Search

Research has been conducted on the layered compound Sr (sub)6 V (sub)9 S (sub)22 O (sub)2. The use of the electronic band structure calculations and metal-metal bonding across the shared edges of the octahedra in investigating the (square root of) 7 by (square root of ) 7 superstructure of this compound is discussed.

The new monoclinic IrTe2 phase m-IrTe2 was synthesized at 750 degrees C and 4.5 GPa, and its crystal structure was determined by X-ray powder diffraction. The relative stabilities of the three known and three hypothetical IrTe2 exhibits polymorphs are discussed on the basis of tight binding electronic structure calculations and they indicate the feasibility of preparing the IrS2- and ramsdellite-type IrTe2 phases.

The influence of the tungsten rate and the thermal/pressure history of the samples of Cu[Mo.sub.1-x][W.sub.x][O.sub.4] series (x

Calorimetry, reflectivity and magnetism techniques were used for analyzing the transition temperature modifications with tungsten substitution. Findings reveal a significant increase in the temperature transition in a parallel way for the heating and cooling mode on substitution of molybdenum for tungsten.

The olivine-type compounds LiMPO4 (M=Mn, Fe, Co, Ni) consist of MO4 layers made up of corner-sharing MO6 octahedra of high-spin M(super 2+) ions. To gain insight into the magnetic properties of these phosphates, their spin exchange interactions were estimated by spin dimer analysis using tight binding calculations and by electronic band structure analysis using first principles density functional theory calculations.

The crystal structure of PdSe2 under pressure at room temperature is investigated by X-ray diffraction in an energy-dispersive configuration. The reason for the difference between the isoelectronic analogues NiSe2 and PtSe2 adopt structures and the PdS2-type structure based on qualitative electronic structure considerations is examined.

Under ambient condition PdSe2 has the PdS2-type structure. The crystal structure of PdSe2 under pressure (up to 30 GPa) was investigated at room temperature by X-ray diffraction in an energy-dispersive configuration using a diamond anvil cell with a mixture of water/ethanol/methanol as a pressure transmitting medium. A reversible structural transition from the PdS2-type to the pyrite-type structure occurs around 10 GPa, and the applied pressure reduces the spacing between adjacent 2/∝[PdSe2] layers of the PdS2-type structure to form the three-dimensional lattice of the pyrite-type structure. First principles and extended Hückel electronic band structure calculations were carried out to confirm the observed pressure-induced structural changes. We also examined why the isoelectronic analogues NiSe2 and PtSe2 adopt structures different from the PdS2-type structure on the basis of qualitative electronic structure considerations. [ABSTRACT FROM AUTHOR]

Using jointly experimental results and first-principles calculations, we unambiguously assign the underlying mechanisms behind two commonly observed luminescence bands for the Al 2 O 3 material. Indeed, we show that the red band is associated with a Ti 3+ d - d transition as expected, while the blue band is the combination of the Ti 3+ + O - → Ti 4+ + O 2- and V O • + e - → V O × de-excitation processes. Thanks to our recent developments, which take into account the vibrational contributions to the electronic transitions in solids, we were able to simulate the luminescence spectra for the different signatures. The excellent agreement with the experiment demonstrates that it should be possible to predict the color of the material with a CIE chromaticity diagram. We also anticipated the luminescence signature of Al 2 O 3 :Ti,Ca and Al 2 O 3 :Ti,Be that were confirmed by experiment.

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., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

La 2 O 2 S 2 was recently used as a precursor to prepare either a new metastable form of La 2 O 2 S by de-insertion of half of sulfur atoms of (S 2 ) dimers or quaternary compounds by insertion of a coinage metal (e.g., La 2 O 2 Cu 2 S 2 ). 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 [Ln 2 O 2 ] slabs separated from each other by a flat sulfur layer of (S 2 ) dumbbells. Nevertheless, all (S 2 ) dimers within a given sulfur layer may rotate in phase by 90° compared to the ideal model that induces an overall atomic disorder in (S 2 ) dimer orientation along the stacking axis. This leads to some imbroglio and much confusion in the description of structural arrangement of Ln 2 O 2 S 2 materials. Herein, the crystal structures of La 2 O 2 S 2 and its Pr and Nd variants are revisited. We propose an alternative model that reconciles pre-existing structural descriptions of Ln 2 O 2 S 2 (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.

