Antiferromagnetic phase transition in garnet-type AgCa2Co2V3O12 and AgCa2Ni2V3O12

Antiferromagnetic phase transition in two vanadium garnets AgCa₂Co₂V₃O₁₂ and AgCa₂Ni₂V₃O₁₂ has been found and investigated extensively. The heat capacity exhibits sharp peak due to the antiferromagnetic order with the Néel temperature T_N=6.39 K for AgCa₂Co₂V₃O₁₂ and 7.21 K for AgCa₂Ni₂V₃O₁₂, respectively. The magnetic susceptibilities exhibit broad maximum, and these T_N correspond to the inflection points of the magnetic susceptibility χ a little lower than T(χ_max). The magnetic entropy changes from zero to 20 K per mol Co²⁺ and Ni²⁺ ions are 5.31 J K⁻¹ mol-Co²⁺-ion⁻¹ and 6.85 J K⁻¹ mol-Ni²⁺-ion⁻¹, indicating S=1/2 for Co²⁺ ion and S=1 for Ni²⁺ ion. The magnetic susceptibility of AgCa₂Ni₂V₃O₁₂ shows the Curie-Weiss behavior between 20 and 350 K with the effective magnetic moment μ_eff=3.23 μ_B Ni²⁺-ion⁻¹ and the Weiss constant θ=−16.4 K (antiferromagnetic sign). Nevertheless, the simple Curie-Weiss law cannot be applicable for AgCa₂Co₂V₃O₁₂. The complex temperature dependence of magnetic susceptibility has been interpreted within the framework of Tanabe-Sugano energy diagram, which is analyzed on the basis of crystalline electric field. The ground state is the spin doublet state ²E(t₂⁶e) and the first excited state is spin quartet state ⁴T₁(t₂⁵e²) which locates extremely close to the ground state. The low spin state S=1/2 for Co²⁺ ion is verified experimentally at least below 20 K which is in agreement with the result of the heat capacity.     

Photoluminescence and energy transfer of Tm doped LiIn (WO4)2 blue phosphors

Room temperature steady and time resolved emission spectra of LiIn_1−xTm_x(WO4)2 (where thulium concentration is 0, 0.5, 1, 5 and 10 at%) blue phosphors, under UV excitation energy have been investigated. The concentration quenching effect on the blue emission, due to the (WO₄)⁻² groups and ¹G₄→³H₆ emission transition of Tm³⁺ were studied. Two energy transfer mechanisms are shown. The first takes place between excited (WO₄)⁻² groups and the ¹G₄ energy level of Tm³⁺, and is mainly analyzed by phonon-assisted energy transfer. The second mechanism is due to an energy transfer from the excited Tm³⁺ ions to the surrounding ground state Tm³⁺ ions. The non-exponential decay curves of the ¹G₄ level observed for higher concentrations are analyzed by the Inokuti–Hirayama model. We think that the quenching effect between Tm³⁺ ions is mainly linked to the dipole–dipole interactions.     

Optical absorption spectrum and local symmetry of Tm ion in TmAl3(BO3)4 crystal

With the help of group theory analysis of absorption spectra of the transition ³H₆ → ³F₃ of Tm³⁺ ion in TmAl₃(BO₃)₄ crystal, measured at several temperatures from 1.8 till 293 K, it has been shown, that the local symmetry of the Tm³⁺ environment is C₃ and it decreases to C₁ at a low temperature. Effective selection rules and polarizations of lines at high enough temperatures (when the line-width is larger than the splitting in C₃ symmetry) have been obtained.     

