Sol-gel growth of Gd2MoO6:Eu nanocrystalline layers on SiO2 spheres (SiO2@Gd2MoO6:Eu) and their luminescent properties

SiO₂@Gd₂MoO₆:Eu³⁺ core-shell phosphors were prepared by the sol-gel process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDS), transmission electron microscopy (TEM), photoluminescence (PL) spectra as well as kinetic decays were used to characterize the resulting SiO₂@Gd₂MoO₆:Eu³⁺ core-shell phosphors. The XRD results demonstrate that the Gd₂MoO₆:Eu³⁺ layers on the SiO₂ spheres begin to crystallize after annealing at 600 °C and the crystallinity increases with raising the annealing temperature. The obtained core-shell phosphors have a near perfect spherical shape with narrow size distribution (average size ca. 600 nm), are not agglomerated, and have a smooth surface. The thickness of the Gd₂MoO₆:Eu³⁺ shells on the SiO₂ cores could be easily tailored by varying the number of deposition cycles (50 nm for four deposition cycles). The Eu³⁺ shows a strong PL luminescence (dominated by ⁵D₀-⁷F₂ red emission at 613 nm) under the excitation of 307 nm UV light. The PL intensity of Eu³⁺ increases with increasing the annealing temperature and the number of coating cycles.     

Properties of thick SiO2/Si structure formed at 120 °C by use of two-step nitric acid oxidation method

Thick (i.e., ∼10 nm) SiO₂/Si structure has been formed at 121 °C by immersion of Si in relatively low concentration HNO₃ followed by that in 68 wt.% HNO₃ (i.e., two-step nitric acid (HNO₃) oxidation method of Si, NAOS) and spectroscopic properties and electrical characteristics of the NAOS SiO₂ layers are investigated. The SiO₂ thickness strongly depends on the concentration of HNO₃ aqueous solutions employed in the initial oxidation, and it becomes the largest at the HNO₃ concentration of 40 wt.%. The MOS diodes with the ∼9 nm SiO₂ layer formed by the NAOS method possess a relatively low leakage current density (e.g., 10⁻⁸ A/cm² at the forward bias of 1 V) and it is further decreased by more than one order of magnitude by post-metallization annealing (PMA) in hydrogen at 250 °C. The good leakage characteristic is attributable to atomically flat SiO₂/Si interfaces and high atomic density of 2.30-2.32 × 10²² atoms/cm³ of the NAOS SiO₂ layers. High-density interface states are present in as-prepared SiO₂ layers and they are eliminated by PMA in hydrogen.     

Structural and electrical properties of (Na0.85K0.15)0.5Bi0.5TiO3 thin films deposited on LaNiO3 and Pt bottom electrodes

(Na_0.85K_0.15)_0.5Bi_0.5TiO₃ thin films were deposited on LaNiO₃(LNO)/SiO₂/Si(1 0 0) and Pt/Ti/SiO₂/Si(1 0 0) substrates by metal-organic decomposition, and the effects of bottom electrodes LNO and Pt on the ferroelectric, dielectric and piezoelectric properties were investigated by ferroelectric tester, impedance analyzer and scanning probe microscopy, respectively. For the thin films deposited on LNO and Pt electrodes, the remnant polarization 2P_r are about 22.6 and 8.8 μC/cm² under 375 kV/cm, the dielectric constants 238 and 579 at 10 kHz, the dielectric losses 0.06 and 0.30 at 10 kHz, the statistic d_33eff values 95 and 81 pm/V. The improved piezoelectric properties could make (Na_1−xK_x)_0.5Bi_0.5TiO₃ thin film as a promising candidate for piezoelectric thin film devices.     

