nanomaterials

Article
Optimizing the Synthetic Conditions of “Green” Colloidal
AgBiS2 Nanocrystals Using a Low-Cost Sulfur Source
Qiao Li 1 , Xiaosong Zheng 1 , Xiaoyu Shen 1 , Shuai Ding 1 , Hongjian Feng 1, *, Guohua Wu 2, *
and Yaohong Zhang 1,3, *

1 School of Physics, Northwest University, Xi’an 710127, China

2 Qingdao Innovation and Development Base of Harbin Engineering University,
Harbin Engineering University, Harbin 150001, China
3 Shaanxi Key Laboratory for Carbon Neutral Technology, Xi’an 710127, China
* Correspondence: hjfeng@nwu.edu.cn (H.F.); ghwu@hrbeu.edu.cn (G.W.); yhzhang@nwu.edu.cn (Y.Z.)

Abstract: Colloidal AgBiS2 nanocrystals (NCs) have attracted increasing attention as a near–infrared
absorbent materials with non–toxic elements and a high absorption coefficient. In recent years,
colloidal AgBiS2 NCs have typically been synthesized via the hot injection method using hexam-
ethyldisilathiane (TMS) as the sulfur source. However, the cost of TMS is one of the biggest obstacles
to large–scale synthesis of colloidal AgBiS2 NCs. Herein, we synthesized colloidal AgBiS2 NCs
using oleylamine@sulfur (OLA–S) solution as the sulfur source instead of TMS and optimized the
synthesis conditions of colloidal AgBiS2 NCs. By controlling the reaction injection temperature and
the dosage of OLA–S, colloidal AgBiS2 NCs with adjustable size can be synthesized. Compared with
TMS–based colloidal AgBiS2 NCs, the colloidal AgBiS2 NCs based on OLA–S has good crystallinity
and fewer defects.

Keywords: AgBiS2 ; colloidal nanocrystals; hot injection; sulfur source

Citation: Li, Q.; Zheng, X.; Shen, X.;
Ding, S.; Feng, H.; Wu, G.; Zhang, Y.
Optimizing the Synthetic Conditions
of “Green” Colloidal AgBiS2 1. Introduction
Nanocrystals Using a Low-Cost
Colloidal AgBiS2 nanocrystal (NC), a member of the I–V–VI2 ternary semiconduc-
Sulfur Source. Nanomaterials 2022, 12,
tor materials [1–7], is a promising eco–friendly material for solar cells owing to colloidal
3742. https://doi.org/10.3390/
AgBiS2 NC having a wide absorption spectrum in the visible to near–infrared region
nano12213742
(300–1600 nm) [8–10], high absorption coefficient (~105 cm−1 ) [1,11–13], and good air sta-
Academic Editor: Efrat Lifshitz bility [8]. The hot injection method is widely used to prepare high quality NCs such as
Received: 23 September 2022
PbS [14], PbSe [15,16], and halide perovskite NCs [17–22]. In 2016, Bernechea et al. syn-
Accepted: 21 October 2022
thesized colloidal AgBiS2 NCs by the hot injection method using hexamethyldisilathiane
Published: 25 October 2022
(TMS) as the sulfur source and first reported colloidal AgBiS2 NC–based solar cells with
a certified power conversion efficiency (PCE) of 6.3% [1]. Subsequently, colloidal AgBiS2
Publisher’s Note: MDPI stays neutral
NC–based solar cells have gradually become one of the mainstays of new generation solar
with regard to jurisdictional claims in
cells. Subsequently, Hu et al. synthesized colloidal AgBiS2 NCs using an improved amine–
published maps and institutional affil-
based synthesis route, improving the PCE of colloidal AgBiS2 NC–based solar cells by 30%
iations.
using colloidal AgBiS2 NCs synthesized using a modified route [23]. Oh et al. improved
the size distribution of colloidal AgBiS2 NCs by an optimized synthetic route, resulting in
enhanced photovoltaic performance [24]. Akgul et al. synthesized colloidal AgBiS2 NCs
Copyright: © 2022 by the authors.
at room temperature using an improved sulfur amine–based synthesis route, reducing
Licensee MDPI, Basel, Switzerland. the production price by 60% and achieving a PCE of 5.5% [25]. These results demonstrate
This article is an open access article that the quality of colloidal AgBiS2 NCs plays an important role in the performance of
distributed under the terms and solar cells. Therefore, it is of extreme importance to synthesize monodispersed colloidal
conditions of the Creative Commons AgBiS2 NCs in the quantum confinement regime and with a high phase purity [26]. Yet, it
Attribution (CC BY) license (https:// should be noted that although synthesis of colloidal AgBiS2 NCs has been developed by
creativecommons.org/licenses/by/ several researchers [1,27–30], it remains challenging to synthesize colloidal AgBiS2 NCs
4.0/). with a perfect crystal structure and complete elimination of defects [31–38]. Furthermore,

Nanomaterials 2022, 12, 3742. https://doi.org/10.3390/nano12213742 https://www.mdpi.com/journal/nanomaterials

Nanomaterials 2022, 12, 3742 2 of 10

using expensive and unstable TMS as the sulfur source in colloidal AgBiS2 NCs synthesis
process results in high cost of the synthesis reaction, which is not conducive to large–scale
preparation of colloidal AgBiS2 NC. It is urgent to explore a method to synthesize high
quality colloidal AgBiS2 NC with low cost.
As a cheap sulfur source, oleylamine@sulfur (OLA–S) solution has been widely used to
synthesize high quality CdS [39], ZnS [40], and PbS NCs [41,42]. Moreover, as a ligand stabi-
lizer, oleylamine can passivate the surface defects of NCs and regulate their growth [23,43].
Recently, Nakazawa et al. successfully synthesized colloidal AgBiS2 NCs with OLA–S as
sulfur source [44]. However, the effect of OLA–S on the growth and quality of colloidal
AgBiS2 NCs has not been studied in detail. In this work, in order to improve the quality of
colloidal AgBiS2 NCs and reduce the preparation cost, we synthesized colloidal AgBiS2
NCs by hot injection method and using OLA–S as the sulfur source to replace TMS, then
investigated the effect of OLA–S on the growth of colloidal AgBiS2 NCs. By regulating
the dosage of OLA–S, high quality colloidal AgBiS2 NCs with low defect density and
uniform size were prepared. It was found that the size of colloidal AgBiS2 NCs could be
controlled by changing the reaction injection temperature. Compared with TMS–based
colloidal AgBiS2 NCs, the colloidal AgBiS2 NCs based on OLA–S have good crystallinity
and fewer defects. In addition, the synthesis cost is significantly reduced.

