Soldering, Brazing, Die and Wire Bonding to Electroless Nickel;

Conditions that Influence Reliability

By Don Baudrand
Consultant for MacDermid, Inc.
Waterbury CT

April 1995

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 ,

Soldering, Brazing, Die and Wire Bonding

to Electroless Nickel;
Conditions that Influence Reliability
By Don Baudrand

htroducti on

Reliable joining to electroless nickel deposits is critically important to the electronic

industry as well as in hardware fabrication. Because electronic devices oflen are
subjected to extreme temperature excursions during fabrication?electroless nickel
deposits may change physical characteristics in bulk and on the surface where joining
takes place.
High temperatures are common for multi-chip modules (MCM-C) and hybrid circuits on
ceramic substrates.

Nickel is a good electrical conductor compared with thick films used to metallize
ceramic substrates. Therefore, it is used to enhance conductivity as well as corrosion
resistance?diffusion barrier and the ability to be soldered, brazed, wire and die bonded.
The conditions for each joining method must be correct for the type of electroless nickel
deposit. Adjustments may be necessary to compensate for the environment to which the
deposit is exposed in he fabrication process.

Electroless nickel deposits have excellent uniformity, good corrosion resistance, strong
adhesion to substrates and superior solderability under the right conditions.

Electroless nickel deposits have been recognized as a satisfactory barrier material. It has
a slow transport rate in the substrate and the adjoining layer, laterally uniform in
thickness and structure,
they are thermodynamically stable against substrate and adjoining material and have low
resistivity.(1&2)

Numerous papers have been published and presented at conferences dealing with the
virtues of electroless nickel for many engineering and hardware applications. Hardness,
wear resistance and corrosion protection are characteristics which make electroless
popular. The ability to plate uniform thickness over all surfaces enhance these
characteristics. One place where advanced applications are found is in the electronics
industry.

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Soldering to Electroless Nickel Dew
, sits

Soldering is usually defined as joining metals at low temperatures (usually below 800
degrees F) (426 C) by fusing a low melting alloy. The interaction between nickel and
solder is important in determining reliability. Nickel-tin compounds form when using
tin-lead solder, Ni3Sn, Ni3Sn2, and Ni3Sn4 have been detected at the interface.(3) Films
on the surface of electroless nickel deposits such as soils, phosphorus compounds and
oxides of nickel can interfere with soldering. Non wetting or dewetting results from
foreign substances on the surface to be soldered. In the absence of these films, good
wetting of the surfaces by the solder results in a reliable joint,

Electroless nickel has many forms. Examples are: Nickel phosphorus deposits having
differing phosphorus (P) content. The physical, electrical and surface characteristics are
different for each level of phosphorus. In addition, the reaction to "heat treat" conditions
differ widely. It is well known that heating nickel phosphorus deposits to temperatures
of 300 degrees C to 400 degrees C cause the formation of nickel phosphide which
hardens the deposit the degree of hardening depends on the amount of P and the heat
treat temperature and time. For example, low P deposits (3-4?6)heat treat to a harder
value and at a lower temperature than high P ( 10.5-12%) deposits. Nickel phosphorus
plating solutions can also host alloying metals which further change the deposit
characteristics. Sometimes as little as 1/2 ppm can cause a profound change.

Nickel (B) boron deposits have different characteristics from those of nickel P deposits.
Similarly, nickel boron deposit characteristics change with boron content. Low B
deposits are best suited for most applications. A nickel boron deposit containing 0.25%
B has a melting point of 1455 degrees C . Nickel P with I Iwt.% P melts at 880 degrees
C. ( a eutectic alloy).
Nickel boron deposits have high as plated hardness (700-770Kn100). They heat treat to
higher values than for nickel phosphorus, and at lower temperatures.(2)
Electronic microcircuits and packaging requires a suitable barrier layer which can sustain
a long period of service. Nickel has the slowest dissolution rate in solder and the
slowest intermetallic compound formation rate compared with gold, silver, copper,
palladium or cobalt.

