Multipeak-structured photoluminescence mechanisms of as-prepared and oxidized Si nanoporous pillar arrays

Silicon dominates the electronic industry, but its poor optical properties mean that it is not preferred for photonic applications. Visible photoluminescence (PL) was observed from porous Si at room temperature in 1990, but the origin of these light emissions is still not fully understood. This paper reports that an Si nanocrystal, silicon nanoporous pillar array (Si-NPA) with strong visible PL has been prepared on a Si wafer substrate by the hydrothermal etching method. After annealing in O₂ atmosphere, the hydride coverage of the Si pillar internal surface is replaced by an oxide layer, which comprises of a great quantity of Si nanocrystal (nc-Si) particles and each of them are encapsulated by an Si oxide layer. Meanwhile a transition from efficient triple-peak PL bands from blue to red before annealing to strong double-peak blue PL bands after annealing is observed. Comparison of the structural, absorption and luminescence characteristics of the as-prepared and oxidized samples provides evidence for two competitive transition processes, the band-to-band recombination of the quantum confinement effect of nc-Si and the radiative recombination of excitons from the luminescent centres located at the surface of nc-Si units or in the Si oxide layers that cover the nc-Si units because of the different oxidation degrees. The sizes of nc-Si and the quality of the Si oxide surface are two major factors affecting two competitive processes. The smaller the size of nc-Si is and the stronger the oxidation degree of Si oxide layer is, the more beneficial for the luminescent centre recombination process to surpass the quantum confinement process is. The clarification on the origin of the photons may be important for the Si nanoporous pillar array to control both the PL band positions and the relative intensities according to future device requirements and further fabrication of optoelectronic nanodevices.     

Chemical Structures of the SiO2Si Interface

As a result of considerable progress in microfabrication technology for ultra-large scale integration (ULSI), it has become necessary to control oxide formation on an atomic scale in order to produce defect-free SiO₂/Si interfaces. However, the possibility of forming an atomically flat interface by oxidizing an atomically flat silicon surface without introducing structural defects is not yet clarified. In this article the present understanding of chemical structures of SiO₂/Si interfaces and initial stage of oxidation of silicon surfaces are reviewed.     

Patterning on single crystalline silicon by laser scanning and alkaline etching

The applicability of laser processing for small-lot micro-electromechanical system devices is discussed in this paper. This simple process could replace conventional complex processes designed with mass production in mind. Ablation, protrusions or surface modification is revealed to occur by argon ion laser scanning into silicon. Which of them occurs depends on the laser power. It is found that the protrusions are covered by a thin layer of oxide; however, oxidation of the modified surface is not established even though some results suggest it. Surface modification is more applicable to surface patterning than coarse protrusion is because the laser-modified surface can be used as a mask in KOH etching to make sharp patterns. The applicability of this method is indicated by demonstrating pattern width control, patterning over a large area and the fabrication of a 16-bit linear scale.     

Transient-enhanced Si diffusion on natural-oxide-covered Si(0 0 1) nano-structures during vacuum annealing

The morphology of annealed patterned Si(0 0 1) wire templates was studied by several techniques. We found an enormous Si-mass transport on the Si surface at usual oxide desorption temperatures around 900°C under UHV conditions. Heat treatment of 5 min transforms the initially rectangular wire profiles with a height of 300 nm to flat (<100 nm) and faceted triangular ridges exhibiting thermodynamically preferred {1 1 1}- and {3 1 1}-facets.It was found that the natural SiO₂ on the predefined wire pattern must be responsible for the degradation of the wire structure. Removing the SiO₂ layer from the Si wires ex situ with an HF dip preserves the rectangular structures during high-temperature annealing. The Si–SiO₂ interface was investigated with high-resolution transmission electron microscopy to image the Si wire surface and the natural oxide layer in detail.     

Rapid fabrication of microhole array structured optical fibers

A microhole array in a common single-mode fiber is fabricated by selective chemical etching of femtosecond-laser-induced fiber Bragg grating (FBG), which has a laser-modified region extending from the fiber core to the cladding-air boundary due to laser self-focusing. The shape and size of the orderly microhole on the fiber surface are controlled via changing conditions of FBG fabrication and chemical etching. A simultaneous sensing for surrounding refractive index and temperature is demonstrated by this microhole array FBG through measurement of the transmission power change and Bragg resonant wavelength shift.     

