Raman spectroscopic investigations of Mn2+ doping effects on the densification of acid-catalyzed silica xerogels

Undoped and Mn²⁺-doped silica xerogels were prepared from hydrolysis and condensation of tetramethyl orthosilicate (TMOS). The xerogels were characterised by density measurements and fluorescence and Raman spectroscopies. Raman measurements over the range 4–1200 cm⁻¹ showed that the number of three- and four-membered rings in the xerogel network depends on the thermal treatment and on the concentration of Mn²⁺ ions. Indeed, both structures are found to be more numerous in the gel network of the doped samples than in the undoped one, showing that doping with Mn²⁺ hampers the destruction of three- and four-membered rings. In the low-wave number region (4–100 cm⁻¹), doping with manganese ions was found to affect the position of the boson peak. The boson peak profiles were used to deduce that the sizes of the cohesive domains in the gel-derived silica network are much larger for doped samples (11 nm for 500 ppm) than for undoped ones (2.1 nm).     

Growth and characterization of Mn2+ doped calcium l‐tartrate crystals

Single crystals of Mn²⁺ doped calcium levo‐ tartrate tetrahydrate (CLTT) were grown by single diffusion gel growth technique in silica hydro‐gel media. The doping of Mn²⁺ was varied by mixing 0.001M, 0.005M, 0.01M, 0.05M, and 0.1M solutions of MnCl₂ with 1M CaCl₂ solution in equal volumes in the supernatant solutions. The actual amount of Mn²⁺ doping in CLTT crystals was estimated by ICP (Inductively Coupled Plasma) technique. The powder XRD of the samples suggested no significant change in the unit cell dimensions and the presence of any extra phase. The FT‐IR spectra indicated the presence of water molecule, O‐H bond, C‐O bond and carbonyl C=O bond. The EPR spectra confirmed the presence of Mn²⁺ ions in the crystals. The variation of the dielectric constant with temperature confirmed the earlier results of pure calcium tartrate crystals and indicated the ferroelectric nature of the doped crystals. As the amount of doping of Mn²⁺ increased the value of dielectric constant increased. The results are discussed. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dielectric constant,loss factor and ac conductivity of Ni2+‐doped K2ZnCl4 crystals in the ferroelectric‐commensurate,incommensurate and normal phases

The dielectric constant (ϵ), dielectric loss (tanδ) and ac conductivity (σ_ac) of virgin and thermally cycled undoped and Ni²⁺‐doped K₂ZnCl₄ (KZC) crystals in the ferroelectric‐commensurate (FC), incommensurate (IC) and normal phases (N) have been studied. Anomalous behaviour at the two‐phase transition points was observed while measuring ϵ along the polar a‐axis for the undoped sample. With increasing Ni²⁺concentration a systematic shift of the phase transition temperature towards lower values and a continuous inhibition of the peak height were detected. ϵ changed linearly with lnf up to f =10⁵ Hz. tanδ along the a‐axis declared the phase transitions by peak changes. After Ni²⁺‐doping this behaviour was preserved at the FC‐IC phase transition point while the IC‐N phase transition was manifested by a change in the slope of the straight line representing the tanδ‐T dependence. The ac conductivity changed lineally with frequency according to a relation of the form σ_ac = σ_o f ^β where 0>β>1.9. σ_ac increased monotonically with increasing temperature and doping concentration in the low‐temperature phases tending to merge in one straight‐line with high activation energy that might be due to superionic dc conduction in the high temperature N‐phase. Doping with Ni²⁺ pinned stripples, decreased the soliton‐soliton interaction, weakened discommensuration effects, shortened the IC‐phase and strongly affected the ‘chaotic' behaviour at the T_C‐IC. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Magnetic resonance study of the crystallization behavior of InF3-based glasses doped with Cu2+, Mn2+ and Gd3+