Herein, we present a methodology based on constrained density functional theory and vibrational mode computations to simulate and interpret the luminescence spectra of periodic solids. A multi-dimension harmonic model is used to combine electronic and vibrational contributions into an overall vibrationally resolved emission spectrum. We applied it to Ti-doped BaZrO 3 to accurately reproduce its blue luminescence and unambiguously assign the observed luminescence to a Ti 3+ + O - → Ti 4+ + O 2- charge transfer.

Ambipolar materials such as carbon nanotubes, graphene, or 2D transition metal chalcogenides are very attractive for a large range of applications, namely, light-emitting transistors, logic circuits, gas sensors, flash memories, and solar cells. In this work, it is shown that the nanoarchitectonics of inorganic Mo 6 cluster-based iodides enable to form thin films exhibiting photophysical properties that enable their classification as new members of the restricted family of ambipolar materials. Thus, the electronic properties of the ternary iodide Cs 2 [{Mo 6 I 8 i }I 6 a ] and those of thin films of the aqua-complex-based compound [{Mo 6 I 8 i }I 4 a (H 2 O) 2 a ]· x H 2 O were investigated through an in-depth photoelectrochemical study. Once hole/electron pairs are created, the holes and electrons turn to be transported simultaneously in opposite directions, and their lifetimes exhibit similar values. The ambipolar properties were demonstrated via the integration of [{Mo 6 I 8 i }I 4 a (H 2 O) 2 a ]· x H 2 O as light harvesters in an all-solid solar cell. A significant photoresponse with a typical diode characteristic clearly provides evidence of the simultaneous transfer and transport of holes and electrons within the [{Mo 6 I 8 i }I 4 a (H 2 O) 2 a ]· x H 2 O layer. The ambipolar behavior results, on the one hand, from the confinement of electrons imposed by the nanometric size of the molecular metal clusters and, on the other hand, from the poor electronic interactions between clusters in the solid state. Such molecular structure-based layers lead naturally to an intrinsic semiconducting behavior.

The never-elucidated crystal structure of metastable iron disulfide FeS 2 resulting from the full deintercalation of Li in Li 2 FeS 2 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 C 2/ m polymorph of iron disulfide, two-dimensional dynamically stable FeS 2 phases are proposed that contain sulfides and/or persulfide S 2 motifs.

After decades of speculation without material proof, the yellow-orange luminescence of scapolite is definitely assigned to (S 2 ) - activators trapped in [Na 4 ] square cages. Synthetic sulfur-doped scapolites confirm the implication of sulfur species in luminescence. Formally, the emission and excitation spectra of various polysulfide species were calculated. The excellent match between theory and experiments for (S 2 ) - dimers provides definitive proof that it is the cause of the yellow-orange luminescence in scapolite.

Several new materials with four structure-types (e.g., Cu 0.32 In 1.74 Ga 0.84 S 4 (CIGS 4 ), Cu 0.65 In 1.75 Ga 1.4 S 5 (CIGS 5 ), Cu 1.44 In 2.77 Ga 0.76 S 6 (CIGS 6 ), and Cu 1.1 In 2.49 Ga 1.8 S 7 (CIGS 7 )) have been evidenced in the Cu 2 S-In 2 S 3 -Ga 2 S 3 pseudo-ternary system. All of them present a 2D structure built upon infinite 2/∞[InS 2 ] layers ((InS 6 ) octahedra sharing edges) on which condense on both sides mono-, bi-, or tri-2/∞[MS] layers ((MS 4 ) tetrahedra (M = Cu, In, Ga) sharing corners). (M(Td)) n -2 (In(Oh))S n slabs are separated from each other by a van der Waals gap, and subscript n refers to the number of sulfur layers within the building block. These compounds have the propensity to display stacking faults but also polymorphic forms. Their optical gap (ca. 1.7 eV) is quite similar to the one of the Cu(In 0.7 Ga 0.3 )S 2 chalcopyrite absorbers used in tandem solar cells, and the major charge carriers are holes. This suggests that they might be very attractive for photovoltaic applications in thin film devices but also for photocatalysis.

