RESEARCH ARTICLE

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Buried Interface Modulation via Preferential Crystallization

in All-Inorganic Perovskite Solar Cells: The Case of
Multifunctional Ti3C2Tx
Mengqi Wang, Wenwen Wu, Yulin Liu, Songyang Yuan, Dehua Tian, Cuili Zhang,
Zhipeng Ma, Jiahuan Deng, Jianhui Chen, Zaizhu Lou, Wenzhe Li,* and Jiandong Fan*

1. Introduction
Despite inorganic CsPbI3−x Brx perovskite solar cells (PSCs) being promising
in thermal stability, the perovskite degradation and severe nonradiative CsPbX3 (X = Br, I) inorganic perovskites
with an ideal band gap (≈1.7 eV) are
recombination at the interface hamper their further development. Herein, the
promising candidates due to their excellent
typical MXene material, that is, Ti3 C2 Tx , is employed to be the buried interface chemical stability. Nevertheless, CsPbI3
prior to the perovskite absorber layer in the device, which multi-functionalizes inorganic perovskites still suffer from rela-
the as-prepared electron-transfer layers by means of both fascinating tively high open-circuit voltage (VOC ) losses
preferential crystallization of perovskite and/or accelerating the charge compared to the widely-used organic–
inorganic hybrid perovskites (≈0.6 eV,
extraction with respect to an ideal energy-level alignment and suppressed trap
Eg /q-Voc , Eg is optical bandgap and q
states. Accordingly, the power conversion efficiency of the modified PSC is element charge).[1] Various advanced
device is substantially enhanced by as high as 19.56% in comparison to their processing techniques/component engi-
counterparts with only the pristine CsPbI3−x Brx active layer. More importantly, neering have been employed with an aim
MXene modification is favorable to improve the wettability of perovskite to alleviate the VOC losses such as additive
precursor solution with enhanced grain size and crystallinity, thereby engineering,[2–5] surface passivation,[6] and
defect passivation.[7,8] Nevertheless, the
increasing the UV long-term stability of solar cells. This work provides a new
severe nonradiative recombination at the
paradigm toward alleviating the severe nonradiative recombination at the interface of the CsPbX3 solar cell is still
interface in the device whilst enhancing the long-term stability via the detrimental to the cell performance and
preferential crystallization process. VOC .
Interfacial modification is certified to be
a facile strategy to relieve/eliminate the
nonradiative recombination in PSCs.[9–11] To date, various stud-
ies on the interfacial modification of inorganic perovskites have

M. Wang, W. Wu, Y. Liu, S. Yuan, Z. Ma, J. Deng, W. Li, J. Fan C. Zhang, J. Chen
Institute of New Energy Technology College of Physics Science and Technology
Department of Electronic Engineering Hebei University
College of Information Science and Technology Baoding 071002, China
Jinan University Z. Lou, J. Fan
Guangzhou 510631, China State Key Laboratory of Crystal Materials
E-mail: [email protected]; [email protected] Shandong University
M. Wang, W. Wu, Y. Liu, S. Yuan, Z. Ma, J. Deng, W. Li, J. Fan Jinan 250100, China
Key Laboratory of New Semiconductors and Devices of Guangdong Higher
Education Institutes
Jinan University
Guangzhou 510631, China
D. Tian, Z. Lou
Guangdong Provincial Key Laboratory of Nanophotonic Manipulation
Institute of Nanophotonics
Jinan University
Guangzhou 511443, China

The ORCID identification number(s) for the author(s) of this article

can be found under https://doi.org/10.1002/adfm.202300700
DOI: 10.1002/adfm.202300700

