Study of Precieus Metal Coatings Using
Sequentia1 Electrochemical Reduction Analysis
by P. Bratin, M. Pavlov, and G. Chalyt,
ECI Technology, East Rutherford, N.J.
resently, tin and solder coatings
P are the main metal finishes em-
ployed in the manufacturing
circuit boards and electronic compo-
of
nents. In order to protect the substrate
from oxidation during the storage and
manufacturing process, the solder or
tin layer has to have a certain thickness
and quality. There are two common
ways to apply solder to the surface of
the board or component+lectroplat-
ing and hot solder levelingldipping.
The plated coatings are usually more
porous and have a higher leve1 of sur-
face oxides than do the coatings ap-
plied in contact with molten solder.
Electroplating is also apt to have other
surface contaminants, for example,
codeposited organics. The presence of
surface contaminants, excessive ox-
ides, and porosity may adversely affect
the solderability. There are some dis-
advantages in hot solder application as
well, particularly the varying of the
solder layer thickness, which can af-
fect the surface planarity.
With increased usage of fine-pitch
devices, the need for a uniform and
consistent solder surface has become
even more critical. Finer pitch compo-
nents such as a thin smal1 outline pack-
age, quad flat pack, and micro-BGA
require a planar surface. To achieve
this, alternatives to tin-lead finishes are
frequently used. These altematives in-
clude precieus-metal coatings such as
gold, palladium, and silver, as wel1 as
azole-based organic coatings.
When selecting an altemative sur-
face finish for printed circuit board
(PCB) assembly, the following key pa-
rameters are to be considered: solder-
ability, ambient stability, high temper-
ature stability, suitability for the use as
contact/switch surface, solder joint in-
tegrity, and wire bondability, as wel1 as
the tost.
In addition to the organic protective
coatings, which were reviewed in a
previous paper,’ a number of different
precieus metals and their combinations
have been proposed. For copper as the
base metal, these coatings include
10
gold/nickel/copper, palladium/nickel/
copper, palladium/co
and silver/copper.
22
per, gold/copper,
The thick gold
and palladium systems produce a pure
and clean surface, which is wire bond-
able. The protective coatings also pro-
vide protection against tamishing and
corrosion resistance by various chem-
icals, resistance to oxidation at high
temperature, and good solderability
even after extended storage.
The migration of copper to the sur-
face can occur when the precieus metal
is placed directly on the copper sub-
strate. Additionally, gold and copper
can form intermetallic compounds, the
growth of which can cause additional
solderability and bondability prob-
lems; therefore, a nickel barrier is gen-
erally placed between the copper sub-
strate and gold or palladium coating.
Even for coatings with nickel banier
layers, if the precieus-metal coating is
thin and porous, nickel can diffuse to
the surface, where it is subsequently
oxidized.5s6 Nickel oxide can then in-
terfere with soldering, wire bonding,
and lid sealing.
The silver finish is not as widely
used as gold or palladium; however,
silver was used in microelectronics as
a base substrate for bonding to semi-
conductor lead frames and as a final
finish for circuit boards.497 The oxidel
sulfide formation and electromigration
of silver during storage have been a
concern for soldering and wire bond-
ing.
Two electroanalytical techniques
have been developed for assessment of
protective effectiveness and solderabil-
ity of different types of surface finish-
es. 1,6s,9 Sequentia1 electrochemical re-
duction analysis (SERA) was developed
for solderability assessment of tin and
tin-lead coatings, and later was extended
to the identification of oxides and other
reducible species as wel1 as the measure-
ment of their thicknesses.rO The poten-
tiometric evaluation of substrate oxida-
tion (PESO) technique was developed
for assessment of precieus metal coat-
ings located on the surface of nickeL6
0 Copyright Elsevier Science Inc.
This article describes some experience
with monitoring of substrate oxidation
through the coating of a precieus metal,
using the SERA technique.
PRINCIPLES OF THE
ELECTROCHEMICAL
TECHNIQUES
In the SERA technique, a constant
current is applied between the part and
an inert counterelectrode in a deaerated
inert electrolyte. The potential of the
test part is monitored as a function of
time. The SERA curve yields a series
of plateaus corresponding to the reduc-
tion or oxidation of the surface species.
The potential of each plateau is a char-
acteristic of the species. The time re-
quired to complete the electrochemical
reaction is a measure of the amount of
species present on the surface. A typi-
