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Thermal expansion properties of solids are of fundamental interest and control of thermal expansion is important for practical applications but can be difficult to achieve. Many framework-type materials show negative thermal expansion when internal cages are empty but positive thermal expansion when additional atoms or molecules fill internal voids present. Here we show that redox intercalation offers an effective method to control thermal expansion from positive to zero to negative by insertion of Li ions into the simple negative thermal expansion framework material ScF 3 , doped with 10% Fe to enable reduction. The small concentration of intercalated Li ions has a strong influence through steric hindrance of transverse fluoride ion vibrations, which directly controls the thermal expansion. Redox intercalation of guest ions is thus likely to be a general and effective method for controlling thermal expansion in the many known framework materials with phonon-driven negative thermal expansion. The positive thermal expansion exhibited by most materials at increased temperatures is a severe issue for many high precision applications. Here, Xing and co-workers show that redox intercalation of Li ions into a ScF 3 framework offers effective control of the thermal expansion for this simple material.

The simple ABO 3 and A-site-ordered AA′ 3 B 4 O 12 perovskites represent two types of classical perovskite functional materials. There are well-known simple perovskites with ferroelectric properties, while there is still no report of ferroelectricity due to symmetry breaking transition in A-site-ordered quadruple perovskites. Here we report the high pressure synthesis of an A-site-ordered perovskite PbHg 3 Ti 4 O 12 , the only known quadruple perovskite that transforms from high-temperature centrosymmetric paraelectric phase to low-temperature non-centrosymmetric ferroelectric phase. The coordination chemistry of Hg 2+ is changed from square planar as in typical A-site-ordered quadruple perovskite to a rare stereo type with 8 ligands in PbHg 3 Ti 4 O 12 . Thus PbHg 3 Ti 4 O 12 appears to be a combinatory link from simple ABO 3 perovskites to A-site-ordered AA′ 3 Ti 4 O 12 perovskites, sharing both displacive ferroelectricity with former and structure coordination with latter. This is the only example so far showing ferroelectricity due to symmetry breaking phase transition in AA′ 3 B 4 O 12 -type A-site-ordered perovskites, and opens a direction to search for ferroelectric materials. There are few reports of ferroelectricity due to symmetry breaking transition in A-site-ordered quadruple perovskites. Here, the authors find one with phase transition from a high-temperature centrosymmetric paraelectric phase to a low-temperature non-centrosymmetric ferroelectric phase in a high pressure synthesized compound.

Resistivity measurements are widely exploited to uncover electronic excitations and phase transitions in metallic solids. While single crystals are preferably studied to explore crystalline anisotropies, these usually cancel out in polycrystalline materials. Here we show that in polycrystalline Mn 3 Zn 0.5 Ge 0.5 N with non-collinear antiferromagnetic order, changes in the diagonal and, rather unexpected, off-diagonal components of the resistivity tensor occur at low temperatures indicating subtle transitions between magnetic phases of different symmetry. This is supported by neutron scattering and explained within a phenomenological model which suggests that the phase transitions in magnetic field are associated with field induced topological orbital momenta. The fact that we observe transitions between spin phases in a polycrystal, where effects of crystalline anisotropy are cancelled suggests that they are only controlled by exchange interactions. The observation of an off-diagonal resistivity extends the possibilities for realising antiferromagnetic spintronics with polycrystalline materials. Recent work has demonstrated the potential of polycrystalIine antiferromagnetic materials for spintronics. Here the authors report evidence of magnetic phase transitions in a polycrystalline non-collinear antiferromagnet, which are explained by a phenomenological model with topological orbital momenta.

Magnetic order in most materials occurs when magnetic ions with finite moments arrange in a particular pattern below the ordering temperature. Intriguingly, if the crystal electric field (CEF) effect results in a spin-singlet ground state, a magnetic order can still occur due to the exchange interactions between neighboring ions admixing the excited CEF levels. The magnetic excitations in such a state are spin excitons generally dispersionless in reciprocal space. Here we use neutron scattering to study stoichiometric Ni 2 Mo 3 O 8 , where Ni 2+ ions form a bipartite honeycomb lattice comprised of two triangular lattices, with ions subject to the tetrahedral and octahedral crystalline environment, respectively. We find that in both types of ions, the CEF excitations have nonmagnetic singlet ground states, yet the material has magnetic order. Furthermore, CEF spin excitons from the tetrahedral sites form a dispersive diffusive pattern around the Brillouin zone boundary, likely due to spin entanglement and geometric frustrations. Some materials can display magnetic order despite having spin-singlet ground state on individual magnetic sites. This arises due to exchange interactions mixing excited crystal electric field states. Here, Gao et al study and example of such a system, Ni 2 Mo 3 O 8 , and find that crystal electric field states in both the paramagnetic and antiferromagnetic states exhibit dispersive excitations.

Control of negative thermal expansion is a fundamentally interesting topic in the negative thermal expansion materials in order for the future applications. However, it is a challenge to control the negative thermal expansion in individual pure materials over a large scale. Here, we report an effective way to control the coefficient of thermal expansion from a giant negative to a near zero thermal expansion by means of adjusting the spontaneous volume ferroelectrostriction (SVFS) in the system of PbTiO 3 -(Bi,La)FeO 3 ferroelectrics. The adjustable range of thermal expansion contains most negative thermal expansion materials. The abnormal property of negative or zero thermal expansion previously observed in ferroelectrics is well understood according to the present new concept of spontaneous volume ferroelectrostriction. The present studies could be useful to control of thermal expansion of ferroelectrics and could be extended to multiferroic materials whose properties of both ferroelectricity and magnetism are coupled with thermal expansion.

