PERSPECTIVE

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Silicon Heterojunction Solar Cells and p-type Crystalline

Silicon Wafers: A Historical Perspective
Bruno Vicari Stefani,* Matthew Wright, Anastasia Soeriyadi, Daniel Chen,
Moonyong Kim, Brendan Wright, Dmitriy Andronikov, Ilya Nyapshaev,
Sergey Abolmasov, Gregory Wilson, and Brett Hallam

c-Si and it can be easily doped (either p-

The first reports of both boron–oxygen (BO)-related light-induced degradation or n-type)[1] allowing the fabrication of elec-
(BO-LID) and amorphous/crystalline silicon heterojunction (SHJ) solar cell fab- tronic heterojunctions.[2]
rication date back to the early 1970s. However, the complete development of the The first reports of a-Si:H/c-Si hetero-
junctions date back to the early 1970s,
“modern” SHJ structure took place well before BO defect stabilization processes
when junctions were prepared by deposit-
were developed. Due to the susceptibility of p-type Czochralski (Cz)-grown silicon ing a-Si:H layers on both sides of a p-type
to BO-LID, such wafers were deemed unsuitable for SHJ solar cells. In addition to c-Si wafer[3] and were found to passivate
stability issues, lower charge carrier lifetimes due to contamination and challenges c-Si surfaces exceptionally well.[4] At that
with surface passivation posed barriers to the adoption of p-type wafers in SHJ time, it was only recently discovered that
applications. Herein, these three key challenges are discussed in detail. Kinetic homojunction solar cells fabricated with
p-type c-Si wafers were susceptible to a
modeling and experimental results reveal the severe impact of BO-LID in p-type
novel light-induced degradation (LID)
SHJ solar cells and provide possible explanations as to why earlier attempts using mechanism.[5] In their report, Fischer
p-type wafers might have failed. The role of gettering and advanced hydrogenation and Pschunder observed a 3–5%rel reduc-
in stabilizing BO defects in SHJ solar cells is demonstrated experimentally. Finally, tion in the conversion efficiency of these
a summary of the effective surface recombination velocities reported in the lit- cells during a 12 hour light-soaking test,
erature for hydrogenated intrinsic amorphous silicon passivation of p- and n-type which was found to be caused by a reduc-
tion in charge carrier lifetime.[5]
crystalline silicon wafers is presented. Based on these findings, the potential of
During the following decade, the first
p-type wafers to enable a next-generation of high-efficiency solar cells featuring a-Si:H/c-Si SHJ solar cell was fabricated
carrier-selective contacts is discussed. by Sanyo.[6] This cell was formed by
depositing a thin layer of B-doped a-Si:H
(a-Si:H(p)) on the front side of an n-type
c-Si wafer via plasma-enhanced chemical
A silicon heterojunction (SHJ) solar cell is formed by a crystalline vapor deposition (PECVD). A transparent conductive oxide
silicon (c-Si) wafer sandwiched between two wide bandgap (TCO) layer was used to form the front contact and aluminum
layers, which serve as carrier-selective contacts. For c-Si SHJ (Al) was deposited directly onto the c-Si to form the back contact.
solar cells, hydrogenated amorphous silicon (a-Si:H) films are This relatively simple structure (illustrated in Figure 1) yielded a
particularly interesting materials to form these carrier-selective conversion efficiency of 12.3% and a modest FF of
74%. In the
contacts. This is because the bandgap of a-Si:H is larger than quest to improve FF, an intrinsic a-Si:H (a-Si:H(i)) layer was

B. Vicari Stefani, G. Wilson M. Wright

CSIRO Energy Department of Materials
Newcastle Energy Centre University of Oxford
10 Murray Dwyer Circuit, Mayfield West, NSW 2304, Australia Oxford OX1 3PH, UK
E-mail: bruno.vicaristefani@csiro.au
A. Soeriyadi, M. Kim, B. Wright, B. Hallam
The ORCID identification number(s) for the author(s) of this article School of Photovoltaics and Renewable Energy Engineering
can be found under https://doi.org/10.1002/solr.202200449. UNSW
Sydney, NSW 2052, Australia
© 2022 Commonwealth Scientific and Industrial Research Organisation.
Solar RRL published by Wiley-VCH GmbH. This is an open access article D. Chen
under the terms of the Creative Commons Attribution-NonCommercial- Sundrive Solar Pty Ltd
NoDerivs License, which permits use and distribution in any medium, Kirrawee, NSW 2232, Australia
provided the original work is properly cited, the use is non-commercial
and no modifications or adaptations are made. D. Andronikov, I. Nyapshaev, S. Abolmasov
R&D Center of Thin Film Technologies in Energetics Hevel Solar
DOI: 10.1002/solr.202200449 St. Petersburg 194064, Russia

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Figure 1. Evolution of the silicon heterojunction (SHJ) solar cell structure over the years.
deposited underneath the front emitter.[7] While successful
in improving the FF, the most exciting gains were observed
in VOC and conversion efficiency of 14.5% was recorded.
Meanwhile, little was known about the defect responsible for
the LID phenomenon affecting p-type silicon wafers. Several
theories were proposed to explain it, which attributed the
observed degradation to complexes of: lattice defects with
silver,[8] vacancies with gold,[9] and iron with boron.[10]
The early 1990s marked another major step in the develop-
ment of SHJ solar cells. Textured c-Si wafers were used and
an additional phosphorus-doped (P-doped) a-Si:H (a-Si:H(n))
layer was formed underneath the back contact to provide a back
surface field (BSF), significantly increasing the SHJ solar cell
conversion efficiency to 18.1%.[7] In parallel, the understanding
of the LID phenomenon in p-type silicon was also advancing.