Magnetic susceptibility of vanadium garnets NaPb2Co2V3O12 and NaPb2Ni2V3O12

Vanadium garnets NaPb₂Co₂V₃O₁₂ and NaPb₂Ni₂V₃O₁₂ have been successfully synthesized. The X-ray diffraction experiments indicate that these compounds have the garnet structure of cubic symmetry of space group with the lattice constant of 12.742 Å (NaPb₂Co₂V₃O₁₂) and 12.666 Å (NaPb₂Ni₂V₃O₁₂), respectively. The magnetic susceptibility of NaPb₂Ni₂V₃O₁₂ shows the Curie-Weiss paramagnetic behavior between 4.2 and 350 K. The effective magnetic moment μ_eff of NaPb₂Ni₂V₃O₁₂ is 3.14 μ_B due to Ni²⁺ ion at A-site and the Weiss constant is −3.67 K (antiferromagnetic sign). For NaPb₂Co₂V₃O₁₂, the simple Curie-Weiss law cannot be applicable. The ground state is the spin doublet and the first excited state is spin quartet , according to Tanabe-Sugano energy diagram on the basis of octahedral crystalline symmetry. This excited spin quartet state just a bit higher than ground state influences strongly the complex temperature dependence of magnetic susceptibility for NaPb₂Co₂V₃O₁₂.     

EPR study of Ce ions in lutetium silicate scintillators Lu2Si2O7 and Lu2SiO5

Two Ce³⁺-doped scintillator crystals, LSO (Lu₂SiO₅:Ce) and LPS (Lu₂Si₂O₇:Ce), are studied by EPR spectroscopy. The analysis indicates that Ce³⁺ substitutes for Lu³⁺ ion in a C₂-symmetry site for LPS and in two C₁-symmetry sites for LSO, with a preference for the largest one, with 6+1 oxygen neighbors. Angular dependence of the EPR spectrum shows that the electronic ground state of Ce³⁺ is different in these two matrices. It is mainly composed of |M_J|=5/2 state in LPS and |M_J|=3/2 state in LSO. The temperature dependence of the linewidth shows a noticeably long spin lattice relaxation time, especially in LPS, which is the result of a stronger crystal field in LPS than in LSO.     

Synthesis and characterization of Co7(OH)12(C2H4S2O6)(H2O)2—a single crystal structural study of a ferrimagnetic layered cobalt hydroxide

A novel layered hydrotalcite-like material, Co₇(H₂O)₂(OH)₁₂(C₂H₄S₂O₆), has been prepared hydrothermally and the structure determined using single crystal X-ray diffraction (a=6.2752(19) Å, b=8.361(3) Å, c=9.642(3) Å, α=96.613(5)°, β=98.230(5)°, γ=100.673(5)°, R1=0.0551). The structure consists of brucite-like sheets where 1/6 of the octahedral sites are replaced by two tetrahedrally coordinated Co(II) above and below the plane of the layer. Ethanedisulfonate anions occupy the space between layers and provide charge balance for the positively charged layers. The compound is ferrimagnetic, with a Curie temperature of 33 K, Curie-Weiss θ of −31 K, and a coercive field of 881 Oe at 5 K.     

Structure, phase transitions and molecular dynamics in 4-methylpyridinium tetrachloroantimonate(III), [4-CH3C5H4NH][SbCl4]

Crystal structure of the 4-methylpyridinium tetrachloroantimonate(III), [4-CH₃C₅H₄NH][SbCl₄], has been determined at 240 K by X-ray diffraction as monoclinic, space group, P2₁/n, Z=8. Differential scanning calorimetry and dilatometric studies indicate the presence of two reversible phase transitions of first order type, at 335/339 and 233/289 K (cooling/heating) with ΔS=0.68 and 2.2 J mol⁻¹ K⁻¹, respectively. Crystal dynamics is discussed on the basis of the temperature dependence of the ¹H NMR spin-lattice relaxation time T₁ and infrared spectroscopic studies. The low temperature phase transition at 233 K of an order-disorder type is interpreted in terms of a change in the motional state of the 4-methylpyridinium cations. The phase transition at 335 K, probably of a displacive type, is characterised by a complex mechanism involving the dynamics of both the cationic and anionic sublattice. The ¹H NMR studies show that the low temperature phase III is characterised only by the dynamics of the CH₃ groups.     