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mainly focused on the top surface of perovskites.[6,12–15] How- mains over 80% of the initial PCE after 400 h aging upon UV
ever, the chemistry and morphology of the substrate indeed light.
have a significant effect on the crystallization of perovskite poly-
crystalline film. The widely-used c-TiO2 has relatively-asperous 2. Results and Discussion
morphology for perovskite nucleation and crystallization, which
critically affects the perovskite crystallinity and thereafter gives 2.1. Morphological Characterizations
rise to unexpected nonradiative recombination with respect to
the relatively lower electron mobility of TiO2 electron trans- Here, we employed the commercial MXene (Ti3 C2 Tx ) as the
port layer (ETL).[16–19] Thus, it is essential to design a novel in- buried-bottom interface between the TiO2 layer and perovskite
terfacial material between the c-TiO2 /perovskite layers toward one, and systematically investigated the effect of the buried in-
addressing the perovskite crystallinity and carrier interfacial terface on the perovskite crystallization and surface/interface de-
transfer issues. Various materials have been widely utilized to fect passivation, charge transport capability, and thereafter the
modify the buried bottom interface to improve the device’s photo- device efficiency. In particular, the MXene deionized water so-
voltaic performance.[20] Very recently, Yue Zhang et al. employed lution with various concentrations (0.05, 0.1, 0.15, and, 0.3 mg
3-sulphonatopropyl acrylate potassium salts to passivate the in- mL−1 ) was spun on the surface of c-TiO2 films before spinning
terfacial defects between TiO2 and CsPbI3 , realizing a record-low the CsPbI3−x Brx perovskite layers. The sample of 0.1 mg mL−1
VOC deficit of 0.451 V.[21] In this scenario, the materials for buried concentration was found to be the optimal concentration by op-
interface modification have the potential to be an important part timizing the photovoltaic performance of PSCs (Figure S1 and
of the toolkit required to scale up and commercialize perovskite Table S1, Supporting Information). It is noted that, in the follow-
photovoltaics. ing sections, MXene with a concentration of 0.1 mg mL−1 was
An emerging 2D material, MXene, is a new type of transi- used unless otherwise stated.
tion metal carbide/carbonitride. The general formula of MXenes First, the SEM top-view images of c-TiO2 film and c-
is Mn+1 Xn Tx , where M is the transition metal atom, X is car- TiO2 /MXene film certify the existence of MXene nanocrystals
bon and/or nitrogen, n can vary from 1 to 4, and Tx (where x (Figure S2, Supporting Information). Compared with the c-TiO2
is variable) represents the surface termination functional groups thin film, the c-TiO2 /MXene thin film displays a homogeneously
on the surface of the transition metal layers, for example, hy- dispersed distribution of MXene nanocrystals on c-TiO2 through-
droxyl, oxygen, or fluorine-containing groups. To be more spe- out the thin film. The corresponding scanning electron micro-
cific, Ti3 C2 Tx MXene has attracted much attention due to its high scope (SEM) image demonstrates that the size distribution of
electrical conductivity, high electron mobility, and excellent ther- MXene is in the range of 50–150 nm. Likewise, we also car-
mal stability.[22–24] In addition, MXene can adjust the work func- ried out the corresponding X-ray photoelectron spectroscopy
tion (WF) and the barrier height of the body materials by means (XPS) characterization to further identify the presence of MX-
of utilizing the surface functional groups of different terminals, ene on the c-TiO2 (Figure S3, Supporting Information). Herein,
thereby speeding up the extraction and transfer of charge carri- we carefully compared the XPS discrepancy between c-TiO2 and
ers. Zhao et al. modified SnO2 by introducing MXene to improve c-TiO2 /MXene. For the wide-scan spectrum of c-TiO2 /MXene
the electron mobility and charge transfer capability of the SnO2 (Figure S3a, Supporting Information), aside from the peaks of
ETL.[25] Ma and colleagues used MXene as an additive inside c-TiO2 , we also find the characteristic peak of MXene, that is, F1s
the perovskite absorber layer, thereby suspending the perovskite peak. We also provided the fine-scan spectra of F1s, C1s, and Ti2p
crystallization and increasing its grain size.[26] Liu and colleagues with high resolution. Again, we can find the characteristic peaks
chose functionalized Ti3 C2 Tx quantum dots as interface passiva- of MXene for all the spectra of F1s, C1s, and Ti2p aside from the c-
tors to enhance the performance of CsPbI3 perovskite solar cells TiO2 signals (Figure S3b–d, Supporting Information), which fur-
(PSCs) and improve the stability of perovskites. Obviously, MX- ther certify the presence of MXene on the c-TiO2 . It should be
ene is an excellent interface doping material for optoelectronic noted that we fabricated the perovskite devices with MXene as
devices and potential interface material between perovskite and the buried interface at a low temperature of 150 °C, which is be-
hole transport layer (HTL).[12,25–27] Nevertheless, as an interfacial low the temperature that allows to spontaneously form the defect
passivator between c-TiO2 and CsPbX3 perovskite layers, it has states via the high-temperature sintering process.[28] Therefore,
not been thoroughly explored. Likewise, the potential physical the different oxidation states of the Ti peaks observed in the Mx-
and chemical mechanism of MXene in affecting the perovskite ene XPS spectra are attributed to the functional groups of MXene
layer and device have not been in-depth understood. itself rather than an interaction between MXene and TiO2 .
Herein, we used the typical MXene material, that is, Ti3 C2 Tx , Figure 1a,b shows the atomic force microscopy (AFM) images
as the buried interface of the perovskite absorber layer. We found of the control and c-TiO2 /MXene films. The root-mean-square-
that the Ti3 C2 Tx as a buried interface can accelerate the charge roughness (Rq ) of the MXene-treated c-TiO2 film decreases from
extraction and realize an ideal energy-level alignment. Mean- 39.2 to 35.8 nm, implying that the surface of c-TiO2 becomes
while, the crystallized dynamics process of the perovskite film much smoother by incorporating MXene, which will be benefi-
can also be effectively modulated during the film formation cial to the afterward perovskite crystallization. To this end, the
process with the incorporation of the MXene additive. Accord- c-TiO2 /MXene-based perovskite films were certified to own rel-
ingly, the champion power conversion efficiency (PCE) of the ob- atively larger grains in comparison to the pristine c-TiO2 -based
tained CsPbI3−x Brx PSC with MXene-modified ETL is as high film using AFM characterization (Figure 1c,d). It indicates that
as 19.56%, overwhelming the controlled one. Importantly, the MXene modification may induce favorable morphology of over-
modified device exhibits excellent UV stability, and the PCE re- lying perovskite film, which likely origins from the change of

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Figure 1. AFM images of a) FTO/c-TiO2 films, b) FTO/c-TiO2 /MXene films, c) c-TiO2 /Perovskite (PVK) films, and d) c-TiO2 /MXene/Perovskite films.
Top-view SEM images of e) c-TiO2 /Perovskite films and f) c-TiO2 /MXene/Perovskite films.

