Chemical Physics Impact 8 (2024) 100610

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Chemical Physics Impact

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Review article

A review of the revolutionary impact of MXene marvel in perovskite

solar cells
Mohamed Sufiyan K T , Prabakaran Karupppanan *
Department of Physics, KPR Institute of Engineering and Technology, Coimbatore 641 407, Tamil Nadu, India

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

Keywords: In recent years, the application of perovskites in photovoltaic and associated sectors has been experienced
MXene remarkable accomplishments. Despite the significant progress made so far, there are still challenges to overcome
Perovskite solar cells to enhance the performance of perovskites and address the stability issues, which are crucial for their successful
ETL and HTL
commercialization in the future. The utilization of a novel two-dimensional (2D) material called MXenes in solar
energy applications was introduced in 2018. The presence of MXenes in solar cells demonstrated the remarkable
properties such as carrier mobility, electrical conductivity, high transparency, exceptional mechanical strength,
and adjustable work function. Due to the availability of various transition elements and surface-terminating
functional groups, MXene exhibits the remarkable capability to adjust the work function. This characteristic
plays a crucial role in achieving appropriate band energy orientation between charge transport layers and the
absorber layer in perovskite solar cells (PSCs), facilitating efficient extraction and collection of charge carriers.
Consequently, this review aims to extensively examine the diverse advantages offered by MXenes. It provides a
comprehensive analysis of their applications and progress in PSCs across various roles, including as additives,
electron/hole transporting layers, interfacial engineering layers, and electrodes. Furthermore, this review elu­
cidates the underlying mechanisms behind these applications, offering a comprehensive understanding of MXene
contributions to the field of PSCs.

1. Introduction first, while the other involves depositing the HTL. This results in what is
known as the "standard architecture" (negative intrinsic positive, n-i-p
From the beginning of technological revolutions utilization of fossil type) and the "inverted architecture" (positive intrinsic negative, p-i-n
fuels habituated for energy consumption, present day enormous type). An initial n-i-p type device is proposed in 2009, utilizing TiO2 as
research have been occurred at reduced cost and is less harmful to the the ETL. Four years later, in 2013, poly(3,4-ethylene dioxythiophene)
environment. Tidal, wind, geothermal, and solar are renewable energy doped with poly(styrene-sulfonate) (PEDOT:PSS) is used as an organic
resources, among them solar energy is an abundant renewable resource HTL as the p-i-n structure [4]. Graphene serves as the foundation for all
[1]. Based on the working principles, solar cells are classified into three fullerene allotropic dimensionalities, such as zero-dimensional spherical
types (generations). First-generation solar cells (SCs) are Silicon (Si) bucky balls, one-dimensional carbon nanotubes (CNTs), which are
based SCs, a thin film based second generation SCs, and third generation further divided into single- and multiwalled CNTs (SWCNTs and
on new concepts Dye-sensitized solar cells (DSSCs), and Perovskite solar MWCNTs, respectively) based on the quantity of graphene layers, as well
cells. Among the various type of solar cells, PSCs have emerged as an as graphite and charcoal. The valence band (VB) and conduction band
alternative to traditional silicon photovoltaic cells for portable power (CB) of single-layer graphene (SLG) touch at the Dirac points, and the
supply devices due to their high light-absorption coefficient, easy scale material contains charge carriers that can be thought of as massless
up and solution processibility preparation, and low production cost [2]. electrons or Dirac fermions. Other important factors to take into account
Typical PSCs are made up of a perovskite active layer inserted between when selecting materials for the various components of SCs include low
two selective charge carriage layers commonly used as hole transport sheet resistance (Rs), a large specific surface area (SSA), high charge
layer (HTL) and electron transport layer (ETL) [3]. There are two carrier mobility and high optical transparency (Tr) [5,6]. In thin-film
possible manufacturing routes for PSCs: one involves depositing the ETL and nanostructured electrodes, these findings imply that graphene is a

* Corresponding author.
E-mail address: [email protected] (P. Karupppanan).

https://doi.org/10.1016/j.chphi.2024.100610
Received 4 December 2023; Received in revised form 11 April 2024; Accepted 16 April 2024
Available online 17 April 2024
2667-0224/© 2024 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC license (http://creativecommons.org/licenses/by-
nc/4.0/).
M.S. K T and P. Karupppanan Chemical Physics Impact 8 (2024) 100610

perfect channel material for the quick transport of charge carriers. PSC PCE of 28.7 %. These findings are supported by the presence of graphene
with graphene oxide (GO), GO applied as an ETL which reached PCE of nanoflakes, which improve electron mobility and electron injection ef­
18.19 % [7] and 13.8 % [8]. Further, reduced graphene oxide (rGO) was ficiency. The MXenes, on the other hand, are in charge of better band
substantiated to be an adequate technique to enhance the conductivity alignment, which enhances charge transfer from perovskite to ETL [37].
of GO followed by introduction in perovskite solar cells. In solar cells, 2D The U.S. Department of Energy’s Solar Energy Technologies Office
materials other than graphene and MXene also employed electron and (SETO) estimates that annual PV deployment levels will need to rise
hole transport layers. For example, TMDs such as MoS2, TiS2, SnS2, and from the 15 GW alternating current (GW) installed in 2020 to 30 GW by
elemental 2D materials like black phosphorus and phosphorene are used 2025, 60 GW by 2030, and over 100 GW by 2035 in order for the country
in the electron transport layer, while Bi2Se3 (group 15 metal chalogi­ to meet its emissions targets for 2035. The main technical obstacles to
nides), In2Se3 (III-IV compounds), Black phosphorus (elemental 2D the commercialization of perovskite photovoltaics (PV) are divided into
material), and Transition metal dichalcogenide (MoS2, MoSe2, WS2, three groups by SETO: manufacturing (yield, process control, etc.),
WSe2, TaS2, NbSe2 etc.) are used as hole transport materials [9]. stability and durability, and module efficiency (scalability). At the time
Two-dimensional materials MXene provide conductivity higher than of deployment, the levelized cost of electricity (LCOE) of perovskite
reduced graphene oxide (rGO) and other two dimensional materials, the photovoltaic technologies must be competitive with that of incumbent
