Progress in Photovoltaics 2003; 11(1): 2732

Short Communication for Accelerated Publication

TiO2 DLAR Coatings for Planar Silicon Solar

Cells
B.S. Richards1 , S.F. Rowlands2 , C.B. Honsberg1 , and J.E. Cotter1
1 Centre

for Photovoltaic Engineering, University of New South Wales, Sydney, NSW 2052,

Australia
2 Department

of Electrical and Electronic Engineering, University of Western Australia,

Nedlands, Perth, WA 6907, Australia

In this paper we demonstrate that a double-layer antireection (DLAR)

coating can be fabricated using only titanium dioxide (TiO2 ). Two TiO2
thin lms were deposited onto planar silicon wafers using a simple atmospheric pressure chemical vapour deposition (APCVD) system under dierent deposition conditions. Weighted average reectances of
6.5% (measured) and 7.0% (calculated) were achieved for TiO2 DLAR
coatings in air and under glass, respectively. An increase in the shortcircuit current density of Jsc = 2.5 mA/cm2 can be expected for an
optimised TiO2 DLAR coating when compared to a commercial TiO2
single-layer antireection coating.

Correspondence to: B.S. Richards, Centre for Photovoltaic Engineering, The University of

New South Wales, Sydney, NSW 2052, Australia, tel: +61-2-9385-5914, fax: +61-2-9662-4240,
email: b.richards@unsw.edu.au
Contract/grant sponsor: ARC; contract/grant number: A00104665.

INTRODUCTION

Controlling the reectance of commercial solar cells fabricated on multicrystalline

silicon (mc-Si) wafers is dicult, primarily due to the inability to adequately texture mc-Si wafers with the standard alkaline etch solution. This work investigates
increasing the optical performance of planar Si solar cells by using a double-layer antireection (DLAR) coating fabricated completely from APCVD-deposited titanium
dioxide (TiO2 ). Two advantages of DLAR coatings over single-layer antireection
(SLAR) coatings are, rstly, that two minima can be achieved in the reectance
spectrum, leading to a lower spectral-weighted reectance. Secondly, that their optical performance is less sensitive to layer thickness variations.1 One disadvantage of
DLAR coatings is that their performance decreases rapidly with increasing thickness
of an intermediary, low-refractive index surface passivation layer.2 However, the use
of such a passivation layer at the AR coating:Si interface, such as silicon dioxide
(SiO2 ), is essential to achieve high conversion eciencies.
In the past, DLAR coatings have been primarily applied to laboratory-scale photovoltaic (PV) devices using two dierent evaporated materials. Common materials that have been used for DLAR coatings of non-encapsulated cells include
SiO2 /TiO2 2 and magnesium uoride/zinc sulphide.3 For encapsulated solar cells,
aluminium oxide/TiO2 DLAR coatings have been implemented.4 Recently, plasmaenhanced chemical vapour deposited (PECVD) silicon nitride (SiN) has become
popular as an AR coating material due to additional electronic benets aorded by
the presence of hydrogen in these lms.5 Research has also been performed on SiN

DLAR coatings, however results show that at high refractive indices (n > 2.4 at
= 600 nm) these lms becoming highly absorbing with extinction coecients of
0.4 at = 400 nm.57
The DLAR coatings presented here rely on TiO2 for both layers. TiO2 has several
advantages: i) it is familiar to the PV industry; ii) depositions can be performed
at atmospheric pressure and low temperatures using a non-toxic liquid precursor;
iii) it has excellent chemical resistance;8, 9 iv) it has a high refractive index and low
absorption coecient; v) materials and processes are low cost; and, vi) methods
for achieving excellent surface passivation with TiO2 coated Si wafers have been
demonstrated.10

DLAR COATING DESIGN

For two quarter-wavelength coatings to achieve zero reectance at two wavelengths,

the necessary refractive indices for the top (nAR1 ) and bottom (nAR2 ) layers of the
DLAR coating are determined by11
n3AR1 = n20 nSi

and

n3AR2 = n0 n2Si .

(1)

while the thickness of each of the layers is given by

dAR1 =

0
4 nAR1

and

dAR2 =

0
.
4 nAR2

(2)

In Equation 1, which does not account for any absorption in the lm, the refractive
indices of air and silicon are assumed to be n0 = 1 and nSi = 3.939 at = 600
nm, respectively. For the case of a DLAR coating in air, the required refractive
3

indices are nAR1 = 1.579 and nAR2 = 2.494. From Equation 2, the optimum layer
thicknesses are dAR1 = 95.0 nm and nAR2 = 60.1 nm at the design wavelength of
0 = 600 nm. For a glass-encapsulated solar cell the desired parameters change
to nAR1 = 2.07 (72.5 nm) and nAR2 = 2.86 (52.4 nm). In comparison, the highest
achievable n values ( = 600 nm) for the anatase and rutile phases of TiO2 are
2.53212 and 2.70,13 respectively.

