J Mater Sci: Mater Electron (2012) 23:12931299 DOI 10.

1007/s10854-011-0587-3

Fabrication and characterization of nano ller-lled epoxy composites for underll application
S. Muhammad Firdaus M. Mariatti

Received: 10 October 2011 / Accepted: 23 November 2011 / Published online: 8 December 2011 Springer Science+Business Media, LLC 2011

Abstract The present research aims to fabricate and characterize different nano ller types and ller loadings in epoxy composites for underll application. The nano ller types were synthetic diamond (SD), boron nitride (BN), and silica (S). The ller loadings which were considered in the study were varied from 1 to 4 vol%. Sonication process was used to facilitate ller dispersion. The results showed that BN had a good ow ability, with higher ow rates than the other ller types. The thermal conductivity of the composites increased with the addition of llers, and higher thermal conductivity value is observed in SD system. The coefcient of thermal expansion (CTE) of composites decreased with the addition of ller with lower CTE value shown by BN system. Generally, SD showed higher exural strength and exural modulus compared with BN and S. A high ller loading also resulted in decreased exural strength but increased exural modulus.

1 Introduction The manufacture of advanced electronic technologies is currently one of the most dynamic, fascinating, and productive global industries. The use of smaller, faster, and cheaper components is the inevitable future trend in such electronic appliances as laptops, digital cameras, cellular phones, etc. Consequently, this trend has set more stringent requirements on packaging technologies related to electronics [13]. Among the methods for interconnecting

S. Muhammad Firdaus M. Mariatti (&) School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Nibong Tebal, Seberang Perai Selatan, Penang, Malaysia e-mail: mariatti@eng.usm.my

semiconductors with external circuitry, ip-chip technology is receiving increased attention. In this method, the contact area between the chip and substrate is much smaller than in wire bonding. A small contact area gives rise to many reliability issues such as decreased thermal performance and mechanical reliability. To address these issues, an underll that lls the gap between the chip and substrate after joining is introduced. The underll is usually dispensed along the periphery of the chip, and ows into the gap between the chip and substrate via the capillary force. This process is very time consuming and expensive. The viscosity of the underll is crucial for decreasing the processing time [2, 4]. Fast-ow underlls for ip-chips are currently being studied because a fast ow can reduce the processing time required for the underll to ow. An underll is normally applied to one or two sides of the integrated circuit (IC) chip during dispensing. Capillary ow drives the underll under the IC chip to ll completely the IC chip/substrate gap. There are many factors that inuence the ow rate of the underll in the gap, such as ller particles (dispersion, density, distribution, loading, material, size, surface area, surface morphology and shape), underll material (density, rheology, surface tension, temperature and viscosity), IC chip/substrate surfaces (roughness, surface structure and temperature), as well as obstructions (bump pattern, bump size, contamination and particle size-to-gap height ratio) [5]. The underll material applied in the gap between the IC chip and substrate distributes the shear stresses at the solder interconnections. These shear stresses occur because of the mismatched coefcient of thermal expansion (CTE) between the IC chip and substrate. Low-CTE llers at high ller loadings are commonly added to underll materials. High ller loadings can decrease the CTE problem, but also creates new problems during the underll processing. High ller loadings result in a highly viscous mixture,

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1294 Table 1 Properties of the epoxy and llers used in the present study Properties Epoxy Synthetic diamond (SD) 3.5 2,000 0.8 10 Spherical 264.4 Boron nitride (BN) 2.3 300 \0.5 60 Spherical 26.3 Silica (S)

J Mater Sci: Mater Electron (2012) 23:12931299

Density (g/cm3) Thermal conductivity (W/mK) CTE (ppm/C) Mean particle size (nm) Shape Surface area (m2/g)