The crystallization of fluoroindate glasses doped with Gd³⁺, Mn²⁺ and Cu²⁺ heat treated at different temperatures, ranging from the glass transition temperature (T_g) to the crystallization temperature (T_c), are investigated by electron paramagnetic resonance (EPR) and ¹⁹F nuclear magnetic resonance (NMR). The EPR spectra indicate that the Cu²⁺ ions in the glass are located in axially distorted octahedral sites. In the crystallized glass, the g-values agreed with those reported for Ba₂ZnF₆, which correspond to Cu²⁺ in a tetragonal compressed F⁻ octahedron and to Cu²⁺ on interstitial sites with a square-planar F⁻ co-ordination. The EPR spectra of the Mn²⁺ doped glasses exhibit a sextet structure due to the Mn²⁺ hyperfine interaction. These spectra suggest a highly ordered environment for the Mn²⁺ ions (close to octahedral symmetry) in the glass. The EPR spectra of the recrystallized sample exhibit resonances at the same position, suggesting that the Mn²⁺ ions are located in sites of highly symmetric crystalline field. The increase of the line intensity of the sextet and the decrease of the background line in the thermal treated samples suggest that the Mn²⁺ ions move to the highly ordered sites which contribute to the sextet structure. The EPR spectra of the Gd³⁺ doped glasses exhibit the typical U-spectrum of a s-state ion in a low symmetry site in disordered systems. The EPR of the crystallized glasses, in contrast, have shown a strong resonance in g ≈ 2.0, suggesting Gd³⁺ ions in environment close to cubic symmetry. The ¹⁹F NMR spin–lattice relaxation rates were also strongly influenced by the crystallization process that takes over in samples annealed above T_c. For the glass samples (doped or undoped) the ¹⁹F magnetization recoveries were found to be adjusted by an exponential function and the spin–lattice relaxation was characterized by a single relaxation time. In contrast, for the samples treated above T_c, the ¹⁹F magnetization-recovery becomes non-exponential. A remarkable feature of our results is that the changes in the Cu²⁺, Mn²⁺, Gd³⁺ EPR spectra and NMR relaxation, are always observed for the samples annealed above T_c.     

Structural and optical response of 2‐Mercaptoethonal capped CdS nanocrystals to Fe3+ ions

Cadmium sulfide (CdS) semiconductor nanocrystals (NCs) doped with Fe³⁺ have been synthesized via a solution‐based method utilizing dopant concentrations of (0–5%) and employing 2‐mercaptoehonal as a capping agent. X‐ray diffraction (XRD) results showed that the undoped CdS NCs are in mixed phase of cubic and hexagonal, where as the doped CdS NCs are in hexagonal phase. The crystallite size was increased from ∼1.2 nm to ∼2 nm. Diffuse reflectance spectroscopy studies (DRS) reveals that the band gap energy was decreased with Fe doping and it lies in the range of 2.58 ‐ 2.88 eV. Photoluminescence (PL) spectra of undoped CdS NCs show a strong green emission peak centered at 530 nm and a weak red emission shoulder positioned at 580 nm. After doping all the luminescence intensity was highly quenched and the green emission peak was shifted to orange region (580 nm), but the position of weak red emission shoulder was unaltered with doping. FTIR studies revealed that the NCs were sterically stabilized by 2‐mercaptoethanol. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Studies on electrical conduction behavior of La1‐3xCaxBaxSrxMnO3 synthesized by chemical route

In the manganite La_1‐xM_xMnO₃ (M = Ca, Ba, Sr) the doping concentration introduces a mixed valency (Mn³⁺, Mn⁴⁺) which governs the magnetic and electrical properties of the compound. The perovskite oxides La_1‐3xCa_xBa_xSr_xMnO₃ (x = 0.00, 0.05, 0.10) were prepared by chemical method. Single‐phase formation is confirmed by XRD studies. The electrical behavior of compositions with x = 0.00, 0.05 and 0.10 in the system La_1‐3xCa_xBa_xSr_xMnO₃ was studied in the temperature range 300‐420 K. It is observed that conductivity decreases with increasing temperature as well as dopants concentration. Metallic behavior of these compositions decreases with increasing dopants concentration (x). The microstructures of these samples have been characterized using scanning electron microscopy (SEM). (© 2007 WILEY ‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Lasing and refractive indices of nanocrystalline ceramics of cubic Yttrium Oxide Y2O3 doped with Nd3+ and Yb3+ ions

A continuous-wave lasing at 1 μm was excited by the radiation of semiconductor laser diodes at room temperature in nanocrystalline ceramics Y₂O₃ doped with Nd³⁺ and Yb³⁺ ions. The refractive indices of the undoped nanocrystalline Y₂O₃ ceramics were measured in the wavelength range 0.4–9 μm.     