TiO2 THIN FILM DEPOSITION

The TiO2 thin lms in this work were deposited using a simple APCVD system. The
TiO2 liquid precursor, tetraisopropyl titanate (97% purity Tyzor TPT, DuPont), was
maintained at 50 C in a stainless steel bubbler, resulting in a vapour pressure of
1 mbar. The TPT vapour is transported via heated lines to a stainless steel nozzle
situated above the Si substrate. The Si wafers are maintained at a temperature of
150 450 C. Deposition temperatures (Tdep ) less than 300 C result in amorphous
TiO2 thin lms, while Tdep = 300 450C favours the formation of polycrystalline
TiO2 lms of the anatase phase.
The TPT can either react via hydrolysis (in the presence of water vapour) or pyrolysis (in the absence of oxygen) to form TiO2 . The bottom TiO2 layer is formed by
pyrolysis at 450 C onto a polished silicon wafer. As deposited, the sample exhibits
a refractive index of about 2.1 (at 600 nm), however after sintering (Tsin = 900 C
for 6 hr) the n increased to 2.489. Scanning electron microscopy (SEM) images of
the lower lm, before and after sintering are shown in Figures 1(a) and (b), respectively, illustrating that signicant lm densication has occurred during sintering.
4

The top TiO2 layer was prepared in the presence of a high concentration of water
(H2 O) vapour at a deposition temperature of 250 C. This resulted in a soft and
porous TiO2 lm as shown in Figure 1(c). The lm hardness is greatly improved by
performing a sinter at Tsin = 700 C for 2 hr, although even extensive sinting of the
porous lm does not increase the lm density, as illustrated in Figure 1(d). This is
attributed to the high void fraction retarding the sintering mechanism.

TiO2 DLAR COATINGS

The DLAR coatings were characterised using reectance spectrophotometry and

variable-angle spectroscopic ellipsometry (VASE, J.A. Woollam Co., Inc). VASE
measurements were performed over the wavelength range 350 1150 nm and at
angles of 65 80 . A double Lorentz oscillator model was used for tting the ellipsometric parameters and and extracting the dispersive refractive indices n()
and extinction coecients k(). A 50% void/50% TiO2 Bruggeman eective medium
approximation (EMA) layer was used to model the surface roughness layers.14 The
optical modelling was performed using the software package WVASE32.15 Figure 2
illustrates the TiO2 DLAR coating sample structure. The optical constants of the
porous top layer and the denser bottom layer are each modelled by a EMA and solid
TiO2 layer. By varying the deposition and sintering condtions, a wide range of TiO2
refractive indices could be achieved, nT iO2 = 1.73 2.63. The n=600 nm , k=400 nm
and thickness d of the four modelled layers for a typical TiO2 DLAR coating are
plotted in Figure 3.
Experimental and modelled reectance data for the TiO2 DLAR coating exhibiting
5

the lowest weighted-average reectance (Rw ) to date is shown in Figure 4. The

characteristic double minimum of a DLAR coating is clearly seen and the modelled
data clearly provides an excellent t. The noisy data in the near infrared (800
1000 nm) is due to poor sensitivity in the spectrophotometers infrared detector.
The lowest weighted-average reectance (350 1150 nm, including back reectance)
measured for a TiO2 DLAR coating in air in this work is Rw = 6.5%, compared to
Rw = 8.6% for a typical commercial TiO2 SLAR coating.
It should be emphasized, rstly, that the performance of the TiO2 DLAR coating is
less than optimal due to the high ntopT iO2 value. Secondly, it is important to realise
that while high-temperature processing was used to achieve dense (high n) layers,
this is primarily due to the limitation of the deposition technology available to the
authors. While such DLAR coatings are compatible with evaporated metal contacts,
alternate deposition methods would need to be used in a production environment to
avoid the incompatibility of screen-printed metallic contacts with high-temperature
processing. For example, high n and low k TiO2 thin lms have been achieved using
alternate deposition methods, such as spray deposition8 and ltered arc deposition.16
The most interesting application for a TiO2 DLAR coating is for planar mc-Si solar
cells encapsulated under glass. Modelling was performed, using the software package
TFCalc,17 with data from experimental coatings to determine the optimum performance that could be expected for this case. The optical models for the 2 mm-thick
B270 Crown glass and 1 mm-thick ethyl-vinyl-acetate (EVA) layers were taken from
Nagel et al.5 As previously discussed, the ideal nAR2 value is nAR2 = 2.86, but as
this is not achievable in practice, the highest value observed for our TiO2 lms was
6

used, nAR2 = 2.63. This subsequently reduces the optimal nAR1 value from 2.07 to
1.95. This model predicts a weighted average reectance of Rw = 7.0% (including
back reectance), transmittance Tw = 91.0% and absorptance Aw = 2.0%. The
reectance spectrum, plotted in Figure 4, is extremely at and lies between 4.7%
and 7.7% for all wavelengths in the range 410 1040 nm. This is excellent, considering that about 4.3% (absolute) is unavoidably lost at the air:glass interface. When
a 10 nm-thick SiO2 surface passivation layer is included in the model, the average
weighted reectance and absorptance increase to Rw = 7.57% and Aw = 2.10%,
respectively, while Tw = 90.33%.

