Physical Chemistry

Journal Review

Submitted by:

Luna, Paula V.

Pestano, Gerald V.
Development of New Class of Electronic Packaging
Materials Based on Ternary Systems of
Benzoxazine, Epoxy, and Phenolic resins
S. Rimdusit, H. Ishida

Background

As the technology of electronics goes high, many different trends in the

development of such technology have been developed. Researches overlapped each other
to produce a new trend in electronic technology developments. On good example is the use
of polymeric materials in manufacturing of electronic packages with ease processing, low
cost, low dielectric constant, adhesive properties, etc. The students Bachelor of Science in
Chemistry of the College of Science of the Polytechnic University of the Philippines had
reviewed a journal of Rimdusit and Ishida of the NSF Center for Molecular and
Microstructure of Composites (CMMC) of the Department of Macromolecular Science, Case
Western Reserve University, Cleveland, Ohio, United States of America about the
development of new class of electronic packaging materials based on ternary systems of
benzoxazine, epoxy and phenolic novolac resins. According to them, they have developed
new polymeric systems that exhibit promising characteristics suitable for the application
as an underfilling encapsulation and other highly filled systems. This underfilling
encapsulation id used to mechanically couple a chip and a substrate, decreasing the
residual stress in the solder joints caused by thermal expansion mismatch between the die
and the substrate. The promising characteristics that is suitable for the application as an
underfilling encapsulant are no void formation, (which acts as a hot spots and weak points
which will be subjected to thermal fatigue, thus affecting the performance and lifetime of
packaging materials), good wetting characteristics, significant adhesion, low stress and
high thermal conductivity that led to the development of the low viscosity liquid resins for
high performance electronic encapsulants.

They also stated that they will examine the modification of thermal curable
benzoxazine resin by partial incorporation of low viscosity epoxy resin in order to reduce
of as-synthesized benzoxazine resin. The modification that they used was elimination of the
need for monomer purification and degassing which is a less cost-competitive practice. It is
because they based on the fact that entrapped air can escape more easily from the low-
viscous liquid material than the high. Another is that they will investigate the effect of
phenolic novolac on the curing of epoxy-diluted benzoxazine resin since phenolic novolac
resin is typically used as a hardener for epoxy resin and acts also as an initiator for
benzoxazine resin.

In the Experimental section, the materials that they used were benzoxazine resin
based on bisphenol A and aniline type propane, epoxy resin (Epon 825), and phenolic
novolac resin (HRJ1166). Benzoxazine resin was synthesized to make cured specimens and
purified to be used for curing studies. Epoxy resin was obtained from Shell Chemicals and
used without purification. And lastly, phenolic novolac resin was obtained from
Schenectady International. The treatment of the said materials was placement in a closed
container at room temperature and digested at about 80 ℃ in an aluminum pan for few
minutes to obtain a homogeneous mixture. After obtaining a mixture, they molded it to
various dimensions depending on the types of experiment, was thermally cured at 200 ℃
with a pressure of 0.1 MPa for one hour and lastly cooled down to room temperature for
about two hours. The instrument and methods that they used were differential scanning
calorimetry (DSC), dynamic mechanical analysis (DMA), thermogravimetric analysis
(TA/TGA), and water absorption.

Polymers

Polymers are everywhere, from natural materials like wood or silk to synthetic
plastics, fibers and gels. The development of the methods for the controlled synthesis of
polymers is one of the most important technological advances in this century, ranking
alongside the discovery of the semiconductors. [1] As they having aromatic backbone, they
possess a high mechanical strength and a high modulus. Their aromaticity increases their
resistance for use in relatively severe conditions especially in aerospace and nuclear
industry for which lifetime prediction is a key issue. [2]

Due to the fact that they have a chain-like structure, they have some characteristic
features, e.g. rubber elasticity and viscoelasticity. For low temperatures, polymers behave
like ordinary solids, i.e. the chains are frozen in and there is no relative movement of chains
and molecules with respect to each other. Elastic behavior is only possible, if the atoms
move relative to each other. However, the elastic modulus, as defined at the beginning, can
be much lower. This is due to the fact, that, besides at the cross-linked points, the forces
between the chains are much smaller, usually Van der Waals Forces. Therefore, for a given
polymer, the elastic modulus at low temperatures reflects the degree of cross-linking. [3]

