Advanced Materials - 2017 - Susner - Metal Thio and Selenophosphates As Multifunctional Van Der Waals Layered Materials

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REVIEW
2D Materials www.advmat.de
Metal Thio- and Selenophosphates as Multifunctional van

der Waals Layered Materials
Michael A. Susner,* Marius Chyasnavichyus, Michael A. McGuire,
Panchapakesan Ganesh, and Petro Maksymovych*
stacked heterostructures, and thin films

Since the discovery of Dirac physics in graphene, research in 2D materials has of layered compounds.[1–4] In the past few
exploded with the aim of finding new materials and harnessing their unique years, a host of promising 2D materials
and tunable electronic and optical properties. The follow-on work on 2D has been extensively researched to aug-
ment the lack of electronic bandgap in
dielectrics and semiconductors has led to the emergence and development of
graphene for device fabrication A survey
hexagonal boron nitride, black phosphorus, and transition metal disulfides. of the electronic functions presented by
However, the spectrum of good insulating materials is still very narrow. Like- 2D materials reveals that metal, insu-
wise, 2D materials exhibiting correlated phenomena such as superconduc- lating, and semiconducting properties are
tivity, magnetism, and ferroelectricity have yet to be developed or discovered. now represented by at least one 2D com-
These properties will significantly enrich the spectrum of functional 2D mate- pound. However, good insulators, for the
most part, are represented by clays and
rials, particularly in the case of high phase-transition temperatures. They will
boron nitride, the latter with a bandgap
also advance a fascinating fundamental frontier of size and proximity effects of 5–6 eV.[5] Boron nitride is arguably the
on correlated ground states. Here, a broad family of layered metal thio(seleno) only insulator to be successfully estab-
phosphate materials that are moderate- to wide-bandgap semiconductors lished in 2D form, likely to be soon joined
with incipient ionic conductivity and a host of ferroic properties are reviewed. by the related compound gallium nitride.[6]
Although the lack of dangling bonds and
It is argued that this material class has the potential to merge the sought-after
commensurability with the graphene lat-
properties of complex oxides with electronic functions of 2D and quasi-2D tice make nitrides superior to SiO2 for use
electronic materials, as well as to create new avenues for both applied and as a substrate for devices, they are linear
fundamental materials research in structural and magnetic correlations. dielectrics with fairly limited functionality.
Most other 2D non-metals have narrow
bandgaps that make them promising
1. Introduction semiconductors. Black phosphorus has a narrow gap of 0.3 eV
and is noted for its high anisotropy within a layer where proper-
Graphene ignited the current era of 2D materials, which are ties depend on whether they are measured along the light or
widely considered to be the next generation of electronic, heavy effective mass directions.[7] While promising for infrared
chemical, and structural materials comprising 2D sheets, optoelectronics, bulk black phosphorus is not useful for shorter
wavelength applications. Similarly, transition metal dichalco-
genides (TMDs) also have a small bandgap that limits poten-
Dr. M. A. Susner, Dr. M. A. McGuire tial device applications at higher energies.[8] Therefore, what is
Materials Science and Technology Division missing from the picture is a range of materials with interme-
Oak Ridge National Laboratory
1 Bethel Valley Rd., Oak Ridge, TN 37831-6056, USA diate bandgaps from 1.6 to 4 eV that would occupy the space
E-mail: michael.susner.ctr@us.af.mil, mike.susner@gmail.com between TMDs and boron nitride.
Dr. M. A. Susner From a general point of view, these materials must have
Aerospace Systems Directorate chemical bonding that is intermediate between covalent and
Air Force Research Laboratory ionic, which implies decreasing their atomic density and
1950 Fifth St., Building 18
Wright-Patterson Air Force Base, OH 45433, USA
increasing the difference between electronegativity of con-
Dr. M. A. Susner
stituent ions. Both of these trends would also imply that such
UES, Inc. materials attain incipient or even finite ionic conductivity at
4401 Dayton Xenia Rd., Beavercreek, OH 45432, USA moderate temperatures. This in turn will usher in the possi-
Dr. M. Chyasnavichyus, Dr. P. Ganesh, Dr. P. Maksymovych bility of structural phase transitions and intriguing new ther-
Center for Nanophase Materials Science mochemistry, both of which are scarce or rare in the present
Oak Ridge National Laboratory envelope of 2D and thin layered sheets.
1 Bethel Valley Rd., Oak Ridge, TN 37831-6487
E-mail: maksymovychp@ornl.gov In this Review, a family of metal thio(seleno)phosphates
(MTPs) are explored, in which metal cations stabilize a
DOI: 10.1002/adma.201602852 [P2S(Se)6]4− framework forming layers that are weakly bonded
Adv. Mater. 2017, 29, 1602852 1602852 (1 of 39) © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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www.advancedsciencenews.com www.advmat.de
together through van der Waals interactions. The abbreviation

MTP will be used here to refer to this set of compounds defined Michael A. Susner earned his
by this structural framework. These materials were discovered B.S. in chemistry (2005) from
in the late 1800s by Friedel[9] and, later, Ferrand.[10] Significant Michigan State University and
research was carried out from the 1970s through the early 2000s his M.S. (2009) and Ph.D.
(Figure 1) driven by the interesting structure of this materials (2012) in materials science
class that in turn allows for multiple material functionalities, and engineering from The
i.e., H2 storage and Li-ion batteries (Figure 2). Ohio State University. He
However, the previous peak of research activity in MTPs joined Oak Ridge National
predates the current era of 2D electronics. MTP compounds Laboratory in 2014 as a
possess the sought after intermediate range of bandgaps, Postdoctoral Research Fellow
1.3–3.5 eV, and incipient ionic conductivity for new electronic in the Correlated Electron
applications. Some of these compounds also exhibit ferroic Materials Group. He is inter-
correlations of atomic positions and the corresponding fer- ested in functional materials and their synthesis in bulk, thin
roic ground states and associated phase transitions; yet others film, and single crystal form for the determination of struc-
possess magnetic ordering. The ferroic correlations of atomic ture–property relationships. He is now an NRC Fellow in the
positions and magnetic moments, all of which are sensitively Aerospace Systems Directorate at the Air Force Research
dependent on the structural aspects and ionic substitution, bear Laboratory at Wright-Patterson Air Force Base, Ohio.
close resemblance to sought-after properties of complex oxides.
Here these properties are combined in MTPs which contain Michael A. McGuire earned
the flexibility associated with a van der Waals structure. In our his B.S. (1999) and M.S.
view, this class of materials may contribute to the next major (2001) in physics from the
frontier in low-dimensional materials. University of Mississippi,
As such, MTP compounds can dramatically expand the range and his Ph.D. in physics from
of practically useful functionalities of 2D materials via proxi Cornell University (2006). He
mity effects. Graphene, for example, must be gated to become joined Oak Ridge National
a good transparent conducting electrode[11,12] and shielded with Laboratory in 2007 as a
a high-k dielectric to produce a desired electron mobility.[13,14] Eugene P. Wigner Fellow, and
With respect to future applications, sensing and energy har- is currently a Senior R&D
vesting devices can be envisioned when pyroelectric and piezo- Staff Scientist. He works at
electric properties are efficiently coupled at an interface. Even the interface of solid state
more intriguing effects such as additional Dirac cones[15] or chemistry and condensed matter physics, on design and
semimetal-semiconductor transitions[16] may be produced in a discovery of functional materials, with emphasis on syn-
periodically modulated graphene lattice, occurring at a ferroic thesis, crystallography, and magnetism.
interface and/or periodic modulation by polarization domains.
Additionally, even graphene superconductivity induced by
proximate dielectrics has been proposed.[17] Petro Maksymovych earned
The first chapter of this review will comprehensively describe his B.S. in chemistry (2001)
the structure of MTPs. The wide variety of MTPs will be from Kiev Taras Shevchenko
divided into a classification scheme based on the metal cation Univeristy in Ukraine and
charge and resultant ordering within the P2X6 (where X = S, Se) Ph.D. in chemistry (2007)
structural sublattice. The previously mentioned diverse func- from the University of
tionalities exhibited in MTP compounds largely derive from Pittsburgh. He joined ORNL
the metal cation present in the structure (see Figure 2). Both in 2007 as a Eugene P.
the electronic structure and alloying of MTP compounds will Wigner Fellow and is currently
be discussed. R&D Staff Scientist at CNMS.
The second chapter of this work will focus on the synthesis His primary interest is the
of these compounds. Our main attention will be paid to the design and discovery of tun-
growth of single crystals; however, powder synthesis is also dis- able materials and understanding of material properties
cussed as well as prospects for scalability. using nanoscale manipulation.
The third chapter of the review will focus on materials func-
tionality in MTPs. Special attention will be paid to the phys-
ical phenomena of ferroelectricity and magnetism as they are The fourth chapter will detail practical considerations for
the most important for potential applications in encapsulated device fabrication. The topics of cleavability of the layered struc-
devices. Here we also include a brief overview integration of 2D ture, the formation of van der Waals bonded heterostructures,
electronic materials with other ferroelectric materials so as to optoelectronic functions and molecular intercalation will be
reveal the immediate opportunities for the MTP family. Other discussed.
interesting phenomena such as ionic conductivity and H2 The fifth chapter will summarize both theoretical and experi-
storage will be discussed as well. mental studies of MTP in 2D and quasi-2D regime. The final
Figure 1. Citespace analysis[18] of materials research in MTP compounds over time. Various research clusters can be sorted by the broad categories
to the right of the figure. The circles mark statistically notable papers, judged by the number of follow-on citations. See main text for more details.
chapter of the review will contain concluding remarks as to labels representing the primary author and year of publica-
future prospects of MTP materials. tion. One can immediately see that the categories span a vast
breadth of modern materials research, ranging from materials
discovery, fundamental magnetic (e.g.[19–26]) and ferroelectric
1.1. Metal Thio(seleno)phosphates at a Glance (e.g.[27–43]) properties to applications such as Li-ion batteries
(e.g.[44–64]) and H2 storage (e.g.,[65–67]). However, we also observe
In Figure 1 we present a Citespace[18] analysis of ≈1000 papers that a large number of papers date back to the 1980s to late
in MTP research dating back over 100 years. The citations are 1990s, and that only very recently has interest in these mate-
organized by year on the horizontal axis and by broad category rials reemerged (e.g.[27–43]).
on the vertical axis. These categories are represented by “clus- From the structural point of view, all of the members of
ters” of related research, sorted by the likelihood of citations. In this family share a defining common feature – a common
addition, the most oft-cited papers are graphically represented P2(S/Se)6 anion sublattice within each lamella of the lay-
by circles with larger diameters. Some of these works, namely ered crystal. Often, these compounds are referred to as
those with the most citations in recent years, are denoted by MPS(Se)3 when referring to compounds with a composition
Figure 2. Functional properties of transition metal thio (top)/seleno (bottom) phosphates organized by chemistry of the transition metal components.
Filled blocks represent elements for which the layered MTP structure has been reported to form.
M2+[PS3]2− (e.g.,[68,69]). On the cation side, MTPs can accom- applications such as electrochemistry and catalysis (Figure 2).
modate most of group I and group II elements, most of the A few compositions with lanthanides and actinides are also
transition metals of the fourth period, and some heavier ones, known, which may suggest that more lanthanides will be com-
such as Pd, Ag, and Cd with [P2S6]4− and [P2Se6]4− anions, or patible with MTP chemistry. On the anion side, P2S64− and
a combination thereof, Figure 2. Based on citation analysis, P2Se64− anions can be alloyed. Structurally, these anions closely
the most studied compounds are Ni2P2S6 and Fe2P2S6, owing relate to [Si2Te6]4−, which itself constitutes a potentially broad
to their magnetic ordering, but also in the context of several material class. These latter compounds can exhibit strong
spin-lattice coupling (e.g., in Cr2Si2Te6[70–73]) and are promising tetrahedral coordination with 3 S atoms and 1 P atom, forming
insulating ferromagnetic compounds below ≈33 K. an ethane-like (P2X6)4− unit. Each S atom is bonded to a single
P atom and coordinated by two M sites.
In Figure 3a we also show six structures representing the var-
1.2. Structure of Metal Thio-/Selenophosphates ious cation sublattices possible in this broad class of materials.
These include the M22+[P2X6]4− type discussed above (Figure 3a)
Throughout this manuscript we refer to MTPs in such a as well as the additional M4+[P2X6]4−, M4/33+Υ2/3[P2X6]4− (where
way as to emphasize the common [P2S(Se)6]4− sublattice. In Υ represents a vacant site), M21+M2+[P2X6]4−, and M1+M3+[P2X6]4−
Figure 3a we see a model representing a lamella in Fe2P2S6,[74] (Figure 3b–f, respectively). The last of these, the M1+M3+[P2X6]4−
both normal and along the MTP layer stacking direction. The class can be further divided into two types based on the nature
sulfur atoms comprise almost close-packed surfaces of the of the cation ordering which will be discussed in more detail
layer. At the same time, a regular pattern of octahedrally coordi- below.
nated sites is formed (Figure 4a). For this specific compound of Though the overall structure within individual lamella is
the M22+[P2X6]4− type, 2/3 of the octahedral centers are filled by essentially the same across the MTP family, the symmetry and
M2+ cations. The remaining ⅓ are filled by PP dimers which stacking arrangements differ depending on the composition.
covalently bond to the sulfur atoms with each P atom having Table 1 and 2 list all layered 2D thio(seleno)phosphates that
Figure 3. Individual layers of six crystal structures adopted by transition metal thiophosphates: a) M22+[P2X6]4−, b) M4+[P2X6]4−, c) M43/+3 [P2 X 6 ] 4 −,
d) M21+M2+[P2X6]4−, e) M1+M3+[P2X6]4−, and f) buckled M1+M3+[P2X6]4− . The M1+ sites in the upper, middle, and lower positions in the bottom of (e) are
partially occupied, with relative occupation depending upon temperature. Both the upper and lower M1+ positions are fully occupied in (d). We note
that the metal–sulfur(selenium) bonds have been omitted to simplify the representation.
Figure 4. a) Representation of Fe2P2S6 lamella showing the octahedral cages containing the M cation and the P–P dimer. The pink spheres represent P,
the yellow spheres represent S, and the blue spheres represent Fe. b) A section of the crystal structure of Hg2P2S6. c) A section of the crystal structure of
Hg2P2Se6. d) Space-filling representation of the Fe2P2S6 structure showing the 2D nature of the material. Two lamellae are present in this representation.
have detailed structural information available. For structural All other mixed-cation compounds are monoclinic, though only
information for many related 3D compounds, please refer to CuVP2S6 and the low temperature phases of CuInP2S6 and
the work of Seidlmayer.[75] Because of close similarities between CuCrP2S6 are non-centrosymmetric.
the hexagonal, trigonal, and monoclinic cells,[69] all phases (save As represented by Figure 3e (bottom), there are three pos-
one[76]) of the MTP family share an essentially identical struc- sible Cu1+ sites in CuInP2S6 whose occupation depends on tem-
tural framework which can be described using either mono- perature. Above 315 K Cu1+ occupation is split evenly between
clinic or trigonal space groups. Of course, the exact stacking is the upper and lower sites. Below 315 K the upper site is pref-
subject to stacking faults as is common for the van der Waals erentially occupied. The Cu1+ ions are shifted upward from
materials.[77] the midplane of the lamella by ≈1.58 Å.[42] The In are also
The widest variety of symmetries is found within the sulfides. offset, but only by ≈0.2 Å and in the opposite direction. The
Almost every M22+[P2S6]4−-type compound crystallizes into the two polar sublattices formed by the two different cations par-
C2/m (12) monoclinic crystal structure. The monoclinic angle tially compensate, producing a ferrielectric material whereby a
β varies with the type of cation present, varying from 106.97° large spontaneous polarization appears normal to the stacking
(M = Mg) to 107.35° (M = Mn). Co2P2S6 and Fe2P2S6 have direction. In CuCrP2S6 a similarly ordered phase exists below
values for β that are very close to an undistorted cell, 107.16[69] 150 K. In this case, however, the Cu in each layer orders in
The stacking sequence in M22+[P2S6]4− monoclinic compounds alternating rows of up- and down-shifted Cu1+ cations whereby
does not vary with the exception of Hg2P2S6 which crystallizes no net polarization is present.[43] No such transitions have been
into a space group of P 1 . The preference of divalent Hg for tet- detected in CuVP2S6 down to 20 K.[80] Of the M1+M3+[P2S6]4−
rahedral coordination results in a tilting of the PP dimers so type thiophosphates, most exhibit an ABAB stacking sequence,
that they are no longer nearly normal to the plane of the layer, regardless of the space group.
allowing for a distorted tetrahedral coordination for the Hg ions AgVP2S6 and AgCrP2S6 exhibit much different crystal struc-
(Figure 4b). tures (Figure 3f). In these two compounds the layers bow notice-
The mixed-cation M1+M3+[P2S6]4− compounds have more ably outwards above the locations of the Ag atoms. This bowing
variability in their structure. Two compounds, AgInP2S6 and does not affect the stacking of the layers across the van der Waals
AgScP2S6, are reported as trigonal (P 13c) and centrosymmetric gap. These features are not found in the Cu analogues of these
at room temperature. Although room temperature crystal struc- compounds, CuVP2S6 and CuCrP2S6, likely because the Ag1+
tures of AgInP2S6[78] and AgScP2S6[79] are known and these ions (ionic radius 1.15 Å in six-fold coordination) are so much
same compounds contain hints of off-center displacements of larger than the Cu1+ (0.77 Å), Cr3+ (0.62 Å), and V3+ (0.64 Å)
the Ag1+ cation through their observed anisotropy in atomic ions.[81] Whereas Cu has the ability to vary its location within
displacement parameters, no investigations have yet concluded the sulfur-defined octahedra (leading to polarization in some
that these compounds contain any type of ferroelectric ordering. instances), Ag is limited in these cases to the center of the layers.
Table 1. Structural information for layered 2D metal thiophosphates.
Lattice parameters
Compound Symmetry a b c β Cell volume [Å3] Lamellar stacking
[Å] [Å] [Å] [°] sequenceb)
M22+[P2S6]4− Cd2P2S6(ht)[74] C2/m 6.195 10.674 6.874 107.24 434.1 AAA (c)
[257]
Cd2P2S6(lt) R3 6.224 6.224 19.49 – 653.9 ABC (c)
Co2P2S6[87] C2/m 5.910 10.240 6.680 107.17 386.4 AAA (c)
Fe2P2S6[74] C2/m 5.947 10.300 6.722 107.16 393.4 AAA (c)
[113]
Mg2P2S6 C2/m 6.085 10.560 6.835 106.97 420.1 AAA (c)
Mn2P2S6[74] C2/m 6.077 10.524 6.796 107.35 414.9 AAA (c)
Ni2P2S6[86] C2/m 5.812 10.07 6.632 106.98 371.2 AAA (c)
[87]
Pd2P2S6 C2/m 5.97 10.32 6.73 107.1 396.3 AAA (c)
Sn2P2S6[258] C2/m 5.99 10.36 6.8 107.1 403.3 AAA (c)
V2P2S6[87]a) C2/m 5.85 10.13 6.66 107.1 377.2 AAA (c)
Zn2P2S6[121] C2/m 5.972 10.342 6.7565 107.14 398.8 AAA (c)
2+ 4− 2+ Hg2P2S6 [76]
6.252 6.262 7.126 – 224.8 AAA (c)
M2 [P2S6] (Hg ) P1
M1+M3+[P 2S6 ]4− CuInP2S6 [43]
Cc (lt) 6.096 10.565 13.623 107.10 838.5 ABAB (c)
C2/c (ht)
AgInP2S6[78] P 31c 6.182 6.182 12.957 – 428.8 ABAB (c)
CuCrP2S6(ht)[21] C2/c 5.916 10.246 13.415 107.09 777.3 ABAB (c)