Gibbs free energy of heterogeneous nucleation brought by the en- quality. The potential mechanism behind the enlarged grain size
hanced hydrophilicity. In addition, we utilized the Kelvin probe is primarily associated with the increase in substrate wettability
force microscopy (KPFM) technique to evaluate the effect of the of the CsPbI3−x Brx perovskite precursors in the condition of
MXene layer on the surface potential of c-TiO2 (Figure S4, Sup- MXene modification. This subsequently facilitates the dispersion
porting Information). Compared with the control one, the c- of perovskite solutions and benefits the upper perovskite film
TiO2 /MXene films exhibit higher surface potential. We envision formation.[35]
that is associated with the reduction in work function after adding The grain size of the perovskite film is closely related to the nu-
MXene, which will be advantageous to achieve higher VOC in the cleation rate. The change of Gibbs free energy for the nucleation
device.[29–31] is given by Equation (1)[37]
( )
4𝜋r 2
ΔG (r ) = 4𝜋r 2 𝛾CL + − RTln (S) (1)
2.2. Nucleation Process and Crystallization Kinetics 3VM

The contact angles of the control and c-TiO2 /MXene films where VM is the molar volume of the nucleus, r is the radius
with perovskite precursor solution were respectively measured size of the atomic group, S is the supersaturation defined as S
(Figure 1e,f). In comparison, it is widely proved that the presence = C/Cs , and 𝛾 CL is the interfacial energy between the liquid and
of MXene increases the number of surface hydroxyl groups than the cluster, and the critical kernel size is defined as the value cor-
that of TiO2 .[32] Clearly, the contact angle decreases from 24.1° responding to the first derivative of zero. Their expressions can
to 15.9° after involving the MXene additive shown in the inset be obtained as follows
figures, which suggests the enhanced polarity and superior
dispersion of perovskite precursor solution, originating from the 16𝜋VM 𝛾CL
2 3
ΔG∗ = (2)
enhancement of the hydrogen groups compared with the bare 3R2 T 2 ln(S)2
c-TiO2 substrate.[33–36] Although both perovskite films display
a uniform coverage free of pinholes, and c-TiO2 /MXene-based
CsPbI3−x Brx film exhibits remarkably enlarged grain size (center 2VM 𝛾CL
on 800 nm) compared to the control film (center on 500 nm) r∗ = (3)
RTlnS
(Figure 1e,f). This indicates a positive effect of the MXene in-
terlayer in regulating the crystallization dynamics of perovskite, To the best of our knowledge, the interfacial energy, and the su-
which can be cross-checked by the full width at half maximum persaturation ratio play a critical role in the thermodynamic bar-
(FWHM) of characteristic X-ray diffractometer (XRD) pattern rier that the nucleation process needs to break through. Since the
(Figure S5, Supporting Information). An obvious decrease in experimental conditions for the two variables are the same, we
the FWHM demonstrates the improvement of the crystalline judge that the supersaturation diversification for these two cases

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Table 1. Determination of surface free energy from polar and dispersive surface energy components of c-TiO2 -based perovskite films and c-TiO2 /MXene-
based perovskite films.

Contact angle [°] Owens–Wendt theory

p
Deionized water Diiodomethane rs [mJ m−2 ] rsd [mJ m−2 ] rs [mJ m−2 ]
W/O MXene 22.1 19.2 36.91 33.10 70.01
With MXene 18.5 11.8 37.45 34.70 72.15

