氧化硅层厚度对Si/SiO2界面电子态结构与光学性质的影响

在氧化硅上生长纳米硅晶,保持氧化硅的直接带隙结构,降低其能带带隙,以用于发光和光伏。采用基于密度泛函理论的第一性原理研究了块体α-方石英、薄膜α-方石英、Si/SiO₂界面的电子态结构和Si/SiO₂界面的光学性质。结果显示,其均为直接带隙半导体,当薄膜α-方石英厚度和Si/SiO₂界面氧化硅层厚度逐渐减小时,能带带隙均逐渐变大,表现出明显的量子限制效应。光学性质计算结果表明：Si/SiO₂界面虚部介电峰和吸收峰的峰值随氧化硅层厚度降低而显著升高,且峰位向高能量方向蓝移。使用脉冲激光沉积制备了氧化硅上硅晶薄膜,测量了Si/SiO₂界面样品的PL光谱,在670 nm处存在一个强的发光峰,在波长超过830 nm后,Si/SiO₂界面样品的发光强度不断升高。因此,可以通过控制Si/SiO₂界面氧化硅层厚度有效地调控Si/SiO₂界面的电子态结构和光学性质,引进边缘电子态,调控其带隙进入1～2 eV区间,获取硅基发光材料...     

高温退火处理下SiNx薄膜组成及键合结构变化

采用等离子增强化学气相沉积法, 以氨气和硅烷为反应气体, p型单晶硅为衬底, 低温下(200 ℃)制备了非化学计量比氮化硅(SiN_x)薄膜. 在N₂氛围中, 于500–1100 ℃范围内对薄膜进行热退火处理. 室温下分别使用Fourier变换红外吸收(FTIR)光谱技术和X射线光电子能谱(XPS)技术测量未退火以及退火处理后SiN_x薄膜的Si–N, Si–H, N–H键键合结构和Si 2p, N 1s电子结合能以及薄膜内N和Si原子含量比值R的变化. 详细讨论了不同温度退火处理下SiN_x薄膜的FTIR和XPS光谱演化同薄膜内Si, N, H原子间键合方式变化之间的关系. 通过分析FTIR和XPS光谱发现退火温度低于800 ℃时, SiN_x薄膜内Si–H和N–H键断裂后主要形成Si–N键; 当退火温度高于800 ℃时薄膜内Si–H和N–H键断裂利于N元素逸出和Si纳米粒子的形成; 当退火温度达到1100 ℃时N₂与SiN_x薄膜产生化学反应导致薄膜内N和Si原子含量比值R增加. 这些结果有助于控制高温下SiN_x薄膜可能产生的化学反应和优化SiN_x薄膜内的Si纳米粒子制备参数. 关键词： x薄膜')" href="#">SiN_x薄膜 Fourier变换红外吸收光谱 X射线光电子能谱 键合结构     

InP/SiO2纳米复合膜的微观结构和光学性质

应用射频磁控共溅射方法在石英玻璃和抛光硅片上制备了InP/SiO₂复合薄膜,并在几种条件下对这些薄膜进行退火.X射线光电子能谱和卢瑟福背散射实验结果表明,复合薄膜中InP和SiO₂的化学组分都大体上符合化学计量配比.X射线衍射和激光喇曼谱实验结果都证实了复合薄膜中形成了InP纳米晶粒.磷气氛保护下的高温(520℃)退火可以消除复合薄膜中残存的In和In₂O₃并得到了纯InP/SiO₂纳米复合薄膜.实验观察到了室温下纳米复合薄膜的明显的光学吸收边蓝移现象和光学非线性的极大增强 关键词： InP 纳米晶粒 微观结构 光学性质     

N掺杂SiO2纳米薄膜的制备及其磁性

利用射频磁控反应溅射技术,制备了氮掺杂的SiO₂纳米薄膜.发现N掺杂SiO₂体系纳米薄膜具有铁磁性.较小的氮化硅颗粒均匀分布在氧化硅基质中有利于磁有序的形成.基底温度为400℃时,样品薄膜具有最大的饱和磁化强度和矫顽力,分别为35 emu/cm³和75 Oe.薄膜的磁性可能产生于氮化硅和氧化硅的界面.理论计算表明,N掺杂SiO₂体系具有净自旋.同时,由氮化硅和氧化硅界面之间的电荷转移导致的轨道磁矩也会对样品的磁性有贡献 关键词： 2薄膜')" href="#">N掺杂SiO₂薄膜 射频磁控反应溅射 界面磁性 基底温度     