CuCrP2S6(lt)[259] Pc 5.935 10.282 13.368 106.78 781.0 ABAB (c)
[80]
CuVP2S6 C2 5.955 10.321 6.699 107.46 392.8 AAA (c)
AgScP2S6[79] P 31c 6.174 6.174 12.897 – 425.7 ABAB (c)
M1+M3+[P2S6]4− AgVP2S6[22] P2/a 5.921 10.684 6.755 106.62 409.5 AAA (a)
(buckled)
AgCrP2S6[260] P2/a 5.892 10.632 6.745 105.82 483.7 AAA (a)
1+
M2 M2+[+[P2S6]4− Ag2MgP2S6[113] C2/n 6.364 10.975 13.999 108.29 928.4 ABAB (c)
Ag2MnP2S6[261] C2/n 6.339 10.933 13.893 108.29 914.2 ABAB (c)
[261]
Ag2ZnP2S6 C2/n 6.295 10.866 27.923 109.18 1804.0 ABCD (c)
M4+[P2S6]4− SnP2S6[258] R3 5.999 5.999 19.424 – 605.4 ABC (c)
M4/33+Y2/3[P2S6]4− Al4/3P2S6[262] C2/m 5.884 10.188 6.788 106.60 390.0 AAA (a)
Cr4/3P2S6[263] monocl. 8.692 7.562 8.344 91.97 548.1 ?
Ga4/3P2S6[114] monocl. 11.842 7.786 8.289 133.41 555.2 ?
In4/3P2S6[36] P2/c 6.803 10.498 18.191 107.49 1239.1 AAA (a)
a)Where (a) or (c) denote the stacking direction; b)The actual composition for this phase is likely to be V [264]
1.56P2S6 where charge balance is maintained through the V
species being mixed-valent.
Mixed-cation phases of the M21+M2+[+[P2S6]4− type have C2/m building blocks are tilted along two different directions in these
symmetry and contain an inversion center. The monovalent monoclinic P21/c unit cells (close to the [0 5 3] and the [0 5 3]
atom, in these cases Ag, is located near the S planes (Figure 3d), directions), necessarily changing how the lamellae are defined.
with two atoms sharing a single octahedral cage, one at We have chosen to thus omit these references from this Review.
the top and one at the bottom. The presence of the large Ag This structure type is favored by rare earth compounds and can
ions results in the twisting distortion of the P2S6 anions. All be found for KLaP2S6,[82] NaSmP2S6,[83] and the newly discov-
M21+M2+[P2S6]4− type compounds also exhibit alternating ered NaPrP2S6, KPrP2S6, RbLaP2S6, CsCeP2S6, CsLaP2S6, and
stacking arrangements with respect to the ordering of the KCeP2S6.[84]
lamellae. Ag2MgP2S6 and Ag2MnP2S6 display a stacking The selenide phases in the greater MTP family have sim-
sequence of ABAB while Ag2ZnP2S6 has a lamellar stacking ilar variability in their structure. The divalent metal cation
sequence of ABCDABCD. structures (M22+[P2S6]4−) are similar as those represented in
In addition to these layered phases, there exist a variety of Figure 3a. However, differences may exist due to increased
other layered compounds containing the [P2S6]4− anion as a PSe bond distances and SePSe bond angles reported for
major structural component. However, the P2S6 ethane-like some of the compounds. For example in the Cd2P2Se6 crystal
Table 2. Structural information for layered 2D metal selenophosphates.
Lattice parameters
Compound Symm. a b c β Cell volume Stacking
[Å] [Å] [Å] [°] [Å3] sequencea)
M22+[P2Se6]4− Cd2P2Se6[86] R 3h 6.512 6.512 20.065 – 736.9 ABC (c)
Cr2P2Se6[86] C2/m 6.13 10.66 6.86 107.1 428.4 AAA (c)

[158]
Fe2P2Se6 R 3h 6.273 6.273 19.812 – 675.2 ABC (c)
[113]
Mg2P2Se6 R 3h 6.404 6.404 20.194 – 717.2 ABC (c)
Mn2P2Se6 [158]
R 3h 6.394 6.394 20.019 – 708.8 ABC (c)
Ni2P2Se6[86] C2/m 6.15 10.66 6.86 107.1 426.8 AAA (c)

[113]
Zn2P2Se6 R 3h 6.290 6.290 19.93 – 682.9 ABC (c)
2+ [76]
M2 [P2Se6 ]4− Hg2P2Se6 C2/c 6.52 11.52 13.64 99.1 1011.6 ABAB (c)
(Hg2+)
M1+M3+[P2Se6]4− CuAlP2Se6[88] R 3h 6.280 6.280 19.97 – 682.0 ABC (c)
(disordered)
AgAlP2Se6[89] C2/m 6.348 10.989 7.028 107.2 468.3 AAA (c)
[89]
AgCrP2Se6 C2/m 6.305 10.917 6.991 107.7 458.4 AAA (c)
M1+M3+[P2Se6]4− CuInP2Se6[89] P 31c 6.392 6.392 13.338 – 472.0 ABAB (c)
AgInP2Se6[89] P 31c 6.483 6.483 13.330 – 485.2 ABAB (c)
CuCrP2Se6 [89]
C2/m 6.193 10.724 6.909 107.2 438.3 AAA (c)
CuBiP2Se6(rt)[111] P 31c 6.541 6.541 13.263 – 491.4 ABAB (c)
CuBiP2Se6(lt2)[111] R 3h 6.553 6.553 39.762 – 1487.9 ABCDEF (c)
CuBiP2Se6 (lt1)[111] R 3h 6.559 6.559 79.385 – 2957.7 ABCDEFGHIJKL

(c)
AgBiP2Se6[111] R 3h 6.652 6.652 39.615 – 1518.3 ABCDEF (c)
AgErP2Se6 [112]
P 31c 6.578 6.578 13.410 – 502.5 ABAB (c)
[89]
AgGaP2Se6 P 31c 6.375 6.375 13.320 – 468.8 ABAB (c)
AgScP2Se6[112] P 31c 6.463 6.463 13.349 – 482.9 ABAB (c)
AgTmP2Se6[112] P 31c 6.567 6.567 13.422 – 501.3 ABAB (c)
AgVP2Se6[265] C2 6.340 11.020 6.982 106.82 466.9 AAA (c)

M4/33+Υ2/3[P2Se6]4− In4/3P2Se6 [90]
R3 6.362 6.362 19.929 – 698.6 ABC (c)
a)where
(a) or (c) denote the stacking direction.
structure Potorii et al.[85] report that the space group is R3 rather All of the selenide compounds crystallize into either mono-
than R 3 as previously reported.[86,87] The lack of an inversion clinic or trigonal crystal structures. Of the monoclinic vari-
center in this structure is due to the above-described distortions ations, all but Hg2P2Se6 exhibit the same lamellar stacking
present in the PSe3 groups located on the bottom halves of the with a single layer per unit cell (AA stacking). Of the trigonal
lamellae. Similarly, the mixed +1 and +3 cation selenophos- R 3 structures, most have lamellar stacking in the sequence
phates (M1+M3+[P2Se6]4−) exhibit structures similar to those ABCABC. The exceptions are the two low-temperature phases
depicted in Figure 3e, despite the variety of crystal structures of CuBiP2Se6 and AgBiP2Se6, all of which have extended
present in this sub-class. We should note that the compounds stacking of 6–12 lamellae before translational symmetry is
CuAlP2Se6,[88] AgAlP2Se6,[89] and AgCrP2Se6[89] are reported to observed. All metal selenophosphate compounds with the
exhibit random cation ordering in contrast to the other mixed trigonal P 13c crystal structure exhibit lamellar stacking of
valent compounds reported for both the sulfide and sele- ABAB. Hg2P2Se6 adopts a unique structure: as with the sulfide
nide compounds. Only one type of +3 valence single cation Hg2P2S6 phase, the tetrahedral coordination preferred by Hg2+
M4/33+Υ2/3[P2Se6]4− type compound is reported to exist for the causes tilting of the PP dimers and in turn distorts the octa-
selenide sub-class of the greater MTP family, In4/3P2Se6. The hedral cages between the P2Se6 units (Figure 4c).
cation and vacant site ordering in this compound are as of yet Using the available crystallographic information on both the
unresolved.[90–92] 2D metal thio- and selenophosphates we have noted trends in
various structural properties with changing

composition (Figure 5). In these plots, we
have excluded structural variants where the
universal layered structure is significantly
distorted (for example, the bowing evident
in AgVP2S6 and AgCrP2S6). We define the
layer thickness as the distance between
the planes defined by the hexagonal array
of sulfur atoms on either side of an indi-
vidual lamella. Similarly, the van der Waals
gap thickness is defined as the shortest dis-
tance between the S layers across the van
der Waals gap. We define the layer spacing
as the distance between the planes defined
by the centers of the stacked lamella, and
it is equal to the sum of the layer thickness
and the van der Waals gap thickness. It can
also be determined by the lattice parameters
and number of layers per unit cell. To esti-
mate the cation size, we use the average
effective cation radius using the values from
Shannon.[81]
With respect to the sulfides we see that
the PP distance is relatively independent
of the choice of cation. There appears to be
some degree of positive correlation between
the average effective cation radius and the
layer thickness (i.e., the thickness of indi-
vidual lamellae) and no real change in van
der Waals gap size, which remains relatively
constant with different cation substitution.
These trends indicate: i) that the sulfide MTP
framework is very accommodating to cations
of sizes ranging from 60–107 pm, ii) there
is little to no correlation of PP distances
or vdW size with cation radius, and iii) what
changes are present in PP distances corre-
late very well with the changes in layer thick-
ness (Figure 5). This last well-defined trend
indicates that, for the sulfide compounds,
important structural information like layer
thickness and PP distance are not affected
by the size of cation present. Rather, it is how
these cations interact within the lamellae
with respect to ordering and electrostatic
repulsion that has the greater effect. More-
over, the trend of layer thickness scaling with
PP distance is very well defined in terms of
the groupings of the cationic mixture in the
sulfide MTP compounds. A general trend is
noted where, in terms of both layer thick-
ness and PP spacing, M21+M2+[P2S6]4− >
M1+M3+[P2S6]4− > M4/33+[P2S6]4− > M22+[P2S6]4−.
Similar analyses of the selenide MTP com-
pounds reveal a slightly different picture.
In these compounds PP distances exhibit
much larger variance. Most of these values Figure 5. Observable structural trends (from near-room temperature data) in sulfide and
fall within a wide band that spans 2.16–2.27 Å. selenide MTP compounds.
Within this band, PP distances follow a “V-shaped” trend with the conduction band is mainly S and P in character. In mate-
respect to cation radius. However, some outliers also are readily rials with filled d-shells, like Zn2P2S6, the sharply localized
apparent that exhibit greater PP distances; these are the In- d-levels appear well below the Fermi energy (Figure 6b).[93]
based M1+M3+[P2Se6]4− compounds (CuInP2Se6, AgInP2Se6) or When partially filled d-levels are present the details of the elec-
CuAlP2Se6 where the PP distances range from 2.35–2.40 Å. tronic structure near the Fermi level are determined by the
Correlations in both layer thickness and gap size are readily crystal field splitting of the d-orbitals and the filling fractions.
apparent with the selenide compounds (Figure 5), indicating Calculations on the band structure of MTP compounds have
that these materials are much more structurally sensitive to mainly focused on the magnetic compounds Fe2P2S6, Mn2P2S6,
the type of cation present than their sulfide counterparts. We and Ni2P2S6 (e.g.[23,94–99]) due to interest in using these com-
see no correlation between layer thickness and PP distance pounds for Li-ion battery electrodes in the 1980s and in the
in the selenide compounds, indicating that there is less rigidity discovery of interesting spontaneous magnetization upon
present in the PSe3 units than in the PS3 units of the sulfide intercalation in the 1990s. Early calculations by Khumalo and
compounds. Hughes[100] and later Piacentini and co-workers[101] of the band
structure of Fe2P2S6 used the ionic extreme of the Wilson–Yoffe
band model[102] which discounted any band mixing between
1.3. Electronic Structure of MTP Compounds the metal and S atoms and proposed an electronic structure
whereby flat M2+ 3d, 4s, and 4p bands were simply added to
Some bandgaps of the generally semiconducting MTP com- the s and p bands originating from the (P2S6)4− ions. This
pounds have been measured (Table 3), with values ranging semi-empirical model, later referred to as the “weak-interac-
from 1.2–3.4 eV. The gaps are smaller in the selenides than tion model” was used to explain optical absorption measure-
in the sulfides, as expected from the relative electronegativity ments which showed that the M2P2S6 compounds exhibited
of the two elements. From a survey of band structure calcula- semiconducting behavior, by which the absorption edges were
tions performed on the MTP compounds several general points measured as 3.0 eV for Mn2P2S6, 1.5 eV for Fe2P2S6, 1.7 eV for
can be made: i) compounds with partially filled d-orbitals order Ni2P2S6, and 3.4 eV for Zn2P2S6.[46]
magnetically and appear to be Mott insulators, ii) there is a Whangbo et al.,[98] followed by Mercier et al.,[99] used extended
sizable bandgap present in all MTP materials on the order of Hückel method-based[103] tight-binding band scheme[104] calcu-
1.3–3.5 eV, iii) the size of the bandgap is highly sensitive to lations to determine the band structures of Fe2P2S6 and, in the
the metal cations present, and iv) the character of the bonding latter case, Fe2P2S6, Mn2P2S6, Co2P2S6, Ni2P2S6, and Cd2P2S6.
between the metal cation and the (P2S6)4− anion is likely mostly The main trend consisted of low-lying bands originating from
ionic, but not completely so. P and S 3s electrons, a large band resulting from S 3p electrons
Figure 6a shows the electronic density of states (DOS) calcu- at a slightly higher energy, followed by bands originating from
lated for Mg2P2S6 using the linear muffin tin orbital method and the metal cation (i.e., the t2g and eg sub-bands). The bands at
the atomic sphere approximation (TB-LMTO-ASA). Mg2P2S6 the highest energies were made of the 4s and 4p bands of the
contains no d-electrons, making the DOS somewhat simpler metal followed by the σP–P* and σP–S* anitibonding bands from
to calculate and interpret than, say, Fe2P2S6 or CuInP2S6. The the (P2S6)4− anion. The results of these models also showed
valence band is composed primarily of S and Mg states, while significant band dispersion. Later refinements of the model by
Mercier et al.[99] used revised structural data together with an
Table 3. Reported room temperature bandgaps for various MTP extended Hückel model to estimate a band structure similar to
compounds.
that of Whangbo et al. but with a bandgap of only ≈2 eV, in
good agreement with experimental values.
Compound Bandgap [eV] Reference
The effects of magnetism[19,23,94,95] were also considered.
Fe2P2S6 1.6, 1.5 [46,266] Zhukov et al.[23] used a linear muffin tin orbital basis method
Mn2P2S6 3.0 [46] with an atomic sphere approximation (LMTO-ASA) to model
Ni2P2S6 1.7 [266] the band structures of Fe2P2S6, Ni2P2S6, and Mn2P2S6. The cal-
culations involving spin polarization yielded lower energies for
Cd2P2S6 3.0 [267]
Fe2P2S6 and Mn2P2S6; however, the correct magnetic structures
Zn2P2S6 3.4 [46]
were not predicted. Kurita and Nakaov[93–95] used an ab initio
CuInP2S6 2.9 [28] linear combination of atomic orbitals (LCAO) approximation[105]
In4/3P2S6 2.7, 3.1 [46,115] to calculate the band diagrams for Zn2P2S6,[93] Ni2P2S6,[95]
Ga4/3P2S6 3.4 [114] Mn2P2S6,[94] and Fe2P2S6.[94] The latter three of these works also
took into account spin polarization. These results produce band
AgBiP2S6 1.7 [111]
gaps that are, with the exception of Fe2P2S6, in agreement with
Fe2P2Se6 1.3 [46]
those inferred from the absorption edge energies, with values
Mn2P2Se6 2.3, 2.5 [46,268] of 1.7 (direct) eV for Mn2P2S6, 0.0 for Fe2P2S6, 0.5 (indirect) for
Cd2P2Se6 2.3 [267] Ni2P2S6, and 2.0 (indirect) for Zn2P2S6. Kurita and Nakao[94]
In4/3P2Se6 1.9 [46] were also able to predict the general magnetic structure in terms
of nearest-neighbor (anti)ferromagnetic interactions for both
CuBiP2Se6 1.2 [111]
Mn2P2S6 and Ni2P2S6. Please refer to the section of magnetism
AgBiP2Se6 1.4 [111]
in these compounds for further details on these interactions.
the same technique, Zn, Cd, and Ni thi-