Luminescent properties of Eu-activated Sr3B2SiO8: A red-emitting phosphor for white light-emitting diodes

Single-phased Sr₃B₂SiO₈:Eu³⁺ phosphor was prepared by a solid-state method at 1020 °C. The luminescence spectra showed that Sr₃B₂SiO₈:Eu³⁺ phosphor can be effectively excited by near ultraviolet light (393 nm) and blue light (464 nm). When excited at 393 or 464 nm Sr₃B₂SiO₈:Eu³⁺ exhibited the main emission peaks at 611 and 620 nm, which resulted from the supersensitive ⁵D₀→⁷F₂ transition of Eu³⁺. The luminescence intensity of Sr₃B₂SiO₈:Eu³⁺ at 611 and 620 nm reached the maximum when the doping content of Eu³⁺ was 4.5 mol%. Its chromaticity coordinates (0.646, 0.354) were very close to the NTSC standard values (0.67, 0.33). Thus, Sr₃B₂SiO₈:Eu³⁺ is considered to be an efficient red-emitting phosphor for long-UV InGaN-based light-emitting diodes.     

Degradation of Y2SiO5:Ce phosphor powders

The degradation of the cathodoluminescence (CL) intensity of cerium-doped yttrium silicate (Y₂SiO₅:Ce) phosphor powders was investigated for possible application in low voltage field emission displays (FEDs). Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS) and CL spectroscopy were used to monitor changes in the surface chemical composition and luminous efficiency of commercially available Y₂SiO₅:Ce phosphor powders. The degradation of the CL intensity for the powders is consistent with a well-known electron-stimulated surface chemical reaction (ESSCR) model. It was shown with XPS and CL that the electron stimulated reaction led to the formation of a luminescent silicon dioxide (SiO₂) layer on the surface of the Y₂SiO₅:Ce phosphor powder. XPS also indicated that the Ce concentration in the surface layer increased during the degradation process and the formation of CeO₂ and CeH₃ were also part of the degradation process. The CL intensity first decreased until about 300 C cm⁻² and then increased due to an extra peak arising at a wavelength of 650 nm.     

Influence of postdeposition annealing on structural properties and electrical characteristics of thin Tm2O3 and Tm2Ti2O7 dielectrics

We describe the structural properties and electrical characteristics of thin thulium oxide (Tm₂O₃) and thulium titanium oxide (Tm₂Ti₂O₇) as gate dielectrics deposited on silicon substrates through reactive sputtering. The structural and morphological features of these films were explored by X-ray diffraction, X-ray photoelectron spectroscopy, secondary ion mass spectrometry, and atomic force microscopy, measurements. It is found that the Tm₂Ti₂O₇ film annealed at 800 °C exhibited a thinner capacitance equivalent thickness of 19.8 Å, a lower interface trap density of 8.37 × 10¹¹ eV⁻¹ cm⁻², and a smaller hysteresis voltage of ∼4 mV than the other conditions. We attribute this behavior to the Ti incorporated into the Tm₂O₃ film improving the interfacial layer and the surface roughness. This film also shows negligible degrees of charge trapping at high electric field stress.     

Stabilization of a very high-k crystalline ZrO2 phase by post deposition annealing of atomic layer deposited ZrO2/La2O3 dielectrics on germanium

The impact of the ZrO₂/La₂O₃ film thickness ratio and the post deposition annealing in the temperature range between 400 °C and 600 °C on the electrical properties of ultrathin ZrO₂/La₂O₃ high-k dielectrics grown by atomic layer deposition on (1 0 0) germanium is investigated. As-deposited stacks have a relative dielectric constant of 24 which is increased to a value of 35 after annealing at 500 °C due to the stabilization of tetragonal/cubic ZrO₂ phases. This effect depends on the absolute thickness of ZrO₂ within the dielectric stack and is limited due to possible interfacial reactions at the oxide/Ge interface. We show that adequate processing leads to very high-k dielectrics with EOT values below 1 nm, leakage current densities in the range of 0.01 A/cm², and interface trap densities in the range of 2-5 × 10¹² eV⁻¹ cm⁻².     

