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 signals and large area displays because of their high effi-
phenyl methyl silicone resin to investigate the influence of ciency, low power consumption, and high durability [1–3].
silicone content on the performance and reliability of epoxy The development of LED technology relies on the improve-
packaged light-emitting diode. The silicone modification of ment of high performance packaging materials. Epoxy res-
epoxy encapsulants was characterized by transform infra- ins, as high performance thermosetting polymer materials,
red (FT-IR) spectrophotometer. Rotational rheometer was have been extensively used for LED encapsulation due to
used to study rheology behavior. Differential scanning calo- the advantages like high adhesion, great dimensional stabil-
rimetry, thermogravimetric analyses, dynamic mechanical ity, low dielectric constant, great machinability, and excel-
analysis, thermomechanical analyzer were introduced to lent resistance to chemicals [4–7].
measure the thermal and mechanical properties. Ultravio- Cycloaliphatic epoxies, especially (3–4-epoxycyclohex-
let visible spectrophotometer was utilized to study heat and ane) methyl 3–4-epoxycyclohexyl-carboxylate (ECC) cured
ultraviolet resistance. In reliability test, scanning acoustic with acid anhydride exhibits excellent performance in LED
microscope and scanning electron microscope were applied encapsulation. Owing to the nonaromatic cyclic structure,
to observe interfacial delamination. Water sorption pro- ECC displays better performance such as higher proces-
cess was monitored using gravimetric measurement. FT-IR sibility, better UV resistance and greater mechanical and
study shows a chemical bonding between hydroxyl group electrical properties than aromatic epoxies [8–10].
of silicone resin and epoxy resin. With the incorporation However, there are still some fundamental works should
of silicone resin, favorable properties were obtained such be done in order to strengthen the performance of epoxy
as higher thermal decomposition temperature, lower equi- resins for LED encapsulation. For example, the moisture in
librium water sorption, and better heat and UV resistance. epoxy resin can induce interfacial delamination and pop-
Among these systems, 10% silicone modified epoxy resin corning during solder reflow process [11–13], therefore,
exhibits the best performance in reliability test. 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
1 Introduction its inherent brittleness arising from its high-cross-linked
structure, leading to a low resistance to crack development
Recently, light-emitting diode (LED) are widely applied in and growth [14, 15]. Besides, the degradation of epoxy res-
numerous applications, such as lighting equipment, traffic 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
* Yingfeng Yu material in heat and UV resistance is necessary [16].
yfyu@fudan.edu.cn Silicone resin is a sort of effective modifier of epoxy res-
1 ins for microelectronic encapsulation as it can improve the
State Key Laboratory of Molecular Engineering of Polymers,
Department of Macromolecular Science, Fudan University, performance of epoxy resins. The main chains of the sili-
Shanghai 200433, China cone are composed of Si–O bond with larger bond energy

