A facile one-pot solvothermal route to tubular forms of luminescent polymeric networks [(C3N3)2(NH)3]n

A facile one-pot solvothermal route has been developed for the synthesis of tubular luminescent polymeric networks [(C₃N₃)₂(NH)₃]_n, structurally related to the proposed g-C₃N₄. XRD patterns showed a characteristic 002 basal plane diffractions, indicating an interlayer d spacing of 3.23 Å. XPS spectra show that the C1s and N1s have a symmetric peak and an asymmetric peak at 288.10 and 399.00 eV, respectively. The bulk composition C₆N_8.9H_4.5 determined by elemental analysis is comparable to the calculated value C₆N₉H₃ for this proposed polymer. FTIR spectra indicated the presence of s-triazine ring, which was further supported by the luminescent and UV-vis absorption characteristics probably depending on π→π^* electronic transition. The tubular structure has been studied by TEM, SAED, and HREM.     

Effects of Zn impurities on the electronic properties of Pr doped CaTiO3

Microcosmic investigations of weak red-emitting materials are crucial for their further development and application. In this work, we have focused on the band structures and electronic properties of Pr mono- and (Zn, Pr) co-doped CaTiO₃ using density functional theory. Zn substitution for Ca or Ti tends to form clusters energetically with Pr substituting for Ca in CaTiO₃. In Pr mono-doped CaTiO₃, the O_2p→Ti_3d transition in CaTiO₃ host corresponds to the centered 330 nm excitation spectra. The gap states above the valence band of ∼1.30 eV and ∼2.06 eV are hybridized by Pr_4f, O_2p and Ti_3d orbitals. They are mainly due to Pr_4f orbitals in CaTiO₃:Pr. The former gap level is related to red emission at 614 nm due to ¹D₂→³H₄ transition of Pr³⁺ activator. The latter is related to the excitation spectra centered at 380 nm due to the low-lying Pr-to-mental intervalence charge transfer transitions (Pr³⁺-O²⁻-Ti⁴⁺?Pr⁴⁺-O²⁻-Ti³⁺). The band structures of (Zn, Pr) co-doped CaTiO₃ keep the similar gap levels to those in Pr mono-doped CaTiO₃. The incorporation of Zn brings out the two stronger localized gap states, which are hybridized by Pr_4f, O_2p and Ti_3d orbitals, in comparison with those in Pr mono-doped CaTiO₃. Therefore, when Zn impurities are added into Pr doped CaTiO₃, the present calculations visualize the two enhanced levels and the distorted structures around Pr.     

Composition depth profiles of Bi3.15Nd0.85Ti3O12 thin films studied by X-ray photoelectron spectroscopy

In the present work, X-ray photoelectron spectroscopy (XPS) was used to investigate the composition depth profiles of Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) ferroelectric thin film, which was prepared on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by chemical solution deposition (CSD). It is shown that there are three distinct regions formed in BNT film, which are surface layer, bulk film and interface layer. The surface of film is found to consist of one outermost Bi-rich region. High resolution spectra of the O 1s peak in the surface can be decomposed into two components of metallic oxide oxygen and surface adsorbed oxygen. The distribution of component elements is nearly uniform within the bulk film. In the bulk film, high resolution XPS spectra of O 1s, Bi 4f, Nd 3d, Ti 2p are in agreement with the element chemical states of the BNT system. The interfacial layer is formed through the interdiffusion between the BNT film and Pt electrode. In addition, the Ar⁺-ion sputtering changes lots of Bi³⁺ ions into Bi⁰ due to weak Bi-O bond and high etching energy.     

