Received: 26 November 2021 Revised: 17 January 2022 Accepted: 19 February 2022

DOI: 10.1002/pip.3552

SPECIAL ISSUE REVIEW

Carrier-selective contacts using metal compounds for

crystalline silicon solar cells

Jesus Ibarra Michel1 | Julie Dréon2 | Mathieu Boccard2 | James Bullock1 |

3
Bart Macco

1
Department of Electrical and Electronic
Engineering, University of Melbourne,
Melbourne, Victoria, Australia
2

Ecole Polytechnique Fédérale de Lausanne
(EPFL), Institute of Electrical and
Microengineering (IEM), Photovoltaics and
Thin Film Electronics Laboratory (PV-LAB),
Neuchâtel, Switzerland
3
Department of Applied Physics, Eindhoven
University of Technology, Eindhoven, The
Netherlands
Correspondence
B. Macco, Department of Applied Physics,
Eindhoven University of Technology, P.O. Box
513, 5600 MB Eindhoven, The Netherlands.
Email: b.macco@tue.nl
Funding information
Australian Centre for Advanced Photovoltaics;
Nederlandse Organisatie voor
Wetenschappelijk Onderzoek; Schweizerischer
Nationalfonds zur Förderung der
Wissenschaftlichen Forschung; Melbourne
Research Scholarship; Australian Center for
Advanced Photovoltaics Fellowship; Swiss
National Science Foundation, Grant/Award
Number: PZENP2_173627; Ministry of
Economic Affairs of The Netherlands, Grant/
Award Number: TEUE119005; Dutch TTW-
VENI, Grant/Award Number: 16775
Abstract
Solar cells rely on the efficient generation of electrons and holes and the subsequent
collection of these photoexcited charge carriers at spatially separated electrodes.
High wafer quality is now commonplace for crystalline silicon (c-Si) based solar cells,
meaning that the cell's efficiency potential is largely dictated by the effectiveness of
its carrier-selective contacts. The majority of contacts currently employed in indus-
trial production are based on highly doped-silicon, which can introduce negative
side-effects including Auger recombination or parasitic absorption depending on
whether the dopants are diffused into the absorber or whether they are incorporated
into silicon layers deposited outside the absorber. Given the terawatt scale of deploy-
ment of c-Si solar cells, the search for alternative contacting schemes that can offer
potential benefits in terms of performance, cost, ease of processing or stability is
highly relevant. One such category of contacting schemes, with the potential to avoid
the above mentioned issues, is that which employs metal compounds as the ‘carrier-
selective’ layer. The last 7 years has seen a surge in interest on this topic and a few
promising families of materials have emerged, most prominently the alkali/alkaline-
earth metal compounds and the transition-metal oxides. The number of successful
selective-contact demonstrations of materials within these families is fast increasing
with the best solar cell demonstrations now exceeding 23%. However, in addition to
improving their efficiency performance, several challenges remain if such contacts
are to be considered for industrial adoption. These are mainly associated with poor
stability, lack of compatibility with transparent electrodes and inability to be depos-
ited using standard industrial techniques. This review covers the historical develop-
ments, current status and future prospects of metal-compound based selective
contacts in the context of c-Si photovoltaics.

KEYWORDS
alkali, carrier-selective contacts, metal compound, passivating contacts, passivation,
photovoltaics, solar cells, transition metal oxides

J. Ibarra Michel and J. Dréon contributed equally to this work.

This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium,
provided the original work is properly cited.
© 2022 The Authors. Progress in Photovoltaics: Research and Applications published by John Wiley & Sons Ltd.

Prog Photovolt Res Appl. 2022;1–34. wileyonlinelibrary.com/journal/pip 1

2 IBARRA MICHEL ET AL.

1 | I N T RO DU CT I O N these approaches face limitations related to the use of doped-silicon

1.1 | Selective contacts in c-Si solar cells
The majority of today's terrestrial photovoltaics industry is composed
of crystalline silicon solar cells utilising variants of the passivated emit-
ter and rear cell or ‘PERC’ architecture, shown in Figure 1A. One of
the driving philosophies of this structure is addressing the lossy metal
contact interfaces by minimising their percentage surface coverage.1
As such, further optimisation of this structure will become increasingly
complex with the need for smaller contact features. One response to
this challenge is to address the losses at the contact interfaces
directly, removing the need to minimise their surface coverage in the
first place. This idea has been driving research activity for over
50 years, with an intensification over the last decade yielding new
efficiency benchmarks just shy of 27%. It has led to the prominence
of contacting approaches relying on the deposition of doped-silicon
layers in between the c-Si wafer and the metal electrode, in architec-
tures such as in the silicon heterojunction (SHJ) shown in Figure 1B
and doped polysilicon/SiO2 (poly-Si),2 shown in Figure 1C.
Although they offer unquestionable improvement compared to
today's PERC technology, particularly in relation to device voltage,
layers as a contact material. A major one is the limited operating cur-
rent due to parasitic light absorption when a silicon layer is used at
the front side. This has triggered in recent years strong interest in
other contacting technologies based on metal compound thin films.
These were implemented in various cell structures, examples of which
are shown in Figures 1D–F, with similarities to the traditional ones
shown in Figures 1A–C. Among the primary possible advantages of
metal compound selective contacts is a wider range of optical proper-
ties. For example, many of the metal oxides and alkali metal halides
are completely transparent across the visible and infrared portion of
the spectrum, effectively eliminating parasitic absorption. Also, the
broad range of refractive indices available opens up opportunities to
tailor antireflection and light trapping characteristics of solar cells.
However, experimental demonstrations of these potential optical ben-
efits have only been shown to a limited degree as discussed in this
review, and it remains an area of active research. Furthermore, metal
compounds also have a variety of electrical properties from insulating
to highly conducting. Overall, whilst metal-compound contacts are
less developed than the doped-silicon approaches, they have the
potential to fulfil multiple optical and electrical roles in the solar-cell,
thus simplifying its design and fabrication process.

F I G U R E 1 Schematics of c-Si solar cell architectures with standard silicon-based contact layers (A–C) or with metal compound contact layers
(D–F). (A) The passivated emitter and rear cell (PERC); (B) the silicon heterojunction (SHJ) cell; (C) the poly-Si rear contact cell (commonly referred
to as the TOPCon cell), (D) the metal-compound partial rear contact (PRC) cell, (E) the metal-compound SHJ hybrid, and (F) the metal-compound
full area rear contact cell [Colour figure can be viewed at wileyonlinelibrary.com]
IBARRA MICHEL ET AL.
The concept of using metal-compound thin films, particularly metal
oxides, as contact interlayers in c-Si cells is not new. Early work in the
1970s on c-Si semiconductor–insulator–semiconductor (SIS) solar cells
identified a number of promising candidates,3 including molybdenum
trioxide MoO3,3,4 a popular choice today as a contacting layer to pro-
vide hole selectivity. Performance at that time was limited to efficien-
cies around 10%, which was still thought of as promising compared to
state-of-the-art.5 Nevertheless, this approach faded out before the
turn of the century for various possible reasons. One of them is likely
the better performance obtained with dopant diffusion at the time.6,7
Nevertheless, a resurgence of activity has occurred since 2014, per-
haps following the realization that c-Si would be a dominating technol-
ogy for the foreseeable future, and the rise of passivating contact
approaches. Impressive improvements in wafer preparation also relax
the need for impurity gettering which occurs during the phosphorus
diffusion (which was a key factor in raising c-Si cell technology to 20%
efficiency in mass production in recent years). In this relatively short
time frame, a large variety of materials have been reported to behave
as electron and hole contacts on c-Si solar cells. Many reports of effi-
ciency values exceeding 20% exist, and a couple of approaches exceed
23%,8,9 thus vying with more conventional contacting approaches.
In this paper, we will review recent work related to the formation
of carrier-selective contacts using metal compounds in lieu of the tra-
ditional doped-silicon. We will restrict the discussion to bulk metal
compound films and hence exclude two-dimensional materials and
fully organic materials, for which the reader is referred to existing
10 11
reviews, see for example previous studies and.
1.2 | Metal-compound families utilised in selective
contacts
The periodic table shown in Figure 2 highlights the elements utilised
in successful demonstrations of metal-compound-based selective con-
tacts for c-Si solar cells. The first material family to be discussed, in
F I G U R E 2 Periodic table highlighting
elements utilised in metal compound
based selective contacts for c-Si solar
cells. The blocks corresponding to alkali
(A), alkaline-earth (AE), transition metals
(TM) and halides (Ha) are shown on top of
the group numbers [Colour figure can be
viewed at wileyonlinelibrary.com]
3
Section 3, are the alkali/alkaline earth ionic compounds. These mate-
rials are used exclusively in electron contacts, perhaps archetypically
represented by lithium fluoride LiF1-x. Section 4 explores the diverse
range of transition metal oxides which have been widely utilised in
both electron and hole contacts. For example, TiO2-x and MoO3-x
have been commonly employed as electron and hole contacts, respec-
tively, both demonstrated in cells with efficiencies exceeding 23%.
Finally, Section 5 groups and discusses the remaining smaller families
of metal compounds, including the transition metal nitrides, III-V and
II-VI materials.
Before addressing the various classes of metal-compound based
contacts in detail, first the status quo in comparison to contacts based
on doped-silicon is discussed. Figure 3 shows a literature comparison
of the various families of selective contacts. Data are shown as a func-
tion of open-circuit voltage Voc and fill factor FF, which is therefore
indicative of the electrical performance. The contour plot displays the
cell efficiency assuming perfect optics, that is, a short-circuit current
density Jsc of 43.31 mA/cm2, which is the ideal Jsc for a 110 μm-thick
c-Si solar cell as modelled by Richter et al.46 Therefore, the difference
between the efficiency indicated by the contour plot and the actual
cell efficiency is a good measure for the optical performance of the
cell. The plot also indicates the limits of the FF and Voc as set by Auger
and radiative recombination in the bulk.
What can be directly seen from the figure is that the doped-sili-
con-based contacts exhibit excellent electrical properties, achieving
Voc and FF values close to the limits. The best electrical performance
is achieved for the SHJ contacts (based on doped amorphous silicon).
Interestingly, the highest efficiency is reported for the Kaneka SHJ
IBC cell, even though LONGi's double side-contacted SHJ cell clearly
boasts the best electrical properties. This stems directly from the
higher Jsc for the IBC cells, which have an optical advantage due to
the absence of front side contacting. Another way of looking at it is
that the electrical performance of LONGi's SHJ cell would enable an
efficiency close to 28.4% for perfect optics, suggesting close to 2%
absolute loss in efficiency due to optical losses from the contacting
4 IBARRA MICHEL ET AL.

F I G U R E 3 Literature overview of cell Voc, FF and efficiency values. The comparison includes reference contacts based on doped-silicon,12–20
hole-selective metal compound contacts,9,21–26 electron-selective metal compound contacts,8,27–40 and fully dopant-free solar cells.41–45 The
contour plot shows the ideal cell efficiency assuming a Jsc of 43.31 mA/cm2, which corresponds to the idealised Jsc of the 110 μm-thick c-Si solar
cell as modelled by Richter et al.46 This ideal solar cell with a 29.43% efficiency is indicated by the star symbol. The hatched areas show limits to
the Voc and FF as a result of Auger and radiative recombination in the bulk. The calculations assume a c-Si(n) wafer with a doping level of
1014 cm
3 and thickness of 110 μm [Colour figure can be viewed at wileyonlinelibrary.com]

F I G U R E 4 Schematic of the working principle of a silicon solar cell. The absorption of light leads to a non-equilibrium carrier distribution
which necessitates the use of separate quasi-Fermi levels for electrons (EFn) and holes (EFp) to describe carrier statistics. After excitation, the
carriers quickly thermalize towards the band edges. The difference in free energy between the two quasi-Fermi levels is known as the implied
voltage (iVoc). The drivers for the electron (Jn) and hole (Jp) currents are the gradients of the quasi-Fermi levels and the electron and hole
conductivities. At either side of the absorber layer, the selective membranes are designed to have a high asymmetry in their conductivity for
electrons and holes. Because of the difference in conductivities in the membrane, there is a strong dissimilarity in the gradients of the quasi-Fermi
levels, resulting in a voltage build-up Vext between both metal contacts that can be used to extract work [Colour figure can be viewed at
wileyonlinelibrary.com]

layers for this both-side contacted cell. The figure also shows that the efficiencies over 23% have been reached. This can be largely attrib-
electrical performance of the metal compound-based contacts is not uted to the fact that silicon-based contacts are much further along
(yet) on par with that of doped-silicon-based contacts, even though the learning curve, with billions of cells processed, enabling more
IBARRA MICHEL ET AL. 5

accurate optimization using statistical analysis.47 Nevertheless, FF
values exceeding 80% have been reached for all families of metal
compound-based contacts, indicating that efficient charge-carrier
extraction is possible. Yet the gap to the FF limit is ostensibly larger
for most metal compound-based contacts. In addition, metal
compound-based contacts that achieve Voc values in line with the best
doped-silicon contacts do so by relying on dedicated a-Si:H passiv-
ation layers. This highlights the fact that whilst some metal compound
materials can establish a strong asymmetry in carrier conductivity (see
also Section 2.1), they lag behind in terms of surface passivation.
Therefore, given the generally excellent transparency of the metal
compound-based contacts, the comparison in Figure 3 underlines the
importance of improving their selectivity—preferably without the use
of a dedicated silicon-based passivation layer—in order to be able to
challenge the status quo of silicon-based contacts.
2 | GENERAL CONSIDERATIONS FOR
M E T A L - C O M P O U N D S E L E C T I V E CO N T A C T S
2.1 | Carrier selectivity with metal-compound
selective contacts
In order for a c-Si solar cell to function, it must selectively extract pho-
toexcited electrons and holes at two spatially separated metal
electrodes. As shown in Figure 4, to achieve this, the path (sometimes
synonymous with the ‘contact’) between the absorber and each of
the two electrodes must present a significant asymmetry in conductiv-
ity favouring one of the carriers. This asymmetry must be strong for
the solar cell to function efficiently. For example, reaching efficiencies
above 25% under standard test conditions (STC) typically requires the
hole contact to provide a resistance below 1 Ωcm2 to holes and
above 500 Ωcm2 to electrons in an idealized full-area cell architec-
ture.48 The ability of a contact to collect just one of the two carriers
selectively is known as ‘carrier-selectivity’ or just ‘selectivity’ and can
be quantified by a range of different metrics.12,13,46,47 However,
rather than a single metric, it has become commonplace to represent
individual contact behaviour as a couple of metrics, the contact resis-
tivity ρc, which represents the resistance presented to the collected
carrier and the contact saturation current J0 which serves as a proxy
to the conductivity provided to the non-collected carrier. Generally
speaking, the goal of passivating contacts is to reduce both of these
parameters simultaneously, with typical target values below 0.1 Ωcm2
and 10 fA/cm2, respectively.
Whilst the contact parameters J0 and ρc provide a useful means
to express the selectivity of the contact, they have a convoluted influ-
ence on the electrical cell parameters Voc and FF. Generally speaking,
a high ρc results in a lower FF due to resistive losses upon carrier
extraction (see Section 3.3) and a high J0 results in a low Voc due to a
high recombination rate in the contact. This is typically due to a high