Ti3C2Tx (MXene) was first introduced by the Gogotsi group in 2011 [10]. technologies in order for them to be commercially viable. It is antici­
MXene nanosheets are two-dimensional materials with incredible out­ pated that cost reductions in silicon and CdTe photovoltaic modules will
puts in various disciplines such as supercapacitors [11], biomedical persist for the next ten years and beyond, making this a challenging task.
applications [12], fuel cell applications [13], sodium-ion batteries [14], Perovskite photovoltaics must last at least 20 years in the field for LCOE
Light emitting diodes [15], transparent electrodes [16], Sensors [17], metrics to approach SETO’s 2030 targets of $0.02/kWh. It is necessary
photocatalysts [18] and more. MXene nanosheets are synthesized from to increase perovskites’ resistance to diverse environmental conditions
MAX phases, MAX phases are layered ternary metal carbides, nitrides, in order to enable this lifetime. Understanding and reducing the chem­
and any combination of them [19]. In this scenario, there has been ical reactions of the perovskite material with oxygen and/or moisture
significant utilization of two-dimensional nano-structured materials due has thus been the subject of a great deal of research [38]. This review
to their exceptional properties, including extraordinary charge carrier delivers a thorough overview of MXenes and their applications as ex­
movement, excellent optical transparency, and notably adjustable tracts or standalone materials in various constituents categorized based
electronic structure. These materials have found extensive applications on the electrode, HTL (n-i-p and p-i-n device architecture), ETL (n-i-p
to address the aforementioned challenges and enhance device perfor­ and p-i-n device architecture), interfaces, and photoactive absorber
mance. Through techniques such as doping and passivation, their layer of PSCs.
bandgap and work function can be extensively modified, allowing for
precise control of selective carrier extraction while minimizing energy 2. Synthesis of MXene
losses and surface recombination. Consequently, these advancements
have led to significant enhancement of the performance of photovoltaic Ti3C2Tx MXene was initially documented by Naguib et al. (2011)
solar cells [20,21]. [39]. MXenes are family of 2D materials composed of transition metal
The properties of MXenes are directly influenced by surface func­ nitrides, carbides, and carbonitrides. They can be denoted by the regular
tional groups, which, in combination with their distinctive two- formula Mn+1XnTx (n ranges from 1 to 4), this term initially employed by
dimensional structure, contribute to their remarkable characteristics, Barsoum in 2000 [40]. In this formula, ’M’ denotes an early transition
including outstanding electrical conductivity, adjustable work function, metal such as Zr, Hf, Ti, Sc, V, Cr, Ta, Nb, Mo, and others. ’X’ represents
hydrophilicity, and flexibility [22–25]. According to density functional nitrogen or carbon, while ’Tx’ refers to the various surface terminations
theory (DFT), surface termination is powerfully important to the density including –F, -O, -OH, and so on [41–43]. By eliminating the A atom
of states and the Work Function [26] of MXenes, which can range from layer from the corresponding MAX phases, it becomes possible to
1.6 eV to 6.25 eV [27,28]. This way unwraps the innovative opening for generate MXenes with various stoichiometric combinations, there are
MXene in optoelectronics and PV applications. Primary studies have three types (M2X, M3X2, and M4X3) and then introducing M5X4 laterally
reported in the Si SCs [29], dye-sensitized SCs [30], organic SCs [31], shown in Fig.1a [44]. This addition increased the number of theoreti­
quantum dot-sensitized SCs [32], and PSCs [33]. In the Perovskite solar cally possible compositions to over 100, encompassing variations with
cells, incorporation of Ti3C2Tx (MXenes) with perovskite layer, these both in-plane and out-of-plane arrangements of the metal atoms. The
performances to get superior power conversion efficiency (PCE) of given Fig. 1b showcases the periodic table, with specific elements
greater than 12 % and enhanced morphology regarding reference cell in highlighted in color to indicate their suitability for the synthesis of
the absence of MXene or ETL constructed by SnO2 to affordable for MXene from MAX phases. In the synthesis of MXene, the selective
enhanced charge transmission way that certified improvement of PCE etching strategy involves the utilization of various etchants, namely HF,
greater than 6.5 % regarding reference cells [34]. For instance, the LiF/HCl, FeF3/HCl, and NH4F/HCl. However, it is worth noting that the
interplanar distance between the two-dimensional MXene sheets LiF/HCl etchant employed in the minimally intensive layer delamina­
increased due to the CoFe2O4 NPs applied to them. These invented tion (MILD) method outperforms the other etchants, resulting in the
MXene/CoFe2O4 composites are used as electrodes to construct a Hybrid production of MXene with superior quality [45]. Throughout the etching
supercapacitor (HSC). Accordingly, these invented composites provided process, the A layer undergoes elimination (shown in Fig. 1c), and the
1268.75 Fg− 1 specific capacitance than the bare MXene (1046.25 F g− 1) corresponding bonds between M–A and A–X are substituted by surface
and 594 F g− 1 specific capacitance of pure CoFe2O4 NPs [35]. Consider functional groups. As a result, the formation of MXene occurs, creating a
tandem solar cells are high-efficiency solar cell systems that lower gap between the two layers. In this structure, A layer is situated between
manufacturing costs and improve performance by combining multiple two M–X layers, where the M–X bond exhibits greater strength
materials. Efficiency levels exceeding 39 % under standard conditions compared to the M–A bond. Therefore, the depletion of the M–A bond
and 47 % under concentration have been attained by III-V based tandem is facilitated, while the M–X bond remains intact, resulting in the for­
solar cells. Combining III-V materials with reasonably priced Silicon (Si) mation of MXene [46–49]. The etching process plays a crucial role in
substrates is a viable way to create tandem solar cells that are both determining the nature and arrangement of surface functional groups
effective and economical. Another third-generation thin-film photovol­ present in MXene. These functional groups predominantly exhibit
taic technology that has developed quickly and affordably is PSCs [36]. electronegative characteristics, allowing them to attract electron density
Agresti et al. (2022) prepared a perovskite top cell in tandem device away from the M atoms in MXenes. This results in a shift of the Fermi
(namely Graphene/MXene/ phenethylammonium iodide) that achieved energy of MXenes towards lower energy levels. Consequently, by

