nanomaterials

Article
High-Pressure Behaviors of Ag2S Nanosheets: An in
Situ High-Pressure X-Ray Diffraction Research
Ran Liu, Bo Liu, Quan-Jun Li and Bing-Bing Liu *
State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012, China;
liuran@jlu.edu.cn (R.L.); jluliubo@jlu.edu.cn (B.L.); liquanjun@jlu.edu.cn (Q.-J.L.)
* Correspondence: liubb@jlu.edu.cn; Tel.: +86-431-8518256




Received: 25 July 2020; Accepted: 14 August 2020; Published: 21 August 2020


Abstract: An in situ high-pressure X-ray diffraction study was performed on Ag2 S nanosheets,
with an average lateral size of 29 nm and a relatively thin thickness. Based on the experimental data,
we demonstrated that under high pressure, the samples experienced two different high-pressure
structural phase transitions up to 29.4 GPa: from monoclinic P21 /n structure (phase I, α-Ag2 S) to
orthorhombic P21 21 21 structure (phase II) at 8.9 GPa and then to monoclinic P21 /n structure (phase
III) at 12.4 GPa. The critical phase transition pressures for phase II and phase III are approximately
2–3 GPa higher than that of 30 nm Ag2 S nanoparticles and bulk materials. Additionally, phase III
was stable up to the highest pressure of 29.4 GPa. Bulk moduli of Ag2 S nanosheets were obtained as
73(6) GPa for phase I and 141(4) GPa for phase III, which indicate that the samples are more difficult to
compress than their bulk counterparts and some other reported Ag2 S nanoparticles. Further analysis
suggested that the nanosize effect arising from the smaller thickness of Ag2 S nanosheets restricts
the relative position slip of the interlayer atoms during the compression, which leads to the enhancing
of phase stabilities and the elevating of bulk moduli.

Keywords: Ag2 S; nanosheets; high pressure; phase transitions

1. Introduction
As a well-known metal sulfide, Ag2 S is a direct narrow band gap semiconductor (~1.5 eV),
with high absorption coefficient (104 m−1 ), good chemical stability and optical properties [1–3]. So far,
Ag2 S materials have been extensively synthesized and studied due to their important applications
including semiconductors, photovoltaic cells, infrared detectors, photoelectric switches and oxygen
sensors [4–6]. Recently, the phase transitions of Ag2 S have attracted much attention and a lot of
research has been conducted around this topic. Under ambient conditions, Ag2 S is stable in a
monoclinic structure with P21 /n space group (α-Ag2 S) [7]. While heating above 450 K, Ag2 S undergoes
a thermo-induced phase transition and reforms into a body-centered cubic (bcc) structure (β-Ag2 S,
space group Im3m) [8,9]. In this high-temperature structure, silver ions are randomly distributed over
the interstitial sites of a bcc sulfur lattice [10,11], leading to a favorable ionic conductivity as high as
5 Ω−1 cm−1 [12]. Thereby, β-Ag2 S is considered as a fast ionic conductor (FIC), which has potential
applications including in energy, analytical chemistry, biomedicine, solid-state ionic devices and so
forth [13–15]. At about 860 K, Ag2 S further converse into a face-centered cubic (fcc) phase (γ-Ag2 S),
then keeping stable up to melting temperature [9].
Instead of temperature, high pressure is an effective approach for tuning both structural
phase transitions and physical properties [16,17]. Under high pressure, the atomic arrangement
of materials would be dramatically changed, and thus, the electronic structures and physical
properties could be improved. For bulk Ag2 S, structural and optical behaviors under high
pressure have been systematically studied by synchrotron X-ray diffraction and infrared spectroscopy

Nanomaterials 2020, 10, 1640; doi:10.3390/nano10091640 www.mdpi.com/journal/nanomaterials

