See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/393463913

Silver and sodium incorporation into wide bandgap CZTS absorbers on

transparent back electrodes and their application in kesterite/c-silicon
tandem solar cells: Experiments and sim...

Article in Solar Energy · July 2025

DOI: 10.1016/j.solener.2025.113751

CITATIONS READS

0 137

7 authors, including:

Ennouhi Naoufal Yassine Chouimi

Moroccan Foundation for Advanced Research Science and Innovation Mohammed VI Polytechnic University
4 PUBLICATIONS 1 CITATION 2 PUBLICATIONS 0 CITATIONS

SEE PROFILE SEE PROFILE

Noureddine Ben Afkir Sanaa Ammari

University of Hassan II Casablanca Mohammed V University
11 PUBLICATIONS 44 CITATIONS 1 PUBLICATION 0 CITATIONS

SEE PROFILE SEE PROFILE

All content following this page was uploaded by Yassine Chouimi on 07 July 2025.

The user has requested enhancement of the downloaded file.

 Solar Energy 299 (2025) 113751

Contents lists available at ScienceDirect

Solar Energy
journal homepage: www.elsevier.com/locate/solener

Silver and sodium incorporation into wide bandgap CZTS absorbers on

transparent back electrodes and their application in kesterite/c-silicon
tandem solar cells: Experiments and simulations
Naoufal Ennouhi a,b, Yassine Chouimi b, Noureddine Ben Afkir b, Abdeljalile Er-rfyg a,b,
Sanaa Ammari b, Massaab El Ydrissi c , Zouheir Sekkat a,b,*
a
Department of Chemistry, Faculty of Sciences, University Mohammed V in Rabat, Rabat, Morocco
b
Optics and Photonics Center, Moroccan Foundation for Advanced Science & Innovation & Research, MAScIR-UM6P, Ben Guerir, Morocco
c
INNOVX, Mohammed VI Polytechnic University, lot 660, Hay Moulay Rachid, Ben Guerir, Morocco

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

Keywords: In recent years, kesterite solar cells have emerged as a promising candidate for integration as top subcells in
Tandem solar cell tandem structures with silicon solar cells. Nevertheless, the production of high-quality kesterite absorbers on
Kesterite transparent substrates has remained a significant challenge. In this study, the combination of silver (Ag) alloying
c-Silicon
and sodium (Na) doping was employed to enhance the properties of copper zinc tin sulfide (CZTS) absorbers
SCAPS-1D
developed on FTO (fluorine-doped tin oxide) back electrodes using the sol–gel method. X-ray diffraction
FDTD simulation
demonstrated a notable enhancement in the crystallinity and phase composition of the kesterite materials with
the introduction of silver. Furthermore, Raman spectroscopy indicated a more organized matrix with a consid­
erable reduction in Cu/Zn disorder and CuZn defect density in the kesterite materials following the incorporation
of silver. Optical analysis exhibited a slight increase in the kesterite optical bandgap from 1.53 to 1.57 eV due to
the presence of silver atoms. A finite-difference time-domain (FDTD) optical simulation was conducted using
realistic optical inputs to calculate the transmitted light from the FTO/CZTS/CdS/ZnO/ITO solar structure.
Subsequently, the performance of a well-established c-Si bottom subcell (with state-of-the-art efficiency) under
calculated transmission was evaluated using the Solar Cell Capacitance Simulator (SCAPS-1D) for electrical
simulation. The simulated tandem device achieved an efficiency of 14.5 %, which is lower than that of a crys­
talline silicon (c-Si) solar cell under AM1.5 due to lower transmittance. This resulted in only 6 % efficiency from
c-Si in the tandem configuration, in addition to the lower electrical performance of the kesterite top subcell with
only 7.8 % efficiency. These findings suggest that incorporating silver represents a promising approach to
enhancing the properties of kesterite materials on transparent back electrodes. However, further optical im­
provements are necessary to fully realize the potential of kesterite materials for tandem applications.

1. Introduction applications. Despite reaching an efficiency of 12.6 % in 2013 [39], the

highest reported value for kesterite material-based solar cells has
Quaternary kesterite compounds, including Cu2ZnSnSSe4 (CZTSSe)- remained unchanged for a decade, despite an increase in several studies
based solar cells and their derivatives, have attracted considerable in­ on kesterite materials. The reduced performance of the CZTSSe solar
terest as potential materials for use as top cells in the forthcoming cells can be attributed to many factors, including a higher open circuit
generation of kesterite/crystalline silicon (c-Si) tandem solar cells Val­ voltage (Voc) deficit (Eg/q-Voc) resulting from the high density of
entini et al. [38]. Due to their low cost, abundance of constituents, charged bulk defects, particularly the dominant CuZn antisite defects,
favorable optical and electrical properties, and long-term stability, and the resistive nature of the CZTSSe/CdS heterointerfaces, which lead
considerable effort has been dedicated to the development of CZTSSe to enhanced carrier recombination [14]. Recently, Gong et al. [11] re­
compounds, which have demonstrated their viability in solar cell ported the first notable enhancement in kesterite efficiency, reaching

* Corresponding author.
E-mail address: [email protected] (Z. Sekkat).

https://doi.org/10.1016/j.solener.2025.113751
Received 4 August 2024; Received in revised form 7 January 2025; Accepted 29 June 2025
0038-092X/© 2025 International Solar Energy Society. Published by Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and
similar technologies.
N. Ennouhi et al. Solar Energy 299 (2025) 113751

