Direct Immersion Gold as a Final Finish

By Shigeo Hashimoto, Masayuki Kiso, Yukinori Oda, Horshi Otake C.Uyemura & Co., Ltd. Central Research Laboratory,
Osaka Japan

George Milad, Don Gudaczauskas Uyemura International Corporation Southington CT

In this study, the DIG process (Direct Immersion Gold), is investigated. Direct Immersion Gold is a
process in which gold is plated directly on copper as a surface finish for printed circuit board and
package applications. By examining the deposition reaction of the electroless flash gold plating bath, it
was confirmed that, copper
does not co-deposit with gold and also that the main driving force or deposition is an auto-catalytic
reaction. In addition the effects of the copper surface roughness and deposition time on the deposit
and solderability characteristics were examined. It was determined that copper surface roughness
affects solder spread-ability, and that solder joint characteristics were excellent when the film thickness
is within the range of 30 to 80 nm. Furthermore, good wire bonding characteristics were confirmed
from deposits plated by a neutral pH, auto-catalytic type heavy electroless gold plating bath, atop the
flash gold.

Introduction

Electronic components are normally mounted on to packages and printed circuit boards using solder.
Lead free solder was investigated as an alternative solder material to tin/lead based material. Although
many lead free solder compositions are available, the use of Sn/Ag/Cu solder materials are widely
accepted in printed circuit board and package applications for its solder joint strength and reliability.
Because the peak reflow temperature for Sn/Ag/Cu solder material ranges from 240 to 260°C and is
higher than that of Sn/Pb eutectic solder, there is concern that surface mounting reliability will
deteriorate. In this study, for printed
circuit board and package surface finishing applications, Direct Immersion Gold (referred to as DIG), is
introduced as a viable surface finish that is able to deposit a fine and uniform gold layer directly on the
copper surfaces. The characteristics required for the success of the Direct Immersion Gold surface
finish are
as follows:

 Minimum corrosion of the copper surface during deposition

(one of the causes of voiding after surface mounting).
 Gold plating layer has excellent coverage.
 Copper does not co-deposit with gold.

It was determined that it would be difficult to achieve feature 1) and feature 2) of the above mentioned
characteristics by a displacement (immersion) gold deposition reaction. Therefore, an electroless gold
plating bath that mainly deposits gold by an auto-catalytic reaction was developed.

Regarding feature 3) Copper co-deposition; theoretical evaluation was conducted by investigating the
oxidation potential of the reducing agent contained in the DIG bath and the deposition potential of
copper. Also, by conducting Auger analysis on the deposit, it was confirmed that copper does not
contaminate the gold layer. Furthermore, by measuring the amount of dissolved copper and comparing
it to the amount of deposited gold it was clear that the auto-catalytic reaction percentage is >80% of
the total depositing reaction, as compared to the immersion reaction.

Gold coverage obtained by the DIG bath was examined by anodic electrical current measurement. By
comparing a plating layer deposited by a displacement (immersion) type gold plating bath and plating
layers deposited by the Direct Immersion Gold bath in various plating times, it was demonstrated that
Direct Immersion Gold exhibits superior coverage as compared to standard immersion gold. Also, gold
coverage on test coupons plated under 10 minutes differed significantly from those plated in excess of
10 minutes.

Test coupons for deposit characterization were plated for 20 minutes to give a gold layer thickness of
approximately 50 nm. This was shown to give the optimum gold coverage as verified by SEM
evaluation.

In order to study the relationship between copper surface roughness conditions and DIG gold deposit
characteristics, solder joint reliability evaluations were conducted on substrates plated by Direct
Immersion Gold with the copper surface micro-roughness adjusted by various copper etching
conditions. Solder joint reliability was evaluated by examining solder ball spreading, ball shear testing,
and inter-metallic (IMC) formation for both Sn/Pb eutectic solder and Sn/Ag/Cu solder.

Gold wire bonding is widely used as a mounting technique for IC chip applications. Test coupons for
gold wire bonding characterization were prepared by plating 50 nm of DIG as above. In addition a 500
nm gold thickness test sample was also prepared by the deposition of an additional layer on top of the
50 nm of DIG. This new layer was deposited by a heavy deposition neutral pH, auto-catalytic electroless
process.

