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.     

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.     

Porous silicon layers prepared by electrochemical etching for application in silicon thin film solar cells

In this paper, multilayer structures of porous silicon were fabricated by using electrochemical etching and characterized for its optical properties and surface morphology. Samples of monolayer of porous silicon were grown to study the characteristics of porous layer formation with respect to applied current density, etching time and hydrofluoric acid concentrations. Photoluminescence peaks of red emission at wavelength 695 and 650 nm were observed from multilayer porous silicon structures. By atomic force microscopy measurement, hillocks like surface were clearly observed within the host material, which confirmed the formation of pores.     

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.     

Depth dependence of photoluminescence and chemical bonding in porous silicon

Porous silicon (PS) is studied by stepwise peeling of the surface layer to clarify the non-uniformity in the photoluminescence (PL) and correlate it with the in-depth chemical bonding and structure of the 30 μm thick layer. The PL intensity grows by an order of magnitude after the peeling off of the first 10 μm and decreases five times in the next 5 μm while the peak maximum position shifts from 730 to 800 nm. X-ray photoelectron spectroscopy (XPS) measurements show that Si–Si and Si–O bonds are present both on the surface and below, and the preferential oxidation state of silicon changes from 3+ and 4+ on the surface to 1+ and 2+ below 10 μm. Using Raman spectroscopy silicon nanocrystals are shown to exist. Their mean size can be estimated at about 3 nm. These results show that the strongest PL comes from a region in the PS layer where silicon nanocrystallites are surrounded by oxides with a low level of oxidation and not from the strongly oxidized surface layer.     

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     

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.     

Improvement of the luminescence in p-type as-prepared or dye impregnated porous silicon microcavities

We have realized distributed Bragg reflectors and microcavities with a remarkable optical quality (R_max.=99.5% at 850 nm, FWHM=5 nm at 772 nm) with low doped p-type silicon. This is due to a strong decrease of the porous Si/bulk Si interface roughness that was obtained by low-temperature anodization. The properties of porous silicon microcavities are investigated by photoluminescence and reflection measurements. We also have filled porous silicon with Rhodamine 800 dye. The spontaneous emission spectrum of the optically excited Rhodamine 800 is drastically modified by microcavity effect: the peak emission intensity is increased, the line width is narrowed. The results demonstrate that using all porous silicon or dye-filled microcavities provides new possibilities to improve the properties of photonic devices.     

Dislocation-related luminescence in Er-implanted silicon

The behavior of luminescence spectra and structural defects in single crystal Czochralski silicon after erbium implantation at 1–1.8 MeV energies and 1×10¹³ cm⁻² dose with subsequent annealing at 1000–1200°C for 0.25–3 h in argon and a chlorine-containing ambience (CCA) was studied by photoluminescence (PL), transmission electron microscopy and chemical etching/Nomarski microscopy. We have found that annealing in CCA gives rise to dislocation loops and pure edge dislocations with dominant dislocation-related lines in the PL spectrum. Pure edge dislocations are responsible for the appearance of the lines.     

Luminescence properties of Er in SiN/PS : Er

The decrease in luminescence from host porous silicon (PS) by thermal annealing prevents the optical activation of Er ions. We prepared a SiN layer on erbium-doped porous silicon (PS : Er) as the capping layer by photo-chemical vapor deposition (photo-CVD). After deposition of SiN, the sample was annealed in pure Ar atmosphere for optical activation. We observed an Er-related emission at 1532 nm with a full-width at half-maximum (FWHM) of 10 nm at 18 K from the sample with the SiN layer. In contrast, no emission was observed from the sample without the SiN layer. At 300 K, the peak intensity of Er³⁺-related photoluminescence (PL) for the sample annealed at 1100°C decreased to 40.0% of that observed at 18 K. From these results, it was found that the SiN layer on PS:Er is useful for both host PS and Er-related 1.5 μm luminescences.     

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.     

Nanostructural and photoluminescence features of nanoporous silicon prepared by anodic etching

The nanostructural and photoluminescence (PL) features of nanoporous Si (NPS) were investigated in terms of various process parameters such as current density, etching time and oxidation conditions. The NPS was prepared by electrochemical anodic etching of p-type (0 0 1) Si wafers of 4 Ω cm resistivity in HF solution. The pores are of polygon-type columns with 5, 6 and 7 side walls. The average diameter of the column-shaped pores is critically determined by the current density, while the etching time plays an important role on the pore depth; in particular, when the current densities of 30 and 100 mA/cm² were applied, the pore diameters were 9 nm and 3.3 μm, respectively. The variation in the PL characteristics of the NPS with oxidation condition and etching current density was measured and then related with their structural changes. The aging and thermal treatments produce oxidation and lattice distortion in the NPS. The degree of deviation from the as-prepared NPS during aging or thermal treatment seems to depend on the nanostructure as well as morphology of the NPS. It is found in this study that etching current density plays an important role on such structural features of the NPS.     