F I G U R E 5 Representation of main possible events occurring when contacting n-type c-Si with a metal where ΦM < ΦSi (Φ represents the
work function): (A) metal and n-type c-Si before contact. (B) and (C) Metal and n-type c-Si after contact in the ideal case of no Fermi level pinning
(B) and in reality (C), where metal-induced gap states (MIGS) create available electron states within the Si band-gap that ‘pin’ the Fermi level,
creating a Schottky barrier. (D) A thin insulating interlayer can passivate defects at the interface and diminish the effect of MIGS on n-type c-Si.
(E) An interfacial dipole at the silicon/metal interface reduces the surface potential for electrons, effectively reducing the work function. (F) Fixed
charges at the interface can create an accumulation of electrons at the silicon surface that enable band bending [Colour figure can be viewed at
wileyonlinelibrary.com]
6 IBARRA MICHEL ET AL.
density of surface defects. Nevertheless, even in case of a low
surface-defect density, the external Voc can still be low if the contact
provides similar resistance to both types of carriers, indicating poor
selectivity.
Practically, selectivity can be achieved using a range of principles
which can be broadly categorised into two groups: manipulating sur-
face carrier concentrations and creating asymmetries in carrier flows
through the contact.
The surface concentration of carriers can be manipulated using,
for example, materials with extreme work functions, or materials with
large positive or negative fixed charges. These elements can alter the
value of the surface potential (ψ s) which, if sufficiently large, can result
in the exclusive accumulation of either electrons or holes at the sur-
face, depending on its polarity. The example conveyed in Figures 5A,B
shows downwards bending of the silicon bands after a low-
work-function electrode is brought into contact with silicon. The
build-up of electrons at the surface, accompanied by the depletion of
holes, results in favourable conditions for an electron contact. The
high electron surface concentration ns increases the electron conduc-
tivity in the surface region and the low hole surface concentration ps
limits the number of holes able to flow to the surface (these holes
would ultimately recombine). Increasing illumination typically
decreases ψ s due to the increase in the pn product. However, a large
ns/ps ratio can still exist under one sun illumination if the initial equi-
librium surface potential is sufficiently high.
Theoretically, ψ s can be controlled by using metals with extreme
work functions if deposited directly on silicon. In practice, however,
this is rarely observed because of Fermi level pinning (FLP), as
evidenced by multiple experiments where the measured Schottky bar-
rier height is independent of the metal. This is shown pictorially in
Figure 5C, where metal-induced gap states or MIGS (localized surface
states induced when metals are placed within 1 nm of a semiconduc-
tor surface) pin the Fermi level at the silicon surface to a charge neu-
trality level around 0.35 eV above the valence band.49 Fortunately,
Fermi level pinning can be mitigated by separating the metal electrode
and silicon, for example, by introducing thin interlayers. This strategy
also has the potential to passivate localised surface defects, formed
due to unsatisfied or strained bonds at the silicon surface. More than
15 years of dedicated research into surface passivation has provided
many candidate thin films and techniques for reducing the density of
unsatisfied/strained bonds at the surface.50–52 Similarly, as shown in
Figure 5D), thin interlayers (even 3 Å), are enough to strongly reduce
the density of metal-induced gap states, by attenuating the projection
53
of the metal's bulk electron's wavefunction into the semiconductor.
A number of interlayer contact systems have now been demonstrated
on c-Si with pinning factors close to 1 (i.e. no pinning), including
54
SiO2. Furthermore, the use of an outer semiconductor/transport
layer rather than a metal has been shown to reduce the effects of sur-
face recombination and FLP.53 This is particularly beneficial when the
outer semiconductor has a desirable work function for electron or
hole collection. Finally, even when pinning is present, the use of
metal-compound materials/stacks with extreme work-function values
can overcome the negative effects of a partially pinned silicon surface.
Relatedly, a dipole at a metal or semiconductor surface will
reduce or increase (depending on its orientation) the work function
proportionally to the magnitude of its dipole moment, as illustrated
in Figure 5E). This effect has been observed, for instance, in molecu-
lar dipoles (e.g. self-assembled monolayers) deposited on clean metal
surfaces.55–58 In general (and more relevant for our discussion),
dipoles can be created at the interface between silicon and a material
with polar components. This is, for instance, a possible occurrence in
c-Si/TMO-based passivating contacts originating from shallow oxy-
gen vacancies which tend to reduce the work function.59–64 Dipole
formation is also relevant when c-Si is combined with highly ionic
materials like alkali/alkaline-earth metal compounds such as LiF1-x. In
these examples, the formation of dipoles at the silicon interface is
thought to be one of the most relevant mechanisms influencing the
change in work function (and ultimately the carrier concentration
asymmetry). This will be addressed more in detail further in
Section 3.
Another method to manipulate ψ s at the c-Si surface is by inter-
layers that possess a large fixed charge density (see Figure 5F). This
fixed charge density is commonly described as a thin sheet of
immobile charges within a dielectric film, and it can be contained
within the first few nanometres.58,59 Their potential use in a contact
structure is complicated. For example, in cases where an interlayer
must be kept extremely thin to allow direct tunnelling, the ‘full
charge’ measured on thicker films, may not completely develop. Fur-
ther, some of this fixed charge may be mirrored in a conductive over-
layer instead of the c-Si, depending on the position of the charge
centroid. Regardless, this possibility is being actively explored.
Preliminary studies were reported on Al2O3/ZnO stacks with limited
results so far,65 others focused on the use of polymer-based Lewis
acids/bases to create a sheet of charge at the c-Si surface, achieving
impressive surface passivation, but so far lacking implementation in a
contact system.66
In addition to controlling the population of carriers at the c-Si
contact surface, carrier-selectivity can also be introduced, or further
assisted by employing layers/interfaces which preferentially conduct
holes or electrons. It has long been recognised that an ideal c-Si solar
cell would comprise two wide band-gap semiconductors asymmetri-
cally straddled on either side of a c-Si wafer. In such a system, the
collected carrier of each heterocontact experiences no barrier en route
to the outer metal electrode whilst the blocked carrier experiences a
prohibitively large barrier for carrier transport, leading to obvious
carrier-selectivity.67 A perfect implementation of this approach is yet
to be demonstrated, notably since it requires suppression of any FLP
or recombination-active defect at the wide-band-gap semiconductor/
c-Si interface. Besides, approximate conduction-band alignment and
sufficient effective n-type doping (resp. valence-band alignment and
p-type doping) are simultaneously required, drastically reducing the
suitable materials.68,69 Several other strategies have been suggested
to achieve selectivity at the contact including the asymmetric
mobility contact,67 or the introduction of carrier selective defects into
a passivating film.70 However, these latter ideas remain at the
concept stage.
IBARRA MICHEL ET AL. 7

2.2 | Transport mechanisms 2.2.2 | Bulk transport

2.2.1 | Interface transport
In today's experimental passivating contact realizations, film stacks
are used, each layer of which performs a specific function. Whilst
excellent surface passivation is achievable (indicating that the flux of
the blocked carrier has been limited), typically small barriers to the col-
lected carrier are unavoidable. Fortunately, c-Si solar cells with full/
large-area contacts can tolerate relatively high ρc values, reducing the
impact of such barriers. Several mechanisms have been used to
describe transport through/over these barriers, including thermionic
emission, direct tunnelling and trap-assisted tunnelling (TAT, see
Section 2.2.2) whereby typically one mechanism dominates ρc. These
three mechanisms are depicted in Figure 6A-1, 2 and 3. In the simple
case of ohmic contacts relying on thermionic emission, barriers below
0.15 eV result in a ρc with almost no impact on cell performance (even
for small contact fractions), and those above 0.5 eV will limit ρc to at
least 0.5 Ωcm at room temperature, which will significantly detract
2
from a cell's efficiency potential.49 In many cases, the use of wide
band gap passivating interlayers is desired since these typically offer
excellent surface passivation and temperature stability (e.g. SiO2,
Al2O3, …). In such a case, barrier heights > > 0.5 eV are commonplace
and hence transport cannot occur via thermionic emission. Instead,
conduction can occur through the interlayer if it is sufficiently thin for
direct tunnelling (i.e. <2 nm) or, for example, if a large density of sub-
74,75
gap states are involved. In recombination junctions (in the case of
hole contacts), holes can recombine with electrons through band-
to-band recombination mechanism (Figure 6A-4) when the band
alignment is favourable, or via hopping of both carriers through defect
0 71
states (Figure 6A-3 ).
When the thickness of the passivating and carrier selective layers is
more than 2 nm, carriers will need to travel through the bulk of the
material in order to reach the metal electrodes. In view of the defec-
tive nature and wide band gap of some of the materials considered
here, the classical band conduction is not expected to be the only
mechanism.
The main bulk conduction mechanisms occurring in the materials
presented in this review72,76 are illustrated in Figure 6B. In wide-band
crystalline semiconductors, carriers move as an electron/hole sea,
feeling an effective potential. They follow band theory equations of
delocalized conduction (Figure 6B-1)—drift and diffusion—with occa-
sional scattering effects, for example, from ionized impurities and lat-
tice vibrations. In amorphous semiconductors, the concentration of
defects is large and defect bands exist, instead of only isolated defect
states. Conduction can then be delocalized following ‘extended states
conduction’ (Figure 6B-2), similar to crystalline diffusion conduction
but with many scattering events so that carriers have a higher effec-
tive mass—and so lower mobility—compared to the crystalline case.
Near band edges and in the band-gap, defect states are less numer-
ous, carriers are trapped in local energy minima and have to cross an
energy barrier to move into other states through ‘thermally assisted
tunnelling’—or ‘trap assisted tunnelling’—(TAT), commonly known as
‘hopping’ and characterized by a mobility exponentially dependent on
temperature (Figure 6B-3). In narrow band and/or polar semiconduc-
tor compounds, transport is influenced by narrower bands and polari-
zation effects. Because of narrow bands, carriers are heavier
compared to the simple crystal case making the electron–phonon cou-
pling, a quasiparticle called ‘polaron’, possible, with a higher effective
mass than the single carrier. This phenomenon is important to