含纳米硅和纳米锗的氧化硅薄膜 光致发光的比较研究

分别以硅-二氧化硅和锗-二氧化硅复合靶作为溅射靶,采用磁控溅射技术在p型硅衬底上淀积了含纳米硅的氧化硅薄膜和含纳米锗的氧化硅薄膜.各样品分别在氮气氛中经过300至1100℃不同温度的退火处理.使用高分辨透射电子显微镜可以观察到经900和1100℃退火的含纳米硅的氧化硅薄膜中的纳米硅粒,和经900和1100℃退火的含纳米锗的氧化硅薄膜中的纳米锗粒.经过不同温度退火处理的含纳米硅的氧化硅和含纳米锗的氧化硅薄膜的光致发光谱均具有相似的峰型,且它们的发光峰位均位于580nm(2.1eV)附近.可以认为含纳米硅的氧化硅和含纳米锗的氧化硅薄膜的光发射主要来自于SiO     

掺纳米锗氧化硅的发光性能研究

由溶胶/凝胶法制备得到的GeO₂/SiO₂玻璃在700 ℃的条件下经H₂还原,得到具有奇特光致发光性质的Ge/SiO₂玻璃,该玻璃在室温条件下用246 nm（5.01 eV）的光激发时,能发射出很强的 392 nm（3.12 eV）、较强的 600 nm（2.05 eV）和次强的770 nm（1.60 eV） 的荧光.利用X射线衍射（XRD）、X射线光电子能谱（XPS）及透射电镜（TEM）实验证明,该玻璃能够发射3种不 关键词： 2')" href="#">Ge/SiO₂ Ge纳米晶粒 溶胶/凝胶法 光致发光     

Au/(SiO2/Si/SiO2)纳米双势垒/n+-Si结构的电致发光研究

利用射频磁控溅射方法,在n⁺-Si衬底上淀积SiO₂/Si/SiO_{2纳米双势垒单势阱结构,其中Si层厚度为2至4nm,间隔为0.2nm,邻近n⁺-S i衬底的SiO2层厚度固定为1.5nm,另一SiO2层厚度固定为3nm.为了 对比研究,还制备了Si层厚度为零的结构,即SiO2(4.5nm)/n⁺-Si 结构.在经过600℃氮气下退火30min,正面蒸上半透明Au膜,背面也蒸Au作欧姆接触后,所 有样品都在反向偏置(n^＋-Si的电压高于Au电极的电压)下发光,而在正向偏压 下不发光.在一定的反向偏置下,电流和电致发光强度都随Si层厚度的增加而同步振荡,位 相相同.所有样品的电致发光谱都可分解为相对高度不等的中心位于2.26eV(550nm)和1.85eV (670nm)两个高斯型发光峰.分析指出该结构电致发光的机制是：反向偏压下的强电场使Au/( SiO2/Si/SiO2)纳米双势垒/n⁺-Si结构发生了雪崩击穿 ,产生大量的电子-空穴对,它们在纳米SiO2层中的发光中心(缺陷或杂质)上复 合而发光. 关键词： 电致发光 纳米双势垒 高斯型发光峰 雪崩击穿}     

含纳米硅和纳米锗的氧化硅薄膜光致发光的比较研究

分别以硅-二氧化硅和锗-二氧化硅复合靶作为溅射靶,采用磁控溅射技术在p型硅衬底上淀积了含纳米硅的氧化硅薄膜和含纳米锗的氧化硅薄膜.各样品分别在氮气氛中经过300至1100℃不同温度的退火处理.使用高分辨透射电子显微镜可以观察到经900和1100℃退火的含纳米硅的氧化硅薄膜中的纳米硅粒,和经900和1100℃退火的含纳米锗的氧化硅薄膜中的纳米锗粒.经过不同温度退火处理的含纳米硅的氧化硅和含纳米锗的氧化硅薄膜的光致发光谱均具有相似的峰型,且它们的发光峰位均位于580nm(2.1eV)附近.可以认为含纳米硅的氧化硅和含纳米锗的氧化硅薄膜的光发射主要来自于SiO₂层中发光中心上的复合发光,对实验结果进行了合理的解释     

纳米锗颗粒镶嵌薄膜的荧光特性研究

研究了不同颗粒尺寸的纳米Ge-SiO₂镶嵌薄膜的室温荧光光谱以及不同激发光能量对荧光峰的影响．实验结果表明，沉积态Ge-SiO₂薄膜样品在可见光区域不发光．退火后的样品（平均锗颗粒尺寸为3.2—6.0nm）在380—520nm波长范围内有明显的蓝光发射现象．当用λ=300nm的光激发，观测到中心波长为420nm（2.95eV）的光致荧光峰；而用633nm波长的光激发，谱图上出现中心波长分别为420和470nm的两个荧光峰．随着纳米锗颗粒尺寸的增加，光致荧光峰的相 关键词：     

