Revisiting the Crystal Structure of Layered Oxychalcogenides Ln2O2S2 (Ln = La, Pr, and Nd).

La2O2S2 was recently used as a precursor to prepare either a new metastable form of La2O2S by de-insertion of half of sulfur atoms of (S2) dimers or quaternary compounds by insertion of a coinage metal (e.g., La2O2Cu2S2). A strong structural relationship exists between the polysulfide precursor and the synthesized products, which highlights the topochemical nature of these reactions. Nevertheless, the crystal structure of the precursor material is still a matter of debate. Namely, several structural models were reported so far in the literature with different space groups and/or crystal systems. All these models were built upon infinite [Ln2O2] slabs separated from each other by a flat sulfur layer of (S2) dumbbells. Nevertheless, all (S2) dimers within a given sulfur layer may rotate in phase by 90° compared to the ideal model that induces an overall atomic disorder in (S2) dimer orientation along the stacking axis. This leads to some imbroglio and much confusion in the description of structural arrangement of Ln2O2S2 materials. Herein, the crystal structures of La2O2S2 and its Pr and Nd variants are revisited. We propose an alternative model that reconciles pre-existing structural descriptions of Ln2O2S2 (Ln = La, Pr, and Nd) materials and highlights the strong dependency of the degree of long-range ordering of the sulfur layers on the synthesis conditions.

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. Here we demonstrate that the chemical composition of a transition-metal oxide, namely, nickel oxide, is drastically affected by its nanostructuration.

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. Conversely, cases where anions play the role of redox centers are very scarce. Here we show that the insertion of copper into two dimensional precursors containing chalcogen dimers (Q2 )2- (Q=S, Se) can produce layered materials with extended (CuQ) sheets. The reality of this topochemical reaction is demonstrated here for different pristine materials, namely La2 O2 S2 , Ba2 F2 S2 , and LaSe2 . Therefore, this work opens up a new synthetic strategy to design layered transition metal compounds from precursors containing polyanionic redox centers.

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), (ZnC2O3H2)n, 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). This result answers the challenges of generating p-type behavior in an n-type-like system. This concept reveals that a new category of hybrid materials, with an embedded continuous metal-oxygen network, lies between the MOs and MOFs. It provides concrete support for the development of p-type hybrid semiconductors in the near future and, more importantly, the enrichment of tuning possibilities in inorganic semiconductors.

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

Nickel carbodiimide (NiCN2) 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 m2/g). This layered material crystallizes in the 2H structure type of delafossite (space group P63/mmc), which is built upon infinite 2/∞[NiN2] layers connected by linear carbodiimide ([N═C═N]2-) 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 N2-. This p-type conductivity was demonstrated by electrochemical impedance spectroscopy measurements, and a flat band potential of 0.90 V vs SCE at pH 9.4 was measured. This value, which is more positive than those of CuGaO2 and CuCrO2 delafossite oxides and NiO, prompted us to test NiCN2 nanoparticles as a photocathode in p-type dye-sensitized solar cells.

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(1.5)Se3](2-). These [Fe1.5Se3](2-) layers contain iron in two valence states, namely, Fe(II+) and Fe(III+) located in octahedral and tetrahedral sites, respectively. Magnetic measurements are consistent with a high-spin state for Fe(II+) and an intermediate-spin state for Fe(III+). Moreover, susceptibility and resistivity measurements demonstrate that Ba2F2Fe(1.5)Se3 is an antiferromagnetic insulator.

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. The optical absorption in the infrared region of the CuCrO2 material can then be fine-tuned via the continuous reduction of nonstoichiometric Cu(II), naturally stabilized in small amounts. This reduction modifies the concentration of positive charge carriers in the material, and thus the conductive and reflective properties, as well as the flat band potential. Indeed, this controllable reduction methodology provides a novel strategy to modulate the (opto-) electronic characteristics of semiconductors.

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. Below the antiferromagnetic transition at 17 K, the application of a magnetic field significantly affects the ferroelectric polarization, revealing thus a large magnetoelectric coupling. Our study suggests that the application of a magnetic field induces a metamagnetic transition which significantly affects the ferroelectric polarization thanks to an exchange striction phenomenon.

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. This opens the way for possible applications in resistive random access memories (RRAM) devices.

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. Topochemistry coupled with this cationic redox not only enables technological applications such as Li-ion secondary batteries but also serves as a powerful tool for structural or electronic fine-tuning of layered transition metal compounds. Over recent years, we have been pursuing materials design beyond this cationic redox topochemistry that was mostly limited to 2D or 1D vdW systems. For this, we proposed new topochemical reactions of non-vdW compounds built of 2D arrays of anionic chalcogen dimers alternating with redox-inert host cationic layers. These chalcogen dimers were found to undergo redox reaction with external metal elements, triggering either (1) insertion of these metals to construct 2D metal chalcogenides or (2) deintercalation of the constituent chalcogen anions. As a whole, this topochemistry works like a "zipper", where reductive cleavage of anionic chalcogen-chalcogen bonds opens up spaces in non-vdW materials, allowing the formation of novel layered structures. This Perspective briefly summarizes seminal examples of unique structure transformations achieved by anionic redox topochemistry as well as challenges on their syntheses and characterizations.