Influence of Si/SiO2 interface properties on electrical performance and breakdown characteristics of ultrathin stacked oxide/nitride dielectric films

In this work, the influence of Si/SiO₂ interface properties, interface nitridation and remote-plasma-assisted oxidation (RPAO) thickness (<1 nm), on electrical performance and TDDB characteristics of sub-2 nm stacked oxide/nitride gate dielectrics has been investigated using a constant voltage stress (CVS). It is demonstrated that interfacial plasma nitridation improves the breakdown and electrical characteristics. In the case of PMOSFETs stressed in accumulation, interface nitridation suppresses the hole traps at the Si/SiO₂ interface evidenced by less negative V_t shifts. Interface nitridation also retards hole tunneling between the gate and drain, resulting in reduced off-state drain leakage. In addition, the RPAO thickness of stacked gate dielectrics shows a profound effect in device performance and TDDB reliability. Also, it is demonstrated that TDDB characteristics are improved for both PMOS and NMOS devices with the 0.6 nm-RPAO layer using Weibull analysis. The maximum operating voltage is projected to be improved by 0.3 V difference for a 10-year lifetime. However, physical breakdown mechanism and effective defect radius during stress appear to be independent of RPAO thickness from the observation of the Weibull slopes. A correlation between trap generation and dielectric thickness changes based on the C-V distortion and oxide thinning model is presented to clarify the trapping behavior in the RPAO and bulk nitride layer during CVS stress.     

Effect of crystallinity of Co layer on perpendicular exchange bias in Au-capped ultrathin Co film on Cr2O3(0 0 0 1) thin film

The effect of the crystalline quality of ultrathin Co films on perpendicular exchange bias (PEB) has been investigated using a Au/Co/Au/α-Cr₂O₃ thin film grown on a Ag-buffered Si(1 1 1) substrate. Our investigation is based on the effect of the Au spacer layer on the crystalline quality of the Co layer and the resultant changes in PEB. An α-Cr₂O₃(0 0 0 1)layer is fabricated by the thermal oxidization of a Cr(1 1 0) thin film. The structural properties of the α-Cr₂O₃(0 0 0 1) layer including the cross-sectional structure, lattice parameters, and valence state have been investigated. The fabricated α-Cr₂O₃(0 0 0 1) layer contains twin domains and has slightly smaller lattice parametersthan those of bulk-Cr₂O₃. The valence state of the Cr₂O₃(0 0 0 1) layer is similar to that of bulk Cr₂O₃. The ultrathin Co film directly grown on the α-Cr₂O₃(0 0 0 1) deposited by an e-beam evaporator is polycrystalline. The insertion of a Au spacer layer with a thickness below 0.5 nm improves the crystalline quality of Co, probably resulting in hcp-Co(0 0 0 1). Perpendicular magnetic anisotropy (PMA) appears below the Néel temperature of Cr₂O₃ for all the investigated films. Although the PMA appears independently of the crystallinequality of Co, PEB is affected by the crystalline quality of Co. For the polycrystalline Co film, PEB is low, however, a high PEB is observed for the Co films whose in-plane atom arrangement is identical to that of Cr³⁺ in Cr₂O₃(0 0 0 1). The results are qualitatively discussed on the basis of the direct exchange coupling between Cr and Co at the interface as the dominant coupling mechanism.     

Optical and gas sensing properties of thick TiO2 films grown by laser deposition

In this work the optical and the gas sensing properties of thick TiO₂ waveguide films, produced by pulsed laser deposition, were investigated by m-line spectroscopy. The films were deposited on (0 0 1) SiO₂ substrates at temperature of 100 °C. The thickness of the films was measured to be in the range from 650 to 1900 nm and the roughness increases from 5 to 14.6 nm. High quality mode spectra, consisted of thin and bright TE and TM modes, were observed in the films with thickness up to 1200 nm. All the films revealed anisotropic optical properties. Gas sensitivity of the films to CO₂ was examined at room temperature on the basis of the variations of the refractive index. CO₂ concentration of 3 × 10⁴ ppm was detected, which corresponds to a refractive index variation of about 1 × 10⁻⁴. The crystal structure and the optical transmittance of the films were also presented and discussed.     