In this article, lanthanum molybdenum oxides (La 2 MoO 6 and La 2 Mo 2 O 9 ) and their Bi-doped derivatives were investigated as potential rare-earth-free phosphors. An X-ray diffraction analysis coupled with an EDX study confirmed the purity of the samples and the insertion of bismuth in a 1 molar % amount. Kubelka-Munk-transformed reflectance spectra clearly indicated that the insertion of Bi induces a shortening of the optical gap in La 2 MoO 6 but has no impact on that of La 2 Mo 2 O 9 . Moreover, excitation and emission spectra evidenced a strong temperature quenching effect in all materials. Also, the CIE x , y parameters at 77 K are almost identical with or without Bi doping for the two host lattices. Clearly, it was shown, by combining experimental data, ab initio calculations, and the empirical positioning of absorption bands that the luminescence of the Bi-doped La 2 MoO 6 sample is mainly related to the host lattice itself and distortions induced by La/Bi substitution. The role of the Bi 3+ dopant is indirect, and the luminescence is mainly due to a Mo-O charge transfer rather than an on-site Bi 3+ 3 P 1,0 S 1 S 0 transition. Concerning La 2 Mo 2 O 9 , there is no effect following the insertion of Bi, implying that the role of Bi is insignificant.

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.

Herein is reported a thorough computational investigation on the bulk TiS 2 material with the CdI 2 structure type and the ideal 1:2 Ti:S stoichiometry. Computations were performed using some of the most refined models, e.g., a hybrid functional together with dispersion effects (Grimme's), the GW ansatz, and the Bethe-Salpether equation for the optical properties. We showed that switching from Perdew-Berke-Enzerhof (PBE) to PBE0 leads to a gap opening. Moreover, our results demonstrate unambiguously that van der Waals interactions must be properly treated with dispersion effects in order to retrieve the experimental crystal structure and the appropriate c/ a ratio. Indeed, the calculations prove that when one uses a highly accurate computational protocol, the bulk hexagonal TiS 2 is a semiconductor with a small gap, whereas using the generalized gradient approximation (GGA) PBE functional leads to a semimetal. Furthermore, the band structure is significantly modified when dispersion parameters are taken into account. Pressure effects were also investigated, and they fully describe the previously simulated electronic transition behavior of the material, e.g., TiS 2 becomes semimetallic under strain.

CdIn 2 S 4 and In 2 S 3 compounds were both previously studied as buffer layers in CIGS-based thin-film solar cells, each of them exhibiting advantages and disadvantages. Thus, we naturally embarked on the study of the CdIn 2 S 4 -In 2 S 3 system, and a series of Cd 1- x In 2+2 x/3 S 4 (0 ≤ x ≤ 1) materials were prepared and characterized. Our results show that two solid solutions exist. The aliovalent substitution of cadmium(II) by indium(III) induces a structural transition at x ≈ 0.7 from cubic spinel Fd3̅ m to tetragonal spinel I4 1 / amd that is related to an ordering of cadmium vacancies. Despite this transition, the variation of optical gap is continuous and decreases from 2.34 to 2.11 eV going from CdIn 2 S 4 to In 2 S 3 while all compounds retain an n-type behavior. In contrast with the Al x In 2-x S 3 solid solution, no saturation of the gap is observed. Moreover, XPS analyses indicate a difference between surface and volume composition of the grains for Cd-poor compounds. The use of Cd 1- x In 2+2 x/3 S 4 compounds could be a good alternative to CdIn 2 S 4 and In 2 S 3 to improve CIGS/buffer interfaces with a compromise between photovoltaic conversion efficiency and cadmium content.

