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Phys. Status Solidi C 8, No. 3, 879 – 882 (2011) / DOI 10.1002/pssc.201000236

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current topics in solid state physics
Effect of wet-chemical substrate
pretreatment on electronic interface
properties and recombination losses of a-Si:H/c-Si
and a-SiNx:H/c-Si hetero-interfaces
Heike Angermann*,1, Frank Wünsch2, Marinus Kunst2, Abdelazize Laades3, Uta Stürzebecher3,
Erhard Conrad1, Lars Korte1, and Manfred Schmidt1
1
Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Institut für Silizium-Photovoltaik, Kekuléstraße 5,
12489 Berlin, Germany
2
Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Institut Solare Brennstoffe und Energiespeichermaterialien,
Hahn-Meitner-Platz, 14109 Berlin Germany
3
CiS Institut für Mikrosensorik GmbH, SolarZentrum Erfurt, Konrad-Zuse-Str. 14, 99099 Erfurt, Germany

Received 30 April 2010, revised 29 June 2010, accepted 1 July 2010

Published online 16 December 2010

Keywords recombination, passivation, crystalline silicon, hydrogenated amorphous silicon, silicon nitride

* Corresponding author: e-mail angermann@helmholtz-berlin.de, Phone: +49 30 8062 1368, Fax: +49 30 8062 1333

Surface charge, surface state density and interface re-
combination behavior on polished float zone (FZ) solar
cell substrates were investigated after various wet-
chemical pre-cleaning procedures and deposition of
amorphous silicon (a-Si:H) or silicon nitride (a-SiNx:H).
Applying surface photo voltage (SPV), microwave de-
tected photo conductance decay (µW-PCD) and transient
microwave conduction (TRMC) measurements, elec-
tronic interface properties were monitored repeatedly
during the preparation processes. As shown for an in-
verted a-Si:H/c-Si hetero-junction structure, with front
side passivation by a-SiNx:H and a p-type a-Si:H emitter
on the rear side, the effect of optimised wet-chemical
pre-treatment can be preserved during the subsequent soft
plasma enhanced chemical vapour deposition of a-Si:H
or a-SiNx:H. This leads to hetero-interfaces with low in-
terface recombination velocities. These results were
compared to previously reported findings, obtained on
textured Czochralski (CZ) single crystalline substrates.
a-SiNx:H is known to result in a field effect passivation.
Nevertheless a strong influence of wet-chemical treat-
ments on surface charge and recombination losses was
observed on both flat and textured a-SiNx:H/c-Si inter-
faces.

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1 Introduction Crystalline silicon (Si) cells currently
share more than 90% of the worldwide photovoltaic mar-
ket [1]. A major advantage of Si is the nearly boundless
technological availability and the environmental sustain-
ability of this material. However, decisive preconditions to
the development of economically attractive Si solar cells
are the development of appropriate interface preparation
and passivation methods as well as the application of thin
film-technologies in order to reduce material consumption
[2]. The reduction of layer thickness shifts the focus on
surfaces and interfaces, because the interface takes up a
major part of the device concerned and interface defects
become increasingly more critical to the solar cell energy
conversion efficiency, which may be severely reduced due
to large interface recombination losses [3, 4, 5]. In wafer-
based high efficiency Si solar cells hydrogenated amor-
phous silicon (a-Si:H) and silicon nitride (a-SiNx:H) layers
are utilised to passivate the Si surface and/or to form the
p/n junction as well as the rear surface field. As is well
known from the microelectronics and sensor technology,
the electronic properties of Si interfaces are strongly influ-
enced by the chemical integrity and morphological struc-
ture of the substrate surface [6]. Therefore, increasing at-
tention should be focused on the monitoring and control of
interface properties after pre-cleaning treatments.
This paper reports on investigations of surface charge,
surface state density and interface recombination behav-
iour on wet-chemically treated Si substrates by surface
photo voltage (SPV), microwave detected photo conduc-
tance decay (µW-PCD) measurements. The effect of opti-

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880 H. Angermann et al.: Electronic interface properties of a-Si:H/c-Si and a-SiNx:H/c-Si hetero-interfaces

