Article

Cite This: Chem. Mater. 2019, 31, 1784−1793 pubs.acs.org/cm

Unraveling the Growth Mechanism Forming Stable γ‑In2S3 and

β‑In2S3 Colloidal Nanoplatelets
Faris Horani and Efrat Lifshitz*
Schulich Faculty of Chemistry, Solid State Institute, Russell Berrie Nanotechnology Institute, Nancy and Stephen Grand Technion
Energy Program, TechnionIsrael Institute of Technology, Haifa 3200003, Israel
*
S Supporting Information

ABSTRACT: Inorganic two-dimensional semiconductor nano-

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structures intrigue the scientific community because of their

tunable and sparse electronic states and their high conductivity.
The current work deals with colloidal nanoplatelets (NPLs)
based on In2S3 compound, focusing on the growth mechanism
that leads to the formation of two different phases, trigonal γ-
In2S3 and defect spinel β-In2S3, both stabilized at room
temperature and characterized by ordered metal voids. In
particular, we substantiate the experimental factors (e.g.,
temperature, reaction duration, and surface ligands) that
control the growth progress. The results indicated the
formation of hexagonal NPLs of the γ-phase at an elevated
temperature and dodecagon NPLs of the γ-phase at a lower
temperature. A long-reaction duration time transformed the
hexagons/dodecagons into truncated triangular shapes. Furthermore, the analysis of thermodynamic and kinetic factors
indicated a phase transformation from the γ-phase to the β-phase. All phases were produced by a new colloidal procedure based
on a single precursor. The structures created were verified by X-ray diffraction, high-resolution transmission electron
microscopy analyses, and Raman measurements. Elementary optical properties were identified by absorption and emission
measurements. The nanoplatelets discussed offer low toxicity and optical activity in the UV and visible spectral regimes and an
option for electrical or magnetic doping, enabled by the existing voids.

■ INTRODUCTION
Chalcogenide semiconductors have attracted considerable
scientific and technological interest because of their combina-
tion of optical and electrical properties. The most commonly
explored chalcogenides are based on the II−VI and IV−VI
groups, such as CdS, CdTe, PbSe, and PbS. However, the
introduction of these materials in modern industrial
applications, including photonics, optoelectronics, and bio-
logical imaging, is limited due to toxicity impact on the
environment.1,2 Therefore, there has been an increased
demand to develop indium-based chalcogenide materials
from the III−VI group of elements.3 Indium sulfide (In2S3)
is a promising candidate because of its low toxicity, high
absorption coefficient,4 photoelectrical properties,5−7 long-
term stability, and wide band gap energy in its bulk form.8
An In2S3 bulk semiconductor has a large exciton Bohr radius
of 33.8 nm and exists in three crystalline polymorphs: α-In2S3
(defect cubic), β-In2S3 (defect spinel), and γ-In2S3 (layered
hexagonal).9 Among the three phases, β-In2S3 is the most
chemically stable (up to 420 °C) and the most studied phase
with n-type conductivity and a wide band gap of 1.9−2.4
eV.10,11 γ-In2S3 was found to be thermally unstable, existing
only at elevated temperatures (7751045 °C) or high
pressures (35 kbar), and therefore, its isolation at ambient
conditions has been an obstacle since 1976.9,12−14 The α-In2S3
phase was prepared at 420−700 °C and showed a partial
chemical stability.15,16 Nevertheless, In2S3 bulk or thin-film
forms have already demonstrated a practical use as a buffer
layer material replacing the CdS thin films in solar cells17−19
and showed improvement of the open circuit voltage and
current collection in the blue wavelength region.18,20 More-
over, In2S3 has been used as efficient photocatalysts,21−23
photodetectors,24,25 electrochemical storage cells, and display
panels.26−29
New efforts have been demonstrated in recent years for the
development of In2S3 two-dimensional (2D) nanostructures,
for example, thin films or nanoplatelets (NPLs), using either
chemical vapor deposition or colloidal chemical proce-
dures.30−35 It is anticipated that these 2D materials should
possess a tunable electronic band structure, high conductivity,
and efficient optical transitions.36,37 Moreover, the unique
defect cubic and defect spinel structures of the In2 S3
compound include voids, which can accommodate functional
electrical or magnetic dopants, useful attribute for practical
Received: January 2, 2019
Revised: February 14, 2019
Published: February 15, 2019

© 2019 American Chemical Society 1784 DOI: 10.1021/acs.chemmater.9b00013

Chem. Mater. 2019, 31, 1784−1793
Chemistry of Materials Article

Figure 1. (a) Schematic illustration of a colloidal synthesis setup (top) and the chemical reactions used for the formation of a single molecule
precursor and its decomposition product, the In2S3 compound (bottom). (b) Representative TEM images of In2S3 NPLs produced at various
temperatures and reaction durations, revealing the formation of hexagon, dodecagon, and truncated triangular-shaped NPLs. The lateral length
values of each shape are given on the diagram. (c) Scheme reproducing the NPL morphologies in correlation with the TEM observations shown in
(b), illustrating the morphology dependence on reaction temperature and on evolution of the reaction stages (nucleation, growth, and morphology
change) with progress in time. (d) Photographs of aliquots withdrawn from a reaction produced at 230 °C, exhibiting a color change as extended
reaction time.

