Flexible, Transparent Electronics for Biomedical Applications

Michael Klopfer, Chris Cordonier*, Koutoku Inoue*, G.-P. Li, Hideo Honma*, Mark Bachman**
University of California, Irvine (Irvine, California, USA)
* Kanto Gakuin University (Yokohama, Japan)
** Corresponding Author: Mark Bachman (mbachman@uci.edu)

Abstract
The development and integration of flexible
biocompatible electronics is of considerable interest in the
biomedical community. Electronic and fluidic based
monitoring and therapeutic platforms can be contoured into
comfortable, low profile devices suitable for implanting in the
body or for wearing on the body or in clothing. Truly
integrated bioflexible devices would incorporate electronics,
optics, photonics, wireless, fluidics, mechanical components,
and power systems on a single flexible biocompatible
substrate. Continued development of applications of this
technology requires further development of biocompatible,
flexible films with integrated electronics which can be mass
produced at low cost.
In this work, we demonstrate the fabrication of flexible
printed circuits on Cyclo Olefin Polymer (COP) thermoplastic
as a substrate material. COP is an attractive polymer for
integrated bioflexible devices due to demonstrated
biocompatibility and excellent material properties, such as
high transparency over a wide band of wavelengths, low
water absorption, and good mechanical properties.
On significant challenge to building bioflxible devices on
polymer films (such as COP) is the need for metalizing and
patterning traces on these materials at low cost, and in a
scalable manner. In this paper, we report work that utilizes a
new technique for patterning metals on polymers that can
result in low cost manufacturing of electronic circuits on
biocompatible films such as COP. The process uses high
intensity UV light that is directed through a quartz mask to
selectively irradiate a film of COP. After processing, the
material can be treated and subsequently metalized using
electroless plating techniques. The great benefit of this
approach is that no photoresists steps are needed--no coating,
exposing, developing, etching, or stripping is required for the
creation of the final device. Furthermore, the process can
pattern traces at high resolution (<2 microns) and can coat the
insides of through hole vias, allowing multi-layer electronics
to be produced. This greatly simplifies the manufacture of the
circuits and reduces production cost considerably, when
compared to conventional processes such as sputtering and
etch.
We demonstrate the production of electronic circuits on
COP for the purpose of making bioelectronic devices and
characterize some of the main properties of the device. We
discuss the advantages of this approach and identify some of
the manufacturing pitfalls.
Introduction
There is great interest in the development of thin, flexible
integrated electronic devices that can also support non-
electrical technologies, such as fluidics, optics, and sensing.
Such devices hold promise for truly portable, implantable, or
wearable biomedical systems that can collect fluids from the
body and perform analysis on them, or provide therapeutic
relief[1-7]. The so-called smart bandage could be placed on
a wound to provide care and then disposed of afterwards. Or
such devices may find utility as patches for drug delivery or
physiological monitoring. Alternatively, the devices may be
placed into clothing, such as an insert into footwear or
undergarments. Such devices will need to be flexible and
biocompatible, and readily manufactured at low cost.
Current methods for producing such devices (e.g., PDMS
casting, flex circuit technology) either do not lend themselves
to low cost integration[8-10], or are not particularly well
suited to biomedical applications[11, 12]. Some work has
progressed in the development of circuit boards using
conductive inks. These must be silk-screened (or stenciled) on
to the surfaces and cured[13]. Lithographic techniques for
building devices are desirable owing to he ability to print very
fine features, do very high alignment, and produce circuits in
batch.



Figure 1: Direct selective metallization of clear COP plastic
can be used to produce traces, pads and through hole vias for
flexible, transparent printed circuit boards.

