J Mater Sci: Mater Electron
DOI 10.1007/s10854-017-7316-5
Effect of silicone resin modification on the performance of epoxy
materials for LED encapsulation
Ruiheng Wen1 · Jizhen Huo1 · Jie Lv1 · Zhuoyu Liu1 · Yingfeng Yu1
Received: 8 March 2017 / Accepted: 7 June 2017
© Springer Science+Business Media, LLC 2017
Abstract Cycloaliphatic epoxy resin was modified by
phenyl methyl silicone resin to investigate the influence of
silicone content on the performance and reliability of epoxy
packaged light-emitting diode. The silicone modification of
epoxy encapsulants was characterized by transform infra-
red (FT-IR) spectrophotometer. Rotational rheometer was
used to study rheology behavior. Differential scanning calo-
rimetry, thermogravimetric analyses, dynamic mechanical
analysis, thermomechanical analyzer were introduced to
measure the thermal and mechanical properties. Ultravio-
let visible spectrophotometer was utilized to study heat and
ultraviolet resistance. In reliability test, scanning acoustic
microscope and scanning electron microscope were applied
to observe interfacial delamination. Water sorption pro-
cess was monitored using gravimetric measurement. FT-IR
study shows a chemical bonding between hydroxyl group
of silicone resin and epoxy resin. With the incorporation
of silicone resin, favorable properties were obtained such
as higher thermal decomposition temperature, lower equi-
librium water sorption, and better heat and UV resistance.
Among these systems, 10% silicone modified epoxy resin
exhibits the best performance in reliability test.
1 Introduction
Recently, light-emitting diode (LED) are widely applied in
numerous applications, such as lighting equipment, traffic
* Yingfeng Yu
yfyu@fudan.edu.cn
1 ins for microelectronic encapsulation as it can improve the
State Key Laboratory of Molecular Engineering of Polymers,
Department of Macromolecular Science, Fudan University,
Shanghai 200433, China
signals and large area displays because of their high effi-
ciency, low power consumption, and high durability [1–3].
The development of LED technology relies on the improve-
ment of high performance packaging materials. Epoxy res-
ins, as high performance thermosetting polymer materials,
have been extensively used for LED encapsulation due to
the advantages like high adhesion, great dimensional stabil-
ity, low dielectric constant, great machinability, and excel-
lent resistance to chemicals [4–7].
Cycloaliphatic epoxies, especially (3–4-epoxycyclohex-
ane) methyl 3–4-epoxycyclohexyl-carboxylate (ECC) cured
with acid anhydride exhibits excellent performance in LED
encapsulation. Owing to the nonaromatic cyclic structure,
ECC displays better performance such as higher proces-
sibility, better UV resistance and greater mechanical and
electrical properties than aromatic epoxies [8–10].
However, there are still some fundamental works should
be done in order to strengthen the performance of epoxy
resins for LED encapsulation. For example, the moisture in
epoxy resin can induce interfacial delamination and pop-
corning during solder reflow process [11–13], therefore,
the water-absorbing quality of epoxy resin is expected to
further decrease. In addition, cycloaliphatic epoxy resin has
limited application in LED encapsulation fields because of
its inherent brittleness arising from its high-cross-linked
structure, leading to a low resistance to crack development
and growth [14, 15]. Besides, the degradation of epoxy res-
ins under exposure to radiation and high temperature lead
to chain scission and discoloration. For more advanced and
durable LED devices, the improvement of encapsulating
material in heat and UV resistance is necessary [16].
Silicone resin is a sort of effective modifier of epoxy res-
performance of epoxy resins. The main chains of the sili-
cone are composed of Si–O bond with larger bond energy
13
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than C–C bond and C–O bond. Therefore, silicone modi-
fied epoxy resin has excellent performance of heat and UV
resistance [17]. In addition, the water sorption tendency
decreases on addition of silicone content due to the hydro-
phobic and partial ionic nature of the Si–O–Si linkage [18].
With so many favorable properties, increasing silicone con-
tent may lead to desirable result. However, phase separation
sometimes limits the incorporation of a large amount of
the silicone components with only methyl group, and more
seriously, leads to bleeding of the silicone components,
impairing the performance of the materials [19]. Among
silicone modifiers, phenyl methyl silicone could not only
offer thermal stability and toughness, but also has good
compatibility with epoxy resins [20].
In early researches, different kinds of silicone modified
epoxy systems had been well studied for other applications
[21–24]. However, the interaction between alicyclic epoxy
resins and phenyl methyl silicone has not been deeply stud-
ied yet. Moreover, few articles discussed the reliability of
LED devices when the silicone modified epoxy resins were
applied to LED encapsulation. As novel packaging material
must consider better optical, electrical, and thermal perfor-
mance as well as chemical and thermal stability [25]. The
reliability tests include thermal shock, aging at constant
temperature and humidity, lifetime test and so on [3, 26].
In our previous work [27], a set of method have been estab-
lished to study the reliability of epoxy encapsulated LED
devices, as well as the influence of different fillers to epoxy
resin. On the basis of the test methods, we further noticed
the reliability improvement of LED devices with the incor-
poration of flexible hydrogenated bisphenol A diglycidyl
ether into ECC materials [28]. However, the introduction
of flexible component would lead to obvious decline the
Scheme 1  Chemical structure
of ECC, silicone, MHHPA, and
TBAB
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J Mater Sci: Mater Electron
thermal and UV stability due to the drop of glass transition
temperature ­(Tg).
As phenyl methyl silicone resin could provide both good
toughness and excellent miscibility with epoxy resin, its
modification would be expected to improve the thermal and
UV stability of materials while decrease the internal stress
during thermal shock and external stress. In this study, a
phenyl methyl silicone resin was incorporated into epoxy
encapsulant to study its effect on the performance and reli-
ability of LED devices.
The reaction and the properties of these silicone modi-
fied epoxy resins were characterized by thermal and
mechanical methods. Water sorption behavior was stud-
ied by gravimetric measurement. The reliability and per-
formance of LED devices encapsulated with these epoxy
materials were tested according to the characterization
methods established previously.
2 Experimental
2.1 Materials
The commercially available epoxy resin, (3-4-epoxy-
cyclohexane) methyl 3-4-epoxycyclohexyl-carboxylate
(ECC) having epoxy equivalent of about 130–135 was
obtained from Dow Inc., USA. The phenyl methyl sili-
cone resin Wackle Silres 604 (Silicone, ­Mn = 2320 g/mol)
was purchased from Wackle Co., Germany. The methyl-
hexahydrophthalic anhydride (MHHPA) and Tetrabutyl
ammonium bromide (TBAB) were purchased from Aldrich
Chemical Co., USA. The chemical structure of materials
is illustrated in Scheme 1. ECC was dehydrated in vacuum
J Mater Sci: Mater Electron

