Advanced Materials - 2019 - Harada - Heteroanionic Materials by Design Progress Toward Targeted Properties

PROGRESS REPORT
Materials Design www.advmat.de
Heteroanionic Materials by Design: Progress Toward

Targeted Properties
Jaye K. Harada, Nenian Charles, Kenneth R. Poeppelmeier, and James M. Rondinelli*
oxides hosts rich dopant-dependent phase
The burgeoning field of anion engineering in oxide-based compounds aims to diagrams that include half-metallicity,
tune physical properties by incorporating additional anions of different size, colossal magnetoresistance, charge den-
electronegativity, and charge. For example, oxychalcogenides, oxynitrides, sity waves, metal–insulator transitions
oxypnictides, and oxyhalides may display new or enhanced responses not (MITs), and superconductivity.[8–11] Like-
wise, advances in thin-film deposition
readily predicted from or even absent in the simpler homoanionic (oxide)
techniques have enabled researchers to
compounds because of their proximity to the ionocovalent-bonding boundary harness strain engineering to unlock prop-
provided by contrasting polarizabilities of the anions. In addition, multiple erties hidden in bulk materials[12] and
anions allow heteroanionic materials to span a more complex atomic isolate novel metastable phases.[13–15] In
structure design palette and interaction space than the homoanionic oxide- addition, ultrashort period oxide super-
lattices that combine two materials can
only analogs. Here, established atomic and electronic principles for the
stabilize unanticipated phenomena, e.g.,
rational design of properties in heteroanionic materials are contextualized. metallic 2D electron gases[16] and novel
Also described are synergistic quantum mechanical methods and laboratory forms of ferroelectricity.[17]
experiments guided by these principles to achieve superior properties. Lastly, Anion-based materials design is less
open challenges in both the synthesis and the understanding and prediction widespread among materials researchers
of the electronic, optical, and magnetic properties afforded by anion- compared to cation substitution and het-
erostructuring, particularly within a class
engineering principles in heteroanionic materials are reviewed.
of TMCs that we refer to as heteroanionic
materials (HAMs)—compounds where the
anion sublattice involves two or more ani-
1. Introduction onic species. HAMs are distinct from polyanionic compounds
with oxyanions (CO32− or BO33−) as they often contain metals
Complex transition metal compounds (TMCs) are utilized in a bonded to more than one elemental anion with the metal–anion
variety of technologies owing to their properties ranging from fragments acting as the basic-building unit of the structure.
ferroelectricity to high-temperature superconductivity supported Nearly all HAMs are constructed from metal–anion polyhedral
by the polarizable oxide anion interacting with transition metal d units, which form when the multiple anions involved are com-
orbitals.[1] The design, discovery, and control of new TMCs with patible with the cation size and the shape of the coordination
novel properties and superior performance are crucial to the polyhedron. Organometallic chemists will differentiate how
continued development of present and future technologies. The many different ligands bond to a metal in molecular units of this
main approaches rely on tuning the chemistry or atomic struc- kind, and here we apply a similar syntax to classify heteroanionic
ture of a known ternary oxide in bulk or thin-film form through materials (solid-state inorganic compounds) into two distinct
a combination of chemical substitution, geometric modifica- categories. First, a HAM may be composed of homoleptic poly-
tions (epitaxial strain and heterostructuring),[2,3] or external hedra such that the cations are coordinated by a single elemental
stimuli such as, temperature, pressure,[4,5] and external fields.[6,7] anion (Figure 1a). This definition of a heteroanionic materials
For example, cation-substituted transition-metal oxides like allows different cations to be coordinated by different anions,
La1-xSrxMnO3 (x is the doping level) and copper-based multinary but each individual cation is coordinated by identical anions,
as in the thermoelectric BiCuSeO with alternating [Bi2O2] and
[Cu2Se2] layers,[18] owing to anion size differences (Figure 1h).
J. K. Harada, Dr. N. Charles, Prof. J. M. Rondinelli Alternatively, a heteroanionic material may consist of het-
Department of Materials Science and Engineering
Northwestern University
eroleptic polyhedral units (Figure 1b), where a cation bonds to
Evanston, IL 60208, USA more than one anion. Examples of such heteroleptic polyhedra
E-mail: jrondinelli@northwestern.edu include the [TaO2N3] trigonal bipyramidal unit in TaON, the
Prof. K. R. Poeppelmeier [MoO3F3] and [NaO3F3] octahedral units in Na3MoO3F3, and the
Department of Chemistry [GeO2S2] tetrahedral unit in LaGeOS2 (Figure 1e–g). Whether a
Northwestern University heteroanionic material is constructed from homoleptic or heter-
Evanston, IL 60208, USA
oleptic polyhedra will profoundly affect the electronic properties
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.201805295.
and the relevant design strategies to pursue.
Heteroanionic materials are frequently referred to as oxyni-
DOI: 10.1002/adma.201805295 trides, oxyfluorides, and oxysulfides, which are obtained by
Adv. Mater. 2019, 31, 1805295 1805295 (1 of 26) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
15214095, 2019, 19, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.201805295 by Institute Of Physics Chinese Academy Of Sciences, Wiley Online Library on [25/07/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.advmat.de
adding the oxy-prefix followed by the additional anion. HAMs

are not limited to oxide-based TMCs, but oxides benefit from Kenneth R. Poeppelmeier
their stability, abundance, and facile synthesis, making them is the Charles E. & Emma
the understandable starting point for anion-focused design. H. Morrison Professor in the
The renaissance in the substitution of anions with sizes, elec- Department of Chemistry at
tronegativities, and charges different from the oxide O2− anion Northwestern University. He
relies on rational control of material structure and properties. received his Ph.D. from Iowa
It has already proved fruitful in understanding electronic phase State University (1978). His
transitions[19] and carrier transport[20] and improving the per- research covers several sub-
formance of materials for acentric functionalities, solid-state jects in the field of inorganic
lighting, and energy storage materials. Nonetheless, challenges solid-state chemistry, growth
remain. Herein, we describe the structural and electronic of single crystals, and the
nuances involved in the design of heteroanionic materials, synthesis of new metal oxides
review technically interesting compounds, and highlight cen- and oxide fluorides, which emphasizes the connections
tral opportunities in the field. Although we attempt to capture between the synthesis and structure of new materials, the
design strategies that can be employed by the general mate- physical properties of new materials, and the technological
rials community for HAMs broadly, given the limited space we advances that result from these discoveries.
focus the main design and decoding discussions of structure
and properties to oxyfluorides. Other reviews can be found in James M. Rondinelli is
refs. [21–23] and opportunities enabled by additional anions not the Morris E. Fine Junior
discussed here are given in ref. [24]. Professor in Materials
and Manufacturing in the
Department of Materials
2. Design Opportunities from Homoanionic Science and Engineering at
Compounds Northwestern University.
He received his Ph.D. in
To motivate the design of new heteroanionic materials, we materials science from the
describe the design of two layered homoanionic cuprates to University of California, Santa
emphasize how key changes to crystal-chemistry and electronic Barbara (2010). His research
structure by a single anion controls material properties. The interests are in electronic
example demonstrates why one anticipates enhanced control structure theory and first-principles design of functional
in heteroanionic materials. First, selection of the atomic spe- inorganic materials using picoscale structure–property
cies for a ternary A2BX4 compound: one may start with either relationships. He focuses on technical challenges and
the A and B cations or the X anion. By specifying the B metal overcoming material disparities by strategically building
and its oxidation state, for example as Cu(II), then both the functionality into materials through multiple tiers of mate-
X anion and counter-charge balancing A cation chemistries rials theory, simulation, and machine-learning tools.
are restricted by the 2-1-4 stoichiometry, which in turn limit
the type of feasible coordination polyhedra based on Pauling’s
principles.[25,26] For the fluoride, A2CuF4 requires a monova- occupies the highest energy eg-symmetry orbital, i.e., corre-
lent A cation whereas the oxide A2CuO4 requires a trivalent A sponding to the one aligned along the short Cu–ligand bonds
cation. Next, corresponding homoleptic polyhedra compatible (because the state is a hole and not an electron). What then gov-
with the stoichiometry are the octahedral [CuF6] and [CuO6] erns the different magnetic properties?
units, which can be assembled to form corner-connected As sketched in Figure 2 in the ab plane of the fluoride, the
infinite sheets. When the 2D layers are combined the layered direction of the long axis of the [CuF6] unit alternates between
Ruddlesden–Popper (RP) structure is possible. sites. This requires that the occupied hole orbitals on adjacent
Two known homoanionic materials with these features are Cu sites are orthogonal to each other. The orbitals alternate
the m = 1 RP phases K2CuF4 (orthorhombic) and La2CuO4 between d x 2-z2 to d y 2-z2 , so called antiferro-orbital order, owing
(tetragonal). Although these compounds exhibit nearly iden- to the bond anisotropy. It is this long-range order that produces
tical RP structures, their properties are distinct. The fluoride is weak ferromagnetic spin exchange in the plane. Although the
an unusual transparent ferromagnet and the oxide is an anti- same local distortion is present in La2CuO4, the oxide exhibits
ferromagnet from which high-temperature superconductivity ferro-orbital order with all of the long axes of the [CuO6] octa-
emerges.[27,28] Both Cu2+ compounds (d9: t2g6eg3 electronic hedra aligned in the same c direction of the crystal. Every site
configuration) exhibit first-order Jahn–Teller distortions, i.e., in La2CuO4 then exhibits a hole in the d x 2-y 2 orbital, so the spin
nonidealities to the ideal octahedral unit, with anisotropic exchange between sites is antiferromagnetic. So what then
CuF or CuO bond lengths owing to the single eg-hole in the governs why the octahedral units assemble differently in the
d-orbital manifold. Each polyhedral building unit in the layered homoanionic materials? The dominant factor is the ligand—
cuprates exhibit two-long and four-short copper–ligand bonds, oxide or fluoride—itself.
which alter the crystal field split eg orbital levels imposed by an In RP-structured oxides, the apical oxide anions of the octa-
ideal octahedral field. In the fluoride and oxide, the hole always hedral units already displace away from the metal centers
Figure 1. From homoanionic to heteroanionic building units for the assembly of oxide-derived heteroanionic materials: Heteroanionic materials are
constructed from building units that exhibit unique local coordination chemistry with multiple anions surrounding a metal center (left) of the same
(a, homoleptic) or different (b, heteroleptic) species. Typically, the number of oxide anions (red) govern: c) the out-of-center metal displacements that
may occur toward a face, edge, or corner of the polyhedron, which reduces the local symmetry for the metal d-orbitals, particularly in heteroanionic
materials with d0 electronic configurations. Local symmetry of the building units also depends on the geometric isomerism of the unit, e.g., cis or trans
coordination. Illustration of the structural and chemical diversity in oxide-derived heteroanionic materials (HAMs), including: d) a subset of those
p-block anions, which combine with the oxide ion to form the structurally and chemically diverse oxynitride (e), oxysulfide (f), and oxyfluoride (g)
materials from heteroleptic polyhedra. h) BiCuOSe is a heteroanionic material comprised of homoleptic polyhedra, which distinguishes it from the
other materials (broken line). The annotated slice of the periodic table in (d) indicates the anion electronegativies based on the Pauling scale, ionic radii
for four-fold coordination (S2- based on sixfold coordination), and the bound coherent scattering lengths. In these materials, the exchange of an anion
for oxide as in O2− → N3− (O2− → F1−) requires compensation of excess (deficit) charge, which often necessitates that binary heteroanionic oxynitrides
are composed of cations with high oxidation states (Ti4+, Zr4+, Ta5+, Nb5+, Mo4+,5+, W5+,6+) as in TaON. In oxyfluorides, on the other, late transition
metal cations are compatible with lower oxidation states.
even in the absence of any Jahn–Teller physics—the unit never in which structure type will those elements stably reside? Such
exhibits ideal cubic symmetry, whereas this built-in anisot- selection criteria are best addressed with a property in mind,
ropy effect is much weaker in the fluorides. Therefore the and the questions are often more tractable with an established
stronger eg splitting and enhanced crystal field splitting of governing model or mechanism for the desired property.
the O2− anion compared to the fluoride F− anion leads to the Crystal-chemistry enables the formulation of structure–
parallel alignment of all long axes of the [CuO6] units (ferro- property models and facilitates the design of new materials
orbital order) and antiferromagnetism. Thus, the orbital order by viewing a complex structure as ordered assemblies of mul-
in these homoanionic materials is directly tuned by the anion. tiple homoleptic or heteroleptic polyhedra. The previous sec-
The aforementioned considerations express broadly how the tion describes the design of the magnetic properties of two
electronic structure of many materials is constructed from homoanionic cuprates—an oxide and fluoride with contrasting
the level of cations and anions and their associated assembly. magnetic order—utilizing homoleptic octahedra alone and
Thus, combining multiple anions in a single material offers a based on the crystal-chemistry procedure outlined below. This
strategy to alter the polyhedral units and the coupling between procedure can be considered as a suitable strategic workflow
them, which is enabled by their connectivity, for ultimate prop- for scientific inquiry and we make no attempt at providing its
erty control. tactical implementation as analogous efforts, applied to other
complex materials, are underway through national Materials
Genome Initiatives.[29–31] The aforementioned homoanionic
3. Principles for Heteroanionic Material Design cuprate materials serve as an example towards understanding
how changes in anion chemistry offers property control. The
When designing materials at the level of atoms, the basic ques- process of identification and assembly for a designer hetero
tions to answer include: which atomic species to combine and anionic material includes:
Figure 2. Structure and properties of homoanionic cuprates: a) K2CuF4 is shown in the same setting as b) La2CuO4 to facilitate structure comparisons
although the crystal symmetries of the fluoride and oxide are Cmca and I4/mcm, respectively.