Fig, 1 a) Chain molecule, stretched and shortened b) Sketch for the rotational degrees of freedom

For higher temperatures, the linking of the molecules along the backbone of the
polymer comes into play, which leads to the phenomenon of rubber elasticity. Due to the
linking of the polymer molecules along the backbone, it is easily possible to rotate the
segments along the bonding axis. As there is a certain angle between two bonding axes, it is
possible to stretch a polymer chain. However, as it is more likely, that a polymer chain is in
a globule like form, the entropy of stretched polymer is smaller than in the globule like
form and therefore, a stretched polymer will increase its entropy by reducing its
dimensions. In a closed system stretching of a polymer leads to decrease in entropy and
increase in temperature. This also explains why the elastic moduli decrease with increasing
temperature in contrast to normal elastic behaviour. [3]

Benzoxazine Resin

Benzoxazines are the reaction products of an amine, a phenol and formaldehyde.

Example of reaction scheme:

Fig. 2 Reaction for Benzoxazine formation

Upon heating, di-functional benzoxazines form a high molecular weight polymer via a ring
opening mechanism. They have no weight loss thus they possess low shrinkage rate due to
a large phenolic-type network in their structure. Because of the ring opening during in
curing mechanism, their shrinkage rate is near zero. Benzoxazines possess a large-
phenolic-type network structure that makes them having high glass transition temperature
as material, low moisture absorption, better flame resistance, stable at room temperature
when stored, low coefficient of thermal expansion, excellent electrical properties, good
chemical reactivity resistance, high modulus material, high thermal oxidative resistance
and high char yield.

With regards to flammability, they have inherent flame retardant properties that are
strongly influenced by their backbone because they create phenolic like structure during
curing mechanism. Other properties of benzoxazine resins are they reduce the level of
phosphorus and residual halogens in epoxies, make the epoxy system more hydrophobic,
reduce the shrinkage of the thermoset systems, increase the modulus of the host systems,
and improve the latency and the shell life at room temperature.

In reactivity adjustment of benzoxazine resins, many catalysts, acid, alkaline

(imidazoles), salts, phenols (Bis-A, Bis-S), amines were reported to be able to reduce the
benzoxazine polymerization temperature and time. Epoxies are able to reduce the
benzoxazine reactivity by increasing the reaction peak temperature. Phenol novolac has
been patented to be an effective accelerator for benzoxazine. Below is the DSC thermogram
of catalyzed Bis-A benzoxazine.

Fig. 3 Differential Scanning Calorimetry (DSC) thermogram of catalyzed Bis-A Benzoxazine

DT310 is a more effective catalyst for curing the benzoxazine. DT300 retains better
properties in the formulation.
 If benzoxazine resins are mixed or formulated withy epoxies, epoxies in
benzoxazine lower viscosity, increase crosslink density therefore elevating glass transition
temperature, reduce brittleness, and improve adhesive strength while benzoxazines in
epoxies, reduce CTE (coefficient of thermal expansion), reduce moisture uptake, improve
thermal oxidative resistance and increase stiffness or modulus. If benzoxazine resins are
mixed with phenolic novolac resins, catalyzes benzoxazine polymerization and reacts with
box/epoxy blends, which is used extensively in electronic laminating formulation. [4]

Epoxy Resin

The term "epoxy resin" is a generic name for compounds that have two or more
oxirane rings (epoxy groups) in one molecule, and are cured three-dimensionally by a
suitable curing agent. However, in most cases, the term refers to bisphenol-A diglycidyl
ether (DGEBA), which is formed by the reaction between bisphenol A and epichlorohydrin,
which currently commands a 75% share of the epoxy-resin market. Of the products of
Three Bond, 50% to 60% of one-part epoxy resin and more than 90% of two-part epoxy
resin are based on DGEBA or compounds containing DGEBA. Therefore, DGEBA is synonym
for epoxy resin.