However, it was not until the mid–late 1990s that the involve-
ment of pairs of boron (introduced as the dopant atoms) and oxy-
gen (introduced in large concentrations during crystal growth via
the Czochralski (Cz) process) in the degradation mechanism was
discovered.[11] In the mid–late 1990s, only a few key characteris-
tics of the defect were known, including the reversible nature
during annealing at temperatures above
200 °C and the ability
to trigger degradation both via illumination and current injection
in the dark.[11,12]
It is important to highlight that at that point in time, p-type
float-zone silicon (FZ-Si) wafers and Cz-Si wafers doped with
gallium (p-type) or phosphorus (n-type) were already known
not to be affected by this defect, which will hereafter be referred
to as the boron–oxygen (BO) defect. On a side note, it was later
(
2009) discovered that gallium- or phosphorus-doped Cz-Si
wafers can be susceptible to BO defects if they are co-doped with
large concentrations of boron.[13–15]
During the late 1990s, electronic properties of the defect were
first reported and the relationship between the concentrations of
boron and interstitial oxygen and the BO defect were further
explored.[16,17] In 1999, Glunz et al. reported conversion effi-
ciency losses of up to 1.7%abs on p-type Cz-Si homojunction solar
cells with a starting conversion efficiency of 21.0%.[18] In their
report, solar cells processed in parallel with p-type gallium-doped
(Ga-doped) Cz-Si wafers exhibited a record stable conversion
efficiency of 22.5%. Yet, a patent application regarding gallium
doping for silicon wafers was filed in that same year, creating a
barrier to the use of gallium as the dopant agent for p-silicon c-Si
wafer manufacturing.[19]
While key properties of the BO defect were being unraveled,
Sanyo was progressing with the development of their novel SHJ
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solar cell technology based on BO-free n-type wafers. In the fol-
lowing year (2000), the latest chapter in the history of the classical
SHJ solar cell development took place. An a-Si:H(i) layer was also
included between the c-Si wafer and the a-Si:H(n) at the back.
This allowed a significant improvement in the rear-side passiv-
ation of the cell, while still maintaining the BSF properties.
Finally, a TCO layer was used to improve the lateral conduction
of carriers and to serve as an anti-reflection coating (ARC) on
both sides of the solar cell. This was followed by metallization
for contact formation also on both sides of the solar cell. It is
not clear which materials were used for both TCO and
metallization as this structure (known as Heterojunction with
Intrinsic Thin-layer, HIT) was patented by Sanyo. Nevertheless,
these improvements resulted in a conversion efficiency of 20.1%
and a remarkably high VOC > 700 mV at that time.[20]
This VOC value was at the same level as the record VOC for a
single-junction silicon solar cell, which was 706 mV (UNSW pas-
sivated emitter with rear locally diffused cell).[21] In their report,
Taguchi et al. noted that their novel SHJ structure was not
affected by BO defects, since it was based on n-type Cz-Si wafers.
Later in 2000, Sakata et al. (Sanyo) reported a record VOC of
719 mV for a large-area (100 cm2) SHJ solar cell, which corre-
sponded to a conversion efficiency of 20.7%.[22]
From a stability point of view, the use of such wafers for solar
cell fabrication was certainly advantageous. Switching to other
silicon wafer types (like n-type) was the only practical solution
to avoid the negative impact of BO defects on solar cell perfor-
mance, as pathways for BO defect stabilization were still far from
being developed. Interestingly, to the authors’ knowledge, there
are no reports of experimentation involving other wafer types
(such as p-type Cz-Si) for SHJ applications dating back to
1990–2000. Either other wafer types were not considered and
tested, or the results from such attempts were judged not rele-
vant to be reported. Still, in 2000 homojunction solar cells based
on p-type B-doped FZ-Si and magnetically confined Cz-Si wafers
(which were also not susceptible to BO defects) were approaching
record conversion efficiencies of 25% with VOC values also above
700 mV.[23]
In the early 2000s, the understanding of the metastable BO
defect was greatly improved. Work from Bothe et al. indicated
that the defect was composed of one substitutional boron atom
and two interstitial oxygen atoms.[24] The kinetics of BO-related
LID were being explored[25,26] and the first wafer-level mitigation
strategies were developed.[27–30] These defect engineering strate-
gies were based on thermal processing, including phosphorus
diffusion, thermal oxidation, and rapid thermal processing.
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This was particularly interesting because these types of processes
were already naturally incorporated in homojunction solar cell
fabrication sequences (e.g., during emitter formation, surface
passivation, and firing). Yet, this purely thermal route was not
sufficient to completely suppress the formation of BO defects
and was only able to reduce the total defect concentration by a
factor of
3.[29] It is important to highlight that these benefits
are not naturally observed in the standard SHJ fabrication
sequence due to the low-temperature regime used.[31] The
low-temperature processing of SHJ solar cells is commonly per-
ceived as a benefit, as high-temperature processes have the
potential to impact silicon’s bulk lifetime negatively.[32,33]
In 2006, the complete stabilization of BO defects in a finished
homojunction solar cell was first demonstrated by Herguth
et al.[34] In their study, cells that were pre-degraded (i.e., BO
defects were formed under illumination) were annealed under
illumination until the VOC was completely recovered. This pro-
cess is often referred to as either regeneration, hydrogen passiv-
ation, permanent deactivation, or stabilization. The latter will be
used in this article as it reflects the key feature of the transition,
which is stability under illumination and temperature.[35] While
the processing conditions used to stabilize BO defects were not
disclosed by Herguth et al. in their 2006 article, the impact of
temperature and carrier injection are now well understood.[35,36]
Furthermore, it is now well understood that the presence of
hydrogen in the c-Si bulk is required for the effective stabilization
of BO defects.[37–39] Despite the first instance of BO defect sta-
bilization dating back to 2006, it was not until the following
decade that the development of accelerated stabilization pro-
cesses suitable for commercial production became available.
