Ultrasonic degradation kinetics and isomerization of 3- and 4-O-caffeoylquinic acid at various pH: The protective effects of ascorbic acid and epigallocatechin gallate on their stability

Caffeoylquinic acids are existed in many plant species with various biological and pharmacological activities. 3-O-caffeoylquinic acid and 4-O-caffeoylquinic acid are two isomers of caffeoylquinic acids, which may be degraded and transformed to their isomers in processing. The present paper found that the stability of 3- and 4-O-caffeoylquinic acid had decreased with the increasing solution alkalinity. 3-O-caffeoylquinic acid was more stable than 4-O-caffeoylquinic acid at the same condition. During degradation, 3- and 4-O-caffeoylquinic acid were partially converted to their isomers. Additionally, ultrasonic effects on the degradation and isomerization of 3- and 4-O-caffeoylquinic acid at different pH were studied. Ultrasound facilitated the degradation and isomerization of these compounds. The degradation kinetics were described by the Weibull equation. The protective effect of ascorbic acid and epigallocatechin gallate were also explored. Ascorbic acid and epigallocatechin gallate could alleviate the degradation of 3- and 4-O-caffeoylquinic acid under certain conditions.     

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.     

OH-对磷酸盐铒玻璃光谱性质的影响

本文系统研究了Yb³⁺、Er³⁺共掺磷酸盐铒玻璃中OH^-含量与铒玻璃荧光寿命和光谱性质的关系.结果表明OH^-基团的存在使得Er³⁺离子的荧光强度显著降低,荧光寿命大大缩短.比较了三种不同Al₂O₃含量(5mol%,8mol%和13mol%)的铒玻璃在2.9μm波长处的红外吸收系数与铒离子荧光寿命的关系,发现玻璃中OH^-在2.9μm的吸收系数和Er³⁺的⁴Ⅰ_13/2能级离子衰减速率成线性关系,不同Al₂O₃含量的玻璃具有不同Er³⁺和OH^-基团的相互作用参量和不同的荧光寿命值及量子效率.并从玻璃结构上解释了Al₂O₃含量对除水机制和光谱性质的影响.经过充分除水后的铒玻璃荧光寿命可达到9.1ms.     

Solvothermal synthesis and luminescence properties of the novel aluminum garnet phosphors for WLED applications

The color rendering index (CRI) and structural stability of cerium doped yttrium aluminum garnet (YAG:Ce) based phosphors have been enhanced by replacing Y³⁺ ions by larger radius ions (Tb³⁺, Gd³⁺, Eu³⁺, and Sm³⁺) at the dodecahedral site and replacing Al³⁺ ions by larger ones (Ga³⁺, Y³⁺, Tb³⁺, Gd³⁺, and Sm³⁺) at the octahedral site. These aluminum garnet crystalline powders were prepared by solvothermal reaction method at 300 °C for 48 h. The lattice constant values of synthetic aluminum garnet crystalline powders are larger than that of YAG and the emission wavelength of Ce³⁺ ion of these samples is longer than that of YAG:Ce. FESEM and TEM studies revealed that the Ln₃Ga₂Al₃O₁₂ and Ln₃Al₂Al₃O₁₂ crystalline powders have 3-dimensional star-like morphology with submicron size and good crystallinity, while, Ln₃(LnAl)Al₃O₁₂ garnet crystalline powders were cubic crystalline phases and shaped as cubes with the round edge having an approximate diameter of about 200–400 nm. All the prepared powders were grown along (100) direction and crystallized into single crystal. Also, the effects of treatment time and reaction temperature on the structure of aluminum garnet crystalline powders have been investigated.     

Tunable afterglow color in Eu and Dy co-activated alkaline earth feldspar solid solutions phosphors

The Eu²⁺ and Dy³⁺ co-activated Ca-Sr feldspar solid solution compounds, (Ca_0.98−xSr_x)Al₂Si₂O₈:Eu_0.01,Dy_0.01 (x=0-0.98), have been prepared by solid-state reaction in weak reductive atmosphere. The fluorescence spectra showed that the emission peaks of these phosphors shifts to shorter wavelength with an increase of Sr²⁺ solid solution quantity and correspondingly the afterglow color changes from blue to purple. All the changes can be attributed to the various crystal fields around Eu²⁺ ions. The afterglow with special short wavelength in near ultraviolet region can be obtained by adjusting the host chemical composition.     

