Solar Energy Materials & Solar Cells 238 (2022) 111412

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Solar Energy Materials and Solar Cells

journal homepage: www.elsevier.com/locate/solmat

Intrinsic layer modification in silicon heterojunctions: Balancing transport

and surface passivation
Christoph Luderer , Dilara Kurt , Anamaria Moldovan , Martin Hermle , Martin Bivour *
Fraunhofer Institute for Solar Energy Systems, Heidenhofstrasse 2, 79110, Freiburg, Germany

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, the intrinsic hydrogenated amorphous silicon (a-Si:H) layer of silicon heterojunction (SHJ) solar
Amorphous silicon cells was modified to improve carrier transport while maintaining excellent passivation of the c-Si absorber
Transport surface. The microstructure of different multilayer intrinsic a-Si:H films was measured and its influence on
Surface passivation
contact resistance and passivation quality was investigated thoroughly. We show that a pronounced trade-off
Microstructure
Silicon heterojunction
between passivation and transport exists and that this trade-off is governed by the a-Si:H properties close to
Contact resistance the c-Si surface. The fact that the same trend was observed for hole and electron contact suggests that the
transport barrier formed by the interfacial a-Si:H layer is governed by a higher resistivity of the void-rich
interfacial layer or a less pronounced induced junction and not by asymmetric hole or electron barriers (band
offsets, tunnel efficiencies, …). Modified intrinsic layers have been tested on cell level, resulting in a series
resistance (Rs) reduction by about 0.3 Ωcm2 and an increase in fill factor (FF) by roughly 1.0 %abs. The power
conversion efficiency (η) was improved by about 0.3 %abs with respect to our baseline. Further, the beneficial
effect of a hydrogen plasma treatment (HPT) on passivation and transport of the hole contact was shown on
device level.

1. Introduction detrimental effects of the void-rich a-Si:H layer on Rs and the

The excellent surface passivation of crystalline silicon (c-Si) by a thin
hydrogenated amorphous silicon (a-Si:H) layer [1,2] enables world re­
cord efficiencies of SHJ solar cells [3]. A key to this outstanding surface
passivation is the prevention of epitaxial growth at the a-Si:H/c-Si
interface [4,5]. It was found that for single intrinsic layers, surface
passivation properties are best just before the transition from amor­
phous to micro-crystalline Si [4,6], presumably because the a-Si:H
network is most relaxed in that case and comprises the lowest dangling
bond density [7]. Therefore, careful control of the a-Si:H deposition
parameters is necessary. Multilayer intrinsic a-Si films with proper
interfacial layer properties have been tested to relax the requirements
for a single layer, i.e., the combination of efficient hydrogenation and
the avoidance of epitaxial growth [8–10].
A void-rich a-Si:H interfacial layer (i1) deposited in pure SiH4 plasma
in combination with a dense a-Si:H layer (i2) deposited in highly H2
diluted plasma has been shown to increase the passivation quality of SHJ
cells (compared to single intrinsic layers deposited in the transition zone
between amorphous and micro-crystalline Si) [9,10]. However,
short-circuit current density (Jsc) have been reported by Sai et al. [11]
for the hole contact. They investigated the modification of the
i1-microstructure by varying deposition parameters like pressure and
power density and its influence on the passivation quality [11].
Recently, Wu et al. reported on an increased valence band offset for
void-rich, high band gap a-Si:H(i) layers, being especially detrimental
for the transport of holes [12]. Moreover, the influence of a hydrogen
plasma treatment (HPT) before, after or in between intrinsic a-Si:H
deposition was studied by several groups [10,13–17] with respect to
improving the surface passivation.
In this work, we follow a similar approach as Sai et al. but extend the
investigations by using test structures to directly compare passivation
and contact resistivity (ρc) of the different intrinsic layer stacks. We also
address the role of the HPT after a-Si:H(i1) and prior to a-Si:H(i2)
deposition to further modify passivation and transport. We performed
similar investigations for the hole and electron contact to check if an
intrinsic difference exists between both types of contacts. By doing so we
provide a holistic picture of the trade-off between transport and
passivation at the SHJ and how this can be engineered towards more

* Corresponding author.
E-mail address: martin.bivour@ise.fraunhofer.de (M. Bivour).

