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Record low surface recombination velocities on 1Ω cm p-silicon using remote

plasma silicon nitride

Article  in  Applied Physics Letters · February 1996

DOI: 10.1063/1.115936

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Record low surface recombination velocities on 1 V cm p-silicon
using remote plasma silicon nitride passivation
Thomas Lauinger, Jan Schmidt, Armin G. Aberle, and Rudolf Hezel
Institut für Solarenergieforschung (ISFH), D-31860 Emmerthal, Germany
~Received 13 November 1995; accepted for publication 18 December 1995!
Outstanding surface passivation of low-resistivity single-crystalline p-silicon is reported using
silicon nitride fabricated at low temperature ~375 °C! in a remote plasma-enhanced chemical vapor
deposition system. The effective surface recombination velocity S eff is determined as a function of
the bulk injection level from light-biased photoconductance decay measurements. On polished as
well as chemically textured silicon wafers we find that our remote plasma silicon nitride provides
better surface passivation than the best high-temperature thermal oxides ever reported. For polished
1.5 and 0.7 V cm p-silicon wafers, record low S eff values of 4 and 20 cm/s, respectively, are
presented. © 1996 American Institute of Physics. @S0003-6951~96!02509-6#

The minimization of surface recombination losses is a
decisive prerequisite for the improvement of a large variety
of silicon-based electronic and optoelectronic devices, such
as high-efficiency solar cells. The most successful and most
widely used passivation scheme for crystalline Si is the ther-
mal oxidation at high temperatures ~;1000 °C!. Thermally
grown Si–SiO2 interfaces provide excellent surface passiva-
tion on high-resistivity ~>100 V cm! n- and p-type Si wa-
fers, as demonstrated by effective surface recombination ve-
locities S eff below 10 cm/s.1,2 However, for substrate
resistivities around 1 V cm, the passivation quality depends
on the doping type: while n-type Si is still well passivated by
SiO2,3 the resulting S eff values on p-type Si are significantly
poorer. For example, the best S eff value reported to date for
0.7 V cm float-zone ~FZ! p-Si wafers oxidized in a top class
clean room environment is 41 cm/s.4 Typically, the reported
S eff values for such substrates lie in the range of 50–500
cm/s at injection levels around 1014 cm23.2,5
The somewhat surprising but well-understood disadvan-
tage of oxidized p-type silicon compared to n-type silicon is
due to the surface band bending induced by the positive fixed
oxide charge density ~ Q f ! as well as a pronounced asymme-
try of the capture cross sections of electrons and holes ( s n
@ s p ! at thermally grown Si–SiO2 interfaces.5,6 In n-type Si
the positive oxide charges electrostatically reduce the
minority-carrier hole concentration at the surface. In con-
junction with the low s p values this effectively reduces the
surface recombination rate. In contrast, in p-type Si, the posi-
tive oxide charges attract the minority-carrier electrons,
which leads to increased S eff values. This effect is reinforced
by the large s n values. Only for relatively low doping levels,
where the surface becomes inverted by the positive oxide
charges, the S eff values reduce significantly since the recom-
bination process becomes limited by the capture of holes.
This effect is reinforced by the small s p values.
Presently, the easiest way to significantly reduce the sur-
face recombination velocity ~SRV! at oxidized low-resis-
tivity ~;1 V cm! p-Si wafers is to evaporate Al onto the
oxide and subsequently anneal the wafer for about 20 min at
400 °C. This so-called Alneal generates atomic hydrogen
~formed during the oxidation of Al by residual water in the
oxide!, which effectively reduces the Si–SiO2 interface state
density. Furthermore, owing to work function differences, an
Al capping layer drives the p-type surface towards inversion,
reducing the surface recombination rate. Both effects are ex-
ploited at the rear surface of 24.0% record efficiency Si solar
cells fabricated on 1–2 V cm p-Si wafers, where S eff values
in the 20–50 cm/s range are obtained at injection levels
around 1014 cm23.7
In addition to the problems with low-resistivity p-Si wa-
fers, there are other problems arising from the high tempera-
tures during the oxide growth. These can severely degrade
the minority-carrier lifetime and are undesirable from pro-
duction cost and throughput considerations. Therefore, sig-
nificant effort has been devoted in recent years to the devel-
opment of low-temperature ~<500 °C! surface passivation
schemes as an alternative to the high-temperature oxidation
of Si. The most successful of these approaches with regard to
the passivation of low-resistivity p-type Si turned out to be
the plasma-enhanced chemical vapor deposition ~PECVD! of
silicon nitride.8 –11 With direct PECVD ~i.e., the wafer is di-
rectly exposed to the plasma!, differential S eff values around
10 cm/s have recently been reported for polished 2.5 V cm
p-Si wafers10 and values of 60 cm/s for 1.5 V cm wafers.11
In this letter, we present new record low S eff values ob-
tained on low-resistivity p-Si wafers passivated by remote
PECVD silicon nitride. The inherent advantage of the remote
technique is that during the deposition process there is no
direct exposure of the wafer to the plasma. This eliminates
the damage to the silicon surface from energetic particles in
the plasma. For polished as well as chemically textured Si
wafers, the passivation quality of remote nitride films is
compared to thermal oxides grown at 1050 °C. Furthermore,
application of the improved silicon nitride films to the rear
surface of bifacial Si solar cells as introduced in Ref. 9 is
discussed.
The material used in this study is single-crystalline pol-
ished ~100!-oriented FZ p-silicon. The wafers are 350 mm
thick and have a resistivity of 0.7 and 1.5 V cm. The textured
surfaces are generated in a K 2 CO3 solution, providing ran-
domly distributed upright pyramids with an average height
of 1–2 mm. 65 nm thick silicon nitride films are deposited
onto both wafer surfaces in a remote PECVD system
~Plasma Technology!, using the following deposition param-

