In-Plane Chirality Control of a Charge Density Wave by Means of Shear Stress.

The transition metal dichalcogenide 1T-TaS exhibits a Charge Density Wave (CDW) with in-plane chirality. Due to the rich phase diagram, the Ferro-Rotational Order (FRO) can be tuned by external stimuli. The FRO is studied by Angle-Resolved Photoelectron Spectroscopy (ARPES), Raman spectroscopy, and Selected Area Electron Diffraction (SAED).

Temperature Induced, Reversible Switching of Ferro-Rotational Order Coupled to Superlattice Commensuralibity.

High-quality 1T-TaS crystals are investigated by angle-resolved photoelectron spectroscopy, Raman spectroscopy, and low-energy electron diffraction. The Ferro-Rotational Order (FRO) of the charge density wave switches configuration at the transition between the commensurate and the nearly commensurate phase. This process requires samples without built-in or externally induced strain.

Anionic Redox Topochemistry for Materials Design: Chalcogenides and Beyond.

Topochemistry refers to a generic category of solid-state reactions in which precursors and products display strong filiation in their crystal structures. Various low-dimensional materials are subject to this stepwise structure transformation by accommodating guest atoms or molecules in between their 2D slabs or 1D chains loosely bound by van der Waals (vdW) interactions. Those processes are driven by redox reactions between guests and the host framework, where transition metal cations have been widely exploited as the redox center.

Enhancing the Resistive Memory Window through Band Gap Tuning in Solid Solution (CrV)O.

Memories based on the insulator-to-metal transition in correlated insulators are promising to overcome the limitations of alternative nonvolatile memory technologies. However, associated performances have been demonstrated so far only on narrow-gap compounds, such as (VCr)O, exhibiting a tight memory window. In the present study, V-substituted CrO compounds (CrV)O have been synthesized and widely investigated in thin films, single crystals, and polycrystalline powders, for the whole range of chemical composition (0 < < 1).

Revisiting the Crystal Structure of Layered Oxychalcogenides LnOS (Ln = La, Pr, and Nd).

LaOS was recently used as a precursor to prepare either a new metastable form of LaOS by de-insertion of half of sulfur atoms of (S) dimers or quaternary compounds by insertion of a coinage metal (e.g., LaOCuS).

Solvothermal and mechanochemical intercalation of Cu into LaOS enabled by the redox reactivity of (S) pairs.

Intercalation of Cu into layered polychalcogenide LaOS was demonstrated to be viable both under solvothermal conditions at 200 °C and mechanical ball milling at ambient temperature. This result evidences the soft-chemical nature of metal intercalation into layered polychalcogenides driven by the redox reactivity of anion-anion bonds.

Design of metastable oxychalcogenide phases by topochemical (de)intercalation of sulfur in LaOS.

Designing and synthesising new metastable compounds is a major challenge of today's material science. While exploration of metastable oxides has seen decades-long advancement thanks to the topochemical deintercalation of oxygen as recently spotlighted with the discovery of nickelate superconductor, such unique synthetic pathway has not yet been found for chalcogenide compounds. Here we combine an original soft chemistry approach, structure prediction calculations and advanced electron microscopy techniques to demonstrate the topochemical deintercalation/reintercalation of sulfur in a layered oxychalcogenide leading to the design of novel metastable phases.

Prediction of a New Layered Polymorph of FeS with FeS(S) Structure.

The never-elucidated crystal structure of metastable iron disulfide FeS resulting from the full deintercalation of Li in LiFeS has been cracked thanks to crystal structure prediction searches based on an evolutionary algorithm combined with first-principles calculations accounting for experimental observations. Besides the newly layered 2/ polymorph of iron disulfide, two-dimensional dynamically stable FeS phases are proposed that contain sulfides and/or persulfide S motifs.

Structure of the water-splitting photocatalyst oxysulfide α-LaOInS and ab initio prediction of new polymorphs.

We unveil the structure and investigate the visible light water-splitting of the photocatalyst α-LaOInS, the second polymorph in this composition. This remarkable oxysulfide exhibits rare mixed anion InSO octahedra leading to both O-2p and S-3p hybridized with indium states in the vicinity of the Fermi level. Ab initio structure prediction shows the stability of such heteroleptic environments and points to other hypothetical polymorphs.

Impact of Nanostructuration on the Chemical Composition of Nickel Oxide Nanoparticles.

Reduction of the size of a particle down to a few tens of nanometers or below may drastically affect its physical properties. That is well-known for quantum dots. Conversely, many works consider the chemical composition of nanoparticles as invariant upon reduction of their dimension.

Unexplored reactivity of (S) oligomers with transition metals in low-temperature solid-state reactions.

We demonstrate here the low temperature topochemical insertion of transition elements (Fe, Ni, and Cu) in precursors containing pre-formed (Sn)2- (n = 2 and 3) oligomers. Indeed, this soft chemistry route opens the door to the easy, orientated synthesis of low dimensional transition metal compounds provided that the elemental metal can retrocede electron(s) to empty antibonding sulfur σ* levels.

A Topochemical Approach to Synthesize Layered Materials Based on the Redox Reactivity of Anionic Chalcogen Dimers.

Layered transition metal compounds represent a major playground to explore unconventional electric or magnetic properties. In that framework, topochemical approaches that mostly preserve the topology of layered reactants have been intensively investigated to tune properties and/or design new materials. Topochemical reactions often involve the insertion or deinsertion of a chemical element accompanied by a change of oxidation state of the cations only.