Studies on the growth and optical characterization of Tm3+‐doped BaY2F8 single crystals

The BaY₂F₈ crystals doped with different concentrations of Tm³⁺ ions were prepared by the temperature gradient technique (TGT). X‐ray powder diffraction was applied to analyze the phase. The cracking phenomenon along (010) and (100) planes of the crystals grown by temperature gradient technique was studied on the basis of the structure of BaY₂F₈ crystals. The absorption spectra were measured and investigated in the ultraviolet‐visible and near‐infrared ranges at room temperature. Several characteristic absorption bands of Tm³⁺‐doped BaY₂F₈ crystal were observed. The emission and excitation spectra were obtained and investigated at room temperature and 12 K, showing the characteristic emission peaks of Tm³⁺ ions. The temperature dependence of Photoluminescence curve was also investigated in the range of 12–296 K. The luminescence intensity of emission bands decreased with increasing temperature, while the effective bandwidth increased. The up‐conversion spectrum excited at 650 nm was recorded and up‐conversion mechanism was analyzed in detail. The result showed the purple, green and yellow emissions corresponding to ³P₁→³F₃, ¹D₂→³H₅ and ³P₀→¹G₄ transitions, respectively.     

Density,Colourability and Conductivity of Sr2+ Doped KCl Crystals

The measurements of colourability and density changes in KCl crystals with different Sr²⁺ contents point to the presence of two separate doping ranges in which different mechanisms of Sr²⁺ incorporation are active. Below 350 ppm Sr/KCl substitutional incorporation and above 350 ppm Sr/KCl precipitation of a second phase predominates. The latter process is accompanied by the formation of larger vacancy clusters. Ionic conductivity measurements imply that in the range between 80 and 350 ppm the aggregation of Sr²⁺ [+] dipols takes place.     

Doping‐induced‐effects on conduction mechanisms in incommensurate ammonium zinc chloride crystals

The dc conductivity (σ) along the polar b‐axis of ammonium zinc chloride (AZC) crystals in its four high‐temperature phases has been measured as a function of temperature. Doping with Mn²⁺ in different concentrations changed strongly both values of σ at all temperatures and the dependence of ln σ_dc on 1/T in the phase transition regions. The activation energy of conduction was calculated from the linear portions of this dependence in each phase. The results were discussed in the light of the decomposition of (NH₄)₂ in the high‐temperature normal phase, the discommensuaration (DC) formation/annihilation in the incommensurate phase and domain wall motion and stripples nucleation in the commensurate‐ and antiferroelectric‐phases. Pinning of DC's in the crystal lattice and/or by the structural defects and the possibility of dislocation formation was also discussed. The bulk‐ and the electrode‐limited conduction mechanisms were also considered. The current density‐voltage gradient relationship according to the usual Richardson‐Schottky (R‐S) equation shows disagreement between extracted parameters and experimentally measured ones. A modified equation was used to solve this difficulty which, in addition, facilitated the calculation of the electronic mobility (μ), the barrier height (φ) at the electrode‐dielectric interface and the R‐S constant (β_RS). The effect of Mn²⁺‐content on values of μ, φ and β_RS in different phases of AZC was also considered. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spray deposition and characterization of undoped and In‐doped tin disulphide thin films

Undoped and Indium doped tin disulphide (SnS₂) thin films had been deposited onto glass substrates at T_s = 300 °C using spray pyrolysis technique under atmospheric pressure with stannous chloride, indium chloride and thiourea as precursors. The structural, optical and electrical properties of the deposited films were characterized. The XRD pattern revealed that the undoped and doped films had preferred orientation along (002) plane with hexagonal structure. FESEM micrographs had shown that morphologies of the films changed with indium doping. Optical constant such as refractive index (n), extinction coefficient (k), real and imaginary parts of dielectric constants were evaluated from transmittance and reflectance spectra in UV‐Visible spectroscopy. The optical absorption data were used to determine the band gap energy and it was found to be 2.75 eV for undoped and 2.50 eV for indium doped films respectively. The room temperature dark resistivity was found to be 4.545 × 10³ Ω‐cm and 5.406 × 10³ Ω‐cm for undoped and In‐doped films respectively.     

