Characterization of Molded Underfill Material for Flip Chip Ball

Grid Array Packages

Fenny Liu, Y. P Wang, Kevin Chai and T. D. Her
Siliconware Precision Industries Co., Ltd.
No. 123, Sec. 3, Da Fong Rd, Tantzu
Taichung, Taiwan, R.O.C.
Tel: 886-4-5341525 ext 3532, Fax: 886-4-5339099
Fenny@spil.com.tw

Abstract problem all been reported in previous studies. Figure 1 shows

Flip chip technology has been utilized for more than 30
years in the field of electronic package. It was developed to
meet the requirements of excellent electrical performance,
small device, high input/output (I/O) density and high speed.
Underfill which is used to fill the gaps between solder bumps
can enhance the fatigue life of solder bumps due to CTE
mismatch between chip and substrate. Underfill materials
usually need longer cure time to cure in process and with
higher cost. Therefore, the molded underfill is studied to
replace the capillary flow underfill for providing higher
productivity, no particle setting and less expensive materials.
The molded underfill material has to contain smaller filler size
to fill the small gap between solder bumps and fast cured
time. The development of molded underfill material is
different from conventional underfill and molding compound
material.
The material characterization of molded underfill
material was analyzed with various methods. The curing
condition was measured by Differential Scanning Calorimeter
(DSC). Thermo-gravimetrical Analyzer (TGA) was used to
study the weight loss of materials. Thermal Mechanical
Analyzer (TMA) was used to investigate the coefficient of
thermal expansion (CTE) of the cured materials. Dynamic
Mechanic Analyzer (DMA) was used to measure the storage
modulus of the cured materials. In this paper, the curing
conditions and materials properties such as CTE (coefficient
of thermal expansion), Tg (glass transition temperature),
storage modulus and weight loss were evaluated from the
measurement results for molded underfill materials. The
results were also compared with conventional underfill
materials and molding compound materials.
Introduction
Flip chip technology was developed more than 30 years
ago. It is widely used in the assembly of high performance
devices. Flip chip technology can offer excellent advantages
such as highest input/output (I/O) density, enhanced electrical
performance, better thermal characteristics at smaller die
areas. To improve the fatigue life of solder bumps due to CTE
mismatch between chip and substrate, underfill process is
usually necessary. Traditionally, underfill material was
dispensed to the periphery of flip-chip die with designed
dispensing pattern, underfill material then flows underneath
the die to fill the gaps between bumps and substrate by
capillary flowing phenomena. Due to the nature of this
capillary flow, there are challenges on slow flow time and
process quality such as underfill void, fillet coverage,
adhesion strength between die and substrate interfaces
the structure of conventionally underfilled FCBGA. Recent
process advances is able to provide a better solution on
aforementioned problems by using transfer molding
technology and Figure 2 shows the structure of molded
underfilled FCBGA. The transfer molded underfill technology
is a simplified one step process to offer fast process, high
throughput volume, high productivity and low cost of
ownership for flip chip [1-10].
Figure 1.The structure of underfilled FCBGA.
Figure 2. Molded underfilled FCBGA structure.
Usually, the void is easy to cause at the undergap of die
and substrate for capillary flow underfill material. The void
may increase the stress on the chip. In addition, the CTE
mismatch nature of capillary flow underfill between the chip,
substrate and solder bumps cause the delamination, stress and
warpage issues. To overcome issues, the molded underfill
material can provides the lower CTE, no void setting and
good warpage performance. The smaller filler size of molded
underfill material is easy to fill the small gap between solder
bumps. The undergap is completely filled by mold compound
to ensure the solder bump reliability. Moreover, the molded
underfill material also provides good moisture resistance.
Therefore, the molded underfill material was developed to
replace the capillary flow underfill [2].
The molded underfill material is a new material for
molded underfill technology. It is very important to evaluate
the material properties, operating process and reliability
concerns. In this study, the properties of material were
measured by using thermal analysis instruments such as
Differential Scanning Calorimeter (DSC), Thermo-
gravimetrical Analyzer (TGA), Thermal Mechanical Analyzer
(TMA) and Dynamic Mechanic Analyzer (DMA). The
material properties such as curing condition, relation between
CTE with the filler size and filler content, weight loss and
modulus for the molded underfill material, capillary flow
underfill and molding compound were discussed.

0-7803-7038-4/01/$10.00 (C)2001 IEEE 2001 Electronic Components and Technology Conference

