Growth and characterization of cerium-substituted yttrium iron garnet single crystals for magneto-optical applications

This paper is concerned with the preparation and characterization of cerium-substituted yttrium iron garnets, which are known to be oxides having a large Faraday rotation effect. Using the improved flux method we successfully grew bulk single crystals of iron garnet doped with Ce³⁺ ions with maximum substitutions up to 0.349. Here we investigate different solution compositions for maximum Ce³⁺ substitution. The Faraday rotation and optical absorption spectra were measured in the near infrared region for different Ce³⁺ ion substituted iron garnets. The specific Faraday rotation of Ce_0.349Eu_0.195Y_2.456Fe₅O₁₂ was found to be 1430 deg/cm at a wavelength of 780 nm and –1280 deg/cm at 1150 nm. The Ce substitution prominently enhances the Faraday rotation effect, and Yb³⁺ and Eu³⁺ ions substituted for Y³⁺ in the dodecahedral sites of YIG can increase the concentration of Ce³⁺ ions, depressing the formation of nonmagnetic Ce⁴⁺ ions by charge compensation. Received: 24 January 2001 / Accepted: 2 March 2001 / Published online: 27 June 2001     

THE INFLUENCE OF THE ADMIXING OF DIFFERENT MULTIPLETS ON THE SPIN MAGNETIC MOMENT AND FARADAY EFFECT OF HARE EARTH IONS IN GARNETS

The influence of the admixing of the excited multiplets of the ground configuration with the ground multiplet on the spin magnetic moment of the crystal- field-and exchange-interaction-split ground state, the Faraday rotation and the magneto-optic coefficient induced by the rare earth ions in rare-earth-substituted garnets Y_3-xR_xFe₅O₁₂ (R=Ce and Pr) has been calculated in this paper. It is found that, in the case of Ce³⁺ ions, the admixing of the 4f^{1 2}F_7/2 multiplet with the ²F_5/2 multiplet makes the spin magnetic moment of the crystal-field- and exchange-interaction-split ground state increase by 140% and the Faraday rotation increase by 180% at 633nm wavelength, and 150% at 1150nm at 294 K. In the case of Pr³⁺ ions, the admixing of the 4f^{2 3}H₅ multiplet with the ³H₄ multiplet makes the spin magnetic moment of the crystal-field- and exchange-interaction-split ground state increase by 34% and the Faraday rotation increase by 59% at 294K. The admixing of different multiplets of the Ce³⁺ ions makes the ratio between the magneto-optic coefficients at 50 and 294K increase by 7% at 633nm wavelength and 15% at 1150nm.     

Tailored photoluminescence of YAG:Ce phosphor through various methods

Trivalent cerium Ce³⁺ (Ce) activated yttrium aluminum garnet Y₃Al₅O₁₂ (YAG) phosphor was synthesized by two methods: solid state reaction (SS), and combustion (CB) with urea, respectively. The crystallization and luminescent properties of the phosphors were studied. Factors influencing on the intensity of luminescence and the location of emission band of YAG:Ce, such as the type of flux used in SS, the reaction atmosphere, the concentration of activator, were investigated in detail. We accomplished red or blue shift of Ce emission band by a number of techniques in order to match with the variable emission wavelength of blue light emitting diodes. The change of emission in color coordinates was illustrated by chromaticity. Co-doping other rare earth ions with Ce³⁺ ions into YAG was attempted to increase the color rendering index.     

Ce3+-doped crystalline garnet films – scintillation characterization using α-particle excitation

Scintillating properties of Ce³⁺-doped (Lu,Y) aluminum garnet single crystalline films (SCF) were investigated. Thin SCF films of thickness between 1 and 30 μm were grown by a liquid phase epitaxy (LPE) method in various fluxes. The α-particle excitation (mainly 5.4857 MeV line of ²⁴¹Am) of pulse height spectra is used to measure scintillation response of SCF, especially peak of those α-rays which are totally absorbed in the films. Detailed studies and evaluation of scintillation measurements of large sets of Ce³⁺-doped SCF (Lu,Y) aluminum garnets showed that at present time (i) YAG:Ce SCF have comparable scintillation properties as YAG:Ce single crystals, especially their N_phels photoelectron yields are the same while (ii) scintillation properties of LuAG:Ce SCF do not reach those of LuAG:Ce single crystal.     