oven before use; the other chemicals were used without fur- 2.3.2 Differential scanning calorimetry (DSC)
ther treatments.
DSC was used for characterizing the curing behaviors of
cure systems and the glass-transition temperature (Tg) of
2.2 Sample preparation
the samples. Calorimetric analyses were carried out on a
TA Q2000 Differential Scanning Calorimeter. Samples of
To investigate the characteristic of silicone modified epoxy
approximately 5 mg were cured in hermetic aluminum pans
resin, silicone with different ratio (silicone parts accounted
under a dry nitrogen atmosphere(50 mL/min) at a heating
for the total mass of 0, 10, 20, 30%) were reacted with
rate of 10 ℃/min. The glass-transition temperature ­(Tg) can
epoxy resin ECC. The formulations of the studied sys-
be measured with the ramp program from 40 to 250 °C by
tems are listed in Table 1. The silicone modified epoxy
10 °C/min, and then from 250 to 40 °C by 20 °C/min, after
are denoted as Neat ECC, silicone-10%, silicone-20%, sil-
that 10 °C/min to 250 °C. The second curve of temperature
icone-30%. When silicone was added, the weight percent
rise can indicate ­Tg.
of catalyst TBAB and epoxy/anhydride molar ratio was
kept unchanged in stoichiometric ratio. For example, sili-
2.3.3 Dynamic mechanical thermal analysis (DMA)
cone-10% represents that the weight percent of silicone in
the blends is 10 wt%.
DMA was introduced to measure the thermal and mechani-
Under magnetic stirring, the mixture of ECC and sili-
cal properties of the samples. Dynamic mechanical meas-
cone reacted in the oil bath at 120 °C for 1 h. After cooling
urement was conducted on Mettler Toledo—DMA/
to 60 °C, a stoichiometric amount of MHHPA and 0.5 wt%
SDTA861e with a large Dual Cantilever mode. The DMA
of catalyst TBAB were added into the mixture to form cure
samples were cured with the size of 30 × 10 × 1 mm3. The
systems. Those systems mixed for another 0.5 h at 60 °C.
measurements were carried out in nitrogen atmosphere
Colorless homogeneous viscous liquids were obtained. To
at the heating rate of 3 °C/min in the range of 50–300 °C.
prepare samples for testing, the resin systems were cured
Mechanical parameter was deformation 10 μm, force
in molds at the temperature of 100 °C for 2 h and 130 °C
applied 0.5 N and the frequency 1 Hz.
for 2 h, and then post-cured at 180 °C for 1 h. The samples
Based on the rubber elasticity theory [29], the cross-
were all colorless transparent slices. For LED encapsula-
linking density ρ of the epoxy resin is obtained from the
tion, 40 wt% of silica filler was added in the epoxy packag-
equilibrium elastic modulus G′ in the rubbery region
ing materials.
above the α-relaxation temperature through the following
equation:
2.3 Characterization �
ρ = G ∕�RT
2.3.1 Fourier transform infrared spectroscopy (FTIR) where ∅, R and T are the front factor, universal gas constant
and the Kelvin temperature respectively. ­Tg + 50 °C is used
FTIR was utilized for characterizing the reaction and the as the temperature for the equilibrated elastic modulus [30],
properties of silicone modified epoxy resin. FTIR spec- where ­Tg is identified as the peak temperature of loss tan-
troscopy experiments were performed on a Thermofisher gent. ∅ is 3 for epoxy resin [31].
Nicolet 6700 Spectrometer with a resolution of 4 cm−1. For
cured epoxy sample sheets, their surfaces were scanned on 2.3.4 Thermogravimetric analyzer (TGA)
a diamond ATR accessory for 128 times. The liquid sam-
ples were sandwiched between two KBr plates and scanned Thermal stability was determined on Perkin-Elmer Pyris 1
from 4000 to 400 cm−1 for 64 times. The reaction process TGA. The samples were around 5 mg. All measurements
of ECC and silicone was tracked at 120 °C for 1 h. The cur- were carried out under nitrogen (40 mL/min) atmosphere
ing process of cure system was track at 130 °C for 1 h. for heating from 25 to 800 °C at the rate of 10 °C/min.

