Nanostructuring Si surface and Si/SiO2 interface using porous-alumina-on-Si template technology. Electrical characterization of Si/SiO2 interface

In this work, anodic porous alumina thin films with pores in the nanometer range are grown on silicon by electrochemistry and are used as masking material for the nanopatterning of the silicon substrate. The pore diameter and density are controlled by the electrochemical process. Through the pores of the alumina film chemical oxidation of the silicon substrate is performed, leading to the formation of regular arrays of well-separated stoichiometric silicon dioxide nanodots on silicon, with a density following the alumina pores density and a diameter adjustable by adjusting the chemical oxidation time. The alumina film is dissolved chemically after the SiO₂ nanodots growth, revealing the arrays of silicon dioxide dots on silicon. In a next step, the nanodots are also removed, leaving a nanopatterned bare silicon surface with regular arrays of nanopits at the footprint of each nanodot. This silicon surface structuring finds interesting applications in nanoelectronics. One such application is in silicon nanocrystals memories, where the structuring of the oxidized silicon surface leads to the growth of discrete silicon nanocrystals of uniform size. In this work, we examine the electrical quality of the Si/SiO₂ interface of a nanostructured oxidized silicon surface fabricated as above and we find that it is appropriate for electronic applications (an interface trap density below 1–3×10¹⁰ eV⁻¹ cm⁻² is obtained, indicative of the high quality of the thermal silicon oxide).     

Polaritonic and photonic gaps in SiO2/Si and SiO2/air periodic structures

The one-dimensional (1D) photonic crystals (PhC) Si/SiO₂, SiO₂/Si and SiO₂/air are studied to investigate the coexistence and interaction of polaritonic and structural gaps. Optical multilayer calculations as well as infrared reflectance measurements in the 2.7–12 μm range for relevant cases have been carried out. The samples were prepared by standard chemical vapor deposition (CVD) processes. Satisfactory agreement between experimental and calculated results was obtained without fitting. The calculated results verify the presence of a polaritonic gap for thicknesses much lower than the wavelength for the cases SiO₂/Si and SiO₂/air. Including also the case Si/SiO₂, we find the polaritonic peak can be strengthened, unchanged, or extinguished by the interaction between structural and polaritonic effects. All these predictions have been experimentally verified.     

A comparative study of electroluminescence from Ge／SiO2 and Si／SiO2 films

Ge/SiO_2 and Si/SiO_2 films were deposited using the two-target alternation magnetron sputtering technique. The Au/Ge/SiO_2/p-Si and Au/Si/SiO_2/p-Si structures were fabricated and their electroluminescence (EL) characteristics were comparatively studied. Both Au/Ge/SiO_2/p-Si and Au/Si/SiO_2/p-Si structures have rectifying property. All the EL spectra from the two types of the structure have peak positions around 650－660 nm. The EL mechanisms of the structures are discussed.     

Interfaces analysis of the HfO2/SiO2/Si structure

The physical and chemical properties of the HfO₂/SiO₂/Si stack have been analyzed using cross-section HR TEM, XPS, IR-spectroscopy and ellipsometry. HfO₂ films were deposited by the MO CVD method using as precursors the tetrakis 2,2,6,6 tetramethyl-3,5 heptanedionate hafnium—Hf(dpm)₄ and dicyclopentadienil-hafnium-bis-diethylamide—Сp₂Hf(N(C₂H₅)₂)₂.The amorphous interface layer (IL) between HfO₂ and silicon native oxide has been observed by the HRTEM method. The interface layer comprises hafnium silicate with a smooth varying of chemical composition through the IL thickness. The interface layer formation occurs both during HfO₂ synthesis, and at the annealing of the HfO₂/SiO₂/Si stack. It was concluded from the XPS, and the IR-spectroscopy that the hafnium silicate formation occurs via a solid-state reaction at the HfO₂/SiO₂ interface, and its chemical structure depends on the thickness of the SiO₂ underlayer.     

Pulsed plasma ion source to create Si nanocrystals in SiO2 substrates

A pulsed KrF excimer laser of irradiance of about 10⁸ W/cm² was utilized to synthesize Si nanocrystals on SiO₂/Si substrates. The results were compared with that ones obtained by applying low bias voltage to Si(1 0 0) target in order to control the kinetic energy of plasma ions. Glancing incidence X-ray diffraction spectra indicate the presence of silicon crystalline phases, i.e. (1 1 1) and (2 2 0), on SiO₂/Si substrates. The average Si nanocrystal size was estimated to be about 45 nm by using the Debye-Scherrer formula. Scanning electron microscopy and atomic force microscopy images showed the presence of nanoparticles of different size and shape. Their distribution exhibits a maximum concentration at 49 nm and a fraction of 14% at 15 nm.     