12.96 % for solar cells based on AgxCu2–xZnSn(SSe)4 (ACZTSSe) and silver (Ag) alloying. The addition of a 20 nm molybdenum oxide
absorber. This improvement was achieved through epitaxial recon­ (MoO3) nanolayer between the FTO and kesterite materials resulted in
struction of the heterointerface using lower-temperature junction post- an efficiency of 11.4 %. This efficiency exceeds that of other thin-film
annealing. Subsequently, Qingbo Meng’s group increased the effi­ solar cells on transparent electrodes Zhou et al. [43]. It can therefore
ciency further to 13.8 % through more precise control over phase evo­ be concluded that the combination of sodium and silver in kesterite
lution during the annealing process Zhou et al. [42]. The same group materials has significant potential for the development of highly effi­
reported a 14.2 % efficiency through introducing elemental alloying to cient kesterite solar cells on transparent electrodes. However, the lower
reduce the material stability and the metal–chalcogen bond strength, bandgap of the sulfo-selinide Sn-kesterite material CZTSSe makes it
thereby facilitating the cation exchange [35]. These higher efficiencies unsuitable for top-cell applications. Consequently, these approaches
represent the foundation of a strong advance in kesterite solar cell should be transferred to large-bandgap kesterite absorbers.
development, and most of the advanced studies reported in 2024 show In this work, we combined Na doping and Ag alloying to enhance the
efficiencies exceeding 14 % for kesterite solar cells [9,20,41]. The im­ properties of wide-bandgap CZTS materials deposited on FTO back
provements observed in these cells are attributed not only to the electrodes and evaluated their application in tandem solar cells through
announced approaches but also to silver incorporation into the ab­ optical and electrical stimulation. First, CZTS solar cells with and
sorbers, as silver alloying (ACZTSSe) significantly enhances kesterite without Ag incorporation on FTO electrodes were prepared using the
properties in many previous works. One of the primary challenges sol–gel method and analyzed by combining X-ray diffraction (XRD),
associated with kesterite materials is the presence of CuZn anti-site de­ scanning electron microscopy (SEM), Raman spectroscopy, atomic force
fects, which occur when zinc (Zn) and copper (Cu) atoms interchange microscopy (AFM), and UV–visible spectroscopy. Then, the obtained
positions within the CZTS matrix. This phenomenon leads to an increase optical data for our absorber were used in Finite-difference time-domain
in carrier recombination and a subsequent reduction in solar cell effi­ (FDTD) optical simulations to estimate the transmission of the CZTS top
ciency. The formation of these defects is facilitated by the similarity in subcells. Finally, the calculated transmittance spectrum was used in
ionic radius between Zn2+ and Cu1+. One solution is to partially sub­ Solar cell capacitance simulator (SCAPS-1D) electrical simulations to
stitute Zn or Cu with other elements that have similar oxidation states. evaluate the c-Si bottom cell under the transmitted light from the top
Although cadmium (Cd) has been demonstrated to be an effective sub­ cell.
stitute for Zn (Yan et al., 2017), its use is constrained by concerns
regarding toxicity. Silver (Ag) has been identified as the most promising 2. Preparation and characterization of kesterite absorbers
substitute for copper (Cu), as the larger atomic size of Ag reduces the
formation of CuZn defects and Cu-Zn disorder. Furthermore, during 2.1. Solution preparation
annealing, Ag also creates a low-melting-point Ag-S liquid phase that
facilitates grain growth by enabling smaller grains to merge into larger Solid solution CZTS materials were synthesized using the cost-
ones, resulting in the formation of high-quality, large grains in the effective sol–gel method. The CZTS solution was prepared according
absorber layer. Furthermore, the addition of silver to the alloying pro­ to the protocol outlined in Fig. 1. Initially, Copper acetate dihydrate (Cu
cess has been observed to result in a slight increase in the bandgap of (CH3COO)2⋅H2O) (0.46 mol/l) was dissolved in 20 ml of 2-methoxyetha­
CZTS, which is an advantageous feature for use in tandem cells. nol, followed by the addition of Tin chloride dihydrate (SnCl2-2H2O)
[8,15,19,32]. (0.27 mol/l), resulting in a greenish solution. Subsequent color changes
In the Kesterite/c-Si tandem configuration, kesterite solar cells occurred upon the addition of Zinc acetate dihydrate (Zn
should be developed on transparent electrodes, which act as tunnel (CH3COO)2⋅2H2O) (0.27 mol/l) and thiourea SC(NH2)2 (2 mol/l), and
junctions in monolithic configurations of tandem solar cells and allow the entire solution was stirred for one hour at 60 ◦ C, yielding a clear and
light transmission to c-Si bottom subcells in mechanically stacked con­ transparent solution. Sodium chloride (NaCl: H2O) was added to the
figurations [16]. Fluorine-doped tin oxide (FTO) represents the most final CZTS solution with NaCl to CZTS molar ratios of up to 10 %. For the
promising candidate for CZTS top cells due to its high transparency, low AgxCu1-xZnSnS4 (ACZTS) solution, silver chloride (AgCl) with a Cu/Ag
resistivity, and high thermal stability at standard temperatures used to ratio of 10 % was added after the addition of Cu (CH3COO)2⋅H2O in the
create kesterite materials Valentini et al. [38]. However, compared with initial step.
Molybdenum-based solar cells, CZTSSe solar cells developed on FTO
electrodes exhibit some limitations in terms of efficiency, mostly due to 2.2. Substrate cleaning and deposition
the higher work function of FTO and lattice mismatch of the FTO/CZTS
interface, complicating charge transfer and increasing unfavorable car­ Before deposition, the FTO-coated soda lime glass (SLG) substrate
rier recombination [3]. In recent years, there has been a notable increase (surface resistivity ~ 7 Ω/sq) thoroughly cleaned in an ultrasonic bath.
in the development of highly efficient tandem solar cells. Most of the The cleaning steps included immersion in deionized water for 10 min,
scientific community considers narrow-bandgap c-silicon to be the most followed by immersion in ethanol for another 10 min, and a final rinse in
suitable option for bottom cells. In the case of large-bandgap top cells, deionized water for an additional 10 min. After rinsing with water and
perovskites have emerged as the most extensively researched option, drying with nitrogen, the substrate was subjected to UV-ozone cleaning
with efficiencies over 31 % having been achieved for Perovskite/c-Si for 10 min. The prepared solution was filtered through a 0.45 μm filter
tandem structures [12]. Nevertheless, despite this progress, the stabil­ and then deposited onto the cleaned FTO substrate via spin-coating at
ity of perovskite solar cells remains a significant challenge before 3000 rpm for 30 s. Subsequently, the substrate was preheated in an at­
commercialization, with ongoing research focused on enhancing both mospheric environment on a hot plate set at 300 ◦ C for 2 min. This
their stability and efficiency [1,21,24],Mohammed [25],Mohammed deposition process was repeated 10 times to achieve the desired thick­
[26]. Conversely, kesterite thin films demonstrate enhanced stability ness of approximately 1 µm.
and flexibility in bandgap tuning. In addition, recent improvements in
performance have led to the suggestion that kesterite-based solar cells 2.3. Sulfurization process
may offer a promising alternative. Considering these reasons, re­
searchers have proposed kesterite/c-Si tandem devices as a cost- The as-deposited CZTS precursors were placed in a graphite box (4x5
effective and potentially highly efficient solution for the next genera­ cm2) with 500 mg of sulfur powder and inserted into a tubular furnace.
tion of tandem solar cells. Before the annealing process, the tube was purged several times with
In 2023, Zhou et al. reported an ACZTSSe (Eg = 1.16 eV) solar cell on nitrogen. The optimized annealing profile, as depicted in Fig. 2, involved
an FTO substrate with an efficiency of 7.6 % using sodium (Na) doping a sulfurization process conducted at 550 ◦ C for 30 min under a pressure

2
N. Ennouhi et al. Solar Energy 299 (2025) 113751

Fig. 1. Protocol used to prepare the CZTS Sol-gel solution.

