IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 40, NO.
6, JUNE 1993
A Novel and Effective PECVD Si02/SiN
Antireflection Coating for Si Solar Cells
Zhizhang Chen, Peyman Sana, Jalal Salami, and Ajeet Rohatgi,
Abstract-It is shown for the first time that sequential plasma-
enhanced chemical vapor deposition (PECVD) of SIN and Si02
can produce a very effective double-layer antireflection (AR)
coating. This AR coating is compared with the frequently used
and highly efficient MgF2/ZnS double layer coating. It is shown
that the Si02/SiN coating improves the short-circuit current
(JJ by 47%, open-citcdit voltage (VoJ by 3.7%, and efficiency
(Eff) by 55% for silicon cells with oxide surface passi-
vation. The counterpart MgF2/ZnS coating gives similar but
slightly smaller improvement in V,, and Eff. However, if silicon
cells do not have the oxide passivation, the PECVD Si02/SiN
gives much greater improvement in the cell parameters, 57%
in J,,, 8% in V,,, and 66% in efficiency, compared to the
MgF2/ZnS coating which improves J,, by 50%, V,,, by 2%, and
cell efficiency by 54%. This significant additional improvement
results from the PECVD deposition-induced surface/defect
passivation. The internal quantum efficiency (IQE) measure-
ments showed that the PECVD Si02/SiN coating absorbs fair
amount of photons in the short-wavelength range ( <500 nm),
however, the improved surface/defect passivation more than
compensates for the loss in J,, and gives higher improvement
in the cell efficiency compared to the MgF2/ZnS coating.
I. INTRODUCTION
R ECENT studies [ 11-[7] have shown that the applica-
ion of PECVD SIN thin film can be very helpful in
improving the efficiency of polysilicon solar cells. It not
only acts as an antireflection coating layer with a suitable
refractive index, but can also improve the performance of
photovoltaic devices by defect/surface passivation. This
is because a large amount of atomic hydrogen is produced
during PECVD process. In addition, PECVD is a low-
temperature process (about 3OO0C), compared to other
CVD processes (LPVCD or APCVD), and has high
throughput, good uniformity, better thickness control
( <5 % ) , and excellent reproducibility, compared to the
physical evaporation techniques. All these advantages
make PECVD SiN film very attractive for solar cells.
Double-layer MgF, /ZnS [8] antireflection coating (AR
coating) is often used in high-efficiency single-crystal sil-
icon cells fabricated in the laboratory today because it has
much better antireflection properties than that of the sin-
Manuscript received September I I , 1992; revised December 18, 1992.
This work was supported in part by Sandia National Laboratory under Con-
tract 78-2488 and by NREL under Contract XX-0-19145-1. The review of
this paper was arranged by Associate Editor P. N. Panayotatos.
The authors are with the University Center of Excellence for Photovol-
taics Research and Education, Georgia Institute of Technology, Atlanta,
GA 30332.
IEEE Log Number 9208285.
0018-9383/93$03.00 0 1993 IEEE
Fellow, IEEE
gle-layer SIN coating. MgP2 has a refractive index of 1.35
and ZnS has an index of 2.4. Refractive index of stoi-
chiometric silicon nitride (Si3N4) is around 2.0, therefore
it is not as suitable for a double-layer AR coating as ZnS.
On the other hand, PECVD SIN is an amorphous form of
Si,N,: H,, in which x, y, and z strongly depend on the
deposition conditions, especially on the gas flow ratio of
NH3 /SiH4 and substrate temperature. The refractive in-
dex of SiN depends on the ratio of N/Si in the film, and
can be controlled in the range of 1.96-3.5 by adjusting
the ratio of NH3/SiH4. Thus the PECVD process pro-
vides an opportunity for obtaining higher index SiN film
by making it silicon-rich. However, silicon-rich films
generally show high absorption, therefore absorption
losses must be considered when higher index SiN films
are used.
The improvements in the minority-camer diffusion
length and quantunl efficiency due to single-layer PECVD
SIN on poly-Si solar cells have been reported [2]-[4], in
addition to the beneficial effects on short-circuit current,
open-circuit voltage, and cell efficiency [5]-[7]. How-
ever, the defect or surface passivation effects due to dou-
ble-layer PECVD SiO, /SIN coating on single-crystal sil-
icon cells have dever been investigated. In the case of
poly-Si, there is significant bulk recombination due to high
concentration of unwanted impurities, dislocations, point
defects, and grain boundary defects. There are relatively
fewer bulk recombination centers in high-quality float-
zone single-crystal Si compared to poly-Si, therefore sur-
face recombination becomes an important loss mecha-
nism. In this paper, a novel Si02/SiN double-layer coat-
ing is prepared by sequential PECVD deposition of SIN
and Si02 on single-crystal Si solar cells. The thickness
and refractive index of the SIN film is tailored for the best
performance. Improvements in reflectivity and cell per-
formance are compared with the conventional MgF, /ZnS
double-layer AR coating, which was deposited by thermal
evaporation. The loss due to photon absorption in the
Si02/SiN is analyzed by internal quantum efficiency
(IQE) measurements, and the defect/surface passivation
due to PECVD Si02/SiN coating is quantified in terms
of reverse saturation current .To and open-circuit voltage
V,,. It is shown that in spite of some absorption in the
PECVD Si02/SiN coating, the net improvement in the
cell performance is greater compared to the MgF2/ZnS
coating due to defect/surface passivation feature of the
Si02/SiN films.
I I62
11. EXPERIMENTAL
