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A Drop-In Lead-Free Solder Replacement

Ning-Cheng Lee, James A. Slattery, John R. Sovinsky


Indium Corporation of America, Utica, NY
and
Iris Artaki
AT&T Bell Laboratories, Princeton, NJ
and
Paul T. Vianco
Sandia National Laboratories, Albuquerque, NM

ABSTRACT Lead Reduction Act of 1990 (S.2637), a bill that would limit or
Environmental and toxicity concerns related to the use of ban the use of lead-containing materials, including
lead have initiated the search for acceptable, alternate electronics solders, was introduced four years ago, by
joining materials for electronics assembly. This paper Senator H. Reid. After intense lobbying by the electronics
describes a novel lead-free solder designed as a "drop in" industry and the Lead Industries Association, electronics
replacement for common tin/lead eutectic solder. The solders were deleted from subsequent revisions to the bill.
physical and mechanical properties of this solder are In its present form, the bill (S.729) will probably be
discussed in detail with comparison to tin/lead eutectic reintroduced in the Senate this year, and while electronics
solder. The performance of this solder when used for solders will be excluded, the bill will have a "new use and
electronics assembly is discussed and compared to other unnecessary inventory" provision, require labeling that
common solders. Fatigue testing results are reported for would include a bar on defenses for products that require
thermal cycling electronics assemblies soldered with this labels, establish an "exposure concern list", and ban certain
lead-free composition. The paper concludes with a lead-containing products.
discussion on indium metal availability, supply and price.
The other legislative initiative involves taxing lead and lead
Key Words: solder, soldering, lead-free, electronic, reflow, containing products. The Lead-Based Paint Hazard
solder paste, SMT, surface mount, Pb-free Abatement Act (H.2922) was introduced in the House by
Congressman Cardin in 1991 and would place a tax of
RATIONALE FOR LEAD-FREE SOLDER $0.75/lb on primary refined lead and a $0.37/lb tax on
Tin-lead solder has been used in electronics assemblies secondary refined lead, irrespective of its final use. The
since the earliest days of radio. Its adequate and well revenues from these measures were targeted as funding for
documented mechanical, electrical and thermal properties, the renovation of older housing units containing lead-based
combined with its low material cost, have made it the material paints. The revised version of this bill, (H.2479) proposes a
of choice for joining active and passive components. tax of $0.45/lb on the lead content of all lead-containing
However, well publicized environmental and toxicity products and is gaining support. A similar bill was
concerns have led to increased controls and legislation (in introduced in the Senate (Bradley S.1347). There is a good
the U.S. and other countries) which if enacted, would reduce, chance that these bills will become law in 1994 either as
tax or eliminate the use of lead in solders for electronics stand alone entities or attached to other legislation.
assembly.
GOALS FOR DEVELOPMENT OF LEAD-FREE SOLDERS
The use of lead in non-solder related materials such as The following goals were established for the development of
tetraethyl lead additive for gasoline, and lead naphthenate a new non-lead containing solder specifically designed for
and lead oxide for paint, have been banned for years. More electronics assembly use:
recently, lead containing solders have been banned for use
in potable water piping, food and beverage cans and 1. Have a melting temperature similar to 63Sn/37Pb
automobile bodies where they were used in repair solder.
applications. 2. Have a narrow plastic range.
3. Have adequate wetting properties.
There are two major federal legislative initiatives on lead 4. Have physical properties similar or better than