Direct experimental observation of the molecular J = 3/2 ground state in the lacunar spinel GaTaSe.

Strong spin-orbit coupling lifts the degeneracy of t orbitals in 5d transition-metal systems, leaving a Kramers doublet and quartet with effective angular momentum of J  = 1/2 and 3/2, respectively. These spin-orbit entangled states can host exotic quantum phases such as topological Mott state, unconventional superconductivity, and quantum spin liquid. The lacunar spinel GaTaSe was theoretically predicted to form the molecular J  = 3/2 ground state.

Experimental and Theoretical Evidences of p-Type Conductivity in Nickel Carbodiimide Nanoparticles with a Delafossite Structure Type.

Nickel carbodiimide (NiCN) was synthesized using a two-step precipitation-decomposition route leading to a brown powder with gypsum-flower-like morphology and a large specific surface area (75 m/g). This layered material crystallizes in the 2H structure type of delafossite (space group P6/mmc), which is built upon infinite /[NiN] layers connected by linear carbodiimide ([N═C═N]) bridges. An X-ray diffraction Rietveld refinement and thermal analyses pointed out some nickel deficiencies in the material, and band structure calculations carried out on the defect compound predicted p-type conductivity in relation to a slight amount of N.

A p-Type Zinc-Based Metal-Organic Framework.

An original concept for the property tuning of semiconductors is demonstrated by the synthesis of a p-type zinc oxide (ZnO)-like metal-organic framework (MOF), (ZnCOH), which can be regarded as a possible alternative for ZnO, a natural n-type semiconductor. When small oxygen-rich organic linkers are introduced to the Zn-O system, oxygen vacancies and a deep valence-band maximum, the two obstacles for generating p-type behavior in ZnO, are restrained and raised, respectively. Further studies of this material on the doping and photoluminescence behaviors confirm its resemblance to metal oxides (MOs).

Modulation of Defects in Semiconductors by Facile and Controllable Reduction: The Case of p-type CuCrO2 Nanoparticles.

Optical and electrical characteristics of solid materials are well-known to be intimately related to the presence of intrinsic or extrinsic defects. Hence, the control of defects in semiconductors is of great importance to achieve specific properties, for example, transparency and conductivity. Herein, a facile and controllable reduction method for modulating the defects is proposed and used for the case of p-type delafossite CuCrO2 nanoparticles.

Ba2F2Fe(1.5)Se3: An Intergrowth Compound Containing Iron Selenide Layers.

The iron selenide compound Ba2F2Fe(1.5)Se3 was synthesized by a high-temperature ceramic method. The single-crystal X-ray structure determination revealed a layered-like structure built on [Ba2F2](2+) layers of the fluorite type and iron selenide layers [Fe(1.

Unravelling the origin of the giant Zn deficiency in wurtzite type ZnO nanoparticles.

Owing to its high technological importance for optoelectronics, zinc oxide received much attention. In particular, the role of defects on its physical properties has been extensively studied as well as their thermodynamical stability. In particular, a large concentration of Zn vacancies in ZnO bulk materials is so far considered highly unstable.

Orbital-ordering-driven multiferroicity and magnetoelectric coupling in GeV₄S₈.

We report here the discovery of multiferroicity and large magnetoelectric coupling in the type I orbital order system GeV₄S₈. Our study demonstrates that this clustered compound displays a para-ferroelectric transition at 32 K. This transition originates from an orbital ordering which reorganizes the charge within the transition metal clusters.

Resistive switching at the nanoscale in the Mott insulator compound GaTa4Se8.

We study the Mott insulator compound GaTa4Se8 in which we previously discovered an electric-field-induced resistive transition. We show that the resistive switching is associated to the appearance of metallic and super-insulating nanodomains by means of scanning tunneling microscopy/spectroscopy (STM/STS). Moreover, we show that local electronic transitions can be controlled at the nanoscale at room temperature using the electric field of the STM tip.

Universal electric-field-driven resistive transition in narrow-gap Mott insulators.

A striking universality in the electric-field-driven resistive switching is shown in three prototypical narrow-gap Mott systems. This model, based on key theoretical features of the Mott phenomenon, reproduces the general behavior of this resistive switching and demonstrates that it can be associated with a dynamically directed avalanche. This model predicts non-trivial accumulation and relaxation times that are verified experimentally.

P-type nitrogen-doped ZnO nanoparticles stable under ambient conditions.

Zinc oxide is considered as a very promising material for optoelectronics. However, to date, the difficulty in producing stable p-type ZnO is a bottleneck, which hinders the advent of ZnO-based devices. In that context, nitrogen-doped zinc oxide receives much attention.

Half-metallic ferromagnetism and large negative magnetoresistance in the new lacunar spinel GaTi3VS8.

The lacunar spinel compounds GaTi(4-x)V(x)S(8) (0 < x < 4), consisting of Ti(4-x)V(x) tetrahedral clusters, were prepared and their structures were determined by powder X-ray diffraction. The electronic structures of GaTi(4-x)V(x)S(8) (x = 0, 1, 2, 3) were examined by density functional calculations, and the electrical resistivity and magnetic susceptibility of these compounds were measured. Our calculations predict that GaTi(3)VS(8) is a ferromagnetic half-metal, and this prediction was confirmed by magnetotransport experiments performed on polycrystalline samples of GaTi(3)VS(8).