ophosphates were obtained by Ferrand.
These materials were largely overlooked for
several decades until Klingen et al.[87,107,108]
and Nitsche and Wild[109,110] began extensive
studies in the mid 1960s through the mid
1970s.
Most syntheses of both the metal thio-
and selenophosphates are accomplished
through simply combining the elements in
the appropriate stoichiometries in a fused
silica ampoule, heating to a temperature
below the material decomposition tempera-
ture for time periods of several days to sev-
eral weeks or months, and then cooling at a
slow rate. This type of reaction mechanism
relies on vapor transport of the species and
can result in the creation of thin single crys-
tals. P, S, and Se all have low melting points
and high vapor pressures (and low boiling
points in the cases of P and S) and presum-
ably act as the vapor transport agents. Se
melts at 220 °C but has a relatively high
boiling point of 684 °C, above the decom-
position temperature of many of the sele-
nium MTP compounds. Temperatures
employed in the synthesis reactions depend
on the material in question, specifically
between the boiling points of P and S and
the material’s decomposition temperature.
For the sulfide compounds, they can vary
from 400–850 °C;[43,109,111] for the selenide
compounds reaction temperatures span the
range of 450–730 °C.[89,111,112] In Figure 7 we
present images of several different crystal
specimens from the MTP family produced
in our group at the Oak Ridge National Lab-
oratory. All samples were made by loading
stoichiometric quantities of the appropriate
elements (or, in the case of CuInP2S6, the
appropriate elements plus the precursor
phase In2S3) into fused silica ampoules
Figure 6. a) The electronic density of states calculated for Mg2P2S6, used here as a simple, and heating to temperatures ranging from
d-electron-free prototype of the structural family. b) The same calculation for Zn2P2S6, with a 600–775 °C over 10–15 h., holding at those
filled d-shell.
temperatures for up to four days, and slow
cooling the samples at rates of 20 °C h−1.
More recently, Bercha et al. [106] calculated the band diagram As these samples were fabricated using the vapor transport
for CuInP2S6 using DFT-based ab initio theory to model the technique, the presence of a large temperature gradient of
Jahn–Teller effect and its contribution to ferrielectric ordering 50 °C or so was beneficial to promoting species transport
in this compound. from the hot end of the ampoule to the growth area in the
colder region of the furnace. This condition could be accom-
plished through careful placement of the sealed ampoule
2. Materials Synthesis in the furnace.
Though most MTP compounds are known to decompose at
2.1. Synthesis Routes high temperatures, some of the selenides have been found to
congruently melt (e.g., AgInP2Se6, AgAlP2Se6, AgGaP2Se6[89]),
The first synthesis of MTP compounds was by Friedel[9] and, enabling the synthesis of large single-crystal ingots. No sulfide
later, Ferrand.[10] In the former example, the authors reacted phase to date has been definitively stated as having a congruent
P4S10 with Fe to produce Fe2P2S6. In the latter example, using melting point.
Figure 7. Images of several single-crystal specimens of MTP compounds produced at the Oak Ridge National Laboratory.
Often, impurity phases appear together with the desired single crystals of Fe2P2Se6. In some cases, I or Cl can addition-
phase. These are usually of two types: i) byproducts of under- ally act as mineralizing agents that accelerate the reaction with
reacting the precursor elements or ii) parasitic phases that pre- the transition metal, as a reaction barrier often forms during
vent the complete formation of the desired phase. In the Cu- the synthesis. In addition to use of halide compounds as a min-
and Ag-based M1+M3+[P2S6]4− compounds, the main impurity is eralizer or vapor transport agent, Jörgens et al.[113] used stoichio-
(Cu/Ag)3PS4.[43,111] Maisonneuve et al.[43] found that using In2S3 metric quantities of starting elements and an AgCl/AgI molten
as a precursor resulted in less impurity phase in CuInP2S6 salt flux at 900 °C for 20 h. in the synthesis of Ag2MgP2S6; simi-
compounds. Indeed, we have used the same precursor to pro- larly, a KCl flux at 500 °C and 15 h. was used for the synthesis of
duce AgInP2S6, CuInP2S6, In4/3P2S6, and CuInP2S6-In4/3P2S6 K2MgP2Se6. In these cases, the MTP crystals are grown by using
heterostructures with little to no impurity phases present.[36] In the molten salt as the transporting agent. Crystals were isolated
addition, we have also utilized this technique, using Sc2S3 as from the flux by simply dissolving the salt mixture in water.
a precursor, to produce CuScP2S6 and AgScP2S6 crystals. Gave Various other novel routes have been attempted for MTP
et al.[111] noted that in the synthesis of AgBiP2S6 both AgPS6 synthesis, most involving metathesis reactions. Pfeiff and
and Ag3PS4 were present as impurity phases. Both of these Kniep[88] used a technique to synthesize selenophosphates of
compounds contain P in the +5 oxidation state rather than the the M1+M3+[P2Se6]4− type whereby salts of the M1+Cl and M3+Cl3
+4 state associated with the [P2S6]4− anion complex. To avoid are combined with Mg2P2Se6 at 530 °C producing a melt. The
this oxidation state and the associated parasitic phases, Gave et desired M1+M3+[P2Se6]4− phase and MgCl2 are produced upon
al. added an additional equivalent of P to the precursor element slow-cooling. A room temperature procedure developed by
mixture and thus achieved the desired reaction product plus Foot and Nevett[118] reacts Ni2+ salts with Na4P2S6 to produce
unreacted phosphorus. Ni2P2S6. The resulting colloid precipitated Ni2P2S6 powder
Vapor transport agents such as I[113–116] or Cl[113] can be after it was mixed with isopropyl alcohol. The Ni2P2S6 that was
added to facilitate the MTP reaction. For the case of I, two produced was found to be of poor crystallinity and required
approaches are typically used to add I to the reaction mixture: annealing at 560 °C for 18 h. for full crystallinity to be observed.
i) direct addition whereby I2 as a solid is added directly to the Fragnaud et al.[119] and Prouet et al.[120] used a similar method
mixture pre-reaction[92,101,122] or ii) the indirect method where I to produce highly disordered Ni2P2S6, excepting that Li4P2S6
becomes available as a vapor transport agent via the decomposi- was used rather than Na4P2S6. Bourdon et al.[127] synthesized
tion or reaction of a precursor compound like AgI.[113] Chlorine ≈20 nm sized Sn2P2S6, using Li4P2S6 together with SnCl2;
has similarly been used via both methods. For example, Taylor an excess of SnCl2 was used to ensure that all of the [P2S6]4−
et al.[117] back-filled their quartz tube with Cl gas to produce anions were reacted.
2.2. Scalability various organic and larger alkali or alkaline earth metals is the
ejection of a metal cation species from the host compound. In
Synthesis of large-scale quantities of MTP compounds is often the ferromagnetic compounds discussed below this frustrates
desired, whether it be for advanced neutron scattering experi- the spin balance and can result in a spontaneous ferrimagnetic
ments requiring 5 g or larger sample sizes or, looking ahead, polarization at low temperatures.[20] Both Li intercalation for
for commercialization purposes. In the former case, Brec and Li-ion batteries and organic and organo–metallic intercalation
co-workers[69] were able to fabricate >50 g pure-phase batches will be discussed in detail below in the ionic conductivity and
for Mn2P2S6, Ni2P2S6, Cd2P2S6, and Co2P2S6. For Co2P2S6 reac- magnetism sections, respectively. The insertion of a neutral
tion times were on the order of months and the impurity phase species (i.e., cobaltocene) as an intercalating material has also
CoS2 was observed. For Zn2P2S6, 20 g batches were synthesized been attempted for various MTP compounds. In these mate-
by Prouzet et al.,[121] although Zn2P3S9 occasionally formed rials, cations do not leave the host structure nor do they change
instead. Overall, scaling of the sulfide MTP compounds is more oxidation state as charge balance is not altered. Rather, the
difficult than the selenide compounds, likely due to the fact that spacing between lamellae increases as evidenced from X-ray
the sulfide phases readily decompose at lower temperatures diffraction experiments.[24,127,128]
and are also more likely to form parasitic secondary phases. For
detailed analysis of the phononic structure in ferrielectric MTP
compounds using the wide angular-range chopper spectrometer 3. Functionality and Applications of
(ARCS) at ORNL, we have synthesized 5–10 g batches of pure-
MTP Compounds
phase material for In4/3P2S6, CuInP2S6, Cu0.2In1.2667P2Se6, and
CuInP2(S0.5Se0.5)6 and near pure phase (i.e., 90%+) of CuInP2S6. 3.1. Ferrielectric Ordering
Stoichiometric quantities of the starting elements were sealed
into a quartz ampoule and heated at 600 °C for 2–3 days. The One of the more interesting functional aspects to MTP com-
resulting powders were removed, ground, pressed into pellets, pounds is the presence of ferrielectric ordering in CuInP2S6
and placed into alumina crucibles that were in turn sealed in and CuInP2Se6. This behavior makes this van der Waals com-
fused silica ampoules. The pellets were heat-treated at 600 °C pound family a promising candidate for the functionalization
for another 2–3 days, tested for phase purity using X-ray diffrac- of layered materials, as discussed below. We have compiled
tion, and, if necessary, re-ground, re-pressed, and re-annealed. a list of all MTP compounds with known ferroic ordering in
The reactions involving S required multiple heat-treatments. Table 4. In addition, the interplay between structure, charge,
Often the synthesis of large single crystals is beneficial for and ordering have made this compound interesting to study
fundamental measurements. As mentioned above, AgInP2Se6, from a fundamental science perspective. Also, small amounts
AgAlP2Se6, and AgGaP2Se6 have been found to melt congru- of element substitution in these materials (either on the In or
ently,[89] enabling easy syntheses of large single crystals using chalcogenide site) leads to strong and interesting changes in
the Bridgman technique (e.g., ref. [122]). the exhibited properties, i.e., from ferrielectric to a dipolar glass
to a non-ergodic relaxor phase to a ferrielectric with increasing
Se content in CuInP2(SxSe1−x)6.[39]
2.3. Intercalation As discussed in the structure section in CuInP2S6, Cu1+
atoms can occupy and move among one or more of three dis-
Intercalation of MTP compounds has been performed in order tinct types of sites: one that is closest to the center of the octahe-
to modify their structure and thus their properties. The main dral cage (Cu2), one that is further off-center and quasi-trigonal
research thrusts for the intercalation of MTP compounds can (Cu1), and a nearly tetrahedral site in the interlayer space
be grouped into two categories, both covered in detail below. (Cu3).[40] Above 315 K, the symmetry of the CuInP2S6 phase is
The first is the intercalation of Li for the purposes of using readily apparent as each of these three sites (1) have both an
MTP compounds like Ni2P2S6 as an electrode in Li-ion bat- “up” or “down” position, represented in Figure 8a and (3) show
teries. Later work (e.g., refs. [20,123,124]) utilized alkali or equal occupation of both the up and down positions.[42] When
alkaline earth metals to investigate the effects of intercalating the CuInP2S6 compound is cooled below its Tc of ≈315 K, the
these elements on the nature of potential ion exchange path- intersite copper motion is restricted, locking the Cu1+ sublattice
ways with various charged organic intercalating compounds. in its displaced state (Cu1, up) together with a compensatory
The second is the intercalation of various organic species for
the purposes of either modifying the magnetic properties (i.e., Table 4. List of ferroically ordered MTP compounds.
the inducing of ferrimagnetism from an antiferromagnetic
ground state in Mn2P2S6) or enhancing the non-linear optical Compound Order Type Ordering Temperature
properties.[125]
CuInP2S6 Ferrielectric[42] 315 K
The insertion of a charged intercalating compound into the
van der Waals gap of a MTP material results in a charge imbal- CuInP2Se6 Ferrielectric[133] 236 K
ance of the MTP compound. For insertion of Li into Fe2P2S6 or CuCrP2S6 Antiferroelectric[25] 150 K
Ni2P2S6 charge balance is maintained by the reduction of one of CuVP2S6 Unknown[132] 20 K
the metal cations (M2+) to a an M0 state.[126] This charge reduc- CuBiP2Se6 Antiferroelectric[111] 97 K < Tc < 173 K
tion is accompanied by the movement of the now-neutral metal
AgBiP2Se6 Antiferroelectric[111] Tc < 298 K
to a tetrahedral coordination.[63] The other route taken by the
Figure 8. a) The position of three “up” copper positions labeled Cu1, Cu2, Cu3. The corresponding “down” positions are also shown. b) An in-plane
view of the layers in the ferrielectric state, showing Cu in the Cu1-up position and the In shifted downward. c) The distorted close packed sulfur net
nearest the Cu atoms. d) The distorted close packed S net nearest the In atoms. S–S distances are reported in Angstroms.
shift in the In3+ sublattice of the opposite polarity, thereby The effects of the application of hydrostatic pressure on the
producing a non-centrosymmetric (Cc) ferrielectric phase (see structural phase transition of CuInP2S6 have been investigated.
Figure 8b). Figure 8c,d show how the sulfur nets at the top Shusta et al.[129] found that the ferrielectric Tc could be tuned
and bottom of the layers are distorted when the cations order with the application of pressure, linearly increasing with P with
into this arrangement. Although the PP bonds are rigid, the ∂Tc/∂p = 210 K GPa−1. This effect points to the order/disorder
sulfur triangles are complacent to ionic displacements. Thus, nature of the transition and the coupling of ferroelectric dipoles
the coupling between the Cu1+ and In3+ displacements occurs across the van der Waals gap. Recent piezoresponse force
in a simple way through the anion sublattice. Though cause microscopy (PFM) studies have confirmed these results by
and effect are not conclusively distinguished, it is perhaps most direct observation of ferrielectric domains persistent across sev-
likely that the transition is driven by Cu ordering into the top eral hundreds of layers along the stacking direction.[35,36] The
layer, distorting the In-coordination sphere and pushing it in spontaneous polarization Ps at room temperature for CuInP2S6
the opposite direction. has been measured and was found to be 2.55 µC cm−2, close
At 305 K occupancies of the Cu1 “up” and Cu1 “down” to the predicted value of 3.01 µC cm−2 based on the crystallo-
sites are split as 85%/11%; above the Tc of ≈315 K, upon the graphic data.[42] At lower temperatures (<150 K), Ps is predicted
CuInP2S6 undergoing a first-order order-disorder phase tran- to be closer to ≈4 µC cm−2.[42] The spontaneous polarization
sition from Cc to the centrosymmetric C2/c, the upper and was also found to rapidly change with temperature with a large
lower Cu1 sites become equivalent and evenly occupied dPs/dT near Tc; the pyroelectric coefficient was measured to be
(cf. Figure 9).[42] At even higher temperatures, i.e., above 353 K, 13 nC cm−2 K at 265 K.[42]
the occurrence of Cu1–Cu3 jumps becomes significant. Since At lower temperatures (i.e., below 175 K) complex dielec-
the Cu3 site is in the van der Waals gap, its occupation can give tric permittivity measurements in CuInP2S6[27] have revealed
rise to Cu1+ migration along the lamellae as confirmed by ionic the presence of dispersions typical for dipolar glasses. Such
conductivity measurements.[29] materials, when cooled down below specific glass transition
Figure 9. Thermal evolution of Cu site occupancies (with corresponding probability density contours) in CuInP2S6. The small crosses denote the refined
positions of Maisonneuve et al.[42] and the dashed lines indicate the upper and lower sulfur planes marking the boundary of an individual lamellae.
Reproduced with permission.[42] Copyright 2017, American Physical Society.
temperature, Tg, enter the state with dipole moments frozen 3.2. Magnetism
in random orientation with no long range ferroelectric
ordering.[130] This behavior is unique for CuInP2S6 as compared The discovery and characterization of magnetic 2D materials
to most ferroelectrics, for which dipolar glass behavior appears has been a major research thrust in recent years (e.g., ref. [134])
only after addition of small amounts of antiferroelectric mate- with the ultimate aim of using this magnetic functionality for
rials or impurities, which randomize the directions of the spintronic or magnetoelectronic applications.[135] Investiga-
dipoles.[131] This behavior was surprising at first, since static tions into MTP magnetic compounds have been numerous
measurements suggested the freezing of the Cu+ cations in the over the years (e.g.[19,77,136–146]) and have led to compounds that
Cu1 position. However the dynamic measurements revealed can be largely grouped into four broad categories: i) pure-phase
that complete freezing of Cu+ cation hopping happens only at compounds of the form M2P2X6 where M = Fe, Mn, Ni and
very low temperatures.[27] X = S, Se; ii) alloys of these compounds; iii) intercalated forms
Another material that is found to exhibit ordered displace- of these compounds; and iv) exotic pseudo-1D materials such
ment of metal ions at low temperatures in the sulfide family as AgVP2S6 and AgCrP2S6[147–149] (see Table 5 for a complete list
is CuVP2S6 which shows similar to the CuInP2S6 Cu+ freezing of magnetic compounds). In addition, the magnetism observed
below 20 K in the trigonal Cu1 site forming acentric C2 in these van der Waals bonded, layered compounds offers an
symmetry.[132]
The other broad range of materials exhibiting ferroelectric Table 5. List of magnetic MTP pure-phase materials.
properties can be found in the selenophosphate class. The main
difference from P2S6 backbone in this case is higher degree Compound Type of magnetism Ordering temperature [K]
of covalence in the P2Se6 bonds. This is made evident from Fe2P2S6 AFM, magnetic axis parallel 116,[136] 123[19]
the Cu+ ion displacement in the lower temperature phase: for to layer stacking direction
CuInP2Se6 the displacement is only 1.17 Å,[133] compared to Mn2P2S6 AFM, magnetic axis parallel 82,[136] 78[19]
1.58 Å for CuInP2S6.[42] This is believed to be the reason of lower to layer stacking direction
phase transitions in CuInP2Se6 compound which consist of a Ni2P2S6 AFM, magnetic axis perp. 155[19,26,136]
second-order phase transition Ti = 248 K and a first order tran- to layer stacking direction
sition at Tc = 236 K.[42] The second order transition in this case
Fe2P2Se6 AFM 112,[136] 119[158]
is attributed to the incommensurate, quasi polar phase forma-
Mn2P2Se6 AFM 74[136,158]
tion,[133] for which e Cu+ cation displacement is modulated with
a period different from the principal period of the crystal lattice. Ni2P2Se6 AFM 206[136]
Several materials in the selenide family where Bi3+ is the AgVP2S6 AFM, pseudo-1D 10–15 K based on ratio of
trivalent cation were found to show antiferroelectric ordering, intrachain to interchain
namely CuBiP2Se6 and AgBiP2Se6.[111] In the case of CuBiP2Se6 coupling constants.[269]
partial antiferroelectric ordering is observed below 173 K, with AgCrP2S6 AFM, pseudo-1D 20[270]
85% of Cu+ ions found in well-defined off-center positions CuCrP2S6 AFM, magnetic axis parallel 30[21]
below 97 K. The increased displacement of Bi3+ compared to to layer stacking direction
In3+ may be an indication of stereoactive lone pair electrons, CuCrP2Se6 AFM ≈40[133]
which could be present in Bi3+ but not In3+. In AgBiP2Se6 sim-
AgCrP2Se6 AFM ≈42[133]
ilar behavior is observed at room temperature.[111]
exciting platform for evaluating the effects of 2D behavior on In the ordered state, Mn2P2S6 has its magnetic axis aligned
magnetism and anisotropy. Recent single-crystal neutron-dif- nearly with the planar stacking direction. Each Mn2+ magnetic
fraction work (e.g., refs. [150–152]) has overturned much of the cation interacts antiferromagnetically with its nearest neighbor
previous literature regarding the magnetic structure of MTP magnetic cation, forming the alternating honeycomb pattern
compounds since the publication of the last review by Brec[69] depicted in Figure 10. Recent work by Ressouche et al.[152] on
and will thus be covered in detail in this section. using single-crystal neutron diffraction has shown that the mag-
The most studied MTP compounds are Fe2P2S6, Mn2P2S6, netic propagation vector is more precisely defined as k = [0 0 0]