currently being pursued in the U.S. Congress. The Toxic those of Sn/Pb solder.
5. Be compatible with existing liquid flux systems. properties but has not found widespread usage.
6. Be capable of fabrication into existing physical
forms of solder i.e. wire, preforms, ribbon, 97Sn/2Cu/0.8Sb/0.2Ag is a lead-free plumbing solder that
spheres, powder, paste, etc. was developed by Kester Solder Company and is marketed
7. Have adequate shelf life and performance as a under the trade name of Aquabond. Its performance mimics
solder paste. that of Sn/Pb eutectic but at a higher melting temperature.
8. Contain relatively non-toxic metals.
9. Possess low dross formation when used in a 95.5Sn/4Cu/0.5Ag is lead-free plumbing solder developed by
wave soldering operation. Engelhard. Its wide melting range of 225°-349°C would
severely restrict its use as an electronics solder.
CURRENT LEAD-FREE ALTERNATIVES
The alternatives available today include a few lead-free Conductive polymers are mixtures of organic chemical
metallic solders and conductive polymers. Of the available components and a conductive metallic filler. The organic
lead-free solders and conductive polymers, all fail to meet chemical component consists of a resin system (that may be
one or more of the goals listed above. Table 1 lists some thermoplastic or thermosetting), a solvent system and
common lead-free solders, their melting properties and a rheological additives. To this mixture is added a metallic
brief description. More details on the solders are given filler, typically silver flake. The resultant paste can be
below: dispensed or screened onto the substrate, heated to drive
off the solvent and initiate a curing process. The resin
52In/48Sn is considered the lowest melting point solder and provides the mechanical attachment whereas the silver flake
is often used as the last step in a sequential soldering provides electrical conductivity between the joined surfaces.
operation, and for soldering to metallizations on temperature Conductive polymers can be isotropic, having electrical
sensitive components. conductivity in all planes, or anisotropic where the electrical
conductivity is only in the "Z" axis.
58Bi/42Sn is relatively inexpensive and has a proven track
record where it has been used in wave soldering of printed The major shortcomings of conductive polymers include
circuit assemblies. However the melting point is lower than substantially lower conductivity compared to metallic
tin/lead eutectic. solders, high cost, rework difficulty, low bond strength and
absence of self alignment. These shortcomings have
91Sn/9Zn has been used to solder aluminum using inhibited their general use for component attachment.
specialized fluxes. Because of its corrosion potential, zinc However, there is intensive research directed to improving
poses a concern. Solder paste incorporating this alloy the performance of these materials and they may in the
would have a poor shelf life due to attack on the metal future prove to be viable replacements for metallic solders
spheres by the organic acids present in the flux vehicle. for some applications.
Additionally, the alloy drosses excessively when used in a
wave soldering operation. HISTORICAL PERSPECTIVE OF Sn/In/Ag ALLOY
DEVELOPMENT
96.5Sn/3.5Ag and 95Sn/5Sb both exhibit good wetting Although tin-lead eutectic solder has adequate physical
characteristics. Additionaly, 95Sn/5Sb has excellent shear properties and has been used succes sfully for a long time in
strength at 100° C. The high melting point of these alloys electronics assembly, certain specialty solders have been
may limit their application. developed to meet the need for specific applications. For
example, the lead-indium system was developed to meet the
65Sn/25Ag/10Sb is a patented alloy developed by Motorola specific requirement for soldering to gold substrates. The
and is commonly known as "Alloy J". It has good fatigue alloy 92.5Pb/5.0In/2.5Ag was developed to meet the need for