Fig. 2. Temperature vs. Time One-Step Annealing Profile.

of approximately 1 bar (initially 600 mbar at 25 ◦ C). The ramping rate 3. Results and discussion
was set to 5 ◦ C/min, and the cooling process occurred naturally over
approximately 3 h. The crystal structure and phase composition of the prepared thin
films were investigated through X-ray diffraction (XRD) analysis. The
2.4. Characterisations obtained diffractograms are shown in Fig. 3. a. The diffraction patterns
of sulfurized thin films, both with (ACZTS) and without silver (CZTS),
Scanning electron microscopy (SEM) images were acquired using a revealed narrow peaks corresponding to the (112), (200), (220), and
FEI FEG 450 (Field Emission Gun) microscope with an acceleration (312) diffraction planes of the polycrystalline kesterite phase (JCPDS #
voltage of 5 kV. X-ray diffraction (XRD) patterns were collected using a 026–0575). These peaks’ relatively narrow and symmetric shape­
Rigaku SmartLab diffractometer in Bragg–Brentano geometry with a s confirm the formation of a single-phase structure. Additionally, some
monochromatized CuK-L3 X-ray source (1.540598 Å). The optical peaks corresponding to the FTO substrate were observed in the XRD
properties of the films were investigated using a Perkin-Elmer Lambda pattern (JCPDS: 35–1001). While the high incorporation of silver into
950 UV–visible spectrophotometer. Raman spectroscopy was conducted CZTS compounds typically results in a structural transformation to the
using a LabRam Aramis microprobe by Horiba Jobin-Yvon Co with 785 stannite phase, no peaks corresponding to stannite phases were observed
nm excitation to study the structural properties and assess the quality of in this study, likely due to the lower amount of silver used. However, the
the ACZTS films. Atomic force microscopy (AFM) images were collected position, shape, and intensity of the main peaks differed significantly
using a Veeco Dimension ICON machine. between the ACZTS and CZTS samples. In particular, the ACZTS sample
exhibited a narrow and much more intense peak corresponding to the

3
N. Ennouhi et al. Solar Energy 299 (2025) 113751

Fig. 3. XRD patterns of CZTS and ACZTS thin films (a) entire acquisition scale and (b) magnification on the main peaks.

(112) orientation (Fig. 3. b), indicating a higher crystallinity of the

kesterite material after silver incorporation, which is consistent with
previous reports on silver alloyed CZTS absorbers [33]. A slight shift of
the principal diffraction peak towards lower angles was observed after
silver incorporation, indicating an improvement in the lattice parameter
with the introduction of larger silver atoms. A small trace of tin sulfide
(SnS) phase is observed in the ACZTS sample with a small peak at about
32◦ , which may be due to the substitution of Cu2+ with Ag+ ions in the
solution that allows some quantity of tin (Sn) ions with 2 + oxidation
state to form of SnS phases. The lattice parameters, deformation, and
crystallite size calculated using the Scherrer formula are presented in
Table 1. The lattice parameter ‘a’ is improved from 5.42 Å for CZTS to
5.47 Å for the ACZTS absorber, where a small decrease in the ‘c’ lattice
parameter from 10.86 Å to 10.83 Å is observed for ACZTS, following the
previous reports on Ag alloyed CZTS sample [27]. This variation in the
lattice parameter is due to the replacement of Cu-S (2.31 Å) by larger Ag-
S (2.57 Å) bond length in the tetragonal structure [19]. Similarly, a
significant increase in the crystallite size was observed, increasing from
32 to 69 nm following silver incorporation.
As some secondary phases cannot be distinguished from CZTS in XRD
Fig. 4. Raman spectra of CZTS and ACZTS thin films.
analysis (To verify the formation of a pure CZTS), Raman spectroscopy
analysis is necessary. The near-resonance Raman spectra obtained with
an excitation wavelength of 785 nm for samples synthesized with and peak in the measured Raman spectra (shown in Table 2.). Previously,
without Ag are depicted in Fig. 4. Both samples exhibit Raman peaks at this was shown to be a possible indicator of changes in defects and/or
283, 321, 334, and 370 cm− 1, corresponding to the vibrational modes of Cu/Zn disorder in kesterite-type compounds [34]. A small decrease in
the kesterite phase [30]. Ag incorporation does not cause any Raman the relative intensity ratio for the ACZTS sample in comparison to that
shifts, possibly due to the low content of Ag in CZTS [13]. However, the for the CZTS sample. This may be explained by the small changes in the
peak sharpness and intensity are notably enhanced for the ACZTS defect concentration, as observed previously for Cu2ZnSnSe4 com­
sample. It is known that the order/disorder of Cu and Zn atoms strongly pounds [28].
influences the Raman peaks in kesterite materials, where sharper and The morphology and chemical composition of the prepared CZTS
more intense peaks indicate a more ordered structure and less defective and ACZTS thin films were evaluated using surface SEM images and
matrix [5]. In CZTS materials, the dominant defects are associated with Energy dispersive spectroscopy (EDS), and the results are presented in
CuZn, owing to their lower formation energy resulting from the similar Fig. 5.a. and Table 3. Both samples show dense and compact surface
ionic radii of Cu+ and Zn2+ ions [31]. In the case of the ACZTS material, morphologies. However, a small density of voids is observed (clear in the
the substitution of 10 % of the copper atoms with larger silver atoms CZTS sample), which can be attributed to the volatility of secondary
significantly reduced the CuZn defects in the resulting absorbers, phases or maybe the decomposition of CZTS during the high-
explaining the sharper and more intense peaks observed in the Raman temperature stage of the annealing process [10]. This phenomenon is
spectra. Semiquantitative analysis of the samples was performed by most likely due to the greater volatility of the Sn-S binary phases at the
calculating the relative integrated intensity of the second most intense annealing temperature[23]. This can be confirmed by the EDS results

Table 2
Table1 The ratio of the relative integrated intensity of the second most intense peak in
Lattice Parameters, Lattice Deformation, and Crystallite Size of CZTS and ACZTS the measured Raman spectra.
thin films.
Samples I283 I334
Q¼ Q’ ¼
Samples a (Å) c(Å) c/2a D(nm) I302 I370 + I365

CZTS 5.42 10.86 1.001 34.7 CZTS 0.098 0.61

ACZTS 5.47 10.83 0.989 69.4 ACZTS 1.012 0.67

4
N. Ennouhi et al. Solar Energy 299 (2025) 113751

Fig. 5. (a) Surface SEM images and (b) 3D-AFM images of CZTS and ACZTS absorbers.