Table 1  Formulation of Sample ECC (wt%) Silicone (wt%) MHHPA (wt%)a TBAB (wt%) Refractive index
silicone modified epoxy resin
investigated Neat ECC 43.6 0 56.2 0.2 1.4892
Silicone-10% 39.2 10.0 50.6 0.2 1.4939
Silicone-20% 34.9 20.0 44.9 0.2 1.4981
Silicone-30% 27.3 30.0 42.5 0.2 1.5022
a
MHHPA are in stoichiometric ratio with epoxies

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2.3.5 Thermomechanical analyzer (TMA)
TMA study which was performed on Mettler Toledo—TMA/
SDTA841e was used to measure the coefficient of linear
thermal expansion coefficient (CTE, α) of the materials. The
samples which had similar size of 4 × 4 × 2 mm3 were heated
from 25 to 300 °C at the rate of 3°C/min. CTE could be deter-
mined by formula:
dL 1 can calculate the diffusion coefficient D.
α= ×
dT LT
where dL/dT is the change rate of length by the time, ­LT
is to the length of sample at certain temperature. α below
­Tg is measured between 75 and 125 °C and α above ­Tg is
measured between 225 and 275 °C.
2.3.6 Lap shear strength measurement
Lap shear strength is an important parameter to determine
the stickiness of epoxy resin. The procedure of preparing lap
samples is processed as standard ASTM D1002 [32]: First,
copper sheets were polished by abrasive paper and cleaned
by ethanol and acetone. And then, samples were disposed
between copper sheets with contact area of 2.54 × 1.27 cm2.
The processed samples were cured in general curing proce-
dure mentioned by this essay. The measurement was con-
ducted by materials testing machine CMT4104. To reduce
the randomness of testing machine, five parallel samples
were prepared for each types of epoxy resin, and average ten-
sile force would reflect lap shear strength.
2.3.7 Gravimetric measurement of water sorption
The sample sheets (20 mm × 20 mm × 1 mm) were polished
with deionized water, and then dried in a vacuum oven at
100 °C for 24 h. Water sorption into sample sheet at 85 °C
was monitored as a function of immersion time [33]. The
samples were taken out from the water at intervals, wiped
with lens paper and weighed on a Mettler Toledo ME204E
microbalance (accuracy, 0.1 mg). The samples were cured in
the mold which was 0.1 cm thickness. Weighing water sorp-
tion ­(Mt) is defined as:
(
Mt = Wt − W0 ∕W0
) scanning acoustic microscope (C-SAM) SONIX C-SAM
where Wt is to the sample mass at t moment, W0 is the sam-
ple mass without water sorption.
The diffusion coefficient is another important index affect-
ing the properties of epoxy materials. It is generally accepted
that the behavior of initial water sorption process of epoxy
conforms to Fickian diffusion [34]:
Mt 4 Dt 1∕2
( )
= 23 °C with the frequency from 0.01 to 100 Hz.
M∞ d 𝜋
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J Mater Sci: Mater Electron
where D is the diffusion coefficient, d is the thickness of
the specimen, Mt is water sorption at time t, and M∞ is the
equilibrium value of the diffusing water at infinite time.
According to Fickian diffusion equation:
( )
π Mt ∕M∞
D=
16 t1∕2 d−1
Once the slope of Mt ∕M∞ versus t1∕2 d−1 is obtained, we
2.3.8 Ultraviolet visible (UV–Vis) spectrophotometer
UV–Vis spectrum was measured by Perkin-Elmer Lambda
750 which was utilized for tracking yellowing of the materi-
als after heat and ultraviolet aging. The samples were cured
in size of 20 mm × 20 mm × 1 mm. The condition of heat
aging was 150 °C in electric heat oven for certain hours. The
ultraviolet aging was conducted in UV203 ultraviolet aging
machine. At the room temperature, the radiation intensity on
sample surface was 360 mW/cm2. In general, the properties
of heat and ultraviolet resistance can be measured by yellow
index (YI). YI can be calculated by [27]:
T620 − T470
YI = × 100
T520
where T620, T470 and T520 are transmittance of material at
wavelength of 620, 470, 520 nm, which correspond to the
red, green, and blue light emitted by LED devices.
2.3.9 Reliability test
The test procedure for LED packaging reliability characteri-
zation involved moisture preconditioning, the thermal shock
cycling test (T/C: −65 to 150 °C), and the infrared (IR) sol-
der reflow process (260 °C × 3 times). The encapsulated LED
devices were subjected to moisture sensitivity level test MSL
3 upon IPC/JEDEC J-STD-020. The LEDs were primarily
baked to remove residual moisture subsequently implemented
with T/C tests or PCT and then exposure to damp environ-
ments at 30 °C and 60% RH for 192 h followed by three times
IR reflow soldering. The fatigue crack, defects, and delami-
nation during the reflow soldering process was analyzed by
LHF-200. Surface cracking of encapsulated LED device was
examined by scanning electron microscope (SEM), Philip XL
39.
2.3.10 Rheology characterization
The rheology characterization was performed on Ther-
mofisher HAAKE MARS III. The study was carried out at
J Mater Sci: Mater Electron
2.3.11 Hardness test
The hardness was measured at room temperature using a
Shore D hardness tester (XHS, China) according to ASTM
standard D2240.
2.3.12 Refractive index test
The refractive index was obtained by WZS-1 abbe’s refrac-
tometer at room temperature. Each sample was measured
three times in parallel.
3 Results and discussion
3.1 Preparation and properties of silicone modified
epoxy resin
3.1.1 Preparation of silicone modified epoxy resin
In this study, hydroxyl group of silicone reacted with epoxy
group or secondary hydroxyl group of epoxy to form sta-
ble Si–O–C bond, which was characterized by means of
FT-IR spectrophotometer. Figure 1 shows FT-IR spectrum
of substances consist in the reaction of silicone and epoxy.
Compared to ECC and silicone mixture before reaction,
the characteristic peak at 3510 cm− 1, corresponding to the
O–H variation sorption of hydroxyl group mainly from sili-
cone [20], declines after reaction, which indicates that the
hydroxyl group of silicone resin has reacted with epoxy
resin. Si–O–C bond, with the broad peak at 1040 cm− 1, has
higher intensity after reaction, corresponding to the combi-
nation between silicone and epoxy.
Fig. 1  FT-IR spectrum of a neat ECC, b neat silicone, c ECC and
silicone mixture before reaction, d ECC and silicone mixture after
reaction
The reaction between ECC and epoxy was tracked by
FTIR in-situ monitoring. It is observed from Fig. 2 that, the
intensity of hydroxy peak decline with the reaction time at
120 °C. Hardly any variation can be seen when the reaction
time came to 1 h. Therefore, in the condition of 120 °C for
1 h, the reaction of ECC and silicone almost complicated.
Above all, these results indicate that the silicone has com-
bined with epoxy successfully.
The refractive indexes of the samples are listed in
Table 1. The result denotes that the refractive indexes of the
samples increased from 1.4892 to 1.5022 with the amount
of silicone, which is caused by the enlargement of the phe-
nyl group from the silicone resin with higher refractive
index value.
3.1.2 Rheology study of silicone modified epoxy resin
The result of rheology characterization for flow and fre-
quency study is shown in Fig. 3. It can be observed that
the rheological behavior of silicone modified epoxy resin
is similar to Newtonian fluid. It is clear that more silicone
content will lead to higher viscosity. The viscosity of sili-
cone-30% system is much higher than other systems. As
the silicone reacts with epoxy to form compound with
higher molecular weight, the relative motion of molecules
encounter larger hindrance. Therefore, the viscosity of the
sample increases.
3.1.3 Curing study of silicone modified epoxy resin
In Fig. 4, the substances in the curing reaction by MHHPA
are studied. For neat MHHPA, the two C=O stretching
vibration peaks of anhydride at 1790 and 1860 cm−1 are
observed. MHHPA with well processed ECC and silicone
Fig. 2  in-situ FTIR monitoring spectrum of the reaction between
ECC and silicone for 1 h at the temperature of 120 °C; the time inter-
val for each spectrum is 1 min
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 J Mater Sci: Mater Electron