Iron-based superconductivity develops near an antiferromagnetic order and out of a bad-metal normal state, which has been interpreted as originating from a proximate Mott transition. Whether an actual Mott insulator can be realized in the phase diagram of the iron pnictides remains an open question. Here we use transport, transmission electron microscopy, X-ray absorption spectroscopy, resonant inelastic X-ray scattering and neutron scattering to demonstrate that NaFe 1− x Cu x As near x ≈0.5 exhibits real space Fe and Cu ordering, and are antiferromagnetic insulators with the insulating behaviour persisting above the Néel temperature, indicative of a Mott insulator. On decreasing x from 0.5, the antiferromagnetic-ordered moment continuously decreases, yielding to superconductivity ∼ x =0.05. Our discovery of a Mott-insulating state in NaFe 1− x Cu x As thus makes it the only known Fe-based material, in which superconductivity can be smoothly connected to the Mott-insulating state, highlighting the important role of electron correlations in the high- T c superconductivity. Whether an actual Mott insulator phase exists in iron pnictides remains elusive. Here, Song et al . demonstrate an antiferromagnetic insulator phase persisting above the Néel temperature in NaFe 1− x Cu x As, indicative of a Mott insulator, highlighting the role of electron correlations in high- T c superconductivity.

The structural and magnetic properties of the ThCr 2 Si 2 -type solid solution LaMn 2 (Ge 1− x Si x ) 2 ( x  = 0.0 to 1.0) have been investigated employing a combination of X-ray diffraction, magnetization and neutron diffraction measurements, which allowed establishing a magnetic composition-temperature phase diagram. Substitution of Ge by Si leads to a compression of the unit cell, which affects the magnetic exchange interactions. In particular, the magnetic structure of LaMn 2 (Ge 1− x Si x ) 2 is strongly affected by the unit cell parameter c , which is related to the distance between adjacent Mn layers. Commensurate antiferromagnetic layers and a canted ferromagnetic structure dominate the Si-rich part of the solid solution, whilst an incommensurate antiferromagnetic flat spiral and a conical magnetic structure are observed in the Si-poor part.

Solid solutions in the Ba(Pb1−xSrx)O3−z system were prepared by aliovalent substitution of Pb4+ by Sr2+ ions to investigate the effect of cation stoichiometry on thermal and electrical properties as x was varied between 0 and 0.4, in the temperature range 300–523 K. The starting compound, barium plumbate (BaPbO3), has a perovskite structure and is known to exhibit metallic conductivity due to an overlap of the O2p nonbonding and the Pb–O spσ antibonding band, which is partially filled by the available electrons. The large difference in the ionic radii between the Pb4+ and Sr2+ ions introduces significant strain into the (Pb/Sr)O6 octahedra of the perovskite structure. Additionally, charged defects are created on account of the different oxidation states of the Pb4+ and Sr2+ ions. Evidence of a metal to insulator transition (MIT) of the Mott–Hubbard type has been observed at a critical concentration of Sr2+ ions.

Rational design of technologically important exotic perovskites is hampered by the insufficient geometrical descriptors and costly and extremely high-pressure synthesis, while the big-data driven compositional identification and precise prediction entangles full understanding of the possible polymorphs and complicated multidimensional calculations of the chemical and thermodynamic parameter space. Here we present a rapid systematic data-mining-driven approach to design exotic perovskites in a high-throughput and discovery speed of the A2BB’O6 family as exemplified in A3TeO6. The magnetoelectric polar magnet Co3TeO6, which is theoretically recognized and experimentally realized at 5 GPa from the six possible polymorphs, undergoes two magnetic transitions at 24 and 58 K and exhibits helical spin structure accompanied by magnetoelastic and magnetoelectric coupling. We expect the applied approach will accelerate the systematic and rapid discovery of new exotic perovskites in a high-throughput manner and can be extended to arbitrary applications in other families.

Intrinsic polarization of ferroelectrics (FE) helps separate photon-generated charge carriers thus enhances photovoltaic effects. However, traditional FE with transition-metal cations ( M ) of d 0 electron in M O 6 network typically has a band gap ( E g ) exceeding 3.0 eV. Although a smaller E g (2.6 eV) can be obtained in multiferroic BiFeO 3 , the value is still too high for optimal solar energy applications. Computational “materials genome” searches have predicted several exotic M O 6 FE with E g < 2.0 eV, all thus far unconfirmed because of synthesis difficulties. Here we report a new FE compound with M O 4 tetrahedral network, KBiFe 2 O 5 , which features narrow E g (1.6 eV), high Curie temperature ( T c ~ 780 K) and robust magnetic and photoelectric activities. The high photovoltage (8.8 V) and photocurrent density (15 μA/cm 2 ) were obtained, which is comparable to the reported BiFeO 3 . This finding may open a new avenue to discovering and designing optimal FE compounds for solar energy applications.