The luminescence properties of Gd 3+ or Tb 3+ ions at La and Sc sites were investigated in LaScO 3 with a distorted perovskite-type structure (ABO 3 ). Although the luminescence of lanthanide ions located at B sites is not common and has not been examined in detail, Gd 3+ or Tb 3+ luminescence from B sites and A sites is clearly observed in Gd 3+ - or Tb 3+ -doped LaScO 3 . The differences in the luminescence characteristics concern peak positions, peak shapes, and decay time, which are all influenced by the crystal field and the site symmetry. The UV luminescence of Gd 3+ at B sites shows a red shift compared to Gd 3+ at A sites, and the green luminescence of Tb 3+ at B sites contrasts with the blue-violet and green luminescence of Tb 3+ at A sites. The decay time of the luminescence from B sites is systematically longer than that from A sites in both the Gd 3+ and Tb 3+ cases.

Nickel carbodiimide (NiCN 2 ) 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 2 /g). This layered material crystallizes in the 2H structure type of delafossite (space group P6 3 /mmc), which is built upon infinite 2 / ∞ [NiN 2 ] 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 N 2- . 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 CuGaO 2 and CuCrO 2 delafossite oxides and NiO, prompted us to test NiCN 2 nanoparticles as a photocathode in p-type dye-sensitized solar cells.

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), (ZnC 2 O 3 H 2 ) 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.

The substitution of lithium for copper in Cu 2 ZnSnS 4 (CZTS) has been experimentally and theoretically investigated. Formally, the (Cu 1-x Li x )ZnSnS 4 system exhibits two well-defined solid solutions. Indeed, single crystal structural analyses demonstrate that the low (x < 0.4) and high (x > 0.6) lithium-content compounds adopt the kesterite structure and the wurtz-kesterite structure, respectively. For x between 0.4 and 0.6, the two aforementioned structure types coexist. Moreover, 119 Sn NMR analyses carried out on a (Cu 0.7 Li 0.3 ) 2 ZnSnS 4 sample clearly indicate that lithium replaces copper preferentially on two of the three available 2-fold crystallographic sites commonly occupied by Cu and Zn in disordered kesterite. Furthermore, the observed individual lines in the NMR spectrum suggest that the propensity of Cu and Zn atoms to be randomly distributed over the 2c and 2d crystallographic sites is lowered when lithium is partially substituted for copper. Additionally, the first-principles calculations provide insights into the arrangement of Li atoms as a function of the Cu/Zn disorder and its effect on the structural (lattice parameters) and optical properties of CZTS (band gap evolution). Those calculations agree with the experimental observations and account for the evolutions of the unit cell parameters as well as for the increase of band gap when the Li-content increases. The calculation of the formation enthalpy of point defect unambiguously indicates that Li modifies the Cu/Zn disorder in a manner similar to the change of Cu/Zn disorder induced by Ag alloying. Overall, it was found that Li alloying is a versatile way of tuning the optoelectronic properties of CZTS making it a good candidate as wide band gap materials for the top cells of tandem solar cells.

Novel melilite-type Ca2Ga2SiO7:Eu(3+) red-emitting phosphors with different Eu(3+) contents were synthesized via high-temperature solid-state reaction. The crystal structure, optical absorption, and photoluminescence properties were investigated, while density functional theory calculations were performed on the host lattice. The excitation spectra indicate that phosphors can be effectively excited by near-UV light for a potential application in white-light-emitting diodes. Because of the abnormally high intensity emission at about 700 nm arising from the (5)D0 → (7)F4 transition of Eu(3+), the phosphors Ca2Ga2SiO7:Eu(3+) show a deep-red emission with chromaticity coordinates (0.639, 0.358).

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.

In the presence of "Ag2O" as a promoter, γ-MnO2 traps dihydrogen in its (2 × 1) and (1 × 1) tunnels. The course of this reaction was examined by analyzing the X-ray diffraction patterns of the HxMnO2/"Ag2O" system (0 ≤ x < 1) on the basis of pair distribution function and density functional theory (DFT) analyses. Hydrogen trapping occurs preferentially in the (2 × 1) tunnels of γ-MnO2, which is then followed by that in the (1 × 1) tunnels. Our DFT analysis shows that this process is thermodynamically favorable.