富硅氮化硅薄膜的荧光发射

室温下在3．45eV的激光激发下,对950℃温度下淀积的LPCVD富硅的SiNx薄膜中,观测到5个高强度的可见荧光的发射。其峰位位置分别为2．7,2．69,2．4,2．3,2．1eV。通过TEM、IR、XPS等的分析研究表明,该样品为纳米硅镶嵌结构的a-SiNx：H复合膜,分析了其微结构的成因及其与膜内应力之间的相互关系。经过1000～1200℃快速退火(RTA)处理,原PL谱蓝移并只出现了峰位为3．0,2．8eV的两个紫蓝色荧光的发射,用能隙态模型对此结果做了初步的分析和讨论。认为薄膜中纳米硅团簇的密度、尺寸的变化和亚稳态缺陷态对其PL峰以及膜应力起着十分重要的作用。     

Green/blue light emission and chemical feature of nanocrystalline silicon embedded in silicon-oxide thin film

2 in the range of annealing temperatures used. The PL intensity, weight of the Si⁴⁺ states, and the volume fraction of Si nanocrystals exhibit a large increase as T_a>750 °C. The PL peak position is independent of the annealing temperature (T_a). From our observations, the green/blue light emission is related to the defects. Received: 10 July 1996/Accepted: 2 April 1997     

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.     

Investigation on preparation and physical properties of nanocrystalline Si/SiO2 superlattices for Si-based light-emitting devices

Structures containing silicon nanocrystals (nc-Si) are very promising for Si-based light-emitting devices. Using a technology compatible with that of silicon, a broader wavelength range of the emitted photoluminescence (PL) was obtained with nc-Si/SiO₂ multilayer structures. The main characteristic of these structures is that both layers are light emitters. In this study we report results on a series of nc-Si/SiO₂ multilayer periods deposited on 200 nm thermal oxide SiO₂/Si substrate. Each period contains around 10 nm silicon thin films obtained by low-pressure chemical vapour deposition at T=625°C and 100 nmSiO₂ obtained by atmospheric pressure chemical vapour deposition T=400°C. Optical and microstructural properties of the multilayer structures have been studied by spectroscopic ellipsometry (using the Bruggemann effective medium approximation model for multilayer and multicomponent films), FTIR and UV–visible reflectance spectroscopy. IR spectroscopy revealed the presence of SiO_x structural entities in each nc-Si/SiO₂ interface. Investigation of the PL spectra (using continuous wave-CW 325 nm and pulsed 266 nm laser excitation) has shown several peaks at 1.7, 2, 2.3, 2.7, 3.2 and 3.7 eV, associated with the PL centres in SiO₂, nc-Si and Si–SiO₂ interface. Their contribution to the PL spectra depends on the number of layers in the stack.     

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.     

Photoluminescence studies of Si nanocrystals

Summary We report room temperature time-resolved photoluminescence (PL) and temperature dependence of continuous wave (cw) PL studies of high fluence (from 3·10¹⁶ to 3·10¹⁷ cm⁻²) Si⁺-implanted thermal SiO₂ layers after annealing at high temperature (T=1000°C). Such measurements were related to TEM analysis of samples. Nancocrystals were observed at TEM only a samples implanted at higher fluence. In these samples a near infrared PL signal peaked at approximately 1.5 eV with decay time of about 100 μs is present. Besides, in all samples a light emission is present in the green region of the spectrum. The intensity of the emission shows large variations with ion fluence, and is characterized by 0.4, 2 and 7 ns decay times. Paper presented at the III INSEL (Incontro Nazionale sul Silicio Emettitore di Luce) Torino, 12–13 October 1995.     

Blue–violet photoluminescence from colloidal suspension of nanocrystalline silicon in silicon oxide matrix

We report room temperature visible photoluminescence (PL), detectable by the unaided eye, from colloidal suspension of silicon nanocrystals (nc-Si) prepared by mechanical milling followed by chemical oxidation. The PL bands for samples prepared from Si wafer and Si powder peak at 3.11 and 2.93 eV respectively, under UV excitation, and exhibit a very fast (～ns) PL decay. Invasive oxidation during chemical treatment reduces the size of the nc-Si domains distributed within the amorphous SiO₂ matrix. It is proposed that defects at the interface between nc-Si and amorphous SiO₂ act as the potential emission centers. The origin of blue–violet PL is discussed in relation to the oxide related surface states, non-stoichiometric suboxides, surface species and other defect related states.     