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M.S. K T and P. Karupppanan Chemical Physics Impact 8 (2024) 100610

Fig. 1. (a) Schematic illustration of the various stoichiometric combinations of MXene [44], (b) Periodic table with colored elements related to the possible
combination of MAX phases and MXenes and (c) Schematic synthesis of MXene by etching from of the MAX phase. (For interpretation of the references to color in this
figure legend, the reader is referred to the web version of this article.)

directing the composition of surface functional groups, it becomes becomes possible to achieve a precise energy balance between the
feasible to readily adjust the electronic configuration and work function charge transport layer and the perovskite active layer. This adjustment
of MXenes [44,50,51]. By fine-tuning the work function (WF), it plays a crucial role in obtaining optimal energy-level alignment at

Fig. 2. (a) Schematic representation of Ti3C2TX MXene structure before and after oxygen plasma treatment [52], (b) Steady-state output of best performing
MXene-based PSC [52],(c) schematic diagram of devices’ each layer based on different ETLs determined by DFT calculation and UPS data [54], (d) Ti 2p core level
XPS spectra HO-Ti3C2TX@ Ti3C2TX [54]. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

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M.S. K T and P. Karupppanan Chemical Physics Impact 8 (2024) 100610

interfaces for applications in PSCs. The ability to control the WF allows plasma-oxidized MXene applied to an ETL exhibits better performance
for establishing a perfect energy-level alignment, ensuring efficient compared to oxidized MXene.
charge transport and performance in PSCs. Majorly transition metal oxide applied as electron transport layers,
some of them noted according to our knowledge is titanium dioxide
3. MXene as ETL and additive in ETL in n-i-p and p-i-n device (TiO2), zinc oxide (ZnO), iron oxide (Fe2O3), and tin dioxide (SnO2),
architecture have garnered significant interest thus far [55–58]. The introduction of a
small quantity of CuCl2 into the SnO2 ETL has the potential to enhance
3.1. n-i-p architecture the concentration of Sn4+ within SnO2, deactivate oxygen vacancies on
the surface of SnO2 nanocrystals, and enhance hydrophobicity, con­
The n-i-p configuration in PSCs leads better conversion efficiency ductivity, and PCE of PSCs attained 20.31 % as compared to as prepared
due to better charge extraction and lower recombination loses. In this PSC (18.15 %) [59]. Typically SnO2 is used as an ETL in PSCs to improve
regard, MXene has been introduced into n-i-p structure to in particular their PCE. However, when SnO2 is used alone without any modifica­
ETL layer by many researchers to improve the overall conversion effi­ tions, it tends to exhibit relatively lower PCE (18.79 %) compared to
ciency. Till date several reports based on chemical process availed for when modified SnO2 (carbon nano dots are incorporated into the SnO2)
the modification of purely conducting behavior to semiconducting na­ as an ETL achieved PCE of 20 % in PSCs [60.61]. Nevertheless,
ture through in-situ oxide formation within MXene structures. Gener­ employing metal oxides as electron transport layers has certain disad­
ally, the surface modification of MXene using UV-ozone, and oxygen vantages when it comes to achieving optimal PCE and exceptional per­
plasma treatment offer distinct advantages over of traditional chemical formance. To overcome these limitations, researchers have employed
routes like N2H4. Wang et al. (2021) used as prepared Ti3C2Tx as an MXene/metal oxides nanocomposites as an alternative ETL, addressing
electron transport layer with negative intrinsic positive device archi­ these disadvantages.
tecture (n-i-p) in PSCs. In this work, Ti3C2Tx was modified through so­ Yang et al. (2019) proposed a composite based on metal oxide and
lution method in an ambient environment, followed by an oxygen two-dimensional materials to enhance the power conversion efficiency
plasma treatment Fig. 2a. The utilization of oxygen plasma treatment, of PSCs. In this work, SnO2-Ti3C2 nanocomposites prepared with
resulted in the formation of numerous randomly distributed Ti-O bonds different amount of Ti3C2 as ETLs in planar-structured perovskite solar
on the MXene material, causing disruption in certain regions of Ti-C cells. The n-i-p structure consists of ITO/SnO2 + Ti3C2Tx/MAPbI3/Spiro-
bonds. This surface modification led to several effects, including a OMeTAD/Ag shown in Fig. 3a and their cross-section SEM depicted
reduction in trap states, improved electron transport along the MXene (Fig. 3b). It observed that the presence Ti3C2 within SnO2 was signifi­
interface, and variable work functions of the MXene material. The cantly reduced LUMO energy level from − 4.39 eV to − 4.63 eV The
optimized device exhibited an impressive 18.9 % power conversion ef­ metallic Ti3C2 MXene nanosheets have a high electrical conductivity,
ficiency. Additionally, it maintained a stable-state outcome photocur­ which can improve electron transfer and mobility. This can lead to
rent (JSC) of 21.5 mA cm− 2 shown in Fig. 2b. Notably, the encapsulated higher photocurrents and reduced electron transfer resistance at the
perovskite solar cell with the MXene (plasma-treated) ETL validated interface between the perovskite and ETL, which can contribute to
longstanding stability, as it retained 90 % of its initial PCE even after 750 higher device performance in PSCs. Furthermore, it is also evidenced
h of storage in room temperature at 25 ◦ C and approximately 50 % from Fig. 3c that photoluminescence intensity is lower in the case of
relative humidity (RH) [52]. The surface area of MXene is enhanced due SnO2-Ti3C2 (1.0 wt.%) to compared other than pristine Ti3C2 and SnO2,
to oxidation treatment, resulting in better performance as Li-ion battery it shows Ti3C2 added to SnO2 enhance the electron extraction and
anodes, as demonstrated by Bilal Ahmed et al. [53]. decreased carrier recombination. SnO2- Ti3C2 (1 wt.%) as ETL has ach­
The similar observations of surface modification of MXene change ieved maximum power conversion efficiency (18.34 %) other than
their metallic behavior to semiconducting behavior also proposed by pristine SnO2 and Ti3C2 [34].
Yang et al. (2021). The authors have studied the performance of the Later, a similar kind of investigation on SnO2/MXene nanocomposite
ETL layer based on lower oxidized MXene (LO-Ti3C2TX), heavily was reported by Zheng et al. (2021). It observed that an incorporation
oxidized MXene (HO-Ti3C2TX), and composites of heavily oxidized of 1.4 wt.% of Ti3C2TX with SnO2 as an ETL to enhance the PCE of planar
MXene with pure MXene as an n-i-p format in PSCs. This process was regular structure PSCs. After the ETL was formed, the perovskite layer,
done to take an advantages of MXenes, with more surface functional specifically MA0.15FA0.85PbIxBr3-x, was spin-coated onto the ETL using a
groups to make them highly appealing for use in PSCs. As a part of usual two-step deposition process shown in Fig. 3d. The authors found
density functional theory (DFT) calculations using Vienna ab initio that an addition of 1.4 wt.% hybrid electron transport layer, the defect
simulation package code (VASP) from the energy levels of Ti3C2TX, density in the perovskite films was significantly reduced from 5.65 ×
shown in Fig. 2c, also evidenced the transformation of metallic to 1015 to 2.25 × 1015 cm3 compared to a pure device with a SnO2 electron
semiconductor behavior through oxidation process. The oxidation of transport layer. This reduction in defect density might be the improved
Ti3C2Tx resulted in the formation of Ti-O bonds at 458.3 and 464.3 eV in electron transport and reduced recombination of charge carriers at the
the high-resolution from XPS spectra as shown in Fig. 2d, effectively SnO2/MXene hybrid ETL interface. Thus the presence of MXenes within
reducing macroscopic imperfections in the spin-coated film. Accord­ metal oxides composite are more stable and efficient PSC. Finally, the n-
ingly, degree of oxidation caused to nanoparticles grew on the Ti3C2Tx i-p architecture-based PSCs with an optimized Ti3C2Tx (1.4 wt.%)/SnO2
films, the surface of Ti3C2Tx partially transformed to semiconductor was notably increased the PCE from 16.28 % to 20.35 %, along with the
behavior which is lightly oxidized and its power conversion efficiency Jsc and FF improving from 20.65 mA cm− 2 and 0.71 to 23.65 mA/cm2
attained 17.09 % is higher than HO-Ti3C2Tx (15.52 %) because of heavy and 0.76 Fig. 3e, respectively. The environmental stability of the PSCs
oxidation led to a substantial replacement of its 2D structure with TiO2 with the hybrid ETL was exhibited an efficiency retention of 74 % even
(PCE is 14.86 %) nanoparticles. By using a hybrid of oxidized and pure after 768 at 25 ◦ C (RH = 30 %) [62].
Ti3C2Tx, there was an improved alignment of energy levels between the Apart from the titanium based MXenes, niobium carbide with metal
electron transport layer and perovskite layer, leading to an achieved oxides also studied as an ETL to enhance power conversion efficiency of
power conversion efficiency of 18.29 % in the PSCs. This improved PCE PSCs. Yingchun Niu et al. (2021) proposed an approach in the con­
can be attributed to enhanced electron mobility within the ETL, which struction ETL by combining Nb2C with SnO2. Due to the incorporation of
facilitates efficient electron transport and reduces electron-hole recom­ Nb2C led to increase the lattice spacing of (101) and (110) planes cor­
bination. The study emphasizes that MXene has significant potential for responding to SnO2 electron transport layer from 0.240 to 0.253 nm
low-temperature processing of perovskite solar cells as well as improved Fig. 4a and 0.32 to 0.33 nm (Fig. 4b). The presence of Nb2C significantly
performance in a cost-effective manner [54]. In terms of PCE, the use of reduces the surface energy in between the ETL and perovskite layer,

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M.S. K T and P. Karupppanan Chemical Physics Impact 8 (2024) 100610

Fig. 3. (a) Device architecture of ITO/ETL/CH3NH3PbI3/Spiro-OMeTAD/Ag based on representative SnO2-Ti3C2 as ETL [34], (b) cross-sectional SEM image of the
PSC device [34], (c) PL excitation at 403 nm [34], (d) Schematic illustration of the preparation processes of the ETL and the perovskite film [62], (e) J − V curves of
pristine SnO2 ETL and the Ti3C2TX/SnO2 hybrid ETL [62].

Fig. 4. (a) & (b) HAADF-STEM images of SnO2–Nb2C [63], (c) The contact angle of the perovskite precursor solution deposited on SnO2 and (d) SnO2–Nb2C ETL
basement films [63], (e) Schematic device structure PSCs [64], (f) J–V curves of flexible device [64].

which improves surface wettability and permits the perovskite solution contact in between the perovskite layer and ETL shown Fig. 4c and d.
to distribute smoothly on the ETL. The inclusion of Nb2C MXenes in Moreover, the electron mobility increases, indicating transfer of elec­
SnO2 ETLs leads to reduced light reflection, enhanced light absorption, trons occurs smoothly from perovskites to ETL. PSCs based on the ITO/
and an increased FF, indicating improved optoelectrical properties. SnO2–Nb2C/Perovskite/Spiro-OMeTAD/Ag architecture exhibit the
Nb2C (MXene) can enhance the polarity of SnO2 (according to polarity, achieved PCE of 22.86 % with progressed VOC, JSC, and FF. In addition to
SnO2 was weaker but perovskite material was strong) as a result of this the previous statement, the PSCs equipped with the modified ETL
successful spreading of perovskite solution, this is caused to the high demonstrate a sustained efficiency of 98 % even after 40 days at 25 ◦ C in

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M.S. K T and P. Karupppanan Chemical Physics Impact 8 (2024) 100610

