Figure 5 was used to
measure LSPR spectra for bovine serum albumin (BSA), a kind of serum
albumin protein that has many biochemical applications in immunoassays.
PerkinElmer spectrometer was used to detect the LSPR spectra at the
wavelength range of 400 - 1000 nm. First a LSPR spectrum was taken in air,
subsequently 1 g/ml phosphate buffered saline (PBS) buffer was added and
the LSPR spectra was taken, and finally BSA was injected and incubated at
room temperature for 1 hour, rinsed with PBS and the LSPR spectrum was
measured.
Figure 9. LSPR spectra of a glass chip with gold nanostructures fabricated for BSA
measurement.
The spectra of the experiment are shown in Figure 9. The extinction peak
wavelength of LSPR in air is 789 nm. BSA adsorption redshifted the spectrum
of PBS buffer obviously but slightly to the right, so it has to be discerned
carefully. Since even in the insert the peaks of the two LSPR spectra look
close, the wavelength shift is better to be identified by averaging the two
wavelengths at the extinction intensity of 1.35, because at 1.35 this shift is
discernable and is very close to the peak intensity of 1.37. For the PBS buffer,
164
the left and right wavelengths at the intensity of 1.35 are respectively 798 and
873.5 nm, thus renders a central wavelength of 835.75 nm. After BSA
adsorption, the left and right wavelengths at the intensity of 1.35 are
respectively 802.5 and 881.5 nm, thus gives a central wavelength of 842 nm.
So the adsorption of BSA caused the wavelength to red shift 6.25 nm.
According to the central wavelength in air and water, the sensitivity of the
LSPR chip was calculated to be 139.69 nm/RIU. Gao et al. [11] also measured
the wavelength shift of a LSPR chip with BSA on nanoholes. But in that work,
the chip was first immersed in BSA and rinsed by PBS, then dried and
measured in air. With the chip sensitivity of 110 nm/RIU, they detected a 7 nm
shift caused by BSA in air. Our chip has higher sensitivity of 139.69 nm/RIU,
for BSA test, our sensitivity is also higher, because the wavelength shift of an
analyte is proportional to the refractive index difference between the analyte
and adjacent medium. If we also dried the chip in air, a wavelength shift
caused by BSA adsorption should be much higher than Ref. [11].
Our biological test results manifest that the BSA adsorption and the
function of our LSPR chip are well and expectable.
5. CONCLUSION
This chapter investigated a method to fabricate LSPR MEMS in a glasssilicon-glass sandwich structure. The fabrication processes of the gold
nanostructures and the microfluidics as well as the package of the device were
described in detail. Both the nanofabrication and MEMS fabrication were costeffective and suitable for mass production. The microfluidics fabrication was
carried out at room temperature without introducing any stress, thus it does not
affect the nanostructures on the bottom layer of the device, which was
revealed by the SEM picture of the nanostructures on the bottom glass chip
after prying the device apart.
Besides mass productive and highly transparent, this device has two major
advantages: PDMS free and the light blockage of the non-sensing area. Our
MEMS fabricated with glass and silicon avoided the optical and biological
signal degradation might be caused by PDMS formed microfluidics. Our
experiments indicate that a 3 mm thick layer of PDMS obviously broadens and
deforms the LSPR spectra. Silicon layer blocks the light out of the sensing
area and increases the signal-to-noise ratio of the device, because this
guarantees that the LSPR signal only generates from a smaller area where the
gold nanostructures are relatively even distributed.
165
The LSPR sensing was conducted by measuring the BSA protein. In this
experiment, the gold nanostructures fabricated by evaporating 50 nm of gold
onto the 170 nm diameter polystyrene nanospheres at the angle of 70 rendered
a LSPR sensitivity of 139.69 nm/RIU, and the LSPR spectrum redshifted 6.25
nm after BSA adsorption. This result is more sensitive than previously
reported BSA sensing with gold nanoholes.
Overall, due to its low-cost, high signal-to-noise ration, biocompatibility,
highly transparency and mass production, the glass and silicon based LSPR
MEMS we proposed is ideal for LSPR based biosensing, and it can also be
fabricated into a LSPR microarray or LSPR/SPR combined microfluidics,
which can be used in a point-of-care medical diagnostic system by just
integrating with a miniature spectrometer.
REFERENCES
Haes, J.; Stuart, D. A.; Nie, S.; Van Duyne, R. P. J. Fluoresc. 2004, 14,
355-367.
[2] Willets, K. A.; Van Duyne, R. P. Ann. Rev. Phys. Chem. 2007, 58, 267297.
[3] Zhao, J.; Zhang, X.; Yonzon, C.; Haes, A. J.; Van Duyne, R. P.
Nanomedicine 2006, 1, 219-228.
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K.; Rogers, J. A.; Nuzzo, R. G. Chem. Rev. 2008, 108, 494-521.
[5] Anker, J. N.; Hall, W. P.; Lyandres, O.; Shah, N. C.; Zhao, J.; Van
Duyne, R. P. Nat. Mater. 2008, 7, 442-453.
[6] Endo, T.; Kerman, K.; Nagatani, N.; Hiepa, H. M.; Kim, D-K.;
Yonezawa, Y.; Nakano, K.; Tamiya, E. Anal. Chem. 2006, 78, 64656475.
[7] Hiep, H. M.; Nakayama, T.; Saito, M.; Yamamura, S.; Takamura, Y.;
Tamiya, E. Jpn. J. Appl. Phys. 2008, 47, 1337-1341.
[8] Homola, J. Anal. Bioanal. Chem. 2003, 377, 528-539.
[9] Homoal, J.; Yee, S. S.; Gauglitz, G. Sensor. Actuat. B-Chem. 1999, 54,
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Nanophotonics 2008, 2, 023502.
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2007, 90, 073901.
[1]

