水热腐蚀时间对铁钝化多孔硅表面形貌和光致发光的影响

采用水热腐蚀法制备了4个腐蚀时间不同的铁钝化多孔硅样品,铁钝化多孔硅样品表面呈海绵结构,随着腐蚀时间增加,样品表面的平整度下降,腐蚀孔尺寸差别有增大的趋势。在250nm光激发下,样品发光峰位于620nm附近,半峰全宽约130nm。腐蚀时间从10min增加到40min,4个样品的发光峰并未出现定向的红移或蓝移。结合样品傅里叶变换红外吸收光谱的结果,铁钝化多孔硅的光致发光行为可归因于量子限制-发光中心作用,相应的辐射复合发光中心为非桥氧空穴。     

蓝光发射多孔硅RTO过程中的尺寸分离效应

对用水热腐蚀技术制备的、具有蓝光发射的多孔硅样品在快速热氧化(RTO)处理前后其光致发光谱、硅纳米颗粒的大小及尺寸分布变化进行了研究.实验发现,新鲜多孔硅样品经过RTO处理后,其光致发光谱整体蓝移并由单发光峰分裂为两个发光峰;与此对应,样品中的硅纳米颗粒在整体减小的同时出现尺寸分离现象.这一结果表明,多孔硅中的短波长发射也具有强烈的尺寸相关性. 关键词：     

多孔硅的微结构与发光特性研究

利用原子力显微镜（AFM）和光致荧光（PL）光谱对一系列直流腐蚀和脉冲腐蚀的多孔硅的微结构及发光特性进行了对比研究．表面和侧面的AFM结果表明，多孔硅表面呈“小山”状，有许多小的、突出的硅颗粒．在相同的腐蚀条件（等效）下，脉冲腐蚀的样品表面Si颗粒更加尖锐、突出，侧面的线状结构更明显，多孔硅层更厚．对应的PL谱，脉冲腐蚀的样品发光更强．量子限制效应的理论可以比较成功地解释这个结果 关键词：     

多孔硅的制备条件对其光致发光特性的影响

不同的实验条件下制备的多孔硅的光致发光(PL)特性是不同的,这是许多研究产生分歧的主要原因。对比分析了阳极氧化电流密度、阳极氧化时间、溶液浓度以及自然氧化时间对多孔硅光致发光光谱的影响。认为在一定的范围内,多孔硅的发光峰位会随电流密度的增大而蓝移,要获得较强的发光,需要选择合适的电流密度;随着腐蚀时间的延长,多孔硅的发光峰位也发生蓝移。当HF酸的浓度较小时,峰位随浓度的增大表现为向低能移动;而当HF酸的浓度较大时,峰位随浓度的增大则表现为移向高能。多孔硅在空气中自然氧化,其发光峰位发生蓝移,而发射强度随放置时间的延长而降低。并用量子限制模型和发光中心模型对实验结果进行解释。     

基于三层模型的多孔硅发光谱双峰结构的研究

基于Litovchenko提出的多孔硅三层模型和在此基础上由Li等人提出的多孔硅三层发光模型,利用半导体异质结理论导出了多孔硅芯部与夹层中载流子浓度、非平衡载流子数目、扩散电流密度、夹层与芯部发光强度的比值等关系式.结果表明:当Egint＞Egcore时,在0.2 eV＜ΔEv+ΔEc＜0.26 eV范围内发光谱将出现双峰,并在ΔEv+ΔEc＞0区域发光峰位不断向高能移动,发生蓝移现象;当Egint＜Egcore时,尽管芯部由于量子限制效应仍将导致发光峰蓝移,但芯部的发光相对夹层的发光相当弱,这时多孔硅发光谱呈现单峰.此模型定量地解释了多孔硅发光峰的蓝移起源于多孔硅量子限制效应,而发光出现发光双峰和发光峰位钉扎是由夹层物质决定,说明了多孔硅的发光存在多种发光机制.     