The development of fast-stabilization processes for BO defects
was based on excess carrier generation via high-intensity
illumination at elevated temperatures. This allows the control
of hydrogen charge states to maximize hydrogen diffusivity
and passivate BO defects.[40] These approaches allowed the
complete stabilization of BO-LID in <10 s.[41,42]
Interestingly, Wright et al. recently reported defect-engineering
processes based on high-intensity illumination at elevated temper-
atures to impact industrial n-type SHJ solar cells’ conversion
efficiency positively.[43] The conversion efficiency gains during
illuminated annealing of SHJ solar cells are thought to be related
to an improvement in both surface passivation and charge trans-
port under illumination, which results in increased VOC and FF
values.[43–46] A pilot study with n-type SHJ solar cells sourced from
six manufacturers found illuminated annealing to increase the
conversion efficiency of cells sourced from all manufacturers,
albeit the magnitude of the improvement was variable.[47] The
same approach was also shown to improve the conversion effi-
ciency of p-type SHJ solar cells based on p-type silicon wafers
not affected by BO defects, such as Ga-doped Cz-Si[48] and
multicrystalline silicon.[49] Together, these results illustrate how
the knowledge acquired developing stabilization processes for
BO defects in homojunction silicon solar cells also benefited
the SHJ technology.
This is particularly interesting as similar illuminated anneal-
ing processes can improve the conversion efficiency of both
homo and heterojunction solar cells despite treating different
defects. This is related to the temperature requirements of each
process. The completeness of the BO defect stabilization reaction
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reduces when the stabilization process temperature increases.[50]
Wilking et al. demonstrated an increase in the residual active BO
defect concentration for illuminated annealing temperatures
above 250 °C[51] (for an illumination intensity equivalent to
2.7 suns). Interestingly, SHJ solar cell fabrication commonly
utilizes a temperature ceiling of 250 °C to avoid potential loss
of hydrogen from the amorphous silicon films.[2] In our recent
work, we verified that higher illuminated annealing tempera-
tures accelerate the conversion efficiency gains in SHJ solar
cells.[52] Hence, realizing illuminated annealing of SHJ solar cells
at the maximum tolerable temperature facilitates shorter process-
ing times (important for high-throughput processing in indus-
trial environments). As such, a similar temperature regime of

200–
300 °C can be used for BO-LID stabilization and illumi-
nated annealing of SHJ solar cells. However, each process’s
illumination intensity and duration might vary.
Here, it is important to highlight the most important point of
this perspective article. The first instance of BO defect stabiliza-
tion in literature dates to 2006. By that time, the development of
the SHJ solar cell structure was already well defined. In fact,
industrial SHJ solar cells commercialized today are very similar
to the device designed by Sanyo in the 1990s. Despite the junc-
tion being shifted to the rear of the device to reduce restrictions
on the front TCO optoelectrical properties[53] and the use of alter-
native carrier-selective contacts (micro- and nano-crystalline
silicon[54–56]) and TCO materials[57,58] by some researchers and
manufacturers, the foundation of the SHJ structure is essentially
the same. This includes the absorber material, which has always
been an n-type Cz-Si wafer. It is, therefore, possible to speculate
that the (relatively) poor understanding of BO-related LID back
then was the major barrier preventing to use of p-type c-Si wafers
in the development of the SHJ technology. The lack of under-
standing about BO defect stabilization during the development
of SHJ technology may be the main reason why the development
process was restricted to n-type c-Si wafers, and if BO defect
stabilization processes were readily available at the time, the tech-
nology could have been developed based on p-type c-Si wafers.
In their 2012 review article (to which the reader is strongly
encouraged to refer), De Wolf et al. outlined the three main rea-
sons why n-type Cz-Si wafers were the material of choice for SHJ
solar cell fabrication.[2] In the following sections, these reasons
will be directly addressed in the context of the significant
advances in understanding the impacts and solutions of defects
in p-type wafers.
1. The Negative Impact of Metallic Impurities on
Cell Performance
The first disadvantage associated with p-type silicon was
attributed to most transition metal point defects having larger
electron-than hole-capture cross-sections, which results in lower
lifetimes for p-type silicon for the same impurity concentra-
tion.[59] Yet, while p-type silicon is more sensitive to contamina-
tion by interstitial iron (Fei),[60] more recent work from Schmidt
et al. concluded that n-type silicon is more susceptible to contam-
ination by other metallic impurities, including copper, cobalt,
chromium, and nickel.[61] Nevertheless, small concentrations
of Fei can result in significant conversion efficiency losses in
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p-type silicon-based solar cells.[59] For this reason, minimizing
the detrimental impact of metallic impurities is essential to
enable high VOC values. There are two main pathways to reduce
the concentration of recombination-active metallic impurities in
silicon solar cells. The first approach is to improve the initial
wafer quality. Continuous improvements by wafer manufac-
turers have recently enabled stable VOC values above 730 mV
on SHJ solar cells fabricated with non-treated p-type Cz-Si
wafers.[48,62] The second approach is utilizing dedicated defect
engineering treatments, such as gettering,[63] which is naturally
incorporated in the production of p-type passivated emitter and
rear cell (PERC) solar cells.[31] A pre-fabrication gettering treat-
ment (i.e., applied to the wafers prior to solar cell fabrication)
has elevated the average conversion efficiency of a large batch
of p-type Cz-Si SHJ solar cells to the same level as their n-type
counterparts.[62] Pre-fabrication gettering treatments have also
been shown to increase the conversion efficiency of SHJ solar
cells fabricated with a range of silicon wafer types, including
n-type Cz-Si wafers commonly used in industry.[49,64–66] It is
important to note that these results (and in fact most of the
results on p-type SHJ solar cells) were achieved without
any optimization of the SHJ structure to accommodate
p-type c-Si wafers, and further optimization will likely lead to
performance improvements.[67]
2. Susceptibility of p-type c-Si to LID
As previously discussed, (uncompensated) n-type c-Si wafers
display a significant intrinsic advantage over their p-type counter-
parts due to the inherent susceptibility of p-type B-doped Cz-Si to
BO-LID. BO defects are meta-stable, and the transitions between
the different defect states can be explained through a multiple
states model. The first model featured three distinct defect states
and was proposed by Herguth et al.[34] and is sufficient to explain
the behavior of the BO defects under operational conditions.[68]
In the degraded state, the lifetime is limited by the recombina-
tion-active BO defects and is stable under illumination at room
Figure 2. Schematic illustrating the boron–oxygen (BO) defect states and the possible state transitions.
