SiNx薄膜中硅纳米粒子的制备及表征

通过等离子增强化学气相沉积(PECVD)法, 以氨气和硅烷为反应气体, P型单晶硅和石英为衬底, 低温下(200℃)制备了含硅纳米粒子的非化学计量比氮化硅(SiN_x)薄膜. 经高温(范围500~950℃)退火处理优化了薄膜结构. 室温下测试了不同温度退火后含硅纳米粒子SiN_x薄膜的拉曼(Raman)光谱、光致发光(PL)光谱及傅立叶变换红外吸收(FTIR)光谱, 对薄膜材料的结构特性、发光特性及其键合特性进行了分析. Raman光谱表明. SiN_x薄膜内的硅纳米粒子为非晶结构. PL光谱显示两条与硅纳米粒子相关的光谱带, 随退火温度的升高此两光谱带峰位移动方向相同. 当退火温度低于800℃时, PL光谱峰位随退火温度的升高而蓝移. 当退火温度高于800℃时, PL光谱峰位随退火温度的升高而红移. 通过SiNx薄膜的三种光谱分析发现薄膜的光致发光源于硅纳米粒子的量子限制效应. 这些结果对硅纳米粒子制备工艺优化和硅纳米粒子光电器件的应用有重要意义.     

Optical property of silicon quantum dots embedded in silicon nitride by thermal annealing

We present the effects on the thermal annealing of silicon quantum dots (Si QDs) embedded in silicon nitride. The improved photoluminescence (PL) intensities and the red-shifted PL spectra were obtained with annealing treatment in the range of 700 to 1000 °C. The shifts of PL spectra were attributed to the increase in the size of Si QDs. The improvement of the PL intensities was also attributed to the reduction of point defects at Si QD/silicon nitride interface and in the silicon nitride due to hydrogen passivation effects.     

Evolution of silicon nanoclusters and hydrogen in SiNx:H films: Influence of high hydrostatic pressure under annealing

Hydrogenated silicon-rich nitride (SRN) films of various stoichiometry (SiN_x:H, 0.7 < x ≤ 1.3) were deposited on single-crystalline Si substrates with the use of plasma enhanced chemical vapor deposition at a temperature of 100 °С. Furnace annealing for 5 h in ambient Ar at 1130 °С under atmospheric and enhanced hydrostatic pressure (HP — 11 kbar, 1.1 GPa) was applied to modify the structure of the films. The properties of as-deposited and annealed films were studied using ellipsometry, Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, photoluminescence (PL), as well as high-resolution transmittance electron microscopy (HRTEM). According to the Raman data, the as-deposited film, in which the stoichiometry parameter x is below 1.0, contains amorphous silicon nanoclusters. Furnace annealing leads to crystallization of the nanoclusters. From the HRTEM and Raman data, the average size of the Si nanocrystals in the annealed films was 6-7 nm. No silicon nanoclusters were observed in the as-deposited films with relatively low concentration of excessive silicon atoms (the case of SiN_x:H, x > 1); furnace annealing leads to segregation of the Si and Si₃N₄ phases, so, the amorphous Si clusters were observed in annealed films according to Raman data. Surprisingly, after annealing with such high thermal budget, according to the FTIR data, the SRN film with parameter x close to that of the stoichiometric silicon nitride contains hydrogen in the form of SiH bonds. From analysis of the FTIR data of the SiN bond vibrations one can conclude that silicon nitride is partly crystallized in the films with x > 1 after annealing for 5 h. No influence of HP on the structure of Si nanoclusters was observed in the case of SRN films with x ≤ 1.1. Dramatic changes in the PL spectra of the SRN films with the x parameter close to that of the stoichiometric silicon nitride (x ≈ 1.3), annealed under atmospheric pressure and HP, were observed. HP stimulates the formation of very small hydrogenated amorphous nanoclusters. The size of amorphous Si nanoclusters determined from the quantum size effect model describing the PL spectra, should be 2-4 nm in this case.     