F I G U R E 6 The main transport mechanisms that can exist in the materials presented in this review. a) Possible charge transport at the
interface between two materials: 1. Thermionic emission, 2. Direct tunnelling of thermally activated carriers, 3. Trap assisted tunnelling (hopping).
In case of recombination junctions, additional recombination via 30 . Trap assisted tunnelling or/and 4. Band to band mechanisms. b) Transport
through a bulk crystalline or an amorphous semiconductor, and a narrow-band and/or polar semiconductor compound: 1. Metallic-like band
conduction, 2. Conduction through extended defect states, 3. Thermally/trap assisted tunnelling (TAT) in localized sub-gap defect states, 4. Large
polaron conduction, 5. Hopping of localized polarons. The main mechanism for interface and bulk transport depends on the material
crystallographic structure, doping, temperature, and band alignment71–73 [Colour figure can be viewed at wileyonlinelibrary.com]
8 IBARRA MICHEL ET AL.
consider in semiconducting oxides or alkali metal halides (ionic com-
pounds), due to strong polar bonding between the metal cations and
oxygen or halogens. Polarons can be ‘large’ when the carrier-phonon
coupling energy is small compared with the carrier-band width, and
transport is delocalized but still affected by polarization effects
(Figure 6B-4). In the other case (generally for bands narrower than
3 eV), the carrier is self-trapped—a trap created by the lattice
polarization—in the lattice, and is called a ‘small polaron’ (Figure 6B-
5), moving via hopping. Additionally, presence of defects states
originating from crystal imperfections (e.g. amorphous compounds,
atom vacancies, impurities, Frenkel and Schottky defects in ionic
crystals,77,78 etc.) and small polaron formation are synergistic effects,
strongly influencing each other and making small polaron formation
possible in compounds with bands wider than 3 eV.
2.3 | Dedicated passivation layers and outer
electrodes
As mentioned above, today's experimental demonstrations of carrier
selective contacts typically employ a stack of thin interlayers, with
each film in the stack contributing in a different way. For example,
the a-Si:H/MoO3-x/ITO/Ag contact stack employs an intrinsic
hydrogenated amorphous silicon (a-Si:H) layer for surface passiv-
ation, MoO3-x for hole selectivity and a transparent conductive
oxide (TCO) for lateral conductivity (to the Ag electrode) and
antireflection.
Commonly used passivating interlayers include silicon oxide
(SiO2-x) and a-Si:H. These layers serve to reduce surface recombina-
tion, through the reduction of interface traps, without themselves
providing a strong preference for electron or hole collection. A thin
interfacial silicon oxide naturally grows on bare silicon surfaces
exposed to air or any oxidising precursor. Since such native oxides are
typically of low quality, they are routinely removed by a hydrofluoric
acid treatment. High-quality interfacial oxides can be grown using a
variety of techniques, including thermal, nitric-acid oxidation, or O3
treatments, and are routinely used in, for example, poly-Si passivating
contacts.79–81 When metal oxides are grown on HF-dipped surfaces,
an interfacial SiO2-x is usually grown inadvertently, presumably
through (a combination of) oxidation by an oxidizing precursor and
migration of oxygen from the deposited metal oxide to the silicon.82
Some metal oxides (e.g. Al2O3) form high-quality passivating oxides by
themselves, whereas for other metal oxides (e.g. ZnO) growing a high-
quality oxide prior to deposition is a prerequisite for attaining a high
passivation quality. There are also metal oxides (e.g. TiO2-x and
Nb2O5-x) that form reasonably passivating interfacial oxides, yet they
can benefit from pre-deposition grown interfacial oxides.82–84
Improvement of passivation at the Si/SiO2-x interface is achievable by
promoting the diffusion of hydrogen to the interface, for example, via
forming gas annealing (FGA), or annealing after the deposition in
presence of a hydrogen rich capping layer. Such a step is oftentimes
critical to ensure a high contact performance, both in terms of passiv-
ation and contact resistivity. One drawback is the wide bandgap of
SiO2-x, requiring a precise control over the thickness to enable direct
tunnelling, or the engineering of pinholes.
Relative to SiO2-x, a-Si:H offers similarly excellent surface passiv-
ation, enabling device voltages well beyond 700 mV, with a compara-
tively weaker dependence of carrier transport on film thickness. The
narrower band gap of a-Si:H compared to SiO2-x enables band-
to-band transport of electrons and holes between c-Si and a-Si:H but
causes parasitic light absorption when used on the sunward side.
Another shortcoming is an inferior thermal stability: passivation from
a-Si:H layers declines upon heating above 250 C, due to hydrogen
loss, which sometimes causes detrimental interaction with the adja-
cent films at similarly low temperatures. Regardless of their shortcom-
ings, these two passivating films have been widely integrated into a
number of contacts since the passivation they can provide is so far
not matched by any other material in the context of passivating
contacts.
Also necessary in some passivating contact stacks, particularly on
the sunward side, is a transparent material that serves to transport
carriers laterally towards the metal fingers. TCOs, typically indium tin
oxide (ITO), perform this function, as well as other roles. Firstly, they
must be of a suitable refractive index and thickness combination to
serve as antireflection coatings (or mirrors when incorporated into a
dielectric/metal rear cavity). Secondly, they must provide a high con-
ductivity whilst remaining highly transparent. This typically means that
a high mobility is desired to avoid detrimental parasitic light absorp-
tion from the free carriers. Therefore, there is an active field pursuing
the development of high-mobility TCOs, for example, by increasing
the crystallite size of indium-oxide based layers through hydrogena-
tion and introduction of more exotic dopants (Zr, W, Ce).85–89 Fur-
thermore, their impact on the performance of underlying films must
be minimised. For example, damage of underlying films due to tem-
perature or ion impact during ITO sputtering is a common consider-
ation for such contacts.90,91 Finally, a low-resistance contact should
be obtained at both adjacent interfaces, that is, with the metal grid on
top and with the carrier-selective layer underneath. The latter typi-
cally requires that the work function of the TCO is appropriately
aligned to the carrier selective layer underneath it, and/or that the
TCO is sufficiently doped. More details can be found in Ref92 which
reviews a broad range of transparent electrodes in electronic devices.
3 | A LK A L I / A L K A L I N E- E A R T H I O N I C
COMPOUNDS
3.1 | Introduction
3.1.1 | Material properties
Alkali/alkaline-earth metal compounds (AMC) have recently gained
attention in the c-Si PV research community as a pathway towards
electron selectivity. Here the term alkali metal compounds (AMC)
refers to ionic compounds A+B
where the cation A+ is an alkali
(group 1) or an alkaline earth (group 2). They respectively have one
IBARRA MICHEL ET AL. 9

and two electrons in their outer s orbital. These electrons are weakly
bound to the atom and for this reason they display the lowest first
(and second) ionization energies and electronegativities of all ele-
ments.93,94 Because of this, most of the compounds formed by alkali
and alkaline-earth metals are ionic in nature. The most relevant anions
(for the purpose of this discussion) taking the B
site in these com-
pounds are halogens and oxygen, though carbonates and


acetylacetonates (Acac ) have also been demonstrated to a lesser
degree in c-Si PV and will be mentioned. A simple schematic following
the structure of an AMC is shown in Figure 7A), where a periodic-
table-like representation also shows the comparative ionic radii of the
components.
Most alkali (and alkaline earth) metal halides have a band gap
larger than 10 eV,100 whilst their corresponding oxides have a smaller
value (e.g. MgO1-x  7.8 eV,101 BaO1-x  4.8 eV 102). These band gaps
are broader than the sun's relevant spectral range minimising parasitic
absorption of light. Theoretically, the bulk conductivity of AMCs
should be very low. As a consequence, AMC as electron contact inter-
layers for semiconductors are typically deposited in thin films at the
nm-scale, around 0.5–2 nm with direct tunnelling of electrons com-
monly ascribed as the transport mechanism.103 However, despite the
large band gaps, non-negligible current has been measured through
thick AMC layers, for example, LiF1-x (40–50 nm)41,104 or MgO1-x
(60 nm).31 These thicknesses are far in excess of the tunnelling thick-
ness regime, but the bulk transport mechanism is still unclear. Some
thermally evaporated alkali metal halide films thinner than 10 nm have
been shown to be crystalline (rock-salt or fluorite structures).105 In
these ionic solids, Schottky and Frenkel defects can be commonplace,

F I G U R E 7 (A) Schematic representation of an alkali metal compound with the typical elements which compose it. The relative size of the ions
is based on reference.95 (B) Literature compilation of specific contact resistivities on n-Si for different AMC films as a function of thickness. The
dashed lines represent typical contact resistivities for the doped-silicon approaches (a-Si and poly-Si). The open symbols represent data with a 5–
6 nm a-Si passivating interlayer between n-Si and the AMC film. (B) Work functions for different AMC films, all measured with ultraviolet
photoelectron spectroscopy (UPS). The filled bars are measurements done with a thin (5 nm) aluminium overlayer. All the data for these figures
are based on previous studies.29,31,32,35,41,96–99 *Films deposited via solution processing [Colour figure can be viewed at wileyonlinelibrary.com]
10
where carriers can be trapped and form F- or H- centres.106 This
introduces the possibility for creation of small radius polarons, as dis-
cussed in Section 2.3.2. Also, because these defects have lower
energy of formation at the surface compared to the bulk,103 the
charge build-up at the interface with other materials has been
suggested to assist with electronic transport.104,107 Even without
clear evidence on the crystallographic properties of the material, the
stoichiometry of some compound films has been experimentally
shown to have a big impact on the electrical behaviour. For instance,
an oxygen-deficient film in thermally evaporated MgO1-x (x = 0.25)

3
enabled a bulk resistivity of 5.8  10 Ωcm (estimated with Hall
measurements). In a different study, MgO1-x films deposited by ALD
were found to be more stoichiometric, especially at higher deposition
temperatures, as well as more resistive.108
3.1.2 | Historical background
Though AMCs are relatively new in silicon PV, they have been used
for more than 20 years to enhance electron injection/extraction in
the field of organic semiconductors. For instance, in OLEDs/
electroluminescent devices,104,107,109–128 bulk heterojunction solar
129–134 135
cells, and even in organic field-effect transistors. Probably
the most prominent example is the LiF1-x/Al system which was first
explored with the intention of enhancing electron injection into a tris
(8-hydroxyquinoline)aluminium (III) (AlQ3) layer.117 Throughout the
years, many other AMCs have been shown to provide the role of elec-
tron injection. These include, MgO1-x,117 NaCl,129 CsF,136 Cs2CO3,126
118
NaF, MgF2,121 and solution-processed salts like Ba (OH)2 and
BaCl2.135 All of them have been successfully applied at the cathode of
different organic devices in order to reduce the injection/extraction
barrier for electrons in the active material.
In the silicon PV domain, AMCs have had a comparatively shorter
history. Around 10 years ago, inspired by some of the aforementioned
studies in organic semiconductors, researchers explored the use of
LiF1-x/Al electrodes in a-Si thin film solar cells and managed to reduce
series resistance substantially at the electron selective region.137,138
They argued that LiF lowers the work function of the Al upper layer
due to either the large dipole moment of nm-scaled LiF or a reaction
between LiF and Al.109 A couple of years later, LiF was tested as an
electron contact on a fully ‘doped-silicon-free’ c-Si solar cell enabling
an efficiency above 19%.41
3.1.3 | Mechanisms for electron selectivity
Despite the popular use of AMCs to enable electron extraction/
injection in multiple organic and inorganic semiconductor devices, no
ultimate consensus has been reached to explain the main physical
mechanism behind this effect. In principle, multiple mechanisms could
be taking place at the same time depending on the metal compound
in particular. With measurements such as X-ray photoelectron spec-
troscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS)
IBARRA MICHEL ET AL.
many reports have shown that the origin of a small energy barrier for
electron flow originates from a reduction in the work function of the
electrode when the AMC film is introduced. In the paragraphs below,
we discuss three main mechanisms that could explain electron selec-
tivity of AMC films on c-Si. Due to the lack of studies in the PV
domain, most of the experimental evidence cited in this sub-
section comes from the field of organic light emitting diodes.
Protecting detrimental semiconductor–metal interaction
A first possible explanation for the enhanced electron selectivity of
AMCs on c-Si is the reduction of the Schottky barrier at the c-Si/metal
interface by de-pinning the interface (see Section 2.1). This would
allow for the work function of the electrode to have a much larger
influence on the semiconductor surface. Note that Fermi level de-
pinning would allow for AMCs to improve hole injection as well, if an
electrode with a sufficiently high work function is used. Earlier publi-
cations in the OLEDs domain have shown improved hole injection
when using a very thin (0.4–5 nm) MgF2 interlayer.121 Similar hole-
injection enhancement has also been observed with LiF in OLEDs139
and organic field-effect transistors.140 This enhancement can be
explained by the influence of ITO's large work function which was
used as the top electrode. However, other studies have compared thin
AMC films with thin insulating materials such as GeO2, and SiO2 at
the electron contact side of devices,117,133 and have shown that
improved electron injection is only achieved for the alkali compound
films, despite the fact that thin SiO2, Si3N4 and GeO2 films are well-
known to help de-pin the Fermi level of conventional semiconductors,
for example, silicon and germanium.141 This suggests that Fermi level
de-pinning might not be the only factor playing a role in the improved
electron transport. Generally speaking, besides reducing MIGS, an
interlayer could also prevent undesired chemical reactions between
the semiconductor and the metal electrode.119
So far, all the demonstrations of low contact resistivities using an
AMC film on n-type c-Si have used either aluminium or magnesium in
direct contact with it, suggesting that a low-work function metal is
essential to enable such ohmic behaviour. In fact, a study on crystal-
line silicon solar cells, explored the impact of different metals on top
of a MgF2-x (1.5 nm) /Mg (20 nm) stack. The performance of the back-
contacted cells decreases substantially with increasing metal work
function (e.g. from an efficiency of 22.1% with Al to 8% with Au), pos-
sibly due to some oxidation of the Mg interlayer. Nevertheless, the
best device was the one with aluminium and not magnesium (which
has the lowest work function of all) as the outermost metal.142
Work function lowering via dipole formation
As mentioned earlier, AMCs have strong ionic bonds and thus display
very large dipole moments at the molecular level. Theoretically, having
a strong dipole at the metal/silicon interface with the correct orienta-
tion would reduce the effective work function of the metal electrode,
creating band bending and accumulation of electrons at the silicon
surface (see Section 2.1). A monolayer of a material with a consis-
tently aligned large dipole moment (similar to self-assembled mono-
layers, SAMs) would create a dipole. For example, if a single layer of
IBARRA MICHEL ET AL.
LiF1-x is deposited on silicon, F
would have a tendency to bond to
the metal and Li+ to the semiconductor, creating a dipole properly
109
aligned to reduce the metal's work function significantly, presum-
ably enabled by the large dipole moment of LiF of 6.3 D.143 It has
been suggested that it would be necessary only for the first LiF1-x
monolayer to be aligned such that a dipole is created, whilst the bulk
molecules are allowed to have a random orientation.144 Enhanced
electron injection has been demonstrated in organic semiconductor
devices when using AMC films in combination with Al, which already
has a low work function but also a combination of LiF1-x/Au, where
Au with no LiF1-x showed very poor performance due to its large work
120,133
function, From the silicon perspective, measurements of
AMC/Al on n-Si have shown work functions as low 2.2 eV (see
Figure 7B), a value much lower than aluminium's work function alone
(4–4.2 eV). This suggests that the work function at the interface has
been greatly reduced. If a dipole created by the AMC film was the
only thing to consider (i.e. if we assumed a perfect interface),
molecules with a higher dipole moment should be expected to have a
stronger influence on the work function and a bigger impact on
electron injection/extraction. This was not observed experimentally
with polymer bulk heterojunction solar cells when comparing for
instance LiF1-x (6.3 D), NaF1-x (8.2 D) and KF1-x (9.0 D).131 In this
study, LiF1-x showed the best performance despite having the
+
smallest dipole moment at the molecular level, though Li is also the
smallest of the ions which could make it easier for it to align with
the interface.
AMC chemical reaction and doping
Lastly, some authors have argued that the work-function change at
the interface silicon/AMC/metal is caused by the reaction of the
alkali-metal film with either Al or with the active semiconductor layer.
Studies on OLEDs show that electrical measurements with Al-LiF, Al-
CsF and CsCO3 composites (deposited by co-evaporation) display
almost-equivalent results as compared with depositing the AMC and
126,136,145
electrode layers in separate steps, It has also been observed
that some alkali metals can diffuse into organic semiconductor mate-
rials after dissociating from the compound film,119,131,132 despite
other studies showing near-perfect stoichiometry for LiF films as thin
119
as 0.5 nm. In the case of crystalline silicon, it is known that Li can
diffuse into the lattice and takes an interstitial place which creates a
donor level.146 Starting from a LiF film, dissociation would form Li+
and F
ions, both of which could diffuse into the c-Si bulk, in principle.
However, whilst some elements from groups I and II, like Li and Mg
create a donor impurity level inside the silicon band-gap at a respec-
tive values of 0.034 and 0.108 eV from the conduction band, this is
not the case for all the other alkali/alkaline earth metals (the next one
49
in proximity being Cs, with a defect at 0.3 eV from Ec). Thus, diffu-
sion of alkali/alkaline-earth metals would not necessarily lead to the
release of free electrons. The same could be argued for diffusion of
fluorine. Finally, if alkali metal doping of the semiconductor absorber
was contributing significantly, the dependence of ρc versus wafer dop-
ing should be very weak. In contrary, ρc was experimentally observed
to increase substantially with decreasing wafer doping (from 1016 to
11
1013 cm
3) in the n-Si/LiF1-x/Al system,96 consistently with therm-
ionic and field-emission theories.
3.2 | Current results in silicon PV
Despite being used in organic electronics for a long time, alkali metal
compounds have only recently gained momentum inside the c-Si-PV
community. This interest sparked in 2016 with a ‘fully silicon dopant
free’ structure using a front a-Si:H(i)/MoO3-x/ITO and rear a-Si:H(i)/
LiF1-x/Al achieving an efficiency of 19.42%.41 The performance for
this device was improved when adding a TiO2-x interlayer right before
LiF1-x, reaching an impressive 20.9% efficiency.43 Attempts at similar
structures have been made with other AMCs. An efficiency of 17.25%
was achieved with BaOx as the electron selective layer at the rear side
and a full-area ITO/Ni/VOx at the front.97 Also, an excellent efficiency
of 22.1% was achieved for an IBC structure employing MoO3-x and
MgF2-x/Mg/Al as hole and electron selective layers, respectively.142
Most explorative studies use a conventional front boron diffusion and
the AMC as the majority carrier contact at the back side. A 20.6% effi-
cient cell employing a LiF1-x/Al double layer with 1% contact-area
fraction was enabled by a ρc value of less than 10 mΩcm2 for this
stack.34 This design was improved by adding a thin passivating TiO2-x
interlayer between n-type c-Si and LiF/Al, leading to a power conver-
sion efficiency of 23.1% which is the highest reported for a c-Si solar
cell employing an AMC film.8 In similar studies (both with a front
boron diffusion process), thermally evaporated MgF2-x and MgO1-x
enabled 20.0% and 20.1% efficiencies combined with Al in a full-area
rear configuration.31,32 An (i) a-Si:H underlayer was required for the
thin MgF2 whereas MgO1-x was deposited directly on the silicon sur-
face. Other results using full-area rear AMC layers directly on silicon
have enabled power conversion efficiencies between 19% and
22%.29,35,98 All the c-Si solar cells employing an AMC, which sur-
passed the 19% efficiency benchmark are displayed in Figure 3.
Figure 7B shows a compilation of contact resistivity results from
literature using different AMCs versus their thickness on n-Si sub-
strates with resistivities of 1–3 Ωcm. Contact resistivity values corre-
spond to the area-normalized resistance between the wafer and the
outer metal electrode, that is, through the whole contact stack, usually
assessed with transfer-length method (TLM) or Cox and Strack mea-
surements. The plot contains structures where an interfacial (i)a-Si:H
layer (typically around 6 nm) is added in between silicon and the AMC
to make up for the lack of passivation obtained from these materials.
Although there is an exponential dependence on contact resistivity
against thickness for some of the materials (e.g. carbonates), films with
thicknesses higher than 10 nm often still show relatively low ρc. Also,
the increase in contact resistivity at very small thicknesses, typically
lower than 1 nm, has been attributed to a poor surface coverage for
such thin layers, allowing for some part of the wafer to have direct
metal-silicon contact. Figure 7C shows the reported work functions
measured for different AMC films, in most cases combined with a thin
aluminium (5 nm) layer on top. All of these values have been
extracted with UPS measurements. Note that many of these layers
12
enable work functions much lower than that of aluminium (4 eV)
and can go as low as 2.2 eV (BaCxOy). These extremely low work
functions support the argument that ohmic contact formation on n-
type c-Si is likely caused by downwards bending of the silicon bands.
The fabrication of AMC electron contacts typically involves a few
simple steps, starting with a silicon surface cleaning procedure
(e.g. RCA and HF dip), followed (sometimes) by a passivating interlayer
like thermal SiOx or PECVD a-Si:H after which the AMC/metal stack is
deposited. The most common and successful deposition technique for
these compounds is thermal evaporation from powder sources. The

