Synthesis,structure, and bonding of the hexagonal form of the oxide carbide ScAlOC

Red single crystals of a hexagonal form of ScAlOC were obtained as a by-product from the synthesis of ScAl₃C₃ by reacting scandium and carbon in an aluminium melt at 1820 °C. The crystal structure (hP8, space group P6₃mc, Z = 2, a = 3.24793(3) Å, c = 10.1739(1) Å, 629 refl., 15 param., R₁(F) = 0.010, wR₂(F²) = 0.023) can directly be derived from the binary nitrides AlN and ScN or the oxide carbides Sc(O,C) and Al(O,C), respectively. ScAlOC-II or h-ScAlOC represents a new structure type with simple closest packing of alternating layers of oxygen and carbon. The stacking sequence is ABAC (=(hc)₂) with oxygen in a cubic and carbon in a hexagonal sequence. According to the difference in size Sc occupies octahedral voids between every second layer leading to layers of edge-sharing ScO₃C₃ octahedra. Aluminium is located in half of the tetrahedral voids. The AlOC₃-tetrahedra are connected to layers by common corners of the carbon atoms. h-ScAlOC continues the row of the rare examples of oxide carbides with ordered anion distribution. Band structure calculations by FP-(L)APW methods revealed that ScAlOC is electron precise with a band gap of 1.2 eV. Calculations of charges by the Bader-method reveal values of Sc^+1.87, Al^+2.33, O^−1.52 and C^−2.67. Together with the charge densities and the values of the Laplacian this stands for a mainly ionic bonding containing significant covalent contributions, too. Despite the close similarity to rhombohedral ScAlOC (r-ScAlOC) there is a striking difference in colour, as r-ScAlOC is black. This is confirmed and explained by the results of the P-DOS, because the lowest states of the conduction band are determined by Sc-d-states. These are significantly lower in r-ScAlOC with ScC₆ and ScO₆ octahedra than in h-ScAlOC leading to a calculated band gap of 0.3 eV.     

Approaching compositional limits of perovskite – type oxides and oxynitrides by synthesis of Mg0.25Ca0.65Y0.1Ti(O,N)3, Ca1–xYxZr(O,N)3 (0.1 ≤ x ≤ 0.4), and Sr1–xLaxZr(O,N)3 (0.1 ≤ x ≤ 0.4)

Partial substitution of cations and anions in perovskite-type materials is a powerful way to tune the desired properties. The systematic variation of the cations size, the partial exchange of O²⁻ for N³⁻ and their effect on the size of the optical band gap and the thermal stability was investigated here. The anionic substitution resulted in the formation of the orthorhombic perovskite-type oxynitrides Mg_0.25Ca_0.65Y_0.1Ti(O,N)₃, Ca_1-xY_xZr(O,N)₃, and Sr_1–xLa_xZr(O,N)₃. A two-step synthesis protocol was applied: i) (nano-crystalline) oxide precursors were synthesized by a Pechini method followed by ii) ammonolysis in flowing NH₃ at T = 773 K (Ti) and T = 1273 K (Zr), respectively. High-temperature synthesis of such oxide precursors by solid–state reaction generally resulted in phase separation of the different A-site cations. Changes of the crystal structures were investigated by Rietveld refinements of the powder XRD data, thermal stability by DSC/TG measurements in oxygen atmosphere, oxygen and nitrogen contents by O/N analysis using hot gas extraction technique, and optical band gaps by photoluminescence spectroscopy. By moving from Mg_0.25Ca_0.65Y_0.1Ti(O,N)₃ via Ca_1–xY_xZr(O,N)₃ to Sr_1–xLa_xZr(O,N)₃, the degree of tilting of the octahedral network is reduced, as observed by an increase in the B–X–B angles caused by the simultaneously increasing effective ionic radius of the A-site cation(s). In general, increasing substitution levels on the A-site (Y³⁺ and La³⁺) are accompanied by an enhanced replacement of O²⁻ by N³⁻. In all three systems, this anionic substitution resulted in a reduction of the optical band gap by approximately 1 eV (Ti) and up to 2.1 eV (Zr) compared to the respective oxides. For Mg_0.25Ca_0.65Y_0.1Ti(O,N)₃ an optical band gap of 2.2 eV was observed, appropriate for a solar water splitting photocatalyst. The Zr-based oxynitrides required a by a factor of 2 higher nitrogen contents to significantly reduce the optical band gap and the measured values of 2.9 eV–3.2 eV are larger compared to the Ti-based oxynitride. Bulk thermal stability was revealed up to T = 881 K. In general, the thermal stability decreased with increasing substitution levels due to an increasing deviation from the ideal anionic composition as demonstrated by O/N analysis.     