applications. Indeed, recent studies used Cu- or Mn-doped β-

In2S3 nanostructures in prototype solar cells and light-emitting
diodes.38−41 The structure of shape stability was discussed only
in a single case, showing transformation of wrinkled
nanostructures into nanodisk shapes.41 Despite the efforts
mentioned in preparation and characterization of nanoscale
In2S3 phases, the fundamental growth mechanism and the
factor inducing structural stabilization or transformation are
inadequately understood.
The current work focuses on colloidal 2D In2S3 NPLs,
having merits beyond the corresponding thin films, when
prepared as free-standing species in solutions, covered by
organic ligands, produced in variable sizes, and suitable for
incorporating in practical applications. The current work deals
with colloidal nanoplatelets based on an In2S3 compound,
focusing on the growth mechanism that leads to the formation
of two different phasestrigonal γ-In2S3 and defect spinel β-
In2S3both stabilized at room temperature. We discuss the
influence of the experimental factors (temperature and reaction
duration) on the phase growth mechanism, and we show, for
the first time, a structural transformation from the γ-In2S3 to
the β-In2S3 phase. The results revealed a variable shape for the
different phases: (a) a dodecagon shape in the γ-In2S3 phase
when using a relatively low temperature and short reaction
duration, (b) a γ-In2S3 hexagon shape that was prepared at an
elevated temperature and short reaction duration, and (c) a β-
In2S3 truncated triangular shape using low/high temperatures
after long reaction duration. All phases were produced by a
new colloidal procedure based on a single precursor, which
lead to creation of structural stability at room temperature. The
phases produced were verified by X-ray diffraction, high-
resolution transmission electron microscopy, and Raman
measurements. The elementary optical properties were
identified by absorption and emission measurements. The
knowledge accumulated indicates future potential use of the
In2S3 phases in various optoelectronic devices.
■ EXPERIMENTAL SECTION
Chemicals and Materials. Indium (III) acetate (In(OAc)3,
99.99%), 1-dodecanthiol (DDT, ≥98%), oleylamine (OLAm;
technical grade, 70%). Methanol (absolute), toluene (analytical),
hexane (analytical), and isopropanol (cp) were purchased from Bio-
Lab Ltd. These chemicals were used without further purification.
Synthesis of Hexagonal and Dodecagonal γ-In2S3 NPLs.
In2S3 NPLs were prepared using a colloidal procedure, involving
either injecting or dissolving precursors in a mother solution,
including stabilizing ligands. All synthesis procedures were undertaken
using standard Schlenk line techniques assisted by a nitrogen-filled
glovebox. The growth of In2S3 NPLs was initiated by preparation of a
precursor consisting of both the indium and chalcogenide elements,
noted here as a single precursor source. The precursor was prepared
by mixing In(OAc)3 (0.292 g, 1 mmol), OLAm (5.0 mL), and DDT
(5.0 mL) in a three-neck round-bottom flask, equipped with a
thermocouple and a magnetic stirrer. Then, the mixture was degassed
at 100 °C for 1 h, leading to the formation of a colorless In thiolate
[In(DDT)3] solution, where In(DDT)3 is considered herein as a
single precursor. Thereafter, the mixture was further heated under a
dry inert nitrogen gas flow until a yellowish color was developed
(≥215 °C), accompanied by decomposition of the single precursor
into In2S3 monomers. The synthesis stages are shown schematically in
Figure 1a. The growth process, which was continued up to 32 min at
250 °C, produced hexagon shapes, whereas reaction duration up to 64
min at 230 °C produced NPLs with dodecagon shapes. The reaction
was terminated by removal of the heating mantle and prompt cooling.
Then, toluene, isopropanol, and methanol were added to the reaction
solution, and the NPLs were separated by centrifugation via two
cycles. Afterward, the NPLs were dried and then redissolved in
organic solvent such as hexane or toluene for further characterization.
Extracentrifugation and drying rounds are responsible for significant
desorption of surface-bound ligands and aggregation of the NPLs.
Structural characterizations as discussed below confirmed the
formation of hexagon and dodecagon NPLs of the γ-phase.
Synthesis of Truncated Triangular β-In2S3 NPLs. The same
chemical procedures used for the growth of the γ-phase were
implemented to the growth of the β-phase; however, the reaction time
was extended up to 128 min at 230 °C or 64 min at 250 °C. The X-
ray and electron microscopy measurements (see Results and
Discussion section) proved the formation of NPLs with a truncated
triangular shape with a β-In2S3 crystallographic structure. Hence,