13
Vol.:(0123456789)
 J Mater Sci: Mater Electron

than C–C bond and C–O bond. Therefore, silicone modi- thermal and UV stability due to the drop of glass transition
fied epoxy resin has excellent performance of heat and UV temperature ­(Tg).
resistance [17]. In addition, the water sorption tendency As phenyl methyl silicone resin could provide both good
decreases on addition of silicone content due to the hydro- toughness and excellent miscibility with epoxy resin, its
phobic and partial ionic nature of the Si–O–Si linkage [18]. modification would be expected to improve the thermal and
With so many favorable properties, increasing silicone con- UV stability of materials while decrease the internal stress
tent may lead to desirable result. However, phase separation during thermal shock and external stress. In this study, a
sometimes limits the incorporation of a large amount of phenyl methyl silicone resin was incorporated into epoxy
the silicone components with only methyl group, and more encapsulant to study its effect on the performance and reli-
seriously, leads to bleeding of the silicone components, ability of LED devices.
impairing the performance of the materials [19]. Among The reaction and the properties of these silicone modi-
silicone modifiers, phenyl methyl silicone could not only fied epoxy resins were characterized by thermal and
offer thermal stability and toughness, but also has good mechanical methods. Water sorption behavior was stud-
compatibility with epoxy resins [20]. ied by gravimetric measurement. The reliability and per-
In early researches, different kinds of silicone modified formance of LED devices encapsulated with these epoxy
epoxy systems had been well studied for other applications materials were tested according to the characterization
[21–24]. However, the interaction between alicyclic epoxy methods established previously.
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 2 Experimental
applied to LED encapsulation. As novel packaging material
must consider better optical, electrical, and thermal perfor- 2.1 Materials
mance as well as chemical and thermal stability [25]. The
reliability tests include thermal shock, aging at constant The commercially available epoxy resin, (3-4-epoxy-
temperature and humidity, lifetime test and so on [3, 26]. cyclohexane) methyl 3-4-epoxycyclohexyl-carboxylate
In our previous work [27], a set of method have been estab- (ECC) having epoxy equivalent of about 130–135 was
lished to study the reliability of epoxy encapsulated LED obtained from Dow Inc., USA. The phenyl methyl sili-
devices, as well as the influence of different fillers to epoxy cone resin Wackle Silres 604 (Silicone, ­Mn = 2320 g/mol)
resin. On the basis of the test methods, we further noticed was purchased from Wackle Co., Germany. The methyl-
the reliability improvement of LED devices with the incor- hexahydrophthalic anhydride (MHHPA) and Tetrabutyl
poration of flexible hydrogenated bisphenol A diglycidyl ammonium bromide (TBAB) were purchased from Aldrich
ether into ECC materials [28]. However, the introduction Chemical Co., USA. The chemical structure of materials
of flexible component would lead to obvious decline the is illustrated in Scheme 1. ECC was dehydrated in vacuum

Scheme 1  Chemical structure

of ECC, silicone, MHHPA, and
TBAB

13
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

13
 J Mater Sci: Mater Electron

2.3.5 Thermomechanical analyzer (TMA) where D is the diffusion coefficient, d is the thickness of

the specimen, Mt is water sorption at time t, and M∞ is the
TMA study which was performed on Mettler Toledo—TMA/ equilibrium value of the diffusing water at infinite time.
SDTA841e was used to measure the coefficient of linear According to Fickian diffusion equation:
thermal expansion coefficient (CTE, α) of the materials. The ( )
π Mt ∕M∞
samples which had similar size of 4 × 4 × 2 mm3 were heated D=
16 t1∕2 d−1
from 25 to 300 °C at the rate of 3°C/min. CTE could be deter-
mined by formula: Once the slope of Mt ∕M∞ versus t1∕2 d−1 is obtained, we
dL 1 can calculate the diffusion coefficient D.
α= ×
dT LT
2.3.8 Ultraviolet visible (UV–Vis) spectrophotometer
where dL/dT is the change rate of length by the time, ­LT
is to the length of sample at certain temperature. α below UV–Vis spectrum was measured by Perkin-Elmer Lambda
­Tg is measured between 75 and 125 °C and α above ­Tg is 750 which was utilized for tracking yellowing of the materi-
measured between 225 and 275 °C. als after heat and ultraviolet aging. The samples were cured
in size of 20 mm × 20 mm × 1 mm. The condition of heat
2.3.6 Lap shear strength measurement aging was 150 °C in electric heat oven for certain hours. The
ultraviolet aging was conducted in UV203 ultraviolet aging
Lap shear strength is an important parameter to determine machine. At the room temperature, the radiation intensity on
the stickiness of epoxy resin. The procedure of preparing lap sample surface was 360 mW/cm2. In general, the properties
samples is processed as standard ASTM D1002 [32]: First, of heat and ultraviolet resistance can be measured by yellow
copper sheets were polished by abrasive paper and cleaned index (YI). YI can be calculated by [27]:
by ethanol and acetone. And then, samples were disposed
T620 − T470
between copper sheets with contact area of 2.54 × 1.27 cm2. YI = × 100
The processed samples were cured in general curing proce- T520
dure mentioned by this essay. The measurement was con- where T620, T470 and T520 are transmittance of material at
ducted by materials testing machine CMT4104. To reduce wavelength of 620, 470, 520 nm, which correspond to the
the randomness of testing machine, five parallel samples red, green, and blue light emitted by LED devices.
were prepared for each types of epoxy resin, and average ten-
sile force would reflect lap shear strength. 2.3.9 Reliability test