Sintering Electroless Nickel Deposits

Let us examine what happens to electroless nickel phosphorus when it is heated under
certain conditions. "Nickel P starts to oxidize at about 400 degrees C and above 800
degrees C, decomposition of phosphorus and evaporation of phosphorus from the coating
occurs. Above 600 degrees C, migration of phosphorus to the surface and formation of
phosphorus oxide has been observed.. "A kinetic study at 800 to 1000 Degrees C
showed that a Ni-P deposit oxidized about 100 times faster than pure nickel. The
addition of even a small amount of boron to the deposit decreased the amount of
oxidation." ( 2 ) Phosphorus in the Ni-P coating is the cause of the poor oxidation

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 resistance of the alloy and the much purer Ni-B coatings may be expected to have a much
improved resistance to oxidation."(2)

Heating nickel-P deposits in air or in moist hydrogen results in removal of phosphorus

from the surface of the deposit making it much more solderable, brazable and wire
bondable. It is interesting that moist hydrogen atmosphere is reducing for nickel but
oxidizing for phosphorus.(2) Phosphorus is oxidized by the oxygen supplied by some
dissociation of water, and vaporized from the surface, leaving a few angstroms of pure
active nickel.

Ohmic contacts are made to thick film deposits on ceramic semiconductors by the use of
electroless nickel and heat treat processes. Thick film conductors of gold, silver
platinum etc. have DC resistivity which is several orders of magnitude higher than
calculated values. Stable low resistance ohmic contacts having ease of solderability and
reliable lead attachments using heat treated nickel-P alloys. This technique can be used to
make ohmic contacts to intermetallic compounds such as gallium arsenide,
thermoelectric semiconductors, bismuth-telluride, silicon and ceramic materials. Heat
treating to 350 -400 degrees C for 10-15 minutes provides the improved contact. If air
oxidation increased the resistance, re-heating will restore the good ohmic contact
characteristics. (4)

Contact angle measurements and miniscograph instruments are commonly used to

measure the wetting ability of solder to the substrate materials. It is reported that solder
contact angle varies with phosphorus content. The higher the phosphorus content, the
higher the contact angle (poorer solderability) for non annealed deposits. (tests were
done in vacuum to avoid atmospheric interference.) Higher contact angles mean less
wetting. However, when deposits were heated to temperatures in excess of 340-4 10
degrees C, prior to soldering, solder contact angles improved. This was true for both
95Pb/5Sn and 63Sn/37Pb solders. annealing time to low contact angle was from 120
seconds minimum to reach equilibrium to about 600 seconds.

So1der FI uxes
Fluxes or special surface cleaning and activation processes are used to prepare electroless
for soldering.
Solder fluxes are many. They are classified by the degree of activity. Inorganic fluxes
being the strongest and rosin the weakest. Inorganic acids such as zinc chloride, are not
used by the electronics irxiustry because the residues which may be left are concsive.
Water soluble organic acids are used as mildly active fluxes and rosins are the least
active. Fluxes are used to remove surface oxides and sulfides. reduce surface tension of
molten solder, and prevent oxidation during the heating cycle. R fluxes are rosin, RMA
are rosin-mildly activated and RA fluxes are rosin- active. Soluble organic acids and
inorganic acid fluxes complete the list.

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Tests were made using dilute sulfamic acid. The results were favorable. However,
although it appears that no harmful residues are left from using sulfamic acid, tests for
long term corrosion have not yet been completed. One successful method to use
sulfamic acid is to rinse thoroughly then dip in a dilute sulfamic acid solution and dry,
leaving a slight film of sulfamic acid on the surface. Since sulfamic acid is a solid the
film remains in tact until ready to solder. The rosin flux contains alcohol and some water
which dissolves the sulfamic acid which in turn activates the electroless nickel deposit
for good soldering. In some cases users of this method have immersed the part to be
soldered in warm water, activating the sulfamic acid film, alcohol dip to remove water
and solder of use pure rosin then solder. This method is not in accordance with Military
specifications, but seems to be quite effective.