PECVD SiN and Si02 films were prepared in a Plasma-
Therm Inc. reactor (series 700) operated at 13.6 MHz.
SiH,, NH3, N2 gases were used for SiN deposition, and
SiH,, N 2 0 , N2 gases were involved in Si02 deposition.
The reactor pressure was held at 0.9 torr for both depo-
sitions. Substrate temperature was 300°C and the RF
power was 30 and 20 W for the SIN and Si02 deposition,
respectivelyb These conditions resulted an growth rate of
about 100 A/min for SIN, and 300 A/min for Si02.
Baseline nf-p-p+ solar cells were fabricated by conven-
tional phosphoriis diffusion on the front and A1 treatment
-
on the back of p-type (0.2 Q cm) Float Zone (100) sil-
icon substrates. The details of the fabrication procedure
are given in [9]. The refractive index and thickness of the
deposited films were measured by an ellipsometer. The
solar cells were characterized by a combination of light
and dark Z-V, reflectivity, spectral response, and internal
quantum efficiency measurements before and after the AR
coating to evaluate the change in the cell parameters. Sev-
eral 1 x 1 cm cells were fabricated on 3-in-diameter wa-
fers and were isolated by mesa etching. A few cells on
each wafer were coated with MgF2/ZnS while others were
coated with Si02/SiN for the controlled comparison of
the two coatings. Thus all the cells experienced the same
fabrication sequence, except for the difference in the AR
coating at the end. After AR coatings, cells were sub-
jected to 350°C / 10 min anneal under tungsten halogen
lamps in forming gas ambient. During the physical evap-
oration of MgF2/ZnS and PECVD deposition of
Si02/SiN, selected areas on the wafers were covered by
thin glass plates to simultaneously obtain AR coated glass
plates. In order to assess the effect of photon absorption
in the coatings, the IQE of the same cell was measured
three times, first with an uncoated glass plate on the top
of the cell, and then with the glass plates coated with
MgF2/ZnS and Si02/SiN coatings, respectively. Since
the reflectance effects are removed in the IQE measure-
ment, any change in the IQE of the cell corresponds to
the absorption in the coating.
111. RESULTSA N D DISCUSSION
The refractive index of PECVD SIN was adjusted by
controlling the NH3/SiH4 gas flow ratio. We were able
to vary the index in the range of 3.5-1.9 in our reactor.
Since an index of 2.4 is desirable, this flexibility allowed
us to optimize PECVD Si02/SiN double-layer AR coat-
ing. It was found that the use of higher index SiN in the
Si02/SIN coating significantly reduced the reflection
losses, Fig. 1, but it also resulted in higher absorption
loss due to the silicon-rich SIN film. Thus a compromise
has to be made between the reflection and absorption
losses to optimize the index of AR c?ating. AR coating
model calculations showed that 590- A-!hick SiN with an
index of 2.3, in conjunction with 950-A-thick Si02 with
an index of 1.45, should give fairly low average reflec-
tance over the entire solar spectrum. It was confirmed ex-
IEEiE TRANSACTIONS ON ELECTRON DEVICES, VOL. 40, NO. 6, JUNE 1993
50, I
SiN single layer
A
0 MgFZ/ZnS d o u b l e l a y e r
Si02/SiN d o u b l e layer
W
0
300 400 500 600 700 800 900 1000 1100
Wovelength(nm)
Fig. 1 . Reflectance as a function of wavelength for silicon cells with a)
SIN AR coating, b) double-layer MgF,/ZnS coating, and c) SiO,/SiN AR
coating. The thickness and refractive index of the films are given in text.
perimentally in this study that a 590-A-thick SiN film wit!
refractive index of about 2.3, underneath a 950-A
PECVD Si02 with an index of 1.45, indeed gave the high-
est J,,. Use of higher index (>2.3) SiN film resulted in
lower reflectance in the short-wavelength range but higher
reflection in the long-wavelength range, along with higher
absorption loss. Fig. 1 shows a comparison of the reflec-
@rice data for a single-layer SiN film (n = 2.0, T 7 700
A); a double-laye; Si02/SiN (n = 1.45, T = 950 A)/(n
= 2.3, T = 590 e);
and a double-layer MgF2/ZnS (n =
1.38, T = 1100 A ) / @ = 2.3, T = 550 A). Fig. 1 shows
that both the double-layer coatings have excellent antire-
flection properties, with less thah 5 % reflection in the en-
tire wavelength range of 400-1100 nm. The Si02/SiN
coating shows a slightly higher reflection than the
MgF2/ZnS coating in the range of 450-700 nm, partly
because Si02 has higher refractive index (1.45) than MgF2
(1.38). Unlike the PECVD SiN, the refractive index of
PECVD Si02 is difficult to change, especially below 1.4.
Table I shows a comparison of the effects of the two
AR coatings on silicon cells, without the Si02 surface
passivation. Several runs were made to check the repro-
ducibility of these results. Table I shows a typical change
in the cell parameters and clearly demonstrates that this
novel Si02/SiN coating gives remarkably large increase
in the cell parameters, 57% in J,,, 8% in V,,, and 66% in
Eff of the unpassivated cells. The counterpart MgF2/ZnS
gave only 50% improvement in Jsc, 2 % in V,,, and 54%
in Eff.
The maximum improvement in J,, (AJ,,/J,,) due to an
antireflection coating, assuming IQE does not change, can
be estimated by
AJ,?, R - R'
--
(1)
J,, 1-R
where R and R ' are the average reflectivities before and
after the coating, respectively. If we assume R = 35% for
the uncoated Si, based on our reflectivity measurements,
and R ' = 0, the maximum improvement due to perfect
AR coating should be only 53 % . Therefore, the observed
57% improvement in the J,, in Table I suggests that de-
fect/surface passivation due to Si02/SIN might contrib-
CHEN rf al.: A NOVEL AND EFFECTIVE AR COATING FOR Si SOLAR CELLS 1 I63