an environment with a humidity level ranging from 40 % to 60 % [63]. dodecyltrimethoxysilane) ETL has been found to possess improved band
Apart from using pristine niobium carbide MXene with metal oxides as alignment, supported by both density functional theory calculations and
an ETL, Zhang et al. (2022) studied the modification of Nb2C with measurements of UPS. Meanwhile, functionalized MXene nanosheets
hydrazine (N2H4) for ETL applications. The introduction of N2H4 with show high mobility and electrical conductivity, allowing them to rapidly
Nb2CTX significantly alters the work function of Nb2CTx by substituting and efficiently create a zero Schottky barrier heterojunction with SnO2.
-F groups along with -NH2 groups. This modification resulted in a Moreover, the incorporation of functionalized MXene additives can lead
reduction in the work function from 4.65 eV to 4.32 eV The device ar­ to the attainment of appropriate surface energy, which in turn can boost
chitecture with ITO/Nb2CTx/FA0.85Cs0.15PbI3/Spiro-OMeTAD/Ag is the grain size of the perovskite thin film. Perovskite solar cells and
shown in Fig. 4e. The PSCs incorporating T-Nb2CTx MXene ETLs and different SnO2 energy levels are depicted in the diagram, and indium tin
T-Nb2CTx MXene nanosheet additives demonstrated a maximum PCE of oxide and perovskite layers are drafted in Fig. 6a. The PCE of devices
21.79 %. Furthermore, when applied to flexible and large-area devices, based on the SnO2− MH electron transport layer with the device design of
the corresponding PCE values reached 19.15 % (Fig. 4f) and 18.31 % ITO/SnO2− MH/FAPbI3/Spiro/MoOx/Ag was noticeably increased from
(Fig. 5a), respectively. These results highlight the beneficial impact of 21 % (pristine form) to 23.66 %. The prime device displayed an extreme
modified (T-Nb2CTx) MXene nanosheets on enhancing the efficiency of PCE of 24.1 % with a Jsc of 25.49 mA cm− 2, a Voc of 1.12 V, and a fill
PSCs in various device configurations. The research demonstrates the factor of 84.4 %. In addition, PCE of SnO2− MF (MXene modified with
broad potential of 2D Nb2CTx MXene in various photoelectric devices, fluoralkylsilane) shows 22.8 % is lower than SnO2− MH as an ETL device
paving the way for their applications in wide range of practical settings due to non-radiative recombination is much higher than that of MXene-
[64]. MH doped SnO2. These results underscore the effectiveness of incorpo­
Further, Yang et al et al. (2021) prepared Ti3C2TX quantum dots rating the SnO2− MH ETL and highlight the potential for achieving
(MQDs) and reinforced with SnO2 as an ETL in negative intrinsic positive higher efficiency in PSCs [66]. Despite being widely used as electron
(n-i-p). The device structure ITO/SnO2− MQD/Perovskite/Spiro/MoOx/ transport materials (ETMs) in PSCs, traditional TiO2 nanoparticulate
Au (Fig. 5b) showed a stable power conversion efficiency of 23.3 %, with films face limitations including low conductivity and a high density of
Jsc 24.96 mA/cm2 and Voc 1.17 V, (Fig. 5c). To improve the crystalline trap states. Essentially, TiO2 treatment comes in two forms (nanorods
quality and durability of perovskite films, modulation of perovskite and nanoflowers) to increase PCE in PSCs. Of the two, nanoflowers
crystallization mechanisms is necessary [65]. According to our current provide a higher PCE than nanorods, so TiO2 composite with metal
understanding, MXene/SnO2 nanocomposites or additives have found carbide can be used to further improve PSC performance [67–69].
extensive applications as ETL in perovskite solar cells to improve their Zhenxing Li et al. (2021). introduced single layered MXenes nanosheets
efficiency and stability. Researchers have achieved a maximum power on TiO2 with Cs2AgBiBr6 double PSCs. This multifunctional electron
conversion efficiency of 23.3 % by incorporating MXene quantum dots transport layer not only ensures stability but also improves the efficiency
into SnO2 as an ETL. of the PSCs. By incorporating single-layered MXene nanosheets, notable
Yin et al. (2022) have conducted further investigations to explore enhancements are achieved in the electrical conductivity and electron
an alternative approach for enhancing the performance of PSCs by extraction rate of TiO2. Simultaneously, these nanosheets also modify
dodecyltrimethoxysilane and fluoralkylsilane functionalized MXene the surface wettability of the ETL, thereby facilitating the crystallization
nanosheets as dopants into the SnO2 as an ETL in the format of n-i-p process of Cs2AgBiBr6 double perovskite in solar cell devices. Appar­
device structure. The SnO2− MH (MXene modified with ently, the efficiency improved significantly from 2.0 % of the original

Fig. 5. (a) J-V curves of the large area devices [64], (b) Schematic of the planar heterojunction structure used for the SnO2-based PSCs [65], (c) J-V curves of one of
the best SnO2-based and MQDs-SnO2-based PSCs devices under both forward and reverse scans [65], (d) Schematic of a cross-sectional view of a planar p-i-n
perovskite solar cell device [71], (e) Current density (J)− voltage (V) curves (reverse scan) of devices with different ETLs or ETL/perovskite interfacial configurations
including M-PC61BM ETL [71] (f) PL spectra of perovskite/glass, perovskite/MXene/glass, perovskite/M-PC61BM/glass, and Perovskite/PC61BM /glass samples [71].
(For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

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M.S. K T and P. Karupppanan Chemical Physics Impact 8 (2024) 100610

Fig. 6. (a) Energy-level diagram of the ITO/ETL/AL structure based on SnO2, SnO2− M, SnO2− MF, and SnO2− MH as the ETLs [66], (b) Photoluminescence spectra of
PCBM and 2 wt% of ZnO, Fe3O4, MXene, MXene/ZnO, and MXene/Fe3O4-doped PCBM onto ITO [73], (c) XRD and (d) Raman Spectra of perovskite films containing
various vol.% of 2D-MXene additive [75], (e) J-V characteristics of the fabricated mPSCs devices [75]. (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)

TiO2 to 2.81 % of the Ti3C2Tx@TiO2 [70]. better stabilized power output and better performance. It is noteworthy
that by obtaining 19.2 % PCE, the use of Ti3C2Tx MXenes in both the
perovskite and PCBM layers improved electron extraction/collection at
3.2. p-i-n architecture
the device counter electrode [72].
PCBM with MXene/metal oxide nanocomposites as an ETL prepared
PSCs of the p-i-n type exhibit several encouraging benefits over those
for inverted PSCs applications by Hussain (2023) and colleagues. The
of the n-i-p type, including lower manufacturing temperatures,
research primarily focused on investigating the performance enhance­
improved adaptability, stable operation, and more. The incompatibility
ment, by incorporating ZnO and Fe3O4, as well as MXene, such as
of the perovskite layer’s conduction type, low crystallinity at the top and
MXene/ZnO and MXene/Fe3O4, along with PCBM. The energy band
bottom perovskite surfaces, and high energy barriers for charge
alignment of PCBM blended with MXene/ZnO and MXene/Fe3O4,
extraction at both n- and p-type contacts cause the efficiency of p-i-n
demonstrates the efficient extraction, dissociation, and transfer of free
type PSCs to be comparatively lower than that of n-i-p type PSCs. Chava
charge carriers within the perovskite devices. From PL spectra depicted
et al. (2021) proposed a new approach to enhance the electrical con­
in Fig. 6b, it is evident that the quenching of photoluminescence is more
ductivity and efficiency of inverted (p-i-n) perovskite solar cells using
pronounced in MXene/Fe3O4 compared to MXene/ZnO. This suggests
MXene doping with 6,6-phenyl-C61-butyric acid methyl ester (M-
that the recombination process of charge carriers is effectively
PC61BM)-based ETL. The device structure of PSC is glass/ITO/NiOX/
restrained in MXene/Fe3O4. Correspondingly, the PCE of MXene/Fe3O4
MAPI/M-PC61BM/BCP/Ag (Fig. 5d) utilizing M-PC61BM as the ETL ex­
and MXene/ZnO are determined to be 13.79 % and 13.31 % respectively
hibits an increased PCE of 18 % compared to control devices based on
[73].
PC61BM ETL, which have a PCE of 15.2 %. The photovoltaic parameters
recorded were a short-circuit current of 22.8 mA/cm2 shown in Fig. 5e, a
4. MXenes as additives in the absorber layers of PSCs
FF of 0.76, and a VOC of 1.04 V. From the Raman spectroscopic studies, it
confirmed that the combination of MXene with PC61BM results in the n-
In the previous section the role of MXene with metal oxides and
doping of PC61BM, potentially enhancing the conductivity of the M-
modified MXenes using oxygen plasma as well by oxidation through
PC61BM film. Fig. 5f shows the PL spectroscopy, comparing the sample
chemical routes. The modified MXenes for ETL layer application was
with PC61BM, the samples containing the M-PC61BM film exhibited a
discussed in detail through n-i-p and p-i-n architectures. Building upon
greater reduction in photoluminescence (PL), indicating effective
these promising findings, researchers have subsequently explored the
extraction of an electron from the perovskite layer [71]. Further
potential applications of 2D materials like MXene, as an additives in the
enhance the PCE and stability of p-i-n architecture, D. Saranin et al.
absorber layer. In 2018, the implementation of (Ti3C2Tx) MXene as an
(2021) proposed NiO (HTL) based inverted PSCs and used MXene as
additive in the perovskite layer of CH3NH3PbI3 was initiated [33,74]. In
dopant in both ETL and perovskite absorber. MXenes allow for easy
this context, Bykkam et al. (2020) reported the different volume per­
adjustment of energy level alignment at the interfaces between the
centages (0 %, 5 %, 10 %, 15 %, and 20 %) of MXene as an additive to the
layers (perovskite and Charge transport layer) and passivation of trap­
MAPbI3 absorber layer for boosting the efficiency of monolithic PSCs.
ped states, so it enhances charge extraction and collection at the elec­
Fig. 6c illustrates the XRD patterns of the perovskite films and MXene
trodes on the other. The MXene-based engineered cells demonstrated