1785 DOI: 10.1021/acs.chemmater.9b00013

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Chemistry of Materials
increase of the reaction duration beyond 64 min at 230 °C (or after
32 min at 250 °C) induced the γ- to β-phase transition accompanied
with a gradual color change from yellow to dark orange. The
purification of the product is similar to the procedure mentioned
above for γ-In2S3 NPLs.
X-ray Diffraction (XRD). Thin films of In2S3 NPLs were prepared
by concentrated suspension drop-casting onto clean glass microscope
slides and drying for further characterization. The X-ray diffraction
patterns were then acquired on a Rigaku SmartLab 9.0 kW
diffractometer with the X-ray source operating at 45 kV and 150
mA. The instrument was equipped with Cu Kα radiation (λ = 1.5418
Å) and was used in the 2θ scan geometry for data acquisition using
parallel beam (PB) geometry.
Transmission Electron Microscopy (TEM) and Elemental
Analysis. Transmission electron microscopy (TEM) images, high-
resolution TEM (HR-TEM) images, and energy dispersive X-ray
spectroscopy (EDS) spectra were taken by using FEI Tecnai T20
operated at 200 keV. High-angle annular dark-field (HAADF)
imaging in an STEM mode (HAADF-STEM) was obtained by an
FEI Titan 300keV S-TEM system. The samples for TEM measure-
ment were prepared by dropping the solution containing NPLs on an
ultrathin carbon-coated copper grid at room temperature.
Absorbance and Photoluminescence Characterization.
Optical absorbance spectra of diluted hexane dispersions of NPLs
were recorded in quartz cuvettes of 1 cm path length at different
reaction stages and times using a JASCO V-570 UV−vis−NIR
spectrometer and a Shimadzu (UV-1800) spectrophotometer. Photo-
luminescence spectra were obtained by a JobinYvon (Fluorolog-3)
fluorometer. Both absorbance and photoluminescence spectra were
collected in air and at room temperature.
Raman Spectroscopy. The sample was prepared by drop-casting
a concentrated suspension onto a clean silicon/glass substrate. The
measurements were performed with a Horiba JobinYvon (LabRAM
HR Evolution) confocal Raman microscope, using a visible laser
excitation source (532 nm). The spectra were recorded by using 50×
and 100× objective lenses and a grating of 1800 gr/mm.
Crystal Structure Design. γ-In2S3 and β-In2S3 NPL crystal
structures were designed by Crystal Maker software. Several
parameters were calculated for each unit cell structure model, for
example, filled space, void space, unit cell volume, density, atoms per
unit cell, and bond lengths. The calculated parameters are corrected
for first-nearest-neighbor sphere overlap and site visibility.
■
RESULT AND DISCUSSION
In2S3 NPLs with Different Morphologies. In2S3 NPLs
were prepared using a colloidal procedure as described in
Experimental Section above, using In(DDT)3 precursors as the
source of In2S3 monomers for the growth of platelets (see
Figure 1a). The nucleation process initiated only after increase
of the temperature up to 230 or 250 °C.
Figure 1b demonstrates a set of TEM images associated with
the produced NPLs, extracted at various stages of the reaction.
The differences among the images reflect the morphology
evolution with temperature and time. Figure 1b shows that a
reaction at T = 230 °C for half an hour induces crystalline
growth of a rounded twelve-sided polygon called a dodecagon.
Then, the extension of the reaction to 1 h at the same
temperature produced a dodecagon with clearly visible sides. A
reaction at T = 250 °C for half an hour led to the formation of
hexagon-shaped In2S3 NPLs. Both hexagon and dodecagon
NPLs have a thickness value of ∼1.8nm (see Supporting
Information, Figure S1). However, the extension of the
reaction duration at each temperature, that is, 230 and 250
°C, beyond 64 and 32 min, respectively, brought about a
transformation from hexagon or dodecagon crystallites to
truncated triangular-shaped NPLs. The lateral dimensions of
the different shapes are shown in Figure 1b. Figure 1c displays
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schemes of the produced NPL transformations, compatible
with the TEM images given in Figure 1b. Figure 1d exhibits a
snapshot photo of aliquots withdrawn from the reaction
solution after 32, 64, and 128 min. This figure reveals a change
in a color from pale yellow through bright orange to dark
orange. The yellow solution is associated with the formation of
both hexagon and dodecagon morphologies, whereas the dark
orange solution corresponds to the truncated triangular
morphology.
In2S3 Crystallographic Structures. The previous section
discussed the correlation of the reaction conditions with the
visual appearance, namely, crystalline morphology and
apparent color, of the reaction solutions. This section supplies
a detailed description of the different In2S3 crystallographic
structures. Figure 2a depicts a set of X-ray diffraction patterns
Figure 2. (a) X-ray diffraction patterns of three aliquots withdrawn
from the reaction solution as different time intervals. The bottom
black line is attributed to the γ-phase and corresponds to an aliquot
taken after 32 min. The top red line is attributed to the β-phase and
corresponds to an aliquot taken after 128 min. The middle pattern
(green line) is attributed to an intermediate phase and corresponds to
an aliquot taken after 64 min at 230 °C (or time interval between 32
and 64 min at 250 °C). Two sets of stick diagrams at the bottom
(black) and the top (red) of the frame are associated with the
database diffraction angles of the γ-In2S3 and β-In2S3 phases,
respectively. (b) Expanded scale of a diffraction regime between 25
and 32° (yellow area) from panel (a), displaying a comparison
between the intermediate pattern (middle) with those of the γ- and β-
phases. The orange Gaussian fit depicts a deconvolution of the green
pattern into two peaks indexed by (I) and (II). The blue vertical lines
are drawn to guide the eye.
of different aliquots taken at intermediate stages during the
NPLs growth. The observed diffraction angles of each aliquot
and the corresponding crystallographic planes and interplanar
d-spacing are summarized in Table 1. The bottom pattern in
Figure 2a (black line) corresponds to an aliquot taken at 32
min, characterized by a yellow color and a hexagon or
dodecagon morphology. This X-ray pattern contains two
intense peaks at diffraction angles as listed in Table 1. The top
pattern in Figure 2a (red line) corresponds to an aliquot taken
after 128 min, characterized by a dark orange color and a
truncated triangular morphology. The top pattern exhibits
eight different diffraction peaks, as given in Table 1. Beside the
experimental observations, Figure 2a contains two sets of stick
diagrams at the bottom and the top of the frame, associated
with the database diffraction angles of the γ-In2S3 and β-In2S3
phases, respectively (see also Table 1). A comparison between
the experimental patterns with the database sets designates that
DOI: 10.1021/acs.chemmater.9b00013
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Table 1. Summary of Diffraction Angles, Interplanar d-
Spacing, and Corresponding Crystallographic Planes of the
X-ray Diffractions Shown in Figure 2a
a
Asterisk (*) denotes the intermediate planes during phase
transformation. bβ-In2S3 reference: (JCPDS 25-0390). cγ-In2S3
reference: (JCPDS 33-0624).
the hexagon and dodecagon morphologies have a γ-In2S3
crystal structure, whereas the truncated triangular shape has
a β-In2S3 crystal structure.
An additional diffraction pattern is illustrated in Figure 2a
(green curve) and related to an aliquot taken from the reaction
solution after 64 min at 230 °C (or time interval between 32
and 64 min at 250 °C). The green pattern nominally includes
two reflection peaks at 27.27 and 47.96° with the
corresponding d-spacing values of 3.26 and 1.90 Å (see
Table 1). A blowup of a diffraction regime between 25 and 32°
(highlighted by a yellow background in Figure 2a) is illustrated
in Figure 2b, enabling a comparison between the green pattern
(middle) with those of the γ- and β-phases. Figure 2b depicts a
deconvolution of the green pattern by a Gaussian fit, revealing
the existence of two diffraction composites at that stage,
emphasized by the dashed orange curves and labeled as (I) and
(II). The comparison shown in Figure 2b emphasizes the
similarity of the green pattern to those of the identified phases
(black and red patterns) and the diffractions angles lying
between those of the phases. Furthermore, the green
diffraction peaks show pronounced broadening. The observa-
tions designate the occurrence of a structural phase trans-
formation. The broadening can be related to the existence of
structural domains at an intermediary stage of phase
transformation, with an inhomogeneous domain strain and
structural reconstruction via creation of vacancies, dislocations,
or layer faults.42 Overall, the X-ray observations discussed
reveal unequivocally, for the first time, the occurrence of
structural phase transition from the γ-In2S3 to β-In2S3 phase.
γ-In2S3 Crystal Structure. The γ-phase of In2S3 accom-
modates a corundum-type structure of crystalline alumina (α-
Al2O3), crystallizing with a trigonal symmetry of D3d and can
be described by a primitive right rhombic prism with lattice
parameters of a = 6.56 Å and c = 17.57 Å (c/a = 2.67). A
polyhedral representation of the γ-In2S3 structure is displayed
in Figure 3a, showing that a single unit cell is built from
octahedral connectivity. Each octahedron is composed of an
In+3 cation binds to six S−2 ions, and each S−2 anion is
surrounded by four In+3 cations. Furthermore, two adjacent
octahedra are arranged with an antiprismatic triangular face-
sharing along the [001] direction and edge-sharing with three
neighboring octahedra along the N[001] direction, as drawn in
Figure 3b. A face- and an edge-sharing induce structural
distortions that are particularly pronounced in materials with
relatively large cations and valence electron volume. Such
structural distortions stimulate displacement of cations from
the octahedral centers or migration to vacant positions, all to
minimize the cation−cation electrostatic repulsion. A displace-
ment of the cation center, a Jahn−Teller distortion, creates
unequal In−S bond lengths (2.746 and 2.513 Å) within a
unitary octahedron, as displays in Figure 3c. Considering the
local distortions, a cut view of a unit cell along the [112̅0]