Electronic structure and quadrupole interactions in triple molybdates Li<Subscript>2</Subscript>M<Subscript>3</Subscript>Al(MoO<Subscript>4</Subscript>)<Subscript>4</Subscript>, M = Cs,Rb

Within the density functional theory the electronic structure of triple molybdates Li₂M₃Al(MoO₄)₄, where M = Cs, Rb, is studied for the first time. It is found that all molybdates studied belong to wide band insulators with a band gap of ~4 eV. Quadrupole frequencies and asymmetry parameters of the electric field gradient near magnetic ⁷Li, ²⁷Al, ⁸⁷Rb, and ¹³³Cs nuclei are calculated and experimental NMR spectra are interpreted.     

X-ray and UV photoemission studies of valence electronic structure of NiO

The X-ray and UV photoemission valence band spectra of NiO are interpreted using the molecular orbital theory for the NiO^10?₆ cluster and the sudden approximation (monopole selection rules). They exhibit the effects of crystal field splitting, multiplet splitting, electron shake-up (O 2pe^b_g→ Ni 3de^a_g). relaxation and Ni 3dO 2p hybridization. Shake-up satellite data indicate that the NiO optical absorption edge near 4 eV is associated with an O 2p → Ni 3d transition. The NiO valence electronic structure obtained in this work is compared with band structure models of Wilson and Mattheiss.     

Synthesis,structure, physical properties,and electronic structure of KGaSe2

The ternary gallium selenide KGaSe₂ has been synthesized by solid-state reactions and good quality crystal has been obtained. KGaSe₂ crystallizes in the monoclinic space group C2/c with cell dimensions of a = 10.878(2) Å, b = 10.872(2) Å, c = 15.380(3) Å, and β = 100.18(3)°. In the structure, adamantane like [Ga₄Se₁₀]⁸⁻ units are connected by common corners forming two-dimensional [GaSe₂]⁻ layers which are separated by K⁺ cations. KGaSe₂ exhibits congruent-melting behavior at around 965 °C. It is transparent in the range of 0.47–20.0 μm and has a band gap of 2.60(2) eV. From a band structure calculation, KGaSe₂ is a direct-gap semiconductor. The band gap is mainly determined by the [GaSe₂]⁻ layer.     

The application of transition metal molybdates (AMoO4, A = Co,Ni, Cu) as additives in acrylonitrile‐butadiene‐styrene with improved flame retardant and smoke suppression properties

In this paper, three different kinds of typical transition metal molybdates (AMoO₄, A = Co, Ni, Cu) were synthesized via a hydrothermal method. X‐ray diffraction and scanning electron microscopy (SEM) were used to characterize their structures. Then, the synthesized molybdates were incorporated into acrylonitrile‐butadiene‐styrene (ABS) matrix via a masterbatch‐based melt blending method. SEM images showed that transition metal molybdates (AMoO₄, A = Co, Ni, Cu) are homogeneously dispersed in the ABS matrix. Thermogravimetric analysis (TGA) results indicated that the introduction of these transition metal molybdates (AMoO₄, A = Co, Ni, Cu) could accelerate the degradation of ABS, especially for the CuMoO₄. The initial thermal degradation temperatures are decreased by 9–12°C for ABS/CoMoO₄ and ABS/NiMoO₄ composites. But for the ABS/CuMoO₄ composite, it is decreased by 45°C. Meanwhile, the peak of heat release rate is decreased by 10%–13% for ABS/CoMoO₄ and ABS/NiMoO₄ composites, and it is decreased by 26% for ABS/CuMoO₄ composite. Moreover, TGA/infrared spectrometry was used to investigate the smoke suppression effect of CuMoO₄ in ABS indirectly; it showed that the addition of CuMoO₄ inhibits the release of hydrocarbons, aromatic compounds, and CO and promotes the generation of CO₂. Copyright © 2014 John Wiley & Sons, Ltd.     