2. Materials and Methods

Chemicals and materials. Bismuth (III) acetate (Bi(OAc)3 , 99.9%, Aladdin, China),
silver acetate (AgOAc, 99.5%, Aladdin, China), oleic acid (OA, 90%, Sigma–Aldrich, USA),
hexamethyldisilathiane (TMS, synthesis grade, Sigma–Aldrich, Switzerland), 1-Octadecene
(ODE, 90%, Aladdin, China), oleylamine (OLA, 80–90%, Aladdin, China), sulfur (S, 99.5%,
Sinopharm, China), acetone (99.5%, Sinopharm, China), toluene (99.5%, Sinopharm, China),
hexane(97.0%, Sinopharm, China).
Synthesis of TMS–based colloidal AgBiS2 NCs. The TMS–based colloidal AgBiS2 NCs
were synthesized following a hot injection method reported previously in the literature [29].
Synthesis of OLA–S–based colloidal AgBiS2 NCs. The synthesis of OLA–S–based
colloidal AgBiS2 NCs was carried out similarly to that of TMS–based colloidal AgBiS2 NCs.
The OLA–S (1 M) solution was prepared by dissolving sulfur powder in OLA solution
at room temperature. To investigate the influence of the reaction injection temperature
(80 ◦ C, 100 ◦ C, 120 ◦ C) on synthesis of OLA–S–based colloidal AgBiS2 NCs, the dosage
of OLA–S solution (1 M) was kept at 3 mL. In contrast, to investigate the influence of
the dosage of OLA–S solution (1 mL, 2 mL, 3 mL and 4 mL) on synthesis of OLA–S–
based colloidal AgBiS2 NCs, the reaction injection temperature was kept at 100 ◦ C. After
rapidly injected the OLA–S solution into the cationic solution, heating was stopped while
stirring was maintained until the reaction solution cooled to room temperature. The
colloidal AgBiS2 NCs were collected using an acetone/toluene solvent system in air, and
the obtained colloidal AgBiS2 NCs precipitate was then dried in a vacuum drying oven at
room temperature. Finally, the colloidal AgBiS2 NCs were dispersed in hexane solution.

Characterization
The phase identification of colloidal AgBiS2 NCs was carried out using powder X–ray
diffraction (XRD, Bruker, D8 ADVANCED, Germany). The morphology and crystal struc-
ture of the prepared colloidal AgBiS2 NCs were characterized using high–resolution trans-
mission electron microscopy (HR–TEM, Thermo Fisher Scientific, Talos F200x, USA). The
TEM samples were prepared as follows: the obtained colloidal AgBiS2 NCs were dispersed
in hexane with a concentration of 2 mg/mL, three drops of the mixture solution were
dropped onto the TEM support film via pipette gun, and the TEM support films were
fully dried in the vacuum drying oven before measurement. The acceleration voltage
of electron beam was 200 KV during the TEM test. Elemental mapping of the colloidal
AgBiS2 NCs was carried out using a TEM equipped with an energy dispersive spectrometer
(EDS). UV–vis–NIR absorption spectra of the colloidal AgBiS2 NCs were recorded with a
Nanomaterials 2022, 12, 3742 3 3of
of 10