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temperature. Since it is recombination-active, this state limits the
performance of p-type Cz silicon solar cells. The degraded state
lifetime can be completely recovered by a low-temperature
annealing in the dark.[11] This is referred to as the annealed state,
where BO defects are recombination-inactive but unstable under
carrier injection. When subjected to carrier injection under
elevated temperatures, BO defects can be transferred to the
stabilized state. In this state, the defects are recombination-
inactive and stable under carrier injection. The total concentra-
tion of BO defects is equal to the sum of the concentration of
defects in the annealed, degraded, and stabilized states.
However, the concentration of BO defect precursors can also
be thermally modulated.[69,70] Based on this key characteristic
of the defect, a revised model incorporating the existence of a
fourth state has been proposed, which is referred to as a
reservoir.[36,70] The transitions between all states are depicted
in Figure 2.
BO defects form easily under illumination for any light capable
of generating excess carriers in the bulk and under carrier injection
in the dark.[12,71] The lifetime decay due to BO defects is observed
to occur in two stages. This is attributed to the formation of fast-
and slow-recombination centers (FRC and SRC, respectively) and it
is commonly referred to as fast and slow degradation.[35,72] The two
stages take place on a different time scale.[25] In commercial-grade
p-type B-doped Cz-Si (with [B]
1  1016 cm3), the fast degrada-
tion occurs within the first few minutes, followed by a slower deg-
radation, which occurs over several hours at room temperature.[35]
When these c-Si wafers are used to fabricate PERC solar
cells, a fraction of the total BO defect precursor concentration
inherently present in the wafers is thermally annihilated during
high-temperature solar cell processing.[30] Processes such as phos-
phorus diffusion for emitter formation,[27] thermal oxidation,[30]
and firing[70] are effective in thermally annihilating a fraction of
BO defects present in the silicon wafers. Therefore, the extent
of BO-LID experienced by cells that undergo such processes is
greatly reduced, in comparison to non-thermally processed silicon
wafers. Yet, commercial PERC solar cells with starting VOC of
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670 mV can experience losses of
20 mV due to the formation of
BO defects. From an industrial perspective, Fertig et al. reported
conversion efficiency losses of up to 5%rel related to BO-LID in
PERC solar cells.[73]
In the context of SHJ solar cells, the impact of BO-LID on solar
cell performance is exacerbated by the excellent surface passiv-
ation provided by the a-Si:H films, with conversion efficiency
losses over 14%rel reported.[74] Additionally, the absence of ther-
mal annihilation of BO defect precursors during fabrication
means that finished p-type SHJ solar cells will have a larger con-
centration of BO defect precursors than PERC solar cells.
Here, we experimentally demonstrate the impact of these two
factors (i.e., excellent surface passivation and absence of BO
defect annihilation) in p-type SHJ solar cells. For this purpose,
Hevel Solar fabricated SHJ solar cells using commercial-grade
p-type Cz-Si wafers with base resistivity (ρ) of 0.8 Ω cm that
did not undergo any additional defect-engineering process.
Figure 3 shows the VOC as a function of a time under the illu-
mination of a p-type SHJ solar cell directly after dark annealing
(200 °C for 600 s). The VOC was monitored in situ using a Sinton
ELITE Suns-VOC tool.[75] The sample was kept immobile during
testing to avoid potential damage to the passivation quality
caused by sample handling. We note that the VOC reported
for stability testing in this section were extracted from Suns-
VOC measurements at an illumination intensity equivalent to
0.9 suns due to a limitation of the tool.
Surprisingly, a VOC drop of
30 mV after just 10 s is observed
under an illumination intensity equivalent to 0.1 suns for the
solar cells with a starting VOC of 724 mV. Since at this illumina-
tion intensity Δn << NA, the rate of degradation is determined
by NA (i.e., by the boron doping concentration), and would be
similar even under milder illumination intensities at a given tem-
perature.[71] It is expected that all BO defects are recombination
inactive but unstable at the end of the SHJ solar cell fabrication,
since the conditions used for the curing process (dark annealing
at >200 °C for >20 min) are sufficient to transfer BO defects to
the unstable dark-annealed state.[76] Consequently, 10 s of acci-
dental exposure to light between curing and the characterization
of the finished solar cell is sufficient to yield poor VOC well below
Figure 3. Open-circuit voltage (VOC) measured (orange circles) and
modeled (blue line) of a p-type SHJ solar cell as a function of time under
illumination (0.1 suns, 25 °C). VOC was extracted at 0.9 suns due to a limi-
tation of the tool.
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700 mV in devices with a starting VOC of 724 mV. This significant
loss in VOC under low illumination conditions illustrates the
inherent susceptibility to BO-LID of SHJ solar cells fabricated
with commercial-grade p-type Cz-Si wafers.
