A pulsed synthesis of β-FeSi2 layers on silicon implanted with Fe ions

Continuous layers and fine-grained films of β-FeSi₂ were synthesized using the implantation of Fe⁺ ions into Si (1 0 0) with subsequent pulsed nanosecond ion-beam treatment of the implanted layers. The X-ray diffraction studies showed that the pulsed ion-beam treatment brings about the formation of a mixture of two phases: FeSi and β-FeSi₂ with strained crystal lattices. Subsequent rapid thermal annealing led to the complete transformation of the FeSi phase into the β-FeSi₂ phase with the formation of a textured layer. The data obtained using Raman spectroscopy corroborate the formation of the β-FeSi₂ phase with a high degree of silicon crystallinity.The results of measuring the optical absorption point to the formation of β-FeSi₂ layers and precipitates with a direct-gap structure, an optical gap of E_g≈0.83 eV. The photoluminescence band peaked at λ≈1.56 μm and caused by direct band-to-band transitions in β-FeSi₂ was observed at temperatures lower than 210 K.     

Anodization of aluminium thin films on pSi and annihilation of strong luminescence from Al2O3

Photoluminescence (PL) of Al₂O₃ films obtained by anodization of thermally evaporated and annealed thin Al films on p⁺⁺Si in 0.3 M oxalic acid has been investigated. Thermal annealing at 200–950 °C under the dry nitrogen atmosphere was used for deactivation of luminescence centres. Luminescence from as grown films was broad and located at 425 nm. This luminescence reached to highest level after annealing at 600 °C. Maximum 10 min was required for full optical activation and prolonged annealing up to 4 h did not change the luminescence intensity. Because of deep levels, absorption band edge of as grown films was shifted to the lower energy which is 3.25 eV. Annealing above 800 °C reduced the PL intensity and this observation was correlated with the blue shift of band edge as the defects annealed out. Disappearing PL intensity and blue shift of band edge absorption after annealing at 950 °C was mainly attributed to the oxygen-related defects and partly to impurities that may be originated from oxalic acid. AFM results did not show any hexagonally ordered holes but uniformly distributed nanosized Al₂O₃ clusters that were clearly seen. XRD measurements on as grown Al₂O₃ showed only [1 1 0] direction of α phase. Debye–Scherer calculation for this line indicates that cluster size is 35.7 nm. XRD and AFM pictures suggest that nanocrystalline Al₂O₃ are embedded in amorphous Al₂O₃.     

Growth of β-FeSi2 thin film on textured silicon substrate for solar cell application

(2 0 2)/(2 2 0)-oriented epitaxial β-FeSi₂ thin films were deposited on textured Si (1 0 0) substrate by magnetron sputtering. The influences of thickness and annealing temperature on the β-FeSi₂ crystallization were studied to find the optimal condition. The results of surface morphology and optical property measurements showed that the inverted pyramid array in the surface of β-FeSi₂ thin films could reduce the surface reflection of β-FeSi₂. In dark condition, the β-FeSi₂/textured-Si heterojunction showed diode property with rectifying ratio of 2.89 × 10⁵ and built-in potential of 0.58 V. These results indicated the potential application of textured Si substrate in β-FeSi₂ solar cells.     

The influence of the annealing conditions on the photoluminescence of ion-implanted SiO2:Si nanosystem at additional phosphorus implantation

The influence of P ion doping on the photoluminescence (PL) of the system of nanocrystals in SiO₂ matrix (SiO₂:Si) both without annealing and after annealing at various temperatures (provided before and after additional P implantation) is investigated. The Si and P implantation was carried out with ion energies of 150 keV and doses Φ_Si=10¹⁷ cm⁻² and Φ_P=(0.1–300)×10¹⁴ cm⁻² (current density j3 μAcm⁻²). The system after Si implantation was formed at 1000°C and 1100°C (2 h). For the case of SiO₂:Si system as-implanted by P, the intensity of PL was drastically quenched, but partially retained. As for the step-by-step annealing (at progressively increased temperatures) carried out after P implantation, the sign and degree of doping effect change with annealing temperature. The possible mechanisms of these features are discussed.     