Fig. 4 Structure and properties of epoxy resin

 The excellent properties of epoxy resin, such as durability and adhesiveness, depend
largely on its structure. Figure 4 shows the relationship schematically. 1) The epoxy groups
at both terminals of the molecule and the hydroxyl groups at the midpoint of the molecule
are highly reactive, allowing room-temperature and high-temperature curing using
suitable curing agents, and a wide range of modifications. In addition, the resin is cured by
ring-opening polymerization, and as a result has a smaller degree of cure shrinkage than
other thermosetting resins. 2) The ether linkages included in the main chain improve the
chemical-resistance and elasticity. 3) The benzene rings in bisphenol A provide chemical-
resistance, adhesiveness, durability, heat-resistance and excellent electrical properties. 4)
The coexistence of hydrophilic groups with hydrophobic groups in the molecule
significantly increases the adhesion to various adherents.

Properties Characteristics

Moderate impregnation properties and strength with heating at

160°C or higher

Resistance to continuous heating at 220°C

Heat resistance
Glass transition temperature of 170°C, strength with heating 200°C,
50 kgf/cm2, peeling strength of 14 kgf/25 mm width

Moderate flowability, strength with heating at 150°C or higher

Dimensional Low coefficient of thermal expansion, high moisture-resistance, high

Stability purity, resistance to P.C.T. (pressure cooker test)

High thixotropy, screen printability

Thixotropy Fast curing at 150 °C, curing in one to two minutes

Moderate flowability, curing at a low temperature of 80°C to 100°C

High thixotropy, high viscosity

Moderate permeability, white cured substance, curing at 150 °C in

one to three minutes
 Fast curing Curing at 150 °C in one to three minutes, machinability

Machinability High shock adhesive force, slump property, and machinability

Impregnation Low viscosity, long shelf life

Low viscosity, low shrinkage ratio

Absorption of the thermal distortion of magnets/yokes, prevention of

cracks in vibration-absorbing magnets

Thermal shock, conformity to terminal bending, adhesion to

Elasticity
engineering plastics

Rubber elasticity

Structural High adhesive strength, peeling adhesive force

adhesion High adhesive strength, peeling adhesive force

Moderate flowability, heat-resistance, weather-resistance

Filling adhesion Moderate permeability, soldering heat-resistance

Moisture-resistance, flowability, low-temperature fast-curing

property

Table 1 Major Properties of Epoxy Resin

Phenolic Novolac Resin

Phenol novolac resins are produced from a phenol formaldehyde phenolic resin. The
stoichiometry used in the production of the phenolic resin will influence the functionality
of the phenolic resin and consequently the epoxy resin made from it. Production of the
phenolic involves a classic addition/condensation reaction. The initial reaction is an
addition reaction of the ketone/aldehyde to phenol. These are ortho and para directed on
the aromatic ring. Phenol formaldehyde reactions are not as stearicly hindered. With
control of reaction condition, catalyst selection, as much as 20-30% of the formaldehyde
reaction can occur at the ortho position. Included are multiple reactions of formaldehyde to
a single phenol molecule. Like phenol/acetone reactions the resultant methyolated resin
will condense. The condensation with phenol of methylol phenol creates Bis phenol F a 2
functional phenolic analogous to Bis phenol A. This condensation will result in a mixture of
o,o, o,p, and p,p isomers. The resultant phenolic displays the classic triplet peak for Bis F
epoxy resin when measured by HLPC or GC. In addition to condensation of methylol
phenol with phenol these condensations can also occur with methylol phenol and with di
and tri methylolated phenol. The resultant phenolic is consequently multifunctional and
shown below:

Fig. 5 Novolac Synthesis

As expected, reaction conditions, catalyst, addition rates and reactant ratios

influence both the concentration of di and multifunctional phenolic formation, and the
distribution of the isomer ratios. The resultant resin will have an average functionality that
is based on the weighted average of these components, but it is safe to say that unless
purification is involved all resins are a mixture of each fraction. In other words all Bis F
phenolics have some multifunctional component and all phenol novolacs have a Bis F
component. Bis Phenol A on the other hand can only be 2 functional for all practical
purposes. [5]
DSC (Differential Scanning Calorimetry)