Figure 3. (a) Right rhombic prism of the In2S3 unit cell represented by polyhedral model. (b) Blowup of a segment of a unit cell, showing face-
sharing (red trigonal plane) and edge-sharing (red line) between neighboring octahedral units. (c) Single distorted octahedral unit composed of
two different In−S bond lengths as marked on the figure. (d) Cut view of the polyhedron shown in (a), exposing the (112̅0) plane and representing
the indium (In+3) and sulfur (S−2) layer sequence along the [0001] direction. The S−2 layers are given by the indexes 1 and 3, and the In+3 layers
are depicted by the symbols A, B, and C. Pink lines represent the unit cell frame, and blue dashed lines exhibit the nonflat indium planes within two
S−2 layers. (e) Hexagonal closed-packed (HCP) crystal structure form of the In2S3 γ-phase, consisting of three right primitive rhombohedral unit
cells. The HCP presentation reveals three types of planes: the m-plane (101̅0), which is marked by the orange area, the a-plane (112̅0) marked by
the green area, and the c-plane (on top). The a- and m-planes are rotated by an angle of 30° (pink arrow). (f) A stereographic projection
representing 12 crystallographic directions, 6 growth directions of the m-planes (orange vectors), and another 6 growth directions of the a-planes
(green vectors). The threefold axis symmetry element of the γ-phase with the D3d point group symmetry is shown at the center (black triangle).