1232 Appl. Phys. Lett. 68 (9), 26 February 1996 0003-6951/96/68(9)/1232/3/$10.00 © 1996 American Institute of Physics
FIG. 1. Measured S eff(Dn) dependence at polished and textured 0.7 V cm
p-Si wafers passivated by remote plasma silicon nitride and thermally grown
SiO2.
eters: temperature 375 °C, pressure 270 mTorr, gas flow 50
sccm NH3 3 sccm SiH4, microwave power 60 W. Prior to the
nitride deposition the wafers receive a standard RCA clean.
The thermal oxides are grown at 1050 °C in dry O2 to a
thickness of 110 nm. Upon oxidation, the wafers receive a
forming gas anneal ~5% H2, 95% N2! at 400 °C for 30 min.
The effective SRV at the passivated p-Si wafers is deter-
mined at room temperature by means of microwave-detected
photoconductance decay ~MW-PCD! measurements, using a
commercially available system ~Phoenicon GmbH!. The wa-
fer is illuminated with pulses from a 904-nm GaAs laser
diode. After termination of every laser pulse, the decay of the
light-induced excess electron concentration is analyzed by
time-resolved measurements of the microwave power re-
flected from the wafer under test. The determined quantity is
the time constant t eff of the monoexponential decay of the
excess electron concentration Dn within the wafer. In addi-
tion to the laser pulses, our system allows to illuminate the
sample with a variable amount of white bias light from a
halogen lamp ~intensity 0.1–50 mW/cm2). This system fea-
ture is indispensable since it is well known that the effective
SRV is highly dependent on the bulk injection level for ther-
mally oxidized2,3,5 as well as nitride-passivated11,12 Si wa-
fers. For light-biased PCD measurements, the SRV deter-
mined from the measured effective lifetime t eff is a
differential SRV S eff,d5]US /]Dn,13 where U S is the surface
recombination rate per unit area. Therefore, at first we cal-
culate the differential SRV as discussed in Ref. 12. Then, the
actual S eff5US /Dn is determined by integration.14 Dn at a
particular bias light intensity is calculated using the device
simulation program PC-1D.15 The bias light intensity is de-
termined with a calibrated Si solar cell. The evaluation of
S eff,d is performed using electron bulk lifetimes ~t n ! of 1.0
and 1.7 ms for the investigated 0.7 and 1.5 V cm p-Si wa-
fers, respectively. The error in S eff ~see error bars in Figs. 1
and 2! is mainly systematic and arises from the uncertainty
in t n . We calculate an upper and a lower bound for S eff for
every measured t eff value using an upper and a lower limit
for t n . As upper limit we use t n →`, while the lower limit
is obtained by depositing additional positive charges onto
both wafer surfaces within a corona chamber.16,17 This
Appl. Phys. Lett., Vol. 68, No. 9, 26 February 1996
FIG. 2. Measured S eff(Dn) dependence at polished and textured 1.5 V cm
p-Si wafers passivated by remote plasma silicon nitride and thermally grown
SiO2.
method improves the surface passivation,18 and therefore the
increased effective lifetime is a lower limit for t n . Using
corona passivation we obtain t eff values of 0.7 and 1.6 ms on
the investigated polished 0.7 and 1.5 V cm p-Si wafers, re-
spectively. The additional error resulting from other sources
~such as spatial inhomogeneities or the measurement error in
t eff! is estimated as <10%.
Figure 1 shows the measured S eff~Dn) dependence for
polished and textured 0.7 V cm p-Si wafers passivated by
thermally grown silicon dioxide and remote PECVD silicon
nitride. All samples exhibit the same characteristic curve
shape: at low injection levels S eff saturates, while with an
increasing injection level S eff decreases. The important result
of Fig. 1 is the fact that, regardless of the injection level and
the surface morphology, remote silicon nitride generates sub-
stantially better S eff values than a thermal oxide. The perfor-
mance advantage of nitride passivation increases with in-
creasing injection level. For example, at Dn55
31013 cm23, the nitride performs ;10 times better than the
oxide on polished surfaces, while the ratio is even a factor of
16 for textured surfaces.
Using the maximum bias light intensity of our PCD sys-
tem, we obtain Dn values around 131015 cm23 for the
nitride-passivated 0.7 V cm wafer. The corresponding S eff
values are 20 cm/s for the polished wafer and 34 cm/s for the
textured wafer ~using t n →`, the upper error limits for S eff
are 35 and 50 cm/s, respectively!. These values are by a clear
margin the best ever reported for a 0.7 V cm p-Si wafer
passivated by a solid film ~note: S values of 0.25 cm/s have
been obtained on ultrapure 150 V cm Si wafers using hy-
drofluoric acid. Although not shown, it is stated that for n-
and p-type Si the SRV remained ‘‘low’’ up to doping levels
of 1017 cm23!.19 Of particular importance for bifacial solar
cells is the result that, at intermediate injection levels, textur-
ing of the surface ~for reduced reflection losses! increases
S eff by less than a factor of 2 on nitride-passivated surfaces.
As can be seen from Fig. 2, we obtain qualitatively very
similar results on 1.5 V cm p-Si wafers. As expected from
the reduced doping level, the obtained S eff values are even
better than for the 0.7 V cm wafer. On the polished nitride-
passivated wafer we measure an S eff value as low as 4 cm/s
Lauinger et al. 1233