1.15 0.23 50.3

2.2 1.5 0.5 7 Spherical 390

this resin is also chemically termed as bisphenol-A-(epichlorohydrin). The curing agent used, Baxxodur EC301 (density = 0.948 g/cm3 at 298 K), was supplied by the BASF Corporation. The mixing ratio of EPON 8281 to Baxxodur EC301 was set at 100:32. Three types of nano llers, namely, synthetic diamond (SD), boron nitride (BN), and silica (S), were used. The properties of SD, BN, and S particles are listed in Table 1. 2.2 Sample preparation The mixing ratio of resin to curing agent was set at 100:32. The nano llers were separately added to the resin at ller loadings of 1, 2, 3, and 4 vol%. Each resulting mixture of epoxy and ller was stirred for approximately 10 min with a homogenizer. Sonication for 10 min followed to facilitate ller dispersion. The mixture was vacuumed for approximately 0.5 h at 35 C to remove bubbles. The curing agent was added, and the mixture was stirred for another 10 min. The mixture was kept in a vacuum oven for 1 h at room temperature to remove remaining bubbles. Finally, the mixture was cured in the same oven at 100 C for 1 h. Post-curing followed at 125 C for 3 h. 2.3 Characterization The ow rates of the underlls were measured using a parallel translucent polypropylene (PP) thermoplastic polymer plate based on the method proposed by Wong et al. [5]. Briey, the glass plates were pre-cleaned using isopropanol. The plates were then preheated at 80 C to help decrease the underll viscosity during ow, to increase the repeatability of the test, and to mimic the actual production underll dispensing process. In the present study, a translucent polypropylene (PP) thermoplastic polymer plate was used instead of a glass plate, which has been used in Wong et al. [5], because it is easy to cut and fabricate to the size of chip for ow rates testing. It is also much cheaper compared to glass. The parallel polymer plate had a chip size of 30 9 30 mm2 and a substrate size of 35 9 35 mm2, in accordance with the previous work of Shih and Young [9]. The two parallel
Time (minute)

which inuences the ller ow ability between the IC chip and substrate. Consequently, the production time and cost in producing a single ip-chip are increased [58]. Advancements in nanotechnology have resulted in heightened interest in the application of nanollers for underll application. Previous studies [47] have demonstrated the use of micron-size llers such as synthetic diamond (SD), boron nitride (BN), silica (S), Alumina (A), silica coated aluminum nitride, etc. as llers for underlls application. In the present study, nano particles of SD, BN, and S were considered as possible llers for the underll. These three nano ller types can be loaded to epoxy at lower percentages (14 vol%) if compared to micron-sized llers which normally been loaded up to 60 vol%. Low ller loadings can decrease the cost of producing underlls for electronic applications. The ow rates of the underll materials were measured using parallel plates. Thermal and mechanical testing were also conducted to characterize the properties of the materials.

2 Experimental method 2.1 Materials The epoxy resin, named EPONTM Resin 8281, used as a matrix was supplied by Hexion Specialty Chemicals, Inc.,
Fig. 1 Flow ability of 0 vol% ller (as a control). The white arrow shows the position of the underll and the black arrow shows the ow direction of the underll

Time (minute)

0 Vol. %

0 Vol. %

20

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Time (minute)

(a) 1 Vol. %
Synthetic diamond (SD) Boron nitride (BN) Silica (S)

20

Time (minute) Synthetic diamond (SD)

(b) 4 Vol. %
Boron nitride (BN) Silica (S)

No flow

20

No flow

Fig. 2 a Flow ability of 1 vol% epoxy lled with synthetic diamond (SD), boron nitride (BN) and silica (S) llers, b Flow ability of 4 vol% epoxy lled with SD, BN, and S llers. The white arrow shows

the position of the underll and the black arrow shows the ow direction of the underll

polymer plates were separated by a 200 lm gap. The plates were pre-cleaned with acetone before being used in the characterization. Thermal conductivity was tested using a Hot-DiskTM Thermal Constant Analyzer. Round specimens 4 mm thick and 30 mm in diameter were prepared. The potential power was xed at 0.02 W/mK, and the time was 40 s. The coefcients of thermal expansion (CTEs) of the composites were measured using a LINSEIS Dilatometer

L75/1550. The specimens with dimensions of 20 mm long, 4 mm wide and, 3 mm thick were prepared, and were tested from 30 to 230 C at a heating rate of 3 C/min. A exural test was performed based on the standard test method ASTM D790. The specimens used were 70 mm long, 12.7 mm wide and 2 mm thick. An Instron 3366 instrument with a crosshead speed set at 5 mm/min was used to measure the exural properties of the underll