Luminescent properties of green- or red-emitting Eu-doped Sr3Al2O6 for LED

Eu²⁺-doped Sr₃Al₂O₆ (Sr_3−xEu_xAl₂O₆) was synthesized by a solid-state reaction under either H₂ and N₂ atmosphere or CO atmosphere. When H₂ was used as the reducing agent, the phosphor exhibited green emission under near UV excitation, while CO was used as the reducing agent, the phosphor mainly showed red emission under blue light excitation. Both emissions belong to the d-f transition of Eu²⁺ ion. The relationship between the emission wavelengths and the occupation of Eu²⁺ at different crystallographic sites was studied. The preferential substitution of Eu²⁺ into different Sr²⁺ cites at different reaction periods and the substitution rates under different atmospheres were discussed. Finally, green-emitting and red-emitting LEDs were fabricated by coating the phosphor onto near UV- or blue-emitting InGaN chips.     

Phosphor-converted light-emitting diode based on ZnO-based heterojunction

A phosphor-converted light-emitting diode (LED) was realized by coating BaMg₂Al₁₆O₂₇:Eu²⁺·Mn²⁺ and (SrCaPO₄)·B₂O₃:Eu²⁺·Na⁺ phosphors onto an n-ZnO/i-MgO/p-GaN heterojunction diode. Two emission bands at around 450 and 520 nm were observed in the phosphor-converted LED under the injection of continuous current. By analyzing the optical properties of the heterojunction diode and phosphors, it is concluded that the emission at 450 nm comes from (SrCaPO₄)·B₂O₃:Eu²⁺·Na⁺ phosphor, while the one at 520 nm comes from BaMg₂Al₁₆O₂₇:Eu²⁺·Mn²⁺ phosphor under the excitation of the light emitted from the n-ZnO/i-MgO/p-GaN heterojunction diode. The results reported in this paper may provide a route to ZnO-based phosphor-converted LEDs for future lighting or displaying purpose.     

X-ray emission study of the electronic structure of nanocrystalline Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Valence states of metal ions and the phase composition of nanocrystalline Al₂O₃ (of the original oxide and the oxide irradiated by high-energy Fe⁺ ions) are studied by using x-ray emission Al L_{2, 3} and O Kα spectra. It is established that the shape of the Al L_{2, 3} spectra strongly changes as one goes from the original (bulk) Al₂O₃ to nanocrystalline oxide, while the O Kα spectra remain practically unchanged. Moreover, irradiation by high-energy Fe⁺ ions results in slight additional changes in the x-ray spectral characteristics of the aluminum oxides under study. The obtained experimental data are compared with the results of theoretical calculations of the electronic structure of α and γ phases of Al₂O₃ performed using the LDA formalism. Using the results of x-ray spectral studies, electronic structure calculations, and x-ray diffraction analysis, it is shown that the revealed spectral differences between the nanocrystalline state of aluminum oxide and the bulk material can be interpreted as a phase transition from the α phase to the γ phase of Al₂O₃ with an addition of bayerite.     

Luminescence of impurity 3d and 4f metal ions in different crystalline forms of Al2O3

The ² E-⁴ A ₂ luminescence spectra of Cr³⁺ ions in Al₂O₃ are investigated in the course of transitions between the structural forms γ-δ-θ-α. The spectral lines observed are assigned to Cr³⁺ ions in these structural forms, which are identified by an X-ray powder diffraction analysis. The lifetimes of the Cr³⁺ excited states in transient forms of Al₂O₃ are measured. Investigations of the luminescence spectra of Al₂O₃: Eu³⁺ demonstrate that the Eu³⁺ ions can form regular centers only in α-Al₂O₃ and, unlike the Cr³⁺ ions, give no rise to similar centers in moderately ordered θ-Al₂O₃.     

