GGraphene, which is a layer of

carbon atoms in a hexagonal lattice, has

been reported to have excellent mechani-
cal, electrical, thermal, and gas barrier
properties. One of the most widely used
applications of graphene is graphene–
polymer composites, which are one of the
most promising solutions, since highly
functional materials can be produced with

image licensed by ingram publishing

a small amount graphene flakes incorpo-
rated in a lightweight polymer matrix.
Graphene–polymer composites have been
investigated for various types of applica-

B-Stage
tions such as thermal interface materials,
electromagnetic interference shielding
materials, gas sensor materials, and gas
barrier materials [1], [2].
In general, the properties of polymer

Graphene-Epoxy
composites can be changed by the filler ori-
entation direction when the fillers with a
high aspect ratio (the ratio of length to
thickness) are aligned to a specific direction.

Composite Films
Therefore, the alignment of nanosized fill-
ers, such as carbon nanotubes and graphene
in polymer composites, has been broadly
investigated, and horizontally aligned gra-
phene/polymer composites have been
reported using various techniques such as
solvent evaporation [3], pressing [4], vacu-
um filtration [5], and electric or magnetic
field application [6]–[8]. Electric field appli-
cation is one of the most promising tech-
niques because it is quite simple and various
Effects of film viscosity changes on the electric
orientations can be possible depending on
applied electric field direction. Polymer
field-induced alignment of graphene flakes.