Nanomaterials 2020, 10, 1640 2 of 9

measurements [15,18,19]. It is demonstrated that Ag2 S bulk material experiences a series of phase
transitions up to 40 GPa. At 5.1 GPa, bulk Ag2 S transforms from the P21 /n structure (α-Ag2 S, phase I)
to an orthorhombic P21 21 21 structure (phase II). Elevating the pressure up to 8.8 GPa, Ag2 S undergoes
the second phase transition, from phase II to a monoclinic P21 /n structure (phase III), which is
isosymmetric to phase I. At 28.4 GPa, phase III further transforms into a Pnma structure (phase IV).
Accompanied by structural transformations, the band gap of Ag2 S is narrowed gradually by increasing
the pressure. Beyond 22 GPa, the pressure effectively tunes the semiconducting Ag2 S into a metal [19].
Up to now, with the rapid development of synthesis technology, many kinds of nanostructured
Ag2 S have been prepared, such as quantum dots [20], nanoparticles [21,22], nanotubes [23],
nanowires [24], nanorods [25], sheet-like and cube-like nanocrystals [26] and so forth. This progress
inspired researchers to begin to focus on the pressure-induced phase transitions of Ag2 S nanomaterials,
where they expected to obtain novel properties under pressure. Thus far, there has been one report
on the high-pressure behaviors of pure and Y-doped Ag2 S nanoparticles [27]. The particle sizes of
the two samples were estimated to be about 30 nm. Indeed, Wang et al. have found that both of
the samples exhibit slightly higher transition pressure values and obviously increased bulk moduli than
that of the corresponding bulk materials. We note that previous studies have been focused on Ag2 S
nanocrystals with random geometric shapes. It is still unclear what behaviors of Ag2 S nanocrystals
with special morphologies will actually be induced by high pressure. In particular, it is still unknown
whether or not they will choose the known structural evolution laws as well as the nanoparticles.
These require further studies.
In this work, we investigate the high-pressure behaviors of Ag2 S nanomaterials with sheet-like
morphologies using the in situ high-pressure X-ray diffraction up to about 30 GPa. A set of phase
transitions of Ag2 S nanosheets were observed. Interestingly, the Ag2 S nanosheets exhibit even
higher structural stability and lower compressibility under high pressure, remarkably different from
the Ag2 S bulk materials and nanoparticles. Further analysis suggested that the stronger nanosize effect
arising from the smaller thickness of Ag2 S nanosheets effectively restricts the relative position slip
of the interlayer atoms during the compression, which leads to the enhancement of phase stabilities
and the elevation of bulk moduli. Our findings give a further insight into high-pressure behaviors of
Ag2 S nanomaterials.

2. Materials and Methods

In this study, Ag2 S nanosheet was provided by Tongshun Wu, Ph. D. of State Key Laboratory
of Inorganic Synthesis and Preparative Chemistry, Jilin University (Changchun, China), which was
prepared by solvothermal method. The initial sample was dispersed in ethanol, with no substrate or
coating. A HITACHI H-8100 (Hitachi, Ltd., Tokyo, Japan) transmission electron microscope (TEM)
with accelerating voltage of 200 kV was employed to analyze the typical product. X-ray powder
diffraction (XRD) was used to characterize the product and the XRD patterns at ambient condition were
collected by a Rigaku D/max-rA XRD (Rigaku Co., Tokyo, Japan) spectrometer (Cu, Kα, λ = 1.5406 Å).
A symmetric diamond anvil cell (DAC) with flat diamond culets of 400 µm in diameter was used
to generate high pressure. The DAC allowed access to the X-ray diffraction angular range 4θ = 50◦ .
A sheet of T301 stainless steel was selected as the gasket and pre-indented in the DAC to an initial
thickness of about 40 µm. Then, a hole of 150 µm in diameter was drilled manually by a tungsten carbide
needle in the middle of the dent, which served as a sample chamber. The Ag2 S nanosheet samples
along with the dispersant were loaded simultaneously into the sample chamber to keep the dispersity.
A mixture of methanol and ethanol at a ratio of 4:1 was used as the pressure transmitting medium.
A tiny ruby ball ~5 µm in diameter was loaded in the sample chamber, and pressure was determined
by the frequency shift of the ruby R1 fluorescence line. High-pressure X-ray diffraction experiments
were carried out up to 30 GPa using a synchrotron X-ray source (λ = 0.386 Å) of the beamline X17C of
National Synchrotron Light Source (NSLS), Brookhaven National Lab (BNL). The monochromatic X-ray
beam was focused down to 25 µm × 25 µm using Kirkpatrick-Baez mirrors. For filtering out the tail of
Nanomaterials 2020, 10, 1640 3 of 9