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1296 Table 2 Velocity and acceleration values of the underlls Specimen Starting velocity 2 min (mm/min) 9.0 3.0 1.0 6.0 3.0 2.5 No ow Ending velocity 20 min (mm/min) 2.0 0.7 0.3 1.9 0.9 0.6 Acceleration (mm/min2) 0.35 0.12 0.04 0.21 0.11 0.10

J Mater Sci: Mater Electron (2012) 23:12931299

0 vol% ller 1 vol% SD ller 4 vol% SD ller 1 vol% BN ller 4 vol% BN ller 1 vol% S ller 4 vol% S ller

Fig. 4 Flexural strength versus ller loading of synthetic diamond-, boron nitride-, and silica-lled epoxy composites

Fig. 3 Thermal conductivity versus ller loading of synthetic diamond-, boron nitride-, and silica-lled epoxy composites

Table 3 CTE values of the epoxy composite underlls Filler loading 0 vol% ller 1 vol% SD ller 4 vol% SD ller 4 vol% BN ller 4 vol% S ller CTE below Tg (ppm/C) 50.3 43.8 37.3 35.1 36.1 CTE above Tg (ppm/C) 184.0 177.6 168.3 166.7 167.8

major role in the ow rates of underlls. An underll with a high viscosity was indicated by a slow ow ability. BN had a lower viscosity and higher ow rates than the other two llers because of the larger particle size. Table 1 shows that the surface area of BN is 26.3 m2/g, and those for SD and S were 264.4 and 390 m2/g, respectively. Large ller particle sizes corresponded to low viscosities of the underll [5]. Despite BN ller had larger particle size, the size are still small if compared to the size of the gap (200 lm) or polymer plates and therefore it is expected that there is no friction occur between the llers and the polymer plates which can decrease the ow rate of the underll. In addition, increasing in viscosity with decreasing particle size is brought about by the interaction of the resin with the larger surface area of the smaller ller [5]. The velocity and acceleration values of the underlls owing with the parallel polymer plate are summarized in Table 2. Evidently, the BN-containing epoxy composites underll had a higher acceleration compared with the other two ller types. 3.2 Thermal conductivity For underll applications, good thermal conductivities are important for the faster dissipation of heat from the IC chip and substrate. Smaller and faster microchips are also correlated to greater heat production [6]. An underll must have a good thermal conductivity to enable the success of a microchip. Generally, the thermal conductivities of the nano ller-containing epoxy composites increased with increased ller loadings, as shown in Fig. 3. The SD-containing composite had a slightly higher thermal conductivity than the BN and S composites because SD itself has a higher thermal conductivity than BN and S (Table 1). With increased ller content, lumps of ller particles easily cohered with one another to provide heat conduction paths. Consequently, the thermal conductivity is increased by the conduction between llers [4], as a result of direct energy exchanges among molecules.

materials at room temperature. The span length-to-specimen thickness ratio was maintained at 16:1.

3 Results and discussion 3.1 Flow rates Figure 1 shows the ow ability of the control sample (0 vol%). Figure 2 illustrates the ow for 1 and 4 vol% SD, BN, and S at 2 and 20 min. Apparently, low ller loadings corresponded to high ow rates. BN showed higher ow rates followed by SD and S. At 4 vol% S in the epoxy, the resin became too viscous. Viscosity is known to play a

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(a)

(b)

(c)

Voids

(d)

Voids

Agglomeration

(e)

(f)

Voids Agglomeration

(g)

(h)

Agglomeration Voids

Fig. 5 Fracture surfaces of (a, b) neat epoxy (c, d) 4 vol% SD-lled epoxy (e, f) 4 vol% BN-lled epoxy, as well as (g, h) 4 vol% S-lled epoxy. The left micrographs (a, c, e, g) are taken at 9500 magnication, and the right micrographs (b, d, f, h) are taken at 92,000 magnication

3.3 Coefcient of thermal expansion (CTE) A low underll CTE (2040 ppm/C) value is required for ip-chip assembly [5, 10, 11]. Low CTEs can decrease the stress that occurs among the substrate, IC chip, and solder interconnection. The CTE can be decreased by increasing the ller loading. Table 3 shows the CTE values for the epoxy composites underlls. Evidently, high ller loadings corresponded to low CTEs. The BN-containing composites had a lower CTE (35.1 ppm/C below Tg and 166.7 ppm/C above Tg) than the S (36.1 ppm/C below Tg and

