energies

Review
Recent Progress and Challenges in Controlling Secondary Phases
in Kesterite CZT(S/Se) Thin Films: A Critical Review
Mohamed Yassine Zaki and Alin Velea *

National Institute of Materials Physics, Atomistilor 405A, 077125 Magurele, Romania; yassine.zaki@infim.ro
* Correspondence: alin.velea@infim.ro

Abstract: Kesterite-based copper zinc tin sulfide (CZTS) and copper zinc tin selenide (CZTSe) thin
films have attracted considerable attention as promising materials for sustainable and cost-effective
thin-film solar cells. However, the successful integration of these materials into photovoltaic devices
is hindered by the coexistence of secondary phases, which can significantly affect device perfor-
mance and stability. This review article provides a comprehensive overview of recent progress
and challenges in controlling secondary phases in kesterite CZTS and CZTSe thin films. Drawing
from relevant studies, we discuss state-of-the-art strategies and techniques employed to mitigate the
formation of secondary phases. These include a range of deposition methods, such as electrodeposi-
tion, sol-gel, spray pyrolysis, evaporation, pulsed laser deposition, and sputtering, each presenting
distinct benefits in enhancing phase purity. This study highlights the importance of employing
various characterization techniques, such as X-ray diffraction, Raman spectroscopy, scanning electron
microscopy, and energy-dispersive X-ray spectroscopy, for the precise identification of secondary
phases in CZTS and CZTSe thin films. Furthermore, the review discusses innovative strategies and
techniques aimed at mitigating the occurrence of secondary phases, including process optimization,
compositional tuning, and post-deposition treatments. These approaches offer promising avenues
for enhancing the purity and performance of kesterite-based thin-film solar cells. Challenges and
open questions in this field are addressed, and potential future research directions are proposed. By
comprehensively analyzing recent advancements, this review contributes to a deeper understanding
of secondary phase-related issues in kesterite CZT(S/Se) thin films, paving the way for enhanced
performance and commercial viability of thin-film solar cell technologies.
Citation: Zaki, M.Y.; Velea, A. Recent
Progress and Challenges in
Keywords: kesterite solar cells; CZTS; CZTSe; secondary phases
Controlling Secondary Phases in
Kesterite CZT(S/Se) Thin Films: A
Critical Review. Energies 2024, 17,
1600. https://doi.org/10.3390/
1. Introduction
en17071600
The kesterite family comprises copper zinc tin sulfide (CZTS), copper zinc tin selenide
Academic Editor: Elisa Artegiani
(CZTSe), and their sulfoselenide variant, copper zinc tin sulfoselenide (CZTSSe). These
Received: 25 February 2024 compounds belong to the class of quaternary semiconductors and share a kesterite crystal
Revised: 24 March 2024 structure. CZTS, CZTSe, and CZTSSe have drawn considerable interest in the realm of
Accepted: 25 March 2024 solar energy due to their abundance, non-toxicity, and promising optical and electronic
Published: 27 March 2024 characteristics [1]. CZTS, the sulfide counterpart, is composed of copper (Cu), zinc (Zn),
tin (Sn), and sulfur (S). On the other hand, CZTSe substitutes selenium (Se) for sulfur,
resulting in a selenide compound. CZTSSe, as the name suggests, is a combination of
both sulfur and selenium [2]. These compounds have been explored for their potential
Copyright: © 2024 by the authors.
in thin-film solar cells, offering a sustainable alternative to conventional materials [3].
Licensee MDPI, Basel, Switzerland.
The direct bandgap of these materials falls within the optimal range for solar absorption,
This article is an open access article
distributed under the terms and
approximately 1.0–1.5 eV [4]. This aligns with the solar spectrum, allowing for efficient
conditions of the Creative Commons
conversion of sunlight into electricity. Additionally, the high absorption coefficient and high
Attribution (CC BY) license (https://
extinction coefficient of kesterite make them promising for the development of thin-film
creativecommons.org/licenses/by/ solar cells with a low thickness requirement [5]. However, achieving high performance
4.0/).

Energies 2024, 17, 1600. https://doi.org/10.3390/en17071600 https://www.mdpi.com/journal/energies

Energies 2024, 17, 1600 2 of 29

kesterite solar cells is still challenging due to the narrow phase stability of the quaternary
phase, the formation of secondary phases, and the presence of defects [6].
Despite their promise, challenges such as phase stability, the formation of secondary
phases, and the presence of defects are obstacles in achieving high-performance solar
cells [7]. Various vacuum and non-vacuum deposition techniques have been explored to
synthesize CZTS and CZTSe thin films [8], such as evaporation, pulsed laser deposition,
magnetron sputtering, electrodeposition, sol-gel, and spray pyrolysis. However, different
deposition techniques and conditions can result in differences in the properties of the films,
such as phase purity, composition, morphology, and electronic properties [9]. This review
will focus on the synthesis methods of copper zinc tin sulfide (CZTS) and copper zinc tin
selenide (CZTSe), emphasizing key techniques to obtain single-phase films. Moreover,
this review aims to provide a comprehensive understanding of the impact of secondary
phases on the performance and stability of kesterite-based solar devices. By analyzing the
challenges associated with secondary phase occurrence, this study aims to identify effective
strategies for mitigating their formation and enhancing the efficiency of CZTS and CZTSe
thin-film solar cells. Additionally, we will explore the role of various deposition techniques
in controlling phase purity and discuss the importance of precise characterization methods
for identifying and quantifying secondary phases. This concise review aims to offer insights
into optimizing CZTS and CZTSe absorber layers for enhanced solar cell applications.

2. Deposition Techniques
Regarding CZT(S/Se) growth, diverse synthesis approaches have been employed for
depositing these absorber layers. In the more prevalent two-step fabrication techniques,
the initial phase involves the preparation of the Cu, Zn and Sn (CZT) metal precursor. This
precursor is then subjected to a sulfurization or selenization, followed annealing treatment,
ultimately leading to the formation of CZT(S/Se) by reaction of the elements. On the other
hand, one-step methods simplify the process by directly producing CZT(S/Se) in a single
step, which is subsequently refined through heat treatment. The efficacy of the resulting
solar cell device depends on critical factors such as the deposition rate, layer thickness,
and the specific synthesis method employed. Achieving optimal performance requires a
detailed understanding of these parameters, and the continuous exploration of synthesis
strategies.

2.1. Solution-Based Approaches

2.1.1. Electrodeposition
The electrodeposition technique has emerged as a versatile and promising approach
for the synthesis of high-quality Cu2 ZnSnS4 (CZTS) and Cu2 ZnSnSe4 (CZTSe) thin films in
solar cell applications. The process includes a three-electrode cell, consisting of a working
electrode (commonly a substrate on which deposition occurs), a counter electrode, and
a reference electrode. The working electrode is usually coated with a precursor solution
containing copper, zinc, tin, and sulfur or selenium sources. The electrochemical cell is
immersed in this precursor solution. A power supply is employed to apply a controlled
potential or current between the working and counter electrodes, facilitating the deposition
onto the working electrode. The reference electrode monitors the electrochemical potential
as sketched in Figure 1.
In recent years, electrochemical deposition techniques have gained importance as
cost-effective and environmentally friendly methods for depositing large-area thin films.
These techniques encompass both single-step and sequential electrodeposition approaches.
In the single-step method, all constituents are sourced from a single electrolyte, while in
sequential electrodeposition, different metal salts are sequentially deposited and annealed
to form the final film. Electrodeposition offers precise control over film composition and
thickness. Numerous studies have investigated the electrodeposition process, focusing on
optimizing various parameters to achieve desired film properties. One important aspect is
the composition of the electrolyte solution, where precise control over the concentration
Energies 2024, 17, 1600 3 of 29

ratios of the metal ions to be electrodeposited is essential. Hreid et al. demonstrated

that adjusting these concentrations influences the stoichiometry and phase purity of de-
posited CZTSe films [10]. Another important parameter is the deposition potential, which
modulates the rate of electrodeposition and thereby influences the crystal structure and
phase composition of the films. Azmi et al. explored this aspect by varying the deposition
potential to tune the electrochemical reduction in metal ions, they revealed that adequate
potential for CZTS phase electrodeposition is −1.1 V [11]. Furthermore, deposition time
plays an important role in determining film thickness, morphology and composition as
shown by Valdes et al. [12]. They have concluded that a CZTSe absorber deposited in
10 min lead to the best performing solar cell, and increasing in deposition time decreases
device performance. The pH of the electrolyte solution also influences the ionization state of
metal ions during electrodeposition. Variations in pH can impact the chemical composition,
morphology, and crystallinity of the deposited films, maintaining a pH = 4.8 is optimal
for achieving high-quality CZTS absorber layers [13]. The role of additives, particularly
complexing agents, should also be taken into account. These agents form stable complexes
with metal ions, influencing deposition processes. Their inclusion has been explored to
enhance uniformity, to control grain size, and to modulate crystallinity. The choice of a
specific complexing agent, or combinations of different agents, and their concentration
plays a role in tailoring the electrodeposition process [14–17] for fine-tuning film properties.
Additionally, stirring or agitation during electrodeposition ensures uniform ion distribution
Energies 2024, 17, x FOR PEER REVIEW 3 of 30
in the electrolyte solution, contributing to enhanced film quality and uniformity [17].

Figure 1. Electrodeposition technique schematic for CZT(S/Se) thin films deposition.

Figure 1. Electrodeposition technique schematic for CZT(S/Se) thin films deposition.

2.1.2. In recent years, electrochemical deposition techniques have gained importance as

Sol-Gel
cost-effective
The sol-gel and environmentally
deposition method friendly methods for
is a cost-effective anddepositing large-area
relatively simple thin films.
technique for
These techniques
synthesizing CZT(S/Se)encompass bothThe
thin films. single-step
process can and be sequential
carried out electrodeposition
in two steps, starting ap-
proaches.
with In the single-step
the preparation method,
of an aqueous all constituents
solution containing arethe
sourced
sol-gelfrom a singlefollowed
precursors, electrolyte,
by
while in sequential electrodeposition, different metal salts are sequentially
spin coating the solution onto the substrate to obtain the desired deposits as presented in deposited and
annealed
Figure to form
2. This the final
technique film. Electrodeposition
is well-developed in the thinoffers precise control
film industry over
due to its film compo-
reproducibility
sition and thickness. Numerous studies have investigated
for large-scale fabrication. However, despite its advantages, very few studies havethe electrodeposition process,
been
focusing on
conducted onoptimizing
the synthesis various parameters
of CZT(S/Se) thintofilms
achieve
usingdesired
sol-gel film properties. One im-
deposition.
portant
Theaspect
synthesisis the
of composition
CZTS and CZTSe of thethinelectrolyte solution,a where
films involves precise
meticulous control over
exploration of
the concentration
several ratios of the
critical parameters, eachmetal ions to be
influencing theelectrodeposited
properties of the is essential.
resulting Hreid
films. etTheal.
demonstrated
precursor that adjusting
composition determinesthesetheconcentrations
elemental ratios influences the stoichiometry
and, consequently, and phase
the stoichiometry
purity
of of depositedVariations
the compound. CZTSe films [10].
in the Another important
precursors concentrationsparameter
in theissolution
the deposition
have been po-
tential, which
studied modulates
to understand theimpact
their rate ofon electrodeposition
film composition. andInthereby
a study influences
conductedthe by crystal
Amrit
structure
et andCZTS
al., sol-gel phasethin
composition
films were of the films. Azmi
prepared withoutet al. explored thisThey
sulfurization. aspect by varying
investigated
the influence
the depositionofpotential
precursor to tune the electrochemical
concentration reductionofinthe
on the properties metal ions,Their
films. they findings
revealed
revealed that optimal
that adequate potentialconcentrations
for CZTS phase resulted in well-defined
electrodeposition is −1.1kesterite phase formation,
V [11]. Furthermore, dep-
uniform filmplays
osition time surfaces, and variations
an important role inindetermining
optical bandgap [18]. The substrate
film thickness, morphology temperature
and com-
is influencing
position as showncrystallinity,
by Valdes grain
et al.size,
[12].and
They structural properties.
have concluded thatKhushaim et al., have
a CZTSe absorber de-
explored
posited in 10 min lead to the best performing solar cell, and increasing in depositionfilms,
the effects of different deposition temperatures on the properties of CZTS time
decreases device performance. The pH of the electrolyte solution also influences the ioni-
zation state of metal ions during electrodeposition. Variations in pH can impact the chem-
ical composition, morphology, and crystallinity of the deposited films, maintaining a pH
= 4.8 is optimal for achieving high-quality CZTS absorber layers [13]. The role of additives,
particularly complexing agents, should also be taken into account. These agents form sta-
Energies 2024, 17, 1600 4 of 29