Ag growth on Si(111) with an Sb surfactant investigated by scanning tunneling microscopy

We have investigated a room-temperature growth mode of ultrathin Ag films on a Si(111) surface with an Sb surfactant using STM in a UHV system. On the Sb-passivated Si surface, small sized islands were formed up to 1.1 ML. Flat Ag islands were dominant at 2.1 ML, coalescing into larger islands at 3.2 ML. Although the initial growth mode of Ag films on the Sb-terminated Si(111) surface was Volmer-Weber (island growth), the films were much more uniform than Ag growth on clean (Si(111) at the higher coverages. From the analysis of STM images of Ag films grown with and without an Sb surfactant, the uniform growth of Ag films using an Sb surfactant appears to be caused by the kinetic effects of Ag on the preadsorbed Sb layer. Our STM results indicated that Sb suppresses the surface diffusion of Ag atoms and increases the Ag-island density. The increased island density is believed to cause coalescence of Ag islands at higher coverages of Ag, resulting in the growth of atomically flat and uniform Ag islands on the Sb surfactant layer.     

First-principles molecular-dynamics study of native oxide growth on Si(001)

Through first-principles molecular dynamics we study the low-temperature oxidation of the Si(001) surface from the initial adsorption of an O2 molecule to the formation of a native oxide layer. Peculiar features of the oxidation process are the early, spontaneous formation of Si4+ species, and the enhanced reactivity of the surface while the reactions proceed, until saturation is reached at a coverage of 1.5 ML. The channels for barrierless oxidation are found to be widened in the presence of both boron and phosphorous impurities.     

Evidence of SiO at the Si-oxide interface by surface soft X-ray absorption near edge spectroscopy

Using synchrotron radiation a new surface sensitive spectroscopy has been applied to determine the local structure of the first surface oxide layer formed on the Si(111) surface. The Surface Soft X-ray Absorption (SSXA) spectra have been measured. From the analysis of the X-ray Absorption Near Edge Structures (XANES) we have extracted structural information. We have first determined that bulk amorphous SiO has a characteristic microsopic structure, which cannot be described by the random alloy or microcrystalline (Si + SiO₂) mixture models. The oxide layer formed on the Si(111) surface by ground-state molecular excitation in ultra high vacuum at temperatures (～700°C) approaching the oxide dissociation point has this unique SiO local structure. Such SiO layer not formed at room temperature is expected to be present in the SiSiO₂ interface grown at high temperature. An electronic transition to empty states at the SiSiO₂ interface has been observed.     

Influence of the thickness of the tunnel layer on the charging characteristics of Si nanocrystals embedded in an ultra-thin SiO2 layer

In this paper, we have studied the effect of the thickness of the initial SiO₂ layer (5–7 nm) on the charge and discharge properties of a 2D array of Si nanoparticles embedded in these SiO₂ layers fabricated by ultra-low-energy ion implantation (ULE-II) and annealing. The structural characteristics of these nanocrystal-based memories (position of the nanocrystals with respect to the electrodes, size and surface density of the particles in the plane) were studied by transmission electron microscopy (TEM) and energy filtered TEM (EF-TEM). Electrical characterizations were performed at room temperature using a nano-MOS capacitor to be able to address only a few nanoparticles (nps). EFTEM gives the measurements of oxide thickness, injection, control and nps distances, size and density. I–V and I–t measurements exhibit current peaks and random telegraph signal fluctuations that can be interpreted as due to quantized charging of the nps and to some electrostatic interactions between the trapped charges and the tunnelling current. We have shown that these characteristics strongly vary with the initial oxide thickness, exhibiting several charging/discharging events for the 7-nm-thick layer while charging events prevail in the case of 5-nm-thick layer. These results indicate that the probability of discharging phenomena is reduced when the tunnel layer thickness decreases.     

Photoemission electron microscopy study of anthracene growth on Si(1 1 1)

The thin film growth of anthracene films on Si(1 1 1) surfaces is studied by photoemission electron microscopy (PEEM). The thin film growth of anthracene on Si(1 1 1) is similar to the growth of pentacene on silicon. Initially a layer of flat lying molecules chemisorbs on the surface. Subsequent growth of fractal islands with standing up molecules proceeds on top of this flat layer.     