2.3.7 Gravimetric measurement of water sorption The test procedure for LED packaging reliability characteri-
zation involved moisture preconditioning, the thermal shock
The sample sheets (20 mm × 20 mm × 1 mm) were polished cycling test (T/C: −65 to 150 °C), and the infrared (IR) sol-
with deionized water, and then dried in a vacuum oven at der reflow process (260 °C × 3 times). The encapsulated LED
100 °C for 24 h. Water sorption into sample sheet at 85 °C devices were subjected to moisture sensitivity level test MSL
was monitored as a function of immersion time [33]. The 3 upon IPC/JEDEC J-STD-020. The LEDs were primarily
samples were taken out from the water at intervals, wiped baked to remove residual moisture subsequently implemented
with lens paper and weighed on a Mettler Toledo ME204E with T/C tests or PCT and then exposure to damp environ-
microbalance (accuracy, 0.1 mg). The samples were cured in ments at 30 °C and 60% RH for 192 h followed by three times
the mold which was 0.1 cm thickness. Weighing water sorp- IR reflow soldering. The fatigue crack, defects, and delami-
tion ­(Mt) is defined as: nation during the reflow soldering process was analyzed by
(
Mt = Wt − W0 ∕W0
) scanning acoustic microscope (C-SAM) SONIX C-SAM
LHF-200. Surface cracking of encapsulated LED device was
where Wt is to the sample mass at t moment, W0 is the sam-
examined by scanning electron microscope (SEM), Philip XL
ple mass without water sorption.
39.
The diffusion coefficient is another important index affect-
ing the properties of epoxy materials. It is generally accepted
2.3.10 Rheology characterization
that the behavior of initial water sorption process of epoxy
conforms to Fickian diffusion [34]:
The rheology characterization was performed on Ther-
Mt 4 Dt 1∕2
( ) mofisher HAAKE MARS III. The study was carried out at
= 23 °C with the frequency from 0.01 to 100 Hz.
M∞ d 𝜋

13
J Mater Sci: Mater Electron

2.3.11 Hardness test The reaction between ECC and epoxy was tracked by
FTIR in-situ monitoring. It is observed from Fig. 2 that, the
The hardness was measured at room temperature using a intensity of hydroxy peak decline with the reaction time at
Shore D hardness tester (XHS, China) according to ASTM 120 °C. Hardly any variation can be seen when the reaction
standard D2240. time came to 1 h. Therefore, in the condition of 120 °C for
1 h, the reaction of ECC and silicone almost complicated.
2.3.12 Refractive index test Above all, these results indicate that the silicone has com-
bined with epoxy successfully.
The refractive index was obtained by WZS-1 abbe’s refrac- The refractive indexes of the samples are listed in
tometer at room temperature. Each sample was measured Table 1. The result denotes that the refractive indexes of the
three times in parallel. 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
3 Results and discussion index value.