In the following paragraphs, we perform kinetic modeling to
complement these experimental results and investigate the
impact of boron-dopant concentration, which determines ρ, on
the impact of BO-LID in p-type SHJ solar cells. The modeling
can provide insights into the possible outcomes of past and
future attempts to fabricate SHJ solar cells with commercial-
grade p-type Cz-Si wafers.
In short, the modeling is based on the single defect theory[77]
and a Python-based ordinary differential equation solver is
used for the kinetic modeling simulation. Degradation rates
based on the values reported by Bothe et al. and Glunz et al.
at 300 K for NA = 2  1016 cm3 were used: 1.66  101 s1
and 1.05  104 s1 for fast and slow degradation, respec-
tively.[25,29] Defect annihilation rates were assumed to be zero
since these are negligible at 300 K.[25] The initial concentration
ratio of the precursor states for fast and slow degradation based
on the values reported by Kim et al. for a dark annealing condi-
tion of 200 °C for 600 s was used.[78] The lifetime limitation due
to a two-level defect from Murphy et al. and adapted by Niewelt
et al. to account for the unknown carrier capture cross sections of
BO defects is used together with the parameterization from
Hallam et al.[79–81] The changes in the injection-dependent effec-
tive lifetime were then modeled to determine the changes in VOC
as a function of BO-related degradation. Four different lifetime
components were used to model the effective lifetime during
degradation: the first corresponding to the lifetime limitation
due to BO defects obtained via the kinetic modeling; the second
representing intrinsic recombination in silicon;[82] the third rep-
resenting surface-related recombination;[83] the fourth represent-
ing all other SRH-related recombination mechanisms present in
the sample. Only the first-lifetime component was varied as a
function of BO defect formation based on the kinetic modeling,
while the last three lifetime components were fixed. The excess
carrier concentration () was determined by multiplying the effec-
tive lifetime by the generation rate. by The VOC at each given
stage was calculated based on the following equation
ΔnN A þ Δn
V OC ¼ kT=q ln (1)
ni2
where ni is the intrinsic carrier concentration, q is the elementary
charge, NA is the acceptor dopant concentration, k is the
Boltzmann constant, and T is the temperature. The model dis-
plays good agreement with the experimental data (see Figure 3)
and is then used to estimate the different degradation scenarios
for p-type SHJ solar cells fabricated with c-Si wafers of different
NA, based on the known relationship between defect generation
rates (Rdeg), total defect concentration (Nt), substitutional boron
concentration ([BS]) and NA[35]
N t ∝ ½BS  ∝ N A (2)
Rdeg ∝ ρillum 2 ∝ N A 2 (3)
It is assumed that all other wafer properties are the same
(e.g., [Oi]), Rdeg and Nt change exclusively due to changes in
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NA (i.e., Δn << NA), and only BO defects are limiting the bulk
lifetime of the samples. It is important to note here that knowing
the exact [Oi] is not required for the modeling. That is possible
because the Nt for each ρ (∝ NA) is calculated relative to the exper-
imentally determined Nt (for NA
2  1016 cm3) based on the
relationship expressed in Equation (2). The surface passivation
quality was represented by a total J0e of 6 fA cm2 and the wafer
thickness was set to 140 μm. The ρ for uncompensated p-type Cz-
Si varied from 0.5 to 14 Ω cm. The resulting 1 sun VOC as a func-
tion of time for the different ρ (∝ NA) scenarios is depicted in
Figure 4.
The modeling results provide an insight into the expected VOC
losses experienced by p-type SHJ solar cells if c-Si wafers of dif-
ferent ρ are used. If c-Si wafers commonly used for the fabrica-
tion of PERC solar cells are used (ρ
0.5–1.8 Ω cm), VOC losses
between 43 and 2 mV could take place under just 10 s under illu-
mination at room temperature for cells with starting VOC of
731–737 mV. This would correspond to VOC losses of
101–72 mV on a long-time scale when BO defects are fully
formed. However, this can be greatly reduced if c-Si wafers with
lower NA are used. In the resistivity range (8–14 Ω cm) reported
by Descoeudres et al. for non-gettered c-Si wafers, the total VOC
losses would be reduced to 22–11 mV.[62] Additionally, the
degradation kinetics are slower for lower NA values, meaning
accidental light exposure will affect such cells even less than
higher doping concentrations.
This result helps to understand the impact of BO defects in the
early work on SHJ solar cells fabricated with p-type B-doped
Cz-Si wafers. If commercial-grade c-Si wafers were used to fab-
ricate SHJ solar cells, the severity of BO-related degradation
would impact the conclusions regarding the potential of such
wafers of achieving the VOC required by SHJ solar cells, if care
was not taken to prevent any unwanted light-exposure prior
(and during) solar cell characterization.
Fortunately, the continuous efforts in solving BO defects in
PERC solar cells over the past two decades provide us with
the knowledge required to defect engineer p-type SHJ solar cells
and fabricate devices with high and stable VOC s. Here, we exper-
imentally show the role of gettering and advanced hydrogenation
Figure 4. Modeled 1 sun VOC of SHJ solar cells fabricated with p-type Cz-Si
wafers of varied ρ (∝ NA), as a function of time as BO defects are gener-
ated under carrier-injection (for Δn << NA). The numbers inline indicate
the corresponding ρ value.
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in stabilizing BO defects in p-type SHJ solar cells. For this experi-
ment, Hevel Solar fabricated p-type SHJ solar cells with p-type
Cz-Si wafers that underwent a pre-fabrication phosphorus diffu-
sion process typically used in PERC solar cells (herein referred to
as gettered), and control p-type Cz-Si wafers that did not undergo
any fabrication processes. Both control and gettered wafers had a
resistivity of 0.8 Ω cm.