Ferromagnetic insulating and reentrant spin glass behavior in Mg doped La0.75Sr0.25MnO3 manganites

In this study, the effect of Mg substitution on structural, magnetic and electrical properties of La_0.75Sr_0.25Mn_1?xMg_xO₃ and La_0.75Sr_0.25?xMg_xMnO₃ (nominal compositions) samples are investigated by XRD, Ac susceptibility and electrical resistivity measurements. It is found that Mg does not replace La in the perovskite lattice. Also the results show that by increasing Mg doping levels, the paramagnetic–ferromagnetic and metal–insulator transition temperatures decrease. The reason for decreasing transition temperatures with increasing Mg concentration is, that the long-range FM order has been destroyed by the Mg, which is randomly occupying Mn site. This leads to the suppression of double-exchange interaction in the Mn³⁺–O–Mn⁴⁺ networks. Also the reentrant spin glass (RSG) state accompanied by FM transition, exists in high doped samples. The RSG state could be understood on the basis of double exchange ferromagnetic interaction in Mn³⁺–O–Mn⁴⁺ and super-exchange antiferromagnetic interaction in the Mn⁴⁺–O–Mn⁴⁺ networks.     

Growth and characterization of pure and Co2+‐doped Li2B4O7 single crystals

Pure and Co‐doped Li₂B₄O₇ (LBO) single crystals were grown by the Czochralski method. Starting concentrations of Co₂O₃ in the melt were: 0.5, 0.85 and 1 mol% relative to Li₂CO₃. Technological factors affecting the quality of both crystals were discussed. Optical absorption and EPR spectra were analyzed to define the oxidation states and lattice sites of cobalt ions. It was shown that Co²⁺ ions enter LBO crystal at octahedral Li⁺ site positions. Low‐temperature EPR measurements revealed that two types of Co²⁺ complexes can be distinguished in the Li₂B₄O₇:Co crystals. Additional absorption calculated for γ‐irradiated crystals showed V_k type defects suggesting the creation of cation vacancies during growth. The concentration of the defects decreases with an increase of intentional Co concentration. Introduction of cobalt ions to LBO crystal is limited probably by the formation of cobalt ion pairs or by the entrance of cobalt as Co⁺. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of some Me2+ impurity ions on the lattice parameter of KCI crystals

The effect of concentration of substitutional Ca²⁺, Sr²⁺, Ba²⁺ and Pb²⁺ ions on the lattice parameter of KCI crystals is examined. The amount of lattice contraction induced by the alcaline earths ions qualitatively correlates with the pertinent ionic radii values (relative unit cell contraction induced by one impurity dipole amounts to −0.905, −0.110 and −0.020 for Ca²⁺, Sr²⁺ and Ba²⁺ ions, respectively). The initial drop of lattice parameter observed at low Me²⁺ concentration is tentatively ascribed to the drop of dislocation density. In Pb²⁺ doped crystals except for the above initial drop, at higher dopant concentration no effect upon the lattice parameter is found.     

Electron irradiation‐induced effects on optical spectra of (NH4)2ZnCl4: x Sr2+ single crystals

The effect of electron‐beam irradiation with different doses on optical constants of (NH₄)₂ZnCl₄: x Sr²⁺ crystals with x=0.000, 0.020, 0.039, 0.087 or 0.144 wt% has been studied. The optical transmission in the energy range 3.4‐6.4 eV was measured hence the absorption coefficient was computed as a frequency function. The absorption coefficient was also calculated as a function of electron‐beam dose. Irradiation with e‐beam did not affect the allowed indirect type of transition responsible for interband transitions of (NH₄)₂ZnCl₄: x Sr²⁺ crystals. Values of the optical energy gap E_g and optical moment E_p for electronic interband transition of unexposed and (NH₄)₂ZnCl₄: x Sr²⁺ crystals after e‐beam exposure were deduced. The area under the absorption band at 5.30 eV was used to evaluate the effect of e‐irradiation on optical parameters of samples with x=0.00, 0.020 or 0.039. A shift in the position and a nonmonotonic change in the intensity of this band with increasing e‐beam dose was observed. Changes in the E_g value were used to evaluate the effect of e‐beam exposure dose on (NH₄)₂ZnCl₄: x Sr²⁺ samples with x=0.087 or 0.144. The obtained results were compared with those obtained for the same crystals after irradiation with different γ‐doses.     