Enhancement of red spectral emission intensity of Y3Al5O12:Ce phosphor via Pr co-doping and Tb substitution for the application to white LEDs

We have enhanced color-rendering property of a blue light emitting diode (LED) pumped white LED with yellow emitting Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce) phosphor using addition of Pr and Tb as a co-activator and host lattice element, respectively. Pr³⁺ addition to YAG:Ce phosphor resulted in sharp emission peak at about 610 nm through ¹D₂→³H₄ transition. And when Tb³⁺ substituted Y³⁺ sites, Ce³⁺ emission band shifted to a longer wavelength due to larger crystal field splitting. Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and (Y_1−xTb_x)₃Al₅O₁₂:Ce³⁺ phosphors were coated on blue LEDs to fabricate white LEDs, respectively, and their color-rendering indices (CRIs, R_a) were measured. As a consequence of the addition of Pr³⁺ or Tb³⁺, CRI of the white LEDs improved to be R_a=83 and 80, respectively. Especially, blue LED pumped (Y_0.2Tb_0.8)₃Al₅O₁₂:Ce³⁺ white LED showed both strong luminescence and high color-rendering property.     

Orange emissive Sr3Al2O5Cl2:Eu2+ phosphor for warm-white light-emitting diodes

Orange-emitting Sr₃Al₂O₅Cl₂:Eu²⁺ phosphors were synthesized by a high-temperature solid-state reaction. The excitation spectrum shows a broad band from the UV region to the blue region. The emission spectrum shows strong orange emission peaking at 610 nm, attributed to the d–f transition of the Eu²⁺ ion. By combining the Sr₃Al₂O₅Cl₂:Eu²⁺ phosphor with 420 nm and 460 nm chips, three white light-emitting diodes (LEDs) were fabricated. The warm-white LEDs show color rendering indexes of 76, 66 and 90 with color temperatures of 2447, 3546 and 4300 K, respectively. This new phosphor exhibits the potential to act as a single host doped with Eu²⁺ phosphor for UV or blue chip excited white LEDs.     

V centers in single crystal Al2O3

From optical and thermal bleaching experiments it is concluded that the 400 nm absorption band which appears in Al₂O₃ after γ-irradiation is a composite V band. One of its components is attributed to the V^-_OH center which also is responsible for a localized vibrational band at 3316 cm^-11 analogous to the one observed for the V_OH center in MgO. The irradiation also results in electron trapping at Cr³⁺ impurity ions to produce a band at 227 nm. Annealing at 170°C destroys the V^-_OH center by releasing holes which convert the Cr²⁺ to Cr³⁺ with an attendant thermoluminescence.     

Green and red up-conversion emissions of Er-Yb-codoped Al2O3 powders prepared by the nonaqueous sol-gel method

The 1 mol% Er³⁺- and 0-20 mol% Yb³⁺-codoped Al₂O₃ powders have been prepared by the nonaqueous sol-gel process using aluminum isopropoxide as precursor, acetylacetone as chelating agent, nitric acid as catalyzer, and hydrated erbium and ytterbium nitrate as dopant under isopropanol environment. The two crystalline types of doped Al₂O₃, γ and θ, and a stoichiometric compound, (Yb,Er)₃Al₅O₁₂, were obtained for all the Er³⁺-Yb³⁺-codoped Al₂O₃ powders at the sintering temperature of 1000 °C. The maximal intensity of both the green and red up-conversion emissions centered at about 523, 545, and 660 nm was observed for the 1 mol% Er³⁺- and 10 mol% Yb³⁺-codoped Al₂O₃ powders. The intensity ratio of the red to green up-conversion emission (I_red/I_green) increased with increasing the Yb³⁺ doping concentration for the Er³⁺-Yb³⁺-codoped Al₂O₃ powders. Furthermore, the intensity ratio of the green up-conversion emission at about 523 to 545 nm (I₅₂₃/I₅₄₅) was proportional to the Yb³⁺ doping concentration and pump electric current, which was associated with the elevated temperature of powders.     