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Chemistry of Materials
direction was derived, as illustrated by a ball-filling
presentation in Figure 3d. The unit cell structure is composed
of six layers, each consisting of close-packed S2− anions (yellow
balls). The In3+ cations (purple balls) occupy two-thirds of the
octahedral hole sites between the adjacent S2− layers. The
layers are stacked in a sequence along the [0001] direction,
when layers 1 and 3 correspond to the S−2 layers, and layer 2
represents the In+3 cations at interstitial positions. The S−2
anion layers are flat and overlap each other. In contrast,
individual In+3 layers have a nonflat appearance, where part of
the cations lies closer to atop anion layer and other cations lie
closer to the bottom anion layer (see small-framed section).
Furthermore, adjacent In+3 layers have a lateral displacement
from one another. They are indexed by A, B, and C. The filled
ball display also reveals a mirror-image arrangement, with a
mirror plane at halfway, and while each fraction has a dipole
polarity, the overall unit cell has a zero-dipole moment.
The correlation between the γ-In2S3 crystal structure and the
morphology of the NPLs is discussed below. It might be easier
to follow such a discussion by viewing the γ-phase crystal
structure as three right primitive rhombohedral unit cells,
enfolded within a primitive hexagonal close-packed (HCP)
frame. An HCP prism is enclosed with two c-planes {0001}, six
first-order m-planes {101̅0}, and six second-order a-planes
{112̅0}, as illustrated in Figure 3e. The angle between the m-
and a-planes is 30°, and overall, the m- and a-planes are normal
to those of the c-planes. Figure 3f illustrates a stereographic
projection of the m- and a-planes shown by orange and green
arrows, respectively, and the direction of the planes is marked
on the circumference of the projection.
β-In2S3 Crystal Structure. β-In2S3 crystallizes with a
tetragonal crystal symmetry, described as a defect spinel
structure with lattice parameters of a = 7.62 Å and c = 32.36 Å
(c/a ratio = 4.25),43 as illustrated by a polyhedron
representation in Figure 4a. The latter presentation reveals
that a defect spinel structure is composed of two kinds of
octahedra and one type of tetrahedron unit, as indicated in the
inset of Figure 4a. Unlike the case of γ-In2S3, In3+ centers are
surrounded either by six or by four S2− anions in the octahedral
(InS6) and tetrahedral (InS4) units, respectively. Figure 4b
illustrates a ball-and-stick presentation of the β-In2S3 phase,
designating the elements as given in the inset. It is seen from
Figure 4b that S2− anions form a distorted cubic closed packing
of a sublattice, within the octahedra are fully occupied;
however, one-third of tetrahedral sites remains unoccupied,
forming negatively charged vacant sites (VIn), which is marked
by a blue cloud. The VIn centers are ordered along the 41 screw
axis, parallel to the z axis, giving rise to a small distortion from
the conventional cubic symmetry of the regular spinel
structure, called a defect spinel. The distortions lead to the
formation of a tetragonal structure of β-In2S3 with the point
group D4h19 and the space group I41/amd. The discussed
distortions also induce variability in the In−S bond lengths.
Figure 4c presents the three different types of coordination,
displayed with a color code to match the polyhedrons in Figure
4a, illustrating from left to right: an octahedron with two
different In−S bond lengths of 2.660 and 2.537 Å, a
tetrahedron with two In−S bond lengths of 2.465 and 2.467
Å, and an additional octahedron with four different In−S bond
lengths of 2.540, 2.629, 2.643, and 2.695 Å. Figure 4d shows
connectivity among the octahedron/tetrahedron units of a
certain fraction in the unit cell, when neighboring units are
connected either through a corner bridge along the [001]
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Figure 4. (a) Tetragonal defect spinel unit cell structure of the β-In2S3
phase, represented by a polyhedral model, including two types of
octahedra, tetrahedron, and vacancies. (b) Ball-and-stick presentation
of the β-In2S3 phase, emphasizing the existence of vacancies, when
sulfur atoms appear as yellow balls, indium atoms as green/red/black
balls, and electron-rich vacancy sites (VIn) are shown by the blue
clouds, whereas the hole-rich centers (VS) are displayed by black
circles. (c) Three types of coordination centers consisting of two
distorted octahedra (left and right) and one tetrahedron (middle);
each coordination geometry is composed of different In−S bond
lengths. (d) Schematic display of the connectivity among the
octahedron/tetrahedron units of a certain fraction in the unit cell,
revealing a corner-bridging connection (pink dashed circle) along the
[001] direction and an edge-sharing bond (pink lines) along the
N[001] direction.
direction or through edge-sharing along the normal direction
N[001], without incidence of a face-sharing connectivity. It is
worth noting that β-In2S3 is characterized by their intrinsic VIn
centers; however, some VS can occur accidentally, and both
defects induce charge trapping of opposing types, which can
eventually lead to the donor−acceptor type of recombina-
tion.44
Correlation between Morphology and Crystal Struc-
ture of the In2S3 Phases. The previous sections discussed
separately the polymorphs and the fundamental crystal
structures of In2S3 NPLs, whereas this section discusses the
correlation between them by following the various observa-
tions, which are illustrated in Figure 5. Figure 5a presents a
TEM image of a hexagon with a lateral dimension of ∼120nm.
Figure 5b shows the fast Fourier transform (FFT) pattern of a
single hexagon similar to that shown in Figure 5a, exhibiting
three rings, each consisting of six diffraction spots. These rings
are ascribed to the {110} planes with d = 0.33 nm, {300}
planes with d = 0.19 nm, and {220} planes with d = 0.16 nm.
The observed diffraction planes in the FFT pattern are
compatible with those shown in the X-ray diffraction as shown
in Figure 2. Figure 5c depicts the same FFT as in Figure 5b,
but it includes additional analysis done by stretching bars
between adjacent diffraction points, creating the sixfold
symmetry frames (color coded with the FFT rings marked in
Figure 5b). It is seen from the frames that the diffraction points
of {110} and {220} (green and blue frames, respectively)
overlay, and both are twisted with respect to the {300} points