TABLE I
CHANGE
I N CELLPARAMETERS SOLARCELLSAFTERTHE Si02/SiN
OF THE UNPASSIVATED AND MgF,/ZnS
ANTIREFLECTION
COATINGS

MgF,/ZnS Coating

Before 22.71 0.600 0.78 10.63 6.4 x 1 0 - 1 ~

After 34.29 0.612 0.778 16.34 5.2 x i o - l 3
Improvement 50% 2% 54 %

SiO,/SiN Coating

Before 22.42 0.602 0.781 10.53 6.0 x 10-l3

After 35.47 0.650 0.76 17.52 1.7 x
Improvement 57 % 7.9% 66 %

TABLE I1
CHANCE
I N CELLPARAMETERS
OF THE OXIDEPASSIVATEDCELLSAFTERTHE SiOZ/SiN A N D MgF,/ZnS
COATINGS

MgF,/ZnS Coating

Before 24.32 0.630 0.756 12. I9 2.58 x IO-"

After 35.71 0.642 0.807 18.55 2.48 x I O - ' '
Improvement 46.8% I .9% 52 %

SiO,/SiN Coating

Before 24.14 0.633 0.7959 12.16 2.47 X IO-''

After 35.69 0.657 0.804 18.87 1.46 X IO-'
Improvement 47.8% 3.7% 55 %

ute toward greater than 53 % improvement in .Is,..