Optical absorption, fluorescence and decay properties of Pr-doped PbO-H3BO3-TiO2-AlF3 glasses

Spectroscopic and laser properties of PbO-H₃BO₃-TiO₂-AlF₃ glasses doped with 0.1, 0.5, 1.0 and 2.0 mol% of Pr₆O₁₁ have been studied. Optical absorption spectra were recorded in the UV-vis-NIR regions and the observed absorption bands were assigned to different electronic transitions from ³H₄ ground state of 4f² configuration. The three phenomenological Judd-Ofelt (J-O) parameters Ω_t (t=2, 4, 6) were determined from the measured oscillator strengths by including as well as excluding the ³H₄→³P₂ hypersensitive transition in J-O analysis. The emission characteristics such as stimulated emission cross-sections (σ_e), measured branching ratios (β_m), measured lifetimes (τ_m), quantum efficiencies (η) and gain parameters (σ_e×τ_m) have been evaluated for the principal intermanifold transitions of Pr³⁺ from the ³P₀ and ¹D₂ states to the lower lying manifolds in the visible region. From the emission and decay measurements, the effect of Pr³⁺ ion concentration on the quenching of the ¹D₂ measured lifetimes has been discussed.     

Coherent Raman spectra of the ν1 mode of BF3 and BF3

High resolution (0.001 cm⁻¹) coherent anti-Stokes Raman spectroscopy (CARS) was used to directly examine the ν₁ symmetric stretching mode of the planar symmetric D_3h molecules ¹⁰BF₃ and ¹¹BF₃. Simulations of the spectra were done using ν₁ rovibrational parameters deduced from published infrared hot-band and difference-band studies and the close similarity to the observed CARS spectra confirms the validity of the infrared constants. No significant perturbations by Fermi resonance or Coriolis interactions with nearby states are observed, in marked contrast to the case of sulfur trioxide, a similar D_3h molecule recently studied. In the harmonic approximation, the ¹⁰BF₃ and ¹¹BF₃ν₁ Q-branches would be identical since the isotopic substitution is at the center of mass but, interestingly, the ν₁ stretching frequency for ¹¹BF₃ is found to be 0.198 cm⁻¹higher than for the lighter ¹⁰BF₃ isotopomer. This counterintuitive result is reproduced almost exactly (0.200 cm⁻¹) by ab initio calculations (B3LYP/cc-pVTZ) that included evaluation of cubic and quartic force constants and x_ij anharmonicity constants. The ab initio computations also predict to within 1% the ΔB, ΔC changes in the rotational constants in going from the ground state to the v₁ = 1 vibrational level. The results illustrate nicely the complementary interplay of modern infrared, Raman, and ab initio methods in obtaining and analyzing rovibrational spectra.     

Electronic structure of BaTiO3 using resonant X-ray emission spectroscopy at the Ba-L3 and Ti-K absorption edges

We have studied the electronic properties of the ferroelectric barium titanate BaTiO₃ using two complementary bulk-sensitive spectroscopic probes, resonant X-ray emission spectroscopy (RXES) and X-ray absorption spectroscopy in the partial fluorescence mode (PFY-XAS) at the Ba-L₃ and Ti-K absorption edges. Contrary to a previous study, we found no fine structure in the pre-edge area of the PFY-XAS spectrum at the Ba-L₃ edge, and no temperature-induced spectral change was observed between room temperature and 150 °C. This result is not supportive of the possible presence of the displacement around Ba²⁺ at the Curie temperature. RXES spectra were measured at the Ti-K edge for BaTiO₃, along with SrTiO₃ and La-doped metallic SrTiO₃. The photon energy of the emission peak is found to be nearly constant throughout the absorption edge for all three compounds. We deduce the Ti 3d states to have a delocalized character, in contrast with the Ba 5d states, a property which is consistent with the proposed scenario of the formation of electric dipoles in BaTiO₃.     

Lyman transitions of high rovibrationally excited H2, HD and D2 molecules

Energies and probabilities of Lyman transitions of high rovibrationally excited H₂, HD and D₂ molecules have been measured and compared with calculations. The experimental results are obtained from laser-induced fluorescence spectra that have been recorded in the spectral range from 60 500 to 83 500 cm⁻¹, covering 2/3 of the hydrogen Lyman band system. The necessary vacuum-UV radiation is produced by stimulated anti-Stokes Raman scattering, providing a widely tunable radiation source with narrow spectral bandwidth to resolve single Lyman transitions. The highest internal energies of detected hydrogen isotopologues are close to the dissociation limit. This extends the available data base of Lyman transitions from and to higher rotational states (J > 10) of HD and D₂.     