i. Selecting the atomic species, choosing two anions and com- Insertion : ABO3- x + x [F] → ABO3- x Fx (1)
patible metal chemistries;
ii. Generating homo- and/or heteroleptic polyhedral building
units with ordered ligands; Exchange : ABO3 + x [F] → ABO3- x Fx + x [0 ] (2)
iii. Assembling the units together to form extended structures,
including connectivity that changes from corner-, edge-, to where x may be an integer or fraction. Insertion of fluorine acts
face-shared polyhedra which make it possible to access a to oxidize the material, increasing the formal oxidation state
range of structure types and dimensionalities; and of the TM cation. For example, Mn3+ transforms on average
iv. Allowing for nonidealities, including ordered arrangements to Mn3.5+ in the process of inserting fluoride into the oxide-
of cation vacancies or displacive distortions such as tilt, deficient manganite Sr2Mn2O5 (or equivalently SrMnO2.5 when
shape, or size perturbations[6] to the polyhedral units as well written with respect to the stoichiometric perovskite). In con-
as misordering of their assembly which affects short- and trast, exchange of an equal amount of fluoride for the oxide ion
long-range anion order in the structure. Filling of anion will reduce the metal, decreasing the formal oxidation state as
vacancies also alters the bond anisotropy present in the poly- in the transformation of KNbO3 into KNbO2F (Nb5+ → Nb4+).
hedral units. Exchange of fluoride for oxide in for example (Rb,La)Nb2O6F
makes it possible to convert an insulating 2D material into a
Shifting the atomic selection from one to multiple anions for semiconductor or bad metal because it produces mixed-valence
heteroanionic materials design both extends and restricts the Nb (4+ and 5+). Routes to achieve such mixed or difficult to
available cation chemistries for incorporation into the crystal access niobium valences are proposed design requirements for
(step i), because the cations contribute the necessary charge transparent metals[32] and metallic photocatalysts.[33] In addi-
compensation imposed by the anions. This simplified schema tion, nonelectroactive processes can also occur, whereby two
is intended to be a framework for understanding heteroanionic fluoride ions replace one oxide anion as in the transformation
materials by untangling the various changes that are forced of Sr2TiO4 to Sr2TiO3F2 to maintain the Ti4+ oxidation state.[34]
upon the cations by the presence of multiple anions. Although This process allows the fluoride to occupy either an existing
many of the possible structures arising from the assembly of oxide site or an empty interstitial site, provided there is no
units may not be synthetically possible, it serves as a future change in structure type. In the case of the layered Sr2TiO3F2,
framework for the design of novel materials as it can isolate the fluoride fractionally occupies both positions.
most important structural contributions for the desired prop- In step i, we focus on compounds exhibiting integer
erty. The schema below are not intended to be interpreted as an stoichiometries to simplify the heteroanionic materials design
absolute guide for synthetic chemical reactions or as a method process, which proceeds next with steps ii and iii. For small
for high-throughput structure searches, but rather for concep- and noninteger values of x, the usual goal is to electron or
tual understanding by de novo design. hole dope a largely oxide-based TMC. Vegard’s principle and
We may consider the nonoxide anionic species, for example, so-called “subscript engineering” approaches[35] can substitute
fluoride in oxyfluorides to be either: 1) inserted into a nonstoi- for the aforementioned steps when designing solid-solution
chiometric or 2) exchanged with a stoichiometric oxide anion heteroanionic materials with tunable carrier densities. Design
sublattice. Note these two limiting processes are not necessarily steps i and ii give substantial degrees-of-freedom for elec-
independent of one another and that the laboratory synthesis tronic, magnetic, and optical property control. Both the relative
of heteroanionic materials may or may not be achieved by such positions of the electronic transition metal dn levels, with asso-
insertion and exchange reactions—HAMs can also be real- ciated orbital filling n = 0–10, and the anion p levels and the
ized via mass transport (diffusion) of stoichiometric ratios of local symmetry of the metal–anion polyhedral unit may be
homoanionic materials. For ABO3 perovskites, these two pro- tuned by means of anion selection and coordination with the
cesses are given by the following schemas: metal. These features affect the covalency of the anion network
and the ensuing electronic, magnetic, or optical properties. The insertion or exchange limit, the substituted anions demon-
important additions to the design suite, afforded by the two strate site preferences about the metal centers[50,51] and partial
anions, are tunable crystal field energies, charge-gap control, or complete order of the heteroleptic unit occurs.[52] Generally,
and local symmetry breaking. For these reasons, it is impor- long-range anion order tends to occur in heteroanionic mate-
tant to understand the elemental differences between anions to rials when the difference in ionic radius of the two anions is
ensure atomic and electronic structure compatibility with the significantly large. For example, oxysulfides tend to have long-
targeted macroscopic properties and solid-state structure. range order owing to the significantly larger ionic radius of
Steps iii and iv expand the number of the plausible crystal S2− (1.84 Å) compared to O2− (1.35 Å) despite the same formal
structures obtained from scaffolding together metal–anion oxidation state, and oxynitrides and oxyfluorides tend to be dis-
coordination polyhedra especially when multiple multivalent ordered. Nonetheless, oxynitrides and oxyfluorides do exhibit
cations are available (step ii). On the other hand, binary HAMs short-range order and the degree of long-range order is sensitive
such as LaOF exist but property control is often limited in com- to processing conditions. These changes in ionic radii and the
pounds with a single cation.[36,37] Although the aforementioned (an)isotropic distribution of multiple anions can affect both
features elevate materials design complexity, structure and the equilibrium lattice constants (of the global crystal structure)
chemistry enumeration is straightforward. Nonetheless, some relative to the homoanionic oxide and local structure in heter-
aspects to steps i–iv can be challenging to achieve through oanionic materials.
laboratory synthesis. One notable synthetic challenge lies in There are multiple configurations of anions about the metal
achieving anion order, as the quasi-random assembly of the centers (i.e., geometric isomers) available for the [MO2F4] and
heteroleptic units will result in a statistically random distribu- [MO3F3] units. For [MO2F4], cis and trans configurations are pos-
tion of anions (i.e., mixed occupancy anion sites or long-range sible and for [MO3F3], fac and mer units can form (Figure 1c).
anion disorder), which can inhibit the desired functionality Changes to the local anion order in the heteroleptic unit lead
of the compound, as in the case of acentric properties. First- to different local site symmetries for the cations (Figure 1c). In
principles based discovery approaches, as applied to multication general, cis and fac units are more favored,[53,54] particularly when
compounds,[15,38,47,39–46] can assess phase stabilities and ordered the cation is a d0 transition metal, because having anions with
arrangements of homoleptic and heteroleptic polyhedra fol- similar Pearson hardness[55] near each other maximizes the
lowed by integrated and iterative experimentation.[48,49] We π-hybridization in the M-anion bonds. The hybridization is
discuss the interplay of these degrees-of-freedom in property reinforced by allowing atomic relaxations toward characteristic
design before we describe the fundamental principles guiding bond lengths.[56–63] The inherent contrast between the anions
considerations of steps i–iv. also causes displacive nonidealities such as rotations and dis-
tortions to the polyhedral units, which are discussed later.
π-hybridization favors the cis configuration for more electron-
3.1. Anion Properties and Metal Coordination Polyhedra egative anions over the trans anion arrangement in heteroan-
ionic materials with d0 transition metal cations, in particular for
Successfully exchanging one anion for another requires careful Mo-centered [MoO2F4] heteroleptic units. In contrast, the trans-
consideration of the size, electronegativity, and valence with anion arrangements with 4/mmm (D4h) point symmetry are
the global composition of the heteroanionic material in deter- frequently observed in Pb5W3O9F10 where trans-oxide anions
mining the final crystallography of the structure. The portion bridge ribbons of trans-[WO2F4] and [WO6] units.[64]
of the periodic table appearing in Figure 1d illustrates the The atomic number and coherent neutron scattering length
inherent physical and chemical differences of a subset of the serve as proxies for the ability of typical structural characteri-
elemental p-block anions to combine with the oxide anion in zation techniques, X-ray and neutron diffraction, respectively,
heteroanionic materials. to distinguish between anions in heteroanionic materials. The
The relative size of anions affects the number and shape of larger the difference between each respective parameter, the
the coordination polyhedra, which may be justified by applying easier it is to distinguish the elements using each technique.
Pauling’s radius-ratio rule. Common polyhedral unit shapes For example, although it is difficult to distinguish N3− from
found in HAMs include tetrahedra, square pyramids, and octa- O2− using X-ray diffraction techniques, neutron diffraction will
hedra. For oxyfluorides with metal anionic octahedral units, readily distinguish the two. Sulfide ions are readily distinguish-
these heteroleptic units may be [MO3F3], [MO2F4], or [MOF5] able from oxide ions owing to their higher atomic scattering
units (Figure 1c). Owing to the ionic size of the anion, usually factor. As a result, anion ordering in oxysulfide materials is
only the nitride and fluoride anions are able to substitute easily more easily determined experimentally than in oxyfluorides
for the oxide anion in these units. Other suitable halides and and oxynitrides.
chalcogenides are typically too large to coordinate the same
transition metal ion, and thus layered structures tend to crystal-
lize with various homoleptic polyhedral motifs in the unit cell. 3.2. Crystal Structure from Polyhedral Assembly
Additional implications of the size similarities of the anions
are that co-occupancy of the same ligand site by two dif- After identifying the atomic species for use in the polyhedral
ferent anions may occur and give rise to disorder about the units, clusters of similar or different polyhedra may be formed
metal center. Naively, one anticipates that heteroanionic mate- (step ii) by joining vertices in various ways (step iii) and linked
rials should exhibit complete disorder of the anion sublattice together to form a crystal. Molecular chemists frequently
defining the polyhedral network; however, even in the dilute exploit this process of cluster assembly for materials design
and, as we describe below, it can be extended to the solid state. created by four [NaO3F3] and [MoO3F3] units (Na4Mo4O18F18
Heteroanionic materials can exhibit one or several types of cluster) exhibiting the topology of rhenium trioxide, as is
polyhedra, e.g., tetrahedra, square-pyramids, and octahedra, typical for the A-site cation in double perovskites. Such fac con-
linked in some fashion. The units may share corners, edges, figurations are favored over mer for a number of heteroanionic
and faces, making connections to form 1D chains, 2D layers, and materials with [BO3Q3] (Q = F, N) octahedral units.[53,54] The
complex 3D networks.[65] Other coordination polyhedra are tendency to form fac configurations is driven by the difference
also possible. Here we use simplified crystal coordination in covalent bonding between the anions. The transition metal
formula[66] when convenient to describe the building blocks and the oxide ion BO bond lengths are significantly shorter
and their linkages. This notation places the polyhedral units than the BF bond lengths, resulting in an off-center distortion
in square brackets and separates the coordination geometry of of the cation toward the oxide face.