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M.S. K T and P. Karupppanan Chemical Physics Impact 8 (2024) 100610

with different volume percentages. Regardless of the additive volume direct addition with the perovskite layer Zhang et al. reported hydrazine
percentage, all the samples exhibit a distinct peak at an angle of 14.2◦ , treated Nb2CTX applied as an ETL (discussed in above section) and ad­
corresponding to the (1 1 0) crystal plane of the MAPbI3 phase. This ditive in perovskite layer for PSCs for the adjusted work function of
indicated that the presence of the cubic phase of the perovskite. In Nb2CTx by substituting -F groups along with -NH2 groups through N2H4.
addition, the consistent change in the peak location suggests that the High-quality and orientated perovskite films are formed more readily
presence of the MXene additive induces stress, leading to a uniform when the abundant surface terminated -NH2 groups of the T-Nb2CTx
distribution of strain during the formation of perovskite crystals. Based MXene nanosheets additive form hydrogen bonds with I− in the perov­
on the Raman spectroscopy (Fig. 6d) analysis, it can be deduced that the skite precursor. The PSCs containing T-Nb2CTx MXene nanosheets ad­
inclusion of 5 vol.% MXene additive in the perovskite film results in a ditive in the perovskite precursor have the highest PCE of 21.79 % [64].
reduced defects, thereby enhancing the photo response of the PSCs. The Multi-dimensional materials are used as intra and inter-layers in meso­
device with 5 vol.% of 2D-MXene demonstrated the highest PCE of 13.62 scopic n-i-p PSCs by S. Pescetelli and his co-authors. PSC efficiency is
%. The device exhibited an open-circuit voltage of approximately 0.81 increased when graphene is combined with both compact and meso­
V, a current density of approximately 27.64 mA/cm2, and a fill factor of porous TiO2, Ti3C2Tx MXenes into the perovskite absorbing layer, and
around 61 % shown in Fig. 6e [75]. functionalized-MoS2 (fMoS2) at the interface between the HTL and
In addition to modifying the absorber layer, researchers are perovskite. This work optimized the as-realized mesoscopic structure:
exploring alternative methods to enhance the performance of PSCs. Li FTO/cTiO2+Graphene/mTiO2+Graphene/perovskite+MXenes/fMoS2/
et al. (2022) utilized two distinct types of MXenes, namely Ti3C2Tx and PTAA/AU on small area cells (active area 0.09 cm2), achieving PCE
V2CTx, as an additional component in the active layers of CH3NH3PbI3. exceeding 20 %. Using the same 2D material-engineered structure, 11 ×
This incorporation led to the formation of perovskite films exhibiting 11 cm2 large area modules (active area 82.62 cm2) showed a top PCE
with better morphology, grain size and hydrophobic properties. In the value of 17.2 %, while 14.5 × 14.5 cm2 (active area 137.16 cm2)
absence of any additive, the device achieves PCE of 15.01 %. However, modules achieved an impressive PCE above 14.7 %. To optimize the
when a 0.03 wt.% Ti3C2Tx additive is introduced, the device’s perfor­ work function of the perovskite absorber layer, graphene is used to
mance improves to 17.20 %, and with a 0.0013 wt.% V2CTx additive master the properties of compact and mesoscopic TiO2, Ti3C2Tx MXenes
(due to reduction in RCT shown in Fig. 7a), the optimal PCE increases to adjust the work function of the absorber, and fMoS2 to lower charge
further to 17.61 %. The pristine perovskite film exhibits an angle of recombination at the interface between the perovskite and HTL, as a
contact of 52.9◦ , while the Ti3C2Tx and V2CTx-added film show contact resulting in a large fill factor and VOC [77].
angles of 85.4◦ and 69.8◦ , respectively. These results indicate that the
surface hydrophobicity of the perovskite films improves upon the 5. Role of MXene as HTL and as an additive in HTL in device
addition of additives. The enhanced hydrophobicity can be attributed to architecture
the presence of -F surface groups in the MXene derived from the HF-
etching process. The carrier lifetime calculated (Fig. 7b) for the pure 5.1. p-i-n architecture
perovskite film, Ti3C2Tx and V2CTx-added film is 7.46 ns, 10.01 ns, and
18.59 ns, respectively. According to efficiency, the devices with the In line with recommendations for PSCs, researchers have extended
pristine film, Ti3C2Tx and V2CTx-added film maintained 9.69 %, 47.16 the usage of MXene into both the ETL and absorber layer that we have
%, and 68.29 % of their initial PCE respectively [76]. Apart from the examined in the previous section. Apart from its significance in

Fig. 7. (a) Nyquist plots of perovskite solar cells without and with Ti3C2TX and V2CTX additive for the optimal device [76], (b) TRPL spectra of pristine perovskite
film, films with Ti3C2TX or V2CTX additive [76], (c) PL measurements for perovskite films grown on different substrates [79], (d) devise structure [79], (e) External
quantum efficiency and integrated JSC curves of different PVSCs [79]. (For interpretation of the references to color in this figure legend, the reader is referred to the
web version of this article.)

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M.S. K T and P. Karupppanan Chemical Physics Impact 8 (2024) 100610

managing the crystallization of the perovskite film, the HTL in PSCs also and corresponding J-V curve depicted in Fig. 8d. Nevertheless, the
plays a vital role in enhancing the efficiency of hole transfer at the calculated EQE values is 17.75 and 19.94 mA cm− 2 align closely with the
interface between the perovskite and HTL [78]. In Zhang (2021) and pointed out differences in short-circuit current density of 19.19 mA
collaborators led a research team that effectively synthesized Nb2CTx cm− 2 and 21.30 mA cm− 2 for the PSCs, both with and without SCA
MXene with outstanding photoelectric properties by employing oxygen shown in Fig. 8e. As a result Ti3C2Tx-SCA demonstrated remarkable
plasma treatment. They subsequently employed this MXene as the HTL stability under ambient air humidity of approximately 20 % .Even after
in inverted perovskite solar cells. Through the application of oxygen 80 h of storage, it retained approximately 80 % of its initial PCE [80].
plasma treatment, the work function of Nb2CTx was modified from 4.68 Poly(3,4-ethylene dioxythiophene):poly(styrenesulfonate) (PEDOT:
eV (pure state) to 5.04 eV This modification was achieved by increasing PSS) has been extensively investigated as the HTL in PSCs. This is
the abundance of oxygen functional groups on the surface of Nb2CTx it attributed to its remarkable properties, including high conductivity,
facilitated the transfer of holes from the perovskite layer to the HTL, suitable work function, and excellent transparency [81,82]. Although
effectively suppressing charge recombination. As a result, the high PEDOT: PSS offers several advantages, it possesses inherent drawbacks
short-circuit current was achieved in the solar cell. Moreover, the PL such as being highly acidic and hydroscopic. These properties can lead
spectra exhibited a significant suppression in PL intensity (Fig. 7c). This to the degradation of ITO anodes, ultimately compromising the effi­
observation strongly suggests an enhanced hole extraction capability of ciency and longevity of the device [83]. Overcome these issues, Hussain
Nb2CTx, indicating its improved efficiency in extracting holes from the et al. (2021) successfully created a novel conductive hybrid network by
perovskite layer. The device architecture of Fig. 7d of ITO/Nb2CTx/­ integrating Mo2C and CNTs, which was implemented for the initial time
MAPbI3/PCBM/Ag, it shows highest external quantum efficiency (EQE) in combination with a PEDOT: PSS hole transport layer (p-i-n architec­
Fig. 7e, integrated short-circuit current density of 22.75 mAcm− 2 and ture) in perovskite solar cells. The device arrangement of consisted
demonstrates a higher PCE of 20.74 % due to indicating the effectiveness ITO/Mo2C CNT@PEDOT: PSS/MAPbI3/PCBM/LiF is shown in Fig. 9a
of the oxygen plasma-treated Nb2CTx HTLs in enhancing charge and the cross-sectional SEM image is shown in Fig. 9b. Based on the
collection and current generation in the PSCs [79]. energy-level diagram shown in Fig. 9c, when light is absorbed by the
Further, Du et al. (2021) conducted a study in which Ti3C2Tx MXene active layer, electron-hole pairs are generated. Following their separa­
treated with varying concentrations (ranging from 0 to 0.7 vol.%) of the tion, these pairs move in the direction of the hole and electron transport
Silane coupling agent (vinyltris (2-methoxyethoxylsilane)) as a HTL in layers. The altered PEDOT: PSS with Mo2C–Carbon nanotubes serves as
inverted PSCs. According to the diagram provided in Fig. 8a, the spray exciton dissociation centers, enabling efficient and rapid separation of
deposition setup, here Ti3C2Tx-SCA dispersion with varying proportions charge between MAPbI3 and indium tin oxide. Additionally, it facilitates
was evenly applied onto the Indium tin oxide substrate. So that Ti3C2Tx fast charge transfer to the anode, promoting overall device performance.
films resulted in improved pathways for hole transfer, leading to Under AM 1.5 illumination at 100 mW cm− 2, the photovoltaic device
enhanced hole extraction with an increased movement of holes from utilizing the hole transport layer achieves a PCE of 12 %. In comparison,
1.30 × 10− 6 to 3.08 × 10− 7 cm2 V− 1 s− 1. Additionally, the transfer the PCE values for the devices with pristine PEDOT: PSS, Mo2C@PEDOT:
resistance at the HTL/perovskite interface decreased from 369.3 Ω to PSS, and CNT@PEDOT: PSS are 9.2 %, 9.82 %, and 10.61 % respectively
194.1 Ω. Consequently, the device composed of ITO/Ti3C2Tx-0.3SCA/ shown in Fig. 9d [84]. In their subsequent research, Hussain et al.
MAPbI3/PC61BM/Ag structure demonstrated (Fig. 8b) an enhanced PCE (2022) prepared a hybrid structure of MXene/WO3 by adding of WO3
with an increase from 11.1 % (for the pristine Ti3C2Tx) to 13.7 % shows nanoparticles onto 2D conductive Ti3C2Tx MXene sheets. Additionally,
in cross-sectional SEM image (Fig 8c) of Ti3C2Tx- 0.3 wt.% of SCA as HTL they incorporated PEDOT: PSS into the HTL for perovskite solar cells