Enhancing the Resistive Memory Window through Band Gap Tuning in Solid Solution (Cr1-xVx)2O3.

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 (V0.95Cr0.05)2O3, exhibiting a tight memory window. In the present study, V-substituted Cr2O3 compounds (Cr1-xVx)2O3 have been synthesized and widely investigated in thin films, single crystals, and polycrystalline powders, for the whole range of chemical composition (0 < x < 1). Physicochemical, structural, and optical properties of the annealed magnetron-sputtered thin films are in very good agreement with those of polycrystalline powders. Indeed, all compounds exhibit the same crystalline structure with a cell parameter evolution consistent with a solid solution over the whole range of x values, as demonstrated by X-ray diffraction and Raman scattering. Moreover, the optical band gap of V-substituted Cr2O3 compounds decreases from 3 eV for Cr2O3 to 0 eV for V2O3. In the same way, resistivity is decreased by almost 5 orders of magnitude as the V content x is varying from 0 to 1, similarly in thin films and single crystals. Finally, a reversible resistive switching has been observed for thin films of three selected V contents (x = 0.30, 0.70, and 0.95). Resistive switching performed on MIM devices based on a 50 nm thick (Cr0.30V0.70)2O3 thin film shows a high endurance of 1000 resistive switching cycles and a memory window ROFF/RON higher by 3 orders of magnitude, as compared to (Cr0.05V0.95)2O3. This comprehensive study demonstrates that a large range of memory windows can be reached by tuning the band gap while varying the V content in the (Cr1-xVx)2O3 solid solution. It thus confirms the potential of correlated insulators for memory applications.

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. However, numerous reviews report the controversial character of p-type conductivity in N-doped ZnO, and recent theoretical contributions explain that N-doping alone cannot lead to p-typeness in Zn-rich ZnO. We report here that the ammonolysis at low temperature of ZnO(2) yields pure wurtzite-type N-doped ZnO nanoparticles with an extraordinarily large amount of Zn vacancies (up to 20%). Electrochemical and transient spectroscopy studies demonstrate that these Zn-poor nanoparticles exhibit a p-type conductivity that is stable over more than 2 years under ambient conditions.

Solvothermal and mechanochemical intercalation of Cu into La2O2S2 enabled by the redox reactivity of (S2)2- pairs.

Intercalation of Cu into layered polychalcogenide La2O2S2 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 La2O2S2.

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. We demonstrate that La2O2S2 may react with monovalent metals to produce sulfur-deintercalated metastable phases La2O2S1.5 and oA-La2O2S whose lamellar structures were predicted thanks to an evolutionary structure-prediction algorithm. This study paves the way to unexplored topochemistry of mobile chalcogen anions.

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). The latter reveal a large negative magnetoresistance (up to 22% at 2 K), which is consistent with the intergrain tunnelling magnetoresistance expected for powder samples of a ferromagnetic half-metal and indicates the presence of high spin polarization greater than 53% in GaTi(3)VS(8).

Synthesis of p-type transparent LaOCuS nanoparticles via soft chemistry.

We report here for the first time on the synthesis of nanoparticles of the p-type transparent conductor LaOCuS. Nanoparticles were obtained via a solvothermal route in ethylenediamine with dehydrated lanthanum chloride (LaCl(3).7H(2)O), copper monooxide, and elemental sulfur as precursors. Powder X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy ascertained our sample to be of high purity, while laser diffractometry evidenced a monodisperse particle size distribution centered on 126 nm. The absorption spectrum and the current-potential curves recorded under chopped illumination asserted the optical transparency and the p-type electronic conductivity of our LaOCuS nanoparticles.

Prediction of a New Layered Polymorph of FeS2 with Fe3+S2-(S22-)1/2 Structure.

The never-elucidated crystal structure of metastable iron disulfide FeS2 resulting from the full deintercalation of Li in Li2FeS2 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 C2/m polymorph of iron disulfide, two-dimensional dynamically stable FeS2 phases are proposed that contain sulfides and/or persulfide S2 motifs.

Structure of the water-splitting photocatalyst oxysulfide α-LaOInS2 and ab initio prediction of new polymorphs.

We unveil the structure and investigate the visible light water-splitting of the photocatalyst α-LaOInS2, the second polymorph in this composition. This remarkable oxysulfide exhibits rare mixed anion InS5O 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.

Simple and reproducible procedure to prepare self-nanostructured NiO films for the fabrication of P-type dye-sensitized solar cells.

Porous and nanostructured thin films of NiO (3.5 microm thick) were prepared on FTO coated glass by annealing nickel acetate films obtained by recrystallization under hydrothermal conditions in the presence of hexamethylenetetramine. The photovoltaic performances of the NiO films were optimized with coumarin C343 as sensitizer and iodide/triodide as redox mediator and led to the following values of V(OC), J(SC), ff, and eta: 117 mV, 0.88 mA/cm(2), 0.28, and 0.036% respectively, under AM 1.5. With the improved PMI-NDI dyad as sensitizer and the tris(4,4'-bis(tertbutyl)bipyridine) cobalt(II/III) couple as redox mediator, the overall photoconversion efficiency reached 0.16%. An essential advantage of this procedure lies in its good reproducibility offering a reliable strategy to test new dyes and other parameters to improve the photoconversion efficiency of this new type of DSSC.