cal SERA curve is shown in Figure 1.
For each metal or alloy, the final po-
tential corresponds to the hydrogen
evolution from the electrolyte. If the
reduction potential of surface species
is either more negative or the same as
the hydrogen evolution potential, the
measurement of such species by SERA
technique is not feasible. This interfer-
ence can be observed when the pre-
cious metals are placed on the nickel
intermediate layer. The hydrogen evo-
0, / /
-1
0 100 ZO0 300 400 500
Tlme (snc)
Figure 1. Typical sequentia1 electrochemical
reduction analysis curve.
METAL FINISHING ?? OCTOBER 1996
 0.3r
0 200 400 600 800 lom
Time /sec)
Figure 2. Effect of immersion time on cor-
rosion potential.
lution process on the surface of pre-
cious metals masks the reduction of
nickel oxide. More information from
such a system can be obtained if the
current is not applied to the tested sur-
face. The potential of the surface is
then monitored in a more aggressive
electrolyte than one used for SERA
measurements.6.” The method can
then provide a nondestructive detec-
tion of both substrate oxidation and
coating porosity.6 Figure 2 shows
PESO results obtained from immersion
gold coatings deposited on the surface
of electroless nickel using the proce-
dure developed by Tench et aL6 As
seen from this figure, the final (corro-
sion) potential increased with increas-
ing immersion time.
EXPERIMENTAL
Procedures used for SERA and
PESO anapses have been described
previously. *12Test specimens used for
SERA measurements were coated ac-
cording to the proprietary processes of
the different suppliers. Electrolytic and
immersion processes were used to
place the final layer of the precieus
metals.
GoldKopper
At ambient conditions, the gold does
not form any oxides when in contact
with moisture and air; thus, upon ap-
plication of the reduction current, gold
does not undergo electrochemical re-
duction that would interfere with the
reduction of the copper oxides that mi-
grated through the pores in the gold
coating. Figure 3 shows the SERA
curves obtained from a copper sub-
strate coated with the immersion gold.
12
- Reflcw on Nitrcgen
Time (sec)
Figure 3. Immersion gold over copper.
This sample was cut into three pieces.
One piece, which was tested as re-
ceived, did not reveal the presence of
any significant amount of the reducible
species. The second piece was re-
flowed in a nitrogen atmosphere, and
again virtually no reducible species
were present on the surface. The third
part of the sample was reflowed in the
air and the SERA curve showed a sig-
nificant amount of copper oxide mi-
grated through the gold pores.
PalladiumKopper
Similar results were obtained from
production samples coated with elec-
trolytic palladium over the copper sub-
strate. The freshly coated sample did
not exhibit any reducible species on
the surface, whereas the sample heated
for about 30 minutes at 250°C in the air
showed two well-defined reduction
plateaus (Fig. 4). Based on the reduc-
tion potentials, these species can be
identified as cuprous (Cu,O) and cu-
pric (CuO) oxides.
A set of two samples coated with
l
0 100 200 300 400
Time (sec)
Figure 4. Immersion palladium over copper.
r
0 200 400 600 800 1000
Time (sec)
Figure 5. Effect of palladium thickness.
different thicknesses of the immersion
palladium (3 and 9 microinches) were
prepared and tested after approxi-
mately 6 months of storage at ambient
conditions. Figure 5 shows the SERA
curves obtained from these samples.
The sample with the thinner palladium
layer revealed a significant amount of
the reducible species, whereas the
sample with the thick coating did not
show any reducible species. This
means that the copper substrate was
unimpededly oxidized through the
pores of the thin palladium layer.
Three reduction plateaus were ob-
served on the SERA curve obtained
from the sample with 3 microinches of
palladium; two of them are most prob-
ably Cu,0 and CuO, whereas the third
one at -0.2 V is presently not identi-
fied.
Note that the sample coated with
immersion gold shows only one copper
oxide (CuO), whereas the samples
coated with the immersion and the
electrolytic palladium show at least
two distinct plateaus. The type of coat-
ing, as wel1 as the aging process, plays
a critical role in the surface condition.
The differente between the number of
reducible species and their reduction
potentials was probably due to the dif-
ferent aging conditions.
Silver/Copper
Figure 6 shows the results obtained
from the sample coated with immer-
sion silver. The obtained SERA curves
reveal two reduction plateaus. Based
500
on the values of the reduction poten-
tials, these species can be identified as
silver oxide (Ag,O) and silver sulfide
(Ag,S).” In order to verify the nature
of the surface film, the samples were
METAL FINISHING . OCTOBER 1996
 -Siker As Is
-Afler Air
-0.4
z
UI -0.6