Blue photo- and electroluminescence of silicon dioxide layers ion-implanted with group IV elements

The microstructural, optical and electrical properties of Si-, Ge- and Sn-implanted silicon dioxide layers were investigated. It was found, that these layers exhibit strong photoluminescence (PL) around 2.7 eV (Si) and between 3 and 3.2 eV (Ge, Sn) at room temperature (RT), which is accompanied by an UV emission around 4.3 eV. This PL is compared with that of Ar-implanted silicon dioxide and that of Si- and Ge-rich oxide made by rf magnetron sputtering. Based on PL and PL excitation (PLE) spectra we tentatively interpret the blue–violet PL as due to a T₁→S₀ transition of the neutral oxygen vacancy typical for Si-rich SiO₂ and similar Ge- or Sn-related defects in Ge- and Sn-implanted silicon dioxide. The differences between Si, Ge and Sn will be explained by means of the heavy atom effect. For Ge-implanted silicon dioxide layers a strong electroluminescence (EL) well visible with the naked eye and with a power efficiency up to 5×10^-4 was achieved. The EL spectrum correlates very well with the PL one. Whereas the EL intensity shows a linear dependence on the injection current over three orders of magnitude, the shape of the EL spectrum remains unchanged. The I-V dependence exhibiting the typical behavior of Fowler–Nordheim tunneling shows an increase of the breakdown voltage and the tunnel current in comparison to the unimplanted material. Finally, the suitability of Ge-implanted silicon dioxide layers for optoelectronic applications is briefly discussed. Received: 9 March 2000 / Published online: 30 June 2000     

多孔硅蓝光发射与发光机制

在制备出光致发光能量为２．７ｅＶ的发射蓝光多孔硅的基础上对它进行了较系统的研究：测量了它的光致发光时间分辨光谱，用傅里叶交换红外光谱分析了其表面吸附原子的局域振动模，研究了γ射线辐照对其发光的影响，并与发红、黄光的多孔硅作了对比，通过空气中长期存放、激光和紫外线照射的方法，研究了光致发光峰能量为２．７ｅＶ的多孔硅发光稳定性．我们及其它文献中报道的多孔硅蓝光发射的实验结果与量子限制模型矛盾，但能用量子限制／发光中心模型解释．我们认为多孔硅的２．７ｅＶ发光是多孔硅中包裹纳米硅的ＳｉＯ_x层中某种特征发光中心引起的． 关键词：     

Poole-Frenkel conduction in Al/ZrO2 /SiO 2 /Si structures

Leakage currents through Al/ZrO₂/SiO₂/n-Si metal-insulator-semiconductor (MIS) capacitors were studied. Thin SiO₂ films were chemically grown on monocrystalline phosphorous doped silicon wafers. Zirconia films with thicknesses of 15 and 50 nm were deposited by radio frequency (rf) magnetron sputtering and, then, annealed in oxygen ambient at 850 ^○C, for 1 h. The dielectric constant of the sputtered and annealed ZrO₂ layer was of about 17.8. The equivalent oxide thickness (EOT) of the stack 15 nm and 50 nm-ZrO₂/SiO₂ structure was estimated to be 3.2 nm and 10.7 nm, respectively. The temperature dependence of the leakage currents was explained by Poole-Frenkel (PF) conduction mechanism. Shallow trap levels in the studied structure of about 0.2 eV and 0.46 eV were calculated. The existence of A and D-defects, due to the sputtering and high temperature annealing in oxygen, was suggested.     

Role of Bi ions for Er ions efficient 1.54 μm light emission in Er/Bi codoped SiO2 thin film prepared by sol-gel method

Er/Bi codoped SiO₂ thin films were prepared by sol-gel method and spin-on technology with subsequent annealing process. The bismuth silicate crystal phase appeared at low annealing temperature while vanished as annealing temperature exceeded 1000 °C, characterized by X-ray diffraction, and Rutherford backscattering measurements well explained the structure change of the films, which was due to the decrease of bismuth concentration. Fine structures of the Er³⁺-related 1.54 μm light emission (line width less than 7 nm) at room temperature was observed by photoluminescence (PL) measurement. The PL intensity at 1.54 μm reached maximum at 800 °C and decreased dramatically at 1000 °C. The PL dependent annealing temperature was studied and suggested a clear link with bismuth silicate phase. Excitation spectrum measurements further reveal the role of Bi³⁺ ions for Er³⁺ ions near infrared light emission. Through sol-gel method and thermal treatment, Bi³⁺ ions can provide a perfect environment for Er³⁺ ion light emission by forming Er-Bi-Si-O complex. Furthermore, energy transfer from Bi³⁺ ions to Er³⁺ ions is evidenced and found to be a more efficient way for Er³⁺ ions near infrared emission. This makes the Bi³⁺ ions doped material a promising application for future erbium-doped waveguide amplifier and infrared LED.