is negligible. Herein, one commonly-used method, that is, the monomer diffusion.[40] During the entire nucleation process, the
Owens–Wendt theory, was applied to calculate the solid surface solution concentration increases to the critical concentration of
energy through the determination of contact angles. Detailed pa- Cmin as the solvent evaporates. Therefore, the value of Cmin is re-
rameters are summarized in Table 1. Combining Young’s Equa- lated to the energy barrier. Nuclei consume monomer in solution
tion with the Owens–Wendt theory, we can get[38] during the formation process, and with continued consumption,
the solution concentration decreases to a value below Cmin , which
( )1 ( p)
1 is insufficient to overcome the nucleation barrier. Eventually, the
𝛾L (1 + cos𝜃 ) = 2 𝛾sd × 𝛾Ld 2 + 2 𝛾sp × 𝛾L 2 (4) nucleation process is completed. Combined with the above dis-
cussion, the usage of MXene can increase the solid–liquid inter-
p
In the formula, 𝛾sd and 𝛾s are unknown (Table S2, Support- face energy. Obviously, the MXene layer increases the interfacial
ing Information). As long as two probe liquids with known 𝛾Ld energy, which elevates the energy barrier for nucleation and thus
p
and 𝛾L are found, the contact angles of these two liquids on the reduces the nucleation rate. Thus, a higher critical concentration
solid surface are measured, and the data of the surface tension of Cmin is required, which shortens the duration of the nucle-
and contact angle of the liquid are respectively substituted into ation. Hence, the nucleation is suppressed and the duration of
the above formula, two independent equations can be obtained, growth is extended for the nuclei to grow larger, consequently
p
and the 𝛾sd and 𝛾s of the film and the surface tension 𝛾 S of the benefiting subsequent perovskite crystallization.
film can be obtained by solving this equation system. These two The detailed crystallization process of perovskites can be
liquids’ contact angles of the FTO/c-TiO2 sample and the FTO/c- revealed by in situ XRD measurements, which allows to dy-
TiO2 /MXene sample were obtained (Figure 2a). Thus, the sur- namically monitor the film formation process.[42] Herein, we
face energies were determined to be 70.01 and 72.15 mJ m−2 , performed in situ XRD characterization to explore the crystalline
respectively (Table 1). The experiment results show that MXene dynamics of perovskite polycrystalline film for mutual verifi-
has obtained improved wettability along with increased surface cation. It can be found that the CsPbI3−x Brx perovskite would
free energy. In particular, the MXene surface is terminated by prefer to crystallize in a shorter time in the case of c-TiO2 /MXene,
functional groups that are typically represented by Tx, and the whereas a small amount of CsPbI3−x Brx perovskite can be ob-
hydrophilic nature of MXenes is attributed to the presence of hy- tained within a relatively long time in the case of c-TiO2 -based
droxyl (–OH), oxygen (–O), or fluorine (–F) terminated surfaces. perovskite film (Figure 3a,b). We propose the forming process of
The interaction between the oxygen atoms of water molecules CsPbI3−x Brx perovskite can be divided into two steps in view of
and the hydrophilic groups on the MXene surface would be pro- the crystallization dynamic.[43] The first step is the formation of
moted with an enhanced negative potential, resulting in superior the DMAPbI3 perovskite intermediate phase. The second step is
hydrophilicity,[39] thereby being favorable to the perovskite nucle- the process of (CH3 )2 NH2 I (DMAI) sublimation and Cs+ enter-
ation and crystallization. ing the lattice position to form CsPbI3−x Brx perovskite during the
Herein, aside from the hydrophilicity of MXene, the increased annealing process. Therefore, the rapid sublimation of DMAI
surface free energy will also significantly affect the nucleation will lead to rapid crystallization of CsPbI3−x Brx , and vice versa. In
barrier, so that the nucleation process is affected. Since the Gibbs this scenario, the competing crystallization relationship between
free energy for the formation of a crystal nucleus can be calcu- DMAPbI3 and CsPbI3−x Brx perovskites is spontaneously estab-
lated as Equation (3), a higher 𝛾 CL leads to higher r*. As discussed lished, which gives rise to the preferential crystallization growth
above, it can be speculated that the increased interface energy of CsPbI3−x Brx perovskite. DMAI is more sensitive to moisture,
enables the nucleation process to be more difficult, which cor- and a suitable atmosphere will be more conducive to removing
responds to the larger nuclei, and a smaller number of nuclei DMAI and promoting the formation of CsPbI3−x Brx .[44] The
(Figure 2b). Aiming to illustrate the relationship between solid- MXene also enhances the surface hydrophilicity of c-TiO2 films,
liquid interface energy and perovskite crystallization, we plot which is related to forming the hydrogen bonds between water
the formed-nuclei concentration curve as the function of crys- and the surface functional groups of MXenes. This provides
tallization time based on the Lamer nucleation kinetics model a suitable atmosphere for the sublimation of DMAI, thereby
(Figure 2c).[30,40,41] The crystallization process of perovskite films promoting the earlier crystallization of CsPbI3−x Brx . The narrow
can be divided into three parts: i) the t1-t2 process is a pre- FWHM of the diffraction peaks of the perovskite film could be
nucleation process and a solvent evaporation process. ii) the t2-t3 associated with its relatively large perovskite crystalline size,
process is a nucleation process in which the monomer concentra- indicating a much more ordered structure with preferential
tion is supersaturated. iii) t3 is followed by a crystal growth pro- crystal orientation. Figure 3c,d shows the peak intensity and
cess in which the crystal is centered on the nucleus, formed by FWHM of the perovskite intermediate phase, that is, DMAPbI3 ,

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Figure 2. a) Contact angle measurements were taken by dropping deionized water droplets on the FTO/c-TiO2 films and FTO/c-TiO2 /MXene films.
Contact angle measurements were taken by dropping Diiodomethane droplets on the FTO/c-TiO2 films and FTO/c-TiO2 /MXene films. b) The difference
in critical nucleation is explained in a schematic diagram using the classical homogeneous nucleation free energy diagram, with MXene in pink and
unused in blue. c) Lamer curve where Cmin is the critical nucleation concentration, Cmax is the maximum supersaturation, and Cs is the solubility limit
of the solution.

with annealing time. The curve from red to purple corresponds position in advance, which promotes the transition process from
to the intensity of FWHM. Obviously, within the same pe- the perovskite interphase to the final perovskite phase.
riod, the FWHM of DMAPbI3 in the c-TiO2 -based perovskite To quantify the growth rate of perovskite films and in situ de-
gradually decreases during the annealing process, while the tect the growth of perovskite films, we monitored the growth of
FWHM of DMAPbI3 in the c-TiO2 /MXene-based perovskite perovskite polycrystalline films by in situ UV–vis spectroscopy.[45]
gradually increases, which is visually displayed through the color Obviously, the c-TiO2 /MXene-based perovskite film has relatively
diversification (Figure 3c,d). This advantageously indicates that higher absorbance than that of the c-TiO2 -based perovskite film
the presence of MXene can promote the ion exchange reaction during the whole annealing process (Figure 4a,b). After anneal-
between Cs+ and DMA+ cations, allowing Cs+ ions to enter the ing, the absorption intensity of the c-TiO2 /MXene-based per-
lattice position in advance. Figure 3e,f shows the peak inten- ovskite film is far higher than that of the c-TiO2 -based perovskite
sity and FWHM evolution of the (110) plane for CsPbI3−x Brx one (Figure S6, Supporting Information). The absorbance at the
perovskite with annealing time. Obviously, the FWHM of the same wavelength (550 nm) during the annealing process was
c-TiO2 -based perovskite film decreased from 0.33 to 0.21 at 250 s counted (Figure 4d). The absorbance values were further plotted
during the annealing process, while the FWHM of the perovskite as the function of time to obtain the growth rate of CsPbI3−x Brx
film as the experimental group decreased from 0.26 to 0.19 at the during the annealing process (Figure 4c). We can obtain the
160 s during the annealing process. This further illustrates that curve basically includes three stages: i) fast rising stage, the crys-
the presence of MXene enables the Cs+ ions to enter the lattice tals growth rate is relatively quick with respect to the existence