-0.8

1 ..l... ._-I -1. -1 . . ’

0 200 400 600 800 1000
0 200 400 600 800 1000
0 200 400 600 600 1000 Time (sec)
Time (sec)
Time (sec)

Figure 6. Immersion silver over copper. Figure 8. Gold-coated sample with nickel Figure 9. Palladium-coated sample with
intermediate layer. nickel intermediate layer.

heated in a programmable oven at wil1 be retested with the PESO tech-

250°C for 3 min. The silver oxide is
not stable at high temperatures
(> 160°C) and starts to lose the oxy-
gen. i4,15 At the same time, silver sul-
fide is stable at high temperatures. Af-
ter heating, the first plateau
disappeared although the second pla-
teau remained without changes. This
confirms that the first plateau corre-
sponds to silver oxide, and the second
plateau corresponds to silver sulfide.
The thickness of both compounds can
be calculated using a previously de-
scribed procedure.”
A commercial silver-based coating
is coupled with a very thin (10 A) layer
of organic inhibitor that eliminates ox-
ide and sulfide formation during stor-
age. Figure 7 compares the SERA
curves obtained from the silver-coated
circuit boards with and without the
organic inhibitor. As can be seen from
this figure, the protected sample did
not reveal any reducible species.
0 100 200 300
Effect of Nickel Intermediate
Layer
A nickel intermediate layer is gen-
erally applied between the base mate-
rial and the topcoat in order to improve
the adhesion between the substrate and
the final finish and to prevent the
growth of intermetallic compounds.7
Two specimens coated with the palla-
dium and the gold were prepared for
testing. The thickness of the final fin-
ish was approximately 3 microinches
for both samples, and both specimens
also employed the electroless nickel
banier layer. The effect of the interme-
diate layer was studied by exposing the
test specimens to the elevated temper-
atures in the air atmosphere, perform-
ing the SERA tests, and comparing
their curves to the ones obtained with
the untreated control specimens.
Figure 8 compares the SERA curves
obtained before and after temperature
treatment of the sample coated with the
immersion gold. Neither of the SERA
curves reveal the presence of any re-
ducible species. The measured poten-
tial rapidly dropped to the value corre-
sponding to the hydrogen evolution
reaction. Only a slight variation in the
final potential was detected, probably
due to the structure of the gold surface.
Figure 9 compares the SERA curves
obtained before and after temperature
treatment of a sample coated with the
immersion palladium. The results were
the same as those observed with the
gold-coated samples; no reducible spe-
cies were presented on the surface of
400 500
nique, and results reported elsewhere.
CONCLUSIONS
Electrochemical analysis using the
SERA technique provides a fast and
nondestructive evaluation of the sur-
face conditions of the precieus metal
coatings. It was shown that the tech-
nique can also be very useful for tbe
evaluation of the protective effective-
ness of the metal finishes. In addition,
this information can be used to select
the best conditions for the soldering
process (reflow). Additional efforts are
currently under way to establish the
correlation of the SERA and PESO
results to the solderability and wireb-
ondability of precieus metal coatings.
References
1. Bratin, P. et al., “New Application of
SERA Method-Assessment of the
Protective Effectiveness of Organic
Solderability Preservatives,” Proceed-
ings of AESF SURFIN’ 95 Technical
Conference, pp. 5388.589; June, 1995
2. Milad, G., “Electroless Palladium: A
Surface Finish for Interconnect Tech-
nology,” Proceedings of the IPC Tech-
nical Conference, p. P12-3; April,
1995
3. Hwang, J.S., “PCB Surface Finish,”
SMT Magazine; p. 20-22; October,
1995
4. Beigle, S., “Altemative Metal Finishes
for Wire Bond and Soldering Applica-
tions,” Proceedings of the IPC Techni-
cal Conference, p. S9-2; March, 1996
5. Winters, E.D. et al., “A Comparison of
Electrolytic and Electroless Ni/Au Fin-

Tima (sec)
the palladium sample. A smal1 differ- ishing Process for Multilayer IC Pack-
ence in the final potential was ob- ages,” Plating and Surface Finishing;
served with untreated and heated pal- 81(4):72; 1994
Figure 7. Effect of organic inhibitor. ladium samples as well. The surfaces 6. Tench, D.M. et al., “Solderability As-

14 METAL FINISHING ?? OCTOBER 1996

 sessment of Circuit Boards and Lead Printed Circuit Board Fabrication,” dation of SERA Test Method,” Solder-
Finishes,” Proceediqs of the SMI Proceedings of the IPC Technical Con- ing and Surface Mount Technology,
Technical Conference, pp. 529-535; ference, p. P12-2; April, 1995 13: 18-29; February, 1993
August, 199.5 10. Bratin, P. et al., “Determination of 13. Weast, R.C., ed., CRS Handbook of
Wlassink, K., Soldering in Electronics, Type and Thickness of Oxides Using Chemistry and Physics, 63rd ed, CRS
2d ed; 1989 SERA,” Proceedings of the IPC Tech- Press Inc., Boca Raton, Fla.; 1983
Tench, D.M. et al. “Solderability As- nical Conference, p. S9-6; March, 14. Remi, H., Lehrbuch der Anorganis-
sessment via SERA,” Journal of Ap- 1996 chwn Chemie, vol. 2; 1960
plied Electrochemistry 24:46-50; De- ll. Morrisey, R.J., “Electrolytic Determi- 1.5. Campbell, W.E. and U.B. Thomas,
cember, 1994 nation of Porosity in Gold Electro- “Tamish Studies,” Transactions of The
Reed, J. and J. Cheng, “Sequentia1 plates 1 Corrosion Potential Measure- Electrochemical Society,, 76th Genera1
Electrochemical Reduction Analysis ments,” Journal of the Electrochemical meeting, vol. LXXVI, p. 303, New
(SERA) Applications on Process Char- Society, 117(6):742-747; 1970 York; September 1939 MF
acterization and Trouble-Shooting for 12. Tench, D.M. et al., “Production Vali-

The Chemical Analysis of Electroplating Solutions

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