We have explored the use of COP as a potential substrate
material for making integrated biomedical circuits. COP is an
ideal candidate for such applications owing to its favorable
properties of low moisture absorption, low dielectric constant,
high transparency, low autofluorescence, low cytotoxicity,
and easy processability. COP is already used for medical
grade products and as a packaging material for food and
medical products. It finds application as high moisture barrier
flexible packaging for medical and pharmaceutical
applications including IV bags, TPN bags, blister packaging,
and overwrap bags. COP is typically produced as an
978-1-4799-0232-3/13/$31.00 2013 IEEE 494 2013 Electronic Components & Technology Conference
extremely pure material with low out-gassing and residual
metals (less than 0.02 ppm). COP exhibits low adsorption of
drugs as compared to polypropylene, and has significantly
less protein adsorption than polypropylene, making it optimal
for biomedical applications that must handle protein rich
fluids, or perform protein analysis on fluids. In addition, COP
exhibits high transparency (92% in visible range 400-800
nm), good moldability (for embossing microfluidics), low
fluorescence (less than polycarbonate or polystyrene), low
birefringence (one third of polycarbonate), low water
absorption (less than 0.01% per 24 hours), high heat
resistance (100 C to 160 C), and good chemical resistance
to acids, bases, alcohols and low adsorbtion of biofluids.
Electrical properties are similar to PTFE (Table 1)[14].



In order to produce circuits, conductive layers must be
created and patterned on the substrate. COP can be metalized
by conventional physical vapor deposition (e.g., sputtering),
but in order to realize large volume production of bioflexible
circuits at low cost, low cost metallization techniques should
be developed, as well as low cost, high resolution patterning
of the metals traces. Conventional patterning of metal films
utilizes a subtractive process. This process uses a photoresist
layer (usually laminated on the surface) which is
lithographically patterned. This requires that the photoresist
layer be carefully deposited on the surface, and the resulting
film laminate exposed to light through a mask. Following this,
the resist must be developed to yield the protective pattern.
The metal is then etched in a corrosive solution, and the
protective photoresist layer is stripped. This is a time
consuming, wasteful process with multiple steps, many of
them resulting in the generation of hazardous materials that
must be managed.
In this paper, we demonstrate the ability to quickly and
cheaply produce high resolution circuits made from thin metal
films that does not require a photoresist and etch step. This
process allows for both sides of a COP film to be metalized
and patterned in a single process. Moreover, the same process
allows for vias to be metalized, allowing for low cost, batch
production of two layer circuits on COP.

Fabrication Methods
Films (0.5 mm thick) of COP (Zeonex) were provided
by ZEON Corporation, Tokyo, Japan for use in this
research[14]. The films were cut to panel sizes and thru-holes
were drilled at known via locations and at alignment points
using a CNC controlled drill. These films were then cleaned
and dried in preparation for the metallization and patterning
process.
Lithographic masks were prepared using quarts plates that
were patterned with high resolution UV blocking material
(AZ 4620, AZ Electronic Material Services Ltd, Middlesex,
UK). Masks were created as a negative image (dark field) of
the traces we wished to pattern on the COP. The COP films
were surface treated by exposing them to high intensity, short
wave UV light through the masks. This surface modification
results in a physical and chemical change to the surface of
COP, allowing for good bonding of metals to the surface in
subsequent electroless plating.
The quartz mask was placed on the COP films and aligned
with the via holes using the drill hole alignment holes. The
film was then exposed to short wave light source utilizing a
high power, low pressure mercury lamp and oven provided by
Koto Electric Co., Ltd, Tokyo, Japan. This lamp has the
unique ability to produce intense UV light at low
wavelengths, which is needed for the surface modification
process (Figure 2).

After exposing to UV through a first mask, the film was
then turned over and a second mask was aligned with the via
holes, and the exposure process repeated. This exposure
process allowed both sides of the film to be exposed, and also
Characterization
COP
PTFE
Flouropolymer
Specific Gravity
1.01 2.14~2.20
Water adsorption (%)
<0.01 <0.01
Dielectric constant
[1.0 GHz]
2.3 2.1
Dielectric dissipation factor
[1.0 GHz]
0.0003 0.0002
Table 1: Some properties of Cyclic Olefin Polymer.

Figure 2: Short wave UV light passed through a pattern
mask is used to pattern the catalyzation process, and
eventual plating pattern onto the substrate. Our process
relied on a low pressure mercury light source
(manufactured by Koto Electric Co., Ltd, Tokyo, Japan).
495
allowed light exposure to occur in the via holes, effectively
modifying the surfaces of the via holes.
Following exposure to UV light, the films were then
cleaned and processed for electroless deposition. No further
patterning work was performed and there was no need to
develop or strip any materials. After cleaning and processing,
the films were placed in an electroless plating bath which
allowed metal films to form on the surface where the UV had
been exposed, effectively patterning the metal on the polymer
substrate. The entire process is shown in Figure 3 below. Our
experiments used two masks and six thru via holes, as shown
in Figure 4.