硅表面抗反射纳米周期阵列结构的纳米压印制备与性能研究

硅表面固有的菲涅耳反射, 使得硅基半导体光电器件(如太阳能电池、红外探测器)表面有30%以上的入射光因反射而损失掉, 严重影响着器件的光电转换效率. 寻找一种方法降低硅基表面的反射率, 进而提高器件的效率成为近年来研究的重点.本文基于纳米压印光刻技术, 在2 英寸单晶硅表面制备出周期530 nm, 高240 nm的二维六角截顶抛面纳米柱阵列结构. 反射率的测试表明, 当入射光角度为8° 时, 有纳米结构的硅片相对于无纳米 结构的硅片来讲, 在400到2500 nm波长范围内的反射率有很明显的降低, 其中, 800到2000 nm波段的反射率都小于10%, 在波长1360 nm附近的反射率由31%降低为零. 结合等效介质理论和严格耦合波理论对结果进行了分析和验证. 关键词： 纳米压印 截顶抛物面阵列 抗反射 等效介质理论     

Structural investigations of silicon nanostructures grown by self-organized island formation for photovoltaic applications

The self-organized growth of crystalline silicon nanodots and their structural characteristics are investigated. For the nanodot synthesis, thin amorphous silicon (a-Si) layers with different thicknesses have been deposited onto the ultrathin (2 nm) oxidized (111) surface of Si wafers by electron beam evaporation under ultrahigh vacuum conditions. The solid phase crystallization of the initial layer is induced by a subsequent in situ annealing step at 700 °C, which leads to the dewetting of the initial a-Si layer. This process results in the self-organized formation of highly crystalline Si nanodot islands. Scanning electron microscopy confirms that size, shape, and planar distribution of the nanodots depend on the thickness of the initial a-Si layer. Cross-sectional investigations reveal a single-crystalline structure of the nanodots. This characteristic is observed as long as the thickness of the initial a-Si layer remains under a certain threshold triggering coalescence. The underlying ultra-thin oxide is not structurally affected by the dewetting process. Furthermore, a method for the fabrication of close-packed stacks of nanodots is presented, in which each nanodot is covered by a 2 nm thick SiO₂ shell. The chemical composition of these ensembles exhibits an abrupt Si/SiO₂ interface with a low amount of suboxides. A minority charge carrier lifetime of 18 µs inside of the nanodots is determined.     

Features of atomic and electronic structure of oxides on porous silicon surface according to XANES data

Based on synchrotron research of the fine structure main parameters of SiL _{2, 3} X-ray absorption edges (X-ray absorption near edge structure (XANES)) in porous silicon on boron-doped Si(100) wafers, the thickness of the surface oxide layer and the degree of distortions of the silicon-oxygen tetrahedron in this layer were estimated. The thickness of the oxide layer formed on the amorphous layer coating nanocrystals of porous silicon exceeds the thickness of the native oxide on the surface of Si(100) : P and Si(100) : B single-crystal (100) silicon wafers by several times. Distortion of the silicon-oxygen tetrahedron, i.e., the basic unit of silicon oxide, is accompanied by Si-O bond stretching and an increase in the angle between Si-O-Si bonds.     

Low energy alkali ion scattering investigation of Au nanoclusters grown on silicon oxide surfaces

The atomic and electronic structures of Au nanostructures grown by deposition onto various silicon oxide surfaces were probed with low energy alkali ion scattering. Charge state-resolved time-of-flight spectra of scattered 2 keV ³⁹K⁺ ions were collected from Au deposited onto an untreated Si wafer with a native oxide, a thermally grown oxide surface, and atomically-clean Si(111). It is shown that nanoclusters form on both oxides, but not on the clean Si. A quantitative analysis of the ion scattering spectra indicates that the nanoclusters are initially flat, two-dimensional structures that start to develop a second layer at about 0.5 Å of deposited Au and then form three-dimensional islands. The neutral fraction of scattered 2 keV ³⁹K⁺ ions decreases with deposition indicating changes in the quantum state occupancy with cluster size. The shapes of the clusters differ on the native and thermal oxides, leading to shape-dependent neutralization.     