Nanomaterials 2020, 10, x FOR PEER REVIEW 3 of 10

the X-ray beam, a pinhole was placed before the sample position as a cleanup aperture. The X-ray
diffraction
mirrors.images wereout
For filtering collected bythe
the tail of a MAR345
X-ray beam, image plate,was
a pinhole located
placed~350 mm
before thebehind
sample the sample.
position
Exposure times were
as a cleanup typically
aperture. 300~600
The X-ray s. Geometric
diffraction images werecorrection and
collected byradial integration
a MAR345 was done
image plate, using
located
the Fit2D
~350 mm software
behind(v12.077, GRENOBLE,
the sample. Exposure times France). The observed
were typically 300~600 intensities were
s. Geometric integrated
correction andas a
radialofintegration
function 2θ in order was done conventional,
to give using the Fit2Done-dimensional
software (v12.077, GRENOBLE,
diffraction France).
profiles. The observed
Rietveld refinement
intensities were integrated as a function of 2θ in order to give conventional,
was performed by GSAS-EXPGUI package (v1.80, Gaithersburg, Maryland, USA). A Birch-Murnaghan one-dimensional
(BM)diffraction
equation of profiles. Rietveld
state (EOS) refinementtowas
was employed performed
fit the by GSAS-EXPGUI
experimental P-V relationship,package (v1.80, Pro
using Origin
Gaithersburg, Maryland, USA). A Birch-Murnaghan (BM) equation of state (EOS) was employed to
software (v8.0, Northampton, MA, USA).
fit the experimental P-V relationship, using Origin Pro software (v8.0, Northampton, MA, USA).
3. Results and Discussion
3. Results and Discussion
To investigate the morphology and structure of the Ag2 S samples, TEM and selected area electron
To investigate the morphology and structure of the Ag2S samples, TEM and selected area
diffraction (SAED) analysis was performed. Figure 1a shows the TEM image and SAED pattern of
electron diffraction (SAED) analysis was performed. Figure 1a shows the TEM image and SAED
the Ag 2 S samples.
pattern of the AgIt2Scan be clearly
samples. It can seen that all
be clearly seenAg 2 S nanocrystals
that are well
all Ag2S nanocrystals aredispersed and possess
well dispersed and
sheet-like morphology; no other shapes can be observed. SAED pattern (inset
possess sheet-like morphology; no other shapes can be observed. SAED pattern (inset in Figure in Figure 1a) determines
1a)
the samples
determines arethe well crystalized
samples are well incrystalized
a monoclinic in a P2 1 /n structure.
monoclinic Figure 1bFigure
P21/n structure. shows1bthe lateral
shows thesize
distribution of distribution
lateral size Ag2 S nanosheets.
of Ag2SThe distribution
nanosheets. is relativelyisnarrow,
The distribution and
relatively the average
narrow, lateral
and the size is
average
29 ±lateral
2 nm. In
sizeprinciple,
is 29 ± 2fornm.theInTEM image,for
principle, thethe
contrast
TEM of the image
image, normally
the contrast of represents
the image the thickness
normally
represents
of samples. The thesmooth
thickness of samples.
contrast The
of each Agsmooth contrastgrain
2 S nanosheet of each Ag2S that
proves nanosheet grain proves
the samples that
have uniform
the samples
thickness. have uniform
Interestingly, the Ag2thickness. Interestingly,
S nanosheets the Ag2S nanosheets
are approximately semitransparentare approximately
(see the sample
semitransparent
overlaps in TEM image), (see the sample
which overlaps inthat
demonstrates TEMthe image), which
thickness ofdemonstrates that the thickness
samples is relatively of
thin, far below
samples is relatively thin, far below 29 nm. All the analyses show that
29 nm. All the analyses show that Ag2 S samples are well crystallized and have an almost-uniform Ag 2S samples are well

crystallized and have an almost-uniform morphology as nanosheets, providing ideal samples for
morphology as nanosheets, providing ideal samples for high-pressure research.
high-pressure research.

Figure
Figure 1. Typical
1. Typical transmission
transmission electron
electron microscope
microscope (TEM)
(TEM) images
images and
and particle
particle size
size distribution:(a)(a)
distribution: TEM
TEM images and selected area electron diffraction (SAED) image (inset) of the samples. (b) Size
images and selected area electron diffraction (SAED) image (inset) of the samples. (b) Size distribution
distribution of Ag2S nanosheets.
of Ag2 S nanosheets.