ISBN 978-1-61668-570-6
Chapter 6
APPLICATION TO ADAPTIVE OPTICS

AND LASER MICROFLUIDICS
Jean-Pierre Delville, Alexis Casner,
Rgis Wunenburger and Iver Brevik
Universite Bordeaux, France
Linear interface deformations can be used for soft lensing with large
variations in accessible focal distances. The nonlinear regime in deformation,
particularly optically driven liquid jetting, offers an even wider range of
application since hydrodynamics starts to couple with light propagation. One
major point here is that, contrary to electro-hydrodynamics where micrometric
features are difficult to implement, these are natural length scales in "optohydrodynamics".
1. ADAPTIVE OPTICS
Beyond soft lensing, the liquid columns stabilized by radiation pressure
can be viewed as appealing structures for optical guiding. Indeed, as the index
of refraction of the columns is necessarily larger than that of the surrounding
fluid, laser beam is automatically captured by total reflection and guided
within the liquid medium. This light confinement is dynamically illustrated in
Figure 1 over its entire development, i.e. from soft lensing ( t = 1 1.5 s ) to
168
Jean-Pierre Delville, Alexis Casner, Rgis Wunenburger et al.
jetting ( t = 2 16 s ) and finally laser guiding ( t = 19 22 s ). The final

liquid fiber length is 455 m .
Figure 1. Dynamical behavior of soft focusing, laser self-trapping by the induced liquid
jet and final optical guiding by the stationary liquid column formed. Parameters are
0 = 3.47 m , P = 470 mW , and (T TC ) = 4 K . The liquid fiber length
is
455 m .
Application to Adaptive Optics and Laser Microfluidics
169
This laser self-guiding is also efficient in smaller liquid bridges as

illustrated in Figure 2a, where a liquid column of aspect ratio = 14 is
stabilized with a glass capillary of height 200 m .
One can therefore put forward the concept of liquid step-index optical
fibre, which provides a very new approach towards self-induced waveguiding.
Indeed, contrarily to optical adaptive waveguides written by
photopolymerisation [1] or laser damage in glasses [2], liquid fibres are nonpermanent. They are thus completely reconfigurable. The laser creates its own
channel that is automatically optimised to its waist and power as illustrated in
Figure 3, where adaptation to incident beam power is clearly observed.
Figure 2. a) Liquid bridge with aspect ratio
= 14
induced and stabilized in a
200 m glass capillary by a laser beam of beam waist 0 = 3.2 m and power
P = 1400 mW . The temperature gap is (T TC ) = 6 K . The brightness of the
column evidences laser self-guiding. b) Same experimental conditions as in a) but with

a tilted exciting beam. c) Liquid elbow created in a two-laser configuration
(upward/downward) at
(T TC ) = 6 K . Both wetting films are destabilized,
intercept and form a wedge. The directions of propagation of each beam (
0 = 3.5 m , P = 800 mW ) are indicated by the arrows.
These tuneable optical fibres can furthermore be oriented in any direction

by tilting the exciting beam. Figure 2b gives an example of such an inclined
liquid bridge stabilized by a laser beam propagating obliquely. Even more
surprising are artificial structures such as the stable liquid elbow created in a
two-laser beams configuration and presented in Figure 2c. Optically induced
170
liquid columns are thus particularly efficient to control beam propagation or to

optimise light coupling devices because self-adaptation considerably reduces
the sensitivity to precise mechanical alignments of the optical components
used.
Figure 3. Adaptation of the liquid fiber diameter to the input power. Parameters are
0 = 3.47 m
and
(T TC ) = 4 K . The liquid fiber length is 334 m . As
demonstrated by the emission of droplets from liquid jets, note that hydrodynamic flow
still persists within the liquid columns as illustrated by the fluid accumulation at their
feet.
2. LASER MICROFLUIDICS
Aside optical guiding, the liquid jets and columns stabilized by radiation
pressure can be viewed as three dimensional microfluidic devices with "soft"
wall because liquid is transported from the upper liquid phase when P P ,
i.e. above interface instability onset. Two types of micro-flow can be
generated: droplet flow and pipe flow.
As illustrated dynamically in Figure 4, droplets are continuously generated
at the tip of a stationary jet. Moreover, since the index of refraction of the
droplet is larger than that of the surrounding fluid, the beam automatically
traps them. This brings directionality in droplet emission and transport that can
171
be actuated by tilting the beam as illustrated in Figure 2b. Finally, at fixed
(T TC ) and 0 ,
the droplet flow rate can be controlled by the incident
beam power. Consequently, contrary to other methods [3], this optical