The pas-
sivation due to SiO, /SiN coating was indeed confirmed
by the measurement of saturation current density Jo from
the detailed dark I-Vanalysis. Table I shows a significant
reduction in the Jo due to the PECVD Si02/SiN which
also accounts for the remarkably high increase in V,, in
Table I. Assuming a near-ideal float zone silicon cell, the
increase in V,, can be estimated by
where J,, and Jo represent the short-circuit and reverse
saturation current densities before AR coating, and Ji, and
Jt, are the corresponding values after the coating. The cal-
culated improvement in V,, of 15 mV for MgF2/ZnS
coating and 44 mV for SiO,/SiN coating, using measured
J,, and Jo, are in good agreement with the measured in-
crease in V,, of 12 and 48 mV, respectively. It should be
noted in Table I that the improvement in V,, and Jo is
much greater for the SiO, /SiN-coated cells compared to
the MgF2/ZnS-coated cells.
Table I1 shows improvement in cell parameters of those
cells which had thin Si02 surface passivation prior to the
AR coating. It is interesting to note that the absolute value
of J,, was virtually the same after both the AR coatings,
even though the SiOz/SiN coating has slightly higher re-
flection. Equally important is the fact that the PECVD
SiO,/SiN coating again gave larger improvements in V,,
and Jo, even when the cells had oxide passivation. How-
ever, the relative improvement was much smaller than in
the case when no oxide passivation layer was present.
The external spectral response (SP) of the cells, before
and after deposition of Si02/SiN and MgF2/ZnS
coatings, is shown in Fig. 2. As expected, coated cells
showed much better external spectral response. It is
noteworthy that the coated cells have slightly lower re-
sponse in the wavelength range of 300-375 nm due to the
absorption in both the coatings at higher energy. In order
to separate antireflection and defect passivation effects,
internal quantum efficiency (IQE) was calculated (IQE =
SP/( 1 - R)), which is independent of the reflection prop-
erties. Fig. 3 shows the comparison of the IQE of
SiO,/SiN and MgF,/ZnS coated cells. Note that the IQE
of MgF2/ZnS coated cell is much higher in the wave-
length range of 300-500 nm, but the IQE of SiO,/SiN
cell is slightly higher beyond the 500 nm, including higher
maximum (IQEmax).The observed higher IQE of the
MgF2/ZnS-coated cell in the short-wavelength region
could result from either lower front surface recombination
in the MgF, /ZnS-coated cell or higher absorption loss in
I164
0.8 I I
I A uncoated S i cell
0.0 4
300 400 500 600 700 800 900 1000
Wavelength(nm)
Fig. 2 . The spectral response of the silicon cells: a) without AR coating,
b) with the double-layer SiO,/SiN coating, and c) MgF,/ZnS coating.
'"" I
%
PP
MgF2/ZnS coated
30
10 --
07
the SiO,/SiN-coated cell. If the former were true, it
would be difficult to explain the higher IQE,,, in the
Si02/SiN-coated cell, which is strongly related to the
surface recombination [ 101. Therefore, absorption due to
the higher refractive index SiN is the more probable cause.
To confirm this hypothesis, IQE of a cell was measured
three times, first by covering the cell with a glass plate,
and then by covering it with glass plates coated with the
SiO, /SiN and MgF2/ZnS double-layer coatings, respec-
tively. Since the same cell was used in these three mea-
surements, surface and bulk recombination should be
identical and should not contribute to the observed differ-
ence in IQE. The most likely cause of any perceived dif-
ference should be the absorption in the films. Fig. 4 shows
that both the coated plates have higher absorption than the
uncoated plate in short-wavelength range, below 400 nm.
The IQE data in Fig. 4 clearly show that much higher
absorption occurs in the Si02/SiN coating compared to
MgF2/ZnS coating below 500 nm. However, the absorp-
tion is very low for the wavelengths above 600 nm, which
agrees with an independent absorption measurement by
multiple angle ellipsometry at a wavelength of 630 nm.
These results confirm that the lower IQE of Si02/SiN-
coated cell in the short-wavelength region is caused by
the absorption. The surface passivation effect of SiO,/SiN
is unable to counter balance the absorption loss in the short
IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 40, NO. 6, JUNE 1993
, V"
I
I
*
a
0 glass only f
I 0
1100 300 400 500 600 700 aoo goo 1000 1100
Wavelength(nm)
Fig. 4. The measured IQE of the same cell covered with a) a clear glass
plate, b) glass plate coated with the Si02/SiN, and c) glass plate coated
with the MgF,/ZnS double-layer AR coating.
I wavelength, therefore, a crossover occurs in the IQE re-
sponse. The higher maximum value of IQE for the
I SiO, /SiN-coated cell supports the notion of SiOz/SiN-
induced defect/surface passivation.
IV. CONCLUSION
A novel PECVD SiO, /SiN double-layer antireflection
coating has been developed which gives greater than 55 %
improvement in the efficiency of the oxide-passivated sin-
gle-crystal Si cells, and about 66% increase in the perfor-
mance of the unpassivated cells. Thf optimized PECVD