nonequivalent ligands from the stoichiometric coefficients of The net alignment of local dipoles arising from the fac-anion
the chemical formula. For example the infinite 3D homoan- polyhedra, even in the absence of Mo out-of-center displace-
ionic perovskite CaTiO3 = 3∞Ca[TiO3 ] = 33 ∞ Ca[TiO6/2′ ], where ments toward the octahedral face spanned by the oxide anions,
the prefixes indicate the material is an infinite 3D solid and leads to the loss of inversion symmetry. The homoanionic
the [TiO3] unit in brackets is the building unit generating the Na3MoO6 exhibits Fm 3m symmetry whereas the prototypical
octahedral framework with Ti coordinated by six oxide anions heteroanionic Na3MoO3F3 exhibits R3m symmetry. This proce-
(6 subscript) and the oxide anion coordinated linearly by two Ti dure generates a pseudocubic cryolite structure, although the
(2′ subscript). The superscripts, here 3 followed by another 3, experimental structure is of lower symmetry (R3) owing to fur-
indicate the dimensionality of the unit in brackets followed by ther nonidealities (e.g., octahedral rotations, as described in the
the dimensionality of the total structure. next section). In the extended structure, the trigonal axis corre-
Owing to the multiple anions in the heteroleptic polyhedral sponds to the polar axis of the structure. Note that assembly of
units, misassembled units can lead to a variety of disorder the polyhedra in an antiparallel arrangement would recover the
(discussed later), which will affect crystal symmetry and often global inversion symmetry in the crystal. Na3MoO3F3 is found
properties. The assembly of heteroleptic polyhedral building as a trigonal variant and other detailed structural studies on
units typically occurs through the most anionic (negative) A2BB′O3F3 (A, B = Na, K, Rb, Cs, Tl; B′ = Mo, W) oxyfluorides
ligand. These anions preferentially form linkages to “direct” exhibit similar distorted room-temperature phases.[68–72] As
the assembly of the extended structure.[67] Although we expect in Na3MoO3F3, rotations of the [MoO3F3] octahedra about the
the nuanced polyhedral packing principles to vary among dif- [111] direction also occur in K3MoO3F3, and Rb2KMoO3F3.[73–76]
ferent structure types and compositions as the optimization
of relevant energy scales (electrostatic, strain, etc.) can vary,
there are some general features common to the assembly of 3.2.1. Directing Polyhedral Assembly
extended structures using heteroleptic polyhedra of the same
or different type. To illustrate the process of heteroleptic poly- The manner in which polyhedral units assemble is sensitive to
hedral assembly, consider the family of A3MoO3F3 oxyfluorides the other cations not in the polyhedra, which are often consid-
with A = Na, K, Rb, and Cs. Each member exhibits local and ered to only provide the necessary countercharge balancing and
long-range ordered [AO3F3] and [MoO3F3] octahedral units. structural rigidity. An example of the importance of the A-cation
How the structure is generated from these units becomes more in ternary HAMs governing long-range connectivity is found in
apparent by rewriting the chemical formula first as a homoan- the ANaNbOF5 family (A = K, Cs) with [NbOF5] and [NaOF5]
ionic oxide (A2)(BB′)O6 with B = A and B′ = Mo. One-third of octahedra. Both crystals exhibit long-range order of the het-
the A atoms act like B atoms, occupying octahedral holes in this eroleptic polyhedra owing to the preference of fluoride to
structure derived from ABO3 perovskite (referred to as cryo- interact with the Na+ cations. Interestingly, the A-site cation
lite since B = A), which exhibits cubic-close packed AO3 layers also determines the distinct equilibrium structures of each
along the pseudocubic [111] direction. Figure 3 illustrates how member of this family. Although the family can be written stoi-
the alternating stacking of 2∞ [NaO3 ] layers and B planes followed chiometrically to resemble perovskite with an ordered A-site
by anion exchange results in alternating (111)pc planes of oxide vacancy, the equilibrium structure for KNaNbOF5 is polar and
and fluoride ions in Na3Mo3O3F3, referenced to a pseudo-cubic noncentrosymmetric[77] with edge-shared polyhedra, whereas
(pc) notation. CsNaNbOF5 is centrosymmetric with perovskite-like corner
Numerous independent studies employing vibrational connectivity of the polyhedra. Chemical hardness in this case
spectroscopy, electron diffraction, and bond valence analyses is important for achieving ordered heteroleptic units that
support fac polyhedral configurations arising from these (111) assemble into nonisostructural compounds with nominally
planes with the oxide and fluoride ordering on opposite faces of the same chemistry. This change in connectivity alters spa-
the [NaO3F3 ] = ∞3 [NaO3/2′F3/2′ ] and 3∞ [MoO3/2′F3/2′ ] octahedra. Note tial parity, which is a symmetry that must be lifted for many
that strictly the denominators in these crystal-coordination for- acentric functionalities, e.g., piezoelectricity, nonlinear optical
mula should be written as ‘1′ + 1′’ to indicate that the oxide (NLO) responses, etc. The absence of additional cations to
and fluoride anions coordinate different B cations (Na or Mo); participate in ion-hardness matching may explain why anion-
however, for simplicity, we use ‘2′’ to reflect the two-coordinate ordered polyhedra are difficult to realize in some binary
environment arising from corner-connected octahedra. These heteroanionic materials, for example, the ReO3-structured
fac ordered polyhedra then assemble with 3D corner connec- oxyfluoride NbO2F. Although local anion order of oxide and
tivity. Note that the remaining Na atoms reside in the cavities fluoride about Nb can be realized experimentally, it is likely
Figure 3. Construction of the heteroanionic material Na3MoO3F3 from the assembly of close-packed planes and ordered heteroleptic polyhedra:
a–e) Illustration of how close-packed metal-oxide planes (atoms depicted using ionic radii) stack along the pseudocubic [111] direction to generate
the ideal Fm3m phase of the cryolite Na2(NaMo)O3F3. In this representation, it becomes clearer that Mo occupies one-third of the octahedral sites
(b), while Na both forms the close-packed NaO3 planes that generate the octahedral interstices and occupies the other one-third of the octahedral
sites in alternating layers with Mo (c). d,e) Fluoride exchange occurs such that each close-packed layer is exclusively oxide or fluoride along the [111]
direction. f) Polyhedral representation of the ideal Na3MoO3F3 shows that the arrangement of fac-ordered building units, i.e., the corner-connected
NaO3F3 octahedra (yellow) with MoO3F3 octahedra (purple), lift inversion symmetry by reducing the 3 symmetry operation about [111]pc to a proper
three-fold operation. g) Nonidealities to the crystal structure include octahedral rotations about the trigonal [001] and [111] directions and cooperative
Na and Mo out-of-center distortions within the octahedra reduce the symmetry of the structure to its equilibrium polar subgroup R3.
synthesis dependent[78] and random distributions of the oxide negative residual charge, the sites were ordered. When they
and fluoride ions frequently occur[79] with short-range corre- were unequal or quite small, the sites were mixed.
lated order.[80]
Chemical hardness differences between oxide and fluoride
ions also guide how polyhedral units connect in the oxyfluorides 3.2.2. Assembly of Layered Structure-Types
Rb3Na(NbOF5)2 ⋅ H2O and Rb3Na(MO2F4) ⋅ H2O (M = Mo, W),[81]
which exhibit partial anion order. These materials would be The heteroleptic polyhedra can also assemble in 2D sheets,
isostructural if their [NbOF5] and cis-[MO2F4] octahedra, respec- stacking together to form quasi-2D structures. Layered heter-
tively, were homoleptic. However, these materials show both oanionic materials are typically synthesized by anion insertion
anion order and disorder about different inequivalent Nb/M or exchange with oxygen in layered homoanionic oxides and will
sites. The partial anion order is largely directed by chemical then often adopt the Ruddlesden–Popper (RP, A2A′m-1BmO3m+1),
hardness, the preferential bonding between Na and F, as in Dion-Jacobson (DJ, AA′m-1BmO3m+1), and Aurivillius (AV, (Bi2O2)
the ANaNbOF5 family. Secondary factors affecting the connec- (A′m-1BmO3m+1)) structure types[82] with m layers of 32
∞ A[BO6/2′ ]
tivity of the units, and thus the anion order, are based on how perovskite blocks forming infinite 2D layers. The change in
“well-matched” the residual charges of the A-site and closest structure topology from 3D to 2D adds a built-in anisotropy in
anion site are. The residual charges can be calculated based on the crystal structure, which can enable ordered arrangements
bond valence sums and the nominal valence of the ions. When of the polyhedral units in a manner compatible with the local
the positive residual charge was large and about equal to the bond anisotropy due to differences in the BO and BX bond
covalency.[19,26,82] For example, in oxyfluorides, the terminal be ubiquitous among compounds in the previously described
apical sites of the perovskite layers in the RP, DJ, and AV struc- A2BB’O3F3 family. In addition, oxyfluorides with anion
tures allow for elongation of the MF bond along the layer- ordered [BOF5] octahedral units (KNaNbOF5, CsNaNbOF5, and
stacking direction, because these ligands are not bonded to a Rb2KTiOF5) exhibit B cations displaced toward the oxide ion
cation in the adjacent layer as in perovskite with 3D polyhedral forming a polar unit with 4mm (C2v) symmetry. In oxynitrides
connectivity. For m = 1 RPs with chemical formula Sr2BO3F AMO2N (A = Er, Sr; M = Nb, Ta) perovskites[93] with ordered
(B = Sc, Mn, Fe, Co, Ni), the ligand at the apical site and the cis-[MO4N2] octahedra, the polyhedra exhibit out-of-center
degree of long-range anion order depends on the choice of the metal displacements towards the N3- anion, resulting in shorter
B cation.[52,82–84] Although all [BO5F] = ∞2 [BO4/2′O1/1′F1/1′ ] poly- MN bonds and local mm2 (C2v) symmetry. In all cases, the
hedra in this family exhibit fluorine on the apical (terminal) site inherent contrast in the covalent interactions between the tran-
and short-range anion order, only Sr2FeO3F exhibits long-range sition metals and multiple anions leads to the formation of
order where the fluorine alternates between the apical sites in local dipoles within heteroleptic polyhedra that are useful for
each perovskite layer, generating an antipolar structure. designing noncentrosymmetric materials.[94]
Similarly, oxysulfides prefer the terminal apical site
owing to the larger volume available between layers.[85]
In contrast, oxynitride RPs[86] such as Sr2TaO3N and the 3.3.2. Octahedral Tilts
(SrO)(SrNbO3-xN)m (m = 1, 2) family tend to have full oxygen
occupancy at the apical sites and mixed O/N occupancy The perovskite oxynitrides SrNbO2N and SrTaO2N exhibit a
in-plane.[87–89] For m = 2, there are two perovskite bilayers that high-temperature tetragonal structure,[63] with space group
repeat in the RP and the arrangement of ordered heteroleptic P4/nmm rather than the expected cubic Pm 3m owing to prefe
polyhedra within the bilayer can be tuned by changing the rential (incomplete) anion order in the [BO4 N 2 ] = ∞3 [BO4/2′N 2/2′ ]
ligand. In RP Ba3In2O5F2, the fluoride ions occupy the terminal octahedra (B = Nb or Ta). A change in the metric shape of the
apical sites[90] such that sheets of corner-sharing indium–oxygen unit cell occurs because the oxide anion is smaller than the
square pyramids are separated by BaF layers. In contrast, in nitride anion and when the [BO4N2] units arrange the c and a lat-
the m = 2 DJs, the fluoride may reside at the equatorial sites tice constants cannot change identically. At room temperature,
and central apical anion sites in the double-layered perovskite these two heteroanionic materials exhibit octahedral rotations
block rather than the apical sites in the A2 layers as in (Rb,La) about the tetragonal axis (a0a0c- in Glazer notation[95]), which
Nb2O6F.[91] The site preference then may be considered to arise were found to depend on the cis-ordering of the two nitrides
from a balance of elastic energies related to the compliance of in each [BO4N2] and the successive connectivity of these poly-
a metal–anion bond versus electronic interactions and bond hedra. Interestingly, this tilt pattern is the same as that found
preferences among the multiple layers of polyhedra for m > 1. in the low-temperature polymorph of the homoanionic oxide
Aurivillius phases are more similar to DJ phases in terms of perovskite SrTiO3, which is known to be an incipient ferroelec-
anion ordering; AV oxyfluorides can have mixed occupancy on tric, and may have motivated searches for ferroelectricity in thin
all anion sites, rather than preferentially sitting only on one film SrTaO2N.[96] One consequence of the octahedral tilts in
anion sites. For example, Bi2TiO4F2 has mixed O/F occupancy heteroanionic materials is that the structural distortion will lift
on all anion sites, including the [Bi2(O,F)2] layer.[92] crystal-site symmetries that require some anion positions to be
equivalent. As a result, these oxynitrides are strictly not tetra
gonal but rather exhibit monoclinic symmetry. In addition, the
3.3. Nonidealities type of octahedral tilting can be tuned with metal chemistry as
in homoanionic materials such as alkaline-earth and rare-earth
The aforementioned Na3MoO3F3 example illustrates three titanate oxides; for example, the substitution of Sr with Ca (and
important nonidealities (step iv), which must be considered other smaller ionic radii metals like La, Ce, and Pr) cause addi-
in designing new heteroanionic materials from polyhedral tional tilts to occur, specifically the pervasive orthorhombic
assembly. These include the polar displacements of transition a-a-c+ Pbnm tilt pattern.[28,51,53] As before, long-range anion order
metal centers, polyhedral distortions (rotations and shape or results in symmetry reductions (although usually preservation
size distortions from electronic and magnetic instabilities), and of inversion symmetry) depending on whether the octahedral
anion sublattice order or disorder among the linked building [TaO4N2] units arrange in two or three dimensions.[97] Similar
units, which we explore further. The latter behavior leads to interplays between (partial) anion order and octahedral tilt
nontrivial dependencies on the former two secondary intra- or patterns are observed in transition metal oxyfluorides.[98]
interpolyhedral distortions. Ultimately, the interplay among all
of these degrees-of-freedom determines the equilibrium crystal
symmetry and properties. 3.4. Electronic Structure
The essence of electronic structure design in TMCs is rooted

3.3.1. Polar Displacements in the modulation of electronic states near the Fermi energy by
changing the chemical interactions between transition metal
Many heteroanionic materials with heteroleptic polyhedra of d states and ligand p states. In solids, the choice of anion can
varying anion-to-oxide ratios exhibit acentric metal displace- greatly determine the size of bandgaps, orbital hybridization,
ments. Metal off-centering within the [BO3F3] units appears to band dispersions, crystal field splitting, etc., because the anion
p levels are completely filled and lie below those of the metal. of dn TMCs with interacting electrons requires additional
The combination of transition metals with d levels that are considerations and is often rationalized within the Zaanen,
either empty or filled with n d electrons (dn-electron configu- Sawatzky, and Allen (ZSA) framework, which was originally
ration) and multiple anions will lead to a variety of electronic introduced to understand the energy scales leading to metal–
structures and physical properties of heteroanionic materials. insulator transitions in homoanionic oxides.[103] The ZSA
In this section, we review the consequences of the metal scheme is sufficiently complete, such that it includes the main
valence (electron filling) and the exchange of anions with elec- energy scale often used to understand the electronic structure
tronegativities and charge that differ from O2− on the distribu- of many materials, that it can be extended to heteroanionic
tion of the low-energy orbital states and electronic properties of compounds with heteroleptic polyhedra as we show below. In
heteroanionic materials. this section, we briefly summarize this scheme and show how
First, we note that even in relatively simple heteroanionic the framework can be used to rationalize and design the elec-
materials, one does not find that the material’s electronic tronic structure of HAMs, focusing on compounds with het-
structure is described simply as a superposition of the elec- eroleptic building units. For a more detailed introduction to the
tronic properties of the homoanionic components. Although ZSA scheme, readers can refer to refs. [11,104].
