Synthesis, vibrational and optical properties of a new three-layered organic-inorganic perovskite (C4H9NH3)4Pb3I4Br6

An organic-inorganic hybrid perovskite (C₄H₉NH₃)₄Pb₃I₄Br₆ was synthesized and studied by X-ray diffraction, Raman and infrared spectroscopies, optical transmission and photoluminescence. The title compound, abbreviated (C₄)₄Pb₃I₄Br₆, crystallises in a periodic two-dimensional multilayer structure with P2₁/a space group. The structure is built up from alternating inorganic and organic layers. Each inorganic layer consists of three sheets of PbX₆ (X=I, Br) octahedra. Raman and infrared spectra of the title compound were recorded in the 100-3500 and 400-4000 cm⁻¹ frequency ranges, respectively. An assignment of the observed vibration modes is reported. Optical transmission measurements, performed on thin films of (C₄)₄Pb₃I₄Br₆, revealed two absorption bands at 474 and 508 nm. Photoluminescence measurements have shown a green emission peak at 519 nm.     

Luminescence characteristics of Pb centres in undoped and Ce-doped Lu3Al5O12 single-crystalline films and Pb→Ce energy transfer processes

At 4.2-350 K, the steady-state and time-resolved emission and excitation spectra and luminescence decay kinetics were studied under excitation in the 2.5-15 eV energy range for the undoped and Ce³⁺-doped Lu₃Al₅O₁₂ (LuAG) single-crystalline films grown by liquid phase epitaxy method from the PbO-based flux. The spectral bands arising from the single Pb²⁺-based centres were identified. The processes of energy transfer from the host lattice to Pb²⁺ and Ce³⁺ ions and from Pb²⁺ to Ce³⁺ ions were investigated. Competition between Pb²⁺ and Ce³⁺ ions in the processes of energy transfer from the LuAG crystal lattice was evidenced especially in the exciton absorption region. Due to overlap of the 3.61 eV emission band of Pb²⁺ centres with the 3.6 eV absorption band of Ce³⁺ centres, an effective nonradiative energy transfer from Pb²⁺ ions to Ce³⁺ ions takes place, resulting in the appearance of slower component in the luminescence decay kinetics of Ce³⁺ centres and decrease of the Ce³⁺-related luminescence intensity.     

X-ray diffraction, vibrational and photoluminescence studies of the self-organized quantum well crystal H3N(CH2)6NH3PbBr4

We have prepared new semiconductor H₃N(CH₂)₆NH₃PbBr₄ crystals which are self-assembled organic-inorganic hybrid materials. The grown crystals have been studied by X-ray diffraction, infrared absorption and Raman spectroscopy scattering. We found that the title compound, abbreviated 2C₆PbBr₄, crystallizes in a two-dimensional (2D) structure with a P2₁/a space group. In the inorganic semiconductor sub-lattice, the corner sharing PbBr₆ octahedra form infinite 2D chains. The organic C₆H₁₈N₂⁺ ions form the insulator barriers between the inorganic semiconductor layers. Such a packing leads to a self-assembled multiple quantum well structure. Raman and infrared spectra of the title compound were recorded in the 50-500 and 400-4000 cm⁻¹ frequency regions, respectively. The assignment of the observed Raman lines was performed by comparison with the homologous compounds. Transmission measurements on thin films of 2C₆PbBr₄, obtained by the spin coating method, revealed a strong absorption peak at 380 nm. Luminescence measurements showed an emission line at 402 nm associated with radiative recombinations of excitons confined within the PbBr₆ layers. The electron-hole binding energy is estimated at 180 meV.     

Electronic structure calculations and optical properties of a new organic-inorganic luminescent perovskite: (C9H19NH3)2PbI2Br2

(C₉H₁₉NH₃)₂PbI₂Br₂ compound is a new crystal belonging to the large hybrid organic-inorganic perovskites compounds family. Optical properties are investigated by optical absorption UV-visible and photoluminescence (PL) techniques. Bands to band absorption peak at 2.44 eV as well as an extremely strong yellow-green photoluminescence emission at 2.17 eV is observed at room temperature. First principle calculations based on the DFT and FLAPW methods combined with LDA approximation are performed as well. Density of state close to the gap is presented and discussed in terms of optical absorption and photoluminescence experimental results. The perfect agreement between experimental data and electronic structure calculations is highlighted.     