and Ni2P2S6. The magnetic structures of these compounds are with moments pointed 8° from the c* axis. Each Mn cation is
represented in Figure 10 where the magnetic cations, arranged also coupled ferromagnetically across the van der Waals gap to
in a honeycomb pattern, sit at the center of trigonally distorted its interplanar nearest neighbor, though this interaction is very
octahedra. The trigonal axis lies parallel to the stacking direc- weak compared to the intraplanar antiferromagnetic interaction
tion. This trigonal distortion has consequences with respect by a factor of 400:1.[153] Magnetic susceptibility data, χ, for this
to the ordering and magnetic behavior of the magnetic MTP compound shows relatively isotropic behavior with temperature
compounds as it can affect the degeneracy of some of the as T decreases toward the Néel point. Just before the Néel point
energy states associated with octahedral crystal field splitting. a broad maximum at 120 K is reached, indicating the presence
In short, the presence of an axial distortion in an octahedral of short-range spin-spin correlations typical to low dimensional
field requires an extra term to be added to the Heisenberg magnetic systems.[19] Upon passing through the Néel tempera-
Hamiltonian which describes the single-ion anisotropy.[19] The ture, TN, the susceptibility data indicate that spins are oriented
details of this distortion are outside the scope of this review primarily along the stacking direction. Above 200 K, χ−1 vs T
but are well-presented in the work of Joy and Vasudevan.[19] In measurements show that in the paramagnetic regime Mn2P2S6
Mn2P2S6 this effect is small and the system can be modeled follows Curie–Weiss behavior exceptionally well; the Weiss con-
using a symmetric Heisenberg Hamiltonian. For Fe2P2S6, the stant θ derived from these data of −160 to −217 K indicates that
trigonal distortion combines with spin-orbit coupling to yield strong antiferromagnetic interactions are present.[19] The value
magnetic interactions that are highly anisotropic in nature such of μeff from the susceptibility data is close to the spin-only value
that the Fe2P2S6 system can be described using an Ising Ham- of 5.9 μB.[19] As mentioned above, the magnetic structure of
iltonian. In Ni2P2S6 the combination of the trigonal distortion Mn2P2S6 can be described in terms of an isotropic Heisenberg
and the spin-orbit coupling results in spins that lie within the Hamiltonian due to the fact that there is minimal effect of trig-
basal plane. Thus Ni2P2S6 can be modeled using an anisotropic onal distortion on the occupied states in these compounds.[19]
Heisenberg Hamiltonian. The anisotropy energy K is small for Mn2P2S6, with a value of
Figure 10. Magnetic structures of a) Fe2P2S6,[157] b) Mn2P2S6,[152] and c) Ni2P2S6.[26] The upper figures, where P is represented by pink spheres, S is
represented by yellow spheres, and the metal cations are represented by green spheres, show projections along the stacking direction. The lower panels
show an isometric projection of just the metal cation sites.
K/kB = 0.13 K,[179] which includes both the dipolar anisotropy specifically, the moment lies predominantly along the a direc-
(Kdip/kB = 0.16 K) and the competing single-ion anisotropy tion with a small component along c. The magnetic propaga-
where Mn moments want to have an in-plane orientation. The tion vector is k = [010]. The value of TN in this material is 155 K.
anisotropy field is small, at 0.075 T.[154] Recent work by Zeng Unlike Fe2P2S6, anisotropy is not observed in the paramagnetic
et al.[155] have noted a large magnetocaloric effect in Mn2P2S6 state of Ni2P2S6. Like in the other magnetic thiophosphates
where, at 2.85 K, a reversible magnetic-entropy change of a broad maximum is present above TN at 270 K. In Ni2P2S6
12.8 J kg−1 K−1 and an adiabatic temperature change of 8 K were the values of μeff from the Curie–Weiss fits at high tempera-
noted for a magnetic field change of 9 T. The effects of pressure tures are close to the spin-only value of the Ni2+ ion (2μB).[19]
have also been noted on the Mn2P2S6 system,[139] where the c Little anisotropy is noted in the values of the Weiss constant
axis decreases rapidly with increasing P, likely due to a com- θ, which are close to −250 K along both directions and indi-
pression of the van der Waals gap. With an applied pressure of cate strong antiferromagnetic interactions.[19] However, refine-
0.9 GPa, TN increased by 10 K to 89 K from the ambient-pres- ments on single crystal neutron diffraction data show that the
sure value of 78 K. Additionally, the spin-flop magnetic field HF moments on the two Ni sites are only ≈1.0 μB, possibly due to
at 10 K decreased from 3.85 T to 3.5 T under the same condi- incomplete ordering or strong fluctuations.[26] Sensitivity of
tions. The magnetic moment as derived from Curie–Weiss fits this material to strain has been found to have strong effects on
to susceptibility data does not change with pressure, remaining magnetization measurements.[26]
close to the spin-only value of Mn. The increases in TN and HF The magnetic metal selenophosphates exhibit similar
indicate an increase of interlayer magnetic interactions between behavior to that of the sulfide compounds. However, much
the Mn cations caused by the decrease in interlayer distance. less work has been performed with respect to characterizing
Like Mn2P2S6, Fe2P2S6 (TN = 116–123 K) has magnetic the magnetic properties of the metal selenophosphates. We
moments aligned with the planar stacking direction; however, particularly note a dearth of measurements on single crystal
Fe2P2S6 has a slightly more complicated magnetic structure. In specimens. Structurally, the selenide compositions are quite
this compound the Fe2+ is antiferromagnetically coupled with similar to their respective sulfide counterparts. Ni2P2Se6 shares
one nearest neighbor and ferromagnetically coupled with the the same space group with Ni2P2S6, C2/m. Both Fe2P2Se6 and
other two (Figure 10). The result is the formation of antifer- Mn2P2Se6 have higher symmetry than their sulfide equivalents
romagnetically coupled chains where the antiferromagnetic as evinced by their R 3 space group (as compared to the C2/m
interactions between chains occur: i) between chains located for the sulfides).
within the same lamella and ii) between chains of neighboring Neutron diffraction studies performed by Wiedenmann
lamella, i.e., along the stacking direction and across the van der et al.[158] show that the magnetic unit cell of Mn2P2Se6 is the
Waals gap. The original structure proposed by Le Flem et al.[136] same as the crystallographic unit cell (i.e., k = [0 0 0]) as no
has the direction of these ferromagnetic chains pointing at an superlattice peaks are visible below the magnetic ordering tem-
angle 60° away from the a-axis direction. A later study by Kuro- perature (74 K[136,158]). The magnetic structure of Mn2P2Se6 was
sawa et al.[156] purportedly confirmed this structure but instead found to be similar to that of Mn2P2S6 depicted in Figure 10
had the direction of the chains pointing along the a-axis. More whereby each metal cation interacts antiferromagnetically with
recent neutron diffraction work by Rule et al.[157] has confirmed each of its nearest-neighbor metal atoms. In contrast to Mn2P2S6,
the structure proposed by Le Flem and has shown that the mag- the magnetic axis of Mn2P2Se6 is aligned such that its moments
netic propagation vector is k = [1/2 1/2 0.34], where the weak lie within the ab plane within the layer. Magnetic measurements
magnetic interactions along the c-axis results in incommensu- have been performed by Jeevanandam and Vasudevan[146] and
rate ordering. In the paramagnetic state, Fe2P2S6 exhibits prop- show: i) a large anisotropy in which magnetization measured
erties that are much more anisotropic in nature than the struc- along the basal plane is always higher than that measured along
turally similar Mn2P2S6 with χ measured along the stacking the stacking direction (at least in the temperature range given,
direction having a value nearly twice that of χ measured 20–300 K), ii) the magnetization measured along the basal plane
orthogonal to this direction.[19] Behavior similar to Mn2P2S6 is decreases rapidly below TN, confirming the direction of the mag-
exhibited where a broad maximum at a temperature slightly netic moments determined by neutron diffraction, iii) as with
higher than TN indicates short-range spin-spin correlations. At the magnetic sulfide compounds there is a broad maximum in
high temperatures, plots of χ−1 vs T obey the Curie–Weiss law magnetization above TN indicating the presence of spin-spin
but, due to the anisotropy present, have different values for the correlations. Recent theoretical work by Li et al.[159] has pro-
Weiss constants. Magnetic susceptibility measured along the posed that ferromagnetism with a Curie temperature of up to
magnetic axis (parallel to the stacking direction) yields a posi- 206 K can be induced in Mn2P2Se6 by electron or hole doping,
tive value of θ, 53 K, and a μeff of 5.67 μB.[19] Perpendicular to achievable through gating the material. This functionalization
this direction θ is −54 K and μeff is 5.23.[19] Joy and Vasudevan is predicted to induce a ferromagnetic state whereby spins can
interpreted these data to imply that a large spin-orbit contribu- be controlled either “up” or “down.” This type of control makes
tion was present since both the values of μeff are greater than this material an interesting candidate for applications in elec-
the spin-only value for Fe2+ (4.94 μB). tric-field controlled spintronic devices.[159]
Ni2P2S6 displays the zigzag magnetic structure similar to The magnetic structure of Fe2P2Se6 was determined via neu-
that of Fe2P2S6, only here the magnetic moments lie mostly tron diffraction in the same study by Wiedenmann et al.[158] in
along the lamella (i.e., the ab plane) and perpendicular to the which the Mn2P2Se6 structure was characterized. The overall
stacking direction. Recent comprehensive single crystal neu- magnetic structure of Fe2P2Se6 was found to be similar to that
tron diffraction work by Wildes et al.[26] has shown that, more of Fe2P2S6, although the magnetic wave vector was found to be
commensurate with a value of k = [1/2 0 1/2]. Like Fe2P2S6, in ii) mixed chalcogen, whereby the S or Se is alloyed with Se or
Fe2P2Se6 each metal cation is ferromagnetically coordinated S; and iii) some combination of the first two of these. In Table 6
with one of its nearest-neighbor cations and antiferromagneti- we give a comprehensive list of MTP alloys and their appro-
cally coordinated with the other two. As a consequence, ferro- priate references. Given the number of elements that lend
magnetic chains which are antiferromagnetically coordinated to themselves to the general MTP structure, the possible combina-
each other are formed. The magnetic ordering temperature of tions are quite large. To date the majority of substitutions have
Fe2P2S6 was found to be ≈115 K.[136,158] To our knowledge no been focused on the more functionally interesting compounds,
papers have been published giving magnetic measurements on in particular those associated with magnetism and ferroelec-
single crystals of Fe2P2Se6. tricity. The effects of alloying on these functional properties will
Though Ni2P2Se6 is reported to have the highest magnetic be discussed below.
ordering temperature of any MTP compound at 206 K[136,160]
there is remarkably little reported on its magnetic properties.
The only paper which describes the magnetic properties is a 3.3.1. Alloying and its Effects on Ferroic Properties
phosphorus NMR study. Taking this value of TN to be correct,
we would probably expect very broad short-range interactions Metal and chalcogen substitutions and alloying allow one to
above this temperature making a Curie–Weiss analysis only effectively tune and bring some new functionalities to the MTP
accurate at very high temperatures. ferrielectric compound CuInP2S6. This important topic has
The final magnetic MTP compounds to be discussed are been therefore widely studied recently. The general approach is
AgVP2S6,[22] AgCrP2S6,[149] CuCrP2S6,[21] CuCrP2Se6,[133] and to either modify one of the components of the two cation sub-
AgCrP2Se6.[133] In the Ag-containing sulfide compounds the lattices or to modify the P2S6 backbone by partial substitution
metal cations are arranged in such a way that, looking down of Se.[161]
the stacking direction, one sees alternating “chains” of V or Cr For example, replacing the Cu+ cation with Ag+ results in the
and Ag (cf. Figure 3). These chains run parallel to each other formation of AgInP2S6 which shows no ferroelectric phase tran-
along the c axis direction (the c axis in this structure is defined sition down to 110 K.[162] Partial substitution of Ag for Cu (e.g.,
as being along the layer rather than perpendicular to it). The Ag0.1Cu0.9InP2S6) reduces the Tc by 30 K,[27] an effect possibly
Ag+ cation has a radius nearly double that of either V3+ or Cr3+ ascribed to the larger size of the Ag1+ cation where lower tem-
and, as a consequence, the structures of both AgVP2S6 and peratures are needed to stop the static hopping of the system.
AgCrP2S6 are distorted above the Ag chains. The SPP angle Substitution of In3+ for Cr3+ ions leads to different pathway for
associated with the P2S6 functional group neighboring the Ag structural relaxation. At room temperature CuCrP2S6 has sym-
atoms is shifted ≈7.23° from that of the Fe2P2S6 type com- metry with Cu1+ cations in two quasi-vertically disposed par-
pounds, creating a noticeable bump in the layer surface above tially filled positions: a slightly off center Cu2 and distinctly
the location of the Ag chains. The chains formed by the mag- shifted Cu1 with the distance of 2.52 Å between the potential
netic cations themselves lead to so-called quasi-1D antiferro- minima.[25] The occupancy ratio between Cu1 and Cu2 posi-
magnetic chains with spins of S = 1 (for AgVP2S6) and S = 3/2 tions was estimated as 0.66 and 0.34 respectively.[25] This partial
(for AgCrP2S6).[149] CuCrP2S6 is a relatively unexplored mate- filling vanishes below 150 K, where CuCrP2S6 has Pc sym-
rial in terms of magnetism. However, magnetization meas- metry. In this case Cu1+ sublattice fully occupies Cu1 positions
urements performed by Colombet et al.[87] have shown that at and the Cr3+ sublattice shifts to complete the antiferroelectric
high temperatures (above 60 K) plots of χ(T) obey the Curie– ordering.[163] Mixed CuInxCr1−xP2S6 crystals were studied in
Weiss law with μeff close to that of the spin-only value of Cr detail due to the wide range of crystal behaviors that drastically
and a positive θ of 32 K, in spite of the obvious AFM response change with the mixed ion concentrations, see Figure 11.[164]
at low temperatures. From the susceptibility data, spins seem Small additions of Cr3+ (x = 0.8) drastically reduce the Tc
to align along the c axis, although the difference in magnetiza- from 315 to 245 K and for higher concentrations (x = 0.4–0.6)
tion between the ab plane and the c axis are small compared to no ferroelectric transition occurs down to the lowest tempera-
normal AFM behavior. The last two compounds, CuCrP2Se6[133] tures. At lower temperatures, a dipolar glass phase emerges,
and AgCrP2Se6,[133] have been shown through neutron diffrac- which coexists with the ferroelectric phase at concentrations of
tion and susceptibility experiments to both antiferromagneti- x > 0.8, similar to the pure CuInP2S6 compound. At the other
cally order at ≈40 K. However, detailed magnetic structure ana end of the phase diagram for x ≤ 0.2 the material presents a
lysis has yet to be performed and magnetization measurements very rich structure with multiferroic behavior with antiferro-
were done on powder samples. magnetic Cr3+ ordering and antiferroelectric Cu+ ordering at
lower temperatures and an incommensurate(quasi-antipolar)
phase at higher temperatures, where Cu+ clusters occasionally
3.3. Alloying flip in overall antipolar material.
Detailed studies of CuInP2(SxSe1−x) crystals where the chal-
Given the large array of available chemistries and functionali- cogen element has been substituted have revealed a complex
ties in MTP compound it is no surprise that the synthesis of phase diagram for these materials (see Figure 12).[39] Among
alloys is often desired. Alloys of MTP compounds can largely be interesting features of this asymmetric phase diagram is
classified as one of three categories: i) mixed metal, whereby the very rapid reduction of Cu1+ ordering for substitution of
valence state of the two or more metals present are balanced to sulfur by selenium (cf. Figure 12, specifically the reduction
be +4 (as the [P2(S/Se)6]4− anion carries a formal charge of −4); in Tc at x = 0.98). On the selenium-rich side of diagram, the
Table 6. MTP alloys organized by type of substitution.
Metal site alloy Ref. Chalcogen alloy Ref. Metal/chalcogen alloy Ref.
AgCr1−xInxP2S6 [271] Ni2P2S6−xSex [272] AgxCu1−xInP2S6−ySey [273]
AgxCu1−xInP2S6 [27] CuInP2S6−xSex [31,39,274–280] CuInxCr1−xP2S6−ySey [281]
FexCd2−xP2S6 [169,282,283] Sn2P2S6−xSex [284–301] PbySn2−yP2S6−xSex [284,302–314]
MnxCd2−xP2S6 [315] Pb2P2S6−xSex [284]
NixCo2−xP2S6 [272]
Cu2xMn2−xP2S6 [316,317]
Ag2xMn2−xP2S6 [316]
CuInxCr1−xP2S6 [164,318]
FexNi2−xP2S6 [142,186,319]
FexZn2−xP2S6 [320]
Mn2−xFexP2S6 [143,321]
Mn2−xMgxP2S6 [141]
MnxZn2−xP2S6 [154,322]
Na2xMn2−xP2S6 [123]
MgxNi2−xP2S6 [77]
NixMn2−xP2S6 [165]
PbxSn2−xP2S6 [284,323–328]
PbxSn2−xP2Se6 [284,328]
Ag2xCd2−xP2Se6 [329]
CdIn2/3P2S6 [167]
FeIn2/3P2S6 [167]
MnIn2/3P2S6 [167]
substitution of S for Se has less effect on Cu+ ordering than the MTP compound and the diluted alloy Ni1.4Mg0.6P2S6 and found
aforementioned substitutions of Se for S. Macutkevic et al.[39] that in the latter case, though the alloy formed an ordered solid
noted that the ferrielectric ordering was not affected up to solution, the ordering was imperfect in that the minority spe-
x = 0.10. Between 0.1 < x < 0.4 ferroelectric properties appear cies was clustered into groups of 10–30 atoms. Considerations
in nanosized domains of what is termed a non-ergodic relaxor such as these must be taken into account when considering the
phase, where polarization appears not in the macroscopic application of a material in a nanoscale environment and could
domains but in nanosized regions. From 0.4 < x < 0.9 a dipolar even allow for nanoscale engineering of ferroic and magnetic
glass phase is evident from the dielectric spectroscopy investi- properties.
gations where dipoles are frozen at random orientations.
Phase separation in MTP alloys is an important topic.
Recently, we have shown[36] that an alloy of In4/3P2S6 and 3.3.2. Alloying and Magnetic Glassiness
CuInP2S6 will phase separate from a single phase alloy into
pure phases of the end-members within the same single crystal Alloying of magnetic MTP compounds has also been accom-
upon cooling (Figure 13). The epitaxial strain caused by the plished with the aim of altering the magnetic properties, for
lattice mismatch between these two phases has consequences example by altering the material to exhibit ferri- or ferromagnetic
for the material properties in that the Tc of the ferrielectrically properties rather than the native antiferromagnetism present in
active CuInP2S6 is increased by up to 30 K. Interestingly, we several of these materials. Either the metal or chalcogen site has
note that the lateral alternation of chemical domains in these been investigated in terms of substitution. In the latter case, Yan
heterostructured materials is synchronized across the van der et al.[165] have synthesized a series of compounds following the
Waals gap. Earlier PFM imaging of the band excitation ampli- general formula Mn2P2SxSe6−x and noted that a solid solution
tude noted a regular network of ferrielectric domains (sepa- was formed across the pseudobinary phase diagram. The value
rated by p radians in piezoresponse between these domains) of TN followed a Vegard-like path from one end-member to the
and areas yielding no piezoresponse (Figure 14), indicating that other, as did the Weiss constants from Curie–Weiss fittings. In
this sample contained trace amounts of the In4/3P2S6 phase and the former case two different types of substitutions have been
thus confirming our earlier interpretation of piezoresponse attempted: i) substitution on the metal site my another metal
force microscopy data (Figure 13).[36] which may or may not have magnetic properties and ii) the
Following a similar vein of research, Goossens et al.[77] have introduction of positively charged intercalates into the van der
looked at other important properties in the magnetic Ni2P2S6 Waals gap through a reaction that maintains charge balance by
Figure 12. Phase diagram of the mixed CuInP2(SxSe1−x)6 crystals