prior work has established that the difference between the The first important energy scale is the on-site Coulomb
cation and anion electronegativities correlate well with the size energy (U), which acts to localize electrons onto the metal site
of bandgaps of many insulating solids,[99] the application of and produce insulating behavior in non-d0 transition metal
Vegard’s law often fails to provide an adequate description of compounds. In such Mott–Hubbard insulators, the bandgap
the electronic structure.[100] scales with U, which is the energetic cost to doubly occupy a
Consider for example the “simple” binary oxynitride Si2ON2. metal orbital manifold with an additional electron from another
Electronic structure calculations based on density functional metal site via the charge transfer process, dndn → dn-1dn+1.
theory (DFT) show that the electronic density-of-states (DOS) of This energy scale competes with the electronic bandwidth
the oxynitride Si2ON2 cannot be reproduced by a superposition (kinetic energy) of the system, W, which is dictated by the
of the homoanionic constituents,[101] Si3N4 and SiO2. How does interatomic hopping strength t. The main hopping interaction
the crystal and local structure of the heteroanionic material favoring electron delocalization is between anion p and metal d,
compare to that of the closest binary homoanionic materials? therefore tpd ∝ W depends on the orbital overlap between the
The silicon nitride (Si3N4) and oxide (SiO2) both exhibit tetra- transition metal and coordinating anion, i, which for a heter-
hedral bonded networks of homoleptic 3∞ [SiN 4/4′ ] and 3∞ [SiO4/4′ ] oanionic material becomes anion dependent Wi. Generally,
units, respectively. The polar oxynitride Si2ON2 (space group Mott insulating behavior arises when the bandwidth is less
Cmc21) also exhibits a tetrahedral silicate-like network; however, than the U interaction, i.e., with localized d electrons and local-
it is composed of heteroleptic 3∞ [SiO1/2′N3/3′ ] units. The structure ized moments, as in early transition metal compounds.
is assembled from units that are corner-connected in a manner In addition, the filled dispersing anion p bands arise from pp
that allows Si to be surrounded by three triple-bridging nitride hopping, and therefore, another key energy scale is the charge
anions and one linear bridging oxide anion. This connectivity transfer energy (ΔCT), which corresponds to the energy needed
leads to an effectively layered anion sublattice in the 3D struc- to transfer an electron from a filled anion band to an empty
ture and the absence of inversion symmetry. Now, how does d band. The charge transfer energy is directly related to the elec-
the change in atomic structure affect the electronic structure? tronegativity of the anion[103] and will have the largest effect on
Because the electronegativity of N3- is less than that of O2-, the electronic structure of heteroanionic materials. A simplified
the SiN bonds are more covalent than the SiO bonds. The description of ΔCT within a single-particle framework is given
covalency (or ionicity) of Si2ON2 is not the same as the average by the reaction dnp6 → dn+1p5 reaction. Chemically one may
covalency of Si3N4 and SiO2 owing to the inductive effect,[102] consider this as O2- → O1- for the oxide anion or equivalently
which causes a redistribution of charge in the chemical bonds. as the formation of a ligand hole L on the anion p orbital and
In homoanionic d0 oxides, the valence band electronic structure a metal dn+1L configuration. The sensitivity of the electronic
is nominally O 2p character (discussed further below), and the structure on this energy scale is explicitly seen in isovalent
inductive effect will destabilize the N 2p states relative to the O homoanionic transition metal oxides and sulfides, which are
2p states such the nitride states form the band edge (Figure 4a). expected to have comparable U values; late transition metals
The net effect is to reduce the overall size of the charge- such as Co, Ni, and Cu oxides are insulating whereas the cor-
excitation gap in the material, shifting the absorption edge from responding sulfides are metallic.[103,105]
the UV to the visible. This materials understanding of the role In non-d0 materials, the ZSA scheme reveals that the bal-
of anion chemistry makes is possible to design optical gaps by ance of U/W versus ΔCT/W determines if a material will be
control of anion-to-oxide ratios.[57] In addition, the added anion- metallic or insulating. The insulator, as discussed above, is
order degree of freedom makes it possible to access a variety of either Mott–Hubbard-like or charge-transfer-like depending
bandgaps because the manner in which the heteroleptic poly- on whether the U or ΔCT energy scale is greater. Note that
hedra assemble together affects the symmetry allowed orbital U systematically increases from left to right along a transi-
hybridizations between ligand p and metal d states.[97] tion metal row while ΔCT decreases for homoanionic mate-
Second, the size and character of the bandgap depend on the rials due to increased nuclear charge. For ΔCT < U, the lowest
d-band filling. For stoichiometric d0 compounds, one expects energy excitation is from a filled p band to an empty d orbital,
the bandgap size to decrease with decreasing electronegativity which leads to the “charge-transfer insulator” classification
from fluorides to sulfides (Figure 4a). The electronic structure for such compounds. In contrast, the charge-gap will be d–d
Figure 4. Electronic-structure changes due to additional anions within a polyhedral unit used to construct the heteroanionic material: modifications to
the transition metal d orbital structure induced by arranging different chemical species on a lattice can alter electronic, magnetic, and optical proper-
ties. a–c) The schematic density-of-states (DOS) for d0 (a) and dn compounds exhibiting Mott-insulating (b) or charge-transfer insulating (c) character
depict the changes in the cation d orbital and anion p orbital energies and bandwidth, indicated by the arrows in the first row, compared to their oxide
analogue. The orange and blue boxes in (c) differentiate positive charge-transfer and negative charge-transfer insulators, respectively. The broken
lines in the negative charge-transfer insulator section indicate the splitting of the O 2p band to form a gap. The inset in (b) is a modified version of
the Zaanen–Sawatzky–Allen diagram, showing the metal–insulator phase boundaries based on values of U and ΔCT. The colored dots represent the
qualitative change in ΔCT upon anion exchange into the homoanionic oxide. The inset in (b) is adapted with permission.[247] Copyright 1994, American
Physical Society.
when ΔCT > U (Figure 4b). Electronic insulator-metal transi to p–d orbital hybridization that opens a covalent-bonding gap
tions then occur for critical values of Coulomb strength with a negative charge transfer energy (ΔCT < 0). In these com-
Uc < U < ΔCT (Mott–Hubbard insulators) and U > ΔCT > Δ cCT. pounds, an electron has fully transferred to the transition metal,
For ΔCT > 0, strong bonding–antibonding splitting of the making the ground state dn+1L. This behavior is also known as
pdσ orbitals leads to bonding orbitals far below the Fermi self-doping,[106] and may result in negative charge transfer insu-
level and antibonding d-derived orbitals as the low-energy lators that are distinct from the other aforementioned insulators
electronic structure. The antibonding states may then be (Figure 4c). Compounds with ΔCT < 0 are of increasing interest
partially occupied by selecting various cation valence states, to chemists and physicists. For example, the anion-hole char-
which makes it possible to design the electronic and magnetic acter has recently been exploited for cathode design[107–109] and
states of homoanionic compounds. As described below, these new charge and orbital ordering states[110] have been reported
states can be further tuned when more than one anion is present in compounds exhibiting unusually high metal oxidation states.
in the coordination polyhedra. Typically, negative charge-transfer oxides contain transi-
As one reduces U or ΔCT, the material should become metallic tion metals with a high formal valence and are found near the
owing to orbital overlap (see inset, Figure 4). Indeed, one would end of the 3d transition metal series, such as NaCuO2[111] and
anticipate that as ΔCT decreases from a finite value (and U ≠ 0), rare earth nickelates.[112] Small or negative ΔCT energies can
a metallic or semimetallic state should emerge, but a signi be designed by selecting transition metals with large electron
ficant number of oxides remain insulating in this regime owing affinities (obtained by a high oxidation state) and/or anions
with smaller electronegativities. Because of their lower elec- the homoanionic oxide and fluoride compounds. However, the
tronegativities, oxynitrides and oxysulfides with late transition electrostatic anisotropy introduced by the ordering of oxide and
metals are expected to be negative charge transfer insulators. fluoride ions lifts the degeneracy of the orbitals in the eg and t2g
Note that Ni3+, Cu3+ and formally Co4+ and Fe4+ will be negative manifolds. We note that the hierarchy of orbitals is also anion-
charge transfer insulators or exhibit mixed-valency, which will order dependent. For example, the energy splitting between
lead to metallicity or narrow gap semiconductivity. In contrast, eg and t2g is straddled by the d x 2-y 2 and dxy orbitals for trans-
oxyfluorides are likely to be positive charge-transfer insulators [MO2F4] and d 3 z2-r 2 and dyz for cis-[MO2F4] configurations.
(Figure 4c). Although there are theoretical examples of positive Figures 5b,c further demonstrates how the choice of anion
charge transfer insulators in oxyfluorides,[54] we are unaware at within a specific octahedral configuration affects the evolution
this time of any published oxynitrides or oxysulfides that are of the crystal field splitting energy in a lattice under a tetragonal
negative charge transfer insulators. distortion, corresponding to the constraint found in many lay-
An example of heteroanionic materials design of electronic ered structures or mechanically imposed by thin-film epitaxy.
properties is in the performance of layered transparent p-type In the trans-[MO4F2] configuration with 4 in-plane oxide ions,
semiconducting oxychalcogenide LnCuOQ (Ln = La, Bi; Q = S, the substitution of fluoride ions on the apical sites results in
Se).[113–117] It was designed and realized by exchanging oxygen a lowering of the electrostatic repulsion along the z direction,
with an isovalent and less electronegative anion to reduce the thus lowering the energy of the d 3 z2-r 2 orbital relative to that
tendency toward hole-carrier localization at the top of the valence of the d x 2-y 2 orbital (Figure 5b). On the other hand, substituting
band. Several compounds in the LaCuOQ family were found the higher valence N3- anion on the apical sites instead of
to be wide bandgap materials with a highly dispersive valence F- results in a larger CFSE and lowering of the d x 2-y 2 orbital
band[117] and p-type electrical conductivity,[114,116] demonstrating compared to the d 3 z2-r 2 (Figure 5c). In addition, the evolution of
the advantage of moving a materials science focus from cations the CFSE is markedly different for the oxyfluoride compared to
to anions—heteroanionic materials design strategies. the oxynitride under the tetragonal distortion. These features
In addition to the U and ΔCT energy scales, crystal field indicate that reliable control of anion order in heteroanionic
interactions and spin–orbit coupling may be exploited for elec- materials offers a platform for band-structure design. In the fol-
tronic structure and spin-crossover control. In heteroanionic lowing sections, we further highlight how heteroanionic mate-
materials, the choice of anion and degree of anion order can rials can enhance technologically useful properties and induce
significantly affect the crystal field splitting and antibonding new exotic phenomena.
d-derived orbital energies, which govern the magnetic and
electronic properties in dn materials. There are two contribu-
tions to the crystal field splitting: the large Coulomb interac- 4. Design in Practice: Understanding Anion Order
tion of the d electron with the charged anions and the smaller
pd hybridization (covalency), which may be equally important The previous section highlights the importance of ordered
for some negative charge transfer insulators.[118] The spectro- anions in the polyhedral units on the atomic and electronic
chemical series approximates the amount by which the elec- structure of heteroanionic materials. Without ordering, techno-
trostatic fields generated by the different ligands modify the logically interesting noncentrosymmetric materials may exhibit
energy difference among the metal d-orbitals. Note that of the inversion symmetry and no longer be functional or the com-
anions discussed in this review, the nitride ion is the strongest pounds may lose the desired electronic or magnetic responses.
ligand while the sulfide is the weakest. The N3- anion therefore Therefore, in practice, the most difficult challenge lies in under-
induces the largest orbital modifications (crystal field splitting) standing the assembly of the metal–anion polyhedra, such
and S2- induces the smallest (Figure 5). Given a hypothetical that the ligands are arranged in an ordered fashion about the
oxyfluoride compound AMOxF3-x where the anion sublattice metal in the long-range structure. In this section, we describe
possesses a statistical distribution of oxide and fluoride ions, anion ordering on the short- and long-range length scales and
the crystal field splitting varies linearly with anion concentration. highlight the challenges associated with the characterization of
However, if the heteroleptic polyhedra are ordered, then the anion order. The main complexity is that complete characteriza-
relationship between crystal field splitting energy and anion tion often requires more than one technique to determine the
concentration is considerably different, to the advantage of the long-range (multiple unit cells) and short-range (within a unit
electronic structure designer. cell or at the polyhedral level) anion order in the compound.