3.1 Preparation and properties of silicone modified 3.1.2 Rheology study of silicone modified epoxy resin
epoxy resin
The result of rheology characterization for flow and fre-
3.1.1 Preparation of silicone modified epoxy resin quency study is shown in Fig. 3. It can be observed that
the rheological behavior of silicone modified epoxy resin
In this study, hydroxyl group of silicone reacted with epoxy is similar to Newtonian fluid. It is clear that more silicone
group or secondary hydroxyl group of epoxy to form sta- content will lead to higher viscosity. The viscosity of sili-
ble Si–O–C bond, which was characterized by means of cone-30% system is much higher than other systems. As
FT-IR spectrophotometer. Figure 1 shows FT-IR spectrum the silicone reacts with epoxy to form compound with
of substances consist in the reaction of silicone and epoxy. higher molecular weight, the relative motion of molecules
Compared to ECC and silicone mixture before reaction, encounter larger hindrance. Therefore, the viscosity of the
the characteristic peak at 3510 cm− 1, corresponding to the sample increases.
O–H variation sorption of hydroxyl group mainly from sili-
cone [20], declines after reaction, which indicates that the 3.1.3 Curing study of silicone modified epoxy resin
hydroxyl group of silicone resin has reacted with epoxy
resin. Si–O–C bond, with the broad peak at 1040 cm− 1, has In Fig. 4, the substances in the curing reaction by MHHPA
higher intensity after reaction, corresponding to the combi- are studied. For neat MHHPA, the two C=O stretching
nation between silicone and epoxy. vibration peaks of anhydride at 1790 and 1860 cm−1 are
observed. MHHPA with well processed ECC and silicone

Fig. 1  FT-IR spectrum of a neat ECC, b neat silicone, c ECC and Fig. 2  in-situ FTIR monitoring spectrum of the reaction between
silicone mixture before reaction, d ECC and silicone mixture after ECC and silicone for 1 h at the temperature of 120 °C; the time inter-
reaction val for each spectrum is 1 min

13
 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

13
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. will lead the system to show incompatibility so that glass
transition temperature decreases significantly.
The thermal stability of silicone modified epoxy resin
3.1.4 Thermal properties 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
Figure 7 and Table 2 show the ­Tg of all systems. The ­Tg resins almost kept their any original weight before the scan-
of silicone modified epoxy resin cured with MHHPA was ning temperature reached up to 280 °C, implying that they
around 200 °C. There is no significant decrease of ­Tg until have good thermal stability below 280 °C. The decomposi-
the content of silicone reached 20%, which means that the tion temperature at 5% of weight loss (­ T5) and decomposi-
addition of small amount silicone does not decrease the ­Tg tion temperature at 10% of weight loss ­(T10) are shown in
remarkably. Table 2. As the scanning temperature rises to 340 °C, the
Silicones commonly have poor compatibility with the TGA curves exhibit a dramatic decrease. However, we find
epoxy resin due to their varied solubility parameters, which that epoxy resins with higher content of silicone exhibited
results in a formation of finely phase-separated structure a relative slow tendency of weight decreasing in compari-
and a considerable sacrifice in glass transition tempera- son with neat ECC epoxy resin. The T ­ 5 increases about
tures in thermosets [35]. However, previous study revealed 8 °C and ­T10 increases 12 °C when the content of silicone
that silicone with phenyl group showed great compatibil- reaches 30%, which suggests that introducing silicone into
ity with epoxy resin [36]. Moreover, the silicone blended epoxy resin system enhance thermal stability of their cured
with epoxy by chemical reaction in this study, which also sample. The improved thermal stability of silicone modified
improved their compatibility. Thus, the glass transition tem- epoxy resin could be attributed to the presence of Si–O–Si
perature decreases inconspicuously when the silicone con- linkages in the polymer backbone. Because Si–O bond has
tent is still low. Nevertheless, too many silicone contents 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