approach of microfluidics provides droplets that are directly produced within
the chosen micrometric size in a contact less way without further processing.
Also, as droplets are produced in three dimensions from a channel that can be
controlled in size by the beam, no particular microfluidic device is required to
manage the droplet flow.
Figure 4. Continuous droplet emission and trapping from a jet of stationary length.
Note the regularity in flow rate and the relative monodispersity of the induced droplets.
The time delay between two pictures is 1 s and the jet length is 330 m . Control
parameters are
(T TC ) = 6 K , 0 = 3.5 m , and P = P = 490 mW .
On the other hand, liquid flow within the jet persists when it reaches the
bottom face of the cell and forms a liquid bridge. This is illustrated in Figure
3, were accumulation of liquid on the bottom window of the cell is clearly
observed. This means that laser-sustained liquid bridges behave as micro-pipes
that can be used to transfer fluid from one reservoir to another. One even more
surprising fact is that the micro-pipe section can be actuated continuously by
varying the incident beam power (see Figure 3).
Finally, let us note that liquid columns are unstable in classical conditions.
As column breaking generally leads to at least bimodal droplet distributions,
often called droplets and satellites [4] (see the left picture of Figure 5, the
172
important drawback for microfluidic applications is control over micro-jet

fission to form a regular assembly of micro-droplets [5, 6]. On the other hand,
for applications motivated by fluid transport alone annular flows are much
more efficient than droplet flows, even if the first situation is difficult to
implement due to the Rayleigh-Plateau instability. Since radiation pressure of
laser waves is able to prevent column breaking, it becomes possible to reverse
the microfluidic approach in order to transform a bubbly flow into an annular
flow. This process is dynamically illustrated in Figure 5. Starting from a linear
assembly of well-separated droplets, the radiation pressure deforms droplets
and forces them to coalesce transforming the initial droplet assembly into a
liquid column.
Figure 5. Transition from droplet to annular flow resulting from droplet deformation
and coalescences driven by the optical radiation pressure. The acquisition frequency is
f = 20 Hz . Control parameters are ( T TC ) = 5 K , 0 = 3.47 m , and
P = 630 mW > P .
CONCLUSION AND PROSPECTS

The main purpose of this review was to theoretically and experimentally
explore fluid interface deformation driven by the optical radiation pressure of
a continuous laser wave. Using near-critical liquid-liquid interfaces, to
strongly reduce surface tension and enhance radiation pressure, we validated a
universal description of the process.
We also investigated nonlinear regimes in deformation. Asides surprising
stable tether shapes, we have presented a new electromagnetic instability
173
mechanism of fluid interfaces driven by continuous laser wave. The very good
agreement observed between measurements and expectations demonstrates the
universality of this nonlinear process. The resulting jet is also expected to
occur quite universally and its regularity, as well as that of the produced
micro-droplets, should be promising in microfluidics and electromagnetic
spraying techniques.
We finally extended this investigation on nonlinear behaviors to the
formation of stable liquid columns. While the results presented here were
obtained with a single laser beam, the method could easily be extended to a
parallel approach by forming liquid-bridge patterns or adaptive liquid gratings
by tailoring the intensity distribution with interfering pump beams.
Even if we try to give an extended view of laser-induced fluid interface
deformation, most of its theoretical description, particularly in the nonlinear
regime, is still missing. For example, we did not explain the observed tether
shape of the deformation. An investigation of liquid jet properties is also
missing. The main reason is linked to the complex nonlinear coupling between
a mobile and deformable interface and a laser beam as the interface adapts its
position to optical excitation. Also, we did not discuss dynamical behaviors,
even in the linear regime in deformation. Even if we do have some results on
this important aspect, particularly for applications, they are too incomplete to
be developed within a general scheme.
Nevertheless, we hope that our exhaustive presentation of the "static"
manifestations of a liquid interface under the radiation pressure of a laser wave
will promote an optical approach to interface actuation and, to build
microfluidic devices with optical forces [7] or, conversely, to anticipate new
optical micro-systems based on microfluidics [8] for flow guiding and light
coupling applications.
REFERENCES
[1]
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S. Shoji, S. Kawata, A. A. Sukhorukov, and Y. S. Kivshar, Optics Lett.