Table 1 Some Common Lead-Free Solders.

Composition Melting Point Comments


52In/48Sn 118o C. (eutectic) lowest mp solder, expensive
58Bi/42Sn 138o C. (eutectic) well established history, inexpensive
91Sn/9Zn 143o C. (eutectic) corrosion concerns, high drossing alloy
96.5Sn/3.5Ag 221o C. (eutectic) excellent wetting and strength
95Sn/5Sb 232o - 240o C. good high temperature shear
65Sn/25Ag/10Sb 233o C. (mp) Motorola patented alloy, high strength
97Sn/2Cu/.8Sb/.2Ag 226o - 228o C. high melting range
95.5Sn/4Cu/.5Ag 225o - 349o C. wide and high melting range
increased fatigue resistance. 90In/10Ag solder was Table 2 shows some of the physical properties of the solder
developed for use in cryogenic environments. A family of alloys. The density was determined with the use of a
solders was developed with melting points lower than tin- pycnometer. The electrical resistivity was measured via a
lead eutectic to allow for soldering to temperature sensitive micro-ohm meter. The thermal conductivity tests were
components and for use in a sequential temperature or conducted by monitoring the temperature differential across
"step" soldering operations. the sample on an axial heat flow apparatus. The thermal
expansion coefficient was determined using a
These solders and others were developed prior to the use of thermomechanical analyzer.
modern analytical instrumentation and before computer
modeling existed. Today the development of unique solders In general, the physical properties of 77.2Sn/20.0In/2.8Ag
that do not contain lead benefits from the availability of were comparable to those of 63Sn/37Pb. The differences
modern analytical instrumentation and computer modeling. observed are considered insignificant in terms of electronics
However, this advantage is offset by the limited number of industry applications. For instance, it has been postulated2
metals that can be incorporated in a lead-free solder due to that the electrical resistance of the solder joints should be
toxicity, physical properties, cost and availability. acceptable at a value no greater than 0.03 mΩ / joint
(approximately 5.9 x 105 µohm.m). Apparently, the electrical
It is generally agreed that tin, with its desirable physical resistivity of 77.2Sn/20.0In/2.8Ag is far lower than this value.
properties, will be alloyed with other metals to produce an As to the density, although being lower than that of
acceptable lead-free solder. The candidates for other metals 63Sn/37Pb, it is quite comparable to that of 96.5Sn/3.5Ag.
include antimony, bismuth, copper, gallium, indium, silver The latter alloy exhibits a density of 7.36 gm/cm3 and has
and zinc. Each metal has its own specific advantages and been successfully used in hybrid industry for higher
disadvantages for incorporation into a lead-free temperature applications. Hence, it can be concluded that
composition. Additionally, the limited solubility of a specific the 77.2Sn/20.0In/2.8Ag solder has comparable physical
metal within a matrix of several other metals also complicates properties to the eutectic Sn-Pb alloy.
the design problem. Thus the development of lead-free
solders is a formidable task, and will certainly involve a Mechanical Properties
trade-off in properties and performance. The key to a The solders were cast into ingot form prior to the preparation
successful alloy will be to minimize these trade-offs. of specimens for mechanical testing. During the casting
process it was noticed that the 77.2Sn/20.0In/2.8Ag drossed
MATERIALS CHARACTERIZATION only slightly , suggesting a low dross formation rate during
In order to meet the target performance, a novel lead-free wave soldering. The mechanical properties of the solder
1
solder, 77.2Sn/20.0In/2.8Ag, was developed . This alloy was alloys are shown in Table 3. First, this Pb-free alloy has both
then evaluated against 63Sn/37Pb with respect to the a higher tensile strength and shear strength than 63Sn/37Pb.
material properties, performance in SMT assembly process, In addition, although having a higher modulus, the tensile
and temperature cycling behavior of the assembled devices, elongation of 77.2Sn/20.0In/2.8Ag is still greater than that of
as described in the following sections. In the case of material 63Sn/37Pb. This behavior suggests that this Pb-free alloy
properties, the solders were evaluated in the form of bulk has adequate ductility for fabrication into various physical
solders. As to the performance in SMT assembly processes, forms, such as wires, ribbons, preforms, etc. The identical
the materials were examined as solder pastes comprising a value in Poisson's ratio for both solders eliminates concern
typical RMA flux and the respective solder powders (- on the possible impact due to variation in the solder volume
325/+500 mesh) at 90% metal load. under stress of this Pb-free alloy. Overall the data indicate
that, in bulk form, 77.2Sn/20.0In/2.8Ag exh ibits superior
Physical Properties mechanical properties than 63Sn/37Pb.

Table 2 Physical Properties of Solder Alloys.