Fig. 8. (a) Schematic representation of spray coating process to form the Ti3C2TX-SCA film and structural formula of vinyl tris (2-methoxyethoxy) silane [80], (b)
Schematic diagram of a device with ITO/HTL/perovskite/PC61BM/Ag structure[82], (c) SEM cross-sectional image of Ti3C2Tx-0.3 % HTL device[82], (d) The J-V
curve of PSCs is based on Ti3C2TX, with different volume fractions of SCA as HTL [80], (e) EQE spectrum and corresponding integrated current density [80].

9
M.S. K T and P. Karupppanan Chemical Physics Impact 8 (2024) 100610

Fig. 9. (a) Device architecture of prepared ITO/HTL/CH3NH3PbI3/PCBM/LiF/Al prototype using Mo2C–CNTs@PEDOT:PSS HTL and (b) cross-sectional FESEM
image [84] (c) Energy level diagram [84], (d) J–V characteristics of pure and 1.5 wt.% of Mo2C, CNTs and Mo2C–CNTs blended PEDOT:PSS HTL using prepared PSC
devices [84], (e) Schematic view [85] and (f) cross-sectional image of ITO/HTL/ MAPbI3/PCBM/LiF/Al prototype structure using MXene/WO3@PEDOT: PSS HTL
[85]. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

p-i-n device structure. Fig. 9e depicts a visual representation of the de­ conductive 2D MXene material known as Ti3C2 to overcome these lim­
vice module that was prepared with different weight percentages (1 %, 2 itations. This material exhibited an energy level equivalent to carbon
%, and 3 %) of the MXene/WO3 hybrid utilized, showcasing the archi­ materials and was utilized as back electrodes in hole transport materials
tecture of ITO/MXene/WO3@PEDOT: PSS/MAPbI3/ETL/LiF/Al. Addi­ and metal halide perovskite (MAPbI3) solar cells without the need for
tionally, Fig. 9f displays a cross-sectional SEM image of the planar noble metals. By employing a simple hot-pressing procedure at 0.4 MPa
device architecture after preparation. The use 2 wt.% concentration of and 85 ◦ C, a seamless and uninterrupted interface was established be­
the MXene/WO3 blended PEDOT: PSS hole transport layer in the con­ tween the perovskite layer of MAPbI3 and the Ti3C2 material as shown in
structed device resulted in a significantly enhanced device performance. Fig. 10a. The work function of the Ti3C2 material was determined to be
Notably, the PCE reached 12.26 ± 0.12 %, the Voc achieved 0.906 ± 4.96 eV, which closely corresponds to the VB (5.4 eV) of the MAPbI3
0.018 V, the Jsc obtained 22.47 ± 0.26 mA cm− 2, and the FF reached layer. This similarity facilitates the smooth transfer of hole charge car­
60.02 ± 0.69 %. The incorporation of MXene/WO3 composite into riers from the perovskite layer to the Ti3C2 electrode, while electrons
PEDOT:PSS results in a reduced root-mean-square (RMS) roughness of from the TiO2 layer readily move to the FTO electrode. In addition, as
21.71 nm, which is lower than that of PEDOT: PSS(53.13 nm), WO3 the thickness of the Ti3C2 electrodes increased from 280 to 330 mm, the
(35.79 nm) and MXene (34.23 nm). So these results represent, the square resistance exhibited a decrease from 30.93 to 25.34 Ω sq− 1.
MXene/WO3 composite structure demonstrates improved surface Under the illumination of 100 mW cm− 2, at a bias voltage of 0.60 V, and
behavior due to the finely dispersed NPs and decreased domain sizes. As across a frequency range of 100 mHz to 1 MHz, the Nyquist plot
a result, it exhibits enhanced interface characteristics with PEDOT:PSS. (Fig. 10b) reveals a comparable series and reduced charge transport
Final outcome is, the incorporation of MXene/WO3 additive in the HTL resistance, reduced charge transport is cause to effectively extraction of
has an important effect on the extraction of charge and ion transport holes. However, as the thickness of the electrode continues to increase
between the HTL and active layer in the device. This effect leads to a beyond the optimal point, the transport resistance rises, resulting in
reduction in charge recombination at the interfaces, thanks to the reduced photovoltaic performance in the PSCs. While PSC based on the
combination of high electronic conductivity, density, and the hydro­ optimally thick Ti3C2 electrode, with a device structure of FTO/TiO2/­
philic nature of the MXene/WO3 additive. The results clearly illustrate MAPbI3/Ti3C2Tx, demonstrated superior performance. It achieved a PCE
the improved performance of the MXene/WO3 (2 wt.%) blended HTL of 13.83 % along with a Voc of 0.95 V, Jsc of 22.97 mA cm− 2, and an FF
[85]. of 63 % showed in Fig. 10c. This success can be attributed to the
enhanced conductivity and favorable interfacial contact between the
6. MXenes as electrodes or additives in electrodes Ti3C2 electrode and the perovskite layer. The obtained PCE is 27 %
higher compared to the control PSCs based on carbon electrodes, which
Traditionally, Au and Ag are commonly used as the standard options had a PCE of 10.87 %. When it stored at room temperature with a
for back contact metals. However, researchers have explored alternative relative humidity of 30 %, the device exhibited enhanced stability
metals such as Pt, Ni, Cu, and Cr for the back contact electrodes in compared to the conventional FTO/compact (c) and mesoporous
perovskite solar cells. Among these metals, Au (16.4 %) and Ag (16.5 %) (m)-TiO2/Perovskite/Spiro-OMeTAD/Au device. The improved stability
demonstrated the highest power conversion efficiency. Nevertheless, it was observed over 360 h. The Ti3C2 electrode acts as a protective
should be noted that both Au and Ag have their limitations, with Au encapsulating layer, safeguarding the active or absorber layer against
being prohibitively expensive and Ag being prone to instability [86]. reactions with water and air [87]. Deviating from the use of unmodified
Cao et al. (2019) made a significant attempt by introducing a highly MXene as an electrode, MI et al. (2020) developed an electrode for

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M.S. K T and P. Karupppanan Chemical Physics Impact 8 (2024) 100610

Fig. 10. (a) Schematic diagram of the fabrication process of Ti3C2 electrode by hot-pressing method [87], (b) The Nyquist plot was measured under illumination at a
bias voltage of 0.60 V [87], (c) J-V curves of devices with different thicknesses of the Ti3C2 electrode [87], (d) Schematic structure of the mixed carbon electrode
CsPbBr3 solar cell [88], (e) J-V curves of the devices with different types of electrodes [88], (f) Schematic of the Ti3C2Tx MXene and the fabrication procedure of
AgNW:MXene flexible transparent conductive electrodes [89]. (For interpretation of the references to color in this figure legend, the reader is referred to the web
version of this article.)

