Surfaces and Interfaces 28 (2022) 101687

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Surfaces and Interfaces

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Dopant-free materials for carrier-selective passivating contact solar cells:

A review
Shiladitya Acharyya a, Sourav Sadhukhan a, Tamalika Panda a, Dibyendu Kumar Ghosh a,
Nabin Chandra Mandal a, Anupam Nandi a, Sukanta Bose a, Gourab Das a, *, Santanu Maity a,
Partha Chaudhuri a, Hiranmay Saha a, Dipali Banerjee b
a
School of Advanced Materials, Green Energy and Sensor Systems (SAMGESS), Indian Institute of Engineering Science and Technology (IIEST) Shibpur, Howrah
711103, India
b
Department of Physics, Indian Institute of Engineering Science and Technology (IIEST) Shibpur, Howrah 711103, India

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

Keywords: The basics of dopant-free materials used as carrier-selective layers at the surfaces and interfaces in c-Si or poly-Si
Si solar cell solar cells have been reviewed. Emphasis has been given to the discussion of a host of transition metal oxides
Carrier selective (TMOs) having wide range of band structures and which have the carrier selective property of allowing only one
Passivation layer
type of carrier (electron or hole) to flow across their junctions with Si. The fabrication process of these materials
Transition metal oxide
Photovoltaic performance
are benign and at low temperatures which make them gradually attractive over the doped Si layers which need
toxic materials and/or high temperatures for their formation. Silicon solar cells having dopant-free carrier se­
lective TMOs fabricated by various groups using different fabrication processes and different contact configu­
rations (Full area contacts, Partial area contacts or Interdigitated back contacts) have been reviewed and
presented alongwith their photovoltaic performance. Different passivation schemes (full area or partial area) that
could be used alongwith these dopant-free carrier selective materials have also been discussed.

1. Introduction
Solar photovoltaics (SPV) as the alternative energy sourcesof elec­
trical power generation are growing exponentially over the last few
years.Worldwide cumulated electrical power generation by SPV reached
628 GW at the end of 2019 [1]. Most recent data shows this capacity will
reach 1.2 TW by the end of 2023 [2]. Our discussions will be restricted
on crystalline or polycrystalline Silicon based SPV which have reached a
market share of 95% at the end of 2019 and will remain so for some
more years [1].From the thermodynamical point of view a single junc­
tion Si solar cell can reach a maximum efficiency of 29.43% under 1 Sun
illumination [3]. However, so far the maximum efficiency reached have
been 26.7% at the cell level [4,5] and 23.01% at the module level [6].
There are various loss mechanisms which affect the current, voltage and
the fill factors of the solar cell. For example, the recombination losses of
the carriers near the front and back surfaces are responsible for the poor
spectral response in the low and high wavelength regions which results
in a poor short circuit current (Jsc). Moreover, due to the high concen­
tration of the dopants required for the formation of the emitter junction
and for producing the back surface field the Auger recombination loss
will be high in these layers, which increases the recombination current
J0 and lowers the open circuit voltage Voc [7]. Recombination losses also
occur at the metal semiconductor junctions. The limit of Al-BSF solar cell
efficiency is thus less than 20%. The losses at the imperfect junctions can
be optimized by optimizing the doping and choosing an appropriate
metal based on its work function such that it makes an ohmic contact
with the semiconductor Si [8].Use of one or more passivating layers and
lessening the direct Si/metal contact areas have resulted in the growth of
new technologies which are gradually entering the commercial pro­
duction like passivated emitter rear cell (PERC), tunnel oxide passivated
contact (TOPCon), Interdigited Back Contact (IBC), Heterojunction
Intrinsic Thin film (HIT) technologies etc. The highest cell efficiencies
reported by different researchers with the abovementioned technologies
are 24.06% for PERC [9] by LONGi solar, 25.7% for TOPCon [10] by
Fraunhoffer ISE, 26.7% for the IBC with Silicon Heterojunction
(IBC-SHJ) [4,5] by Kaneka and 25.6% for HIT [11] by Panasonic
respectively.The 2021 report says that “the concepts on n-type and
p-type material with passivated contacts using tunnel oxide passivation

* Corresponding author.
E-mail address: gourab_electron@hotmail.com (G. Das).

https://doi.org/10.1016/j.surfin.2021.101687
Received 17 August 2021; Received in revised form 26 November 2021; Accepted 13 December 2021
Available online 17 December 2021
2468-0230/© 2021 Elsevier B.V. All rights reserved.
S. Acharyya et al.
stacks at the rearside will gain market share from about 6% in 2021 up to
50% within the next 10 years” [2]. Various wide band-gap materials like
SiNx, SiO2, Al2O3, intrinsic a-Si:H etc. are being used as passivation
layers so as to reduce the recombination losses [12,13]. In this review,
solar cells employing various carrier-selective dopant-free materials like
TMOs alongwith supporting passivation schemes and steps taken for
their commercialization have been discussed.
1.1. Conventional silicon based solar cell structures
In this section we will describe the evolution of the important c-Si
solar cell structures for enhancement of the efficiency towards the
theoretical limit. A solar cell is a large area device for collection
andabsorption of a large number of photons of the solar spectrum by a
semiconductor, generation of excess charge carriers using the energy of
these photons and collection of these charge carriers in an external
circuit. There are different layers in a solar cell and depending on the
role they play in the solar cell they have widely different properties and
thicknesses. Firstly, there is the absorber layer which should be a
semiconductor with band gap appropriate for the absorption of the
maximum range of the solar spectrum. In this study the absorber is sil­
icon wafer with thickness ranging between 180–200 μm which is suit­
able for the absorption of sunlight from 400–1150 nm. The wafer should
have low concentration of defects so that the bulk recombination loss is
less. Secondly, a transparent front layer with wide band-gap serves as an
anti-reflection coating (ARC) which together with the texturized front
surface minimizes the loss due to reflection of sunlight. Thirdly, there
are junctions in the front and back which are used for the creation of the
internal fields for separation and collection of the electrons and holes at
the opposite electrodes of the solar cell. These junctions may be created
by appropriate doping of the base material silicon or may be formed by
the deposition of other suitable non-silicon material layers which
behave as semi-permeable membranes for one or the other type of car­
riers. Thus there are electron transport (hole-blocking) layers and hole
transport (electron-blocking) layers. These layers are usually termed as
carrier selective layers. These layers may be symmetric (homojunction
with c-Si) or asymmetric (heterojunction with c-Si). Smit has stated in
his thesis work the advantages of a heterojunction over a homojunction
for the criteria of carrier-selectivity [14]. The criteria of low recombi­
nation losses at the interfaces restrict the choice of the appropriate
materials for the junction formation. Fourthly, there are metal elec­
trodes at the front and back which transfer the photo generated charge
carriers to external circuits. The work functions of these metals should
be suitable that the semiconductor/metal contact at both ends may be
Ohmic for the respective carriers. The front metal contact is usually in
the form of a grid designed to minimize the losses due to shading and
series resistances. Finally, there are dielectric layers deposited to reduce
the metal/Si contact defects which may have thicknesses varying in a
wide range from a few hundreds of nm (in case of PERC etc.) to <2 nm
(in case of TOPcon). It should be kept in mind that the same layer may
serve the multiple purposes as described above. For example in case of
solar cells involving TiO2 as carrier selective layer, the same TiO2 acts as
a passivation layer as well as an Anti-Reflection coating [15].
For a solar cell with good performance both passivation and carrier
selectivity is essential. A good passivation near the interface ensures that
the desired charge carrier does not recombine at the contact, whereas a
good carrier-selective contact determines the maximum amount of
desired charge carriers are collected at the interface blocking the
opposite type of charge carrier. In case of chemical passivation the
dangling bonds are entirely satisfied and hence such kind of passivation
is suitable to prevent recombination of both type of charge carriers, i.e.
both electrons and holes. However in case of field-effect passivation due
to presence of fixed charges an electric field is created which repels one
kind of charge carriers away from the interface, but the other kind of
charge carriers are attracted towards the interface. Practically all
passivation layers provide a certain amount of chemical passivation as
2
Surfaces and Interfaces 28 (2022) 101687
well as field effect passivation more or less.
In case of a hole selective layer, a field effect passivation layer that
repels electrons is required whereas in case of an electron-selective layer
a hole repelling field-effect passivation layer is required. However better
chemical passivation helps in carrier selectivity for both electrons and
holes. In most of the solar cells featuring dopant-free contacts there is an
i-a-Si:H or SiOx passivation layer both of which exhibits more chemical
passivating property and less field-effect passivation property. Carrier-
selective TMOs have also got some passivating property but are infe­
rior compared to conventional passivation layers [12].
In the Fig. 1(a) the structure of a basic p-type Al-BSF c-Si solar cell is
shown. The front surface has an n+-p emitter junction formed by
diffusion of phosphorus (P) into the p-Si wafer. The emitter junction
allows the flow of electrons into the n-layer which are collected in the
external circuit by metal (Ag) grid contacts at the front optimized to
minimize the losses due to shading and series resistance. To minimize
the reflection and the recombination losses the front surface is textured
and is coated with a layer of SiNx. The SiNx layer here plays the dual role
of a passivation layer and an anti reflection coating (ARC). On the rear
side a screen printed coating of Al paste cured at high temperature
formes the back metal contact and also diffuses into p-Si wafer to form a
highly doped p+-region generating a back surface field to push the mi­
nority carriers (electrons) towards the emitter junction. In this structure
a significant amount of recombination loss occurs at the direct Si/Al
contact at the rear which increases the reverse saturation current density
J0 and thus lowers the open circuit voltage Voc of the solar cell [7]
according to the Eq. (1);
nkT
VOC = ln(JL / J0 + 1) (1)
q
Where JL is the current generated by light absorption, n the diode
quality factor, k the Boltzman’s constant, T the absolute temperature
and q the electronic charge.
A p-type PERC solar cell structure is shown in the Fig. 1(b). Here, the
front side of the cell is exactly the same as an Al-BSF cell described
above. A double layer consisting of a thin Al2O3 layer capped with a
thick SiNx layer serve as the passivation layer at the rear side of the cell
through which narrow lines are scribed by ablation with a green laser for
making metal contacts. The passivation layer reduces the surface
dangling bonds while the reduction of the metal/semiconductor contact
areas reduces the corresponding recombination loss. The low J0of the
PERC increases the Voc. However, due to the non-uniform collection of
the carriers the series resitance of the cell is high which lowers the fill
factor. For further improvement of the efficiency use of full-surface
passivation has been applied giving rise to the development of TOP­
Con structureas shown in Fig. 1(c). In TOPCon solar cells an ultra-thin
dielectric layer of Al2O3 or SiO2 (<2 nm) is deposited at the rear side
of the p- or n-type Si wafer capped with a heavily doped p+/n+ poly-Si
layer. The ultra thin dielectric layer at the rear end of the solar cell serves
the dual purpose of the passivating layer as well as an electron/hole
tunnel layer which is highly conducting thereby eliminating the direct
metal/semiconductor junction.The heavily doped p+/n+ -poly-Si layer
act as carrier selective layer.
A HIT solar cell is fabricated by depositing multiple layers of a-Si:H
on crystalline Si wafer(c-Si)as shown in Fig. 1(d). In this case, the i-a-Si:
H layer acts as the passivation layer whereas the doped p+/n+-a-Si:H
layers act as carrier selective layers.
Finally, for maximizing the throughput of photons in the solar cell
the IBC structure has been developed which has both emitter and BSF
junctions separated by dielectric layers at the back of the solar cell as
shown in Fig. 1(e). This scheme not only completely removes shading
loss at the front but also enables full-area passivation at the front surface.
Recently Dopant-free ASymmetric Heterocontact (DASH) solar cells
[16] involving wide-band gap materials have been found to possess
great potential ascarrier selective layers with Si, which will be the main
focus of this review.A c-Si solar cell with dopant-free emitter and BSF
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

Fig. 1. (a) Normal c-Si BSF cell (p-type); (b)PERC solar cell (p-type); (c)TOPCon solar cell (n-type);(d) HIT solar cell (n-type); (e) IBC-SHJ solar cell (n-type); (f) A
DASH solar cell having dopant-free contacts with TiO2as emitter and MoO3as BSF which is a relatively new concept.

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S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

contacts is shown in Fig. 1(f).Use of poisonous gases like diborane and • Vi= Internal Voltage Bias
phosphine for doping can be avoided. As they are wide band gap ma­ • VTh = Thermal Voltage
terials with a high transparency, they don’t have the problem of para­ • JS= Interface Recombination Current
sitic absorbance unlike a-Si or poly-Si layers. Previously these • JS0= Interface Recombination Current at zero bias
dopant-free materials have been used in organic [17] and perovskite • Σr = Differential Selectivity
[18] solar cells, but now researchers have ventured applying these • However, according to REL model [51] an expression for selectivity
materials in Si solar cells. has been provided in terms of minority and majority carrier con­
Wide band-gap materials especially the Transition Metal Oxides or centrations in Eq. (3) as:-
TMOs are of great interest since they provide cheap, newerless toxic and ( )
low-cost deposition methods and less material is required due to their ciM/m
Ji(M/m) = Ji(M,0/m,0) i − 1 (3)
smaller thickness.TMOs are suitable in terms of optical properties due to cM,0/m,0
their transparency and low parasitic absorption. However they exhibit
poor electrical properties such as low mobility of the excited charge
carriers as well as a lower conductivity and hence they face some • where, J(M/m) = Current density for majority/minority carriers at the
challengesto substitute doped silicon materials used in PV but still they respective contact i=1,2
can be used as permeable transport layers. • J(M,0/m,0) = Saturation Current density for majority/minority carriers
Transition metals are the d-block chemical elements which lie be­ • CM/m= Ratio of majority and minority charge carriers
tween the p- and s-block elements in the periodic table. The oxides of • CM,0/m,0 = Ratio of majority and minority charge carriers at
these metals are called transition metal oxides or TMOs.Some of the saturation
TMOs that are used as hole-selective layers are CrO3 [19,20], NiO [21], • These two models have been summarized by Rau and Kirchartz [52].
MoO3 [22],V2O5 [23], WO3 [24], ReO3 [25], Cu2O [26], CoO [27], etc.
whilesome other TMOs used as electron-selective layers are TiO2 [15],
2.2. Classifying carrier-selective materials for c-Si
Ta2O5 [28], ZnO [29],Nb2O5 [30,31], CdO [32], Sc2O3 [33], etc. MgO
[34], SnO2 [35], BaO [36] are some non-TMO oxides that can be used as
These are the materials which when fabricated as a thin layer on Si
electron-selective contacts. In2O3:Sn (ITO) can be used as both
provides a large barrier for one type of carrier while providing a smaller
hole-selective [37] as well as electron-selective contact [38]. Other ox­
barrier for other type of carrier as studied by Xue et al. [53]. To make it
ides like HfO2 [39], Al2O3 [40,41], ZrO2 [42], GaO [43] are used as
clear we have to study band-diagrams and relative band positions.These
passivation layers on Si.There are also some non-oxide wide band gap
relative band positions and band-offsets mainly depend on
materials used as carrier selective layers include PEDOT:PSS [44],CuI
Electron-Affinity (χ), band-gap (Eg), Ionization Energy (IE) and Work
[45], LiF [46], Cs2CO3 [47], MgF2 [48], etc. All of them will be discussed
Function (Φ) of the material [54] as shown in Fig. 2a according to
in the later sections, with emphasis on the metal oxides especially the
Anderson’s model for heterojunctions [55] as well as that studied by
TMOs.
Kahn [56] in Fig. 2, although the Anderson’s model has got many lim­
itations as it takes into account vacuum electron affinity parameter in a
2. Carrier-selective dopant-free materials for c-Si solar cells
junction filled with solid crystals, real chemical bonding effects are not
taken into account. Antoine Kahn studied these limitations in details
Carrier-selectivecontacts for c-Si using doped Si thin films such as
[56].
n+/p+ a-Si:H, µc-Si:H and poly-Si:H have been quite common in the past
Band edges Ecand Ev vacuum level EVAC, workfunction Φ, energy gap
few years. However, recently dopant-free wide band-gap materials are
EG, ionization energy IE and electron affinity χ are defined.
being used as alternatives, so as to reduce the use of poisonous gases like
An excellent work has been done by Xue et al. [53] in which carrier
diborane and phosphine.These dopant-free wide band-gap materials
selective contacts for Si have been studied with NiO as a hole-selective
have higher transparency due to which the front surface parasitic
contact and TiO2 as an electron-selective contact. The corresponding
absorbance can be improved by a value of 1 mA/cm2 [49]. Moreover the
band-diagrams are shown below. The filled circles indicate electrons
doped layers of Si are highly defective and act as recombination centers
for generated charge carriers both at the metal interface as well as the
silicon substrate, so the use of a passivation layer is seen in between.
However, the dopant-free carrier-selective materials being dielectrics
passivates the silicon substrates as tabulated by Black et. al. [12] which
can be due to the interfacial SiOx formed between the Si substrate and
the carrier-selective material.