Properties Alloy
77.2Sn/20.0In/2.8Ag 63Sn/37Pb

Density @ 20o C (gm/cm3 ) 7.25 8.36


Electrical resistivity @ 20o C (µ ohm.⋅m) 0.170 0.146
Thermal conductivity @ 30o C (W/m⋅k) 53.5 50.9
Thermal expansion coefficient @ 20o C (ppm/ o C) 28 25
Table 3 Mechanical Properties of Solder Alloys.

Properties Alloy
77.2Sn/20.0In/2.8Ag 63Sn/37Pb

Tensile strength @ 20o C (psi) 6800 3900


Tensile elongation @ 20o C (%) 47 35
Shear strength @ 20o C (psi) 4800 3450
Poisson's ratio @ 20o C 0.40 0.40
Young's modulus @ 20o C (x106 psi) 5.6 4.5

Creep Behavior from which the melting point was determined from the onset
The creep behavior is also relevant to solder joint fatigue temperature of the peak (s). The first run (20°C/min) shows
reliability performance. Materials being more creep resistant an endotherm with an onset of 165.3°C and a peak
usually exhibit a better fatigue resistance. In this study, the temperature of 185.5°C. The second run of the sample (1°
creep test was conducted on the bulk solders per ASTM C/min), and from which the thermal properties were obtained
E139-83 at 20°C. As shown in Figure 1, the data indicate that (Fig. 2), showed that there is a small low temperature peak at
the steady creep rate of 77.2Sn/20.0In/2.8Ag is about two 113.5°C. As to the main peak, although a slight sign of
and half orders of magnitude lower than that of 63Sn/37Pb. melting may be noticed at 150°C, significant melting really
This superior creep resistance behavior suggests an occurs between 174.7°C and 186.5°C, with the latter as the
improved solder joint reliability with the 77.2Sn/20.0In/2.8Ag peak temperature. The source of the small low temperature
alloy. peak is likely a depression of the 118°C eutectic point
accompanying the formation of 52In-48Sn caused by the
Melting and Softening Behavior high indium content in the material. Of course, without
The melting properties of the Sn/In/Ag solder were metallographic data, the formation of a low temperature
determined by Differential Scanning Calorimetry. (DSC). The ternary phase cannot be ruled out.
procedure was to initially run the sample at a heating/cooling
rate of 20°C/minute past the liquidus temperature in order to: The higher temperature (or main) peak will allow to define the
(1) allow it to conform to the sample pan, thereby minimizing processing temperature of the solder during product
thermal lag in the peak positions, and (2) homogenize the manufacturing (which is typically 30-50°C above the liquidus
microstructure. Then, the sample was scanned at 1°C/minute point). On the other hand, the low temperature peak may
define the maximum service temperature of the solder. The
close proximity in the main peak temperature of
1E-4
Creep at 20C 77.2Sn/20.0In/2.8Ag and 63Sn/37Pb suggests that the
processing temperature required for the two alloys should be
1E-5 very comparable. Hence, this solder has utility as a "lead-
Steady Creep Rate (s-1)

free alternative" if a processing temperature similar to that of


tin-lead solders is acceptable and the service requirements
1E-6
are not jeopardized by the presence of structural changes to
the alloy responsible for the low temperature peak.
1E-7
63Sn/37Pb
In order to further understand the relation between the
melting range and the softening behavior, both solders were
1E-8
77.2Sn/20.0In/2.8Ag examined on a thermo mechanical analyzer (TMA). Again,
the measurement was conducted at 1°C/min heating rate.
1E-9 Also, the load on the sample was set at 14.2 psi. As shown
1E-1 1E+0 1E+1 1E+2 in Figure 3, regardless of the temperature difference at the
onset of melting process, the softening point of
Apparent Stress (MPa)
77.2Sn/20.0In/2.8Ag was found to be almost identical to