13
 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.
Fig. 9  The transmittance curves of aging experiment for sili-
Figure 9 shows that the transmittance of silicone-10% cone-10%: a heat aging, b UV aging
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 increasing the silicone content will improve the thermal
silicone has higher transmittance after 168 h. Therefore, resistance of epoxy resin.
increasing the amount of silicone will improve the heat
resistance of epoxy resin. At the same time, the results of 3.2 Reliability test for LED devices
ultraviolet aging experiment have the same tendency as the
heat aging experiment. The YI of all samples is described 3.2.1 Reliability test
in Fig. 11. Whether heat aging or ultraviolet aging, silicone
modified epoxy resin shows better yellowing resistance Until now, most of the aging tests were simply based on
than neat epoxy resin. In conclusion, the introduction of thermal aging or UV aging. For in-depth investigation of
silicone in epoxy resin system could enhance the heat and epoxy resin, moisture/reflow sensitive test and scanning
ultraviolet resistance. acoustic micrograph were introduced to study the reli-
It can be explained that bond energy of Si–O bonding is ability for LED devices [27, 28]. In this work, moisture/
larger than those of C–C and C–O bonding, which makes reflow sensitive tests upon IPC/JEDEC JSTD-020 had been
the silicone modified epoxy resin have stronger thermal employed as the reliability test criteria for LEDs.
resistance than neat epoxy resin [37]. Besides, it is proved The reliability test result of LED devices encapsulated
that the thermal oxidation of the surface of the cured resins with epoxy resins modified by various silicone content is
is more serious than that of the bulk during thermal aging, collected in Table 3. As seen from Table 3 that, the LED
and the enriched silicone acted as a protecting layer against devices encapsulated with different silicone modified res-
thermal oxidation. The enrichment degree of silicone is ins show different outcome. After the test on the condi-
enhanced with increasing silicon content [21]. Therefore, tion of 30 °C, 60% RH, 192 h and MSL 3 Reflow Profile

13
J Mater Sci: Mater Electron

Fig. 10  The transmittance curves of aging experiment after 168 h: a

heat aging, b UV aging Fig. 11  Yellow index of aging experiment: a heat aging, b UV aging

3 rounds, no device lose efficacy. However, reliability 3.2.3 Delamination observation

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

13
 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. 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-
Fig. 12  Blue light luminous flux change of LED devices encapsu-
lated with various silicone modified epoxy resins 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
3.3 Relationship between the reliability of LED devices epoxy resins at low temperature (50 °C) is in the range of
and properties of encapsulating materials 1500–1650 MPa.
The hardness of the sample is displayed in Table 4. The
To further discuss the relationship between the reliability 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

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
Fig. 14  SEM micrographs of the interfaces for encapsulated LED the storage modulus decreases as the content of silicone
devices: a good LED device, b delaminated LED device
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-
Fig. 15  DMA curves of silicone modified epoxy resins cured with tion almost keeps unchanged even if the silicone modifier is
MHHPA

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. performance of the material. Moreover, moisture diffuses
As the temperature is above ­Tg, the motion of molecular into the package, makes the package swell, and reduces
chain will change the conformation of epoxy matrix. For interfacial adhesion strength. The mismatching coeffi-
silicone modified epoxy resin, the Si–O–Si linkage displays cients of moisture expansion will cause hydromechanical
flexibility due to its longer bond length and larger bond stress in the package.
angle. Thus, these flexible chains make for conformation The behavior of water sorption during initial period has
rearrangement, which leads to less expansion of the matrix been studied. According to Fickian diffusion equation, the
[42–44] and lower modulus. Such situation can decrease results of the equilibrium value of the diffusing water at
the internal stress of epoxy matrix. infinite time (M∞ and diffusion coefficient (D) reflect that
although silicone modified epoxy resins exhibit higher dif-
3.3.2 Water sorption properties fusion coefficient at the beginning of water sorption, they
have lower equilibrium water content. On one hand, due
Figure 17 shows that the equilibrium water contents of to the hydrophobic and partial ionic nature of the Si–O–Si
silicone modified epoxy resins are lower than neat epoxy linkage,the water sorption tendency decreases on addition
resin because the introduction of silicone decreases the of silicone [18]. On the other hand, in our previous study
polarity of epoxy resin. Therein, epoxy resin containing [27, 33],we have found that D is mainly determined by
20% silicone shows the lowest water sorption. In elec- the free volume of the epoxy matrix. Compared to neat
tronics industry, water sorption is unexpectable due to epoxy, silicone modified epoxy resin has higher free vol-
the “popcorn effect” [45]. That is, water evaporation dur- ume, which results in a higher D during initial period in the
ing processing which acts like popcorn might impair the water sorption test.