In order to further study the crystal structure of Ag2S nanosheets, XRD analysis was carried
In order to further study the crystal structure of Ag2 S nanosheets, XRD analysis was carried out.
out. Figure 2 shows the typical XRD pattern of the samples and its Rietveld refinement under
Figure 2 shows the typical XRD pattern of the samples and its Rietveld refinement under ambient
ambient conditions. It can be seen that the diffraction pattern can be indexed into α-Ag2S phase
conditions. It can be seen that the diffraction pattern can be indexed into α-Ag2 S phase (Joint Committee
(Joint Committee on Powder Diffraction Standards (JCPDS) card no. 14-0072) (monoclinic structure,
on Powder Diffraction
space group P21/n). Standards (JCPDS)
Vertical markers card the
indicate no.Bragg
14-0072) (monoclinic
reflections of the structure, space group
P21/n monoclinic P21 /n).
structure.
Vertical markers
It can be seenindicate
that no the
otherBragg reflections
diffraction the P2
peaksofexist, 1 /n monoclinic
which means that structure. It can be
no other phases or seen
otherthat
no other diffraction
impurities peaks in
are mixing exist,
the which
sample. means that no other
The Rietveld phasesoforthe
refinement other
XRDimpurities
pattern atare mixing in
ambient
the sample.
pressureThe Rietveld
yields refinement
a = 4.214 ± 0.001 Å,ofb the XRD± pattern
= 6.912 0.001 Å,at c =ambient pressure
7.853 ± 0.001 Å, βyields a = ±4.214
= 99.580° ± 0.001
0.010°, V0 = Å,
b = 6.912
225.55± ±0.001
0.034Å,Åc =for
3 Ag2±S 0.001
7.853 Å, β = 99.580
nanosheets, ◦
slightly ±smaller ◦ V0 =30
0.010 ,than 225.55
nm Ag ± 0.034 3
Å for Ag2 Sand
2S nanoparticles nanosheets,
bulk
materials
slightly smaller[27,28].
than The
30 nmexistence of a lattice shrinking
Ag2 S nanoparticles and bulk phenomenon of Ag2SThe
materials [27,28]. nanosheets
existencecould be
of a lattice
attributed
shrinking to the stronger
phenomenon nanosize
of Ag 2 S effect
nanosheets as a result
could of
be their smaller
attributed tothickness.
the stronger nanosize effect as a
result of their smaller thickness.
Nanomaterials 2020, 10, 1640 4 of 9
Nanomaterials 2020, 10, x FOR PEER REVIEW 4 of 10

Figure
Figure 2. The
2. The typical
typical X-ray
X-ray powderdiffraction
powder diffraction (XRD)
(XRD) pattern
pattern of
of Ag
Ag2S2 Snanosheets
nanosheetsunder ambient
under ambient
conditions; Rwp = 0.3133, Rp = 0.2028, and chi^2 =
conditions; Rwp = 0.3133, Rp = 0.2028, and chiˆ2 = 84.89.84.89.

To systematically
To systematically explore
explore the the high-pressurebehavior
high-pressure behavior ofof Ag
Ag2S2 Snanosheets,
nanosheets, wewe carried
carriedoutout
an in an in
situ high-pressure X-ray diffraction study. Figure 3 shows synchrotron X-ray diffraction patterns of
situ high-pressure X-ray diffraction study. Figure 3 shows synchrotron X-ray diffraction patterns of
Ag2S nanosheets under different pressures. It is clear that under high pressures, two phase
Ag2 S nanosheets under different pressures. It is clear that under high pressures, two phase transitions
transitions for the samples are observed up to 29.4 GPa. With pressure increasing, all the peaks of
for the samples are observed up to 29.4 GPa. With pressure increasing, all the peaks of α-Ag2 S
α-Ag2S phase shift to smaller d-spacing, indicating a pressure-induced reduction of d-spacing and
phase shift to smaller
shrinkage d-spacing,
of the unit indicating
cell. The initial phaseacan pressure-induced
be maintained up reduction
to 8.9 GPa, d-spacing
of much moreand
stableshrinkage
than
of the
that in Ag2S nanoparticles and bulk materials [19,27]. At 5.4 GPa (the first phase transition point ofthat
unit cell. The initial phase can be maintained up to 8.9 GPa, much more stable than
in Ag 2 S nanoparticles
bulk Ag2S), the measuredand bulk XRDmaterials
pattern is[19,27].
consistent Atwith
5.4 GPa (the first
the starting phase transition
monoclinic point of
P21/n structure
bulk(phase
Ag2 S),I).the
Themeasured XRD pattern
mutual agreements encourageis consistent withsubsequent
us to perform the starting finemonoclinic P21 /n on
Rietveld analysis structure
our
(phase I). The mutual
experimental agreements
data by using the P2 encourage us toAsperform
1/n structure. shown in subsequent
Figure 4, the fine Rietveld
fitting givesanalysis
a successfulon our
result to the
experimental experimental
data by using the data.P2 The
1 /n lattice constants
structure. As of Ag
shown 2Sin
nanosheets
Figure 4, at 5.38
the GPa
fitting are as
gives follows:
a successfula
= 4.107 ± 0.002 Å, b = 6.659 ± 0.003 Å, c = 7.616 ± 0.004 Å, β = 99.62° ± 0.03,
result to the experimental data. The lattice constants of Ag2 S nanosheets at 5.38 GPa are as follows: V 0 = 205.3 ± 0.1 Å 3.