Figure 5 shows the VOC as a function of time during light-
soaking for SHJ solar cells fabricated with commercial-grade
p-type Cz-Si wafers that underwent different defect-engineering
processes prior to light-soaking. Despite the control and gettered
samples displaying similar starting VOC (measured after
dark annealing) of 724 and 725 mV, respectively, gettering
significantly reduces the extent of degradation. After 10 s of
light-soaking, a VOC drop of
2.4 mV was recorded for the get-
tered sample, while the VOC losses in the control sample
exceeded 30 mV as previously discussed. After complete forma-
tion of BO defects (i.e., when VOC stabilizes, in this case after
light soaking for >105 s) the total VOC degradation is reduced
from
100 (control) to
60 mV (gettered). Yet, this level of
degradation is unacceptable for manufacturing.
As previously discussed, bulk hydrogen is required for the
stabilization of BO defects on finished devices. This poses a
challenge to the stabilization of BO defects in p-type SHJ solar
cells since hydrogenation via SiNX:H deposition and firing does
not take place in the SHJ fabrication sequence. However, recent
results showed that the SHJ fabrication sequence can introduce
similar amounts of hydrogen into the bulk of the wafer,[84,85]
resulting in stable VOC over 734 mV on p-type Cz-Si wafers after
a post-fabrication advanced hydrogenation process (AHP).[74]
Here, we experimentally demonstrate the stabilization of BO
defects in SHJ solar cells fabricated with commercial-grade
p-type Cz-Si wafers. More specifically, the complementary nature
of gettering and AHP is evidenced. During AHP, illumination
generates excess carriers that are used to manipulate the hydro-
gen already existing in the solar cell.[40] A continuous-wave laser
with a wavelength of 980 nm was used to illuminate the whole
solar cell area simultaneously for a period of 30 s with an
Figure 5. VOC as a function of time under illumination (0.1 suns, 25 °C) of
p-type SHJ solar cells that underwent different defect engineering pro-
cesses. The open-circuit voltage (VOC) was extracted at an illumination
intensity of 0.9 suns due to a limitation of the tool.
www.advancedsciencenews.com
illumination intensity of 55 kW m2 (equivalent to
100 suns in
terms of illumination intensity at 980 nm). During the process,
solar cells were heated on a hot plate with a temperature of
200 °C. During AHP, the solar cell’s temperature was monitored
with an infrared thermometer, and a peak temperature of 255 °C
was recorded at 30 s under illumination.
The effective BO defect concentration (denoted N*BO) was
calculated to quantify the effectiveness of the AHP process in
stabilizing BO defects. The N*BO, in units of an inverse lifetime,
has served as a convention for BO defect studies[35] as it allows
the assessment of N*BO from minority carrier effective lifetime
measurements. The N*BO after LS and after the AHP þ LS was
calculated for each sample using Equation (4)
1 1 1 3. Surface Passivation of p-type c-Si Wafers
N BO ¼ ¼  (4)
τBO τdegraded τannealed
where τBO is the effective lifetime attributed to BO defects,
τannealed is the background effective lifetime after DA and
τdegraded is the effective lifetime after LS.[35] The effective life-
times were extracted from the injection-dependent lifetime
curves obtained from the Suns-VOC measurements at a fixed-
injection level of Δn = 1.4  1014 cm3 to minimize the impact
of small concentrations of Feiþ that could be present in the sam-
ples.[86] It is important to note that a fixed-injection level is used
when determining N*BO to account for any additional lifetime
change due to a reduction in the injection level at a fixed bias.[87]
The percentage of passivated BO defects in each sample was
calculated by taking the ratio between the N*BO on samples after
LS and after the AHP þ LS.
The AHP treatment alone increased the VOC of the previously
degraded sample to 729 mV. Upon subsequent stability testing, a
loss of VOC of
26 mV is observed. This corresponded to the pas-
sivation of
96.7% of BO defects, and a final VOC of 703 mV.
However, the stable VOC was greatly improved with the addition
of gettering. Directly after AHP, the gettered sample exhibited a
VOC of 731 mV. After light-soaking, a VOC loss of only
3 mV is
observed, which translated into a final stable VOC of 728 mV. This
corresponded to the stabilization of
97.2% of BO defects and
illustrates the complementary nature of gettering and hydrogena-
tion via AHP in stabilizing the BO defects in p-type SHJ solar
cells. It is important to note that a similar fraction of the
stabilized BO defects, despite the more significant VOC losses
between control and gettered samples, is caused by an initial
BO defect concentration reduction due to gettering. The similar
fraction of stabilized defects via AHP in both control and gettered
cells indicates that the final stable VOC is highly dependent on the
concentration of remaining defects.
A perhaps more elegant––and timely––solution to the stability
issues associated with p-type SHJ solar cells would be switching
to p-type Cz-Si wafers doped with gallium, which are predicted to
completely replace boron as the dopant agent for p-type c-Si
wafers by 2025.[88] We have recently (July 2021) demonstrated
a stable VOC of 734 mV (and conversion efficiency of 22.6%)
in a p-type Ga-doped SHJ solar cell fabricated in an industrial
environment.[48] More recently (March 2022), two groups
independently reported conversion efficiencies of 24.47%[89]
and 25.47%[90] for p-type Ga-doped SHJ solar cells, highlighting
the potential of this approach.
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Nevertheless, the results presented in this section illustrate
how BO-LID can be mitigated and p-type SHJ solar cells can
be made stable based on knowledge acquired over the past
two decades of research on BO-LID in homojunction solar cells.
It can be speculated that the great sensitivity of SHJ solar
cells fabricated with commercial-grade p-type Cz-Si wafers to
BO-LID could have impacted the conclusions surrounding the
performance of such cells in comparison to their n-type counter-
parts. Perhaps, if the BO defect stabilization process were already
well-established at the time when the core of the SHJ structure
was developed, p-type Cz-Si wafers could have been potential
candidates for the absorber material.