In situ X-ray photoelectron spectroscopy characterization of Al2O3/GaSb interface evolution

GaSb(0 0 1) was treated with (NH₄)₂S_x and the evolution of the interfacial chemistry was investigated, in situ, with monochromatic X-ray photoelectron spectroscopy (XPS), following heat treatment and exposure to trimethylaluminum (TMA) and deionized water (DIW) in an atomic layer deposition reactor. Elemental Sb (Sb-Sb bonding) as well as Sb³⁺ and Sb⁵⁺ chemical states were initially observed at the native oxide/GaSb interface, yet these diminished below the XPS detection limit after heating to 300 °C. No evidence of Ga-Ga bonding was observed whereas the Ga¹⁺/Ga-S chemical state was robust and persisted after heat treatment and exposure to TMA/DIW at 300 °C.     

The electrical properties of dielectric stacks of SiO2 and Al2O3 prepared by atomic layer deposition method

We produced dielectric stacks composed of ALD SiO₂ and ALD Al₂O₃, such as SiO₂/Al₂O₃, Al₂O₃/SiO₂, and SiO₂/Al₂O₃/SiO₂, and measured the leakage currents through the stacks in comparison with those of the single oxide layers. SiO₂/Al₂O₃ shows lowest leakage current for negative bias region below 6.4 V, and Al₂O₃/SiO₂ showed highest current under negative biases below 4.5 V. Two distinct electron conduction regimes are observed for Al₂O₃ and SiO₂/Al₂O₃. Poole-Frenkel emission is dominant at the high-voltage regime for both dielectrics, whereas the direct tunneling through the dielectric is dominant at the low-voltage regime. The calculated transition voltage between two regimes for SiO₂ (6.5 nm)/Al₂O₃ (12.6 nm) is −6.4 V, which agrees well with the experimental observation (−6.1 V). For the same EOT of entire dielectric stack, the transition voltage between two regimes decreases with thinner SiO₂ layer.     

Preparation and characterization of Zn2SiO4: Mn phosphors with hydrothermal methods

Mn²⁺-doped Zn₂SiO₄ phosphors had been prepared by hydrothermal method in stainless-steel autoclaves. Effects of synthesized methods, reaction temperature, ambience of heat treatment on the structure and the luminescence properties of this silicate were studied with X-ray diffraction apparatus (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM) and fluorescence spectrum. Results show that Zn₂SiO₄ nanocrystalline can be obtained by hydrothermal method at relatively low temperatures. The absorption pattern shows an absorption edge at about 380 nm originated from ZnO crystals and two absorption bands at about 215 and 260 nm. Mn²⁺-doped Zn₂SiO₄ has a luminescence band with the wavelength at about 522 nm under 255 nm excitation, and the luminescent intensity increases after being heat treated.     

Synthesis of Y2Si2O7:Eu nanocrystal and its optical properties

Nanocrystalline Y₂Si₂O₇:Eu phosphor with an average size about 60 nm is easily prepared using silica aerogel as raw material under ultrasonic irradiation and annealing temperature at 300-600 °C and this nanocrystalline decomposes into Y₂O₃:Eu and silica by heat treatment at 700-900 °C. The excitation broad band centered at 283 and 254 nm results from Eu³⁺ substituting for Y³⁺ in Y₂Si₂O₇ and Y₂O₃/SiO₂, respectively. Compared with Y₂O₃:Eu/SiO₂ crystalline, the PL excitation and emission peaks of Y₂Si₂O₇:Eu nanocrystalline red-shift and lead to the enhance of its luminescence intensity due to the different chemical surroundings of Eu³⁺ in above nanocrystallines. The decrease of PL intensity may be ascribed to quenching effect resulting from more defects in Y₂O₃:Eu/SiO₂ crystalline.     

