Combustion synthesized MgAl2O4:Cr phosphors—An EPR and optical study

Magnesium aluminate (MgAl₂O₄) doped with trivalent chromium (Cr³⁺) was synthesized by the combustion method. The prepared sample was characterized by X-ray powder diffraction, Brunauer-Emmet-Teller (BET) adsorption isotherms and diffuse-reflectance UV-vis spectroscopy techniques. Electron paramagnetic resonance (EPR) and photoluminescence (PL) studies have been performed at room temperature and at 110 K. The EPR spectrum exhibit resonance signals at g=5.37, 4.53, 3.82, 2.26 and 1.96 characteristic of Cr³⁺ ions. The luminescence of Cr³⁺-activated MgAl₂O₄ exhibits a red emission peak around 686 nm from the synthesized phosphor particles upon 551 nm excitation. The luminescence is assigned to a transition from the upper ²E_g→⁴A_2g ground state of Cr³⁺ ions. By correlating EPR and optical data the crystal field splitting parameter (D_q), Racah inter-electronic repulsion parameter (B) and the bonding parameters have been evaluated and discussed. The bonding parameters suggests that the ionic nature of Cr³⁺ ions with the ligands and the Cr³⁺ ions are in distorted octrahedral environment.     

Magnetic ordering in manganites substituted by chromium ions

NdMn_1?x Cr _x O₃ and Nd_0.6Ca_0.4Mn_1?x Cr _x O₃ solid solutions have been studied by neutron diffraction and magnetic measurements. NdMn_0.5Cr_0.5O₃ is found to have a magnetic structure consisting of an antiferromagnetic G-type component and a ferromagnetic component, which are caused by 3d ions. The magnetic moments of the neodymium ions are parallel to the ferromagnetic component. Nd_0.6Ca_0.4Mn_0.5Cr_0.5O₃ mainly has a G-type magnetic structure, and the magnetic moments of the neodymium ions are normal to the antiferromagnetism vector. Magnetic phase diagrams are plotted for both systems. They are interpreted on the assumption that the Mn³⁺-O-Cr³⁺ superexchange interactions are positive and the Mn⁴⁺-O-Cr³⁺ interactions are negative; the fact that manganese and chromium ions are not ordered in a crystal lattice is taken into account. Concentration magnetic phase transformations proceed through a two-phase state because of the internal chemical inhomogeneity of the solid solutions.     

Effect of growth temperature on characteristics of Cr-doped ZnO nanorods by magnetron sputtering

Cr-doped ZnO nanostructures, in well-aligned Zn_0.92Cr_0.06O nanorods array, were synthesized by radio frequency (RF) magnetron sputtering deposition at different temperatures. The effects of growth temperature on the structure and optical properties of Zn_0.92Cr_0.06O nanorods were investigated in terms of scanning electron microscope (SEM), X-ray diffraction (XRD), Raman spectra, X-ray photoelectron spectroscopy (XPS) and spectrophotometer. With increase the growth temperature, Zn_0.94Cr_0.06O nanorods have a strong improved crystalline quality. High growth temperature enhances the build-in electric field in the depletion region in the grain of the nanorods, which trap free carriers from the bulk of the grains. XPS results shows that Cr³⁺ ions substitute Zn²⁺ ions, and no secondary phases in the sample are found, meanwhile the oxygen vacancies decrease with increasing growth temperature. The high growth temperature causes a significant increase in optical transmittance of the Zn_0.92Cr_0.06O nanorods, which can be attributed to the weakening of scattering and absorption of light because of the increase of grain size. The red shift of the optical band gap can be mostly likely related to the Burstein–Moss effect.     

