CARBON NANOTUBE TRANSPARENT ELECTRODES: A CASE FOR
PHOTOVOLTAICS
Paul Glatkowski.' Evgeniya Turevskaya.' David Britz," David Rich,1 Matt DiCologero,1 Timothy Kelllher.' John Sennott,'
David Landis,' Robert Braden,' Patrick Mack, 1Joseph Piche1
1Eikos Inc, 2 Master Drive, Franklin, MA 02038
ABSTRACT
A wide range of thin film photovoltaics (PVs) use
transparent conductors (TCs). ZnO:AI, Sn02:F, and
In203:Sn (ITO) are the most commonly used TCs in PV
cells. However, these materials are not ideal for all solar
applications. As an alternative, single walled carbon
nanotube (SWNT) coatings can be used as a TC. The
SWCNT thin films are essentially hole conducting and
highly transparent, which is a desirable and previously
unobtainable combination of properties for use in
photovoltaics. SWNT coatings are solution deposited
using standard wet coating processes. Optically, nanotube
coatings exhibit high transparency, especially in the near-
infrared. Additionally we form multifunctional composites
by infiltrating the CNT network with materials suited for a
wide range applications and device structures.
INTRODUCTION
Single walled carbon nanotube (SWNT) networks have
been used successfully in several devices as a
replacement for more traditional vacuum deposited
transparent conductive oxides (TCOs) (see Fig. 1).[1-4]
These groups have been motivated to replace transparent
conductors both because of the difficulty and cost of
manufacturing high quality TCOs and because carbon
nanotube networks are expected to be both more versatile
and more electronically compatible than TCOs. As an
example, SWNT coatings have been found to be a
preferentially hole-conducting contact, whereas most
TCOs are electron conducting contacts.[5]
E·Paper
Solar
FPD i 'OO
·········•·•··.•..
E···.
?O
~ ~. "' Curre nt
....•......•... ~ driv7
I'Q'• • • • • •
= 80 ••••
EMI g hlgl
I~ i~ '
~
shield: ' "
6OoC-..L....._...---_ _...,.-_
100
' 000
Sheet Resist ance n 's q
Fig. 1. Applications for SWNT TCs based on conductivity.
978-1-4244-2950-9/09/$25.00 ©2009 IEEE
We have integrated carbon nanotube coatings into a wide
range of devices, including anti-static protection, touch
screens, e-paper, photovoltaics, and EMI shielding.
Fabricated photovoltaic devices with SWNT TCs have
included organic photovoltaics, CulnzSeJ!CdS (CIGS), and
CdTetCdS devices. [6, 7, 8] This early work has
demonstrated that SWNT TCs are capable of producing
high-efficiency devices at the laboratory scale. Further
improvements are made by incorporating a refractive
index-tuned binder to reduce surface reflections.
SWNTs (Fig. 2) are one dimensional conductors and
narrow bandgap semiconductors with a diameter of about
1 nanometer and a length of several micrometers. Carbon
nanotubes are made of hexagonally bonded carbon, like
planar graphite. Physically, carbon nanotubes can be
viewed as rolled sheets of graphite with a hollow core.
SWNTs exhibit exceptional electronic conduction
properties, including electron and hole mobilities of ca.
80 ,000 cmzNs , substantially higher than all other known
semiconductors.[9] Long metallic nanotubes have been
found to have volume conductivities of ca. 700,000 Stem
which is almost as conductive as pure copper.
Touch screen ESD
9
riven
IS lYe
Fig. 2. Artist's rendition of a SWNT on a surface. Inset:
TEM of bundles of carbon nanotubes.
Because of their spz hybridization, carbon nanotubes are
optically and electrically stable. Additionally, the covalent
bonding of SWNTs eliminates electromigration. Because
of their conductance and carrier mobility, SWNTs can be
spread thinly over a surface to create a virtually
_ ....,J
transparent, highly conductive film. Carbon nanotube
'0000
electrodes are unlike doped wide band gap TCOs (e.g.
ITO and AlO) used in solar cells. The transparency of
001302
TCOs is fundamentally limited by band-edge absorption of conductivity that is appropriate for the specific device
light in the UV and free carrier plasma absorption in the application.
NIR. Because a SWNT TC is a nanoscopically thin
conductive grid, the large majority of light penetrates
through the pores and through the thickness of the film,
maintaining conductivity and uniform surface appearance. l:
90% Superior Near IR
0
·iii Transpar'pn cy - - - -
.!!l
Eikos has branded our SWNT TC as Invisicon". E 80% ..-
lnvlsicon" is a composite coating made using a two-step '"
l: "...-- "':---- '"
coating process, followed by curing (see Fig. 3). In the first ~ /
C 70% /
step, an ink containing only carbon nanotubes, water, and
alcohol is printed onto a substrate. Once the solvent dries,
~'" /
/ • hJisiconl0001o