2.1. Quantifying carrier selectivity

In solar cells selectivity of carriers are generally quantified with

respect to minority carriers but the effect of majority carriers are dis­
cussed qualitatively. But recently Brendel and Peibst [50] as well as Roe
et al. [51] quantified carrier selectivity with respect to both minority as
well as majority carriers but in different approaches. According to BP
model [50] an expression for differential selectivity has been stated in
Eq. (2) as:
∑∼ ( )− 1
1 dJ s V th
:= = exp (− Vi / VTh) (2)
r
RC dV i RC JS0

• where, Rc= Ohmic resistance for majority carriers

( )− 1 Fig. 2. Energy diagram of a single material (semiconductor) with flat bands to
dJs
• dV i
= Recombination resistance for minority carriers the surface [54].

4
S. Acharyya et al.
Fig. 3. Band alignment of MIS junction (a) Al/TiOx/n-Si, and (b) Pt/NiOx/p-Si [53].
while the empty circles denote holes:
From the band diagrams in Fig. 3 it is clear that a smaller conduction
band offset (ΔEC) and a larger valence band offset (ΔEV)with Si is pre­
sent for TiO2 due to which it acts as an electron-selective contact.
Similarly in case of NiO a larger conduction band offset (ΔEC) and a
smaller valence band offset (ΔEV) with Si is present due to which it acts a
hole-selective contact.In the Table 1 below the criteria for a material
layer to act as carrier selective contact with c-Si is shown. They have
been categorized into 5classes on the basis of band-offsets and band
structures. In the band diagrams electrons are shown in dark red and
holes in dark blue, these band diagrams are very important to categorize
the materials into these 5 classes.Class-II represents a-Si and μc-Si which
have band-gaps comparable to that of c-Si.
The class-I materials can be made electron or hole selective but the
band gap is so high that most carriers are blocked. Some of them are
therefore used as dielectric passivation layers on Si. It is clear from the
band diagrams in Class-I of Table 1 that they are impermeable for both
charge carriers and hence blocks both electrons and holes.The carrier
flow through these materials may occur only through barrier tunneling.
A very thin layer may be used which facilitates quantum tunneling
through the energy barrier or thermionic emission over the energy
barrier as in TOPCon solar cell. Common examples are SiO2, Al2O3.
In case of class-II materials, if the material is n-doped it becomes
electron-selective, but if p-doped it becomes hole-selective as clear from
the band diagrams in Class-II of Table 1. In the above figure both n-a-Si
and p-a-Si are shown, that are typical examples of these class-II mate­
rials. If an intermediate thin i-a-Si layer is present, barrier tunneling is
predominant. They can be made permeable for both electrons and holes.
Common examples are a-Si:H, µc-Si:H. They don’t provide any carrier-
selectivity unless they are doped and in this context theydo not belong
to dopant-free carrier selectivity materials which are mainly discussed.
The class-IIImaterials are hole selective materials with a band gap
greater than Si andclass-II materials but generally less than class-I ma­
terials and a smaller ΔEVas shown in the band diagrams in Group-III
Table 2. If ΔEV is slightly high, barrier tunneling is required to facili­
tate hole selectivity. They act as permeable contact for holes but blocks
electrons and hence act ashole-selective contact. This type of materials
allows holes to pass through them but blocks electrons, and thus it is a
semi-permeable membrane for holes. They may replace p-doped-Si hole
transport layers as shown in Fig. 3. NiO and Cu2O are the hole-selective
TMOs belonging to this category.
The class-IVmaterialsare electron selective materials with a band gap
greater than Si &class-II materials but generally less than class-I
5
Surfaces and Interfaces 28 (2022) 101687
materials and a smaller ΔECas shown in the band diagrams in Group-IV
Table 2. If ΔECis slightly high,barrier tunneling is predominant,
although not desired.They act as permeable contact for electrons but
blocks holes and hence act as electron-selective contact. This type of
materials allows electrons to pass through them but blocks holes, and
thus it is a semi-permeable membrane for electrons. They may replace n-
type electron transport layers as shown in Fig. 2b. Common examples
are TiO2, ZnO, LiF.
The class-V materialsare electron selective materials with a band gap
similar to class-III and class-IV materials but a p+-inversion layer is
formed due to their highχ and Φ. The work function gap between these
materials and Si is larger than the band-gap of Si as shown in the band
diagrams in Class-V, due to which holes at the interface outnumber the
electrons for n-type Si. For p-type Si, the hole concentration is so high
that a very highly doped degenerate induced p++-layer is formed at the
interface.Trap Assisted Tunneling (TAT) and Band to Band (B2B)
tunneling occurs. WhenTAT occurs, holes tunnel from the Valence Band
(VB) of the p+ inversion layer to the traps in the material however when
B2B tunneling occurs holes tunnel from the VB of the p+ inversion layer
to the Conduction Band (CB) of the material. A p+ inversion layer is
formed which provides hole selectivity enabling these materials to act
ashole-selective contact. This type of materials allows holes to pass
through them but blocks electrons, but the mechanism is through a p+-
inversion layer formed at the interface due to staggered or broken-gap
heterojunction between the TMO and Si. It is due to the higher elec­
tron affinity or work function of these TMOs. MoO3, WO3 and V2O5 are
the hole-selective TMOs belonging to this category. These are n-type but
hole-selective.
Thus it is clear from the Table 1 above that the type of materials that
belong to the class III and class V act as hole-selective contacts while
those in the class IVelectron-selective contacts respectively. Class-III and
Class-IV materials are carrier-selective due to their lower ΔEVand lower
ΔEC respectively, whereas the Class-V materials are hole-selective due to
the formation of a p+ inversion layer near the Si interface. The work of
Xue et al. [53] also takes account of variation of carrier selectivity on
different annealing temperatures. A theoretical modeling of
carrier-selective contacts with NiO/Si and TiO2/Si was also done by
Imran et al. [57]. In case of TiO2/Si effects of interfacial defects and
Fermi-level pinning (FLP) are studied quantitatively.In case of NiO/Si
effects of optimal doping, surface-defects and band-gap have been
studied quantitatively.Simulation results showed that Fermi level
pinning at the metal/TiO2/Si interface degrades the cell efficiency when
the Schottkey barrier height at the contact exceeds 0.25 eV [57]. In case
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

Table 1
Categorizing materials on the basis of band-offsets and work functions
of NiO, it was found that the band-gap of NiO should be limited so that
there is a small-offset (≤0.5 eV) at the hole-contact, because a higher
band-offset will not facilitate hole-selectivity [57], so tunneling becomes
the only way to allow carrier flow, thus in that case NiO behaves like
that of materials in the first column i.e., as an insulator. Also in case of
NiOwhen the density of surface states increases above 1011 cm− 2eV− 1,
the cell efficiency starts degrading.Bullock [46] investigated the LiF
based electron-selective contact on Si, replacing the need for phosphorus
diffusion to form an n+-layer. Measurements using Transfer Length
Method (TLM) show that there is a reduction in Contact-resistivity (ρc)
when the n+-diffused layer is replaced by an LiFx layer, with only 1.5 nm
thin LiFxlayer [58]. The cell fabricated by Bullock’s group [46] were
n-type and featured LiFx layer as the back electron selective contact
layer instead of n+-layer. The cell parameters achieved were VOC = 676
mV, JSC = 38.9 mA/cm2, FF = 78.3%, Eff = 20.6%. The front side of the
cell was same as that of a conventional cell with partial front contact. A
simulation work done with LiFx/n-µc-SiO stacked layer at the front has
also been done using AFORS-HET [59]. Though the layer n-µc-SiO is not
absolutely dopant-freebut still it has a wider band-gap than an n+-µc-Si:
H layer, thus it does not have a high parasitic absorbance. On the other
hand LiFx provides as excellent electron selectivity alone as well as with
the doped SiO layer. A thin i-a-Si:H was used for passivation. Effect of
cell performance on various parameters such as thickness, work function
and the electric field of the LiFx layer were studied. The result was
optimized for a 2 nm thickness of LiFx layer. An efficiency of 23.74% was
obtained with Jsc = 38.73 mA/cm2 and Voc = 746.4 mV. But it would
better if they would study the effect of a single LiFx layer without the
n-µc-SiO layer, so that the sole role of the LiFx layer can be obtained.
However Fig. 2aalthough applicable for all electron-selective TMOs
is not applicable for hole-selective TMOs other than NiO and Cu2O.
Carrier-selective contacts such as NiOxand cuprous oxide (Cu2Ox) act as
holeconductingoxides due to smaller valence-band offsets. TMOsother
than NiO and Cu2O allow hole selectivity through a different mechanism
which is not related to smaller valence band-offsets, but more related to
work function [60]. In these materials belonging to class-V of the
Table 1, the work function is almost equal to their electron affinity due
to their highly n-type behavior (i.e. their work function and electron
affinity are almost equal) same as that of the materials categorized in
class-IV of Table 1, because they have tendency to form d0 TMOs
[61–64], i.e. with vacant penultimate d-orbitals.It can be understood
from the band-diagram charts summarized by UNSW [65] as well as by
KAUST [66]. In this article a more number of electron and hole-selective
materials have been summarised in Fig. 4 based on their band-positions
similar to that of Fig. 3.In Table 2 electron-affinity, work function and
band gap of all electron and hole-selective materials to the best of our
knowledge are shown. MoOx is the most explored hole-selective material
for Si, which does not have a small valence band offset. It ensures
hole-selectivity using a different mechanism as shown in the band dia­
grams in Table 1, Class-V. On the other hand NiO, Cu2O, CoO are p-type
TMOs due to oxygen interstitials [67–69], as opposed to oxygen va­
cancies in n-type TMOs like MoO3, WO3, V2O5, TiO2, Ta2O5 and from
their electronic configuration it is quite obvious that they don’t form d0
oxides.This will be discussed later in this paper in detail. All these spe­
cific studies on carrier-selective materials, whether experimental or
modeling, need some deeper understanding of physics.
Some metals also act as carrier-selective contacts. Alkaline earth
metals like Ca, Mg act as electron-selective contacts with Si due to its low
work function while metals like Pt, Ni are found to form electron-
blocking hole-selective contacts with Si due to their high work func­
tion [102,108]. This is clear from the metal semiconductor junction
concepts of Ohmic and Rectifying or Schottkey contacts. The class-VI
metals are low work function metals which form ohmic contacts with
n-Si but rectifying contacts with p-Si and hence they are
electron-selective whereas class-VII metals are high work function
metals that form ohmic contacts with p-Si but rectifying contacts with
n-Si and are hence hole-selective. The electron-selective and