XPS analysis for degraded Y2SiO5:Ce phosphor thin films

X-ray photoelectron spectroscopy (XPS) results were obtained for standard Y₂SiO₅:Ce phosphor powders as well as undegraded and 144 h electron degraded Y₂SiO₅:Ce pulsed laser deposited (PLD) thin films. The two Ce 3d peaks positioned at 877.9 ± 0.3 and 882.0 ± 0.2 eV are correlated with the two different sites occupied by Ce in the Y₂SiO₅ matrix. Ce replaced the Y in the two different sites with coordination numbers of 9 and 7. The two Ce 3d XPS peaks obtained during the thin film analysis were also correlated with the luminescent mechanism of the broad band emission spectra of the Y₂SiO₅:Ce X₁ phase. These two different sites are responsible for the two main sets of cathodoluminescent (CL) and photoluminescence (PL) peaks situated at wavelengths of 418 and 496 nm. A 144 h electron degradation study on the Y₂SiO₅:Ce thin film yielded an increase in the CL intensity with a second broad emission peak emerging between 600 and 700 nm. XPS analysis showed the presence of SiO₂ on the surface that formed during prolonged electron bombardment. The electron stimulated surface chemical reaction (ESSCR) model is used to explain the formation of this luminescent SiO₂ layer.     

Preparation and characterization of novel Pd/SiO2 and Ca-Pd/SiO2 egg-shell catalysts with porous hollow silica

Novel egg-shell structured monometallic Pd/SiO₂ and bimetallic Ca-Pd/SiO₂ catalysts were prepared by an impregnation method using porous hollow silica (PHS) as the support and PdCl₂ and Ca(NO₃)₂·4H₂O as the precursors. It was found from transmission electron microscope (TEM), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) that Pd was loaded on PHS with a particle size of 5-12 nm in Pd/SiO₂ samples and the Pd particle size in Ca-Pd/SiO₂ was smaller than that in Pd/SiO₂ since Ca could prevent Pd particles from aggregating. X-ray photoelectron spectroscopy (XPS) analyses exhibited that Pd 3d_5/2 binding energies of Pd/SiO₂ and Ca-Pd/SiO₂ were 0.2 and 0.9 eV lower than that of bulk Pd, respectively, as a result of the shift of the electron cloud from Pd to oxygen in Pd/SiO₂ and to both oxygen and Ca in Ca-Pd/SiO₂. The activity of Ca-Pd/SiO₂ egg-shell catalyst for CO hydrogenation and the selectivity to methanol, with a value of 36.50 mmol_CO mol⁻¹_Pd s⁻¹ and 100%, respectively, were much higher than those of the catalysts prepared with traditional silica gel as the support, owing to the porous core-shell structure of the PHS support.     

Preparation of sol-gel ZrO2-SiO2 highly reflective multilayer films and laser-induced damage threshold characteristic

Sol-gel (ZrO₂/SiO₂)¹² ZrO₂ films were prepared by spin coating method. The reflectivity spectrum of the films was measured with a Lambda 900 spectrometer. In order to investigate laser-induced damage threshold (LIDT) characteristic of highly reflective films, one-layer ZrO₂ and SiO₂ films, two-layer ZrO₂/SiO₂ and SiO₂/ZrO₂ films were also prepared by spin coating method. LIDT of each film was measured. Damage morphology after laser irradiation was characterized by optical microscopy (Nikon E600K). The experimental results showed that the reflectivity of (ZrO₂/SiO₂)¹² ZrO₂ film at 1064 nm and 355 nm wavelength is 99.7%. The LIDT results decreases as the number of layer of films increases. All the films have similar damage morphology. The experimental results are explained by the different temperature profiles of the films.     

