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Move Over Silver …

This article is based off the NanoMarkets report Silver Inks and Pastes for Printable Electronics: 2008-
2015

Alternatives to Silver Inks


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NanoMarkets predicts that by 2015, 184.5 million ounces of silver will be used by the electronics
industry (see report, Silver Inks and Pastes for Printable Electronics: 2008-2015). This isn’t
surprising, given that silver is more conductive than copper, gold or any other element; even its
oxide is conductive. Unfortunately, silver prices often reflect demands completely unrelated to
availability, causing squeamishness among industrial users. Even without the drama of the Hunt
Brothers infamous 1980 attempt to manipulate the market, it is prudent to consider lower-cost
alternatives to silver. These could be in any form from other minerals to silver alloys and even
novel production methods.

Alternatives -- Materials

In some applications, such as medical implants, silver can be replaced with substitute materials
such as titanium or biocompatible polymers. But in industrial applications where conductivity is
important, the first alternative that comes to mind is usually copper.

Pure Copper

Initially, copper may seem like an ideal substitute for silver. While it has 95 percent of silver’s
conductivity, it’s only one percent of its price. What’s not to like? Plenty, as it turns out.

Copper oxide, the verdigris that makes the Statue of Liberty green, is non-conducting. While it
does protect the underlying metal from oxidizing further, the challenge of oxidation remains at
any scale, if there is a chance of exposure to air. Worse, at a small enough size, copper powder is
so reactive, it can ignite. This may be fun in high school chem lab, but a disaster for large-scale
manufacturing.

Formulations have been created that reduce the chances of oxidation, but they add to the price.
Silver-plated copper inks remain a potential option for printed RFID tags, especially in situations
where economics dictate that they can barely be priced above paper barcodes (such as
inventory-tracking of inexpensive parts and goods).

One solution is the creation of copper nanoparticles. According to Vivek Subramanian, associate
professor of electrical engineering and computer sciences at the University of California,
Berkeley, copper nanoparticles are as conductive as silver, but suffer from the oxidation
problem, and therefore require sintering in nitrogen or formalin gas. Subramanian’s team
studies the metallic, semiconductor, and insulating nanoparticles for use in printable inks.

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Alloys

As Cecil Adams once wrote in his Straight Dope column, one of the more infamous copper-silver
alloys was the mixture in Tyco Brahe’s artificial nose. Supposedly, Brahe’s purpose was to get a
more flesh-like color, but lower cost may have been a factor too, as it often is with silver alloys.
Carbon-silver inks, for example, were developed in response to the 1980s price hikes, and are
still in use today. They are a balance of trade-offs: While they are lower cost, they are also less
conductive than silver alone. In addition, the R&D cost to create the perfect admixture is not Page | 2
inconsiderable.

Carbon/Graphite

The allotropes of carbon have such contrasting identities, the element could almost star as a
science fiction superhero. Carbon itself is non-conductive, as is its best-known form, diamond;
but as graphite, it is conductive enough to be placed high on the list of silver alternatives.
According to Michigan State Chemical Engineering professor Lawrence Drzal, graphites have the
potential to be competitors to traditional conductive additives like copper and silver. His lab has
fashioned xGnP Exfoliated Graphite NanoPlatelets, which as monolayer coatings have a
conductivity similar to that of ITO. They are currently being commercialized by XG Sciences, Inc.

Carbon Nanotubes

Carbon nanotubes may prove to be the ultimate in good news/bad news. IBM Fellow Phaedon
Avouris and Columbia University professor Tony Heinz just won the Julius Springer Prize for
Applied Physics for demonstrating the possibilities of nanotubes as transistors and logic circuits,
along with their optical properties, which open up new realms for nanophotonics. But while
carbon nanotubes may thrill physicists and chemists, the medical community is considerably less
impressed. Last May, Ken Donaldson of the University of Edinburgh published a report in Nature
Nanotechnology [1] that showed mice exposed to carbon nanotubes exhibited tissue damage
similar to the effects of asbestos inhalation. The research suggests that far from being benign
configurations, carbon nanotubes may be potential cancer agents. Calls for regulation are
already being promulgated, what this will ultimately mean for large-scale manufacturing is yet
unknown, but it does reduce some of the brave new world optimism.

Alternatives -- Methods

Another approach makes perfect sense in a world becoming ever more conscious of limited
natural resources: simply use less silver, as in smaller particles.

Silver and other Nanoparticles

Nano-sized silver and other conductive inks can be ink-jetted, without the risk of clogging
nozzles, thus saving both material costs and production runs. According to silver ink supplier
Cabot, the cost savings of ink-jet over screen printing could be considerable, given the potential
reduction in thickness of the ink jet layer. In Cabot’s example, the company compared an 8

NanoMarkets, LC | PO Box 3840 | Glen Allen, VA 23058 | TEL: 804-360-2967 | FAX: 804-360-2967
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micron screen-printed layer to an 0.4 micron ink jet printed layer, to calculate it would only cost
0.76 for ink jet printing versus $15.12 for screen printing.

Nanoparticle-sized inks also can be cured at much lower temperatures, thus opening up a wider
range of substrates, including lower-cost plastics. For example, last year Bayer Materials Science
(BMS) introduced BayInk, which the company touts as having a cure temperature compatible
with plastics. BMS also suggests that BayInk would be ideal for RFID, which is no coincidence
since this is the major new market for conductive inks. Page | 3

Inks can also be sintered. In this process, particles are bonded together at just below the melting
point. The great advantage is that they are joined, rather than merely touching, greatly
increasing the inter-particle contacts.

This is one of the ways that using smaller particles improves “conductivity efficiency.”
Remember that in essence, inkjet printing is depositing dots. But current can only flow between
dots where they touch. As with polka dots, larger dots are surrounded by proportionately more
“white space,” where current cannot flow. With nanoparticles, there are many more, smaller
dots, closer together, and thus more dots coming into contact with more surface area of other
dots—for the same, or less, volume of silver, you get greater conductivity.

Still, Drzal cautions, while the intrinsic conductive properties of individual particles can be very
high, once they are assembled into a composite, the contact resistance—where the particles
come together—can become high as well. As a result, conductivity requirements of the bulk
materials can be lower.

Unfortunately, there are also human health and environmental concerns with nanosilver
particles, since they are small enough to be inhaled and could also possibly penetrate human
skin. While their toxicity to bacteria is more welcome, it is still a concern, since it is possible
nanosilvers could also kill beneficial bacteria. Worse, surviving generations of bacteria could
potentially grow resistant. Given these concerns, regulatory agencies in many countries will
likely examine the use of nanosilvers, which could affect both the cost, and even the possibilities
for manufacturing nanosilver-based products.

While there are many silver alternatives already in the marketplace, they are not without
concerns. Fortunately, the price of silver will continue to drive innovative solutions for
replacements. At the moment, however, the quest for a material that is cheaper than silver, as
or nearly as conductive, and doesn’t oxidize leaves you, in the words of Drzal, “Without too
many choices.”

Bibliography

[1] Nature Nanotechnology 3, 423 - 428 (2008) Published online: 20 May 2008

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NanoMarkets, LC | PO Box 3840 | Glen Allen, VA 23058 | TEL: 804-360-2967 | FAX: 804-360-2967

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