Electron-acoustic-phonon scattering in the quantum control of qubit states near the Si/SiO2 interface

We suggested a new mechanism for quantum control of a donor electron spin qubit state next to a Si/SiO₂ interface. The theoretical calculation results show that the shuttling time versus the donor depth (or electric field strength) exhibits a double-valley feature. The origin of the double-valley feature is discussed.     

Photoluminescence of Si from Si nanocrystal-doped SiO2/Si multilayered sample

A multilayered Si nanocrystal-doped SiO₂/Si (or Si-nc:SiO₂/Si) sample structure is studied to acquire strong photoluminescence (PL) emission of Si via modulating excess Si concentration. The Si-nc:SiO₂ results from SiO thin film after thermal annealing. The total thickness of SiO layer remains 150 nm, and is partitioned equally into a number of sublayers (N = 3, 5, 10, or 30) by Si interlayers. For each N-layered sample, a maximal PL intensity of Si can be obtained via optimizing the thickness of Si interlayer (or d_Si). This maximal PL intensity varies with N, but the ratio of Si to O is nearly a constant. The brightest sample is found to be that of N = 10 and d_Si = 1 nm, whose PL intensity is ∼5 times that of N = 1 without additional Si doping, and ∼2.5 times that of Si-nc:SiO₂ prepared by co-evaporating of SiO and Si at the same optimized ratio of Si to O. Discussions are made based on PL, TEM, EDX and reflectance measurements.     

Excess Si concentration dependence of the photoluminescence of Si nanoclusters in SiO2 fabricated by ion implantation

A method for the fabrication of luminescent Si nanoclusters in an amorphous SiO₂ matrix by ion implantation and annealing, and the detailed mechanisms for the photoluminescence are reported. We have measured the implanted ion dose, annealing time and excitation energy dependence of the photoluminescence from implanted layers. The samples were fabricated by Si ion implantation into SiO₂ and subsequent high-temperature annealing. After annealing, a photoluminescence band below 1.7 eV has been observed. The peak energy of the photoluminescence is found to be independent of annealing time and excitation energy, while the intensity of the luminescence increases as the annealing time and excitation energy increase. Moreover, we found that the peak energy of the luminescence is strongly affected by the dose of implanted Si ions especially in the high dose range. These results indicate that the photons are absorbed by Si nanoclusters, for which the band-gap energy is modified by the quantum confinement effects, and the emission is not simply due to direct electron–hole recombination inside Si nanoclusters, but is related to defects probably at the interface between Si nanoclusters and SiO₂, for which the energy state is affected by Si cluster–cluster interactions. It seems that Si nanoclusters react via a thin oxide interface and the local concentrations of Si nanoclusters play an important role in the peak energy of the photoluminescence.     

Characterization of Si nanocrystals into SiO2 matrix

Silicon nanocrystals (nc-Si) have gained great interest due to their excellent optical and electronic properties and their applications in optoelectronics. The aim of this work is the study of growth mechanism of nc-Si into a-SiO₂ matrix from SiO/SiO₂ multilayer annealing, using non-destructive and destructive techniques. The multilayer were grown by e-beam evaporation from SiO and SiO₂ materials and annealing at temperatures up to 1100 °C in N₂ atmosphere. X-rays reflectivity (XRR) and high resolution transmission electron microscopy (HRTEM) were used for the structural characterization and spectroscopic ellipsometry in IR (FTIRSE) energy region for the study of the bonding structure. The ellipsometric results gave a clear evidence of the formation of an a-SiO₂ matrix after the annealing process. The XRR data showed that the density is being increased in the range from 25 to 1100 °C. Finally, the HRTEM characterization proved the formation of nc-Si. Using the above results, we describe the growth mechanism of nc-Si into SiO₂ matrix under N₂ atmosphere.     

Photon emission from clean and oxygenated Si and SiO2 surfaces bombarded by 5 keV krypton ions

The effect of oxygen on the light emission from a Si (1 0 0) semiconductor bombarded by energetic Kr⁺ ions has been studied in the 200–300 nm wavelength range. The influence of oxygen was verified by studying the optical spectra of SiO₂ bombarded under similar experimental conditions. It has been found that the measured intensities of the emitted photons are always higher in the presence of oxygen, even higher than those obtained for SiO₂. The electron-transfer model can explain our experimental observations. We do believe that in the presence of oxygen, an intermediate structure of silicon sub-oxide SiO_X<2 is formed on silicon surface, which is responsible for the increase of photon emission. In addition, the radiative dissociation process and breaking of chemical bond seems contribute to the enhancement of emitted photons intensity.     