Figure 5a illustrates the evolution of the crystal field split- Last, we highlight a few previously developed strategies to
ting for a transition metal cation octahedrally coordinated by design HAMs with ordered ligands.
oxide and fluoride ions with varying anion configurations with
uniform metal–anion distances. Here only the electrostatic
effect is included. The eg orbitals exhibit stronger electrostatic 4.1. Description and Characterization of Anion Order
repulsions (and larger hybridization, not shown) than the t2g
orbitals because the ligands are pointed directly at them. As Ordering in heteroanionic materials must be specified on both
dictated by the spectrochemical series, the crystal field splitting the local and long-range scales. This is because anion order is
energy (CFSE) of the eg (d x 2-y 2 and d 3 z2-r 2 ) and t2g (dxy, dxz, dyz) often first characterized by techniques which characterize the
is smallest (5 Dq) for the [MF6] fluoride unit compared to the average structure and hidden local ordering (also called corre-
[MO6] oxide (10 Dq). In an ideal octahedral geometry, the con- lated disorder) may be missed. Most often, structures that show
stituent orbitals of the eg and t2g manifolds are degenerate for long-range disorder have local ordering of the heteroleptic
Figure 5. Crystal field effects in heteroanionic compounds with multiple anions in a single coordination unit: a) Changes in d orbital degeneracies
and energy splitting for a transition metal (M) cation with d1 electronic configuration in the regular octahedral coordination with no bond distortions,
[MOxF6-x] (x = 1–6). b,c) Calculated crystal field energy, Dq, under tetragonal distortion of the octahedral unit for a trans-[MO4F2] (b) and trans-[MO4N2]
(c) heteroanionic building unit, where two fluoride or nitride ions, respectively, are located at the apical sites and four oxide ions occupy the equatorial
sites as illustrated in the insets of (b) and (c).
polyhedral units (e.g., all units in the structure are [MO5Q ], or spectroscopy cannot distinguish the characteristic Ti–O and
cis-[MO4Q2], or trans-[MO4Q2], etc.), but this is not always the Ti–F stretch modes and single-crystal X-ray diffraction resolves
case. For example, in FeOF, structured diffuse scattering meas- [TiOF5] octahedra with mixed occupancies on the anion sites
urements suggest that the compound is ordered in the (110) and no out-of-center distortion of the Ti.[120] However, IR spec-
and (110) directions, with no correlation between layers.[53] To troscopy distinguishes the Ti–O and Ti–F peaks, suggesting
fully describe the crystal structures of these materials, ordering that the [TiOF5] octahedra reorient rapidly (or display dynamic
should be assessed on the local scale (i.e., polyhedral unit or the disorder) under the X-ray and Raman measurements. Indeed,
atomic unit-cell level) and at the 100s of nanometer length scale repeating the Raman spectroscopy with a 514 nm laser (rather
(i.e., long-range scale usually called the crystal structure). Here, than a 1064 nm laser) readily resolves the Ti–O and Ti–F peaks,
we define the different types of anion order and disorder that suggesting that the higher wavelength laser induces a strong
can occur in heteroanionic materials and briefly list techniques increase in the frequency of the jumping [TiOF5] rotations.
that can characterize the local and long-range order. Kageyama Anion order on the local scale can be investigated using tech-
et al. provide a more comprehensive review of techniques to niques such as IR spectroscopy, Raman spectroscopy, 19F NMR,
characterize anion order.[24] A summary of the different types of pair distribution function (PDF) analysis, and diffuse scattering
anion (dis)order is given in Figure 6. experiments. Combining one or more of these methods is par-
In heteroanionic materials, an ordered local structure indi- ticularly useful in making anion-order assignments.
cates that the compound only contains one specific configura- Long-range ordering is understood to occur over the
tion of the heteroleptic polyhedral unit. This specifies the anion “average” structure as seen over multiple unit cells. This is
order about the metal cation, meaning that the compound distinct from local ordering because structures with locally
would exhibit exclusively one type of [MO6-xQx] unit, but not ordered polyhedral units can still show disordered anions in the
more than one. At the opposite end of the ordering spectrum, long-range structure. (Note that the opposite is not true; disor-
polyhedral disorder occurs when multiple polyhedral units are dered local units must always have long range anion disorder.)
observed on the local scale. For example, NbO2F exhibits local Long-range ordered anions occur when each anion site is fully
anion order (OOFOOFOOF) along columns in the 〈001〉 occupied by one anionic element. Descriptions of disordered
directions with no correlation between columns, which allows systems come in few different flavors. In a fully disordered
for [MOF5], cis-[MO2F4], and fac-[MO3F3] polyhedral configura- system, all anion sites have equal fractional occupancies. In a
tions in the structure.[119] We refer to this scenario as a HAM partially disordered system, one or more anion sites are fully
exhibiting heteroleptic polyhedra with fully disordered anion occupied and the other sites are occupied by equal fractional
sites. The last flavor of anion order involves dynamic disorder, occupancies. In a preferentially disordered material, all anion
which falls between the fully ordered and fully disordered sites are fractionally occupied but the sites would have different
extremes. Dynamic disorder in a HAM consists of ordered fractional occupancies. Last, in fully disordered materials, all
polyhedral units, but the anion sites appear disordered because anion sites have the same fractional occupancies of the con-
the polyhedral units rotate or vibrate on a timescale faster than stituent ions. Long-range order is typically assessed with X-ray
the measurement. This is seen in Rb2KTiOF5, where Raman and neutron diffraction. Characterizing the anion sublattice
Figure 6. Schematic anion order and anion disorder on the local (polyhedral) and long-range structure (multiple unit cells): The first row illustrates
different types of anion (dis)order on the local scale. The second row represents the different types of anion (dis)order on a long-range (averaged)
structure, where each disc represents a pie chart illustrating the ordering statistics for multiple anion sites based on averaging over multiple unit
cells. An example of partially ordered long-range structures is Sr2ScO3F, where the equatorial anions are always oxide and the apical anions exhibit a
50/50 oxide/fluoride mixed occupancy.[84] We note that disordered heteroleptic polyhedra will always exhibit disorder in the long-range structure, but
structures with fully ordered heteroleptic polyhedra may or may not exhibit long-range disordered structures.
with X-rays is particularly difficult in oxynitrides and oxyfluo- processing–structure relationships for anion order remain in
rides because the electron density surrounding the anions is their infancy. As previously discussed, many strategies rely
very similar. Anion order can sometimes be determined using on interactions from the A-site cations to direct the polyhedral
a combination of structure refinements from high-resolution units. For example, in Na1.5Ag1.5MO3F3 (M = Mo, W), the
X-ray diffraction (single crystal or powder) and bond valence bonding preferences of the A-site cations are used to direct
sums,[121] but this typically is only successful for structures with the anions of the [MO3F3] octahedra.[124] The structure adopts
fully ordered anions. Unlike X-rays, neutrons can distinguish a distorted LiNbO3 structure and the hard (Na+) and soft (Ag+)
oxygen and nitrogen, making it a common technique in oxyni- cations drive the orientation of the [MO3F3] octahedra such that
tride research.[63,87,93] the Na+ are exclusively coordinated to fluoride ions and Ag+ to
oxide, resulting in a fully anion ordered structure.
Chemical pressure is also being investigated as an approach
4.2. Synthetic and Computational Strategies to Achieve to achieve anion order. Recent investigations into the
Anion Order Ba1-xSrxTaO2N series of perovskite oxynitrides show a cross-
over from 3D to 2D anion disorder as x increases.[125] The sta-
Synthesizing materials with multiple anions presents new bilization of the 2D phase is analogous to the stabilization of
challenges compared to typical homoanionic synthesis. Heter- planar structures for aromatic organic molecules, where elec-
oanionic materials are often metastable owing to the increased tron delocalization stabilizes their shape; in the case of a 2D
entropy from occupying the anion sublattice with two different anion disorder with cis-[TaO4N2] octahedra, the TaN bonds
anions; therefore, methods beyond standard solid-state syn- must form rings in the 2D planes. The stability of these rings is
theses, such as hydrothermal synthesis, may be required to pro- then sensitive to the shift in TaN bond lengths. Thus, the shift
duce the desired material. The most commonly used methods from 3D to 2D disorder is attributed to a lattice contraction as
to produce heteroanionic materials are listed in Table 1, and we x increases, which increases the TaN orbital hybridization and
refer the reader to more extensive reviews on the synthesis of stabilizes the 2D anion order.
HAMs.[24,122,123] However, the more difficult challenge lies in Another technique that may seem straightforward is topo-
ordering the heteroleptic polyhedra to produce a long-range tactic reduction to remove anions from specific sites and then
anion ordered material, which may be a requirement for the fluorinate/nitridate the vacancy-ordered material to produce an
appearance of the desired properties. Here, we highlight a few ordered HAM. To our knowledge, this has only been done suc-
different synthetic and computational strategies that have been cessfully once with the starting material Sr7Mn4O15 to produce
used to create or understand how to achieve anion order in het- Sr7Mn4O13F2.[126] This synthesis uses CaH2 in a low-temperature
eroanionic materials. topotactic reduction to remove some of the oxygen from the
Experimental strategies to achieve anion order in com- starting oxide material which produces the vacancy-ordered
pounds have been developed, although attempts to develop Sr7Mn4O13. This material is subsequently fluorinated using a
Table 1. Common synthetic routes to realize heteroanionic materials. A check mark in the different chemical bonding environments
corresponding synthetic method row and oxy-X column indicate that there is a published of the anions. For example, high-pressure
report of the synthetic method producing an oxy-X compound.
experiments were needed to obtain accurate
interatomic potentials in KNaNbOF5 from
Synthetic method Oxynitrides Oxyfluorides Oxysulfides
which subsequent MD simulations were car-
Bulk Solid state synthesis ✓ ✓ ✓ ried out.[131] Monte Carlo methods can also
Hydrothermal and solvothermal ✓ ✓ take into account temperature effects and
Nitridation/fluorination ✓ ✓ – are most often used to calculate transport
✓
phenomena in solids and to assess phase
Thin film Pulsed laser deposition
transitions (structural order, ferroic, etc.). In
Chemical vapor deposition ✓ ✓
heteroanionic materials, Monte Carlo simula-
RF sputtering ✓ ✓ tions have previously been used to confirm
the measured structure of locally ordered,
5% F2/N2 atmosphere to produce Sr7Mn4O13F2, in which the long-range disordered K3MoO3F3 given a set of constraints
fluorine occupies the vacant anion sites in Sr7Mn4O13. We note determined from electron diffraction studies.[119] A combination
that this method has been largely unsuccessful in producing of one or more of the aforementioned computational materials
ordered oxyfluorides from other vacancy-ordered structures, approaches is likely required to understand the full temperature,
such as brownmillerites. It typically produces a disordered het- pressure, and field dependence of structure–property relation-
eroanionic material, either by F replacing the same amount ships in heteroanionic materials.
of anion vacancies[127] or by a partial substitution of O with
F.[128,129] Results of fluorinated vacancy-ordered oxide thin films
also show that F substitution onto an O site is slightly more 5. Property Design and Discovery in Oxyfluorides
energetically favorable than occupying the vacant site,[130] sug-
gesting that even if anion-vacancy ordering could be controlled, 5.1. Magnetic and Electronic Transitions
fluorination of these vacant sites is not guaranteed.
In addition to experimental techniques, a variety of materials Phase transitions driven by changes in chemical composition,
computational tools can provide insight into the structural com- temperature, pressure, and magnetic fields are of broad tech-
ponent of heteroanionic materials and aid experimentalists in nological interest[11] because they offer access to different spin,
the synthesis of new materials. In addition to investigations of charge, and conductivity states. In this context, chemical doping
electronic structure, DFT has been used in combination with through a small amount of anion substitution has sought to
experiments to determine the ground states of HAMs.[131,132] induce or enhance electronic and magnetic responses in TMCs.