Urbach tail energy (EU), with a lower value indicating less band-tailing.
Table 3
An estimate of the EU is obtained by taking the inverse of the slope of the
Cationic ratios of CZTS and ACZTS calculated from EDS results.
linear region below the bandgap. We found that the EU for CZTS devices
Ratio Ag/Ag þ Cu I/II þ IV Zn/Sn Cu/Zn is ~ 152.7 meV and that for ACZTS devices is ~ 146 meV. This implies a
ACZTS 0.634 1.18 1.43 2.01 small reduction in band tailing/antisite defects with Ag substitution
CZTS − - 1.32 1.18 2.43 [34].

shown in the table. The Zn/Sn ratio for both samples is 1.43, which is 4. Optical and electrical analysis of CZTS/c-Si tandem cell
lower than the ratio of the precursors. This problem of tin loss is largely
reported in kesterite materials [18], and several groups have attempted In this section, we will use numerical simulations to evaluate the
to add Sn during the annealing process; however, addressing this behavior of the above-prepared ACZTS absorber in tandem applications.
problem is still challenging in kesterite materials. The ACZTS sample has Specifically, we will use FDTD and SCAPS-1D optical and electrical
large grains (between 800 and 1500 nm), whereas the CZTS sample has simulations due to their proven accuracy[4],Et-taya et al. [7,44].
relatively fewer grains (between 500 and 1000 nm). The large grains in Tandem solar cells can be prepared using different configurations, as
ACZTS are probably due to the formation of low-melting point phases in shown in Fig. 7. The two-terminal (2 T), or monolithic, configuration is
the lower temperature stage of the annealing process [36]. However, the primary type of tandem solar cell. In this configuration, the top cell is
sodium is present in both samples, and Ag-S is reported to have a lower deposited directly on top of the bottom cell and connected through a
melting point and help the grain growth of kesterite materials during the tunnel junction. This configuration is sensitive to the top cell’s bandgap
annealing process. AFM analysis was conducted to gain a better un­ and is limited to the matching conditions where both cells produce
derstanding of the surface topology and roughness of the CZTS and similar currents. On the other hand, in the four-terminal 4 T-configu­
ACZTS thin films, and the results are presented in Fig. 5.b. The 3D im­ ration, the two cells are mechanically stacked, and the outputs are
ages of the ACZTS sample exhibit more rough surfaces and fewer grain collected independently using four electrodes. The four-terminal
boundaries than those of the CZTS sample, in accordance with the SEM configuration provides more flexibility in choosing materials with
results. A rougher surface and fewer grain boundaries in the ACZTS different bandgaps. In this work, we simulated the tandem behavior
sample are detrimental to the absorption and generation of CZTS using our ACZTS material in a 4 T-configuration with a c-Si bottom cell.
materials. Given that the bandgap of our material is about 1.57 eV, the 4 T
The optical properties of the ACZTS and CZTS thin films were configuration with c-Si as the bottom cell is more suitable and theoret­
determined via UV–visible spectroscopy, and the results of the absorp­ ically leads to higher performance than the 2 T configuration[6].
tion coefficient and band gap calculations are shown in Fig. 6. A small The kesterite top subcell (FTO/kesterite/CdS/ZnO/ITO) with ACZTS
increase in the bandgap from 1.53 to 1.57 eV is observed for the CZTS absorber was numerically simulated, particularly light transmission
and AZCTS samples, suggesting that the low content of Ag in CZTS does from the proposed cell, using a 3D finite-difference time-domain (FDTD)
not significantly change the bandgap and that this small change might with Lumerical software (FDTD solution R2.2, Lumerical Inc.,Vancou­
be due to the reduction in Cu/Zn disorder, which strongly affects the ver, Canada). The input illumination spectrum is based on a plane wave
bandgap in kesterite materials [22]. To characterize the band-tailing for source whose spectral power is similar to the AM1.5 solar spectral
these absorbers, the plot ln(α)) vs the bandgap energy to estimate the irradiance [1], and the simulation was conducted in the wavelength
range of 300–1200 nm. In our simulations, database values for refractive

5
N. Ennouhi et al. Solar Energy 299 (2025) 113751

Fig. 6. Absorption coefficients, bandgap, and Urbach energy calculations from UV–visible spectroscopy analysis of CZTS and ACZTS materials.

Fig. 7. Schematics of different tandem device architectures, namely two-terminal, three-terminal, and four-terminal configurations.

index (n) and (k) of ACZTS are calculated using equations (1) and (2). illuminated along the (− ) z direction by a continuous plane wave source
The CdS and ZnO layers were derived from ellipsometry data compiled polarized along the y direction. The frequency-domain power monitors
by Et-taya et al.Et-taya et al. [7], while those for ITO were obtained from are employed to measure total reflected (R) and transmitted (T) light.
the baseline data for kesterite/c-Si reported in[17]. The thickness of √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
( )
( ) √
each layer is similar to that of the state-of-the-art CZTS solar cell on a 1+R √ 4R
n= +√ − K 2 (1)
transparent electrode reported in [29], with our absorber’s thickness 1− R (1 − R)2
estimated to be approximately 1 µm using profilometry measurements.
The perfectly matched layer (PML) boundary conditions are applied λα
along the z-direction, with anti-symmetric boundaries in the x-direction k= (2)
4π
and symmetric boundaries in the y-direction. In addition, the non­
uniformly meshing regions with fine meshing of 0.25 nm were used over R is the reflectance, α is the absorption coefficient, λ is the wavelength,
the whole 3D simulation volume. The top surface of the cell is and n s is the refractive index.