6
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

Table 2 categorized as Class-VII.Band gap Eg, Electron affinity χ, Work Function

Band-gap, work function and electron affinity of different Electron and hole- Φ and ionisation Energy IE of all materials are provided in Table 2.
selective contacts for Si solar cellsobtained from various literature sources Fig. 4 band diagrams shows the conduction and valence bands as
[[25,27,31,32,36,49,57,67,70–101,107,108], Supplementary Info.,[243]]. well as work functions (Fermi level positions) (shown in red) of most of
TMO Eg χ (eV) Φ IE¼Egþ Class the electron-selective (shown in green) and hole-selective (shown in
(eV) (eV) χ (eV) purple) materials for Si solar cells, in accordance with the data sum­
Hole-selective metal oxides
marised in Table 2. Metal carrier-selective contacts are shown in cor­
MoO3 3.00 6.70 6.90 9.70 Class-V
V2O5 2.70 5.00 6.14 7.70 Class-V responding darker shades (dark green for electron-selective and dark
WO3 3.30 6.50 6.70 10.0 Class-V purple for hole-selective). The upper bands in the band structure show
CrO3 3.90 3.60 4.80 7.50 Class-V the conduction band while the lower bands indicate the valence band.
NiO 3.60 2.10 5.15 5.70 Class-III
Cu2O 1.90 3.20 4.84 5.10 Class-III
CoO 2.70 2.63 4.80 5.13 Class-III
2.3. Carrier-selective TMOs for c-Si
ReO3 3.13 6.02 6.70 9.15 Class-V
Electron-selective metal oxides 2.3.1. Basics of a TMO
TiO2 3.30 4.00 4.10 7.30 Class-IV There are already a handful number of Transition Metal Oxides that
ZnO 3.27 4.50 4.90 7.77 Class-IV
have been used as carrier selective contacts with Si, some of them being
Ta2O5 4.40 3.20 4.05 7.60 Class-IV
Nb2O5 3.40 4.10 4.05 7.50 Class-IV electron-selective and some others being hole-selective. But the reason
CdO 2.46 5.94 4.90 8.40 Class-IV behind why these TMOs act as carrier selective contacts still requires a
Sc2O3 6.30 0.90 2.35 7.20 Class-IV systematic generalized study. A study in 2012 by Greiner et al. [60] has
MgO 6.55 0.85 2.80 7.40 Class-IV been done on TMOs regarding the influence of oxidation states and
BaO 2.70 0.60 0.78 3.30 Class-IV
SnO2 3.50 4.53 4.75 8.03 Class-IV
cationic oxygen vacancieson the work function of TMOs. Most of the
Other Eg (eV) χ Φ (eV) IE¼Egþ Class TMOs are d0 oxides, excepting those TMOs in which the transition metal
Materials (eV) χ (eV) follows half-filled stability rule (d5 in Cu, Ni, Co, Fe, Mn) so they are
Hole-selective slightly different and completely d5 cationic TMOs (Fe2O3 and MnO)
CuI 3.10 2.10 5.60 5.20 Class-
[103] are stable and have poor carrier transport properties. The valence
III
Cu2S 2.20 3.07 4.97 5.27 Class- band maxima of those d0 oxides are mainly composed of O 2p-states and
III their conduction band minima is mainly composed of transition metal
PEDOT:PSS 1.30 3.60 5.00 4.90 Class- d-states [104] according to the Ligand Metal Charge Transfer (LCMT)
III rule. As most TMOs are d0 oxides, so oxygen vacancy is a common
Electron-selective
LiF 13.60 1.80 2.86 15.60 Class-
property of them [105], as ligand (oxide) to metal charge transfer is easy
IV due to completely vacant d orbitals. The most important property which
MgF2 6.84 2.76 3.50 9.60 Class- determines whether a TMO (or any material) is electron or hole selective
IV is its work function. Changes in work function on one hand can improve
CdS 2.40 4.05 4.55 6.45 Class-
photovoltaic performance due to better carrier-selectivity or can even
IV
Cs2CO3 1.90 2.26 2.36 4.16 Class- deteriorate carrier-selectivity resulting in poor FF and S-shaped curves
IV [106], and it is very well known that work function has to be high for a
GaN 3.40 4.10 4.60 7.50 Class- hole-selective TMO and low for an electron-selective TMO. However it
IV has been found that the work function of a TMO varies [109] and is
TiN 3.20 4.05 4.30 7.25 Class-
IV
difficult to reproduce due to stoichiometric variations caused by mul­
TaN 2.90 4.10 4.30 7.00 Class- tiple cation oxidation states. In the book written by Heinrich and Cox
IV [109] it has been stated that there is a wild inconsistency of the work
GaP 2.26 4.35 4.40 6.61 Class- function of TMOs due to different sample preparation methods that
IV
cause stoichiometric variations. Other factors include surface dipole
ZnSnN2 1.80 4.10 4.20 5.90 Class-
IV variation due to crystallographic orientations [110], surface termination
ZnS 3.72 3.85 4.40 7.57 Class- and reconstruction and surface roughness [110,111]. In case of these d0
IV TMOs, the Fermi level lies very close to the Conduction Band as shown
In2S3 2.59 4.13 4.26 6.72 Class- by Ultra-violet Photoemission Spectroscopy (UPS) and Infrared Photo
IV
PFN 3.47 2.14 3.60 5.61 Class-
Emission Spectroscopy (IPES) measurement results [61–64], and hence
IV they act like n-type semiconductors. Even in case of p-type hole-selective
Histidine 3.80 2.80 3.63 6.60 Class- TMOs like NiO and Cu2O slight changes in stoichiometry causes signif­
IV icant changes in work function and hence photovoltaic performance
Electron-selective metals
[54]. P-Type TMOs like NiOxand Cu2Oxhave a lower electron-affinity
Ca 0 2.90 2.90 2.90 Class-
VI and its work function is almost equal to its Ionization Energy (IE), as
Mg 0 3.70 3.70 3.70 Class- the Fermi-level lies close to the valence band [56,67,68]. NiO, Cu2O as
VI well as CoO are the TMOs that tend to form d5 oxides instead of d0 oxides
Hole-selective metals owing to their electronic configurations according to the half-filled
Pt 0 5.70 5.70 5.70 Class-
stability rule. They exhibit cationic vacancies instead of oxygen va­
VII
cancies and hence these oxides are p-type in nature owing to the vacncy
of electrons (presence of free holes) in the lattice [54,56,67,68].
hole-selective metals have been categorized into class-VI and class-VII In the work by Greiner et al. [60], the results show that small changes
respectively.Including these metal carrier-selective contacts there are in stoichiometry cause noticeable changes in the work function. Plot of
total 7 classes of carrier selective contacts. Other than metals all work function vs cationic oxidation in Fig. 5 state showed that work
dopant-free carrier-selective materials belong to Class III, IVand V. function decreases as the cationic oxidation state becomes lower.
Table 2 has been divided into TMO metal oxide based carrier-selective However, there are other factors that change with the change in cationic
contacts and other materials. Ca and Mg act as electron-selective oxidation states like oxide crystal structure and stoichiometric defects;
metals categorized as Class-VI and Pt as hole-selective metal hence the studies cannot be done independently.

7
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

Fig. 4. Band diagrams of i) TMOs and ii) other dopant-free materials iii) c-Si and a-Si:H as obtained from various literature sources [[25,27,31,32,36,49,57,67,
70–101,107,108],Supplementary Info.,[243]] (For interpretation of the references to color in this figure, the reader is referred to the web version of this article.).

8
S. Acharyya et al.
The work function of binary compounds is also related to their
electronegativity values. It is already known that work function directly
depends on the position of the Fermi level in the Energy band diagram in
Fig. 2b. Nethercott provided a relation in 1974, to calculate the Fermi
level of binary compound [112] in terms of the electronegativities of the
constituent elements present in the binary compound as shown in Eq. (4)
as:-
( )1/(m+n)
EF = xmA xB n
• for the binary compound AmBn
• where,χA=Electronegativity of A
• χB=Electronegativity of B
• m and n denotes the stoichiometries of elements A &B in the
compound
This relation was applied to the TMOs. Although group electroneg­
ativity yields the midgap position, the work function does not do so due
to the intrinsic gaps present in the TMOs. Thus Experimental midgap
was plotted vs calculated midgap using ionic electronegativities [112]
and the correlation was studied for several TMOs. The linear regression
in the plot follows the relation y = 0.925x + 2.83.Dependence of oxide’s
work function when defects are introduced was also studied and shown
Fig. 5. Plots of work function versus nominal average oxidation state [60]of metal atoms in several transition metals and transition metal oxides. The oxides were
grown as thin films via in situ oxidation.
Surfaces and Interfaces 28 (2022) 101687
in the plot of work function vs oxygen deficiency (x) in case of MoO3-x.
This was repeated with WO3-x and TiO2-x and in all cases the work
function decreased rapidly in the beginning but slowly afterwards. It
was also seen that for thin TMO films, work function varied with the
variation of film thickness, though after a certain thickness it gets stable
at a maximum value. This is present in a plot as studied by Irfan et. al.
[113] for MoO3 film.Photoemission Spectroscopy results from [60]
clearly show the increase in Mo6+ species with increasing thickness,
(4) while Mo0 diminishes, whereas Mo5+ is present only is present only
within first few nanometers of thickness. It has also been seen that the
higher oxidation state of a TMO is not possible when the TMO is in
contact with the corresponding Transition metal; this occurs especially
when the TMO has got multiple stable oxides, which is the case for most
of the TMOs. For example in Mo, when an MoO3 thin film is deposited an
MoO2 like interface is formed, i.e. we get an Mo/MoO2/MoO3 interface.
Other such metal TMO configurations are Cu/Cu2O/CuO, Ti/TiO/TiO2,
V/VO/V2O3/V2O5, etc. These reduced cationic oxides may also affect
work functions. In another study Greiner [114] showed how work
function depends not only on thickness of the TMO (MoO3) in this case
but also on the metal with which it is in contact. This is because every
metal has different work functions (Fermi levels) and when a metal is in
contact with a TMO a charge transfer takes place from the metal Fermi
level to the conduction band minima of the TMO. This also occurs if the
MoO3is reduced by the oxidation of the metal with the help of O-atoms
9
S. Acharyya et al.
Fig. 6. Curves showingvariation of work function of MoO3with oxide thickness on different metal substrates (Au, Ni, Mo, V, Cu) [114].
in MoO3. Thus it depends on not only the work function of the metal but
also its tendency to form oxides. From the Fig. 6 below it is clear that the
general trend of the curves is same as the curves obtained by Irfan et. al.
[113].However Fig. 6 clearly reveals that the work function of the TMO
is highly dependant on the choice of the metal contact.
The elaborated study by Greiner et al. [60] actually showed how and
why TMOs have tunable work functions, which can be used as an
application for electron and hole transport layers.
2.3.2. Hole-selective TMOs with Si
We already know that NiO acts as hole-selective contact, due to
lower valence band-offset and high work function, but the same does not
apply for MoOx and some other hole-selective TMOs for Si. MoOx [16,22,
25,47,81,106,115–120,128–137,141–155,194,165,167,168,169,170]
is the most explored hole-selective TMO given in Table 3. A review has
been done on Si solar cells [126] featuring hole selective MoOx alone.
Thus it is quite obvious that MoO3 is very popular among Si PV re­
searchers. This has been followed by V2O5, WO3, CrO3, NiO, Cu2O, CoO
and ReO3 [16,19,20,23,24–27,36,37,54,70,81,138–141,143,150,
156–164,166,172–174]and is given in Table 4. CoO [27,173] also forms
a good hole-selective contact with silicon although silicon solar cells
using cobalt oxide but needs more exploration. The record efficiency of
the Si solar cell featuring MoO3 is 23.5% [131]. This is followed by using
V2O5 with 21.60% efficiency [23] with full rear contact and CrO3with
20.30% efficiency [19,20] with multi-layer PERC-like structure. Gerling
[120,121] studied hole-selective TMOs for n-type c-Si, and according to
their analysis a band-diagram [120] was provided as shown in the Fig. 7
below:-
The formation of a p+ inversion layer in n-Si by high work function
TMOs is due to Fermi level alignment across the interface [119,122,
123].Before contact formation, a large electrochemical potential dif­
ference is present due their work function difference ΔΦ = ΦTMO - Φn-Si
= 5.4 - 4.2 eV. Electron transfer takes place from the valence band of n-Si
to the oxygen vacant defect states of the TMO so as to align the Fermi
levels. Due to this electron transfer from n-Si surface a p+ inversion layer
is induced.
In a simulation work by Fraunhofer ISE [124] two tunneling mech­
anisms have been shown that facilitate hole selective TMO/i-a-Si:
H/c-Sicontacts with Si, one is Band to band tunneling (B2B)as shown
in Fig. 8(a) and the other is Trap assisted tunneling (TAT) [125] as
shown in Fig. 8(b).
10
Surfaces and Interfaces 28 (2022) 101687
According to simulation results [124]three requirements for TMO
hole-selective contacts were concluded:
1.After contact is formed between the TMO and the c-Si, the Fermi
level alignment causes band-bending in c-Si, denoted by φc-Si. The p+
induced charge at the c-Si interface is proportional to the amount of
band bending φc-Si, and should be sufficiently high. This is possible for a
high TMO work function Φ that is close to the valence band energy of the
absorber.
2. Band to band (B2B) tunneling of excess holes is possible when the
conduction band energy of the TMO is greater than the valence band
energy of the Si layer (a-Si(i) layer since it has used for passivation of c-Si
surface). This is similar to the case of a broken-gap or type III
heterojunction.
ECTMO > EVa-Si then B2B tunneling occursas shown in Fig. 8.
3. If ECTMO < EVa-Si, then hole transport takes place with the help of
the trap states present in the TMO. This is similar to the case of a
staggered-gap or type II heterojunction. In this case TAT or trap-assisted
tunneling occurs. These traps can be classified into 4 types α,β,γ and δ by
Fraunhoffer group as shown in Fig. 8, based on trap-density as well as
the trap energy level [124].
α denotes metal-like defects, β denotes metal-like defects but with
much lesser trap density, γ denotes traps from valence band to a certain
cutoff energy level Ecut to study the effect of omission of the energy
levels close to the conduction band and δ denotes a single defect level at
an energy level Elevel with respect to the Conduction band. The simu­
lation study has been done by Fraunhoffer ISE [124] to study the effect
of all these traps on the Trap-Assisted Tunneling and ultimately the solar
cell performance. Due to the Fermi level alignment a band bending is
introduced at the c-Si in such a way that the valence band in c-Si bends
upward near the conduction band of the TMO but not as high as the
Conduction band of the TMO so B2B tunneling does not take place.
However the traps present in the TMO act as intermediate energy levels
to aid the holes present in the valence band to tunnel to the conduction
band. As tunneling takes place through these traps the phenomenon is
known as trap assisted tunneling.
In a review paper [126] by Hussain et. al. hole-selective MoOx con­
tacts for Si were discussed. The work function was found to be increasing
with increasing thickness of MoOx layer from the UPS spectraby Ding
et al. [127], similar to the study of Irfan et. al. [113].The plot is given
below in Fig. 9.For the MoOx film thickness of 0.2, 0.4, 0.8, 1.6, 3.2, 4.8
and 6.4 nm, the work function was calculated as 4.80, 5.20, 5.55, 5.90,
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