'"
0.. 60% /
- hvisicon 200 Oln
a uniform film of nanotubes with 50% void space is left. In - lrMs icon 400 n lo
I • - • Commercial ITO
the second step, a solution of a polymer or metal oxide I - - p-type CuAI02

precursor is deposited into the SWNT film. The binder 50%

penetrates through the pores of the SWNT layer down to 200 600 1000 1400 1800 2200
Wavelength (nm)
the substrate, providing adhesion, as well as changing the
optical characteristics of composite. The curing step is Fig. 4. UV-Vis-NIR transparency of SWNT films, ITO, and
used to densify and cross-link the binder. The conditions p-type CuAI02.
of curing are dictated by the binder and underlying
materials. After an extensive literature survey, we believe that SWNT
electrodes demonstrate the best figures of merit of any
(1) CNT known p-type TC in terms of transparency, conductivity,
transparent)
Substrate conduct ive Substrate and environmental stability, making it an ideal electrode
layer for many types of PVs (Fig. 5). Carbon nanotube

••.•.•.•.•......•.••••.•.•.•..•••...... (3) Cure

I Substrate I E
Fig. 3. Schematic diagram of the solution coating process
to make lnvlsicon" on solar cells.
Binders impart adhesion and abrasion resistance for
aircraft canopies, heat and humidity stability for touch
panels, or UV resistance for solar cells. These binders are
either organic or inorganic, depending on accessible
processing conditions and application needs. Both
nanotube inks and binders can be printed roll-to-roll on
plastic sheets or conformally on complex surfaces using
gravure, inkjet printing, or spray coating.
j (2) Anti-reflect ive
binder
electrodes exhibit a volume conductivity of ca. 5,000 S/cm,
>90% transparency, are deposited at less than 150°C,
and are thermally stable to at least 550 °C. p-Type
Substrate transparent conductive oxides were first reported in 1997,
when a Japanese group found that CuAI0 2 selectively
conducted holes with a volume conductivity of 0.01 S/cm
at room temperature.[10] The field has continued to
progress, achieving conductivities as high as 220 S/cm in
CuCrMg02 films, though at the expense of
transparency.[11] Many p-type TCOs that exceed 10
S/cm have visible transmission less than 50%, making
them unsuitable for solar applications. Additionally, many
p-type TCs are deposited at high temperatures and react
with moisture and air, making them unsuitable for
processing and long product life.

This process has several general advantages over ITO for

designing an application-tailored TC. Because the SWNT 5000 -
and binder layers are deposited separately, the two "§" 4500 -
systems can be engineered independently to have optimal ci5 4000 -
electronic and optical properties. The process is low z: 3500 -
temperature and atmospheric, which reduces cost of :~ 3000 -
ts
processing and the potential for device damage. Because => 2500 -
"0
the layers are printed sequentially, in-line testing and § 2000
refinishing of coatings is possible to achieve higher ~ 1500
manufacturing yields. As a result of the deposition § 1000
process, lnvisicon® is a particularly versatile transparent ~ 500
electrode. 0-