inorganic perovskite solar cells by incorporating carbon nanotubes with utilizing the device arrangement of PET/AgNW: MXene/NiOx/ Perov­
a 1D structure, Ti3C2− MXene nanosheets with a two-dimensional skite/PC61BM/Ag (as shown in Fig. 11a) and with an area of 0.1 cm2
structure, and carbon paste. The constructed devise structure is achieves an impressive PCE of 20.22 %. In comparison, the cell with
FTO/c-TiO2/CsPbBr3/mixed carbon as shown in Fig. 10d. The mixed pristine AgNWs alone achieved PCE of 18.7 %. This high PCE is
carbon electrode, unlike the pristine carbon electrode, exhibits a accompanied by a Voc of 1.06 V, Jsc of 25.16 mA cm− 2, and FF of 75.5 %
point-to-point contact, creating a network structure and enabling shown in Fig. 11b [89].
multidimensional charge transfer pathways. This configuration signifi­
cantly enhances the conductivity of the carbon electrode and facilitates 7. MXene in interfacial layer
the transport of carriers. After incorporating CNTs and MXene into the
carbon paste, the PCE achieved 7.09 %. The solar cell accomplished a Interface engineering assumes a crucial role, particularly in scenarios
Voc of 1.357 V, Jsc of 7.16 mA cm− 2 (shown in Fig. 10e), and an FF of involving the utilization of MXenes. T. Chen et al. (2019) built planar
72.97 % [88]. SCs using the FTO/c-TiO2/CsPbBr3/Ti3C2− MXene/Carbon architecture
In comparison to Cao et al. (2019) the utilization of one- as shown in Fig. 11c. Here, Ti3C2− MXene thin film acts as an interlayer
dimensional CNTs and 2D titanium carbide MXene in conjunction between the perovskite layer and carbon electrode, thereby enhancing
with carbon paste as an electrode resulted in low efficiency, which is due the efficiency of hole extraction. Based on the AFM analysis of the
to incompatibility and interface issues. Accordingly other than nano­ CsPbBr3 film, it exhibits an ultra-smooth surface with a roughness
tubes Chen et al. (2022) developed flexible solar cell devices by measurement of 18.6 nm. The high quality and smoothness of the sur­
combining 1D AgNWs (silver nanowires) and 2D Ti3C2Tx MXene nano­ face greatly facilitate the deposition of the Ti3C2− MXene film, ensuring a
sheets. This resulted in the fabrication of composite Ti3C2Tx MXene FTEs sufficient distance for establishing strong contact with the CsPbBr3
(Flexible Transparent Electrodes). Fig. 10f illustrates the formation of a layer. After incorporating the Ti3C2− MXene film into the device, sig­
conductive AgNW:MXene composite network by coating the MXene nificant enhancements in device performance are observed. The device
nanosheets onto hydrophilic PET substrates with deposited 1D AgNWs. exhibits a higher PCE of 9.01 %, accompanied by an open circuit voltage
The capillary force is employed to facilitate the infiltration of 2D MXene of 1.444 V, short circuit current density of 8.54 mA cm− 2, and attained a
nanosheets into the gaps within the silver nanowires networks, thereby fill factor of 73.08 % during reverse scanning. Additionally, under for­
creating connections between the wires. Furthermore, the AgNW:MXene ward scanning, the device achieves a PCE of 7.85 %, meanwhile without
FTEs demonstrate excellent long-term stability, maintaining their per­ Ti3C2TX− MXene interlayer achieved PCE 8.21, 7.11 % under reverse and
formance even after 240 h of exposure to 60 % relative humidity and a forward scanning respectively shown in Fig. 11d. The CsPbBr3/
temperature of 120 ◦ C. Additionally, it also exhibited the remarkable Ti3C2− MXene devices demonstrate remarkable resilience to moisture,
mechanical resilience, enduring 1000 cycles of bending tests with a maintaining 80 % of their initial efficiency even after more than 1900 h
curvature radius of 5 mm. Moreover, achieving a suitable work function in a humid environment. This excellent humidity tolerance is further
match is crucial for enhancing the efficiency of charge transfer pro­ complemented by the devices retaining 80 % of their initial PCE even
cesses. The calculated work function of Silver nanowires: MXene is after aging for 600 h under thermal conditions at 80 ◦ C. These findings
determined to be 4.81 eV, which falls within the optimal range for indicate the significant potential of 2D Ti3C2− MXene in enhancing the
typical optoelectronic devices. Consequently, the inverted planar PSC extraction of holes and improving the performance of inorganic

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M.S. K T and P. Karupppanan Chemical Physics Impact 8 (2024) 100610

Fig. 11. (a) Flexible PSCs with the structure of PET/AgNW:MXene/NiOX/perovskite/ PC61BM/Ag and the schematic diagram of the active layer perovskite molecule
[89], (b) J–V curves of the flexible PSCs [89], (c) Schematic of CsPbBr3/Ti3C2− MXene based solar cell [90], (d) J-V curves s with/without Ti3C2 MXene [90]. (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

perovskite solar cells [90]. Similarly, Agresti et al. also introduced a this interlayer was to passivate the interface in PSCs, addressing issues
Titanium-carbide (MXenes) for work function and interface engineering such as low efficiency and high energy loss. Ti3C2Fx QDs exhibit effective
in perovskite solar cells with power conversion efficiency of 26 %. passivation properties that can be attributed to three main aspects.
Enhancing band alignment, adjusting the perovskite absorber’s and the Firstly, p-type Ti3C2Fx QDs enable the tuning of the energy level within
TiO2 electron transport layer’s work functions, and designing the per­ perovskite films, facilitating efficient hole transfer. Secondly, Ti3C2Fx
ovskite/ETL interface are all possible with MXenes. The addition of QDs are adept at defect passivation, effectively reducing interfacial
Ti3C2Tx to halide perovskite and TiO2 layers allows the materials’ WFs to non-radiative recombination. Lastly, the inclusion of Ti3C2Fx QDs forms
be tuned without affecting other electronic properties, according to a protective barrier layer that hinders water infiltration, leading to
calculations using density functional theory and ultraviolet photoemis­ enhanced stability in CsPbI3 PSCs. As a result, successfully attained a
sion spectroscopy measurements [91]. high PCE of 20.44 % and demonstrated impressive stability with 93 %
In another work, a hybrid Bathocuproine (BCP):MXene interlayer retention after 600 h of operation [94]. The selective results published in
was designed by Anastasia Yakusheva et al. (2022) and utilized as a recent literatures were summarized in Table.1
composite film with the following architecture: ITO/NiOx/CsFAPbI3/
C60/BCP:MXene/Cu for electron charge transport and surface trap 8. Summary
passivation at the interface with the metal cathode in p-i-n PSC. Ac­
cording to the investigation, using the BCP:MXene interlayer improves This review was comprehensively outlined various methodologies
PSCs power conversation efficiency marginally (from 16.5 for reference employed in the production of MXenes, while also providing an analysis
to 17.5 %) and contributes to long-term stabilization (it reduced output of their distinct physical and chemical properties. The wet chemical
power by only 4 % after 2300 h of continuous light soaking, compared to processing is a common approach to synthesis of MXene, which involves
430 h for the reference device) [92]. the usage of fluoride compounds as an etchants to eliminate layers from
MXene-SWCNT hybrids were employed as an intermediate layer MAX phase materials. This method has gained significant popularity in
between the SnO2 and perovskite layers in the context of PSCs by Bati obtaining MXenes due to its effectiveness, resulting in a wide range of
et al. (2021). The performance of the devices significantly improved surface chemical morphologies. Exploiting this capability, MXene
when utilizing an optimized 2:1 ratio for the MXene/m-SWCNTs inter­ nanosheets can be manipulated in various ways and applied in diverse
facial layer. Moreover, the lifetime charge carrier reduced to 185 ns, roles within PSCs. MXenes offer versatile applications as additives,
these results show that electron transport increased from the perovskite electron transport layers/hole transport layers, interfacial layers, and
layer to the electron transport layer when MXene-SWCNT placed an electrodes, thanks to their diverse structures and customizable surface
interfacial layer between them. The investigation of charge transfer designs. Incorporating MXenes as additives in solution-processed pe­
resistance implies MXene-SWCNT (2:1) is 23.0 Ω, these results show that rovskites can enhance crystallinity, provide controlled morphology, and
the addition of a small number of nanotubes into MXene has the po­ facilitate the charge transfer through their high carrier mobility,
tential to enhance its electrical conductivity, thereby improving the metallic conductivity, and unique 2D structure. When, MXenes utilized
electron transport properties at the SnO2/perovskite interface. Conse­ as an ETL, MXene adjusts the work function of the electron transport
quently, this leads to an improved fill factor (0.80), JSC is 25.09 mA layer to achieve optimal band positioning relative to the perovskite
cm− 2, VOC of 1.07 V, and obtained PCE is 21.42 % [93]. To overcome the layer, thereby facilitating the efficient movement of electrons. Similarly,
challenges posed by non-radiative recombination in CsPbI3 perovskite MXenes employed as HTLs, it offers an advantageous pathway for hole
films, Xu et al. (2022) implemented a solution by introducing func­ transportations, leading to improved hole extraction and reduced charge
tionalized Ti3C2FX quantum dots (QDs) as an interlayer. The purpose of transfer resistance at the HTL/perovskite interface. The incorporation of

