1999 International Symposium on Advanced Packaging Materials

Characterization of Silver Flakes Utilized for Isotropic Conductive Adhesives

Deanna L. Markley and Quinn K. Tong
Corporate Research
Dorothy J. Magliocca and Thomas D. Hahn
Central Analytical Group
National Starch & Chemical Company
Bridgewater, NJ 08807
(908) 685 - 5227
quinn.k.tong@nstarch.com
Abstract
Silver (Ad flakes are widely used as conductivefillers for isotropic conductive adhesives. Silver provides superior
conductivity and has reasonable costs associated with it, compared to other precious metals utilized in the
electronics industry. As a result, production of silverflakes and powders has developed into an industry of its own.
The silver fillers are typicallyfabricated into jlakes and lubricated with certain organic compounds such as fatty
acids. The organic lubricants on the su$ace of silverflakes play an important role in the pdormance of isotropic
conductive adhesives. In particular, improvements in rheology and electrical conductivity have been observed.
However, the exact nature of the lubricants on the silverflake su$ace as well as its impact on the adhesive rheology
and conductivity has not been fir& understood. This study identified the structure of the organic lubricants on the
silver flake suqace. The results using DSC (Differential Scanning Calorimetry), AFS (X-ray Photoelectron
Spectroscopy), SEM (Scanning Electron Microscopy), Raman Spectroscopy, and DRIFTS ( D i m e Reflectance
Infiared Fourier TransformSpectroscopy) techniques to characterize silverjlakes will be discussed in detail.
Key words: silver (Ag), silver fillers, lubricants, silver particle lubrication, surface characterization, Differential
Scanning Calorimetry (DSC), X-ray Photoelectron Spectroscopy (XPS),Scanning Electron Microscopy (SEW,
Raman Spectroscopy, Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIR, DRIFTS).

1. Introduction stability. Therefore it is important to understand how

Surface Mount Conductive Adhesives (SMCAs), a
class of isotropic conductive adhesives, provide an
attractive alternative to current soldering technology,
which has the ability to eliminate processing steps,
and reduce heating and environmental hazards
associated with TdLead solders. Isotropic
conductive adhesive (ICAs) are composed of a
polymer matrix and metal fillers that impart the
desired adhesive and electrical properties,
respectively. Typically, silver flakes and powders
are utilized because of their high electrical
conductivity, chemical stability and low cost [11. As
a result, recent growth in demand for consumer
electronics has led to the development of the silver
fillers industry.
Processed silver powders and flakes must have
suitable properties in order to fabricate compatible
ICAs [2]. For example, 1-3 pm size silver flakes
with a loading of 7580% by weight in ICAs can give
good conductive and adhesive properties.
Manufacturers can control the particle size, particle
size distribution, and other important characteristics
by manipulating various processing conditions, such
as lubricant concentration used during the formation
of neutral silver particles. Slight variations in the
concentration of the lubricant, such as oleic acid,
could cause significant changes in application
properties such as adhesive conductivity and
silver flakes impact the properties of ICAs.
Previous experimental efforts found that the presence
of acid h c t i o ~ l i t yin adhesive fonndations causes
the SMCA viscosity to increase at room temperature
[3]. This phenomenon suggests that acidic lubricants
on the surface of silver flakes or powders play an
important role in the performance of SMCAs,
including particle dispersion, thermal and electrical
conductivity, and rheology. Various analytical
techniques have been utilized in the past to
characterize the chemical nature of the lubricant and
how it interacts with silver particles [3].
Nevertheless, a more complete description of the
lubricant structure on the silver particles is desirable.
In an effort to establish a more complete description
of the adsorbed lubricant structure and its influence
on the silver particles, several analytical techniques
are employed. The techniques and findings are
described below.
2. Exuerimental
2.1 Samde Preparation
For this study, commercial silver flakes were
purchased and used as supplied.
2.2 Scanning Electron Microscow (SEM)

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 1999 InternationalSymposium on Advanced Packaging Materials