Interaction of iron atoms with the silicon surface coated with a native oxide layer

The solid-phase epitaxy of iron silicide on the Si(111) surface coated with a native oxide layer is studied by high-resolution photoelectron spectroscopy using synchrotron radiation and by atomic force microscopy. The iron deposition dose changes up to 1 nm, and the annealing temperature changes up to 500°C. At room temperature, the native oxide layer is shown to be impermeable to Fe atoms and an iron film grows on the sample surface. An increase in the annealing temperature to ～100°C results in a change in the film morphology, increasing its heterogeneity. As the annealing temperature increases to ～250°C, Fe and Si atoms diffuse through the oxide layer and undergo a solid-phase reaction. As a result, stable iron monosilicide ?-FeSi forms.     

An AFM study of the processing of hydrogen passivated silicon(1 1 1) of a low miscut angle

We present atomic force microscopy (AFM) measurements from a passivated silicon crystal miscut by 0.1° and show the etching regime to be significantly different from surfaces with a larger miscut angle. A simple kinetic model is developed to explain the results and is used to derive the optimal etching conditions for nominally flat Si(1 1 1)–(1×1)H. We show that small changes in miscut angle can alter the kinetic steady state and promote the formation of deep etch pits, even on the least stable, miscut surface. Collisions of steps with these pits result in arrays of stable, self-aligned ‘etch hillocks' over micron dimensions. Following preparation, we use AFM to observe the initial growth of native oxide on the Si(1 1 1)–(1×1)H surface, and demonstrate that AFM is a sensitive probe to surface oxidation in the sub-monolayer regime.     

Structural and optical properties of metastable SiGe/Si films with a low germanium concentration

The properties of metastable Si_{1 ? x} Ge _x /Si (10% < x < 16%) layers grown by molecular beam epitaxy on Si(100) substrates have been investigated using atomic force microscopy, X-ray diffraction, and low-temperature luminescence spectroscopy. It has been shown that ring-like aggregates are formed on the surface of layers grown at temperatures of 500–700°C. The size and shape of these aggregates suggest that their formation is associated with the diffusion instability arising due to the existence of a relationship between the surface diffusion, stresses, and the wetting potential during the growth of the epitaxial film. The existence of deviations from the homogeneous germanium distribution in the layer plane has been confirmed by a detailed analysis of the X-ray rocking curves and two-dimensional diffraction patterns. The structures with severe surface disturbances are characterized by an abnormal change in the decay times of the emission lines of bulk silicon, which indicate the presence of local electric and/or strain fields in subsurface regions. The perturbations of the flat crystallization front are suppressed as the growth temperature of layers decreases to 350°C. Despite the absence of a coating layer of silicon, the photoluminescence spectra of the layers themselves depend weakly on their thickness and growth temperature and remain sensitive only to the technological concentration of germanium. A slowly decaying luminescence associated presumably with the localization of excitons near the SiGe-Si interface has been observed in one of the samples grown at a temperature of 700°C and containing a dense array of ring-like aggregates.     

Highly resolved scanning tunneling microscopy study of Si(0 0 1) surfaces flattened in aqueous environment

A surface preparation method with fine SiO₂ particles in water is developed to flatten Si(0 0 1) surfaces on the nanometer scale. The flattening performance of Si(0 0 1) surfaces after the surface preparation method is investigated by scanning tunneling microscopy. The observed surface is so flat that 95% of the view area (100 × 100 nm²) is composed of only three atomic layers, namely, one dominant layer occupying 50% of the entire area and two adjacent layers. Furthermore, a magnified image shows the outermost Si atoms regularly distributed along the 〈1 1 0〉 direction on terraces.     

(100) and (110) SiSiO2 interface studies by MeV ion backscattering

Thin oxide layers on (110) and (100) Si have been studied by ion scattering experiments in a channeling grazing exit angle geometry. Oxides are found to be stoichiometric SiO₂ to within 10 Å of the (100) substrate surface, and 7 Å of the (110). The transition interface region between single crystal Si and the SiO₂ layer is abrupt and is characterized by approximately one to two monolayers of Si which is out of registration with the substrate lattice for the (110) case. The possibility of a layer of O-deficient oxide is also explored.