Luminescence studies on lanthanide ions (Eu, Dy and Tb) doped YAG:Ce nano-phosphors

Yttrium aluminum garnet nanoparticles both undoped and doped with lanthanide ions (Ce³⁺, Eu³⁺, Dy³⁺ and Tb³⁺) having average size around 30 (±3 nm) nm were prepared by glycine nitrate combustion method followed by annealing at a relatively low temperature of 800 °C. Increase in the annealing temperature has been found to improve the luminescence intensity and for 1200 °C heated samples there exists strong energy transfer from Tb³⁺ to Ce³⁺ ions in YAG:Ce(2%),Tb(2%) nanoparticles as revealed by luminescence studies. Co-doping the YAG:Ce nanoparticles with Eu³⁺ results in significant decrease in the emission intensity of both Ce³⁺ and Eu³⁺ ions and this has been attributed to the oxidation of Ce³⁺ to Ce⁴⁺ and reduction of Eu³⁺ to Eu²⁺ ions. Dy³⁺ co-doping did not have any effect on the Ce³⁺ emission as there is no energy transfer between Dy³⁺ and Ce³⁺ ions.     

Absorption and photoluminescence of YAG:Er3+, YAG:Ce3+, and YAG:Er3++Ce3+ crystals

We have studied absorption and luminescence spectra of yttrium-aluminum garnets doped with Er³⁺ and Ce³⁺ ions, as well as co-doped with Er³⁺+Ce³⁺ impurity ions. Luminescence of studied crystals was excited by cw laser radiation at the wavelengths 457 and 980 nm. We revealed obvious display of the energy transfer processes occurring in the impurity subsystem of a YAG: Er³⁺+Ce³⁺ crystal.     

Time-resolved luminescent spectroscopy of YAG:Ce single crystal and single crystalline films

The peculiarities of the luminescence and energy transfer from YAG host to the emission centers formed by the Y_Al antisite defects and Ce³⁺ ions have been studied in YAG:Ce single crystals, grown from the melt by modified Bridgman method in Ar and CO₂ + H₂ atmospheres, and YAG:Ce single crystalline film, grown by liquid phase epitaxy method, using the comparative time-resolved luminescent spectroscopy under excitation by synchrotron radiation in the range of fundamental adsorption of this garnet.     

Luminescent properties and energy transfer of Y3Al5O12:Ce3+, Ln3+ (Ln=Tb,Pr) prepared by polymer-assisted sol–gel method

Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and Y₃Al₅O₁₂:Ce³⁺, Tb³⁺ nano-particles have been synthesized by polymer-assisted sol–gel method. Crystal structure, luminescent properties and energy transfer of the phosphors are analyzed. XRD study of polycrystalline powders shows that all the samples are of YAG phase without impurity. Photoluminescence (PL) emission and excitation spectra illustrate that in YAG:Ce, Pr phosphors, energy transfer occurs mutually between Ce³⁺ and Pr³⁺, while in YAG:Ce, Tb systems, only one-way path energy transfer of Tb³⁺→Ce³⁺ is observed.     

Luminescence sensitization in Nd-Cr-Ce doped yttrium aluminates

Energy transfer from Ce to Cr in YAG is radiative and relatively inefficient. If excited below 500 nm, the opposite transfer is dominant. YAP: Ce, Cr showed relatively efficient CeCr transfer only. The sensitization of Nd³⁺ luminescence by Ce³⁺ ions depends on the overlap of the Ce³⁺ emission band with Nd³⁺ absorption lines. Cr³⁺Nd³⁺ transfer is characterized by an expressive non-radiative portion. It is inefficient in YAG but very efficient in YAP. No UV-induced colour centres were found in YAG: Nd, Cr grown under Ar-H₂ atmosphere and doped with 10^–3 wt. % Cr, but at a higher Cr concentration anomalous absorption between UV absorption edge and 650 nm was stabilized. Ce³⁺ admixture in YAG:Nd, Cr and/or reducing treatment of the crystals facilitate the decomposition of the centres. The decomposition is accompanied with a strong Nd³⁺ luminescence. Therefore, YAG: Nd, Ce, Cr is an advisable active laser material. On the other hand the same centre in YAP: Nd, Cr seemed to be more stable even in the presence of cerium ions.     

Luminescence properties of Y3Al5O12:Ce nanoceramics

Comparative analysis of the luminescent properties of Y₃Al₅O₁₂:Ce (YAG:Ce) transparent optical ceramics (OС) with those of single crystal (SC) and single crystalline film (SCF) analogues has been performed under excitation by pulsed synchrotron radiation in the fundamental absorption range of YAG host. It has been shown that the properties of YAG:Ce OC are closer to the properties of the SCF counterpart, where Y_Al antisite defects are completely absent, rather than to the properties of SC of this garnet with large concentration of Y_Al antisite defects. At the same time, the luminescence spectra of YAG:Ce OC show weak emission bands in the 200-470 nm range related to Y_Al antisite defects and charged oxygen vacancies (F⁺ and F centers). YAG:Ce ОС also possesses significantly larger contribution of slow components in the Ce³⁺ luminescence decay under high-energy excitation in comparison with SC and SCF of this garnet due to the involvement of antisite defects, charged oxygen vacancies as well as boundaries of grains in the energy transfer processes from the host to the Ce³⁺ ions.     