Figure 11. Phase diagram of CuInxCr1−xP2S6 crystals: P, paraelectric
(FE – ferroelectric phase, NR – non-ergodic relaxor phase, DG – dipolar
phase; IC, incommensurate phase; AF, antiferroelectric phase; AFM,
glass phase, FE+DG – ferroelectric and dipolar glass coexistence) Repro-
antiferromagnetic phase; G, dipolar glass phase; F, ferrielectric; F + G,
duced with permission.[39] Copyright 2017, American Physical Society.
coexistence of ferrielectric and dipolar glasses. The solid lines are a guide
for the eye. Reproduced with permission.[164] Copyright 2017, American
Physical Society. Fe and Mn with the respective formulae FeIn2/3P2S6 and
MnIn2/3P2S6 so as to maintain charge balance. Next-neighbor
“leaching out” the magnetic metal cation and leaving behind a magnetic interactions were disrupted due to the presence
vacancy. It is these latter two examples which will be the focus of vacant sites necessary for charge balance with In doping.
of this section as they provide the most opportunity for func- For both MnIn2/3P2S6 and FeIn2/3P2S6 the magnetic proper-
tionalization of the magnetic MTP compounds. ties were diminished compared to their respective pure-phase
In the case of simple metallic substitution, two effects are counterparts in terms of Weiss constant θ, effective moment
generally noted. In the case of a non-magnetic metal a dilution μeff, and TN. For example, the value of TN shifted from 110 K
effect is present. In this case the magnitude of the paramagnetic for the pure-phase compound Mn2P2S6 to 15 K for the alloy
response above the ordering temperature is decreased con- MnIn2/3P2S6. The effect on the Fe-containing compound was
comitantly with the decrease in the concentration of the mag- not so severe; where TN was measured at 126 K for Fe2P2S6, it
netic cation species. In addition, the value of TN is predicted was seen to be less distinct at 100 K for FeIn2/3P2S6. We should
to fall with dilution until a percolation threshold is reached of note that these data were taken on powder samples and there-
pc ≈ 0.7, the critical concentration necessary for a honeycomb fore ignore the effects on anisotropy in these samples.
lattice entirely described by nearest-neighbor exchange inter An interesting consequence of alloying a magnetic MTP
actions.[166] However, in diluting Mn2P2S6 with Zn following the compound with a different magnetic element is the creation of
formula Mn2−xZnxP2S6, Goossens and Hicks[141] found anoma- a spin glass or magnetic glass. The former case, a spin glass,
lies in χ(T) data indicative of the presence of an albeit dimin- is the result of a lack of long-range magnetic order, i.e., mag-
ished TN for compositions as high as x = 1, demonstrating the netic moments are frozen into a non-periodic arrangement
need to consider second- and third-nearest-neighbor interac- below the spin freezing temperature. In the case of a magnetic
tions. Later work by the same group[154] showed that all spins glass, moments are ordered in local clusters but the clusters are
participated in the long-range order of the magnetic lattice, not ordered with respect to one another.[142] Both phenomena
though the moments were more weakly bound as the mag- can result from the presence of competing interactions, i.e.,
netism became more diluted. different end-members in the phase diagram having different
Similarly, Manríquez and co-workers[167] synthesized a series ground states with different magnetic structures. For example,
of samples where In was substituted for the magnetic cations as depicted in Figure 10, in Mn2P2S6 each magnetic cation is
Figure 13. Periodic modulation of piezoresponse (upper panels) and topography (lower panels) in Cu1−xIn1+x/3P2S6 compounds: a) Cu/In = 0.94,
b) Cu/In = 0.67, c) Cu/In = 0.22, and d) Cu/In = 0.15. In these figures we see the periodic modulation of the CuInP2S6(light) and In4/3P2S6 (dark)
phases. Reproduced with permission.[36] Copyright 2017, American Chemical Society.
antiferromagnetically coupled to all three nearest-neighbor the Fe2+ metal cations in Fe2P2S6 are ferromagnetically coupled
metal cations within a layer and ferromagnetically with the most to two nearest neighbor metal cations and antiferromagneti-
adjacent metal cation across the van der Waals gap. In contrast, cally coupled to one. This creates ferromagnetic zigzag chains
that are antiferromagnetically coupled both within a layer and
across the van der Waals gap (cf. Figure 10), though in the latter
instance the coupling is of course weaker. However, in both of
these compounds the magnetic axis is aligned with the stacking
direction. The differences in magnetic order can create frustra-
tion, culminating in a glassy state where the magnetic spins
of the metal cations are not arranged in a regular pattern. For
(Mn1−xFex)P2S6 the magnetic phase diagram was mapped out by
Masubuchi et al.[168] and is presented in Figure 15. In this mate-
rials system both end-members retain their respective magnetic
structures until fairly high compositions, up to ≈20% substitu-
tion in both cases. Between 0.3 ≤ x ≤ 0.45 and 0.6 < x ≤ 0.7
reentrant spin glass states are present where, at low tempera-
tures, the spin glass emerges from the ordered AFM state. For
the composition range 0.5 ≤ x ≤ 0.6 a pure spin glass is present.
In their investigations into alloys of the (Fe1−xNix)P2S6
system, Rao and Raychaudhuri[235] found that the system
formed a solid solution with no evidence of magnetic frustra-
tion. This is surprising considering that the magnetic struc-
tures of Fe2P2S6 and Ni2P2S6 are so different. Indeed, both
TN and magnetization followed Vegard’s law in this system, a
phenomenon Rao and Raychaudhuri attribute to the strong ani-
sotropy of Fe2P2S6 dominating the magnetism of the system.
In the same work the authors found no evidence of spin-glass
Figure 14. Local piezoelectric response of CuInP2S6 surface containing behavior. However, a more recent publication by Goossens
small quantity of In4/3P2S6 impurity. This microscopy image shows a et al.[142] it was found that a magnetic glass is present in the
rich domain network consisting of 1–3 µm sized domains. Ferroelec-
mixed system FeNiP2S6 where the magnetic transition through
tric domain walls are seen as thin blue lines intersecting continuous
domains. Finally, there are small regions lacking any piezoresponse TN is arrested depending on the thermal history of the sample.
(noisy white patches). Reproduced with permission.[35] Copyright 2017, Léaustic et al.[169] synthesized a series of Fe2−xCdxP2S6 single-
American Chemical Society. crystal specimens and, through X-ray diffraction, found that
intercalating MTP compounds in general. Potential applica-