The third drawback of using p-type c-Si wafers in SHJ solar cells
outlined by De Wolf et al. relates to surface passivation.
Particularly, it relates to the fact that surface states (e.g., silicon
dangling bonds) feature a large electron-to-hole capture cross-
section ratio. For this reason, the chemical passivation of p-type
c-Si wafers can be more challenging to achieve in comparison to
n-type c-Si wafers.[91,92] This means that for the same passivation
scheme, the effective surface recombination velocity (Seff ) mea-
sured on a p-type wafer would be higher than that measured on
an n-type wafer (for a similar doping concentration). Improving
surface passivation quality (e.g., reducing Seff ) has been an ongo-
ing effort across all c-Si-based technologies.[93] We have surveyed
the literature and identified Seff values reported for p- and n-type
c-Si wafers passivated with a-Si:H(i) films, with the aim of under-
standing the evolution and status of surface passivation quality
for a-Si:H(i)/c-Si interfaces. A nonexhaustive list of the best Seff
values reported by several authors for a minority carrier density
Δn = 1  1015 cm3 as a function of the time of publication is dis-
played in Figure 6, where results on p-type c-Si wafers are rep-
resented by blue markers and on n-type c-Si wafers by orange
markers. Figure 6––and the accompanying articles––provide
interesting insights into the evolution of the a-Si:H/c-Si technol-
ogy. Initially, it appears that the passivation of p-type c-Si wafers
with a-Si:H(i) films was investigated as a potential approach for
the rear passivation in homojunction devices.[94] This was moti-
vated by the lower temperature regime required for surface pas-
sivation, which reduces both the energy budget and the risk of
bulk silicon contamination.[95] Additionally, a-Si:H(i) passivation
has an intrinsic advantage over SiNX:H for the passivation of
p-type surfaces as it avoids parasitic shunting effects caused
by the fixed positive charge of SiNX:H films.[96]
The Seff values reported over the past two decades show an
improvement in the surface passivation quality of a-Si:H(i) for
both p- and n-type c-Si wafers over time. However, to the authors’
knowledge, there are no recent reports of Seff values for a-Si:H(i)
passivation of p-type c-Si wafers, despite of the impressive Seff of
1 cm s1 reported by Gloger et al. back in 2011.[97] At that point in
time, the Seff values reported for p-type c-Si wafers were at the
same level as the Seff values reported for their n-type counter-
parts. The reason for the apparent reduction in the research out-
put related to a-Si:H(i) passivation of p-type c-Si wafers is unclear.
Yet, it can be speculated that this might be related to the
increased interest on Al2O3 passivation of p-type c-Si wafers,
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Figure 6. Nonexhaustive list of the lowest effective surface recombination velocity (Seff ) values of a-Si:H(i) passivated c-Si wafers reported by several
authors (for a minority carrier density Δn = 1  1015 cm3) as a function of the time of publication. Results on p-type wafers are represented by blue
markers and on n-type wafers by red markers. Open/closed markers represent results on float-zone silicon (FZ-Si)/ Czochralski (Cz)-Si wafers, respec-
tively. This figure is reproduced with data from.[92,94,95,97–105]

which was rapidly increasing in the early 2010s. Al2O3 was found
to be particularly interesting for the passivation of p-type surfaces
due to the built-in negative charge, which provided excellent
field-effect passivation.[106] A search on Scopus for article titles
including the key words “Al2O3” and “silicon” reveals a sharp
increase in the number of publications between 2012 and
2014 (from 10 to 35 publications per year). In contrast, the
continuous development and optimization of a-Si:H(i)
passivation of n-type c-Si wafers have enabled Seff values as
low as 0.3 cm s1 in 2021.[98]
In p-type SHJ solar cells, surface-related recombination
affecting the low-injection range is known to severely limit
the FF of such devices.[74,92,107] This was illustrated by
Descoeudres et al. in 2013, where SHJ solar cells fabricated with
n- and p-type FZ-Si wafers with conversion efficiencies >21%
were compared.[107] In their report, despite both p- and n-type Figure 7. Minority carrier effective lifetime as a function of injection-level
for p- and n-type wafers passivated with inþ and ipþ stacks reported by
devices achieving comparable peak-VOC values the conversion
Descoeudres et al. in 2013 and 2020. The data displayed in this figure
efficiency of the champion p-type SHJ solar cell (21.38%) was
was extracted from.[62,107]
limited by a
1.3%abs lower FF when compared to the champion
n-type device (22.14%). The reduced FF was found to be related
to a reduced minority carrier lifetime in the low-injection range can maintain a high level of passivation upon deposition of
rather than resistive losses. This is illustrated in Figure 7, where the a-Si:H(p) layer were made. Here, it is essential to mention
the injection-dependent minority carrier lifetimes of p- and that n-type SHJ solar cells can also be susceptible to surface-
n-type Fz-Si wafers passivated with inþ and ipþ stacks are dis- related recombination, reducing the lifetime at low injection.
played. It was noted by Descoeudres et al. that the reduction Adachi et al. demonstrated that improving the surface passiv-
in minority carrier lifetime at the low-injection range could ation quality of the a-Si layers can minimize such recombina-
not be explained by bulk recombination, as high-quality FZ-Si tion.[109] These results indicate that overcoming the surface
wafers were used in their experiment. Moreover, they noted that passivation barrier preventing the adoption of p-type c-Si wafers
longer low-injection lifetimes are observed when similar p-type in SHJ solar cells is possible. These results also highlight low Seff
FZ-Si wafers are passivated with Al2O3,[108] which provides fur- values can be achieved via a-Si:H(i) passivation of p-type c-Si
ther evidence that the lower lifetimes at low-injection are related wafers and illustrate that continuous efforts in optimizing such
to recombination at the a-Si:H/c-Si interface. a structure can lead to further reductions in Seff.