Ionization of helium-like ions with excitation of nl states by high-energy photon scattering

The kinetic and spectral characteristics of the complex dielectric constant of a Ce: YAG crystal under laser irradiation in 250–275 nm spectral range are investigated. The lifetimes of free charge carriers and charge carriers, localized at the lattice defects (color centers), are estimated. It was established that photoconductivity signal of the sample is essentially caused by one-photon ionization processes from the ² F _5/2 ground state of Ce³⁺ ions.     

Luminescent and scintillation properties of YAG:Dy and YAG:Dy,Ce single crystalline films

The paper is devoted to investigation of the luminescent properties of Dy³⁺ and Dy³⁺-Ce³⁺ doped single crystalline films (SCF) grown by LPE method from PbO–B₂O₃ flux. We have found that the YAG:Dy and YAG:Dy,Ce SCFs possess bright cathodoluminescence in the visible range and good scintillation figure of merit. For this reason LPE grown YAG:Dy and YAG:Dy,Ce SCF are proposed for different applications, namely, as cathodoluminescence screens or screens for microimaging. The Dy³⁺ co-doping can be also proposed for improvement of the scintillation efficiency of the Ce³⁺ doped garnet compounds in the SCF form due to Dy³⁺→ Ce³⁺ energy transfer and removing the trap related centers in the above RT range.     

Luminescence properties of phosphors based on Tb<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> (TbAG) terbium-aluminum garnet

The processes of excitation energy transfer in phosphors based on single-crystal Tb₃Al₅O₁₂:Ce (TbAG:Ce) and Tb₃Al₅O₁₂:Ce,Eu (TbAG:Ce,Eu) garnet films have been investigated. These films are considered to be promising materials for screens for X-ray images and luminescence converters of blue LED radiation. The conditions for excitation energy transfer from the matrix (Tb³⁺ cations) to Ce³⁺ and Eu³⁺ ions in TbAG:Ce and TbAG:Ce,Eu phosphors have been analyzed in detail. It is established that a cascade process of excitation energy transfer from Tb³⁺ ions to Ce³⁺ and Eu³⁺ ions and from Ce³⁺ ions to Eu³⁺ ions is implemented in TbAG:Ce,Eu via dipole-dipole interaction and through the Tb³⁺ cation sublattice.     

Energy transfer-based spectral properties of Tb-, Pr-, or Sm-codoped YAG:Ce nanocrystalline phosphors

Tb³⁺-, Pr³⁺-, or Sm³⁺-codoped YAG:Ce nanocrystalline phosphors were prepared using a modified polyol process. Possible tunability of Ce³⁺-related yellow emission in codoped YAG:Ce nanocrystalline systems was investigated. Dual emission of yellow and red spectral component with a single excitation wavelength was observed from YAG:Ce, Pr or YAG:Ce,Sm codoped systems via an energy transfer from Ce³⁺ and Pr³⁺ or Sm³⁺ ion. It was also observed that the energy transfer event in YAG:Ce, Pr nanocrystalline phosphor occurs mutually between Ce³⁺↔Pr³⁺, while in YAG:Ce, Sm and YAG:Ce, Tb the energy transfer progresses one way. The detailed pathways for transferring an excitation energy are explained based on the energy level diagrams of respective Ce³⁺, Pr³⁺, Sm³⁺, Tb³⁺ ion.     

Changes in optical absorption in iron garnet films due to impurity incorporation

The incorporation of impurities in films of Bi-substituted iron garnets grown by liquid phase epitaxy has been studied by successively adding small amounts of SiO₂ and CaCO₃ to the melt before film growth. It is found that very small additions of CaCO₃ to the melt profoundly influences the optical absorption coefficient and the electrical properties. The impurity absorption ofn-type YIG doped with Si⁴⁺ and Pb²⁺ ions is investigated and its wavelength dependence compared to that ofp-type YIG. The optical transitions involved in the impurity absorption of iron garnets are discussed in terms of transition reaction, photon energy and dependence on the impurity concentration. Depending on the photon energy, one or several transitions may give rise to impurity absorption.     