Effects of hydrogen annealing on the room temperature ferromagnetism and optical properties of Cr-doped ZnO nanoparticles

We explore the effects of hydrogen annealing on the room temperature ferromagnetism and optical properties of Cr-doped ZnO nanoparticles synthesized by the sol-gel method. X-ray diffraction and x-ray photoelectron spectroscopy data show evidence that Cr has been incorporated into the wurtzite ZnO lattice as Cr²⁺ ions substituting for Zn²⁺ ions without any detectable secondary phase in as-synthesized Zn_0.97Cr_0.03O nanopowders. The room temperature magnetization measurements reveal a large enhancement of saturation magnetization M_s as well as an increase of coercivity of H₂-annealed Zn_0.97Cr_0.03O:H samples. It is found that the field-cooled magnetization curves as a function of temperature from 40 to 400 K can be well fitted by a combination of a standard Bloch spin-wave model and Curie–Weiss law. The values of the fitted parameters of the ferromagnetic exchange interaction constant a and the Curie constant C of H₂-annealed Zn_0.97Cr_0.03O:H nanoparticles are almost doubled upon H₂-annealing. Photoluminescence measurements show evidence that the shallow donor defect or/and defect complexes such as hydrogen occupying an oxygen vacancy H_o may play an important role in the origin of H₂-annealing induced enhancement of ferromagnetism in Cr-H codoped ZnO nanoparticles.     

EPR studies of highly pure,pure and doped chromium oxide powders

Abstract

EPR absorption measurements on ‘pure’, highly pure and A1₂O₃ doped Cr₂O₃ powder have been made. The EPR absorption in the ‘pure’ powders obtained below Ntel temperature is shown to be due to background magnetic impurities present in the powders and not due to superparamagnetism as suggested by earlier authors. No EPR absorption could be observed below Nkl temperature in highly pure powders (total background impurity concentration less than 5 ppm). ‘Pure’ powders or highly pure powders mixed with A1₂O₃ powder and annealed at high temperatures showed a symmetrical EPR absorption line at room temperature. The shape and the g value of this line are practically the same as those obtained for Cr³⁺ ions in Cr₂O₃ above Nee1 temperature or in other nonmagnetic crystals. It is concluded from these results that the impurities diffuse into Cr₂O₃ powder, the antiferro-magnetic coupling between some of the Cr³⁺ ions is broken and these Cr³⁺ ions become paramagnetic, even when the bulk of the material is in antiferromagnetic state. The variation of half-width of EPR lines with impurity concentration shows that the dipolar coupling between Cr³⁺ ions decreases with the increase in impurity concentration and when the impurity concentration is high the Néel temperature seems to shift to lower temperatures. A longer heat treatment of the ‘pure’ B powder resulted in the production of shining metal particles in the powder. The EPR of this powder showed excessive increase in the intensity of EPR absorption when the temperature of the powder was raised to a value just above the Néel temperature. A comparison of these reuslts with the work of earlier authors suggests that the shinning metal particles are those of chromium metal and are responsible for this increase in EPR absorption.     

Preparation and optical properties of ZnGa2O4:Cr thin films derived by sol-gel process

ZnGa₂O₄:Cr³⁺ thin films with bright red emission were synthesized using a sol-gel process, characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Auger electron spectroscopy (AES) and UV-vis and fluorescence spectrophotometry measurements. Effects of calcining temperature, film thickness, calcining duration and substrates on the crystal structure and photoluminescent property have been investigated. It is found that the crystallinity, Ga/Zn ratio and band gap energy (E_g) are significant factors influencing optical characteristics, while the nature of substrates affect the surface morphologies of ZnGa₂O₄:Cr³⁺ thin films.     

Cr3+ doped Al2O3 nanoparticles: Effect of Cr3+ content in intensifying red emission

Cr³⁺-doped α-Al₂O₃ nanoparticles (Al_2−xCr_xO₃, 0.005 ≤ x ≤ 0.05) were synthesized by co-precipitation method. X-ray diffraction (XRD) patterns of Cr³⁺:Al₂O₃ nanoparticles revealed the crystallite size of ∼53 nm and electron microscopy (SEM & TEM) confirmed the spherical nanoparticle formation. Diffuse reflectance spectra (DRS) displayed peaks at 406 and 558 nm corresponding to the Cr³⁺ transitions which became prominent with the increase in Cr³⁺ concentration which was also evidenced by the gradually increasing pink coloration of the samples. Photoluminescence (PL) studies showed the sharp red emission at 694 nm (ruby line) which was observed for all samples. The Dq/B value for all samples was found to be greater than 2.3 confirming the presence of Cr³⁺ ions in the octahedral sites. Chromaticity diagrams displayed the maximum red appearance for the sample with x = 0.01 and a lifetime of 4 ms. The synthesized Cr³⁺:Al₂O₃ nanoparticles with smaller crystallite sizes and narrow near monochromatic emission can be used in various applications including sensing, lasing, and bioimaging applications.     