(yellow frame) by α = 30°. An angle of 30° is consistent with
the tilt angle between the m- and a-planes, as shown
schematically in Figure 3d,e for γ-In2S3. It is important to
note that FFT patterns of the dodecagonal NPLs exhibit
identical crystallographic diffractions as shown in Figure 5c,d;
hence, the dodecagon morphology is also identified with the γ-
In2S3 phase, in agreement with the X-ray observations. Figure
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Figure 5. (a) TEM image of hexagon of γ-In2S3. (b) FFT pattern of
hexagonal γ-In2S3 NPL, taken from the [001] zone axis (ZA) from the
image in (a). Diffraction spots are gathered into three circumferences
emphasized by different colors, attributed to {110} (green), {300}
(yellow), and {220} (blue) planes, and the corresponding d-spacing
values are shown on the pattern. (c) FFT pattern of the image in (a),
marked by sixfold symmetry frames, showing α = 30° rotation angle
between two adjacent frames. (d) FFT pattern of two overlapping
NPLs, exhibiting a relative rotation angle of 5°. (e) Derived image
based on the FFT pattern in (d), representing the superimposition of
two or more rotated NPLs forming [ABAB] alternating atomic
arrangement. (f) TEM image of two overlapping NPLs, generating a
mutual Moiré structure (see scheme at the inset). (g) FFT image of a
Moiré pattern zone exhibits a 2−3° rotation along the {110} planes.
(h) TEM image of truncated triangular morphology of the β-In2S3
phase. (i) HR-TEM image of a representative β-In2S3 NPL and the
sharp FFT diffraction pattern (inset). (j) Blowup image of (i)
represents three planes {204}, {408}, and {219} as marked in the
panel. (k) TEM image including several overlapping with the β-
structure, forming a Moiré pattern (see dashed frame). (l) FFT image
taken from the Moiré pattern area in panel (k), showing two rings of
the planes {109} and {116} with the corresponding d-spacing values
of 0.32nm (pink) and 0.38nm (yellow), respectively.
5d displays an FFT pattern of two superimposed NPL
hexagons with a 5° rotation between them. Figure 5e shows
the derived image of the FFT shown in Figure 5d, indicating
an alternating arrangement of [ABAB]. Figure 5f displays an
image of two or more NPL hexagons overlapping along the
[0001] direction, experiencing a crystalline mismatch, leading
to the formation of a Moiré pattern (see scheme in inset). A
Moiré pattern becomes feasible only in regions in which the
NPL surfaces accommodated a low concentration of
surfactants because of the sample preparation procedure (see
methods section), allowing a mutual orientation between
adjacent platelets. Figure 5g presents the FFT of a Moiré
pattern zone in Figure 5f, showing a 2−3° rotation angle along
the {110} planes. The hexagonal morphology of the γ-In2S3
NPLs and their overlapping phenomenon are further displayed
by HAADF-STEM measurements (see Supporting Informa-
tion, Figure S2). An acquired HAADF line that is stretched
over a thin γ-In2S3 NPL shows a staircase line profile, which
indicates the existence of several adjacent overlapping NPLs
(see Figure S2).
Figure 5h displays a TEM image of the β-In2S3 exposing the
truncated triangular shape as discussed in Figure 1, and the
corresponding high-resolution image is shown in Figure 5i.
The FFT image is seen in the inset of Figure 5i, whereas a
close-up of a small region of the image is shown in Figure 5j. A
few diffraction planes, {204}, {408}, and {219}, and their d-
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spacing values are marked on Figure 5j, showing compatibility
with the diffractions measured by an X-ray method. Figure 5k
exemplifies a TEM image of a superposition between two or
more β-In2S3 NPLs, which formed a Moiré pattern. The
corresponding FFT pattern is shown in Figure 5l, displaying
two rings, the inner ring belongs to {116} and the outermost
ring belongs to {109} planes with d-spacing values of 0.38 and
0.32 nm, respectively. The diffractions observed in Figure 5l
confirm the first- and second-order reflection peaks in the X-
ray diffraction pattern of the β-In2S3 phase.
Kinetic and Thermodynamic Effects in the Growth
Mechanism of In2S3 NPLs. Keeping in mind the correlation
between the observed polymorphs and the crystal structures of
the In2S3 phases, the discussion in this section reviews a
plausible growth mechanism of each polymorph provided with
a qualitative analysis. Figure 6a displays the NPLs formation
Figure 6. (a) Scheme of NPL formation mechanism including circle
frames and bar above, indicating from left to right, the formation
stages, starting from the initial reactants, generation of the In thiolate
single precursor, formation of monomers, and growth into two
different polymorph shapes. (b) Scheme presentation of different
growth directions, leading to the formation of nanoprism, hexagon,
and dodecagon shapes (top to bottom). Control of the final shapes is
driven by the rate of monomer deposition, indicated by Ri (i = 1, 2,
3). A potential gradient scale is shown on the right. The bar below
designates symbols of chemical constituents of (a) and (b).
stages from left to right, starting from the preliminary
materials, generating the single precursor, formation of
monomers, and the growth into two different polymorph
shapes. The bar below designates symbols of chemical
constituents. The growth process after nucleation is analyzed
in depth. Although the monomer formation and the nucleation
stage are determined solely by thermodynamic considerations,
the growth stage is dictated by a kinetically controlled reaction,
combined with thermodynamic effects.
The nucleation stage generated polyhedron-shaped seeds
with some defined faceting. Anisotropy of a polyhedron
induces growth along specific crystallographic directions and
eventually leads to the formation of an anisotropic
morphology. The growth on top of a seed is dictated by the
chemical potential of the bulk solution, which is dependent on
the concentration of [In2S3] monomers, and consequently, the
kinetic diffusion rate of the monomers toward nucleus faceting
can be affected. A facet surface energy depends on the atomic
compactness and chemical reactivity of surface atoms. Figure
6b depicts a scheme presenting a few different growth
directions. An exemplary polyhedron with an HCP crystal
structure is shown at the left side of the scheme; the {0001}
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Chemistry of Materials Article