Figure 1 Relation Between Steady Creep Rate and Apparent


Stress.
that of 63Sn/37Pb. This result strongly suggests that the wetting behavior of 77.2Sn/20.0In/2.8Ag is comparable to
upper limit of the service temperature of both solders should that of 63Sn/37Pb solder.
be very comparable.
SURFACE MOUNT ASSEMBLY EVALUATIONS
Wetting The manufacturing assembly performance of the Sn/In/Ag
The wetting property is one of the most important solder was assessed relative to that of the Sn/Pb and Sn/Bi
characteristics of solders. The wetting tests were determined solders, for which extensive processing information already
with the use of a wetting balance at 200°C and 240°C. The exists in the literature. The surface mount assembly
temperatures chosen here represent the lower temperature evaluations were conducted on test vehicles consisting of
limits for reflow and wave soldering, respectively. Copper 0.4 mm, 0.5 mm, 0.6 mm (25 mil) and 1.2 mm (50 mil) pitch
coupons were used and preconditioned at 100°C for 3 hours leaded surface mount IC packages (PQFPs, PLCCs and
prior to testing in order to mimic the "difficult to solder" TSOPs) and 0803 discrete capacitors.
condition. The geometric mean of the wetting data, as shown
in Table 4 and Table 5, of four fluxes with different flux To avoid the metallurgical effects caused by lead
chemistries were used to determine the overall wetting contamination in lead-free solders, the conventional Sn/Pb
capability of the solders. surface finishes on printed wiring boards and component
leads were replaced with lead-free alternative finishes. The
Overall, 77.2Sn/20.0In/2.8Ag wets somewhat slower than the two printed wiring board surface finishes evaluated in this
conventional 63Sn/37Pb. However, the difference in the study were immersion tin and organic azole (imidazole) on
wetting time is fairly insignificant when compared with the copper. The components were hot dipped in 100% tin after
soldering time typically employed by the assembly process. chemical removal of the Sn/Pb layer.
For example, the typical reflow profile demands a total
heating time of 4 to 6 minutes, with 30 to 90 seconds above Each of the three solder paste materials was printed on 2
the liquidus temperature. In the case of a wave soldering imidazole and 2 immersion tin coated test vehicles. For the
process, a 1 to 2 minutes preheat step followed by 4 seconds Sn/In/Ag and the Sn/Pb solders, the boards were fully
in-contact with a 250°C wave solder is very common. In both populated and reflowed under the optimum condition
cases, the soldering process time well exceeds the wetting established for 63Sn/37Pb solder. In the case of the Sn/Bi
time needed for the "difficult to solder" situation. solder, the boards were reflowed under its own optimum
reflow condition. The solder reflow was performed in a
The wetting force of 77.2Sn/20.0In/2.8Ag appears to be nitrogen atmosphere with oxygen levels not exceeding 20
slightly lower than that of 63Sn/37Pb. The small difference ppm.
observed suggests that any effect should be negligible.
Therefore, it can be concluded that, in a practical sense, the The defect analysis was based on a visual inspection under

Table 4 Wetting Time (seconds) of Solders.

Fluxes 77.2Sn/20.0In/2.8Ag 63Sn/37Pb


200o C 240o C 200o C 240o C
Flux A 10.60 4.60 2.87 1.48
Flux B 1.53 0.42 1.03 0.50
Flux C 5.08 2.40 1.65 1.00
Flux D 5.73 2.09 2.50 1.44
Geometric Mean 4.66 1.76 1.87 1.02

Table 5 Wetting Force (mN/mm) of Solders.

Fluxes 77.2Sn/20.0In/2.8Ag 63Sn/37Pb


200o C 240o C 200o C 240o C
Flux A 0.70 0.71 0.73 0.72
Flux B 0.72 0.56 0.71 0.61
Flux C 0.72 0.64 0.75 0.72
Flux D 0.67 0.67 0.73 0.73
Geometric Mean 0.70 0.64 0.73 0.69
Table 6 Defect Analysis.