100 groups convert thoroughly. Nevertheless, it is necessary to

Neat ECC
Silicone-10% post-cure the sample at higher temperature to convert the
Silicone-20%
Silicone-30% remaining group. The spectrum of silicone modified ECC
sample after post-cure shows no intensity at 1790 and
10 1860 cm−1, which means that the anhydride has converted
completely. After post-cure, strong characteristic bands for
η(Pas)

Si–O–C bonds are observed at 806 and 1040 cm−1.

The exothermic curves are shown in Fig. 6, onset tem-
1 perature ­(To), peak temperature ­(Tp), final temperature (­ Tf)
and enthalpy are summarized in Table 2. From Fig. 6 and
Table 2, it is observed that only one exothermal peak in
temperature zone and the peak temperature of all systems
0.1 are around 150 °C. Besides, there is just little difference of
0.01 0.1 1 10 100
Frequency(Hz)
normalized enthalpy of the polymerization among the four
systems. It could also be found that higher content of sili-
cone in epoxy-silicone system leads to slightly higher T ­o
Fig. 3  Flow and frequency study of silicone modified epoxy resins
and ­Tp. However, the difference between those systems are

mixture before cured keeps these features. However, these

two peaks disappear after cured, especially after post-
cured and the C=O stretching vibration peak of ester at
1730 cm−1 increases. In addition, the characteristic peak
of MHHPA at 902 cm−1 also declines in curing process.
The peak between 950 and 1000 cm−1 corresponding to
the C–O stretch vibration from the anhydride MHHPA
also decreases simultaneously. It denotes that the MHHPA
reacts with well processed ECC and silicone mixture to
form thermoset resin.
The curing reaction was also tracked by FTIR in-situ
monitoring. Figure 5 indicates the change of characteris-
tic peaks at 130 °C. Within an hour, most of the anhydride