The electronic structures of vanadate salts: Cation substitution as a tool for band gap manipulation

The electronic structures of six ternary metal oxides containing isolated vanadate ions, Ba₃(VO₄)₂, Pb₃(VO₄)₂, YVO₄, BiVO₄, CeVO₄ and Ag₃VO₄ were studied using diffuse reflectance spectroscopy and electronic structure calculations. While the electronic structure near the Fermi level originates largely from the molecular orbitals of the vanadate ion, both experiment and theory show that the cation can strongly influence these electronic states. The observation that Ba₃(VO₄)₂ and YVO₄ have similar band gaps, both 3.8 eV, shows that cations with a noble gas configuration have little impact on the electronic structure. Band structure calculations support this hypothesis. In Pb₃(VO₄)₂ and BiVO₄ the band gap is reduced by 0.9-1.0 eV through interactions of (a) the filled cation 6s orbitals with nonbonding O 2p states at the top of the valence band, and (b) overlap of empty 6p orbitals with antibonding V 3d-O 2p states at the bottom of the conduction band. In Ag₃VO₄ mixing between filled Ag 4d and O 2p states destabilizes states at the top of the valence band leading to a large decrease in the band gap (E_g=2.2 eV). In CeVO₄ excitations from partially filled 4f orbitals into the conduction band lower the effective band gap to 1.8 eV. In the Ce_1−xBi_xVO₄ (0≤x≤0.5) and Ce_1−xY_xVO₄ (x=0.1, 0.2) solid solutions the band gap narrows slightly when Bi³⁺ or Y³⁺ are introduced. The nonlinear response of the band gap to changes in composition is a result of the localized nature of the Ce 4f orbitals.     

Tunable phase transition,band gap and SHG properties by halogen replacement of hybrid perovskites [(thiomorpholinium)PbX3, X = Cl,Br, I]

By the replacement of halogen anion, three new multifunctional organic-inorganic hybrid perovskites (thiomorpholinium)PbX₃ (X = Cl, Br, I) were successfully synthesized and underwent reversible structural transformation above room temperature, accompanied by the anomalous change of dielectric constant. With the adjustment of the halogen anion from Cl to I in the inorganic skeleton, the space group is transformed from centrosymmetric space group P2₁/c ((thiomorpholinium)PbCl₃) to chiral one P2₁2₁2₁ ((thiomorpholinium)PbBr₃, (thiomorpholinium)PbI₃) at room temperature. The ordered-disordered transition of organic cations and the change of hydrogen bonds with the increase of temperature lead to above-room-temperature phase transitions. Ultraviolet absorption and second-harmonic generation (SHG) measurements confirmed that both the band gap and SHG activity of (thiomorpholinium)PbX₃ (X = Cl, Br, I) crystals were tunable. The band gaps reveal a broadening trend with 3.532 eV, 3.410 eV and 3.175 eV along the Cl → Br → I series. This work provides an effective molecular design for multifunctional organic-inorganic perovskites.     