Differential Scanning Calorimetry (DSC) is a common method to locate phase

transitions and to determine the associated transition enthalpy. The differential power
necessary to maintain a given temperature for two pans containing the material and a
reference sample is recorded. A discontinuous phase transition is indicated by a sharp
endotherm or exotherm which causes changes in the differential power supplied to the
sample. [1] And it is the most widely used technique of all the thermal analysis methods
(most of all in purity measurements for example in polymer or pharmaceutical industry).
There are two different types of DSC-methods, namely power compensated DSC and heat
flux DSC, which, although the same properties are measured, differ in their
instrumentation. The output of a DSC measurement, the so called thermogram is a plot of
the difference of heat delivered to the sample and to the reference as a function of the
sample temperature. If a physical or a chemical process which is endothermic (consuming
energy as heat) is taking place, in order to maintain the same temperature of the two pans,
more heat must be delivered to the sample pan than to the reference pan (where of course
no transition occurs). The effect is a positive or negative peak in the thermogram (the sign
of the peak is depending on the definition of the sign for the direction of the heat flow). The
opposite is true for an endothermic process. Since the enthalpy change of the transition
ΔtrsH is linearly related to the area under the curve of the thermogram it can be easily
calculated from the integral. [6]
 Fig. 6 An example of a thermogram

DMA (Dynamic Mechanical Analysis)

Dynamic mechanical properties refer to the response of a material as it is subjected

to a periodic force. These properties may be expressed in terms of a dynamic modulus, a
dynamic loss modulus, and a mechanical damping term. Typical values of dynamic moduli
for polymers range from 106-1012 dyne/cm2 depending upon the type of polymer,
temperature, and frequency. [7]
 Fig. 7 Example of DMA spectra

If, as in the case of DMA, a sinusoidal oscillating stress is applied to a specimen, a

corresponding oscillating strain will be produced. Unless the material is perfectly elastic,
the measured strain will lag behind the applied stress by a phase difference (δ) shown in
here. The ratio of peak stress to peak strain gives the complex modulus (E*) which
comprises an in-phase component or storage modulus (E’) and a 90° out-of-phase
(quadrature) component or loss modulus (E”). The storage modulus, being in-phase with
the applied stress, represents the elastic component of the material’s behaviour, whereas
the loss modulus, deriving from the condition at which d /dt is a maximum, corresponds
to the viscous nature of the material. The ratio between the loss and storage moduli (E
”/E’) gives the useful quantity known as the mechanical damping factor (tan δ) which is a
measure of the amount of deformational energy that is dissipated as heat during each cycle.
The relationship between these quantities can be illustrated by means of an Argand
diagram, commonly used to visualise complex numbers, which shows that the complex
modulus is a vector quantity characterised by magnitude (E*) and angle (δ) as shown in
Figure 3. E’ and E” represent the real and imaginary components of this vector thus:

E* = E’ + iE" = (E'2 + E"2) (1)

So that:

E’ = E* cos δ (2)

and

E" = E* sin δ

Fig. 8 Methods of determining Tg

In the figure (a) multiple methods of determining Tg are shown for DMA. Tg varies by up to
10°C in this example, depending on the value chosen. The differences, as great as 25°C,
have been reported. (b) Four of the different methods used to determine Tg in DSC are
shown. The half-height and half-width methods are not included. [8]

TA/TGA (Thermogravimetric Analysis)

Thermogravimetric analysis (TGA) is one of the members of the family of thermal

analysis techniques used to characterize a wide variety of materials. TGA provides
complimentary and supplementary characterization information to the most commonly
used thermal technique, DSC. TGA measures the amount and rate (velocity) of change in
the mass of a sample as a function of temperature or time in a controlled atmosphere.

The measurements are used primarily to determine the thermal and/or oxidative
stabilities of materials as well as their compositional properties. The technique can analyze
materials that exhibit either mass loss or gain due to decomposition, oxidation or loss of
volatiles (such as moisture). It is especially useful for the study of polymeric materials,
including thermoplastics, thermosets, elastomers, composites, films, fibers, coatings and
paints. [9]

Water Absorption

Water absorption was not neglected by Rimdusit and Ishida because it is also
important that this moisture uptake by the resin is a major cause of “popcorn” failure in the
molding compounds during fabrication process. The Table shows the numerical
comparison of the water absorption of the materials used. They stated that water
absorption of the ternary system improved from their pure epoxy counterpart due to
presence of lower water uptake benzoxazine resin in the mixture.