Table 3
MoOx hole-selective contacts for Si solar cells.
Research Group Wafer and MoO3 deposition method Passivated contact Solar cell Parameters Refs.
cell type Emitter/Front BSF/ Back VOC JSC FF Eff (%)
(mV) (mA/ (%)
2
cm )
Berkeley n-type FZ Thermal Evaporation Ag/ITO/MoOx/ i-a-Si/n-a-Si/ITO/ 711 40.40 67.20 18.80 [128]
i-a-Si Ag
IIT Delhi n-type CZ Thermal Evaporation Ag/ITO/MoOx LiFx/Al 575 35.60 75.02 15.36 [129]
University of Chinese n-type CZ Hot wire oxidation-sublimation Ag/WOx (ARC)/ i-a-Si/ SiO2/ 696 38.61 75.31 20.24 [194]
Academy of Sciences IBC deposition MoOx/ i-a-Si TiO2/Mg/Al/Ag
Sungkyunkwan University n-type CZ Thermal Evaporation Ag/ITO/ MoOx/ i-a-Si/ n-a-Si/ 695 38.88 74.00 20.00 [130]
i-a-Si ITO/Ag
EPFL n-type FZ Thermal Evaporation Ag/ITO/ MoOx/ i-a-Si/ n-a-Si/ 734 39.20 81.80 23.50 [131]
i-a-Si ITO/Ag
EPFL n-type FZ Thermal Evaporation Ag-Cu/ IO:H/ i-a-Si/ n-a-Si/ 725 38.60 80.36 22.50 [132]
MoOx/i-a-Si ITO/Ag
Berkeley, EPFL and ANU n-type FZ Thermal Evaporation Ag/ITO/ MoOx/ i-a-Si/ TiOx/ LiFx/ 706 38.40 76.20 20.70 [133]
i-a-Si Al
Berkeley n-type Thermal Evaporation Ag/ITO/ MoOx i-a-Si/ n-a-Si/ 580 37.80 65.00 14.30 [134]
ITO/Ag
Berkeley n-type FZ Thermal Evaporation Ag/ITO/ MoOx/ i-a-Si/ LiFx/Al 716 37.10 73.15 19.42 [49]
i-a-Si
IIT Bombay n-type FZ Thermal Evaporation Pd/Ag/ ITO/ TiO2/Al 520 30.50 34.80 5.52 [135]
MoO3
ENEA p-type FZ Thermal Evaporation Al/AZO/ n-µc- i-a-Si/ MoOx/ Ag 661 37.60 72.90 18.10 [136]
SiO /i-a-Si
UNIST, Korea n-type CZ Thermal Evaporation Al/ MoOx Al/LiFx 561 36.80 74.60 15.40 [137]
(IBC)
SYSU China n-type FZ Thermal Evaporation Ag/ MoOx Ag/ Cs2CO3 594 38.42 66.13 15.09 [16]
(IBC)
UPC Spain n-type FZ Thermal Evaporation Ag/ ITO/ MoOx Ti/Al/i-a-SiCx/ 581 34.10 68.80 13.60 [141]
n+-a-SiC/ i-a-SiCx
IIT Delhi n-type CZ RF Sputtering Ag/ITO/MoOx/ Ag/ITO 358 25.00 48.54 4.30 [142]
SiOx
ANU Canberra n-type FZ Thermal Evaporation Ag/ITO/ MoOx/ SiOx/n -poly-Si
+
637 35.00 75.00 16.70 [22]
SiOx
p-type FZ Al/SiNx/n+-Si Ag/ MoOx 616 37.00 72.00 16.40
Fraunhofer ISE n-type FZ Thermal Evaporation Ag/ ITO/ MoOx/ i-a-Si/ n-a-Si/ 710 33.40 80.00 19.00 [143]
i-a-Si ITO/Ag
ANU Canberra p-type FZ Thermal Evaporation Ag/SiNx/ n+-Si Al2O3/ SiNx/ 658 39.80 77.80 20.40 [144]
PERC MoOx (partial)
Table 3. MoOx hole-selective contacts for Si solar cells (contd.)
Research Group Wafer and MoO3 deposition method Passivated contact Solar cell Parameters Refs.
cell type Emitter/ Front BSF/ Back VOC JSC FF Eff
(mV) (mA/ (%) (%)
cm2)
UPC Spain n-type FZ Thermal Evaporation Ag/ITO/ MoOx Ti/Al/ i-a-SiCx/ n+-a- 563 33.00 72.10 13.40 [145]
SiC/ i-a-SiCx
University of Chinese n-type FZ Hot wire oxidation- Ag/ITO/ n -a-Si/ i-a-
+
MoOx/Ag 550 34.18 74.96 14.09 [146]
Academy of Sciences sublimation deposition Si SiOx/ MoOx/Ag 644 36.88 70.54 16.74
(HWOSD) i-a-Si/ MoOx/Ag 690 36.72 70.35 17.83
* denotes pre annealing HF i-a-Si*/ MoOx/Ag 713 37.50 78.92 21.10
process beforeMoOx deposition
SYSU China n-type FZ Thermal Evaporation Ag/ MoOx/ Ag/ Ag/ Cs2CO3 583 29.43 75.83 13.01 [147]
MoOx
Shanghai University n-type CZ Thermal Evaporation Ag/ITO/MoOx SiOx/ 600 38.20 72.90 16.70 [148]
n+-polySi/
Al
ECN Netherlands n-type FZ Thermal Evaporation Ag/ITO/MoOx/ i-a-Si SiOx/ 686 35.90 73.00 18.10 [149]
n+-polySi/
Al
EPFL n-type FZ Thermal Evaporation Ag/IZO/MoOx/ i-a-Si i-a-Si/ n-a-Si/ ITO/Ag 705 38.60 72.80 19.80 [150]
NIMTE China n-type CZ E-beam Ag/ITO/MoOx Al 578 31.20 68.80 12.40 [151]
MgOx/Al 595 32.60 73.40 14.20
MLU Germany n-type FZ ALD Ti/Ag/ ITO/ MoOx/ i-a-Si/ n-a-Si/ ITO/Ag/ 631 30.10 53.80 10.20 [152]
i-a-Si Ti
NTU Singapore n-type CZ Spin coating Ag/ITO/MoOx Ti/Pd/Ag 490 29.92 49.07 7.26 [153]
NTU Singapore n-type CZ Spin coating Ag/ITO/MoOx Ti/Pd/Ag 463 31.16 56.87 8.22 [154]
NTU Singapore n-type CZ Spin coating Ag/ITO/MoOx/ Ti/Pd/Ag 557 33.58 68.47 12.46 [155]
E-beam interface-SiOx 574 32.99 71.90 13.33
UPC Spain n-type FZ Thermal Evaporation Ag/ITO/MoOx Ti/Al/ i/n+-a-SiCx/i-a- 581 29.60 73.10 12.60 [25]
PERC SiCx
SYSU China n-type FZ Thermal Evaporation Ag/ MoOx/ Ag/ Ag/ Cs2CO3 591 36.40 65.37 14.06 [47]
IBC MoOx
EPFL and SYSU n-type FZ Thermal Evaporation Ag/ MoOx/ i-a-Si Al/Mg/ MgFx/ i-a-Si 718 41.50 74.20 22.10 [48]
IBC
(continued on next page)

11
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

Table 3 (continued )
Chinese Academy of p-type CZ ALD Ag/SiNx/n+-Si Ag/CrOx(protective) 614 36.45 68.98 15.45 [165]
Sciences MoOx
SYSU, EPFL & CSEM n-type FZ Thermal Evaporation i-a-Si/ MoOx/Ag i-a-Si/MgFx/Al/Ag 709 41.50 75.60 22.20 [167]
IBC i-a-Si/ MoOx/Ag i-a-Si/MgOx/Al/Ag 663 40.30 48.20 12.90
National Formosa p-type FZ Thermal Evaporation Ag/SiNx/ n+-Si Ag/MoOx/Ag/MoOx/ 659 36.70 80.00 18.70 [168]
University, Taiwan Ag/MoOx
Nankai University China n-type CZ Thermal Evaporation i-a-Si/ MoOx/Ag i-a-Si/ ZnO:B/Ag 599 38.12 72.70 16.60 [169]
i-a-Si/ n-a-Si/Ag 593 35.97 67.60 14.40
University of Chinese p-type CZ Thermal Evaporation Ag/SiNx/ n -Si
+
UV-SiOx/ MoOx/ 626 38.50 82.80 20.00 [170]
Academy of Sciences V2Ox/ITO/Ag
University of Chinese p-type CZ Thermal Evaporation Ag/SiNx/ n+-Si MoOx/Ag 632 36.21 80.89 18.49 [171]
Academy of Sciences
UNIST Korea n-type CZ Thermal Evaporation Ag/MgF2(ARC)/ n+-Si/Al 608 37.10 75.30 17.00 [242]
MoOx
SYSU China p-type CZ Thermal Evaporation Ag/ITO/ In2S3 MoO3/Ag 461 36.93 62.94 10.72 [243]
EPFL n-type FZ Thermal Evaporation i-a-Si/ MoOx/Ag i-a-Si/ n-a-Si/Ag 710 38.75 76.00 20.80 [106]

6.30, 6.50, and 6.65 eV as the Kinetic Energy peaks. This trend is same as
that in Greiner et. al. [60], as well as Irfan et. al [113] thus providing a
clear proof that work function increases with increase in oxide (MoOx)
thickness.
MoO3 has been explored as a TMO hole-selective contact by a large
number of groups. The summary of MoOx hole selective contacts for Si
solar cells is given belowin Table 3. Process of fabrication of the hole-
selective TMO as well as the cell results have been provided along
with other useful information that would help researchers to find
possible scopes of improvement in the cell structures. ITO has also been
implemented as hole-selective contact [37].
2.3.3. Electron-selective TMOs and other oxides with Si
TMOs like TiO2 are electron-selective due to their low work function
and lower conduction band offset with silicon. The same is applicable for
non-oxide electron-selective materials with silicon like LiF, Cs2CO3,etc.
TiO2 is the most explored electron-selective contact [133,135,139,161,
166,180–182,185–200]. The band-diagram of TiO2 with Si has been
already given in Fig. 2a. However exact band-diagrams are dependant
on work functions, which are tunable in case of a TMO. Furthermore, it
also depends on the method of deposition of the TiO2 film as well as
deposition conditions, due to which stoichiometry of the film varies,
which is the main reason for tunability. Given below in Fig. 10is another
band-diagram of a TiO2/n-Si heterojunction in which the TiO2 is
deposited using ALD.
Here it is quite clear that the Fermi level and hence the work function
of TiO2 is quite different for the ALD sample deposited at 500 ◦ C than at
200 ◦ C. Although in the above work TiO2 is used as a passivation layer
and an ARC yet the above results are quite useful. Lee et. al. [176]
calculated exact band offsets of thermally evaporated TiO2 with Si given
in Fig. 11.
In another recent work [177], Fermi energies and work functions of
different TiO2 phases as well as made by different processes have been
measured as shown in Fig. 12 and Table 5.
TiO2 has also been shown as an electron-injector in p-type Si solar
cells [178,179] due to its electron selective nature. In case of TiO2, it has
been shown by Fraunhofer ISE group that it can also act as a
hole-selective layer with Si [183] if its fixed charges, Fermi level and
work functions are tuned slightly by varying the ALD parameters during
deposition and the same is applicable for most of the TMOs. Even ZnO
has an amphoteric property to act as a hole-selective oxide [184]
although it has been used as an electron-selective oxide in most cases
[28,29,201–203]. Similar studies have been done on hole-selective
MoO3 with Si [115] showing the variation of intrinsic and silicon de­
fects in MoO3 that cause stoichiometric defects.
Amphoteric properties of TiO2 are due to the fact that the work
function, band gap and other electronic properties of TiO2 varies. Work
function of TiO2 is varies from below4eV to above 6 eV [177] as shown
in Fig. 12 and Table 5. The same thing occurs in case of ZnO [184].
Instead of behaving as group-IV materials they behave as group-V ma­
terials. They don’t become p-type like group-III materials since they
have oxygen vacancies and therefore are n-type, only their work func­
tion and electron affinity becomes higher.
Several TMOs other than TiO2 are used as electron-selective contacts,
such as ZnO, Ta2O5, Nb2O5, CdO, Sc2O3 [28,29,32,33,169,201–206] as
well as other metal oxides like MgO and SnO2 [34,36,151,167,
207–209]. ITO (In2O3:Sn) has also been used as electron-selective con­
tact [38].The record efficiencies of such solar cells include 23.10%
involving partial rear contacts [193] by Bullock et. al. involving LiF/­
TiO2as electron-selective bilayers and 22.10% involving full area rear
contact [191] by Yang et. al. involving TiO2single layer as
electron-selective contact.With MgO as electron-selective full area con­
tact efficiency of 20.00% has been obtained by Wan et. al [34]. The list
of solar cells featuring TiO2 is given in Table 6 and that of other oxides is
given in Table 7.
2.4. Other hole-selective contacts with Si
Among non-oxide hole-selective materials for Si solar cells [Table 8],
there are both organic and inorganic materials used as hole-selective
contacts with Si. PEDOT:PSS [44,71,158,186,187,196,197,200,202,
207,209–226,233,237,238,245,259] is the most explored organic
hole-selective material for Silicon heterojunction with record efficiency
of upto 20.60% [219] by ISFH Germany followed by other hole-selective
organic materials [214,227]. This is followed by inorganic hole-selective
contacts like CuI [228–231] and Cu2S [80] with efficiencies of 20.70%
and 21.04% respectively involving partial rear contacts i.e. PERC
structure. With SnSe [241] and n-type silicon a low efficiency of 6.44%
was obtained, but it has not been used with Si solar cells by any other
group.MoO3 when used as an ARC enhances the current and improves
the efficiency of PEDOT:PSS/Si solar cell as shown by Liu et. al.group
[259]. However deposition of cuprous iodide for hole-selective contacts
for silicon solar cells still needs some further experimental studies, as it
is a new emerging material in this field.
2.5. Other electron-selective contacts with Si
There are many non-oxide materials which act as electron selective
contacts with silicon [Table 9]. Among them there are alkali and alka­
line earth metal fluorides such as LiF [46,49,129,133,137,138,193,197,
198], MgF2 [48,232,73,167],KF [49], CaF2 [49], CsF [49] as well as
other salts TiN [234,75], GaN [78], ZnSnN2 [77], GaP [79,236], ZnS
[81] and In2S3 [243]. However Si solar cells featuring KF, CaF2, CsF as
electron-selective contacts are yet to be fabricated. Wan and Bullock
group fabricated solar cells featuring electron selective contacts using
alkali and alkaline-earth metal carbonates [74] such as K2CO3, Rb2CO3,
Cs2CO3, CaCO3, SrCO3 and BaCO3. Among these metal carbonates
application of Cs2CO3 as electron selective contacts in silicon solar cells

12
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

Table 4
Other TMO hole-selective contacts for Si solar cells.
Research Group Wafer type TMO deposition Passivated contact Solar cell Parameters Refs.
method Front Back VOC JSC (mA/ FF (%) Eff
(mV) cm2) (%)
IIT Delhi n-type FZ Thermal Evaporation Ag/ITO/ NiOx/SiOx SiOx/ LiFx/Al 580 36.90 71.06 15.20 [138]
Stanford University thin Si 2 µm (pin E-beam Evaporation Al/TiOx/ SiOx/ n+-a- i-Si/ p+-Si/ SiOx/ NiOx/Pt 620 20.60 82.40 10.50 [139]
cell) Si/i-a-Si
Stanford University thin Si 3 µm p- Thermal Evaporation Al/SiOx/ n+-Si/ p-Si/ p+-Si/ NiOx/ Pt/Ag 630 23.70 82.10 12.30 [140]
type p-Si
SYSU China n-type FZ (IBC) Thermal Evaporation Ag/V2Ox Ag/ Cs2CO3 610 38.85 70.00 16.59 [16]
Ag/WOx 539 37.67 61.30 12.44
UPC Spain n-type FZ Thermal Evaporation Ag/ITO/ V2Ox Ti/Al/i-a-SiCx/ n -a-SiC/ i-a- 606
+
34.40 75.30 15.70 [141]
Thermal Evaporation Ag/ITO/ WOx SiCx 577 33.30 65.00 12.50
UPC Spain n-type FZ Thermal Evaporation Ag/ITO/ V2Ox i-a-Si/ n-a-Si/ ITO/Ag 684 34.00 79.00 18.30 [143]
Thermal Evaporation Ag/ITO/ WOx/ i-a-Si 685 33.80 78.00 17.90
EPFL n-type FZ Thermal Evaporation Ag/IZO/WOx/ i-a-Si i-a-Si/ n-a-Si/ ITO/Ag 638 40.20 70.10 18.00 [150]
UPC Spain n-type FZ IBC Thermal Evaporation Al/Ni/ V2Ox Al/ i-a-SiCx/ n+-a-SiC/ n+-Si 656 40.70 74.00 19.70 [156]

