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：     

Er3+、In3+等金属离子对多孔硅光致发光性质的影响

用阳极腐蚀的方法制备了多孔硅样品,用电化学方法在多孔硅中注入Ｅｒ＾３＋、Ｉｎ＾３＋等金属离子,并对注入离子后多孔硅的光致荧光光谱进行了研究,结果表明：注入Ｅｒ＾３＋及Ｉｎ＾３＋后的多孔硅在５８８ｎｍ处的妇光峰强度大大增加,同时发光峰稍有展宽。随着离子注入时间的增长,强度继续增加,但当离子溶液浓度一定时,这种增强对时间具有饱和性。     

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：     

大气中长期存放与长时间热氧化后多孔硅光致发光峰能量的会聚

改变阳极氧化的工艺条件,制备出光致发光峰能量位于1.4—2.0eV范围内的大量多孔硅样品,其中45块样品在大气中存放一年,102块样品在200℃下热氧化(累计达200小时).在上述两种情况下,光致发光峰能量在氧化后都会聚到1.70—1.75eV能量范围.假设在充分氧化的多孔硅中包裹纳米硅的氧化层中,存在发光能量处于～1.70—1.75eV的发光中心,上述实验结果可以用量子限制/发光中心模型解释. 关键词：     

CdS纳米颗粒填充的自支撑多孔硅光致发光特性

为了研究CdS纳米颗粒填充的自支撑多孔硅的光致发光特性,选用电阻率为0.01~0.02Ω·cm的P型硅片,先采用二步阳极氧化法制备自支撑多孔硅,再利用电泳法将CdS纳米颗粒填充入该自支撑多孔硅中.采用扫描电子显微镜、X射线能谱分析、X射线衍射分析、光致发光谱分析对所制备样品的形貌、相结构、组份及发光性能进行研究.实验结果表明:自支撑多孔硅内部成功填充了CdS纳米颗粒,该CdS纳米颗粒衍射峰为(210);CdS纳米颗粒填充的自支撑多孔硅光致发光峰峰位发生红移,且从570nm转移到740nm;电泳时间直接影响CdS纳米颗粒的填充量,导致相关的发光峰强度及发光峰位明显不同.     

有机吸附物对多孔硅微腔发光的影响

理论上,采用Bruggeman有效介质近似,研究了有机吸附物对多孔硅微腔的折射率及其光致发光谱的影响.实验上,采用计算机控制的电化学腐蚀法制备了多孔硅微腔样品,并利用机械泵油的蒸气分子与该微腔样品进行相互作用.研究发现,多孔硅微腔发射的窄化光致发光谱对泵油蒸气分子的吸附与脱附很敏感,与之伴随的是该窄化光致发光谱发生明显的峰位移动(可达71nm)和强度变化.结合Bruggeman近似和表面态对多孔硅发光的影响,对实验结果进行了定性解释.实验结果与理论模拟结果符合较好. 关键词： Bruggeman近似 吸附物 多孔硅微腔 光致发光谱     

获得多孔硅蓝绿光发射的新方法

对多孔硅进行“胺液浸泡＋快速热氧化”处理,光致发光谱显示,经处理样品的发光峰值波长短到５００ｎｍ,而且在干燥空气中存放１６０ｄ后,发光强度变化很小．红外吸收谱表明,处理后的多孔硅的主要成分是硅和氧,胺液没有在发蓝绿光的样品中留下残迹．电子自旋共振谱表明,这种蓝绿光样品有相当低的悬挂键密度．这些结果揭示,量子限制效应和表面态在多孔硅蓝绿光发射中起着关键性的作用．这种制备发蓝绿光样品的方法简单易行,成功率可达７０％．     

多孔硅镶嵌C102的蓝绿发光特性

利用多孔硅(PS)独特的微孔结构、非常大的比表面积、很强的吸附能力和灵敏的表面光学性质等特点,将激光染料香豆素102(C102)镶嵌在多孔硅中,得到多孔硅镶嵌C102的复合膜。研究复合膜的荧光特性,我们发现：镶嵌在多孔硅中的C102荧光光谱与其在无水乙醇溶液中的荧光光谱相似,主要呈现单体发光特性;通过比较镶嵌在不同孔隙率中的C102荧光光谱,得知镶嵌在不同多孔硅中的染料分子主要以同种形式存在。另外还发现,放置一段时间后的镶嵌复合膜,荧光强度明显增强,对称性提高,保留了激光染料发光的很多优点。多孔硅镶嵌C102的荧光特性展示了多孔硅在发展固体激光器方面有一定的应用,并为实现硅基蓝绿发光打开新的途径。     