Fig. 4  FT-IR spectrum of a neat MHHPA, b mixture of ECC and

silicone after reaction, c MHHPA with well processed ECC and sili- Fig. 5  in-situ FTIR monitoring spectrum of the curing reaction
cone mixture before cured, d MHHPA with well processed ECC and between MHHPA and well processed ECC and silicone mixture for
silicone mixture after cured. e Silicone modified ECC sample after 1 h at the temperature of 130 °C; the time interval for each spectrum
post-cure is 1 min

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J Mater Sci: Mater Electron

Neat ECC
Silicone-10% (a)

Heat Flow Exothermic

Silicone-20%
Heat Flow Exothermic

Silicone-30%
(b)

(c)

(d)

50 100 150 200 250 50 100 150 200 250

o Temperature(oC)
Temperature( C)

Fig. 7  DSC curves of silicone modified epoxy resin cureds with

Fig. 6  DSC curves of silicone modified epoxy resins cured with
MHHPA for ­Tg: a neat ECC, b silicone-10%, c silicone-20%, d sili-
MHHPA for curing study
cone-30%

not so significant. It could be considered that introducing

the silicone make little difference to the curing temperature.
3.1.4 Thermal properties of silicone modified epoxy resin
Figure 7 and Table 2 show the ­Tg of all systems. The ­Tg
of silicone modified epoxy resin cured with MHHPA was
around 200 °C. There is no significant decrease of ­Tg until
the content of silicone reached 20%, which means that the
addition of small amount silicone does not decrease the ­Tg
remarkably.
Silicones commonly have poor compatibility with the
epoxy resin due to their varied solubility parameters, which
results in a formation of finely phase-separated structure
and a considerable sacrifice in glass transition tempera-
tures in thermosets [35]. However, previous study revealed
that silicone with phenyl group showed great compatibil-
ity with epoxy resin [36]. Moreover, the silicone blended
with epoxy by chemical reaction in this study, which also
improved their compatibility. Thus, the glass transition tem-
perature decreases inconspicuously when the silicone con-
tent is still low. Nevertheless, too many silicone contents
will lead the system to show incompatibility so that glass
transition temperature decreases significantly.
The thermal stability of silicone modified epoxy resin
was evaluated by thermal gravimetric analysis (TGA). The
result was shown in Fig. 8. It is found that the cured epoxy
resins almost kept their any original weight before the scan-
ning temperature reached up to 280 °C, implying that they
have good thermal stability below 280 °C. The decomposi-
tion temperature at 5% of weight loss (­ T5) and decomposi-
tion temperature at 10% of weight loss ­(T10) are shown in
Table 2. As the scanning temperature rises to 340 °C, the
TGA curves exhibit a dramatic decrease. However, we find
that epoxy resins with higher content of silicone exhibited
a relative slow tendency of weight decreasing in compari-
son with neat ECC epoxy resin. The T ­ 5 increases about
8 °C and ­T10 increases 12 °C when the content of silicone
reaches 30%, which suggests that introducing silicone into
epoxy resin system enhance thermal stability of their cured
sample. The improved thermal stability of silicone modified
epoxy resin could be attributed to the presence of Si–O–Si
linkages in the polymer backbone. Because Si–O bond has
larger bond energy than C–C bond and C–O bond, higher

Table 2  Curing characteristics System Neat ECC Silicone-10% Silicone-20% Silicone-30%

and thermal properties of
silicone modified epoxy resins To (°C) 93.3 91.4 96.3 96.3
cured with MHHPA
Tp (°C) 149.1 149.8 150.4 151.4
Tf (°C) 176.5 178.9 182.7 202.3
Enthalpy (KJ/mol) 100 102 96 94
Tg (°C)DSC 206.9 204.3 203.1 178.7
T5 (°C) 309.2 310.7 312.1 317.0
T10 (°C) 320.4 323.3 326.8 332.8

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 J Mater Sci: Mater Electron

Fig. 8  TGA curves of silicone modified epoxy resins cured with

MHHPA

temperature is needed to cause the decomposition of sili-

cone modified epoxy resin [17].