FIG. 3. Measured S eff values at the nitride-passivated surfaces of polished
and textured 1.5 V cm FZ p-Si wafers at a fixed bias light intensity of 50
mW/ cm2. The two bars to the right show the case where an ohmic Al metal
grid was evaporated onto both wafer surfaces prior to the nitride deposition.
In the case of the two left bars, evaporation of the metal grid has been
omitted.
at Dn51.331015 cm23, while the textured wafer yields an
S eff of 20 cm/s at Dn51.931015 cm23 ~the case t n →`
shows that S eff is definitely below 15 cm/s for the polished
and below 30 cm/s for the textured wafer!. These values are
the lowest SRVs ever reported for p-Si wafers with resistiv-
ities below 2 V cm, regardless of the process temperature
during the fabrication of the passivating film.
In order to demonstrate the potential of the remote ni-
tride films for actual devices, we briefly discuss their appli-
cation to the rear surface of bifacial Si solar cells. The p-type
substrate of such cells typically has a resistivity around 1
V cm. For these relatively high doping levels (;131016
cm23) the ohmic rear metal grid can be generated by direct
evaporation of Al and subsequent sintering.9 The spacing of
the 140 mm wide Al fingers is 2 mm, leading to a metalliza-
tion fraction of 7%. After evaporation of the metal grid onto
both surfaces of a 1.5 V cm FZ p-Si wafer, the remote Si
nitride films presented above are deposited onto both wafer
surfaces, followed by a sintering step at 500 °C for 10 min.
The results of the MW-PCD measurements taken on such
metal-grid covered wafers are summarized in Fig. 3.
The S eff values are shown for a fixed bias light intensity
of 50 mW/cm2 ~i.e., 0.5 suns!, which is a typical operating
condition for terrestrial Si solar cells. The two left bars rep-
resent the case where no metal grid has been evaporated onto
both wafer surfaces ~see Fig. 2!, while the two right bars
show the results from the polished and textured metal-grid
covered wafer, respectively. Figure 3 indicates that even in
the case of a metal-grid covered surface the effective ~area-
averaged! SRV is only 150 cm/s for a polished and 200 cm/s
for a textured wafer. As can be demonstrated with PC-1D
simulations, these S eff values allow for rear efficiencies of
bifacial Si solar cells of 18%, a remarkable achievement with
regard to the simplicity of the surface design and the speed
and the low temperatures of the nitride deposition. Already
the first few batches of bifacial Si solar cells fabricated in our
lab demonstrated rear efficiencies of 15%,20 highlighting the
enormous potential of the new passivation scheme for these
devices. Further details on the properties of our remote Si
1234 Appl. Phys. Lett., Vol. 68, No. 9, 26 February 1996
View publication stats
nitride films ~such as excellent chemical, thermal, and UV
stability! will be reported elsewhere.21
In conclusion, significant progress in the area of surface
passivation of low-resistivity ~;1 V cm! crystalline p-type
Si is reported. Using silicon nitride films generated at low
temperature ~375 °C! in a remote PECVD system, we suc-
ceeded to obtain record low effective SRVs of 4 and 20 cm/s
on 1.5 and 0.7 V cm polished p-Si wafers, respectively.
These values are by a clear margin the best S eff values ever
reported for any solid passivation film on such substrates,
regardless of the simplicity and the temperature of the film
fabrication process. The applicability of the new passivation
scheme to actual devices is demonstrated by S eff values of
200 cm/s for textured, metal-grid covered rear surfaces of
low-cost bifacial Si solar cells. We anticipate that these re-
mote silicon nitride films will also be extremely beneficial
for other surface-dominated Si devices.
We thank all members of the photovoltaic group at ISFH
for their contributions to this work. The support by the State
of Lower Saxony and the German Bundesministerium für
Bildung, Wissenschaft, Forschung und Technologie is grate-
fully acknowledged. The ISFH is a member of the For-
schungsverbund Sonnenenergie, Germany.
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