According
a = 4.107 ± 0.002to the
Å, bfitting
= 6.659data, all of Å,
± 0.003 thecdiffraction
= 7.616 ± peaks
0.004 can
Å, βbe = indexed
99.62◦ ±to0.03, the initial monoclinic
V0 = 205.3 ± 0.1 Å3 .
P2 1/n structure. No new phases were observed at this pressure.
According to the fitting data, all of the diffraction peaks can be indexed to the initial monoclinic P21 /n
While compressing up to 8.9 GPa, several new peaks (marked as asterisks) start to emerge
structure. No new phases were observed at this pressure.
obviously and their intensity grows with pressure increasing (see Figure 3), indicating that α-Ag2S
While compressing up to 8.9 GPa, several new peaks (marked as asterisks) start to emerge
undergoes a phase transition. According to previous reports, these new peaks located at 8.96°, 9.18°,
obviously and their
9.39°, 10.90° and intensity
11.05° cangrows with pressure
be indexed increasing
into the (120), (see Figure
(112), (121), (113) and 3), indicating that α-Ag
(201) diffractions of 2 S
undergoes a phase transition. According to previous reports, these new peaks located at 8.96 ◦ , 9.18◦ ,
orthorhombic P212121 structure (phase II). Both phase I and phase II of Ag2S coexist under this
9.39◦pressure.
, 10.90◦ No andpure
11.05 ◦ can be indexed into the (120), (112), (121), (113) and (201) diffractions of
phase II structure could be obtained in our work. With continuous compression,
orthorhombic
all the peaksP21of21ambient
21 structure
phase(phase
I became II). Both
weakphase I and phase II of Ag2 S coexist under this pressure.
gradually.
No pure phase II structure could be obtained in our work. With continuous compression, all the peaks
of ambient phase I became weak gradually.
Further compressed to 12.4 GPa, it can be clearly seen that a set of new diffraction peaks (2θ = 9.39◦ ,
9.78 , 10.87◦ , 11.30◦ ) emerged (marked as arrows in Figure 3), indicating that Ag2 S nanosheets undergo
◦

the second phase transition. These new diffraction peaks can be indexed into (022), (12-1), (200)
and (014) diffractions of monoclinic P21 /n structure (phase III), isosymmetric to the ambient phase. Both
phase II and phase III coexist under this pressure. However, the peaks corresponding to phase II lost a
lot of intensity and then completely disappeared at the pressure of 16.5 GPa. Under this pressure, all of
the remaining peaks can be indexed to phase III, indicating Ag2 S nanosheets crystallized in monoclinic
P21 /n structure completely. Typical Rietveld refinement for phase III is plotted in Figure 5, yielding
a = 4.079 ± 0.003 Å, b = 5.800 ± 0.006 Å, c = 7.948 ± 0.008 Å and β = 93.15◦ ± 0.07 (V = 187.7 ± 0.2 Å3 ).
Compressing the samples up to 29.4 GPa, the highest pressure in our study, no new diffraction peaks
were observed, Ag2 S nanosheets are mainly still maintaining in phase III.
Nanomaterials 2020, 10, 1640 5 of 9
Nanomaterials2020,
Nanomaterials 2020,10,
10,x xFOR
FORPEER
PEERREVIEW
REVIEW 5 5ofof1010

Figure
Figure
Figure Synchrotron
3.3.3.Synchrotron X-raydiffraction
SynchrotronX-ray diffraction
diffraction patterns
patterns
patterns of
ofofAg
Ag Ag
2S 2 S nanosheets
2Snanosheets
nanosheets under
under under different
different
different pressures.
pressures.
pressures. The
The
The asterisks
asterisks
asterisks and and
and arrows
arrows
arrows denote
denote
denote the the occurrences
theoccurrences
occurrences of new
ofofnew
new peaks
peaks
peaks for phase
forphase
for phaseIIIIand IIphase
and and
phasephase III, respectively.
III,respectively.
III, respectively.

