Optical properties of multilayer structures

The possibility of using the ellipsometry method for investigation of the optical properties of multilayer films and structures is shown. The optical properties of structures HfO₂/SiO₂/Si, HfO₂/Si, ZrO₂/Si, Ta₂O₅/Si, and Al₂O₃/Si are studied. It is found that a layer of hafnium silicate is formed at the interface between the HfO₂ film and Si. Annealing of the structures in oxygen shows that oxides studied are oxygen-permeable and that the thickness of SiO₂ at the film-substrate interface increases. The growth rate of SiO₂ layers depends on the chemical nature of an oxide. Al₂O₃ films are impermeable for oxygen diffusion. The production of layers of alloys (Al₂O₃) _x (HfO₂)_{1 ? x} is optimized, which allows one to obtain layers with a homogeneous distribution of elements over the thickness.     

Nondestructive investigation of interface states in high‐k oxide films on Ge substrate using X‐ray absorption spectroscopy

The unoccupied electronic structures of 5 nm thick high permittivity (k) oxides (HfO₂, ZrO₂, and Al₂O₃) and SiO₂ films on Ge substrates were examined using O K‐edge X‐ray absorption spectroscopy. Comparative studies with those on Si substrates showed contrasts in the conduction bands, which should be due to the formation of interface states. In the Al₂O₃ and SiO₂ films, GeO₂ layers are formed at the interface and they suppress in part the formation of detrimental germanate phases. In contrast, in the HfO₂ and ZrO₂ films, no signature of the Ge‐oxide phase is observed but some germanate phases are expected to prevail, suggesting a degradation of the gate oxide characteristics. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

X-ray photoemission and X-ray absorption studies of Hf-silicate dielectric layers

Photoelectron spectroscopy and X-ray absorption spectroscopy (XAS) measurements have been performed on HfSi_xO_y and HfSi_xO_yN_z dielectric layers, which are potential candidates as high-k transistor gate dielectrics. The hafnium silicate layers, 3-4 nm thick, were formed by codepositing HfO₂ and SiO₂ (50%:50%) by MOCVD at 485 °C on a silicon substrate following an IMEC clean. Annealing the HfSi_xO_y layer in a nitrogen atmosphere at 1000 °C resulted in an increase in the Si⁴⁺ chemical shift from 3.5 to 3.9 eV with respect to the Si⁰ peak. Annealing the hafnium silicate layer in a NH₃ atmosphere at 800 °C resulted in the incorporation of 10% nitrogen and the decrease in the chemical shift between the Si⁴⁺ and the Si⁰ to 3.3 eV. The results suggest that the inclusion of nitrogen in the silicate layer restricts the tendency of the HfO₂ and the SiO₂ to segregate into separate phases during the annealing step. Synchrotron radiation valence band photoemission studies determined that the valence band offsets were of the order of 3 eV. X-ray absorption measurements show that the band gap of these layers is 4.6 eV and that the magnitude of the conduction band offset is as little as 0.5 eV.     

Low-temperature deposition of stoichiometric HfO2 on silicon: Analysis and quantification of the HfO2/Si interface from electrical and XPS measurements

An understanding of the exact structural makeup of dielectric interface is crucial for development of novel gate materials. In this paper a study of the HfO₂/Si interface created by the low-temperature deposition ultrathin stoichiometric HfO₂ on Si substrates by reactive sputtering is presented. Analysis, quantification and calculation of layer thickness of an HfO₂/Hf-Si-O_x/SiO₂ gate stack dielectrics have been performed, using X-ray photoelectron spectroscopy (XPS) depth profile method, angle resolved XPS and interface modeling by XPS data processing software. The results obtained were found to be in good agreement with the high frequency capacitance-voltage (C-V) measurements. The results suggest a development of a complex three layer dielectric stack, including hafnium dioxide layer, a narrow interface of hafnium silicate and broad region of oxygen diffusion into silicon wafer. The diffusion of oxygen was found particularly detrimental to the electrical properties of the stack, as this oxygen concentration gradient leads to the formation of suboxides of silicon with a lower permittivity, κ.     