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R. Dreyfus, P. Tabeling, and H. Willaime, Phys. Rev. Lett. 90, 144505
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INDEX
A
absorption,viii,2,4,6,34,117,150,151
acceptors,108
accuracy,70,158
acetone,27,28,138
acid,6,7,124,125
actuation,137,173
actuators,79,137
adaptation,169,170
adhesion,26
adsorption,125,131,163,164,165
AFM,21
air,ix,11,14,16,20,37,135,158,159,160,
162,163,164
albumin,xi,150,152,163
alcohol,137
alkaline,125
alternative,127,137,143
aluminosilicate,6
aluminum,31
amine,124
amino,120,124
aminoacid,120,124
ammonium,153
ammoniumchloride,153
amorphous,6
annealing,18,20,21,24,45
annihilation,108,127
anode,112,121
application,xi,167
appropriatetechnology,2
aqueoussolution,7,123
Asia,125
aspectratio,7,10,169
assumptions,62
atoms,4,6
attachment,140
automation,2,106,146
averaging,163
B
back,31,111
background,xi,109,116,125,141,150
baking,7,36
bandwidth,32
barriers,138
beams,11,12,13,20,32,33,36,40,170,
173
behavior,vii,ix,56,59,60,61,65,68,72,
73,75,76,77,78,79,81,84,86,92,93,
94,95,96,97,147,168
bending,25
binding,4,124,151
bioanalytical,128
biocompatible,x,137,142,149,151
biologicalbehavior,viii,2
Index
176
biomarker,150
biomaterial,148
bioreactors,146
biosensor,134
biotechnology,vii,50,145,146
biotin,124
blocks,x,150,164
Boltzmannconstant,62,82
Boltzmanndistribution,62
bonding,xi,3,7,138,139,150,151,153,
154,158
boundaryconditions,62,63,83
bovine,xi,150,152,163
broadspectrum,32
bubble,116
buffer,viii,55,57,110,111,114,116,117,
118,122,140,151,163
bulkcrystal,41
C
CAD,143
candidates,125
capillary,vii,viii,ix,56,57,58,80,103,104,
116,117,120,123,131,169
carbon,114,123,125
carboxyl,124
casting,136,140,142
catalysis,123
cathode,121
cell,11,14,43,44,113,124,140,144,145,
148,171
cellculture,148
cerium,6
challenges,viii,2,3
channels,viii,x,3,7,11,13,49,55,57,80,
109,121,122,124,136,137,142,143,
144,147,151,152
character,113
chargecoupleddevice,5
chargedensity,ix,56,61,62,63,80,81,82
chargedparticle,109
charm,136
chemicaletching,6,7,15,17,18,21,49
chemicalproperties,4
chemicalreactions,109
chemicalsensing,136,145
chemicals,x,149,151
chemiluminescence,104,132,134
chloride,153
chromatography,109,117,120
classes,108
classical,80,90,108,138,171
cleaning,119,140,153
clusters,6
coatings,114
collaboration,50
color,iv,107
commercialization,128
compaction,24
compatibility,49,148
complexity,3,136
components,vii,viii,2,3,6,7,16,20,26,
38,44,48,49,56,57,61,81,106,108,
117,148,170
composition,114
compounds,108,140
computerization,106
concentration,viii,ix,7,55,56,62,81,82,
92,93,94,96,104,106,110,117,118,
120,137,151
conduction,80,86,87,91,150
conductivity,87,113,117
configuration,9,35,82,114,121,169,170
confinement,167
consumption,105,124
contaminant,119
continuity,ix,56,60,61,81
control,vii,viii,ix,46,55,57,80,106,107,
115,118,135,137,139,140,141,142,
147,170,172
convective,117
convex,19,23,24,26,35
cooling,117,140,141
copper,26,27,28,29
Index
correlation,123
correlationcoefficient,123
cosine,79
cost,x,xi,3,7,16,30,43,105,112,113,
132,136,149,150,151,164,165
costeffective,30,136,151,164
coupling,24,25,36,37,170,173
crack,116
crosslinking,136
crosssectional,13,36,38,39,87
crystalline,6
crystallites,14,17
crystals,41
culture,144
curing,142
currentlimit,131
customers,138
cycles,x,136,138,142
D
dataprocessing,110
decay,151
defects,viii,56,57
definition,67,91,96,104,124
deformation,xi,167,172,173
degradation,164
delivery,80
density,ix,56,60,61,62,63,80,81,82
deposition,158
derivatives,108
detection,vii,ix,16,30,103,104,105,106,
107,108,109,110,112,113,114,115,
116,117,118,119,120,121,122,123,
124,125,126,127
detectionsystem,105,112,115,116
detectiontechniques,vii
deviation,71,80
diamond,119,125
diaphragm,136
dielectricconstant,61,77,81
dielectricmaterials,27
177
dielectrics,30
diffraction,7,20,23,49
diffusion,116,117,118,120,137
directionality,171
discontinuity,69
discs,136
dispersion,viii,56,57,117,118
displacement,137,142,145
dissolvedoxygen,125
distilledwater,17,80
distribution,ix,11,12,42,56,62,64,65,
66,67,69,70,72,79,80,81,82,87,92,
97,137,142,173
divergence,19,36
DNA,134,139,151
donors,108
dopamine,123
doped,6,41,125,133
drawing,37
drugdelivery,80
drugdiscovery,150
drying,153
durability,123,142,158
duration,4,31