mised wet-chemical treatment was verified for an inverted mixing SiH4 with H2 diluted B2H6 for p-type doping
a-Si:H/c-Si hetero-junction structure, with front side pas- (2000 ppm B2H6 in SiH4). Microwave power was set to
sivation by a-SiNx:H and a p-type a-Si:H emitter on the 50 W and the process pressure was 0,5 mbar.
rear side [7]. 2.3 a-SiNx:H passivation layers were prepared in a
PECVD reactor (AK 1000 from Roth & Rau AG) operat-
(p)a-Si:H emitter ing with a microwave (MW) excited plasma by means of a
n+-layer linear antenna array at a frequency of 2.45 GHz. The sub-
metalization strate temperature was 380 °C. Film deposition was carried
SiNx out by decomposition of a silane/ammonia gas mixture.
Figure 1 Inverted a-Si:H/c-Si hetero-junction structure, front- 2.4 Inverted a-Si:H/c-Si hetero-junction cell as
side passivation by a-SiNx:H and a-Si:H(p) emitter on the rear- shown in Fig. 1 has advantages over the standard TCO/a-
Si(p)/c-Si(n)/a-Si(n+) heterojuction solar cell with an a-S:H
2 Preparation of Si hetero-interfaces
front emitter layer [11]. These are a higher sensitivity in
2.1 Wet-chemical substrate conditioning In or-
the short wavelength region because of the wider SiN gap
der to analyse the effect of surface conditioning in detail,
and the loss of transparent conductive oxide (TCO) front-
wet-chemical treatments were carried out on polished n-
coverage and the less restrictions of the rear side a-Si:H
type float-zone (FZ) Si(111) substrates (3 Ωcm) under
emitter layer thickness.
cleanroom ambiance as well as on saw damage etched (in
2.5 Interface characterisation The surface photo
KOH solution [8]) n-type high-quality Magnetic Czochral-
voltage technique (SPV) was utilized for contact-less
ski (MCZ) solar substrates (thickness of 270 µm, 2.5 to
measurement of the surface band-bending and the ener-
3.0 Ωcm) under technological conditions. The substrates
getic distribution of the interface state density Dit(E) to es-
were cleaned using the standard process of the Radio Cor-
tablish correlations between the wet-chemical substrate
poration of America (RCA) consisting of RCA I (APM:
preparation, the resulting charge, density and energetic dis-
ammonia / hydrogen peroxide mixture), HF 1% dip and
tribution of rechargeable interface states [10]. A laser di-
RCA II (HPM: hydrochloric acid / hydrogen peroxide mix-
ode (902 nm, 150 ns pulse length) was used as the excita-
tures) [9]. Afterwards, wet-chemically oxidized surfaces
tion light source. The surface photovoltage pulses as
were prepared applying (1) (RCA I), (2) oxidation in de-
shown in Fig. 2a were recorded with a transient recorder
ionized water (DIW) at 80°C (hot water oxidation) [10]
(time resolution 5 ns). From the maximum value of large-
and (3) boiling solution of sulphuric acid and hydrogen
signal photovoltage pulse UPh the surface potential was ob-
peroxide (1:1) for 10 minutes (H2SO4/H2O2). The hydrogen
tained. From a series of photovoltage pulses with different
(H)-termination was completed by removing the so pre-
field voltages UF between a transparent electrode and the
pared wet-chemical oxide in diluted hydrofluoric acid
Si wafer, Dit(E) (Fig. 2b) was determined [12].
(HF 1%) and (4) drying in N2 or (5) rinsing in DIW at
The microwave detected photoconductance decay
room temperature (RT).
(µW-PCD) was used to determine the spatially resolved
2.2 a-Si:H emitter layers - consisting of a stack of
minority charge carrier lifetime [13]. Interface recombina-
~3 nm (i)a-Si:H and ~8 nm (p+)a-Si:H - were deposited by
tion losses were investigated by transient microwave con-
plasma enhanced chemical vapour deposition (PECVD)
duction (TRMC) measurements after excitation by an illu-
and electron cyclotron resonance-CVD (ECR-CVD), re-
mination pulse at a wavelength of λ = 1064 nm [14].
spectively, at about 130 °C in a pure SiH4 process and by
Surface PhotoVoltage decay Interface state density 3 Effect of wet-chemical Si substrate pre-
Uph [V]

14
wet-chemical oxides: 10
treatment on electronic interface properties
Dit [cm eV ]

(1) RCA I
-1

(2) hot water oxidation

(3) H2SO4 / H2O2 wet-chemical oxides (3) 3.1 Charge and Dit(E) on polished substrates
-2