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M.S. K T and P. Karupppanan Chemical Physics Impact 8 (2024) 100610

Table 1
Applications of MXene in PSCs and their functions.
MXene in PSCs

Utilization PSC structure Function Reference

oxygen plasma treated Ti3C2Tx MXene as the ETL ITO/MXene/Perovskite/ Spiro-OMeTAD/Au Formation of numerous randomly distributed Ti-O bonds on [52]
the MXene material
Higher and lower oxidized MXene treated as ETL ITO/ETL/CH3- NH3PbI3/spiroOMeTAD/Ag formation of Ti-O bonds and partially transformed to [54]
semiconductor behavior
SnO2-Ti3C2 MXene as ETLs ITO/SnO2 + Ti3C2Tx/MAPbI3/Spiro- it lead to higher photocurrents and reduced electron transfer [34]
OMeTAD/Ag resistance
Ti3C2TX MXene in-corporate with SnO2 as an ETL ITO/Ti3C2Tx-SnO2/perovskite/Spiro- the defect density in the perovskite films was significantly [62]
OMeTAD/Ag reduced from 5.65 × 1015 to 2.25 × 1015 cm3
Nb2C MXene with SnO2 as an ETL ITO/SnO2–Nb2C/Perovskite/Spiro-OMeTAD/ which also led to an amplify in lattice spacing of (101) and [63]
Ag (110) planes corresponding to SnO2 ETL from 0.240 to 0.253
nm
hydrazine treated Nb2CTX applied as an ETL ITO/Nb2CTx/FA0.85Cs0.15PbI3/Spiro- by substituting -F groups along with -NH2 groups through [64]
OMeTAD/Ag hydrazine. This modification resulted in a reduction in the
work function
Introducing of Ti3C2TX quantum dots into the SnO2 ITO/SnO2− MQD/Perovskite/Spiro/MoOx/Au by taking benefit of the outstanding extraction charge [65]
as an ETL capabilities of the MXene quantum dots-SnO2 layer. To
improve the crystalline quality and durability of perovskite
films
Dodecyltrimethoxysilane and fluoralkylsilane ITO/SnO2− MH or MF/FAPbI3/Spiro/MoOx/ functionalized MXene nanosheets show high mobility and [66]
functionalized MXene nanosheets as dopants into Ag electrical conductivity, allowing them to rapidly and
the SnO2 as an ETL efficiently create a zero Schottky barrier heterojunction with
SnO2
incorporating single-layered MXene nanosheets into FTO/Ti3C2Tx@ TiO2/Cs2AgBiBr6/Spiro- to improve the stability and PCE of PSCs when compared to [70]
titania as an ETL OMeTAD/MoO3/Ag. conventional tin oxide treatment.
MXene doping with M-PC61BM based electron glass/ITO/NiOX/MAPI/M-PC61BM/BCP/Ag combination of MXene with PC61BM results in the n-doping of [71]
transport layer PC61BM, potentially enhancing the conductivity of the M-
PC61BM film
NiO-based inverted perovskite solar cells with glass-ITO/NiO/perovskite+MXenes/ allow for easy adjustment of energy level alignment at the [72]
MXene doping applied to both the ETL and the PCBM+MXenes/BCP/Ag interfaces between the perovskite and the charge transporting
perovskite absorber layer layer on the one hand, and passivation of trapped states inside
the cell structure on the other
ZnO and Fe3O4 between MXene sheets for use as the ITO/PEDOT:PSS/ Cs0.1MA0.9PbI3/MXene- rapid charge carrier movement and minimal recombination in [73]
supporting geometry of PCBM ETL Fe3O4@PCBM/LiF/Al PSCs
MXene used as an additive in perovskite layer glass/FTO/compact-TiO2/mesoporous-TiO2/ perovskite improved the crystallinity [75]
mesoporous-ZrO2/monolithic carbon/MXene-
perovskite/HTL
Ti3C2Tx and V2CTx, as an additional component in ITO/PTAA/MAPbI3/PCBM:BCP/Ag perovskite films exhibiting enhanced morphology, larger [76]
the active layers of CH3NH3PbI3 grain size, and heightened hydrophobic properties
graphene is combined with both compact and FTO/cTiO2 +G/mTiO2 +G/ adjust the work function of the absorber layer [77]
mesoporous TiO2, Ti3C2Tx MXenes into the Perovskite+MXenes/fMoS2/ PTAA/AU
perovskite absorbing layer
oxygen plasma treated MXene used as HTL ITO/Nb2CTx/MAPbI3/PCBM/Ag high transmittance and improved conductivity [79]
Silane coupling agent treate MXene as an HTL ITO/Ti3C2Tx-0.3SCA/MAPbI3/PC61BM/Ag leading to enhanced hole extraction [80]
Mo2C and CNTs, implemented with a PEDOT: PSS ITO/Mo2C CNT@PEDOT: PSS/MAPbI3/ enabling efficient and rapid separation of charge between [84]
hole transport layer PCBM/LiF MAPbI3 and indium tin oxide
MXene used as an electrode FTO/TiO2/MAPbI3/Ti3C2Tx reduced charge transport resistance [87]
carbon/CNT/MXene as an electrode FTO/c-TiO2/CsPbBr3/mixed carbon effectively increases the conductivity of the carbon electrode [88]
and carriers transport
AgNW and 2D Ti3C2Tx MXene nanosheet as PET/AgNW: MXene/NiOx/ Perovskite/ enhancing the efficiency of charge transfer processes [89]
electrode PC61BM/Ag
Ti3C2− MXene thin film acts as an interlayer FTO/c-TiO2/CsPbBr3/Ti3C2− MXene/Carbon enhancing the efficiency of hole extraction [90]
between the perovskite layer and carbon
electrode
MXene act as an interlayer between the perovskite FTO/cTiO2+G-nfs/mTiO2+G-nfs/ Enhancing band alignment, adjusting the perovskite [91]
layer and HTL perovskite+MXenes(MX)/ PEAI/PTAA/ absorber’s and the TiO2 electron transport layer’s work
MoO3/ITO functions
hybrid Bathocuproine:MXene interlayer ITO /NiOx/CsFAPbI3/ C60/BCP:MXene/Cu electron charge transport and surface trap passivation at the [92]
interface with the metal cathode
MXene-SWCNT hybrids were employed as an ITO/SnO2/ MXene-SWCNT electron transport increased from the perovskite layer to the [93]
intermediate layer between the SnO2 and /(FAPbI3)x(MAPbBr3)1 − x/Spiro-OMeTAD/ ETL
perovskite layer Au
Ti3C2FX quantum dots as an interlayer FTO/TiO2/CsPbI3(Ti3C2Fx QDs)/ Spiro- tune the energy level of perovskite films and provide an [94]
OMeTAD/Au efficient pathway for hole transfer and prevent water invasion
and improve the stability of CsPbI3 PSCs

MXene into electrodes enhances adhesion to substrates and facilitates MXenes. These approaches hold significant potential for enhancing the
the formation of continuous conductive paths, resulting in improved properties and expanding the range of applications of MXene in a
electrical conductivity. MXenes also serve as promising electrodes due to supercapacitors, biomedical applications, fuel cell applications, sodium-
their low resistance, making them highly desirable for various applica­ ion batteries, light emitting diodes, transparent electrodes, sensors,
tions. Furthermore, it is imperative to explore various novel preparation photocatalysts, etc. Since, the initial application of MXenes in PSCs in
paths and post-treatments, such as UV-ozone treatment, laser irradia­ 2018, the research in this area has been primarily focused on feasibility
tion, and more, to achieve pristine, better-quality, and functionalized exploration through experimental investigations. However, it is

13
M.S. K T and P. Karupppanan Chemical Physics Impact 8 (2024) 100610

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