Polycrystalline yttrium iron garnet (Y3Fe5O12, hereafter labeled YIG) has been synthesized by solid-state reaction, characterized by X-ray diffraction, Mössbauer spectroscopy, and UV-vis-NIR diffuse reflectance spectroscopy, and its optical properties from room temperature (RT) to 300 °C are discussed. Namely, its greenish color at RT is assigned to an O(2-) → Fe(3+) ligand-to-metal charge transfer at 2.57 eV coupled with d-d transitions peaking at 1.35 and 2.04 eV. When the temperature is raised, YIG displays a marked thermochromic effect; i.e., the color changes continuously from greenish to brownish, which offers opportunities for potential application as a temperature indicator for everyday uses. The origin of the observed thermochromism is assigned to a gradual red shift of the ligand-to-metal charge transfer with temperature while the positioning in energy of the d-d transitions is almost unaltered. Attempts to achieve more saturated colors via doping (e.g., Al(3+), Ga(3+), Mn(3+), ...) remained unsuccessful except for chromium. Indeed, Y3Fe5O12:Cr samples exhibit at RT the same color than the undoped garnet at 200 °C. The introduction of Cr(3+) ions strongly impacts the color of the Y3Fe5O12 parent either by an inductive effect or, more probably, by a direct effect on the electronic structure of the undoped material with formation of a midgap state.

The material Cu2ZnSn(S,Se)4 (CZTS) offers a promising indium-free alternative to Cu(In,Ga)Se2 for the absorber layer in thin-film solar cells. It is known that the highest solar energy conversion efficiencies are reached for Cu-poor, Zn-rich CZTS compositions and that too much disorder at the Cu and Zn sites can have a negative impact on the device performance. In this article, we investigate the structures of [VCu + ZnCu] A-type and [2ZnCu + ZnSn] B-type defect complexes and their impact on the long-range Cu/Zn disorder. To that end, we use (119)Sn, (65)Cu, and (67)Zn solid-state NMR and Raman spectroscopy to characterize powdered CZTS samples. For both A- and B-type substitutions, our NMR investigations demonstrate the clustering of the complexes. Moreover, we show that (A+B)-type compounds should be considered as A-type and B-type compounds, since no interaction seems to exist between [VCu + ZnCu] and [2ZnCu + ZnSn] defect complexes. In addition, it is worth noting that [2ZnCu + ZnSn] complexes have only a minor impact on the level of disorder at the Cu and Zn sites. In contrast, [VCu + ZnCu] complexes seem to restrain the random distribution of Cu at the Zn site and of Zn at the Cu site; i.e., the long-range Cu/Zn disorder. Raman characterization of the CZTS samples was also conducted. The Q = I287/I303 and the newly introduced Q' = I338/(I366 + I374) ratios determined from Raman spectra collected at 785 nm turn out to be very sensitive to the level of Cu/Zn disorder. Moreover, they can be used to differentiate the nature of the substitution in slow-cooled materials.

Ultrathin Ag2Mo3O10·2H2O nanowires (NWs) were synthesized by soft chemistry under atmospheric pressure from a hybrid organic-inorganic polyoxometalate (CH3NH3)2[Mo7O22] and characterized by powder X-ray diffraction, DSC/TGA analyses, FT-IR and FT-Raman spectroscopies, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Their diameters are a few tens of nanometers and hence much thinner than that found for silver molybdates commonly obtained under hydrothermal conditions. The optical properties of Ag2Mo3O10·2H2O NWs before and after UV irradiation were investigated by UV-vis-NIR diffuse reflectance spectroscopy revealing, in addition to photoreduction of Mo(6+) to Mo(5+) cations, in situ photogeneration of well-dispersed silver Ag(0) nanoparticles on the surface of the NWs. The resulting Ag@Ag2Mo3O10·2H2O heterostructure was confirmed by electron energy-loss spectroscopy (EELS), X-ray photoelectron spectroscopy (XPS), and Auger spectroscopy. Concomitant reduction of Mo(6+) and Ag(+) cations under UV excitation was discussed on the basis of electronic band structure calculations. The Ag@Ag2Mo3O10·2H2O nanocomposite is an efficient visible-light-driven plasmonic photocatalyst for degradation of Rhodamine B dye in aqueous solution.