Experiment from unity. The values for the kinetic parameters n, Ea and Z
The thermal analysis instruments will help to understand are obtained by a multiple linear regression analysis of this
the material properties that are the functions of time and data. Figure 3 shows the DSC measurement curve for molded
temperature for molded underfill material. The curing underfill material. Using DSC kinetic software, it can obtain
condition was measured by using DSC. The fast curing time the curing degree verses time for molded underfill material as
will reduce the cycle time and increase the unit per hour show Figure 4. From Figure 4, it can be found the curing
(UPH). TGA was used to understand the weight loss and temperature is higher with decrease curing time.
decomposition temperature of material. TMA was used to
investigate the coefficient of thermal expansion (CTE) of the
material. The lower CTE of material can reduce thermal
expansion mismatch between the chip, substrate and solder
bumps. The modulus helps to know the mechanical
performance of the material. So the modulus was measured by
using DMA. The detailed experiments are described as
following.
A. Differential Scanning Calorimeter, DSC
The DSC instrument (TA Instruments, Model 2910) was
used to measure heat flow into or out of molded underfill
material. The sample was put into a hermetic DSC sample pan
and weighted before and after the experiment. Then, the
sample was put in the DSC cell at 5oC/min heating rate from
room temperature to 280oC. The curing profile was obtained
after DSC experiment. After that, DSC curve can be analyzed
to determine specific kinetic parameters using the Borchardt Figure 3. DSC measurement curve of molded underfill
and Daniels kinetic software [11]. material.
The heat of reaction of molded underfill material can be
represented by the following equation:
k B+∆H
A
Where:
A = The material before reaction
B = The material after reaction

H = Heat of reaction
k = Arrhenius rate constant.
The Borchardt and Daniels approaches also assumes
Arrhenius behavior, it is expressed as:
k=Z e-Ea/ RT
Where:
Z = pre-exponential factor (sec-1)
Ea = activation energy of the reaction (J/mole)
R = gas constant (8.314J/mole K)
k = Arrhenius rate constant Figure 4. DSC curve of curing degree verses time for molded
T = absolute temperature (K) underfill material.

The reaction rate dα/dt is obtained from the DSC B. Thermal Mechanical Analyzer, TMA
measurement curve. Assuming the reaction follows nth order TMA (TA Instruments, Model 2940) is used to measure
kinetic, so the relationship is: the dimension change of material as a function of temperature
or time. TMA can be used to measure the CTE (coefficient of
dα/dt=k(1-α)n
thermal expansion) and Tg (glass transition temperature) of
Where: cured molded underfill material. The sample (length x width x
α = fractional conversion thickness: 8.37mm x 0.4mm x 0.38mm) was placed in the
k = Arrhenius rate constant TMA instrument with film/ fiber probe, and was heated from
n = reaction order room temperature to 300oC at a heating rate of 5oC/min. The
CTE is calculated as the slope of dimension change from
Combining the above equations and assuming a nth
expansion profile that is shown at Figure 5. Figure 5 shows
order reaction, the equation becomes:
TMA measurement curve of cured molded underfill material.
dα/dt= Z e-Ea/ RT (1-α)n CTE1 is the slope of first line and CTE2 is the slope of second
The unreacted fraction (1-α) is obtained by measuring line. The TgTMA is determined by the onset of the slopes of
the ratio of the partial area to the peak area, then subtracting α CTE1 and CTE2. The CTE and TgTMA were determined from
TMA measurement curve. The CTE1, CTE2 and TgTMA of

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molded underfill material are 18.5 ppm/oC, 69.6 ppm/oC and
202.09oC. The higher Tg can endure the higher temperature
environment.
Figure 5. TMA measurement curve of cured molded underfill
material.
C. Dynamic Mechanic Analyzer, DMA
DMA (TA Instruments, Model 2980) is used to measure
the modulus of molded underfill material. The modulus was
measured by DMA instrument as a function of temperature,
time, stress, amplitude, frequency and static force. The cured
sample (length x width x thickness: 14.13mm x 2.8mm x
0.4mm) was placed in the DMA instrument. The measurement
was performed on a film/ fiber mode under 1 Hz. A dynamic
temperature ramp of 5oC/min was used from room
temperature to 300oC. The storage modulus (E’) and loss
modulus (E”) were calculated by the software. The ratio of the
sample loss modulus to storage modulus properties is tan delta
(tanδ). The peak temperature of tanδ was defined as the
TgDMA. Figure 6 shows the DMA measurement curve of cured
molded underfill material. The modulus of molded underfill
material is 11.108 GPa at 35oC.
Figure 6. DMA measurement curve of cured molded undefill
material.
D. Thermogravimetrical Analyzer, TGA
The TGA instrument (TA Instruments, Model 2050) is
used to measure the weight loss and decomposition
0-7803-7038-4/01/$10.00 (C)2001 IEEE
temperature of molded underfill material. The sample was
uniformly put into the platinum sample pan. Then, the sample
was heated to 600oC at a heating rate of 10oC/min under
nitrogen purge gas. Figure 7 shows the weight loss and
decomposition temperature of molded underfill material. It
can be seen the weight loss of molded underfill material
during cure temperature was determined from TGA
measurement curve. And the decomposition temperature of
molded underfill material was also obtained. From Figure 7,
the weight loss of molded underfill is 0.2844% after curing.
The decomposition temperature of molded underfill material
is above 350oC, so the curing temperature was accepted in
process.
Figure 7. The weight loss and decomposition temperature of
molded underfill material.
Results and Discussion
In DSC measurement result, Table 1 shows the
comparison of the curing condition of molded underfill,
capillary flow underfill and traditional molding compound
materials. It can be found the curing is faster with higher
curing temperature. The curing time of molded underfill
material is much faster than capillary flow material at 135oC
and 150oC curing temperature. The curing time of molded
underfill material and molding compound are almost the
same.
Table 1. The curing condition for molded underfill material.
Temperature
135oC 150oC 165oC
Time(min)
Molded underfill 14.62 7.15 3.67
Capillary flow underfill 244.74 14.68 1.07
Molding compound 12.17 6.10 3.20
Table 2 shows the material properties of molded
underfill, capillary flow underfill and molding compound
materials. It can be seen the filler content increased with
lower CTE value for molded underfill and capillary flow
underfill materials that are almost the same filler particle size.
In addition, the viscosity increases with increasing filler
content. It has been reported in literature that the viscosity as a
function of filler loading [12-13]. Figure 8 shows the
relationship of CTE and filler content for molded underfill
and caipllary flow underfill materials. Figure 9 shows the
2001 Electronic Components and Technology Conference
CTE verses particle size for molded underfill and molding 70
compound. The filler size decreases, the CTE also decreases 60
Capillary flow underfillm aterial
for molded underfill material and molding compound that are