Probing the electronic structure of mono-nitrogen doped aluminum clusters using anion photoelectron spectroscopy

We report a photoelectron spectroscopic investigation of mono-nitrogen doped aluminum cluster anions Al_nN^- (n = 2-22). Well-resolved spectra were obtained at three photon energies (355, 266, and 193 nm), revealing the structural and electronic evolution as the number of aluminum atoms increases in the doped clusters. For small Al_nN (n < 9) clusters, the Al atoms may be viewed to be monovalent, similar to pure aluminum clusters. Even-odd alternation of the electron affinities was observed for Al_nN clusters, suggesting that neutral clusters with odd n are closed shell and those with even n are open shell. The most interesting observation is the similarity between the spectra of Al_nN^- and Al_(n-1)^- for n>12. This observation suggests that these clusters can be described as (AlN)Al_(n-1)^-, i.e., an AlN unit weakly interacting with Al_(n-1)^- clusters. The electronic and atomic structural implications of this observation are discussed.     

Synthesis and luminous characteristics of Ba2MgSi2−xAlxO7: 0.1Eu, 0.1Mn phosphor for WLED

The shift of the emission band to longer wavelength (yellow-orange) of the Ba₂MgSi_2−xAl_xO₇: 0.1Eu²⁺ phosphor under the 350-450 nm excitation range has been achieved by adding the codoping element (Mn²⁺) in the host. The single-host silicate phosphor for WLED, Ba₂MgSi_2−xAl_xO₇: 0.1Eu²⁺, 0.1Mn²⁺ was prepared by high-temperature solid-state reaction. It was found experimentally that, its three-color emission peaks are situated at 623, 501 and 438 nm, respectively, under excitation of 350-450 nm irradiation. The emission peaks at 438 and 501 nm originate from the transition 5d to 4f of Eu²⁺ ions that occupy the two Ba²⁺ sites in the crystal of Ba₂MgSi_2−x Al_xO₇, while the 623 nm emission is attributed to the energy transfer from Eu²⁺ ions to Mn²⁺ ions. The white light can be obtained by mixing the three emission colors of blue (438 nm), green (501 nm) and red (623 nm) in the single host. When the concentrations of the Al³⁺, Eu²⁺ and Mn²⁺ ions were 0.4, 0.1 and 0.1 mol, respectively, the sample presented intense white emission. The addition of Al ion to the host leads to a substantial change of intensity ratio between blue and green emissions. White light could be obtained by combining this phosphor with 405 nm light-emitting diodes. The near-ultraviolet GaN-based Ba₂MgSi_1.7 Al_0.3O₇: 0.1Eu²⁺, 0.1Mn²⁺ LED achieves good color rendering of over 85.     

Photoluminescence quenching in zinc oxide modified by Al2O3 and Al2O3 · CeO2 Nanopowders under proton irradiations

The photoluminescence spectra of initial ZnO powder and that modified by Al₂O₃, Al₂O₃ · CeO₂ nanopowders are investigated in the range 360–660 nm before and after 100-keV proton irradiation. It is found that the introduction of nanoparticles causes a decrease in the UV-band intensity and a change in the luminescence bands in the visual spectrum due to V _O ⁺ oxygen vacancies, O _int ^- interstitial oxygen, and V _Zn ^- zinc vacancies. Luminescence quenching in the UV and visible spectra occurs under the effect of protons. The decomposition of the spectra into elementary defects and analysis of changes in their integrated intensity during modification and irradiation of the powders are carried out.     

Growth and interfacial properties of atomic layer deposited Al0.7Ti0.3O y high-k dielectric on Ge substrate

Growth and interfacial properties of atomic layer deposited Al_0.7Ti_0.3O _y on Ge have been investigated as a potential high-k gate dielectric for future Ge-based metal oxide semiconductor devices. A sandwich structure of Al₂O₃/TiO₂ stack is proposed for Al₂O₃/TiO₂ intermixing and high-k/Ge interfacial passivation. The film thicknesses and interface microstructure are characterized by spectroscopy ellipsometry and high-resolution transmission electron microscopy. X-ray photoelectron spectrometry is used to analyze the chemical composition and bonding states, and to reveal the band alignment of high-k/Ge heterojunctions. Metal-oxide-capacitors are formed by depositing aluminum electrodes to perform capacitance–voltage measurements for electrical characteristics. All evidences show a positive prospect of employing atomic layer deposited Al_0.7Ti_0.3O _y as high-k gate dielectric for future Ge-based devices.     