Analysis of excimer laser annealing of amorphous SiGe on La2O3//Si structures

The reduction of complementary metal oxide semiconductor dimensions through transistor scaling is in part limited by the SiO₂ dielectric layer thickness. Among the materials evaluated as alternative gate dielectrics one of the leading candidate is La₂O₃ due to its high permittivity and thermodynamic stability. However, during device processing, thermal annealing can promote deleterious interactions between the silicon substrate and the high-k dielectric degrading the desired oxide insulating properties.The possibility to grow poly-SiGe on top of La₂O₃//Si by laser assisted techniques therefore seems to be very attractive. Low thermal budget techniques such as pulsed laser deposition and crystallization can be a good choice to reduce possible interface modifications due to their localized and limited thermal effect.In this work the laser annealing by ArF excimer laser irradiation of amorphous SiGe grown on La₂O₃//Si has been analysed theoretically by a numerical model based on the heat conduction differential equation with the aim to control possible modifications at the La₂O₃//Si interface. Simulations have been carried out using different laser energy densities (0.26-0.58 J/cm²), different La₂O₃ film thickness (5-20 nm) and a 50 nm, 30 nm thick amorphous SiGe layer. The temperature distributions have been studied in both the two films and substrate, the melting depth and interfaces temperature have been evaluated. The fluences ranges for which the interfaces start to melt have been calculated for the different configurations.Thermal profiles and interfaces melting point have shown to be sensitive to the thickness of the La₂O₃ film, the thicker the film the lower the temperature at Si interface.Good agreement between theoretical and preliminary experimental data has been found.According to our results the oxide degradation is not expected during the laser crystallization of amorphous Si_0.7Ge_0.3 for the examined ranges of film thickness and fluences.     

Sol-gel preparation and characterization of nanoporous ZnO/SiO2 coatings with broadband antireflection properties

Nanoporous ZnO/SiO₂ bilayer coatings were prepared on the surface of glass substrates via sol-gel dip-coating process. The structural, morphological and optical properties of the coatings were characterized. The refractive indices of ZnO layer and SiO₂ layer are 1.34 and 1.21 at 550 nm, respectively. The transmittance and reflectance spectra of the coatings were investigated and the broadband antireflection performance of the bilayer structure was determined over the solar spectrum. The solar transmittances in the range of 300-1200 nm and 1200-2500 nm are increased by 6.5% and 6.2%, respectively. The improvement of transmittance is attributed to the destructive interference of light reflected from interfaces between the different refractive-index layers with an optimized thickness. Such antireflection coatings of ZnO/SiO₂ provide a promising route for solar energy applications.     

Characterization of Y2O3 gate dielectric on n-GaAs substrates

Physical and electrical properties of sputtered deposited Y₂O₃ films on NH₄OH treated n-GaAs substrate are investigated. The as-deposited films and interfacial layer formation have been analyzed by using X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS). It is found that directly deposited Y₂O₃ on n-GaAs exhibits excellent electrical properties with low frequency dispersion (<5%), hysteresis voltage (0.24 V), and interface trap density (3 × 10¹² eV⁻¹ cm⁻²). The results show that the deposition of Y₂O₃ on n-GaAs can be an effective way to improve the interface quality by the suppression on native oxides formation, especially arsenic oxide which causes Fermi level pinning at high-k/GaAs interface. The Al/Y₂O₃/n-GaAs stack with an equivalent oxide thickness (EOT) of 2.1 nm shows a leakage current density of 3.6 × 10⁻⁶ A cm⁻² at a V_FB of 1 V. While the low-field leakage current conduction mechanism has been found to be dominated by the Schottky emission, Poole-Frenkel emission takes over at high electric fields. The energy band alignment of Y₂O₃ films on n-GaAs substrate is extracted from detailed XPS measurements. The valence and conduction band offsets at Y₂O₃/n-GaAs interfaces are found to be 2.14 and 2.21 eV, respectively.