Rh6G/氧化多孔硅复合膜的荧光光谱

为了发展性能良好的固体染料激光器,多孔介质中镶嵌激光染料是一种可行的途径。将氧化多孔硅作为基质材料,通过浸泡的方式将激光染料Rh6G嵌入其中,形成Rh6G/氧化多孔硅复合膜,对比研究了Rh6G在无水乙醇、多孔硅、多孔氧化硅中的荧光特性。结果表明,经高温氧化后,氧化多孔硅透明度提高,其荧光强度明显变弱,在复合膜中已检测不到其荧光行为。相比于在无水乙醇溶液中,在氧化多孔硅中Rh6G发射光谱的半峰全宽有所展宽,峰值波长略有红移,对称性大为提高,具有类似单体发光特性,这种现象与纳米孔对Rh6G的聚集程度的限制有关。     

多孔硅的不同制备方法及其光致发光

目前，多孔硅的制备方法已有许多种。我们用电化学方法、光化学方法和化学方法分别制备出了室温下在可见光区发射光荧光的多孔硅。通过对实验装置、制备条件、样品的成膜过程及其光致发光(PL)光谱的比较，分析解释了其成膜机理和PL光谱的特点。认为虽然这三种方法都可以制备出多孔硅，但相比较而言，通过电化学方法制备的样品最均匀、实验的可重复性较强、因而电化学方法是被普遍采用的一种方法。另外在多孔硅的成膜过程中，自由载流子起着至关重要的作用。     

Blue Photoluminescence of Oxidized Films of Porous Silicon

It is found that the films of n ⁺-type porous silicon of low (10–50%) porosity exhibit photoluminescence in the region 400–500 nm after a 5-month storage in an air atmosphere. The spectrum of blue photoluminescence of the least porous but strongly oxidized films has maxima at 417, 435, and 465 nm. The same spectrum structure manifests itself upon the introduction of an Er³⁺- and Yb³⁺-containing complex. The mechanisms of blue photoluminesence are discussed.     

Stabilization of porous silicon surface by low temperature photoassisted reaction with acetylene

A hybrid approach of forming a stabilizing layer of bonded carbon on porous silicon (PSi) surface by photoassisted reaction of acetylene gas at low temperatures is described. The PSi samples were made by anodization in a HF/H₂O₂ electrolyte at a current density of 80 mA/cm². Samples show a strong luminescence with a peak at 644±4 nm. The photoluminescence (PL) intensity shows a very strong quenching under the influence of continuous laser illumination (∼0.25 W/cm², 488 nm). The PSi samples were subjected to flowing acetylene under optical illumination from quartz halogen lamp (20 mW/cm²). The PL intensity is initially quenched to very low values (less than 5% of initial value) and then recovers on further exposure to acetylene to a final value ∼30% of the initial value. No quenching is observed on further exposure to laser illumination in ambient air instead an improvement of 15–25% in PL intensity is observed. This behaviour is a good indicator of the formation of a practically stable PSi surface.     

Local structure of porous silicon studied by means of X-ray emission spectroscopy

2,3 X-ray emission spectra of porous silicon (P-Si) and of spark-processed silicon (sp-Si). Both types of Si-structure display strong photoluminescence in the visible range of the spectrum. Porous samples were prepared by anodization of n^-- and p⁺-Si-wafers. Whereas for the P-Si processed from p⁺-Si the presence of some amorphous silicon is detected, the X-ray emission spectra of porous Si prepared from n^--Si display a higher content of SiO₂. For spark-processed Si the Si L_2,3 X-ray emission spectra reveal a much stronger degree of oxidation which extends to depths larger than 10000 Å. Furthermore, the chemical state of silicon atoms of sp-Si measured at the center of the processed area is close to that of silicon dioxide, and it has an influence on the photoluminescence energy. Specifically, green photoluminescent sp-Si shows a higher degree of oxidation than the blue luminescent specimen. However, the depth of oxidation consistently decreases in areas with weak or no PL. Possible origins of the observed photoluminescence are discussed. Accepted: 6 March 1997     