https://doi.org/10.1016/j.solmat.2021.111412
Received 7 May 2021; Received in revised form 21 June 2021; Accepted 21 September 2021
Available online 14 January 2022
0927-0248/© 2021 Published by Elsevier B.V.
C. Luderer et al.
efficient transport.
2. Experimental details
Solar cells and lifetime test structures were fabricated on random
pyramid textured 1 Ωcm, 180 μm thick n-type FZ silicon wafers (Fig. 1).
The monofacial solar cells were fabricated in the rear-emitter design and
metallized at the front and rear side via screen printing of an Ag paste
cured at 200◦ C in a belt furnace. As TCO, indium tin oxide (ITO) was
used, deposited via DC magnetron sputtering with a target composition
of In2O3:SnO2 (90:10 weight-%). Contact resistance test structures for
the hole (electron) contacts where fabricated on textured p-type (n-type)
FZ silicon wafers as described elsewhere [18]. For the doped a-Si:H
layers, the plasma-enhanced chemical vapor deposition (PECVD) pa­
rameters were kept constant throughout this work and an effective
thickness on textured surface of ≈12 nm and ≈9 nm on test structures
and solar cells was used, respectively. For the intrinsic a-Si:H multi­
layers, the deposition parameters like power density, pressure and H2
dilution (ratio R of H2 to total gas flow) were varied. The intrinsic a-Si:H
stack was formed by the deposition of two a-Si:H layers and additionally
an intermediate hydrogen plasma treatment (HPT) was used to further
modify the properties of the first layer and of the a-Si:H/c-Si interface
(i1+HPT+i2). The a-Si:H(i) layer properties and microstructure was
studied via spectroscopic ellipsometry and Fourier-transformed infrared
spectroscopy (FTIR). For FTIR, 9 nm thick a-Si:H(i) layers on a planar
c-Si substrate were investigated using an attenuated total reflection
(ATR) setup to increase the absorption signal of the thin film.
3. Results
3.1. Influence of different a-Si:H(i) layers and layer stacks
Fig. 2 shows ρc of SHJ electron (a) and hole (b) contacts comprising
the intrinsic a-Si:H stack or only the individual layer, all with a similar
total thickness of ≈6 nm. Different colors represent different cumulative
post-deposition thermal treatments of 10 min each. Average implied
open-circuit voltages (iVoc) measured by the equally processed lifetime
samples at 1 sun illumination are indicated for each group as a measure
of the passivation quality. The passivation quality was found to be in­
dependent of the annealing temperature up to 220 ◦ C. Basically, a very
similar trend was observed for hole and electron contacts but with lower
overall ρc and recombination for the electron contact. Without intrinsic
a-Si:H layer, the passivation quality was poor and ρc limited by the TCO/
a-Si:H(n/p) interface [19]. Adding a dense intrinsic a-Si:H layer (i2)
between c-Si and doped a-Si:H did not increase ρc. The iVoc was
improved to some extent, but still poor, especially for the hole contact.
Fig. 1. Sketches of the utilized test structures and solar cells for a-Si:H(i)
variation at the hole contact. For a-Si:H(i) variation at the electron contact
resistance test structures with n-type doping was used for c-Si and a-Si:H at the
front and rear side.
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Solar Energy Materials and Solar Cells 238 (2022) 111412
Using a void-rich i-layer and the hydrogen plasma treatment (i1+HPT)
instead, increased the iVoc significantly at the cost of higher ρc. The stack
of i1+HPT+i2, in which both i1 and i2 were 3 nm thick, showed the best
passivation but also the highest ρc. These results clearly show that a
void-rich i-layer (i1) is necessary for good passivation at the hole and
electron contact but it is also mainly responsible for resistive losses.
3.2. a-Si:H(i1) modification
In the previous section, it was shown that i1 is necessary to obtain
excellent passivation of the c-Si absorber, but ρc is increased thereby.
The goal for further optimization is therefore to modify the i1 micro­
structure towards slightly more dense properties to improve transport
while maintaining a high passivation quality. By varying the deposition
conditions the a-Si:H(i) microstructure can be altered.
Fig. 3a shows the absorption band associated with Si–H stretching
modes obtained from infrared spectroscopy of different a-Si:H(i) layers
with a total thickness of 9 nm on a planar c-Si wafer. A figure of merit for
the a-Si:H microstructure is the so-called microstructure factor R*,
which is determined from the Gaussian deconvolution of the Si–H
stretching modes into a low (LSM) and a high stretching mode (HSM),
located at ≈ 2000 cm− 1 and ≈2100 cm− 1, respectively [20–22]:
IHSM
R* = (1)
ILSM + IHSM
A clear difference in the microstructure between i1, i2 and the stack
can be seen. In the dense i-layer i2 the LSM is dominant, corresponding
to isolated monohydrides (SiH) [23], resulting in a low R* of 0.15. In
contrast to that, in the void-rich i-layer i1 the HSM plays a major role,
corresponding to hydrogen bonded to a void surface [21] as well as
dihydrides (SiH2) [23], displayed by a high microstructure factor (R* =
0.88). Consequently, in the stack of i1 and i2 a combination of both
microstructures was measured (R* = 0.34).
As one approach to lower the void density and to improve the
structural quality of i1 (thereby reducing the i1 R* value), the H2 dilu­
tion ratio R in the plasma was increased (Fig. 3b). Whereas the LSM
intensity was basically unchanged, the HSM intensity decreased mark­
edly (red). This can be explained by an increased diffusion energy on the
c-Si surface by a higher rate of exothermic hydrogen exchange reactions
due to the increased density of atomic hydrogen in the plasma [24].
The optical band gap Eg, determined by spectroscopic ellipsometry,
decreased with increased H2 dilution ratio (not shown), also indicating a
densification of the intrinsic layer. In Ref. [25] the positive correlation
between the microstructure factor R* obtained from infrared spectros­
copy and the optical band gap Eg extracted from spectroscopic ellips­
ometry measurements was shown. Therefore, usually a higher Eg and
higher R* indicate a film with more voids, less order whereas a lower Eg
and lower R* indicate a denser, more ordered film.
Further, a plasma power reduction during layer growth (green)
similarly decreased R* and Eg, presumably due to a lower void fraction
as a result of a lower deposition rate.
R* was also lower for the i1 after an HPT of 35 s (blue) compared to
the untreated reference i1 (black). In this case, however, a different
trend in Eg was observed as Eg increased with increasing HPT duration
(not shown). The total intensity of the Si–H stretching band and espe­
cially the LSM intensity was increased after HPT, which is a sign for
more hydrogen in the a-Si:H layer [23].
The a-Si:H(i) thickness was unchanged up to 35 s of HPT and
decreased for longer HPT durations (not shown). This confirms the
etching effect of such an HPT reported in Refs. [14,16,26] with an in­
cubation time of ≈35 s for our process conditions during which
hydrogen diffusion into the film dominates over etching [14,26].
As a next step, transport (ρc) and passivation (τ) with modified
intrinsic a-Si:H layers at the hole contact were tested on co-fabricated
test structures. In Fig. 4, ρc after 180 ◦ C annealing of various hole con­
tact stacks comprising different a-Si:H(i) layers is plotted against the
C. Luderer et al.
Fig. 2. ρc and iVoc of SHJ electron (a) and hole (b) contacts comprising different undoped a-Si:H layer (stacks) as indicated by the sketch above the graphs. Colors
refer to different annealing temperature. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)
Fig. 3. (a) Infrared spectroscopy signal of different a-Si:H(i). (b) Infrared spectroscopy signal as indicator of the a-Si:H(i1) microstructure for several process pa­
rameters. The intensity was normalized on the a-Si:H(i) layer thickness.
Fig. 4. ρc and τ at an injection level of 1.0 × 1015 cm− 3 for i-layer stacks with
different microstructure and i1 thickness fractions. The black closed square
represents the reference process with an i1 thickness ratio of 0.55 and a i1 R
value of 0%. Closed symbols refer to ≈6 nm and open symbols to ≈4.5 nm total
effective i-layer stack thickness on textured surface. Semi-closed symbols
represent i1 deposition with lower power. Different shades of red and yellow
represent the i1 thickness fraction variation and different shades of blue
represent the i1 H2 dilution variation. (For interpretation of the references to
color in this figure legend, the reader is referred to the Web version of
this article.)
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Solar Energy Materials and Solar Cells 238 (2022) 111412
minority carrier lifetime (τ). Each data point represents the median
value of at least ten measurements. The symbol size was chosen pro­
portional to Eg of the particular intrinsic layer. The reference (closed
black square) comprised a high power i1 (3 nm) with no H2 dilution, an
HPT of 7 s and a highly H2 diluted i2 (3 nm) and yielded τ ≈ 4.3 ms and
ρc ≈ 214 mΩcm2.
As indicated by the arrow, generally an increase in τ comes at the cost
of higher ρc. However, there were i-layers providing similar passivation
as the baseline reference (closed black square) while ρc was reduced.
Reducing the total thickness of our reference a-Si:H stack from ≈6
(closed black square) to ≈ 4.5 nm (open black square) reduced both τ
(from 4.3 to 1.3 ms) and ρc (from 214 to 91 mΩcm2) significantly,
highlighting the strong trade-off between high passivation quality and
efficient transport linked to the intrinsic layer’s thickness. For compar­
ison, results of groups "only i2" and "only i1+HPT" from Fig. 2b are
shown as dark red respectively yellow closed circles. The mediocre
passivation level of "only i1" (1.2 ms) was further reduced to 1.1 ms by
reducing the total a-Si:H(i) thickness from ≈6 to ≈ 4.5 nm, while ρc was
reduced significantly from 185 to 110 mΩcm2 (closed vs. open yellow
circle).
In another attempt, starting from "only i1" the i1 thickness fraction
(i1 thickness to total a-Si:H(i) thickness) was gradually reduced to zero
("only i2") while a total a-Si:H thickness of 6 nm was maintained (see
legend, closed yellow to red circles). The optimum i1 fraction regarding
τ remained at 0.55, as for our baseline reference. However, a slightly
reduced i1 thickness fraction (0.44) led to similarly high τ and a
C. Luderer et al. Solar Energy Materials and Solar Cells 238 (2022) 111412