For the very first time, sulfonium polyoxometalate (POM) assemblies are shown to develop efficient solid-state photochromism in ambient conditions. The optical properties of the already known Rb(0.75)(NH(4))(5.25)[(Mo(3)O(8))(2)O(O(3)PC(CH(2)S(CH(3))(2))OPO(3))(2)]·8H(2)O (1) and a new material (Me(3)S)(4)[Mo(8)O(26)] (2) under UV excitation are investigated by diffuse reflectance spectroscopy, revealing that the color change effect is highly tunable playing with the nature of the POM. A mechanism involving the photoreduction of Mo(6+) cations associated with electron transfers from the sulfonium cations toward the POMs is proposed.

Here we present for the very first time a single-crystal investigation of the Cu-poor Zn-rich derivative of Cu(2)ZnSnS(4). Nowadays, this composition is considered as the one that delivers the best photovoltaic performances in the specific domain of Cu(2)ZnSnS(4)-based thin-film solar cells. The existence of this nonstoichiometric phase is definitely demonstrated here in an explicit and unequivocal manner on the basis of powder and single-crystal X-ray diffraction analyses coupled with electron microprobe analyses. Crystals are tetragonal, space group I ̅4, Z = 2, with a = 5.43440(15) Å and c = 10.8382(6) Å for Cu(2)ZnSnS(4) and a = 5.43006(5) Å and c = 10.8222(2) Å for Cu(1.71)Zn(1.18)Sn(0.99)S(4)., (© 2012 American Chemical Society)

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., (© 2011 American Chemical Society)

Two new hybrid organic-inorganic molybdates based on layered (2/∞)[Mo(n)O(3n+1)](2-) blocks and organoammonium cations (+)(Me(x)H(3-x)N)(CH(2))(6)(NH(3-x)Me(x))(+) (x = 0-1), namely, (H(3)N(CH(2))(6)NH(3))[Mo(7)O(22)]·H(2)O (1) and (MeH(2)N(CH(2))(6)NH(2)Me)[Mo(9)O(28)] (2), have been synthesized under hydrothermal conditions. The (2/∞)[Mo(9)O(28)](2-) unit in 2 is an unprecedented member of the (2/∞)[Mo(n)O(3n+1)](2-) family with the n value extended to 9. The structural filiation between the (2/∞)[Mo(n)O(3n+1)](2-) (n = 5, 7, 9) blocks is well established, and their structural similarity with the (2/∞)[MoO(3)] slabs in α-MoO(3) is also discussed. Single-crystal X-ray analyses show that the (2/∞)[Mo(n)O(3n+1)](2-) layers in 1 and 2 are pillared in the three-dimensional networks by the organic cations with a similar connection at the organic-inorganic interface. In addition, a correlation between the topology of the (2/∞)[Mo(n)O(3n+1)](2-) blocks in 1 and 2 and the overall sizes of the associated organic cations is pointed out. Finally, the efficiency of Fourier transform Raman spectroscopy to easily discriminate the different (2/∞)[Mo(n)O(3n+1)](2-) blocks (n = 5, 7, 9) in hybrid organic-inorganic layered molybdate materials is clearly evidenced.

A new concept of photoresponsive composites has been elaborated by intimately connecting a Photochromic Phase (PP), (H(2)DABCO)(2)(HDMA)(0.5)Na(0.75)(H(3)O)(0.75)[Mo(8)O(27)]·3H(2)O (1), with a second hybrid organic-inorganic molybdate material, (H(2)DABCO)(HDABCO)[Fe(OH)(6)Mo(6)O(18)]·4H(2)O (2) acting as an Oxidation Catalytic Phase (OCP) toward the former once photoexcited. The association of both the PP and the OCP in the composite drastically improves the bleaching process of the PP alone because of efficient electronic transfers through the OCP-PP interface without affecting significantly its photoinduced color change characteristic. Two OCP-PP composites with different PP weight percents have been obtained by associating 1 with 2. The optical properties of these composites before and after UV irradiation have been investigated by Diffuse Reflectance Spectroscopy, and the strong impact of the OCP on the fading kinetics of the PP has been clearly highlighted.