Luminescence and crystal field analysis of Eu in Eu[Co(CN)6]·4H2O

The vibrational spectra of Eu[Co(CN)₆]·4H₂O and luminescence spectra of Eu³⁺ in this compound, using 355 nm excitation at temperatures down to 10 K, have been assigned. A clear distinction is made between the n=5 and 4 members of the Ln[M(CN)₆]·nH₂O series from the vibrational spectra. The electronic spectra show prominent vibronic structures, particularly for the ⁵D₀→⁷F₂ sideband. A resonance occurs between the transitions ⁵D₀→⁷F₁(III) and ⁵D₀→⁷F₀+ν(Eu−N). A crystal field analysis of the derived energy data set is presented for Eu³⁺ in eight coordination geometry.     

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.     

Structure and phase transitions in chloroantimonate(V) crystals: [(C2H5)3NH]SbCl6 and [(C2H5)3NH]SbCl6·1/2[(C2H5)3NH]Cl

New triethylammonium salts: [(C₂H₅)₃NH]SbCl₆ (TCA) and [(C₂H₅)₃NH]SbCl₆·1/2[(C₂H₅)₃NH]Cl (TCAT) have been synthesized. The compounds crystallise in monoclinic symmetry: space groups P2₁/n and P2₁/c, for TCA at 293 K and TCAT at 100 K, respectively. The crystal structure of [(C₂H₅)₃NH]SbCl₆ consists of discrete ionic pairs—triethylammonium cations and hexachloroantimonate anions—linked via the bifurcated N-H?Cl hydrogen bonds. The crystal structure of [(C₂H₅)₃NH]SbCl₆·1/2[(C₂H₅)₃NH]Cl is composed of three symmetrically independent triethylammonium cations, chlorine anion and two symmetrically independent hexachloroantimonate anions. TCA undergoes a structural phase transition at 336 K (on heating) into the orthorhombic C222 space group, whereas TCAT reveals a structural phase transition at 332 K. The phase transitions are of the first order type. TCA shows a ferroelastic domain structure below 336 K. Differential scanning calorimetry, dilatometric, dielectric dispersion and Raman scattering measurements have been used to study the phase transition mechanisms in these triethylammonium salts.     

169Tm Mössbauer effect and magnetic study of Tm6Mn23 and its ternary hydride

The magnetic properties and the lattice constants of Tm₆Mn₂₃ were determined before and after hydrogen absorption. The compound Tm₆Mn₂₃ is ferrimagnetic with an ordering temperature T_c = 404 K. After hydrogen absorption the magnetization is strongly reduced and does not point to the occurrence of magnetic ordering. The strongly increasing hyperfine splitting observed by means of ¹⁶⁹Tm Mössbauer spectroscopy in the hydride for temperature below 60 K, however, shows that the Tm sublattice becomes magnetically ordered after H₂ absorption as well. In uncharged and charged Tm₆Mn₂₃ the values of the Tm moments are close to the free ion values.     

Temperature-dependent photoluminescence spectra of Er-Tm-codoped Al2O3 thin film

Er-Tm-codoped Al₂O₃ thin films with different Tm to Er concentration ratios were synthesized by cosputtering from separated Er, Tm, Si, and Al₂O₃ targets. The temperature dependence of photoluminescence (PL) spectra was studied. A flat and broad emission band was achieved in the 1.4-1.7 μm and the observed 1470, 1533 and 1800 nm emission bands were attributed to the transitions of Tm³⁺: ³H₄ → ³F₄, Er³⁺: ⁴I_13/2 → ⁴I_15/2 and Tm³⁺: ³F₄ → ³H₆, respectively. The temperature dependence is rather complicated. With increasing measuring temperature, the peak intensity related to Er³⁺ ions increases by a factor of five, while the Tm³⁺ PL intensity at 1800 nm decreases by one order of magnitude. This phenomenon is attributed to a complicated energy transfer (ET) processes involving both Er³⁺ and Tm³⁺ and increase of phonon-assisted ET rate with temperature as well. It should be helpful to fully understand ET processes between Er and Tm and achieve flat and broad emission band at different operating temperatures.     