6
deposition pressure is normally at around 10 mbar and evaporation
rates are reported in the range of 0.1–0.3 Å/s. Despite starting the pro-
cess with a stoichiometric powder, reactions during sublimation of the
compounds can lead to non-stoichiometric films. This is the case, for
instance, for alkali/alkaline-earth metal carbonates, which deviate sig-
nificantly from the expected chemical composition as measured by
XPS on the films.88 Other approaches for deposition of AMC films
include solution processing, where powders are dissolved in solvents
that can wet the silicon surface properly, that is, with a low surface ten-
sion such as methanol and ethanol. Spin coating is then performed as a
simple way to lay down the inks on the silicon surface.29,35 Finally, one
study reported successful ALD deposition of MgO1-x employed as pas-
108
sivating contact on a front junction n-type c-Si solar cell.
Probably the biggest weakness of AMCs as electron contacts is
the low level of passivation that they provide (though it might still be
better than direct metallization on silicon). Because of this, the most
successful implementations of AMCs are always in combination with a
passivating interlayer (e.g. a-Si:H, TiO2-x and SiO2-x) or for extremely
small coverage fractions in partial rear contact architectures, as
mentioned in the examples above. Nevertheless, some passivation has
been observed when using a couple of AMCs. For example, MgO1-x on
n-type c-Si showed a recombination current pre-factor
J0 = 950 fA/cm 2108
(likely aided by hydrogenation during the ALD pro-
cess) and BaO1-x achieved a minority carrier lifetime (at 1  1015 cm
3)
of 160 μs, 97
passivation which could originate from band-bending at
the n-Si/BaOx interface (note that a low work function of 2.2 eV was
measured). In this case, there might also be some influence from an
unintended SiO2-x interlayer which could enable an interface with less
defects. In some cases, authors reported an increase of Voc of cells with
AMCs as compared with only aluminium references, which in principle
might suggest an enhanced level of passivation. However, this
improvement is more likely due to the ohmic characteristics of the con-
tact, since rectifying contacts using direct metal can cause a voltage
loss (poor selectivity). Another weak point of AMCs is their negligible
lateral conductivity and thus the requirement for a conductive layer
(e.g. a TCO). To date, there has not been a successful study reporting
the implementation of AMC films together with a TCO, which is why
these materials are always used at the rear side of the cells and their
potential for low light absorption is not fully exploited. One attempt
has been made in the past with LiF1-x/Al in combination with ZnOx:Al,
147
but the devices suffered from instability.
Finally, other compounds which are thought to be highly ionic but
do not contain an alkali or alkaline earth parent metal are EuF336 and
IBARRA MICHEL ET AL.
CeF3.39 Similar mechanisms as discussed in this section might be tak-
ing place due to the similar ionic nature of the building molecules.
These materials have been used only at the rear side of a c-Si(n) solar
cell and have enabled efficiencies higher than 20%.
3.3 | Perspective and limitations
The lack of hydrogen during the favoured deposition methods (thermal
evaporation being the most popular) probably explains why the passiv-
ation performance is not on par with PECVD or ALD-deposited films.
Some people have used metal halide films to explore the potential of
fluorine to passivate silicon dangling bonds in a similar fashion as hydro-
gen does.148 However, as mentioned earlier, AMCs for electron contacts
are typically 0.5–2 nm and in such thin films the number of fluorine
atoms might not be sufficient. From the large-scale manufacturing per-
spective, thermal evaporation is not part of the mainstream c-Si PV
mass-scale fabrication process and even if it were, implementing a step
with the required throughput whilst trying to keep the thickness of the
films in the usually optimum 1 to 2 nm range seems challenging.
Another consideration to be made for these alkali compound films is
their limited stability. The fact that these compounds contain a parent
metal with a low ionization potential, means they have a tendency to
react in humid or oxidizing atmospheres. A recent study showed an
increased work function for the LiFx/Al electrode after interaction with
air which likely led to an increased fill factor of the cells over time.147
Also, at moderate to high temperatures (300–400 C), some of these
films start showing a degradation in performance, due to an increased
contact resistance.8,98 This could happen for instance, because the
nanometer scale AMC films might not provide protection of the passiv-
ating underlayer from the metal on top at elevated temperatures.43 The
300–400 C temperature threshold could still be maintained in the pro-
cess flow of SHJ solar cells but is still far from the thermal budgets
employed in poly-Si or conventional PERC solar cells.
Despite some important shortcomings, AMCs are still maturing
and have already shown many successful demonstrations with effi-
ciencies higher than the 20% mark. Even if these films are at the
moment not relevant for large-scale production, the opportunity to
make solar cells using such thin layers with a single evaporation step
is very attractive and aids in the study of ohmic contact formation on
silicon. It also allows for many research groups worldwide to get
involved in c-Si PV without an expensive toolset and avoiding the
handling of hazardous gases such as silane or phosphine.
4 | T R A N S I T I O N M E T A L OX I D E S
4.1 | Introduction
4.1.1 | Material properties
Transition metal oxides (TMOs) are widely studied in most microelec-
tronics fields due to their unique physical and chemical features.149,150
IBARRA MICHEL ET AL.
By definition, transition metals are elements which can give rise to
cations whose sub-shell d is partially filled,151 forming most of the d-
block in the periodic table. Their numerous available outer d electrons
enable a very wide range of stable oxidation states, from
III to +VIII.
Because of these outer d electrons, TMOs can act as strongly corre-
lated materials, that is, materials in which electrons behave neither as
localized electrons nor as collective delocalized electrons (electron-
sea-like in a solid). Their intermediate behaviour induces non-
negligible Coulombic interaction with neighbouring electrons. This
causes small overlap between metal d and oxygen p orbitals, giving
rise to narrow electronic d bands whose bandwidth is 1 to 2 eV
152
instead of the usual 5 to 15 eV for most metals. The present
quantic behaviour is at the origin of their singular properties and
makes them behave like metals (e.g. TiO, WO2, VO2 and MoO2),
semimetals (e.g. VO), n- or p-type semiconductors (MoO3-x, Ni1-xO),
or insulators (e.g. FeO, TiO2 and MoO3). Most of them can also switch
between two states, for example, from metal to insulator
under composition, temperature or pressure variation.152 Other
mechanisms such as the presence of potentially mobile and correlated
O
holes (p sub-shell partially filled)—in addition to divalent O2
(filled
p sub-shell)—in the solid state,152 ordered point defect structures
leading to sub-stoichiometry accompanied by crystallographic shears
like in WO3, MoO3 and TiO2 structures, or mixed valence
compounds—thanks to their various stable oxidation states—like in
FeO,153 give rise to continuous series of compositions (e.g. TiO1.900 to
TiO1.934)152,154–156 hence rich diversity in properties and transitions.
For these reasons, TMOs are used and studied in several
areas like organic electronics,61,157–161 smart windows and gas
sensors,162–164 battery-cathode materials,165–167 electronic and opti-
cal switches168,169 like resistance random access memory (ReRam) or
170–173
memristors.
4.1.2 | Historical background
As for alkali metals, interest for the introduction of TMOs in c-Si PV
arose from the OLED domain—whose first electronic device was
realized in 1965174—as researchers, pushed by the high potential
applications such as flat panels, raced to reduce the operating volt-
age whilst increasing emission efficiency and durability.175–178 After
several groups noticed that the band alignment and carrier confine-
ment in the heterostructure was closely linked to the device
performance,179–181 Adachi et al. demonstrated that decreasing the
barrier height at the interface between the hole transport layer
(HTL) and the anode improved operating voltage and durability.182
Tokito et al.157 extended their study in 1996 using different metal
oxides (V2O5-x, MoO3-x and RuO2-x), linking metal-oxide work
function to device performance. Since then, metal oxides were
extensively studied and used in this field and that of organic photo-
voltaics and recently came to inorganic silicon-based PV to be used
as electron or hole contacts. In this section, we will discuss the per-
formance and limitations of different metal oxides used as contacts
in silicon solar cells.
13
4.1.3 | TMO classification through the d band
occupancy
The diverse and complex interactions between transition metals and
oxygen, as well as the variety of crystallographic structures, result in a
wide range of optoelectronics properties for the TMOs. Sub-grouping
them under similar electronic behaviour is thus challenging. However, a
common criterion for classification, adopted by several chemists and
physicists, lies in the oxide d bands occupancy since it is closely linked
to their electronic behaviour.183 In their review on TMOs for organic
electronics, Greiner and Lu used it to divide them under 4 classes184
which we illustrate in Figure 8. Class 1 groups oxides with empty
d bands (d0), which simply follows the collective delocalized electrons
models and have a natural tendency to form oxygen vacancies which
result in defect donor states in the bandgap (oxygen-deficient TMOs),
mostly due to unstable oxygen interstitials. These states are occupied
and reside below the band conduction minimum, making the TMOs
from class 1 generally behaving as n-type semiconductors (sub-class
1a), such as MoO3-x, TiO2-x, WO3-x, ZrO2-x, V2O5-x, CrO3-x. Reduction
of these oxides tends to form TMOs with metallic behaviour (d bands
partially filled) stemming from the filling of few electrons in the d bands
(e.g. d1, d2 and d3). They can be regrouped in class 2 as for instance
WO2, TiO, MoO2, Cr2-xO3. In class 3, d bands are also partially filled
but the large number of electrons in the bands makes TMOs of this
class behave as strongly correlated materials, with differing electronic
band structure compared to the one predicted by the delocalized elec-
trons theory. They can be Mott-Hubbard and charge-transfer insula-
tors, with transitions from metallic to insulator behaviour according to
pressure, doping, etc. Materials of this class have complex behaviour,
not really well modelled yet, and Ni1-xO, Cu1-xO and Co1-xO, which are
p-type semiconductors, may belong to this class. Oxides with
completely filled bands (d10), class 4, tend to be p-type semiconductors,
generally due to metal-cation vacancies, like Ag2-xO or Cu2-xO.
Metals from the last column of the d-block are usually not consid-
ered as transition metals and referred to as poor metals. Their oxides
have a different electronic behaviour due to their full d band. Some of
these oxides are used as passivating layers (e.g. Al2O3 and Ga2O3) or
TCOs (ZnO, SnO2, In2O3). As some have also been used as electron-
selective contacts for solar cells, like SnO2 or ZnO, we will include
them in the following discussion.
4.1.4 | Mechanism for carrier selectivity
When used as hole or electron transport layers, selectivity is typically
provided by the TMO work function which produces upward or
downward band bending. Their wide band gap ensures optical trans-
parency, and can also be used as an additional barrier for the unde-
sired carrier, when an electron (resp. hole) selective contact is formed
by a n-type (resp. p-type) TMO.184 However, this is usually not the
case, and in particular for high work function n-type TMOs acting as
hole contact, such as MoO3-x or WO3-x, for which the TMO-Si inter-
face acts as a recombination junction. A lowering of the work function
14 IBARRA MICHEL ET AL.