Spectroscopic investigations and configuration-interaction-assisted crystal field analysis of Pr in YPO4 single crystal

An optical study of a Y_0.99Pr_0.01PO₄ single crystal is presented. Measurements of optical absorption, excitation, and emission by selective excitation into ¹D₂, ³P₀ and ³P₁, at different temperatures between 20 and 295 K, are described. A detailed account of the line assignments is given for absorption in the 4300-23 000 cm⁻¹ spectral range, and for emission in the 6400-23 000 cm⁻¹ range. The lifetimes of the emitting levels are determined. Vibronic sidebands accompanying absorption, emission and excitation spectra are reported. The decay processes of the ³P₁, ³P₀ and ¹D₂ levels are discussed. The aim of this study is a test of the configuration-interaction-assisted crystal field analysis as well as the accurate experimental determination of the energy level scheme. It was reported previously that the introduction of configuration interaction between the ground 4f² configuration with the excited 4f6p configuration always resulted in a decrease (≈50-60%) in the standard deviations between the observed and calculated energy levels. In the present work the 4f5d configuration is included as well. The crystal field is analysed in the theoretical D_2d site symmetry with and without configuration interaction. The results with 4f², 4f²+4f5d, 4f²+4f6p and 4f²+4f5d+4f6p are given. The calculation on the basis of the 315 (4f²+4f5d+4f6p) levels gives the best overall standard deviation lowering it by 75% with regard to the calculation on the 91 4f² levels only.     

Microstructures, surface bonding states and room temperature ferromagnetisms of Zn0.95Co0.05O thin films doped with copper

Zn_0.95−xCo_0.05Cu_xO (ZCCO, where x = 0, 0.005, 0.01 and 0.015) thin films were deposited on Si (1 0 0) substrates by pulsed laser deposition technique. Crystal structures, surface morphologies, chemical compositions, bonding states and chemical valences of the corresponding elements for ZCCO films were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and X-ray photoelectron spectroscopy (XPS). XRD and FESEM results indicate that crystallite sizes of the highly (0 0 2)-oriented ZCCO films slightly decrease with increasing Cu content. When the Cu content increases from 0 to 0.015, Zn 2p_3/2, Co 2p, Cu 2p_3/2 and O 1s peaks of the ZCCO film shift towards higher or lower binding energy regions, and the reasons for these chemical shifts are investigated by fitting the corresponding XPS narrow-scan spectra. Both in-plane and out-of-plane magnetization-magnetic field hysteresis loops of the ZCCO films reveal that all the films have room temperature ferromagnetisms (RTFMs). The conceivable origin of the RTFM is ascribed to the combined effects of the local structural disorder resulted from (Co²⁺, Cu²⁺, Cu¹⁺)-cations which substitute Zn²⁺ ions in the ZnO matrices, ferromagnetic coupling between coupled dopant atoms caused by Co²⁺ (3d⁷4s⁰) and Cu²⁺ (3d⁹4s⁰) spin states, and exchange interactions between the unpaired electron spins originating from lattice defects induced by Cu doping in the Zn_0.95Co_0.05O matrices.     

Comparative structural and photoluminescent study of Eu-doped La2O3 and La(OH)3 nanocrystalline powders