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Figure 3. a) In situ XRD patterns of c-TiO2 -based perovskite films and b) in situ XRD patterns of c-TiO2 /MXene-based perovskite films. c) The
FWHM changes of DMAPI3 in c-TiO2 -based perovskite films and d) c-TiO2 /MXene-based perovskite films during annealing. e) The FWHM changes of
CsPbI3−x Brx in c-TiO2 -based perovskite films and f) c-TiO2 /MXene-based perovskite films during annealing.

of sufficient reactants at the early stage. ii) Transition stage, the where J0 is a kinetic constant, k is the Boltzmann constant, and
reactants are decreased and the growth process gradually slows T is the temperature. The decreasing contact angle/substrate hy-
down. iii) Slow rising stage, the reactants are mostly consumed drophilic will lead to the increase of the nucleation rate on the
and the growth process is almost finished. We can conclude that substrate. The large surface tension on wetting substrates im-
the fast-rising stage of the perovskite film using MXene earlier, poses a friction force that drags down the ion diffusion, which
and the transition stage and the slow-rising stage are longer, slows the diffusion of ions, leading to a slower crystal growth
compared to the c-TiO2 -based perovskite film, consistent with the rate.[46]
in situ XRD results above. The MXene layer can promote the ion The abundant functional groups on the MXene surface make
exchange reaction to occur in advance, thereby allowing the Cs+ it highly hydrophilic. The homogeneously dispersed distribution
ions to enter the lattice position, prolonging the perovskite crys- of MXene will promote the preferential nucleation of perovskite
tallization time, and finally realizing a larger crystallization grain. at the site of MXene due to its highly hydrophilic groups (Figure
According to the classical heterogeneous nucleation theory,[30] S7, Supporting Information). It is analogous to the “isolated is-
the free energy barrier needed for heterogeneous nucleation land” that results from Volmer–Weber (V–W) growth. This is
(ΔGhet ) is equal to the product of the homogeneous nucleation more conducive to the preferential formation of larger grains,
free energy barrier (ΔGheom ) and a function of the contact angle compared to layered growth using bare c-TiO2 .[47] Subsequently,
(𝜃) based on the thermodynamic Gibbs–Thompson mechanism, the
small-size particles with a high chemical potential tend to dis-
solve and re-deposit on the surface of the large-size particles. The
2 − 3cos𝜃 + cos3 𝜃
f (𝜃 ) = (5) large particles with a lower chemical potential could grow further.
4 Accordingly, the average radius of the particle increases during
this coalescence process (Figure S7, Supporting Information),[40]
The wettability of the substrate surface has a strong effect on which would finally enable to form the perovskite thin film with
the nucleation rate (J) via the inverse exponential dependence on large grain size by means of preferentially regulating the nucle-
ΔGhet ation and crystallization process.
On the basis of the discussion above, we propose a nucleation
2−3cos𝜃+cos3 𝜃
and growth route of perovskite film using MXene as the buried-
J = J0 e−▵Gheom 4kT (6) bottom interface, as shown in Figure 5. First, deionized water

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Figure 4. Change in UV absorption during annealing of a) c-TiO2 -based perovskite films and b) c-TiO2 /Mxene-based perovskite films. The same color
represents the same time. c) The crystallinity of c-TiO2 (blue) and c-TiO2 /MXene (pink) spin-coated perovskite thin films. d) The absorbance (at 550 nm)
evolution of perovskite films without MXene and with the MXene process.

with or without MXene was spin-coated onto c-TiO2 and annealed which is terminated until the evaporation of the solvent in the
at 150 °C for 30 min. The perovskite precursor solution was then intermediate is completed. Rapid nucleation followed by a slow
spin-coated onto both surfaces. As depicted in Figure 5, Ti3 C2 Tx crystal growth forming high-quality perovskite films with more
possesses various termination groups, that are, O2− , OH− , and surface coverage and fewer defects.
F− , on its surface.[48] The hydroxyl groups on the surface of
Ti3 C2 Tx are hydrophilic groups, which will provide an environ-
ment for the rapid sublimation of DMAI and promote the form- 2.3. Defects and Carrier Transport
ing of CsPbI3−x Brx perovskites.[49] In addition, the presence of
MXene increases the interfacial energy, which elevates the energy We performed the fluorescence lifetime imaging microscopy
barrier for the nucleation and reduces the nucleation site and nu- (FLIM) characterization to explore the charge transfer kinetics
cleation density, which allows to realize the perovskite single crys- of perovskite thin films (Figure 6). Clearly, for both the cases of
tal with large size and high crystallinity. This ultimately leads to FTO/perovskite and c-TiO2 /perovskite, the incorporation of MX-
a larger grain size of the perovskite film through the usage of ene can remarkably and homogeneously quench the photo lumi-
MXene. In the research of Hagfeldt and co-workers, they used nescence (PL) lifetime throughout the whole thin films, which is
N-doped graphene as an additive. The basic sites on N-doped likely associated with either superior charge injection or more
graphene could interact with the hydrogen atoms of [HC(NH2 )2 ] trap-assisted recombination. Generally, the spontaneous radia-
(FA).[50] This retards the crystallization process and leads to large tive recombination between trap states would lead to a red-shifted
perovskite grains. Moreover, Ma and co-workers found that the emission peak compared with that from the band edge transition,
OH groups have interaction with MAI, forming OH···I− van der whereas the passivation of these trap states can blue-shift the PL
Waals interaction. This can effectively increase the grain size of peak.[51] Herein, in the presence of MXene, the PL peaks display
perovskite film.[26] Therefore, in our case, the abundant surface a clear blue shift (Figure 6e), which points out toward the effec-
terminated –OH groups of MXene additive are hypothesized to tive passivation of the trap states with the incorporation of MX-
form hydrogen bonds with I− in the perovskite precursor and re- ene. In this scenario, the quenched PL is originated from the su-
tards the crystallization process. The slow growth of perovskite perior charge injection rather than trap-assisted recombination.
also provides time for Oswald ripening.[31] Small particle per- The result is consistent with the UV absorption spectra (Figure
ovskites are more easily dissolved during the growth process due S8, Supporting Information).
to their relatively high chemical potential. Therefore, large par- To reveal the charge carrier transport and separation at the in-
ticle coarsening occurs upon the adsorption of small particles, terface domain between the ETL and the perovskite layer, the