reduction of ρc from 214 to 150 mΩcm2.
Reducing the power during i1 deposition, but maintaining similar
thickness, reduced ρc by about ≈50 mΩcm2 while τ degraded only
slightly ("i/p 2") compared to the reference. Using the lower power i1 at
reduced i1 thickness fraction led to further ρc reduction down to 140
mΩcm2 and similar τ ("i/p 3"). Increasing the H2 dilution of i1 while
trying to keep the thickness constant (closed blue symbols) led to a
reduction in ρc by about ≈80 mΩcm2 down to 130 mΩcm2 at R = 30%
while τ was essentially unaffected ("i/p 1"). Increasing R further reduced
τ significantly for R > 30% while ρc gradually approached the lower
limit of ρc ≈ 90 mΩcm2 for samples without intrinsic layer (not shown).
The positive influence of an HPT after i1 deposition on transport and
passivation can be seen by comparing the reference with a group that did
not receive the treatment (black square vs. green diamond).
To summarize, compared to the baseline reference (Ref., black
square) a slight reduction in the i1 thickness fraction from 0.55 to 0.44
(orange closed circle), as well as a slightly denser i1 due to deposition
with lower power ("i/p 2") or using some H2 dilution ("i/p 1") reduced ρc
markedly, while τ was still on a high level. Another interesting candidate
was the combination of a slightly denser i1 by using lower power and
adapting the i1 thickness fraction to 0.44 ("i/p 3"). The i1 microstructure
can be further modified with a post-deposition HPT, which can be
beneficial for both transport and passivation.
comparable to the reference. Jsc (not shown) was very similar for all
groups. This resulted in an increased η by about 0.3 %abs compared to
our baseline reference with very similar maximum η of 22.0% for all
three modifications. Please note that the cell performance is limited by a
low Jsc due to a simplistic grid design with a busbar shading of 4% of the
total cell area.
In another cell batch, the total thickness of the i-layer stack at the
hole contact was varied by changing the i1 thickness, while the HPT and
the i2 thickness was constant (Fig. 6). Again, the lower power i1 was
used, as in “i/p 2” and “i/p 3”. A strong correlation of the i1 thickness and
Rs was observed. A linear fit was performed, yielding a slope of ≈340
mΩcm2/nm. Since exact determination of the i1 thickness is difficult and
considerable scatter is present in the Rs data, this is only intended as a
rough estimate to highlight the significant impact of the i1 thickness on
Rs.

3.3. Solar cells with modified a-Si:H(i) at the hole contact

The most promising modified a-Si:H(i)/a-Si:H(p) hole contact stacks

taken from Fig. 4 were tested on cell level. Namely, "i/p 1" with a 30% H2
diluted plasma during i1 deposition (dark blue pentagon), "i/p 2" with a
reduced i1 deposition power (black semi-closed square) and "i/p 3" with
lower i1 power as in "i/p 2" and reduced i1 thickness ratio (orange semi-
closed circle). Solar cell parameters of the three modified hole contacts
are shown in Fig. 5 in comparison to the baseline reference. The bene­
ficial transport properties seen on test structures are reflected in the
significant reduction in Rs and increase in FF. The difference in Voc is
small, which shows that the passivation quality is at similar level with a
Fig. 6. Rs as a function of the i1 thickness in the i-layer stack at the hole
Voc loss of 1–2 mV for the i/p 3 process. The pseudo fill factor (pFF), also
contact. The HPT and i2 thickness were kept constant.
reflecting the passivation quality, remained on a high level for all groups

Fig. 5. SHJ solar cell parameters of three modified i/p stacks compared to our reference process. Group i/p 1 comprised a H2 diluted i1. For groups i/p 2 and i/p 3 the
i1 deposition power was lower and for group i/p 3 the i1 thickness fraction was also lower compared to the reference. Jsc (not shown) was constant for all groups.