(2)
0,2
H-termination : Wet-chemical cleaning processes for Si wafers can be clas-
(1) (4) HF 1% : 60 s
13
(1) sified according to the final surface condition into two
10
(5) HF 1% + rinsing
groups: the surface passivation by H-termination or by thin
(2)
(3)
wet-chemical oxide layers, resulting in hydrophobic and
0,1
(5) hydrophilic surfaces, respectively.
(4) 12
Surface photovoltage pulses UPh(t) and the calculated
10 H-termination interface state distributions Dit(E) obtained by SPV-
(4)
a b (5) Dit, min measurements on wet-chemically treated polished n-type
0,0
2x10
-5
4x10
-5
-0,4 -0,2 0,0 0,2 0,4 FZ Si are shown in Fig. 2a and b. In order to verify the in-
field voltage UF [V] E-Ei [eV] fluence of surface charge and Dit(E) on recombination
Figure 2 (a) Surface photovoltage pulses and (b) interface state losses of subsequently prepared a-Si:H/c-Si and
distributions Dit(E) obtained on n-type FZ Si after wet-chemical a-SiNx:H/c-Si interfaces, various hydrophilic and hydro-
oxidation in RCA I (curves 1), in hot DIW (curves 2), in phobic processes were applied. The maximal values of UPh
H2SO4/H2O2 (curves 3), and after H-termination by HF (1%) and the time decays of the photo voltage pulse (Fig. 2a) -
(curves 4) and subsequent DIW rinsing at RT (curves 5). which yield information about interface recombination be-

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 Contributed
Article

Phys. Status Solidi C 8, No. 3 (2011) 881

haviour [15] - were found to be strongly influenced by the
wet-chemical substrate pre-treatment (Fig. 2a).
Hydrophilic surfaces arise from H2O2-containing solu-
tions, RCA I (Fig. 2a, curve 1) or H2SO4/H2O2 (Fig. 2a,
curve 3) or hot water oxidation (Fig. 2a, curve 2). After
different wet-chemical oxidation procedures characteristic
values of surface band bending were obtained, resulting
from the interface-trapped charge Qit and different oxide
charges [10]. Hydrophobic surfaces, mainly covered by
Si(−H)x, were prepared by HF 1% (Fig. 2a, curve 4) and
HF 1 % followed by rinsing in DIW (Fig. 2a, curve 5).
Significantly slower time decays of UPh were observed
on the HF 1% treated surfaces (Fig. 2a, curves 4,5) as
compared to wet-chemical oxides (Fig. 2a, curves 1-3).
Due to the initial oxidation, DIW rinsing at RT changes the
surface charge of the H-terminated surface (Fig. 2a, curve
4) by appearance of polarized ≡Si−OH (Fig. 2a, curve 5).
This leads to different surface Fermi level positions and
thus changes in band bending, as visible in the difference
of maximal Uph values.
The rapid and irregular wet-chemical oxide growth in-
creases the interface micro-roughness [10] and results in
high interface state densities Dit(E) ≥ 1013 cm-2eV-1 (Fig. 2b,
curves 1,3). Significantly lower Dit(E) ≈ 1012 cm-2eV-1 were
obtained by non-aggressive hot water oxidation (Fig. 2b,
curve 2) and Dit(E) ≤ 5x1011 cm-2eV-1 on hydrophobic, H-
terminated surfaces (Fig. 2b, curves 4,5).
3.2 Photovoltage and recombination losses on
a-SiNx:H/c-Si and a-Si:H/c-Si interfaces Which sub-
strate surface conditioning can successfully be applied to
550
back side
500
450
solar cells largely depends upon on the details of the de-
vice structure and the kind of subsequent layer deposition.
The influence of different wet-chemical treatments on sur-
face photovoltage and interface recombination losses was
investigated by combined SPV (Figs. 2,3) and TRMC (Fig.
5) measurements on an inverted a-Si:H(p)/c-Si(n) hetero-
junction structure, with front side passivation by a-SiNx:H
and a-Si:H emitter on the rear side [7] prepared on pol-
ished FZ Si substrates.
In Fig. 3 the maximal values of UPh are given as ob-
tained (i) after surface pre-treatments: oxidation by RCA I
(curve 1), hot water (curve 2), and H2SO4/H2O2 (curve 3),
and after H-termination by HF 1 % (curve 4) and HF 1% +
rinsing (curve 5), (ii) after subsequent front side passiva-
tion by a-SiNx:H, and (iii) after removing wet-chemical
oxides and subsequent deposition of the rear side a-Si:H
hetero emitter. Preparation-induced surface charges (Fig
2a) result in different UPh values on wet-chemically treated
substrates as shown in Fig. 3 (i). The passivation by a-
SiNx:H is based on the band bending caused by the posi-
tive fixed charge in the a-SiNx:H. Therefore, as expected,
no variation of UPh between the different treatments was
found after a-SiNx:H deposition, cf. Fig. 3 (ii).
As demonstrated in Fig. 3 (iii), after subsequent re-
moval of wet-chemical oxides and a-Si:H deposition, how-
ever, a strong influence of surface treatment on UPh was
observed on the rear side a-Si:H/c-Si, as well as on the
front side a-SiNx:H/c-Si interface. Highest UPh and best
energy conversion efficiency η =13.96% [7] were obtained
for cells with H2SO4/H2O2 treatment (Fig. 3, curve 3).
Front side: a-SiNx:H passivation