3.1.5 Heat and ultraviolet resistance properties

For LED encapsulation, the heat and ultraviolet resistance

of epoxy resin determine the life time of the devices. In
general, the properties of heat and ultraviolet resistance can
be measured by yellow index (YI). UV–Vis spectropho-
tometer is utilized for tracking yellow index of the materi-
als after heat and ultraviolet aging.
Figure 9 shows that the transmittance of silicone-10%
sample after heat aging. The transmittance in low and
medium wavelength decreases by the aging time. It can
be observed from Fig. 10 that sample with higher ratio of
silicone has higher transmittance after 168 h. Therefore,
increasing the amount of silicone will improve the heat
resistance of epoxy resin. At the same time, the results of
ultraviolet aging experiment have the same tendency as the
heat aging experiment. The YI of all samples is described
in Fig. 11. Whether heat aging or ultraviolet aging, silicone
modified epoxy resin shows better yellowing resistance
than neat epoxy resin. In conclusion, the introduction of
silicone in epoxy resin system could enhance the heat and
ultraviolet resistance.
It can be explained that bond energy of Si–O bonding is
larger than those of C–C and C–O bonding, which makes
the silicone modified epoxy resin have stronger thermal
resistance than neat epoxy resin [37]. Besides, it is proved
that the thermal oxidation of the surface of the cured resins
is more serious than that of the bulk during thermal aging,
and the enriched silicone acted as a protecting layer against
thermal oxidation. The enrichment degree of silicone is
enhanced with increasing silicon content [21]. Therefore,
Fig. 9  The transmittance curves of aging experiment for sili-
cone-10%: a heat aging, b UV aging
increasing the silicone content will improve the thermal
resistance of epoxy resin.
3.2 Reliability test for LED devices
3.2.1 Reliability test
Until now, most of the aging tests were simply based on
thermal aging or UV aging. For in-depth investigation of
epoxy resin, moisture/reflow sensitive test and scanning
acoustic micrograph were introduced to study the reli-
ability for LED devices [27, 28]. In this work, moisture/
reflow sensitive tests upon IPC/JEDEC JSTD-020 had been
employed as the reliability test criteria for LEDs.
The reliability test result of LED devices encapsulated
with epoxy resins modified by various silicone content is
collected in Table 3. As seen from Table 3 that, the LED
devices encapsulated with different silicone modified res-
ins show different outcome. After the test on the condi-
tion of 30 °C, 60% RH, 192 h and MSL 3 Reflow Profile

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J Mater Sci: Mater Electron
Fig. 10  The transmittance curves of aging experiment after 168 h: a
heat aging, b UV aging
3 rounds, no device lose efficacy. However, reliability
performance of LED devices encapsulated with 30% sili-
cone modified epoxy deteriorates dramatically after 300
rounds T/C test. After 500 rounds T/C test, only LED
devices encapsulated with 10% silicone modified epoxy
resin pass without failure through, displaying better per-
formance than other samples.
3.2.2 Luminance change during the reliability test
Meanwhile the luminance change during the reliability
tests was taken as an important index for performance eval-
uation. Figure 12 displays the luminance change during the
reliability test, which shows similar tendency as acceler-
ated hygrothermal test. Apart from 30% silicone modified
epoxy, the other systems have better performance than neat
ECC system. Among these systems, 10% silicone modified
epoxy systems show the lowest luminous flux decrease,
which are no more than 4% after 1000 h aging time.
Fig. 11  Yellow index of aging experiment: a heat aging, b UV aging
3.2.3 Delamination observation
Scanning acoustic micrograph was utilized to study the
degree of delamination at the die-attach/pad interface of
LED devices. Figure 13 shows delamination degree of LED
devices encapsulated with various silicone modified epoxy.
As on can see, silicone content has a positive effect on the
adhesion to the die pad substrate. LED devices with neat
ECC generate delamination after IR3 flow while those with
silicone modified epoxy are not. After moisture-IR flow,
complete delamination takes place in LED devices with
neat ECC. The LED devices with 10% silicone modified
epoxy has the best performance in the test, which corre-
sponds to the outcome of reliability test. In order to observe
the phenomenon of delamination of LED devices, SEM
was applied to examine the interfacial cracking of encap-
sulated LED devices. It can be seen from the Fig. 14 that
the interface of good LED devices is integrated while LED
devices with delamination shows delaminated and incom-
plete interface.
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 J Mater Sci: Mater Electron

Table 3  Reliability test results Test item Neat ECC Silicone 10% Silicone 20% Silicone 30%
of LED devices packaged by
silicone modified epoxy resin −65–150 °C, 5T/C 200/200* 200/200 200/200 200/200
30 °C, 60% RH, 192 h 200/200 200/200 200/200 200/200
MSL 3 Reflow Profile 3 Rounds 200/200 200/200 200/200 200/200
−65–150 °C, 100T/C 183/200 200/200 195/200 179/200
−65–150 °C, 300T/C 172/200 200/200 193/200 95/200
−65–150 °C, 500T/C 153/200 200/200 184/200 41/200

*Pass/test pieces

of LED devices and the properties of encapsulating materi-

als, more characterizations need to be finished. The inter-
nal stress, water sorption ability and adhesion strength of
encapsulating material has great influence on reliability
test.