The process of metallization at select sites on the polymer
(and the resulting excellent adhesion) is believed to occur
through two mechanisms. Deep UV (short wavelength) light
exposed to the COP surface results in breakage of polymer
chains and the formation of radials. This process is also
assisted by the generation of ozone (O
3
) from ambient oxygen
immediately above the surface of the COP. These allow for a
number of chemical moieties to form on the surface when the
electroless process is initiated. In addition the UV exposure is
known to create a thin layer of nanopores in the surface which
act as a physical anchors for catalyst particles and the
resulting metal that is formed (Figure 5). Since the pores are
very tiny (few tens of nanometers), the resulting surface of the
film remains smooth and metals can be patterned at high
resolution (Figure 6).
The surface modification areas of the COP surface that
promote plate-out of metal in the area of sensitization using
an electroless copper or nickel plating process. In general,
increased plating time results in increased thickness for plated
metal on the COP substrate, up to a maximum thickness of a
few micrometers. If electrical contact is provided to the
electroless coated metal, a second layer of metal may be
electrolytically coated on top of the COP. Commonly nickel is
deposited first followed by copper for electrical circuits.
From our experience, a thickness of 0.5 to 1 micron for the
full metal coat thickness allows uniform conductivity across
the trace while allowing flexation without buckling or
delamination of the metal layer from the COP substrate. The
electroless process overview is shown in table 2.



If no mask is used, the entire surface of the COP may be
coated with metal, and this layer may be used as a seed layer
for subsequent plating steps allowing wide assortment of
metals to be coated on the polymer. The use of quartz masks
allows the electroless layer to be patterned directly into traces
without the need for resists and etching. However, this also
results in traces that may not be readily accessible to make
electrical contact for subsequent plating. This, the direct
patterning process, which highly beneficial for producing low
cost, patterned metal traces on COP, has limitations on the
ability to grow more (and thicker) metals on the surface.
Nevertheless, the current process is highly beneficial for
producing quality traces on thin films.


Figure 4: Mask pattern for the front and back of the
COP substrate. The front and the back are sensitized
sequentially, followed by a metallization of both sides
and vias that occurs simultaneously.

Figure 3: A summary of the workflow process outlined
in this publication is shown. UV treatment followed by
surface pretreatment, surface catalyzation, and
subsequent metal electroless plating(s) result in
conductive surface traces.
496

Figure 5: Cross sectional electron microscopy image of
nanopores generated in surface of polymer after UV
irradiation. The image is taken after plating and the metal has
plated inside the nanopores. This layer is 30-40 nanometers
thick. The scale bar is 10 nm.



Figure 6: Fine lines may be patterned on COP due to the
highly smooth surfaces of the COP after surface treatment.
These traces were patterned using a subtractive process.

Electroless nickel plating bath
NaH
2
PO
2
H
2
O
(NH
4
)
2
SO
4

Glycine
Temperature 45 C

This approach provides ability to produce a two-sided
circuit in a single manufacturing process without the need to
perform special via filling steps. To demonstrate this, we
fabricated a working circuit using the UV patterning and
metallization processes described above.

Electroless copper plating bath
EDTA4 H
2
O
2.2-Bipyridine
Polyethylene glycol - 1000
Ph-CHO
Temperature 60 C

Process parameters
pH Adjustment for bath (titration) -- NaOH or H
2
SO
4

UV lamp to sample distance -- 30 mm
UV Intensity (@253.7 nm) -- 80.36 mW/cm
2

UV Exposure Time -- 5min
Sample time in plating bath -- 30 min

Table 2: Formulations for the electroless copper and nickel
baths for metallization on COP post UV sensitization.

The circuit, a simple NOR gate oscillator device, was
fabricated for demonstration purposes only (Figure 7).
The board was designed specifically to demonstrate the
ability to produce traces on the COP that can connect to a
second layer through metalized vias and produce a working
circuit. The process proceeded as described above. First via
holes were drilled, followed by cleaning of the COP film,
followed by exposure to UV light through the masks. After
the plating process was complete, the film emerged from the
baths with patterned copper traces and conductive coated vias.
Surfaces were prepared for bonding by gently wiping
mounting pads and component leads with isopropanol.
Following this, electrical components were assembled on
the circuits and bonded using conductive epoxy (GC
Electronics, Rockford, Il. CAT# 19-2092). The components
were carefully aligned and brought in contact with the epoxy
coated circuit board pads. Curing of epoxy to hardness for
handling was achieved in about 1 hour in room temperature.
Rapid curing to handing hardness can be accomplished by
placing the uncured epoxy in a 70 degree C oven for 10
minutes. Full strength hardness was achieved in about 24
hours at room temperature. Faster processes for surface
mounting components using conductive epoxy are readily
available.