有机-无机杂化钙钛矿自组装量子阱结构的能带调控和光电性能的研究

有机-无机杂化钙钛矿材料具有分子尺度上调节能带结构的特点,在光、电、磁等领域均表现出了优异的性能.通过简单的旋涂方法,成功的制备了具有不同无机层层数的杂化钙钛矿材料(C₆H₁₃NH₃)₂(CH₃NH₃)_n-1Pb_nI_3n+1 (简写为C₆Pb关键词： 杂化钙钛矿 量子阱 带隙 光电性能     

Magnetic properties of the intermetallic compound Ce5Ge4

Magnetic and magnetocaloric properties of the compound Ce₅Ge₄ have been studied. This compound has orthorhombic Sm₅Ge₄-type structure (space group Pnma, no. 62) and orders ferromagnetically at ~12 K (T_C). The paramagnetic Curie temperature is ~−20 K suggesting the presence of competing ferromagnetic and antiferromagnetic interactions in this compound. The magnetization does not seem to saturate even in fields of 90 kOe at 3 K consistent with the presence of competing interactions. Saturation magnetization value (extrapolated to 1/H→0) of only 0.8μ_B/Ce³⁺ is obtained compared to the free ion value of 2.14μ_B/Ce³⁺. This moment reduction in the ordered state of Ce₅Ge₄ could be due to partial antiferromagnetic/paramagnetic ordering of the Ce moments and may also be due to crystalline electric field effects. Magnetic entropy change near T_C, calculated from the magnetization vs. field data, is found to be moderate with a maximum value of ~9 J/kg/K at ~11 K for a field change of 90 kOe.     

Electrical and optical absorption studies of Cu7GeS5I fast-ion conductor

Electrical conductivity and fundamental absorption spectra of monocrystalline Cu₇GeS₅I were measured in the temperature ranges 95-370 and 77-373 K, respectively. A rather high electrical conductivity (σ_t=6.98×10⁻³Ω⁻¹ cm⁻¹ at 300 K) and low activation energy (ΔE_a=0.183 eV) was found. The influence of different types of disordering on the Urbach absorption edge and electron-phonon interaction parameters were calculated, discussed and compared with the same parameters in Cu₇GeS₅I, Cu₆PX₅I (X=S,Se) and Ag₇GeX₅I (X=S,Se) compounds. We have concluded that the P→Ge and Cu→Ag cation substitution results in an increase of the electrical conductivity and a decrease of the activation energy. Besides, P→Ge substitution, results in complete smearing and disappearance of the exciton absorption bands and in blue shift of the Urbach absorption edge, an increase of the edge energy width and an electron-phonon-interaction enhancement.     

Construction of novel quantum-confined structure with lead halide/gemini surfactant hybrids

Novel organic–inorganic hybrid compounds, C₁₆H₄₄N₄Pb₃I₁₀ and C₁₄H₃₄N₂Pb₂I₆, were synthesized by solvent diffusion recrystallization from the dimethylsulfoxide solution containing PbI₂ and gemini ammonium surfactants with different head groups. The results of single crystal X-ray structural analysis showed that the inorganic region of C₁₆H₄₄N₄Pb₃I₁₀ has quasi one-dimensional chains of [Pb₃I₁₀]^4? units, whereas that of C₁₂H₃₀N₂Pb₂I₆ has one-dimensional chains of face-sharing PbI₆ octahedra. The absorption and fluorescence spectra of these compounds also indicate the formation of one-dimensional inorganic chains and quantum-confined structures.     

Organic compounds in the C3H6O3 family: Microwave spectrum of cis-cis dimethyl carbonate

Geometry optimization calculations on 13 members of the C₃H₆O₃ family of organic species have been carried out to determine their relative binding energies. Dimethyl carbonate [(CH₃)₂CO₃] is one of the lower energy species in this family, which includes the C₃-sugars 1,3-dihydroxyacetone and glyceraldehyde. The microwave spectrum of dimethyl carbonate has been measured over the frequency range 8.4-25.3 GHz with several pulsed-beam Fourier-transform microwave spectrometers and from 227 GHz to 350 GHz with direct absorption spectrometers. The spectrum of the lowest-energy cis-cis conformer of dimethyl carbonate has been assigned, and ab initio electronic structure calculations of the three possible conformers have been performed. Stark effect measurements were carried out on the cis-cis conformer to provide accurate determinations of the dipole moment components.     

Investigation of the nonlinear absorption and optical limiting properties of two [Q]2[Cu(C3S5)2] compounds

The nonlinear absorption properties of two organometallic compounds, [(C₂H₅)₄N]₂[Cu(C₃S₅)₂] (DCu1) and [(C₄H₉)₄N]₂[Cu(C₃S₅)₂] (DCu2), have been investigated using an open-aperture Z-scan technique at 1064 nm with 40 ps pulse width and at 1053 nm with 18 ns pulse width. The reverse saturable absorption (RSA) which was observed in both samples with nanosecond pulse excitation was much larger than that observed with picosecond pulse excitation. The nonlinear absorption properties were analyzed theoretically by a five-level model. Optical limiting based on RSA was performed and limiting thresholds were evaluated for both samples under three conditions. DCu1 exhibited the better limiting characteristics because of its stronger RSA response.     

