Fortunato E., Ginley D., Hosono H. - Transparent Conducting Oxides For Photovoltaics (2007) PDF
Fortunato E., Ginley D., Hosono H. - Transparent Conducting Oxides For Photovoltaics (2007) PDF
Fortunato E., Ginley D., Hosono H. - Transparent Conducting Oxides For Photovoltaics (2007) PDF
Conducting Oxides
for Photovoltaics
Introduction
There is a plethora of emerging approaches to low-cost, high-efficiency solar
cells. Nearly all of these photovoltaic (PV)
technologies employ transparent conducing oxides (TCOs) as an integral part of
the basic device structure. These solar cell
architectures are based on the use of new
lower-cost semiconductors, thin films of
conventional semiconductors, and organic
inorganic hybrids, and many are rapidly
attaining commercial viability. Each PV technology has different requirements for the
TCO layer, leading to a reexamination of
these materials. Coupled to this is an effort
to make conventional cells more efficient
by improving the junction characteristics.
As can be seen in Table I, many of the
needs and requirements of new PV technologies extend well beyond the conventional TCO characteristics of transparency
and conductivity. There is, for instance, an
increasing desire to employ TCO layers as
diffusion barriers, to control the contact work
function, to provide an interface with organic and other materials, and to have the
TCO also act as a light trap. Low process
temperatures and increased process flexibility are critical for many devices. This need
for improved performance in a wide range
of areas coupled with the ever-rising price
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TCO Needs
Materials Goals
Heterojunction with
intrinsic thin layer
(HIT) cell
Smooth, good
interfacial properties,
very good
conductivity, lowtemperature
deposition, light
trapping
Copper indium
gallium selenide
(CIGS)
Intrinsic-ZnO/Al:ZnO
Interfacial stability to
CdS, low-temperature
deposition, resistance
to diffusion and
shorting, need to
make/improve the
junction
Single-layer TCO to
replace two layers and
CdS layer
CdTe
(SnO2)
Zn2SnO4 /Cd2SnO4
Stable interface to
CdS/CdTe at
temperature, diffusion
barrier
Doping of ZnSnOx
materials, single-layer
TCO
Nano-hybrid polymer
cell
Nanostructure with
right length scale,
work-function
matching, interface
with organic, correct
doping level for
carrier transport
Self-organized structures
coreshell structures,
new nonconventional
TCOs
Grtzel cell
TiO2
Nanostructure with
high electron mobility
Amorphous Si
Temperature stability,
chemical stability, and
appropriate texture for
both TCO layers
Improved TiO2
morphology and possible
use of doped materials,
new non-TiO2 materials
Higher conductivity,
texture, and ohmic
contact for both TCO
layers
TCO Materials
The first TCO was reported in 1907 by
Baedeker,2 who used a primitive vapor deposition system to deposit thin-film CdO
that was both optically transparent and
electrically conducting. Since then, three
oxides have emerged as commercially important transparent conductors: indium
oxide, tin oxide, and zinc oxide. The properties and crystal chemistry of the transparent conducting indium oxide family of
materials is discussed in some detail in the
following sections because it is the highestperformance, best-understood material in the
TCO class. By volume, however, the mostdeposited TCO today is SnO2, which is
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ZnO
Another important oxide used in PV window and display technology applications
is doped ZnO,7 which has been reported to
have a thin-film resistivity as low as 2.4
104 cm. Although the resistivity of ZnO
TCO thin films is not yet as good as the ITO
standard, it does offer the significant benefits of low cost relative to In-based systems
and high chemical and thermal stability. In
the undoped state, zinc oxide is highly resistive8 because, unlike In-based systems,
ZnO native point defects are not efficient
donors. However, reasonable impurity doping efficiencies can be achieved through
substitutional doping with Al, In, or Ga.
Most work to date has focused on Aldoped ZnO, but this dopant requires a
high degree of control over the oxygen potential in the sputter gas because of the
high reactivity of Al with oxygen.9 Gallium, however, is less reactive and has a
higher equilibrium oxidation potential,
which makes it a better choice for ZnO
doping applications. Furthermore, the
slightly smaller bond length of GaO
(1.92 ) compared with ZnO (1.97 ) also
offers the advantage of minimizing the
deformation of the ZnO lattice at high
substitutional gallium concentrations.
Fortunato reports low-resistivity Gadoped ZnO (45 104 cm) deposited
by rf sputtering at room temperature.10
This class of TCO material is of particular
interest for organic PV applications because
it can be readily grown into nanowires
and rods, which makes it ideal for infiltration of the polymeric absorption layer.
Figure 1. Typical configuration for (a) the Sanyo heterojunction with intrinsic thin layer (HIT)
cell and (b) an amorphous Si nip cell. In (b), i stands for intrinsic, c is microcrystalline,
and a is amorphous.
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Figure 3. Actual photovoltaic structures: (a) Copper indium gallium selenide (CIGS) and
(c) CdTe seen in cross section using SEM. (b), (d) Schematic illustrations of the structures in
(a) and (c), respectively.
Organic Photovoltaics
Organic photovoltaic (OPV) devices have
recently emerged as a natural extension of
the success of organic light-emitting diode
(OLED) technology. This approach to PVs is
of great interest because it could potentially
be implemented as a low-temperature, lowcost, atmospheric-pressure, large-area technology. Initial device efficiencies of nearly
5% have been obtained, and the improvements needed for higher efficiency have
been identified.2628 The needs of the TCO
in an OPV device include work-function
matching, stability on a deformable surface,
the ability to protect the OPV layer from the
atmosphere, and low resisitivity. These requirements make the organic transparent
conductors unusable for this application.
Inorganic TCOs, however, are suitable
and also offer the possibility of being
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References
Summary
Current photovoltaic technologies, as
well as next-generation approaches to PVs,
will place specific demands on the transparent contact layers beyond transparency
and low resistivity. The mainstay of the
transparent conducting oxides used today
is based on indium tin oxide because, at
present, no other TCO delivers the same
performance and versatility. The high cost
of In as a raw material and process restraints, however, make this oxide system
less attractive for low-cost, high-volume PV
applications. Alternative TCO materials,
such as ZnO, appear to be promising for
some of these applications, but processing
and performance issues remain. In many
of the novel PV technologies currently
under development, such as organic
photovoltaics and Grtzel cells, control of
the morphology and surface chemistry of the
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