However, Descoeudres et al. have recently demonstrated that
this low-injection minority carrier lifetime limiting the perfor-
mance of p-type c-Si can be suppressed. Although no specific 4. Final Thoughts
method was disclosed, the authors noted that improvements
in the silane plasma conditions, hydrogenation of the a-Si: In this perspective article, we first reviewed the history of SHJ
H(i)/c-Si interface, and efforts in ensuring the a-Si:H(i) layer solar cells and BO defects. This helped us to draw a timeline

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of events, which highlighted that the first instance of BO defect
stabilization took place well after the core of the SHJ technology
was already developed. This historical review was followed by a
discussion surrounding the three key barriers preventing the use
of p-type c-Si wafers in SHJ solar cells. It was shown that the
continuous improvements in wafer lifetime, stability, and
surface passivation quality of p-type c-Si have enabled stable
VOC values compatible with the SHJ technology.[48,62,74]
These improvements have recently enabled a record conver-
sion efficiency of 25.47% (VOC of 747.6 mV) for a full-area p-type
SHJ solar cell fabricated with a Ga-doped Cz-Si wafer, with a
remarkably high FF of 83.80%.[90] Descoeudres et al. presented
promising results with p- and n-type SHJ solar cells processed in
parallel with FZ-Si wafers. The p-type SHJ solar cells exhibited a
peak conversion efficiency of 23.76%, while their n-type counter-
parts achieved 24.21%. This small gap (0.45%abs) in conversion
efficiency is interesting as it is close to the target conversion effi-
ciency required to enable the switch from n- to p-type wafers in
SHJ solar cell manufacturing. According to the techno-economic
analysis by Chang et al., based on a wafer premium of 8%, the
conversion efficiency of p-type SHJ solar cells needs to be
within 0.4%abs of n-type SHJ solar cells for the transition to
be cost-effective.[110] It is also important to emphasize another
key result of the work from Descoeudres et al., which was noted
earlier in this article. The conversion efficiency of a large batch of
SHJ solar cells fabricated with p-type (B-doped) and n-type Cz-Si
wafers was at the same level, with the only difference that the
p-type wafers underwent a pre-fabrication gettering treatment.[62]
The conversion efficiencies achieved by p-type c-Si wafers in
other carrier-selective contact technologies, such as TOPCon
solar cells are even more impressive. In such devices, p-type
c-Si wafers have enabled record conversion efficiencies of
26.0% and 26.1% by Richter et al. and Haase et al., respectively,
which are currently higher than the record conversion efficiency
for n-type TOPCon solar cells (25.80%).[111,112]
The continuous improvements in wafer quality, hydrogena-
tion of bulk and surface defects, and surface passivation
approaches could bring the performance of p-type devices to a
point, where other intrinsic and processing-related advantages
of p-type doping of silicon might play a major role in the wafer
choice for next-generation high-efficiency solar cells featuring
carrier-selective contacts. These advantages include the higher
diffusivity of minority carriers, the ease of forming n-type doped
layers via phosphorus diffusion, and the better segregation coef-
ficient for boron (close to unity),[113] which improves ingot utili-
zation. The former enables a higher theoretical limit for the
conversion efficiency of p-type solar cells.[114] The latter relates
to material usage and is particularly important due to the high
sensitivity of SHJ solar cells (and other cell structures where
surface-related recombination is minimized) to changes in bulk
lifetime, which can be significantly impacted by doping varia-
tions across the ingot.[115–117] In addition to these intrinsic advan-
tages of p-type c-Si wafers, the adoption of such wafers would
further benefit from the cheaper wafer cost, since p-type Cz-Si
wafers are currently 8–10% cheaper than their n-type counter-
parts (for the same wafer size/thickness).[118] Yet, the SHJ
solar cell’s strict lifetime requirements also apply to p-type
wafers. As such, p-type wafers with a high initial lifetime are
required to fabricate high-efficiency SHJ solar cells, which might
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be more expensive than the p-type wafers used in PERC cells.
However, our previous work shows that commercial-grade p-type
Ga-doped Cz-Si wafers can yield comparable VOC values to ref-
erence SHJ solar cells fabricated with n-type Cz-Si wafers.[48]
Further work is required to evaluate the impact of variations
in wafer quality across different p-type Cz-Si ingots (and ingot
positions) on the performance of p-type SHJ solar cells.
Nevertheless, the historical perspective presented in this arti-
cle illustrates how the lack of timely solutions for a single defect
can result in a material being considered unsuitable for novel
applications. This is particularly important as the industry rapidly
shifts from boron to gallium as the main dopant agent for p-type
silicon. It is of great importance to identify the defect(s) respon-
sible for lifetime instabilities recently observed in solar cells fab-
ricated with p-type Ga-doped c-Si wafers,[119–122] as these wafers
have the potential to enable a next-generation of high-efficiency
silicon solar cells based on p-type c-Si wafers.
Acknowledgements
This work was supported by the Australian Government through the
Australian Centre for Advanced Photovoltaics (ACAP) and the
Australian Renewable Energy Agency (ARENA) (2017/RND005). The views
expressed herein are not necessarily the views of the Australian
Government, and the Australian Government does not accept responsi-
bility for any information or advice contained herein. B.V.S acknowledges
the CSIRO Research Office for his post-doctoral fellowship. M.K. acknowl-
edges the support of ACAP for his post-doctoral fellowship.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
heterojunction, passivation, p-type, silicon, stability
Received: May 20, 2022
Revised: July 24, 2022
Published online:
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