Figure 4.The
The refinement resultfor
forthe
themonoclinic
monoclinicP2 P2 1/nstructure
structure(phase
(phaseI)I)ofofAg
Ag
2S2Snanosheets
nanosheetsatat
1 /n structure (phase I) of Ag2 S nanosheets at
Figure
Figure 4.4.The refinement
refinement result
result for the monoclinic P21/n

5.38
5.38
5.38 GPa,
GPa,Rwp
GPa, Rwp = 0.3011,
Rwp==0.3011, Rp
Rp =
0.3011, Rp = 0.1836
= 0.1836
0.1836and and chi^2 = 109.9.
chiˆ2==109.9.
andchi^2 109.9.
plotted in Figure 5, yielding a = 4.079 ± 0.003 Å, b = 5.800 ± 0.006 Å, c = 7.948 ± 0.008 Å and β = 93.15°
± 0.07 (V = 187.7 ± 0.2 Å3). Compressing the samples up to 29.4 GPa, the highest pressure in our
study, no new diffraction peaks were observed, Ag2S nanosheets are mainly still maintaining in
phase III.
Nanomaterials 2020, 10, 1640 6 of 9

Figure Figure The refinementresult

5. The5. refinement result for
forphase
phaseIII of
IIIAgof2 S Ag
nanosheets at 16.5 GPa,
2S nanosheets 16.5= GPa,
at Rwp Rp = 0.1402
0.1921, Rwp = 0.1921, Rp =
and chiˆ2 = 67.78.
0.1402 and chi^2 = 67.78.
In previous studies, we noted that bulk Ag2 S undergoes the phase transition sequence P21 /n
In (phase
previous I) →studies, we noted
P21 21 21 (phase II) →thatP21 /nbulk
(phaseAgIII)
2S undergoes
→ Pnma (phase the IV)
phase transition
at pressures sequence P21/n
of 5.1GPa,
(phase I) → P212121 (phase II) → P21/n (phase III) → Pnma2 (phase IV) at pressures of 5.1GPa, 8.8 GPa
8.8 GPa and 28.4 GPa, respectively [19]. For pure 30 nm Ag S nanoparticles, the transition pressures
and 28.4 elevate
GPa,slightly compared
respectively to the
[19]. Forbulk: from
pure 30phase
nm IAg to 2phase II at about 6.83the
S nanoparticles, GPatransition
and then topressures
phase III elevate
at 9.3 GPa [27]. Compared to these reports, we noted that phase transition pressure in Ag2 S nanosheets
slightly compared to the bulk: from phase I to phase II at about 6.83 GPa and then to phase III at 9.3
was about 2–3 GPa higher than that in 30 nm Ag2 S nanoparticles and bulk crystals. Moreover,
GPa [27].phase Compared
IV [19], whichto these
formed reports, we noted
at 28.4 GPa in bulk that phase transition
counterparts, pressure
was not observed in Ag
in our 2S nanosheets
samples.
was aboutThus,2–3ourGPa
workhigher than
reveals that Agthat in 30 nmexhibit
2 S nanosheets Ag2Sananoparticles and bulk
different high-pressure crystals.
property Moreover,
compared with phase
previous reports. According to the analysis in the TEM image
IV [19], which formed at 28.4 GPa in bulk counterparts, was not observed in our samples. before, it was shown that the Ag S
2 Thus, our
nanosheets have a relatively thin thickness, far below 29 nm (the
work reveals that Ag2S nanosheets exhibit a different high-pressure property compared with average size of the sample). Therefore,
we suggest that the stronger nanosize effect arising from the smaller thickness of Ag S nanosheets
previous reports. According to the analysis in the TEM image before, it was 2shown that the Ag2S
effectively restricts the relative position slip of the interlayer atoms during compression, which leads to
nanosheets have aofrelatively
the enhancing thin thickness, far below 29 nm (the average size of the sample).
phase stabilities.
Therefore, Figure
we suggest
6 shows that
the the strongerbehavior
compressive nanosize effect
of Ag arising from
2 S nanosheets. the smaller
A third-order BM thickness
EOS was of Ag2S
introduced
nanosheets to fit ourrestricts
effectively pressure-volume data. For
the relative monoclinic
position slip P2of1 /n
thestructure (phase
interlayer I), by fixing
atoms duringthe compression,
first