Solder/Flux Bridges Opens # Components Wettability Solder Balls PWB Cond.


ppm ppm misplaced 1 poor, 5 good 1 poor, 5 good 1 poor, 5 good
Sn/In/Ag
imidazole 0 0 0 3.9 5.0 5.0
immersion 0 0 1 4.6 5.0 5.0
tin
Sn/Bi
imidazole 2300 180 1 4.1 5.0 5.0
immersion 0 180 0 4.8 5.0 5.0
tin
Sn/Pb
imidazole 0 0 0 5.0 5.0 5.0
immersion 0 0 0 5.0 5.0 5.0
tin

a stereo microscope. The defects were categorized as THERMAL CYCLING PERFORMANCE


bridges, opens or misaligned devices. Also, the wettability Preliminary reliability data was obtained for the Sn/In/Ag
of the pads, the quality of the solder joint fillets, formation of solder by an evaluation of thermally cycled solder joints on
solder balls and any thermal damage suffered by the board prototype circuit boards. The test vehicles were constructed
were assessed. of FR-4 laminate and contained 50 mil pitch 68 I/O plastic
leaded chip carrier (PLCC) and 24 I/O small outline integrated
A few random bridged and open joints (5-10 total) were circuit (SOIC) package solder joints. Discrete 1206 chip
observed on the Sn/Bi solder test vehicle, and were due to capacitors were also assembled on the circuit boards. The
printing and placement inaccuracy. device packages and circuit board layout were daisy-chain
connected for monitoring the electrical conductivity of the
Due to the large number of pads associated with the test solder joints.
vehicle, the extent of pad wetting was judged on a relative
scale of 1 to 5, 5 indicating that the pad is 100% wetted by The test vehicles were exposed to the following thermal
the solder, 3 indicating that it is ∼ 75% wetted and 1 that it is cycling conditions under a laboratory atmosphere: (1) lower
less than 50% wetted. Wetting figures of merit were temperature limit of 0°C; (2) upper temperature limit of 100°
individually assigned to each device and then averaged over C; (3) 5 min soak time at each of the temperature limits; and
the entire test vehicle. The defect analysis is summarized in (4) 10°C/min ramp rate between temperature limits. The
Table 6 . testing apparatus did not permit the continuous electrical
monitoring of the solder joints in the test vehicle. Therefore,
After analysis of the results in Table 6 above, the following the first test vehicle was initially subjected to 1052 cycles.
conclusions can be drawn: Then, it was monitored electrically for open solder joints
over a subsequent 54 cycles (for a total of 1106 thermal
Overall, 0.4 mm pitch assembly is feasible with the cycles). The electrical monitor was then removed and the
Sn/In/Ag alloy. The processing windows, as for any prototype was exposed to an additional 1296 cycles followed
other lead-free solder, are narrower than for Sn/Pb, and by 59 cycles under electrical monitoring. The particular test
further process improvements (fine-tuning the thermal vehicle was subjected to a grand total of 2461 thermal cycles,
profiles and solder paste composition) should further after which the solder joints on selected PLCC, SOIC, and
improve the performance level. All solder fillets look chip capacitor units were cross sectioned and prepared for
good. Solder balls are minimal. metallographic observations. A second test vehicle was
introduced into the thermal cycling chamber for exposure to
The immersion tin surface finish enhances the wetting of 5000 thermal cycles; that test sequence is currently in
both the Sn/In/Ag and Sn/Bi solders by providing a more progress.
favorable metallurgical substrate for solder spreading.
The metallographic cross sections were used to evaluate the
Lastly, it is not possible to clearly establish the evolution solder joint microstructure. It was noted that the
performance of the new alloy composition based on solder joints contained some void formation. The pattern of
manufacturing assembly evaluation alone. The validation the voids suggested that they were not due to the thermal
will need to be based on the results of long term cycling exposure but rather, were a result of the soldering
reliability assessment studies. process used to fabricate the prototype units. The location
of the voids was at the interfaces of the substrate and the
solder and the solder and the leads, and suggested that their utilized, each possessing characteristic advantages and
probable source was a wettability problem with the copper disadvantages, and which may or may not contain indium.
lands on the circuit boards or with the device leads or The characteristic advantages of the 77.2Sn/20.0In/2.8Ag
teminations. Similar voiding phenomena, maybe to a less solder are fatigue resistance, high reliability and a melting
extent, were observed on the Sn/Pb solder joints. The point similar to 63Sn/37Pb.
voiding phenomena appeared to have been the result of
either poor solder paste performance (the flux utilized was Indium Supply/Price History
formulated for 63Sn/37Pb solder) or an inappropriate furnace Producers have been expanding availability to meet the
schedule (although the latter was optimized for 63Sn/37Pb increasing demand on supply . Figure 4 shows that the
solder, the alloy to be replaced by the present lead-free indium availability has increased some 300% from the 50 to
candidate). Plastic deformation and excessive interfacial 53 metric tons per year requirement of the early 1980's to the
intermetallic compound layer growth were not observed in 160 metric tons today. Indium producers have responded to
any of the solder joints. what the market has required over this period, in increased
production of indium for both growth in current uses for the
The electrical monitoring at either of the interrupted cycle metal and meeting the demands for new applications
sequences showed no opens in the Sn/In/Ag solder joints, developed during the mid 1980's. Figure 5 shows the
suggesting that t he voids observed may not be a concern. historical price trend for the metal. As consumption of the
metal increased, its price decreased, evidence that supply is
INDIUM METAL AVAILABILITY, SUPPLY AND PRICE ahead of demand. To increase future capacity, indium
Historically there has always been an ample supply of lead producers will need to add new facilities and/or improve on
to meet the need for electronics solders. In fact, electronics extraction technology. We believe that the favorable long
solder accounts for only 0.6% of the total consumption of term outlook for the metal will provide the impetus to
lead, in contrast to the 80% of the metal used to manufacture accomplish these tasks.
lead-acid storage batteries. Besides the advantage of
supply, the low cost of lead at well under $0.50/lb makes it Present and Future Indium Supply
the least expensive metal that can be used in solder Indium was discovered in sphalerite ores at the Freiburg
(excluding disposal, safety and potential future liability School of Mines in Germany in 1863. It is found as a trace
costs). Lower toxicity substitute metals for lead in solder element in many minerals, particularly the sulfides of zinc but
certainly will be more expensive and will require a careful also in copper, tin and lead. Indium is currently recovered
examination of the present and future availability. principally as a by- product of zinc processing.