F I G U R E 8 Classification of the most common TMOs used for LED and PV applications according to the d band occupancy and the metal
cation oxidation state. Oxides of poor metals like SnO2 or ZnO, and unsuited oxides with metallic behaviour like MoO2,WO2 or CrO2 are not
represented. Metal cations in their highest oxidation state (fully oxidized, class 1) have empty s and d valence orbitals (so empty d bands, d0, in the
solid case): all electrons are captured in surrounding oxygens (more electronegative) p orbitals. Darkest shades represent most investigated and
efficient TMOs as selective contacts, whilst lightest the less investigated and/or efficient. For more information about their properties and
(potential) use, the reader is referred to the text. *Stars indicate the TMO has never been reported as a carrier selective contact in c-Si PV [Colour
figure can be viewed at wileyonlinelibrary.com]

for these TMOs of a few hundreds of meV would enhance parasitic
thermionic emission of electrons and hamper Voc.
Precise knowledge of the work function of the TMOs used in
solar cells is hard to achieve, and even more so when incorporated in a
contact stack. Indeed, work function measurement is in general highly
sensitive to small changes at the material surface such as defects
(dangling bonds, vacancies, adsorbates, surface reconstruction, etc.),
dipole creation, or Fermi level pinning. For TMOs, the work function is
notoriously more sensitive since these materials can additionally be
easily oxidized or reduced183 with ambient air or in proximity to the
material/metal-oxide interface184–186 through an exchange of oxygen
(redox reaction) and/or electrons (Fermi level differences at the inter-
face). This sensitivity of TMOs is at the origin of oxygen or metal cat-
ion deficiency, generally introducing band-gap defects or changes in
the cation oxidation state. The bandgap defects tune the TMO carrier
concentration (electrons or holes) and shift the Fermi level towards
one band whereas changing the oxidation state modifies electronega-
185
tivity, which is directly linked to the material work function. We
generally observe that the higher the metal cation oxidation state, the
higher the electronegativity, the higher the work function. Interest-
ingly, TMO hole contacts stand in an inner part of the d-block com-
pared with electron ones (see periodic table Figure 2).
4.2 | Transition metal oxides as hole contacts
A summary of the best solar cell performances reached with
TMO-based hole contacts is shown in Figure 3.
4.2.1 | MoO3-x, V2O5-x and WO3-x
Among the various TMOs having hole-selective properties, MoO3-x,
V2O5-x and WO3-x are the ones with the highest work function and
are the most investigated. The first silicon solar cell to integrate a
TMO as a selective contact, namely molybdenum oxide (MoO3-x), was
made in 2011 with the thin-film a-Si: H-based technology,187 and in
2014 in a c-Si heterojunction solar cell with the same material.188,189
MoO3-x remains by far the most tested.9,22,41,44,45,62–64,188–198 It is
today the TMO providing the best performance amongst
devices using at least one metal-compound contact. Fewer
studies were conducted with V2O5-x25,26,62,63,97,199–205 and
62,63,192,194,195,206,207
WO3-x with highest efficiencies achieved of
21.6%25 and 17.9%,192 respectively. Less interest in the latter material
could come from the too high contact and bulk resistivity it provides
when implemented in SHJ cells.62,63,194
Passivation quality
One limitation of hole-selective TMOs lies in the fact that they do not
provide excellent passivation to c-Si surfaces (see Figure 9). In their
work, Gerling et al.63 showed that MoO3-x, V2O5-x and WO3-x have an
inherent (but limited) passivation that stems from the reduced density
of surface electrons induced by the high work function, as well as the
presence of a substoichiometric SiO2-x layer originating from the
redox reaction between the TMO and c-Si. The authors emphasize
that the induced band bending is probably lowered by dipole effects,
and the SiO2-x layer formed may be too defective, which limits passiv-
ation of the interface. Among the three, V2O5-x is the one providing
the highest passivation on n-type c-Si with an implied Voc of 653 mV
and saturation current of 150 fA/cm2, followed by MoO3-x (637 mV
and 230 fA/cm2) and WO3-x (543 mV and 420 fA/cm2). Those
results and range of values have been confirmed by several
groups,22,193,194,196,199,216 yet with an iVoc record above 670 mV pro-
vided by V2O5-x25 (see below).
Structures involving a TMO as hole selective contact without
passivation layer did not exceed 16.7% for MoO3-x,217 17.7% for
WO3-x (after annealing at 180 C)192 and recently 19.0% for
V2O5-x.205 For the case of V2O5-x, Masmitjà et al. could push the
IBARRA MICHEL ET AL. 15

F I G U R E 9 Compilation of literature values of

the contact resistivity ⍴c for hole-selective (A) and
electron-selective (B) contacts as well as the
contact saturation current J0 (C) as a function of
film thickness. The wafer doping type and
resistivity has been included in parentheses, since
this can strongly affect contact resistivity.2
Electron-selective materials are shown in closed
symbols, hole-selective materials in open symbols.
For multilayer stacks, the contact material of
which the thickness is referred to is denoted in
bold. The data for Ta2O5-x and SiO2/ZnO:Al
included SiNx and Al2O3 as sacrificial capping
layers, respectively. (A) The plot contains data for
evaporated a-Si:H/MoO3-x/ITO/Ag,208 MoO3-x/
Pd,189 WO3-x/Au,209 WO3-x/Al,194 CrOx/Ag,210
NiO/Ag211 and ALD (a-Si:H/)V2O5-x/Ag.25 (B) The
plot contains data for ALD TiO2-x,212 Nb2O5-x,84
Ta2O5-x213 and ZnO:Al,81 PVD ITO,214 LPCVD
ZnO44 and sol–gel SnO2.215 (C) In addition to the
materials referred to in the top and middle panel,
the data points include evaporated MgOx31 and
MgF232 as well as ALD SiO2/MoO3-x82 [Colour
figure can be viewed at wileyonlinelibrary.com]