3.3.1 Thermal mechanical properties of the cured epoxy

resins

DMA curves of the cured epoxy resins are shown in

Fig. 12  Blue light luminous flux change of LED devices encapsu-
lated with various silicone modified epoxy resins
3.3 Relationship between the reliability of LED devices
and properties of encapsulating materials
To further discuss the relationship between the reliability
Fig. 15, and the data are summarized in Table 4. The ­Tg
(the peak temperature of the loss tangent) of silicone
modified epoxy resin systems shows the same tendency
as the result of DSC analysis, in which higher content of
silicone leads to lower ­Tg. The gap between the results of
DSC and DMA is because the degree of post-cure is dif-
ferent. The low glass transition temperature of this system
is considered due to the existence of the siloxane segments
in the epoxy backbone. The storage modulus of these
epoxy resins at low temperature (50 °C) is in the range of
1500–1650 MPa.
The hardness of the sample is displayed in Table 4. The
result reveals that higher silicone content will lead to higher

Fig. 13  Scanning acoustic

micrograph (C-SAM ) images
of LED devices showing the
extent of delamination at the
interface during reliability tests

13
J Mater Sci: Mater Electron
Fig. 14  SEM micrographs of the interfaces for encapsulated LED
devices: a good LED device, b delaminated LED device
Fig. 15  DMA curves of silicone modified epoxy resins cured with
MHHPA
hardness. When the silicone content is below 10%, the
hardness is around 80. Nevertheless, the hardness comes
to around 90 when the content reaches 20% or more. The
high hardness is attributed to hydrogen bonds in silicone
modified epoxy resin [38]. As the hardness can reflect the
modulus in low temperature, it means that higher silicone
content systems will bear higher internal stress at very low
temperature during thermal shock [39].
It was revealed that the cross-linking density has a close
relationship with T ­ g and storage modulus. The molecular
motion of the polymer chains became more restricted and
the amount of energy dissipated throughout the polymer
decreased dramatically when the cross-linking densities
increased [20, 40]. It is known that the cross-linking den-
sity can be determined by the storage modulus at the tem-
perature of T ­ g + 50 °C. It is observed from the result that
the storage modulus decreases as the content of silicone
increases. Thus, it is reasonable to denote that the addition
of silicone decrease the cross-linking density of the encap-
sulating materials.
The measurement of linear thermal expansion coef-
ficient (CTE, α) was carried out by TMA. The values of
α for silicone modified epoxy resin are depicted in Fig. 16
and Table 4. It can be seen from Table 4 that α above ­Tg
decreases when the content of silicone increases. However,
α below T ­ g show little change.
The internal stress between two material interfaces pro-
duced by CTE mismatch during the thermal cycling test or
the reflow soldering process can be obtained by integral of
modulus and CTE versus temperature as below [41]:
S = ∫ E (T)𝛼(T)dT
Commonly, the curing temperature of epoxy resin is
below ­Tg. The thermal stress of curing temperature can be
regard as zero. Therefore, the internal stress during IR sol-
der reflow can be calculated by:
S260 = E260 × (260 − Tg ) × 𝛼2 + E25 × (Tg − 180) × 𝛼1
where S260 are the internal stress during the IR solder
reflow process, E260 and E25 are elastic modulus through
the test process at 260 and 25 °C. T ­ g, α1, and α2 are the
glass transition temperature and CTE below and above ­Tg
respectively.
As the T­ g are very close to 180 °C in this study, the sec-
ond term of equation can be ignored. It can be concluded
that S260 is chiefly dependent on the elastic modulus and
CTE above ­Tg. Therefore, epoxy resin with lower thermal
expansion coefficient will lead to lower internal stress dur-
ing the IR solder reflow process.
It is well known that CTE relates to the conformation
of epoxy matrix. When the temperature is below ­Tg, the
motion of molecular chain is limited so that the conforma-
tion almost keeps unchanged even if the silicone modifier is
13
 J Mater Sci: Mater Electron

Table 4  Thermal mechanical System Neat ECC Silicone-10% Silicone-20% Silicone-30%

properties and water sorption
result of silicone modified Tg (°C)DMA 214.2 210.4 199.0 194.0
epoxy resin cured with MHHPA
Storage 50 °C 1500 1600 1560 1650
Modulus (MPa) Tg + 50 °C 4.30 4.00 3.30 3.10
Hardness (shore D) 80 81 89 92
ρ(10−3 mol cm−3) 0.32 0.29 0.25 0.24
α(ppm/K) Below ­Tg 73 84 72 81
Above ­Tg 177 166 161 114
Tg(°C)TMA 194 183 179 167
D(×10−9) 8.00 10.73 18.48 11.01
M∞(%) 6.07 5.48 5.32 5.45

Fig. 16  TMA curves of silicone modified epoxy resins cured with Fig. 17  The results of water gravimetric measurements of water
MHHPA sorption at 85 °C