6
N. Ennouhi et al. Solar Energy 299 (2025) 113751

The transmission curves in Fig. 8.a. correspond to the top subcell

structure of FTO/ACZTS/CdS/ZnO/ITO (with an absorber bandgap
calculated using FDTD. Fig. 7. b. displays the filtered spectrum from the
top subcell, which serves as the incident light for the c-Si bottom subcell
simulation in tandem configurations. These curves reveal three distinct
regions. For energies higher than the bandgap of ACZTS material
(wavelengths < 700 nm), there is minimal light transmission due to the
high absorption coefficient of ACZTS materials, as observed from
UV–visible data. Around the bandgap (between 700–900 nm), trans­
mission gradually increases, reaching approximately 80 % with large
fluctuations. These fluctuations may originate from the interference
effect caused by both incident and reflected light at each interface of the
stack. This phenomenon occurs when the thicknesses of the layers are
comparable to the wavelengths of the incident light [2]. Similar results
have been reported in previous simulation studies on tandem solar cells
using the transfer-matrix method (TMM), particularly with kesterite
[17]and chalcopyrite[37]absorber in the top cell. At higher wavelengths
below the bandgap of ACZTS films, transmission curves start to
decrease, ranging from 50 to 80 %. These results explain the significant Fig. 9. The fraction of light absorbed in each layer and the total reflection of
decrease in the light transmitted from the top subcells observed in Fig. 8. the ACZTS solar cell.
b.
To understand the origins of the above-observed results, Fig. 9. For this reason, the subsequent optical calculations of this study do not
provides insights into the light absorption distribution within each layer consider ARCs.
of the top cell (FTO/CZTS/CdS/ZnO/ITO) and the overall device The above transmission spectra were used as a filter in the electrical
reflection. At higher wavelengths below the bandgap of the kesterite simulation with SCAPS-1D to evaluate the c-Si solar cells in the me­
material (>750 nm), where the light transmitted should be adequate for chanically stacked configuration of ACZTS/c-Si tandem solar cell. The c-
a better response of the c-Si bottom cell, the reflection dominates the Si subcell baseline used in this work reproduces one of the champion lab-
spectra, with values ranging from 20 to 40 %, as well as the absorption of scale c-Silicon solar cells[12]. The main electrical parameters used in the
the FTO back electrode, with values ranging from 10 to 20 %. The ab­ simulation are summarized in Table 1S. This c-Si bottom subcell
sorption of the transparent conducting oxides (TCOs) materials at higher exhibited an efficiency of 24.7 % with an open circuit voltage (VOC) of
wavelengths are mostly shown in previous studies and might be due to 639 mV, a short circuit current density (JSC) of 41.9 mA/cm2, and a fill
some plasmonic phenomena resulting from the higher density of carriers factor (FF) of 79.4 %. The J-V curve and external quantum efficiency
in these materials[40]. However, it is critical to address the issues of the (EQE) of the simulated c-Si bottom subcell are shown in Fig. 10. This
reflection in the infrared (IR) region through optical engineering to solar cell exhibits an efficiency of 23.95 % with a VOC of 695 mV, a JSC of
improve the performance of the tandem device. Given the importance of 40.85 mA/cm2, and a fill factor of 84.3 %, which are in good agreement
anti-reflective coatings (ARCs) in reducing reflection losses in solar cells, with the experimental results of the real solar cells.
we have incorporated an MgF2 ARC layer into the modeled structure. The J-V curves of c-Si solar cells simulated under the AM1.5 solar
This is based on a champion kesterite solar cell with an FTO back spectrum and the light transmitted from the ACZTS top cell are shown in
electrode, as reported in[29], with its optical data extracted from [17]. Fig. 11. a. A large difference in the photovoltaic performances between
The MgF2 layer, optimized at a thickness of 115 nm, has been demon­ both simulation results. The c-Si simulated under the filtered spectrum
strated to effectively reduce reflectivity in the visible region around the shows a much lower efficiency of 6 % compared to the reference cell
kesterite bandgap. However, at lower energy levels around the c-Si simulated under the AM1.5 solar spectrum which shows about 24 %
bandgap, the impact is minimal or even slightly increases reflection (see efficiency. This large decrease in the efficiency is due to the large
Fig. 3S). The use of the ARC layer does not affect the transmission decrease in the short circuit density Jsc wish is decreased from 41 to 12
spectrum towards the c-Si bottom cell, this observation suggests that the mA after filtering the solar spectrum with the top cell. However, there is
transmission issue in the lower energy range cannot be resolved using no strong effect on the Voc and FF is observed. The Quantum efficiency of
the ARC developed for kesterite single-junction solar cells. Thus, further both solar cells is shown in Fig. 11. b. At higher energies, all the spectra
research is necessary to develop ARCs specifically designed for tandem are absorbed by the top cell, and the electron-hole pair generation and
cells that are able to reduce reflection across the entire solar spectrum. collection are not observed in the QE curves of c-Si cells. However, at

Fig. 8. (a) Transmission spectrum of the ACZTS solar cell, (b) Filtered light from the ACZTS top cell calculated using FDTD simulation.

7
N. Ennouhi et al. Solar Energy 299 (2025) 113751

Fig. 10. J-V Characteristics and EQE of Simulated c-Si bottom Sub-cell.

Fig. 11. (a) J-V Characteristics and (b) Quantum Efficiency Comparison of c-Si Solar Cells under AM1.5 and Filtered Spectrum by ACZTS Top Cell.

higher wavelength below the bandgap of ACZTS where the higher per­
formance of c-Si subcells are required, the QE curves show values be­
tween 60 and 80 % wish are lower than the QE of c-Si under AM1.5.
These results originate from the higher reflection at lower energies as
well as the absorption of the TCOs at this region as observed before.
The results showed that the current density of c-Si solar cell in tan­
dem configuration with ACZTS solar cells is too low. In this case, the Jsc
of the c-Si bottom cell is lower than the state-of-art current for kesterite
top subcells on a transparent substrate[29]), making it challenging to
combine both subcells in 2 T-configuration. However, the obtained
electrical performance is combined with the electrical data for the best-
reported CZTS solar cell on a transparent substrate (with a similar
bandgap) in a 4 T-configuration kesterite/c-Si. The baseline reported by
Alex et al[17], reproduces one of the records of CZTS solar cell devel­
oped on the transparent substrate [16]. However, some optical input
modifications (e.g.: absorption coefficient, optical filters, and interface
defects) are used to fit exactly the metric parameters of the real solar
cell. The inputs used in this simulation including bulk/interface defects
are shown in Tables 1S and 2S. This solar cell exhibits an efficiency of
7.70 %, with VOC = 0.68 V, JSC = 17.8 mA/cm2, and FF = 63 %. A Fig. 12. Comparison of Reported and Simulated Performance of CZTS Solar
comparison of reported and simulated CZTS solar cell performance is Cells on Transparent Electrode.
shown in Fig. 12. The calculated photovoltaic parameters for both cells
are summarized in the inset table of Fig. 11. The simulated device ex­
hibits an efficiency of 7.69 % with VOC = 0.67 V, JSC = 17.85 mA/cm2, Table 4
and FF = 63.85 %, suggesting that the difference between the experi­ Efficiency of Kesterite/c-Si Tandem Device and Respective Subcells.
mental and simulated data is insignificant. Cell Efficiency%
The photovoltaic parameters of the Kesterite/c-Si tandem device,
Top subcell (Ref) (under AM1.5) 7.69
along with their respective cells, are summarized in Table 4. The tandem Bottom subcell (c-Si) (under filtered light) 6.73
device using ACZTS/CdS as the top cell exhibits an efficiency of only Tandem cell 14.42
14.42 %. This lower efficiency primarily arises from the decreased Jsc of
the c-Si bottom cells, attributable to light transmission from the top cell,
consequently impacting the overall performance of the c-Si cell.