Characterization and Demonstration
The circuit described in (Figure 7) was realized using the
mask shown in Figure 4. A plating time of 30 minutes in a Ni
plating bath followed by 30 min in a copper plating bath
resulted in ~1 micrometer total thickness traces of copper on
nickel on COP. The formulations for the plating baths are
detailed in Table 2. The final unpopulated board was washed
with isopropanol followed by DI water, then placed in a 60 C
oven for 1 hour to dry residual water. Components were
manually placed and bonded using conductive epoxy are
previously described. Curing was accomplished using the
497
accelerated method (at elevated temperatures) described
above. The resulting circuit is shown in Figure 8a.

We used a NOR gate dual oscillator as a demonstration
circuit as a proof of concept for the ability of this plating
process to be used as a PCB replacement (Figure 7). An
alternating flashing between a pair of LEDs is used to indicate
operation of the oscillator. All circuit operation was
accomplished on the board, and the only input interface was a
constant 5 volt DC power supply. Operation of the circuit was
maintained even with vigorous flexing of the COP substrate.
This indicated that the traces maintained conductivity before,
during, and after the flexation of the board. Continued
flextation eventually lead to failure.
The quality of the board traces and vias were inspected via
electron and optical microscopy methods. Destructive and
non destructive inspection were used in characterization. In
destructive inspection, the COP was carefully cut using a
scalpel and viewed under light and electron microscopy. At
~20x, clear inner plating of the vias can be seen. Under a
scanning electron microscope, the continuity of the copper
can be confirmed (Figure 9a and 9b).
When viewed from the top of the board, bottom traces
appear black due to the nickel that is first applied to the PCB
before the copper is applied. All traces showed good
conductivitythe largest resistance was 3 ohms. Traces were
approximately 200 microns wide.
Qualitative assessment of the circuit durability was
performed by manually flexing the device under operation.
The flashing LEDs were observed while flexing the board by
hand to a bend angle of 45 degrees. Testing continued to
board failure. We flexed the board along the short and long
side of the COP. After 27 flexations, the through-hole vias
began to fail at the sharp edge of the through-hole.
Reinforcement of the electrical conductivity for the through
vias was accomplished by applying a thin layer of conductive
epoxy to the top and bottom of the via holes. High angle
flexing (bending approaching 180 degrees) create large forces
between the traces (which conformed to the bending of the
substrate) and the epoxy interface that links the components
to the surface of the board, resulting in epoxy delamination.
The separation generally occurred within the epoxy itself or
right at the interface with little damage to the underlying trace
itself. Repairs to these type of failures could be accomplished
by stripping of residual epoxy and replacement of
components.


Typically the epoxy separated from the traces and the
traces themselves were not destroyed. Slight bending and
unbending of the board during the early curing process
seemed to help reduce failures from this mechanism. The
quality and quantity of epoxy on the bond pads seemed to
correlate with improved durability. Notably, ductility in the
boding epoxy between the component and the trace seemed to
improve the chances of the components remaining in good
electrical contact during flexing.
Discussion
This investigation demonstrated that two layer circuits,
with conductive thru vias can be fabricated in a biocompatible
polymer film, Cyclo Olefin Polymer. Selective metallization
of COP substrate has been demonstrated indicating a possible
low cost, highly scalable manufacturing process for circuits
that is compatible with common manufacturing infrastructure,
such as panel-based lamination and roll-to-roll processes.
COP is a solid candidate for conformal, bioflexible, and
optically transparent PCBs which can be fabricated at low
cost. These results show a promising direction for producing