efficiency to 19.7% by the introduction of a thin Ni interlayer
between V2O5-x and the metal electrode in an IBC structure.203
Later, Kim et al. manage to reach 17.25% in a standard front-back
contacted cell, with the same additional Ni layer, fully dopant free
contacts and a double anti reflective coating.97 Still both solar cells
are limited by a low Voc (656 and 621 mV, respectively). To date,
achieving higher efficiencies requires the presence of an additional
passivation layer at c-Si interface as for standard SHJ, like (i)a-Si:H,
SiO2:H or Al2O3, partially offsetting the current gain provided by
their transparency.
16
Deposition methods
For all the deposition methods presented hereunder, the TMOs all
grow in an amorphous arrangement. In the case of MoO3-x, thermal
evaporation is the most used deposition method and provides the
highest solar cell performance. However, it is far from the ideal
deposition process since it is difficult to control the oxygen concentra-
tion, a critical factor for TMOs as mentioned in the previous sections. A
few studies have explored more tunable deposition processes such as
reactive sputtering195,218 and atomic layer deposition (ALD).198,219–221
Final devices in these studies showed systematically limited
performance—low Voc and FF—ascribed to poorer selectivity compared
with thermally evaporated MoO3-x which appears as the most straight-
forward method to prepare contact-grade MoO3-x films. The reason is
yet unclear, and possibly stems from excessively oxygen-deficient
material or too resistive oxides, and/or degradation due to the deposi-
tion atmosphere (plasma, hydrogen (typically 3%–11%222), water, etc.).
In view of the limited amount of publications explaining this
underperformance, and vast parameter space, it is nevertheless prema-
ture to conclude authoritatively on the (un)suitability of sputtered or
atomic layer deposited MoO3-x to act as carrier-selective contacts to
223
silicon heterojunction solar cells. In a recent study, Li et al. used hot
wire oxidation-sublimation deposition (HWOSD), claiming this novel
technique could be easily upscaled and in which MoO3-x oxygen rate
can be well controlled—without showing the effect of oxygen rate on
cell performance though. The present deposition method could be a
promising alternative to the standard Joule effect evaporation, com-
bining evaporation and controlled oxygen rate. In a configuration with
a full area 14-nm-MoO3-x layer placed at the back side of the absorber,
an (i)a-Si:H passivation interlayer annealed prior to MoO3-x deposition
(‘pre-annealing’), they reached an efficiency of 21.10% and remarkable
Voc of 714 mV.
The same tendency is observed for WO3-x and V2O5-x with a pre-
dominance of thermal evaporation and few results with alternative
deposition techniques. Sputtered WO3-x also provides lower Voc and
FF compared with the thermally evaporated one.195,207,224 In the lat-
ter work, Mews et al. reached 16.6% efficiency and a Voc around
700 mV with front-contact sputtered WO3-x and (i)a-Si:H passivation
layer. The best thermally evaporated V2O5-x involved as front hole
contact, with an efficiency of 21.01% and an impressive FF of 83.25%
ascribed to UV/O3-treated SiOx passivation layer, was recently
achieved by Du et al.26 In 2020, Yang et al.25 demonstrated superior
performance for V2O5-x deposited by ALD at 230 C compared with
2
evaporated—J0 of 44 fA/cm and iVoc above 670 mV on both p- and
n-type c-Si. A record efficiency for V2O5-x-based hole contact SHJ of
21.6% was achieved with pre-annealed (i)a-Si:H passivation layer and
V2O5-x deposited by ALD at 230 C as full-area back contact. The
improvement is partly attributed to the high deposition temperature
which results in a high work function, a result also reported in a previ-
ous study.225 Again, strong conclusions are hard to make due to the
limited amount of published studies on the different ways of deposi-
tions, yet forming good contacts with WO3-x and V2O5-x seems less
particular to thermal evaporation compared to the use of MoO3-x.
IBARRA MICHEL ET AL.
Structures and their record efficiencies
A rich variety of architectures, principally involving n-type c-Si for the
absorber, have been used for the different hole-selective
TMOs.9,25,41,64,190–192,207,223,226,227 The structures presented in this
paragraph involve a dedicated passivation layer in addition with the
TMO selective contact, and results achieved without passivation
layers are mentioned above.
For front-back-contacted structures, the highest-efficiency
device using a TMO-based hole contact reached 23.5% and was
achieved by Dréon et al. using MoO3-x.9 It utilized a thermally evap-
orated 4-mn thick MoO3-x layer in between an (i)a-Si:H passivating
layer and an ITO film. The MoO3-x contact is placed on the front-
side of the device, which uses an Ag-screen printed metallization
cured at a temperature of 130 C, and a traditional SHJ architecture
on the rear side. The high efficiency is mostly attributed to excellent
passivation provided by the (i)a-Si:H layer, and the high transpar-
ency (higher than (p)a-Si:H) and good selectivity of the thin MoO3-x
layer. The best V2O5-x double-side contacted solar cell (21.6% effi-
cient) was already mentioned in the deposition methods paragraph,
made by Yang et al.25 For the WO3-x-based double-side contacted
cells, no devices with record efficiency were made recently and the
best cell remains the above-mentioned one processed by Bivour
et al.199 in 2015 reaching 17.9%. Solar cells employing both front
and back Si-free contacts were also processed41,97 with record
efficiency for this category of 21.4% using Ag/ITO/MoO3-x/(i)a-Si:H
as a front hole contact and Al/ZnO/LiFx/(i)a-Si:H, achieved by
Zhong et al.44 The same structure was used in a bifacial architecture
by Lin et al. in 2021 and could reach 21 mW/cm2 in bifacial
operation considering 0.15 sun rear irradiance.228
More complex structures were also explored. Among them, IBC
architectures are the most investigated, typically using MoO3-x in
the hole-contact stack.193,194 The highest efficiency of 22.1% was
142
obtained by Wu et al. using (i)a-Si:H as a passivation layer and
thermally evaporated MoO3-x/Ag and MgFx/Mg/Al as hole- and
electron-selective contacts. In addition, WO3-x with no passivation
layer achieved an efficiency of 16.6%,194 and finally V2O5-x194
attained 19.7%,203 again with no passivation layer, and a V2O5-x/Ni
contact stack are also worth notice. Structures with partial rear con-
tacts, like with MoO3-x on a p-type wafer by Bullock et al.22
(20.4%), or with chromium oxide (see Section 4.2.2) have demon-
strated the versatility of such contacts. The Shen group further
tested hole contact TMOs in a multilayer stack for selective
transparent conductive electrodes, following the organic electronic
alternative TCO exploration.229–234 Stacks of WO3-x/Ag/WO3-x,235
V2O5-x/Ag, Ca or Au/V2O5-x,201 MoO3-x/Ag/MoO3-x236 and CrOx/
Ag/CrOx21 (see “Deposition methods” section for more details
about CrO3-x) were all trialled via thermal evaporation, with notable
efficiencies of 19.0% in the V2O5-x/Au/V2O5-x IBC configuration
with no dedicated passivation layer (Voc of 651 mV). Yet such
electrodes generally require more than 5–10 nm of metal to reach
good conductivities which still limits transmittance and reflectance
of the stack.
IBARRA MICHEL ET AL.
Stability towards air exposure, reducing species and thermal
treatments
The electronic properties of TMOs are known to be sensitive to air
exposure, contact with reducing species and heating, which are all
involved when fabricating a solar cell, and might affect the solar cell
final performance. Air exposure can reduce the metal oxide through
reaction with hydrogen, water, or adsorption of other elements like
carbon63 and other metals. This applies typically to MoO3-x,188,237,238
V2O5-x239 and WO3-x.240,241 Some studies reported that reduction of
the TMO occurs at the interface TMO/element (Si, perovskites,
metals, TCOs), by oxygen (redox reaction) or electron (charge transfer)
186,242 
exchanges. Upon thermal treatments above 150 C—as cur-
rently often required for Si-based solar cells—V2O5-x243,244 and
MoO3-x190,191,196,197,226,245 undergo severe degradation. This degra-
dation was ascribed to H effusion from the underlayers (reducing the
TMO), thickening of the SiOx interlayer, or oxygen exchange with the
top TCO. All these degradation mechanisms tend to raise a barrier to
hole extraction, be it by WF reduction or introduction of an insulating
layer, resulting in an ‘S-shape’ in the solar cell J-V characteristics that
can strongly impede Voc and FF. Yet WO3-x seems more resilient than
its counterparts to air exposure (tends to have a fully—or over-
oxidized surface62), plasma treatment246 and thermal post-annealing
 192
at 180 C at least (showed to turn non-ohmic after annealing at
 247
200 C on test structures ). More investigation is required to con-
clude on WO3-x layer stability. A couple of pre-treatment strategies
have been developed to prevent TMOs from some of the aforemen-
tioned degradations, more particularly for MoO3-x-based contacts.
Essig et al.197 recommended to anneal the (i)a-Si:H passivation layer
prior to MoO3-x deposition at 250 C to restrict the amount of effused
H from the intrinsic layer to the MoO3-x layer during subsequent
annealing (e.g. Ag-paste curing in case of screen-printing) This
resulted in significantly improved performance for final cells cured at
190 C. Recently, Mazzarella et al.64 suggested a plasma treatment
before MoO3-x deposition, with the aim of mitigating the dipole
moment formed at the MoO3-x/SiOx/a-Si:H interface. Applying it prior
to the deposition of MoO3-x layers of 3.5–8 nm thickness mitigated
the S-shape in the J-V characteristics. Nevertheless, a pretreatment is
not mandatory for high performance, as the 23.5%-efficient MoO3-x-
based device using a 4-nm-thick layer was achieved without any pre-
treatment, albeit restricting the post-MoO3-x-growth thermal
treatments to 130 C.9 During evaporation of the TMO, increasing the
oxygen rate to increase WF was attempted by some groups, yet with
limited success probably explained by MoO3-x thermodynamic nature
of being oxygen deficient.184
4.2.2 | Other hole-selective TMOs
Other TMOs, less common in the c-Si PV field, have been tried as hole
contacts as well, including chromium oxide, nickel oxide and copper
oxide.
Chromium oxide is known to have numerous oxide phases like
Cr2O, CrO, Cr3O4, Cr2O3, CrO2, Cr8O11 and CrO3.248,249 Cr2O3
17
(+III oxidation state, belonging to class 2) is the most stable phase,
with a tendency to be Cr deficient (Cr2-xO3) making it p-type with a
work function around 5.0 eV.184,250 The second most stable phase is
CrO3 (+VI oxidation state, class 1), which tends to be oxygen deficient
(CrO3-x) and behaves as an n-type semiconductor with a high work
function around 6.75 eV in absence of air exposure.184,250 However,
pure CrO3-x or Cr2-xO3 phases are hard to reach, and oxidation states
of +III, +IV and +VI generally coexist,249 with a predominance of +III
or +VI depending on the ambient environment. A couple of studies
from perovskite and organic photovoltaics reported the use of
Cr2-xO3-predominant chromium oxide,248,251–255 obtained by evapo-
ration or RF sputtering of pure Cr initially used as a barrier to chemical
reactions and metal diffusion, then as a hole transporting layer. In
2018, Lin et al. 21,210
used CrO3-x-predominant oxide, obtained by
evaporation of stoichiometric CrO3 particles, as a hole contact in SHJ.
They studied the phases' predominance under different annealing
temperatures in N2- or O2-rich atmospheres. The best solar cell effi-
ciency obtained was 20.3%, using a p-type c-Si absorber and afore-
mentioned multilayer stack CrO3-x/Ag/CrO3-x (with CrO3-x: 67.9%, Cr
(OH)3: 16.1% and Cr2-xO3: 16% for the chromium oxide layer) as par-
tial rear hole-contact and an Al2O3/SiNx rear passivation layer. A work
function of 4.8 eV was obtained, probably limited by reduction with H
and presence of the Cr2-xO3 phase. Recently, Xu et al.256 processed
aqueous solution of a copper doped chromium oxide (mixed phase of
Cr2-xO3, Cr (OH)3, CrO3-x and CrO2), spin-coated at the rear side of p-
type Si absorber, post annealed at 150 C. They obtained a work func-
tion of 5.04 eV for the films, and solar cell efficiency of 16.6% (15.9%
without Cu doping). Other work has not been reported yet, maybe
due to CrO3-x high toxicity.
TiO2-x is a well-known TMO electron-selective contact, a selectiv-
ity widely attributed to the specific band alignment with c-Si (see
Section 4.3.2 below). However, Matsui et al. have demonstrated that
under the right conditions, a stack of TiO2-x/ITO can also be used as a
hole-selective contact, resulting in an efficiency of 21.1%.24,257 The
contact has proper characteristics, as witnessed by the external volt-
age and FF of 677 mV and 76.8%, respectively. Owing to the high
transparency of the stack, a noteworthy Jsc of 40.5 mA/cm2 was
obtained. The authors examined both plasma and thermal ALD TiOx
and showed that for the case of thermal ALD a proper hole-selective
contact can be formed by the application of a hydrogen plasma to the
TiO2-x, followed by ITO sputtering and annealing in an oxygen-
containing ambient. This leads to the formation of a TiOxSiy interface,
which is thought to aid in passivation and selectivity. The hole-
selectivity is attributed to a strong upward band bending in the c-Si
which originates from a combination of the negative fixed charge in
the TiOx, the high WF of the ITO and the depinning of the Fermi level
by the passivating TiOx. Furthermore, the authors demonstrated that
the FF does not strongly depend on the TiOx thickness for at least
5–10 nm, suggesting that the VB offset does not affect transport,
indicating transport is dominated by hopping through defects in the
TiOx layer.
NiO is the most studied class 3 TMO, both fundamentally and
experimentally. Even though understanding its electronic behaviour is
18
still highly challenging and debated,258–260 NiO is a long-time-known
p-type semiconductor—due to its natural tendency to be metal-
deficient (Ni1-xO)—, 261
which must belong to the Mott (or ‘charge
transfer’) insulators family.184,261,262 With a band-gap reported to
vary from 3.2 eV to 4.3 eV —depending on computation and
262–269
theoretical models, measurements methods, or how the band edge is
defined—and a work function ranging from 6.3 eV with no air expo-
sure, to 5 eV, 184,268,270
it seems to be a perfect hole contact for
solar cells applications. It has been widely used in organic, dye-
sensitized and perovskite photovoltaics and is well established to help
268,271–284
for hole transport, limited however by non-ideal interfacial
conditions.285–287 For crystalline silicon solar cells, modelling was
largely used to investigate the suitability of NiO as hole con-
tact.68,288–291 Experimentally, a few SHJ devices were processed
211,290–294
since 2016 with no passivation layers for most of them, and
performances limited by non-ideal interface (low Voc) in all cases. The
211
best efficiency of 15.2% was obtained by Nayak et al. with a ther-
mally evaporated 10-nm-thick Ni1-xO on a chemically grown silicon
oxide as passivation layer, n-type c-Si as the absorber and SiO2-x/
LiF1-x/Al as electron contact. The Voc was limited to 580 mV indicat-
ing poor passivation or selectivity. Woods-Robinson et al.291 tried
sputtered Ni1-xO with (i)a-Si:H passivation layer as hole contact on an
n-type c-Si absorber, giving very poor results. Surprisingly, thermally
evaporated Ni1-xO in combination with a high quality passivation layer
(e.g. SiOx:H and (i)a-Si:H) has not been reported to date.
Cuprite oxide (CuO, class 3 oxide) and cuprous oxide (Cu2O, class
1 oxide) are the two most stable phases of copper oxide, and well
known to be naturally p-type semiconductors through Cu cation
deficiency.295–297 They are abundant and non-toxic materials, with
high work functions (5.9 eV and 4.8–5 eV, respectively).184,295,298,299
However, they both have small to moderate band-gaps of 1.2–1.8 eV
for Cu1-xO and 2.1–2.2 eV for Cu2-xO,184,300,301 making them quite
absorbent if used as front contacts. In fact, they were used in the
diode industry before c-Si became standard. In the field of
perovskite solar cells, these materials were shown to improve the hole
extraction,297,302,303 whilst for crystalline Si solar cells, mostly
using Cu2-xO, the few available studies showed very limited
efficiencies up to 3.5%,304–307 probably due to the particularly defec-
tive interface.
4.3 | Transition metal oxides as electron contacts
4.3.1 | General considerations
In recent years, a variety of TMOs has been explored and
implemented as electron contacts, including TiO2-x, Nb2O5-x,
Ta2O5-x and common TCO materials such as ZnO, ITO and
SnO2.38,84,213–215,308 Similarly as for the hole-selective contacts dis-
cussed above, the exact electronic properties of these electron-
selective TMOs can depend strongly on, for example, stoichiometry
and defects. For example, oxygen vacancies in TiO2-x and ZnO are
known to contribute to conductivity through free electrons.309,310
IBARRA MICHEL ET AL.
Hydrogen is known to be an electron donor in, for example, ZnO and
In2O3 but also to aid in the passivation of defects at grain boundaries
in polycrystalline materials, and can therefore contribute greatly to
the overall conductivity of the material.85,88,311–313 The deposition
method and conditions as well as post-deposition annealing, in partic-
ular whether an oxidizing or reducing environment is used, can there-
fore strongly influence the electrical properties.81
Comparing n- and p-type TMOs, it appears that extrinsic n-type
doping of TMOs is much more readily available than for p-type mate-
rials, with a wide library of available n-type dopants such as Al, B, Ga
and H for ZnO, Sn, Zn, W, Zr and H for In2O3 and Nb and Ta for
TiO2-x.87,92,313–318 Also, as can be clearly seen in Figure 9C) many of
the TMO electron contacts such as TiO2-x, Nb2O5-x and ZnO have
been found to give good surface passivation to c-Si sur-
faces.81,83,319,320 This contrasts from most hole-selective TMOs which
often require a dedicated a-Si:H passivation layer.82,190,321 Part of this
discrepancy could be related to the role of embedded H, which is
known to aid the surface passivation, but is typically avoided in case
of high WF hole-selective TMOs such as MoO3-x, WO3-x and V2O5-x
as it can impair their selectivity.322 In that respect, it also makes sense
that most successful demonstrations of electron-selective TMO con-
tacts have been primarily made using deposition techniques that
incorporate a significant amount of hydrogen in the film such as ALD
and CVD, whilst H-devoid deposition techniques such as thermal
evaporation or sputtering have typically been more employed for the
preparation of the hole-selective contacts.
4.3.2 | Titanium dioxide
Of the various electron contact TMOs, TiO2-x has been the most
widely researched in the past few years. TiOx is not a newcomer in
c-Si PV, as historically it has been used as an antireflection coating on
c-Si until the late 1990s thanks to its refractive index of 2.4 at a
wavelength of 600 nm. Later on it was replaced by SiNx, since that
material yields a higher surface passivation quality and furthermore
aids bulk-defect passivation of (multicrystalline) silicon by the release
of hydrogen in the high-temperature processing steps. The resurgence
in the interest in TiO2-x can most likely be linked to two discoveries:
Firstly, Avasthi et al. showed in 2013 that TiO2-x can act as a
hole-blocking layer on c-Si surfaces, and secondly, its growing use in
dye-sensitized, polymer and perovskite solar cells.323 The origin of
selectivity was at that time attributed to the negligible conduction
band offset, enabling electrons to flow, combined with a large
valence-band offset which prevents the hole extraction. Although
attractive, this explanation is currently being revisited in light of the
recent demonstration of hole-selective contacts based on TiO2-x as
discussed in the previous section. Nevertheless, this work clearly
demonstrated the selective potential of TiO2-x, in spite of the limited
efficiency due to the rudimental cell design. Around the same time,
Liao et al. demonstrated that TiO2-x can yield a high surface passiv-
ation quality using low-temperature ALD followed by post-deposition
annealing and light-soaking.319
IBARRA MICHEL ET AL.
Following these demonstrations, great strides were quickly made
in improving the efficiency of TiO2-x-based contacts as well as in
gaining insights into the underlying mechanisms governing the passiv-
ation and selectivity of the contact. In 2016, Yang et al. progressively
improved the efficiency to 22.1%.38,324,325 The main improvement
came from a boost in the Voc of the cell by the introduction of an
ultrathin thermally grown SiO2 layer to improve the surface passiv-
ation quality at the expense of a small increase in contact resistivity
(see also Figure 9B). Additionally, the capping aluminium electrode
was shown in this work to play a key role in the electron selectivity.
Specifically, Al was shown to aid in reducing the contact resistivity,
which was attributed to a thermodynamically favourable migration of
oxygen from the TiO2-x to the Al, resulting in the formation of more
conductive, oxygen-deficient TiO2-x and a thin Al2O3 layer that appar-
ently does not hamper the transport significantly.324 Besides improv-
ing the contact resistivity by reducing the TiO2-x, the authors
demonstrated that the Al also aids in improving the passivation of the
TiO2-x contact considerably. This was attributed to an alneal-like pro-
cess as is common for SiO2/Al systems, as this effect was not
observed for the other metals investigated.38 Yang et al. also demon-
strated thermal stability of the TiO2-x contact to mild firing conditions
with a peak temperature of 575 C.38 Although this is below the firing