13
J Mater Sci: Mater Electron

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

References

1. P. Anithambigai, M.K.D. Chakravarthii, D. Mutharasu, L.H.

Huong, T. Zahner, D. Lacey, I. Kamarulazizi, J. Mater. Sci.
Fig. 18  Lap shear strength of silicon modified epoxy resins 28(1), 856 (2017)

13
 J Mater Sci: Mater Electron

2. N. Gao, W.Q. Liu, S.Q. Ma, C.Y. Tang, Z.L. Yan, J. Polym. Res. 26. M.Y. Tsai, C.H. Chen, W.L. Tsai, IEEE Trans. Compon. Packag.
19(8), 10 (2012) Technol. 33(4), 738 (2010)
3. J.C. Huang, Y.P. Chu, M. Wei, R.D. Deanin, Adv. Polym. Tech- 27. T. Li, J. Zhang, H.P. Wang, Z.N. Hu, Y.F. Yu, ACS Appl. Mater.
nol. 23(4), 298 (2004) Interfaces 5(18), 8968 (2013)
4. H. Kim, J.Y. Bae, Y.H. Kim, Y.B. Kim, B.S. Bae, J. Appl. 28. Z. Chen, Z.Y. Liu, G.B. Shen, R.H. Wen, J. Lv, J.Z. Huo, Y.F.
Polym. Sci. 131(6), 7 (2014) Yu, Ind. Eng. Chem. Res. 55(28), 7635 (2016)
5. J.F. Fu, L.Y. Shi, S. Yuan, Q.D. Zhong, D.S. Zhang, Y. Chen, J. 29. T. Iijima, N. Yoshioka, M. Tomoi, Eur. Polym. J. 28(6), 573
Wu, Polym. Adv. Technol. 19(11), 1597 (2008) (1992)
6. F.L. Jin, X. Li, S.J. Park, J. Ind. Eng. Chem. 29, 1 (2015) 30. M.R. Xie, Z.G. Wang, Y.F. Zhao, J. Polym. Sci. 39(16), 2799
7. B. Francis, S. Thomas, R. Sadhana, N. Thuaud, R. Ramaswamy, (2001)
S. Jose, V.L. Rao, J. Polym. Sci. B 45(17), 2481 (2007) 31. M. Kaji, K. Nakahara, T. Endo, J. Appl. Polym. Sci. 74(3), 690
8. Y.Y. Zong, D.Y. Gui, S. Yu, C.Q. Liu, W. Chen, Z.N. Qi, 17th (1999)
International Conference on Electronic Packaging Technology 32. G.J. Jorgensen, K.M. Terwilliger, J.A. DelCueto, S.H. Glick,
(Icept), 244 (2016) M.D. Kempe, J.W. Pankow, F.J. Pern, T.J. McMahon, Sol.
9. J.J. Park, C.Y. Yoon, J.Y. Lee, J.H. Cheong, G.B. Kang, Trans. Energy Mater. Sol. Cells 90(16), 2739 (2006)
Electr. Electron. Mater. 17(3), 155 (2016) 33. L. Li, Y.F. Yu, H.H. Su, G.Z. Zhan, S.J. Li, P. Y. Wu, Appl.
10. Z.Q. Tao, S.Y. Yang, J.S. Chen, L. Fan, Eur. Polym. J. 43(4), Spectrosc. 64 (4), 458 (2010)
1470 (2007) 34. J. Crank, G.S. Park, Diffusion in Polymers, 1st edn. (Academic
11. H.P. Wang, Y. Liu, J. Zhang, T. Li, Z.N. Hu, Y.F. Yu, RSC Adv. press, London, 1973)
5(15), 11358 (2015) 35. Y. Chen, C. Zhou, J. Chang, H.W. Zou, M. Liang, RSC Adv