It is estimated that 4500 metric tons of lead are consumed per The primary sources of indium in recent times have been and
year in the U.S.3 to manufacture electronic solder; the world likely will continue to be Canada, South America and Japan.
wide consumption is probably three times this figure. If The former Soviet Union, (the CIS) which is the largest zinc
indium were to replace lead at this usage (40% lead in producer in the world has also been a significant producer of
solder), an adjustment to account for the different densities indium. While their plants may need to be modernized, the
of lead and indium would need to be applied, in order to CIS potential from a resource and reserve point of view can
maintain the volume of solder. Since the density of indium is not be discounted. Indium currently is recovered in lead/zinc
7.3 and the density of lead is 11.35, the required U.S. metallurgical complexes, which extract but a small portion of
consumption of indium would be 2894 metric tons per year. the available indium. CIS total production of indium is
(7.3/11.35 times 4500). However, if the solder contained 20% thought to be 1/4 to 1/3 of what it could be if indium was
indium (which is more realistic), the U.S consumption would extracted from all of the ores that contain indium.
be one-half that amount or 1,447 metric tons, and world wide Additionally, substantial known, but undeveloped, deposits
consumption would be 4,341 metric tons. While it is true that exist in China and Australia and there are potential new
today's indium metal production of 160 metric tons per year indium sources in Bolivia, China, Czechoslovakia, France,
could not meet this demand, indium does in fact have a Hungary, Japan, Peru, and Sweden, as well as here in the
future as an alloying metal in lead-free solders. Consider the U.S.
following:
It is important to realize that the figures on indium metal
Conversion from Sn/Pb Solder to Lead-Free Solder production often cited are from the U.S. Bureau of Mines
At the present moment, it is very unlikely that lead Statistics which are estimates derived from zinc reserves
containing electronic solder "will be banned". The more only. They do not take into consideration the indium
likely scenario will be that leaded solder will be taxed, which content of copper, lead or tin ores. A further complication is
will make lead-free solders more viable from an economic the fact that indium production is a by-product of other
perspective. An orderly conversion to lead-free solders will metal recovery operations and often smelters do not report
allow time for expansion of other metal production capacity. values. In the face of steadily increasing indium production,
It is also very likely that a family of lead free solders will be which should lower available resources, the USBM reserve
METRIC TONS DOLLARS PER TROY OUNCE
160
11

