Evolution of Structural Defects in SiOx Films Fabricated by Electron Cyclotron Resonance Plasma Chemical Vapour Deposition upon Annealing Treatment

We study the structural defects in the SiO, film prepared by electron cyclotron resonance plasma chemical vapour deposition and annealing recovery evolution. The photoluminescence property is observed in the as-deposited and annealed samples. [-SiO3]^2- defects are the luminescence centres of the ultraviolet photoluminescence （PL） from the Fourier transform infrared spectroscopy and PL measurements. [-SiO3]^2- is observed by positron annihilation spectroscopy, and this defect can make the S parameters increase. After 1000℃ annealing, [-SiO3]^2- defects still exist in the films.     

Room temperature photoluminescence from amorphous silicon nanoparticles in SiOx thin films

Amorphous SiO_x thin films with four different oxygen contents (x=1.15, 1.4, 1.5, and 1.7) have been prepared by thermal evaporation of SiO in vacuum and then annealed at 770 or 970 K in argon for various times ?40 min. The influence of annealing conditions and the initial film composition on photoluminescence (PL) from the annealed films has been explored. Intense room temperature PL has been observed from films with x?1.5, visible with a naked eye. It has been shown that PL spectra of most samples consists of two main bands: (i) a ‘green’ band centered at about 2.3 eV, whose position does not change with annealing conditions and (ii) an ‘orange-red’ band whose maximum moves from 2.1 to 1.7 eV with increasing annealing time and temperature and decreasing initial oxygen content. These observations have been explained assuming recombination via defect states in the SiO_x matrix for the first band and emission from amorphous Si nanoparticles for the second one.     

Correlation between optical properties and Si nanocrystal formation of Si-rich Si oxide films prepared by plasma-enhanced chemical vapor deposition

We have investigated the phase separation and silicon nanocrystal (Si NC) formation in correlation with the optical properties of Si suboxide (SiO_x, 0 < x < 2) films by thermal annealing in high vacuum. The SiO_x films were deposited by plasma-enhanced chemical vapor deposition at different nitrous oxide/silane (N₂O/SiH₄) flow ratios. The as-deposited films show increased Si concentration with decreasing N₂O/SiH₄ flow ratio, while the deposition rate and surface roughness have strong correlations with the flow ratio in the N₂O/SiH₄ reaction. After thermal annealing at temperatures above 1000 °C, Fourier transform infrared spectroscopy, Raman spectroscopy, and transmission electron microscopy manifest the progressive phase separation and continuous growth of crystalline-Si (c-Si) NCs in the SiO_x films with increasing annealing temperature. We observe a transition from multiple-peak to single peak of the strong red-range photoluminescence (PL) with increasing Si concentration and annealing temperature. The appearance of the single peak in the PL is closely related to the c-Si NC formation. The PL also redshifts from ∼1.9 to 1.4 eV with increasing Si concentration and annealing temperature (i.e., increasing NC size). The good agreements of the PL evolution with NC formation and the PL peak energy with NC size distribution support the quantum confinement model.     

Strong Green Light Emission from Low-Temperature Grown a-SiNx:H Film after Different Oxidation Routes

Room-temperature deposited amorphous silicon nitride （a-SiNx ：H） films exhibit intense green light emission after post-treated by plasma oxidation, thermal oxidation and natural oxidation, respectively. All the photoluminescence （PL） spectra are peaked at around 500nm, independent of oxidation method and excitation wavelength. Compared with the PL results from oxidized a-Si：H and as-deposited a-SiNx：H samples, it is indicated that not only oxygen but also nitrogen is of an important role in enhancing light emission from the oxidized a-SiNx：H. Combining the PL results with the analyses of the bonding configurations as well as chemical compositions of the films, the strong green light emission is suggested to be from radiative recombination in luminescent centres related to N Si-O bonds.     

Preferential orientation of modified SrBi2Nb2O9 ferroelectric thin films prepared by pulsed laser deposition

We report on the deposition of SrBi₂Nb₂O₉ and Sr_1-xNa_xBi_2-xTe_xNb₂O₉ ferroelectric thin films on Pt/TiO₂/SiO₂/(100)Si substrates using the pulsed laser deposition technique. Deposition on substrates heated to 600-700 °C produces {11l} film texture and dense films with grain sizes up to about 500 nm. The recrystallization at 700 °C of amorphous films deposited at lower temperatures enhances the contribution of the {100} and {010} orientations. These films show smaller grain size, namely 50-100 nm. {11l}-oriented Sr_1-xNa_xBi_2-xTe_xNb₂O₉ films have remnant polarization P_rۆ 7C/cm², a coercive field E_c䏐 kV/cm and dielectric constant, )𪓴. The low value of P_r is probably related to the low fraction of grains with the ferroelectric axis in the direction of the applied field, E. The recrystallized films have more grains with the ferroelectric axis parallel to E; however, they have a low resistivity which so far has prevented electrical characterization.     