Eu³⁺-doped La₂O₃ nanocrystalline powder was prepared by polymer complex solution method and further used for preparation of Eu³⁺-doped La(OH)₃. Structural and optical characterization was carried out by powder X-ray diffraction and photoluminescent spectroscopy. XRD measurements confirmed the formation of hexagonal La₂O₃ and its recrystallization into La(OH)₃ in a humid atmosphere. Excitation spectra show redshift of host lattice and charge transfer emission bands in La(OH)₃ while bands that correspond to Eu³⁺f–f transitions are placed at same wavelengths in both samples. Photoluminescence spectra recorded over the temperature range from 10 K to 300 K show that intensities of emission lines in Eu³⁺-doped La₂O₃ do not depend on temperature as much as in La(OH)₃ sample. Observed dominant ⁵D₀→⁷F₂ and markedly visible ⁵D₀→⁷F₀ emissions in doped La₂O₃ indicate that Eu³⁺ ion is located in a structural site without an inversion center. On the other hand, in Eu³⁺-doped La(OH)₃⁵D₀→⁷F₀ transition is barely visible while ⁵D₀→⁷F₂ is not prominent, and with temperature drop three ⁵D₀→⁷F_J (J=1, 2, 4) transitions become almost of the same intensity. In both La₂O₃ and La(OH)₃ structures Eu³⁺ ion replaces La³⁺ in non-centrosymmetric C_3v and C_3h crystallographic sites, respectively, and difference in symmetry of the crystal field around europium ion is explained by comparing shape and volume of these sites. Decay times of the ⁵D₀- level recorded over the temperature range 10−300 K revealed that emission lifetime values in La₂O₃ (~0.7 ms) are almost two times higher than in La(OH)₃ (~0.4 ms), and unlike in La₂O₃, lifetime in La(OH)₃ is temperature dependent.     

Electrical transport properties of CaMnO3 thermoelectric compound: a theoretical study

The electrical transport coefficients of anti-ferromagnetic CaMnO₃ have been investigated by density functional theory calculation within generalized gradient approximation. The calculated transport coefficients exhibit the anisotropic nature, in agreement with its electronic states. The transport property results reveal the stronger carrier transport along the O1–Mn–O1 plane within the O–Mn–O octahedron, indicating that the Mnd and O1p orbitals are mainly responsible for electrical transport. The maximum power factor values as a function of relaxation time reach 8.4×10²³ Wm⁻¹ K⁻² s⁻¹, 7.9×10²³Wm⁻¹ K⁻² s⁻¹ and 4.9×10²³ Wm⁻¹ K⁻² s⁻¹ within c, a and b direction, respectively. The dimensionless figure of merit ZTxx, ZTyy as well as ZTzz is estimated with 1.28, 0.8 and 1.37 at 1000 K, respectively.     

Spectroscopic investigations of Nd-, Er-, Er/Yb-, and Tm-ions doped SiO2-Al2O3-CaF2-GdF3 glasses

This paper reports on the absorption, visible and near-infrared luminescence properties of Nd³⁺, Er³⁺, Er³⁺/2Yb³⁺, and Tm³⁺ doped oxyfluoride aluminosilicate glasses. From the measured absorption spectra, Judd-Ofelt (J-O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been calculated for all the studied ions. Decay lifetime curves were measured for the visible emissions of Er³⁺ (558 nm, green), and Tm³⁺ (650 and 795 nm), respectively. The near infrared emission spectrum of Nd³⁺ doped glass has shown full width at half maximum (FWHM) around 45 nm (for the ⁴F_3/2→⁴I_9/2 transition), 45 nm (for the ⁴F_3/2→⁴I_11/2 transition), and 60 nm (for the ⁴F_3/2→⁴I_13/2 transition), respectively, with 800 nm laser diode (LD) excitation. For Er³⁺, and Er³⁺/2Yb³⁺ co-doped glasses, the characteristic near infrared emission bands were spectrally centered at 1532 and 1544 nm, respectively, with 980 nm laser diode excitation, exhibiting full width at half maximum around 50 and 90 nm for the erbium ⁴I_13/2→⁴I_15/2 transition. The measured maximum decay times of ⁴I_13/2→⁴I_15/2 transition (at wavelength 1532 and 1544 nm) are about 5.280 and 5.719 ms for 1Er³⁺ and 1Er³⁺/2Yb³⁺ (mol%) co-doped glasses, respectively. The maximum stimulated emission cross sections for ⁴I_13/2→⁴I_15/2 transition of Er³⁺ and Er³⁺/Yb³⁺ are 10.81×10⁻²¹ and 5.723×10^-21 cm². These glasses with better thermal stability, bright visible emissions and broad near-infrared emissions should have potential applications in broadly tunable laser sources, interesting optical luminescent materials and broadband optical amplification at low-loss telecommunication windows.     