非桥氧空穴发光中心对铁钝化多孔硅光致发光的影响

采用水热腐蚀法制备了铁钝化多孔硅样品,样品光致发光谱的荧光峰位于2.0eV附近,半峰宽约为0.40eV。激发波长从240nm增大到440nm的过程中,荧光峰先红移再蓝移,最后基本稳定,变化曲线呈勺型。通过分析15片发光多孔硅样品的统计结果,发现荧光峰逆转所对应的激发波长位于330nm附近,相应的激发光子能量约为3.8eV。样品光致发光谱随激发波长的勺型变化过程与≡Si—O↑和≡Si—O↑…H—O—Si≡两类非桥氧空穴发光中心共同作用时的发光行为一致。     

离子注入对多孔硅可见光发射特性的影响

本文在前期对多孔硅发光机理研究的基础上,研究了离子注入对多孔硅光致发光的影响.实验表明离子注入除了可以降低多孔硅光致发光的强度外,还将使多孔硅的光致发光光谱谱峰产生蓝移、半高宽展宽,并在多孔硅发光谱带中产生一些发光减弱区和次峰结构.文中最后对实验现象做了解释.     

铁钝化多孔硅的制备及光致发光机理研究

采用水热腐蚀法在相同环境下制备了不同晶型的铁钝化多孔硅样品。同一样品表面具有相似的孔隙结构,不同样品形貌存在差异。在300 nm光激发下,样品发光峰位于618 nm附近,半高宽约为132 nm。傅立叶红外变换光谱显示样品中有强的Si—Si、Si—O—Si、O y—Si—H x化学键振动吸收。结果表明,水热腐蚀法制备的铁钝化多孔硅表面形貌与腐蚀过程的局域电极分布关系密切。样品的光致发光行为可归因于量子限制-发光中心作用,并受非桥氧空穴发光中心数量影响。     

n型多孔硅光致发光研究

对在无光照条件下,电化学阳极腐蚀方法制备的n型多孔硅进行了光致发光性能研究.在325nm的激发光照射下,多孔硅样品的发光峰在620nm处,其橙红色的发光肉眼可见,并随阳极电流密度与腐蚀时间乘积的增加.先增强,后减弱.其发光峰位置与量子限制效应、表面态及缺陷态有关,发光强度与样品表面深度较浅孔洞所占的面积比成正比.     

发光不衰减的多孔硅

用一种新的方法制备出了具有不同衰减的光致发光特性的多孔硅。如此制备的多孔硅新鲜样品,其发光峰位强度比普通多孔硅高２￣２．５倍,将样品在室温下暴露于空气中,其发光强度在前４个月中单调增加,然后达到饱和。在随后的８个月中,没有观察到发光衰减,发光峰位也没有发生变化,这种发光稳定性被归因子于多孔硅表面所形成的稳定的Ｆｅ－Ｓｉ键。文章探讨了发光不衰减、峰位不蓝移的机理,并为多孔硅发光的量子限域模型提供了强     

Optical Analysis of Nanocrystalline ZnO Films Coated on Porous Silicon by Radio Frequency (RF) Magnetron Sputtering

Zinc oxide thin films have been deposited onto porous silicon (PSi) substrates at high growth rates by radio frequency (RF) sputtering using a ZnO target. The advantages of the porous Si template are economical and it provides a rigid structural material. Porous silicon is applied as an intermediate layer between silicon and ZnO films and it contributed a large area composed of an array of voids. The nanoporous silicon samples were adapted by photo electrochemical (PEC) etching technique on n-type silicon wafer with (111) and (100) orientation. Micro-Raman and photoluminescence (PL) spectroscopy are powerful and non-destructive optical tools to study vibrational and optical properties of ZnO nanostructures. Both the Raman and PL measurements were also operated at room temperature. Micro-Raman results showed that the A₁(LO) of hexagonal ZnO/Si(111) and ZnO/Si(100) have been observed at around 522 and 530 cm^–1, re- spectively. PL spectra peaks are distinctly apparent at 366 and 368 cm^–1 for ZnO film grown on porous Si(111) and Si(100) substrates, respectively. The peak luminescence energy in nanocrystalline ZnO on porous silicon is blue-shifted with regard to that in bulk ZnO (381 nm). The Raman and PL spectra pointed to oxygen vacancies or Zn interstitials which are responsible for the green emission in the nanocrystalline ZnO.     