tions range from 2D devices[170] to non-linear optics.[20] Interca-
lation of magnetic MTP compounds is generally accomplished
through the introduction of a species into the van der Waals
gap. If the inserting species is charged, then to maintain charge
balance the metal cation species either: i) leaves the structure or
ii) is reduced (as is the case with Li intercalation in Ni2P2S6[63]
or Fe2P2S6[171]) such that charge balance is maintained.
At this point it is useful to refer back to the structural
description of MTP compounds in general. The chemistry of
MTP compounds is very much ionic in nature and the struc-
ture itself can even be viewed as an ionic salt (i.e., M22+[P2S6]4−,
M+M3+[P2S6]4−, etc.) where the metal ions are held together by
[P2S6]4− bridging ligands.[20] With this framework a mechanism
has been proposed to explain the high mobility of the metal
cations in the ion-exchange mechanism used to describe inter-
calation in Mn2P2S6:[20]
Mn 2P2S6 + 4 xKCl ( aq ) → 2Mn 2+ + [P2S6 ] + 4 xKCl ( aq )

4−
Figure 15. Magnetic phase diagram of (Mn1−xFex)2P2S6. The notations SG,
(1)
RSG, AF, and Para indicate a spin glass phase, a reentrant spin glass phase, → ( Mn 1 − x )2 P2S6 K 4 x ( H2O)≈1 + 2xMnCl 2 ( x ≈ 0.2)
an antiferromagnetic ordered phase, and a paramagnetic phase, respec-
tively. Reproduced with permission.[168] Copyright 2017, Elsevier Limited.
whereby Mn2P2S6, in a solution of aqueous KCl (or other
the phase diagram appeared to exhibit the characteristics of a charged species such as tetraethylammonium[20] or cobalti-
monophase solid solution. However, careful examination of cinium chloride[20]) is partially dissolved on a local level allowing
their magnetization data yielded interesting results that show for the ready introduction of an intercalating compound into
that the solid solution may also contain some degree of order. the host structure and the relatively easy loss of Mn whereby
At high Cd concentrations long-range correlations between the vacancies are created within the lamellae. These reactions are
Fe cations are suppressed; however, the samples still exhibit noted by two interesting phenomena: i) the reaction always goes
antiferromagnetic ordering, albeit at lower temperatures due to completion, i.e., when the intercalation material becomes
to the weak antiferromagnetic interlayer interactions. As the fully packed into the van der Waals gap (cf. Figure 16 where
Fe concentration increases, the high values of χT at low tem- the intercalation of different species into Mn2P2S6 is pictured).
peratures in the Cd diluted samples can only be rationalized as Therefore the composition is not adjustable; when limiting the
resulting from high spin clusters of at least four Fe2+ cations amount of intercalating species a two-phased region is formed
interacting ferromagnetically with each other. However, the of fully intercalated material and parent Mn2P2S6. ii) the inser-
samples themselves still exhibit antiferromagnetic ordering due tion of intercalating material which is too big will not work and
to the antiferromagnetic interactions between individual layers. a second ion exchange reaction is necessary. In this scheme a
small hydrated alkali species intercalated and then exchanged
for the larger species.[20] This type of ion-exchange reaction
3.4. Molecular Intercalation and Magnetic Properties is most successfully used with Mn2P2S6. Fe2P2S6 has been
attempted with limited success. However, the addition of EDTA
Intercalation of magnetic MTP compounds to elicit a change as a complexing agent for the Fe2+ ions leaching out of the
in magnetic behavior has been one of the main foci of structure can help drive the reaction forward.[172] Ion-exchange
Figure 16. Schematic representations of some organic intercalating species in their host structure. a) [M(salen)]+ intercalted into Mn2P2S6 where
M = Fe3+ and Mn3+ and salen = N,N′-ethylene-bis(salicylaldimine); b)[Co3+(salen)]+ intercalated into Mn2P2S6; c) possible arrangement of BEDT-
TTF (bis(ethylenedithio)tetrathiafulvalene) intercalating compound in Fe2P2S6; and d) Proposed arrangement of pyridium intercalating compound in
Fe2P2S6 a,b) Reproduced with permission.[330] Copyright 2017, Elsevier Limited; c) Reproduced with permission.[331] Copyright 2017, Springer Publica-
tions. d) Reproduced with permission.[332] Copyright 2017, Elsevier Limited.
was found not to have worked for Ni2P2S6,[172] though a redox Evans et al.[175] whereby the excess of spin caused by the vacancy
process has been used to intercalate cobaltocene. For the ordering would lead to this magnetic ordering (Figure 10)
Ni2P2S6 and, to a lesser extent, Fe2P2S6, it was suspected that where Mn2P2S6 intercalates exhibit spontaneous magnetization
the bonding was stronger between the metal cation species and is noted in the above-mentioned intercalates at 20 K and 45 K,
the [P2S6]4− ligands.[172] respectively. If the model of Figure 17 is assumed, then the
Mn2P2S6 has been the most studied MTP material with value of saturation magnetization will be equal to 1/6(NAμBgS)
respect to intercalation. Upon intercalation the host lattice where NA is Avogadro’s number, µB is the Bohr magneton,
experiences both an increase in interlayer spacing and a sig- g = 2 is the electron spin g-factor and S = 5/2 for Mn2+. It is
nificant degree of vacancy concentration on the Mn2+ site noted that the data provided by Clément and Léaustic[20] shows
which varies depending on the species of intercalating com- a correlation between vacancy concentration and TC where TC
pound investigated. For example, intercalating with potassium decreases with increased vacancy concentration. In addition,
hydrates[173,174] yields a composition of Mn1.62P2S6K0.76(H2O)2 there is a significant degree of scatter in the magnetization
(19% vacancy concentration) while intercalation with octyl-ammo- data with respect to the type of intercalating compound chosen,
nium[20] yields a composition of Mn1.78P2S6(octyl NH3)0.44(H2O) as 10 K saturation magnetizations vary widely. This some-
(11% vacancy concentration). Both neutron and X-ray diffrac- what counter-intuitive observation was explained by the model
tion have been applied to intercalates and have shown that proposed by Evans et al.[175] which implies that the ferrimag-
the metal site vacancies are ordered within the individual netic ordering and saturation magnetization will be extremely
Mn2P2S6 lamellae. This ordering is important in view of the dependent on the deviation of the vacancy concentration from
magnetic structure, Figure 10. If the vacancy sites preferen- an ideal value of ≈1/6.
tially sit on either the “spin up” or “spin down” sites then the This vacancy ordering mechanism accounts very neatly for
AFM ordering would be broken and spontaneous ferrimagnetic the observed ferrimagnetic behavior in intercalated Mn2P2S6
ordering would appear. In other words, the imbalance of spins where each Mn2+ cation has only antiferromagnetic interac-
resulting from the vacancy ordering would result in a net mag- tions with its metal neighbors. However, the case for Fe2P2S6 is
netization and thus the intercalated Mn2P2S6 compound would geometrically more complicated as each metal cation interacts
become a ferrimagnet. This is indeed the model proposed by ferromagnetically with two of its three neighboring cations and
Figure 17. a) Schematic of model proposed by Evans et al.[175] of the ab plane in Mn2P2S6 showing ordered metal vacancy sublattice. b) An expanded
view of the model showing that the overall magnetization has a maximum magnetization equal to 1/6 of a fully aligned system of S = 5/2. Reproduced
with permission.[175] Copyright 2017, Wiley-VCH.
antiferromagnetically with the remaining one. This arrange- using a capacitance bridge in the wide 20 Hz–1 MHz fre-
ment leads to “stripes” of ferromagnetically interacting cations quency range.[180] Results for the DC conductivity as measured
that interact antiferromagnetically with each other and across between 150 and 400 K in CuInP2S6 followed an Arrhenius-
the van der Waals gap (Figure 10), though neutron diffraction type behavior σDC = (σ0/T)exp(−EA/kBT) where T, kB, and EA
shows that these latter interactions are weak as the magnetic have their usual meanings. The conductivity perpendicular to
unit cell is incommensurate.[157] Many studies have been per- the layers was found to correlate with the sublattice ordering
formed on Fe2P2S6 to investigate changes in magnetic behavior where much higher conductivities (by several orders of mag-
with intercalation (e.g., refs. [48,197,230,257,261–263]). One of nitude) were exhibited for the ordered ferrielectric phase than
the more interesting results was that of ferrimagnetic behavior the paraelectric phase (ferroelectric phase EA = 1.16 eV and
below temperatures as high as 90 K with pyridinium intercala- σ0 = 5.6 × 1012 S m−1; paraelectric phase EA = 0.92 eV and
tion.[176] However, no vacancy ordering was observed. Léaustic σ0 = 2.66 × 107 S m−1).[181]
et al.[169] synthesized a series of Fe2−xCdxP2S6 single crystals in In the selenide compound CuInP2Se6 measured under the
an attempt to find a mechanism that explains this spontaneous same conditions the activation energies were smaller than
magnetic ordering. the sulfide analog, EA = 0.8 eV for the paraelectric phase and
As mentioned above, intralayer ferromagnetic correlations EA = 0.59 eV for the ferrielectric phase;[181] this behavior is
within Fe clusters were suggested to explain magnetic sus- believed to be a consequence of the shallower potential for Cu1+
ceptibility data for the virgin samples. Intercalation of meth- cations in the selenide compound.[182] Conductivity measure-
ylviolegen had two main effects in the system: i) As revealed ments showed much lower values: σ0 = 1.21 S m−1 for para-
by 57Co(Cr) Mössbauer spectroscopy, intercalation resulted electric phase and σ0 = 2.35 S m−1 for ferroelectric phase. The
in a distortion of the coordination geometry surrounding higher conductivity in the case of CuInP2S6 compound is likely
the Fe cation and ii) intercalation also increased the separa- due to the dynamic hopping of the Cu1+ cations in the lattice
tion between layers. Léaustic et al.[196] proposed that the dis- down to low temperatures[27] while in CuInP2Se6 the Cu1+ cat-
tortions in Fe coordination caused by intercalation would ions are almost frozen on the off center positions in the ferri-
result in the favoring of ferromagnetic interactions. The electric state due to the double minimum potential present in
increased layer separation was proposed to further reinforce the selenide phase, as previously described.[30]
the ferromagnetic interactions as magnetic dipole interac- Although there is no direct conformation of the ionic nature
tions were predicted[177,178] to favor ferromagnetic coupling of the electrical conductivity in these materials, several indi-
between 2D slabs at distances similar to those observed in the rect characteristics indicate the presence of ionic conduction.
intercalates.[169] Firstly, the motion of the Cu1+ ions across the layers would
Fewer intercalations have proven successful with the host require more energy than motion inside the layers or inter-
compound Ni2P2S6. However, Manova et al.[24] managed to layer space. Supporting this argument is experimental evi-
intercalate the neutral cobaltocene into Ni2P2S6 by simply dence that found that the activation energy EA is almost two
reacting the host structure in a toluene/cobaltocene solution at times larger measured in the direction across the layers than
130 °C for two days.[179] Elemental analysis showed that no Ni parallel to them.[181]
left the host structure after intercalation and that the elemental The research on lithium ion conduction was motivated by a
composition was NiPS3(CoCp2)0.37.[24] Magnetization measure- possibility to replace TiS2 as a cathode material in Li-ion bat-
ments showed that the intercalated compound exhibited ferri- teries Ni2P2S6 exhibited the highest degree of Li intercalation[49]
magnetic behavior with a TC of 70 K. No definitive mechanism with six atoms of Li intercalated per formula unit Ni2P2S6, and
has yet been put forward to explain this spontaneous magneti- four being reversible.[49] Incorporation of Li occurs via a very
zation at low temperatures, though Clément and Léaustic[20] simple chemical intercalation procedure. One of the most
do postulate that the increased layer separation induced by the common variants is to immerse microcrystalline powders into
presence of cobaltocene can in fact, like the case of Fe2P2S6, a dilute solution of n-butyllithium in hexane over extended
lead to increased ferromagnetic interactions. periods of time, typically 1–2 weeks.[183] Careful investigations
using infrared transmission spectroscopy and Raman spectros-
copy have shown that Li sits in the van der Waals gap in octahe-
3.5. Ionic Conductivity dral coordination with six S atoms.[183] The presence of Li was
said to cause little to no structural distortion as no change in c
Much research has been performed with respect to the ionic lattice parameter was noted upon intercalation, thus providing
conductivity in MTP materials, mainly falling along two lines the potential for increased cycling life.[183] However, later work
of study: i) intrinsic conductivity due to the native species in the by Fragnaud et al.[184] showed that a fully reduced end com-
MTP compound (e.g., Cu in CuInP2S6) and ii) conductivity due pound Li4Ni2P2S6 is likely present which exhibits subtle differ-
to ionic transport of an intercalated species (e.g., Li in M2P2S6 ences in structure from the parent Ni2P2S6 compound. How-
where M = Ni, Fe, Mn). ever, the authors warn that these results must be taken carefully
Recent work has been attempted to correlate the Cu1+ ion as the proposed fully reduced phase is based on only a few low
ordering on the ionic conductivity of CuInP2(S6/Se6) mate- intensity diffraction peaks. In contrast to the majority of the
rials.[180–182] As previously mentioned, the Cu1+ cations have organic intercalation compounds, the presence of Li in Fe2P2S6
high mobility and can escape the octahedral cages and even or Ni2P2S6 does not necessitate the ejection of some of the tran-
reach van der Waals gap at higher temperatures.[42] Con- sition metal cation for the purposes of charge balance. Rather,
ductivity measurements in these materials were performed reports claim that some of the metal is reduced from an initial
oxidation state of +2 to zero, as shown through both 57Fe Möss- to pristine Ni2P2S6 for pyridine-intercalated Ni2P2S6 and the
bauer[171] and EXAFS[126] measurements. This unusual oxida- alloy Ni0.6Fe0.4P2S6.[186] Though the reason for the enhanced
tion state is possible because, at least in the case of the Ni2P2S6 behavior was not entirely clear, it was correlated to the lack
compound, the reduced Ni move from the distorted octahedral of any degradation product like PS43− found in these latter
positions to a tetrahedral coordination with S.[63] materials.
Open-circuit electrical-discharge curves for Li-intercalated
LixNi2P2S6 show much more promising behavior than the ini-
tial LixTiS2 material used for Li-ion batteries by Whittingham 3.7. Hydrogen Storage
and colleagues.[185] The cell voltage was maintained over a
wider range of Li (as the Ni2P2S6 structure can hold more Li) Physisorption of H2 into a solid state material is attractive
and the theoretical energy density was shown to be greater than as this technique allows for reversible storage of this energy-
1 kW h kg−1. Though initially a promising cathode material, the relevant diatomic compound. Ideally, one would want a
low ionic diffusion coefficient and low electronic conductivity material with high storage density, favorable sorption ther-
of Ni2P2S6 in its pure form made commercialization unfeasible modynamics and kinetics, and long-lasting cycling ability
for a long lifetime.[65] Recent work by Ismail and co-workers
has looked at several compounds of the MTP class of mate-
3.6. Catalysis rials in relation to H2 storage ability, including Fe2P2S6,[65]
Mn2P2S6,[66] and Ni2P2S6[67] In evaluating these compounds
Intercalation of MTP compounds like Ni2P2S6 have been shown for use as a sorbent material for H2, Ismail subjected the dif-
to have potential for environmental applications. Specifically, ferent materials to multiple cycling of pressure–composition
given that S2− is a pollutant commonly found in industrial isotherms.
waste and sewage water, the oxidation of this anionic species to In the case of Fe2P2S6 the 80 K H2 adsorption was found
elemental S which can be removed by simple biological treat- to be >2 wt% at 20 bar of pressure and ≈3.2 wt% at 30 bar.
ments or filtration[186] is of utmost importance to mitigating the Multiple cyclings of the pressure-composition experiment
human footprint on the environment. To this end, Ni2P2S6 has showed a ≈9% decrease in H2 storage ability when going to
been shown to be an effective catalyst in the oxidation of S2− in 20 bar, though this number was reduced when the pressure
compounds like Na2S to elemental S.[186–188] Under normal cir- was kept under 12 bar. At room temperature the H2 storage
cumstances, S2− is oxidized from air as represented by the fol- capacity was ≈0.2 wt%. Comparison of absorption/desorption
lowing reaction scheme: kinetics showed favorable behavior, with H2 saturation occur-
ring within 30 minutes and full desorption present within
1 only a slightly longer time period. Interestingly, Ismail et al.[65]
S2− + O2 + H2O → S + 2OH− (2)
2 noted that samples with better crystallinity (controlled by the
reaction heating rate) performed better than poorly crystal-
This process is catalyzed by the presence of Ni2P2S6, which line material in nearly every measurable test with respect to
acts as an oxidizing agent in a complex intercalation reaction. In H2 storage. This effect was ascribed to a surface area which
effect, the Ni2P2S6 host lattice captures the two electrons from was increased by a factor of two (60 m2 g−1 for the mate-
the S2− anion as it is oxidized to elemental sulfur. The reduced rial with better crystallinity vs 28 m2 g−1) and a micropore
host lattice is in turn stabilized by the presence of Na+ cations volume which was similarly increased (19 × 10−3 cm3 g−1 vs
and H2O, which serve to form an intercalate by migrating into 8 × 10−3 cm3 g−1). Though these numbers represent properties
the host van der Waals gap according to the reaction proposed that are as of yet currently inadequate for applications,[189] they
by Andreev:[187,188] do show that MTP materials present an interesting capability
for H2 storage. With only three compounds thus far evalu-
x 2− ated for H2 storage applications, the breadth of compositional
xNa + + S + yH2O + [Ni 2P2S6 ]
2 (3) phase-space in MTP compounds offers an exciting opportunity
x 0
→ (Na + )x ( H2O)y [Ni 2P2S6 ] + for energy storage related research.
x−
S
2
In turn, oxygen acts as an oxidizing agent to de-intercalate 3.8. Other Novel Functionalities and Approaches
the compound:
Kang et al.[190] have grown self-assembled Cd2P2Se6 nano-
lenses at the water–air interface while attempting to synthe-
x
(Na )
+
x
(H2O)y [Ni 2P2S6 ]x − + O2
2 (4)
size free-standing tri-n-octyl phosphine oxide (TOPO)-coated
CdSe nanocrystals. Rather than the desired product of TOPO-
→ Na + + ( y − x ) H2O + [Ni 2P2S6 ] + 2xOH− coated CdSe nanocrystals, Kang and co-workers discovered

that nano-plates of Cd2P2Se6 were formed, each with a dia
In the case of Ni2P2S6, infrared spectroscopy showed that meter of 20–400 nm and a radius of curvature ranging from
the intercalation resulted in the partial degradation of the host 1000–2000 nm (Figure 18). The lens shape of the Cd2P2Se6 was
lattice whereby the impurity PS43− anion was formed.[186] Later thought to be due to differential intercalation of an organic
investigations showed increased catalytic activity as compared species where the van der Waals gaps at the center of the lens
4. Recent Efforts on the 2D Limit of Metal