pressure derivative of isothermal bulk modulus (B 0 ) to 4, the bulk modulus (B ) was obtained
which leads to the enhancing of phase stabilities. 0 0
as 73(6) GPa. The obtained bulk modulus B0 for phase I, the ambient phase, was much higher
Figure 6 shows the compressive behavior of Ag2S nanosheets. A third-order BM EOS was
than that of the bulk Ag2 S (~34–38(2) GPa), even higher than that of the 30 nm Ag2 S nanoparticles
introduced
(B0 = to fit our
57.3(6) GPa) pressure-volume
[19,27]. For phase data. For monoclinic
III, during the fitness, theP2values
1/n structure (phase I), by fixing the
of the bulk modulus (B0 )
first pressure derivative of isothermal bulk modulus (B ’) to
and zero pressure cell volume (V 0 ) were left to vary freely, and the first derivative
0 4, the bulk modulus
of B0 with(B 0) was obtained
pressure
0 P-V ambient B0 higher
as 73(6)(BGPa.
0 ) was fixed
The to 4. As shown
obtained in Figure 6,Bthe
bulk modulus fitting
0 for phase to the
I, the curve yields a bulkwas
phase, modulus
much of than
141(4) GPa and unit cell volume V of 207(6) Å 3 . Compared to previous studies, the obtained bulk
that of the bulk Ag2S (~34–38(2) GPa), 0 even higher than that of the 30 nm Ag2S nanoparticles (B0 =
modulus B0 for phase III of Ag2 S nanosheets was also larger than the bulk counterparts (102(4) GPa)
57.3(6) GPa) [19,27]. For phase III, during the fitness, the values of the bulk modulus (B0) and zero
and 30 nm nanoparticles (123.1(0) GPa) [19,27]. According to the above analysis, we consider that
Ag2 S nanosheets exhibit significant difference in compression properties under high pressure, a much
lower volume compressibility than previous reports. A similar phenomenon was observed in some
other nanomaterials, e.g., C60 nanosheets and ZnO nanocrystal [29,30], and has potential benefits in
keeping the stability of materials. It is well known that nanosize effect can strongly influence the bulk
 GPa and unit cell volume V0 of 207(6) Å3. Compared to previous studies, the obtained bulk modulus
B0 for phase III of Ag2S nanosheets was also larger than the bulk counterparts (102(4) GPa) and 30
nm nanoparticles (123.1(0) GPa) [19,27]. According to the above analysis, we consider that Ag2S
nanosheets exhibit significant difference in compression properties under high pressure, a much
lower volume
Nanomaterials 2020, 10,compressibility
1640 than previous reports. A similar phenomenon was observed in some 7 of 9
other nanomaterials, e.g., C60 nanosheets and ZnO nanocrystal [29,30], and has potential benefits in
keeping the stability of materials. It is well known that nanosize effect can strongly influence the
modulus; thereby, the
bulk modulus; 30 nm the
thereby, nanoparticles exhibit higher
30 nm nanoparticles bulk modulus
exhibit thanmodulus
higher bulk the bulk materials. In our
than the bulk
experiment, the Ag S nanosheets have a very small size in thickness, much lower than
materials. In our 2experiment, the Ag2S nanosheets have a very small size in thickness, much lower their grain
sizethan
of 29 nm.grain
their Thus, theofstronger
size nanosize
29 nm. Thus, effect from
the stronger our samples
nanosize mayour
effect from cause the bulk
samples maymodulus
cause theto
bulkelevate.
largely modulus to largely elevate.

Figure
Figure 6. Room-temperature
6. Room-temperature equationequation of state
of state data for Agdata for Ag2S nanosheets. A third-order
2 S nanosheets. A third-order Birch-Murnaghan
Birch-Murnaghan (BM) equation of state (EOS) is introduced to fit ourdata.
(BM) equation of state (EOS) is introduced to fit our pressure-volume pressure-volume data.