Luminescence enhancement of Eu-doped calcium magnesium silicate blue phosphor for UV-LED application

(Ca_1−x,Eu_x)MgSi_2yO_6+δ blue phosphor was prepared by spray pyrolysis and the photoluminescence properties were optimized by controlling concentration of Si element and the activator content. At y=1.0, the concentration quenching in the luminescent intensity appeared when the Eu²⁺ content (x) was 0.01 (1 at%). Such quenching concentration was changed with the concentration of silicon (y), which was increased with an increase in the quantity of excess Si (y>1.0). The highest luminescent intensity was achieved when the Eu²⁺ content (x) and the Si concentration (y) were 0.04 and 1.3, respectively. According to X-ray diffraction (XRD) analysis, the tetragonal SiO₂ phase was formed as a minor phase when the y value was larger than 1.3. The formation of SiO₂ phase, however, did not reduce but increased the luminescent intensity when the Eu²⁺ content was optimized again. As a result, the luminescent intensity of the phosphor particles optimized in the content of both Si and Eu²⁺ was about 150% improved compared with that of the CaMgSi₂O₆:Eu sample (x=0.01, y=1.0).     

Crystal structure and luminescence properties of Lu3+ and Mg2+ incorporated silicate garnet [Ca3−(x+0.06)LuxCe0.06](Sc2−yMgy)Si3O12

The yellow-emitting phosphor [Ca_3?(x+0.06)Lu_xCe_0.06](Sc_2?yMg_y)Si₃O₁₂ obtained from Lu³⁺ and Mg²⁺ co-modified green-emitting silicate garnet Ca₃Sc₂Si₃O₁₂:Ce³⁺ (CSS:Ce³⁺) exhibits promising applications for white LEDs. In this paper, we discuss the effect of charge balance on the garnet structure formation. The changes of bond length and covalence caused by the replacement of Lu³⁺ and Mg²⁺ for Ca²⁺ and Sc³⁺ are analyzed. The shift of the Ce³⁺ emission and excitation can be attributed to the combined results from crystal field splitting effect and centroid shift of Ce³⁺ 5d levels. Thermal stability is analyzed according to configurational coordinate diagram.     

Enhanced magneto-optical Kerr effects in nanocrystalline Sc-doped CoFe2O4 thin films

Nanocrystalline CoFe_2−xSc_xO₄ (x=0-0.4) thin films were prepared on silicon substrates at reduced temperature by a sol-gel process, and the doping effects of scandium on the microstructure, magnetism and polar magneto-optical Kerr effects of the as-deposited films were examined. It was shown that the intensities of both of the Kerr rotation peaks increase with the doping content x of Sc³⁺. The increase for the peak at 540 nm is due to the decrease of the electrostatic polarization of O²⁻ resulting from the relatively large radius of Sc³⁺, and that for the peak at 620 nm was a result of the migration of Co²⁺ from octahedral to tetrahedral sites in the presence of the dopant of Sc³⁺.     

Metalorganic chemical vapor deposited DyScO3 buffer layer in Pt/Bi3.25Nd0.75Ti3O12/DyScO3/Si metal–ferroelectric–insulator–semiconductor diodes

High-k DyScO₃ linear dielectric films were considered as a buffer layer for the metal-ferroelectric-insulator-semiconductor (MFIS) structures with Aurivillius Bi_3.25Nd_0.75Ti₃O₁₂ ferroelectric films. The DyScO₃ films on Si substrates were amorphous and dense with a smooth surface morphology, showing negligible CV hysteresis and low leakage current. The remnant polarization of ～20 μC/cm², dielectric constant ～400, and the loss tangent ～0.04 were obtained for the ferroelectric Bi_3.25Nd_0.75Ti₃O₁₂ film on Pt/TiO₂/SiO₂/Si substrates. The Pt/Bi_3.25Nd_0.75Ti₃O₁₂/DyScO₃/Si MFIS capacitors showed a large memory window of 4.0 V and excellent retention up to 1000 s, encouraging results for practical applications in nonvolatile RAM.     