167.8 ppm/C above Tg) and SD (37.3 ppm/C below Tg and 168.3 ppm/C above Tg) composites because BN itself has a lower CTE than those two llers (Table 1). The unlled sample had the highest CTE below and above the glass transition temperature (Tg) because of the increased free volume content at any temperature (50.3 ppm/C below Tg and 184.0 ppm/C above Tg). Consequently, more uctuations in the molecular structure were generated, and the rate of expansion increased upon heating. However, as previously reported [1214], increasing the ller content decreases the free volume content. Hence, the

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1298

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Fig. 6 Flexural modulus versus ller loading of synthetic diamond-, boron nitride-, and silica-lled epoxy composites

space for expansion of the polymer decreases, and the CTEs of the composites are further decreased. Thermal expansion is directly related to the ller binding among matrix in the composites system. The ller binds the matrix and prevents it from expanding as much as it would on its own. Filler had lower CTE value compared to the epoxy matrix (Table 1). Therefore, composites with higher ller contents have much lower CTEs because of the greater binding forces present by the llers in the matrix [10, 15]. 3.4 Flexural properties Figure 4 shows the exural strengths of epoxy, as well as of the SD-, BN-, and S-lled epoxy composites. The exural strength decreased with increased amount of ller loadings. At the high ller loading of 4 vol%, the exural strengths of the SD, BN, and S systems decreased by 41, 29, and 28%, respectively, compared with the control sample (0 vol%). According to a previous work [15], at high ller loading, the insufciency of epoxy resin to coat the ller resulted in low ller-matrix interaction which lowered the exural strength if compared to the low ller loading samples. High ller loadings also lead to increased viscosity, which subsequently decreases the ease of processing. This phenomenon increases the void content and ller agglomerations which decreases the strength of the composites. Filler agglomerations at high ller loading composites results in inhomogeneous distribution and hence weaken the interfacial interaction between the ller and the matrix. This mean that agglomerates resulting as a weak point and act as stress concentrator that initiate the initial failure under applied load which in turn lower the exural strength. On the other hand, llerller interaction is much more dominant than ller-matrix interaction. This llerller interaction will result on ller agglomeration and subsequently reduces the exural strength of the composites system [10]. Based on error bars at 1 vol% ller loading, the three types of composites had slightly similar exural strengths and the trends drop for higher ller concentration. Obvious drop in exural strength is

observed for SD, for example if compared at 3 and 4 vol% of SD, BN and S, the exural strength drop at about 33, 4 and 8%, respectively. The agglomeration and voids in the SD composite system are apparently shown in the scanning electron microscopy (SEM) images in Fig. 5c, d. The agglomeration and voids are observed in BN and S system, however with a smaller size and quantity if compared to that of SD system. Figure 6 shows the exural modulus versus ller loading of SD-, BN-, and S-lled epoxy composites. As expected the exural modulus of the nano ller-containing epoxy composite increased with increased amount of ller loading. The addition of llers, which were usually stiffer than the matrix, generally led to an increased exural modulus (Fig. 6). A previous study [15] has indicated that high ller loadings decrease the ultimate elongation of the matrix and increase the Youngs modulus. The direct relationship of the exural modulus with ller loading also conforms with the rule of mixtures. The rule of mixtures suggests that theoretically, the moduli of composite materials increase with increased ller loading.

4 Conclusions The present study showed that the ow rates of lled epoxy composites decreased with increased ller loadings. BN had better ow rates than the other llers because of the larger particle size and smaller surface area. This showed that as the ller particle size increased, the ow rate increased. Generally, thermal conductivity increased with increased ller loading, and SD had the highest thermal conductivity. On the other hand, the CTE decreased with increased ller loading, and the lowest CTE was shown by BN system. Expectedly, high ller loadings resulted in decreased exural strengths, but increased in exural moduli. SD had the highest exural strength and exural modulus. These trends in the exural properties of the composites were supported by SEM images. The images indicated that the agglomeration of ller and voids decreased the exural strengths at high ller loadings of the SD epoxy composites.
Acknowledgments The present work was supported by a research university grant (814055), Malaysia Government under MyBrain15 in MyMaster nancing program and graduate assistant scheme.

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