Figures 8a and 8b: A populated PCB is shown (Figure
4a) using surface mount components and 2 sided
construction. A close-up of a mounting pad set and a
through hole via (Figure 8b) shows uniform plating across
the traces.
Figure 7: Oscillator circuit used for the demonstration of
the proposed metallization process to produce PCBs.
498

such devices on COP, however, significantly more work is
needed to quantitatively investigate the quality and reliability
of the devices.
New research should be performed to produce useful and
relevant bioelectronics devices in COP, to investigate the
practical, large scale manufacture of integrated biodevices,
and to produce quantitative assessment of the performance
and reliability of such devices.
The use of microelectronics manufacturing to produce
integrated bioflexible devices is an exciting new direction for
the electronics manufacturing industry. Miniaturized
integrated bioflexible devices for human use represents a
potentially large emerging market, with applications in health
monitoring, portable diagnostics, and therapeutics. However,
current materials and processes are not well suited for
biomedical applications or are too expensive to produce large
scale disposable devices at low cost. New manufacturing
methods and materials, such as those described in this
investigation, will be needed for the microelectronics industry
to adequately service this new market.


References
[1] V. F. Curto, N. Angelov, S. Coyle et al., "My sweat
my health: Real time sweat analysis using wearable
micro-fluidic devices." pp. 196-197.
[2] R. Oliver, J. Tillotson, and A. Toomey,
Bioengineered Textiles and NonwovensThe
Convergence of Bio-miniaturisation and
Electroactive Conductive Polymers for Assistive
Healthcare, Portable Power and Design-led
Wearable Technology, Journal of Fiber
Bioengineering and Informatics, no. 1, 2010.
[3] G. Raupp, (Invited) Flexible Thin Film Transistor
Arrays as an Enabling Platform Technology:
Opportunities and Challenges, ECS Transactions,
vol. 37, no. 1, pp. 229-240, 2011.
[4] F. Benito-Lopez, S. Coyle, R. Byrne et al., Pump
less wearable microfluidic device for real time pH
sweat monitoring, Procedia Chemistry, vol. 1, no.
1, pp. 1103-1106, 2009.
[5] B. Ma, S. Liu, Z. Gan et al., A PZT insulin pump
integrated with a silicon microneedle array for
transdermal drug delivery, Microfluidics and
Nanofluidics, vol. 2, no. 5, pp. 417-423, 2006.
[6] B. Gyselinckx, C. Van Hoof, J. Ryckaert et al.,
"Human++: autonomous wireless sensors for body
area networks." pp. 13-19.
[7] R. Scarlet, R. Deliu, and L. R. Manea, SMART
TEXTILE SYSTEMS. SOLUTIONS FOR
DIFFERENT APPLICATIONS.
[8] F. J. DiBartolomeo, and C. A. Trinkle, "High
Throughput Continuous Fabrication of Large Surface
Area Microstructured PDMS."
[9] N. Lion, F. Reymond, H. H. Girault et al., Why the
move to microfluidics for protein analysis?, Current
opinion in biotechnology, vol. 15, no. 1, pp. 31-37,
2004.
[10] A. Mata, A. J. Fleischman, and S. Roy,
Characterization of polydimethylsiloxane (PDMS)
properties for biomedical micro/nanosystems,
Biomedical microdevices, vol. 7, no. 4, pp. 281-293,
2005.
[11] K. M. Miller, V. RoseCaprara, and J. M.
Anderson, Generation of IL1like activity in
response to biomedical polymer implants: A
comparison of in vitro and in vivo models, Journal
of biomedical materials research, vol. 23, no. 9, pp.
1007-1026, 2004.
[12] K. Miller, and J. Anderson, In vitro stimulation of
fibroblast activity by factors generated from human
monocytes activated by biomedical polymers,
Journal of biomedical materials research, vol. 23,
no. 8, pp. 911-930, 1989.
[13] J. Fjelstad, Flexible circuit technology, [2nd ed.,
Sunnyvale, CA: Silicon Valley Publishers Group,
1998.
[14] Z. C. LP., Multi-purpose Transparent Engineering
Plastics: 1020R Datasheet, 2013.

Figures 9a and 9b: Inspection of the vias was
accomplished through electrical conductivity initially
followed by imaging using electron microscopy (Figure
9a) and optical microscopy (Figure 9b). Visual inspection
of the vias with electron microscopy allowed visualization
of the surface structure to confirm a true conformal coating
of metallization was indeed what was producing electrical
conductivity through the via.
499