镶嵌在氧化硅薄膜中纳米晶硅的可见光荧光谱与发光机制的研究

采用对非晶氧化硅薄膜退火处理方法，获得纳米晶硅与氧化硅的镶嵌结构．室温下观察到峰位为2.40eV光致发光．系统地研究了不同退火温度对薄膜的Raman谱、光荧光谱及光电子谱的影响．结果表明，荧光谱可分成两个不随温度变化的峰位为1.86和2.30eV的发光带．Si2p能级光电子谱表明与发光强度一样Si⁴⁺强度随退火温度增加而增加．Si平均晶粒大小为4.1—8.0nm，不能用量子限制模型解释蓝绿光的发射．纳米晶硅与SiO₂界面或SiO₂中与氧有关的缺陷可能是蓝绿光发射的主要原因 关键词：     

Electroluminescence of Si Nanocrystal-Doped SiO2

We perform a comparative st udy on the electroluminescence （EL） and photoluminescence （PL） of Si nanocrystaldoped SiO2 （nc-Si：SiO2） and SiO2, and clarify whether the contribution from Si nanocrystals in the EL of nc-Si：SiO2 truly exists. The results unambiguously indicate the presence of EL of Si nanocrystals. The difference of peak positions between the EL and PL spectra are discussed. It is found that the normal method of passivation to enhance the PL of Si nanocrystals is not equally effective for the EL, hence new methods need to be explored to promote the EL of Si nanocrystals.[第一段]     

Measurement and Analysis of Composition and Depth Profile of H in Amorphous Si1-xCx:H Films

Composition in amorphous Si1-xCx：H heteroepitaxial thin films on Si （100） by plasma enhanced chemical vapour deposition （PECVD） is analysed. The unknown x （0.45-3.57） and the depth profile of hydrogen in the thin films are characterized by Rutherford backscattering spectrum （RBS）, resonance-nuclear reaction analysis （R-NRA） and elastic recoil detection （ERD）, respectively. In addition, the depth profile of hydrogen in the unannealed thin films is compared to that of the annealed thin films with rapid thermal annealing （RTA） or laser spike annealing （LSA） in nitrogen atmosphere. The results indicate that the stoichiometric amorphous SiC can be produced by PECVD when the ratio of CH4/SiH4 is approximately equal to 25. The content of hydrogen decreases suddenly from 35% to 1% after 1150℃ annealing. RTA can reduce hydrogen in SiC films effectively than LSA.     

Atomic Diffusion in Cu/Si （111） and Cu/SiO2/Si （111） Systems by Neutral Cluster Beam Deposition

The Cu films are deposited on two kinds of p-type Si （111） substrates by ionized duster beam （ICB） technique. The interface reaction and atomic diffusion of Cu/Si （111） and Cu/SiO2/Si （111） systems are studied at different annealing temperatures by x-ray diffraction （XRD） and Rutherford backscattering spectrometry （RBS）. Some significant results are obtained： For the Cu/Si （111） samples prepared by neutral dusters, the interdiffusion of Cu and Si atoms occurs when annealed at 230℃. The diffusion coefficients of the samples annealed at 230℃ and 500℃ are 8.5 ×10^-15 cm^2.s^-1 and 3.0 ×10^-14 cm^2.s^-1, respectively. The formation of the copper-silicide phase is observed by XRD, and its intensity becomes stronger with the increase of annealing temperature. For the Cu/SiO2//Si （111） samples prepared by neutral dusters, the interdiffusion of Cu and Si atoms occurs and copper silicides are formed when annealed at 450℃. The diffusion coefficients of Cu in Si are calculated to be 6.0 ×10^-16 cm^2.s^-1 at 450℃, due to the fact that the existence of the SiO2 layer suppresses the interdiffusion of Cu and Si.     