Electronic structure and Raman spectroscopy study of dibarium magnesium orthoborate,Ba2Mg(BO3)2

The samples of dibarium magnesium orthoborate Ba₂Mg(BO₃)₂ were synthesized by solid-state reaction. The X-ray diffraction (XRD) patterns and Raman spectra of the samples were collected. Electronic structure and vibrational spectroscopy of Ba₂Mg(BO₃)₂ were systematically investigated by first principle calculation. A direct band gap of 4.4 eV was obtained from the calculated electronic structure results. The top valence band is constructed from O 2p states and the low conduction band mainly consists of Ba 5d states. Raman spectra for Ba₂Mg(BO₃)₂ polycrystalline were obtained at ambient temperature. The factor group analysis results show the total lattice modes are 5E_u + 4A_2u + 5E_g + 4A_1g + 1A_2g + 1A_1u, of which 5E_g + 4A_1g are Raman-active. Furthermore, we obtained the Raman active vibrational modes as well as their eigenfrequencies using first-principle calculation. With the assistance of the first-principle calculation and factor group analysis results, Raman bands of Ba₂Mg(BO₃)₂ were assigned as E_g (42 cm⁻¹), A_1g (85 cm⁻¹), E_g (156 cm⁻¹), E_g (237 cm⁻¹), A_1g (286 cm⁻¹), E_g (564 cm⁻¹), A_1g (761 cm⁻¹), A_1g (909 cm⁻¹), E_g (1165 cm⁻¹). The strongest band at 928 cm⁻¹ in the experimental spectrum is assigned to totally symmetric stretching mode of the BO₃ units.     

Photo-luminescence studies of strontium barium niobate crystals doped with Cr3+ ions

This paper reports the photo-luminescence spectroscopic results of Strontium–Barium–Niobate, Sr_x,Ba_1−xNb₂O₅ (SBN, x = 0.61 for near congruent composition) crystals doped with Cr₂O, at cryogenic temperature (20 K). The experimental results reveal the need of re-assignment of the Cr³⁺ ions defect centres in this material. For first time, a broad emission band in the near infrared region centred at ca. 950 nm is reported. This emission band has micro-seconds decaytime constant and a FWHM band-width > 1700 cm⁻¹ and has been ascribed to the vibronically assisted ⁴T₂ → ⁴A₂ transition. A much narrower emission band centred at ca. 764 nm with milli-seconds decaytime constant and a FWHM band-width of ca. 170 cm⁻¹ is correlated to the ²E → ⁴A₂ radiative transition (R-line).     

Enhanced photoluminescence properties of Gd (x-1) Sr x O: CdO nanocores and their study of optical,structural, and morphological characteristics

Synthesis of Gd doped Sr_x O: CdO (x = 1.4, 1.6, 1.8) nanostructures (NS) was achieved through the coprecipitation method by using CTAB (cetyl trimethyl ammonium bromide) with the purpose to investigate the effect of Gd doping on the optical, structural, morphological, and photoluminescence properties at room temperature. Mixed phase of tetragonal crystal structure verified via X-ray diffraction technique, no structural variation was observed except lattice distortion. Size of the crystallites (D), morphology studied by SEM (scanning electron microscopy) analysis, nanoparticles (NPs) crystalized roughly flake-like morphology with homogeneous particle distribution centered at ~ 78 nm, ~56 nm, ~65 nm, ~88 nm for pure and Gd _(x-1) doped Sr _xO: CdO nanostructure, respectively. Fourier transform infrared spectroscopic investigation (FTIR) revealed the presence of Gd–O–Gd, Cd–O, Sr–O, and OH peaks appeared at ~1321 cm ^?1, ~1550 cm ^?1, ~1400 cm ^?1–3300 cm ^?1 with small variation in vibration modes due to Gd doping. Optical absorptivity observed in the range of 325 nm–359 nm (redshifted) with absorption edges at 346 nm, 364 nm, and 380 nm for Gd _(x-1) doped Sr _xO: CdO nanostructure, respectively. This redshift on the bandgap was discussed in terms of new band levels below conduction band. The energy gap was calculated using Kubelka-Munk theory and was found to be in the range of 3.22 eV–2.61 eV. X-ray photoelectron spectroscopy (XPS) performed to determine chemical composition and binding energies of Gd 3d _3/2, Sr 3d _3/2, and Cd 3d _3/2, O1s, and C1s observed at 150.8 eV, 141.6 eV, 411.0 eV, 530.4 eV, and 285.6 eV indicating Gd⁺³ ion replaces Sr⁺² in all concentrations. Our results showed that Gd-doped Sr _xO: CdO nanoparticles exhibited enhanced photoluminescence (PL) properties in contrast to the pure Gd₂O₃ with Gd⁺³ randomly incorporated into crystal structure, probably in tetrahedral sites. The composition of Gd _0.6 doped Sr _x O: CdO NS exhibited photoluminescent emission spectra, peaks centered at 433 ± 3 nm, 449 ± 3 nm, and 469 ± 2 nm (λ _excitation = 318 nm) and for Gd _0.8 doped Sr _x O: CdO nanostructure showed broad emission peak at 412 ± 2 nm to 433 ± 2 nm (λ _excitation = 380 nm), which indicates a reduction in defects with an increase in Gd doping. The transitions can be ascertained with shielding of 4f shells of Gd ⁺³ ions by 6s, 5d shells by the interaction of other Gd ⁺³ ions.     