Scanning Electron Microscopy (SEM) was used to

qualitatively characterize the flake size and shape of SEM micrographs in Figures la-lc show the effect of
the silver particles. The SEM model Jeol JXL-6400 lubricant on the morphology of the lubricated silver
was utilized throughout this study. The samples were flakes. Figure l a shows that the untreated particles
applied to adhesive coated stubs and characterized at appear as aggregates of submicron silver spheres.
magnifications ranging from 1,000 to 2,500X. The clusters of spherical silver particles have an
average diameter of 100 microns. The agglomeration
2.3 Differential Scanning Calorimeter (DSC) may be due to the high surface tension of the
untreated metal. Ball milling with oleic acid (Figure
The Influence of lubricant on thermal transitions was lb) or stearic acid (Figure IC)results in a mixture of
characterized by Differential Scanning Calorimeter 5-10 pm flat flakes (80%) and 1-5 pm irregular
(DSC) using a TA Instruments model DSC-2920. particles (20%).
For reproducible results, approximately 10 mg of
sample was added to a non-hermetic pan without a Figure la. Non-lubricated Silver Particles
lid, and heated at a rate of 10C/minute with an air
purge flow rate of 50 "in.
2.4 Ash Determination
Ash method was used to determine the total amount
of organic lubricant on the silver flakes. In this
method, a quartz crucible is fmt heated to 600 "C
and dried to constant weight (within 2 0.001g). The
silver flakes were dried at 55 "C for 3 hours. About 2
g of the dried silver sample was then placed in the
dried crucible, placed in a muffle oven and heated up
to 600 "C for 16 hours to ash the sample. The
amount of organic lubricant on the silver may be
determined by the weight difference before and after Figure 1b. Oleic Acid Lubricated Silver Particles
the 16 hour heating.
2.5 X-ray Photoelectron Suectroscouv ( X P S )
The elements present near the surface of the treated
silver flakes were identified with X-ray Photoelectron
Spectroscopy ( X P S ) using an ESCA-300
spectrometer (Scienta Instruments, Sweden). The
silver flakes were pressed on a sample holder plate
and the binding energy spectra of Cls and 01s of the
samples were taken.
2.6 Diffuse Reflectance Infrared Fourier Transform
Spectroscopy (DRIFTS)
Figure IC. Stearic Acid Lubricated Silver Particles
The functionality of adsorption for the low amounts
of lubricant (approximately 0.1 YOby weight) present
on the silver flakes, was characterized using a
Diffuse Reflectance M a r e d Fourier Transform
Spectroscopy (DRIFTS) accessory in a Perkin Elmer
1750 spectrometer. Samples were prepared by
mixing 3-6% by weight of silver flakes in KBr
powder and adjusted to a KBr powder background.
2.7 Raman Suectroscouy
As a complimentary technique to DRIFTS, the
chemical structure of the adsorbed lubricants on the
silver flakes was also characterized with Raman
Spectroscopy using a Nicolet 950 FT-Raman
Spectrometer. Silver samples were placed in NMR 3.2 Ash Determination for the Amount of Lubricant
tubes for the analysis. on Silver

3. Results and Discussion Ash determination summarized in Table 1 shows the

percent by weight of organic material on the
3.1. The Shape and Size of the Silver Flakes lubricated silver surfaces. This method is capable of

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 1999 International Symposium on Advanced Packaging Materials

quantifying the signifkantly small levels of organic
material present. Secondly, assuming the organic
material is all lubricant, this information can be used
along with estimated surface areas to give an
indication of the thickness of the lubricant adsorbed
on the surfaces. In the case of both oleic acid and
stearic acid shown in Table 1, the amount of material
present is consistent with films of molecular
dimensions (monolayer or bilayer).

Table 1. Residue Results for Silver Flakes with a Variety of Lubricants

None 0.03
Oleic Acid 0.10
I Stearic Acid I 0.29 I

3.3. Differential Scanning Calorime? "XC) Study

DSC thermograms show the temperature dependence
of thermal transitions on the lubricated silver. Figure 3. Oleic Acid Lubricated Silver in the
Presence of oleic acid c1+ stearic acid, (Figure 2), Presence of Air and N,
result in an exothemc transition when heated in the
presence of air. The transition is also dependent on
the thermal history and heating conditions. In a
nitrogen purge, the transition is not observed (Figure I
3). After annealing the oleic acid at elevated
temperatures, the heat given off in the transition is
reduced (Figure 4). With additional heating cycles
the exotherm is not observed indicating that the
tqmsition is irreversible (Figure 5). In addition, the
temperature of the exothem depends on the type of
lubricant used. However, the neat lubricants do not
go through exothermic transitions in the transition
region shown for the lubricated silver flakes (Figure
6). Instead, the only transitions that are observed are
the endotherms that would correspond with the phase
transitions of the materials.
Figure 4. As Received Oleic Acid Lubricated Silver
Figure 2. Oleic Acid and Stearic Acid Lubricated Compared to as Received Oleic Acid Lubricated
Silver Lubricated to Non-lubricated Silver Silver Annealed for 6 Hours at 135C

-- I I

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 1999 International Symposium on Advanced Packaging Materials

Figure 5. Oleic Acid Lubricated Silver Subjected to Figure 7.90" Cls X P S Spectrum
Multiple Heating Cycles

- M

41
-I -T m ..tu-

Figure 8.90" 0 1s X P S Spectrum

Figure 6. Neat Stearic Acid Lubricated to as
Received Stearic Acid Lubricated Silver