Thiophosphates
The studies of the metal thiophosphates in 2D form are still in
their early days. However, several successful attempts to isolate
quasi-2D flakes of the material have been shown. The physical
and functional properties, not unexpectedly, revealed significant
dependences on thickness. Notably, deviation from bulk behavior
in this case can manifest in the nanoscale regime, i.e., as few as
5–10 layers. This is not in small part due to correlation length-
scales associated with the order parameters of polarization and/
or magnetization in these materials, as well as depolarizing
effects. The lack of necessity for ultimate scaling may provide an
easier pathway to further fundamental studies and prospective
applications. Of course, as control dielectrics and intercalation
media metal thiophosphates are anticipated to play an important
role even as moderately thick films, as we have discussed above.
Mukherjee reported a rather strong enhancement of catalytic
activity for the few layer Fe2P2S6 compared to the bulk crystal
in a reaction involving electrochemical hydrogen evolution.[191]
This work was preceded by Liu et al.,[192] who computationally
explored the band structure of single sheets of various metal
Figure 18. Bright-field TEM image of Cd2P2Se6 Nanolenses as synthe- thiophosphates, also in the context of catalytic activity toward
sized by Kang et al.[190] Reproduced with permission.[190] Copyright 2017 the water splitting reaction, that requires a minimum energy
Springer Publications. of 1.24 eV (and therefore bandgaps in excess of that value for
the possibility of photo-induced water splitting). Both direct and
indirect bandgaps can be found in this family of materials, with
were filled with an intercalating compound otherwise absent or the indirect gap typically due to valence-band maximum located
diminished in quantity at the edge of the lens. at the K-point, while conduction band-minimum at the G-point
Another interesting phenomenon associated with MTP com- of the Brillouin zone. Tensile strain was found to decrease the
pounds is the presence of optical non-linearity. Lacroix et al.[125] bandgap, somewhat counter-intuitively, with approximately
intercalated the organic dye 4-[2-(4-dimethylamino-phenyl) 0.1 eV per % strain sensitivity. Overall the conclusion derived
ethenyl]-1-methylpyridinium (DAMS+) into both Mn2P2S6 was that these materials must be excellent in water splitting
and Cd2P2S6, yielding the compositions Mn1.72P2S6(DAMS)0.56 due to tunable bandgaps and the ideal combination of elec-
and Cd1.72P2S6(DAMS)0.56, respectively. The intercalated com- tron affinity and electronegativity that allows both the redox of
pounds were shown to exhibit spontaneous polarization H+/H2 and O2/H2O to be located below the conduction band min-
through analy ses of the second harmonic generation. For imum and valence band maximum, correspondingly. Recently,
the Mn-containing intercalate the efficiency was measured to Zhang et al.[193] have performed a series of first principle calcula-
be 300 times greater than urea; for the Cd containing inter- tions on MTP compounds in the monolayer form Figure 19) and
calate the efficiency was 700 times that of urea. In addition, have found that Mn2P2Se6, a direct-bandgap semiconductor, is
Mn1.72P2S6(DAMS)0.56 was shown to exhibit ferrimagnetic an especially promising photocatalyst for water splitting due to
behavior below 40 K. its strong absorption in the visible-light spectrum, the ability
Figure 19. The location of valence band maxima (VBM) and conduction band maxima (CBM) calculated for various MTP monolayers. The redox poten-
tials of water splitting at pH = 0 (orange dashed lines) and pH = 7 (cyan dashed lines) are shown for comparison Reproduced with permission.[193]
Copyright 2017 John Wiley and Sons.
to simultaneously photocatalytically split water into H2 and O2, with an emphasis on the potential of these materials for spin-
broad applicability in a wide pH spectrum (0–7), and high carrier tronics. The overall conclusion is that most single-layer mate-
mobility (electron mobility of 625.9 cm2 V−1 s−1, hole mobility of rials are antiferromagnetic semiconductors, while bandgaps
34.7 cm2 V−1 s−1). These results were shown by Zhang et al. to decrease with increasing atomic number of the chalcogen, as
favorably compare to many other 2D semiconductors, especially expected. Both strain and carrier doping, achievable efficiently
considering that in the case of Mn2P2Se6 has a large difference in the monolayer geometry, should cause the transition from
between electron and hole mobility whereby the probability of antiferromagnetic semiconductor to ferromagnetic half-metallic
electron and hole recombination is drastically reduced.[193] state – an exciting prospect for van der Waals heterostructures
Chittari et al.[194] carried out detailed computational study of (Figure 20). The AFM–FM transition is rather symmetric with
electronic structure and magnetic properties of various MTPs, respect to carrier type, with the exception of Cr and a few of
Figure 20. Influence of in-plane strain on the magnetic configurations of selected M2P2X6 (X = S, Se, Te) compounds. Magnetic phase transitions are
introduced by in-plane biaxial compressive and expansive strains for several magnetic M2P2X6 compounds at zero carrier density. Particularly sensitive
strain dependence is seen for Fe2P2S6, Fe2P2Se6, and Fe2P2Te6, where small strains of the order of 1% of the lattice constant can switch the magnetic
phases Reproduced with permission.[194] Copyright 2017, American Physical Society.
Mn compounds. Notably, Cr2P2S6, and particularly the Se and limit using Raman spectroscopy (Figure 22) and determined
Te derivatives were found to be ferromagnetic, whereas the crit- that this compound exhibits Ising-type antiferromagnetic
ical temperatures estimated from Monte–Carlo simulations far behavior down to the monolayer limit in good agreement with
exceed room temperature for V, Cr, Mn, Fe, and Ni derivatives. the Onsager solution for a two-dimensional order-disorder tran-
Using Raman spectroscopy Wang et al. reported noticeable, sition.[200] If further success is demonstrated, the properties of
but still comparatively weak size-dependence of the Néel tem- this system in finite fields or under strain gradients will pro-
perature of Fe2P2S6,[195] with magnetic transitions observable vide experimental test-beds for systems that are not exactly solv-
down to 1 unit cell (Figure 21). able.[201] Similar scenarios could be envisioned for the Heisen-
Li et al. predicted strong coupling of the valley degree of berg and 2D XY systems that are apparently manifested by the
freedom to the antiferromagnetic spin order on the monolayer transition metal dichalcogenides.[19,202]
of Mn2P2S/Se6,[196] leading to spin-valley dependent optical In a conceptually similar way, metal thiophosphates provide
selection rules and topological quantum transport. model systems to explore size-effects on ferroelectric order
Very recently, Sugita et al. have used ab initio calculations to parameters. This topic has captivated the interest of the ferro-
show that MTPs in monolayer form may exhibit Dirac cones electric community for the past 20 years (see topical reviews,
with tunable gaps. Moreover, the same study showed that that refs. [203–205]). Layered metal thiophosphates provide a nat-
MTP compounds are a candidate for investigating topological ural avenue to explore such phenomena because size-reduction
ferromagnetism.[197] does not necessitate creation of dangling bonds and chemical
Based in part on these findings, Park[198] suggested that these defects, both of which are inevitable in the case of thin films of
systems may be excellent models for magnetic behavior in the perovskite ferroelectrics.
ultrathin limit. For example, they could provide a model system Two separate works reported on ultrathin effects on fer-
for the fundamental Onsager solution of the Ising model in roelectric polarization in CuInP2S6 with the primary ques-
2D, that so far has only been demonstrated in quasi-2D mate- tion of whether a “ferroelectric graphene” is possible. The
rials.[199] Indeed, inspired by this supposition, Lee et al. have reports do, however, differ in their conclusion. Chyasnavichus
performed an exhaustive investigation of Fe2P2S6 in the 2D et al.[206] report strong suppression of ferroelectric polarization,
Figure 21. a) Plots of Raman peak intensity (at 88 cm−1) versus temperature of samples of different thicknesses; b) Plot of Néel temperature (TN)
measured via optical methods versus thickness of samples compared to the results from a bulk sample measured via vibrating sample magnetometry
on a Quantum Design Physical Property Measurement System; c) Plots of FWHM of the Raman peak at 88cm−1 versus temperature of trilayer and
bulk samples Reproduced with permission.[195] Copyright 2017, IOP Publishing.
Figure 22. a,b) Optical contrast (a) and atomic force microscopy (b) images of 1L Fe2P2S6 on SiO2/Si substrate. c) Temperature dependence of Raman
spectrum of 1L Fe2P2S6 with polarization direction of α = β = 45°. *indicates a signal from the Si substrate. d) Thickness dependence of P3 and P4 with
polarization direction of α = 45° (red curves) and α = 90° (blue curves) at 300 K. e) Temperature dependence of P1a peak height for different thick-
nesses Reproduced with permission.[200] Copyright 2017, American Chemical Society.
with Curie temperature dropping below room temperature at is produced by CuInP2S6 sandwiched between two metal
≈10 nm (Figure 23). In contrast, Liu et al.[207] reported switch- electrodes. We should note that with respect to the ultimate
able polarization down to ≈5 layers. Liu et al. also demonstrate size-effect on ferroelectricity, polarization screening and more
a diode-type device wherein current rectification and hysteresis generally interfacial chemistry are key questions. For example,
Figure 23. a–i) Amplitude (a,b,c) and phase (d,e,f) of local piezoresponse and topography profiles (g,h,i) for a series of CuInP2S6 flakes at room tem-
perature. Ferroelectric domains are not observed for ≈10 nm thick flake. j) 2D histogram plot of the PFM amplitude on the flakes of different height.
k) Calculated thickness dependence of up- and down-directed polarizations.[206] Reproduced with permission.[206] Copyright 2017, AIP Publishing.
the well-known paper by Junquera and Ghosez who compu- way that enables functionalization of 2D electronic materials
tationally demonstrated hardening of the BaTiO3 soft-mode for the next generation of encapsulated electronic devices. To
below ≈6 unit-cell thickness even in the idealized short-circuit this end, the following section will briefly summarize some
conditions due to small residual depolarizing field.[208] Several specific properties of MTP materials and how they can relate to
years later, Stengel et al. have showed that electrostatic depolar- current and future research needs.
izing effects can be efficiently compensated by the chemistry of
the metal-ferroelectric interfaces, which may lead to vanishing
size-effects and stable switchable polarization, even in 1 u.c. of 5.1. Brief Overview of Integration of 2D and
PbTiO3.[209] Ferroelectric Materials
So far, the size-effect in CuInP2S6 has been quantified only
within the continuum limit provided by the Landau–Ginzburg– Integrating graphene with ferroelectric materials was pursued
Devonshire model[206] (Figure 23k). Curiously, even stability at very soon after the early graphene devices were made, with
10 nm requires sufficiently strong screening of the open sur- the first successful demonstration in 2009.[211] We would like
faces (that are studied experimentally). The authors have pro- to refer the interested reader to recent dedicated reviews on
posed the existence of an intrinsic, heavily doped and possibly the topic, by Hong et al.[212] and by Jie and Hao.[213] Generally,
conducting layer on the surface of CuInP2S6[206] – an intriguing [ ferroelectric]/[graphene] or a similar structure couples ferroe-
perspective that echoes early proposals for a conducting sur- lectric, piezoelectric, high-k dielectric, and/or pyroelectric func-
face in BaTiO3. However, an understanding of the stability of tions as well as the non-linear optical response of ferroelectrics
polarization will have to consider the detailed chemical inter- with the electronic conductivity of graphene. Graphene devices
actions of Cu atoms at the open surface or the van der Waals therefore gain memory and significant electronic response
interface. Given the large offset of the Cu+ ions within the layer to mechanical deformation or thermal history. As a result,
of CuInP2S6, we cannot rule out direct chemical interactions numerous applications, such electronic switches, transistors,
that may stabilize ferroelectricity down to 1 unit-cell. These infrared sensors, photodetectors and thermal switches have
interactions may also potentially modulate the proximate 2D been envisioned.
electronic materials through stronger, but controllable, direct A fundamental interesting aspect of these involves the
chemical interaction. regime of comparatively high carrier density that can be sus-
A very recent investigation by Wang et al.[210] has analyzed tained in device geometry, and does not require the use of ionic
AgInP2S6 in the 2D limit in terms of optical second harmonic liquids. These phenomena generally require carrier densities
generation (SHG). This effect was noted to occur only in odd- in excess of 1013 cm−2, that are readily achievable with good
layer (1 and 3) samples of AgInP2S6. This observation was ferroelectrics. In addition to band-crossings that were already
mined to probe the crystal symmetry where even numbered reported in few-layer graphene devices,[214] increasing carrier
layers were shown to have inversion symmetry while this was doping beyond linear dispersion could be fundamentally very
broken for the odd layered samples. It was pointed out by the interesting.[215–217]
authors of this study that these properties, similar to TMDs Arguably the most interesting properties of ferroelectric
with respect to lattice symmetry, has exciting implications for graphene devices are associated with spatial modulation of the
AgInP2S6 (and perhaps other MTP compounds), for example carrier density. The p–n junctions in graphene were demon
valleytronic properties in the monolayer. strated by Williams et al. using a gated geometry.[218] Theore
Altogether, even early evidence points to substantial scaling tical proposals for these junctions include Klein tunneling[219]
of catalytic activity, electronic properties, magnetic proper- and Veselago lensing.[220]
ties and ferroelectric properties. These studies are still in the Oppositely oriented polarization domains in the ferroelectric
infancy and necessitate further investigations. It is fair to say should fulfill the role of a spatially modulated gate without the
that most of these compounds have yet to experience their need of external gating or patterning. The induced p–n junction
“graphene” moment – i.e., occurrence of an outstanding prop- would coincide with the ferroelectric domain wall in that case.
erty specific to few-layer thickness. Given the diversity of antici- Crucially, the intrinsic width of domain walls in ferroelectric
pated phenomena, such events will very likely occur in the near can be as small as a few nm, as recently analyzed by Morozo-
future. vska et al.[221] Such a sharp transition is likely not achievable
by lithographic methods. It is in this case that the long-sought
Veselago lensing effect can become substantial.[222]
5. Prospects for the MTP family Spatial modulation can also lead to very attractive opto-
electronic effects. Jin et al.[223] predicted that a ferroelectrically
The structures of the various MTP compounds are remark- modulated graphene sheet can act as a plasmon waveguide,
ably similar with all materials sharing an essentially identical wherein plasmon modes in graphene couple to phonon–polar-
[P2S(Se)6]4− framework. It is truly astonishing that such a large iton modes in the ferroelectric. Notably, this effect does not
variety of functionality can be exhibited by simply changing the require a very large magnitude of spontaneous polarization,
metal cation species located within the two distorted octahedral and is already manifested with a polarization of ≈5 µC cm−2.[223]
cages within this essentially unchanging backbone. The next Goldflam et al. have recently made a spectacular demonstration
obvious step in researching this materials class is to engineer of switchable graphene plasmons using polycrystalline lead
properties such as bandgap energy, ferrielectric transition tem- zirconate titanate (PZT) as a ferroelectric support,[224] Intense
perature, ferrimagnetic ordering temperature etc. in a rational plasmon scattering was observed from the grain-boundaries
of the PZT, while the plasmon wavelength was efficiently tun- with graphene without the necessity to exfoliate the material or
able by applied electric field due to the combination of dielec- grow thin films.
tric tunability of PZT and the modulation of carrier density in
graphene.
More recently, ferroelectrics have been invoked as tunable 5.2. Cleavability
materials for 2D semiconductors. Ferroelectric carrier con-
trol in MoS2 was demonstrated by Wang et al.,[225] Nguyen The cleavability of a 2D material is an essential material prop-
et al.,[226,227] and in black phosphorus.[228] erty that needs to be considering it for potential applications.
Though theoretically promising, the integration of ferroelec- We have observed the MTP materials we have synthesized to
trics and 2D materials has thus far not been straightforward.[212] be easily cleavable, whether by the “Scotch Tape” method[230]
The choice of ferroelectric largely bifurcates between perovskite or through insertion of a wedge between layers. Recently, Du
oxides (such as BaTiO3 and PbZrxTiyO3) or the ferroelectric et al.[68] have calculated the theoretical cleavage energies of
polymer PVDF. In either case, the stability of the ferroelec- some MTP compounds by analyzing the layer separation when
tric surface (and therefore its interface) is not warranted, and the material is fractured compared to the layer separation of the
numerous extrinsic or intrinsic compensating mechanisms in “virgin” unit cell using density functional theory. Calculations
the form of electrochemical reactions, surface reconstructions were performed using a scheme where three layers of the MTP
or vacancy centers occur to screen spontaneous polarization compound were separated from each other by an equilibrium
[See Ref. [212] and the references therein]. In this regard, one distance d0; a variable distance d separated successive three-
of the interesting explanations for the so-called antihysteresis layer blocks. In-plane structures were fully relaxed until the
effect in the ferroelectrically modulated conductance of the cou- forces were less than 0.01 eV per Å. The cleavage energies were
pled graphene sheet lies in the partial formation of graphene calculated by determining the differences in planar energy den-
oxide by the electrochemical reaction at the interface.[229] PVDF sity between the “fractured” model and the virgin structure as a
is an oxygen-free ferroelectric and is comparatively easy to inte- function of d. We reproduce these data below (Figure 24). The
grate with almost any matching material. In fact, most of the theoretical cleavage energy plateaus at ≈0.15–0.4 J m−2 for the
successful demonstrations of devices up to present involve the various compounds that were investigated. Nearly every com-
use of PVDF. However, as with all polymer films, the questions pound has cleavage energy lower than that of graphite (≈0.36[68]
of uniformity, interface smoothness, and related issues are not to 0.43[134] J m−2), thus indicating the suitability of MTP mate-
trivial to resolve. rials for exfoliation and assembly into device architectures.
We believe that metal thiophosphates will play a unique role Mukherjee et al. prepared few layer flakes of Fe2P2S6 by exfo-
in this merger. They are oxygen-free ferroelectrics and multi- liation of bulk crystals. The crystals were dispersed in 10 mL
ferroics. Unlike perovskite oxides, surface formation does not of distilled acetone and sonicated for 4 h. Following centrifu-
create dangling bonds, thus producing stable and relatively gation, stable, clear supernatant containing large quantities of
inert surfaces. Though the defect structure of these materials is Fe2P2S6 flakes were obtained.[191]
still not well understood, it is easy to anticipate a large energy Successful mechanical exfoliation of Ni2P2S6 using the
of the anion P2S64− vacancy in contrast to the oxygen vacancy Scotch-Tape method was reported by Kuo et al.[231] Raman spec-
in the perovskite lattice. Yet, these are still solid-state mate- troscopy detected deviations of the single-flake structure from
rials with well-defined long-range order that can be difficult to the bulk, as judged by the red-shift of the A1g(1) vibrational
achieve with polymers. Therefore, metal thiophosphates are mode, corresponding to “compressive” motion of the sulfur
anticipated to provide clean, controllable, native van der Waals atoms within the layer. Other sulfur modes likewise undergo
interfaces for 2D materials. Obviously, interesting effects may subtle changes. Mechanical exfoliation was also used to prepare
occur even at the boundary of bulk crystals of layered ferroics thin flakes of CuInP2S6[206,207] (Figure 20a–c) and Fe2P2S6.[222]
Figure 24. a) Cleavage energy (Ecl) vs separation (i.e., interlayer distance). b) Comparison of the saturated cleavage energy of various MTP compounds
and graphite Reproduced with permission.[68] Copyright 2017, American Chemical Society.
5.3. Van der Waals Heterostructures 5.4. Optoelectronic Functions
The intermediate bandgaps of MTP compounds taken together Recently, Wu et al.[233] have realized nanocavity lasers with
with their 2D nature and low cleavage energies offers an expan- optical pumping thresholds (27 nW at 130 K) using the tran-
sion of possibilities for both electronics and optoelectronic sition metal disulfide as a gain medium at the surface of a
applications such as transistors and solid state lasers. It is nec- photonic crystal cavity (PCC). The gain medium confines the
essary to integrate layers of MTP compounds with either each electrons to the PCC surface, a geometry that allows for the
other or other 2D materials in the form of heterostructures in tailoring of the gain properties via gating and current injec-
order to realize these device architectures. One way of doing tion.[233] Devices such as these have multiple requirements,
this is through manual stacking of exfoliated nanosheets, including bandgaps in the appropriate frequency range and a
though this transfer method potentially allows for the introduc- desirably high photoluminescence quantum yield.
tion of contaminants at the interface, as is often seen in TMD The MTP family offers an intriguing possibility for devices
compounds.[170] Another technique employed for the creation with the same requirements. As previously mentioned, the
of heterostructures in 2D materials such as WSe2/MoSe2 is in bandgaps of MTP compounds that have been reported in the
situ growth, which limits interfacial contamination and also literature range from 1.2–3.5 eV, extending the range of band-
allows for more precise control of stacking orientation.[170,232] gaps for layered van der Waals compounds (with TMDs having
Similar heterostructures have been produced at ORNL a low bandgap of <2 eV). This increased energy range opens
on MTP compounds using a single-step growth procedure up the possibilities of new optoelectronic functions at shorter
(Figure 25). Given the amenability to vapor transport syntheses wavelengths.
of both TMD and MTP compounds, it is likely that either Interestingly, Gáldamez et al.[234] reported the generation of
single- or two-step growth procedures can be readily used to photoexcited carriers in the selenide compounds CuBiP2Se6,
synthesize MTP compounds on a variety of substrates. The suggesting that the MTP class of materials could be attractive
advantage of the single-step process is of course the ease of for possible solar energy applications
growth. The two-step process allows for the spatial control of In addition, photoluminescence (PL) has been observed in
the heterostructures, a key criterion for device fabrication. many MTP compounds (e.g., refs. [235,236]) where it is seen
Recently we have shown that in-plane heterostructures in that not only do MTP compounds have a large PL peak, but
the MTP ferrielectric CuInP2S6 can be engineered using phase that the intensity of the peak can be increased by an order of
separation which allows tuning of the Tc through interfacial magnitude by the presence of intercalating compounds.[235]
strain effects (cf. Figure 13).[36] Here the interfaces are formed MTP compounds present an interesting opportunity for quanti-
within each lamella rather than across the heterointerfaces. In- fying PL intensity in terms of MTP composition or in terms of
plane heterostructures impose strain on both members of the investigating bandgaps and PL intensity as the monolayer limit
heterostructure and are an approach complementary to (and is approached as very little work in either of these areas has
arguably more scalable than) out-of-plane heterostructures. We been reported to date. However, recent theoretical work by Li
showed that we could control the size of chemical and, there- et al.[196] predicts that in Mn2P2S6 and Mn2P2Se6 the domain
fore, ferroelectric domains by simply altering the cooling rate walls of the antiferromagnetic honeycomb enables valley-pro-
from above the high-temperature phase-transition temperature. tected edge states which in turn support spin-dependent trans-
Extending this logic to new material combinations presents port. In addition, Berry curvature-induced topological quantum
new opportunities for material engineering, including spatially transport and valley-dependent optical selection rules are pre-
modulated bandgaps, non-linear optics, and non-linear dielec- dicted in these two MTP compounds through coupling of the
tric responses. valley degree of freedom to the antiferromagnetic order which
Figure 25. SEM back-scattered image (left) of in situ grown heterostructures of (Mg2−xSnx/2)P2S6 crystals synthesized at ORNL using a single-step
process. The right-hand image shows an EDS map of the same region.
in turn produces an emergent electronic degree of freedom compositions, stability of respective compounds, their elec-
(resulting from spin and valley indices).[196] The most impor- tronic bandgaps, propensity toward structural instabilities,
tant conclusion of this theoretical prediction is that the optical and even magnetic ordering seems to be well within reach of
and magnetic properties of Mn2P2S6 and Mn2P2Se6 allow for modern predictive materials techniques.
optical polarization in spin-valley space. Electrical detection and The closely related Te-containing structural analogues of the
manipulation will thus be enabled through induced fluxes in MTP family of materials have been partially explored via theory.
spin, valley, and charge.[196] As one can readily imagine, this These materials contain the same van der Waals stacking as the
opens up new and exciting possibilities for the next generation MTP compounds; however, in this case the [P2S(Se)6]4− groups
of electronic devices. As the theoretical candidates for study are are replaced by [Si2Te6]4−. For example, we have theoretically
proposed to have antiferromagnetism in a honeycomb lattice, predicted bandgaps and magnetic ground-states of single layer
be a direct bandgap semiconductor, and have interband transi- hexagonal MTP materials belonging to the CrSiTe3 prototype;[70]
tions in near valleys that support circular dichroism, there are in addition, we have also predicted newer potential members
many possibilities in the MTP family that will be the subject of in this family of materials that can potentially be thermody-
much future investigation. namically stable as single layers.[239] While single layers of
these materials are easier to deal with from the point of view
of materials modeling, advances in accurate description of van
5.5. Predictive Framework der Waals density functional theory for magnetic systems are
necessary to properly capture the magnetic ground state and
Graphene, a structurally simple material with no phase tran- excitations in the bulk. This is because the magnetic coupling
sitions, has been in the center of experimental and theo- between layers, though weak, is important, and is very sensi-
retical investigations for the past decade, resulting in tens of tive to the layer spacing. Very recent advances[240,241] along this
thousands of publications. More recently, other 2D materials direction are promising, and need to be applied more regularly
systems have been systematically researched, including BN, to these materials. The few computational papers that deal with
black phosphorus, and transition metal dichalcogenides (MX2 these systems essentially use density functional theory with
where M is a transition metal and X = S, Se, or Te). This latter local or semilocal functionals.[242,243] Since the band edges are
family, generally referred to as TMDs, is noted for containing predominantly derived from the d-orbitals of the transition
a variety of direct-gap semiconductors whose carrier type metal atoms where effects of electron correlation arising from
(p or n) and bandgap energies can vary with composition.[8] The the localization of the orbitals become important, predictions
greater TMD family also contains materials that exhibit other of bandgaps using these functionals fail. Improvements using
interesting correlated properties such as insulating behavior DFT+U or hybrid-DFT methods can be achieved,[36,238,244–246]
(e.g., HfS2), low-temperature superconductivity (e.g., NbS2, but have not been regularly applied to study the electronic prop-
NbSe2, and TaS2), and charge density waves (NbSe2). In the erties of these materials. Because of the large combinatorics
form of single or few-layered specimens these properties are, involved in the choice of the metal cation atoms for a given thi-
for the most part, stable.[8] However, confinement effects may ophosphate host system, with the main change in the ground
reveal additional behaviors as well (e.g., ref. [237]). This array state being off-lattice distortions or chemical phase separation,
of materials properties has enabled the development of new MTP is a fascinating ground for performing high-throughput
devices ranging from energy storage to optoelectronics such as computations to screen potential candidate for photovoltaic
lasers[233] and LEDs.[238] applications, i.e., a small direct bandgap of ≈1.2 eV and high
Compared with the wide variety of compounds and mate- electron-hole mobility.
rials properties exhibited for the TMD family with just 40 com- Furthermore, while ionic conductivity is thought to be impor-
pounds,[8] the greater metal thiophosphate (MTP) family is, in tant in this family of materials, very little theoretical study has
comparison, relatively untapped with over 200 known com- been performed to benchmark the possible ionic conducting
pounds reported which include most 3d and many 4d and 5d pathways of intrinsic or extrinsically doped ions in this mate-
transition metals. As detailed in this review, materials within rial. A family of layered materials, the MXene phases[247,248]
the MTP family are insulators with bandgaps ranging from have been recently shown to be very good ionic conductors, and
1.3–3.5 eV that also exhibit Mott behavior, antiferromagnetism, suitable for pseudocapacitive applications. At the same time,
and ferrielectricity. In addition, up to the time of writing, the some of the faster so called “superionic” conductors belong to
optoelectronic functions in this materials class are relatively the thiophosphate family of materials,[51,249] but they are three
unexplored. This makes the MTP family a fertile research area. dimensional, with Li/Na acting as interstitials, which can be
However, given the flexibility toward ionic substitution intercalated. Given the robustness of the MTP layers, and the
within the MTP family the total number of possible materials ease of achieving ion intercalation, it is a fruitful opportunity
can be much larger than the several scores of known pure- to compute ionic conduction barriers and estimate ionic con-
phase compounds, possibly numbering in the thousands or ductivity in these systems to predict possibly new superionic
even more. Clearly, an experimental effort to synthesize all systems.
these compounds and investigate their properties is vast and Ferroelectricity has long been discussed in this family
unlikely to be achieved, even in a community-wide effort. This of materials. We have recently explored ferroelectricity in
diversity of structure, composition, and application present in CuInP2S6, and have found that the Cu off centering couples to
MTP compounds makes it very easy to advocate the need for a P2S6 distortion to give rise to a ferroelectric distortion, with a
material genomics. Screening for the relevant criteria of ionic well depth of ≈45 meV.[36] This is significantly larger than that
of BaTiO3 (≈30 meV), a quintessential ferroelectric solid. With such as dichalcogenides and graphite. This is especially evident
the ability to have a magnetic ion such as Ni substituted for in almost complete lack of papers on thin films and quasi-
the Cu offers an excellent opportunity to couple magnetism 2D layers of these compounds but is true also of properties
with ferroelectric distortion. In addition, to the theoretical treat- more related to the bulk, such as electronic and optoelectronic
ment of electron correlations and non-bonded interactions, the properties.
accurate modeling of these systems to predict phase transi- We envision that MTP will play a unique role in 2D and
tions is hampered by the inherent configurational disorder in quasi-2D materials once research activities expand. In fact, we
the cation lattice. Improved methods, going beyond the virtual argue that MTP can be thought of as layered analog to com-
crystal approximation or the coherent potential approxima- plex metal oxides, and therefore all the rich functionalities of
tions are needed, since the cations off-center, with the degree the latter materials class can be brought into the domain of
of off centering dependent on the type of cation atom and the 2D materials via native van der Waals interfaces. The unique
coupling to the local mode (i.e., dependent on the local sur- distinctions of MTP compounds are correlated ferroic proper-
rounding). A more efficient scheme is necessary to take into ties, such as ferroelectricity and magnetism, which stem in
account the effects of the disorder on the local off centering of large part from ionic bonding in MTPs. Ionic bonding is also
the ions, and the resulting effect on the electronic structure. responsible for the comparatively large bandgaps of these mate-
A supercell approach along the lines of constructing a special rials which fall within a range 1.3–3.5 eV, largely unavailable
quasi-random structure (SQS)[250] is very attractive, but has not to present 2D materials and yet enticing for optoelectronic
been applied until now. Efficient construction of SQS for the applications. At the same time, MTPs may be a rich source of
MTP family of materials can lead to construction of improved insulators for encapsulation or gate-media for 2D electronic
structural models for property prediction. materials, adding memory and control functionalities to other
The materials phase space can become exponentially larger wise uniform conducting or semiconducting sheets without
if we start including modifications to the anion sublattice, doping or broken lattice symmetry.[252–256]
such as mixed (S,Se) lattices. In these cases, efficient property We also emphasize that ferroelectric ordering and incipient
predictions of mixed anionic lattices will be required starting ionic conductivity themselves make MTP a new model system
with computed properties of the end members based on to answer long-standing problems such as size-effects, superi-
machine learning (ML) techniques. These methods are quite onic conductivity, and polar glassiness. MTPs bring the relative
nascent at this stage, and require a rather large training set ease of synthesis, clean surface and nanocrystal preparation
(hundreds to thousands) to improve the confidence to even that have been historically complicated in complex oxides, but
≈100 meV atom−1 in the formation energy. Recent success are inherent properties of van der Waals crystals. At the same
in elpasolite family of materials[251] is very promising in this time, the electronic and magnetic states of the bulk crystals
regard, where DFT formation energies were trained to a ML with d-metal ions (Fe, Ni, Mn, V, etc.) deserve further attention,
algorithm, with very good success in predicting the properties as they may exhibit sufficiently strong electron correlations,
of the millions of combinations. An accuracy of 0.1 eV atom−1 crossover of magnetic orders and coupling of ferroic degrees of
was reached after training with nearly 10 000 DFT-data. But freedom in the general context of multiferroic behaviors.
given the robust backbone of the MTP family of materials, the Finally, MTPs do not have industrial applications at the
chances of finding structure-property correlations and extrapo- moment, although catalytic, ionic and intercalation-related bulk
lating them across the elemental phase space promises to be properties have been reported. We anticipate that a more expan-
very successful. sive investigation of the synthesis, scalability and stability of
MTPs will eventually produce practical materials. Most notably,
further development of MTPs may accelerate technological
6. Conclusions adoption of complex material properties, such as ferroic and
correlated electron properties, and instabilities proximate to
Layered metal thio(seleno)phosphate (MTP) compounds are phase transitions that have long been pursued in the realm of
a large materials family of structurally similar van der Waals complex oxides.
gapped materials. The structural backbone of this family con-
sists of an hexagonal array of [P2S(Se)6]4− complexes. The
metal cations stabilizing this structure can be readily varied, Acknowledgements
giving rise to correlated behaviors such as magnetism and fer-
roelectricity. These materials feature comparably strong ionic Research was sponsored by the Laboratory Directed Research and
Development Program of Oak Ridge National Laboratory, managed by
bonding, which is the root of their rich functionalities as well UT-Battelle, LLC, for the U.S. Department of Energy (P.M., P.G., M.C.,
as the key distinction to transition metal dichalcogenides and M.A.S. and M.A.M.). Experiments were partially conducted (AFM) at
single-element layered materials with predominantly covalent the Center for Nanophase Materials Sciences, which is sponsored at
bonding. Oak Ridge National Laboratory by the Scientific User Facilities Division,
Here, we have summarized the progress in the growth, Office of Basic Energy Sciences, US Department of Energy. Manuscript
characterization and understanding of the material proper- preparation was funded by the Air Force Research Laboratory under an
Air Force Office of Scientific Research grant (LRIR No. 14RQ08COR) and
ties of these compounds over the past two decades. Despite a grant from the National Research Council. Special thanks are also in
a number of papers on the subject, it is fair to say that the order to Brian C. Sales and Jianqing Yan for their assistance with respect
potential of MTP as a material class has yet to be thoroughly to synthesis conditions, their helpful discussions and, most importantly,
explored, particularly in comparison to other layered materials their guidance and enthusiasm.
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Advanced Materials - 2017 - Susner - Metal Thio and Selenophosphates As Multifunctional Van Der Waals Layered Materials