Correlation between impurities in Fe-Si amorphous layers synthesized by Fe implantation and photoluminescence property of β-FeSi2 precipitates in Si

Completely amorphous Fe-Si layers are formed by Fe implantation into Si substrate at a dosage of 5×10¹⁵ cm⁻² using a metal vapor vacuum arc (MEVVA) ion source under 80 kV extraction voltage and cryogenic temperature. After thermal annealing, β-FeSi₂ precipitates are formed in Si matrix. The influence of impurities in these amorphous Fe-Si layers on the photoluminescence (PL) from β-FeSi₂ precipitates is investigated. PL is found to be significantly enhanced by optimizing the impurity concentration and annealing scheme. After 60 s of rapid thermal annealing (RTA) at 900 °C, β-FeSi₂ precipitates in medium boron-doped Si substrate give the strongest PL intensity without boron out-diffusion from them.     

Effect of BiFeO3 addition on Bi2O3–ZnO–Nb2O5 based ceramics

In this paper, low temperature sintering of the Bi₂(Zn_1/3Nb_2/3)₂O₇ (β-BZN) dielectric ceramics was studied with the use of BiFeO₃ as a sintering aid. The effects of BiFeO₃ contents and the sintering temperature on the phase structure, density and dielectric properties were investigated. The results showed that the sintering temperature could be decreased and the dielectric properties could be retained by the addition of BiFeO₃. The structure of BiFeO₃ doped β-BZN was still the monoclinic pyrochlore phase. The sintering temperature of BiFeO₃ doped β-BZN ceramics was reduced from 1000 °C to 920 °C. In the case of 0.15 wt.% BiFeO₃ addition, the β-BZN ceramics sintered at 920 °C exhibited good dielectric properties, which were listed as follows: ε_r = 79 and tan δ = 0.00086 at a frequency of 1 MHz. The obtained properties make this composition to be a good candidate for the LTCC application.     

An ab initio calculation of O and Si NMR parameters for SiO2 polymorphs

Ab initio molecular orbital calculations (Hartree–Fock, HF and density functional theories, DFTs) have been carried out for SiO₂ polymorphs coesite, low cristobalite, and α-quartz, in order to investigate the reliability of this method for predicting ²⁹Si and ¹⁷O nuclear magnetic resonance (NMR) properties of silicates. Oxygen- and silicon-centered clusters consisting of one (1T) to three tetrahedral (3T) shells (one to four atomic shells), taken from real crystal structure, have been investigated. It is found that for reasonable predication of both the ²⁹Si and ¹⁷O chemical shifts (δ_i^Si and δ_i^O), the minimum cluster is one that gives the correct second neighbors to the nucleus of interest. Both the δ_i^Si and δ_i^O have reached convergence with respect to cluster size at the OH-terminated two tetrahedral (2T) shell (three atomic shells around Si and four atomic shells around O) model. At convergence, the calculated δ_i^Si values agree well (within ±1 ppm) with experimental data. The calculated ¹⁷O electric field gradient (EFG)-related parameters also agree with experimental data within experimental uncertainties. The calculation also reproduces small differences in δ_i^O for O sites with similar tetrahedral connectivities, but shows deviations up to about 10 ppm in relative difference for O sites with different tetrahedral connectivities. The poor performance for the latter is mainly due to the approximations of the HF method. Our study thus suggests that the ab initio calculation method is a reliable mean for predicting ²⁹Si and ¹⁷O NMR parameters for silicates. Such an approach should find application not only to well-ordered crystalline phases, but also to disordered materials, by combining with other techniques, such as the molecular dynamics simulation method.     

磁控溅射法合成纳米β-FeSi2/a-Si多层结构

β-FeSi₂作为一种环境友好的半导体材料，颗粒化及非晶化正在成为提高其应用性能和改善薄膜质量、膜基界面失配度的有效途径.利用射频磁控溅射法在单晶Si基体上沉积Fe/Si多层膜，合成纳米β-FeSi₂/Si多层结构.通过透射电子显微镜、高分辨电子显微术等分析手段，研究了多层结构和制备工艺之间的相互关系.研究结果表明，采用磁控溅射Fe/Si多层膜的方法，不需要退火就可以直接沉积得到β-FeSi₂相小颗粒.β-FeSi₂相 关键词： 2')" href="#">β-FeSi₂ 磁控溅射 透射电子显微镜 半导体薄膜     

Low temperature thermal annealing-induced α-FeSi2 derived phase in an amorphous Si matrix