Temperature dependence of impurity quenched luminescence in Tm:LiLuF4

The study of the optical properties of a LiLuF₄ crystal doped with Tm³⁺ yielded the discovery of a strong temperature dependence of the Tm-Tm diffusion coefficient. Spectroscopic characteristics have been investigated as a function of the sample temperature, with particular regard to the luminescence decay following pulsed excitation. An appreciable excitation of the lifetime of the ³F₄ manifold is observed over the temperature range 8.9-298 K. The Judd-Ofelt calculations point out a radiative lifetime considerably longer than the experimental one. These facts suggest a theoretical interpretation based on the presence of impurities that quench the manifold and on a temperature-dependent energy migration between Tm³⁺ ions. A one-parameter best fit of the experimental measurements strongly confirms this hypothesis. Weak OH⁻ ion concentration is detected by means of IR and UV spectra, thus supporting the theoretical interpretation.     

Single color upconversion emission in Ho/Yb and Tm/Yb doped P2O5-MgO2-Sb2O3-MnO2-AgO glasses

The Ho³⁺/Yb³⁺ and Tm³⁺/Yb³⁺ doped P₂O₅-MgO₂-Sb₂O₃-MnO₂-AgO glasses were prepared by high temperature melting method. Under a 975 nm laser diode (LD) excitation, the single red and single blue upconversion (UC) emissions were observed in Ho³⁺/Yb³⁺ and Tm³⁺/Yb³⁺ doped samples, respectively. By studying the spontaneous radiative and multiphonon relaxation probabilities, we find that the multiphonon relaxation probability of ⁵I₆ (Ho³⁺) state is very large (1.39 × 10⁶ s^− 1), which is helpful to the population of ⁵I₇ state. The multiphonon relaxation probability of ³H₅ and ³F_2,3 (Tm³⁺) is also very large, which results in lots of population in ³F₄ and ³H₄ states. The results are that the red UC emission of Ho³⁺ and the blue UC emission of Tm³⁺ are stronger.     

AgGaSe2 : A highly photoconductive material

High resistivity single crystals of AgGaSe₂ were grown by the horizontal Bridgman technique. The near band edge photoconductivity of the grown crystal at room temperature was found to be up to 2×10⁴ times higher than the dark conductivity, under the illumination of 10⁻³ W/cm². The photoconductivity spectrum consists primarily of three peaks, which are attributed to the transitions from Γ₇(A), Γ₆(B) and Γ₇(C) states of valence band to the conduction band Γ₆. The crystal field splitting and the spin-orbit splitting were determined from these peak energy positions of the photoconductivity spectrum.     

Impurity-induced magnetic order in the mixture of two spin gap systems (CH3)2CHNH3CuCl3 and (CH3)2CHNH3CuBr3

The ground state of the solid solution of the two spin gap systems (CH₃)₂CHNH₃CuCl₃ and (CH₃)₂CHNH₃CuBr₃ has been investigated by ¹H NMR. The existence of a magnetic ordering in the sample with the Cl-content x=0.85 was clearly demonstrated by a drastic splitting in a resonance line at low temperatures below T_N=13.5 K. The observed NMR spectra in the ordered state was qualitatively consistent with the simple antiferromagnetic state.     

Study of magnetotransport in double-layered La1.4Ca1.6Mn2O7 manganite: Presence of nano-ferromagnetic domains in paramagnetic matrix

Double-layered manganite La_1.4Ca_1.6Mn₂O₇ has been synthesized using the solid-state reaction method. It had a metal-to-insulator transition at temperature T_M1≈127 K. The temperature dependence of ac susceptibility showed a broad ferromagnetic transition. The two-dimensional (2D)-ferromagnetic ordering temperature (T_C2) was observed as ≈245 K. The temperature dependence of its low-field magnetoresistance has been studied. The low-field magnetoresistance of double-layered manganite, in the temperature regions between T_M1 and T_C2, has been found to follow 1/T⁵. The observed behaviour of temperature dependence of resistivity and low-field magnetoresistance has been explained in terms of two-phase model where ferromagnetic domains exist in the matrix of paramagnetic regions in which spin-dependent tunneling of charge carriers occurs between the ferromagnetic correlated regions. Based on the two-phase model, the dimension of these ferromagnetic domains inside the paramagnetic matrix has been estimated as ∼12 Å.     

