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thin film | organic | printable | electronics

Materials  Developments  to  Enable  Roll­to­Roll  Printing  of  CIGS 

This article is based in part on research from Materials Markets for CIGS Photovoltaics 
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Significant efforts are underway to enable the use of roll-to-roll printing to manufacture CIGS PV
cells. NanoMarkets believes that these will result in significant new business revenues. Our
research suggests that inks for the CIGS absorber layer will grow from $8.4 million in 2011, to
close to $189 million in 2016, about 18 percent of total revenues for the CIGS absorber layer

Because the choice of manufacturing process goes hand in hand with the type of materials that
can be used, these efforts to develop printed CIGS center around materials developments. In
particular, several firms and research institutions are developing nanoparticle-based ink
formulations and flexible substrates to allow for roll-to-roll printing of the absorber layer and the

CIGS PV is coming to be known as the rising star of the TFPV world. It has achieved the highest
efficiency of any thin-film PV technology--20.0 percent efficient champion cell created in its lab.
Although this falls below the efficiency of crystalline silicon solar cells (barely below that of
multicrystalline cells at 20.3 percent efficiency), CIGS cells can be substantially cheaper because of
their reduced material usage and the ability to manufacture them using low-cost processes.

However, most of the current CIGS PV cells are manufactured using costly evaporation processes.
This, in part, could hinder the ramp up of CIGS PV once the economy turns around. As such, firms
including HelioVolt, International Solar Electric Technology (ISET), and Nanosolar are developing
nanoparticle-based inks for high-volume manufacture of CIGS PV. NanoMarkets believes that ink-
based processes, while not significant in 2009, will grow to account for more than 25 percent of
CIGS volume by 2016. As the pioneering companies demonstrate inks in high-volume
manufacturing, we expect more companies to enter with outsourced nanoparticles and inks.
thin film | organic | printable | electronics

Printing Absorber Layer

The inks currently being used for the CIGS absorber layer consist of oxide or selenide nanoparticles
of the metals copper, indium, and gallium, dispersed as a colloidal suspension in a solvent. The
nanoparticles are intended to form a solid layer of CIGS upon heat treatment, similar in function to Page | 2 

layers applied by the conventional methods.

ISET is one example of a company using nanoparticle oxides for its CIGS ink formulation. HelioVolt
and Nanosolar, on the other hand, offer metal selenide nanoparticles. The companies claim that
selenides avoid the need for reduction of the oxides and the additional thermal processing step
that the reduction requires. The use of these selenide nanoparticles is made possible by the low
melting points of copper selenide and indium selenide. At the annealing temperature, these
compounds melt and help form the new CIGS phase and grain structure.

Nanosolar has developed a method to embed CIGS into thin poly mer films using a roll-to-roll
process. To sinter the ink coating, the company uses rapid thermal processing (RTP) to flash heat
a thin layer for several picoseconds, leaving the rest of the material untouched. Not only does this
process reduce materials costs, but it also reduces energy consumption compared with other
approaches, according to the company.

HelioVolt's FASST process creates the CIGS absorber layer in two steps. The first step deposits two
precursor layers that form the chemical basis of the CIGS layer. The second step synthesizes those
materials into an actual CIGS layer: rapid heating induces a chemical reaction between the two
precursor films, a process that is said to be similar to anodic wafer bonding.

Currently, it appears that CIGS manufacturers prefer to develop and produce their own
nanoparticles and ink formulations. However, there are several firms, including American Elements
and Nanoco Technologies, that offer nanoparticles of CIGS and its precursors, and new CIGS PV
entrants may choose to outsource their nanoparticle and ink production.

This printing concept is not necessarily limited to the CIGS layer. Printing of the zinc oxide top
electrode, though not yet feasible for CIGS PV, could result in additional cost savings.
thin film | organic | printable | electronics

Flexible Substrates

The full potential of manufacturing CIGS PV cells via printing will not be obtained without the use
of flexible substrates, which will allow for roll-to-roll processing. But changing the substrate has
proven to be a non-triv ial exercise. The following are some of the issues that arise from using a Page | 3 

flexible substrate: Undesirable impurities may be introduced into the absorber layer; sodium, which
diffuses from glass in the standard process but is not necessarily present with flexible substrates,
actually improves the absorber layer film quality by increasing its charge carrier density; the
allowed processing temperatures may not be sufficient for high film quality, and additional films
may become necessary, such as an insulating layer to allow monolithic interconnection on
conductive substrates. Despite the challenges, Global Solar, Odersun, and Solarion have
commercially produced CIGS PV modules on flexible substrates in 2008, and more companies are
eager to do so in 2009.

Soda lime (aka, glass) is the standard material currently used as the CIGS PV substrate. For
flexibility, firms are using and developing poly mer and metal foil substrates. Metal foils are already
in widespread use in a variety of applications. While CIGS PV manufacturers demand specific alloy
formulations and dimensions, such requests are common for metal foil providers, and the CIGS PV
demand is expected to simply increase the volume of business done by the metal foil suppliers.

Polymer films, especially polyimide, are expected to grow significantly in volume due to demand
from CIGS PV and other flexible electronics. Only a small percentage of CIGS PV production
currently uses poly mer films, but several firms are interested in developing cells on them. With
polyimide film substrates expected to grow to nearly 20 percent of CIGS PV volume within the next
eight years, nearly four million square meters of polyimide film will be required, a significant chunk
of global polyimide film production. NanoMarkets believes polyimide will be the fastest-growing
substrate material until flexible glasses and composites are demonstrated and quickly outpace it.

Based on all of the above NanoMarkets believes printing CIGS has a lot of potential because it
offers a way to produce CIGS PV cells using high-speed, roll-to-roll processing--a likely path to low-
cost manufacturing. But before this can happen in any big way, producers will need to
demonstrate that they can achieve high efficiencies using high-speed printing. This they still have
to prove.