spectra (FT–IR) of colloidal

spectrophotometer (Shimadzu, AgBiS 2 NCsPLUS,
UV–3600 were Japan).
recorded usingtransform–infrared
Fourier an infrared spectrometer
spectra
(Bruker,
(FT–IR) of INVENIO,
colloidal Germany).
AgBiS2 NCs The photoluminescent
were recorded using(PL) spectra of
an infrared the colloidal(Bruker,
spectrometer AgBiS2
NCs were measured
INVENIO, Germany).byThe using a fluorescence spectrophotometer(Zolix
photoluminescent (PL) spectra of the colloidal instruments
AgBiS2 NCs Co.,
Ltd,
wereFST1–MPL303–OP1,
measured by using China). a fluorescence spectrophotometer (Zolix instruments Co., Ltd,
FST1–MPL303–OP1, Beijing, China).
3. Results and Discussion
3. Results and Discussion
Following the schematic diagram of the synthesis of colloidal AgBiS2 NCs by hot in-
Following
jection method, the which schematic
is shown diagram
in Figureof 1,
thewe synthesis
adoptedof colloidal
two methods AgBiS 2 NCs by col-
to synthesize hot
injection method, which is shown in Figure 1, we adopted two
loidal AgBiS2 NCs using TMS (path 1) and OLA–S (path 2) as the sulfur source. The vari- methods to synthesize
colloidal
ation of theAgBiS 2 NCs
crystal using and
structure TMSphase
(pathof1)TMS–based
and OLA–Sand (path 2) as the sulfur
OLA–S–based source.
colloidal The2
AgBiS
variation of the crystal structure and phase of TMS–based and
NCs were studied using X–ray diffraction (XRD). Figure 2a shows the XRD patterns of the OLA–S–based colloidal
AgBiS2 NCs and
TMS–based wereOLA–S–based
studied using X–ray colloidaldiffraction
AgBiS2 (XRD). Figure of
NCs (dosage 2a OLA–S:
shows the XRDinjection
3 mL, patterns
of the TMS–based and OLA–S–based colloidal
temperature: 100 °C). For both samples, six XRD peaks are AgBiS NCs (dosage of OLA–S: 3 mL,
2 found at 13.75°, 15.85°, 22.89°,
injection temperature: 100 ◦ C).can
Forbeboth samples, ◦
27.12°,
◦
28.20°, ◦
and 33.11°,
◦
which
◦
assigned
◦
to thesix XRD
facets peaks
(111), are(220),
(200), found at 13.75
(311), (222),,
15.85(400)
and , 22.89 , 27.12
of AgBiS , 28.20 , and 33.11 , which can be assigned to the facets (111), (200),
2 cubic rock salt structure (JCPDS No. 21–1178), respectively [8,12,37,45–
(220), (311), (222), and
47]. This indicates that colloidal(400) of AgBiS
AgBiS22NCscubiccanrock salt structure
be successfully (JCPDSby
prepared No. 21–1178),
using OLA–
respectively [8,12,37,45–47]. This indicates that colloidal AgBiS
S as the sulfur source. For NC materials, the broadening of XRD peaks can be roughly 2 NCs can be successfully
prepared by using OLA–S as the sulfur source. For NC materials, the broadening of XRD
attributed to the size effect of NCs and lattice strain, which is closely related to defects in
peaks can be roughly attributed to the size effect of NCs and lattice strain, which is closely
the NCs [48]. The lattice strains in TMS–based and OLA–S–based colloidal AgBiS2 NCs
related to defects in the NCs [48]. The lattice strains in TMS–based and OLA–S–based
were calculated using the Williams–Hall plot method [49], with the results shown in Fig-
colloidal AgBiS2 NCs were calculated using the Williams–Hall plot method [49], with the
ure S1 and the corresponding Table S1. The obtained values of the lattice strains for TMS–
results shown in Figure S1 and the corresponding Table S1. The obtained values of the
based and OLA–S–based colloidal AgBiS2 NCs are 0.33 and 0.27, respectively. It can be
lattice strains for TMS–based and OLA–S–based colloidal AgBiS NCs are 0.33 and 0.27,
seen that the lattice strain for TMS–based colloidal AgBiS2 NCs is2 larger than that of the
respectively. It can be seen that the lattice strain for TMS–based colloidal AgBiS2 NCs is
OLA–S–based NCs, with the larger lattice strain leading to more defects in the NCs. Thus,
larger than that of the OLA–S–based NCs, with the larger lattice strain leading to more
the results demonstrate that OLA–S–based colloidal AgBiS2 NCs have lower defect den-
defects in the NCs. Thus, the results demonstrate that OLA–S–based colloidal AgBiS2 NCs
sity than TMS–based NCs. In other words, as a new sulfur source, OLA–S can be used to
have lower defect density than TMS–based NCs. In other words, as a new sulfur source,
synthesize
OLA–S canhigh quality
be used colloidal AgBiS
to synthesize 2 NCs.
high quality colloidal AgBiS2 NCs.

Figure 1. Syntheticroute
1. Synthetic routeforfor colloidal
colloidal AgBiS
AgBiS 2 NCs
2 NCs using
using different
different sulfur
sulfur sources
sources (path(path 1: TMS,
1: TMS, path
2: OLA–S).
path 2: OLA–S).

Furthermore, in
Furthermore, in order
order to
to reveal
reveal the
the influence
influence ofof the
the sulfur
sulfur source
source onon the
the morphology
morphology
and size distribution of colloidal AgBiS NCs, transmission electron microscopy
and size distribution of colloidal AgBiS22 NCs, transmission electron microscopy (TEM) (TEM)
measurement was
measurement was carried
carried out.
out. Figure
Figure S2
S2 shows
shows that
that colloidal
colloidal AgBiS
AgBiS22 NCs
NCs prepared
prepared using
using
TMS and OLA–S have a uniform spherical shape. The average diameters
TMS and OLA–S have a uniform spherical shape. The average diameters of TMS–based of TMS–based and
colloidal AgBiS 2 NCs are about 4.3 ±
and OLA–S–based colloidal AgBiS2 NCs are about 4.3 ± 1.6 nm (Figure S2a) and 7.8 ± nm
OLA–S–based 1.6 nm (Figure S2a) and 7.8 ± 1.9 1.9
(Figure
nm S2b),S2b),
(Figure respectively. High–resolution
respectively. TEMTEM
High–resolution (HR–TEM)
(HR–TEM) images of spherical
images colloidal
of spherical col-
AgBiS2AgBiS
loidal NCs 2based
NCs on TMS
based onand
TMS OLA–S are shown
and OLA–S are in Figure
shown in2b,c [50–52].
Figure Lattice spacing
2b,c [50–52]. Lattice
of about 0.32 nm, corresponding to (111) crystal plane spacing of
spacing of about 0.32 nm, corresponding to (111) crystal plane spacing of cubiccubic rock salt structure
rock salt
AgBiS2 , can
structure be clearly
AgBiS seen, which is consistent with the XRD results above. Elemental
2, can be clearly seen, which is consistent with the XRD results above. El-
mapping of TMS–based colloidal AgBiS2 NCs was carried out using a TEM equipped with
emental mapping of TMS–based colloidal AgBiS2 NCs was carried out using a TEM
EDS. Elemental mapping images are provided in Figure S3a–c, where the Ag, Bi, and S
equipped with EDS. Elemental mapping images are provided in Figure S3a–c, where the
Nanomaterials 2022, 12, 3742 4 of 10
Nanomaterials 2022, 12, 3742 4 of 10
Nanomaterials 2022, 12, 3742 4 of 10