SYSU China n-type CZ IBC Thermal Evaporation Al/V2Ox Al/LiFx 635 38.65 71.65 17.58 [157]
Al/V2Ox/Au/V2Ox 651 38.70 75.49 19.02
NCKU, Taiwan Si nano-wire Spin coating ITO/ V2Ox/ PEDOT: Al 541 45.40 58.31 14.40 [158]
PSS
KAUST, Saudia Arabia n-type FZ ALD Ag/ITO/n+-a-Si/ i-a-Si i-a-Si/ V2Ox/Ag 721 38.30 78.20 21.60 [23]
Table 4. Other TMO hole-selective contacts for Si solar cells (contd.)
Research Group Wafer and cell TMO deposition Passivated contact Solar cell Parameters Refs.
type method Emitter/ Front BSF/ Back VOC JSC (mA/ FF Eff
(mV) cm2) (%) (%)
UPC Spain n-type FZ Thermal Evaporation Ag/ITO/V2Ox i-a-Si/ n-a-Si/ a-SiCx/ Al 615 31.80 75.10 14.70 [159]
Ag/ITO/ n-a-Si/ i-a-Si V2Ox/Ni/Al 617 30.40 75.30 14.20
UPC Spain n-type FZ Thermal Evaporation Ag/ITO/V2Ox/ SiOx i-a-Si/ n-a-Si/ ITO/Ag 642 37.50 68.50 16.50 [160]
UPC Spain n-type FZ Thermal Evaporation Ag/V2OxAg/Au/ V2Ox Al2O3/ TiO2/ Mg/Al 618 27.10 79.50 13.30 [161]
UPC Spain n-type CZ Thermal Evaporation Ag/ITO/V2Ox i-a-Si/ n-a-Si/ ITO/Ag 665 33.70 66.30 14.80 [162]
n-type CZ PERL i-a-SiCx/ n+-a-SiC/ i-a-SiCx/ 601 33.00 68.00 13.50
Al
NUS Singapore n-type FZ Thermal Evaporation MgF2/ ITO/Ni/ V2Ox BaOx/Al 621 37.05 75.11 17.25 [36]
UPC Spain n-type FZ IBC Thermal Evaporation Al/Ni/ V2O5 Al/Mg/ TiO2/ Al2O3 633 40.00 75.40 19.10 [166]
Helmholtz- n-type CZ Sputtering Ag/Ti/ ITO/ WO3/ i-a- i-a-Si/ n-a-Si/ ITO/Ag 695 37.00 66.50 16.60 [24]
Zentrum Berlin (HZB) Si
UPC Spain n-type FZ PERC Thermal Evaporation Ag/ITO/ReO3 Ti/Al/ i-a-SiCx/ n+-a-SiC/ i- 245 28.90 44.40 3.10 [25]
Ag/ITO/ WO3 a-SiCx 570 29.10 71.00 11.80
Ag/ITO/V2O5 593 29.60 73.10 12.60
IISC Bangalore n-type CZ Sputtering Au/ Cu2O/ SiO2 Al 528 13.20 48.60 3.39 [26]
IISC Bangalore n-type CZ Sputtering ITO/ Cu2O:N Al 450 17.90 65.00 5.23 [163]
SYSU and Jinan University n-type FZ Spin Coating Ag/ MoOx */ Ag/Cu2O Mg/Ag 528 30.08 60.01 9.54 [164]
China *MoOx acts as an ARC
SYSU China p-type CZ PERC Thermal Evaporation Ag/SiNx/n+-Si Al2O3/ SiNx/ CrOx/Ag/CrOx 638 39.80 80.10 20.30 [19] [20]
(partial)
SYSU China n-type FZ IBC Thermal Evaporation Ag/CrOxAu/CrOx LiFx/Al 605 39.20 66.60 15.80 [70]
Shanghai University n-type CZ Sputtering Ag/ In2O3:Sn/SiOx n+-Si/ Ag/Al 480 34.20 70.00 11.50 [37]
UPC Spain n-type FZ Thermal Evaporation Ag/ITO/ V2Ox i-a-Si/Al 340 28.50 64.00 6.20 [174]
i-a-Si/ PFN/Al 590 30.10 78.20 13.90
i-a-Si/ n-a-Si/Al 640 33.00 76.20 16.10
i-a-Si/ n-a-Si/ PFN/Al 670 33.60 76.40 17.20
SYSU China p-type CZ Thermal Evaporation Ag/ITO/ ZnS WO3/Ag 525 33.75 66.73 10.94 [81]
SYSU China n-type CZ Thermal Evaporation WOx/Ag/WOx Ag 420 18.96 65.39 5.21 [172]
California Institute of n-type CZ Sputtering CoOx n-Si 290 18.00 39.00 2.05 [173]
Technology Si
NiOx 250 28.00 35.00 2.40 substrate
and the
TMO are
the
electrodes
KAIST Korea p-type CZ E-beam Evaporation Ag/ITO/n-a-Si NiOx/Pd/Ag 565 31.65 79.60 14.23 [54]

has been done by other groups [16,43,47,147,233].Organic materials
like PTB7-NSO3 [237], PTB7-NBr [237], histidine [239,240] and PFN
[174] have also been implemented as electron-selective contacts in sil­
icon solar cells. The record efficiency is the same 23.10% [193] using
TiOx/LiFx bilayer by Bullock et. al. as mentioned previously using
PERC-like structure but is only 20.60% [46] when using only LiFx with
PERC-like structure. With MoOx and MgFx as hole and electron-selective
layers respectively a record efficiency of 22.20% [167] has been ob­
tained. With TiN as partial rear contact [75] an efficiency of 20.00% has
been obtained. With TaNx as full area electron-selective contact an ef­
ficiency of 20.10% has been obtained [76,235]. Even alkaline earth
metals withlow work function like Ca [244] and Mg [245] have been
used as electron contacts with silicon.
2.6. Summary of dopant-free carrier selective contacts
From theabove Tables 3,4,6– 9 containing solar cells with dopant-
free carrier selective materials alongwith their references, many
important information can be obtained. Some of the solar cells have
been found to implement partial area passivating contacts although
majority of them implement full area passivating contacts, some are
even seen to follow back contact configuration to reduce shading losses

13
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

Fig. 7. . Band diagram ofhole-selective TMO/n-Si interface [120]. (a) Before contact, the transfer of electrons is depicted from the valence band of n-Si toward the
hole-selective TMO which has got a higher work function. (b) After contact is formed along with a passivating SiOx interlayer, a p+ inversion layer is induced on the
c-Si surface when the Fermi levels (EF) reachequilibrium.

at the front totally. MoOx [238], CrOx [19,20], TiOx [192,193], LiF [46,
193], MgOx [209], CuI [228], Cu2S [80], LiF [46] and Ca [244] have
been implemented as partial contacts instead of p+/n+ locally doped
layers and some have even produced better results compared to the full
area passivation counterparts. This is because full area passivation in­
volves fabrication of ultra-thin layers that facilitate tunneling which is
challenging due to the non-uniformity of those layers on silicon surface,
so in that case the deposition method has to be slower for more uniform
deposition.
Some of the TMOs like MoOx [47,147,168], V2Ox [157,161], CrOx
[19,20,70], WOx [172] have been seen to be implemented as a multi­
layer structure, and are shown to show improvement compared to a
single layer structure.Although implementation of multilayer TiOx and
ZnOx in silicon solar cells have not been done, yet it is shown that there
is a resistivity reduction with a multi-layer structure with a thin silver
layer sandwiched in between [246,247] and the sheet resistivity
reduction being the main reason. It has also been found that increasing
the inter-metal thickness decreases the contact resistance; whereas

Fig. 8. (a) B2B and (b) TAT band diagrams [124] for TMO/i-a-Si/n-c-Si carrier selective layers.

14
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

decreasing the TMO thickness does the opposite [255].These structures

Fig. 9. UPS spectra [127] of Si and Si/MoOxlayer thickness showing secondary
electron cut-off region.
when fabricated at the front introduces a loss of JSC due to the metal in
between but can be applied at the back with proper light trapping
schemes and introduction of rear reflectors [47] to reduce absorption
loss in the metal.The work function of the metal layer [157] in between
is also crucial to determine whether the contact is Ohmic or Schottkey.
Different fabrication processes, deposition temperatures and
ambient conditions effect the photovoltaic performances of these
dopant-free solar cells as we can see in the above Tables 2,3,5–8 as well
as from Bivour’s work [116] and the PhD thesis of Zhang from UNSW
[260].Annealing is also a crucial step because the carrier selective ma­
terials (especially the TMOs) when as-deposited are in amorphous form
and crystallization is needed to improve their stability, proper
bond-formation with the substrate as well as forming a defect-free
interface adjoining the TCO or metal. This annealing generally tunes
optical band gap, work function and transmittance of the material
[248]. It has also been found that O-vacancies in the TMO cause
reduction in work function of the TMO film [248]. However, in case of
certain metal oxides oxygen vacancy increases on annealing in N2
ambient, which may aid electrical conductivity through the oxide but
increases defect states due to which some groups [15,30,53,135,139,
150,156,176,190,191,193,195,166,200,253] have used Forming Gas

Fig. 10. Band diagrams ofTiO2/Si interface with ALD at 200 ◦ C(a) beforeand (b) after contact formation and at 500 ◦ C (c) before and (d) after contact forma­
tion [175].

15
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

Table 5
Sample descriptions and surface potentials [177] for Fig 14. All values are in eV.
No. Sample Description EF ϕ IP
1 rutile (110) (i) same as #2; 2.68 5.96 8.64
(ii) O2 plasma,
RT, 15 min
2 rutile (110) (i) 500 ◦ C, 0.5 3.24 4.43 7.67
Pa O2, 2 h; (ii)
600 ◦ C,
10− 6 Pa, 1 h
3 rutile (110) same as #2 3.12 4.31 7.43
4 rutile (001) same as #1 2.57 6.08 8.65
5 rutile (001) same as #2 3.26 4.31 7.57
6 rutile (001) same as #2 3.07 4.29 7.36
7 anatase same as #2 2.93 4.26 7.19
(101)
8 anatase same as #2 + 3.35 3.65 7.00
(101) air exposure
9 anatase O2 plasma, RT, 2.83 5.55 8.38
(101) 15 min
10 anatase same as #9 + 2.90 3.90 6.80
(101) air exposure
11 anatase (i) same as #12; 3.25 5.05 8.30
Fig. 11. Band diagrams ofTiO2/Si interface for thermally evaporated (101) (ii) O2 plasma,
TiOx [176]. RT,
15 min; (iii)
annealing in
10− 6 Pa, 200
◦
C, 20 min

12 anatase cycles of 3.55 4.62 8.17

(101) sputtering +
annealing 600
◦
C,
10− 6 Pa, 1 h
13 anatase (i) same as #12; 2.80 5.91 8.71
(101) (ii) O2 plasma,
RT,
15 min
14 anatase stoichiometric 2.84 5.23 8.07
(101) as in
manuscript
15 anatase (i) same as #14; 3.08 4.40 7.48
(101) (ii) H2O
adsorption
16 anatase reduced as in 3.23 4.72 7.95
(101) manuscript
17 anatase (i) same #16; 3.4 4.36 7.76
(101) (ii) H2O
adsorption
18 anatase oxidized as in 2.69 6.76 9.45
(101) manuscript
Fig. 12. Extended set of work function and Fermi energy data [177]. The
19 anatase (i) same as #18; 2.91 5.03 7.94
description of the sample numbers are given in Table 5. (101) (ii) H2O
adsorption
(95%N2+5%H2) Annealing (FGA) and these are not annealed at high 20 anatase same as #7 3.05 4.36 7.41
(001)
temperatures because there may be grain boundaries [254] in the
21 anatase same as #8 3.44 3.61 7.05
annealed polycrystalline films that can act as defects.The advantage of (001)
using FGA is that the small percentage of hydrogen present in it pas­ 22 anatase same as #9 2.83 5.55 8.38
sivates most of the bulk defects in the metal oxide. However, these (001)
transition d-metals have less affinity for hydrogen than oxygen, but they 23 anatase same as #10 2.90 3.90 6.80
(001)
can cause reduction in the oxidation state of the metal [249]. Some have 24 anatase same as #11 3.25 5.05 8.30
even used air ambient [131,133,143,154,250–252] to reduce oxygen (001)
vacancies. In case of TOPCon solar cells the back highly doped poly-Si 25 anatase same as #12 3.55 4.62 8.17
layer is formed by annealing the as-deposited doped a-Si:H layer in (001)
26 anatase same as #13 2.80 5.91 8.71
Forming Gas environment [256,257] at high temperature which pas­
(001)
sivates the bulk of the poly-Si layer.However some factors like reduction 27 anatase same as #14 2.84 5.23 8.07
in contact resistivity [258] due to annealing at high temperature can be (001)
beneficial for annealing, however passivation quality suffers and hence 28 anatase same as #15 3.08 4.4 7.48
multi-step annealing could also be beneficial. Pre-deposition annealing (001)
29 anatase same as #16 3.23 4.72 7.95
is also sometimes shown to be beneficial to avoid reduction of work (001)
function (in case of high work function hole-selective TMOs like MoOx) 30 anatase same as #17 3.40 4.36 7.76
during annealing [106], so as to improve carrier-selectivity and avoid (001)
the S-shaped J-V curve that arises due to deteriorated carrier-selectivity (continued on next page)
caused due to post-deposition annealing.