added. Therefore, the CTE below ­Tg shows no regulation.
As the temperature is above ­Tg, the motion of molecular
chain will change the conformation of epoxy matrix. For
silicone modified epoxy resin, the Si–O–Si linkage displays
flexibility due to its longer bond length and larger bond
angle. Thus, these flexible chains make for conformation
rearrangement, which leads to less expansion of the matrix
[42–44] and lower modulus. Such situation can decrease
the internal stress of epoxy matrix.
3.3.2 Water sorption properties
Figure 17 shows that the equilibrium water contents of
silicone modified epoxy resins are lower than neat epoxy
resin because the introduction of silicone decreases the
polarity of epoxy resin. Therein, epoxy resin containing
20% silicone shows the lowest water sorption. In elec-
tronics industry, water sorption is unexpectable due to
the “popcorn effect” [45]. That is, water evaporation dur-
ing processing which acts like popcorn might impair the
performance of the material. Moreover, moisture diffuses
into the package, makes the package swell, and reduces
interfacial adhesion strength. The mismatching coeffi-
cients of moisture expansion will cause hydromechanical
stress in the package.
The behavior of water sorption during initial period has
been studied. According to Fickian diffusion equation, the
results of the equilibrium value of the diffusing water at
infinite time (M∞ and diffusion coefficient (D) reflect that
although silicone modified epoxy resins exhibit higher dif-
fusion coefficient at the beginning of water sorption, they
have lower equilibrium water content. On one hand, due
to the hydrophobic and partial ionic nature of the Si–O–Si
linkage,the water sorption tendency decreases on addition
of silicone [18]. On the other hand, in our previous study
[27, 33],we have found that D is mainly determined by
the free volume of the epoxy matrix. Compared to neat
epoxy, silicone modified epoxy resin has higher free vol-
ume, which results in a higher D during initial period in the
water sorption test.

13
J Mater Sci: Mater Electron
3.3.3 Lap shear strength of silicone modified epoxy resin
The most significant application of epoxy resin is adhe-
sion. Lap shear strength is an important parameter to deter-
mine the stickiness of epoxy resin. The result was exhib-
ited in Fig. 18. It is learned from the results that the lap
sheer strength of silicone modified epoxy resin cured with
MHHPA is around 5 MPa. The epoxy resin containing sili-
cone shows higher lap shear strength than neat epoxy resin
and the sample with the highest content of silicon has the
best performance in this experiment. Silicone is introduced
into cured epoxy to form flexible part, which decreases
internal stress of epoxy matrix. And silicone act as stress
relief point in matrix to offers excellent toughness [46–48].
In addition, lower crosslink density of silicone modified
epoxy resins also benefit their adhesion strength. Moreover,
silicone can form Si–O–M bond on the surface between
metal and encapsulating materials, results in enhancement
of the adhesion strength [49]. It can be concluded that, the
introduction of silicone in epoxy resin might be able to
improve the performance of metal adhesion.
In summary, it can be explained that the high internal
stress and brittleness induced delamination of neat ECC
system during IR reflow process. Epoxy modified with
silicone released internal stress while lower water sorption
improved the interfacial bonding of encapsulating materi-
als to LED devices, thus the reliability is improved. Further
increase of silicone content results in higher water diffu-
sion and lower ­Tg, both decrease the hygrothermal stabil-
ity (interfacial bonding under moisture and high tempera-
ture condition) and caused interfacial delamination during
reflow. Moreover, epoxy modified with silicone also has
greater adhesion strength, which causes less delamina-
tion in experimental condition. Among these systems,
epoxy modified with 10% silicone displays the best perfor-
mance in reliability test. Because it has pretty lower water
Fig. 18  Lap shear strength of silicon modified epoxy resins
sorption ability, higher lap shear strength, higher ­Tg espe-
cially. Although 30% silicone modified epoxy shows better
performance on heat and UV resistance as well as thermal
expansion coefficient, the T
­ g decreases too much with such
silicone content. In addition, the hardness of the material
changes little when the silicone content is only 10%, while
higher silicone content will cause sharply rising of hard-
ness. It means that the internal stress in low temperature
increases significantly. Therefore, the sample cannot pass
thermal shock cycling in reliability test. Take all sorts of
factors into consideration, 10% silicone modified epoxy
resin has most desirable properties in this study.
4 Conclusions
A series of transparent encapsulating materials were pre-
pared by phenyl methyl silicone modified cycloaliphatic
epoxy resins. Compared with the neat epoxy resin, silicone
modified epoxy resin has comparable glass transition tem-
perature because of good compatibility between epoxy and
phenyl silicone. Silicone modified epoxy resin also exhib-
its higher thermal stability and higher heat and ultravio-
let resistance due to the higher bond energy of Si–O than
C–O and C–C. Introducing silicone resin can decrease the
internal stress of epoxy matrix, and thus reduce interfacial
delamination. Because Si–O–Si linkage has longer bond
length and larger bond angle, which will offer flexible part
into epoxy matrix. The water sorption ability declines after
silicone modification as the hydrophobic nature of Si–O–Si
linkage protect epoxy resin from water sorption. Besides,
the lower crosslink density and the bonding Si–O–M on the
surface between metal and encapsulating materials induce
great lap shear strength of silicone modified epoxy resin.
During the reliability test, 10% silicone modified epoxy
resin displays the most desirable properties for LED encap-
sulation. Because it has relatively great mechanical prop-
erties, low water sorption ability and good heat and UV
resistance. Especially, it has much higher glass transition
temperature and lower internal stress at very low tempera-
ture than 30% silicone modified epoxy resin. Therefore, it
shows much greater performance in thermal shock cycling
test.
Acknowledgements This research work was supported by the
National Natural Science Foundation of China (Grant 21274031).
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