Viscosity

Viscosity of a polymer solution depends on concentration and size (i.e., molecular

weight) of the dissolved polymer. By measuring the solution viscosity we should be able to
get an idea about molecular weight. Viscosity techniques are very popular because they are
experimentally simple. They are, however less accurate and the determined molecular
̅𝑣 depends on
weight, the viscosity average molecular weight, is less precise. For example, 𝑀
a parameter which depends on the solvent used to measure the viscosity. Therefore the
measured molecular weight depends on the solvent used. Despite these drawbacks,
viscosity techniques are very valuable.
 Fig. 9 A piece of a liquid moving at shear rate 𝛾̇ under an applied shear stress of 𝜏.

Figure 9 shows a piece of a liquid moving at a strain rate 𝛾̇ under an applied shear
stress of 𝜏. The viscosity of the liquid is the ratio of the applied shear stress to the resulting
strain rate (or equivalently, the ratio of the shear stress required to move the solution at a
fixed strain rate to that strain rate). The shear strain in Fig. 9 is:
𝑑𝑢
𝛾= (3)
𝑑𝑦

where u is displacement in the 𝑥 direction. The strain rate is therefore:

𝑑 𝑑𝑢 𝑑 𝑑𝑢 𝑑𝑣𝑥
𝛾̇ = = = (4)
𝑑𝑡 𝑑𝑦 𝑑𝑦 𝑑𝑡 𝑑𝑦

where 𝑣𝑥 is velocity in the x direction. The relations between viscosity (𝜂), shear stress (𝜏),
and shear rate (𝛾̇ ) are:
𝜏 𝜏
𝜏 = 𝜂𝛾̇ or 𝛾̇ = or 𝜂= (5)
𝜂 𝛾

Glass Transition Temperature (Tg)

The glass transition is the temperature where the polymer goes from a hard, glass
like state to a rubber like state. The best way to envision this type of transition is to put a
rubber band (rubber like state, very flexible) into a container of liquid nitrogen. When
removed the rubber band is solid and inflexible (glass state) and in fact the rubber band
can be shattered. Upon standing and warming to room temperature the rubber band will
again become flexible and rubbery (rubber like state).

Fig. 10 Location of Tg

DSC defines the glass transition as a change in the heat capacity as the polymer
matrix goes from the glass state to the rubber state. This is a second order endothermic
transition (requires heat to go through the transition) so in the DSC the transition appears
as a step transition and not a peak such as might be seen with a melting transition. [10]

Loss Tangent (tan δ)

The angle delta, 𝛿, is known as the loss angle, and tangent delta is sometimes
referred to as the dielectric dissipation factor (D), the loss tangent, or the cotangent of the
phase angle, 𝜃. [11]

Ternary System

Ternary systems are those having three components. It is not possible to describe
the composition of a ternary alloy with a single number or fraction, as was done with
binary alloys, but the statement of two independent values is sufficient. For example, the
composition of an Fe-Cr-Ni alloy may be described fully by stating that it contains 18% Cr
and 8% Ni. There is no need to say that the iron content is 74%. But the requirement that
two parameters must be stated to describe ternary composition means that two
dimensions must be used to represent composition on a complete phase diagram. The
external variables that must be considered in ternary constitution are temperature,
pressure, composition X, and composition Y. To construct a complete diagram representing
all these variables would require the use of a four-dimensional space. This being out of the
question, it is customary to assume pressure constant (atmospheric pressure) and to
construct a three-dimensional (3-D) diagram representing, as variables, the temperature
and two concentration parameters. Therefore, in any application of the phase rule, it
should be recalled that one degree of freedom has been exercised in the initial construction
of the 3-D diagram by electing to draw it at one atmosphere of pressure. There is a
representation for ternary systems namely Gibbs Triangle. Gibbs Triangle is an equilateral
triangle; the three pure component metals are represented at the corners, A, B, and C, as
shown in Fig. 10.7. Binary composition is represented along the edges, that is, the binary
systems AB, AC, and BC. And ternary alloys are represented within the area of the triangle,
such as at point P in Fig. 11.

Fig. 11 A representation of Gibbs Triangle

If lines are drawn through Alloy P parallel to each of the sides of the triangle, it will be
found that these have produced three smaller equilateral triangles: aaa, bbb, and ccc. The
sum of the lengths of the nine sides of these three triangles is equal to the sum of the
lengths of the three sides of the major triangle, ABC, within which they are inscribed; or the
sum of the lengths of one side from each of the minor triangles is equal to the length of one
side of the major triangle: a + b + c = AB = AC = BC. Also, the sum of the altitudes of the
minor triangles is equal to the altitude of the major triangle: a¢ + b¢ + c¢ = AX.