dust,139
dyes,33,127
dynamicviscosity,ix,56,58,59,65,73,74,
79
dynamics,viii,2,151
E
earth,42
EastAsia,125
ecology,104
education,145
election,142
electriccurrent,113
electricfield,viii,4,55,57,59,61,68,73,
74,77,78,80,109,110,115,117,118,
120,122
electricpower,26
Index
178
electricalconductivity,87,113
electricalproperties,80
electroanalysis,128,129,131
electrochemicalreaction,105
electrochemistry,104,150
electrodes,29,41,108,113,114,115,119,
120,121,123,124,125,127,134
electrohydrodynamics,xi,167
electrolysis,104,106,107,117,119,120,
125
electrolyte,61,66,81,113
electromagnetic,4,146,151,173
electromagneticwave,4
electron,6,105,108,139,157
electroosmosis,57,61,109
electrophoresis,vii,viii,ix,56,57,103,104,
105,109,110,111,123,131
emission,31,32,106,109,113,121,123,
124,127,170,171
emitters,108
encapsulated,14,46
energy,4,11,12,17,20,32,42,91,108,
153
engineering,vii,118,145
enlargement,122
epoxy,x,150,154,158
equipment,50,118
etching,6,7,14,15,17,18,21,36,45,48,
49,138,147,152
ethanol,31,138
evaporation,43
evolution,146
excitation,6,106,107,108,118,120,127,
173
experimentalcondition,169
exposure,6,7,14,15,153,154
extinction,x,42,149,150,153,158,163
F
fabrication,viii,x,2,3,4,5,6,7,13,14,20,
27,28,30,31,36,45,49,56,57,125,
127,149,151,152,153,154,156,160,
164
failure,viii,56,57
fatigue,viii,56,57
feedback,114
fiber,36,37,38,168,170
film,26,27,113,123,125,138,146,151
filters,107
filtration,117
financialsupport,128
fission,172
flagellum,44,46,47
flexibility,145
flowfield,58,60,61,63,81,139
flowrate,ix,56,68,69,75,77,78,79,80,
81,86,90,94,95,97,171
fluid,ix,56,57,58,59,60,61,65,70,72,
73,74,75,76,79,80,92,93,94,95,118,
136,137,141,142,153,167,170,171,
172,173
fluidinterfaces,173
fluidtransport,94,172
fluorescence,11,30,34,104
focusing,5,10,11,19,20,36,49,168
food,104
foodindustry,104
formula,19
fouling,119,120
fracture,116
freshwater,44
friction,ix,56,80,81,91,96,97,142
futures,ix,103,120
G
gas,17
gel,136,138,142,145
generation,42,108,116
gold,x,119,124,149,151,152,154,156,
157,158,159,160,163,164,165
goldnanoparticles,151
gracilis,44,45,46,47,48
Index
grants,145
gratings,173
gravitationalforce,82
gravity,42
groups,82,114,150
growth,2,47,140
H
handling,136
hardships,118
healthcare,2
heat,4,6,17,45,58,80,139,140,141
heattransfer,80
height,7,36,61,78,80,81,82,91,95,169
helium,17
heterogeneity,117
highpressure,x,150
hightemperature,x,36,150,151
highspeed,43,44,47
hip,vii,26,35,36,37,38,50,140,151,152,
163
histidine,124
housing,138
HPLC,137,142
human,104
humanactivity,104
hybrid,viii,2,3,30,48
hybridoma,140
hydrodynamic,91,139,170
hydrofluoricacid,6
hydrogels,137,147
hydrogen,116,124,137
hydrogenbonds,137
hydrogenperoxide,124
hydrophobic,138
hydrostaticpressure,80
hyperbolic,58,59,66,79
hypothesis,66
179
I
ideal,vii,1,6,114,125,165
identification,109
illumination,11
image,24,26,28,34,35,37,38,39,46,48
immobilization,127
immunoassays,163
implementation,105
impurities,106,107
insitu,137
incompressible,60,81
indices,11,20,38
indium,104,114
indiumtinoxide(ITO),104,114,122,123,
125,134
industry,viii,2,104,113
inertia,57
inertness,113,125
infinite,73
informationtechnology,50
infrared,127
infringement,117
inhomogeneity,49
injection,viii,45,55,57,111,122,137,142,
145
inspection,34
instability,170,172,173
instruments,105,115
insulators,28,30
integratedcircuits,vii,1
integratedoptics,41
integration,vii,1,3,16,24,26,29,34,40,
50,65,69,70,124,136,146
integrity,157
intensity,173
interaction,viii,ix,x,2,4,6,56,61,81,82,
97,124,149
interface,xi,20,115,140,167,170,172,
173
interval,16,29,151
ionic,ix,56,81,91,93,94,96,97,110,117
Index
180
ions,6,62,70,80,82,91,94,118,124,153
IRspectroscopy,151
irradiation,6,11,12,13,14,17,20,21,36,
41,49
isolation,115
isotropic,11
issues,108,119
J
Japanese,124
Jouleheating,117,130
K
kineticenergy,91
KOH,138,139
L
labelfree,150
LangmuirBlodgett,130
laserablation,26,38
lasingthreshold,32
law,vii,ix,56,58,59,60,61,63,64,65,68,
73,76,77,79,81,85,90,91,92,97
leakage,43,137,139
lens,5,7,19,20,24,36,43,44,49
leucine,124
lifetime,142
lift,138
ligand,150
lightbeam,17,25,36
lightscattering,151
limitations,112,131
linear,xi,4,6,24,26,59,88,106,119,122,
123,167,172,173
linearfunction,26,59
liquidchromatography,117
liquidinterfaces,172
liquidphase,170