Thermal annealing-induced recrystallisation in Fe ion-implanted Si was investigated by transmission electron microscopy. Single crystals of Si(111) were implanted with 120 keV Fe ions to a fluence of 1.0×10¹⁷ cm^-2 at cryogenic temperature. A buried amorphous Fe-Si layer in an amorphous Si matrix was formed in the as-implanted sample. Nanobeam electron diffraction revealed that metastable α-FeSi₂ precipitates embedded in the amorphous Si matrix were formed after annealing at 350 °C for 8 h. The formation of this α-FeSi₂-derived phase was unusual, because it has been observed only in epitaxially grown thin films. Based on the Fe_1-xSi (0<x<0.5) phase with the CsCl structure, which is another metastable phase in the Fe-Si binary system, we discuss the formation process of the metastable α-FeSi₂ in the amorphous matrix. PACS 61.43.Dq; 61.14.Lj; 61.80.Jh     

Volatile metal β-diketonates — new precursors for the sonochemical synthesis of nanosized materials — sonolysis of thorium(IV) β-diketonates

Ultrasonic irradiation (22 kHz, Ar atmosphere) of Th(IV) β-diketonates Th(HFAA)₄ and Th(DBM)₄, where HFAA and DBM are hexafluoroacetylacetone and dibenzoylmethane respectively, causes them to decompose in hexadecane solutions, forming solid thorium compounds. The first-order rate constants for Th(IV) β-diketonate degradation were found to be (9.3±0.8)×10⁻³ for Th(HFAA)₄ and (3.8±0.4)×10⁻³ min⁻¹ for Th(DBM)₄, (T=92°C, I=3 W cm⁻²). The rate of the sonochemical reaction increased with the rising β-diketonate volatility and decreased with the rising hydrocarbon solvent vapor pressure. Solid sonication products consisted of a mixture of thorium carbide ThC₂ and Th(IV) β-diketonate partial degradation products. The average ThC₂ particle size was estimated to be about 2 nm. ThC₂ formation was attributed to the high-temperature reaction occurring within the cavitating bubble. The thorium β-diketonate partial degradation products formed in the liquid reaction zones surrounding the cavitating bubbles.     

纳米β-FeSi2/a-Si多层膜室温光致发光分析

采用射频磁控溅射的方法,在Si（100）基片上制备了纳米β-FeSi₂/Si多层结构,利用X射线衍射、透射电子显微镜、光致发光光谱等表征技术,研究了β-FeSi₂/Si多层结构的结构、成分和光致发光特性.研究结果表明：利用磁控溅射法得到的Fe/Si多层膜,室温下能够检测到β-FeSi₂的1.53 μm处光致发光信号;未退火时多层膜是（非晶的FeSi₂+β-FeSi₂颗粒）/非晶Si结构,退火后则是 关键词： 2')" href="#">β-FeSi₂ 磁控溅射 XRD 光致发光光谱     

Controlled fabrication of Si nanostructures by high vacuum electron beam annealing

Silicon nanostructures, called Si nanowhiskers, have been successfully synthesized on Si(1 0 0) substrate by high vacuum electron beam annealing (EBA). Detailed analysis of the Si nanowhisker morphology depending on annealing temperature, duration and the temperature gradients applied in the annealing cycle is presented. A correlation was found between the variation in annealing temperature and the nanowhisker height and density. Annealing at 935 °C for 0 s, the density of nanowhiskers is about 0.2 μm⁻² with average height of 2.4 nm grow on a surface area of 5×5 μm, whereas more than 500 nanowhiskers (density up to 28 μm⁻²) with an important average height of 4.6 nm for field emission applications grow on the same surface area for a sample annealed at 970 °C for 0 s. At a cooling rate of −50 °C s⁻¹ during the annealing cycle, 10–12 nanowhiskers grew on a surface area of 5×5 μm, whereas close to 500 nanowhiskers grew on the same surface area for samples annealed at the cooling rate of −5 °C s⁻¹. An exponential dependence between the density of Si nanowhiskers and the cooling rate has been found. At 950 °C, the average height of Si nanowhiskers increased from 4.0 to 6.3 nm with an increase of annealing duration from 10 to 180 s. A linear dependence exists between the average height of Si nanowhiskers and annealing duration. Selected results are presented showing the possibility of controlling the density and the height of Si nanowhiskers for improved field emission properties by applying different annealing temperatures, durations and cooling rates.     