and have found that a substrate temperature of 350 ◦ C is ideal for obtaining adequate
properties [19]. Preheating annealing is a common practice to enhance crystallinity and
phase purity, and the variation in different environments, as explored by Ahmoum et al.,
demonstrating that CZTS films preheated in Ar and N2 exhibit enhanced crystallinity, larger
grains, uniform surface morphology and optimal elemental composition [20]. Furthermore,
additives and complexing agents in the precursor solution can influence nucleation and
growth as demonstrated by Chaudhari et al., can influence nucleation and growth [21].
Post-deposition annealing is commonly employed to enhance the crystallinity and phase
purity of CZTS and CZTSe films. The annealing conditions, including temperature and
duration, can significantly impact the structural and optoelectronic properties of the films.
Ahmed et al. investigated the effect of annealing temperatures on CZTS compounds [22].
They revealed that annealing at 450 ◦ C results in high crystalline films, with a decrease
in optical band gap to 1.6 eV and improved electrical conductivity. On the other hand,
Shaikh et al., studied the impact of annealing time on the properties of CZTS films, and
Energies 2024, 17, x FOR PEER REVIEW 4 of 30
demonstrated that longer annealing times leads to improvements in conductivity, light
absorption, and mechanical stability [23].

Figure2.2.Sol-gel
Figure Sol-gelschematic
schematicprocess
processfor
forthin
thinfilm
filmdeposition.
deposition.

2.1.3. The
Spray synthesis
Pyrolysis of CZTS and CZTSe thin films involves a meticulous exploration of
several critical parameters,
Spray pyrolysis deposition eachisinfluencing
a widely used the properties
technique in of thin
the resulting films. The
film production duepre-
to
cursor
its easy composition determines
process and relatively the elemental
simple ratios This
manipulation. and, method,
consequently,
thanksthe to stoichiometry
its simplicity
of the
and compound. Variations
reproducibility, is well-known in thefor precursors concentrations
its application in large-scalein the solutionofhave
synthesis been
thin film
studied to understand
semiconductors. One oftheir impact
the most on film composition.
significant advantages of Inthis
a study conducted
technique is thatbyitAmrit
does
et al.,
not sol-gel
require CZTS
any vacuumthin films
stepswere prepared
throughout thewithout sulfurization.
process, They investigated
making it suitable for industrial the
influence of precursor concentration on the properties of the films.
commercial production. Spray pyrolysis involves atomizing a precursor solution onto a Their findings revealed
that optimal
heated concentrations
substrate. The equipment resulted in well-defined
includes kesterite
a substrate holder, phase
spray formation,
nozzle, heater, and uniform
gas
film surfaces,
delivery systemand variations
(Figure 3). in optical bandgap [18]. The substrate temperature is influ-
encing crystallinity,
Spray grain size,
pyrolysis stands as aand structural
versatile methodproperties.
for CZTSKhushaim et al., haveoffering
thin film synthesis, exploreda
the effects of
multitude of adjustable
different deposition
parameters temperatures
that influence on the properties
resulting filmof CZTS films, and
properties. have
Among
found
these that a substrate
parameters, substratetemperature
temperature of holds
350 °Csignificance,
is ideal fordictating
obtaining adequate properties
crystallinity and grain
[19].development
size Preheating annealing is a common
[24]. Additionally, practice to
precursor enhance crystallinity
concentration serves asand phase purity,
a critical factor,
impacting film thickness
and the variation in differentand environments,
elemental composition [25].byThe
as explored pH of the
Ahmoum solution
et al., can also
demonstrating
have an influence
that CZTS the different
films preheated in Arproperties of the obtained
and N2 exhibit enhancedCZTS films aslarger
crystallinity, statedgrains,
by Kumaruni-
et al. [26].
form Furthermore,
surface morphology theandchoice of annealing
optimal elemental conditions
compositionpost-deposition is important
[20]. Furthermore, addi-
in determining
tives the finalagents
and complexing film structure and properties
in the precursor [27].can
solution Kamoun
influenceet al. shown that
nucleation and
variations in spray duration influences the resulting CZTS films,
growth as demonstrated by Chaudhari et al., can influence nucleation and growth [21]. with the film having
the most adequate
Post-deposition properties
annealing being obtained
is commonly at antoannealing
employed enhance the temperature
crystallinity 550 ◦phase
of and C in
10 min [28].
purity of CZTS and CZTSe films. The annealing conditions, including temperature and
duration, can significantly impact the structural and optoelectronic properties of the films.
Ahmed et al. investigated the effect of annealing temperatures on CZTS compounds [22].
They revealed that annealing at 450 °C results in high crystalline films, with a decrease in
optical band gap to 1.6 eV and improved electrical conductivity. On the other hand,
Shaikh et al., studied the impact of annealing time on the properties of CZTS films, and
demonstrated that longer annealing times leads to improvements in conductivity, light
absorption, and mechanical stability [23].

2.1.3. Spray Pyrolysis

Spray pyrolysis deposition is a widely used technique in thin film production due to
its easy process and relatively simple manipulation. This method, thanks to its simplicity
 Energies2024,
Energies 2024,17,
17,1600
x FOR PEER REVIEW 55 of
of 29
30

Figure3.3.Sketch
Figure Sketchof
ofSpray
Spraypyrolysis
pyrolysisdeposition
depositionmethod.
method.

2.2. Physical-Based
Spray pyrolysis Approaches
stands as a versatile method for CZTS thin film synthesis, offering a
2.2.1. Evaporation
multitude of adjustable parameters that influence the resulting film properties. Among
theseEvaporation
parameters,techniques
substrate have temperature holdsemployed
been widely significance, dictating crystallinity
by researchers for depositing and
grain size development
CZT(S/Se) absorber layers. [24]. Additionally,
The development precursor
of these concentration
layers throughserves
variousas evaporation
a critical fac-
tor, impacting
technologies film
such as thickness
electron beamand evaporation,
elemental composition [25]. The
co-evaporation, rapidpH of the evaporation,
thermal solution can
also have an influence the different properties of the obtained
and thermal evaporation has led to the fabrication of high-quality absorber materials. CZTS films as stated by
Evap-
Kumar methods
oration et al. [26].areFurthermore,
straightforward the choice of annealing
in principle and enableconditions post-deposition
the production of films is im-
with
portant in
excellent determining
quality. However, thecontrolling
final film structure and properties
the stoichiometry [27]. Kamoun
of the elements et al. shown
is challenging [29],
that variations
resulting in lower in cell
spray durationAdditionally,
efficiency. influences thetheresulting CZTS films,
vacuum-based with the
deposition film wastes
process having
the most
source adequate
materials, properties
leading being obtained
to relatively high costs.at an annealing temperature of 550 °C in 10
min This
[28]. technique utilizes a vacuum chamber and an evaporation source, typically a
heated crucible. In this process, the material is vaporized and deposited onto a substrate
2.2. Physical-Based
placed strategicallyApproaches
within the vacuum environment. The substrate may have controlled
movement for
2.2.1. Evaporation uniform film deposition (Figure 4). The deposition of CZT(S/Se) films
by evaporation can be achieved through two different approaches: single-step deposi-
Evaporation techniques have been widely employed by researchers for depositing
tion [30,31], where all the precursors are simultaneously deposited and then followed by
CZT(S/Se) absorber layers. The development of these layers through various evaporation
sulfurization, and sequential two-step deposition using different metallic or binary precur-
technologies such as electron beam evaporation, co-evaporation, rapid thermal evapora-
sors, in different combinations and sequences, such as Cu/Sn/Zn/Cu, Cu/Sn/Cu/Zn [32],
tion, and thermal evaporation has led to the fabrication of high-quality absorber materials.
Cu-ZnS-Sn [33] or CuSn/Zn/Se/CuSn/Se [34], followed by annealing with a sulfur or
Evaporation methods are straightforward in principle and enable the production of films
selenium source.
with excellent quality. However, controlling the stoichiometry of the elements is challeng-
ing [29],
2.2.2. resulting
Pulsed Laserin lower cell efficiency. Additionally, the vacuum-based deposition pro-
Deposition
cess Pulsed
wastes Laser
sourceDeposition
materials, (PLD)
leadingremains
to relatively
one ofhigh costs.methods for producing high-
the best
quality CZT(S/Se) thin films with complex compositions. evaporation
This technique utilizes a vacuum chamber and an This technique source,
is knowntypically
for itsa
heated crucible. In this process, the material is vaporized and deposited
numerous advantages, such as its simplicity and process flexibility, improved crystallinity, onto a substrate
placed
and the strategically
ability to obtain withincleanthefilms
vacuumowingenvironment.
to the absence Theofsubstrate maygases.
atmospheric have controlled
The PLD
movement for uniform film deposition (Figure 4). The deposition
comprises a laser system, target material, vacuum chamber, and a substrate holder. of CZT(S/Se) films byA
evaporation can be achieved through two different approaches:
high-energy laser vaporizes the target, creating a plume that deposits onto a substrate single-step deposition
[30,31],
in where all
the vacuum the precursors
chamber (Figure 5). arePLD
simultaneously
systems manage deposited and then
deposition followed
rate, by sul-
temperature,
furization, and sequential two-step deposition using different metallic
and pressure, often incorporating in situ monitoring tools for real-time analysis. However, or binary precur-
sors,
the in different
literature showscombinations
limited work andconducted
sequences,usingsuch this
as Cu/Sn/Zn/Cu,
method, despite Cu/Sn/Cu/Zn [32],
its significant
Cu-ZnS-Sn for
advantages [33]CZT(S/Se)
or CuSn/Zn/Se/CuSn/Se [34], followed by annealing with a sulfur or sele-
thin film deposition.
nium source.
Energies 2024, 17, x FOR PEER REVIEW 6 of 30
Energies 2024, 17, 1600 6 of 29

Figure 4. Evaporation schematic setup for CZT(S/Se) films synthesis.

2.2.2. Pulsed Laser Deposition

Pulsed Laser Deposition (PLD) remains one of the best methods for producing high-
quality CZT(S/Se) thin films with complex compositions. This technique is known for its
numerous advantages, such as its simplicity and process flexibility, improved crystallin-
ity, and the ability to obtain clean films owing to the absence of atmospheric gases. The
PLD comprises a laser system, target material, vacuum chamber, and a substrate holder.
A high-energy laser vaporizes the target, creating a plume that deposits onto a substrate
in the vacuum chamber (Figure 5). PLD systems manage deposition rate, temperature,
and pressure, often incorporating in situ monitoring tools for real-time analysis. However,
the literature shows limited work conducted using this method, despite its significant ad-
vantages for CZT(S/Se)
Evaporation
Figure 4.4.Evaporation
Figure thin setup
schematic
schematic film
setupdeposition.
forCZT(S/Se)
for CZT(S/Se) films
films synthesis.
synthesis.