SOLAR CELLS WITH TiO2 DLAR COATINGS

To predict the performance of solar cells with these DLAR coatings, the weighted
average reectance curves were used as an input to a PC1D18 simulation. The
intensity of the AM1.5 global spectrum was reduced to 98.35 mW/cm2 to account
for absorption in the glass, EVA and TiO2 layers. The main source of absorptance
is the 1 mm thick EVA layer. The electrical parameters for a standard buriedcontact solar cell were taken from Honsberg et al.19 On 1 cm p-type Si, this
modelled device resulted in a Jsc of 37.5 mA/cm2 without a surface passivation layer
present, reducing slightly to Jsc = 37.2 mA/cm2 with the inclusion of 10 nm SiO2
at the TiO2 :Si interface. The emitter dark saturation current density (J0e ) was
kept constant for TiO2 DLAR coatings both with and without an SiO2 passivation
layer present. While it is not realistic to expect a J0e of 1 1013 A/cm2 with no
SiO2 layer, this value was used to indicate the maximum optical performance of the
7

TiO2 DLAR coating. For the device with a surface passivation layer, an open-circuit
voltage (Voc ) of 640.6 mV and eciency of = 18.6% were calculated. The ll-factor
of this solar cell was 78.1%, which the authors believe can be achieved for a BC solar
cell fabricated on mc-Si substrates. The bulk minority carrier lifetime was assumed
to be b = 100 s. The DLAR coating results represent a 7% improvement in Jsc over
a typical commercial APCVD TiO2 SLAR coating (Tdep = 320 C and Tann = 850 C
for 1 min to simulate ring of the front screen-printed contacts). Using the same
PC1D model, the latter SLAR coating (n600 nm = 2.275 and k400 nm = 0) results in
a Jsc of 34.7 mA/cm2 (Voc = 621.3 mV and = 16.8%).

SUMMARY

In this work we have demonstrated that a simple, low-cost deposition system can
be used to realise a DLAR coating, fabricated from a single material, TiO2 . Initial
experimental results from TiO2 DLAR coatings, measured in air, indicate that a
non-optimized weighted average reectance of 6.5% can be achieved. This compares
favourably with a typical commercial SLAR coating (Rw = 8.6%). Of primary
interest is the performance of such a DLAR coating under glass, and our results
have shown that an extremely low weighted average reectance of 7.0% (including
the silicon back reectance) can be achieved using TiO2 layers. When implemented
into a buried-contact solar cell model, the TiO2 DLAR coating results in increase
in Jsc of 2.5 mA/cm2 (7%) compared to a commercial TiO2 SLAR coating. SLight
losses due to the inclusion of 10 nm-thick SiO2 passivation layer at the TiO2 :Si
interface were taken into consideration.
8

Acknowledgments
B.S. Richards would like to thank Prof. Trevor Redgrave (Department of Physiology,
UWA) for generous access to the VASE instrument and the Faculty of Engineering
(UNSW) and the Centre for Photovoltaic Engineering for nancial support. This
work was supported by an Australian Research Council 2001 Large Grant number
A00104665.

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[13] M.W. Ribarsky. Titanium dioxide (TiO2 ) (rutile). In E. Palik, editor, Handbook
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Figure 1: SEM images of the lower TiO2 film (Tdep = 450C) (a) before and (b)
after sintering; and the porous, upper TiO2 film (Tdep = 250 C in H2 O vapour) (c)
before and (d) after sintering (Tsin = 1000C for 6 hr).

12

air or glass

n0

EMA

ntopEMA , ktopEMA

TiO2

ntopTiO2 , ktopTiO2

EMA

nbotEMA , kbotEMA

TiO2

nbotTiO2 , kbotTiO2

silicon

nSi , kSi

Figure 2: TiO2 DLAR coating sample structure, showing the link between the n and
k nomenclature and the layers in the optical model.

13

Figure 3: Optical constants for the two pairs of dense and EMA layers in a TiO2
DLAR coating.

14

TiO 2 SLAR in air(R w =8.6% )

TiO 2 D LAR in air(R w =6.5% )
Encapsulated TiO 2 D LAR (R w =7.0% )

R eflectance,R (% )

50
40
30
20
10
0
300

400

500

600 700 800 900 1000 1100 1200

W avelength, (nm )

Figure 4: Experimental (points) and modelled reflectance data (solid curve) for a
TiO2 DLAR coating, compared to a typical commercial TiO2 SLAR coating (dashed
curve). The modelled reflectance spectrum (dotted curve) of an encapsulated TiO2
DLAR coating is also plotted.

15