4
C. Luderer et al.
Motivated by the beneficial effect of the HPT after i1 deposition on ρc
and on τ seen in Fig. 4, an HPT duration time variation was conducted on
cell level. The HPT duration time was varied between 0 and 35 s. As can
be seen in Fig. 7, the HPT is clearly beneficial for the surface passivation.
This is reflected in an increased Voc and pFF of groups with HPT
compared to the group without HPT. No clear trend for the passivation
quality in dependence on the duration time was observed. The Voc is very
similar for 35 and 7 s HPT, whereas pFF values for the 7 s process are
slightly higher compared to 18 respectively 35 s.
Regarding transport, Rs after 7 s HPT is similar to the untreated
group, but a significant Rs reduction was obtained for 18 and 35 s HPT.
The beneficial effect of the HPT on transport can be also seen in the
increased FF with increasing HPT duration, reaching a maximum value
of 83.5% for the 35 s process. Overall, this trend transferred to η with a
maximum of 22.6% after 35 s of HPT. Longer HPT durations up to 90 s
did not further increase η (not shown). An HPT duration variation was
also performed at the electron contact on cell level (not shown), but
besides an initial improved passivation after 7 s of HPT, a longer HPT did
neither affect passivation nor transport. Note that ρc of the electron
contact is generally much lower and that the i-layer stack at the electron
contact and had a lower total thickness and a lower i1 thickness fraction
compared to the reference i-layer stack used for the hole contact.
4. Discussion
4.1. Induced band bending and possible transport paths
For efficient passivation at the hole contact, recombination of pho­
togenerated minority electrons and majority holes at and close to the a-
Si:H/c-Si interface must be avoided. For efficient transport, a sufficiently
high hole conductivity in the contact region along the hole transport
path, from the induced c-Si junction towards the TCO electrode, needs to
be ensured [27,28].
Regarding transport, a sufficiently high band bending at the surface
of the c-Si absorber and in the undoped a-Si:H(i), induced by the doped
a-Si:H layer, is a necessary condition for a well-working contact, i.e., low
ρc. It provides the high hole concentration and thus hole conductivity at
Fig. 7. SHJ solar cell parameters in dependence of the HPT duration at the hole contact. Jsc (not shown) was constant for all groups.
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Solar Energy Materials and Solar Cells 238 (2022) 111412
and close to the c-Si surface necessary for efficient hole extraction from
the absorber [29]. With respect to the detrimental role of the i-layer for
transport, it was shown for p-type and n-type doped a-Si:H [30,31] and a
high work function metal oxide [32] that the a-Si:H(i) layer can reduce
the induced band bending in the c-Si absorber which leads to reduction
of accumulated holes and thus to a reduction of hole conductivity in the
vicinity of the a-Si/c-Si interface.
Thus, one possible explanation for the higher ρc for structures con­
taining i1 could be that the structural differences between i1 and i2
cause a greater potential drop across i1 than across i2, and thus less c-Si
band bending. In an attempt to probe this effect, the surface photo­
voltage method [33] was used. However, no significant difference in the
induced bend bending for the hole contacts comprising an i-layer in
Fig. 2b could be detected, i.e., either only i2, only i1 (with and without
HPT) or the i1+HPT+i2 stack (not shown). However, this does not mean
that this effect must be excluded, as it is possible that the resolution of
the measurement method is not sufficient.
Besides insufficient induced band bending, structural properties of a-
Si:H(i) and the a-Si:H/c-Si interface might influence transport. In Fig. 8,
a sketch of the band structure of the a-Si:H(p)/a-Si:H(i)/c-Si hetero­
junction (under illumination at maximum-power point) is shown.
Possible hole transport paths from the c-Si into the a-Si:H(p) contact
layer are indicated, as partly adapted from Ref. [34]:
1) emission of charge carriers across the hetero-barrier
2) trap-assisted tunneling (TAT) across the hetero-barrier
3) tunnel hopping in valence band tail states
4) tunneling and subsequent emission.
In addition to a large hole concentration in the contact region,
thermionic emission across the band offsets requires a small barrier
height and trap-assisted tunneling transport requires sufficient valence
band tail states and defect states at the right energetic position. In the
following, we try to correlate the experimental trends with the possible
influencing factors mentioned above.
C. Luderer et al.
Fig. 8. Sketched band diagram of the a-Si:H/c-Si junction at maximum-power
point at the hole contact. Recombination at the a-Si:H/c-Si interface or at defect
states close to the interface must be avoided for high-quality surface passiv­
ation. Possible transport paths 1)-4) are illustrated and discussed in the text.
The resistance is governed by the a-Si:H/c-Si interface and the i1 and i2 "bulk"
properties, like the energetic position and density of defects and valence band
tail states, as indicated by the series connection at the top.
4.2. i1 vs. i2: Passivation and transport
Using a single layer of dense a-Si:H(i2) without a-Si:H(p) layer
deposited on top, a good passivation of the c-Si surface with iVoc values
above 730 mV (not shown) can be obtained. However, after a-Si:H(p)
layer deposition, the passivation quality was impeded substantially and
the iVoc decreased to ~640 mV, as depicted in Fig. 2b. Doped layer
deposition was found detrimental by several other groups (e.g., Refs.