2.2.2. Pulsed Laser Deposition

Pulsed Laser Deposition (PLD) remains one of the best methods for producing high-
quality CZT(S/Se) thin films with complex compositions. This technique is known for its
numerous advantages, such as its simplicity and process flexibility, improved crystallin-
ity, and the ability to obtain clean films owing to the absence of atmospheric gases. The
PLD comprises a laser system, target material, vacuum chamber, and a substrate holder.
A high-energy laser vaporizes the target, creating a plume that deposits onto a substrate
in the vacuum chamber (Figure 5). PLD systems manage deposition rate, temperature,
and pressure, often incorporating in situ monitoring tools for real-time analysis. However,
the literature shows limited work conducted using this method, despite its significant ad-
vantages for CZT(S/Se) thin film deposition.

Figure5.5.Schematic
Figure Schematicof
ofaaclassical
classicalPulsed
PulsedLaser
LaserDeposition
Depositiontechnique.
technique.

PLD
PLDcan canbebeused
used forfor
depositing
depositing thin films
thin on diverse
films substrates,
on diverse offering
substrates, versatility
offering [35].
versatility
Recognized
[35]. Recognizedfor its for
high itsdeposition rate and
high deposition quality
rate film growth
and quality facilitated
film growth by high-energy
facilitated by high-
processes [36], PLD[36],
energy processes presents
PLD apresents
convenient method for
a convenient CZTS film
method synthesis.
for CZTS film This can occur
synthesis. This
in
cana one-step
occur in aprocess
one-step by process
employing a CZTS target
by employing a CZTSandtarget
a heated andsubstrates at elevated
a heated substrates at
temperatures, or in a two-step process involving the deposition
elevated temperatures, or in a two-step process involving the deposition of metallic (Cu,of metallic (Cu, Zn, and
Sn)
Zn,films
and Sn) followed by sulfurization
films followed [37]. Key [37].
by sulfurization parameters, includingincluding
Key parameters, the substrate-to-target
the substrate-
distance,
to-targetsubstrate
distance,orientation and temperature,
substrate orientation laser energy,
and temperature, andenergy,
laser target composition, influ-
and target compo-
ence film
sition, properties.
influence filmThe choice ofThe
properties. metallic
choice targets allows targets
of metallic control allows
over layer thickness
control and
over layer
roughness, while a single CZTS target, comprising is preferred for achieving stoichiometric
Cu2 ZnSnS4 materials [38]. Despite its advantages, PLD encounters challenges such as
droplet formation leading to unwanted phases and inhomogeneity, especially when using
Figure
multiple5. Schematic
crystallineof aphase
classical PulsedDrawbacks
targets. Laser Deposition
includetechnique.
extended processing times for large
film thicknesses and challenges in producing extensive area films [39,40].
PLD can be used for depositing thin films on diverse substrates, offering versatility
[35].
2.2.3.Recognized
Magnetronfor its high deposition rate and quality film growth facilitated by high-
Sputtering
energySputtering
processesis[36],a widelyPLD used
presents a convenient
fabrication methodmethod
offeringfor CZTS film
uniformity andsynthesis. This
reproducibility
can occur in a one-step process by employing a CZTS target and
in large-scale production, particularly in solar cell manufacturing. Magnetron sputtering a heated substrates at
elevated temperatures, or in a two-step process involving the
system is a physical vapor deposition technique widely used for producing thin films deposition of metallic (Cu,
Zn,
withand Sn) films
excellent followed by
uniformity. sulfurization
This [37]. Key
system employs parameters, including
a magnetron—a the substrate-
high-powered magnet
to-target distance,
that enhances the substrate
sputteringorientation and temperature,
process (Figure laser energy,
6). Key parameters and target
like pressure, compo-
power, and
sition, influence film properties. The choice of metallic targets allows
deposition time can be adjusted for optimal film quality and desired properties. However, control over layer
 2.2.3. Magnetron Sputtering
Sputtering is a widely used fabrication method offering uniformity and reproduci-
bility in large-scale production, particularly in solar cell manufacturing. Magnetron sput-
tering system is a physical vapor deposition technique widely used for producing thin
Energies 2024, 17, 1600 films with excellent uniformity. This system employs a magnetron—a high-powered7mag- of 29
net that enhances the sputtering process (Figure 6). Key parameters like pressure, power,
and deposition time can be adjusted for optimal film quality and desired properties. How-
ever, challenges
challenges such
such as theas theofloss
loss tinof tin during
during high-temperature
high-temperature post-deposition
post-deposition treatment
treatment and
andformation
the the formation of secondary
of secondary phases phases
needneed
to beto be addressed.
addressed.

Figure 6.
Figure 6. Schematic
Schematic diagram
diagram of
of Magnetron
Magnetron sputtering
sputtering deposition
deposition method.
method.

Magnetronsputtering
Magnetron sputteringis is renowned
renownedfor forits
its ability
ability to
to synthesize
synthesize thin
thin films
films on
on extensive
extensive
substrates [41].
substrates [41]. In CZTS synthesis, the system allows for substrate heating during deposi-
tion or
tion or sulfurization
sulfurization after
after sputtering
sputtering [42,43].
[42,43]. It supports
supports diverse
diverse targets,
targets, including
including metallic
metallic
precursors,
precursors, binary
binary sulfide
sulfide targets,
targets, or
or single
single quaternary
quaternary targets
targets [44].
[44]. The
The choice
choice of
of direct
direct
current
current (DC)
(DC) sputtering
sputtering for
for elemental
elemental conductive
conductive targets
targets (Cu,
(Cu, Zn,
Zn, Sn)
Sn) and
and radio frequency
frequency
(RF)
(RF)for
forbinary
binaryand quaternary
and quaternary targets ensures
targets efficient
ensures deposition
efficient [45,46].
deposition Magnetron
[45,46]. sput-
Magnetron
tering provides
sputtering control
provides overover
control chemical composition,
chemical composition,film film
thickness, uniformity,
thickness, adhesion,
uniformity, adhe-
and
sion,substrate coverage,
and substrate achieving
coverage, high deposition
achieving rates and
high deposition ratespurity [47,48].[47,48].
and purity Challenges
Chal-
such as target poisoning and cracking at high power need consideration
lenges such as target poisoning and cracking at high power need consideration [49,50]. [49,50].

3.
3. Secondary
Secondary Phases
Phases in
in CZT(S/Se)
CZT(S/Se)
3.1. Formation of Secondary Phases
3.1. Formation of Secondary Phases
The formation of secondary phases stands out as a significant challenge in the growth
The formation of secondary phases stands out as a significant challenge in the growth
of CZTS and CZTSe absorber layers. Its primary source is the off-stoichiometric compo-
of CZTS and CZTSe absorber layers. Its primary source is the off-stoichiometric composi-
sition in the CZT(S/Se) films [51,52]. Various factors such as the decomposition of the
tion in the CZT(S/Se) films [51,52]. Various factors such as the decomposition of the
CZT(S/Se) at high temperatures [53], variations in precursor deposition methods [54],
CZT(S/Se) at high temperatures [53], variations in precursor deposition methods [54], or
or the sulfurization/selenization treatment parameters [55] influences the formation of
the sulfurization/selenization
secondary phases. While theretreatment parameters
are various secondary [55] influences
phases theappear
that can formation of sec-
within the
ondary phases. While there are various secondary phases that can appear within the
CZTS or CZTSe films, in this review we will focus on the most frequently occurring phases CZTS
orthe
in CZTSe
two films, in this Binary
compounds. review alloys
we will focus
like Cux on the most
(S/Se), frequently
Zn(S/Se), occurring
Snx (S/Se) phases in
y , Mo(S/Se)x or
ternary compositions such as Cu-Sn-(S/Se) are the most common phases to form during
CZT(S/Se) film growth. The delicate balance of precursor ratios and an overabundance of
the Cu, Zn, Sn and S/Se elements can influence the composition, introducing unwanted
phases and affecting the properties of the absorber layer.
The formation of copper-based phases such as CuS and Cu2 S is common under excess
of copper conditions [56]. Cu-rich environment can lead to increased doping of CZTS,
proving harmful to solar cells. For this reason, the current focus is on growing CZTS with
a Cu-poor and Zn-rich composition. Moreover, the excess in zinc might contribute to
the appearance of zinc sulfide (ZnS) [57]. This phase is highly observed at both the front
and back interfaces within the CZTS compound. The impact of ZnS phase was found to
be detrimental to the solar device, especially on the surface of CZTS. Further, tin sulfide
compounds (Snx Sy ) and their impact on CZTS solar cells have been less explored. The
formation of the SnS, SnS2 and Sn2 S3 phases is due to the presence of a surplus of tin in
the development of CZTS [58,59]. Snx Sy can be detected on both the surface and back of
Energies 2024, 17, 1600 8 of 29

the CZTS film. Additionally, the emergence of MoS2 can be attributed to the reaction of
the molybdenum back contact with sulfur, presenting another facet of secondary phase
formation influenced by the synthesis environment. In the case of Cux Sny Sz compounds
such as Cu2 SnS3 (CTS), which the most frequent secondary phase in CZTS films, the
apparition of these phases is due to several reasons such as low zinc content, incomplete
reaction at low temperature during film growth, or the decomposition of the CZTS at high
temperature.
Similarly, in the context CZTSe thin films, secondary phases may arise due to the same
factors. Binary phases such as Cux Se, Snx Sey , ZnSe and MoSe2 may form as a consequence
of the reaction of Se with the related elements if they are in excess [60], while the case
of Cux Sny Sez and mainly the Cu2 SnSe3 (CTSe) phase is resembling its homologue CTS.
Similar to CZTS, the balance of precursor ratios plays a role in determining the composition
and subsequent phase evolution in CZTSe films.
Understanding and controlling the deposition parameters and chemical reactions are
essential for minimizing the presence of unwanted secondary phases, thereby optimiz-
ing the structural and electronic properties of CZT(S/Se) absorber layers for enhanced
photovoltaic performance. Additionally, consideration of annealing treatments becomes
imperative in managing secondary phase formation, adding another layer of complexity to
the fabrication process.

3.2. Identification of Secondary Phases

The characterization of secondary phases in CZTS and CZTSe thin films leads to the
understanding the structural and compositional properties. Several main characterization
techniques are employed for this purpose. X-ray diffraction (XRD) is a fundamental
technique that helps identify the crystalline phases present in the films by analyzing
their diffraction patterns. Raman spectroscopy is employed to study vibrational modes,
providing insights into the chemical composition and crystal structure. Scanning electron
microscopy (SEM) and transmission electron microscopy (TEM) are essential for visualizing
the microstructure and morphology, aiding in the identification of secondary phases.
Energy-dispersive X-ray spectroscopy (EDS) coupled with SEM or TEM provides elemental
composition information, aiding in mapping the distribution of elements and phases
within the films. X-ray photoelectron spectroscopy (XPS) is valuable for determining the
chemical states of elements and detecting surface composition variations. These techniques
collectively offer a comprehensive understanding of secondary phases in CZTS and CZTSe
films, contributing to the optimization of their growth processes and enhancing their
potential in solar cell applications. Here, we will address how some of the most used
characterization techniques such as XRD, Raman, and SEM-EDX can be utilized to detect
the presence of secondary phases in CZT(S/Se) films.