SEUNG-YOON JUNG AND KYUNG-WOOK PAIK

Digital Object Identifier 10.1109/MNANO.2015.2472695

Date of publication: 23 September 2015

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 viscosity should be maintained at the lowest
value for better graphene alignment. There-
fore, it was reported that graphene was easi-
ly aligned to a specific direction in very
low-viscosity liquid polymer composites.
However, this alignment method has pro-
cess problems such as postpolymer solidifi-
cation processes and a mold [7], [8].
B-stage epoxy films have been widely
used in various electronic packaging appli-
cations. The term B-stage means that the
chemical curing reaction of thermosetting
adhesives such as epoxies and acrylics did
not occurr at room temperature. One of
the unique properties of B-stage adhesive
films is that the viscosity of the film can
be controlled by temperature. At room
temperature, the B-stage films are in a
solid format; however, when heated, the
viscosity of the B-stage films rapidly
reduces to a very low value and then
increases again due to the curing reaction
of polymer resins. Because of their viscosi-
ty characteristics, B-stage adhesive films
can be used to attach chips to substrates
with uniform thickness without any voids
and residuals, and are currently being
used for various electronic packaging
Sonication
Organic Solvent
Graphene
FIGURE 1  An illustration of the B-stage graphene–epoxy composite film fabrication processes.
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applications, such as anisotropic conduc-
tive films, wafer-level packaging, and
three-dimensional chip-stacking technol-
ogies [9], [10].
This rapid viscosity reduction by tem-
perature would be effective in aligning
graphene flakes by applying an electric
field. However, the reduced viscosity of
B-stage adhesive films cannot be main-
tained for a sufficient amount of time
because of the curing reaction. Because of
this reaction, the film viscosity increases
with time at high temperatures. There-
fore, it is important to investigate the
effects of viscosity change on the gra-
phene alignment in B-stage epoxy films.
In this article, the effects of time-tem-
perature dependent viscosity changes on
electric field-induced alignment of gra-
phene flakes in B-stage graphene–epoxy
composite film are investigated. The align-
ment direction was parallel to the compos-
ite film (horizontal direction). Electric
fields were applied to the graphene-epoxy
composite film at various temperatures and
times. The aligned graphene structure was
characterized in terms of film morphology
and electrical resistance.
Mixing with Epoxy Resin
Solvent Evaporation
Graphene Dispersion
Roll
Resin
Releasing Film
Roll
EXPERIMENT
FABRICATION OF B-STAGE
GRAPHENE–EPOXY
COMPOSITE FILMS
Graphene flakes used in this study were
commercially available exfoliated gra-
phene nanoplatelet flakes. The mean size
of the flakes was 5 µm with a thickness of
6–8 nm. Epoxy resins and adipic acid dihy-
drazide were used as the polymer matrix
and curing agent, respectively. Methyl-eth-
yl ketone was used as an organic solvent.
Graphene–epoxy composite was pre-
pared by solution-mixing and a comma-
roll coating, schematically illustrated in
Figure 1. First, graphene flakes were dis-
persed in an organic solvent, then the
epoxy resin and curing agent were mixed
into the solution. After that, the mixed
solution was heated to dry out the sol-
vent while preventing the graphene flake
agglomeration. Later, B-stage graphene–
epoxy composite films were coated on a
releasing film using a comma-roll film
coater. The amount of graphene flakes
was 3 wt. % in epoxy resin, and the coat-
ed final film thickness was 40 µm.
Graphene–Epoxy
Composite
 HORIZONTAL ALIGNMENT OF
GRAPHENE FLAKES IN B-STAGE
COMPOSITE FILM BY APPLYING
AN ELECTRIC FIELD
The experimental setup of electric field
applications is illustrated in Figure 2. The
electric field direction is parallel to the film
direction. An electric field of 200 V/mm
was applied to the films coated on a releas-
ing film. The films were placed on a glass
on a hot plate to apply the electric field at
a high temperature. The electric field was
applied right after the film started to be
heated, and the heating times and tempera-
tures were summarized in Table 1.
B-STAGE GRAPHENE–EPOXY
COMPOSITE FILM CHARACTERIZATION
Film viscosity was measured by a rota-
tional plate-to-plate rheometer to mea-
sure the viscosity changes during the
alignment process. Composite films were
laminated into 1-mm thick samples, and
the samples were heated from 30 °C to
target temperatures at the heating rate of
20 °C/min and held at the target tem-
perature for 60 min while viscosities were
measured. The target temperatures were
80, 100, and 120 °C.
Graphene alignment was characterized
in terms of flake orientation and electrical
sheet resistance. To measure the flake ori-
entation, the angle of graphene flakes with
respect to the electric field direction was
directly measured from the cross-sectional
scanning electron microscope (SEM)
images, and the degree of graphene align-
ment was defined as the portion of gra-
phene flakes that had an orientation of less
than 5°. The degree of alignment was
compared for various electric field applica-
tion conditions.
To observe the property changes
induced by graphene flake alignment, a
B-Stage Graphene–Epoxy Composite Film (3 wt. %, 40 µm)
E
Glass
dc Power
Hot Plate Supply
FIGURE 2  An illustration of the experimental setup for applying an electric field on B-stage com-
posite films.
laminated films. The electric field applica- lines that could easily determine orien-
tion time was 60 min and the tempera- tation. In addition, as the electric field
tures were 80, 100, and 120 °C. was applied, more graphene flakes were
aligned toward the electric field, as shown
RESULTS AND DISCUSSION in Figure 4(b).
To investigate the degree of graphene
FILM VISCOSITY OF B-STAGE alignment, flake orientation was measured
GRAPHENE–EPOXY with various electric field application times
COMPOSITE FILMS and temperatures. Figure 5 shows the
Figure 3 shows film viscosity of the com- degree of graphene alignment increment
posite films as a function of time at vari- as a function of time and temperature.
ous heating conditions. Arrows in each First, as the applying electric field times
graph indicate the time taken to reach the increased, the degree of graphene align-
target temperature. First, as the tempera- ment increased. At about 10 min, the
ture increased, film viscosity decreased oriented flakes still remained at random
to a certain point and then
drastically increased because
of the curing reaction to the T A B L E 1 E xperimental variables of temperatures
and times for applying electric field.
epoxy. The minimum vis-
cosity values were different
between various isothermal Temperature Viscosity Field application
(°C) (Pa · s) times (min)
temperatures. The lowest vis-
80 1,756 10, 20, and 60
cosity was obtained when the
100 735 10, 20, and 60
film samples were heated to
120 473.5 10, 20, and 60
120 °C. However, the vis-
cosity increasing speed was
the fastest because the curing
reaction occurred at a faster
106
rate at higher temperatures.
Viscosity (Pa ⋅ s)

105
four-point probe method was used to EFFECTS OF TIME
measure the sheet resistance of composite AND TEMPERATURE 104
films. Graphene–epoxy composite films ON DEGREE OF
120 °C
with various graphene contents (1, 3, and GRAPHENE ALIGNMENT 103 100 °C
10 wt. %) were fabricated using the same Figure 4 shows the cross- 80 °C
procedure as mentioned above. As a ref- sectional SEM images of 102
erence, the nonaligned graphene films 3 wt. % filled graphene–
0