It is common practice to overplate electroless nickel with gold or palladium to preserve

solderability. However, the overplate must be pore free to prevent oxidation
(passivation)of the nickel at the pore sites. Porous precious metal over plating can
accelerate passivation of the nickel due to the galvanic cell created by the dissimilar
metals.
for example, Steam-aged porous gold over electroless nickel will not solder easily due to
the passivation of the nickel.

Die Bondins

Electroless nickel Phosphorus for die bonding requires a heat excursion above 700
degees C, usually about 800 degrees C in a Nitrogen/hydrogen for atmosphere for 8-1 0
minutes, leaves a nearly pure nickel surface that when gold plated, will alloy for the
formation of a nickel silicide thereby giving rise to an excellent die bond. The best
results were achieved when the temperature was at 500 degrees C for 3 minutes then
raised to 800 degrees C for 8 minutes then die bonded using 400 degrees C for 0.75
minutes in the nitrogenlhydrogen atmosphere. Phosphorus can inhibit formation of
nickel silicide during die bonding. Gold phosphorus silicide is very brittle and can cause
die delamination. Nickel boron can be die bonded without this thermal excursion.(3)

Die bonding using conductive epoxy materials is usually successful on various electroless
nickel deposits. Success depends somewhat on the epoxy formulation, as well as the
condition of the deposit.

Wire bondirg

Aluminum wire ultrasonic wire bonding testing was performed using nickel boron plated
printed wiring boards. Long term reliability of the wire bond joint was measured by the
destructive pull test at time zero and after 2000 hours of temperature humidity (85
degrees C and 81% RH).” The MIL-STD specifies a minimum time zero destructive pull
strength of 3 grams. The aluminum wire was approximately 0.00 I25 inches in diameter,
99% AI, 1% Si, 19-2 1 grams tensile strength. The samples tested ranged from 13.5-14.0
grams at time zero. At the end of the 2000 hour test, all samples recorded a pull strength

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 of 12- 13 grains.(5 ) Thus electroless nickel boron deposits wire bond well. Higher
ultrasonic energy is required for wire bonding to electroless nickel than for bonding to
gold. Bonding gold wire to electroless nickel boron requires thermosonic techniques.
Similarly, higher ultrasonic energy is usually required. (not higher pressure).

Wire bonding to nickel phosphorus is not usually done unless specific thermal excursions
are done to prepare the nickel surface as noted above.

Summary

~ Soldering, brazing wire bonding and die bonding can be successful using electroless
nickel plating processes provided that the conditions for reliability are observed. Proper
sintering condition, proper selection of flux, joining time, temperatures and the right
furnace atmosphere make it possible to solder to any electroless nickel regardless of
phosphorus content. Wire bonding energy level, for ultrasonic bonding to aluminum
wire, preparation by sintering, if necessary, and the use of thermosonic methods for
bonding gold wire make reliable joints.
Proper preparation of electroless nickel deposits make electroless nickel suitable for die
bonding.

References

1. Chwan-Ying Lee and Kwang-Lung Lin Materials Interaction in Pb-Sn-PIA1 and

'I

Pb-Sn/Ni-B/Al Solder Bumps on Chips". Thin Solid Films, 229, 1993 63075
2. W. 'Tomlinson and G Wilson. "Oxidation of electroless Ni-B and Ni-P Coatings in Air
at
800-1000 degrees C., Chapman and Hall Ltd.
3. Kwang-Lung Lin and Jien-Ming Jang. "Wetting behavior Between Solder and
Electroless
Nickel". Materials Chemistry and Physics 38 ( 1994) 33-41.
4. N. Gajbhite and T. Kutty. "Omic Contacts By Electroless Nickel Plating". Bulletin of
Electrochemistry May-June, 1986, pp.23 1-236
5. D. Crot?y and T Jackson. "Electroless Nicke! Plating of Printed Wlring Bcards Fcr
Solderability and Wire Bonding." Sur-FIN 92

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