A Mössbauer study of La1−xEuxB6 compounds synthesized at high pressure and temperature

A series of hexaborides La_1?xEu_xB₆ (x=0.0–1.0) were synthesized under a pressure of 3.5 GPa and at a temperature of 1600^○C using La₂O₃, Eu₂O₃ and amorphous boron as the starting materials. The products were characterized by X‐ray Diffraction (XRD) and Mössbauer spectroscopy. XRD data analysis shows that all samples crystallize in a cubic CsCl‐type structure, and the cell volume increases with x. Room temperature ¹⁵¹Eu Mössbauer measurements reveal that Eu ions in all samples are in the divalent state, except for the x=1.0 sample where a small amount of Eu³⁺ ions was detected. The quadrupole splitting of the Eu²⁺ ions is positive. Eu ions were reduced from trivalent to divalent during the high‐pressure and ‐temperature processes. The isomer shifts of the Eu²⁺ ions are all smaller than ?12.5 mm/s, suggesting that there is no valence fluctuation in the samples. The hexaborides doped by divalent Eu are not metallic.     

Characterization of Cr/SiO2 catalysts and ethylene polymerization by XPS

Cr/SiO₂ catalysts with 1 or 3 wt.% Cr loadings and different chromium precursors were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). A method to determine chromium species in the sample was developed through the decomposition of the Cr 2p XPS spectrum in Cr⁶⁺ and Cr³⁺ standard spectra. The results of the binding energy from the Cr 2p region and of the distribution of chromium species allowed to evaluate the dynamic photo-reduction of the surface chromium species during XPS analysis. Photo-reduction of surface Cr⁶⁺ to Cr³⁺ species was verified for all samples supported in silica, depending on the precursor and chromium content. Bulk CrO₃ and Cr₂O₃ standards did not reveal variation in the binding energy of Cr 2p_3/2, but a physical mixture of CrO₃ with SiO₂ presented photo-reduction. The behavior of this mixture resembled to the catalysts and suggests the participation of the surface hydroxyls of silica in the photo-reduction process. XPS intensity measurements for assessing dispersion of chromium oxide were used to compare the calcined and reduced catalysts to different chromium precursors. Polyethylene chains were detected by in situ XPS, while oligomerization products were not observed.     

Synthesis and characterization of layered perovskite oxides La1 + x Sr2 − x MnCrO7 (x = 0.2, 0.5)

Intergrowth perovskite type complex oxides of composition La_1.2Sr_1.8MnCrO₇ and La_1.5Sr_1.5MnCrO₇ have been synthesized by ceramic method. Rietveld profile analysis shows that the phases crystallize with tetragonal unit cell in the space group I4/mmm. Both the phases behave as insulators in the high temperature region and the linearity of log ρ versus T ^?1/4 plot in the temperature range 150–300 K shows that the electronic conduction occurs by a 3D variable range hopping mechanism. The phases show insulator-metal transition at low temperature which could be due to the mixed valence state of Mn³⁺/Mn⁴⁺ by double exchange mechanism. The ferromagnetic interactions observed for the samples arises from double exchange interaction between Mn ³⁺ and Mn⁴⁺ and Cr³⁺ and Mn³⁺ ions.     