Emission characteristics of Dy3+ ions in lead antimony borate glasses

Glasses with the composition 30PbO–25Sb₂O₃–(45?x)B₂O₃–xDy₂O₃ for x=0 to 1 were prepared in steps of 0.2 by the melt-quenching method. Various physical parameters, viz., density, molar volume, and oxygen packing density, were evaluated. Optical absorption and luminescence spectra of all the glasses were recorded at room temperature. From the observed absorption edges optical band gap, the Urbach energies are calculated; the optical band gap is found to decrease with the concentration of Dy₂O₃. The Judd–Ofelt theory was applied to characterize the absorption and luminescence spectra of Dy³⁺ ions in these glasses. Following the luminescence spectra, various radiative properties, like transition probability A, branching ratio β and the radiative life time τ for different emission levels of Dy³⁺ ions, have been evaluated. The radiative lifetime for the ⁴F_9/2 multiplet has also been evaluated from the recorded life time decay curves, and the quantum efficiencies were estimated for all the glasses. The quantum efficiency is found to increase with the concentration of Dy₂O₃.     

Infrared and auger spectra of dysprosium silicate films

Dysprosium silicate films, Dy _x Si _y O _z , have been investigated using infrared (IR) and Auger spectroscopy. The films have been formed by oxidizing dysprosium metal films on 5.2-nm-thick silicon dioxide films at a temperature of 600°C. It is shown that the composition of the Dy _x Si _y O _z dysprosium silicate films is close to that of dysprosium pyrosilicate, Dy₂Si₂O₇, and irregular in thickness. On going from the film outer surface to the silicon substrate, the amount of dysprosium decreases and that of silicon bound to oxygen increases. Silicon dioxide, SiO₂, predominates in the layer composition near the silicon substrate. The dielectric leakage current density in the accumulation mode is one order of magnitude lower in the Dy _x Si _y O _z films than in the SiO₂ films of the same equivalent thickness due to the larger physical thickness of the former.     

Crystal structure and photoluminescence of (Ba1−x−ySryEux)9Sc2Si6O24

Divalent europium-doped alkaline earth metal silicate phosphors, (Ba_1?x?ySr_yEu_x)₉Sc₂Si₆O₂₄ (x=0.005–0.1, y=0–0.95), have been successfully prepared by solid-state reaction at 1350 °C. The analysis of X-ray diffraction shows that the compounds are in a single phase at the proper concentration of Sr²⁺. At room temperature, the Eu²⁺-activated Ba₉Sc₂Si₆O₂₄ phosphor exhibits a single emission band peaking at about 506 nm. With the increasing content of Sr²⁺, the luminescent intensity of (Ba_1?x?ySr_yEu_x)₉Sc₂Si₆O₂₄ weakens, and the emission peak shifts towards red. Luminescence concentration quenching occurs when Eu²⁺ content x is more than 1 mol% in (Ba_1?x?ySr_yEu_x)₉Sc₂Si₆O₂₄ (y=0/0.2). At low temperatures (Ba_0.9?ySr_yEu_0.1)₉Sc₂Si₆O₂₄ (y=0/0.2) phosphors have two emission bands corresponding to different Eu²⁺ crystallographic sites. The high energy peak (P₁) is quenched at room temperature, while the low energy peak (P₂) weakens much more slowly owing to the energy transfer from P₁ to P₂.     

Formation of W/HfO2/Si gate structures using in situ magnetron sputtering and rapid thermal annealing

The W(150 nm)/HfO₂(5 nm)/Si(100) structures prepared in a single vacuum cycle by rf magnetron sputtering were subjected to rapid thermal annealing in argon. It is found that at an annealing temperature of 950°C, the tungsten oxide WO _x phase and the hafnium silicate HfSi _x O _y phase grow at the W/HfO₂ and HfO₂/Si(100) interfaces, respectively. Herewith, the total thickness of the oxide layeris 30% larger than that of the initial HfO₂ film. In addition, a decrease in the specific capacitance in accumulation C _max and in the dielectric constant k (from 27 to 23) is observed. At an annealing temperature of 980°C, intensive interaction between tungsten and HfO₂ takes place, causing the formation of a compositionally inhomogeneous Hf _x Si _y W _z O oxide layer and further decrease in C _max. It is shown that a considerable reduction in the leakage currents occurs in the W/HfO₂/X/Si(100) structures, where X is a nitride barrier layer.     