Change of exciton-phonon interaction in layered ferroelastic crystals (Cs3Bi2I9)

The half-width of exciton absorption band (n=1) of Cs₃Bi₂I₉ layered ferroelastic crystals was studied carefully as function of temperature in the range from 5 to 300 K. For the first time, we have found a new physical effect: change of exciton-phonon interaction (from weak to strong) in the same sample as temperature increases. It was established that the temperature value T^*=150 K may be considered as characteristic one, below which a crystal loses the nature of layered substance. The effect is explained using a model that takes into account the reconstruction of the crystal lattice from non-layered to layered one.     

Exciton photoluminescence, photoconductivity and absorption in GaSe0.9Te0.1 alloy crystals

The photoluminescence, photoconductivity and absorption in GaSe_0.9Te_0.1 alloy crystals have been investigated as a function of temperature and external electric field. It has been observed that the exciton peaks shift to lower energy in GaSe_0.9Te_0.1 alloy crystals compared to GaSe crystals. The long wavelength tails of interband photoluminescence, photoconductivity and absorption spectra are determined by the free exciton states and show an Urbach-Martienssen-type dependence to the photon energy. The maxima of the extrinsic photoluminescence and photoconductivity spectra were found to be determined by the acceptor centers with an energy of E_A=E_V+0.19 eV formed by the polytypism and defects complexes that include Se and Te anions.     

Transient differential reflectivity of ferromagnetic and paramagnetic phases in the bilayered manganite La1.24Sr1.76Mn2O7

Photoinduced effects in a single crystal of bilayered manganites, La_2−2xSr_1+2xMn₂O₇ (x=0.38), were investigated in a wide range of temperatures by pump-probe measurement at a photon energy of 1.6 eV. In a ferromagnetic metallic state, significant enhancement of positive rise in differential reflectivity with a slow relaxing time of 100 ps was observed just below T_C=127 K, indicating that the reflectivity change with the slow relaxation time constant is induced by laser heating. We have also observed an unconventional fast relaxing component that has a time constant of the order of 10 ps. This fast relaxing component, whose absolute value has an asymmetric peak at T_C, is presumably due to short-range correlation of Jahn-Teller distortion.     

Three- and two-dimensional topological insulators in Pb2Sb2Te5, Pb2Bi2Te5, and Pb2Bi2Se5 layered compounds

The electronic structure of ternary compounds Pb₂Sb₂Te₅, Pb₂Bi₂Te₅, and Pb₂Bi₂Se₅, which have a layered structure that consists of nine-layer atomic blocks separated by van der Waals gaps, has been theoretically studied. It has been shown that all studied compounds are three-dimensional topological insulators. The possibility of the existence of a two-dimensional topological insulator has been found in ultrathin (0001) Pb₂Sb₂Te₅ and Pb₂Bi₂Te₅ films. Oscillations of the ℤ₂ topological invariant with an increase in the film thickness have been observed in the latter compound.     

Switching phenomenon and optical properties of Se85Te10Bi5 films

Se₈₅Te₁₀Bi₅ films of different thicknesses ranging from 126 to 512 nm have been prepared. Energy-dispersive X-ray (EDX) spectroscopy technique showed that films are nearly stoichiometric. X-ray diffraction (XRD) measurements have showed that the Se₈₅Te₁₀Bi₅ films were amorphous. Electrical conduction activation energy (ΔE_σ) for the obtained films is found to be 0.662 eV independent of thickness in the investigated range. Investigation of the current voltage (I-V) characteristics in amorphous Se₈₅Te₁₀Bi₅ films reveals that it is typical for a memory switch. The switching voltage V_th increases with the increase of the thickness and decreases exponentially with temperature in the range from 298 to 383 K. The switching voltage activation energy (ε) calculated from the temperature dependence of V_th is found to be 0.325 eV. The switching phenomenon in amorphous Se₈₅Te₁₀Bi₅ films is explained according to an electrothermal model for the switching process. The optical constants, the refractive index (n) and the absorption index (k) have been determined from transmittance (T) and reflectance (R) of Se₈₅Te₁₀Bi₅ films. Allowed non-direct transitions with an optical energy gap (E_g^opt) of 1.33 eV have been obtained. ΔE_σ is almost half the obtained value of E_g^opt, which suggested band to band conduction as indicated by Davis and Mott.     

Extremely large binding energy of biexcitons in an organic-inorganic quantum-well material (C4H9NH3)2PbBr4

We have confirmed biexciton formation in an organic-inorganic hybrid quantum-well material (C₄H₉NH₃)₂PbBr₄ by photoluminescence and two-photon absorption measurements. The biexciton has extremely large binding energy, 60 meV, which to our knowledge is the largest value ever reported for a semiconductor. By analyzing the spectrum of biexciton luminescence, the biexciton gas temperature was found to be much higher than the bath temperature due to a higher local temperature arising from the large biexciton binding energy.     