Ag, Bi, and S elements are distributed throughout all NCs. Moreover, the atomic percent-
Ag, Bi, and S elements are distributed throughout all NCs. Moreover, the atomic percent-
elements
ages of Ag, are
Bi,distributed
and S elementsthroughout
are 41.3,all NCs.
22.3, andMoreover, the atomic
36.4, respectively. percentages
These of Ag,that
results indicate Bi,
ages of Ag, Bi, and S elements are 41.3, 22.3, and 36.4, respectively. These results indicate that
and S elements
the surface are 41.3, 22.3,
of TMS–based and 36.4,
colloidal AgBiSrespectively.
2 NCs should These results indicate
be silver–rich that the surface
and sulfur–poor. Figure
the surface of TMS–based colloidal AgBiS2 NCs should be silver–rich and sulfur–poor. Figure
of TMS–based
S3d–f shows thecolloidal
element AgBiS
mapping2 NCs should
images be silver–richcolloidal
of OLA–S–based and sulfur–poor.
AgBiS2 NCs. Figure S3d–f
The atomic
S3d–f shows the element mapping images of OLA–S–based colloidal AgBiS2 NCs. The atomic
shows the element mapping images of OLA–S–based colloidal AgBiS NCs.
percentages of Ag, Bi, and S elements are 42.6, 12.3, and 45.1, respectively. 2This means that theThe atomic
percentages
percentages ofofAg,
Ag,Bi,Bi,
and S elements
and S elementsare 42.6,42.6,
12.3, 12.3,
and 45.1,
andrespectively. This means that the
surface of OLA–S–based colloidal AgBiS2areNCs is both 45.1,and
silver–rich respectively.
sulfur–rich.This means
Combined
surface
that of OLA–S–based colloidal AgBiS 2 NCs is both silver–rich and sulfur–rich. Combined
withthethesurface of OLA–S–based
XRD result colloidal
of the OLA–S–based AgBiS2AgBiS
colloidal NCs is both the
2 NCs, silver–rich
signal ofand
Ag2sulfur–rich.
S is not ob-
with the
Combined XRD result
with2a. of the OLA–S–based
theTherefore,
XRD result colloidal AgBiS 2 NCs, the signal of Ag2S is not ob-
served in Figure weof the OLA–S–based
speculate colloidal
that the excess Ag andAgBiS 2 NCs,on
S are coating thethe
signal of
surface
served
Ag in Figure 2a. Therefore, we2a.
speculate that the
weexcess Ag and S are
thecoating
excess on
Agthe surface
2 S is notAgBiS
of colloidal observed in Figure Therefore, speculate
2 NCs rather than forming Ag2S impurities.
that and S are
of colloidal
coating on AgBiS 2 NCs rather than forming Ag2S impurities.
the surface of colloidal AgBiS NCs rather than forming Ag S impurities.
2 2

Figure 2. (a) XRD patterns of colloidal AgBiS2 NCs based on TMS and OLA–S; (b,c) HR–TEM images
Figure 2.
2. (a)
(a)XRD
XRD patterns of
of colloidal AgBiS 2 NCs
2 NCs2based on
onTMS
TMSand
andOLA–S;
OLA–S; (b,c)
(b,c) HR–TEM
HR–TEM images
Figure
of TMS–based andpatterns
OLA–S–basedcolloidal AgBiSAgBiS
colloidal based
NCs, respectively. images
of TMS–based and OLA–S–based colloidal AgBiS 2 NCs, respectively.
of TMS–based and OLA–S–based colloidal AgBiS NCs, respectively.
2

To further reveal the effect of the sulfur source on the quality of the obtained colloidal
To To further
further reveal
reveal thethe effect
effect of of the
the sulfursource
sulfur sourceononthe
thequality
qualityof ofthe
the obtained
obtained colloidal
AgBiS NCs,
AgBiS222 NCs,
NCs, thethe photoluminescent
the photoluminescent (PL) spectra of
(PL) spectra
spectra of the TMS–based and OLA–S–based
AgBiS photoluminescent (PL) of the TMS–based and OLA–S–based OLA–S–based
colloidal AgBiS 2 NCs solutions were measured at room temperature [53]. The PL spectra of
colloidal AgBiS22NCs solutions were measured at room temperature [53]. The PLPL
colloidal AgBiS NCs solutions were measured at room temperature [53]. The spectra
spectra of
colloidal
of colloidalAgBiS
AgBiS2 NCs based on TMS and OLA–S are shown in Figure 3a. We detected PL
colloidal AgBiS 2 NCs
2 NCs basedbased on TMS
on TMS andand OLA–S
OLA–S are are shown
shown in Figure
in Figure 3a. 3a.
We We detected
detected PL
signals
PL in the
signals emission
in the range
emission of 400–1000
range of 400–1000nm using a 330 nm excitation wavelength. It can
signals in the emission range of 400–1000 nm nmusingusing a 330
a 330 nm nm excitation
excitation wavelength.
wavelength. It canIt
be seen
canseen that
be seen the
thatPLPL intensity
theintensity of
PL intensity OLA–S–based
of OLA–S–based colloidal AgBiS
colloidal 2 NCs is stronger than that of
be that the of OLA–S–based colloidal AgBiSAgBiS
2 NCs 2 isNCs is stronger
stronger than thatthanof
TMS–based
that colloidal
of TMS–based AgBiS2 NCs under
colloidal the same concentration. This indicates that there
TMS–based colloidal AgBiS2AgBiS 2 NCs the
NCs under under theconcentration.
same same concentration. This indicates
This indicates that
that there
are
therefewer
are nonradiative
fewer nonradiativecharge recombination
charge recombination centers, which
centers, which is closely
is closely related
related to
to lower
lower
are fewer nonradiative charge recombination centers, which is closely related to lower
defect density,
defect density, in the the OLA–S–based colloidal
colloidal AgBiS22 NCsNCs compared
compared to to the TMS–based
TMS–based
defect density, in in the OLA–S–based
OLA–S–based colloidal AgBiS AgBiS2 NCs compared to the
the TMS–based
colloidal AgBiS
colloidal NCs.
AgBiS222NCs.
NCs.
colloidal AgBiS

Figure 3.
Figure 3. (a) PL
(a) PL spectra of
PL spectra
spectra TMS–based and
of TMS–based
TMS–based and OLA–S–based
OLA–S–based colloidal
colloidal AgBiS NCs,
AgBiS222NCs, (b)
NCs,(b) UV–vis–NIR
(b)UV–vis–NIR ab-
UV–vis–NIRab-
ab-
Figure 3. (a) of and OLA–S–based colloidal AgBiS
sorption spectra of the colloidal AgBiS2 NCs in hexane, and (c) FT–IR spectra of colloidal AgBiS2 NCs.
sorption spectra of the colloidal AgBiS22 NCs
NCs in
in hexane,
hexane, and (c) FT–IR spectra of colloidal AgBiS2 NCs.