10
140

9
120
8

100 7

6
80

60
4

40 3
1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1988 1989 1990 1991 1992 1993 1994
YEAR YEAR
Figure 4 Estimated Indium Consumption. Figure 5 Average Annual Indium Price.

Table 7 Reserves of Select Metals (metric tons).

Metal Annual Production Reserves Years of Supply


indium 140 2300* 16
lead 3,200,000 63,000,000 20
silver 13,700 280,000 20
zinc 7,365,000 140,000,000 19
*zinc ores only.

Table 8 Silver vs. Indium.


To summarize, the current 160 metric tons per year
Metal Concentration in Current production of indium is insufficient to fully substitute for
Earth's Crust Market lead in all electronic solder used today. However, for the
indium ∼0.1 ppm 160 MT high-fatigue-reliability-required applications, indium does
silver ∼0.1 ppm 15,000 MT have a future as an alloying metal in lead-free solders for the
following reasons:

figures have actually increased 54% from their 1987 Availability of the metal should not be a concern.
tabulation. Another indicator of potential availability is
years of reserves left based on production levels. Using Published indium reserves and resources are
USBM conservative data, Table 7 shows that indium is substantially understated and based on indium-
presently about the same position as lead, silver and zinc in containing zinc ore only. Substantial indium deposits
terms of years of reserves at their respective production exist worldwide in other ore types.
levels. Reserves are only a confirmation that adequate ore
exists to assure a 15 - 20 year supply and not a scientific Extraction efficiency of producing indium from ore is very
evaluation of the total amount of the metal that is low. Improvements in extraction technology can provide
recoverable in the earth's crust. a substantial increase to indium production without the
need for geological exploration.
Finally, an interesting comparison can be made between
indium and silver. Table 8 shows that while the abundance SUMMARY
of indium and silver in the earth's crust is about the same, A novel lead-free solder, 77.2Sn/20.0In/2.8Ag solder alloy,
today's market for indium is only 160 metric tons compared has been developed and evaluated as a replacement for
to the 15,000 metric tons of silver. Silver, like indium is 63Sn/37Pb. In general, this Sn/In/Ag alloy exhibits
typically recovered as a secondary metal. The production of comparable physical and wetting properties, but superior
silver over time, increased to meet marketplace demand. The mechanical and creep properties than Sn/Pb solder. Test
same scenario has always and will continue to apply to results from the surface mount assembly process and
indium.
temperature cycling study indicate that this alloy is indeed a
viable candidate as an electronic soldering material. The
availability and price of indium have been reviewed, with the
conclusion that the potential supply is very promising in
terms of meeting the demand.

REFERENCES
1. J.A. Slattery and C.E.T. White, "Lead-Free Alloy
Containing Tin, Silver and Indium, " U.S. Patent 5,256,370
(Oct. 26, 1993).
2. R.N. Wild, "Some Fatigue Properties of Solders and Solder
Joints", INTERNEPCON, Brighton, England (Oct., 1975).
3. Annual Report on Lead, U.S. Bureau of Mines, 1991.