Test Procedures and Results

Confirmation of deposition reaction:

In order to determine the oxidation reaction of “DIG R”, which is the reducing agent of Direct
Immersion Gold, the rest potential was measured using a gold electrode and a copper electrode. The
standard electrode was Ag/AgCl, and the working electrode was copper and gold plate. Measuring
temperature was 85°C.

Measuring solution:

 Solution A): DIG solution with no gold salts.

 Solution B): DIG solution with no gold salts and no reducing
agent “DIG R”

Test method and results are shown in Fig 1

Fig 1 Rest Potential measurement of DIG plating solution

From the results of this testing method, it should be noted that during the comparison of the solution
with and without “DIG-R” (comparison of solution A and B), the rest potential of the gold electrode
surface and copper electrode both fluctuate to a rest noble potential. This fluctuation in potential
demonstrates the possibility that “DIG-R” is oxidizing at the gold electrode and copper electrode
surface. Also, this potential was near equal at the copper electrode and gold electrode surface. This
type of potential fluctuation demonstrates that it is difficult for a copper corrosion current to ocuur even
if copper is immersed in the plating solution.
If it is difficult for a copper corrosion current to generate during plating, then the copper dissolution
amount according to the plating reaction is reduced. Also, because the oxidation reaction of the
reducing agent is nearly equal to the rest potential of copper, it is easily seen that it is difficult for
copper to deposit with the gold.

Moreover, by conducting a plating test using a 10 L test cell and measuring the gold deposition amount
and the amount of copper dissolution into the plating solution, it was determined that the main
deposition reaction is an auto-catalytic reaction. The Direct Immersion Gold bath was adjusted during
plating by analyzing the
gold concentration amount with atomic absorption spectrometry, and gold cyanide and “DIG-R” were
replenished according to the gold consumption amount. Copper clad laminate boards (FR-4) were used
as test substrate printed circuit boards. Bath load factor was 2dm2/L, and test substrate boards were
changed by two methods, every twenty minutes and every 8 hours. The relationship between the gold
deposition amount and copper dissolution concentrationin the plating solution is shown in Fig. 2.
Fig 2 Measurement of Cu displacement Ratio in DIG Au plating solution

From this result, it was confirmed that the dissloved copper concentration in Direct Immersion Gold
solution is lower compared to the copper dissolution concentration that can be theoretically calculated
assuming the plating bath deposition reaction is 100% displacement (immersion) reaction. It was also
confirmed that the copper dissolution amount differs according to the exchanging cycle times of the
test printed circuit boards.
From these results, we assume that the main reaction for DIG bath is an auto-catalytic reaction. This
result confirm the rest potential measurement.

Also, by conducting Auger qualitative analysis of gold film deposited on test coupons that were plated
with plating baths containing 50mg/L of copper, results showed that copper does not co-deposit within
the gold (refer to Fig.3 Auger analysis).

Fig 3 Elemental analysis of DIG deposit by Auger

1. Deposit Characteristics

The standard DIG plating process utilized to evaluate the gold deposit is shown in table 1.

Table 1 Standard DIG process (Add Table)

In order to confirm the optimum plating time, the relationship between gold coverage and plating time
were investigated by anodic electric current measurement. This method to measure gold coverage is
performed by using 5% sodium sulfate with 0.1% tartaric acid as the electrolyte, and measuring the
anodic current density
when a electric potential of 70mV is applied to the Ag/AgCl reference electrode. Test substrates were
prepared by applying electrolytic acid copper plating (20um) to copper clad laminate boards and
adjusting the surface area to 1 cm X 1 cm dimensions with masking tape. Measurement results of the
relationship between DIG plating time and anodic current density are shown in Fig.4. The comparison
with a conventional 100% displacement (immersion) reaction electroless gold plating bath is shown in
Fig.5. Also, the relationship between Direct Immersion Gold plating time and gold plating layer
thickness is shown in Fig.6.