A new generation UV absorber is obtained by microwave-heating-assisted hydrothermal synthesis: [Hgua](2)·(Ti(5)O(5)F(12)). The structure of this hybrid titanium(IV) oxyfluoride is ab initio determined from powder X-ray data by combining a direct space method, Rietveld refinement [orthorhombic, Cmm2, a = 22.410(1) Å, b = 11.191(1) Å, c = 3.802(1) Å], and density functional theory geometry optimization. The three-dimensional network is built up from infinite inorganic layers (∞)(Ti(5)O(5)F(12)) separated by guanidinium cations. The theoretical optical gap (3.2 eV) estimated from density of state calculations is in good agreement with the experimental gap (3.3 eV) obtained by UV-vis diffuse reflectivity. The optical absorption is mainly due to O(2p) → Ti(3d) and F(2p) → Ti(3d) transitions at higher energies. The refraction index is low in the visible range (n ≈ 1.9) compared to that of TiO(2) and, consequently, [Hgua](2)·(Ti(5)O(5)F(12)) shows a good transparency adapted to UV shielding. Under UV irradiation at 254 nm for 40 h, the white microcrystalline powder turns to light purple-gray. This color change is caused by the reduction of Ti(IV) to Ti(III), confirmed by magnetic measurements., (© 2011 American Chemical Society)

A series of compounds of Co(1-x)Mg(x)MoO(4) compositions has been prepared by a conventional ceramic route. The members of the whole solid solution exhibit a reversible first-order phase transition which was probed by using thermal expansion and low-temperature reflectivity techniques. Whereas the α → β transition temperature evolves linearly on warming from 435 to 200 °C with x going from 0 to 0.9, the β → α transition temperature variation falls down on cooling from -40 °C to -140 °C going from CoMoO(4) to Co(0.1)Mg(0.9)MoO(4) with an asymptotic evolution. The phase transition temperatures have been explained on the basis of a crystal polarization effect under substitution of Mg for Co. Thus, from an applicative point of view, new thermochromic pigments with tunable transition temperatures are here proposed.

We investigate the reactivity of MoO(4)(2-) toward six organoammonium cations (+)(Me(3-x)H(x)N)(CH(2))(2)(NH(y)Me(3-y))(+) (x, y = 1-3) at different synthesis temperatures ranging from 70 to 180 °C. A total of 16 hybrid organic-inorganic materials have been synthesized at an initial pH of 2, via ambient pressure and hydrothermal routes, namely, (H(2)en)[Mo(3)O(10)]·H(2)O (1), (H(2)en)[Mo(3)O(10)] (2), (H(2)en)[Mo(5)O(16)] (3), (H(2)MED)(2)[Mo(8)O(26)]·2H(2)O (4), (H(2)MED)[Mo(5)O(16)] (5), (N,N-H(2)DMED)(2)[Mo(8)O(26)]·2H(2)O (6), (N,N-H(2)DMED)(2)[Mo(8)O(26)]·2H(2)O (7), (N,N'-H(2)DMED)(2)[Mo(8)O(26)] (8), (N,N'-H(2)DMED)[Mo(5)O(16)] (9), (H(2)TriMED)(2)[Mo(8)O(26)]·4H(2)O (10), (H(2)TriMED)(2)[Mo(8)O(26)]·2H(2)O (11), (H(2)TriMED)[Mo(7)O(22)] (12), (H(2)TMED)(2)[Mo(8)O(26)]·2H(2)O (13), (H(2)TMED)(2)[Mo(8)O(26)] (14), (H(2)TMED)(2)[Mo(8)O(26)] (15), and (H(2)TMED)[Mo(7)O(22)] (16). All of these compounds contain different polyoxomolybdate (Mo-POM) blocks, i.e., discrete β-[Mo(8)O(26)](4-) blocks in 6, 10, 13, 14, (1)/(∞)[Mo(3)O(10)](2-), and (1)/(∞)[Mo(8)O(26)](4-) polymeric chains in 1, 2, 4, 7, 8, and 15, respectively, and (2)/(∞)[Mo(5)O(16)](2-) and (2)/(∞)[Mo(7)O(22)](2-) layers in 3, 5, 9, 12, and 16, respectively. The structures of 5, 9, and 14 have been resolved by single-crystal X-ray analyses. The characterization of the different Mo-POM blocks in 1-16 by Fourier transform Raman spectroscopy is reported. The impact of the synthesis temperature on both the composition and topology of the Mo-POM blocks is highlighted.