16
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

Table 5 (continued ) 3. Wide band-gap materials for c-Si surface passivation

31 anatase same as #18 2.69 6.76 9.45
(001) 3.1. Quantifying surface passivation
32 anatase same as #19 2.91 5.03 7.94
(001) Perhaps the most direct way to obtain the degree of passivation is by
33 powder sol-gel, as 3.18 3.94 7.12
prepared
measuring the Surface Recombination Velocity (SRV or Seff) of a
34 powder hydrothermal, 3.44 3.87 7.31 particular surface. In the well known Shockley Read Hall equation
as prepared Shockley and Read Jr [262] deduced a dependence of the lifetime of the
35 nanocrystals (101) facetted 3.41 4.32 7.73 injected charge carriers (minority carriers in case of solar cells) upon the
36 sprayed film 0.5 Pa O2, 400 3.21 5.25 8.46
injected charge carrier density as well as the equilibrium conductivity of
◦
C, 12 h
37 sprayed film 0.5 Pa Ar, 400 3.24 5.14 8.38 the sample. Hall derived the lifetime [263] in equilibrium conditions in
◦
C, 12 h terms of dopant concentration and he matched the results with a
38–42 sprayed film same as #36 2.98–3.45 4.85–5.25 7.88–8.62 germanium sample. SRH equation actually determines the recombina­
43–50 sprayed film as received 3.47–3.60 3.75–3.96 7.29–7.46 tion rate from which recombination velocity can be determined both at
51 thin film (i) in situ 2.98 5.53 8.51
the surface and the bulk. From both the published works the Shockley
magnetron
sputtering at Read Hall (SRH) equation for effective surface recombination velocity is
RT; obtained in Eq. (5) as:
(ii) 0.5 Pa O2,
600 ◦ C, 1 h 1 n p − n2i
Seff = ( s s ) (5)
52 thin film (i) in situ 3.09 5.37 8.46 ΔnS ns +ni ps +ni
magnetron Sp
+ Sn
0 0
sputtering at
RT;
(ii) 0.5 Pa O2,
• where, electron recombination velocity, Sn0= ¼ vthDitσn
400 ◦ C, 1 h
53 sprayedfilm same as #11 3.24 4.82 8.06 • and hole capture velocity, Sp0= ¼ vthDitσp
54 sprayedfilm same as #12 3.23 4.51 7.74 • σn=Capture cross-section area for electrons
55 sprayedfilm same as #13 2.85 5.70 8.55 • σp=Capture cross-section area for holes
56 sprayedfilm stoichiometric 3.12 5.16 8.28
• nsand ps are the concentrations of electrons and holes at the surface
as in
manuscript
• ΔnSis the excess minoritycarrier concentration formed at the surface
57 sprayedfilm (i) same as #58; 3.31 4.23 7.32 of theSemiconductor
(ii) H2O
adsorption Surface passivation can also be expressed in terms of the effective
58 sprayedfilm reduced as in 3.09 4.23 7.32
minority carrier lifetime [264], which can be derived from surface
manuscript
59 sprayedfilm (i) same as #60; 3.37 4.22 7.59 recombination velocity as shown in Eq. (6).
(ii) H2O
1 1 Sfront + Srear
adsorption = + (6)
60 sprayedfilm stoichiometric 3.12 5.16 8.28 τeff τbulk W
as in
manuscript
61 sprayedfilm (i) same as #62; 3.16 4.94 8.10 • where, τeff=Effective lifetime of the minority carriers
(ii) H2O • τbulk= Bulk lifetime of the minority carriers (assuming ideal passiv­
adsorption ation on both front and rear surfaces
62 sprayedfilm oxidized as in 2.94 5.62 8.56
• Sfront and Srear denotes the surface recombination velocities at the
manuscript
front and the rear sides
• W = the thickness of the silicon wafer
S-shaped curves are due to poor carrier-selectivity in a solar cell,
such cells have higher series resistance and poor Fill Factor, resulting in The bulk lifetime depends on the quality of the wafer as stated by the
shifting of the maximum power point to a lower value [261]. When the chapter published by the ANU group [264]. Thus, it has been found that
band-offsets at the conduction band are higher electron-selectivity is when the passivation quality of the surface is poor, then the silicon
hampered and similarly when the band-offsets at the valence band is waferto be taken should have a higher lifetime, in order to get better cell
high hole-selectivity (group-III materials) is hampered. In case of results.From the continuity equation and Fick’s law of diffusion, the
group-V materials if the offset between conduction band of the material recombination current density is related to the lifetime of minority
and valence band of silicon is high hole-selectivity gets hampered as carriers in Eq. (7) as:-
band to band tunneling does not take place and trap-assisted tunneling is
qcm L
not favoured by the offset or barrier present at the interface [106]. Even J0 = (7)
τ
in case of a tunneling oxide layer or an i-a-Si passivation layer, a large
thickness increases the series resistance thereby deteriorating
carrier-selectivity. Also if in HIT, TOPCON or IBC-SHJ cells if the doping
of the emitter is not sufficiently high S-shaped curves may form due to • where, cm=Minority charge carrier concentration
poorer carrier-selectivity. • q= Electronic charge
Improvements have also been found in p-i-n-based thin silicon solar • L=Diffusion Length of minority carrier
cells using a hole-selective layer on the p-side and an electron-selective • Τ=Minority carrier lifetime
layer on the n-side [139] by not only improving contact passivation but
also providing carrier selectivity; however doped layers need to be and, VOC = nkTq ln(JL /J0 +1) as from the Eq. (1) and thus as the minority
removed completely.Overall these dopant-free approaches are newer carrier lifetime decreases, recombination current density J0 increases, as
technologiesand more research work is expected to be done in the a result of which VOC decreases. VOC is one of the most vital parameters
coming years. in determining the solar cell efficiency and hence minority carrier

17
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

Table 6
TiOx electron-selective contacts for Si solar cells.
Research Group Wafer and TiO2 deposition Passivated contact Solar cell Parameters Refs.
cell type method Emitter/ Front BSF/ Back VOC JSC (mA/ FF Eff
(mV) cm2) (%) (%)
Berkeley, EPFL and ANU n-type FZ ALD Ag/ITO/ MoOx/ i-a-Si i-a-Si/ TiOx/ LiFx/ 706 38.40 76.20 20.70 [133]
Al
Stanford University thin Si 2 µm ALD Al/TiOx/ SiOx/ n -a-Si/
+
i-Si/ p+-Si/ SiOx/ 620 20.60 82.40 10.50 [139]
(pin cell) i-a-Si NiOx/Pt
UPC Spain n-type FZ Thermal Ag/V2OxAg/Au/ V2Ox Al2O3/ TiO2/ Mg/ 618 27.10 79.50 13.30 [161]
Evaporation Al
Princeton University p-type FZ MOCVD Al/TiOx Al 520 19.30 70.00 7.10 [189]
ANU Canberra n-type FZ ALD Cr/Pd/ Ag/SiNx/Al2O3/ SiOx/ TiOx/Al 650 39.50 80.00 20.50 [180]
p+-Si
ANU Canberra n-type FZ ALD Cr/Pd/ Ag/SiNx/Al2O3/ SiOx/ TiOx/Al 676 39.60 80.70 21.60 [181]
p+-Si
Princeton University n-type FZ CVD with precursor Ag/ PEDOT:PSS TiOx/Al/Ag 620 29.00 72.10 12.90 [182]
ANU Canberra n-type FZ ALD Cr/Pd/ Ag/SiNx/Al2O3/ i-a-Si/ TiOx/Al 570 40.50 57.00 13.20 [185]
p+-Si
Princeton University n-type FZ CVD with precursor Ag/ PEDOT:PSS TiOx/Al/Ag 614 24.00 76.20 11.20 [186]
Princeton University n-type FZ CVD with precursor Ag/ PEDOT:PSS TiOx/Al/Ag 641 29.10 74.40 13.88 [187]
Stanford University thin Si 2 µm p- ALD Al/Ti/ TiOx/ n+-Si/ p-Si/ p+-Si/Al 645 16.70 82.20 8.90 [188]
type p-Si
Table 6. TiOx electron-selective contacts for Si solar cells (contd.)
Research Group Wafer and TiO2 deposition Passivated contact Solar cell Parameters Refs.
cell type method Emitter/ Front BSF/ Back VOC JSC (mA/ FF Eff
(mV) cm2) (%) (%)
ANU Canberra n-type FZ ALD Cr/Pd/ Ag/SiNx/Al2O3/ TiOx/Al 639 39.20 79.20 19.80 [190]
p+-Si
IIT Bombay n-type FZ ALD Pd/Ag/ ITO/ MoO3 TiO2/Al 520 30.50 34.80 5.52 [135]
ANU Canberra n-type FZ ALD Cr/Pd/ Ag/SiNx/Al2O3/ SiO2/ TiO2/Al/Ag 674 39.80 82.50 22.10 [191]
p+-Si
ANU Canberra, EPFL, n-type FZ ALD Cr/Pd/ Ag/SiNx/Al2O3/ SiNx/ TiO2/Ca/Al 681 39.60 80.90 21.80 [192]
Berkeley PERC p+-Si (partial)
ANU Canberra and Berkeley n-type FZ ALD Cr/Pd/ Ag/SiNx/Al2O3/ SiNx/ TiO2/ LiFx/Al 695 41.50 80.00 23.10 [193]
PERC p+-Si (partial)
University of Chinese n-type CZ IBC Spin-coating (sol- Ag/WOx (ARC)/MoOx/ i-a-Si/ SiO2/ TiO2/ 696 38.61 75.31 20.24 [194]
Academy of Sciences gel) i-a-Si Mg/Al/Ag
KUL and IMEC Belgium n-type CZ E-beam Ag/ITO/ p-a-Si/ i-a-Si i-a-Si/ TiOx/Ca/ Al 674 34.80 71.80 16.90 [195]
Evaporation
ALD i-a-Si/ TiOx/Ca/ Al 711 35.10 72.90 18.20
Saitama University Japan n-type CZ Spin-coating Ag/ PEDOT:PSS TiO2/Al/Ag 616 30.00 70.90 13.08 [196]
ANU Canberra n-type CZ ALD Ag/ PEDOT:PSS TiOx/ LiFx/Al 626 31.90 75.60 15.10 [197]
ANU Canberra n-type CZ ALD Cr/Pd/ Ag/SiNx/Al2O3/ TiOx/ LiFx/Al 660 40.80 79.20 21.30 [198]
p+-Si
Imec Belgium n-type CZ ALD Ag/ITO/ p-a-Si/ i-a-Si i-a-Si:H/ TiOx/Yb/ 723 33.80 78.60 19.20 [199]
Ag
UPC Spain n-type FZ IBC ALD Al/Ni/ V2O5 Al/Mg/ TiO2/ 633 40.00 75.40 19.10 [166]
Al2O3
National Chung Hsing n-type CZ Liquid Phase Ag/ITO/TiO2*/ TiO2/Al 630 35.91 65.00 14.70 [200]
University Deposition PEDOT:PSS/Si NHs
*Passivation (full
area)

lifetime and surface passivation play a crucial role in determining the
solar cell performance.
3.2. Different passivating layers on a crystalline silicon surface
Wide band-gap emerging materials like TiO2, MoO3, NiO, LiF,etc.
that provide carrier selective contacts with Si, don’t provide as effective
surface passivation as with conventional passivating layers like i-a-Si:H,
SiO2, SiNx, Al2O3 as it is clear from the table provided by Black et al.
[12]. This is generally due to the lattice mismatch between TMOs as well
as metal salts and Si. The analysis clearly shows that i-a-Si:H deposited
by PECVD and i-poly-Si deposited by LPCVD provide the lowest values
of surface recombination velocity. TiO2 provides the best surface
passivation among all TMOs and that too without any pre-grown SiO2
layer, but still the conventional passivating materials are better candi­
dates as it is clear from the effective SRV values. However among the
emerging materials used for Si surface passivation HfO2 and TiO2 are the
best and that too without any grown SiO2 layer as it is clear from the
effective SRV values provided in the tableby Black et. al. [12].Passiv­
ation in hole-selective TMOs in which inversion layer is formed has been
studied by XPS analysis of the interfacial SiOx layer and the TMO [120],
and it was found that oxygen defient TMO species were formed at the
interface that enhanced the formation of the inversion layer, which aids
carrier selectivity. TiO2 was also used as ARC [265] in 1970s due to its
low extinction coefficient and suitable refractive index ranging from
1.9–2.45.They fabricated a solar cell with TiO2 as front contact passiv­
ation as well as ARC and SiNx at the back with partial contacts, and the
cell basically was of an n-type PERx solar cell, the n+ layer at the back
was locally diffused. The best solar cell achieved VOC = 655 mV, JSC =
39.1 mA/cm2, FF = 79.9%, and Eff = 20.45%, with TiO2 as front layer,
whereas if we use Al2O3/SiNx stack to passivated the front p+-Si emitter
layer, the results are better, i.e. VOC = 665 mV, JSC = 39.5 mA/cm2, FF
= 81.2%, and Eff = 21.30%, thus proving that Al2O3 provides better
surface passivation and that Al2O3/SiNx stacks serve as a better candi­
date for surface passivation and ARC [266]. However the deposition of
TiO2 serves as a dual purpose as an ARC and passivation layer, whereas
in case of Al2O3/SiNx stack Al2O3 is used as passivation where SiNx is
used as ARC, thus we need an extra deposition step. TiO2 deposition also
become cost-effective if cheap industry-compatible deposition processes
like spatial ALD, APCVD are used and it has to be kept in mind that