If one side of the Gibbs triangle is divided into 100 equal parts, representing 100% on the
binary composition scale, it is found that the same units can be used to measure the
composition at point P. Let the length a represent the percentage of A in P, the length b the
percentage of B, and the length c the percentage of C. Because these lengths total the same
as one side of the Gibbs triangle, and together they must equal 100%, it is evident that 1%
has the same length, whether measured along an edge of the diagram or along any
inscribed line parallel to an edge. A similar result could be obtained by using altitudes, but
this is less convenient. It should be noted that in either case, the percentage of A is
measured on the side of P away from the A corner and similarly with B and C.

Fig. 12 Gibbs Triangle with composition lines

For convenience in reading composition, an equilateral triangle may be ruled with lines
parallel to the sides (Fig. 12). Composition may then be read directly, for example, P = 20%
A + 70% B + 10% C. At point P, the percentage of A is represented by the line Pa (or
equivalently Pa¢), which is 20 units long; the percentage of B by the line Pb (or Pb¢), 70
units long; and the percentage of C by the line Pc (or Pc¢), 10 units long. Other examples
shown in Fig. 12 are: Alloy R = 30% A + 40% B + 30% C, Alloy S = 80% A + 10% B + 10%
C, and Alloy Q = 60% A + 0% B + 40% C. [12]

Objectives

The main objective of this journal review is to know the dependability of the
findings of the research, by checking and re-analyzing of the results, the authors can look at
how reliable the results are. First is to re-analyze the properties, both physical and
chemical, of the materials used. With this re-analysis of the materials, the authors can make
certain if these materials are really suitable for the experiment. Second is to check the
theories behind these methods and how can it have an effect on the reliability of estimated
results. Lastly, the authors will check if the findings yielded in a successful manner. The
data that were obtained from their experiments and analyses should commit to their
estimated findings. Otherwise, there will be inquiries about the dependability of their
findings.

Significance of the Review

The significance of this review is to understand how electronic packaging materials

are used to make a flip-chip which is a trend in semiconductor devices technology in our
present time and maybe in the future. With this review, we can look at the development in
manufacturing of less cost and environment-friendly things we use in our daily lives like
cellphones, gadgets and other electronic devices. Researchers are very eager to develop
and/or produce new class of matter because of very high and rapid demand in technology
but with high quality, high consideration in environmental protection and health of people
and conservation of energy.

Significance of the Result

The significance of the result is to exhibit promising suitable electronic packaging

materials for application as underfilling encapsulation and other highly filled system.

Conclusion

Low-viscosity ternary mixtures of benzoxazine, epoxy, and phenolic resins have been
developed and it was proven effective. But the methods used to conduct the experiments
were very expensive.

References

[1] Hamley Ian, W, (2000). Introduction to Soft Matter. Baffins Lane, Chichester, West
Sussex, England, UK: John Wiley & Sons, Ltd.

[2] Richaud, E.; Audouin, L.; Colin, X.; Fayolle, B.; & Verdu, J., New Developments in the
Field of Radiochemical Ageing of Aromatic Polymers, Arts et Metiers ParishTech, CNRS,
PIMM, France.

[3] M306, Dynamic-Mechanical Analysis of Polymers, Technische Fakultat der Christian-

Albrechts-Universitat.

[4] Dr. Chih Chang, (2011). Benzoxazine Chemistry and Application Overview, Huntsman
Advanced Materials, APAC.
[5] John Cech, Characteristics of Bis F and Phenol Novolac Epoxy Resins, CVC Specialty
Chemicals, Inc.

[6] Lesinski, E.; & Duschmale, J., (Nov. 20, 2006), Differential Scanning Calorimetry.

[7] & [8] 2006, Dynamic Mechanical Analysis, IPTME, Loughborough University, UK.

[9] Sichina, W. J., Characterization of Polymers Using TGA, Perkin Elmer Instruments.

[10] Retrieved: www.arlon-med.com, Measuring and Understanding Tg (Glass Transition

Temperature),

[11] ASTM, Standard Terminology Relating to Thermophysical Properties, 100 Barr

Harbor Drive, West Conshohocken, USA.

[12] Campbell, F. C., (2012), Ternary Phase Diagrams, ASM International.