Optical excitation and emission processes of Si-QD/SiO2 multilayer films with different SiO2 layer thicknesses

Si-rich oxide/SiO₂ multilayer films with different SiO₂ layer thicknesses have been deposited by the plasma enhanced chemical vapor deposition technique, and crystallized Si quantum dot (Si-QD)/SiO₂ multilayer films are obtained after annealing at 1100 ^°C. The photoluminescence (PL) intensity of the multilayer films increases significantly with increasing SiO₂ layer thickness, and the PL peak shifts from 1.25 eV to 1.34 eV. The PL excitation spectra indicate that the maximal PL excitation intensity is located at 4.1 eV, and an excitation–transfer mechanism exists in the excitation processes. The PL decay time for a certain wavelength is a constant when the SiO₂ thickness is larger than 2 nm, and a slow PL decay process is obtained when the SiO₂ layer is 1 nm. In addition, the PL peak shifts toward high energy with decreasing temperature only when the SiO₂ layer is thick enough. Detailed analyses show that the mechanism of PL changes from the quantum confinement effect to interface defects with decreasing SiO₂ layer thickness.     

Size control of Si nanocrystals by two-step rapid thermal annealing of sputtered Si-rich oxide/SiO2 superlattice

Controllable size of silicon (Si) nanocrystals can be achieved by a two-step rapid thermal annealing technique consisting of rapid annealing at 1000°C in nitrogen ambient and rapid oxidation at 600–800°C of a radio frequency magnetron co-sputtered Si-rich oxide/SiO₂ superlattice structure. The photoluminescence (PL) spectra related to Si nanocrystals were observed in the visible range (600–900 nm). After rapid oxidation, the size of the nanocrystals was reduced and the quality of the Si nanocrystal/SiO₂ interface was improved, resulting in a blue shift and an increase of the PL peak intensity. Finally, annealing in air increases the PL intensity further.     

Fabrication and Characterization of Si Nanocrystals Synthesized by Electron Beam Evaporation of Si and SiO2 Mixture

Silicon nanocrystals synthesized by electron beam （e-beam） evaporation of Si and SiO2 mixture are studied. Rutherford backscattering spectrometry of the as-deposited Si-rich silicon dioxide or oxide （SRO） thin film shows that after evaporation, the Si and SiO2 concentration is well kept, indicating that the e-beam evaporation is suitable for evaporating mixtures of Si and SiO2. The SRO thin films are annealed at different temperatures for two hours to synthesize silicon nanoerystals. For the sample annealed at 1050℃, silicon nanoerystals with different sizes and the mean diameter of 4.5 nm are evidently observed by high resolution transmission electron microscopy （HRTEM）. Then the Raman scattering and photoluminescence spectra arising from silicon nanocrystals are further confirmed the above results.     

Defects in Si-Rich SiO2 Films Prepared by Radio-Frequency Magnetron Co-sputtering Using Variable Energy Positron Annihilation Spectroscopy

Si-rich SiO2 films prepared by rf magnetron co-sputtering method are studied by slow positron beams. The nega- tively charge point defects （probably Pb centres or peroxy radicals） at the silicon nanocluster （nc-Si）/SiO2 interface are observed by Doppler broadening spectra. Coincidence Doppler-broadening spectra show that positrons have a higher annihilation probability with core electrons nearby oxygen atoms than silicon atoms. The formation of N-related bonds may be the reason for the prevention of the migration reaction of Si and 0 atoms, hence nc-Si formation is inhibited by annealing in nitrogen compared to in vacuum.     

Structural and photoluminescence properties of silicon nanocrystals embedded in SiC matrix prepared by magnetron sputtering

Si nanocrystals (NCs) embedded in an SiC matrix were prepared by the deposition of Si-rich Si_1?xC_x/SiC nanomultilayer films using magnetron sputtering, subsequently followed by thermal annealing in the range of 800～1200 °C. As the annealing temperature increases to 1000 °C, Si NCs begin to form and SiC NCs also start to emerge at the annealing temperature of 1200 °C. With the increase of annealing temperature, two photoluminescence (PL) peaks have an obvious redshift. The intensity of the low-energy PL peak around 669～742 nm gradually lowers, however the intensity of high-energy PL peak around 601～632 nm enhances. The low-energy PL peak might attribute to dangling bonds in amorphous Si (a-Si) sublayers, and the redshift of this peak might be related to the passivation of Si dangling bonds. Whereas the origin of the high-energy PL peak may be the emergence of Si NCs, the redshift of this peak correlates with the change in the size of Si NCs.     

Study on morphology and photoluminescence of Au/SiO2 nanocomposite films

Au/SiO₂ nanocomposite films were fabricated on Si (111) substrates by radio frequency (RF) magnetron sputtering technique and annealing at different temperature for 20 min (mode A) and at 1000 °C for different annealing time (mode B). The nanocomposite films were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and photoluminescence (PL). SEM results demonstrate that the size of Au crystallites in mode A first increases and then decreases, on increasing annealing temperature, according to the results of XRD spectra. Analysis of PL spectra in mode B shows that the intensity of the emission peak at 440 nm and 523 nm early increases and late decreases, with increasing annealing time at 1000 °C. The origin of the emission peak at around 440 nm was related to the size and quantity of Au particles and one of the emission peak at around 523 nm was related to the nanostructure of films in agreement with SEM imagines. Experimental results indicated that morphology, microstructure and luminescence of Au/SiO₂ nanocomposite films showed close affinity with annealing temperature and annealing time.     