18
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

Table 7
Other metal oxide electron-selective contacts for Si solar cells.
Research Group Wafer and TMO deposition method Passivated contact Solar cell Parameters Refs.
cell type Emitter/ Front BSF/ Back VOC JSC (mA/ FF Eff
(mV) cm2) (%) (%)
Berkeley and ANU Canberra n-type FZ ALD Ag/SiNx/Al2O3/ Ag/Mg/ Ta2Ox 638 37.80 79.30 19.10 [28]
p+-Si
University of Chinese Academy n-type CZ Spin Coating Ag/ITO/p-a-Si/ i-a- ZnO/Al 603 35.74 70.36 15.18 [29]
of Sciences Si SiOx/ ZnO/Al 603 35.56 65.20 13.97
i-a-Si/ ZnO/Al 629 37.19 66.31 15.51
i-a-Si/ ZnO:Al/ 672 38.23 71.95 18.46
Al
ZnO/ ZnO:Al/Al 645 37.11 71.60 17.13
Universiti Sains Malaysia p-type CZ Thermal Evaporation Ag/CdO Al 460 18.80 68.50 5.92 [32]
ANU Canberra and Berkeley n-type CZ Thermal Evaporation Ag/SiNx/Al2O3/ MgOx/Al 629 39.50 80.60 20.00 [34]
p+-Si
NIMTE China n-type CZ E-beam Ag/ITO/MoOx MgOx/Al 595 32.60 73.40 14.20 [151]
University of Chinese Academy n-type CZ Spin Coating (sol-gel) Ag/ITO/p-a-Si/ i-a- i-a-Si/ SnO2/ 526 35.98 71.52 13.53 [35]
of Sciences Si Mg/Al
SiOx/ SnO2/ 605 35.23 66.18 14.11
Mg/Al
i-a-Si/ SiOx/ 685 37.45 71.52 18.35
SnO2/ Mg/Al
SYSU, EPFL &CSEM n-type FZ IBC Thermal Evaporation i-a-Si/ MoOx/ Ag i-a-Si/MgOx/Al/ 663 40.30 48.20 12.90 [167]
Ag
Helmoltz-Zentrum Berlin (HZB) n-type FZ ALD Ag/Ti/ ITO/ p-a-Si/ MgO/Al 664 33.40 73.80 16.40 [208]
i-a-Si i-a-Si/ MgO/Al 687 33.80 72.40 16.80
Chinese Academy of Sciences n-type CZ E-beam Evaporation Ag/ PEDOT:PSS MgO/Al 623 33.80 73.90 15.50 [209]
and ANU PERC (partial)
NUS Singapore n-type FZ Thermal Evaporation MgF2/ ITO/Ni/ BaOx/Al 621 37.05 75.11 17.25 [36]
V2Ox
University of Chinese Academy n-type CZ Ebeam evaporation Ag/SiNx/Al2O3/ SiOx/ ScOx*/Sc/ 621 32.30 75.50 15.10 [33]
of Sciences *interfacial p+-Si Al
University of Technology Iraq p-type CZ Spray Pyrolysis Al/ZnO Al 375 20.00 72.00 6.79 [201]
University of Chinese Academy n-type CZ Spin coating Ag/ PEDOT:PSS i-a-Si/ ZnO:Li/ 623 33.58 72.38 15.10 [202]
of Sciences Al
University of Babylon p-type CZ Spray Pyrolysis Al/ZnO Al 110 29.00 40.90 2.70 [203]
North ChinaElectric Power n-type CZ Spin coating Ag/PEDOT:PSS SiOx/ EDTA- 562 28.80 71.20 11.52 [207]
University SnO2/Ag
Table 7. Other metal oxide electron-selective contacts for Si solar cells (contd.)
Research Group Wafer and TMO deposition method Passivated contact Solar cell Parameters Refs.
cell type Emitter/ BSF/ Back VOC JSC (mA/ FF Eff
Front (mV) cm2) (%) (%)
Polish AcademyofSciences and p-type CZ ALD Al/AZO/ZnO: Al 320 34.00 66.00 7.10 [204]
WUT Poland Mg
Nankai and Hebei University n-type CZ Sputtering (ZnS target in Ag/SiNx/ p+-Si ZnO:S/ Mg/Ag 566 35.70 79.50 16.10 [205]
China O2 atmosphere)
EPFL and HZB Berlin n-type FZ Co-sputtering with SiO2 Ag/ITO/p-a- i-a-Si/ SiO2/ ZnO:Al/ 701 37.30 74.70 19.50 [206]
Si/ i-a-Si Al
Nankai University China n-type CZ Thermal Evaporation i-a-Si/ MoOx/ i-a-Si/ ZnO:B/ Ag 599 38.12 72.70 16.60 [169]
Ag i-a-Si/ n-a-Si/Ag 593 35.97 67.60 14.40

post-deposition annealing temperature and annealing environment of
TiO2 is very crucial.
Passivation can be achieved by two methods, either by saturating the
incomplete silicon dangling bonds at the rear or the front surface or by
using interface fixed charges similar (not opposite) to the charge carrier
that would recombine at the interface. All passivation layers on contact
with silicon form some amount of positive and negative interfacial fixed
charges [288] and also produce some amount of completion of the
dangling bonds. More the lattice mismatch of the passivation layer with
silicon more is the deterioration of passivation quality. Similarly, more is
the magnitude of the favourable fixed charge (+ve for n-type and –ve for
p-type) better is the passivation and better is the cell efficiency as shown
using TCAD simulation [267]. Similarly, lesser the magnitude of the
undesired fixed charges (-ve for n-type and +ve for p-type) better is the
passivation and hence the cell efficiency [267]. This is because a solar
cell is a minority carrier device where the fixed charge is expected to
repel the minority carriers away from the dangling bonds at the inter­
face, this kind of passivation being called as Field-Effect Passivation
(FEP).
For full area passivation of Si solar cells, for example in TOPCon thin
layers of passivation (oxide passivating contact) is required, which is
one of the most important criteria for carrier selectivity. It can also be
seen that even in dopant-free contact solar cell, a passivating layer
(either SiO2 or i-a-Si) improves the cell efficiency as it can be seen in
most of the references in Tables 2,3,5–8. In some tables, solar cells have
been fabricated using the concept of partial front as well as partial rear
dopant-free passivating contacts. Dopant-free passivating contacts
implanted in these tables contain a dopant-free material as well as an
extra layer for passivation in most cases. However, full area passivation
means the implementation of HIT/TOPCon structure (with i-a-Si:H/
SiOxpassivation layer) in which tunneling mechanism plays the most
important role for the current flow through the passivating layer. In case
of HIT solar cells a comparative thicker layer may be used because i-a-Si:
H layer is non-dielectric material with a smaller band-gap and there is a
considerableohmic current flow through it. That’s why most of the
dopant-free carrier selective contacts implement i-a-Si:H layer for
passivation, which is quite clear from those tables. However imple­
mentation of full surface passivation using oxides (mainly SiOx) is a bit
challenging, as an ultra-thin layer (≤2 nm) is needed otherwise
tunneling won’t occur. This is due to the high band-gap of SiO2 and
moreover it is a dielectric. A clear concept of tunneling mechanism in
TOPCon solar cells has been given by Rvandervosen thesis [268] a well

19
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

Table 8
Non-oxidehole-selective contacts for Si solar cells.
Research Group Wafer and cell Contact layer Passivated contact Solar cell Parameters Refs.
type deposition method Emitter/ Front BSF/ Back VOC JSC (mA/ FF Eff
(mV) cm2) (%) (%)
Soochow University n-type nano- Spin Coating Ag/ PEDOT:PSS Al 586 28.60 64.90 10.80 [44]
structured Si Cs2CO3/Al 621 32.20 68.40 13.70
NCKU, Taiwan Si nano-wire Spin coating ITO/V2Ox/ PEDOT: Al 541 45.40 58.31 14.40 [158]
PSS
Princeton University n-type FZ Spin coating Ag/ PEDOT:PSS TiOx/Al/Ag 620 29.00 72.10 12.90 [182]
Princeton University n-type FZ Spin coating Ag/ PEDOT:PSS TiOx/Al/Ag 614 24.00 76.20 11.20 [186]
Princeton University n-type FZ Spin coating Ag/ PEDOT:PSS TiOx/Al/Ag 641 29.10 74.40 13.88 [187]
Saitama University Japan n-type CZ Spin-coating Ag/ PEDOT:PSS TiO2/Al/Ag 616 30.00 70.90 13.08 [196]
ANU Canberra n-type CZ Spin coating Ag/ PEDOT:PSS TiOx/ LiFx/Al 626 31.90 75.60 15.10 [197]
University of Chinese n-type CZ Spin coating Ag/ PEDOT:PSS i-a-Si/ZnO:Li/Al 623 33.58 72.38 15.10 [202]
Academy of Sciences
HZB Berlin n-type FZ Spin coating Ag/ PEDOT:PSS/ i-a-Si/ n-a-Si/ 663 31.90 70.00 14.80 [71]
native SiOx ITO/Ti/ Ag
NCTU Taiwan n-type Si nano- Spin coating Ag/PEDOT:PSS/ Al 540 34.76 69.50 13.01 [210]
wire TAPC
University of Chinese n-type CZ Spin coating Ag/PEDOT:PSS Ga/In 640 26.27 75.50 12.69 [211]
Academy of Sciences (double)
University of Chinese n-type CZ Spin coating Ag/PEDOT:PSS CPTA/Al 632 34.70 76.30 16.73 [212]
Academy of Sciences (double)
Shenzen University n-type CZ Spin coating Ag/PEDOT:PSS Al 555 30.58 72.01 12.22 [213]
NCTU Taiwan p-type CZ Blade coating Ag/n+-Si Ag/ PEDOT:PSS 576 31.68 79.68 14.55 [214]
Ag/PFO 560 29.05 65.50 10.82
Ag/ Green B 560 28.77 63.65 9.77
Ag/DMFL-NPB 540 28.79 77.70 12.09
Ag 545 28.79 78.73 12.36
University of Chinese n-type CZ Spin coating Ag nano-wire/Ag/ Al 560 27.07 72.15 11.07 [215]
Academy of Sciences PEDOT: PSS
Princeton University n-type FZ Spin coating Ag/PEDOT: PSS Al 570 27.80 73.00 11.70 [216]
ISFH Germany n-type FZ Spin coating Ti/Pd/Ag/ PEDOT: n+-Si/Al 603 29.00 70.60 12.30 [217]
PSS/SiOx/
ISFH Germany n-type FZ Spin coating Al/SiNx/ n+-Si Ag/ PEDOT:PSS/ 653 39.70 67.20 17.40 [218]
SiOx
ISFH Germany p-type FZ Spin coating Al/SiNx/ Al2O3/n+-Si Ag/ PEDOT:PSS/ 657 38.90 80.60 20.60 [219]
n-type CZ SiOx 654 36.60 76.40 18.30
Xidian University China n-type CZ Spin coating Ag/ PEDOT: PSS/ Ga/In 607 33.72 65.01 13.31 [220]
native SiOx
UPC Spain n-type FZ Spin coating Ag/ PEDOT: PSS/ i-a-Si/ n-a-Si/ a- 569 33.50 61.00 11.60 [221]
native SiOx SiCx/ Ti/Al
ISFH Germany p-type FZ Spin coating Ag/ITO/ n-a-Si/ i-a-Si Ag/ PEDOT:PSS 652 32.70 71.20 15.20 [222]
Soochow University n-type CZ Spin coating Ag/PEDOT: LiF/Al 570 28.71 68.00 11.09 [223]
PSS
Chinese Academy of Sciences n-type CZ Spin coating Ag/PEDOT:PSS i-a-Si/ n-a-Si/Al 634 36.50 70.00 16.20 [225]
(DEP)
Chinese Academy of Sciences n-type CZ Spin coating CuI/Ag/ PEDOT: Ga/In 656 28.00 78.10 14.30 [226]
PSS/SiOx
North ChinaElectricPower n-type CZ Spin coating Ag/PEDOT:PSS SiOx/EDTA-SnO2/ 562 28.80 71.20 11.52 [207]
University Ag
Saitama University Japan n-type CZ Spin coating Ag/ PEDOT: PSS Al/ Cs2CO3 583 34.22 63.80 12.74 [233]
Al 553 29.43 59.90 9.77
NTU Singapore n-type CZ Spin coating SiNRs/Spiro- Al 570 30.90 58.80 10.30 [227]
OMeTAD/PH500/Ag
Chinese Academy of Sciences n-type CZ PERC E-beam Evaporation Ag/ PEDOT:PSS MgO/Al (partial) 623 33.80 73.90 15.50 [209]
and ANU
Chinese Academy of Sciences n-type FZ Spin coating Ag/ PEDOT:PSS Al 616 29.30 72.20 13.00 [237]
Al/PTB7-NBr 636 30.20 78.50 15.10
Al/PTB7-NSO3 627 29.60 74.40 13.80
Ag/CuI (ARC)/ Al/PTB7-NBr 638 32.80 76.50 16.00
PEDOT:PSS
National Taiwan University n-type CZ Spin coating Ag/ITO/ PEDOT: Cs2CO3/Ag 530 37.15 67.16 13.23 [238]
PSS/TPD/ Si-NHs
National Chung Hsing n-type CZ Liquid Phase Ag/ITO/ TiO2*/ TiO2/Al 630 35.91 65.00 14.70 [200]
University Deposition PEDOT: PSS/Si-NHs
*Passivation (full
area)
Chinese Academy of Sciences n-type CZ Spin Coating Ag/ PEDOT: PSS SiOx/Mg/Al 610 33.40 73.50 15.00 [245]
Soochow University n-type CZ Spin Coating Ag/MoO3/PEDOT: Al 630 29.20 74.90 13.80 [259]
PSS
SYSU China p-type CZ PERC Thermal Evaporation Ag/SiNx/ n+-Si Ag/CuI/ SiNx/ 639 40.10 80.70 20.70 [228]
Al2O3 (partial)
SYSU and Temple South p-type CZ PERC Thermal Evaporation Ag/SiNx/ n+-Si Ag/ Cu2S/ SiNx/ 640 41.29 79.61 21.04 [80]
University USA Al2O3 (partial)
Ain Shams University n-type CZ Thermal Evaporation In/SnSe Al 425 17.23 44.00 6.44 [241]