Luminescent properties of trivalent praseodymium-doped lanthanum aluminum germanate LaAlGe2O7

The luminescent characteristics of Pr³⁺-activated LaAlGe₂O₇ were investigated. In response to excitement using 448 nm blue light, the emission spectra involved most of the ³P₀→³H_J transitions. The dominant emission came from the ³P₀→³H₄ transition at 487 nm. ¹D₂ fluorescence quenching was observed in highly doped samples and is related to the cross-relaxation processes among neighboring Pr³⁺ ions. In contrast with conventional Pr³⁺-activated phosphors, the extraordinary excitation spectra showed only intense f-f transition of Pr³⁺ ions, while the 4f-5d transition was eliminated. This is ascribed to photoionization. By analyzing absorption and excitation spectra, it is recognized that no efficient energy transfer occurs between Pr³⁺ and the host lattice in LaAlGe₂O₇.     

Synthesis and luminescence properties of red-emitting phosphors NaY0.87Eu0.13(WO4)1.2(MoO4)0.8

A series of NaY_1−yEu_y(WO₄)_2−x(MoO₄)_x (x=0−2 and y=0.06−0.15) phosphors have been prepared by a combustion route. X-ray powder diffraction, photoluminescence excitation and emission spectra were used to characterize the resulting samples. The excitation spectra of these phosphors show the strongest absorption at about 396 nm, which matches well with the commercially available n-UV-emitting GaN-based LED chip. Their emission spectra show an intense red emission at 616 nm due to the ⁵D₀→⁷F₂ electric dipole transition of Eu³⁺. As the Mo content increases, the intensity of the ⁵D₀→⁷F₂ emission of Eu³⁺ activated at wavelength of 396 nm increases and reaches a maximum when the relative ratio of Mo/W is 2:3. The intense red-emission of the tungstomolybdate phosphors at near-UV excitation suggests that the material is a potential candidate for white light emitting diode (WLEDs).     

The rotational spectrum of BiO radical in its X1Π1/2 and X2Π3/2 states

Rotational spectra have been observed for BiO produced in a DC discharge through a low pressure mixture of O₂, Ar, and Bi vapor. Because of the highly non-thermal distribution of states, it has been possible to observe spectra arising from the X₁²Π_1/2 level up to v = 9 and for the X₂²Π_3/2 level up to v = 5 near 10 538 cm⁻¹. Precise rotational and hyperfine parameters have been determined for the observed states. By using available near infrared (NIR) data in a merged fit, the 0-0 and 1-1 fine structure intervals have been more precisely determined. Although the quality of the fit is very good, the interpretation of the hyperfine constants is complicated by relativistic effects and the interaction of the X₂ state with A₁⁴Π_3/2 state. The magnetic and quadrupole coupling constants will be compared with those of the Bi atom and related molecules.     

High-precision frequency measurements of the ν1 + ν3 combination band of C2H2 in the 1.5 μm region

A pair of 1.5 μm semiconductor laser frequency standards have been developed for optical telecommunications use, stabilised to transitions of ¹²C₂H₂ and ¹³C₂H₂, using cavity-enhanced Doppler-free saturation absorption spectroscopy. The absolute frequencies of 41 lines of the ν₁ + ν₃ band of ¹²C₂H₂, covering the spectral region 1520-1545 nm, have been measured by use of a passive optical frequency comb generator, referenced to ¹³C₂H₂ transitions of known frequency. The mean experimental uncertainties (coverage factor k = 1) of the frequency values are 3.0 kHz (type A) and 10 kHz (type B). Improved values of the band origin ν₀, rotational constants B′ and B″, and centrifugal distortion coefficients D′, D″, H′, and H″ are presented.     