3.2.1. Structural Analysis

X-ray Diffraction
X-ray diffraction (XRD) is employed to analyze the crystallographic structure of CZTS
thin films and identify the presence of unwanted secondary phases. The distinctive peaks
in the XRD pattern allow for the discrimination of various phases, such as Cux S, Snx Sy ,
ZnS, MoSx , CTS and others, based on their unique crystal structures. Challenges may
arise, particularly when secondary phases such as cubic ZnS and cubic, monoclinic or
tetragonal CTS have similar crystal structures to CZTS, making their identification more
complex. Despite these challenges, XRD remains a fundamental technique, providing
valuable information about the composition and crystalline nature of CZTS films. Several
studies have analyzed the XRD patterns of CZTS, ZnS, and CTS compounds, in order to
understand the main divergences of these phases [61–63]. Berg et al. prepared CZTS, ZnS
and CTS films by electrodeposition and compared the X-ray diffractograms of the different
samples. They confirmed that ZnS and CTS closely resemble CZTS in their X-ray patterns.
While cubic ZnS has the fewest peaks, the tetragonal CZTS phase and monoclinic ternary
Energies 2024, 17, 1600 9 of 29

phase exhibit additional minor peaks due to lower symmetry [64]. Distinguishing between
CZTS, ZnS and CTS relies on identifying these minor peaks, although their absence does
not conclusively exclude the presence of the respective phase, especially in the context
of a textured film. In the same study, the group compared between the three phases’
main peak at approximately 2θ = 28.5◦ . They found that the angular positions of ZnS,
CTS and CZTS main peaks, are differing within an angular range of 0.2◦ , suggesting the
potential possibility to distinguish individual CTS and ZnS phases from the CZTS [12]. As
an example of secondary phases identification relying on minor peaks, Zaki et al., prepared
CZTS films by annealing in different atmospheres and for different durations sputtered
ZnS layers with two thicknesses (150 and 200 nm) deposited onto a CTS layer [13]. The
International Center for Diffraction Data (ICDD) were used to identify the CZTS and the
coexistent secondary phases. They reported that most the peaks in the diffractograms
belong to the CZTS phase, while a tiny peak at 2θ = 26.91◦ makes it possible to identify the
presence of the hexagonal ZnS phase. On the other hand, the SnS2 is easily distinguished
with a peak at around 2θ = 50◦ in the films annealed in Sn+S atmosphere, due to excess
in Sn. Contrarily, the CuS (2θ = 31.97◦ ) phase was observed in one of the sulfurized
(annealed in S only) CZTS films, due to the Sn-poor composition of the film as observed
in Figure 7 [65]. The case of copper sulfides such as CuS and Cu2 S is different, since
they can be easily identified through XRD, as their unique diffraction peaks (2θ = 31.88◦ ,
52.58◦ , and 48.23◦ for CuS; and 2θ = 27.83◦ , 32.23◦ , 46.28◦ , and 54.78◦ for Cu2 S) significantly
differ from those of CZTS. Furthermore, secondary phases like SnS, SnS2 , and Sn2 S3 are
readily detectable within CZTS films using X-ray diffraction. This detection is facilitated by
the distinct diffraction patterns exhibited by these phases, which differ significantly from
that of CZTS. Each secondary phase possesses characteristic diffraction peaks at specific
angles as presented in Table 1, providing clear signatures for their identification. For
instance, SnS typically displays intense peaks at 2θ angles of 22.01◦ , 26.00◦ , 27.47◦ , 30.47◦ ,
31.53◦ , 31.97◦ , 39.04◦ , 45.49◦ , 48.50◦ , 51.31◦ , 53.14◦ , and 56.67◦ . Similarly, SnS2 presents
distinctive peaks at 2θ angles of 15.02◦ , 28.19◦ , 30.26◦ , 32.12◦ , 41.88◦ , 46.12◦ , 49.96◦ , and
52.45◦ . Moreover, Sn2 S3 can be identified by its prominent peaks at 2θ angles of 12.63◦ ,
16.10◦ , 21.49◦ , 23.77◦ , 27.33◦ , 27.68◦ , 30.91◦ , 32.53◦ , 33.53◦ , 33.79◦ , 35.89◦ , 36.49◦ , 37.93◦ ,
and 39.85◦ . These distinctive diffraction patterns enable the straightforward detection and
characterization of Sn-containing secondary phases within CZTS films using XRD analysis.
These last three phases are rarely observed in the CZTS system probably due to the very
volatility aspect of tin. MoS2 has distinct peaks in its XRD pattern that can be differentiated
from the peaks of CZTS. MoS2 typically exhibits prominent peaks at specific angles, such as
14.4◦ , 33.8◦ , 39.6◦ , and 58.1◦ (2θ), corresponding to its crystal structure. By comparing the
measured XRD pattern of the CZTS film with reference patterns for MoS2 , one can identify
the presence of this secondary phase.
The detection of secondary phases in CZTSe films, it is quite similar with its homologue
CZTS, since CZTSe along with cubic ZnSe and cubic or monoclinic Cu2 SnSe3 (CTSe) have
nearly identical XRD patterns. However, unlike Cu2 S in CZTS system, the cubic Cu2 Se
also share remarkably similar structures and unit cell sizes with CZTSe [66,67]. Despite
CZTSe having a tetragonal-based structure, its reflections often overlap with those of
the mentioned phases due to their common cubic structures, close lattice parameters, and
similar atomic scattering factors of Cu+ and Zn2+ . In the case of CZTSe, similar observations
(as for CZTS, ZnS and CTS) can be made regarding the angular differences in main peaks
compared to ZnSe and CTSe. The largest difference observed for ZnSe is 0.15◦ , while
for the cubic-CTSe, it is 0.16◦ as explained by Salome et al. [68]. These slight angular
variations, though relatively small, hint at the potential to distinguish between CZTSe
and its constituent phases, ZnSe and CTSe. In Figure 8, are presented the diffractograms
of annealed CTSe\ZnSe stacks prepared by magnetron sputtering along with the XRD
patterns of the most frequent secondary phases in CZTSe films. Catana et al., synthesized in
a first step CTSe films from different stacks (Sn\Cu, SnSe2 \Cu, Sn\Cu2 S, and SnSe2 \Cu2 Se),
then a ZnSe layer was added on top of the obtained CTSe films and the combinations were
 Energies 2024, 17, 1600 10 of 29

annealed in Se atmosphere at 550 ◦ C [69]. The identification of the ZnSe phase was almost
impossible when they compared its XRD patterns to the prepared CZTSe films. While the
diffraction peaks of cubic-ZnSe and cubic-CTSe overlap with those of CZTSe, each of the
three phases exhibits additional tiny peaks, which can help in distinguishing between them.
On the other hand, CZTSe has double peaks near 65◦ and 72◦ with a very low intensity,
yet, the peaks at 53.39◦ and 53.53◦ are used for confirming the presence of CZTSe [68].
Here again, using only XRD measurements can be challenging to ascertain the existence of
these phases, and the absence of the unique peaks does not definitively imply their absence.
Some distinguishable phases, such as CuSe, monoclinic Cu2 Se, SnSe, SnSe2 , and Sn2 S3 can
be differentiated from CZTSe in XRD due to their distinct structures and cell parameters
as observed in Figure 8. The identification of secondary phases, particularly CuSe and
monoclinic Cu2 Se, in CZTSe using X-ray diffraction is a well-established process. The
unique crystal structures of CuSe and monoclinic Cu2 Se contribute to their characteristic
XRD peaks at specific 2θ angles, making them easily distinguishable from the main CZTSe
phase. Similarly, the detection of tin selenide secondary phases, including SnSe and SnSe2 ,
in CZTSe is facilitated by XRD analysis. The distinctive crystal structures of these tin
selenides result in characteristic diffraction patterns with well-defined peaks at specific
angles. The main XRD characteristic peaks of the MoSe2 phase typically include prominent
peaks at 2θ around 14.4◦ , 33.8◦ , 39.6◦ , and 58.1◦ . Detecting MoSe2 in CZTSe films using
XRD can be both feasible and challenging. Feasibility depends on factors such as the
concentration of MoSe2 , film thickness, and the overall crystalline quality of the sample. If
MoSe2 is present in a sufficient quantity and is well crystallized, its characteristic peaks can
be distinguished in the XRD pattern. However, challenges may arise if MoSe2 is present
in low concentrations or if the film has poor crystallinity, leading to broader or weaker
diffraction peaks that might be harder to identify against the background of CZTSe peaks.
Energies 2024, 17, x FOR PEER REVIEW In Table 2 are summarized the most intense XRD peaks of the CZTSe phase and the 10 related
of 30
recurrent secondary phases following their ICDD card number.

Figure
Figure7. X-ray diffractograms
7. X-ray diffractogramsof of
CZTS
CZTSfilms obtained
films onon
obtained ZnSZnSlayers with
layers two
with different
two thick-
different thicknesses
nesses (150 and 200 nm) deposited on top of CTS films and annealed in different atmospheres for
(150 and 200 nm) deposited on top of CTS films and annealed in different atmospheres for different
different times. The ZnS phase (hexagonal, ICDD 04-012-8144) is indicated with “*”, the CuS phase
times. The ZnS phase (hexagonal, ICDD 04-012-8144) is indicated with “*”, the CuS phase (hexagonal,
(hexagonal, ICDD 04-008-8460) is indicated with “#”, and the SnS2 phase (hexagonal, ICDD 00-021-
ICDD
1231) 04-008-8460)
is indicated with is indicated
“@”. with “#”,
Reproduced with and the SnS[65].
permission 2 phase (hexagonal, ICDD 00-021-1231) is
indicated with “@”. Reproduced with permission [65].
Table 1. CZTS and most frequent secondary phases XRD main peaks following their ICDD cards.
The most intense peak of each phase is bolded.

Compound Most Intense XRD Peaks (°) ICDD Card Number

16.32, 18.24, 23.12, 28.44, 29.64, 32.93, 36.97,
Cu2ZnSnS4 37.90, 44.94, 47.31, 56.17, 58.85, 69.08, 69.21, 01-080-8225
Energies 2024, 17, 1600 11 of 29

Table 1. CZTS and most frequent secondary phases XRD main peaks following their ICDD cards.
The most intense peak of each phase is bolded.