High temperature spectroscopy of manganese and chromium doped glasses with the basic composition 16Na2O · 10CaO · 74SiO2

Glasses doped either with chromium or manganese or with both chromium and manganese were melted from the raw materials and studied by UV–vis–NIR spectroscopy. The measurements were carried out at temperatures in the range from 25 to 800 °C. In the glasses doped with only one transition metal oxide, the intensity of the absorption lines decreases and the full width at half maximum increases with increasing temperatures. Simultaneously, the peaks were shifted to larger wave numbers. In glasses doped with both chromium and manganese, the same behaviour was observed up to a temperature of 600 °C. At larger temperatures, the absorption band at 27 500 cm⁻¹ due to Cr⁶⁺ increases again, while the absorption band at 20 300 cm⁻¹ caused by Mn³⁺ decreases more strongly than in glasses solely doped with manganese. The behaviour observed was explained by the redox reaction Cr⁶⁺ + 3Mn²⁺ ⇄ Cr³⁺ + 3Mn³⁺ which is shifted to the left while increasing the temperature.     

Influences of Yb3+ ion concentration on the spectroscopic properties of silica glass

We investigated optical spectroscopic properties of silica glass doped with ytterbium (Yb³⁺) ions to assess their lasing performance in diode-laser pumped systems. The Yb-doped silica glass preforms were fabricated by solution doping technique using the MCVD process. The stimulated emission cross-section and laser performance parameters were determined from the measured absorption spectra using the method of reciprocity. Fluorescence decay characteristics were observed to be deviated from exponential behavior as the Yb³⁺ ions doping level increases and there exists a lifetime quenching behavior related to the cluster effect of Yb³⁺ ions into silica glass. Nevertheless, lasing parameters indicated that clustering of Yb³⁺ ions does not significantly affect the spectral properties relevant to the predicted lasing performance when concentration is low, but becomes predominant at higher concentration.     

Effect of change of state of aggregation of impurity on tl and microhardness of KClxBr1–x mixed crystals doped with Ca2+

Microhardness and Thermoluminescence (TL) measurements have been made in KCl_xBr_1–x mixed crystals doped with Ca²⁺ impurity. The variation of hardness in undoped and Ca²⁺ doped KCl_xBr_1–x crystals with quenching temperature is investigated. TL studied of KCl_xBr_1–x crystals doped with Ca²⁺, both in as-grown state and after quenching them from various elevated temperatures indicate that the positions of the glow peak which has been attributed to F-centers is found to depend upon the state of dispersion of impurity.     

The coloration effect in KCl: Eu2+ crystals γ-irradiated at 200 K

The formation of colour centers at 200 K in γ-irradiated KCl crystals doped with Eu²⁺ ions in a wide concentration range is studied by optical absorption, EPR, and ITC method. The EPR and ITC measurements reveal the drastic decrease of concentration of isolated europium dipoles induced by irradiation at 200 K. Moreover, no correlation between concentration changes of colour centers and Eu²⁺ dipoles induced by irradiation and postirradiated annealing has been found. The results obtained are explained by radiation stimulated aggregation of Eu²⁺ dipoles into small clusters at 200 K.     

Magnetic phase transitions in LaMnO3+λ

Magnetic properties of nonstoichinometric lanthanum manganite LaMnO_3+λ as a function of the Mn⁴⁺ concentration (from 0 to 27%) and temperature (from 77 to 300 K) are investigated. The Mn⁴⁺ ions concentration depends on the degree of oxidation λ. It is shown that at 0–10% Mn⁴⁺ there exists an antiferromagnetic ordering and at 10–14% — mixed ferro-antiferromagnetic ordering, while at Mn⁴⁺ concentration exceeding 14% the ferromagnetic ordering takes place. The concentrational antiferromagnetic-ferromagnetic transition at 14% Mn⁴⁺ is due to the crystal structural O' — O orthorhombic transition. In ferromagnetic O-orthorhombic lanthanum manganite the phase ferromagnetic-paramagnetic transition occurs via intermediate magnetic state where in the paramagnetic matrix there are noninteracting ferromagnetic impurity clusters. The presence of such magnetic state gives rise to anomalous behaviour of magnetic and galvanomagnetic properties of LaMnO_3+λ near Curie temperature.