Given the difficulty in accurately characterizing the local and Insulator-to-superconductor transitions occur in Nd2CuO4[139]
long-range ordering of the anions, DFT can help elucidate if and Cd2Re2O7[140] upon fluorine doping, as well as in other
local and long-range anion orders are compatible with experi- oxyhalides such as (Ca,Na)2CuO2Cl2 with hole doping.[141] In
mental observations. It can also predict stable anion orders of designing magnetic oxyfluorides, researchers are limited to
novel heteroanionic materials and potential synthetic routes open shell transition metal cations (d1–d9). In practice, there are
to produce the desired phase. Recent studies have verified the few non-d0 oxyfluorides in the current literature compared to
accuracy of first-principles calculated Pourbaix diagrams,[133] the abundance of d0 Nb5+ and Ta5+ compounds. One avenue to
which can aid the synthesis of heteroanionic materials in hydro- obtain a dn electronic configuration in an oxyfluoride includes
thermal reactions or other syntheses in aqueous conditions. starting with a non-d0 transition metal or reducing Nb5+ and
Medium- and high-throughput techniques, which have shown Ta5+ to produce a magnetic HAM. In this section, we highlight
success in discovering novel materials with enhanced prop- one material from each approach and emphasize that these are
erties in oxides,[47] have also begun to be used in HAMs.[134] intended to be illustrative examples: Sr2CoO3F, which exhibits
Derivative structure algorithms such as enumlib[135–137] and spin multiplets, and an electronic phase transition in Nb2O2F3,
SOCCR[138] can be used to generate the large structure set of in which the niobium cations possess an average oxidation
potential anion orderings from which, high-throughput DFT state of +3.5 that leads to a charge-order instability.
calculations can be used to evaluate their stability. Difficulties To rationally achieve spin-state transitions, we start with a
in simulating HAMs with mixed occupancy will be discussed transition metal ion that can access multiple spin states of sim-
in later sections. ilar energies arising from crystal field splitting energy (CFSE),
Other computational methods include using molecular Hund’s exchange, and thermal energy. Co3+ and Fe2+ transition
dynamic (MD) simulations, which can model temperature and metal cations are ideal as they can access low- (S = 0), interme-
dynamical effects on longer time scales. MD has been used in diate- (S = 1), and high-spin (S = 2) configurations under a cubic
combination with experimental techniques and DFT to suc- crystal field (octahedral coordination). For example, Sr2CoO3Cl
cessfully determine the structure of high-temperature phases exhibits the layered m = 1 Ruddlesden–Popper structure with
in KNaNbOF5[131] and BaTaO2N.[56] However, we note that this corner-connected heteroleptic [CoO5Cl] = ∞2 [CoO4/2′O1/1′Cl1/1′ ]
method requires suitable atomic potentials exist to describe units.[142] The terminal chloride anion in the octahedral unit
interatomic interactions. Although ab initio MD methods forms a relatively long CoCl bond such that the polyhedra
(AIMD) can be performed, most MD simulations use empir- are closer to square pyramids than octahedra in the structure.
ical potentials, which may have difficulty in capturing the The layered crystal habit and the reduced coordination number
stabilize the high-spin state, limiting access to a spin-state tran- allows for short Nb–Nb distances (≈2.57 Å) and the units are
sition and supporting a transition from short-range 2D spin then linked though shared vertices to produce a quasi-2D struc-
correlations to long-range 3D order.[143] Additional perturba- ture similar to the homonanioic oxide ζ-Nb2O5. Although the
tions to either the chemistry or structure (bond lengths) of the heteroleptic units are likely ordered, the site specificity could
building unit are required to achieve a transition to S = 0 or 1. not be determined using their X-ray diffraction methods.
Increasing the ligand strength from Cl- to F- in the spectro Temperature-dependent magnetic measurements show an
chemical series increases the CFSE, which could favor lower increase in the magnetic susceptibility upon cooling from a
spin configurations, e.g., in the oxyfluoride Sr2CoO3F. The paramagnetic S = 1/2 insulating state with a precipitous drop
constituent polyhedra forming this structure are similar to below 90 K, indicating a transition that quenches the magnetic
the oxychloride, with octahedral ∞2 [CoO4/2′O1/1′F1/1′ ] units and moment (S = 0). The quenching of the moment resembles the
the fluoride ions also located at the terminal apical sites.[52] formation of a spin-gap, typically seen in spin-Peierls mate-
Although the heteroleptic [CoO5F] octahedra are ordered, par- rials, and coincides with the observed semiconductor-to-metal
tial ordering of the long-range structure occurs with a 50/50 transition in the transport data. Below 90 K, Nb2O2F3 single
O/F occupancy on the apical sites. Magnetic susceptibility crystals transition from monoclinic (I2/a) to triclinic (P 1) sym-
and electrical resistivity measurements reveal that Sr2CoO3F metry and the loss of a the body-centering operation permits
is an antiferromagnetic insulator with a Néel temperature, two inequivalent Nb2X10 dimers with dissimilar Nb–Nb bond
TN = 323 K.[144] Because the octahedra are locally ordered, the lengths in the triclinic structure (Figure 7a). The dissimilar
Co ions off-center, forming [CoO5] square pyramids such that bond lengths suggest a charge density wave state emerges
the CoF (≈2.48Å) bond is weak, but nonetheless shorter than from the localized Nb dimerized state according to 2[Nb2]7+
the Co–Cl distance (≈3.10 Å) in the isoelectronic oxychloride. (semiconducting) → [Nb2]6+ + [Nb2]8+ (semimetallic), where
Upon increasing hydrostatic pressure, the CoF bond length the different “charge ordered” [Nb2]6+ (d2) and [Nb2]8+ (d1)
shortens gradually to transform the [CoO5] square pyramids dimers have double and single bonds, respectively. Owing to
into [CoO5F] octahedra without a symmetry change to drive a the orbital overlap of these dimerized molecular orbitals in
spin-crossover transition.[145] The high spin Co3+ cation (S = 2) momentum space, the material transforms into semimetal
gradually evolves to a low-spin state (S = 0) at 12 GPa similar state upon cooling.
to the well-known spin-crossover transition in the homoan-
ionic TMC LaCoO3. The anion sublattice plays an important
role in the spin crossover transition in the heteroanionic oxy- 5.2. Acentric Functionality
fluoride because the enhanced CFSE is due to the changes in
Co-ligand covalency. This leads to abrupt changes in the long In order for materials to exhibit properties such as piezoelec-
apical Co(O/F) bond lengths and in-plane OCoO bond tricity, ferroelectricity, and second harmonic generation (SHG),
angle above 10 GPa.[145] Such anisotropic pressure effects on it is necessary that they crystallize in a noncentrosymmetric
the electronic structure are difficult to achieve in homoanionic space group.[148] Although noncentrosymmetry is common
analogues. mathematically, i.e., 16 out of 32 crystallographic point groups
For transition metal cations with d1 and d2 electron configu- are either polar or chiral (21 are noncentrosymmetric), less than
rations, temperature controlled electronic MITs often occur 20% of known inorganic materials exhibit polar or chiral sym-
when the correlation strength is comparable to or greater metries.[149] Heteroanionic materials are attractive because of
than the bandwidth of the compound. Early transition metals their inherently polar polyhedral units; in particular, the study
such as Nb4+ and Nb3+ exhibit orbital degeneracies and strong of oxyfluoride materials that possess the octahedral hetero-
metal–metal bonding, which can be utilized to design electronic leptic units [MOxF6-x] (x = 1, 2, 3) where M is a d0 early transi-
transitions relying on charge fluctuations from the instabilities tion metal has intensified over the last three decades.[69,150,151]
derived from formally mixed-valence cation configurations.[146] Despite exhibiting building units with large local dipoles (e.g.,
The charge fluctuations will often support a metallic state and fac-[MoO3F3] has a dipole moment of ≈6.1 debye[152]) only a few
the insulating phase will emerge as the electrons localize over oxyfluorides are found in noncentrosymmetric structures. This
one or more (atom-center or bond-centered) sites in the crystal is due in large part to our limited knowledge of the mecha-
due to U, which leads to a gap in the electronic structure and nisms that control the cooperative assembly of the units and
often crystal symmetry breaking. The design of these types of the tendency for order–disorder transitions.
MIT materials requires combining cations with instabilities to Aligning the assembly of polar polyhedral units to a non-
the ordered state that are not so strong that the metallic state is centrosymmetric structure will generate a large polarization,
never accessible. One avenue to realize such materials is to use however we note that this polarization is nonswitchable under
reduced oxides, which can be achieved by anion control rather electric fields. As of this publication we are unaware of any suc-
than through (co)substitution of cations. cessfully switched polar oxyfluorides. The measured ferroelec-
To this end, Tran et al. reduced Nb5+ (d0) to produce the tric hysteresis loop of Na3MoO3F3, which crystallizes in the R3
magnetic oxyfluoride Nb2O2F3 using a flux growth synthesis space group is a “banana,” thus it does not conclusively indicate a
method known for producing reduced Nb compounds.[147] The true electric-field-induced polarization reversal.[75,153] Because the
room-temperature crystal structure is monoclinic (I2/a) with a polarization arises from the order of the anions in the lattice,
fully disordered anion sublattice and [Nb2O4F6] dimeric units possible switching mechanism would require rearrangement
consisting of two NbX6 (X being the ligand) octahedra that are of ions through some kinetic mechanism. Moreover, the
collapsed onto each other by sharing edges. This building unit measured polarization for polar oxyfluorides is typically small
Figure 7. Electronic and optical property control in heteroanionic oxyfluorides: a) Formation of the molecular orbitals from the high-temperature
monoclinic and the low-temperature triclinic phases in Nb2O2F3. The [NbO3F3] polyhedra shown in the upper right exhibit cooperative distortions with
symmetric metal–anion bond stretching in the charge ordered state. b) The transmittance spectra of the deep-ultraviolet nonlinear optical materials
β-BaB2O4 and KBe2BO3F2. The inset shows the KBe2BO3F2 crystal grown for these measurements. c) The structure of KBe2BO3F2, where the [BeO3F]
tetrahedra link together with a [BO3] borate network through a shared oxide ion. a) Adapted with permission.[248] Copyright 2016, Elsevier. b,c) Adapted
with permission.[166] Copyright 2009, Springer Nature.
compared to ferroelectrics like BaTiO3. The approximated spon- anionic group theory, the design of efficient SHG-active crystals
taneous polarizations (Ps) of Na3MoO3F3 and KNaNbOF5 are requires strong uniaxial orientational alignment of polar ani-
Ps = 0.021 µC cm−2 (ref. [75]) and Ps = 0.21 µC cm−2 (ref. [154]) onic units, seemingly playing to the strength of ordered oxyflu-
respectively, compared to Ps = 26 µC cm−2 in BaTiO3.[155] Piezo- orides.[157] Indeed, noncentrosymmetric oxyfluorides routinely
electric strain measurements found a d33 value of ± 6.3 pC N−1 display SHG responses rivaling crystalline quartz, however few
for KNaNbOF5. Although larger than α-quartz, the response is demonstrate phase matching, which is necessary to achieve
small compared to industrial standards such as lead zirconate highly efficiently nonlinear optical processes.[158] For instance,
titanate (PZT) where the d33 component of the tensor can be as NaVOF4(H2O) and NaVO2-xF2+x originate from identical rea-
large as ± 480 pC N−1.[156] gent mixtures, but are synthesized at different temperatures.
Interestingly, noncentrosymmetric oxyfluorides have found Although both display SHG responses, only NaVO2-xF2+x is
greater utility in SHG applications. According to Chen’s phase matchable.[159]
A particularly active research area focuses on synthesizing anion electronegativity; in other words, (oxy)nitrides would
NLO crystals for deep-ultraviolet (deep-UV) frequency conver- emit the highest wavelength of light, oxides would be slightly
sion for use in semiconductor photolithography, attosecond lower, and (oxy)fluorides would be the lowest. As discussed in
pulse generation, and advanced instrument applications.[160–164] Section 5.1, the choice of ligand affects the crystal field split-
For noncentrosymmetric crystals to be efficiently used in ting between the highest and lowest d orbital. In phosphor
deep-UV NLO applications, the following attributes are neces- materials, the distortion of the coordination geometry about the
sary: i) wide bandgap, ii) large SHG response, iii) moderate activator ion may have a larger effect on the CFSE. Overall, an
birefringence, iv) high laser damage threshold, and v) large oxyfluoride structure will likely blueshift the emission spectra,
single crystals.[160] Currently, many of the best performing UV though it is dependent on the degree of anisotropy of the acti-
NLO materials are borate crystals.[163] However, the incorpora- vator ion coordination. Additional properties needed for effi-
tion of boron-oxide anionic groups also has a tendency to induce cient solid state lighting, such as quantum efficiency (QE) and
a redshift in the absorption edge, thus reducing the possibility good thermal stability, are largely determined by the structure
for deep-UV applications.[163] Perhaps the most promising pure of the host lattice.