Effects of lattice and local dynamics in EPR spectra and electron spin relaxation of vibronic Cu(imidazole)6 complexes in Zn(imidazole)6Cl2·4H2O crystals

Cu(im)₆ complexes in Zn(im)₆Cl₂·4H₂O exhibit a strong Jahn-Teller effect which is static below 100 K and the complex in localized in the two low-energy potential wells. We have reinvestigated electron paramagnetic resonance (EPR) spectra in the temperature range 4.2-300 K and determined the deformation directions produced by the Jahn-Teller effect, energy difference 11 cm⁻¹ between the wells and energy 300 cm⁻¹ of the third potential well. The electron spin relaxation was measured by electron spin echo (ESE) method in the temperature range of 4.2-45 K for single crystal and powder samples. The spin-lattice relaxation is dominated by a local mode of vibration with energy 11 cm⁻¹ at low temperatures. We suppose that this mode is due to reorientations (jumps) of the Cu(im)₆ complex between the two lowest energy potential wells. At intermediate temperatures (15-35 K), the T₁ relaxation is determined by the two-phonon Raman processes in acoustic phonon spectrum with Debye temperature Θ_D=167 K, whereas at higher temperatures the relaxation is governed by the optical phonon of energy 266 cm⁻¹. The ESE dephasing is produced by an instantaneous diffusion below 15 K with the temperature-independent phase memory time , then it grows exponentially with temperature with an activation energy of 97 cm⁻¹. This is the energy of the first excited vibronic level. The thermal population of this level leads to a transition from anisotropic to isotropic EPR spectrum observed around 90 K. FT-ESE gives ESEEM spectrum dominated by quadrupole peaks from non-coordinating ¹⁴N atom of the imidazole rings and the peak from double quantum transition ν_dq. We show that the amplitude of the ν_dq transition can be used to determine the number of non-coordinating nitrogen atoms.     

Absolute sense of pyroelectric p3 and piezoelectric d33 coefficients in 3La (IO3)3.HIO3.7H2O

The pyroelectric coefficient p₃ in 3La(IO₃)₃.HIO₃.7H₂O has an average value 2.0×10^-5 Cm^-2 in the temperature range 152 to 240 K. The resistivity decreases from 10¹² to 10¹⁰ ohm-cm between 258 and 338 K. At 298 K, the piezoelectric coefficient d₃₃  19×10^-12CN^-1. Positive polarity is generated on (001) by increasing temperature or tensile stress. A displacement toward (001) by La³⁺ or H₃O⁺ ions of 1×10^-4 Å per K or 10⁶Nm^-2, or rotation of the water molecule or iodate ion dipoles by about 5 arc minutes per K or 10⁶Nm^-2, produces the observed polarity.     

Enhanced luminescence of Dy in Y3Al5O12 by Bi co-doping

In the present paper, phosphors with the composition Y_3−x−yAl₅O₁₂:Bi³⁺_x, Dy³⁺_y were synthesized with solid state reactions. The luminescence properties of Bi³⁺ and Dy³⁺ in Y₃Al₅O₁₂(YAG) and the energy transfer from Bi³⁺ to Dy³⁺ were investigated in detail. Bi³⁺ in YAG emits one broad band peaking at 304 nm which can be ascribed to the transition from excited states ³P_{0, 1} to ground state ¹S₀. Dy³⁺ in YAG emits two groups of peaks around 484 and 583 nm, respectively, which can be ascribed to the transitions from excited state ⁴F_9/2 to ground states ⁶H_15/2 and ⁶H_13/2. The co-doping of Bi³⁺ enhances the luminescent intensity of Dy³⁺ by ∼7 times because Bi³⁺ can transfer the absorbed energy to Dy³⁺ efficiently. The mechanism of energy transfer was also discussed.