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Figure 5. Schematic diagrams of the nucleation and growth pathways of perovskite films without and using MXene as the buried bottom interface.

charge carrier difference was calculated. Figure 6f,g illustrates where 𝜖 and 𝜖 0 are the relative dielectric constant of the
the charge carrier distribution at the interface of the two per- perovskite, the vacuum permittivity, L is the thickness of the
ovskites. Yellow regions represent charge accumulation and cyan corresponding perovskite, and e is the elementary charge, re-
regions represent charge depletion. At the perovskite side, sur- spectively. We calculate the Ntrap of the perovskite films with
face atoms are mainly dominated by the cyan area, whereas the and without MXene modification to be 1.53 × 1015 and 9.74 ×
surface atoms at MXene or c-TiO2 side are dominated by yel- 1014 cm−3 , respectively, from pure electronic devices. Compared
low regions. Accordingly, the MXene layer shows a stronger abil- to c-TiO2 /PVK (Ntrap = 4.40 × 1015 cm−3 ), c-TiO2 -MXene/PVK
ity to facilitate charge transfer at the interface that has a richer (Ntrap = 3.19 × 1015 cm−3 ) has a lower trap density for pure hole
charge distribution. This is consistent with the results of the devices. The low trap density is responsible for improving the
FLIM characterizations as discussed above. It should be noted photoelectric performance of the device. In addition, we can also
that the enhanced crystallinity and larger grain size of the c-TiO2 - obtain charge mobility through the Mott–Gurney Law
MXene/PVK film would also lead to a decrease in the trap states.
In order to rule out the possibility of this cause, again, Figure S9, 8JD d3
𝜇 = (8)
Supporting Information, demonstrates the reduced defect den- 9𝜀𝜀0 V 2
sity of perovskite devices with MXene.
As shown in Figure S9, Supporting Information, the space- where JD is the dark current density and V is the applied voltage.
charge-limited current (SCLC) curves under a dark condition It can be obtained by calculation that after using MXene, the
are used for investigating the trap state density (Ntrap ) and the electron mobility of the perovskite device increases from 3.99 ×
charge carrier mobility (𝜇). The electron trap-state density and 10−3 to 2.40 × 10−2 cm2 V−1 s−1 . Similarly, the hole mobility in-
hole trap-state density were calculated by dark current–voltage creases from 8.71 × 10−3 to 1.66 × 10−2 cm2 V−1 s−1 . These results
curve, which can be clearly divided into three regions: the Ohmic demonstrate the reduced defect density of perovskite devices with
region, trap-filled limit region, and Child’s region.[19,52,53] From MXene, which can be attributed to the enhanced crystallinity and
the data obtained in the figure, the defect density of states Ntrap larger grain size. This result is consistent with the results of XRD
can be calculated according to the following equation and SEM. Once again, the quench of steady state PL lifetime for
the sample with MXene treatment implies better charge injection
rather than trap-assisted recombination. In addition, mobility
Ntrap = (2𝜀𝜀0 VTFL )∕(eL2 ) (7) is also significantly improved after using MXene, which is

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Figure 6. a) FTO/Perovskite and b) FTO/MXene/Perovskite bulk fluorescence lifetime imaging of the corresponding films. c) c-TiO2 /Perovskite and d)
c-TiO2 /MXene/Perovskite bulk fluorescence lifetime imaging of the corresponding films. e) Corresponding UV fluorescence spectra of points A, B, C,
D, and E in the film spectrum. The charge density of f) c-TiO2 /Perovskite and g) MXene/Perovskite. Yellow regions represent charge accumulation and
cyan regions represent charge depletion.