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.

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.

The synthesis of lanthanum phosphates in molten LiCl-KCL eutectic was chosen to address the preliminary treatment of chlorinated wastes containing fission products that are already present in a Li/Cl eutectic. The obtained monazite compound shows interesting properties to be considered as a good candidate to trap lanthanum for a long-time. The synthesis route based on LaCl(3) reaction with NH(4)H(2)PO(4) in a stoichiometric amount is a key point to obtain monazite as a pure phase. Hence, the salt composition is not modified during the synthesis reaction. The chemical reactivity of ammonium dihydrogenphosphate (NH(4)H(2)PO(4), hereafter abbreviated ADP) toward lanthanum chloride (LaCl(3)) in molten LiCl-KCl eutectic is probed by NMR spectroscopy to follow the formation of LaPO(4). Formally, a direct transformation of the two aforementioned precursors into LaPO(4), NH(4)Cl and HCl can be discarded on the basis of the low thermal stability of ADP. To shed some light on the formation of LaPO(4), in situ and ex situ NMR experiments were carried out on LiCl-KCl/LaCl(3)/ADP, as well as LiCl-KCl/ADP, KCl/ADP, and LiCl/ADP mixtures. First, the reactivity of the precursors in contact with the eutectic was studied from room temperature to 600 degrees C by means of (31)P, (35)Cl, and (139)La high temperature NMR. Second, ex situ room temperature magic angle spinning (MAS) and RadioFrequency driven recoupling (RFDR) (31)P solid-state NMR experiments were carried out on solid samples prepared in different conditions (i.e., temperature and atmosphere) and quenched at room temperature to identify frozen intermediate species in their metastable state. On the basis of this approach, we propose a model for the LaPO(4) formation based on a multistep mechanism which highlights the strong reactivity of ADP toward the alkaline salts but without final change in the composition of the solvent.

The excellent photochromic properties of (H(2)DABCO)(2)(HDMA)(0.5)Na(0.75)(H(3)O)(0.75)[Mo(8)O(27)] x 3 H(2)O (4), a new member of the (H(2)DABCO)(2)(A)(x)[Mo(8)O(27)] x n H(2)O series, are compared with those of (H(2)DABCO)(2)(NH(4))(2)[Mo(8)O(27)] x 4 H(2)O (1), (H(2)DABCO)(2)(H(2)pipz)[Mo(8)O(27)] (2), and (H(2)pipz)(3)[Mo(8)O(27)] (3). All these powdered materials turn from white to purple under illumination at 365 nm, which is associated with photoreduction of Mo(6+) cations into Mo(5+) cations. We show that the rates of coloration, which increase in the order 1 < 3, 2 < 4, are related to the decrease in the concentration of reducible Mo(6+) centers with irradiation time and follow a second-order reaction law because the event of light absorption at a reducible Mo(6+) site does not necessarily coincide with that of the N(+)-H bond breaking in the N(+)-H...O hydrogen bond associated with the Mo(6+) site. First-principles density functional electronic structure calculations were carried out to find that this trend correlates with the homolytic dissociation energies of the N(+)-H bonds in the organic cations HDMA(+), H(2)pipz(2+), H(2)DABCO(2+), and NH(4)(+). This observation is consistent with a photochromic mechanism based on the homolytic cleavage of N(+)-H bonds rather than on the heterolytic cleavage of N(+)-H bonds.