liquids,11,38,44,74,76,78,79
lithium,6,14,17,19,29,41
lithography,vii,x,2,3,136,142,146,150,
152
loading,140
LOD,104,105,106,110,112,117,120,
122,123,124,127
losses,37,123
luminescence,108,112
lysine,124
M
mainstream,vii,2
majority,109
manifold,138,139,143
manufacturing,viii,2,7,34,48,148
masstransfer,58
matrix,6,19,49,107,109,118,123
measurement,35,110,119,138,151,160,
163
media,38,106,119,144,150,158,159
membranes,ix,135
memory,43,146
MEMS,v,x,149,151,152,154,156,158,
159,160,162,164,165
mercury,124
metalnanoparticles,x,149,150
metals,114
meter,32
methanol,138
methionine,118
methodology,ix,103
MFC,104,105,109,110,111
microarray,151,165
microcavity,30
microchip,2,24,25,34,35,36,38,43,44,
45,46,47,105,122,123,124,125,131
microelectrodes,29,30,41,124
microelectronics,vii,1,3,48,50,136
microfabrication,vii,2,3,4,6
microfluidicchannels,3,7,11,13,48,147,
151,152
Index
microfluidicdevices,viii,25,55,57,58,76,
79,105,121,124,148,170,173
microgels,147
micrometer,4
microorganisms,viii,2,3,42,43,44
microscope,19,23,24,26,27,28,34,35,
45,46,140,141,157
microstructure,10,36,44
microsystem,138,144,146
microvoids,11
migration,110
miniature,146,165
MinistryofEducation,145
mixing,viii,11,38,55,57,124
mobility,109,110,111,118
modulation,124,140
molecules,105,108,121,139
momentum,viii,ix,56,58,60,63,81,83,
97,151
monoclonal,140
monoclonalantibodies,140
monolayer,151
motion,viii,14,45,46,47,55,57,61,109,
118
motors,144
movement,42,43,44,46,47
N
nanoclusters,6
nanocrystal,134
nanodots,19
nanofabrication,x,146,149,150,151,164
nanometer,4,30
nanoparticles,x,6,20,24,104,127,149,
150
nanostructures,x,30,149,151,152,154,
156,157,158,159,160,162,163,164,
165
nanotechnology,148
nanotube,123,125
NationalResearchCouncil,126
181
nationalsecurity,2
natural,xi,167
NavierStokesequation,viii,56,58
neon,17
network,14,17
Newtonian,v,viii,ix,55,56,58,59,60,65,
66,68,70,71,73,74,76,77,78,79,81,
84,88,96
nitrate,27,28
nitrogen,17
nitrogengas,17
noise,viii,xi,56,57,104,116,118,150,
158,159,164,165
nonlinear,xi,167,173
nonNewtonian,viii,56,58,59,81
nonNewtonianfluid,viii,56,58,59,81
normal,138
nuclei,6
numericalaperture,5
O
observations,43,45,46
ofloxacin,123,125
oligomers,151
onedimension,20
online,52
opportunities,125,128
opticalfiber,36,37,38
opticalmicrographs,45
opticalproperties,6,17,19,49
optics,41,150
optimization,49,119
organic,108,127
organiccompounds,108
organism,44
OSA,51
oscillation,150
overlap,11,42
oxalate,127
oxidation,109,114,119,124
oxygen,125
Index
182
P
packaging,3
parabolic,70
parallel,7,11,16,21,41,45,57,85,173
parameter,58,59,71,87
particles,ix,109,110,135,137,138,139
passive,118,140
PDMS,v,x,xi,104,122,123,124,135,
136,137,140,142,143,144,145,150,
151,158,159,164
PEEK,138
performance,19,114,118,157
permit,121
permittivity,70,91
peroxide,124
petridish,43
petroleum,126
pharmaceuticals,123,125
phenylalanine,120
phosphate,163
photoabsorption,30,37
photochemical,20
photoexcitation,106
photographs,16
photolithography,3
photon,6,13,106,122,150
photonic,13,20,34
photopolymerization,138
physicalproperties,24
physicists,50
physics,vii,80,90
physiological,42
piezoelectricity,150
pitch,20,23,45
planar,vii,1
plastic,156
platinum,119,123,124,125,140
play,109
PMMA,142,143
Poissonequation,62
PoissonBoltzmannequation,57
polarity,114
polarization,125
polydimethylsiloxane,xi,104,122,150,151
polymer,x,47,58,114,138,149,151
polymerchains,138
polymerelectrolytes,58
polymethylmethacrylate,118
polystyrene,153,165
poor,6,49,108,110
pore,139
portability,105
powder,138
power,vii,ix,26,27,29,32,56,59,60,61,
63,64,65,68,73,75,76,77,78,79,81,
85,90,91,92,97,140,142,169,170,
171
powerlaw,vii,ix,56,59,60,61,63,64,65,
68,73,76,77,78,81,85,90,91,92,97
pressure,viii,ix,x,55,56,57,60,61,72,80,
81,84,85,86,91,92,93,94,95,96,97,
117,120,135,139,145,150,167,170,
172,173
problemsolving,131
problemsolvingstrategies,131
production,xi,2,105,117,150,151,164,
165
promote,173
propagation,xi,6,7,24,25,167,169,170
properties,4,6,17,19,24,49,80,109,
110,118,127,137,173
protein,140,163,165
proteomics,150
prototype,152,156
pulse,4,5,17,20,24,31,32,104,119,140
pumps,viii,55,57,79,136,146
Q
quanta,123
quantum,104,108,127
quantumdot,104,127
Index
R
radiation,106,167,170,172,173
radicals,108
radius,19,34,38,39,127
range,viii,xi,2,5,13,24,56,57,58,95,