associated with the high conductivity of MXene itself. Moreover, vis and ultraviolet photoelectron spectroscopy (UPS) (Figure
MXene was utilized as the rear interface modification to highlight S11, Supporting Information). Figure 7a depicts the band gap
the role of MXene in passivating the defect states of perovskite, alignment of the c-TiO2 /MXene-based PSCs. Compared to
and the SCLC curves were measured in Figure S10, Supporting the c-TiO2 , MXene has a relatively lower WF. Therefore, the
Information. It is also found that the incorporation of MXene can surface functional groups of MXene can modify the electronic
effectively passivate defects on the surface of perovskite films to structure of the c-TiO2 surface. According to the energy level
reduce the nonradiative charge recombination. Again, the blue alignment theory, the MXene-based films match better with
shift of the PL peak is partially associated with the decreased de- the energy level of the CsPbI3−x Brx perovskite layer, and the
fect states induced by the MXene incorporation in this scenario. electrons can be effectively extracted from the perovskite layer
to the ETL without drastic barriers for electrons transfer,[27]
and the combined effect of work function tuning and interfa-
2.4. Device Photovoltaic Performance cial engineering can alter the electric field distribution in the
layer, increasing the built-in potential and affecting VOC and
The conduction band minimum (CBM) and valence band current density. Figure 7b compares the J–V curves of the
maximum (VBM) of control and c-TiO2 /MXene-based PSCs PSCs based on the control group and the c-TiO2 /MXene-
were obtained by fitting and calculating the spectra of UV– based PSCs, respectively. The optimized c-TiO2 /MXene-based

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Figure 7. a) Schematic diagram of the band energy alignment for c-TiO2 /MXene-based perovskite solar cells. b) J–V curves of the champion c-
TiO2 /MXene-based and c-TiO2 -based perovskite solar cells, inset displays the PCE distribution. c) EQE spectrum and integrated current density of
c-TiO2 /MXene-based and c-TiO2 -based perovskite solar cells. d) Dark J–V curves of the control and MXene PSCs. e) VOC and f) JSC dependence of light
intensity measurements of the control and MXene PSCs. g) SPO and current density of the champion c-TiO2 /MXene-based and c-TiO2 -based PSCs mea-
sured at the maximum power point. The long-term stability of c-TiO2 and c-TiO2 /MXene-based perovskite solar cells, stored in controlled environments
of h) dark/25 °C/R.H. = 15% in air atmosphere and i) UV irradiation/25 °C/R.H. = 30% in the air.

PSCs demonstrated a remarkably enhanced photovoltaic defects, thus leading to reduced leakage current. At room tem-
performance, yielding a VOC of 1.159 V, JSC of 20.35 mA perature, we also plotted VOC and the logarithm of light intensity
cm−2 , and FF of 83.0% for a PCE 19.56%. The inset statistical (P) by linear fitting (Figure 7e). The following relation has been
histograms give the PCE distributions for the control and c- proposed[54,55]
TiO2 /MXene-based PSCs. The PCE enhancement can be mainly
attributed to the increased Voc and FF, which were likely related nkT
Voc (P) = ln (P) + C (9)
to the tunable work function and/or reduced interface trap states. q
Moreover, because of the downward shift of the work function,
the treatment enables the layer of Ti3 C2 Tx more appropriate to where q is the elemental charge, k is the Boltzmann constant,
transfer electrons and reduce current recombination, leading to T is the temperature, C is a constant, and n is the ideality fac-
the increasement of JSC from 19.2 to 19.8 mA cm−2 (Figure 7c). tor. The ideality factor is expected to approach 1 when bimolecu-
The dark current curve shown in Figure 7d indicates that the c- lar recombination is the dominant mechanism. We obtained the
TiO2 /MXene-based PSC provides a smaller dark current density. corresponding slopes for the c-TiO2 /MXene-based perovskite de-
This confirms the c-TiO2 /MXene-based perovskite film has fewer vice, and the c-TiO2 -based perovskite device are 1.26 and 1.64 kT

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www.advancedsciencenews.com www.afm-journal.de