8
N. Ennouhi et al. Solar Energy 299 (2025) 113751

Conversely, the lower electrical performance of the kesterite top subcell (TSCs).
imposes limitations on the design of highly efficient tandem cells.
However, simulation results indicate that further advancements in the Appendix A. Supplementary data
optical and electrical properties of kesterite single-junction cells could
enable kesterite/c-Si tandem devices to achieve efficiencies close to Supplementary data to this article can be found online at https://doi.
those predicted by theoretical studies. This suggests a promising way to org/10.1016/j.solener.2025.113751.
overcome the limitations of single-junction solar cells.
Despite the lower efficiency achieved in this tandem solar cell work, Data availability
these results are promising for further development, and better results
can be expected with additional optimization. Two main factors All data used for the optical and electrical simulation will be shared
contribute to the observed lower efficiency: first, the current limitation on request.
of the electrical performance of large bandgap kesterite solar cells on
transparent back electrodes, with reported efficiencies of only 7–8 %; References
and second, the significant role of optical transmission in the tandem
performance. As shown in our results, the efficiency of the silicon solar [1] D.S. Ahmed, B.K. Mohammed, M.K.A. Mohammed, Long-term stable and
cell dropped from 24 % to only about 7 % when using light transmitted hysteresis-free planar perovskite solar cells using green antisolvent strategy,
J Mater Sci 56 (2021) 15205–15214, https://doi.org/10.1007/s10853-021-06200-
through the CZTS top cell. Much of the research on transparent solar w.
cells has focused primarily on electrical performance, overlooking the [2] J.M. Ball, S.D. Stranks, M.T. Hörantner, S. Hüttner, W. Zhang, E.J.W. Crossland,
significant impact of the optical behavior of CZTS solar cells on tandem I. Ramirez, M. Riede, M.B. Johnston, R.H. Friend, H.J. Snaith, Optical properties
and limiting photocurrent of thin-film perovskite solar cells, Energy Environ. Sci. 8
efficiency. Improving the performance of the tandem structure will (2015) 602–609, https://doi.org/10.1039/C4EE03224A.
require improvements in both the electrical performance and optical [3] I. Becerril-Romero, D. Sylla, M. Placidi, Y. Sánchez, J. Andrade-Arvizu,
transmission of CZTS solar cells. Only through simultaneous advances in V. Izquierdo-Roca, M. Guc, A. Pérez-Rodríguez, S. Grini, L. Vines, B. Pusay,
R. Almache, J. Puigdollers, P. Pistor, E. Saucedo, M. Espíndola-Rodríguez,
these areas can kesterite materials become viable for tandem configu­
Transition-metal oxides for kesterite Solar cells developed on Transparent
rations and achieve the higher efficiencies required for practical substrates, ACS Appl. Mater. Interfaces 12 (2020) 33656–33669, https://doi.org/
applications. 10.1021/acsami.0c06992.
[4] M. Burgelman, P. Nollet, S. Degrave, Modelling polycrystalline semiconductor solar
cells, Thin Solid Films 361–362 (2000) 527–532, https://doi.org/10.1016/S0040-
5. Conclusion 6090(99)00825-1.
[5] M. Dimitrievska, F. Oliva, M. Guc, S. Giraldo, E. Saucedo, A. Pérez-Rodríguez,
In summary, this study has explored the incorporation of sodium V. Izquierdo-Roca, Defect characterisation in cu 2 ZnSnSe 4 kesterites via resonance
raman spectroscopy and the impact on optoelectronic solar cell properties,
doping and silver alloying in large bandgap CZTS materials. This J. Mater. Chem. A 7 (2019) 13293–13304, https://doi.org/10.1039/C9TA03625C.
approach has shown promise, resulting in improved structural and [6] G.E. Eperon, M.T. Hörantner, H.J. Snaith, Metal halide perovskite tandem and
morphological properties along with a slight increase in the bandgap. multiple-junction photovoltaics, Nat Rev Chem 1 (2017) 0095, https://doi.org/
10.1038/s41570-017-0095.
Optical and electrical simulations have been conducted to assess the [7] L. Et-taya, T. Ouslimane, A. Benami, Numerical analysis of earth-abundant
viability of using ACZTS solar cells as top cells in mechanically stacked Cu2ZnSn(SxSe1-x)4 solar cells based on spectroscopic Ellipsometry results by using
tandem solar cells with c-Si bottom cells. However, the simulation SCAPS-1D, Sol. Energy 201 (2020) 827–835, https://doi.org/10.1016/j.
solener.2020.03.070.
outcomes have indicated lower efficiencies for ACZTS/c-Si tandem cells, [8] M. Gansukh, Z. Li, M.E. Rodriguez, S. Engberg, F.M.A. Martinho, S.L. Mariño,
primarily attributed to the decreased performance of c-Si solar cells E. Stamate, J. Schou, O. Hansen, S. Canulescu, Energy band alignment at the
operating under light transmitted from the top cell. This underscores the heterointerface between CdS and ag-alloyed CZTS, Sci Rep 10 (2020) 18388,
https://doi.org/10.1038/s41598-020-73828-0.
need for further optical and electrical advancements to establish kes­
[9] Y. Gong, A. Jimenez-Arguijo, A.G. Medaille, S. Moser, A. Basak, R. Scaffidi,
terite materials as a feasible option for the development of highly effi­ R. Carron, D. Flandre, B. Vermang, S. Giraldo, H. Xin, A. Perez-Rodriguez,
cient tandem solar cells. E. Saucedo, Li-Doping and Ag-Alloying interplay shows the pathway for kesterite
Solar cells with efficiency over 14%, Adv Funct Materials 2404669 (2024) https://
doi.org/10.1002/adfm.202404669.
CRediT authorship contribution statement [10] Y. Gong, Y. Zhang, Q. Zhu, Y. Zhou, R. Qiu, C. Niu, W. Yan, W. Huang, H. Xin,
Identifying the origin of the V oc deficit of kesterite solar cells from the two grain
Naoufal Ennouhi: Writing – review & editing, Writing – original growth mechanisms induced by sn 2+ and sn 4+ precursors in DMSO solution,
Energy Environ. Sci. 14 (2021) 2369–2380, https://doi.org/10.1039/
draft, Visualization, Validation, Methodology, Investigation, Formal D0EE03702H.
analysis, Data curation, Conceptualization. Yassine Chouimi: Writing – [11] Y. Gong, Q. Zhu, B. Li, S. Wang, B. Duan, L. Lou, C. Xiang, E. Jedlicka,
original draft, Investigation, Formal analysis, Data curation. Nour­ R. Giridharagopal, Y. Zhou, Q. Dai, W. Yan, S. Chen, Q. Meng, H. Xin, Elemental
de-mixing-induced epitaxial kesterite/CdS interface enabling 13%-efficiency
eddine Ben Afkir: Writing – review & editing, Software, Methodology. kesterite solar cells, Nat Energy 7 (2022) 966–977, https://doi.org/10.1038/
Abdeljalile Er-rfyg: Writing – review & editing, Validation, Data s41560-022-01132-4.
curation, Conceptualization. Sanaa Ammari: Writing – review & edit­ [12] M.A. Green, E.D. Dunlop, M. Yoshita, N. Kopidakis, K. Bothe, G. Siefer, X. Hao,
Solar cell efficiency tables (version 62), Prog. Photovolt. 31 (2023) 651–663,
ing, Data curation, Conceptualization. Massaab El Ydrissi: Writing – https://doi.org/10.1002/pip.3726.
review & editing. Zouheir Sekkat: Writing – review & editing, Super­ [13] A. Guchhait, Z. Su, Y.F. Tay, S. Shukla, W. Li, S.W. Leow, J.M.R. Tan, S. Lie,
vision, Project administration, Methodology, Funding acquisition, O. Gunawan, L.H. Wong, Enhancement of open-circuit voltage of solution-
processed cu 2 ZnSnS 4 Solar cells with 7.2% efficiency by incorporation of silver,
Conceptualization. ACS Energy Lett. 1 (2016) 1256–1261, https://doi.org/10.1021/
acsenergylett.6b00509.
Declaration of competing interest [14] J. Guo, L. Wang, L. SiQin, C. Yang, Y. Wang, Y. Wang, S. Li, R. Liu, C. Zhu, H. Luan,
CdS(In)/CZTSSe bandgap alignment engineering for performance enhancement of
solar cells without ZnO layer, Sol. Energy Mater. Sol. Cells 269 (2024) 112787,
The authors declare that they have no known competing financial https://doi.org/10.1016/j.solmat.2024.112787.
interests or personal relationships that could have appeared to influence [15] C.J. Hages, M.J. Koeper, R. Agrawal, Optoelectronic and material properties of
nanocrystal-based CZTSe absorbers with ag-alloying, Sol. Energy Mater. Sol. Cells
the work reported in this paper.
145 (2016) 342–348, https://doi.org/10.1016/j.solmat.2015.10.039.
[16] A.R. Jeong, S.B. Choi, W.M. Kim, J.-K. Park, J. Choi, I. Kim, J. Jeong, Electrical
Acknowledgements analysis of c-Si/CGSe monolithic tandem solar cells by using a cell-selective light
absorption scheme, Sci Rep 7 (2017) 15723, https://doi.org/10.1038/s41598-017-
15998-y.
This work is carried out within the framework of the R&D agreement [17] A. Jimenez-Arguijo, A.G. Medaille, A. Navarro-Güell, M. Jimenez-Guerra, K.
between INNOVX and MAScIR, under the Tandem Solar Cells project J. Tiwari, M. Placidi, M.S. Mkehlane, E. Iwuoha, A. Perez-Rodriguez, E. Saucedo,