Photoluminescence studies of porous silicon microcavities

Narrow photoluminescence peaks with a full-width at half-maximum of 14–20 nm are obtained from porous silicon microcavities (PSM) fabricated by the electrochemical etching of a Si multilayer grown by molecular beam epitaxy. The microcavity structure contains an active porous silicon layer sandwiched between two distributed porous silicon Bragg reflectors; the latter were fabricated by etching a Si multilayer doped alternatively with high and low boron concentrations. The structural and optical properties of the PSMs are characterised by scanning electron microscopy and photoluminescence (PL). The wavelength of the narrow PL peaks could be tuned in the range of 700–810 nm by altering the optical constants.     

On the origin of 1.5 μm luminescence in porous silicon coated with sol–gel derived erbium-doped Fe2O3 films

Sol–gel derived Fe₂O₃ films containing about 10 wt% of Er₂O₃ were deposited on porous silicon by dipping or by a spin-on technique followed by thermal processing at 1073 K for 15 min. The samples were characterized by means of PL, SEM and X-ray diffraction analyses. They exhibit strong room-temperature luminescence at 1.5 μm related to erbium in the sol–gel derived host. The luminescence intensity increases by a factor of 1000 when the samples are cooled from 300 to 4.2 K. After complete removal of the erbium-doped film by etching and partial etching the porous silicon, the erbium-related luminescence disappears. Following this, luminescence at 1.5 μm originating from optically active dislocations (“D-lines”) in porous silicon was detected. The influence of the conditions of synthesis on luminescence at 1.5 μm is discussed.     

Investigation of porous silicon carbide as a new material for environmental and optoelectronic applications

In this paper, we present an experimental study on the chemical and electrochemical etching of silicon carbide (SiC) in different HF-based solutions and its application in different fields, such as optoelectronics (photodiode) and environment (gas sensors). The thin SiC films have been grown by pulsed laser deposition method. Different oxidant reagents have been explored. It has been shown that the morphology of the surface evolves with the etching conditions (oxidant, concentration, temperature, etc.). A new chemical polishing solution of polycrystalline 6H-SiC based on HF:Na₂O₂ solution has been developed. Moreover, an electrochemical etching method has been carried out to form a porous SiC layer on both polycrystalline and thin SiC films. The PL results show that the porous polycrystalline 6H-SiC and porous thin SiC films exhibited an intense blue luminescence and a green-blue luminescence centred at 2.82 eV (430 nm) and 2.20 eV (560 nm), respectively. Different device structures based on both prepared samples have been investigated as photodiode and gas sensors.     

Effect of surface modification by thermally oxidization and HF etching on UV photoluminescence emission of porous silicon

Photoluminescence of porous silicon (PS) is instable due perhaps to the nanostructure modification in air. The controllable structure modification processes on the as-prepared PS were conducted by thermal oxidization and/or HF etching. The PL spectra taken from thermally oxidized PS showed a stable photoluminescence emission of 355 nm. The photoluminescence emission taken from both of PS and oxidized porous silicon (OPS) samples etched with HF were instable, which can be reversibly recovered by the HF etching procedure. The mechanism of UV photoluminescence is discussed and attributed to the transformation of luminescence centers from oxygen deficient defects to the oxygen excess defects in the thermal oxidized PS sample and surface absorbed silanol groups on PS samples during the chemical etched procedure.     