Temperature dependent Raman study of SB → SC transition in liquid crystalline compound N-(4-n-pentyloxybenzylidene)-4′-heptylaniline (5O.7)

Temperature dependent Raman study of C–H in-plane bending mode (～1163 cm^?1 and ～1190 cm^?1) and C–C stretching mode of phenyl ring (～1571 cm^?1 and ～1594 cm^?1) of N-(4-n-pentyloxybenzylidene)-4′-heptylaniline (5O.7) has been done. Vibrational assignment and potential energy distribution (PED) of individual modes have been calculated employing density functional theory (DFT) for the first time. The S_B → S_C transition is nicely depicted in the variation of the linewidth of the ～1163 cm^?1 band and the peak position of ～1594 cm^?1 band with temperature. Because of a small amount of charge density transfer from the core part to the alkyl chain region, the ～1163 cm^?1 band shifts towards lower wavenumber side whereas the ～1190 cm^?1 band towards higher wavenumber side at S_B → S_C transition. The ～1571 cm^?1 and ～1594 cm^?1 bands are assigned as 8a and 8b modes, whose relative intensity variation with temperature gives the evidence of increased possibility of C–H bending motion of the linking group and the C–C stretching of the alkyl chain in S_C phase.     

Synthesis and luminescent properties of Eu2+ doped nitrogen-rich Ca-α-SiAlON phosphor for white light-emitting diodes

Yellow/orange-emitting nitrogen-rich Ca_0.9Si₉Al₃(O,N)₁₆: Eu²⁺ phosphors were successfully prepared by solid-state reaction synthesis. The fluorescence excitation spectra of all of the nitrogen-rich Ca_0.9Si₉Al₃(O,N)₁₆: Eu²⁺ phosphor powders displayed two broad bands centered at about 300 nm and 400–475 nm. The first peak was assigned to the absorption of the host lattice and the second to the 4f⁷ → 4f⁶5d¹ absorption of the Eu²⁺ ions, its means enhanced 4f⁷ → 4f⁶5d excitation of Eu²⁺ ion. The absorption peak intensity increased upon increasing the Eu²⁺ doping amount, but only up to a Eu²⁺ concentration ratio of 0.15. The emission spectra of the prepared Ca_0.9Si₉Al₃(O,N)₁₆: Eu²⁺ phosphors all exhibited a single broad band in the 500–700 nm region, maximum emission peak observed at 591 nm. The room temperature decay times were observed τ₁ = 1.27 μs and τ₂ = 9.90 μs.     

A novel nitridogallate fluoride LiBa5GaN3F5 – Synthesis,crystal structure,and band gap determination

LiBa₅GaN₃F₅ was obtained as red crystals by reaction of Ba, Ga, NaN₃ and EuF₃ in a Na/Li flux at 760 °C in weld-shut tantalum crucibles. The crystal structure (Pnma (no. 62), a = 15.456(3), b = 5.707(1), c = 12.259(3) Å, Z = 4) was solved on the basis of single-crystal X-ray diffraction data. In the solid there are trigonal planar [GaN₃]^6? ions and zigzag chains of vertex sharing LiF₆ octahedrons surrounded by Ba²⁺ ions. Optical measurements and calculations of the electronic structure revealed a band gap of ≤1.9 eV. According to the calculations, the observed transition occurs from a nitrogen state into a hybrid Ba/N state.     