Structural,electronic and magnetic properties of the double perovskite Pb2FeReO6

The structural, electronic and magnetic properties of the double perovskite Pb₂FeReO₆ have been studied by using the first-principles projector augmented wave (PAW) potential within the generalized gradient approximation (GGA) as well as taking into account the on-site Coulomb repulsive and exchange coupling interactions (GGA+U). The optimized crystal structure of the Pb₂FeReO₆ is a body-centered tetragonal (BCT) with a space group of I4/m and the lattice constants of a=b=5.59 Å and c=7.93 Å, consistent with the experimental results. The two axial transition metal and oxygen (TM–O) distances are slightly larger than the four equatorial TM–O distances and shows the existence of the Jahn–Teller structural distortion in FeO₆ and ReO₆ octahedra. The Fe³⁺ and Re⁵⁺ ions are in the states (3d⁵, S=5/2) and (5d², S=1) with magnetic moments 3.929 and −0.831μ_B respectively and thus antiferromagnetic (AFM) coupling via oxygen between them. The half-metallic (HM) ferromagnetic (FM) nature implies a potential application of this new compound in magnetoelectronic and spintronics devices.     

Crystal structure,ionic conductivity and dielectric relaxation studies in the (C5H10N)2BiBr5 compound

The synthesis and crystal structure of the bis (3-dimethylammonium-1-propyne) pentabromobismuthate(III) salt are given in the present paper. After an X-ray investigation, it has been shown that the title compound crystallizes at 298 K in a centrosymmetric monoclinic system, in the space group C₂/c with the following lattice parameters a=12.9034(3) Å, b=19.4505(6) Å, c=8.5188(2) Å, β=102.449(2). Not only were the impedance spectroscopy measurements of (C₅H₁₀N)₂BiBr₅ carried out from 209 Hz to 5 MHz over the temperature range of 318 K–373 K, but also its ac conductivity evaluated. Besides, the dielectric relaxation was examined using the modulus formalism. Actually, the near values of activation energies obtained from the impedance and modulus spectra confirms that the transport is of an ion hopping mechanism, dominated by the motion of the H⁺ ions in the structure of the investigated material.     

Rotational and hyperfine spectra for a sandwich titanium complex, C5H5TiC7H7

Microwave spectroscopy measurements and density functional theory calculations are reported for the cyclopentadienyl cycloheptatrienyl titanium complex, C₅H₅TiC₇H₇. Rotational transition frequencies for this symmetric-top complex were measured in the 4-13 GHz range using a Flygare-Balle-type pulsed beam spectrometer. The spectroscopic constants obtained for the normal C₅H₅⁴⁸TiC₇H₇ isotopomer are B = 771.78907(38), D_J = 0.0000295(41), and D_JK = 0.001584(73) MHz. The quadrupole hyperfine splittings for C₅H₅⁴⁷TiC₇H₇ were clearly observed and the measured constants are B = 771.79024(32) MHz, D_J = 0.0000395(33), D_JK = 0.001646(24), and eQq_aa = 8.193(40) MHz. Analysis of the experimental and theoretical rotational constants indicates that the η⁷-C₇H₇Ti and η⁵-C₅H₅Ti bond lengths in the gas phase are about 0.02 Å longer than those reported for the solid-state X-ray structure. The calculated Ti-C bond lengths are shorter for the C₇H₇ ligand (r(Ti-C) = 2.21 Å) than for the C₅H₅ ligand (r(Ti-C) = 2.34 Å), and the C₇H₇ H atoms are displaced 0.15 Å out of the C₇ plane, toward the Ti atom.     

Efficient blue upconversion emission due to confined radiative energy transfer in Tm-Nd co-doped Ta2O5 waveguides under infrared-laser excitation

Intense blue upconversion emission at 480 nm has been obtained at room temperature in Tm³⁺-Nd³⁺ co-doped Ta₂O₅ channel waveguides fabricated on a Si substrate, when the sample is excited with an infrared laser at 793 nm. The upconversion mechanism is based on the radiative relaxation of the Nd³⁺ ions (⁴F_3/2 → ⁴I_11/2) at about 1064 nm followed by the absorption of the emitted photons by Tm³⁺ ions in the ³H₄ excited state. A coefficient of energy transfer rate as high as 3 × 10⁻¹⁶ cm³/s has been deduced using a rate equation analysis, which is the highest reported for Tm-Nd co-doped systems. The confinement of the 1064 nm emitted radiation in the waveguide structure is the main reason of the high energy transfer probability between Nd³⁺ and Tm³⁺ ions.