Compound Most Intense XRD Peaks (◦ ) ICDD Card Number

16.32, 18.24, 23.12, 28.44, 29.64, 32.93, 36.97, 37.90,
Cu2 ZnSnS4 01-080-8225
44.94, 47.31, 56.17, 58.85, 69.08, 69.21, 76.39, 78.71
28.44, 32.96, 47.31, 56.13, 58.86, 69.14, 76.38, 78.75
01-089-2877 (cubic);
(cubic); 16.06, 18.02, 20.88, 28.40, 31.37, 32.89, 47.20,
Cu2 SnS3 04-010-5719 (monoclinic);
56.07, 76.17 (monoclinic); 28.53, 33.07, 47.47; 56.32,
04-009-7947 (tetragonal)
69.38, 76.68, 79.04 (tetragonal)
10.80, 27.12, 27.68, 29.27, 31.78, 32.85, 38.83, 43.10,
CuS 44.30, 47.78, 47.94, 52.71, 56.25, 57.20, 58.68, 59.34, 00-006-0464
63.53, 67.30, 69.34, 69.99, 73.99, 77.77, 79.07
Cu2 S 15.91, 22.58, 27.76, 32.11, 36.10, 39.64, 46.10, 51.92, 54.67 00-053-0522
22.01, 26.00, 27.47, 30.47, 31.53, 31.97, 39.04, 45.49,
SnS 00-039-0354
48.50, 51.31, 53.14
SnS2 15.02, 28.19, 30.26, 32.12, 41.88, 46.12, 49.96, 52.45 00-023-0677
12.63, 16.10, 21.49, 23.77, 27.33, 27.68, 30.91, 32.53,
Sn2 S3 00-014-0619
33.53, 33.79, 35.89, 36.49, 37.93, 39.85
28.42, 32.93, 47.27, 56.08, 58.81, 69.08, 76.32, 78.68
(cubic); 26.91, 28.50, 30.52, 39.61, 47.56, 51.77, 55.49, 01-071-5976 (cubic);
ZnS
56.39, 57.57, 59.00, 63.55, 66.00, 72.92, 76.03, 77.81, 79.05 00-036-1450 (hexagonal)
(hexagonal)
14.37, 29.02, 32.67, 33.50, 35.87, 39.53, 44.15, 49.78,
MoS
Energies 2024, 17, x FOR
2 PEER REVIEW 55.97, 58.33, 60.14, 62.81, 66.46, 68.47, 68.99, 70.14, 00-037-1492 12 of 30
72.78, 75.98, 77.57, 78.11, 80.18, 85.16, 86.71

Figure8.8.X-ray
Figure X-raydiffractograms
diffractogramsof
ofCZTSe
CZTSefilms
filmsdeposited
depositedon
onSLG
SLGusing
usingdifferent
differentstacks.
stacks.Reproduced
Reproduced
withpermission
with permission[69].
[69].

Table 2. CZTSe and most frequent secondary phases main XRD peaks following their ICDD cards.
The most intense peak of each phase is bolded.

Compound Most Intense XRD Peaks (°) ICDD Card Number

15.61, 17.41, 22.06, 27.14, 28.31, 35.25, 36.12,
38.81, 42.78, 42.88, 45.00, 45.09, 48.60, 53.34,
Cu2ZnSnSe4 04-019-1866
53.51, 54.10, 60.90, 63.83, 65.53, 65.81, 68.59,
72.29, 72.43, 72.87, 72.93, 83.10, 83.29
Energies 2024, 17, 1600 12 of 29

Table 2. CZTSe and most frequent secondary phases main XRD peaks following their ICDD cards.
The most intense peak of each phase is bolded.

Compound Most Intense XRD Peaks (◦ ) ICDD Card Number

15.61, 17.41, 22.06, 27.14, 28.31, 35.25, 36.12, 38.81,
42.78, 42.88, 45.00, 45.09, 48.60, 53.34, 53.51, 54.10,
Cu2 ZnSnSe4 04-019-1866
60.90, 63.83, 65.53, 65.81, 68.59, 72.29, 72.43, 72.87,
72.93, 83.10, 83.29
27.09, 31.38, 44.97, 53.29, 55.86, 65.49, 72.23, 74.42
03-065-7524 (cubic);
Cu2 SnSe3 (cubic); 15.33, 19.99, 27.08, 29.66, 29.98, 31.02, 37.45,
00-056-1111 (monoclinic)
45.06, 53.28, 65.60, 72.30 (monoclinic)
25.70, 26.29, 27.80, 30.15, 31.01, 40.73, 45.11, 45.47,
CuSe 00-027-0185
49.75, 53.34, 54.16, 56.10, 64.82, 66.06, 69.75, 73.39
27.10, 31.39, 44.99, 53.31, 55.89, 65.52, 72.26, 74.45,
83.01, 89.32 (cubic); 12.95, 25.25, 25.36, 26.07, 26.32,
26.44, 35.88, 37.04, 38.32, 38.49, 38.68, 38.82, 39.05,
39.20, 39.31, 39.42, 39.66, 40.04, 40.27, 40.42, 40.93,
41.24, 41.34, 41.64, 41.84, 42.37, 43.00, 43.20, 43.57,
43.88, 44.16, 44.34, 44.42, 44.95 47.92,48.88, 49.89, 51.23, 01-088-2043 (cubic)
Cu2 Se
51.51, 51.71, 51.85, 52.01, 52.32, 52.64; (monoclinic) 00-058-0228 (monoclinic)
12.96, 25.24, 25.35, 26.08, 26.46, 38.55, 38.71, 38.98,
39.59, 39.77, 39.85, 40.07, 40.68, 41.39, 41.66, 42.74,
43.49, 43.60, 43.87, 44.39, 44.98, 45.18, 45.46, 45.71,
45.99, 47.65, 50.52, 51.07, 51.42, 51.68, 52.10, 52.60,
53.21, 53.66, 53.93, 60.61
15.40, 21.47, 25.31, 26.45, 29.42, 30.46, 31.08, 37.28,
37.78, 38.03, 40.58, 41.36, 43.34, 43.53, 44.32, 47.04,
SnSe 47.25, 49.10, 49.71, 51.04, 51.95, 52.04, 52.43, 52.55, 00-048-1224
54.47, 56.85, 57.66, 60.00, 61.05, 61.63, 62.22, 63.31,
63.90, 66.21, 67.07, 67.79, 69.10
14.42, 26.99, 29.07, 30.73, 40.09, 44.23, 47.68, 50.08,
SnSe2 52.59, 55.65, 56.82, 57.81, 60.27, 64.01, 67.07, 67.23, 01-089-2939
73.70, 76.26, 77.74, 78.11, 80.267
ZnSe 27.13, 31.43, 45.05, 53.38, 55.96, 65.61, 72.37, 74.56, 83.14 01-071-5978
13.68, 27.57, 31.38, 32.15, 34.37, 37.83, 41.89, 42.25,
47.45, 53.26, 55.86, 56.93, 57.80, 59.61, 63.41, 65.48,
MoSe2 65.93, 66.46, 67.26, 69.45, 72.20, 72.46, 73.14, 73.82, 04-004-8782
76.26, 80.83, 81.74, 83.87, 86.15, 90.31, 91.36, 91.36,
92.26, 92.99, 95.03, 97.90, 98.56, 99.22, 99.72

Raman Spectroscopy
The detection of secondary phases in CZT(S/Se) films presents distinct challenges
when employing only XRD. This technique relies on the distinct patterns of diffraction
peaks to identify different phases based on their crystal structures. As shown, CZT(S/Se)
and certain secondary phases may exhibit similar XRD patterns due to comparable crystal
structures, making their differentiation challenging. On the other hand, Raman spec-
troscopy offers a complementary approach. It is highly sensitive to molecular vibrations
and provides detailed information about chemical composition. Raman spectra can reveal
unique vibrational modes for each phase, offering a more specific fingerprint for identifi-
cation. Despite the challenge of similar XRD patterns in CZT(S/Se), Raman spectroscopy
becomes a valuable tool in distinguishing secondary phases, providing a nuanced analysis
of the molecular composition and facilitating a more precise characterization of complex
CZT(S/Se) thin films. However, few signals of some secondary phases can also overlap
with the main CZTS or CZTSe phases, making it challenging to precisely identify sec-
ondary phases. Additionally, the laser power used in Raman spectroscopy may induce
Energies 2024, 17, 1600 13 of 29

sample heating, potentially altering the material properties during analysis. Another no-
table disadvantage of micro-Raman spectroscopy in the context of CZT(S/Se) films is its
inherently localized analysis. The technique typically probes a small area of the sample,
which can be a limitation when dealing with heterogeneous films or when aiming for a
comprehensive understanding of the material across larger surfaces. This localized nature
may lead to a potential oversight of variations in secondary phase distribution throughout
the sample, for that reason, it is mandatory to perform several analyses on different areas
of the sample. In addition, one of the Raman spectroscopy aspects is its sensitivity to
the excitation wavelength. Different phases within CZT(S/Se) films may exhibit distinct
Raman signatures under specific excitation wavelengths. This wavelength dependence
can be advantageous for selectively probing certain phases, enhancing the specificity of
the analysis. However, it also introduces a challenge because optimal wavelengths for one
phase might not be suitable for others. Therefore, the choice of excitation wavelength in
Raman spectroscopy is an important consideration, and a comprehensive understanding of
the material may require experimentation with various wavelengths to ensure effective de-
tection and characterization of all relevant phases. Therefore, careful consideration of these
advantages and limitations is crucial when employing Raman spectroscopy for secondary
phase detection, necessitating complementary techniques to ensure comprehensive and
accurate characterization of these thin films.
Various wavelengths from UV to IR can be used to identify the CZTS phase in thin
films. Green or red excitation wavelengths (514, 532 and 633 nm) are commonly used to
observe the vibrational modes of the CZTS phase, and the main peaks are located at 287,
337, 266 and 374 cm−1 . Demitrievska et al. [70], realized a complete analysis of all Raman
active modes by measuring CZTS films under six different excitations. Through their
work they discovered additional CZTS peaks accumulating a total of 18 peaks attributed
to 27 optical modes relative to the kesterite phase, as summarized Table 3. Regarding
secondary phases and in contrast to XRD, Raman spectroscopy proves advantageous in
the straightforward identification of secondary phases like ZnS and various structures
of CTS in CZTS films. While CZTS is commonly analyzed using green or red excitation
wavelengths, the detection of ZnS requires UV light (325 nm exclusively), due to its
resonance characteristics (typically 347–350 cm−1 ), and to the fact that ZnS has a bandgap
close to the 325 nm wavelength (3.8 eV) [71]. Furthermore, CTS crystalizes in three distinct
structures (cubic, monoclinic, and tetragonal) each characterized by unique Raman peaks.
In a previous work, we studied the polymorphic nature of CTS films prepared by magnetron
sputtering of two different stacks (SLG\SnS2 \Cu and SLG\Cu\SnS2 ) annealed at different
temperatures and in different atmospheres. We have tried to compare Raman spectra of
the CTS films with the reported values in the literature (Figure 9a). It was found that the
literature regarding the assignment of Raman modes to the three Cu2 SnS3 structures create
challenges. While agreement exists on the main Raman peaks for each structure, such
as 290 cm−1 for monoclinic CTS, 303 cm−1 for cubic CTS, and 337 cm−1 for tetragonal
CTS, contradictions arise in assigning other modes. The modes at 350–354 cm−1 , the peaks
between 292–295 cm−1 and at 370–374 cm−1 are debated between different phases of the
Cu-Sn-S family. This complexity extends to the Raman modes in the region 314–318 cm−1 ,
which could belong to Cux Sny Sz or SnS2 according to different studies [72–75]. If the
analyzed samples contain zinc, some of the previously listed peaks can overlap with other
phases. For instance, the peaks at 315 and 353 cm−1 , which are indicative of CZTS, may also
represent other phases (for instance SnS at 314 cm−1 and CTS at 353 cm−1 , respectively).
Additionally, the peak at 350 cm−1 , typically associated with the ZnS phase, further increase
the complexity of the identification process. Similarly, for the CuS secondary phase, the
primary mode is at 465–467 cm−1 , accompanied by another smaller peak at 261–264 cm−1
(Figure 9b), which may lead to potential uncertainty with the 262 cm−1 CZTS mode. In the
case of SnS, the main peak appears at 190–192 cm−1 , accompanied by a less intense peak at
160–164 cm−1 , posing a possible misinterpretation as CZTS has a peak at 164 cm−1 . The
 also represent other phases (for instance SnS at 314 cm−1 and CTS at 353 cm−1, respectively).
Additionally, the peak at 350 cm−1, typically associated with the ZnS phase, further in-
crease the complexity of the identification process. Similarly, for the CuS secondary phase,
the primary mode is at 465–467 cm−1, accompanied by another smaller peak at 261–264
Energies 2024, 17, 1600 cm−1 (Figure 9b), which may lead to potential uncertainty with the 262 cm−1 CZTS mode. 14 of 29
In the case of SnS, the main peak appears at 190–192 cm−1, accompanied by a less intense
peak at 160–164 cm−1, posing a possible misinterpretation as CZTS has a peak at 164 cm−1.
The other
other frequently
frequently occurring
occurring secondary
secondary phases
phases in the
in the CZTS
CZTS system,
system, such
such as Cu
as Cu 2S, Sn2S3,
2 S, Sn2 S3 , and
and MoS 2, exhibit distinct Raman modes, making them easily detectable (Table 3).
MoS , exhibit distinct Raman modes, making them easily detectable (Table 3).
2

Figure 9. 9.
Raman spectra of of
(a)(a)
SLG\SnS 2\Cu stacks annealed in S atmosphere at different temper-
SLG\SnS
Figure Raman spectra 2 \Cu stacks annealed in S atmosphere at different temper-
atures and (b) Raman spectra of CuS secondary phase depicted inin
one ofof
the SLG\SnS 2\Cu films
SLG\SnS
atures and (b) Raman spectra of CuS secondary phase depicted one the 2 \Cu films
annealed at 500 °C.◦ Figures were reproduced with permission [20].
annealed at 500 C. Figures were reproduced with permission [20].