[10,35]). De Wolf and Kondo explained that with a lowered Si–H bond
rupture energy in a-Si:H(i) due to the shift of the Fermi level in the
presence of a doped layer [35]. Liu et al. argued that partial crystalli­
zation occurred at the a-Si:H/c-Si interface by hydrogen bombardment
during a-Si:H(p) deposition [10]. In that case, dangling bonds at the c-Si
surface are no longer passivated efficiently, resulting in a high defect
density at the interface [12].
With respect to transport, the defect state density in i2 will be lower
than in p-doped a-Si:H, but sufficient states at the right energetic posi­
tion might still be available to explain the negligible difference in ρc
between groups "w/o i-layer" and "only i2" in Fig. 2.
Applying a void-rich a-Si:H(i1) ensures an abrupt a-Si:H(i)/c-Si
interface with a low defect density (with and without HPT) [10]. On the
one hand, this low-defective interface enables a lower minority carrier
recombination rate and therefore higher iVoc compared to "only i2". On
the other hand, ρc was increased with a void-rich a-Si:H(i) at the c-Si
surface. One explanation for that involves path 1 in Fig. 8. Due to the
larger Eg for void-rich i1 (Eg ≈ 1.9 eV) than for dense i2 (Eg ≈ 1.7 eV), the
barrier height for thermionic emission would be increased in the case of
i1.
A reduction of the i1 thickness also reduced ρc and Rs ("i/p 3", Figs. 4
and 5). Thus, besides increased band offsets at the a-Si:H/c-Si interface,
a-Si:H “bulk” properties, like the energetic position and density of gap
defect states and valence band tail states, might contribute to the higher
ρc of i1 than of i2. This would mean that the energetic position of these
states, which enable transport paths 2, 3, and 4 in Fig. 8, are more
favorable in i2 than in i1.
A lower “bulk” conductivity of void-rich a-Si:H compared to denser,
lower band-gap a-Si:H was reported in Ref. [25]. It must be mentioned,
however, that these results were obtained from measuring the lateral
conductivity of “thick” a-Si:H(i) films deposited on glass and this might
not be relevant for the vertical transport through the contact stack of the
ultra-thin layers discussed here. In general, the properties of such “thick”
layers might have limited relevance for the multi-layer heterojunction
6
Solar Energy Materials and Solar Cells 238 (2022) 111412
stack. Reasons for this are the dominance of interfaces over bulk effects
and that the properties of the films, which are only a few nanometers
thin, are determined by the initial growth regime. Thus, an alternative
description is that the thin, void-rich a-Si:H(i1) layer might have an
effectively smaller contact area to the c-Si due to a lower effective sur­
face coverage of the c-Si absorber [36]. This might contribute to the
increased ρc for structures including i1.
Moreover, a reduced i1 thickness increases the probability of direct
tunneling transport through i1. This is supported by the observation that
ρc with a i1+HPT+i2 stack of a total thickness of 4.5 nm (i1 thickness ≈
2 nm) dropped to ≈ 90 mΩcm2 (Fig. 4), a value also reached with no i-
layer present. Thus, although an i1 and the corresponding a-Si:H/c-Si
interface was present, the i-layer contribution to ρc was negligible,
which might indicate very efficient transport through i1 via tunneling
once the i1 thickness is below a certain critical thickness.
The above-mentioned effects modify both hole and electron trans­
port, explaining the same qualitative trend for the hole and electron
contact in Fig. 2. However, the increase in ρc due to the insertion of i1 is
about three times higher for the hole contact (≈+150 mΩcm2 compared
to ≈+50 mΩcm2 for the electron contact). The electron contact is not as
heavily reliant on tunneling as the hole contact, since thermionic
emission across the smaller conduction band offset is more efficient.
Moreover, the doping efficiency in a-Si:H(n) is higher [37] and as a
result of the asymmetric band-line up, the induced junction is less pro­
nounced for the hole contact compared to the electron contact [30]. A
further role for less efficient majority carrier transport for the hole
contact might be the lower mobility of holes compared to electrons [38].
With respect to the i-layer stack, the passivation quality is further
improved with the deposition conditions of the dense i2 (Fig. 2) on top of
the i1 and the c-Si interface. Hydrogen can penetrate the void-rich i1 and
saturate defects at the a-Si:H/c-Si interface and thereby further reduce
the interface defect density [10]. Beyond this, the role of the i2 in the
i-layer stack might also be to function as a “spacer” to screen the a-Si:H
(p) defects from the minority carriers at the well passivated a-Si:H
(i1)/c-Si interface [39].
4.3. Influence of lower power and H2 dilution
The high power density enabling a high i1 deposition rate ( > 1.0
nm/s compared to ≈ 0.1 nm/s for i2) is one key factor to achieve a void-
rich a-Si:H(i) layer and to prevent epitaxial growth [11]. Hence,
reducing the power during i1 deposition ("i/p 2", "i/p 3" in Figs. 4 and 5)
leads to a denser a-Si:H(i), as indicated by the lower R* (and lower Eg) in
Fig. 3b. Similarly, H2 dilution results in a denser a Si:H(i) layer, as
mentioned above ("i/p 1"). Since denser layers more readily lead to
epitaxial growth, this can also lead to increased defect density at the
a-Si:H(i)/c-Si heterojunction. This is accompanied by a higher majority
and minority carrier recombination at and close to the interface. This
has a detrimental effect on surface passivation, as observed in the lower
minority carrier lifetime on test structures and in the slightly lower Voc
on cell level compared to the reference.
The structural properties of the modified i1 layers are still very