CTE (ppm/C)
almost the same filler content. However, the CTE of the filler 50
is much lower than the resin. The total surface area will 40
increase with finer filler particle size. The interface between
30
the filler and resin is increased. The CTE decreases due to the Molded underfill material
increasing surface area. 20
10
Table 2. The comparison of material properties for molded
underfill, capillary flow underfill and molding compound 0
materials. 30 40 50 60 70 80 90
Capillary
Type Molded Molding Filler Content (%)
flow
Properties underfill compound
underfill
o
Figure 8. The relationship of CTE and filler content for
CTE (ppm/ C) 18.5 55.6 25.1 molded underfill and capillary flow underfill materials.
11108(35oC) 7243(35oC) 16624(35oC)
Modulus (MPa)
1038(290oC) 68(290oC) 1705(290oC) 30
M olding com pound
Ash content (%) 80 50 77.4
25
Tg (oC) M olded underfillm aterial
202.09 141.68 178.18
(TMA) 20

CTE (ppm/C)
Particle Avg. 9~10um 0.7um 60 ~70um
15
size Max. 50um 3 ~ 5um 100um
Heat of reaction 10
46.13 180.4 55.86
(J/g)
5
Weight loss (%) 0.2844% 2.5250% 0.2206%
Curing peak 0
137.44 149.28 129.58
temperature (oC) 1 11 21 31 41 51 61 71
Decomposition Filler Particle Size (microns)
363.03 387.89 356.55
temperature (oC)
Figure 9. The CTE verses particle size for molded underfill
From above results, the filler size is smaller and filler and molding compound.
content is higher for molded underfill material. Moreover, the Summary
CTE of molded underfill material is lowest among capillary The molded underfill material was studied to replace the
flow underfill and molding compound materials. Therefore, capillary flow underfill material. In this study, thermal
the lowest CTE of molded underfill material can easy to analysis instruments such as DSC, TMA, DMA and TGA are
match the CTE of substrate. useful tools for analyzing the material properties of molded
From Figure 6, it can be seen that the higher underfill. It is very important to understand the basic material
temperature would contribute to lower modulus. From results properties before evaluation of process and reliability.
in Table 2, the higher filler content has higher modulus for In DSC measurement result shows the material cures
molded underfill and capillary flow underfill materials that are faster at higher temperature. The molded underfill material
almost the same filler particle size. can be cured in shorter time. From TMA results showed that
From Table 2, the weight loss of molded underfill as the filler content is increased, the CTE is decreased. As the
material is lower than capillary flow underfill material filler particle size is decreased, the CTE is also decreased. So
because of the solvent residue of molded underfill is less. The the CTE of molded underfill material is lower than capillary
higher weight loss of the capillary underfill cause higher flow underfill and molding compound materials. Therefore,
outgassing during curing temperature. The lower weight loss the CTE mismatch is lower to the substrate. The higher
for molding compound and transfer mold underfilling, so temperature would decrease the modulus of the material. The
there is no outgassing issue. It is very important to monitor the higher weight loss during curing process would increase the
outgassing problem during the process evaluation for molded possibility of outgassing which creates the reliability
underfill material. concerns.
From this study, molded underfill materials do not only
solve the drawback of molding compound and underfill but
also inherit the advantages of those materials. Therefore, the
molded underfill material is an excellent alternative material
used transfer molded underfill technology to shorter the
processing time and enhance the reliability.

0-7803-7038-4/01/$10.00 (C)2001 IEEE 2001 Electronic Components and Technology Conference

Acknowledgments
The authors would like to thank Plaskon and Dexter for
providing materials and Johnson Hsu for the assistance in
providing thermal analysis instruments. Su-Yung Pan and
Dragon Sue are greatly appreciated for preparing and
measuring of the sample. Finally the material technology
section’s colleagues are acknowledged for their kindly
supports.
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0-7803-7038-4/01/$10.00 (C)2001 IEEE 2001 Electronic Components and Technology Conference