On the influence of the surface roughness onto the ultrathin SiO2/Si structure properties

The surface roughness of the semiconductor substrate substantially influences properties of the whole semiconductor/oxide structure. SiO₂/Si structures were prepared by using low temperature nitric acid oxidation of silicon (NAOS) method and then the whole structure was passivated by the cyanidization procedure. The influence of the surface morphology of the silicon substrate onto the electrical properties of ultrathin NAOS SiO₂ layer was investigated. Surface height function properties were studied by the AFM method and electrical properties were studied by the STM method. The complexity of analyzed surface structure was sensitive to the oxidation and passivation steps. For describing changes in the oxide layer structure, several fractal measures in an analysis of the STM images were used. This fractal geometry approach enables quantifying the fine spatial changes in the tunneling current spectra.     

Nitric acid oxidation of Si (NAOS) method for low temperature fabrication of SiO2/Si and SiO2/SiC structures

We have developed low temperature formation methods of SiO₂/Si and SiO₂/SiC structures by use of nitric acid, i.e., nitric acid oxidation of Si (or SiC) (NAOS) methods. By use of the azeotropic NAOS method (i.e., immersion in 68 wt% HNO₃ aqueous solutions at 120 °C), an ultrathin (i.e., 1.3-1.4 nm) SiO₂ layer with a low leakage current density can be formed on Si. The leakage current density can be further decreased by post-metallization anneal (PMA) at 200 °C in hydrogen atmosphere, and consequently the leakage current density at the gate bias voltage of 1 V becomes 1/4-1/20 of that of an ultrathin (i.e., 1.5 nm) thermal oxide layer usually formed at temperatures between 800 and 900 °C. The low leakage current density is attributable to (i) low interface state density, (ii) low SiO₂ gap-state density, and (iii) high band discontinuity energy at the SiO₂/Si interface arising from the high atomic density of the NAOS SiO₂ layer.For the formation of a relatively thick (i.e., ≥10 nm) SiO₂ layer, we have developed the two-step NAOS method in which the initial and subsequent oxidation is performed by immersion in ∼40 wt% HNO₃ and azeotropic HNO₃ aqueous solutions, respectively. In this case, the SiO₂ formation rate does not depend on the Si surface orientation. Using the two-step NAOS method, a uniform thickness SiO₂ layer can be formed even on the rough surface of poly-crystalline Si thin films. The atomic density of the two-step NAOS SiO₂ layer is slightly higher than that for thermal oxide. When PMA at 250 °C in hydrogen is performed on the two-step NAOS SiO₂ layer, the current-voltage and capacitance-voltage characteristics become as good as those for thermal oxide formed at 900 °C.A relatively thick (i.e., ≥10 nm) SiO₂ layer can also be formed on SiC at 120 °C by use of the two-step NAOS method. With no treatment before the NAOS method, the leakage current density is very high, but by heat treatment at 400 °C in pure hydrogen, the leakage current density is decreased by approximately seven orders of magnitude. The hydrogen treatment greatly smoothens the SiC surface, and the subsequent NAOS method results in the formation of an atomically smooth SiO₂/SiC interface and a uniform thickness SiO₂.     

Theoretical modeling of excitation and de-excitation processes of Er in SiO2 with Si nanocrystals

We construct the theory of carriers confined in Si quantum dots with finite energy barriers for electrons and holes in the framework of the multiband effective mass theory. We apply this theory for theoretical modeling of the excitation of erbium inside and outside of Si nanocrystals in SiO₂ matrix due to the Auger process induced by the recombination of a confined electron-hole pair as well as the intraband transitions of “hot” confined carriers. Auger de-excitation processes of the Er³⁺ ion leading to the quenching of erbium luminescence are discussed as well.     

Temperature dependence of compositional changes of SiO2 surface during ion and electron bombardment

The influence of ion (Ar⁺ 0.5 keV, 2 microA/cm²) and electron (2 keV, 2 mA/cm²) bombardment on the elemental composition of SiO₂ was investigated in the temperature range of 270–790 K. Elemental composition was controlled by AES. It was found that both ion and electron bombardment resulted in an increasing amount of Si₉₂ (elemental silicon) and in decreasing amounts of both O₅₁₀ and Si₇₈ (silicon bound to oxygen). The temperature influence on the composition of SiO₂ is negligible under ion bombardment while the amount of Si₉₂ strongly increases under electron bombardment at temperatures exceeding 600 K. The mechanism of temperature dependence is discussed.     