9
N. Ennouhi et al. Solar Energy 299 (2025) 113751

S. Giraldo, Z. Jehl Li-Kao, Setting the baseline for the modelling of kesterite solar [31] D. Payno, S. Kazim, S. Ahmad, Impact of cation substitution in all solution-
cells: the case study of tandem application, Sol. Energy Mater. Sol. Cells 251 (2023) processed cu 2 (cd, Zn)SnS 4 superstrate solar cells, J. Mater. Chem. C 9 (2021)
112109, https://doi.org/10.1016/j.solmat.2022.112109. 17392–17400, https://doi.org/10.1039/D1TC04527J.
[18] V. Kheraj, K.K. Patel, S.J. Patel, D.V. Shah, Synthesis and characterisation of copper [32] Y.E. Romanyuk, S.G. Haass, S. Giraldo, M. Placidi, D. Tiwari, D.J. Fermin, X. Hao,
zinc tin sulphide (CZTS) compound for absorber material in solar-cells, J. Cryst. H. Xin, T. Schnabel, M. Kauk-Kuusik, P. Pistor, S. Lie, L.H. Wong, Doping and
Growth 362 (2013) 174–177, https://doi.org/10.1016/j.jcrysgro.2011.10.034. alloying of kesterites, J. Phys. Energy 1 (2019) 044004, https://doi.org/10.1088/
[19] J. Kumar, S. Ingole, Structural and optical properties of (AgxCu1-x)2ZnSnS4 thin 2515-7655/ab23bc.
films synthesised via solution route, J. Alloy. Compd. 727 (2017) 1089–1094, [33] M.H. Sayed, J. Schoneberg, J. Parisi, L. Gütay, Influence of silver incorporation on
https://doi.org/10.1016/j.jallcom.2017.08.222. CZTSSe solar cells grown by spray pyrolysis, Mater. Sci. Semicond. Process. 76
[20] Y. Li, C. Cui, H. Wei, Z. Shao, Z. Wu, S. Zhang, X. Wang, S. Pang, G. Cui, (2018) 31–36, https://doi.org/10.1016/j.mssp.2017.12.007.
Suppressing element inhomogeneity enables 14.9% efficiency CZTSSe Solar cells, [34] J.J.S. Scragg, J.K. Larsen, M. Kumar, C. Persson, J. Sendler, S. Siebentritt, C. Platzer
Adv. Mater. 36 (2024) 2400138, https://doi.org/10.1002/adma.202400138. Björkman, Cu–Zn disorder and band gap fluctuations in cu 2 ZnSn(S,se) 4 :
[21] S.M. Majeed, D.S. Ahmed, M.K.A. Mohammed, Anti-solvent engineering via theoretical and experimental investigations, Physica Status Solidi (b) 253 (2016)
potassium bromide additive for highly efficient and stable perovskite solar cells, 247–254, https://doi.org/10.1002/pssb.201552530.
Org. Electron. 99 (2021) 106310, https://doi.org/10.1016/j.orgel.2021.106310. [35] J. Shi, J. Wang, F. Meng, J. Zhou, X. Xu, K. Yin, L. Lou, M. Jiao, B. Zhang, H. Wu,
[22] C. Malerba, F. Biccari, C.L. Azanza Ricardo, M. Valentini, R. Chierchia, M. Müller, Y. Luo, D. Li, Q. Meng, Multinary alloying for facilitated cation exchange and
A. Santoni, E. Esposito, P. Mangiapane, P. Scardi, A. Mittiga, CZTS stoichiometry suppressed defect formation in kesterite solar cells with above 14% certified
effects on the band gap energy, J. Alloy. Compd. 582 (2014) 528–534, https://doi. efficiency, Nat Energy (2024), https://doi.org/10.1038/s41560-024-01551-5.
org/10.1016/j.jallcom.2013.07.199. [36] C.M. Sutter-Fella, J.A. Stückelberger, H. Hagendorfer, F. La Mattina, L. Kranz,
[23] J.A. Márquez, J.-P. Sun, H. Stange, H. Ali, L. Choubrac, S. Schäfer, C.J. Hages, S. Nishiwaki, A.R. Uhl, Y.E. Romanyuk, A.N. Tiwari, Sodium assisted sintering of
K. Leifer, T. Unold, D.B. Mitzi, R. Mainz, High-temperature decomposition of cu 2 chalcogenides and its application to solution processed cu 2 ZnSn(S,se) 4 thin film
BaSnS 4 with sn loss reveals newly identified compound cu 2 Ba 3 sn 2 S 8, J. Mater. Solar cells, Chem. Mater. 26 (2014) 1420–1425, https://doi.org/10.1021/
Chem. A 8 (2020) 11346–11353, https://doi.org/10.1039/D0TA02348E. cm403504u.
[24] M.K.A. Mohammed, Efficient perovskite photovoltaics by a nanostructured ga 2 O 3 [37] K.J. Tiwari, S. Giraldo, M. Placidi, A. Gon Medaille, A. Thomere, S. Resalati,
hole-blocking layer, Energy Fuels 38 (2024) 6387–6396, https://doi.org/10.1021/ E. Saucedo, Z. Jehl Li-Kao, Feasibility of a full chalcopyrite tandem Solar cell: a