OPTOELECTRONIC PROPERTIES: SWNTS

A unique advantage of the lnvisicon" SWNT coating is its

ability to tailor sheet resistance (Rs) over a broad range
from 1 010 to 100 MOlD. SWNT films have a flat
transmittance profile, compared to PEDOT:PSS, ZnO:AI,
FTO and ITO, giving the film more uniform coloration (Fig.
4). This ability also allows the device designer to choose a
Fig. 5. Comparison of volume conductivities of hole
conducting electrodes.
Based on the work function of carbon nanotubes (ca. 4 .8
eV) and their selective hole transport, we believe that

978-1-4244-2950-9/09/$25.00 ©2009 IEEE 001303

nanotube electrodes could offer performance
improvements in devices, such as amorphous silicon PVs,
organic photovoltaics, and as a back contact or a
transparent back contact for CdTe or wide bandgap CIS
devices.
OPTICAL PROPERTIES: BINDERS
Nanotube coatings are expected to be excellent light
trapping TCs because they are inherently rough,
compared to sputter deposited TCOs. AFM images (Fig.
6, left) of CNT layers show an RMS roughness typically of
-50 nm, with high feature spacing of approximately 500
nm. The lnvisicon® roughness and feature spacing is
considered ideal for light trapping TCOs.
Fig. 6. AFM image of Invisicon nanotube film (left) with no
binder and (right) with AR binder.
Fig 6 shows typical atomic force microscope images of an
lnvisicon" layer with and without binder. The left image
shows a wispy network of nanotubes with a significant
fraction of void space. The right image shows a nanotube
network with a solution-deposited anti-reflective binder.
The binder adheres to the substrate and protects carbon
nanotube films from abrasion, but is thin enough to allow
surface conductivity. The CNT-binder composite inherits
the optical properties of the binder, reducing surface
reflections down to 0.1% when using appropriate refractive
index binder. The binder coating does not appreciably
affect the CNT surface roughness (Fig. 6, right). Unlike
ITO, CNT-binder composites can have their thickness
continuously tuned to reach quarter wave thickness.
100
90
80 - Bare PET
70
.... 60 - AR PET
?f'.
50
'"
c:: 40
?f'. - Bare Si wafer
30
20 I-
10
0
250 350 450 550 650 750
Wavelength in om
Fig. 7. Transmission and reflection spectra for AR coatings
designed for PET and Si wafers.
By tuning the composition, density, thickness, and
roughness of the binder materials, we also can obtain
978-1-4244-2950-9/09/$25.00 ©2009 IEEE
effective anti-reflective (AR) coatings on varied substrates,
including silicon wafers and polyethylene terephthalate
(PET) (Fig. 7).
To create an AR coating for PET (RI = 1.48), we targeted
solution processed materials with refractive indices -1 .24.
We infiltrated this material into the carbon nanotube
network on commercial PET and found that it produced a
single layer AR coating with 0.45% single side reflection at
peak. When both sides of a PET film were coated, we
observed peak transmission of 99.1% at 710 nm. Typical
PET is approximately 88-90% transparent in the visible
region. Such coatings also are applicable to glass and
give similar results in terms of maximum transparency and
reflection.
A different material was used as an AR coating for a
silicon wafer. Silicon wafer surface reflection varies from
as much as 75% in the UV to 33% in the NIR. By solution
depositing a single layer coating onto silicon, we found a
reduction in surface reflection by as much as 62%. For a
non-optimized coating, minimum reflection was found to
be 1% at 332 nm. By carefully controlling thickness and by
adding layers of other materials, the window of low
reflection can be extended significantly.
CONCLUSIONS
Single walled carbon nanotube electrodes demonstrate
significant benefits for usage in photovoltaics. Nanotubes
form the highest performing hole conducting electrode
currently known, making them suitable as a direct contact
to p-type semiconductors. Additionally, nanotube
conductivity is tunable to suit the specific device
requirements. Binders have been shown to reduce surface
reflections to less than 1%, which significantly aids in light
capture for photovoltaics and other devices.
ACKNOWLEDGEMENTS
This work was supported by the U.S. Department of
Energy under Contract No. DE-FG36-08G088005. The
authors would like to acknowledge helpful discussions and
data collection with our collaborators at the National
Renewable Energy Lab, especially Drs. Teresa Barnes
and Tim Coutts.
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