I Molar
concentration
0.0 1
S O , 2 - : Pd2+
0.1
H : Pd
0.007
I
0.75
H : Pd
0.0017 0.177
0.02 0.2 0.0004 0.041 0.0004 0.044
0.05 0.5 0.0003 0.037 0.0002 0.021
0.1 1 0.0002 0.025 0.0003 0.035
0.2 2 0.0006 0.063 0.00 1 5 0.155
four times as high as that of hard gold (gold- 'I'his is explained by the lower diffusion
cobalt, gold-nickel, gold-iron alloys) layers, coefficients of metals such as copper and zinc
which is 2 to 3 p R cm, but similar to the value through to palladium, compared with gold.
of I 8 carat gold-copper-cadmium deposits (8). The different diffusion rate also plays a role,
However for contact applications, the resistivity in the solderability of palladium layers (1,14).
of the deposits in most cases is not as important In general, dissolution of palladium is consider-
as the contact resistance and its change with ably slower than that of gold in 60 tin-40
time under different environmental conditions. lead solder, but the intermetallic compounds
The contact resistance of as-deposited formed at the dissolving interface may result in
palladium, measured against gold, is in the fracture. It is therefore suggested that the
range of that of hard gold and varies- amount of palladium dissolved in the solder be
depending on the measuring method-between kept below I per cent by weight (14). The
I and 7 m a (1,3,8 to 12). In extensive tests growth of intermetallic compound layers at
carried out in atmospheres containing various room temperature is fairly rapid. After six
amounts of sulphur dioxide, hydrogen sulphide, months its thickness has increased to 3 p m (14),
nitrogen dioxide and hydrogen it was demons- while after 25 days at IOOT it is between 3 (15)
trated t h a t under these conditions and 60 pm (14). The compound seems to be a
electrodeposited palladium shows only a slight lead-tin phase, with the rejected lead
increase in contact resistance of up to about 30 accumulating at the solder interface (14).
mQ, at the most (1,3,8,9,10,12,13). Under the The other method of connecting leads to con-
same conditions I 8 carat gold-copper-cadmium nector pins is by wire wrapping. From practical
layers exhibit much worse behaviour, their experience it is known that palladium layers
resistance becoming about twice as high as that behave in a similar way to hard gold, especially
of palladium (4, I 0). if they are heat treated. The microhardness of
The contact resistance of a 2.5 pm thick the deposits is generally in the range of 140 to
palladium layer on copper did not change after 300 HV, this depending on the deposition
a heat treatment of 200 hours at 1 ~ 5 ° Cor one parameters (8,9, I 6, I 7). It increases in the first
of I 5 minutes at 2ooOC (3,9). However, that of hours after deposition and stays constant at
a comparable gold layer had doubled under the longer times, or even drops slightly. This is due
same conditions (9), a behaviour confirmed for to the out-diffusion of hydrogen and to the
2 hours at 165OC and 250 hours at IOOOC(12). correspondifig volume changes ( I 6, I 7, I 8).
Citrates have a similar effect. If the cirrate con- from hydrogen : palladium<o.or to 0.18 (0.5
centration is 0.5 mol/l, the hydrogen concentra- molar sodium salicylare at 2 Mdm'). Benzoates
tion increases from hydrogen : palladium 0.02 and salicylates, as well as heterocyclic N-
to 0.08 at 2 &'dm2. In general citrate reduces containing compounds result in a sharp fibrous
the tensile stresses, but the deposits are still ( I 10) orientation. At concentrations above 5
highly stressed ( I 50 N/mniL) and tend to crack mmoVl phenacetine reduces the tensile stress of
as illustrated in Figure 9 (20). Sodium the deposits to values below those of deposits
salicylates increase the hydrogen concentration from addition-free electrolytes (20).
The influence of deposition parameters on
the porosity of deposits from a palladosammine
solution and the influence of saccharin were
investigated by Fatzer ( 2 5 ) . Apparently
saccharin reduces hardness, but increases the
porosity of the layers. The best deposits were
obtained at room temperature and 60 g/I
Pd(NH,),C12 at a current density of 2.4 A/dm2.
Such deposits are glossy or bright and at thick-
nesses greater than 1.25 ,um are pore free. A
soluble anode process with a Na,PdCI, solution
produced highly stressed, porous deposits (25).
Referenees
I F. H. Keid, Plating, 1965, 5 2 , 531 I 7 F. Simon, op. cit., ref. I 6
2 M. Antler, Platirium Metals Reo., 1982, 26), )@, I 8 H. D. Hedrich and Ch. J. Raub, Meralloberflaeche,
106 19777 3’3 ( 1 11, 512
3 H. Grossmann, M. Huck and G. Schaudt, 19 J. M. Locarnini and N. Ibl, in Proc. AES 2nd
Galoanotechitik, 1980, 71, ( 5 ) , 484 International Pulse Plating Symp., Am.
H. Hermance and T. F. Egan, Bell Syst. Tee. y., Electroplat. Soc., Winter Park, Fla., 1981
4
‘9587 37,739 20 H. D. Hedrich and Ch. J. Raub, Merallobei$aeche,
5 H. J. Keefer and K. H. Gumley, Bzll Syr. Tec. 3., 1979, 337 (81, 308
1958, 37,777 2 1 H. D. Hedrich and Ch. J. Raub, Surj. Technol.,
6 L. €1. Germer and J. L. Smith, Bell Sysr. Tec. 3., 1979, 8, (41, 347
1 9 ~ 7 ~ 3769
6, 2 2 H. D. Hedrich and Ch. J. Kaub, Galoanocechnik,