20
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

Table 9
Non-oxide electron-selective contacts for Si solar cells.
Research Group Wafer and cell Contact layer Passivated contact Solar cell Parameters Refs.
type deposition method Emitter/ Front BSF/ Back VOC JSC (mA/ FF Eff
(mV) cm2) (%) (%)
Berkeley, ANU Canberra n-type FZ PERC Thermal Evaporation Ag/SiNx/ AlOx/ p+-Si LiFx/ SiNx/Al 676 38.90 78.30 20.60 [46]
and EPFL (partial)
IIT Delhi n-type FZ Thermal Evaporation Ag/ITO/ NiOx/SiOx SiOx/ LiFx/Al 580 36.90 71.06 15.20 [138]
IIT Delhi n-type CZ Thermal Evaporation Ag/ITO/MoOx LiFx/Al 575 35.60 75.02 15.36 [129]
Berkeley n-type FZ Thermal Evaporation Ag/ITO/ MoOx/ i-a-Si i-a-Si/ LiFx/Al 716 37.10 73.15 19.42 [49]
ANU Canberra n-type CZ Thermal Evaporation Ag/ PEDOT: PSS TiOx/ LiFx/Al 626 31.90 75.60 15.10 [197]
ANU Canberra and n-type FZ PERC Thermal Evaporation Cr/Pd/ Ag/SiNx/ SiNx/ TiO2/ LiFx/ 695 41.50 80.00 23.10 [193]
Berkeley Al2O3/ p+-Si Al (partial)
Berkeley, EPFL and ANU n-type FZ ALD Ag/ITO/ MoOx/ i-a-Si i-a-Si/ TiOx/ LiFx/ 706 38.40 76.20 20.70 [133]
Al
UNIST, Korea n-type CZ (IBC) Thermal Evaporation Al/MoOx Al/LiFx 561 36.80 74.60 15.40 [137]
ANU Canberra n-type CZ Thermal Evaporation Cr/Pd/ Ag/SiNx/ TiOx/ LiFx/Al 660 40.80 79.20 21.30 [198]
Al2O3/ p+-Si
EPFL and SYSU n-type FZ IBC Thermal Evaporation Ag/ MoOx/ i-a-Si Al/Mg/ MgFx/ i-a- 718 41.50 74.20 22.10 [48]
Si
ANU Canberra n-type FZ Thermal Evaporation Ag/SiNx/Al2O3/ p -Si
+
i-a-Si/ MgF2/Al 687 37.80 77.30 20.10 [232,
73]
SYSU, EPFL & CSEM n-type FZ IBC Thermal Evaporation i-a-Si/ MoOx/Ag i-a-Si/MgFx/Al/Ag 709 41.50 75.60 22.20 [167]
SYSU China n-type FZ (IBC) Thermal Evaporation Ag/MoOx Ag/ Cs2CO3 594 38.42 66.13 15.09 [16]
Ag/V2Ox 610 38.85 70.00 16.59
Ag/WOx 539 37.67 61.30 12.44
Soochow University n-type nano- Spin Coating Ag/ PEDOT: PSS Cs2CO3/Al 621 32.20 68.40 13.70 [44]
structured Si
SYSU China n-type FZ IBC Thermal Evaporation Ag/ MoOx/ Ag/MoOx Ag/ Cs2CO3 591 36.40 65.37 14.06 [47]
SYSU China n-type FZ Thermal Evaporation Ag/MoOx/ Ag/MoOx Ag/ Cs2CO3 583 29.43 75.83 13.01 [147]
Saitama University n-type CZ Spin coating Ag/ PEDOT: PSS Al/ Cs2CO3 583 34.22 63.80 12.74 [233]
Japan Al 553 29.43 59.90 9.77
National Taiwan n-type CZ Spin coating Ag/ITO/ PEDOT: Cs2CO3/Ag 530 37.15 67.16 13.23 [238]
University PSS/TPD/ Si-NHs
ANU and Berkeley n-type CZ Thermal Evaporation Ag/SiNx/Al2O3/ p+-Si Al/ K2COx 624 38.89 79.94 19.40 [74]
Al/ Rb2COx 609 39.11 79.20 18.80
Al/ Cs2COx 610 38.40 80.80 18.90
Al/ CaCOx 610 38.38 80.00 18.70
Al/ SrCOx 608 38.88 79.40 18.70
Al/ BaCOx 595 38.10 79.65 18.10
Al 565 37.45 74.40 15.75
ANU and Chinese n-type CZ Sputtering Cr/Pd/ Ag/SiNx/ TiN/Al/Ag 608 38.70 80.10 18.70 [234]
Academy of Sciences Al2O3/ p+-Si Al/Ag 574 37.70 74.00 16.00
ANU and KAUST n-type CZ Sputtering Cr/Pd/Ag/SiNx/ Al 585 37.80 74.20 16.40 [75]
MgF2/ Al2O3/p+-Si TiN(full) 619 37.50 80.30 18.60
SiO2/TiN(partial) 644 37.90 81.90 20.00
ANU and KAUST n-type FZ ALD Cr/Pd/Ag/SiNx/ Al 583 37.70 73.10 16.10 [76,
MgF2/ Al2O3/p+-Si TaNx/Al 632 38.80 81.80 20.10 235]
EPFL and NREL n-type FZ Sputtering Ag/ITO/ p-a-Si/ i-a-Si ZnSnN2/Al 520 28.00 28.00 4.08 [77]
i-a-Si/ZnSnN2/Al 550 26.00 67.00 9.58
EPFL n-type FZ PECVD Ag/ITO/ p-a-Si/ i-a-Si GaN/Al 574 20.40 26.20 3.10 [78]
Arizona State University n-type FZ MBE Ag/ITO/ p-a-Si/ i-a-Si GaP/ ITO/Ag 608 33.10 58.00 11.50 [79]
Fraunhofer ISE p-type FZ MOVPE Ag/GaP p+-Si/ SiO2/ SiNx/ 561 29.20 75.70 12.40 [236]
Al
Chinese Academy of n-type FZ Spin coating Ag/ PEDOT: PSS Al 616 29.30 72.20 13.00 [237]
Sciences Al/PTB7-NSO3 627 29.60 74.40 13.80
Al/PTB7-NBr 636 30.20 78.50 15.10
Ag/CuI (ARC)/ Al/PTB7-NBr 638 32.80 76.50 16.00
PEDOT: PSS
Fraunhofer ISE n-type FZ Spin coating Ti/Pd/Ag/SiNx/ Histidine/Al 625 37.50 76.10 17.90 [239,
Al2O3/p+-Si Al 570 35.90 75.10 15.40 240]
UPC Spain n-type FZ Spin coating Ag/ITO/ V2Ox i-a-Si/Al 340 28.50 64.00 6.20 [174]
i-a-Si/ PFN/Al 590 30.10 78.20 13.90
i-a-Si/ n-a-Si/Al 640 33.00 76.20 16.10
i-a-Si/ n-a-Si/ 670 33.60 76.40 17.20
PFN/Al
SYSU China p-type CZ Thermal Evaporation Ag/ITO/ ZnS WO3/Ag 525 33.75 66.73 10.94 [81]
SYSU China p-type CZ Thermal Evaporation Ag/ITO/ In2S3 MoO3/Ag 461 36.93 62.94 10.72 [243]
ANU, Berkeley and NSW n-type FZ PERC Thermal Evaporation Cr/Pd/ Ag/SiNx/ SiNx/Ca/Al 652 39.60 78.60 20.30 [244]
Al2O3/ p+-Si (partial)
Chinese Academy of n-type CZ Thermal Evaporation Ag/ PEDOT: PSS SiOx/Mg/Al 610 33.40 73.50 15.00 [245]
Sciences

21
S. Acharyya et al.
Fig. 13. Field-assisted passivation in DASH Si solar cells using Al2O3 [311].
in many other research works [269–271]. The basic equation for oxide
tunneling current density is given below in Eq. (8):
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
qn2io vth − qn2io vth
(8)
2tox
2qmeff ,ox Φox
Jtunnel = e ћ = Ptunnel
Neff Neff
• where, Jtunnel= Oxide tunneling current density
• q= Electronic charge
• nio= Charge carrier density in intrinsic silicon
• Neff= Effective charge carrier density
• vth= Thermal velocity of the charge carrier (holes for p-type and
electrons for n-type)
• meff,ox= Effective mass of the charge carriers in the oxide
• Φox= Barrier height of the oxide (if holes are the charge carriers then
the barrier height is at the valence band and vice versa)
• tox= Oxide thickness
• Ptunnel=Probability of tunneling
From the above equation it is quite clear that lower oxide barrier
height Φox and lower oxide thickness tox facilitates better tunneling.
SiO2and Al2O3belong to the 1st column in the Table 1 as they havelarger
ΔEV and larger ΔEC. If the charge carriers that tunnel are electrons, then
barrier height Φox = ΔEC otherwise Φox = ΔEV. Till now full area
passivating contacts have been implemented using i-a-Si:H and SiOx, as
it can be seen in the Tables 2,3,5–8. However, TOPCon and HIT struc­
tures replacing SiO2 [272, 273] and i-a-Si [274,275] with Al2O3 as
passivation layers have also been studied. Al2O3as a tunneling passiv­
ation layer [309] has also been reviewed by Liu et.al.Al2O3 based partial
rear contacts for p-type PERC solar cells have been used by many groups
[40,41,276–284], as well as for passivation in p-doped emitters for
n-type PERL and PERT [285,286]. This is due to the negative fixed
charges in Al2O3 [305,306]. Recently HfOx has also attracted interest
forn-type PERC solar cells with efficiencies greater than 22% [291] due
to the positive fixed charges present in HfOx [287–292]providing
field-effect passivation to n-type Si surfaces, though it has been less
explored. Different fabrication techniques may also change the proper­
ties of the passivating layer, which is present on the silicon surface, for
example SiOx grown thermally, chemically or deposited by plasma ex­
hibits different properties [297,310], similarly in AlOx also we can see
that sputtering, thermal ALD, spatial ALD changes the passivation
quality on the silicon wafer [40]. In case of HfOx it was also seen that the
fixed charges depend on the type of ALD precursors [290,294], impu­
rities [293] as well as annealing [290]. On the other hand SiNx [288,
295] is used to passivate front n+-Si emitters but for boron-doped p+-Si
emitters the passivation is inferior and additional layers are needed
22
Surfaces and Interfaces 28 (2022) 101687
[296] due to positive fixed charges present in it. Recently some oxides
like GaOx [43,298,299] and ZrOx [42] have also been used as surface
passivation layers with silicon. Before being used as an electron contact
with silicon, TiOx was also used for passivation of silicon surfaces [265,
300–302], which has been discussed before already.SiCx [303,304] has
also attracted researchers among PV community for Si surface passiv­
ation. TaOx [307,308] has also been used for passivation of silicon
owing to its high negative fixed charges, and defects in it have been
reported to reduce further when it is capped with an SiNx layer same as
that of SiNx capping in Al2O3 PERC, which not only protects the Al2O3
but improves the passivation as well [313], similarly TiO2 capping layer
has also been used withAl2O3 for surface passivation of silicon [314,
315], however these are more suitable for thick passivation stacks for
partial area passivation.Comparative studies of fixed charge passivation
and dielectric (chemical) passivation have been done by many groups
[40,12,288,303]. However an extensive summary of all dielectric ma­
terials fabricated by different processed for passivation of silicon solar
cells [13] has been done by Bonilla et. al. In this work many important
parameters like surface recombination velocity, deposition process,
fixed charges, as well as merits and demerits have been discussed in a
tabulated form.
From the tables of the dopant-free carrier selective contacts one can
see that both full-area and partial area passivation schemes have been
used. However, a DASH (Dopant-free Asymmetric Heterocontact) solar
cell involving full area passivation schemes with new emerging passiv­
ating materials like HfO2, GaOxhave not been fabricated. The use of
Al2O3for NiO contacts in DASH solar cells [311]have been proposed by
Scott Chow and Harvey Mudd of Stanford University as shown in Fig. 13.
An ultra-thin layer of Al2O3 has been used as a full area passivation for
dopant-free TiOx electron selective contacts by UPC group [161,166,
184], and the DASH solar cells featured V2Ox as the hole-selective
contact.Al2O3 can also be used as passivating tunneling contact with
hole-selective MoOx [312], instead of i-a-Si:H.
3.3. Different possible structures for solar cells involving dopant-free
carrier selective passivated contacts i.e. DASH solar cells
The evolution Si solar cell from normal BSF to PERC and then to HIT
and TOPCon and finally IBC-SHJ structure has taken place over the last
few decades, the main improvement being the introduction of the rear
surface passivation and then from partial area passivation (as in PERC)
to full areapassivation (TOPCon and HIT) and finally the IBC where front
surface is free from metal contacts and hence shading losses. As we know
very well HIT uses i-a-Si passivation and TOPCon uses SiO2 rear
passivation, however other materials like Al2O3 can also be used for full
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

area passivation (tunneling properties of these materials need to be

favourable), a structure has already been shown in Fig. 13. In Fig. 14
below we show dopant-free solar cells with PERC, HIT, TOPCon and IBC
structures with MoO3 as hole-selective material and ZnO as electron-
selective material alongwith different passivating layers, although it
can be represented using any other dopant-free hole-selective or
electron-selective material. However as compared to doped p+ or n+-Si
Front Surface Field (FSF) layers in conventional IBC/IBC-SHJ structures,
in back-contacted DASH structured solar cells the FSF layers used may
be (SiO2) stacked layers [16,70,157] or Al2O3 [137] which also acts as a
passivation layer in the contactless front of the solar cell.

4. Conclusion and future scope

In this paper different materials (especially the TMOs) have been

Fig. 14. Various structures of conventional crystalline Si solar cells (a,c,e,g,i
and k) (left) alongwith corresponding dopant-free asymmetric heterocontact
structures (b,d,f,h,j and l) (right).
studied for application as dopant-free carrier-selective passivating con­
tacts in silicon solar cells.The materials have been classified in terms of
their carrier-selectivity, related band-diagrams at the interfaces and
charge carrier transport mechanisms have been studied in detail. The
material properties of TMOs were discussed in detail since those metal
oxides have been most popular for Dopant-free Asymmetric Hetero­
contact (DASH) solar cells. We have also shown different passivation
schemes, both full-area and partial-area. It is already known that partial
area and full area passivation both have their own limits but partial area
contacts limit the fundamental efficiency for solar cells, so most of the
groups have implemented full area passivation layers. Full area passiv­
ation schemes implementing HIT structure are mostly implemented due
to challenges in fabricating ultra-thin dielectrics (TOPCon structure)
which require a thinner layer and its fabrication is quite challenging.
Partial area passivation schemes implementing PERC structure are
becoming quite popular as seen in the references in this article, as these
structures can be fabricated using thicker passivation layers with small
laser scribed opening for carrier-selective contacts. However, full area
passivation schemes using ultra-thin dielectrics require anultra-thin
passivation layer to facilitate proper carrier flow which is a challenge
for the research laboratories as well as the industries mostly due to non-
uniformity of those ultra-thin layers. Intrinsic amorphous silicon (i-a-Si)
and SiO2 are the most commonly used passivation schemes; however
researchers can try other passivation layers like Al2O3, HfOx, SiCx, GaOx
etc. (tunneling properties are to be kept in mind if full area passivation is
implemented using these materials) for full area passivation and do a
comparative study. Dopant-free ASymmetric Heterocontact (DASH)
solar cells involving fully back contacted structure have also attracted
interest and can show the paths in future for high efficiency DASH solar
cells.Some of the TMOs like Sc2Ox, CrOx, CoOx, CdOx, Ta2Ox, Nb2Ox
have been less explored for silicon photovoltaics and need further
research. Other than TMOs, the organic and inorganic carrier-selective
contacts have also been seen to be used in high efficiency solar cells
like PEDOT:PSS, PFN, etc. and Cs2COx, LiFx, CuI, TiN, etc. as well as
alkaline-earth metals like Ca and Mg as seen in the Tables 7 and 8. Some
of those materials need further exploration for application in silicon
photovoltaics. These dopant-free materials can be applied on thin
amorphous or microcrystalline pin Sisolar cells to reduce the amount of
silicon used. Researchers need to work further on these novel carrier-
selective passivating materials, low cost industry compatible deposi­
tion techniques and understanding the deeper physics involving these
selective passivated contact studies with a systematic approach. Dopant-
free back contacted structure with a full area or partial area passivation
can bring good photovoltaic performance with correct contact optimi­
zation as well as suitable fabrication processes. Fabrication of back
contacted silicon solar cells need proper patterning and precision.
However on integrating these back contact solar cells in modules the use
of busbar metal will be reduced.There has not been a systematic detailed
study on the Front-surface field (FSF) in IBC-DASH solar cells, which
needs to be focussed on for further developments. modeling studies will
also help in better understanding the feasibility of these proposed

23
S. Acharyya et al. Surfaces and Interfaces 28 (2022) 101687

contact structures as well as analyzing losses that leads to reduction of Conversion (WCPEC) (A Joint Conference of 45th IEEE PVSC, 28th PVSEC & 34th
EU PVSEC),INSPEC Accession Number, 2018, 18288711, 10.1109/
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