0
60

20

80

40

00

60
1,

1,

2,

3,

3,

were laminated on a glass substrate and epoxy composite films with

Time (s)
cured at 100 °C for 60 min. To compare and without applying elec-
the effect of horizontal alignment of gra- tric field. Graphene flakes in
phene flake, an electric field of 200 V/mm graphene–epoxy composite FIGURE 3  Film viscosity as a function of time at various
heating temperatures.
was applied during the curing of films were shown as white

december 2015 | IEEE nanotechnology magazine | 15

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 Electric Field Direction

Acc.V Spot Magn Det WD 10 µm Acc.V Spot Magn Det WD 10 µm

10.0 kV 3.0 2000x SE 7.0 10.0 kV 4.0 2000x SE 6.7

(a) (b)

FIGURE 4  Cross-sectional SEM images of (a) nonaligned composite film and (b) aligned composite film with applied electric field (200 V/mm,
100 °C, and 60 min).

orientations and then gradually aligned as graphene alignment in B-stage composite

longer field times were applied. In addi- films. Further investigation is needed on
Alignment Increment (% p)

tion, maximum degree of alignment how these viscosity changes affect gra-
Degree of Graphene

20 18.7
14.7 increase was obtained at 100 °C, which phene alignment.
15
9.5 was higher than 80 and 120 °C. This can
10 7
be explained by the minimized film viscosi- THEORETICAL APPROACH: EFFECTS
5 1.9
0.5 5.8 ty and moderate viscosity increase by cur- OF VISCOSITY CHANGES ON THE
0 0.2 2.2 ing, as shown in Figure 3. Even though the ALIGNMENT OF GRAPHENE FLAKE
10 20 60 minimum isothermal viscosity was the low- Several authors have theoretically inves-
Field est at 120 °C rather than 100 °C, a better tigated the rotation of an ellipsoid par-
Application Time (min) degree of graphene alignment was observed ticle induced by an external electric field.
at 100 °C since the viscosity drastically When an electric field is applied to a flake,
80 °C 100 °C 120 °C
increased at 120 °C rather than 100 °C. the electrically polarized flake interacts
It was found that both the minimum with the electric field, rotating toward
FIGURE 5  The degree of graphene alignment ­viscosity and the viscosity increasing rate the direction of the electric field. On the
increments at various times and temperatures.
were important for electric field-induced other hand, the viscous polymer suppress-
es the rotation and these electrostatic and
hydrodynamic torque forces balance each
other [11], [12].
Electricstatic
Torque (τe)
Based on the work on liquid crystalline
flake by Kosz et al. [12], the equation of
E
motion was expressed as follows when the
Hydrodynamic
θ z electric field was applied to a single flake,
Torque (τh)
illustrated in Figure 6:

di = K $ h $ sin i $ cos i,
Rotation dt E2
Direction
where i is the angle shown in Figure 6, h
is the viscosity of polymer matrix, E is the
x y electric field, and K is the coefficient relat-
Viscosity of Polymer Matrix: η ed to dielectric constant difference and
flake size. Here, the value K was assumed
FIGURE 6  An illustration of a graphene flake rotation suspended in a polymer matrix an applied as constant because resins and graphene
electric field (E ).
flakes were all the same in this study.

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 T A B L E 2 A summary of theoretically calculated integration value of viscosity changes
and experimental degree of graphene alignment increments.
0.4
Integration Value

0.3
Field application condition Integration Degree of alignment
0.2 value increment (%p)
0.1 Temperature Time (min)
(°C)
0.0
10 0.18 1.9
80 20 0.30 2.2
0
0
0
0
0

0
60
20
80
40

00

60 60 0.31 5.8
1,
1,
2,

3,

3,
Time (s)
10 0.34 0.5
Isothermally Held at 120 °C
100 20 0.37 14.7
Isothermally Held at 100 °C
Isothermally Held at 80 °C 60 0.38 18.7
10 0.32 0.2
120 20 0.33 7
FIGURE 7  The calculated integration value
of viscosity changes from Figure 3. 60 0.33 9.5

As shown previously, the viscosity of

B-stage composite film changed with
times during heating. Therefore, by tak- Film viscosity was measured by a rotational
ing the viscosity as a function of time and
assuming the initial angle of i 0 at initial plate-to-plate rheometer to measure the
state (t = 0), the differential equation can
be solved as
viscosity changes during the alignment process.
t
In ` tan i j = KE 2 # 1 dt.
tan i 0 h (t)
0

This result suggested that a single gra- composites at the same time when the the sample, calculation included viscosity
phene flake will be aligned more to the integration value of viscosity change was of films during heating. The maximum
electric field at shorter time when the higher during certain conditions. calculated integration value of viscosity
integrated value of the inverse of viscosity Figure 7 shows the calculated data change was obtained at 100 °C because
was higher. In addition, more graphene from viscosity as a function of time. Since of its low viscosity and moderate viscosity
flakes can be aligned in graphene–polymer the electric field was applied after heating increasing speed.