Fig 4 Effect of plating time on gold coverage

Fig 5 Comparison of gold coverage of conventional displacement bath and DIG bath
Fig 6 Gold deposition rate of Direct Immersion Gold bath

In the anodic eletrolysis conditions used in this evaluation, gold does not dissolve and only copper
dissolves.

Therefore we understand it is possible to compare the gold surface coverage ratio by measuring the
anodic current density. The results in Fig.4 demonstrate that the surface coverage ratio does not
increase much after the first ten minutes of plating. In this study, the plating time was adjusted so that
it was possible to deposit a gold plating layer of 50 nm (20 minutes) on the test substrates.

Fig 7 SEM of DIG gold deposit over time

The surface SEM photographs of variable plating time coupons are shown in Fig. 7. Because the gold
plating layer thickness deposited by Direct Immersion Gold is 50 nm, copper surface roughness has a
great influence on gold coverage characteristics. In order to investigate the relationship between
copper surface roughness
and gold plating layer characteristics, test cuopons with relatively severe buff polishing after
electrolytic acid copper plating were prepared. Solder mask was applied to the test cuopons, and by
using a special copper etching agent CZ (Mec Company Ltd.) process, test coupons of different surface
roughness were made
by adjusting the CZ copper etching amounts to 0, 1, 2, and 3um. An SPS (sodium persulfate) bath and a
sulfuric acid/hydrogen peroxide bath were utilized as a soft etching process before plating with DIG in
order to adjust surface roughness. By using test coupons with different copper surface roughness and
different soft etching conditions in the pre plating process, the influence copper surface roughness has
on solder joint characteristics was confirmed. The relation between each soft etching condition and
surface roughness is shown in Fig.8. A laser microscope (KEYENCE Corporation VK-8550) was utilized
for surface roughness
measurement.

As a result, a smoother (more even) copper surface was obtained by a sulfuric acid/hydrogen peroxide
type etching bath compaired to a sodium persulfate etching bath.

Direct Immersion Gold was deposited for 20 minutes to the copper surface roughness test substrates
shown in Fig. 8. Solder spreading ratio was evaluated using these test cuopons. The test results are
shown in Fig.9. Also, solder spreading ratio comparison between eutectic Pb/Sn solder and lead free
solder are shown in Fig.10.

Fig 8 Effect of soft etch on surface roughening

The test method for solder spread ratio measurement was as follows:

R type flux (Alpha metal Co. R5003, R Type) was applied on the test coupon and solder balls (Pb/Sn
eutectic and Sn/4.0%Ag/0.5%Cu) of 0.75 mm in diameter were placed on the coupon which was then
placed on a hot plate (230 oC for Pb/Sn eutectic solder, 260°C for lead free solder) for 40 seconds. At
the respective temperature the solder ball would melt down and spread out on the coupon. The solder
spreading ratio was then calculated as follows:

Solder spreading ratio = (Solder spreading area) / (Original solder ball volume)

Fig 9 Effect of surface roughness on solder spread ratio

Fig 10 Effect of solder ball material on solder spread ratio

The results indicate that the solder spreading ratio was larger when the copper surface was rougher.
Also, lead free solder results were inferior (spread less) as compared to Pb/Sn eutectic solder. It is
necessary to understand this characteristic when lead free solder is utilized.

Solder ball shear testing procedure was as follows. After the DIG finish was applied to the test
substrate, Pb/Sn eutectic and Sn/Ag/Cu solder balls of 0.75 mm in diameter were soldered to 0.6 mm
pads in diameter. Evaluation conditions are shown in Table 2 and test results are shown in Fig.11.