ns2np4 (n = 4, 5) lone pair triplets whirling in M*F2E3 (M* = Kr,Xe): Stereochemistry and ab initio analyses

The stereochemistry of ns²np⁴ (n = 4, 5) lone pair LP characterizing noble gas Kr and Xe (labeled M*) in M*F₂ difluorides is examined within coherent crystal chemistry and ab initio visualizations. M*²⁺ in such oxidation state brings three lone pairs (E) and difluorides are formulated M*F₂E₃. The analyses use electron localization function (ELF) obtained within density functional theory calculations showing the development of the LP triplets whirling {E₃} quantified in the relevant chemical systems. Detailed ELF data analyses allowed showing that in α KrF₂E₃ and isostructural XeF₂E₃ difluorides the three E electronic clouds merge or hybridize into a torus and adopt a perfect gyration circle with an elliptical section, while in β KrF₂ the network architecture deforms the whole torus into an ellipsoid shape. Original precise metrics are provided for the torus in the different compounds under study. In KrF₂ the geometric changes upon β → α phase transition is schematized and mechanisms for the transformation with temperature or pressure are proposed. The results are further highlighted by electronic band structure calculations which show similar features of equal band gaps of 3 eV in both α and β KrF₂ and a reorganization of frontier orbitals due to the different orientations of the F-Kr-F linear molecule in the two tetragonal structures.     

First-principles calculations of Cd-doped ZnO thin films deposited by pulse laser deposition

Zn_1−xCd_xO thin films are deposited on quartz substrate by pulse laser deposition. Their band structure and optical properties are experimentally and theoretically investigated. By varying Cd concentration, the band gap of Zn_1−xCd_xO films can be adjusted in a wide range from 3.219 eV for ZnO to 2.197 eV for Zn_0.5Cd_0.5O, which produces different emissions from ultraviolet to Kelly light in their photoluminescence spectra. Simultaneity, the electronic structure and band gap of Zn_1−xCd_xO are investigated by the density functional theory (DFT) with a combined generalized gradient approximation (GGA) plus Hubbard U approach, which precisely predicts the band-gaps of ZnO and Zn_1−xCd_xO alloys. Both the experimental results and theoretical simulation reveal that with increasing Cd concentration in Zn_1−xCd_xO alloys, their absorption coefficients in visible light range are evidently enhanced. The adjustable photoluminescence emission and enhanced visible light absorption endow Zn_1−xCd_xO alloys potential applications in optoelectronic and photocatalytic fields.     

Prefabrication of two-dimensional Ni–W/TiN films on oil-gas X52 steels by pulse electrodeposition

The main aim of this investigation was to prefabricate two-dimensional Ni–W/TiN films on oil-gas X52 steel substrates via pulse electrodeposition (PE). The influences of the TiN content in the bath on the surface morphology, nano-hardness, wear, and corrosion properties of the films were also discussed. The results indicated that the TiN particle size was only ～33 nm in 8 g/L TiN electrolyte, which was ～2.4 times less than that of TiN in 16 g/L solution. The Ni–W/8TiN film exhibited a uniform, smooth surface, and the depression depth and protrusion height were 45.3 nm and 81.7 nm, respectively. Three diffraction peaks at 43.72, 50.78, and 75.26° in the Ni–W/4TiN film emerged as the sharpest and narrowest peaks among the four films. Three XPS peaks for the Ni 2p_3/2 were present at 852.13, 856.35, and 861.87 eV in the Ni–W/8TiN film, corresponding to Ni, Ni²⁺ (Ni(OH)₂), Ni³⁺ (NiOOH) species. Besides, the XPS peak of W 4f_7/2, which located at 33.85 eV belonged to elemental W. The Ni–W/8TiN film had the lowest wear depth and width at 32.1 μm and 5.7 mm, respectively. Only some narrow and shallow scratches were found on the Ni–W/8TiN film surface, showing its outstanding tribological properties among the films tested. In addition, the Ni–W/4TiN film showed the highest mean frictional coefficient of 0.73, which was ～1.6 times more than that of the Ni–W/8TiN film.     