400
photovoltage UPh (mV)

(iii) a-Si:H deposition (3)

350

300
(1) (2)
250
(2) (1)
200 (4)
150
(5)
(3)
100
(i) substrate pre-treatment
(5)
x10-6 Time [s]
(4)
50 (ii) SiNx:H deposition Back side: a-Si:H(p) / c-Si(n)
0

-50
front side
-100 (2)
(3)
IW
°C
I

2
2O

/N
2
A

/D
80
RC

4 /H

F
2O

F
2 SO

H
H

(4)
H

(i) front side: Si surface (1)

(ii) front side: c-Si / a-SiNx:H interface
(ii) back side: Si surface after a-SiNx:H deposition
(iii) back side: c-Si / a-Si:H interface (heteroemitter)
(iii) front side: after back front side a-Si:H deposition
Figure 3 Maximal value of UPh on n-type FZ Si interfaces (i)
after surface pre-treatments: oxidation by RCA I (curve 1), hot
water (curve 2), and H2SO4/H2O2 (curve 3), H-termination by
HF 1 % (curve 4) and HF 1% + DIW rinsing (curve 5), (ii) after
subsequent front side passivation by a-SiNx:H, and (iii) after
subsequent HF 1% and a-Si:H deposition on rear side.
(5)
x10-6 Time [s]
Figure 4 TRMC measurements on inverted a-Si:H/c-Si hetero-
junction structures, with front side passivation by a-SiNx:H (ii) de-
posited after oxidation by RCA I (curves 1), hot water (curves 2),
H2SO4/H2O2 (curves 3), and H-termination by HF 1% (curves 4)
and HF 1% + DIW rinsing (curves 5) and on a-Si:H(p) emitter de-
posited on the rear side (iii) after removing wet-chemical oxides in
HF 1%.

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882 H. Angermann et al.: Electronic interface properties of a-Si:H/c-Si and a-SiNx:H/c-Si hetero-interfaces

Due to the field effect passivation on a-SiNx:H/c-Si, as 500

n-type CZ Silicon (saw damage etched)
passivated by SiNx:H
expected, no relation was obtained between Dit(E) (Fig. 2b) (4)
and interface recombination (Fig. 4). Nevertheless, Fig. 4
demonstrates a strong influence of surface treatments on in- 400 (6)

τeff (µs)
(2)
terface recombination velocities as measured by microwave
detected photo conductance decays on the same inverted 300

a-Si:H/c-Si hetero-junction structures, after front side pas- (1)

sivation by a-SiNx:H (ii) and subsequently removing wet- 200

chemical oxides in HF 1% and depositing an a-Si:H emitter (5)
on the rear side (iii). Lowest interface recombination losses
100 (3)
were achieved on a-SiNx:H/c-Si by H2SO4/H2O2 (Fig. 4 (ii),
curve 3) and on a-Si:H/c-Si by oxidation in H2SO4/H2O2 or
hot water and subsequent HF 1% -dip (Fig. 4 (iii), curves 0
A HF F F
RC DIW +H DIW +H
2,3). On both interfaces rinsing in DIW at RT significantly RC
A+
F +H
ot
otD
IW
F +H
ot
otD
IW
+H +H H
increases the recombination velocities (Fig. 4, curves 5). RC
A+
H
HF
RC
AI +H
F+
A+ AI
3.3 Passivation of saw damage etched solar RC RC

cell substrates by a-SiNx:H µW-PCD measurements Figure 5 Lifetime distribution over the area obtained by µW-PCD
on damage etched n-CZ-Si solar cell substrates after different wet-
[13] were utilized to verify the influence of wet-chemical
chemical treatments and passivation by a-SiNx:H.
treatments on recombination losses on saw damage etched
solar cell substrates [8] under technological conditions. On Acknowledgements The author would like to thank
so prepared a-Si:H/c-Si interfaces also strong correlations Dagmar Patzek for technical support. This work has been par-
were obtained between interface recombination losses and tially funded by the European Commission through the FP7 pro-
wet-chemical conditioning steps (cf. Fig. 5). Thereby gen- ject ”Heterojunction Solar Cells based on a-Si c-Si” (HETSI),
erally lower recombination losses were obtained on hydro- grant no. 211821, and by the Funded by the German Federal Min-
phobic surfaces achieved by final HF 1% steps (Fig. 5 col- istry for the Environment, Nature Conservation and Nuclear
umns 2,4,6). The oxidation in RCA I (Fig. column 5) was Safety (BMU) within the project “TopShot” (FKZ 0325114B).
also found to increase significantly the recombination
losses, whereas previous hot DIW oxidation steps (Fig. 5 References
columns 4,6) markedly reduce recombination losses due to
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