Magnetic and transport properties of Dy substituted layered perovskite La1.3Sr1.7Mn2O7

The effect of Dy substitution for La site in layered manganese oxides La1.3-x Dyx Sr1.7 Mn2O7 on the magnetic and electrical properties has been investigated.With the La 3+ substituting by Dy3+,the long range three-dimensional ferromagnetism transition and the insulator-metal transition disappear.These effects are attributed to the lattice distortion due to the substitution of the smaller Dy3+.Addtionally,the small Dy3+ is inclined to occupy the R site which is in the rock-salt layer,then the distribution of La,Sr,Dy ions in Dy-doped sample should be more orderly than that in La1.3 Sr1.7 Mn2O7,so there is only one insulator-metal transition in the ρ-T curve of the sample with x = 0.05 and x = 0.1.     

Synthesis and luminescent properties of BaGd2O4:Dy3+, an novel scintillating phosphor

The BaGd_2?x O₄:xDy³⁺ (0 ≤ x ≤ 0.08) phosphors were synthesized at 1,300 °C in air by the solid-state reaction route. The as-synthesized phosphors were characterized by X-ray powder diffraction, photoluminescence excitation spectra, photoluminescence (PL) spectra, X-ray excited luminescence (XEL) spectra, and thermoluminescence (TL) spectra. It is found that the quenching concentration of Dy³⁺ ions in BaGd₂O₄ host is dependent on the selected excitation wavelength. The optimal PL intensity for the investigated BaGd_2?x O₄:xDy³⁺ phosphors is found to be x = 0.01, 0.02, and 0.04, upon excitation by 234, 277, and 350 nm ultraviolet light, respectively. The energy transfer among Dy³⁺ ions upon excitation by 350 nm is confirmed to be an electric dipole–dipole interaction mechanism based on the fitting of Huang’s rule. In addition, the intensive XEL from BaGd₂O₄:Dy³⁺ phosphor is observed by the naked eyes at room temperature, and TL properties of the investigated phosphors are analyzed and discussed. All the results imply that the investigated phosphors could be a promising scintillating phosphor.     

Thickness measurement of a thin hetero-oxide film with an interfacial oxide layer by X-ray photoelectron spectroscopy

The general equation T_ove = L cos  θ ln(R_exp/R₀ + 1) for the thickness measurement of thin oxide films by X-ray photoelectron spectroscopy (XPS) was applied to a HfO₂/SiO₂/Si(1 0 0) as a thin hetero-oxide film system with an interfacial oxide layer. The contribution of the thick interfacial SiO₂ layer to the thickness of the HfO₂ overlayer was counterbalanced by multiplying the ratio between the intensity of Si⁴⁺ from a thick SiO₂ film and that of Si⁰ from a Si(1 0 0) substrate to the intensity of Si⁴⁺ from the HfO₂/SiO₂/Si(1 0 0) film. With this approximation, the thickness levels of the HfO₂ overlayers showed a small standard deviation of 0.03 nm in a series of HfO₂ (2 nm)/SiO₂ (2-6 nm)/Si(1 0 0) films. Mutual calibration with XPS and transmission electron microscopy (TEM) was used to verify the thickness of HfO₂ overlayers in a series of HfO₂ (1-4 nm)/SiO₂ (3 nm)/Si(1 0 0) films. From the linear relation between the thickness values derived from XPS and TEM, the effective attenuation length of the photoelectrons and the thickness of the HfO₂ overlayer could be determined.     

119Sn and121Sb Mössbauer studies of BaSn1−x Sb x O3 Perovskite system

The relations between the electrical characteristics of BaSn_1?x Sb _x O₃ perovskite system and the contents of BaO, Sb₂O₃ and silicate sintering agent were studied by X-ray diffraction analysis and Mössbauer spectroscopy. It was found that the electrical conductivity is related to the substitution of Sb³⁺ for Sn⁴⁺, the content of sintering agent and the phase constitutents in samples. BaSnO₃, Ba₃Sn₂O₇, Ba₂SnO₄ and SnO₂ phases might appear in different fractions when the contents of BaO change from 0.5 mole to 3.5 mole. In low antimony percentage condition, pentavalent Sb³⁺ ions inserted in Sn⁴⁺ sites and formed the donor center. In high antimony percentage (x≥0.20) condition, the existence of an insulating phase (BaSb₂O₆) was confirmed.     