different from those of i2, but have been altered in this direction (e.g.,
lower R*). Following the argument above, this could imply bandgap
states with more favorable energetic positions for tunneling transport in
the modified i1 than in the reference i1.
4.4. Influence of the HPT
The effect of an HPT on the passivation quality was already discussed
by other groups: The HPT introduces hydrogen which can diffuse easily
through the void-rich a-Si:H(i1) and saturate dangling bonds at the
interface, thereby improve the passivation [10,17]. The HPT can also
induce a-Si:H network relaxation by replacing strained Si–Si bonds with
Si–H bonds [40]. This can even cause an epitaxial layer at the a-Si:H/c-Si
interface for a transition-zone a-Si:H film [10]. In the case of heavily
C. Luderer et al.
disordered, void-rich a-Si:H films, however, network relaxations re­
quires more energy [10]. Therefore, an epitaxial layer is avoided for the
void-rich i1 even after HPT. A thinner i1 could further facilitate
hydrogen diffusion to the interface [10] and might therefore be bene­
ficial for passivation. However, a too thin i1 might not protect the a-Si:
H/c-Si interface sufficiently from the plasma, resulting in damage
detrimental for passivation [13–15]. Schulze et al. reported on the band
gap widening effect of hydrogen [41]. They also discussed that the
retreat of the valence band is responsible for the increased Eg. As a result,
the valence band offset increased systematically with higher hydrogen
content (higher Eg), whereas the conduction band offset remained
basically unchanged [41]. The introduced hydrogen might therefore be
responsible for the band gap widening after HPT observed here and also
in Ref. [16]. The increased valence band offset was used by Wu et al. to
explain impeded hole transport after hydrogen modification of the
intrinsic layer [12]. However, they mentioned that this effect was
overestimated in their simulation since they did not include tunneling
transport. Nevertheless, here a significant Rs reduction by applying the
HPT at the hole contact was observed. The beneficial structural changes
regarding transport induced by the HPT clearly over-compensated the
potentially increased valance band offset, i.e., transport barrier. In
addition, since the hole transport is heavily reliant on tunneling anyway
[28,42], the possibly slightly further increased barrier height due to a
valence band retreat after HPT might not be relevant. Possible would be
an increased valence band tail state density due to changes in the a-Si:H
network introduced by the HPT. This could facilitate hole transport
(paths 2 and 3 in Fig. 8), if the broadened valence band tail (increased
Urbach energy) over-compensates the retreat of the valence band (by an
increased Si–H bond density) [41]. However, that case would result in a
decreased Eg measured via spectroscopic ellipsometry after HPT, which
was not observed. Mews et al. also reported that an HPT did not increase
the Urbach energy of their a-Si:H(i) layers [17].
The HPT might reduce mid-gap defects in the i1 and at the a-Si:H/c-
Si interface and by that reduce surface recombination and increase the
hole concentration at the c-Si surface, which would increase the prob­
ability for (trap-assisted) tunneling transport to the a-Si:H(p). However,
this would not explain the overall strong trade-off between surface
passivation and transport observed in Fig. 4.
R* was decreased after HPT, a sign for a slightly more ordered film
with a lower void density [16,21]. This correlates with a slightly
decreased broadening term observed via fitting the spectroscopic
ellipsometry data with a Tauc-Lorentz model [43] (not shown). For the
cells presented in Fig. 7, the HPT therefore apparently i) provided a
low-defective interface by supplying hydrogen for the saturation of
dangling bonds and ii) reduced voids and improved the transport across
the i1, similarly to the other i1 modifications. The etching effect of the
HPT and accompanied i1 thickness reduction only plays a minor role for
the cell results in Fig. 7, since the i1 thickness was almost constant up to
35 s (incubation regime) and only started to decrease for longer
durations.
Basically, more structural characterization like the measurement of
Urbach energies with very high spatial resolution is necessary to find a
definitive explanation for the experimental results discussed here.
Detailed numerical device simulations would further help to deepen the
understanding.
5. Conclusion
In this article, we showed that the void-rich a-Si:H(i1) used to pre­
vent epitaxial growth is the main source of i-layer induced transport
losses. Higher resistance was observed for both the electron and the hole
contact, showing that it is not dominated by asymmetric effects like
different band offsets for electrons or holes. Instead, several other
possible influencing factors have been discussed. Among those, less
favorable energetic position of defect states was suggested to be the
reason for impeded transport using void-rich a-Si:H(i), in combination
7
Solar Energy Materials and Solar Cells 238 (2022) 111412
with a possibly lower effective contact area of such void-rich films, and
the alteration of the induced band bending, affecting the hole density in
the contact region (a-Si:H(i), c-Si surface). Carefully modifying the void-
rich a-Si:H(i) toward more order and higher density as well as adapting
its thickness, reduced Rs significantly and resulted in improved η despite
slightly decreased passivation quality. Further, a prolonged HPT after a-
Si:H(i1) deposition at the hole contact was found to decrease Rs while
also being beneficial for passivation. This was ascribed to the simulta­