20.0 M
10.6 M 500 k
426.4 k
15.0 M 3 wt%, 200 V/mm
Sheet Resistance (Ω/sq)

Sheet Resistance (Ω/sq)

400 k
10.0 M 232.7 k
3.7 M 300 k
5.0 M 235.0 k
187.0 k
200 k
426.4 k
400.0 k
100 k
200.0 k
31.2 k
0.0 0
Epoxy 1 3 10 As-Cured 80 °C 100 °C 120 °C
wt. % 60 min 60 min 60 min
(a) (b)

FIGURE 8  (a) The sheet resistance of graphene–epoxy composite films with various graphene contents. (b) Sheet resistance of 3 wt. % gra-
phene–epoxy composite films with various electric field application conditions (E = 200 V/mm).

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B-stage adhesive films can be used to attach
chips to substrates with uniform thickness
without any voids and residuals and are
currently being used for various electronic
packaging applications.
Table 2 summarizes the integration
value and degree of graphene alignment
defined previously. A higher degree of
alignment was obtained when the calculat-
ed integration value of the viscosity chang-
es was higher. The degree of alignment
increment reached a maximum of 19.7% at
the maximum calculated value obtained at
100 °C for 60 min. Even though there was
an error at 10 min due to the minimum
viscosity state mentioned above, the trends
in the experimental results shown in
­Figure 5 were well matched with the cal-
culated integration value of viscosity
changes using viscosity data. Therefore,
viscosity changes with time can be used to
predict the degree of graphene alignment
when the electric field was applied at a spe-
cific time and temperature.
EFFECTS OF THE DEGREE
OF GRAPHENE ALIGNMENT
ON ELECTRICAL PROPERTIES
OF GRAPHENE–EPOXY
COMPOSITE FILMS
Figure 8 shows the sheet resistance data
of graphene–epoxy composite films with
various graphene contents and various
electric field application conditions at
3 wt. % graphene content. As graphene
content increased, sheet resistance drasti-
cally dropped to 31.2 kX /sq at 10 wt. %,
as shown in Figure 8(a). Figure 8(b) shows
the sheet resistance of 3 wt. % compos-
ite films with various electric field appli-
cation conditions. As shown in Figure
8(b), the sheet resistance decreased as
graphene flakes were aligned, and the
minimum sheet resistance was obtained
at the best alignment condition (100 °C,
60 min). The electrical conductivity of
graphene was much higher in the in-plane
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direction. Therefore, if the flakes were
aligned parallel to the film, the sheet
resistance and electrical resistivity can be
significantly reduced since the aligned
direction would be parallel to the electri-
cal current path direction.
CONCLUSION
Aligned B-stage graphene–epoxy com-
posite films were successfully demon-
strated by applying an electric field at an
elevated temperature. The electric field
was applied at various times and tem-
peratures to evaluate the degree of gra-
phene alignment. It was observed that
the degree of alignment mainly depended
on the viscosity changes induced by heat-
ing. By using the theoretical approach,
graphene alignment can be predicted
from the viscosity change versus time
and the integration value of viscosity
changes is the determining factor of the
graphene alignment. The minimum inte-
gration value was obtained at 100 °C for
60 min of heating, where the best gra-
phene alignment of 18.7% was obtained.
In addition, as the degree of graphene
alignment increased, electrical sheet
resistance decreased from 426.4 kX /sq.
to 187 kX /sq. Property improvement
of solid B-stage graphene–epoxy com-
posite films can be achieved by aligning
graphene at applied electric fields under
reduced film viscosity.
ACKNOWLEDGMENT
This work was financially supported by
Graphene Materials and Components
Development Program of MOTIE/KEIT
(10044412, the development of basic and
applied technologies for L organic light-
emitting diodes with graphene).
ABOUT THE AUTHORS
Seung-Yoon Jung (gaiusjsy@kaist.ac.kr)
is with the Department of Materials and
Science Engineering, Korea Advanced
Institute of Science and Technology,
Daejeon, South Korea.
Kyung-Wook Paik (kwpaik@kaist.ac.kr)
is with the Department of Materials and
Science Engineering, Korea Advanced
Institute of Science and Technology,
Daejeon, South Korea.
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