Table 2 Solder Ball Shear Conditions

Sn/Pb: 63/37 Senjyukinzoku, SaprkballS, 0.76mm

Sn/Ag/Cu: 95.5/4.0/0.5 Senjyukinzoku, Eco-solderball S, 0.76mm

Reflow Conditions
Sn/Pb solder: 230°C, 40 sec, hot plate in air

Sn/Ag/Cu: 260°C, 40 sec, hot plate in air

Flux: Alphametal R5003 (Rtype)

Equipment and Test Conditions

Dage#4000

Shear Speed: 4,000 μm/sec

Tool height: 50 μm

Fig 11 Effect of solder ball material on ball shear test results

In the case of Pb/Sn eutectic solder, a significant difference in ball shear test results could not be
confirmed. On the other hand, Sn/Ag/Cu solder results showed that copper surface etching methods
had a direct effect on voids in the solder, and therefore indicate that it is necessary for an optimum
etching method to be chosen.
Fig 12 Effect of time at temperature on sheer strength

It is concluded, that the higher reflow temperature was a reason why the solder spreading ratio results
for Sn/Ag/Cu solder were inferior. It may be necessary for future testing to actaully pull an IC chip after
it has been mounted.

Furthermore, in order to confirm long term joint reliability after mounting, shear testing and IMC cross
section observation were conducted on test cuopons that were heat treated at 150°C for 1,000 hours.
Shear test results are shown in Fig.12 and IMC cross section SEM photographs are shown in Fig.13.

Fig 13 Intermetallic propagation over time at 150°C temperature

In order to confirm the wire bonding characteristics of DIG finishing, test coupons with gold thickness of
50 nm (Flash gold only) and 500 nm (Flash and heavy gold) were prepared (standard plating process is
shown in Table 3).

Two types of 50 nm gold thickness test substrates were prepared, one without heat treatment and one
with heat treatment at 155°C for 3 hours. Also, the 500 nm test coupons were heat treated per in-
house pre-wire bonding procedure (heat treatment at 175°C for 3, 6, 10 and 16 hours), and wire
bonding characteristics were evaluated. The results are shown in Fig.14 and Fig.15. The wire bonding
conditions are shown in Table 4.
It is known that bonding strength will decrease or bonding would fail, if there are oxidized metals on the
gold surface. Good wire bonding results were obtained from flash gold test coupons (Direct Immersion
Gold finishing) that were not heat treated (Fig 14). This reconfirmed that the Direct Immersion Gold film
was high
in purity and had excellent gold coverage.

Table 3 Standard DIG plating process with Heavy Gold

Cleaner ACL-009 50°C 5 min

Rinse Amb 1 min

Acid Dip 10%H2SO4 25°C 1min

Rinse Amb 1 min

Micro-etch 25°C 2 min

Rinse Amb 1 min

Acid Dip 10%H2SO4 25°C 1min

Rinse Amb 1min

Im Gold Flash Gold 85°C 20 min

Rinse Amb 2 min

E’less Gold Heavy Dep. 50°C 30 min

Rinse Amb 2 min

Fig 14 Wire bonding test results of Thin (50 nm) DIG gold deposit
Fig 15 Wire bonding test results of Thick (460 nm) DIG gold deposit

Fig 16 Wire bonding test results of Electroless Ni-P/thick gold after 16 hours at 175°C

Table 4 Wire Bonding Conditions

Model KS 4524A

Semi-auto
Wire size 25μm
Capillary part # 4047220010-320
Frequency US 60Hz
1st Bond 2nd Bond
Power 130 mW 190mW
Time 10msec 15msec
 Force 30g 90g

Although the wire bonding evaluation results after heat conditioning of thicker gold films (falsh and
heavy dep) were inferior compared to the conventional test coupons that include a Ni-P layer (As a
reference, bonding data of electroless nickel immersion gold ENIG is shown in Figs.15 and 16), it was
demonstrated that it is possible to wire bond on heavy gold films which have been deposited directly
on copper.

Conclusion

Many processes are being proposed as a final finishes for printed circuit board and package
applications. In this study, a finishing process that can directly deposit gold onto the copper surface by
utilizing an electroless plating process has been presented. It was confirmed that it is possible to
directly deposit gold on the copper
surface with excellent coverage and without creating defects on the copper surface, because the main
gold depositing reaction is an auto-catalytic and not a displacement one. Furthermore, by combining a
neutral auto-catalytic heavy gold electroless plating bath, a heavy gold layer was deposited directly on
the copper
surface. The applicability of solder mounting and gold wire bonding on these gold plating layers (flash
50 nm and heavy 500 nm) directly on copper was demonstrated.