106,108,122,123,127,158,163,167
reactant,7,110,120
reactions,24,105,106,108,109,113,114,
119,120,122
reactiveion,138
reactivity,114,124
reagent,2,14,123,124
recovery,124
recycling,125
redshift,164
redistribution,80
redox,113,120,122
redoxactive,122
redshift,153
reflection,17,31,167
refractiveindex,5,6,11,19,20,24,34,36,
37,38,49,150,154,158,164
refractiveindices,11,20,38
regular,119,125,172
relationship,60
relativesize,156
reliability,viii,56,57,158
reparation,110
repeatability,158
requirements,45,108,113,151
reservoir,46,48,58,110,116,140,171
resolution,5,6,7,12,14,20,30,49,158
respect,61,81,118
responsetime,106
returns,138
Reynoldsnumber,91
RIE,138,139
robotics,139
robustness,16
roomtemperature,x,19,135,137,163,
164
183
roughness,17,19,26,49,117
routing,14
ruthenium,104,108,130,133,134
S
saline,163
salt,138
sample,viii,2,5,6,7,9,11,13,16,17,18,
20,32,36,37,45,56,57,105,106,109,
110,111,118,140,151,158
satellites,172
scalar,59
Scanningelectron,139
scatteredlight,34
scattering,17,36
security,2
selectivity,104,105,106,108,109
selfadaptation,170
SEM,22,157,164
semiconductor,3,127,152
sensing,x,136,145,149,150,151,152,
153,156,160,164,165
sensitivity,37,106,107,109,112,116,118,
120,124,125,127,147,151,158,164,
165,170
sensors,79,120,136,137,147
separation,41,105,109,110,111,115,
116,117,118,120,121,122,123,125
series,36,85,119
serum,xi,150,151,152,163
serumalbumin,xi,150,152,163
shape,7,11,19,36,146,151,152,158,173
shear,ix,56,58,59,60,64,65,72,79
shunts,116
sieveplate,139,144
sign,63,83
signaltransduction,150
signals,113,151
signaltonoiseratio,104,158,159,164,
165
silica,26,123,125,158
184
Index
silicon,vii,x,1,14,112,137,138,140,142,
144,145,146,147,149,151,152,153,
156,158,159,164,165
silicondioxide,153
silver,6,20,24,27,28,151
simulation,58,131
sine,58,59,66
singular,92
smoothing,45
smoothness,19
softlithography,3,136,142,146
software,140
solidstate,125
solidsurfaces,68,80
solubility,108,109
solvent,138,151
space,5,11,43,137,138,142
spatial,5,14,20,30,49,106
species,viii,56,57,106,108,109,110,118,
120
specifications,91
spectroscopy,xi,30,106,150,151
spectrum,x,32,33,34,149,150,151,152,
158,159,160,163,165
speed,11,17,20,26,27,29,43,44,47
spin,153,154
SPR,151,164,165
stability,16,106,113,123,125,158
stages,109,110
standardization,2
steadystate,80
storage,11,13
strain,59,60,63,83
strategy,123
strength,68,74
stress,ix,x,56,59,60,64,65,72,79,150,
164
structuring,vii,2
substances,104,108,109,140
substrates,3,14,27,28
supply,7
suppression,4
surfaceproperties,118
surfaceroughness,17,19,26
surfacetension,172
suspensions,145
swelling,x,136,137,138,151
switching,14,137,140,142,145
symmetry,61,72,81,87
synthesis,136
systems,173
T
temperature,x,19,26,28,36,62,70,79,
82,91,132,135,137,139,140,146,
150,151,163,164,169
temporal,106
tension,172
testing,156
thermaltreatment,24
thinfilm,27,28,123,125
thinning,60
threedimensional,11,43
threshold,viii,2,4,14,30,32
time,171
tin,104,114
tinoxide,104,114
tolerance,125
totalinternalreflection,31
TPA,124
tracks,41
trade,6
trans,11
transduction,150
transfer,58,80,105,108,171
transition,137,147
transitiontemperature,137
translation,11,42
transmission,x,16,24,25,47,142,149
transparent,vii,x,2,3,4,5,20,41,48,149,
150,151,158,164
transport,94,118,124,171,172
transpose,60
traps,171
Index
tryptophan,118
twodimensional,58,61
tyrosine,118
U
ultraviolet,127
uncertainty,49
uniform,7,72
uniquefeatures,ix,103
universality,173
urine,123
UVexposure,6,7,154
UVlight,154
V
vacuum,70
valence,62,70,82,91
valine,120,124
values,24,59,65,71,72,73,75,76,77,79,
84,92,117,118,140
vapor,117
variables,119
variation,96,117,139
vector,60
velocity,viii,ix,14,56,57,58,59,60,61,
63,64,65,66,67,68,69,70,71,75,76,
77,79,80,81,83,84,85,86,87,88,92,
93,97,109,110
versatility,119
185
viscosity,ix,56,58,59,60,63,64,65,73,
74,79,80,81,83,90,95,97
visible,19,24,150
VitaminC,134
voltammetric,118
W
waste,2,111
water,17,43,44,47,60,80,108,119,125,
127,138,139,141,153,158,159,164
waveguide,20,24,34,35,38,39,41,49,
151
wavelengths,4,33,163
wetting,80,87,169
windows,153
withdrawal,140
writing,vii,2,3,4,5,7,8,14,19,20,24,26,
27,28,30,40,42,48,49,50,51
writingprocess,3
Y
yield,153
yttrium,31
Z
zetapotential,ix,56,57,62,68,70,77,81,
82,91,93,94,95,97
zirconia,125,133