The UV–vis–NIRabsorption
absorption spectraofof TMS–based and OLA–S–based colloidal Ag-
The UV–vis–NIR
UV–vis–NIR absorptionspectra spectra ofTMS–based
TMS–based and
andOLA–S–based
OLA–S–based colloidal AgBiS
colloidal Ag-2
BiS
NCs 2 NCs are shown in Figure 3b. It can be seen that the absorption spectra of
are shown in Figure 3b. It can be seen that the absorption spectra of both of TMS–basedboth of TMS–
BiS 2 NCs are shown in Figure 3b. It can be seen that the absorption spectra of both of TMS–
based
and and OLA–S–based
OLA–S–based colloidal
colloidal AgBiS AgBiS
2 NCs 2 NCs do exhibit
do not not exhibit
any any exciton
exciton absorption
absorption peakpeak
or
based and OLA–S–based colloidal AgBiS 2 NCs do not exhibit any exciton absorption peak
or sharp
sharp absorption
absorption edge
edge in in
thethe rangeofof300–1600
range 300–1600nm, nm,which
whichisissimilar
similar to
to the
the previously
or sharp absorption edge in the range of 300–1600 nm, which is similar to the previously
reported colloidal AgBiS 2 NCs and other ternary semiconductor NCs such as colloidal colloidal
reported colloidal AgBiS22 NCs and other ternary semiconductor NCs such as colloidal
CuInS22,, AgInS
AgInS22andandAgBiSe
AgBiSe 2 NCs
2 NCs [6,54–56].
[6,54–56].The absorption
The spectrum
absorption spectrumof OLA–S–based
of OLA–S–based col-
CuInS2, AgInS2 and AgBiSe2 NCs [6,54–56]. The absorption spectrum of OLA–S–based col-
colloidal AgBiS
loidal AgBiS 2 NCs
2 NCs extends
extends to a to a
largerlarger
IR IR
regionregion
thanthan
the the TMS–based
TMS–based colloidal
colloidal AgBiSAgBiS
2 NCs,
loidal AgBiS2 NCs extends to a larger IR region than the TMS–based colloidal AgBiS2 NCs,2
NCs, which may be owing to the size effect of larger grain size of OLA–S–based colloidal
AgBiS2 NCs. This result is consistent with the result of the TEM images shown above.
Nanomaterials 2022, 12, 3742 5 of 10

Nanomaterials 2022, 12, 3742 5 of 10

which may be owing to the size effect of larger grain size of OLA–S–based colloidal AgBiS2
NCs. This result is consistent with the result of the TEM images shown above.
FT–IR
FT–IR spectroscopy
spectroscopy was was employed
employed toto investigatethe
investigate thefunctional
functionalgroups
groupson onthe
the obtained
obtained
colloidal AgBiS22 NCs NCs [44,57].
[44,57]. Figure
Figure 3c
3c shows
shows thethe FT–IR
FT–IR spectra of colloidal AgBiS22 NCs. NCs.
−1
For TMS–based colloidal colloidal AgBiS
AgBiS22 NCs, the =C–H stretching peak peak at at 3006
3006 cm cm−1, C–H
absorption stretching
stretchingpeakspeaksatat2961,
2961,2929,
2929, and 2854 −1 , and C=O stretching mode at
absorption and 2854 cmcm−1, and C=O stretching mode at 1678
1678 − 1
cm assigned
are assigned
cm−1 are to OA to OA ligands
ligands on theon the surface
surface of colloidal
of colloidal AgBiSAgBiS
2 NCs 2 NCs [55,58].
[55,58]. For
For OLA–
OLA–S–based colloidal AgBiS NCs, the peaks at 903 cm −1 , 721 cm−1 ,−1and 641 cm−1
S–based colloidal AgBiS2 NCs, the 2 peaks at 903 cm , 721 cm , and 641 cm are attributed
−1 −1