White LED based on nano-YAG:Ce3+/YAG:Ce3+,Gd3+ hybrid phosphors

Nano-YAG:Ce³⁺ and YAG:Ce³⁺,Gd³⁺ phosphors were synthesized by glycothermal method. The X-ray diffraction (XRD) measurements showed that the samples can be well-crystallized at 600 °C. The transition electron microscope (TEM) showed that the particles have sizes mostly in the range between 35 and 100 nm. The YAG:Ce nano-phosphor had a wide emission band ranging from blue to yellow peaking at 532 nm, due to the transition from the lowest 5d band to ²F_7/2, ²F_5/2 states of the Ce³⁺ ion. Red-shift of emission peak wavelength from 532 nm to 568 nm has been achieved as doping Gd³⁺ ions into the YAG:Ce³⁺ to substitute some Y³⁺ ions. White LEDs were fabricated by combining GaN (460 nm) chip with the YAG:Ce³⁺ and YAG:Ce³⁺,Gd³⁺. Color rendering index of the white LED as a function of the ratios of theses two kinds of phosphors was studied. As the ratio of YAG:Ce³⁺,Gd³⁺ phosphor increased, the color rendering index of the LED improved significantly under the forward bias of 20 mA. As the ratio of YAG:Ce³⁺ and YAG:Ce³⁺,Gd³⁺ was 11:9, the white LED had a color rendering index, CIE chromaticity coordinates and color temperature T_c of 85, (0.3116, 0.3202) and 6564 K, respectively.     

Luminescence and Tb-Ce-Eu ion energy transfer in single-crystalline films of Tb3Al5O12:Ce,Eu garnet

The paper is devoted to investigation of the processes of excitation energy transfer between the host cations (Tb³⁺ ions) and the activators (Ce³⁺ and Eu³⁺ ions) in single-crystalline films of Tb₃Al₅O₁₂:Ce,Eu (TbAG:Ce,Eu) garnet which is considered as a promising luminescent material for the conversion of LED's radiation. The cascade process of excitation energy transfer is shown to be realized in TbAG:Ce,Eu: (i) from Tb³⁺ ions to Ce³⁺ and Eu³⁺ ions; (ii) from Ce³⁺ ions to Eu³⁺ ions by means of dipole-dipole interaction and through Tb³⁺ ion sublattice.     

Luminescence of Mn ions in Tb3Al5O12 garnet

The paper is dedicated to investigation of the Mn²⁺ luminescence in Tb₃Al₅O₁₂ (TbAG) garnet, as well as the processes of excitation energy transfer between host cations (Tb³⁺ ions) and activators (Mn²⁺ and Mn²⁺-Ce³⁺ pair ions) in single crystalline films of TbAG:Mn and TbAG:Mn,Ce garnets which can be considered as promising luminescent materials for conversion of LED's radiation. Due to the effective energy transfer between TbAG host and activator, Mn²⁺ ions in TbAG possess the bright orange luminescence in the bands peaked at 595 nm with a lifetime of 0.64 ms which are caused by the ⁴T₁→⁶A₁ radiative transitions. The simultaneous process of energy transfer is realized in TbAG:Mn,Ce: (i) from Tb³⁺ to Mn²⁺ ions; (ii) from Tb³⁺ cations to Ce³⁺ ions and then partly to Mn²⁺ ions through Tb³⁺ ion sublattice and Ce-Mn dipole-dipole interaction.     

Effect of post-annealing temperature on the microstructure and magnetic properties of Ce:YIG thin films deposited on Si substrates

Amorphous Ce₁Y₂Fe₅O₁₂ (Ce:YIG) thin films deposited on single crystal Si(1 0 0) and thermally oxidized Si(1 0 0) substrates by pulsed laser deposition were annealed in the temperature range of 700-1000 °C in air. The annealing temperature dependence of microstructure and magnetic properties of Ce:YIG films was studied using X-ray diffraction combined with vibrating sample magnetometer. The results show that single phase of polycrystalline Ce:YIG thin films can be obtained by the post-annealing of as-deposited films at the temperature of 700 °C. However, two steps of phase segregation of Ce:YIG occur as the post-annealing temperature increases: at first, Ce:YIG is decomposed into YIG and non-magnetic CeO₂ when annealed at 800 °C; then YIG continues to be decomposed forming Fe₂O₃ when the temperature is increased up to 900 °C. Consequently, the saturation magnetization of Ce:YIG films decreases first and then increases with the post-annealing temperature going up, which indicates that the saturation magnetization of Ce:YIG films is mainly related to the phase composition of the films. Meanwhile, the presence of SiO₂ buffer layer can significantly enhance the saturation magnetization of Ce:YIG films.     

Pulsed cathodoluminescence of yttrium-aluminum garnet in the visible spectral range

The spectra of the pulsed cathodoluminescence of yttrium-aluminum garnet (YAG) laser crystals activated with various impurities (YAG:Nd; YAG:Nd,Ce; YAG:Cr; YAG:Cr,Ce; YAG:Er; and YAG:Sm) are studied. The bands of the rare-earth ions in the visible spectral range are identified. Luminescence of Ce²⁺ ion is revealed in the YAG:Cr,Ce crystal. Original Text ? Astro, Ltd., 2006.