镶嵌于多孔硅微腔中8-羟基喹啉铝的窄峰发射

利用浸渍法将8羟基喹啉铝(Alq₃)镶嵌到多孔硅微腔中,制备了多孔硅微腔—Alq₃镶嵌膜,研究了多孔硅微腔对镶嵌其中的Alq₃自发发射的微腔效应,观察到了光谱窄化、发光强度增强等现象。镶嵌于多孔硅微腔中的Alq₃荧光光谱的半峰全宽只有15nm,而非微腔样品,即镶嵌于普通的单层多孔硅中Alq₃荧光谱半峰全宽在85nm以上。并且有微腔时Alq₃发光强度比没有微腔时Alq₃发光强度增强一个数量级。随机改变微腔中Bragg反射镜高折射率层的几何厚度可使高反射区展宽,从而更加有效地抑制了多孔硅本身的发光模,使发光色度更纯,但由于峰值透射率减小,导致共振峰强度有所减小。多孔硅微腔有机镶嵌膜有可能成为进一步发展Alq₃在电致发光器件方面应用的一条新途径。     

Thermal annealing dependence of some optical properties of plasma-modified porous silicon

The photoluminescence and reflectance of porous silicon (PS) with and without hydrocarbon (CH_x) deposition fabricated by plasma enhanced chemical vapour deposition (PECVD) technique have been investigated. The PS samples were then, annealed at temperatures between 200 and 800 °C. The influence of thermal annealing on optical properties of the hydrocarbon layer/porous silicon/silicon structure (CH_x/PS/Si) was studied by means of photoluminescence (PL) measurements, reflectivity and ellipsometry spectroscopy. The composition of the PS surface was monitored by transmission Fourier transform infrared (FTIR) spectroscopy. Photoluminescence and reflectance measurements were carried out before and after annealing on the carbonized samples for wavelengths between 250 and 1200 nm. A reduction of the reflectance in the ultraviolet region of the spectrum was observed for the hydrocarbon deposited polished silicon samples but an opposite behaviour was found in the case of the CH_x/PS ones. From the comparison of the photoluminescence and reflectance spectra, it was found that most of the contribution of the PL in the porous silicon came from its upper interface. The PL and reflectance spectra were found to be opposite to one another. Increasing the annealing temperature reduced the PL intensity and an increase in the ultraviolet reflectance was observed. These observations, consistent with a surface dominated emission process, suggest that the surface state of the PS is the principal determinant of the PL spectrum and the PL efficiency.     

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：     

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：     

Porous Silicon as an Intermediate Buffer Layer for Zinc Oxide Nanorods

Zinc thin films were deposited onto porous silicon (PSi) substrates by dc sputtering using a Zn target. These films were then annealed under flowing (6 l/min) oxygen gas environment in the furnace at 600°C for 2 h. Porous silicon is used as an intermediate layer between silicon and ZnO films and it provides a large area composed of an array of voids. The PSi samples were prepared using photoelectrochemical method on n-type silicon wafer with (111) and (100) orientation. To prepare porous structures, the samples were dipped into a mixture of HF:ethanol (1:1) for 5 min with current densities of 50 mA/cm², and subjected to external illumination with a 500 W UV lamp. The surface morphology and the nanorod structure of the ZnO films were characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD). We synthesized the ZnO nanorods with diameter of 80–100 nm without any catalysts or templates. The XRD pattern confirmed that the ZnO nanorods were of polycrystalline structure. The surface-related optical properties have been investigated by photoluminescence (PL) and Raman measurements at room temperature. Micro-Raman results showed that A₁(LO) of hexagonal ZnO/Si(111) and ZnO/Si(100) have been observed at 522 cm^–1 and 530 cm^–1, respectively. PL spectra peaks are clearly visible at 366 cm^–1 and 368 cm^–1 for ZnO film grown on porous Si(111) and Si(100) substrates, respectively. The PL spectral peak position in ZnO nanorods on porous silicon is blue-shifted with respect to that in unstrained ZnO (381 nm).     

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.     

硅表面硅镱键合与量子级联结构的发光

用纳秒强激光脉冲制备了纳米硅和硅表面的硅镱键合结构,检测了纳米硅表面硅镱键合的发光特性,并对这种结构相应的光致发光(PL)和电致发光(EL)的动力学机理进行了研究。观察到纳米硅表面硅镱键合在700nm附近尖锐的强发光峰,结合第一性原理计算认为是硅镱键合在弯曲纳米硅表面的局域态发光;利用纳秒脉冲激光沉积技术(PLD)制备多晶硅薄膜,发现由硅镱界面的失配形成表面的突触,其上的硅镱键合产生带隙中的电子局域态,该局域态发光分布在1250~1650nm波长范围,有增强的EL发光;用PLD方法制备硅镱多层膜量子级联结构,测量到光通信窗口的多个发光峰,并观察到随膜层数增加且发光峰增多。     

Interrelation between microstructure and optical properties of erbium-doped nanocrystalline thin films

Nanocrystalline silicon thin films codoped with erbium, oxygen and hydrogen have been deposited by co-sputtering of Er and Si. Films with different crystallinity, crystallite size and oxygen content have been obtained in order to investigate the effect of the microstructure on the photoluminescence properties. The correlation between the optical properties and microstructural parameters of the films is investigated by spectroscopic ellipsometry. PL response of the discussed structures covers both the visible wavelength range (a crystallite size-dependent photoluminescence detected for 5–6 nm sized nanocrystals embedded in a SiO matrix) and near IR range at 1.54 μm (Er-related PL dominating in the films with 1–3 nm sized Si nanocrystals embedded in a-Si:H). It is demonstrated that the different PL properties can be also discriminated on the basis of ellipsometric spectra.