oxide borate was β-BaB2O4 owing to a large birefringence of To investigate the effects of fluoride substitution in a phos-
0.1127.[165] However, β-BaB2O4 exhibits a highly anisotropic phor material, Seshadri et al.[175] studied solid solutions of
thermal expansion and is only transparent down to 189 nm.[160] the anion-ordered oxyfluoride Sr3AlO4F and Sr3SiO5 as hosts
As a result β-BaB2O4 cannot directly produce deep-UV coherent for Ce3+ activator ions. These materials are isostructural and
light by second-harmonic generation.[166] charge balanced with fluoride substitution though a stoichio-
The first suitable deep-UV birefringent crystal was the metric substitution of the B-site cation. The resulting phos-
oxyfluoride KBe2BO3F2 (KBBF) engineered by Chen et al.[167] phor materials, Sr2.975Ce0.025Al1-xSixO4+xF1-x (SASF:Ce3+),
Here, the addition of fluorine aids in shifting the band edge emitted yellow-green light, had high quantum yield values,
further into the deep UV region (Figure 7b).[168] KBBF has and tunable excitation and emission wavelengths with
relatively large SHG coefficient, moderate birefringence, a fluorine content. 19F NMR confirmed the fluorine sits in
bandgap of ≈8.3 eV, and exhibits phase matchability over a a single crystallographic site in all compositions and con-
wide range of wavelengths. In addition, KBBF has a high firmed the oxyfluoride end member has a fully ordered
damage threshold and relatively high thermal conductivity.[166] long-range structure. The excitation wavelengths range
The excellent NLO properties of KBBF stem from the 2D from 390 to 450 nm with increasing x (or decreasing F con-
2
∞ [(BeO3/(2′+1′ )F1/1′ )2 BO3/(1′+2′ ) ] layers, which are composed of tent, Figure 8a), which agrees well with excitation sources
[BO3] and [BeO3F] units (Figure 7c).[164] However, this layered in LED chips. The emission spectra in these materials were
morphology leads to a major shortcoming of KBBF: difficulty in generally broad (comparable to commercial materials) and
growing large single crystals.[169,170] Moreover, the high toxicity the peaks ranged from 474 to 537 nm with increasing x. As
of beryllium oxide used during synthesis places limitations on expected, a redshift in emission spectra occurs with a
the practical use of KBBF in many technologies. These chal- decrease in fluoride content. The crystal field splitting also
lenges have motivated the search for alternative oxyfluorides contributes to the increased redshift with decreased fluorine
and other heteroanionic materials with improved properties for content. Somewhat surprisingly, coordination about both
NLO application.[162–164,169,171,172] This research has led to many Sr sites becomes increasingly anisotropic as the fluoride
new and interesting phases including Na3Ba2(B3O6)2F, which content decreases. Room-temperature QE measurements of
can be grown as large single crystals and exhibits large birefrin- the oxyfluoride and oxide end-members shows that the oxy-
gence (Δn = 0.0750−0.2554) from the IR (3.35 µm) to the deep fluoride has a higher QE (83% and 62%, respectively), though
UV (175 nm) range.[173] this only increases monotonically until x = 0.5, which has a
maximum QE of 85%. Previous work on a related compound
has attributed this to the softer phonon modes associated
5.3. Phosphors for Solid-State Lighting with the fluorine atoms.[176] Thermal quenching of QE is also
generally diminished in compositions with more fluoride,
To design new heteroanionic phosphors for solid-state lighting, for the same reasons. Similar trends in fluoride content and
the methodology must be changed slightly because the coordi- excitation wavelength, emission wavelength, QE, and thermal
nation environment around the activator ion, rather than the quenching have been obtained from other oxyfluoride solid
transition metal, is key in understanding the relevant prop- solutions.[177]
erties in these materials. Typical activator ions in phosphor
materials are Ce3+ or Eu2+ because the transition between 4f
and 5d states is largely responsible for the down conversion of 5.4. Energy Storage Materials
light.[174] Additionally, activator ion–ligand polyhedral units are
rarely octahedral, tetrahedral, or other standard polyhedra; they The benefits of fluoride substitution in battery materials can
typically sit on the A-site owing to their large size. In typical be initially assessed with Vegard’s law. Assuming oxyfluorides
phosphor materials, the principle governing the shift of emis- will lie somewhere between its oxide and fluoride end mem-
sion spectra is the centroid shift and crystal field splitting in bers, fluoride battery cathode materials feature higher (theo-
the 5d states. The centroid shift, or the change of the 5d levels retical) specific capacities and higher reduction potentials
because of a change in interelectron repulsion, generally shifts compared to oxides. However, they also suffer from worse
downward (redshifting the emission spectra) with decreasing electrode cycle life, lower conductivities, and large hysteresis
Figure 8. Heteroanionic oxyfluorides for lighting and energy applications: a) Excitation and emission spectra of the solid-solution phosphor
Sr2.975Ce0.025Al1-xSixO4+xF1-x with various x values indicated. The Sr1X8 and Sr2X10 polyhedra looking down the [100] direction show the change in coordina-
tion environment (right inset). Light gray, black, orange, and green spheres represent Sr1, Sr2, O, and F atoms, respectively. Fluoride exchange leads to
a decrease in peak excitation/emission wavelength with increase in fluoride content (lower panel). b) Theoretical capacities of Mn-redox based cathode
materials with decreasing oxidation state. c) Voltage profiles and capacity retention of Li2Mn2/3Nb1/3O2F when cycled from 1.5 to 4.6 V at 20 mA g−1.
a) Adapted with permission.[175] Copyright 2011, Wiley. b,c) Adapted with permission.[183] Copyright 2018, Springer Nature.
of lithiation/delithiation voltages, which makes them poor in situ XRD and EPR reveal an Ag+/Li+ displacement lithia-
candidates for commercial applications.[178,179] The goal of tion mechanism occurs from Li0Ag4V2O6F2 to Li≈4.0Ag4V2O6F2
oxyfluoride research in battery materials has therefore been and appears to be nearly entirely irreversible. The reversible
to maintain the higher capacities and potentials of fluorides capacity arises from a redox mechanism (V5+ to V3+), but it
while avoiding their pitfalls. To generate novel oxyfluorides for is accompanied by an unfavorable decrease in the cathode
battery materials, the transition metal cation must have mul- polarization.
tiple attainable oxidation states to enable the necessary redox Fluorine can also be used to stabilize low-valence transi-
reactions. Here, the coordination of the polyhedra facilitates tion metal for improved capacity in Li-ion cathode materials.
the anion order in the structure. For intercalation batteries, A new strategy for high capacity Mn-based Li-ion cathode
which lithiate through insertion of Li into the crystal, the units materials has been to stabilize the Mn2+ state, such that a
are typically assembled into a layered structure-type. Many double oxidation reaction can be triggered and achieve high
oxyfluorides investigated as battery cathodes phase separate or theoretical capacities (Figure 8b) without O redox. Although O
decompose as they are charge and discharged, indicating that redox can improve the capacity of the materials, it also causes
the materials are likely lithiating the fluorine through a conver- O loss, which results in voltage and capacity fade. Lowering
sion mechanism.[180] the Mn valence can be achieved through incorporation of a
Silver vanadium oxyfluorides such as Ag4V2O6F2 (SVOF) high-valent cation and by substitution of O2− with F−. Recent
have been proposed as cathode materials for implantable car- experiments on Li2Mn2/3Nb1/3O2F and Li2Mn1/2Ti1/2O2F show
dioverter defibrillator in primary batteries. To improve over high reversible capacities of 238 and 259 mAh g−1 (Figure 8c),
the current industry standard, Ag2V4O11 (SVO), new materials respectively, with little O redox.[183] Additionally, X-ray absorp-
need higher volumetric capacities and greater capacities over tion spectroscopy measurements show that the electro
3 V. Fluoride substitution is an ideal candidate for this applica- chemical process is reversible with Mn2+ being fully recovered
tion because it generally increases the cell potential. Ag4V2O6F2 on discharge and minimal oxygen redox over electrochemical
contains isolated chains of corner connected [VO4F2] octahedra cycling.
and [VO4] tetrahedra, with Ag ions between the chains forming
a relatively open structure. Preliminary Li insertion electro-
chemical results as a primary cathode were promising; SVOF 6. Heteroanionic Materials Frontiers
exhibited a higher capacity above 3 V and a higher silver reduc-
tion potential (48 mAh g−1 and 300 mV, respectively, higher We conclude with an outlook on heteroanionic materials,
than SVO).[181] However, upon further investigation of SVOF discussing an incomplete set of challenges where their rich
as a secondary battery cathode, it was found that a nearly half chemical and structural landscape may both advance our
of the capacity is irreversible on the second charge, largely understanding of modern materials physics and chemistry and
owing to the irreversible Ag reduction.[182] A combination of spur further progress in materials synthesis and simulation.
6.1. New Insights into Older Materials and their Models tuning the Ni valence (orbital filling) for a 2D single-band elec-
tronic structure by changing the local atomic structure.[196,197] A
Electronic MITs are of particular interest to the oxide electronics key component to achieving a large orbital polarization relies
community[48] as they could be exploited to realize Mottronic- on creating an asymmetric local environment for the transition
based devices[184] in which charge carriers collectively rearrange metal cation. The crystal field can be tuned by anion selection
locally rather than move over finite length scales. The collective and through variations in the local anion (cis or trans) arrange-
response of a correlated electron system results in device char- ment on the polyhedral building units, suggesting large orbital
acteristics that are not achievable with traditional materials like polarizations are possible in heteroanionic materials without
main group semiconductors.[185–188] The electric field gating the need for complex heterostructuring or large epitaxial strains
of such a phase transition is a potential route to “steep slope” in homoanionic materials. For example, if one could stabi-
devices that operate at very low voltage. Beyond metal–insulator lize aligned trans-[NiO4F2] octahedra in a perovskite structure,
transitions, the formation of excitonic or other electronic con- a large orbital polarization may exist. In a related aspect, the
densates, and various transitions involving structural degrees of anion linkages also control how magnetic interactions are medi-
freedom are of interest. Indeed, entirely new switching para- ated, which is of keen interest to scaffolding lattices and chem-
digms and next-generation electronic materials will be needed. istries supporting unusual magnetic states.[104] Such phases
Among the most promising candidates are TMCs;[189] however may be obtained for U > W and spin–orbit coupling quenches
they face numerous challenges. A key challenge for the prac- any orbital degeneracies that would be susceptible to first-order
tical realization is developing MITs that respond to realiz- Jahn–Teller distortions. Thus, exploiting multiple anions for
able external stimuli, i.e., practically achievable voltages.[190] control over the orbital valence filling, crystal field energies, and
Overcoming this challenge will require going beyond existing magnetic interactions offers a new avenue towards electronic
materials that function in multiple electronic states, which property control in correlated materials.
could be designed by changes to the anion chemistry.
The electronic transition in the AB2 rutile structured
homoanionic oxide VO2 is routinely exploited for the afore- 6.2. Materials for Novel Phenomena Enabled by Broken
mentioned applications. It is one of the oldest MIT compounds Inversion
studied,[191] and yet remains potentially the most controversial
in terms of the origin of the MIT. In this context, heteroanionic The absence of inversion symmetry is an important charac-
materials offer the ability to resolve open questions in oxides teristic that enables many ferroic responses[198] as well as new
exhibiting correlated electrons which presently are unsolvable quantum states of matter.[199,200] Pierre Curie was among the
(or irreconcilable) owing to the restrictions imposed by the first to state that “Asymmetry is what creates a phenomenon.”[201]
cation chemistry (size and valence). An article by Hiroi has Today this insight is exploited to design new NLO materials
called into question traditional ideas regarding the role of for quantum communications and to discover new topological
Peierls distortions, electron correlation (Mott–Hubbard physics), phases from quantum transitions driven by changes in sym-
and has emphasized the role of metal–metal bonding and local- metry, topology, and metallicity.[202] One can transform from an
ized electrons in the distorted low-temperature phases of these insulator to a metal in which each phase exhibits distinct topo-
materials.[192] Characteristic of the more extended d-states of logical character. Weyl semimetals are topological metals that
early transition metals, these systems tend to localize partially exhibit two bands that approach linearly and touch at points on
filled d-levels through the formation of metal–metal bonds the Fermi surface. This feature in the electronic band structure
and molecular orbital crystals when permitted. Rather than requires that either the material is magnetic (exhibits broken
assessing various models for the MIT with respect to perturba- time-reversal symmetry) or is noncentrosymmetric (broken
tions on the A site (doping with Cr or substituting with Nb), inversion), otherwise the electronic bands would be doubly
heteroanionic materials design enables the ability to mimic degenerate. The carriers arising from this crossing are no longer
vanadate physics in V-free compounds by selecting neighboring simple electrons, but rather are quasiparticles called massless
transition metals on the periodic table and exchanging the oxide chiral fermions. Although there has been considerable progress
anion for another p-block element (e.g., TiOF, CrON). Provided in the discovery and characterization of these materials,[203]
the resulting heteroanionic material forms in a rutile-like struc- finding and designing 3D Weyl semimetals are challenging for
ture, the dimerization, metal–metal bonding, and electronic two reasons distinct from their asymmetric constraints. First,
correlation physics could be disentangled. the Weyl band-crossings occur away from the chemical poten-
The transformation of a normal metal or doped insulator tial and second, the Weyl states are often entangled with other
to a coherent superconductor relies on a delicate balance of bands. Demonstrating the chiral nature and related properties
multiple energy scales maintained by the low-energy orbital is challenging unless the material can be doped into a regime to
structure and crystal structure. The high-temperature supercon- make the crossing occur at the correct band filling. Because
ducting cuprates, for example, exhibit layered structures with most proposed Weyl semimetals rely on 4d and 5d transition
square planar CuO2 sheets and hole-doping, which results in a metals where spin–orbit interactions are nontrivial, heteroan-
2D Fermi surface with partial hole occupancy corresponding to ionic materials offer a solution as intermediate U/W ≈ 1 values
large d x 2-y 2 orbital polarization.[193] Efforts over the last decade of correlation can be obtained by anion exchange. For example,
have sought to mimic these orbital polarizations in copper- homoanionic oxide pyrochlore iridates are proposed to be proxi-
free compounds, focusing largely on layered nickelates[194] and mate to a Weyl semimetallic phase, and their stability may be
perovskite nickelates in artificial structures[195] with the aim of tuned by anion exchange or insertion.