Anneal temperature dependence of Si/SiO2 superlattices photoluminescence

Photoluminescence spectroscopy, Fourier transform infrared spectroscopy, X-ray reflectometry and high resolution electron microscopy have been used to interpret the photoluminescence properties of annealed (3/19 nm) Si/SiO₂ multilayers grown by reactive magnetron sputtering. The multilayers show an emission in the visible and near-infrared range after heat treatment from 900°C which tends to decrease from 1200°C. Three different origins for the photoluminescence activity have been found. An anneal temperature of 1200°C is necessary to optimise the silicon crystallisation within the silicon sublayers.     

First-principles study of the segregation of boron dopants near the interface between crystalline Si and amorphous SiO2

We investigate the stability of boron dopants near the interface between crystalline Si and amorphous SiO₂ through first-principles density functional calculations. An interstitial B is found to be more stable in amorphous SiO₂ than in Si, so that B dopants tend to segregate to the interface. When defects exist in amorphous SiO₂, the stability of B is greatly enhanced, especially around Si floating bond defects, while it is not significantly affected near Si–Si dimers, which are formed by O-vacancy defects.     

SiO2/Si衬底上石墨烯的制备与结构表征

在分子束外延(MBE)设备中,利用直接沉积C原子的方法在覆盖有SiO₂的Si衬底(SiO₂/Si)上生长石墨烯,并通过Raman光谱和近边X射线吸收精细结构谱等实验技术对不同衬底温度(500℃,600℃,700℃,900℃,1100℃,1200℃)生长的薄膜进行结构表征.实验结果表明,在衬底温度较低时生长的薄膜是无定形碳,在衬底温度高于700℃时薄膜具有石墨烯的特征,而且石墨烯的结晶质量随着衬底温度的升高而改善,但过高的衬底温度会使石墨烯质量降低.衬底温度为1100℃时结晶质量最好.衬底温度较低时C原子活性较低,难以形成有序的C-sp²六方环.而衬底温度过高时(1200℃),衬底表面部分SiO₂分解,C原子与表面的Si原子或者O原子结合而阻止石墨烯的形成,并产生表面缺陷导致石墨烯结晶变差.     

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}     

Structural and optical properties of Si/SiO2 multi-quantum wells

Structural and optical properties of Si/SiO₂ multi-quantum wells (MQW) were investigated by means of Raman scattering and photoluminescence (PL) spectroscopy. The MQW structures were fabricated on a quartz substrate by remote plasma enhanced chemical vapour deposition (RPECVD) of alternating amorphous Si and SiO₂ layers. After layer deposition the samples were subjected to heat treatments, i.e. rapid thermal annealing (RTA) and furnace annealing. Distinct PL signatures of confined carriers evidenced formation of Si-nanocrystals (nc-Si) in annealed samples. Analyses of Raman spectra also show presence of nc-Si phase along with amorphous-Si (a-Si) phase in the samples. The strong influence of the annealing parameters on the formation of nc-Si phase suggests broad possibilities in engineering MQW with various optical properties. Interestingly, conversion of the a-Si phase to the nc-Si phase saturates after certain time of furnace annealing. On the other hand, thinner Si layers showed a disproportionately lower crystalline volume fraction. From the obtained results we could assume that an interface strain prevents full crystallization of the Si layers and that the strain is larger for thinner Si layers. The anomalous dependence of nc-Si Raman scattering peak position on deposited layer thickness observed in our experiments also supports the above assumption.     

Electric-field-controlled photoluminescence of CdSe nanocrystal-doped SiO2 on Si

Dense-packed CdSe nanoclusters synthesized by sequential ion implantation of Cd⁺ and Se⁺ in thermally grown SiO₂ are subjected to high electric field strengths in a metal oxide semiconductor (MOS) structure. The nanocrystal-containing device shows efficient CdSe band-edge photoluminescence (PL) when excited by a cw-HeCd laser operating at a wavelength of 442 nm at room temperature. An effective PL quenching and enhancement has been observed. Depth-resolved μ-PL measurements reveal an exponential decrease, which is depth-correlated with a layer of nanoparticles near the surface, whereas the optical non-linearity of the PL increases in parallel. The PL spectra and particle size distribution suggest an energy transfer from the nanoscopic to adjacent large particles. It can be concluded from these results that charge injection into the near-surface region of the nanocluster/SiO₂ system might be the reason for the asymmetric and hysteretic electro-optic response.