areN–H
to attributed
vibrationsto N–H vibrations
of OLA. of OLA. Additionally,
Additionally, a C–N stretching a C–N modestretching
peak was mode peak was
observed at
observed
1145 cm−1.atThe 1145peakcm−at 1 . The peak at 1678 cm−1 can be assigned to C=O stretching of
1678 cm−1 can be assigned to C=O stretching of OA ligands,
OA ligands,
indicating thatindicating that the OLA–S–based
the OLA–S–based colloidal AgBiScolloidal AgBiS2 NCs
2 NCs are coated by OLA are and
coatedOAby OLA
ligands
and OA ligands and that there are no amide–type ligands on
and that there are no amide–type ligands on the surface of the colloidal AgBiS2 NCs. the surface of the colloidal
AgBiS NCs. to reveal the influence of reaction temperature on the synthesis of OLA–S–
In2 order
In order
based colloidal toAgBiS
reveal2 the
NCs, influence of reaction
a synthetic experimenttemperature
was carried on the
out synthesis of OLA–S–
at 80 °C, 100 °C, and
based colloidal AgBiS NCs, a synthetic experiment was carried out at 80 ◦ C, 100 ◦ C, and
120 ◦°C. The crystal structure 2 and phase transition of colloidal AgBiS2 NCs based on OLA–
120
S wereC. investigated
The crystal structure
using XRD. and phase
Figuretransition
4a showsofthe colloidal AgBiS2 NCs
XRD patterns based on OLA–S
of OLA–S–based col-
were investigated using XRD. Figure 4a shows the XRD patterns
loidal AgBiS2 NCs which were synthesized under different injection temperatures. of OLA–S–based colloidal
The
AgBiS NCs which
results2show were synthesized
that colloidal AgBiS2 NCsundercan bedifferent
successfully injection temperatures.
prepared The 120
at 100 °C and results
°C.
show that colloidal AgBiS2 NCs can be successfully prepared at 100 ◦ C and 120 ◦ C. For
For sample prepared at 80 °C, the weak diffraction peak intensity indicates poor crystal-
sample prepared at 80 ◦ C, the weak diffraction peak intensity indicates poor crystallinity of
linity of the obtained product and there are peaks belonging to monoclinic structure Ag2S
the obtained product and there are peaks belonging to monoclinic structure Ag2 S (JCPDS
(JCPDS No. 14–0072) at which impurities can be found. Therefore, pure colloidal AgBiS2
No. 14–0072) at which impurities can be found. Therefore, pure colloidal AgBiS2 NCs
NCs cannot be synthesized at low temperature when using OLA–S as the sulfur source.
cannot be synthesized at low temperature when using OLA–S as the sulfur source. The
The lattice strains of OLA–S–based colloidal AgBiS2 NCs obtained at◦ 100 °C and◦ 120 °C
lattice strains of OLA–S–based colloidal AgBiS2 NCs obtained at 100 C and 120 C were
were calculated using the Williams–Hall plot from Figure S4, the corresponding results
calculated using the Williams–Hall plot from Figure S4, the corresponding results are
are shown in Table S2. The values of the lattice strains for OLA–S–based colloidal AgBiS2
shown in Table S2. The values of the lattice strains for OLA–S–based colloidal AgBiS2 NCs
NCs prepared at◦ 100 °C and◦ 120 °C are 0.27 and 0.38, respectively. It can be seen that the
prepared at 100 C and 120 C are 0.27 and 0.38, respectively. It can be seen that the lattice
lattice strain of OLA–S–based colloidal AgBiS2 NCs produced ◦at 120 °C is greater than the
strain of OLA–S–based colloidal AgBiS2 NCs produced at 120 C is greater than the lattice
lattice strain OLA–S–based
strain OLA–S–based colloidal colloidal
AgBiS2AgBiS NCs prepared
NCs 2prepared at 100 at◦ C,100
with°C,larger
with larger
lattice lattice
strain
strain leading to more defects in the NCs. These results show that
leading to more defects in the NCs. These results show that the defect density OLA–S– the defect density OLA–
S–based colloidal
based colloidal AgBiS
AgBiS 2 NCs prepared at 100 ◦ °C was lower than that of OLA–S–based
2 NCs prepared at 100 C was lower than that of OLA–S–based NCs
NCs produced
produced at 120at◦ C,120meaning
°C, meaning that◦ 100
that 100 °Cbe
C can can be used
used to synthesize
to synthesize high high
qualityquality col-
colloidal
loidal AgBiS
AgBiS2 NC. 2 NC.

Figure
Figure 4.
4. (a)
(a) XRD
XRD patterns of OLA–S–based
patterns of OLA–S–based colloidal
colloidal AgBiS
AgBiS2 NCs synthesized at 80 ◦°C, 100 ◦°C, and
2 NCs synthesized at 80 C, 100 C, and
120 ◦°C; (b–d) EDS elemental mapping (TEM) images of OLA–S–based colloidal AgBiS2 NCs pre-
120 C; (b–d) EDS elemental mapping (TEM) images of OLA–S–based colloidal AgBiS2 NCs prepared
pared at 120 °C.
at 120 ◦ C.
Nanomaterials 2022, 12, 3742 6 of 10

TEM measurement was used to reveal the influence of reaction temperature on the
morphology and size distribution of OLA–S–based colloidal AgBiS2 NCs. Figure S5 shows
that the colloidal AgBiS2 NCs prepared at 120 ◦ C have a uniform spherical shape and that
the average diameter of the obtained NCs is 12.1 ± 3.5 nm (Figure S5a). An HR–TEM
image of colloidal AgBiS2 NCs prepared at 120 ◦ C is shown in Figure S5b. The cubic rock
salt structure of AgBiS2 with a lattice spacing of about 0.32 nm corresponding to the (111)
crystal plane spacing can be seen, and is consistent with the XRD results. Figure 4b–d
provides elemental diagram images of OLA–S–based colloidal AgBiS2 NCs synthesized at
120 ◦ C. The atomic percentages of Ag, Bi, and S are 48.4, 17.1, and 34.6, respectively. These
results show that the surface of the obtained colloidal AgBiS2 NCs should be silver–rich and
sulfur–rich. Because the lattice strain of the OLA–S–based colloidal AgBiS2 NCs prepared at
120 ◦ C is larger than that prepared at 100 ◦ C, high reaction temperature may be detrimental
to the preparation of high quality OLA–S–based colloidal AgBiS2 NCs.
Figure S6a shows the UV–vis–NIR absorption spectra of OLA–S–based colloidal
AgBiS2 NCs prepared at 100 ◦ C and 120 ◦ C. The absorption spectrum of the sample
synthesized at 120 ◦ C extends to more IR regions than that of the NCs prepared at 100 ◦ C,
which is mainly caused by the size effect of the colloidal AgBiS2 NCs. To further reveal
the effect of reaction injection temperature on the quality of the obtained colloidal AgBiS2
NCs, the PL spectra of OLA–S–based colloidal AgBiS2 NCs prepared at 100 ◦ C and 120 ◦ C
were measured using 330 nm excitation wavelength at room temperature. The PL intensity
of OLA–S–based colloidal AgBiS2 NCs synthesized at 100 ◦ C is stronger than that of NCs
synthesized at 120 ◦ C (Figure S6b). This reflects that the OLA–S–based colloidal AgBiS2
NCs prepared at 100 ◦ C has fewer defects than the colloidal AgBiS2 NCs synthesized at
120 ◦ C.
In addition, the influence of OLA–S dosage in the reaction when synthesizing colloidal
AgBiS2 NCs was investigated. We carried out the synthesis of colloidal AgBiS2 NCs
using different amount of OLA–S (1 M). The crystallinity and phase purity of OLA–S–
based colloidal AgBiS2 NCs synthesized under different conditions were examined by
XRD. (Figure 5). It can be seen that only Ag2 S was produced in the reaction when using
1 mL OLA–S, while both Ag2 S and AgBiS2 were formed when the dosage of OLA–S was
increased to 2 mL. Thus, pure phase colloidal AgBiS2 NCs can be successfully prepared
using 3 mL and 4 mL OLA–S. Based on these results, we speculate that the reaction process
of OLA–S–based colloidal AgBiS2 NC synthesis should be that: H2 S being released in situ
from OLA–S after OLA-S was injected into high temperature cationic solution [59], and
then reacting with Ag+ to form Ag2 S, subsequently, the produced Ag2 S reacts with Bi3+ to
form AgBiS2 NCs. The reaction equations are as follows:

2Ag+ + H2 S → Ag2 S + 2H+ , (1)

2Ag2 S + Bi3+ → AgBiS2 + 3Ag+ (2)

The lattice strain values calculated for the colloidal AgBiS2 NCs prepared by using
3 mL and 4 mL OLA–S are 0.27 and 0.40, respectively, as shown in Figure S7 and Table S3.
The smaller lattice strain in colloidal AgBiS2 NCs prepared using 3 mL OLA–S indicates
a lower defect density in the NCs. To clarify the effect of the dosage of OLA–S on the
morphology and size distribution of colloidal AgBiS2 NCs, we carried out HR–TEM mea-
surements of the obtained AgBiS2 NCs. Figure S8a shows that colloidal AgBiS2 NCs
prepared using 4 mL OLA–S have a uniform spherical shape and the average diameters
of NCs are about 8.3 ± 2.7 nm, which is a little larger than that based on 3 mL OLA–S
(7.8 ± 1.9 nm; see Figure S2b). Figure S6c shows the UV–vis–NIR absorption spectra of
3 mL and 4 mL OLA–S–based colloidal AgBiS2 NCs. The absorption spectrum of the
4 mL OLA–S–based colloidal AgBiS2 NCs extends to more IR regions than that of the
3 mL OLA–S–based colloidal AgBiS2 NCs, which is mainly caused by the size effect of the
colloidal AgBiS2 NCs.
Nanomaterials 2022,12,
Nanomaterials2022, 12,3742
3742 77 ofof1010

Figure5.5.XRD
Figure XRDpatterns
patternsofofcolloidal
colloidalOLA–S–based
OLA–S–basedAgBiS
AgBiS NCsusing
2 2NCs using11mL,
mL,22mL,
mL,33mL,
mL,and
and4 4mL.
mL.