Figure 7. (a) Raman spectra of γ-In2S3 and β-In2S3 phases at room temperature. The black curve corresponds to the experimental spectrum of
hexagon/dodecagon NPLs, whereas the green curves are associated with the spectrum of truncated triangular-shaped NPLs. The green and orange
peaks are the Lorentzian best fit of each spectrum. The numbers of Raman modes are marked by ascending order (left to right). (b) Absorbance
spectra of NPLs (solid curves), prepared at 230 °C with duration times as indicated in the inset. The absorbance spectrum is accompanied by
extrapolation lines (dashed curves), indicating the Tauc fit to each curve. (c) Absorbance spectra of γ-In2S3 and β-In2S3 after storage time as
indicated in the legend. (d) Representation of PL spectra (solid curves) with the same synthesis time intervals as given in (b). The PL spectra are
associated with Gaussian best fit of each spectrum.

Table 2. Summary of the Number of Vibration Modes and Their Corresponding Frequencya
number of vibration frequency number of vibration frequency number of vibration frequency
phase mode (cm−1) mode (cm−1) phase mode (cm−1)
β-In2S3 1 60.9 9 201.4 γ-In2S3 1 117.8
2 73.8 10 220.5 2 125.1
3 92.1 11 246.9 3 132.5
4 103.1 12 269.7 4 181.7
5 117.8 13 299.1 5 192.6
6 136.1 14 309.9 6 205.3
7 165.3 15 329.6 7 293.7
8 182.8 16 364.4
a
Data derived from the Raman spectra shown in Figure 7a.