Table 3. Raman peaks of CZTS and most common secondary phases. The highest peak of each phase
is bolded.

Compound Raman Shift (cm−1 ) References

67, 81, 96, 139, 150, 164, 255, 262, 271, 287, 302,
Cu2 ZnSnS4 [70]
315, 331, 337, 347, 353, 366, 374
267, 299, 302, 302–303, 351, 354–356, 365 (cubic);
222–225, 249–250, 254–255, 258, 268, 287, 290–295,
Cu2 SnS3 314–317, 346–348, 349–354, 371–374 (monoclinic); [76]
286, 289, 297, 300, 317, 330–331, 334–337, 343,
351–353, 356 (tetragonal)
CuS 261–264, 465–467 [77]
Cu2 S 472–475 [78]
SnS 93–95, 160–164, 190–192, 218 [79,80]
SnS2 312–314 [81,82]
Sn2 S3 232, 305–308 [81,82]
ZnS 350, 697, 1045 [83,84]
MoS2 385, 403–405 [85,86]

In contrast to XRD, where it is advised to depend on minor peaks for distinguishing

between secondary phases and the primary CZTS phase, in Raman spectroscopy, the most
intense modes of all phases are distinct, while the minor peaks can occasionally lead to
uncertainty.
In the same manner, Raman spectroscopy serves as a valuable tool for discerning
secondary phases in CZTSe compounds. This technique aids in the identification of various
phases through the analysis of their distinct Raman modes. However, the interpretation
of Raman spectra in CZTSe is not without challenges, and there may be discrepancies in
assigning specific modes to certain structural features. The most common Raman modes
relative to the CZTSe phase are 173, 195, 232, and 244 cm−1 as shown by Zaki et al. in a
study of Cu2 ZnSnSe4 films synthesized from different stacks and shown in Figure 10 [87].
However, an investigation by Dimitrievska et al. [88] has facilitated the discovery and
identification of novel Raman modes associated with the CZTSe phase. In their study they
prepared CZTSe absorbers by annealing a Sn/Cu/Zn stack in a graphite box containing Sn
and Se powders. The resulted films were then extensively analyzed by Raman spectroscopy
Energies 2024, 17, 1600 15 of 29

using nine different excitation wavelengths (325, 442, 457.9, 514.5, 532.1, 632.8, 784.6, 830
and 1064 nm). They stated that the exploration of Raman spectroscopy in CZTSe reveals
a capability to influence the intensities of intrinsic Raman peaks when using different
wavelengths. While this enhancement can reveal previously unreported Raman peaks
(55, 80, 135, 158, 171, 188, 213, 251 cm−1 ), caution is warranted as it might introduce
misinterpretations. Here as well, while the detection of secondary phases is facilitated by
their distinctive and intense Raman peaks, a challenge arises with the less intense peaks, as
they may overlap with CZTSe peaks. In fact, the Raman modes of cubic CTSe (236 cm−1 ),
monoclinic CTSe (230 cm−1 ), and CZTSe (232–234 cm−1 ) present a challenge due to the
closely similar relative peaks position. However, the CTSe phase in both structures can be
easily detected when relying on the other peaks presented in Table 4. Furthermore, the
overlapping of tiny peaks at 242 cm−1 between MoSe2 and CZTSe introduces complexity to
the identification process. It is noteworthy that the most intense peak of ZnSe at 250 cm−1 as
well poses potential confusion with the small peaks of cubic CTSe at 252 cm−1 , monoclinic
CTSe at 248 cm−1 and CZTSe at 251 cm−1 . A meticulous examination is imperative 16
Energies 2024, 17, x FOR PEER REVIEW to of 30
navigate through these complexities and ensure accurate interpretation. The distinctiveness
of the Raman peaks of other secondary phases such as Cu2-x Se, SnSe, and SnSe2 stands as
an advantage, facilitating their clear discrimination from those of CZTSe. In addition to the
scanninganalysis
nuanced electronofmicroscopy
Raman spectra, coupled with energy-dispersive
complementary analyses such X-ray spectroscopy
as scanning electron pro-
vides valuable
microscopy insights
coupled with into the morphology
energy-dispersive X-rayand composition
spectroscopy of thevaluable
provides materials under in-
insights
into the morphology and composition of the materials under investigation, offering
vestigation, offering a comprehensive understanding of their structural and elemental a
comprehensive
properties. understanding of their structural and elemental properties.

Figure10.
Figure 10. Raman spectra of
Raman spectra of CZTSe
CZTSe films
films from
from different
different stacks.
stacks. The
The figure is reproduced
figure is reproduced with
with per-
mission [87].
permission [87].

Table 4. Raman peaks of CZTSe and most common secondary phases. The highest peak of each
phase is bolded.

Compound Raman Shift (cm−1) References

55, 80, 135, 158, 171, 173–176, 181, 195–196, 213, 220, 232–
Cu2ZnSnSe4 [88]
234, 242–244, 251
68, 77, 180, 200, 236, 252 (cubic); 66, 76, 179, 203, 210, 230,
Cu2SnSe3 [89,90]
248 (monoclinic)
Cu2-xSe 258–262 [91]
SnSe 33, 71, 108, 130, 150 [92]
SnSe2 119, 185, 314 [58]
Energies 2024, 17, 1600 16 of 29

Table 4. Raman peaks of CZTSe and most common secondary phases. The highest peak of each
phase is bolded.

Compound Raman Shift (cm−1 ) References

55, 80, 135, 158, 171, 173–176, 181, 195–196, 213,
Cu2 ZnSnSe4 [88]
220, 232–234, 242–244, 251
68, 77, 180, 200, 236, 252 (cubic); 66, 76, 179, 203,
Cu2 SnSe3 [89,90]
210, 230, 248 (monoclinic)
Cu2-x Se 258–262 [91]
SnSe 33, 71, 108, 130, 150 [92]
SnSe2 119, 185, 314 [58]
ZnSe 206, 250 [93]
MoSe2 242, 285 [94]

3.2.2. Morphological and Compositional Analysis

SEM-EDX
While scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy
(EDS) are valuable techniques for examining the morphology and elemental composition of
materials, they may not be as effective in directly identifying secondary phases in CZTS and
CZTSe films compared to previous described techniques. SEM provides high-resolution
images of the surface, revealing details about the film structure, grain boundaries, and other
morphological features. EDS, on the other hand, detects the elemental composition. How-
ever, identifying secondary phases often requires information about the crystal structure,
which is more effectively obtained through techniques like XRD or Raman spectroscopy.
In spite of that, SEM and EDS and/or EDS mapping analyses can still provide valu-
able indirect indicators of the presence of secondary phases in CZTS and CZTSe films.
Differences in grain shapes and sizes observed through SEM images may suggest a het-
erogeneous composition, hinting the possible existence of multiple phases [95]. Moreover,
off-stoichiometric compositions, where certain elements are in excess, may raise suspi-
cions about the formation of secondary phases [96]. An elevated concentration of certain
elements not corresponding to the desired kesterite composition can signify the presence
of secondary phases. EDS mapping is particularly useful in this context, as it can reveal
spatial variations in elemental distribution. Regions with higher concentrations of specific
elements may correspond to secondary phases, and this can be visually represented by
denser and colored areas in the EDS maps [97].
For instance, the detection of Cu2 S secondary phase in CZTS films can be achieved
through SEM analysis. By examining the surface morphology of the films, isolated large
grains can be observed, often distributed non-uniformly across the surface. These large
grains, are indicative of Cu2 S crystallites [98,99]. Additionally, the use of EDS further
confirms the presence of Cu2 S by analyzing the elemental composition of these large grains.
The combination of SEM and EDS provides an effective method for identifying and charac-
terizing Cu2 S secondary phase in CZTS films, aiding in the comprehensive analysis of their
structural composition as reported in various studies [100,101]. Similarly, Buffiere et al.,
discovered particles measuring around 80 nm, situated at the base of the CZTSe film, which
when analyzed by EDS found to be rich in Cu and Se, meaning the presence of Cu2 Se [102].
The same observations were reported by Fella et al., in another study [103]. Contrarily,
Zn(S/Se) particles are mainly located at bottom and may appear as small, distinct entities,
often distinguished by their morphology or contrast within the micrograph [104]. Bishop
et al., revealed that the presence of ZnSe can be distinctly highlighted through illuminated
charging regions in SEM images of their CZTSe films, particularly when employing in-lens
secondary electron detection [105]. The in-lens detector boasts enhanced efficiency in
capturing low-energy electrons, resulting in a superior signal-to-noise ratio. This improved
efficiency and signal quality contribute to heightened contrast, facilitating clearer visibility
Energies 2024, 17, 1600 17 of 29

and differentiation of impurities. Similar conclusions were drawn in these studies on

CZTS films, where bright particles were observed and when analyzed by EDS showed
compositions rich in zinc and sulfur, aiding in the identification and confirmation of the
ZnS secondary phase in the CZTS films [106,107]. On the other hand, the identification of
SnS and SnS2 secondary phases in CZTS films is facilitated through various SEM and EDS
observations. Zaki et al., detected the presence of larger white particles, exceeding the size
of CZTS grains, corresponds to the SnS2 secondary phase, as confirmed by EDS mapping
and shown in Figure 11 [65]. In other studies, SEM images reveal sheet-like structures
identified as SnS2 on the surface of CZTS films, EDX mapping further substantiates the
presence of Sn and S elements in the identified sheet-like grains [108,109]. Additionally, the
SnS phase is discernible as flake-like features in CZTS films, evident in SEM images and
verified by EDX analysis in an investigation by Engberg et al. [110]. Similarly, the detection
of SnSex secondary phases in CZTSe films involves SEM imaging and EDS analysis. Lin
et al., observed distinct morphologies when analyzing CZTSe films, categorized as a rod-
like appearance and a round or semicircular shaped grains. By measuring EDS analysis on
these morphologies, they confirmed their predominantly comprising Sn and Se elements,
which is synonym of SnSe2 presence [111]. Temgoua et al., stated that the SnSe2 compounds
can be spotted as hexagonal structures on the surface of CZTSe [112]. Furthermore, the
SEM images of CZTSe absorbers realized by Becerril-Romero et al., revealed elongated
grains (SnSex ), which consist of mainly Sn and Se elements after EDX measurements [113].
Additionally, cross-sectional SEM images can reveal the layered structure of thin films. In
the case of CZTS and CZTSe films, the presence of secondary phases like molybdenum
Energies 2024, 17, x FOR PEER REVIEW 18 of 30
disulfide and molybdenum diselenide can be discerned through these images [114]. Specif-
ically, Mo(S/Se)2 tends to form a thin layer situated between the Mo substrate and the
CZTS or CZTSe layer. The distinct visual separation in the cross-sectional view helps in
separation
identifyingin theconfirming
and cross-sectional view helps
the presence in identifying
of this and confirming
secondary phases [115,116].the presence
These of
observa-
this
tionssecondary phases [115,116].
from cross-sectional These observations
SEM provide frominto
valuable insights cross-sectional SEM
the structural provide val-
composition of
uable insights
the films, into
aiding inthe structural composition
a comprehensive of the films,
understanding aiding
of their in aarchitecture
layered comprehensive
and un-
the
derstanding of theiroflayered
potential existence architecture
additional phases. and the potential existence of additional phases.