Judd–Ofelt analysis and photoluminescence properties of RE3+ (RE = Er & Nd): Cadmium lithium boro tellurite glasses

Rare earth (Er³⁺ and Nd³⁺) ions doped cadmium lithium boro tellurite (CLiBT) glasses were prepared by melt quenching method. The vis–NIR absorption spectra of these glasses have been analyzed systematically. Judd–Ofelt intensity parameters Ω_λ (λ = 2, 4, 6) have been evaluated and used to compute the radiative properties of emission transitions of Er³⁺ and Nd³⁺: CLiBT glasses. From the NIR emission spectra of Er³⁺: CLiBT glasses a broad emission band centered at 1538 nm (⁴I_13/2 → ⁴I_15/2) is observed and from Nd³⁺: CLiBT glasses, three NIR emission bands at 898 nm (⁴F_3/2 → ⁴I_9/2), 1070 nm (⁴F_3/2 → ⁴I_11/2) and 1338 nm (⁴F_3/2 → ⁴I_13/2) are observed with an excitation wavelength λ_exci = 514.5 nm (Ar⁺ Laser). The FWHM and stimulated emission cross-section values are calculated for Er³⁺ and Nd³⁺: CLiBT glasses. FWHM × σ_e^P values are also calculated for Er³⁺: CLiBT glasses.     

Synthesis, crystal structure, and structural conversion of Ni molybdate hydrate NiMoO4·nH2O

The synthesis and crystal structure of NiMoO₄·nH₂O were investigated. The hydrate crystallized in the triclinic system with space group P−1, Z=4 with unit cell parameters of a=6.7791(2) Å, b=6.8900(2) Å, c=9.2486(2) Å, α=76.681(2)°, β=83.960(2)°, γ=74.218(2)°. Its ideal chemical composition was NiMoO₄·3/4H₂O rather than NiMoO₄·1H₂O. Under hydrothermal conditions the hydrate turned directly into α-NiMoO₄ above 483 K, giving nanorods thinner than the crystallites of the mother hydrate. On the other hand, it turned into Anderson type of polyoxomolybdate via a solid-solution process in a molybdate solution at room temperature.     

Obtain full visible spectrum light-emitting diode illumination via bismuth-activated cyan phosphors

Developing highly efficient cyan-emitting fluorescent materials is essential to bridge the cyan gap in phosphor-converted white light-emitting diodes for full-spectrum white illumination. Here, a Bi-doped cyan phosphor has been reported to solve this gap. The phase purity, photoluminescence emission/excitation spectra, concentration quenching, lifetime decay curves, and temperature-dependent photoluminescence emission spectra were systematically investigated. SrLaGaO₄:Bi³⁺ exhibits a broad excitation band (250–400 nm), which matches with the emission of a commercial near-ultraviolet light-emitting diode chip. The cyan light peaked at 475 nm is observed, which is attributed to the ³P₁→¹S₀ transition of Bi³⁺. The thermal quenching experiment was performed, and the activation energy was calculated as 0.36 eV. Finally, full-spectrum white light-emitting diode devices were fabricated using SrLaGaO₄:Bi³⁺ phosphors, commercial blue BaMgAl₁₀O₁₇:Eu²⁺ phosphor, green (Ba, Sr)₂SiO₄:Eu²⁺ phosphor, and red CaAlSiN₃:Eu²⁺ phosphor, which displayed an International Commission on an illumination coordinate of (0.3732, 0.3850), a correlated color temperature of 4290 K, and a color rendering index of 93.2 at a drive current of 20 mA. This result indicates that SrLaGaO₄:Bi³⁺ plays an essential role in bridging the cyan gap, providing new inspiration for applying cyan-emitting phosphors in full-spectrum white lighting.