SiO,/SiN coating consists of 590-A-thick SiN with an
index of 2.3 under a 950-A-thick SiO, with an index of
1.45. The properties of this novel coating are compared
with one of the best and frequently used MgF2/ZnS dou-
ble-layer AR coating. The reflectivity of the Si02/SiN
coating is slightly higher but comparable to that of the
MgF, /ZnS coating. The defect/surface passivation due
to the PECVD SiO, /SiN deposition was supported by the
decrease in Jo, and increase in V,, and IQE. Even though
the SiO, /SiN coating has higher absorption and reflection
losses compared to the MgF2/ZnS coating, the passiva-
tion effect of the PECVD films results in higher V,, and
overall cell efficiency. The passivation feature of the
PECVD coating significantly reduces the gap between the
oxide passivated and unpassivated cells. Therefore, it is
possible to realize both passivation and AR coating by the
PECVD technique proposed in this paper for a commer-
cial cell process. Finally, cell efficiency improvement due
to the Si02/SiN coating depends on the front surface re-
combination velocity S, before the AR coating deposition.
The larger the S,' the higher the relative improvement due
to the PECVD coating.
ACKNOWLEDGMENT
The authors would like to acknowledge the help of other
members of the University Center of Excellence for Pho-
tovoltaics Research and Education at the Georgia Institute
of Technology. They would also like to thank J. Gee and
H. Tardy of Sandia National Laboratories for the helpful
CHEN cI a l . : A NOVEL AND EFFECTIVE AR COATING FOR Si SOLAR CELLS
technical discussions and absorption measurements on SiN
films.
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[6] R. Kisshore, S. N. Singh, and B. K. Das, “Growth of silicon nitride
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[7] S . Narayanan, S. Ronein, and J. Wohlgemuth, “Silicon nitride AR
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[8] M. A. Green, A. W. Blakers, S. Jiqun, E. M. Keller, and S. R. We-
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[IO] H. J. Hovel, Semefals and Semiconductors. New York: Academic
Press, 1975, ch. 2.
Zhizhang Chen received the B.S. and M.S. de-
grees in electronics from Nankai University, Tan-
jin, China, in 1982 and 1985, the M.S. degree in
physics from Oregon State University, Corvallis,
in 1987, and the Ph.D. degree in materials engi-
neering science from Virginia Polytechnic and
State University, Blacksburg, in 1991.
In 1991 he joined the research faculty of the
Electrical Engineering Department, Georgia In-
stitute of Technology, Atlanta. His research in-
terests are in high-efficiency silicon and poly-Si
solar cells, minority-camer recombination at interface in MOS structure,
and low-temperature surfaceldefect passivation in silicon materials.
I I65
Peyman Sana received the B.S. and M.S. degrees
in electrical engineering in 1987 and 1989, re-
spectively, both from the University of Tehran,
Tehran, Iran.
He is currently working toward the Ph.D. de-
gree in electrical engineering at Georgia Institute
of Technology, Atlanta. He is also a member of
the University Center of Excellence for Photovol-
taic Research and education at Georgia Tech. His
present research interests include design, model-
ing, fabrication, and characterization of high-ef-
ficiency polycrystalline silicon solar cell.
Jalal Salami received the B.S. degree in chemical
engineering from University of Florida, Gaines-
ville, in 1984, and the M.S. degree in electrical
engineering from Georgia Institute of Technol-
ogy, Atlanta, in 1990.
He is a senior member of technical staff of the
University Center of Excellence for Photovoltaics
Research and Education at Georgia Tech. His
present research interests include design, model-
ing, fabrication, and characterization of high-ef-
ficiency silicon solar cells.
Ajeet Rohatgi (M’78-SM’86-F’91) received the
B.S. degree in electrical engineering from Indian
Institute of Technology, Kanpur, India, in 1971,
the M.S. degree in materials engineering from
Virginia Polytechnic Institute and State Univer-
sity, Blacksburg, in 1973, and the Ph.D. degree
in metallurgy and material science from Lehigh
University, Bethlehem, PA, in 1977.
Before joining the Electrical Engineering Fac-
ulty at Georgia Institute of Technology, Atlanta,
in 1985, he was a Westinghouse Fellow at the Re-
search and Development Center in Pittsburgh, PA. He received the West-
inghouse Engineering Achievement Award for the “Design and Fabrica-
tion of High Efficiency Silicon Solar Cells.” He is a Georgia Power
Distinguished Professor in the School of Electrical Engineering and the
director of the University of Excellence for Photovoltaic Research and Ed-
ucation at Georgia Tech. His current research interests include modeling
and fabrication of high-efficiency silicon and compound semiconductor so-
lar cells; silicon MOS devices; semiconductor material and device char-
acterization; defects and recombination in semiconductors; and MBE and
MOCVD growth of compound semiconductors for optoelectronic and pho-
tovoltaic devices.