facets have the highest atomic density per unit area compared
to the normal directions, when the c-plane is terminated by
In+3 cations (In rich), as also shown in the scheme of Figure 3f.
Hence, the In2S3 NPL surface contains a large number of
undercoordinated cations, bounded to three anions only rather
than six, as in a bulk position. The undercoordinated surface
can probably be passivated by organic ligands, such as thiols
and amines (see low bar), which bind to an In rich surface via a
single or a multiple bonding,45 and accordingly, a stabilization
of the exterior surface energy. The capping ligands screen the
surface from a flux of diffusing monomers, reducing the rate of
the deposition, and avoiding any further growth along the
<0001> direction. Rate of deposition is defined in following
texts as the rate of diffusion per unit area of a facet and
indicated by Ri (i = 1, 2, 3), so the growth along the <0001>
direction is defined as R1 (see Figure 6b). Alternatively, the
growth develops along the lateral dimensions, when monomer
units [In2S3] are deposited either on the {101̅0} m-planes or
on the {112̅0} a-planes, with deposition rates R2 and R3,
respectively. Under nonequilibrium kinetic growth with a high
flux of monomers, preferential growth takes place along the
kinetically most favorable direction with low activation energy
barriers. The diffusion of the free monomer units is driven by
1790
the potential gradient (ΔP) between the bulk potential (Pbulk)
and a facet potential (Pa,m). Schematic scaling of a potential
gradient is shown at the right side of Figure 6b. Increasing the
growth temperature to 250 °C brings about an initial
monomer-rich solution with a high chemical potential,
increasing the gradient between the bulk solution and the
NPL a- and m-planes, namely, ΔPbulk→a,m ≫ 0. However, as
defined above, the deposition rate is governed by the diffusion
rate per unit area of a facet, and because m-planes have smaller
area than the a-planes; thus, under ΔPbulk→a,m ≫ 0, a
preference growth normal to the m-planes occurs to
compensate for their larger surface strain. This preference
leads to the formation of hexagonally shaped γ-In2S3 NPLs. At
a temperature of 230 °C, there is a relatively low [In2S3]
monomer concentration in the bulk solution, and although
ΔPbulk→a > ΔPbulk→m > 0, the overall deposition rate is nearly
equivalent because of the difference in the plane surface area.
Such a uniform deposition rate advances for the formation of a
dodecagon shape of the NPLs. Thus, Figure 6b elucidates
three routes: option (I) considers R1 ≫ R2, R3, a case that is
not relevant to our study because of passivation of the c-planes;
option (II) considers R1 ≪ R3 < R2, leading to a dominant
development of a hexagon shape; and option (III) considers R1
DOI: 10.1021/acs.chemmater.9b00013
Chem. Mater. 2019, 31, 1784−1793
Chemistry of Materials
≪ R2 ≈ R3, directing to a development of a dodecagon shape.
Therefore, a minor change in the temperature (ΔT = 20 °C)
can give rise to a new growth pathway, because the monomer
formation rate and the NC growth rate depend exponentially
on the temperature.46
Optical Measurements. The formation of the γ-In2S3 and
β-In2S3 phases is further confirmed by recording their Raman
spectra at room temperature, as shown in Figure 7a. The
bottom (black) curve corresponds to the experimental
spectrum of hexagon/dodecagon NPLs, whereas the green
curves are the Lorentzian best fit. The black curve consists of
seven Raman modes, marked by numbers with an ascending
order from left to right, whose corresponding frequencies are
summarized in Table 2. The top (red) curve is associated with
the spectrum of truncated triangular shaped NPLs, and the
accompanied orange curves are the Lorentzian best fit of 16
different frequency modes, as listed in Table 2. The analysis of
the Raman spectra was done by comparison with anticipated
modes derived from symmetry considerations.
The γ-In2S3 phase has the R3̅C space group and D3d point
group symmetry; the latter is sufficient for the analysis of
vibration modes of the structures. The irreducible representa-
tion of the D3d point group is given as Γ = 2A1g + 2A1u + 3A2g +
2
A2u + 4Eu + 5Eg, where 2A1g + 5Eg are the Raman vibration
active modes. The prediction of seven modes is compatible
with the appearance of the same number of resonance modes
in the Raman spectrum of the hexagon/dodecagon above a
frequency of 100 cm−1, hence corroborating the association of
those morphologies with the γ-In2S3 phase. The Raman active
band below 100 cm−1 was identified (see Supporting
Information, Figure S3) by a remnant of oleylamine ligands,
used during the synthesis, and in typically, is difficult to
remove.
The β-In2S3 phase has the I41/amd space group and the
D4h19 point group, used for predicting the following infrared
and Raman active modes at the center of the Brillouin zone:
ΓIR = 10A2u + 16Eu and ΓRaman = 9A1g + 9B1g + 4B2g + 14Eg.47
Although the prediction indicates possible occurrence of 36
modes, the experimental observation exhibits 17 modes.
Previous Raman studies of the β-In2S3 phase designated a
similar spectrum to our observations of the Raman modes,47
compatible with part of the theoretical prediction. It is possible
to conclude that the Raman spectrum given by the red curve is
associated with the β-In2S3 structure with a truncated
triangular morphology. It is useful to note that the red curve
does not include a resonance related to ligand impurities, and
it is also important to mention that the frequencies of both the
γ- and β-In2S3 Raman vibrations might deviate slightly from a
theoretical prediction of a bulk material because of the
existence of a quantum size and surface effects.
Optical transitions were observed in the absorbance and
photoluminescence (PL) spectra as shown in Figure 7b−d.
Figure 7b displays the absorbance (dashed curves) of NPLs
that were prepared at 230 °C with duration time as indicated
in the inset. Because of the relatively slow reaction rate, it was
feasible to follow intermediate stages, one of which exhibits a
dodecagon shape. It is seen from the spectra that a
distinguishable feature built up in the absorbance curve
already after 8 min, and it is shifted to low energies until a
reaction time of 32 min. However, the trend is distracted after
64 min. In the following stage, after 128 min, it is possible to
see a completely different absorbance curve. It is likely to that
the reaction of 32 min produced the dodecagons; after 64 min,
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Article
there is an initiation of phase transformation, whereas at 128
min, the NPLs transformed into truncated triangular-shaped
NPLs. The absorbance curves are accompanied by extrap-
olation lines, indicating the Tauc fit to each curve. Overall, the
intersection with the x-axis designates the energy band gap of
each sample, ranging between 3.5 and 3.7 eV. A literature
report supplied information about the β-In2S3 bulk energy
band gap between 2.0 and 2.4 eV, although to the best of our
knowledge, the bulk band gap of γ-In2S3 has not been reported.
In any event, band-edge optical transitions shifted by ∼1.5eV
from bulk values can be related to the quantum confinements
induced by an NPL thickness of ∼1.8nm, considerably smaller
than the bulk exciton Bohr radius (33.8 nm). The chemical
solidity of the NPLs against air and moisture was examined by
recording their absorbance after couple of months, as shown in
Figure 7c. It is seen from the figure that the features in the
absorbance curves of γ-In2S3 and β-In2S3 phases remained
intact after air exposure over 3 months, corroborating the
chemical stability over time.
Figure 7d represents the PL spectra (solid curves) with the
same synthesis time intervals as given in Figure 7b. The spectra
are composed from a dominant band and another very weak
one at deeper energies (see additional details in the Supporting
Information, Figure S4). The dominant PL bands were fitted
to two Gaussian curves (dashed lines). The small Stokes shift
of the high-energy Gaussian from that of the band gap
designates its association with an exciton recombination. The
deep energy broad band is a characteristic of donor−acceptor
or defect-to-band recombination emission. The association of
vacancies in the recombination process was also suggested
before,48 proposing involvement of indium at interstitial
positions, and occupation substitution of sulfur sites with
oxygen atoms. Indeed, the energy dispersive X-ray spectros-
copy (EDS), designated the existence of a small percent of
oxygen in the examined In2S3 phases (see Supporting
Information, Figure S5). The assignment of the mid-energy
band can be correlated with a bound exciton to a defect center.
Obviously, further investigations are required to identify the
emission components.
■
CONCLUSIONS AND OUTLOOK
In summary, the present work extensively explored the growth
mechanism, which govern the formation of chemically and
structurally stable In2S3 semiconductor NPLs at room
temperature. The work focused on formation of various
morphologies of two different phases of In2S3: trigonal γ-In2S3
and defect spinel β- In2S3. Growth in the two phases was based
on colloidal procedures starting from single precursors and the
existence of ligands that templating the following morpholo-
gies: γ-hexagon, γ-dodecagon, and β-truncated triangular. The
structural and optical observations presented in this study
exposed the correlation between the crystal structure, reaction
conditions, and the morphology of the NPLs. In particular, this
work revealed the mechanism for a structural phase transition
from the γ-In2S3 to the β-In2S3 phase. The proposed structures
exhibit an efficient exciton recombination in the blue-to-green
spectral range, with an additional minor contribution from a
defect radiative recombination at deep energies. The reported
analysis and observations of this work pave the way for the
implementation of In2S3 phases in diverse areas such as solar
cells, photocatalysis, doping, and more. In addition, the NPLs
discussed in this paper are based on chemical elements with
DOI: 10.1021/acs.chemmater.9b00013
Chem. Mater. 2019, 31, 1784−1793
Chemistry of Materials
low toxicity, so they would be attractive for various
applications involving environmental considerations.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.chemma-
ter.9b00013.
Sided TEM images of γ-In2S3 NPLs, HAADF-STEM
images of γ-In2S3 NPLs, Raman spectra of OLAm and
DDT ligands, representative PL spectra of In2S3 NPLs,
and EDS elemental analysis (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: ssefrat@technion.ac.il.
ORCID
Efrat Lifshitz: 0000-0001-7387-7821
Author Contributions
F.H. carried out experiments, performed characterizations, and
analyzed the data. E.L. supervised the research. F.H. and E.L.
wrote the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors acknowledge the financial support from the Israel
Council for Higher−Focal Area Technology (No. 872967), the
Volkswagen Stiftung (No.88116), the Israel Science Founda-
tion (No.914/15), the Israel Science Foundation Bikura
Program (No.1508/14), and the Neubauer Family Founda-
tion.
■
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1793 DOI: 10.1021/acs.chemmater.9b00013

Chem. Mater. 2019, 31, 1784−1793