neous reduction of void density enabling more efficient transport and
the saturation of interface states during HPT for a high passivation
quality.
The results shown allow further fine-tuning of the hole and electron
contact in terms of the trade-off between passivation and transport, but
also show that there is still a need for further improved fundamental
understanding of thin-film heterojunction stacks.
CRediT authorship contribution statement
Christoph Luderer: Conceptualization, Methodology, Investigation,
Writing – original draft, Visualization. Dilara Kurt: Investigation,
Visualization. Anamaria Moldovan: Writing – review & editing. Mar­
tin Hermle: Writing – review & editing, Supervision. Martin Bivour:
Conceptualization, Writing – review & editing, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors would like to thank A. Leimenstoll, F. Schätzle, K.
Zimmermann for sample preparation, Z. Newcomb-Hall for sample
preparation and dark I–V measurements, F. Martin for measuring the
solar cells and C. Messmer for fruitful discussions. This work was funded
by the German Federal Ministry for Economic Affairs and Energy under
contract numbers 03EE1031A (PaSoDoble) and 0324293E (Dynasto).
References
[1] S. de Wolf, A. Descoeudres, Z.C. Holman, C. Ballif, High-efficiency silicon
heterojunction solar cells: a review, green, 2, 7-24, https://doi.org/10.1515/green-
2011-0018, 2012.
[2] S. Dauwe, J. Schmidt, R. Hezel, Very low surface recombination velocities on p-
and n-type silicon wafers passivated with hydrogenated amorphous silicon films,
in: Conference Record of the Twenty-Ninth IEEE Photovoltaic Specialists
Conference, New Orleans, LA, USA, IEEE, Piscataway, NJ, 2002, pp. 1246–1249.
[3] K. Yoshikawa, W. Yoshida, T. Irie, H. Kawasaki, K. Konishi, H. Ishibashi, T. Asatani,
D. Adachi, M. Kanematsu, H. Uzu, K. Yamamoto, Exceeding conversion efficiency
of 26% by heterojunction interdigitated back contact solar cell with thin film Si
technology, Sol. Energy Mater. Sol. Cell. 173 (2017) 37–42, https://doi.org/
10.1016/j.solmat.2017.06.024.
[4] H. Fujiwara, M. Kondo, Impact of epitaxial growth at the heterointerface of a-Si:H/
c-Si solar cells, Appl. Phys. Lett. 90 (2007) 13503, https://doi.org/10.1063/
1.2426900.
[5] T.H. Wang, E. Iwaniczko, M.R. Page, D.H. Levi, Y. Yan, H.M. Branz, Q. Wang, Effect
of emitter deposition temperature on surface passivation in hot-wire chemical
vapor deposited silicon heterojunction solar cells, Thin Solid Films 501 (2006)
284–287, https://doi.org/10.1016/j.tsf.2005.07.196.
[6] A. Descoeudres, L. Barraud, R. Bartlome, G. Choong, S. De Wolf, F. Zicarelli,
C. Ballif, The silane depletion fraction as an indicator for the amorphous/
crystalline silicon interface passivation quality, Appl. Phys. Lett. 97 (2010)
183505, https://doi.org/10.1063/1.3511737.
[7] S. De Wolf, M. Kondo, Abruptness of a-Si:H/c-Si interface revealed by carrier
lifetime measurements, Appl. Phys. Lett. 90 (2007) 42111, https://doi.org/
10.1063/1.2432297.
[8] H. Fujiwara, T. Kaneko, M. Kondo, Application of hydrogenated amorphous silicon
oxide layers to c-Si heterojunction solar cells, Appl. Phys. Lett. 91 (2007) 133508,
https://doi.org/10.1063/1.2790815.
[9] Y. Zhang, C. Yu, M. Yang, L.-R. Zhang, Y.-C. He, J.-Y. Zhang, X.-X. Xu, Y.-Z. Zhang,
X.-M. Song, H. Yan, Significant improvement of passivation performance by two-
step preparation of amorphous silicon passivation layers in silicon heterojunction
C. Luderer et al.
solar cells, Chin. Phys. Lett. 34 (2017) 38101, https://doi.org/10.1088/0256-
307X/34/3/038101.
[10] W. Liu, L. Zhang, R. Chen, F. Meng, W. Guo, J. Bao, Z. Liu, Underdense a-Si:H film
capped by a dense film as the passivation layer of a silicon heterojunction solar
cell, J. Appl. Phys. 120 (2016) 175301, https://doi.org/10.1063/1.4966941.
[11] H. Sai, P.-W. Chen, H.-J. Hsu, T. Matsui, S. Nunomura, K. Matsubara, Impact of
intrinsic amorphous silicon bilayers in silicon heterojunction solar cells, J. Appl.
Phys. 124 (2018) 103102, https://doi.org/10.1063/1.5045155.
[12] Z. Wu, L. Zhang, W. Liu, R. Chen, Z. Li, F. Meng, Z. Liu, Role of hydrogen in
modifying a-Si:H/c-Si interface passivation and band alignment for rear-emitter
silicon heterojunction solar cells, J. Mater. Sci. Mater. Electron. 31 (2020)
9468–9474, https://doi.org/10.1007/s10854-020-03486-5.
[13] S.N. Granata, T. Bearda, F. Dross, I. Gordon, J. Poortmans, R. Mertens, Effect of an
in-situ H$_2$ plasma pretreatment on the minority carrier lifetime of a-Si:H(i)
passivated crystalline silicon, Energy Procedia 27 (2012) 412–418, https://doi.
org/10.1016/j.egypro.2012.07.086.
[14] J. Geissbühler, S. De Wolf, B. Demaurex, J.P. Seif, D.T.L. Alexander, L. Barraud,
C. Ballif, Amorphous/crystalline silicon interface defects induced by hydrogen
plasma treatments, Appl. Phys. Lett. 102 (2013) 231604, https://doi.org/10.1063/
1.4811253.
[15] J. Schüttauf, C. van der Werf, W. van Sark, J.K. Rath, R. Schropp, Comparison of
surface passivation of crystalline silicon by a-Si:H with and without atomic
hydrogen treatment using hot-wire chemical vapor deposition, Thin Solid Films
519 (2011) 4476–4478, https://doi.org/10.1016/j.tsf.2011.01.319.
[16] A. Descoeudres, L. Barraud, S. De Wolf, B. Strahm, D. Lachenal, C. Guérin, Z.
C. Holman, F. Zicarelli, B. Demaurex, J. Seif, J. Holovsky, C. Ballif, Improved
amorphous/crystalline silicon interface passivation by hydrogen plasma treatment,
Appl. Phys. Lett. 99 (2011) 123506, https://doi.org/10.1063/1.3641899.
[17] M. Mews, T.F. Schulze, N. Mingirulli, L. Korte, Hydrogen plasma treatments for
passivation of amorphous-crystalline silicon-heterojunctions on surfaces promoting
epitaxy, Appl. Phys. Lett. 102 (2013) 122106, https://doi.org/10.1063/
1.4798292.