The occurrence of the exotherm suggests that the
reaction occurring involves a chemical change on the
silver surface rather than a change in the state of
lubricant. However, the temperature dependence of
the exotherm on the lubricant type suggests that
lubricant binding inhibits the exothermic reaction
that occurs and therefore would have an activation
energy that is lubricant dependent. Related studies
have suggested that the exotherm corresponds to a
combination of oxidation of the silver surface andor
oxidation of the lubricant [3].
3.4 X-ray Photoelectron Suectroscoov (XPS)Results
XPS data also supports the presence of the lubricant
only at molecular dimensions, specifically
monolayer. Both the Cls, (Figure 7), and Ols,
(Figure 8), spectra for all the samples showed no sign
I: ~i
3.5 Diffise Reflectance Infrared Suectroscouv
(DRIR) Results
Further evidence of chemical bonding is given in the
vibrational spectra. DRIFTS spectra of a lubricant
adsorbed to silver flakes is given in Figure 9. The
presence of a strong peak centered around 1398 cm-'
can be assigned to the [0-C-01 symmetric stretch [4],
which suggests that a sigmkant amount of the
lubricant is forming a salt with the silver surface.
The virtual absence of any intensity around 1700 cm-
for the C=O stretch of the acid dimer suggests that
all the acid functionality on the Ag surface was
modified.
Figure 9. DRIFT Spectrum of Oleic Acid Lubricated
Silver Flake
I
I NglsilWpatids

of free acid groups on the silver flakes. The 01s

spectrum shows a peak at binding energy of 530.5
eV, which indicates the symmetric 0-C-0 structure
on silver surface. Likewise, the Cls spectrum shows
a peak at binding energy of 287.5 eV indicating O-C-
0 group symmetrically bound on the silver surface.
These results support the notion that the lubricant is
chemically bonded to the surface as a monolayer.

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 1999 International Symposium on Advanced Packaging Materials

3.6 Raman SpectroscoDy
Further evidence for lubricant bonding to the silver
surface comes from the Raman spectrum of the
treated powders. Spectra in Figure 10 show that the
[O-C-01 symmetric stretch peak appears around
1395 cm- [5]. In addition, the 1609 cm- is likely
due to a C= stretch coordinated with the silver
surface for a small amount of oleic acid which is
usually found in stearic acid.
Figure 10. Raman Spectrum of Stearic Acid
Lubricated Silver Compared with Neat StearicAcid
the silver flakes is possible with the DRIFTS and
Raman spectra. The DRIFTS spectra clearly shows
the presence of the 0-C-0 in the form of a symmetric
stretch. In the Raman spectrum, the same symmetric
stretch peak is observed. In addition, the spectra
suggests the presence of a small amount of oleic acid
(C=C stretch) as a contaminant.
5. References
1. Y. Iwasa et al., Conductive Adhesive for Sui$ace
Mount Devices, Electronic Packaging &
Production, pp. 93-98, Nov. 1997.
2. U.S. Patent, 5,413,617, Process for the
Preparation of Sliver Powder with a
Controlled Surface Area by Reduction
Reaction.
3. D. Lu et al., A Fundamental Study on Silver
Flakes for Conductive Adhesives4th
M A P S Proceedings, Braselton, Georgia,
15-18 March 1998, U.S.A., pp. 256-260.
4. H. Han et al., D i m e Reflectance Infiared
Spectra of 4-Nitrobenzioc Acid and 4-
Cyanobenzoic Acid Self-Assembled on Fine
Silver Particles, Applied Spectroscopy, vol.
52, n. 8, 1998.
5. Dollish, Francis R.; Fateley, William G.;
Bentley, Freeman F.; Characteristic Raman
Frequencies of Organic Compounds, 1974,
John Wiley and Sons,Inc., New York.

4. Conclusion:
Overall, the data suggest that acid lubricants form
stable monolayers chemically bonded to the silver
surfaces. The effect is shown in the ultimate
morphology and physical properties. These physical
and morphological properties can be related to the
rheological properties previously shown for SMCAs.
The SEM data show that ball milling with lubricants
gives a completely different morphology of silver
particles versus not lubricating the particle at all. It
also shows that the presence of lubricant reduces the
clustering of silver particles.
The DSC results indicate that the lubricant is
chemically bonded to the silver powders. The
temperature dependence of the exothermic peak may
be a consequence of the chemical binding. The
exothermic process does not likely occur untd after
the lubricant is debonded from the surface during the
heating process and may be due to either lubricant or
silver oxidation at the elevated temperatures.
X P S data confirms the presence of carbon and
oxygen at levels consistent with oleic acid. In
addition, the spectra also suggests that the oleic acid
is bonding to the silver surface as a salt. The virtual
absence of free acid in the X P S data indicates that the
lubricant is present as a monolayer.
Direct observation of the change in the state of the
stearic acid from the solid state to the monolayer on

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