Another unique materials class without inversion sym- multiferroics (Ni3B7O13I) reported by Hans Schmid[219] and
metry are compounds that are simultaneously band conduc- today their complex conducting domain wall structures can
tors. These materials exhibit a well-defined Fermi surface that be controlled by applied electric fields.[220] Searches for new
does not arise from degenerately doping a noncentrosym- improper ferreoelectrics may benefit from focusing on hetero
metric semiconductor. These materials are now referred to anionic materials where multiple polyhedra can interact to lift
as noncentrosymmetric metals for which a subset are polar inversion symmetry.
metals,[204] and are proposed to host unconventional properties, In addition to coupling multiple polyhedral distortions, the
including skyrmions and other complex spin textures,[205] short-range and long-range assembly of heteroleptic polyhedra,
giant NLO responses,[206] dynamical piezoelectricity and which are important in obtaining useful ferroelectric responses
magnetopiezoelectricity,[207] among others.[208] Recent efforts in polar structures, can be tuned by changing the synthesis
have focused on designing and realizing oxide based polar strategy. For example, bulk ceramics of SrTaO2N exhibits local
metals for which there are very few examples,[204,209,210] with order among cis-[TaO4N2] octahedra and displays ferroelectric
several opportunities in oxide-derived ABO3 perovskites (such hysteresis owing to the cooperative alignment of the acen-
as HgPbO3[211]) and A2B2O7 pyrochlores, including Cd2Re2O7. tric heteroleptic units.[221] The nanoscale arrangement of
Understanding how and why these polar phases exist in mate- cis-[TaO4N2] polyhedral connectivity lifts inversion symmetry by
rials with free electrons that should screen long-range electro- linking the [TaO4N2] octahedra through a common axial nitride
static interactions, which stabilize cooperative electric dipoles anion and rotating the nonshared nitride anion by 90° from
remains an open question. By tuning the electronic and atomic the adjacent octahedra.[222] This bulk preferred cis arrangement
structure through anion exchange, new models may be formu- can be transformed to a polar trans configuration by growing
lated that would lead to a better understanding of the short- and compressively strained thin films of SrTaO2N on (001) perov-
long-range interactions underlying the polar metallic state. skite SrTiO3.[96] Experimentally, it was suggested that both local
For example, oxide exchange with sulfur in Cd2Re2O7-xSx and anion orders (cis -and trans-[TaO4N2]) exist along with variations
A2Re2O7 (A = Ca and Pb),[212] show that the A-site cation sub- in the assembly of the units on a large length scale (or mixed
stitution and anion interactions govern whether inversion sym- phase) that give only short-range order in the material. The role
metry is broken in the metallic phase. Analogous experiments of elastic strain in these films is to bias the preference of one
on the isoelectronic dielectric analog Cd2Nb2O6S show that phase (alignment of the ordered polyhedral unit) relative to that
S increases the critical temperature at which inversion sym- of other competing configurations. Owing to the strong phase
metry is broken by enhancing the covalent metal–ligand bonds, competition, as the energy scale for the various configurations
favoring polar displacements.[213] Although a dearth of homoan- is quite small, these oxynitrides exhibit relaxor ferroelectric
ionic polar metals appears to be the circumstance in which the behavior and high dielectric permittivities arising from the lack
community presently finds itself,[214] heteroanionic materials of ideal (long-range ordered) [TaO4N2] connectivity. Interest-
may change the future status quo. ingly, relaxor-type behavior is obtained without the chemical
New heteroanionic ferroelectrics are not expected to display inhomogeneity as in most homoanionic materials, which sug-
the same type of “proper” or soft-mode ferroelectricity observed gests that heteroanionic materials could be exploited to realize
in BaTiO3 because the acentric heteroleptic polyhedra are likely digital relaxors with morphotropic phase boundaries and large
to arrange in antiparallel alignments to preserve global inver- piezoelectric responses by tuning the coherence of polar nano-
sion symmetry. Because these compounds can exhibit nonide- domains derived by changes to the short-range connectivity
alities related to octahedral distortions, geometric (improper of ordered multianionic polyhedra. They also can be used as
or hybrid improper) ferroelectric mechanisms are likely to be a materials class to answer unresolved questions governing
more pervasive in heteroanionic materials. These more complex relaxor-like phenomena observed in a broad range of properties.
forms of ferroelectricity involve the activation of polar dis-
placements by coupling a hard infrared-active mode to
multiple polyhedral rotation or distortion modes.[215] Applying 6.3. Challenges to Prediction and Simulation
these mechanisms for ferroelectric heteroanionic materials design
requires examining how symmetry reductions and multimode The computational design of functional heteroanionic mate-
couplings occur in the presence of ordered heteroleptic poly- rials requires the structural phase space be sampled accurately,
hedra.[138,216] Although the structural complexity may appear because structure is a necessary input for every property pre-
less appealing for property design, one should remember that diction based on an electronic structure method. Phase stability
early discoveries in ferroelectricity occurred outside of simple assessment is vital for making progress in the field, if a mate-
homoanionic compounds. Among the first identified ferro- rial is not thermodynamically or dynamical stable in the com-
electrics were heteroanionic boracites[217,218] with chemical for- puter, then it is often unlikely to be realized in the laboratory.
mula A3B7O13Q (A = divalent 3d transition metal Cr–Zn or Mg; Today, a number of methods now exist to sample such configu-
Q = Cl, Br, I). These materials exhibit a corner-connected borate rational spaces, which were originally pioneered for semicon-
([BO4] and [BO3]) network within which multianion [BO4Q2] ductor and metal-alloy design,[223] including cluster expansion
polyhedra link together through the halogenide Q anion, methods[224] and derivative structure generation methods
forming chains in all three directions. The polyhedral rotations based on random sampling, particle-swarm optimization algo-
lift inversion symmetry in the centrosymmetric cubic structure, rithms, global space-group optimization, and evolutionary
making these materials improper ferroelectrics.[215] In addition, algorithms.[225–228] Although these approaches have enabled
these compounds became the first family of magnetoelectric computational researchers to tackle a variety of problems, they
may require significant user involvement for heteroanionic necessary to describe the dielectric and thermal-transport
materials, which tend to maintain well-defined anion order properties of materials. A VCA for a 50% O, 50% N ion has
on multiple polyhedra. Recent attempts have been made to been created and used to calculate the stability of Sr2TaO3N.[236]
address these issues[138] and additional alternative approaches Although this study compared the VCA and supercell methods
may rely on models for structures and properties obtained from with respect to dynamical stability calculations, no electronic
machine learning algorithms;[229–231] however, they have not yet properties were assessed. A thorough study comparing the cal-
been earnestly applied to heteroanionic materials. culated electronic structure using these methods is needed.
In addition, performing accurate DFT simulations on het-
eroanionic materials requires careful attention to additional
intricacies underlying the quantum-mechanical method. The 6.4. Toward Rational Synthesis
first involves a key component of the Kohn–Sham reformula-
tion of the many-electron Schrodinger equation into a set of Electronic structure design in heteroanionic materials relies in
single-electron equations with mean-field like interactions. part on control of anion order on the homoleptic or heteroleptic
The accuracy (and often efficiency) of all DFT-based methods polyhedral units and their long-range assembly. Depending on
relies on the exchange-correlation functional, which adds the the property of interest, disorder of the multianion sublattice
necessary energy interactions accounting for the quantum could limit materials performance. Whether the polyhedral
nature of interacting electrons. The approximations come in units are required to be the active species present in solution-
a variety of flavors, starting from those like the LDA to more based synthesis of HAMs remains largely unknown;[237]
complex hybrid functionals, which contain (portions of) exact although it seems reasonable that the concentration and avail-
Fock exchange.[232] The strength of the chemical bond between ability of the units during synthesis is likely to play a key role
a metal and anion can vary considerably with choice of the in controlling anion order. While anion-ordering principles
functional,[233] which has important implications on predicting exist for a handful of anion-substituted materials, the details
heteroanionic materials stabilities because multiple bond envi- of anion order–disorder phenomenon are generally under
ronments are present. For example in oxyfluorides, bonding developed. Researchers have identified important factors that
can be both highly covalent and ionic over a subnanometer influence anion ordering, such as electrostatic interactions and
length scale. chemical hardness (see Section 3.2), but quantitative assess-
Related to phase stability is whether such functionals can ments of these factors remain to be published. Additionally,
accurately describe the metastable structural landscape, since because a majority of the literature on anion ordering in oxyflu-
many metastable heteroanionic materials do not need to exist on orides has been on compounds with d0 transition metals, these
the convex hull connecting the homoanionic end members. The factors remain to be evaluated for d or f electron containing
ability to assess whether or not the heteroanionic material will materials.
decompose into simple homoanionic components is critical in Understanding the synthetic pathways to heteroanionic
guiding discovery efforts in the laboratory. At present, the energy materials, where a multitude of compounds are possible and
scale for metastable heteroanionic materials is unknown. None- subtle variations in pathway can impact phase stability, struc-
theless, efforts are underway to determine if existing functionals ture, and properties, is a challenge for the field. How does one
are sufficiently accurate to describe heteroanionic materials and go from precursor units to material products as selectivity in
whether new (semi)empirical or nonempirical functionals can their assembly dictates the final solid-state structure? One
be used to discriminate among different bonding behavior to avenue to explore pathway-dependent products in HAMs relies
accurately predict structures and properties.[234] on systematically studying the effects of different synthetic
Another aspect to consider concerns how to represent the methods on the product’s structure and properties. Regarding
anionic species in a heteroanionic material especially when the the structure, to what extent does the synthesis route control the
anion lattice exhibits random site occupancy (similar to a solid degree of anion order? Although some have noted that syn-
solution). One approach uses supercells compatible with the thetic methods have little to no effect on anion (dis)order of a
overall composition.[78] The anionic species coordinating the material, particularly in oxyfluorides,[82] there are studies which
metal in the heteroleptic polyhedra are then varied to mimic suggest otherwise. For example, Sr2FeO3F exhibits fully ordered
partial site occupancy. These methods can be quite accurate anion sites in the long-range structure and can be synthesized
since local interactions are accounted for but they are often using conventional and high-pressure solid-state syntheses.
computationally expensive. An alternative method uses the so- Tsujimoto et al. found that samples synthesized at high tem-
called virtual-crystal approximation (VCA) whereby a composite peratures and pressures (1800 °C and 6 GPa) showed 5%/95%
pseudopotential is used to represent a fictitious anion com- O/F mixed occupancy on the apical sites, suggesting that syn-
posed of partial oxygen and another p-orbital anion character theses at lower temperatures and pressures are desirable when
(e.g., 75% O and 25% F). How the averaging is performed can attempting to generate HAMs with ordered anion sublattices.
significantly influence the computational results,[235] although In addition, a key question to address is how are the mate-
the method has the advantage that only a primitive cell is rials that result from a synthetic reaction dependent upon the
required in the calculation. Whether or not the VCA can capture concentration of (or absence of) the relevant homoleptic and
the nuances involved in heterovalent anion exchange requires heteroleptic species which may ultimately combine in metath-
further investigation, as many physical properties are related to esis-like reactions? It may be necessary to shift from thermo-
derivatives of the total energy of the system. Accurate second- dynamic to kinetically controlled reactions.[238–240] To that end,
and third-order interatomic force constants, for example, are in situ experiments that directly observe materials evolution
during the course of synthetic reactions may provide the nec- of Northwestern University. N.C. and J.M.R. were supported by NSF
essary insight to allow for the selective making and breaking (DMR-1454688). This work benefited from numerous discussions with
of chemical bonds in reagents to assemble the heteroanionic students and collaborators for which there are too many to include herein.
materials. Such “panoramic synthesis”[241] may involve the use
of structural or spectroscopic tools based on X-ray radiation
and nuclear magnetic resonance (NMR) spectroscopies.[242,243] Conflict of Interest
Efforts focused on advancing and interfacing multiple charac-
The authors declare no conflict of interest.
terization techniques within reaction compatible containers to
probe chemistry could lead to synthesis-on-demand of theory-
predicted heteroanionic materials.
Spectroscopic characterization methods have been also been Keywords
suggested as a valid method of determining the local coordi- electronic structure, heteroanionic materials, materials design,
nation of metal–ligand polyhedra. Oka et al. used linearly oxyfluorides, transition metal compounds
polarized X-ray near-edge structure (LP-XANES) and electron
energy loss spectroscopy combined with scanning transmis- Received: August 14, 2018
sion electron microscopy electron (STEM-EELS) to reveal an Revised: January 16, 2019
increase in the N occupancy of apical sites in epitaxial thin Published online: March 12, 2019
films of Ca1-xSrTaO2N with increased compressive strain.
Previous studies using neutron diffraction failed to evaluate the
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Advanced Materials - 2019 - Harada - Heteroanionic Materials by Design Progress Toward Targeted Properties

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Materials Design www.advmat.de

Heteroanionic Materials by Design: Progress Toward

adding the oxy-prefix followed by the additional anion. HAMs

The essence of electronic structure design in TMCs is rooted

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