q−1 , respectively. This indicates that the smaller ideal factor, in the tallinity of CsPbI3−x Brx perovskite. The presence of Ti3 C2 Tx can
presence of Mxene as the functional layer, is in favor of obtain- increase the surface free energy, which elevates the energy barrier
ing high VOC and FF values when the interface recombination for the nucleation, reduces the nucleation rate, and finally, real-
is largely suppressed.[56] Figure 7f presents the relationship be- ize the CsPbI3−x Brx films with large grains and high crystallinity.
tween JSC and P on a double logarithmic scale, yielding slopes Likewise, the Ti3 C2 Tx acts as a multi-functional modulator to op-
of 0.91 and 0.86, respectively, corresponding to c-TiO2 /MXene- timize the interfacial energy level alignment, which is attributed
based perovskite devices and c-TiO2 -based perovskites device. to the modification of c-TiO2 surface electronic properties by the
From the Schottky equation, we get that the slope of an ideal functional groups on the Ti3 C2 Tx surface. The improved ener-
device without free-carrier bimolecular recombination should be getic alignment and effective defect passivation cooperatively re-
shown to be close to 1.[57,58] Therefore, the larger the slope, the sult in faster carrier transport and inhibited charge accumulation.
less the bimolecular recombination phenomenon, which is more Accordingly, these characteristics enable the fabrication of highly
favorable for the charge collection process. From this, we can also efficient and stable CsPbI3−x Brx PSCs with an excellent PCE of
obtain the c-TiO2 /MXene-based perovskite devices with higher 19.56%. More importantly, the device exhibits excellent UV sta-
mobility and more efficient extraction of free charges. For the bility, and the PCE still has a retention rate of 80% of the initial
c-TiO2 /MXene-based perovskite device, Figure 7g displays the PCE after 400 h aging upon UV light. We anticipate that our find-
stabilized power output (SPO) as the function of time for the ings will provide new insights into the ongoing development of
champion solar cell, which exhibits extremely stable performance inorganic CsPbI3−x Brx perovskite material and device design that
with an SPO value as high as 19.3% and a stable photocurrent of can prohibit perovskite degradation and thus increase long-term
19.7 mA cm−2 , which is superior to the c-TiO2 -based perovskite stability.
device. In addition, we summarized the recent development re-
garding the photovoltaic performance of inorganic PSCs by in-
terfacial regulation strategy (Table S3, Supporting Information). 4. Experimental Section
Among them, the photovoltaic performance in the current study
Materials: Cesium iodide (99.999%) and lead (II) bromide (99.999%)
is the highest.
were purchased from Alfa Aesar. Isopropanol (≥99.9%) and ethanol
We further investigated the steady-state PCE output for more (99.5%) were purchased from Aladdin. Poly (3-hexylthiophene-2,5-diyl)
than 1000 h under an air atmosphere (temperature: 25 °C, (P3HT) and hydrogen lead iodide (HPbI3 ) were purchased from Xi‘an Poly-
relative humidity: 15%), and the results demonstrate that the mer Light Technology Corp. MXene was purchased from HWRK Chem.
as-fabricated CsPbI3−x Brx PSC based on the c-TiO2 /MXene Dimethyl sulfoxide (DMSO) (anhydrous, ≥99.9%) chlorobenzene and
substrate, 89% of its initial PCE is still retained after 1000 h. dimethylformamide (DMF) were purchased from Aladdin. DMSO was ob-
However, under the same conditions, the PCE of c-TiO2 -based tained from Alfa Aesar.
Preparation of the Solution: Preparation of dense titanium oxide solu-
perovskite cells decreased by a factor of 40%. Again, this en- tion: dissolved 70 μL of hydrochloric acid (2 mol L−1 ) in 5 mL of ethanol,
hanced stability is likely due to the large amounts of oxygen and then took 700 μL of isopropyl titanate and dissolved it in 5 mL
functional groups, for example, –OH, existing on the surface of of ethanol. Poured the ethanolic solution of isopropyl titanate into the
MXene, which suppress the I− migration by forming hydrogen ethanolic solution of hydrochloric acid, shook it for 3 h to fully react, stored
bonds.[59] Due to the sensitive nature of c-TiO2 to UV light, it in the refrigerator, and filtered it before use. After ultrasonic dispersion
we also tracked the steady-state PCE output under UV light and centrifugation of MXene, the concentration was diluted to 0.05, 0.1,
0.15, and 0.03 mg mL−1 . A 0.7 m perovskite precursor solution was ob-
irradiation for 450 h. After being continuously irradiated by UV
tained by dissolving CsI, HPbI3, and PbBr2 (molar ratio was 1:1.15:0.05)
light for 450 h, the c-TiO2 /MXene-based CsPbI3−x Brx PSC still in a mixed solvent of DMF/DMSO (v:v = 19:1).
maintained the original efficiency of 81%, while the efficiency The patterned fluoride-doped tin oxide (FTO) glass (8 Ω sq−1 ) was
of the c-TiO2 -based CsPbI3−x Brx PSC plummeted. It is well washed by sonication with Hellmanex (TM) III detergent, deionized wa-
known that large amounts of oxygen vacancies at the surface of ter, and ethanol for 15 min, in this order. Then the FTO glass was dried
c-TiO2 film would be induced upon UV-light illuminating for with a nitrogen gun and treated with oxygen plasma for 10 min to remove
organic matter remaining on the surface of the substrate and increased
a long time, which might react with the oxygen in the ambient
the hydrophilicity of the surface. First, the UV-treated FTO was placed on
environment. Upon oxygen desorption on the surface of c-TiO2 , a spin coater, and the dense titanium oxide solution was spin-coated at
electrons could be generated in this domain, and rapidly recom- 2000 rpm for 30 s. The dense layer was then heated in steps of 100, 200,
bine with the hole in the valence band of perovskite, thereafter 350, and 550 °C, respectively. The experimental group was spin-coated at
resulting in a faster interfacial charge recombination.[60] In 1500 rpm min−1 with different concentrations of MXene, and heated at
this scenario, the UV light-induced oxygen-vacancy defects 150 °C for 30 min. Then the CsPbI3−x Brx precursor was spin-coated on
in the c-TiO2 film would be effectively passivated by the =O the c-TiO2 film (or with MXene coating) at 4000 rpm for 30 s. Next, the
CsPbI3−x Brx precursor film was heated at 210 °C for 5 min to obtain black
groups of the MXene surface, which enables to improve the CsPbI3−x Brx films. The P3HT solution was obtained by adding 10 mg P3HT
UV stability of the c-TiO2 /MXene-based device.[61,62] The above into the 1 mL CB solution and then relaxed overnight. The P3HT spins
characterizations demonstrate that the MXene we report here as on the treated substrate at 3000 rpm for 30 s. The films were then an-
buried-bottom interfaces are an effective approach to enhancing nealed at 100 °C for 1 h. Finally, 100 nm Ag electrodes were sequentially
the performance of all-inorganic perovskite solar. deposited by thermal evaporation. In addition, all filmmaking was handled
in a nitrogen-filled glove box. All details of material preparation and sam-
ple characterization can be found in the Supporting Information.
3. Conclusion Characterizations: AFM images and KPFM images were obtained on
MultiMode. SEM images were measured by scanning electron microscopy
In summary, we demonstrate an optimization strategy by means (SEM, Ultra-55) under 10 kV at various magnifications. The perovskite
of employing Ti3 C2 Tx as the buried interface to promote the crys- film structure was characterized by a TDM-20 Advance XRD with Cu K𝛼

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radiation at 30 kV and 15 mA. UV–vis spectra were measured by plac-

ing the thin films in a double-beam spectrophotometer equipped with
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