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PHYSICS RESEARCH AND TECHNOLOGY

PHYSICS RESEARCH AND

Additional E-books in this series can be found on Novas website

PHYSICS RESEARCH AND TECHNOLOGY

Nova Science Publishers, Inc.

Copyright 2010 by Nova Science Publishers, Inc.

Published by Nova Science Publishers, Inc. New York

This book chapter consists of two parts. In Part 1, electroosmotic flow of

In: Microfluidics: Theory and Applications

State Key Laboratory of High Field Laser Physics, Shanghai Institute of

Ya Cheng, Koji Sugioka, Katsumi Midorikawa et al.

Microbiochips Monolithically Integrated with Microfluidics

fabricating LOC. For example, enclosed microfluidic structures such as

Ya Cheng, Koji Sugioka, Katsumi Midorikawa et al.

2. CONCEPT OF 3D DIRECT WRITING INSIDE

Microbiochips Monolithically Integrated with Microfluidics

pulses. Mainly as a result of this unique characteristic, 3D femtosecond laser

Figure 1. Schematic of a typical system for 3D femtosecond laser direct writing.

In principle, 3D femtosecond laser direct writing can be performed inside

Ya Cheng, Koji Sugioka, Katsumi Midorikawa et al.

Microbiochips Monolithically Integrated with Microfluidics

3. FEMTOSECOND LASER FABRICATION OF 3D

Ya Cheng, Koji Sugioka, Katsumi Midorikawa et al.

loosely focused in the direction perpendicular to the slit, which laterally

Figure 2. A large-scale crossed-channel buried in Foturan glass.

Microbiochips Monolithically Integrated with Microfluidics

Figure 3. A chemical microreactor with a vertical configuration.

Figure 4. (a) A horizontal Y-branched microchannel structure embedded 300 m

Ya Cheng, Koji Sugioka, Katsumi Midorikawa et al.

Microbiochips Monolithically Integrated with Microfluidics

Ya Cheng, Koji Sugioka, Katsumi Midorikawa et al.

Microbiochips Monolithically Integrated with Microfluidics

To demonstrate the effectiveness of the crossed-beam irradiation

Figure 7. Optical micrographs of the cross-sectional shapes of the microfluidic hollow

Ya Cheng, Koji Sugioka, Katsumi Midorikawa et al.

Microbiochips Monolithically Integrated with Microfluidics

Figure 8. Schematic illustration of the femtosecond laser exposure for fabricating a

Figure 9. Schematic illustration of the microplate functioning as a microvalve in a

Ya Cheng, Koji Sugioka, Katsumi Midorikawa et al.

Figure 10 shows two photographs of the fabricated sample. It is clear that

Figure 10. Photographs of a fabricated microreactor in which a freely movable

Microbiochips Monolithically Integrated with Microfluidics

scanned 140 parallel lines to form a plane structure vertically embedded in

Ya Cheng, Koji Sugioka, Katsumi Midorikawa et al.

We overcame this problem by including an additional annealing process.

Microbiochips Monolithically Integrated with Microfluidics

Ya Cheng, Koji Sugioka, Katsumi Midorikawa et al.

Microbiochips Monolithically Integrated with Microfluidics

Ya Cheng, Koji Sugioka, Katsumi Midorikawa et al.

Microbiochips Monolithically Integrated with Microfluidics

Figure 14. Schematic illustration and optical microscope images of a plano-convex

Ya Cheng, Koji Sugioka, Katsumi Midorikawa et al.

Even femtosecond laser direct writing without postannealing can increase

Microbiochips Monolithically Integrated with Microfluidics

highly effective for laser beam transmission. As mentioned above, the

Ya Cheng, Koji Sugioka, Katsumi Midorikawa et al.

Figure 17. Optical microscope image and characterization of 3D integration of two

Microbiochips Monolithically Integrated with Microfluidics

With the purpose of realizing selective metallization on surfaces of

Ya Cheng, Koji Sugioka, Katsumi Midorikawa et al.

Microbiochips Monolithically Integrated with Microfluidics

In our experiment, a 3-mm-thick lithium niobate (LiNbO3) crystal was

Figure 21. Optical micrographs of microelectrodes embedded in a LiNbO3 crystal: (a)