激光促进多孔硅内表面氧化与光致发光的退化

本文对刚制备的以及分别经以下三种情况:1.样品在1大气压的氧气中经激光(Ar~+激光器的48.80nm线,功率密度为1.77W/cm~2)连续照射1小时;2.样品在1大气压的氧气中在没有激光照射的情况下保持1小时;3.样品在1.3×10~2Pa真空度下用激光连续照射1小时处理后的多孔硅在室温下进行了光致发光谱和傅里叶变换红外吸收测量,研究了处理前后光谱的变化。实验发现经第一种情况处理后光致发光峰位蓝移了约0.1eV,发光强度衰减了二十几倍,相应的其红外光谱中与氧有关的吸收峰强度大幅度增长,而经第二,三两种情况处理后它们的光致发光及红外吸收谱则无大的变化。研究表明在氧气中激光辐照能大大加速多孔硅内表面的氧化。我们认为很可能是多孔硅内表面的氧化作用使光致发光峰位蓝移,由氧化作用产生的非辐射复合中心导致光致发光效率的下降。     

Luminescence and photoconductivity properties of porous polycrystalline silicon

In recent years, the photoluminescence and the photoconductivity of porous silicon were comprehensively studied. But the photoluminescence and the photoconductivity of porous polycrystalline silicon have not been wholely studied. In this paper, the results showed that luminescent property of the samples prepared by poly-crystal silicon wafers may be related to the defects on Si complexes surface, which can be proved by microwave-detected photoconductivity decay measurements. Furthermore, the luminescence of samples was disappeared under the external illumination, which may be related to the elimination of luminescent-centers. In addition, the conductivities of the samples were dependent on etched time and current density, and the large porosity of samples led to isotropic photoconductivity, which may be related to the change of energy band structure of the devices.     

An investigation of natural oxidation process on stain-etched nanoporous silicon by micro-Raman spectroscopy

Micro-Raman spectra of porous silicon (PS) samples as-formed, from stain etching process using heavily doped silicon wafers, and after 750 days storage in air were analyzed around Si peak (300-600 cm⁻¹) and at photoluminescence (PL) range (300-8000 cm⁻¹). The first-order Raman spectra in the vicinity of Si peak were fitted from phonon confinement model including a term taking into account the amorphous phase. This analysis allowed the determination of the correlation length, which corresponds to the crystallite size, also considering the PS natural oxidation process. The photoluminescence band, generated by Si crystallites located on the outermost part of the PS layer, was also fitted with a Gaussian distribution. In order to investigate the porous silicon nanostructure, the micro-Raman spectra were measured for different sets of porous silicon samples. These spectra showed good reproducibility and the effects of the natural oxidation at different periods. A slight decrease in the crystallite size was observed for all samples sets studied, while the spectral part related to the amorphous phase did not describe significant changes. The central position of PL band, analyzed after the oxidation process, exhibited consistently a shift to higher energies. In addition, top view high resolution scanning electron microscopy (HRSEM) images also confirmed a reasonable reproducibility and homogeneity. The results showed that after storing in air, natural oxidation can modify the Si crystallites size at the surface but not increase the amorphous phase.     

Annealing and amorphous silicon passivation of porous silicon with blue light emission

The photoluminescence (PL) of the annealed and amorphous silicon passivated porous silicon with blue emission has been investigated. The N-type and P-type porous silicon fabricated by electrochemical etching was annealed in the temperature range of 700-900 °C, and was coated with amorphous silicon formed in a plasma-enhanced chemical vapor deposition (PECVD) process. After annealing, the variation of PL intensity of N-type porous silicon was different from that of P-type porous silicon, depending on their structure. It was also found that during annealing at 900 °C, the coated amorphous silicon crystallized into polycrystalline silicon, which passivated the irradiative centers on the surface of porous silicon so as to increase the intensity of the blue emission.     

多孔硅的分形结构及其荧光特性

用扫描电子显微镜(SEM)对多孔硅的结构进行了分析.结果显示多孔硅具有分形特性,同计算机模拟结果一致;用荧光光谱仪,研究了多孔硅的荧光特性与激发波长的依赖关系.激发光谱测量结果发现,当激发波长从650 nm变到340 nm时,荧光谱峰位从红端780 nm连续蓝移到500 nm.综合分析说明：正是由于多孔硅的分形微结构以及量子限制效应,导致了多孔硅的荧光特性随激发波长改变的物理现象.     

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.