Low-temperature growth of Y2O3 thin films by ultraviolet-assisted pulsed laser deposition

Thin Y₂O₃ films have been grown on (100) Si using an in-situ ultraviolet-assisted pulsed laser deposition (UVPLD) technique. When compared to conventional pulsed laser deposited (PLD) films under similar conditions, the UVPLD-grown films exhibited better structural and optical properties, especially those grown at lower substrate temperatures, from 200 °C to 400 °C. X-ray diffraction investigations showed that the films grown were highly crystalline and textured. According to X-ray photoelectron spectroscopy and Rutherford backscattering spectrometry investigations, UVPLD-grown Y₂O₃ films have a better overall stoichiometry and contain less physisorbed oxygen than the conventional PLD-grown films. The refractive index values, measured in the range 300-750 nm by using variable-angle spectroscopic ellipsometry, were similar to those of a reference Y₂O₃ film.     

Synthesis and photoluminescence of aligned SiO<Subscript>x</Subscript> nanowire arrays

Aligned SiO_x nanowire arrays standing on a Si substrate were successfully synthesized using a simple method by heating a single-crystalline Si slice covered with SiO₂ nanoparticles at 1000 °C in a flowing Ar atmosphere. The SiO_x nanowire arrays were characterized by scanning electron microscopy and transmission electron microscopy. The SiO_x nanowires become progressively thinner from bottom to top. The formation process of the SiO_x nanowire arrays is closely related to a vapor–solid mechanism. Room-temperature photoluminescence measurements under excitation at 260 nm showed that the SiO_x nanowire arrays had a strong blue–green emission at 500 nm (about 2.5 eV), which may be related to oxygen defects. Received: 29 April 2002 / Accepted: 30 April 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +86-551-559-1434, E-mail: gwmeng@mail.issp.ac.cn     

掺饵氢化非晶氧化硅1.54μm发光性质的研究

采用等离子体增强化学汽相沉积技术生长不同氧含量的氢化非晶氧化硅薄膜(a-SiO_{x∶H),离子注入铒及退火后在室温观察到很强的光致发光.当材料中氧硅含量比约为1和 1.76时,分别对应77Ｋ和室温测量时最强的1.54μm光致发光.从15到250Ｋ的变温实验显示 出三个不同的强度与温度变化关系,表明氢化非晶氧化硅中铒离子的能量激发和发光是一个 复杂的过程.提出氢化非晶氧化硅薄膜中发光铒离子来自于富氧区,并对实验现象进行了解 释.氢化非晶氧化硅中铒发光的温度淬灭效应很弱.从15到250Ｋ,光致发光强度减弱约1/2. 关键词： 铒 光致发光 氧含量}     

Optical Properties of Co-BaTiO3/Mg（100） Nano-Composite Films Grown by Pulsed Laser Deposition Method

Co nanoparticles embedded in a BaTiO3 matrix, namely Co-BaTiO3 nano-composite films are grown on Mg（100） single crystal substrates by the pulsed laser deposition （PLD） method at 650℃. Optical properties of the CoBaTiO3 nano-composite films are examined by absorption spectra （AS） and photoluminescence （PL） spectra. The results indicate that the concentration of Co nano-particles strongly influences the electron transition of the Co BaTiO3 nano-composite films. The PL emission band ranging from 1.9 to 2.2eV is reported. The AS and PL spectra suggest that the band gap is in the range of 3.28-3.7eV.     

Microstructure and photoluminescence of Er-doped SiOx films synthesized by ion beam assisted deposition

Er-doped SiO_x films were synthesized at 500℃ by ion beam assisted deposition technique and annealed at 800 and 1100℃ for 2h in the air atmosphere. The analysis by using energy dispersive x-ray spectroscopy showed that the ratio of Si to O decreased from 3 in the as-deposited films to about 1 in the annealed films. The investigation by using transmission electron microscopy and x-ray diffraction indicated that annealing induces a microstructure change from amorphous to crystalline. The grain sizes in the films were about 10 and 40nm when annealed at 800 and 1100℃, respectively. The films annealed at temperatures of 800 and 1100℃ exhibited a sharp photoluminescence (PL) at 1.533μm from the Er centres when pumped by 980nm laser. The influence of microstructure and grain size on the PL from Er-doped SiO_x films has been studied and discussed.