acs.energyfuels.4c00376. quantitative Numerical approach, Sol. RRL 5 (2021) 2100202, https://doi.org/
[25] M.K.A. Mohammed, 21.4% efficiency of perovskite solar cells using BMImI 10.1002/solr.202100202.
additive in the lead iodide precursor based on carbon nanotubes/TiO2 electron [38] M. Valentini, C. Malerba, L. Serenelli, M. Izzi, E. Salza, M. Tucci, A. Mittiga,
transfer layer, Ceram. Int. 46 (2020) 27647–27654, https://doi.org/10.1016/j. Fabrication of monolithic CZTS/Si tandem cells by development of the
ceramint.2020.07.260. intermediate connection, Sol. Energy 190 (2019) 414–419, https://doi.org/
[26] M.K.A. Mohammed, High-performance hole conductor-free perovskite solar cell 10.1016/j.solener.2019.08.029.
using a carbon nanotube counter electrode, RSC Adv. 10 (2020) 35831–35839, [39] W. Wang, M.T. Winkler, O. Gunawan, T. Gokmen, T.K. Todorov, Y. Zhu, D.B. Mitzi,
https://doi.org/10.1039/D0RA05975G. Device Characteristics of CZTSSe thin-film Solar cells with 12.6% efficiency, Adv.
[27] L.P. Mwakyusa, L. Leist, M. Rinke, A. Welle, U.W. Paetzold, B.S. Richards, Energy Mater. 4 (2014) 1301465, https://doi.org/10.1002/aenm.201301465.
M. Hetterich, Impact of silver incorporation at the back contact of kesterite solar [40] Z. Wang, C. Chen, K. Wu, H. Chong, H. Ye, Transparent conductive oxides and their
cells on structural and device properties, Thin Solid Films 709 (2020) 138223, applications in Near Infrared plasmonics, Physica Status Solidi (a) 216 (2019)
https://doi.org/10.1016/j.tsf.2020.138223. 1700794, https://doi.org/10.1002/pssa.201700794.
[28] D. Nowak, F. Atlan, D. Pareek, M. Guc, A. Perez-Rodriguez, V. Izquierdo-Roca, [41] Zhong, X., Wang, J., Han, L., Chi, J., Liu, T., Kou, D., Zhou, W., Zhou, Z., Yuan, S.,
L. Gütay, Influence of the precursor composition on the resulting absorber Meng, Y., Qi, Y., Meng, Q., Wu, S., 2024. Li, Ag Co-Doping Enables Efficient
properties and defect concentration in Cu2ZnSnSe4 absorbers, Sol. Energy Mater. Kesterite Solar Cell with a High Fill Factor of 74.30%. Adv Funct Materials
Sol. Cells 256 (2023) 112342, https://doi.org/10.1016/j.solmat.2023.112342. 2418548. https://doi.org/10.1002/adfm.202418548.
[29] E. Ojeda-Durán, K. Monfil-Leyva, J. Andrade-Arvizu, I. Becerril-Romero, [42] J. Zhou, X. Xu, H. Wu, J. Wang, L. Lou, K. Yin, Y. Gong, J. Shi, Y. Luo, D. Li, H. Xin,
Y. Sánchez, R. Fonoll-Rubio, M. Guc, Z.J. Li-Kao, J.A. Luna-López, E. Saucedo, High Q. Meng, Control of the phase evolution of kesterite by tuning of the selenium
efficiency cu 2 ZnSnS 4 solar cells over FTO substrates and their CZTS/CdS interface partial pressure for solar cells with 13.8% certified efficiency, Nat Energy 8 (2023)
passivation via thermal evaporation of al 2 O 3, J. Mater. Chem. C 9 (2021) 526–535, https://doi.org/10.1038/s41560-023-01251-6.
5356–5361, https://doi.org/10.1039/D1TC00880C. [43] Y. Zhou, C. Xiang, Q. Dai, S. Xiang, R. Li, Y. Gong, Q. Zhu, W. Yan, W. Huang,
[30] D. Palma-Lafuente, P. Diez-Silva, V. Rotaru, T. Jawhari, T. Bertram, P. Reyes- H. Xin, 11.4% efficiency kesterite Solar cells on Transparent electrode, Adv. Energy
Figueroa, M. Guc, J.M. Merino, R. Caballero, Sulfurization of co-evaporated Mater. 13 (2023) 2300253, https://doi.org/10.1002/aenm.202300253.
Cu2ZnGeSe4 layers: influence of the precursor cation’s ratios on the properties of [44] S.H. Zyoud, A.H. Zyoud, N.M. Ahmed, A.R. Prasad, S.N. Khan, A.F.I. Abdelkader,
Cu2ZnGe(S,Se)4 thin films, Sol. Energy Mater. Sol. Cells 254 (2023) 112243, M. Shahwan, Numerical modeling of high conversion efficiency FTO/ZnO/CdS/
https://doi.org/10.1016/j.solmat.2023.112243. CZTS/MO thin film-based Solar cells: using SCAPS-1D Software, Crystals 11 (2021)
1468, https://doi.org/10.3390/cryst11121468.

10

View publication stats