Luminescence centers in thin films of yttrium oxide and yttrium-aluminum garnet activated with bismuth

Luminescence spectra and photoluminescence excitation spectra of Y₂O₃:Bi and Y₃Al₅O₁₂:Bi thin films were investigated. Luminescence was stimulated by the emission from two types of centers that were associated with the substitution of Bi³⁺ for Y³⁺ in sites of the crystal lattice of Y₂O₃ (Y₃Al₅O₁₂) with point symmetries C₂ and C_3i (D₂ and C_3i). The emission of Bi³⁺ in the site with point symmetry C_3i causes blue luminescence in both Y₂O₃:Bi and Y₃Al₅O₁₂:Bi films with maxima at 3.03 eV and 3.15 eV, respectively, that is related to the ³P₁-¹S₀ transition. The emission of Bi³⁺ in the site with point symmetry C₂ gives green luminescence in Y₂O₃:Bi with the maximum at 2.40 eV that is also related to the ³P₁-¹S₀ transition. The emission of Bi³⁺ in the site with point symmetry D₂ leads to ultraviolet luminescence in Y₃Al₅O₁₂:Bi with the maximum at 3.75 eV that corresponds to the ³P₁-¹S₀ transition. The red luminescence band with the maximum at 1.85 eV in Y₂O₃:Bi is due to the presence of structural defects. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 202–207, March–April, 2008.     

Properties of an Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Si interface

The phase chemical composition of an Al₂O₃/Si interface formed upon molecular deposition of a 100-nm-thick Al₂O₃ layer on the Si(100) (c-Si) surface is investigated by depth-resolved ultrasoft x-ray emission spectroscopy. Analysis is performed using Al and Si L_{2, 3} emission bands. It is found that the thickness of the interface separating the c-Si substrate and the Al₂O₃ layer is approximately equal to 60 nm and the interface has a complex structure. The upper layer of the interface contains Al₂O₃ molecules and Al atoms, whose coordination is characteristic of metallic aluminum (most likely, these atoms form sufficiently large-sized Al clusters). The shape of the Si bands indicates that the interface layer (no more than 10-nm thick) adjacent to the substrate involves Si atoms in an unusual chemical state. This state is not typical of amorphous Si, c-Si, SiO₂, or SiO_x (it is assumed that these Si atoms form small-sized Si clusters). It is revealed that SiO₂ is contained in the vicinity of the substrate. The properties of thicker coatings are similar to those of the 100-nm-thick Al₂O₃ layer and differ significantly from the properties of the interfaces of Al₂O₃ thin layers.     

Effect of boric acid on structure,morphology and luminescent properties of divalent europium doped calcium aluminate phosphors

Blue phosphors Ca_1 − xAl₂O₄: xEu²⁺ were prepared by high temperature solid-state method. Their structure, morphology and luminescent properties were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM) and fluorescence spectroscopy. The effect of different amounts of fluxing agent H₃BO₃ on structure, morphology and luminescent properties of blue phosphors Ca_1 − xAl₂O₄: xEu²⁺ luminous intensity caused by different amount of H₃BO₃ was also investigated. The amount of H₃BO₃ doped Ca_1 − xAl₂O₄: xEu²⁺ in optimal luminous intensity had been determined. The results showed that both the excitation and emission spectra of samples were all broad bands, and that the peak of emission spectra was near 442 nm, which was corresponding to the 4f⁶5d → 4f⁷ transition of Eu²⁺ illuminating blue light. Ca_1 − xAl₂O₄: xEu²⁺ (x = 3.5 mol%) could be gained with good morphology and the best luminous intensity when H₃BO₃ mass ratio was 0.5 wt%.