Figure
Figure 11.
11. SEM
SEMimages
imagesof ofthe
theCZTS
CZTSfilms
filmsfrom
fromSLG\CTS\ZnS-150
SLG\CTS\ZnS-150stack
stackannealed
annealedininSnSn++S Satmos-
atmo-
phere for (a) 30, (b) 45, and (c) 60 min, respectively; and the SLG\CTS\ZnS-200 stack sulfurized
sphere for (a) 30, (b) 45, and (c) 60 min, respectively; and the SLG\CTS\ZnS-200 stack sulfurized for
(d) 30, (e) 45, and (f) 60 min, respectively. The red circles represent grains of the SnS2 secondary
for (d) 30, (e) 45, and (f) 60 min, respectively. The red circles represent grains of the SnS2 secondary
phase; the inset shows the SnS2 grains observed by EDS mapping. Reproduced with permission [65].
phase; the inset shows the SnS2 grains observed by EDS mapping. Reproduced with permission [65].
There
There isis consensus
consensus among
among researchers
researchers regarding
regarding the
the distinctive
distinctive features
features of of certain
certain
secondary phases in CZTS and CZTSe films. Large grains correspond
secondary phases in CZTS and CZTSe films. Large grains correspond to Cu2 S and Cu to Cu 2 S and Cu22Se,
Se,
while
while smaller
smaller white
white spots,
spots, notably
notably visible
visible inin contrast,
contrast, are
are indicative
indicative ofof ZnS
ZnS or
or ZnSe.
ZnSe. Sim-
Sim-
ilarly,
ilarly, SnS
SnS22 isis identified
identifiedasaslarge
largegrains
grainsatatthe thesurface
surfaceofofthe film,
the and
film, andSnSe 2 manifests
SnSe as
2 manifests
round-shaped discs or hexagonal structures easily distinguishable as
as round-shaped discs or hexagonal structures easily distinguishable as represented inrepresented in Fig-
ure 12. A
Figure 12.thin
A thinlayer of MoS
layer 2 or MoSe
of MoS 2 is typically
2 or MoSe observed
2 is typically between
observed the molybdenum
between the molybdenum sub-
strate and the CZTS or CZTSe layer, respectively. However, some secondary phases elude
detection through SEM or EDX, and their identification through these techniques remains
unreported. While the combination of SEM imaging and EDX mapping is valuable for
detecting and characterizing various secondary phases, it is essential to acknowledge the
limitations, as some of the secondary phases (such as CTS or CTSe) cannot be observed
 There is consensus among researchers regarding the distinctive features of certain
secondary phases in CZTS and CZTSe films. Large grains correspond to Cu2S and Cu2Se,
while smaller white spots, notably visible in contrast, are indicative of ZnS or ZnSe. Sim-
Energies 2024, 17, 1600 ilarly, SnS2 is identified as large grains at the surface of the film, and SnSe2 manifests as
18 of 29
round-shaped discs or hexagonal structures easily distinguishable as represented in Fig-
ure 12. A thin layer of MoS2 or MoSe2 is typically observed between the molybdenum sub-
strate andand
substrate the the
CZTS or CZTSe
CZTS layer,
or CZTSe respectively.
layer, However,
respectively. somesome
However, secondary phases
secondary elude
phases
detection through SEM or EDX, and their identification through these techniques
elude detection through SEM or EDX, and their identification through these techniques remains
unreported.
remains While the
unreported. combination
While of SEM
the combination of imaging and EDX
SEM imaging mapping
and EDX is valuable
mapping is valuablefor
detecting and characterizing various secondary phases, it is essential to acknowledge
for detecting and characterizing various secondary phases, it is essential to acknowledge the
limitations,
the as some
limitations, of the
as some of secondary phases
the secondary (such(such
phases as CTS
as or CTSe)
CTS cannot
or CTSe) be observed
cannot be ob-
through
served SEM orSEM
through identified by EDXby
or identified and their
EDX definitive
and identification
their definitive may require
identification may comple-
require
mentary methods
complementary such assuch
methods XRDasorXRD
Raman spectroscopy.
or Raman spectroscopy.

Figure 12.Representation
Figure12. Representationofofthe
thedistribution
distributionand
andmorphology
morphologyof of
CuCu
2 (S/Se), Sn(S/Se)2 ,2,Zn(S/Se)
2(S/Se), Sn(S/Se) Zn(S/Se) and
and
Mo(S/Se) secondary phases within the CZT(S/Se) film.
Mo(S/Se)22 secondary phases within the CZT(S/Se) film.

3.3. Strategies to Enhance Phase Control

Achieving single-phase CZTS and CZTSe absorber layers has posed challenges due
to the tendency for secondary phase formation. The abundance of studies reporting the
coexistence of these secondary phases has highlighted the complexities involved. However,
amidst these challenges, obtaining single-phase CZTS and CZTSe is achievable. Two main
strategies are employed to address and remove secondary phases, ensuring the attainment
of single-phase CZTS or CZTSe films. The first approach involves prevention through the
meticulous optimization of deposition parameters by fine-tuning the synthesis conditions
to avoid the formation of undesired secondary phases. The second strategy employs
etching techniques. When secondary phases are present on the surface, etching methods
can effectively remove them, leaving behind a purified CZTS or CZTSe structures.
Optimizing the growth conditions, such as deposition temperature, time, and rates,
influences crystal structure and minimizes secondary phase occurrence [117,118]. Stoi-
chiometry control during fabrication is also important, by ensuring accurate control over
the precursor ratios and compositions during deposition. Post-deposition annealing un-
der controlled atmospheres aids in achieving better phase purity by facilitating atomic
rearrangements. Improvements in sulfurization or selenization parameters such as tem-
perature, time, and atmosphere are essential to enhance the incorporation of sulfur or
selenium and reduce secondary phases. Besides optimizing the deposition parameters,
researchers have explored inventive approaches to improve this process. Comparison of
annealing atmospheres, temperatures, and annealing time across different studies reveals
variations in phase purity achieved, highlighting the importance of optimizing annealing
conditions for controlling secondary phase formation in CZT(S/Se) thin films [119–121].
For instance, the addition of Sn with sulfur or selenium during annealing has been found
effective in reducing Sn losses, contributing to improved stoichiometry and minimizing
secondary phases [122,123]. Additionally, the use of a graphite box during annealing offers
distinct advantages. The graphite box acts as a protective shield, preventing the loss of
volatile elements and maintaining the required sulfur or selenium content. This controlled
atmosphere during annealing facilitates better compositional stability and reduces the
likelihood of secondary phase formation [124,125].
In certain studies, researchers have employed a two-step deposition strategy, involving
the sequential deposition of Cu2 SnS3 or Cu2 SnSe3 followed by a layer of ZnS or ZnSe as
 Energies 2024, 17, 1600 19 of 29

presented if Figure 11a–c). Various techniques, including hydrothermal [126], spray pyrol-
ysis [127], chemical bath deposition [128], sonochemical reactions [129], and magnetron
sputtering [65,87], have effectively employed a two-step synthesis process. This innovative
approach is effective in mitigating secondary phases when the process is meticulously
optimized. The rationale behind this two-step deposition is to carefully control the pre-
cursor materials, and deposition parameters at each stage. Figure 13 is a schematic of the
two-step synthesis process, for both CZTS and CZTSe phases. In the first stage, the focus
is on achieving a single-phase CTS or CTSe film devoid of secondary phases. This initial
step requires meticulous control of precursor materials, concentrations, and deposition
parameters to ensure the desired phase purity. Once an optimized CTS or CTSe film is
obtained, the second stage involves the addition of a carefully optimized layer of ZnS or
ZnSe. This subsequent layer reacts with the existing CTS or CTSe film during the annealing
processes, fostering the formation of the desired CZTS or CZTSe phase. The controlled
interaction between the layers is a key aspect of this approach, aiming to enhance the crys-
tallinity and phase purity of the final CZTS or CZTSe film while mitigating the presence
of undesirable secondary phases. This nuanced two-step deposition process illustrates a
Energies 2024, 17, x FOR PEER REVIEW
strategic methodology to achieve high-quality, single-phase CZTS and CZTSe absorber20 of 30
layers for improved solar cell performance.

Figure
Figure13.
13.Schematic
Schematicofofthe
themagnetron
magnetronsputtering
sputteringdeposition
depositionand
andannealing
annealingprocess
processofof(a)
(a)the
theCZTS
CZTS
films (b) the CTSe layer and (c) the CZTSe final films. Reproduced with permission [65,87].
films (b) the CTSe layer and (c) the CZTSe final films. Reproduced with permission [65,87].

On
Onthetheother
otherhand,
hand,chemical
chemicaletching
etchingemerged
emergedasasaatool toolfor
foreliminating
eliminatingsecondary
secondary
phases
phasesCZTS
CZTS and CZTSe films.
and CZTSe films. Various
Variousetching
etchingmethods
methods have
have been
been employed
employed to selec-
to selectively
tively
removeremove specific
specific secondary
secondary phases,phases, contributing
contributing to the production
to the production of single-phase
of single-phase absorber
absorber layers.
layers. For For Cu(S/Se)
Cu(S/Se) secondary
secondary phases,phases,
a common a common
solutionsolution
is the useis the use ofetching,
of KCN KCN
etching,
a methoda method established
established throughthrough routine application
routine application in the processing
in the processing of CIGSSe offilms
CIGSSe
and
films and effectively
effectively adaptableadaptable to kesterites
to kesterites as wellZnS,
as well [66,130]. [66,130].
whenZnS, when
present, canpresent, can be
be successfully
successfully
eliminated by eliminated
immersing by the
immersing
film in athe filmhot
5–10% in aHCl
5–10% hot HCl
solution ◦ C [131].
solution
at 75 at The
75 °Cremoval
[131].
of ZnSe
The often
removal ofinvolves an oxidation
ZnSe often involves an route, whereroute,
oxidation KMnOwhere
4 /H2 SO 4 is applied
KMnO 4/H2SO4followed by
is applied
followed by a Na2S solution rinse, proving to be an effective technique [132]. To address
Sn(S,Se)2 secondary phases, (NH4)2S etching solution has been identified as a promising
approach, offering a potential possibility to mitigate the presence of these unwanted
phases [133,134]. In a separate investigation conducted by Wang et al. [109], they demon-
strated the successful removal of the SnS2 secondary phase located on the surface of the
Energies 2024, 17, 1600 20 of 29

a Na2 S solution rinse, proving to be an effective technique [132]. To address Sn(S,Se)2

secondary phases, (NH4 )2 S etching solution has been identified as a promising approach,
offering a potential possibility to mitigate the presence of these unwanted phases [133,134].
In a separate investigation conducted by Wang et al. [109], they demonstrated the successful
removal of the SnS2 secondary phase located on the surface of the CZTS thin film. This
was achieved through a method involving physical adhesion, utilizing a conductive tape
known for its resistance to debonding. These selective etching routes provide targeted
solutions for specific secondary phases, contributing to the enhancement of CZTS and
CZTSe film purity.