Spectroscopy of nickel chloride: Identification of the [15.0] Π3/2 and [15.0] Δ5/2 states

Vibrational bands belonging to the [15.0] ²Δ_5/2-A²Δ_5/2, [15.0] ²Δ_5/2-X²Π_3/2, and [15.0] ²Π_3/2-X²Π_3/2 electronic transitions of NiCl have been observed in the 14 000-16 000 cm⁻¹ region. The [15.0] ²Δ_5/2 and [15.0] ²Π_3/2 states are identified for the first time. The observed bands have been recorded at high spectral resolution using several techniques, which include intracavity laser spectroscopy (ILS), Fourier transform emission spectroscopy (FTS), and laser induced fluorescence (LIF) spectroscopy. For the ILS absorption spectra, NiCl molecules were produced in a nickel hollow cathode operated with a small amount of CCl₄. For the FTS emission spectra, excited NiCl molecules were produced in a King-type carbon tube furnace loaded with NiCl₂ and heated to 1600 °C. In the LIF work, NiCl molecules were produced by reacting laser-ablated nickel with PCl₃ seeded in argon. Detailed analysis of rotational transition lines indicates that the observed [15.0] ²Δ_5/2 and [15.0] ²Π_3/2 states are only separated by 10 cm⁻¹ and are interacting with each other. Molecular constants for these newly observed electronic states are reported.     

Luminescence of Ca(NbO3)2:Pr at ambient and high hydrostatic pressure

In this contribution, photoluminescence and time-resolved photoluminescence spectra of Ca(NbO₃)₂ doped with Pr³⁺ obtained at high hydrostatic pressure up to 72 kbar applied in a diamond anvil cell are presented. At ambient conditions, the emission spectrum obtained in the time interval 0-1 μs is dominated by spin-allowed transitions from the ³P₀ state. On the other hand, transitions from ¹D₂, characterized by a decay time equal to 30 μs dominate the steady-state luminescence.At pressures lower than 60 kbar, the continuous wave emission spectrum consists of sharp lines peaking between 600 and 625 nm, related to the ¹D₂→³H₄ transition and three lines at 500, 550 and 650 nm related to emission transitions originating from the ³P₀ level of Pr³⁺. The emission from the ¹D₂ excited state depends weakly on the pressure. Its decay time decreases from 33 μs at ambient pressure to less than 22 μs at 68 kbar. On the other hand, the ³P₀ emission is strongly pressure dependent. At pressures of 60 kbar and higher, the Pr³⁺ emission intensity from the ³P₀ state decreases. This is accompanied by a strong shortening of the luminescence decay time.The observed pressure quenching of the f-f emission transitions and the concomitant lifetime shortening have been attributed to increasing crossover from the ³P₀ state of Pr³⁺ to a Pr³⁺-trapped exciton state.     

Electronic excitations in phosphorus-containing molecules. I. Inner shell electron energy loss spectra of PH3, P(CH3)3, PF3 and PCL3

Electron energy loss Spectroscopy has been used to obtain the inner shell electronic excitation spectra of PH₃, PF₃, PCl₃ and P(CH₃)₃ in the phosphorus L-shell (P 2p, 2s) region as well as the respective ligand K -shells (F 1s, C 1s) and L-shell (Cl 2p and 2s) regions. The spectra were obtained under small momentum transfer conditions so that dipole-allowed transitions dominate. An impact energy of 2.5 ke V was used and inelastically scattered electrons were detected at a typical scattering angle of about 1°. A dipoleforbidden transition of unusual character is observed at 135.11 eV in the P 2p spectrum of PCl₃. Although optically forbidden, as indicated by its absence in a soft X-ray absorption spectrum, the intensity of this transition rises very rapidly with increase in momentum transfer.     

Optical properties of Eu:CsGd2F7 downconversion phosphor

Luminescence spectra and excitation spectra in 150-420 nm spectral region have been recorded at room temperature for polycrystalline sample of (0.5%)Eu³⁺:CsGd₂F₇. The relatively intense emission has been observed from ⁵D₃, ⁵D₂ and ⁵D₁ levels. Emission and excitation spectra prove that the excitation energy is efficiently transferred from the ⁶G_J and ⁶I_J levels of Gd³⁺ ions to Eu³⁺ ions. The visible quantum cutting via downconversion has been detected, with efficiency of the cross-relaxation step of ∼50%.