Flat layered structure and improved photoluminescence emission from porous silicon microcavities formed by pulsed anodic etching

Single-mode, highly directional and stable photoluminescence (PL) emission has been achieved from porous silicon microcavities (PSMs) fabricated by pulsed electrochemical etching. The full width at half maximum (FWHM) of the narrow PL peak available from a freshly etched PSM is about 9 nm. The emission concentrates in a cone of 10° around the normal of the sample, with a further reduced FWHM of ∼5.6 nm under angle-resolved measurements. Only the resonant peak is present in such angle-resolved PL spectra. No peak broadening is found upon exposure of the freshly prepared PSM to a He-Cd laser beam, and the peak becomes somewhat narrower (∼5.4 nm) after the PSM has been stored in an ambient environment for two weeks. At optimized etching parameters, even a 4-nm FWHM is achievable for the freshly etched PSM. In addition, scanning electron microscopy (SEM) plane-view images reveal that the single layer porous Si formed by pulsed current etching is more uniform and flatter than that formed by direct current (dc) etching, demonstrated by the well-distributed circular pores with small size in the former in comparison with the irregular interlinking pores in the latter. The SEM cross-section images show the existence of oriented Si columns of 10 nm diameter along the etching direction within the active layer, good reproducibility and flat interfaces. It is thus concluded that pulsed current etching is superior to dc etching in obtaining flat interfaces within the distributed Bragg reflectors because of its minor lateral etching. Received: 7 March 2001 / Accepted: 23 July 2001 / Published online: 30 October 2001     

Time-resolved photoluminescence study of the red emission in nanoporous SiGe alloys

Porous Si_1−xGe_x (PSiGe) layers with efficient room temperature visible photoluminescence (PL) were elaborated by anodical etching from p-type doped epitaxial layers with Ge contents from 5 to 30%. The luminescence is characterised by a broad PL band centred at 1.8 eV. Time resolved photoluminescence decay is studied in porous silicon germanium as a function of germanium content, temperature, emission energies and surface passivation. The PL decay line shape is well described by a stretched exponential in all cases. The effective lifetime at low temperature in as prepared porous Si_1−xGe_x is 400 μs, i.e. an order of magnitude less than in porous silicon. After the formation of a 20 Å thick oxide surface layer we observe a decrease of the effective lifetime to 20 μs at T=4 K.     

Structural and optical properties of thin films porous amorphous silicon carbide formed by Ag-assisted photochemical etching

In this work, we present the formation of porous layers on hydrogenated amorphous SiC (a-SiC: H) by Ag-assisted photochemical etching using HF/K₂S₂O₈ solution under UV illumination at 254 nm wavelength. The amorphous films a-SiC: H were elaborated by d.c. magnetron sputtering using a hot pressed polycrystalline 6H-SiC target. Because of the high resistivity of the SiC layer, around 1.6 MΩ cm and in order to facilitate the chemical etching, a thin metallic film of high purity silver (Ag) has been deposited under vacuum onto the thin a-SiC: H layer. The etched surface was characterized by scanning electron microscopy, secondary ion mass spectroscopy, infrared spectroscopy and photoluminescence. The results show that the morphology of etched a-SiC: H surface evolves with etching time. For an etching time of 20 min the surface presents a hemispherical crater, indicating that the porous SiC layer is perforated. Photoluminescence characterization of etched a-SiC: H samples for 20 min shows a high and an intense blue PL, whereas it has been shown that the PL decreases for higher etching time. Finally, a dissolution mechanism of the silicon carbide in 1HF/1K₂S₂O₈ solution has been proposed.     

Structural and optical features of nanoporous silicon prepared by electrochemical anodic etching

Nanoporous silicon (NPS) samples were prepared by electrochemical anodic etching of p-type (0 0 1) silicon wafers in HF solution, and some of them were aged in air. The nanostructural, optical and chemical features of the NPS were investigated in terms of etching and aging conditions. The surface of the porous Si exhibits an etched layer with a thickness of 30–40 nm; this layer appears to consist of aggregates of 5–10 nm size nano-crystallites. The NPS exhibited broad photoluminescence (PL) spectra with its peak in the red light region (740 nm). After aging the porous samples for 4 weeks in air, we observed the PL intensity became approximately a fifth of that of the as-prepared one, along with a blue shift. It is very likely that the blue shift of the PL peak was caused by the shrinkage of the Si nano-crystallites due to the oxidation in the surface of the nano-crystallites.