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15214095, 2017, 38, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.201602852 by Peking University, Wiley Online Library on [15/11/2022].

Metal Thio- and Selenophosphates as Multifunctional van

stacked heterostructures, and thin films

together through van der Waals interactions. The abbreviation

Table 1. Structural information for layered 2D metal thiophosphates.

CuCrP2S6(ht)[21] C2/c 5.916 10.246 13.415 107.09 777.3 ABAB (c)

Table 2. Structural information for layered 2D metal selenophosphates.

Cr2P2Se6[86] C2/m 6.13 10.66 6.86 107.1 428.4 AAA (c)

Ni2P2Se6[86] C2/m 6.15 10.66 6.86 107.1 426.8 AAA (c)

AgInP2Se6[89] P 31c 6.483 6.483 13.330 – 485.2 ABAB (c)

CuBiP2Se6(lt2)[111] R 3h 6.553 6.553 39.762 – 1487.9 ABCDEF (c)

CuBiP2Se6 (lt1)[111] R 3h 6.559 6.559 79.385 – 2957.7 ABCDEFGHIJKL

AgScP2Se6[112] P 31c 6.463 6.463 13.349 – 482.9 ABAB (c)

AgTmP2Se6[112] P 31c 6.567 6.567 13.422 – 501.3 ABAB (c)

AgVP2Se6[265] C2 6.340 11.020 6.982 106.82 466.9 AAA (c)

various structural properties with changing

the same technique, Zn, Cd, and Ni thi-

Table 6. MTP alloys organized by type of substitution.

Figure 12. Phase diagram of the mixed CuInP2(SxSe1−x)6 crystals

intercalating MTP compounds in general. Potential applica-

Mn 2P2S6 + 4 xKCl ( aq ) → 2Mn 2+ + [P2S6 ] + 4 xKCl ( aq )

4. Recent Efforts on the 2D Limit of Metal

5.3. Van der Waals Heterostructures 5.4. Optoelectronic Functions

Conflict of Interest [26] A. R. Wildes, V. Simonet, E. Ressouche, G. J. McIntyre, M. Avdeev,

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