temperatures of typically 700–800 C employed in the production of
PERC cells, it does show that the TiO2-x contacts are significantly
more thermally stable than a-Si:H based contacts as well as, for
example, MoO3-x, thereby possibly enabling contacting by higher-
temperature conductive pastes.
Besides Al, a variety of low work function metals has been suc-
cessfully used to make selective contacts with TiO2-x. The rationale
behind the use of a low work function metal such as Ca or Yb is that
they induce downward band bending at the Si surface, whilst the
TiO2-x aids in reducing Fermi level pinning. Using Ca as contacting
metal, Allen et al. demonstrated a very low contact resistivity of
5 mΩcm2.326 At the same time, it was shown that the application of
Ca impairs the surface passivation quality considerably, going from
50 fA/cm2 prior to metallization to an estimated <10 000 fA/cm2
post-metallization. Because of the combination of very low contact
resistivity and reasonably high J0,met the stack is mostly suited for use
as partial rear contact, and a notable efficiency of 21.8% was
achieved. Compared to a similar cell without TiO2-x, a gain in 1.5%
absolute was demonstrated, which was attributed to a reduction in
Fermi level pinning by the presence of the TiO2-x.326 Similarly, Cho
et al. explored the use of both Ca and Yb as low work function
contacting materials.327,328 Key difference is the use of a dedicated
a-Si:H passivation layer, whose enhanced passivation enabled Voc
values up to 732 mV. Importantly, the TiO2-x layer also acts as a
diffusion barrier between the metal and the a-Si:H, and specifically in
the case of Yb prevents the formation of a silicide during annealing. In
all experimental demonstrations, the TiO2-x/metal stack was used on
the rear of the device, and there is no report of leveraging its
transparency in a front-contact stack, notably due to the
unsuccessfulness of combining it with a TCO. Note that this contrasts
to the use of TiO2-x as hole-selective contact in the previously
19
mentioned work of Matsui et al., where it was used as front contact in
combination with ITO.24
4.3.3 | Other electron-selective TMOs
Nb2O5 exhibits almost equal band positions as TiO2-x, and as such also
Nb2O5-x has for example been used as an electron-selective layer in
perovskite solar cells329–.330 In 2018, Macco et al. demonstrated that
similarly to ALD TiO2-x, ALD Nb2O5-x can yield good passivation of sil-
icon surfaces, with benefits from a dedicated SiO2 interlayer, a post-
deposition forming gas anneal, as well as light soaking.83 Moreover,
when an RCA SiO2 interlayer is used, the passivation level remains
equally high for ultrathin films down to 1 nm (see also Figure 9). In
subsequent work, it was shown that Nb2O5-x/Al stacks can also yield
relatively low contact resistivity values of 70 and 124 mΩcm2 for
1 and 2 nm-thick films, respectively, although a solar cell demonstra-
tion is lacking.84 Interestingly, as also frequently reported for TiO2-x,
part of the excellent passivation of the Nb2O5-x film is attributed to
the strong negative fixed charge Qf of 1.6–1.9  1012 cm
2, which
induces an upward band bending of 850 mV in 3 Ωcm n-type c-Si.
Such band bending is similarly strong as induced by hole-selective
MoO3-x and is sufficient to form a hole-selective space charge region
in the c-Si.331 Therefore, it is in principle remarkable that a good
n-type contact can be formed. In this respect, it is most likely that the
Al interacts with the Nb2O5-x, overcompensating the fixed charge
and/or that the WF of Al overrules the band bending. Interestingly,
since Nb2O5-x is capable of inducing a strong upward band bending, it
is conceivable that it can yield a similar ambipolar function as TiO2-x
and act as a hole-contact when contacted with ITO, although this has
so far not been reported.
SnO2, Ta2O5-x and ZnO(:SiO2) have also been demonstrated to
yield notable efficiencies of 18.6%, 19.1% and 19.5%, respec-
tively.213,215,332 These layers have so far only been shown to work in
combination with a low work function metal, in these cases Mg or
Al. Therefore, it cannot be said for sure that these materials by them-
selves give proper electron-selectivity, or that they merely help the
selectivity by reducing Fermi level pinning, whilst not impeding
electron-extraction significantly. For Ta2O5-x, Wan et al. argued that
the ALD layer, which can also yield good surface passivation, draws
its electron-selectivity from a small CB and large VB offset, similar as
for TiO2-x.213 Interestingly, they show that hydrogenation from a sac-
rificial SiNx capping layer is crucial for the contact formation, as it
helps reduce the stoichiometry of Ta2O5-x film and at the same time
reduces the WF from approximately 3.57 to 3.27 eV. For 6 nm-thick
films they found the best trade-off between improving passivation
and increasing contact resistivity with thickness. On the device level,
the obtained Voc of 638 mV strongly lags behind the iVoc of 690 mV,
pointing to a reduction in surface passivation quality upon evapora-
tion of the Mg metal or lack of selectivity. Liu et al. demonstrated the
use of SnO2 prepared by sol–gel in an electron-selective contact
structure.215 Since SnO2 does not yield surface passivation, they
explored the role of a passivating interlayer (a-Si:H and/or SiO2), as
20
well as the influence of the metal used for contacting. There was a
clear dependency of device performance on the work function of the
contacting metal, where Mg worked best, followed by Al, whereas
poor cells were obtained for the higher WF metals Ni, Ag and
Au. Extremely good contact properties of 2.4 fA/cm2 and 35 mΩcm2
were obtained from test structures, although this was not per se
reflected by the device characteristics, with the Voc and FF being
695 mV and 71.1%, respectively. Simultaneously, Zhong et al. focused
on ZnO:SiO2/metal stacks, and studied the impact of the ZnO:SiO2
layer composition, its thickness, and the nature of the metal. They
evidenced that good solar cell performance can be reached indepen-
dent of the ZnO:SiO2 layer composition, but that its thickness needs
to be 2 nm and the capping electrode needs to be a low work func-
tion metal such as Al or Mg (Cu and Au giving poor results). Still a
remarkable 19.5% efficiency was demonstrated, notably using reac-
tive sputtering for the deposition of the electron-selective contact.
4.3.4 | Transparent conductive oxides
Also TCO materials such as Sn-doped In2O3 (ITO) and Al- and B-
doped ZnO (ZnO:Al, ZnO:B) have been explored as electron-selective
contacts, often paired with thin SiO2 or a-Si:H for passivation. The
appeal of such an approach is that in addition to being a contacting
material, the TCO can serve as an antireflection coating as well as lat-
eral conductor. There was early interest in this approach, especially in
the 1970s where the use of ITO as Schottky contact to c-Si was
333
explored and efficiencies in excess of 12% were obtained. In 2014,
Young et al. revived this approach, looking at Si/SiO2/ITO contact
structures.214 Relatively good contact properties were obtained after