Structural characteristics and morphology of SmxCe1−xO2−x/2 thin films

Effect of the deposition temperature (200 and 500 °C) and composition of Sm_xCe_1−xO_2−x/2 (x = 0, 10.9–15.9 mol%) thin films prepared by electron beam physical vapor deposition (EB-PVD) and Ar⁺ ion beam assisted deposition (IBAD) combined with EB-PVD on structural characteristics and morphology/microstructure was investigated. The X-ray photoelectron spectroscopy (XPS) of the surface and electron probe microanalysis (EPMA) of the bulk of the film revealed the dominant occurrence of Ce⁴⁺ oxidation state, suggesting the presence of CeO₂ phase, which was confirmed by X-ray diffraction (XRD). The Ce³⁺ oxidation states corresponding to Ce₂O₃ phase were in minority. The XRD and scanning electron microscopy (SEM) showed the polycrystalline columnar structure and a rooftop morphology of the surface. Effects of the preparation conditions (temperature, composition, IBAD) on the lattice parameter, grain size, perfection of the columnar growth and its impact on the surface morphology are analyzed and discussed.     

The effect of Si surface nitridation on the interfacial structure and electrical properties of (La2O3)0.5(SiO2)0.5 high-k gate dielectric films

Thermal stability, interfacial structures and electrical properties of amorphous (La₂O₃)_0.5(SiO₂)_0.5 (LSO) films deposited by using pulsed laser deposition (PLD) on Si (1 0 0) and NH₃ nitrided Si (1 0 0) substrates were comparatively investigated. The LSO films keep the amorphous state up to a high annealing temperature of 900 °C. HRTEM observations and XPS analyses showed that the surface nitridation of silicon wafer using NH₃ can result in the formation of the passivation layer, which effectively suppresses the excessive growth of the interfacial layer between LSO film and silicon wafer after high-temperature annealing process. The Pt/LSO/nitrided Si capacitors annealed at high temperature exhibit smaller CET and EOT, a less flatband voltage shift, a negligible hysteresis loop, a smaller equivalent dielectric charge density, and a much lower gate leakage current density as compared with that of the Pt/LSO/Si capacitors without Si surface nitridation.     

Growth process of β-FeSi2 epitaxial film on Si(1 1 1) by molecular beam epitaxy

We have reported a one step growth of a high quality β-FeSi₂ epitaxial film on hydrogen terminated Si(1 1 1) by using molecular beam epitaxy (MBE) without template layer or post-growth annealing. In the present work, the growth process was studied by analyzing X-ray diffraction (XRD) spectra, reflective high energy electron diffraction (RHEED) and atomic force microscopy (AFM) observations on the samples grown with different growth times from 10 s to 1 h. A phase transformation from γ-FeSi₂ to β-FeSi₂ was confirmed existing in the crystal film growth, as well as the growth mode changing from three-dimensional (3D) to two-dimensional (2D) mode.     

Epitaxial growth and optical characterization of compound semiconductor β-FeSi2 prepared by pulsed laser deposition

β-FeSi₂ thin films were prepared on FZ n-Si (1 1 1) substrates by pulsed laser deposition (PLD). The structural properties and crystallographic orientation of the films were investigated by X-ray diffraction (XRD) analysis. This indicates that β-FeSi₂/Si (2 0 2/2 2 0) and the single-crystalline β-FeSi₂ can be prepared using PLD. In photoluminescence (PL) measurements at 8 K detected by Ge detector, the PL spectra of the samples annealed at 900 °C for 1, 5, 8 and 20 h showed that the PL intensity of the A-band peak increased depending on annealing time in comparison with those of as-deposited samples. The intrinsic PL intensity of the A-band peak at 0.808 eV of the β-FeSi₂ from the 20-h-annealed sample was investigated for the first time by the PLD method detected by an InGaAs detector. This result has been confirmed by temperature dependence and excitation power density of the 20-h-annealed sample with the comparison of other defect-related band peaks of the sample. Cross-sectional scanning electron microscopy (SEM) observation was also performed and the thickness of the thin films was found to be at 75 nm for 20-h-annealed. The thermal diffusion for the epitaxial growth of β−FeSi₂/Si was observed when the compositional ratio of Fe to Si was around Fe:Si=1:2 for 20-h-annealed carried out by energy dispersive X-ray spectroscopy (EDX). We discussed high crystal quality of the epitaxial growth and optical characterization of β-FeSi₂ achieved after annealing at 900 °C for 20 h.     