Substitutional effect of Cr ions on the properties of Mg–Zn ferrite nanoparticles

The effect of Cr³⁺ substitution in Mg–Zn ferrite, with a chemical formula Mg_0.5Zn_0.5Cr_xFe_2−xO₄ (x=0.0–1.0), synthesized by a sol–gel auto-combustion reaction is presented in this paper. The resultant powders were investigated by various techniques, including X-ray diffractometry (XRD), transmission electron microscopy (TEM), infrared spectroscopy (IR), vibrating sample magnetometry (VSM), and DC resistivity. The XRD pattern revealed that the cubic spinel structure is maintained for the all the compositions. The particle sizes measured from XRD and TEM are in good agreement with each other. The cation distribution suggests that Mg²⁺, Cr³⁺ and Fe³⁺ have strong preference towards octahedral B-site. The theoretical lattice constant and experimental lattice constant match each other very well. The IR analysis supports the presently accepted cation distribution. The saturation magnetization decreases linearly with increasing Cr³⁺ content. Curie temperatures are obtained by the Laoria and AC susceptibility techniques. The dc resistivity has been investigated as a function of temperature and composition.     

An XAS study of the defect structure of Ti-doped α-Cr2O3

The bulk defect structure in Cr_2−xTi_xO₃ (x = 0.05, 0.20 and 0.30) has been studied by X-ray absorption spectroscopy measurements at the Cr and Ti K-edges. The results show that the Ti is predominantly present in the IV oxidation state and resides on the normal Cr host lattice site. The dopant is charge compensated by Cr³⁺ vacancies and there is evidence for the formation of defect clusters; however, the detailed structure of these clusters could not be deduced.     

Mn, Cr-co-doped MgAl2O4 phosphors for white LEDs

The Mn-, Cr-doped and Mn, Cr-co-doped MgAl₂O₄ powders have been synthesized via a gel-solid reaction method. Energy transfer from Mn²⁺ to Cr³⁺ has been observed for the first time in the co-doped MgAl₂O₄ phosphors. When excited with blue light with a wavelength of 450 nm at room temperature, both green emission from Mn²⁺ around 520 nm and red emission from Cr³⁺ around 675and 693 nm were generated. Moreover, the color of the emission can be modified by controlling the doping concentrations of Mn²⁺ and Cr³⁺. Therefore, MgAl₂O₄: Mn²⁺, Cr³⁺ could be used as a single-phased phosphor for white LED with a blue LED chip. The energy transfer in terms of Mn²⁺ to Cr³⁺ is determined by means of radiation and reabsorption.     

Features of the local structural disorder in Li2O-CaF2-P2O5 glass-ceramics with Cr2O3 as nucleating agent

Li₂O-CaF₂-P₂O₅ glasses mixed with different concentrations of Cr₂O₃ (ranging from 0 to 1.0 mol%) were crystallized. The samples were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy (EDS), differential thermal analysis and conventional spectroscopic techniques. The X-ray diffraction and scanning electron microscopic studies reveal the presence of lithium phosphate, calcium phosphate and chromium phosphate (complexes of Cr³⁺, Cr⁵⁺ and Cr⁶⁺ ions) crystal phases. The study on DTA suggests that the crystallization is predominantly due to the surface crystallization when the concentration of nucleating agent Cr₂O₃ is around 0.8 mol%. The IR and Raman spectral studies of these samples indicate that the sample crystallized with 0.8 mol% Cr₂O₃ is more compact and possesses high rigidity due to the presence of chromium ions largely in tetrahedral positions.     

Low-temperature synthesis of nanocrystalline NiCuZn ferrite and the effect of Cr substitution on its electrical properties

In this study, nano-sized ferrites of compositions (Ni_0.6Cu_0.20Zn_0.20Fe_2−xCr_xO₄), where x=0-1.0, were synthesized through nitrate-citrate auto-combustion method at relatively low temperature. XRD revealed the formation of nano-sized ferrite particles with cubic spinel structure. An exception was obtained for samples with Cr content ≤0.2, where weak diffraction peaks attributed to the presence of CuO and Fe₂O₃ were appeared. The average crystallite sizes are much dependent on the chromium content and were found to decrease with its increase. The lattice parameter (a) slightly decreases with Cr substitution, which can be explained on the basis of the relative ionic radii of Cr³⁺ and Fe³⁺ ions. X-ray density was found also to decrease slightly with increase in chromium content, which indicates lower densification by the addition of Cr. FT-IR measurements show the characteristic ferrite bands. The Mössbauer spectra varied from Zeeman sextets to a relaxed doublet by increase in Cr content, which indicates a decrease in the hyperfine field at the octahedral site. Electrical property measurements revealed that Cr³⁺ ions do not participate in conduction process but limit the degree of Fe³⁺-O²⁻-Fe³⁺ conduction resulting in a decrease in the conductivity and increase in conduction activation energy.     