[18] C. Luderer, C. Messmer, M. Hermle, M. Bivour, Transport losses at the TCO/a-Si:H/
c-Si heterojunction: influence of different layers and annealing, IEEE J.
Photovoltaics 10 (2020) 952–958, https://doi.org/10.1109/
JPHOTOV.2020.2983989.
[19] C. Luderer, L. Tutsch, C. Messmer, M. Hermle, M. Bivour, Influence of TCO and a-
Si:H doping on SHJ contact resistivity, IEEE J. Photovoltaics 11 (2021) 329–336,
https://doi.org/10.1109/JPHOTOV.2021.3051206.
[20] M.H. Brodsky, M. Cardona, J.J. Cuomo, Infrared and Raman spectra of the silicon-
hydrogen bonds in amorphous silicon prepared by glow discharge and sputtering,
Phys. Rev. B 16 (1977) 3556–3571, https://doi.org/10.1103/PhysRevB.16.3556.
[21] A.H.M. Smets, W.M.M. Kessels, M.C.M. van de Sanden, Vacancies and voids in
hydrogenated amorphous silicon, Appl. Phys. Lett. 82 (2003) 1547–1549, https://
doi.org/10.1063/1.1559657.
[22] J. Mouro, A. Gualdino, V. Chu, J.P. Conde, Microstructure factor and mechanical
and electronic properties of hydrogenated amorphous and nanocrystalline silicon
thin-films for microelectromechanical systems applications, J. Appl. Phys. 114
(2013) 184905, https://doi.org/10.1063/1.4829020.
[23] A.A. Langford, M.L. Fleet, B.P. Nelson, W.A. Lanford, N. Maley, Infrared absorption
strength and hydrogen content of hydrogenated amorphous silicon, Phys. Rev. B 45
(1992) 13367–13377, https://doi.org/10.1103/PhysRevB.45.13367.
[24] A. Matsuda, Thin-film silicon –growth process and solar cell application, Jpn. J.
Appl. Phys. 43 (2004) 7909–7920, https://doi.org/10.1143/JJAP.43.7909.
[25] W. Liu, L. Zhang, X. Yang, J. Shi, L. Yan, L. Xu, Z. Wu, R. Chen, J. Peng, J. Kang,
K. Wang, F. Meng, S. De Wolf, Z. Liu, Damp-heat-stable, high-efficiency, industrial-
size silicon heterojunction solar cells, Joule 4 (2020) 913–927, https://doi.org/
10.1016/j.joule.2020.03.003.
Solar Energy Materials and Solar Cells 238 (2022) 111412
[26] A. Fontcuberta i Morral, P. Roca i Cabarrocas, Etching and hydrogen diffusion
mechanisms during a hydrogen plasma treatment of silicon thin films, J. Non-
Cryst. Solids 299-302 (2002) 196–200, https://doi.org/10.1016/S0022-3093(01)
01001-8.
[27] M. Hermle, F. Feldmann, M. Bivour, J.C. Goldschmidt, S.W. Glunz, Passivating
contacts and tandem concepts: approaches for the highest silicon-based solar cell
efficiencies, Appl. Phys. Rev. 7 (2020) 21305, https://doi.org/10.1063/
1.5139202.
[28] C. Messmer, M. Bivour, J. Schön, M. Hermle, Requirements for efficient hole
extraction in transition metal oxide-based silicon heterojunction solar cells,
J. Appl. Phys. 124 (2018) 85702, https://doi.org/10.1063/1.5045250.
[29] M. Bivour, C. Messmer, L. Neusel, F. Zähringer, J. Schön, S.W. Glunz, M. Hermle,
Principles of carrier-selective contacts based on induced junctions, in: Proc. 33rd
Eur. Photovolt. Sol. Energy Conf, . Exhib., Amsterdam, The Netherlands, 2017,
pp. 348–352.
[30] C. Leendertz, Effizienzlimitierende Rekombinationsprozesse in amorph/
kristallinen und polykristallinen Siliziumsolarzellen. Dissertation, Technische
Universität Berlin, Berlin, 2012.
[31] C. Leendertz, N. Mingirulli, T.F. Schulze, J.P. Kleider, B. Rech, L. Korte, Discerning
passivation mechanisms at a-Si:H/c-Si interfaces by means of photoconductance
measurements, Appl. Phys. Lett. 98 (2011) 202108, https://doi.org/10.1063/
1.3590254.
[32] L. Neusel, M. Bivour, M. Hermle, Selectivity issues of MoO x based hole contacts,
Energy Procedia 124 (2017) 425–434, https://doi.org/10.1016/j.
egypro.2017.09.268.
[33] K. Heilig, Determination of surface properties by means of large signal
photovoltage pulses and the influence of trapping, Surf. Sci. 44 (1974) 421–437,
https://doi.org/10.1016/0039-6028(74)90128-9.
[34] T.F. Schulze, L. Korte, E. Conrad, M. Schmidt, B. Rech, Electrical transport
mechanisms in a-Si:H/c-Si heterojunction solar cells, J. Appl. Phys. 107 (2010)
23711, https://doi.org/10.1063/1.3267316.
[35] S. De Wolf, M. Kondo, Boron-doped a-Si:H/c-Si interface passivation: degradation
mechanism, Appl. Phys. Lett. 91 (2007) 112109, https://doi.org/10.1063/
1.2783972.
[36] T.F. Schulze, H.N. Beushausen, C. Leendertz, A. Dobrich, B. Rech, L. Korte,
Interplay of amorphous silicon disorder and hydrogen content with interface
defects in amorphous/crystalline silicon heterojunctions, Appl. Phys. Lett. 96
(2010) 252102, https://doi.org/10.1063/1.3455900.
[37] W.E. Spear, P.G. Le Comber, Substitutional doping of amorphous silicon, Solid
State Commun. 17 (1975) 1193–1196, https://doi.org/10.1016/0038-1098(75)
90284-7.
[38] R.A. Street, Trapping parameters of dangling bonds in hydrogenated amorphous
silicon, Appl. Phys. Lett. 41 (1982) 1060–1062, https://doi.org/10.1063/1.93400.
[39] M. Bivour, Silicon Heterojunction Solar Cells: Analysis and Basic Understanding,
Fraunhofer Verlag, Stuttgart, 2015.
[40] S. Sriraman, S. Agarwal, E.S. Aydil, D. Maroudas, Mechanism of hydrogen-induced
crystallization of amorphous silicon, Nature 418 (2002) 62–65, https://doi.org/
10.1038/nature00866.
[41] T.F. Schulze, L. Korte, F. Ruske, B. Rech, Band lineup in amorphous/crystalline
silicon heterojunctions and the impact of hydrogen microstructure and topological
disorder, Phys. Rev. B 83 (2011) 554, https://doi.org/10.1103/
PhysRevB.83.165314.
[42] P. Procel, H. Xu, A. Saez, C. Ruiz-Tobon, L. Mazzarella, Y. Zhao, C. Han, G. Yang,
M. Zeman, O. Isabella, The role of heterointerfaces and subgap energy states on
transport mechanisms in silicon heterojunction solar cells, Prog. Photovoltaics Res.
Appl. 28 (2020) 935–945, https://doi.org/10.1002/pip.3300.
[43] G.E. Jellison, F.A. Modine, Parameterization of the optical functions of amorphous
materials in the interband region, Appl. Phys. Lett. 69 (1996) 371–373, https://
doi.org/10.1063/1.118064.