Preparation and electrical properties of a pyrochlore-related Ce2Zr2O8−x phase

A pyrochlore-related Ce₂Zr₂O_8−x phase has been prepared in a reduction reoxidation process from Ce_0.5Zr_0.5O₂ powders. Ce₂Zr₂O_8−x, based on a cubic symmetry with a=1.053 nm, decomposes in nitrogen at 800 °C, but remains stable up to 900 °C in air. It shows mixed oxygen ionic and electronic conductivity. The bulk conductivity at 700 °C is 4×10⁻⁴ S cm⁻¹ in air and 1×10⁻² S cm⁻¹ in nitrogen, and the activation energy is 1.27 eV in air. In nitrogen, the Arrhenius law is not obeyed, and a curved plot was obtained from 400 to 700 °C; then, the conductivity decreased rapidly due to the thermal decomposition of Ce₂Zr₂O_8−x.     

Ar irradiation of Si nanocrystal-doped SiO2: Evolution of photoluminescence

We report the evolution of photoluminescence (PL) of Si nanocrystals (nc-Si) embedded in a matrix of SiO₂ during Ar⁺ ion bombardment. The integrated intensity of nc-Si PL falls down drastically before the Ar⁺ ion fluence of 10¹⁵ ions cm⁻², and then decreases slowly with the increasing ion fluence. At the meantime, the PL peak position blueshifts steadily before the fluence of 10¹⁵ ions cm⁻², and then changes in an oscillatory manner. Also it is found that the nc-Si PL of the Ar⁺-irradiated sample can be partly recovered after annealing at 800 °C in nitrogen, but can be almost totally recovered after annealing in oxygen. The results confirm that the ion irradiation-induced defects are made up of oxygen vacancies, which absorb light strongly. The oscillatory peak shift of nc-Si can be related to a size-distance distribution of nc-Si in SiO₂.     

CEMS Investigations of Fe-Silicide Phases Formed by the Method of Concentration Controlled Phase Selection

Conversion electron Mössbauer spectroscopy (CEMS) measurements have been made on Fe-silcide samples formed using the method of concentration controlled phase selection. To prepare the samples a 10 nm layer of Fe₃₀M₇₀ (M=Cr, Ni) was evaporated onto Si(100) surfaces, followed by evaporation of a 60 nm Fe layer. Diffusion of the Fe into the Si substrate and the formation of different Fe–Si phases was achieved by subjecting the evaporated samples to a series of heating stages, which consisted of (a) a 10 min anneal at 800°C plus etch of the residual surface layer, (b) a further 3 hr anneal at 800°C, (c) a 60 mJ excimer laser anneal to an energy density of 0.8 J/cm², and (d) a final 3 hr anneal at 800°C. CEMS measurements were used to track the Fe-silicide phases formed. The CEMS spectra consisted of doublets which, based on established hyperfine parameters, could be assigned to - or -FeSi₂ or cubic FeSi. The spectra showed that -FeSi₂ had formed already at the first annealing stage. Excimer laser annealing resulted in the formation of a phase with hyperfine parameters consistent with those of -FeSi₂. A further 3 hr anneal at 800°C resulted in complete reversal to the semiconducting -FeSi₂ phase.     

Photoluminescence properties of thenardite activated with Eu

Na₂SO₄:Eu phosphors were prepared by heating pure natural thenardite with EuF₃ at 900 °C for 20 min in air. The photoluminescence (PL) and excitation spectra of as-prepared and γ-ray-irradiated phosphors were observed at 300 K. The PL spectrum under 394 nm excitation consisted of strong narrow bands with peaks at 579, 592, 616, 652, 697 and 741 nm, assigned to the ⁵D₀→⁷F_J (J=0, 1, 2, …, 5) transitions, respectively, within Eu³⁺. The PL spectrum under 340 nm excitation consisted of a broad Eu²⁺ band with a peak at 435 nm. The excitation spectrum obtained by monitoring the violet luminescence consisted of a weak band with a peak at approximately 261 nm and a broad Eu²⁺ band with a peak at approximately 338 nm. The relative efficiency of the violet luminescence of the γ-ray-irradiated phosphor at the exposure of 46 kGy increased up to 3.0 times that of the unirradiated phosphor. The enhancement of violet luminescence by γ-ray irradiation was ascribed to the conversion of Eu³⁺ to Eu²⁺ in Na₂SO₄.