Mössbauer study of CaFeO3 under external high—Pressure

⁵⁷Fe Mössbauer and X-ray diffraction measurements have been performed on a perovskite CaFeO₃ under external high pressure upto 50 GPa at room temperature using a diamond anvil cell. Above 29 GPa the⁵⁷Fe magnetic hyperfine splitting appears superimposing with usual paramagnetic pattern of CaFeO₃. Magnitude of hyperfine field is 16 T and much smaller than 33 T of typical Fe⁴⁺ in SrFeO₃ suggesting a transition from high-spin S=2 to low-spin S=1 state in CaFeO₃.     

Cr3+掺杂的Cd3Al2Ge3O12光谱特性及晶场参数计算

采用高温固相法合成了Cd₃Al₂Ge₃O₁₂：Cr³⁺多晶材料,利用X射线衍射对其结构进行了分析,通过Cr³⁺的室温吸收光谱、室温和77K发射光谱分别对其光谱特性和晶场参数进行了分析和计算.结果表明：在450 nm的蓝光激发下,Cd₃Al₂Ge₃O₁₂：Cr³⁺室温发 关键词： 3Al₂Ge₃O₁₂：Cr³⁺')" href="#">Cd₃Al₂Ge₃O₁₂：Cr³⁺ 荧光光谱 晶场参数 可调谐激光     

Magnetic exchange interactions induced by Cr-doping in perovskite manganites

The effect of Cr-doping on the structural, magnetic and transport properties of perovskite manganites La_0.8Ca_0.2Mn_1−xCr_xO₃ (0≤x≤0.7) has been investigated. The Curie temperature (T_C) of the Cr-doped samples is almost unchanged up to 30% of Cr-doping. The Cr-doped samples, however, undergo a transition from the parent metallic state to the insulating state below T_C. The dc and ac magnetization data suggest that ferromagnetic clusters induced by double exchange interaction between Cr³⁺ and Mn³⁺ ions and antiferromagnetic components driven by Cr³⁺/Mn⁴⁺ and Cr³⁺/Cr³⁺ interactions are present in the Cr-doped system, which is supported by comparative studies on magnetic and transport properties of LaMnO_3+δ and LaMn_0.75Cr_0.25O_3+δ.     

Optical and structural properties of nanosized ZnGa2O4:Cr phosphor

Nanosized ZnGa₂O₄:Cr³⁺ powder is synthesized through hydrothermal method. The average particle size is 20 nm and they are spherical in shape. The excitation band from the charge transfer between Cr³⁺-O²⁻ shows a blueshift behavior due to quantum confinement effect. X-ray diffraction pattern, Fourier transform-infrared spectrum, and electron paramagnetic resonance signal indicate that nanosized ZnGa₂O₄:Cr³⁺ phosphor shows many defect-related energy states and heavy lattice distortion in comparison with bulk ZnGa₂O₄:Cr³⁺ phosphor. Many defect states result in more nonradiative loss and shorter decay time.     

Mössbauer and magnetic study of Mn2+- and Cr3+-substituted spinel magnesioferrites of the composition Mg1−xMnxFe2−2xCr2xO4

Chromium and manganese co-substituted spinel magnesioferrites of the composition Mg_1?x Mn _x Fe_2?2x Cr_2x O₄ (x?=?0.0, 0.1, 0.2, 0.3, and 0.5) were investigated with X-ray diffraction (XRD), Mössbauer spectroscopy and magnetic measurements. The cation distribution inferred suggests that Mn²⁺ and Cr³⁺ ions dominantly occupy the A- and B-sites respectively. The gradual decrease of the hyperfine fields and Curie temperatures with increasing x reflects a gradual weakening in the AB exchange interaction. Mössbauer data of the sample with x = 0.5 is suggestive of cation clustering and/or superparamagnetism. The magnetization data is suggestive of Yafet-Kittel-type canted magnetism.