Finally,
Finally,we
wecalculated the cost
calculated the costand
andyield
yieldofofthe
the synthesis
synthesis of colloidal
of colloidal AgBiS
AgBiS 2 NCs2 NCs
using
using
TMS TMS and OLA–S
and OLA–S as sulfur
as sulfur sources.
sources. Compared
Compared with the
with TMS, TMS, theofcost
cost of synthesis
synthesis using
using OLA–S
OLA–S was reduced
was reduced about
about 57% (see 57%
Table(see Table
S4 for S4 for
details). Wedetails).
found thatWethefound
yield that the yield
of colloidal of 2
AgBiS
colloidal
NCs basedAgBiS 2 NCs
on TMS based
and on TMS
OLA–S wereand86.9%OLA–S were respectively.
and 90.5%, 86.9% and 90.5%, respectively.
This indicates This
that OLA–
indicates that OLA–S
S can replace TMS forcan replace TMS
synthesizing for synthesizing
colloidal AgBiS2 NCscolloidal AgBiSsulfur
as a low–cost 2 NCssource.
as a low–cost
sulfur source.
4. Conclusions
4. Conclusions
In summary, we optimized the synthesis conditions of colloidal AgBiS2 NCs using
In summary,
OLA–S we optimized
as the sulfur the synthesis
source. Colloidal AgBiS2 conditions
NCs with high of colloidal
quality AgBiS 2 NCs
and pure using
phase can
OLA–S as the sulfur source. Colloidal AgBiS 2 NCs with high quality and
be synthesized by rationally optimizing the dosage and reaction injection temperature pure phase canof
be synthesized by rationally optimizing the dosage and reaction injection temperature of
OLA–S. Compared with TMS as the sulfur source, OLA–S–based colloidal AgBiS2 NCs
OLA–S. Compared with TMS as the sulfur source, OLA–S–based colloidal AgBiS2 NCs
have lower defect density and a wider absorption spectrum. More importantly, the cost
have lower defect density and a wider absorption spectrum. More importantly, the cost
of synthesis is greatly reduced, as the yield of colloidal AgBiS2 NCs is increased when
of synthesis is greatly reduced, as the yield of colloidal AgBiS2 NCs is increased when
using OLA–S to replace the more expensive TMS. In addition, the pungent odor and air
using OLA–S to replace the more expensive TMS. In addition, the pungent odor and air
sensitivity of TMS can be avoided. As a low–cost sulfur source, OLA–S has the potential
sensitivity of TMS can be avoided. As a low–cost sulfur source, OLA–S has the potential to
to for use in synthesizing other sulfide NCs in the future.
for use in synthesizing other sulfide NCs in the future.
Supplementary Materials: The supporting information can be downloaded at:
Supplementary Materials: The supporting information can be downloaded at: https://www.mdpi.
https://www.mdpi.com/article/10.3390/nano12213742/s1. Figure S1. The William–Hall plots for (a)
com/article/10.3390/nano12213742/s1. Figure S1. The William–Hall plots for (a) TMS–based and
TMS–based and (b) OLA–S–based colloidal AgBiS2 NCs. Figure S2. TEM images of (a) TMS–based
(b) OLA–S–based
and (b) OLA–S–based colloidal AgBiS2AgBiS
colloidal NCs.2Figure S2. TEM
NCs. Insets areimages of (a) TMS–based
the statistical histogramsand (b) OLA–S–
of the NCs size
based colloidal AgBiS 2 NCs. Insets are the statistical histograms of the
distribution. SAED images of (c) TMS–based and (d) OLA–S–based colloidal AgBiS2 NCs. Figure NCs size distribution. SAED S3.
images of (c) TMS–based and (d) OLA–S–based colloidal AgBiS NCs.
EDS–Mapping images of (a), (b) and (c)TMS–based. EDS–Mapping images of (d), (e) and (f) OLA–
2 Figure S3. EDS–Mapping
images
S–based of (a), (b) and
colloidal (c)TMS–based.
AgBiS 2 NCs. Figure EDS–Mapping images of (d),
S4. The William–Hall plots(e)for
and
(a)(f)
andOLA–S–based
(b) OLA–S–basedcolloidalcol-
AgBiS NCs. Figure
loidal2 AgBiS S4. The at
2 NCs prepare William–Hall
100 °C and 120 plots°C.forFigure
(a) andS5.(b) OLA–S–based
TEM images of (a) colloidal AgBiS2 colloi-
OLA–S–based NCs
prepare at 100 ◦ C and 120 ◦ C. Figure S5. TEM images of (a) OLA–S–based colloidal AgBiS NCs
dal AgBiS 2 NCs prepare at 120 °C. Insets are the statistical histograms of the NCs size distribution. 2
prepare ◦ C. Insets are the statistical histograms of the NCs size distribution. (b) HR–TEM
at 120 images
(b) HR–TEM of OLA–S–based colloidal AgBiS2 NCs prepare at 120 °C. (c) SAED image of
images of OLA–S–based
OLA–S–based colloidal colloidal
AgBiS2 NCs AgBiS 2 NCs
prepare atprepare at 120 ◦S6.
120 °C. Figure C. (a)
(c) UV–vis–NIR
SAED image absorption
of OLA–S–based
spectra
of the colloidal
colloidal AgBiS2 NCs AgBiS 2 NCs in
prepare ◦
at hexane. (b) PL S6.
120 C. Figure spectrum and fittingabsorption
(a) UV–vis–NIR curves of spectra
OLA–S–based colloidal
of the colloidal
AgBiS
AgBiS NCsinprepare
2 2NCs hexane. at(b)
100PL°Cspectrum
and 120 °C. and(b)fitting
UV–vis–NIR
curves of absorption
OLA–S–based spectra of the 3AgBiS
colloidal mL and 4 mL
2 NCs
colloidal
prepare 100 ◦ C2 NCs
at AgBiS and 120 ◦ C. (b)Figure
in hexane. S7. Theabsorption
UV–vis–NIR William–Hall plotsoffor
spectra the(a)3 3mL
mLand
and4(b)mL4 colloidal
mL OLA–
S–based
AgBiS 2 NCs colloidal AgBiS
in hexane. 2 NCs.
Figure S7.Figure S8. TEM images
The William–Hall plotsoffor
(a)(a)
4 mL
3 mL OLA–S–based
and (b) 4 mLcolloidal
OLA–S–basedAgBiS2
NCs. Insets are the statistical histograms of the NCs size distribution.
colloidal AgBiS2 NCs. Figure S8. TEM images of (a) 4 mL OLA–S–based colloidal AgBiS2 NCs. Insets (b) HR-TEM images of 4 mL
OLA–S–based colloidal AgBiS NCs. (c) SAED image of 4 mL OLA–S–based
are the statistical histograms of the NCs size distribution. (b) HR-TEM images of 4 mL OLA–S–based
2 colloidal AgBiS 2 NCs.
Table S1. Half–peak widths and lattice strains of OLA–S–based
colloidal AgBiS2 NCs. (c) SAED image of 4 mL OLA–S–based colloidal AgBiS2 NCs. Table S1. 2 and TMS–based colloidal AgBiS
NCs. Table
Half–peak S2. Half–peak
widths and latticewidths
strainsand lattice strainsand
of OLA–S–based of OLA–S–based colloidalAgBiS
TMS–based colloidal AgBiS2NCs.
NCs prepare
Table S2.at
2
Half–peak widths and lattice strains of OLA–S–based colloidal AgBiS2 NCs prepare at 100 ◦ Ccolloi-
100 °C and120 °C. Table S3. Half–peak widths and lattice strains of 3 mL and 4 mL OLA–S–based and
dal◦AgBiS
120 C. Table 2 NCs. Table S4. Raw material usage, price and yield of AgBiS2 NCs based on TMS and OLA–
S3. Half–peak widths and lattice strains of 3 mL and 4 mL OLA–S–based colloidal
S. Reference [60] is cited in the Supplementary Materials.
Nanomaterials 2022, 12, 3742 8 of 10

AgBiS2 NCs. Table S4. Raw material usage, price and yield of AgBiS2 NCs based on TMS and OLA–S.
Reference [60] is cited in the Supplementary Materials.
Author Contributions: Q.L. and Y.Z. conceived and designed the experiments; Q.L., X.Z., X.S.
and S.D. performed the experiments; Q.L., X.Z. and Y.Z. analyzed the data; H.F., G.W. and Y.Z.
contributed reagents/materials/analysis tools; Q.L. wrote the paper; Y.Z. and G.W. corrected the
paper. All authors have read and agreed to the published version of the manuscript.
Funding: This research was supported by the National Natural Science Foundation of China under
grant No. 52103223.
Data Availability Statement: The data that support the findings of this study are available from the
corresponding author upon reasonable request.
Conflicts of Interest: The authors declare no conflict of interest.

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