Structure of Na2O·MO·SiO2·CaF2 (M=Mg,Ca) oxyfluoride glasses

(9−x)CaO·xMgO·15Na₂O·60SiO₂·16CaF₂(x=0, 2, 4, 6, and 9) oxyfluoride glasses were prepared. Utilizing the Raman scattering technique together with ²⁹Si and ¹⁹F MAS NMR, the effect of alkaline metal oxides on the Q species of glass was characterized. Raman results show that as magnesia is added at the expense of calcium oxide, the disproportional reaction Q³→Q⁴+Q² (Qⁿ is a SiO₄ tetrahedron with n bridging oxygens) prompted due to the high ionic field strength of magnesia, magnesium oxide entered into the silicate network as tetrahedral MgO₄, and removed other modifying ions for charge compensation. This reaction was confirmed by ²⁹Si MAS NMR. ¹⁹F MAS NMR results show that fluorine exists in the form of mixed calcium sodium fluoride species in all glasses and no Si–F bonds were formed. As CaO is gradually replaced by MgO (x=6, 9), a proportion of the magnesium ions combines with fluorine to form the MgF⁺ species. Meanwhile, some part of Na⁺ ions complex F⁻ in the form of F–Na(6).     

Morphology, composition and thermal stability of thin SiO2/HfO2 layers grown on silicon by electron-beam evaporation in vacuum

The results of integrated studies of thin-film structures based on silicon and hafnium dioxides on silicon grown by electron-beam evaporation in vacuum are presented. The surface morphology, structural and phase composition of these films depending on the annealing temperature within 500–1100°C are studied. Special consideration is given to the change in the state of the interfaces after annealing. It is determined that annealing in a flow of nitrogen with the addition of oxygen (～10 vol %) at 700°C does not lead to structural and phase changes in the films, but the intensity of the electron paramagnetic resonance (EPR) spectra of uncompensated bonds on the HfO₂-Si interface decreased. Annealing at higher temperatures stimulates crystallization of the HfO₂ films and hafnium silicate is formed on the SiO₂-HfO₂ interface and suboxide SiO _x appears on the HfO₂-Si interface.     

Effect of Sr substitution on photoluminescent properties of BaAl2O4:Eu, Dy

Phosphor material BaAl₂O₄:Eu²⁺, Dy³⁺ with varying compositions of Sr substitution were prepared by the solid-state synthesis method. The phosphor compositions were characterized for their phase and crystallinity by XRD, SEM and TEM. Photoluminescence (PL) properties were investigated measuring PL and decay time for varying Ba/Sr compositions. The PL results show the blue shift in the luminescence properties in Sr substituted BaAl₂O₄:Eu²⁺, Dy³⁺ compared to parent BaAl₂O₄:Eu²⁺, Dy³⁺. It is probably due to the influence of 5d electron states of Eu²⁺ in the crystal field because of atomic size variation causing crystal defects. Dy³⁺ ion doping in the phosphor generates deep traps, which results in long afterglow phosphorescence.     

Photoluminescence and afterglow behavior of Eu, Dy and Eu, Dy in Sr3Al2O6 matrix

This paper reports the photoluminescence and afterglow behavior of Eu²⁺ and Eu³⁺ in Sr₃Al₂O₆ matrix co-doped with Dy³⁺. The samples containing Eu²⁺ and Eu³⁺ were prepared via solid-state reaction. X-ray diffraction (XRD), photo luminescent spectroscope (PLS) and thermal luminescent spectroscope (TLS) were employed to characterize the phosphors. The comparison between the emission spectra revealed that Sr₃Al₂O₆ phosphors doped with Eu²⁺, Dy³⁺ and Eu³⁺, Dy³⁺ showed different photoluminescence. The phosphor doped with Eu³⁺, Dy³⁺ showed an intrinsic f-f transition generated from Eu³⁺, with two significant emissions at 591 and 610 nm. However, the phosphor doped with Eu²⁺, Dy³⁺ revealed a broad d-f emission centering around 512 nm. After the UV source was turned off, Eu²⁺, Dy³⁺ activated Sr₃Al₂O₆ phosphor showed excellent afterglow while Eu³⁺, Dy³⁺ activated phosphor almost showed no afterglow. Thermal simulated luminescence study indicated that the persistent afterglow of Sr₃Al₂O₆: Eu²⁺, Dy³⁺ phosphor was generated by suitable electron traps formed by the co-doped rare-earth ions (Dy³⁺) within the host.