In our
In our high-pressure
high-pressure research,
research, the quench
the quench process
process is implemented.
is implemented. TEM TEM
imagesimages and pattern
and XRD XRD
pattern
of Ag of Ag2S nanosheets quenched to the ambient conditions are shown in Figure 7. According to
2 S nanosheets quenched to the ambient conditions are shown in Figure 7. According to the TEM
image of the image
the TEM of the
quenched quenched
sample, sample,
although Ag2although
S samplesAg 2S samples could not maintain their uniform
could not maintain their uniform shape because
shape because of the high pressure and high shear stresses, it still keeps
of the high pressure and high shear stresses, it still keeps the sheet-like the sheet-like
morphology morphology
in nanoscale. Based
in nanoscale. Based on this result, we can reasonably draw a conclusion
on this result, we can reasonably draw a conclusion that during the compressing process, Ag that during
S the
samples
2
compressing process, Ag2S samples in our experiment remain nanomaterials, and no agglomeration
in our experiment remain nanomaterials, and no agglomeration took place. After decompressing
took place. After decompressing to ambient pressure, the shapes of all the diffraction peaks for
to ambient pressure, the shapes of all the diffraction peaks for Ag2 S nanosheets return to the initial
Ag2S nanosheets return to the initial monoclinic P21/n structure (phase I), indicating the reversibility
monoclinic P21 /n structure (phase I), indicating the reversibility of the pressure-induced structural
of the pressure-induced structural transitions. Further analysis showed that the (-112), (-103) peak
transitions. Further analysis showed that the (-112), (-103) peak was enhanced after compression.
was enhanced after compression. The effect of non-hydrostatic pressure and high pressure gives
Thenanosheet
effect of non-hydrostatic
samples a certainpressure and and
orientation hightexture.
pressure gives nanosheet samples a certain orientation
and texture.
Nanomaterials 2020, 10, x FOR PEER REVIEW 8 of 10

Figure 7. (a) TEM images and (b) Rietveld refinement result of Ag2S nanosheets quenched to
Figure 7. (a) TEM images and (b) Rietveld refinement result of Ag2 S nanosheets quenched to ambient
ambient conditions; Rwp = 0.3982, Rp = 0.2929 and chi^2 = 160.3.
conditions; Rwp = 0.3982, Rp = 0.2929 and chiˆ2 = 160.3.

4. Conclusions
In summary, we studied the high-pressure behaviors of Ag2S nanomaterials with sheet-like
morphologies using in situ high-pressure X-ray diffraction up to about 30 GPa. Under high pressure,
Ag2S nanosheets undergo the phase transition sequence P21/n (phase I) → P212121 (phase II) → P21/n
(phase III) at pressures of 8.9 GPa and 12.4 GPa. Interestingly, the Ag2S nanosheets exhibit a wide
Nanomaterials 2020, 10, 1640 8 of 9

4. Conclusions
In summary, we studied the high-pressure behaviors of Ag2 S nanomaterials with sheet-like
morphologies using in situ high-pressure X-ray diffraction up to about 30 GPa. Under high pressure,
Ag2 S nanosheets undergo the phase transition sequence P21 /n (phase I) → P21 21 21 (phase II) → P21 /n
(phase III) at pressures of 8.9 GPa and 12.4 GPa. Interestingly, the Ag2 S nanosheets exhibit a wide field
of structural stability and much lower compressibility under high pressure, remarkably different from
the corresponding bulk materials and 30 nm nanoparticles. Further analysis suggests that a stronger
nanosize effect arising from smaller thickness in Ag2 S nanosheets effectively restricts the relative
position slip of the interlayer atoms during the compression, which leads to the enhancing of phase
stabilities and the elevating of bulk moduli. Our findings give a further insight into high-pressure
behaviors in Ag2 S nanomaterials.

Author Contributions: Conceptualization, R.L. and B.-B.L.; investigation, R.L.; writing—original draft preparation,
R.L. and B.L.; writing—review and editing, Q.-J.L. and B.-B.L.; project administration, B.-B.L.; funding acquisition,
B.-B.L. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by National Key R&D Program of China (2018YFA0305900) and the NSFC
(11634004, 51320105007, 11604116, 11847094 and 51602124), Program for Changjiang Scholars and Innovative
Research Team in University (IRT1132).
Acknowledgments: We thank Tongshun Wu (Ph.D. of State Key Laboratory of Inorganic Synthesis and Preparative
Chemistry, Jilin University, Changchun, China) for providing ideal Ag2S nanosheet samples, thank Dongmei Li
(State Key Laboratory of Superhard Materials, Jilin University, Changchun, China) for helping us to get excellent
TEM images; we also thank Zhiqiang Chen (X17C, NSLS, BNL, Upton, NY, USA) for helping us to collect perfect
HP in-situ synchrotron XDR data.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design of the study;
in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish
the results.

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