4. Influence of Secondary Phases on the Solar Device Efficiency

Although the exact impact of residual secondary phases on the performance of
kesterite-based solar cells remains poorly understood, recent research suggests that the pres-
ence of secondary phases in CZT(S/Se) thin-film solar cells can significantly impact their
efficiency and stability [135,136]. These secondary phases, such as CTS, Cux S, ZnS, Snx Sy , in
the CZTS compound and similarly, CTSe, Cux Se, ZnSe, and Snx Sey , for CZTSe, often act as
recombination centers for charge carriers, leading to increased non-radiative recombination
losses. This hinders the overall charge transport within the material, ultimately reducing
the solar cell performance. Moreover, the formation of secondary phases can introduce
defects and grain boundaries, causing additional electron-hole recombination sites and
reducing carrier lifetime. As a consequence, the device power conversion efficiency is
adversely affected. The presence of various secondary phases in CZTS-based solar cells
significantly impacts their performance. For instance, ZnS, characterized by a wide band
gap of 3.5 eV, acts as an insulator, reducing the effect sunlight-absorbing area available for
generating electron-hole pairs leading to a decrease in current collection [137]. On the other
hand, highly conductive Cu2 S may create short circuits in solar cells, potentially compro-
mising their efficiency [138]. However, another investigation revealed that the presence of
the Cu2 S secondary phase is not detrimental to the photovoltaic performance of CZTS [139].
On the contrary, it was found that the Cu2 S phase might play a constructive role, potentially
contributing to the enhancement of the overall photovoltaic performance. SnS2 , being an
n-type semiconductor with a band gap of approximately 2.2 eV, has the potential to form a
pn junction with the absorber layer, acting as a barrier to charge collection and leading to
increased photocarrier recombination [74]. The presence of Cu2 SnS3 (CTS), observed in
Zn-poor CZTS cells, is noteworthy. While CTS is a p-type semiconductor with a band gap
similar to CZTS, recent studies suggest its lower efficiency compared to CZTS thin films,
highlighting the potential detrimental impact of this unwanted secondary phase on CZTS
solar cell performance [140].
In the context of CZTSe solar cells, the presence of secondary phases, notably ZnSe
and MoSe2 , poses challenges related to increased series resistance, potentially impeding
the efficient flow of current [141,142]. SnSe2 adversely impacted solar cell performance
by diminishing shunt resistance [112]. Furthermore, the high conductivity inherent in
Cu–Se phases can potentially lead to shunting in CZTSe solar cells, further influencing their
photovoltaic performance [143]. Additionally, the emergence of Cu2 SnSe3 phases in CZTSe
absorber layers may contribute to a decrease in the open-circuit voltage (Voc) [144]. This
effect is important, especially considering the energy bandgap variations (Eg = 0.84 eV).
For that reason, it is mandatory to understand and mitigate these specific influences of
secondary phases for optimizing CZTSe-based solar devices.
Figure 14 compares the highest efficiencies achieved in solar cells based on CZTS
and CZTSe absorber layers deposited by various methods, considering the presence or
absence of secondary phases. Among the electrodeposition techniques, CZTS devices
reached a peak efficiency of 7.30% in the absence of secondary phases [145], while CZTSe
solar cells achieved 8.20% [146]. However, when secondary phases were present, the
efficiency slightly decreased to 7.10% for CZTS [118] and 7% for CZTSe [114]. Sol-gel
deposition yielded 8.84% efficiency for solar devices based on single-phase CZTS films [147],
Energies 2024, 17, 1600 21 of 29

but only 5.10% when secondary phases were present [148]. In spray pyrolysis, CZTS
achieved 6.40% efficiency without secondary phases [149], whereas the CZTSe-based device
reached 6.80% [150]. Evaporation techniques resulted in the good efficiencies, with CZTS
absorbers reaching 9.20% without secondary phases [151] and CZTSe absorbers achieving
11.70% [152]. However, the presence of secondary phases slightly reduced the efficiency to
8.90% for CZTSe [153]. The CZTS absorber layer deposited by PLD resulted in a device
achieving an efficiency of 6.62% [154]. The highest efficiencies were recorded on the devices
obtained by magnetron sputtering, particularly for CZTSe films, with efficiencies of 12.50%
for single-phase films [155] and 11.40% for films with secondary phases [156]. While for
Energies 2024, 17, x FOR PEER REVIEW 22 of 30
the CZTS material, the efficiency is a bit lower with 11.01% for the single phase-based
device [157] and 9.70% in the presence of secondary phases [158].

Figure14.
Figure 14.Efficiency
Efficiencycomparison
comparisonofofCZTS
CZTSand
andCZTSe
CZTSefilms
filmsdeposited
depositedby
byvarious
variousmethods,
methods,with
withand
and
without the presence of secondary phases.
without the presence of secondary phases.

Table55summarizes
Table summarizesthe theperformance
performanceof ofCZTS
CZTSandandCZTSe
CZTSedevices
devicesfabricated
fabricatedby byusing
using
someof
some ofthe
thedescribed
describeddeposition
depositiontechniques.
techniques. Solar
Solar devices
devices with
withaasingle-phase
single-phaseCZTSCZTSor or
CZTSeexhibit
CZTSe exhibithigher
higher efficiencies
efficiencies compared
compared to those
to those with
with the the presence
presence of secondary
of secondary phases.
phases. Furthermore,
Furthermore, we foundwe thatfound
CZTSethat CZTSe consistently
consistently outperformsoutperforms
CZTS in termsCZTSofinefficiency,
terms of
efficiency, of
regardless regardless of the deposition
the deposition technique technique
employed.employed. This superior
This superior performance
performance of CZTSe of
CZTSe
can can be attributed
be attributed to its optimal
to its optimal bandgapbandgap
alignment,alignment,
offering offering
improved improved light ab-
light absorption
sorption
and and electron-hole
electron-hole pair generation,
pair generation, ultimatelyultimately
enhancingenhancing
the overallthe overall efficiency
efficiency of the solarof
device.
the solarHowever, the highest
device. However, therecorded efficiencyefficiency
highest recorded in solar devices
in solar was achieved
devices with a
was achieved
CZTSSe-based solar cellsolar
with a CZTSSe-based (13.6%)
cell[159], when
(13.6%) combining
[159], the advantages
when combining of both CZTS
the advantages and
of both
CZTSe
CZTS andmaterials.
CZTSe By understanding
materials. and effectively
By understanding controlling
and effectively the formation
controlling of these
the formation
unwanted phases, through
of these unwanted careful optimization
phases, through of deposition
careful optimization methods,
of deposition post-deposition
methods, post-dep-
annealing treatments, and compositional engineering, researchers can
osition annealing treatments, and compositional engineering, researchers can pave pave the way forthe
the development of high-performance CZT(S/Se) thin-film solar cells, contributing
way for the development of high-performance CZT(S/Se) thin-film solar cells, contrib- to the
advancement of renewableof
uting to the advancement energy technologies.
renewable energy technologies.

Table 5. Comparison of efficiencies in different CZTS and CZTSe single phases cells and the influ-
ence of the of secondary phases, depending on the depositions method.

PCE (%)
Deposition Method Single Phase Secondary Single Phase Secondary
CZTS Phases CZTS CZTSe Phases CZTSe
Electrodeposition 7.30 [145] 7.10 [118] 8.20 [146] 7 [114]
Energies 2024, 17, 1600 22 of 29

Table 5. Comparison of efficiencies in different CZTS and CZTSe single phases cells and the influence
of the of secondary phases, depending on the depositions method.

PCE (%)
Deposition Method Secondary Phases Secondary Phases
Single Phase CZTS Single Phase CZTSe
CZTS CZTSe
Electrodeposition 7.30 [145] 7.10 [118] 8.20 [146] 7 [114]
Sol-gel 8.84 [147] 5.10 [148] - -
Spray pyrolysis 6.40 [149] 5.80 [160] 6.80 [150] -
Evaporation 9.20 [151] - 11.70 [152] 8.90 [153]
PLD 6.62 [154] - - -
Magnetron sputtering 11.01 [157] 9.70 [158] 12.50 [155] 11.40 [156]

5. Conclusions
In summary, this review has explored the field of kesterite materials, with a partic-
ular focus on the formation and controlling of secondary properties in CZTS and CZTSe
films. By describing a range of deposition techniques, spanning from solution-based
methods like electrodeposition, sol-gel and spray pyrolysis to vacuum methods such as
evaporation, pulsed laser deposition, and magnetron sputtering, we have highlighted
the diverse approaches employed in single phase CZTS and CZTSe synthesis. Moreover,
the details associated with secondary phases formation, such as Cux (S/Se), Snx (S/Se)y ,
Zn(S/Se), CT(S/Se), and Mo(S/Se)x , has been examined in detail, demonstrating the com-
plexity of these materials. We have emphasized the significant role of characterization
techniques like X-ray diffraction, Raman spectroscopy, and scanning electron microscopy
with energy-dispersive X-ray spectroscopy in accurately identifying these phases. Further-
more, strategies aimed at mitigating or removing secondary phases have been explored,
signaling a pathway toward achieving single-phase CZTS or CZTSe films. Lastly, insights
into the implications of secondary phases on solar device performance have been provided,
emphasizing the need for an in-depth understanding and precise control of material com-
position for optimal photovoltaic efficiency. Future research could explore the investigation
of novel approaches to suppress secondary phase formation and enhance phase purity,
leading to the development of more efficient and stable CZTS and CZTSe thin-film solar
cells. Additionally, the integration of advanced characterization techniques, could provide
deeper insights into the morphology and composition of kesterite thin films, facilitating
further identification of subtle secondary phases. This comprehensive exploration could
serve as a foundational resource to guide future research endeavors and advancements in
the synthesis and utilization of CZT(S/Se) materials in solar energy conversion.

Author Contributions: Conceptualization, M.Y.Z. and A.V.; methodology, M.Y.Z. and A.V.; formal
analysis, M.Y.Z.; resources, M.Y.Z. and A.V.; data curation, M.Y.Z.; writing—original draft preparation,
M.Y.Z.; writing—review and editing, M.Y.Z. and A.V.; visualization, M.Y.Z.; supervision, A.V.; project
administration, M.Y.Z. and A.V.; funding acquisition, M.Y.Z. and A.V. All authors have read and
agreed to the published version of the manuscript.
Funding: The authors acknowledge the financial support provided by Executive Unit for Financing
Higher Education, Research, Development and Innovation (UEFISCDI), within the framework of
the project PN–III–P1–1.1–PD–2021–0240 (contract no. PD 41/2022) and by the Core Program of the
National Institute of Materials Physics, granted by the Romanian Ministry of Research, Innovation
and Digitization through the Project PC3-PN23080303.
Data Availability Statement: The data presented in this study are available in this article.
Conflicts of Interest: The authors declare no conflicts of interest.
Energies 2024, 17, 1600 23 of 29

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