12. X.S. Ma, K.M.B. Jansen, L.J. Ernst, W.D. van Driel, O. van der 4(105), 60685 (2014)
Sluis, G.Q. Zhang, Microelectron. Reliab. 47(9–11), 1685 (2007) 36. W.J. Wang, L.H. Perng, G.H. Hsiue, F.C. Chang, Polymer
13. Z. Y. Liu, J. Z. Huo, Y. F. Yu, Mater. Today Commun. 10, 80 41(16), 6113 (2000)
(2017) 37. E.H. Wong, R. Rajoo, S.W. Koh, T.B. Lim, J. Electron. Packag.
14. B. Kim, J. Choi, S. Yang, S. Yu, M. Cho, Polymer 60, 186 (2015) 124(2), 122 (2002)
15. S.J. Park, F.L. Jin, J.H. Park, K.S. Kim, Mater. Sci. Eng. A 38. M. Zhao, Y.K. Feng, G. Li, Y. Li, Y.L. Wang, Y. Han, X.J. Sun,
399(1–2), 377 (2005) X.H. Tan, Polym. Adv. Technol. 25(9), 927 (2014)
16. X. Yang, W. Huang, Y.Z. Yu, J. Appl. Polym. Sci. 120(2), 1216 39. T.V.T. Velan, I.M. Bilal, Bull. Mater. Sci. 23(5), 425 (2000)
(2011) 40. C.Q. Zhang, H.C. Wu, M.R. Kessler, Polymer 69, 52 (2015)
17. S.T. Lin, S.K. Huang, Eur. Polym. J. 33(3), 365 (1997) 41. L.L. Lin, T.H. Ho, C.S. Wang, Polymer 38(8), 1997 (1997)
18. K.S. Meenakshi, E.P.J. Sudhan, S.A. Kumar, M.J. Umapathy, 42. J.I. Meijerink, S. Eguchi, M. Ogata, T. Ishii, S. Amagi, S.
Silicon 3(1), 45 (2011) Numata, H. Sashima, Polymer 35(1), 179 (1994)
19. K. Matsukawa, K. Hasegawa, H. Inoue, A. Fukuda, Y. Arita, J. 43. I.M. Low, J. Appl. Polym. Sci. 39(3), 759 (1990)
Polym. Sci. 30(9), 2045 (1992) 44. T.T. Wang, T.K. Kwei, J. Polym. Sci. A 7(5PA2), 889 (1969)
20. Z.G. Heng, Z. Zeng, Y. Chen, H.W. Zou, M. Liang, J. Polym. 45. P. Alpern, R. Dudek, R. Schmidt, V. Wicher, R. Tilgner, IEEE
Res. 22(11), 7 (2015) Trans. Compon. Packag. Technol 25(1), 56 (2002)
21. T.H. Ho, C.S. Wang, J. Appl. Polym. Sci 54(1), 13 (1994) 46. M. Ochi, K. Takemiya, O. Kiyohara, T. Nakanishi, Polymer
22. R. Li, C. Zhou, Y. Chen, H.W. Zou, M. Liang, Y. Li, High Per- 39(3), 725 (1998)
form. Polym. 29(1), 36 (2017) 47. M. Ochi, S. Shimaoka, Polymer 40(5), 1305 (1999)
23. Q. Liu, X. Bao, S.Q. Deng, X.F. Cai, J. Therm. Anal. Calorim. 48. M. Ochi, N. Fukushima, N. Fujita, Jpn J. Polym. Sci. Technol.
118(1), 247 (2014) 52(5), 265 (1995)
24. N. Gao, W.Q. Liu, Z.L. Yan, Z.F. Wang, Opt. Mater. 35(3), 567 49. S.B. Wu, M.T. Sears, M.D. Soucek, Prog. Org. Coat. 36(1–2), 89
(2013) (1999)
25. D. Lu, C.P. Wong, Materials for Advanced Packaging Physics
(Springer, Dordrecht, 2009), pp. 644–645

13