forming gas annealing at 450 C, with a J0 of 93.5 fA/cm and ⍴c of
2
11.5 mΩcm2. Remarkably, such low contact resistivity was obtained
for SiO2 layers as thick as 4.5 nm, which would not be expected
purely on the basis of a tunnelling-argument. Presumably, the rela-
tively harsh conditions during sputtering lead to modifications of the
thin SiO2 such as intermixing of the layers.
In 2017, Wang et al. showed electron-selectivity for MOCVD
ZnO:B on an a-Si:H passivation layer.334 The relatively low FF of
72.7% and especially external Voc of 599 mV (despite a high passiv-
ation level provided by a-Si:H) however point to a selectivity issue.
Interestingly, it was noted in their work that ZnO:B directly deposited
on c-Si led to a lifetime of almost half a millisecond, indicating at least
some level of surface passivation. In 2019, Zhong et al. improved
upon the ZnO:B contact, reaching an efficiency of 21.4%.308 The key
improvement here compared to other doped-silicon-free electron-
selective contacts was that high electrical performances were
achieved for ZnO thicknesses ranging from a few nm to 100 nm.
Using a ZnO layer of several tens of nm mitigated the plasmonic
absorption in the rear metal layer. Interestingly, in spite of this
relatively thick layer, a low work function electrode was still shown to
be necessary, and the use of an electrode consisting of a stack of a
thin LiF layer followed by Al was key to achieve a low contact resistiv-
ity of 136 mΩcm2. Also, in this work, there were indications that ZnO
IBARRA MICHEL ET AL.
can give surface passivation, as an external Voc of 629 mV was
obtained without a-Si:H passivation layer, compared to up to 716 mV
for a cell with a-Si:H passivation layer. This contact was nevertheless
shown to be unstable in air ambient, which was attributed to a work
function increase of the LiF/Al electrode.147
Whereas ZnO:B has been shown to be a carrier-selective contact
on a-Si:H passivation layers, in combination with a SiO2 tunnel layer it
has been shown to yield a high level of surface passivation as well as
good contacting with c-Si, provided the c-Si is n+-doped.81 In this con-
figuration, the ZnO:B is not a passivating contact in the classical
sense, but more of a hybrid homo-/heterojunction contact, where the
n+ doping of the c-Si is necessary for contact formation, yet the struc-
ture can benefit from full-area passivation of the c-Si surface (i.e. no
Si-metal contact). Very good surface passivation by ALD ZnO:B has
been demonstrated by van de Loo et al., with iVoc values reaching up
to 725 mV on undiffused 3 Ωcm n-type c-Si.320 They showed a few
key steps that are required to reach such a high passivation level.
Firstly, the ZnO layer has to be prepared on a thin interfacial SiO2
layer (e.g. RCA and NAOS), as ALD ZnO does not yield a high-quality
interface with c-Si by itself. Proper hydrogenation of this interfacial
oxide seemed most important, and an Al2O3 capping layer and subse-
quent anneal at 450 C were shown to result in excellent hydrogena-
tion. This can be understood from the fact that even though ALD ZnO
contains ample hydrogen, the hydrogen can effuse already at 200 C
along the grain boundaries of the polycrystalline material. The amor-
phous Al2O3 capping layer prevents this effusion, enabling activation
of the passivation at 450 C. After annealing, the Al2O3 can be
removed by a selective wet etch. Also, the use of a soft deposition
method—in this case, ALD—to preserve the interfacial oxide is crucial,
since similar experiments using sputtered ZnO did not yield apprecia-
ble passivation levels. Finally, doping of the ZnO aids in improving the
passivation, since it lowers the WF of the TCO and thereby enhances
the downward band bending in the c-Si. In subsequent work, Macco
et al. demonstrated contacting properties of a SiO2/ALD ZnO:Al/Ag
stack on n+-diffused c-Si.81 It was shown that the contact resistivity
strongly depends on the doping level of both the c-Si(n+) and ZnO:Al
and device-relevant contact resistivities of 15 and 23 mΩcm2 and J0
parameters of 21 and 15 fA/cm2 were obtained on 130 Ω/sq and
260 Ω/sq n+-diffused c-Si surfaces, respectively.
4.4 | Middle d-block transition metal oxides
Referring to the periodic table, one can note that most transition
metals from the centre of the d-block (like group VII and VIII), with
some others on the edges, are not highlighted as hole or electron
selective contacts (see Figure 6). Their oxides have indeed not or
sparsely been investigated in c-Si solar cells technology, for clear or
unclear reasons. To our knowledge, HfO2-x and ZrO2-x have not been
reported as carrier selective contact for c-Si, probably due to their
insulating properties. ALD-deposited HfO2 has however been
recorded as an excellent passivation layer for c-Si surfaces.335,336
Group VII of the periodic table rallies transition metals whose oxides
IBARRA MICHEL ET AL.
are mostly not usable in standard conditions (liquid, volatile, highly
reactive and/or highly toxic) like Mn2O7, MnO3, Tc2O7 and TcO3, to
which we can add RuO4, OsO4 and Ir compounds from group VIII, not
tried as contacts for the aforementioned reasons. Re2O7 and ReO3
have moderate stability. The former is reported to be more stable—
yet highly reactive with water—than the latter but has a low melting
point around 220 C. ReO3 is known to have a low resistivity
(1  10
5 Ohm.cm at 300 K) behaving like a metal,153 and was used
in organic electronics as hole transport layer—yet with no clear infor-
mation on the final stoichiometry of the film—.337–339 Some groups
attempted to use it as hole contact for (n) c-Si, which showed similar
properties as MoO3-x, but actually appeared to be very unstable.209
Mn1-xO is the most stable oxide of Mn, but has not been reported as
selective contact for c-Si solar cells. From group VIII, OsO2 and RhO2
exhibit metallic behaviour, as well as the more famous MoO2, WO2
and Ti4O7—generally met in c-Si PV as undesired product of the
reduction of MoO3-x, WO3-x and TiO2-x—which might be less suited
for PV applications. Rh2O3 holds interesting TCO properties suited for
hole contacts, as recorded in OLED literature,340 with no results dem-
onstrated in c-Si PV yet. Cobalt oxide has been used as an efficient
hole contact in organic and perovskite photovoltaics,341–343 and
RuO2-x in the past as a hole transport layer for OLED,157 both never
thus far reported in c-Si field. Iron oxides are not reported either, pre-
sumably because diffusion of Fe ions into Si would induce active
recombination centres. In addition, Re, Ru, Rh, Pd and Pt are noble,
expensive and scarce materials, which lowers the probability for
investigation of their oxides. Ag2-xO and AgO are used as an absorber
in dye sensitized solar cells,344 with a band-gap around 1.4 eV which
is too small for transparent contact applications.
4.5 | Perspectives and limitations
To conclude, it can be seen that great strides have been made in push-
ing selective TMO contacts, and efficiencies well above 20% have
been demonstrated. In principle, TMOs hold the promise to be a ver-
satile contact material, as they are generally highly transparent, have
tunable properties and can reach high selectivities. However, these
concepts so far do not seem to contest the status quo of doped-
silicon, be it diffused junctions, doped a-Si:H or doped poly-Si
contacts. Despite their impressive electronic properties, TMOs are
sensitive toward air exposure, reducing elements or thermal treat-
ments which generally tend to reduce their work function, and special
care needs to be taken when manipulating them as nm-thin contacts.
In addition, they do not yet yield obvious process simplifications as
several layers are still required to form an excellent selective contact.
Hole-selective TMOs reach efficiencies over 23%, but since they do
not provide excellent passivation to c-Si surfaces so far, the use of
additional passivation layers, generally Si-based, is indispensable to
obtain such results. This aspect hinders their transparency and the
potential of the investigated hole-contact TMO to be the ideal ‘all-
in-one’ material for metal compound-based contacts to c-Si. Hole
selective TMOs are often deposited by thermal evaporation, a process
21
not really suited for industrial applications. The electron selective
TMOs have been shown to give sufficient surface passivation as well
as carrier-selectivity, but their behaviour in a contact is highly depen-
dent on surrounding layers: TiO2-x can be passivating and electron-
selective when contacted with Al, but Al is not transparent. TiO2-x
combined with low WF metal oxides such as Mg and Yb seems to
work best with dedicated a-Si:H passivation layers, presumably
because of the lack of an ‘alneal-effect’. LPCVD ZnO layers have
been shown to be carrier-selective and yield good optics; however,
they have only been demonstrated to work with a dedicated a-Si:H
passivation layer and with an opaque electrode. Conversely, ALD
ZnO:Al layers on a tunnel SiO2 layer have been demonstrated to yield
good surface passivation, transparency and lateral conductivity, but
require n-type doping of the c-Si substrate to reach low contact resis-
tivity values. Fortunately, among all the available compounds, only a
few binary oxides have been reported in c-Si PV literature, some
intensively like MoO3-x, WO3-x, V2O5-x, or TiO2-x, some under-
explored like Ni1-xO, whilst others not reported, partly due to physical
instability in standard conditions. In addition, various deposition
methods start to be further explored and give promising results, as an
alternative to the standard thermal evaporation, like ALD for V2O5-x
or HWOSD for MoO3-x. Overall, significant progress was made in just
a few years both in terms of performance and understanding of Si-
TMO contacts. This progress is still ongoing, and the diversity of the
material library is largely underexplored considering the option of
using ternary, quaternary or even more complex metal oxides, This
gives hope that an all-round ideal contact might be unveiled in the
near future.
5 | OTHER METAL COMPOUNDS
To form contacts without doped-silicon, Schottky diodes using metals
have been widely studied in the past decades. More recently,
very-low work function metals such as Mg, Ca, Li or Sc were shown
to act as efficient electron-selective contacts when combined with a
passivating layer, typically a-Si:H or SiO2, to prevent recombination at
the metal-Si interface.27,28,33,345 Since an (i)a-Si:H passivating layer
does not reduce Fermi level pinning significantly (S value still around
0.3), the metal work function needs to be about one electron volt
lower than the silicon electron affinity. The high reactivity of the
employed metals, causing device instabilities such as oxidation or
metal-induced crystallization of the passivation layer, is a limitation of
this approach. Another one is that metals are obviously opaque,
preventing their use as a full-area window layer. Noteworthily, the
reported contact resistance values are not low enough to enable par-
tial contact on lightly doped wafers.28,33,345 Additionally, even on the
rear side, the presence of a metal in close vicinity of the silicon (as is
required with this contact strategy) is undesirable as it causes
plasmonic parasitic light absorption, which was shown to be more
severe for low-WF metals.33 With the current state of research, these
shortcomings severely limit the attractiveness of using metals as the
selective layer in carrier-selective contacts.
22
Other semiconducting or semi metallic compounds, which do not
fall into the categories mentioned earlier in the text, were tested with
limited results so far. This includes materials from the II-VI (ZnS, CdS,
ZnTe), transition-metal-nitride (TiN, MoN, TaN), and III-V (GaP, GaN)
families. These are briefly discussed in the following paragraphs.
Unique materials include CuI, which is the only p-type material of this
section and enabled over 20%-efficient devices when combined with
Ag as partial rear contact.346 Another one is ZnSnN2, which showed
underwhelming performance,347 but belongs to the very vast and
underexplored family of ternary metal-nitrides. This family includes a
very large number of thermodynamically stable compositions with rel-
evant material properties and might deserve further exploration.348
Among the II-VI family, CdS was reported as electron contact
already in the early 1980s with an efficiency below 10%.349 Doping
was used to promote CdS conductivity. Recently though, interest in
this material vanished, possibly partly due to Cd toxicity. Conversely,
even though ZnS has long been used as anti-reflective coating,350 the
first reports using ZnS as electron-selective contact date from the
351,352
early 2010s. Efficiency below 10% was also reported, but note-
worthily ZnS was used as a window layer combined with AZO. Inter-
est still sparks for this material, notably in compounds such as
Zn(O,S).353 The addition of oxygen was shown to improve the con-
ductivity of the layer and the overall contact performance, and an effi-
ciency above 16% was obtained. However, this time a rear contact
approach was used, with a low work function opaque electrode
(Mg/Ag stack), which reduces the appeal of this approach.
Transition metal nitrides are attracting attention in recent
years.354–356 Amongst them, TiN stands out so far since it forms an
electron-selective contact as a single-layer. This elegant simplicity
however comes with limited performance, notably due to the absence
of passivation, high parasitic light absorption, and modest contact
resistivity.356 Alloying TiO2-x and TiN notably enabled an efficiency
over 22% for a device using a TiOxNy-based electron selective
contact.40
Turning to III-V materials, their integration on silicon has long
generated considerable interest in view of the numerous possible
applications it opens.357 GaP possesses several attractive properties
suited to electron-selective contacts in silicon solar cells: a small
conduction-band offset, demonstrated high n-type doping and con-
ductivity, and even a small lattice mismatch (with [100] silicon), which
introduces the possibility of epitaxial growth. Nevertheless, experi-
mental demonstrations of GaP-contacted Si devices fall short of the
358–363
promising simulations. A crucial limitation of this approach is
the classical use of MOCVD or molecular-beam epitaxy (MBE) to
grow GaP, which is not standard for Si-cell processing. This can trigger
bulk-silicon degradation which needs appropriate precautions.364–366
Nevertheless, this remains an attractive material, and low-deposition-
temperature approaches are being trialled.363 GaN shows similar
attractiveness, or even higher due to its wider bandgap, yet also faces
similar implementation challenges.367–369 There are even fewer
reports about this approach, in spite of the prospect of epitaxial GaN
growth on (111) Si, which is attractive when using textured Si. One
common difficulty in the growth of III-V on Si is that traditionally,
IBARRA MICHEL ET AL.
relatively thick inactive ‘buffer’ layers are used by the III-V community
when growing on foreign substrates (be it sapphire or silicon), to guar-
antee a high-quality active layer despite the lattice mismatch. This
approach is however not applicable when attempting to use the III-V
layer as contact for the silicon device, since the first few nanometers
of growth are in such cases the most relevant ones.
6 | C O N C LU S I O N A N D P E RS P E C T I V E S
The use of simple metal compound heterostructures to fabricate c-Si
solar cells is not a new concept, with the promise of this approach
being demonstrated more than four decades ago. Impressive improve-
ments in cell efficiencies have been made, now reaching over 23%. By
looking into the main categories used in such structures, we identified
a few key challenges to improve the efficiency further, notably the
absence of passivation and limited conductivity from most of these
layers. This renders necessary the use of a three-layer stack (incorpo-
rating a passivation layer and a conductive electrode) to form an effi-
cient contact, making processing complicated. Furthermore, stability
was discussed to be limited for many (binary) materials. Based on the
current understanding of silicon solar-cell operation, there is however
no fundamental limit precluding a high efficiency with a simple
heterostructure. There are however several key requirements that
need to be fulfilled, and not all the materials listed above fail for the
same reason. The answer depends probably on the material, and
broad categories can be made as discussed here below.
A first category groups highly investigated materials, such as
TMO and AMC based electron-selective contacts, which have only
been proven efficient in combination with a low work function
opaque metal electrode. Two strategies are offered to alleviate this
need: either render the contact layer electrode-agnostic, that is,
improve on its selectivity to enable combination with a transparent
electrode, or develop a low work function transparent electrode. The
former requires material modification, for example, by alloying or by
doping. This has proven challenging for the few experimentally tested
cases, and has limited applicability for evaporated materials. Develop-
ing a low-work-function transparent electrode is very attractive but
also experimentally challenging. However, shall a transparent con-
ducting material with a work function below 4 eV be found, such
material could be an excellent electron-selective contact in itself with-
out any additional dedicated layer. Concerning TMO-based hole con-
tacts, similar performance limitations as doped-silicon-based contacts
were shown, with similar complexity of processing and sensitivity to
post-processing steps, precluding large-scale adoption. Further inves-
tigation would be needed to understand the necessary material prop-
erties better, to replicate them in an industrial environment. Such
understanding is however uneasy since the complete stack of very
thin and interacting layers has to be considered as a whole.
A second category gathers together materials (or material sys-
tems) which offer a large tunability but were little investigated so far
in the context of carrier-selective contacts for c-Si solar cells. This
includes III-V semiconductors and ternary compounds, such as metal
IBARRA MICHEL ET AL.
nitrides or perovskite oxides. In the latter case, promising properties
were established for high-quality layers grown epitaxially on
dedicated substrates, but integration on silicon is difficult. In the case
of III-V semiconductors, the direct growth of high-quality material on
Si without a sacrificial nucleation layer needs to be demonstrated.
Dedicated effort towards fabricating thin layers with adequate prop-
erties on silicon with minimal nucleation phase is thus critically
needed. This requires drastic adaptations from traditional growth
approaches, and most probably making compromises on the film
quality to preserve interface quality. This approach is attractive,
notably as it could open prospects of various optoelectronic devices
on silicon beyond PV application.
Overall, the supremacy of doped-silicon towards forming efficient
contacts to c-Si can be related to the combination of a perfect band
alignment (or excellent for amorphous silicon) and an adequate work
function. The latter being achieved with doping, a (relatively) high
density of free charges makes it resilient to the influence of the elec-
trode or to depletion from the silicon wafer, enabling a combination
with numerous electrodes including transparent ones. For an efficient
selective contact, excellent band alignment together with an appropri-
ate work function appear indeed to be two necessary require-
ments.68,69 Adding to these two properties a wide bandgap, only
highly p- or n-type doped materials qualify. This is likely to require
extrinsic doping in view of the natural tendency of the Fermi level to
stabilize around mid-gap of silicon in most semiconductor
materials.370,371 This imposes a restriction on the defectivity of the
material, since defects will tend to induce counter-doping. Addition-
ally, efficient extrinsic doping is expected to be more efficient when
using (nano)crystalline layers than amorphous ones which are
unavoidably defective when doped, which presumably hampers
efficient doping of compound materials.372 Conversely, efficient
silicon surface passivation from a (nano)crystalline film has so far
never been reported, making up for another challenge to demonstrate
experimentally the long-dreamed-about single-layer passivating
contact approach. Nevertheless, the use of a very thin interfacial pas-
sivating layer (such as SiO2) shall not be excluded since it can be
industrially processed at little cost, and induce negligible resistive or
optical losses in the device. With such an approach, a 24%-efficient
device was notably recently demonstrated using a nitrogen-doped (n-
type) nanocrystalline silicon-carbide layer combined with a very thin
SiO2 passivation layer.18 This remarkable result stemmed from over a
decade of material development and required fine and delicate tuning
of the film processing,373,374 highlighting the need for extensive mate-
rial science to unveil excellent contacts to silicon solar cells. With the
continuous improvements in understanding and the expansion of the
library of metal compounds to be tested on c-Si solar cells, ample
opportunities to find materials with excellent performance remain. In
the meantime, solar cells using contacts based on doped-silicon
showed steady progress. Whereas in 2014 the highest laboratory-cell
efficiency was 25% and typical industrial-cell efficiency did not reach
20%, in 2021 multiple contacting structures enable over-26%-
efficient devices, and production lines typically output solar cells with
23% efficiency (reaching 25% for premium technologies). Whilst
23
metal-compound based contact approaches still trail the conventional
doped Si contacts, this is primarily because they are at an earlier stage
of development, with some of the advantages to be fully realized.
However, given the rapid improvements of the metal-compound
based contacts, we can expect the margin between these two tech-
nologies to decrease in the future.
AC KNOW LEDG EME NT S
Dr. A. Richter of Fraunhofer ISE is gratefully acknowledged for the
calculation of the FF limit due to Auger and radiative recombination.
The work of B. Macco was supported by The Netherlands Organiza-
tion for Scientific Research under the Dutch TTW-VENI Grant 16775
and the Top Consortia for Knowledge and Innovation (TKI) Solar
Energy Program ‘PERCspective’ (TEUE119005) of the Ministry of
Economic Affairs of The Netherlands. M. Boccard and J. Dréon
acknowledge support from the Swiss National Science Foundation
under project ICONS with grant number PZENP2_173627. J. Bullock
acknowledges support from the Australian Center for Advanced
Photovoltaics Fellowship. J. Ibarra Michel acknowledges support from
the Melbourne Research Scholarship.
DATA AVAILABILITY STAT EMEN T
Data sharing is not applicable to this article as no new data were cre-
ated or analyzed in this study.
OR CID
Julie Dréon https://orcid.org/0000-0003-0659-6389
Bart Macco https://orcid.org/0000-0003-1197-441X
RE FE RE NCE S
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