常压化学气相沉积方法制备非晶硅薄膜及其光致发光性能研究

使用改进的常压化学气相沉积(APCVD)系统制备了非晶硅薄膜,测量了样品的光致发光特性,使用Raman光谱和X射线光电子能谱(XPS)谱测量了薄膜的微结构特征.样品在523 nm出现发光峰,Raman光谱和XPS谱表明制备的薄膜结构中存在富氧相和富硅相的分相现象,分析认为相界面的存在是产生发光的原因.Raman光谱分峰结果表明薄膜中存在纳米晶粒.     

Amorphous silicon carbide thin films (a-SiC:H) deposited by plasma-enhanced chemical vapor deposition as protective coatings for harsh environment applications

We investigated amorphous silicon carbide (a-SiC:H) thin films deposited by plasma-enhanced chemical vapor deposition (PECVD) as protective coatings for harsh environment applications. The influence of the deposition parameters on the film properties was studied. Stoichiometric films with a low tensile stress after annealing (< 50 MPa) were obtained with optimized parameters. The stability of a protective coating consisting of a PECVD amorphous silicon oxide layer (a-SiO_x) and of an a-SiC:H layer was investigated through various aging experiments including annealing at high temperatures, autoclave testing and temperature cycling in air/water vapor environment. A platinum-based high-temperature metallization scheme deposited on oxidized Si substrates was used as a test vehicle. The a-SiO_x/a-SiC:H stack showed the best performance when compared to standard passivation materials as amorphous silicon oxide or silicon nitride coatings.     

Improved growth of GaN layers on ultra thin silicon nitride/Si (1 1 1) by RF-MBE

High-quality GaN epilayers were grown on Si (1 1 1) substrates by molecular beam epitaxy using a new growth process sequence which involved a substrate nitridation at low temperatures, annealing at high temperatures, followed by nitridation at high temperatures, deposition of a low-temperature buffer layer, and a high-temperature overgrowth. The material quality of the GaN films was also investigated as a function of nitridation time and temperature. Crystallinity and surface roughness of GaN was found to improve when the Si substrate was treated under the new growth process sequence. Micro-Raman and photoluminescence (PL) measurement results indicate that the GaN film grown by the new process sequence has less tensile stress and optically good. The surface and interface structures of an ultra thin silicon nitride film grown on the Si surface are investigated by core-level photoelectron spectroscopy and it clearly indicates that the quality of silicon nitride notably affects the properties of GaN growth.     

Effects of silicon nitride interlayer on phase transformation and adhesion of TiNi films

TiNi films with different Ti/Ni ratios were deposited on Si substrates with and without silicon nitride interlayer. Near-equiatomic TiNi films were found to have the lowest residual stress and the highest recovery stress regardless of the existence of silicon nitride interlayer. The addition of silicon nitride interlayer between film and Si substrate did not cause much change in phase transformation behavior as well as adhesion properties. X-ray photoelectron spectroscopy (XPS) analysis revealed that there is significant interdiffusion of elements and formation of Ti-N and Si-Si bonds at TiNi film/silicon nitride interface. Scratch test results showed that adhesion between the TiNi film and substrate was slightly improved with the increase of Ti content in TiNi films.     

Formation and photoluminescence of Si nanocrystals in controlled multilayer structure comprising of Si-rich nitride and ultrathin silicon nitride barrier layers

The effect of ultrathin silicon nitride (Si₃N₄) barrier layers on the formation and photoluminescence (PL) of Si nanocrystals (NCs) in Si-rich nitride (SRN)/Si₃N₄ multilayer structure was investigated. The layered structures composed of alternating layers of SRN and Si₃N₄ were prepared using magnetron sputtering followed by a different high temperature annealing. The formation of uniformly sized Si NCs was confirmed by the transmission electron microscopy and X-ray diffraction measurements. In particular, the 1 nm thick Si₃N₄ barrier layers was found to be sufficient in restraining the growth of Si NCs within the SRN layers upon high annealing processes. Moreover, X-ray photoelectron spectroscopy spectra shown that films subjected to post-anneal processes were not oxidized during the annealing. X-ray reflection measurements revealed that high annealing process induced low variation in the multilayer structure where the 1 nm Si₃N₄ layers act as good diffusion barriers to inhibit inter-diffusion between SRN layers. The PL emission observed was shown to be originated from the quantum confinement of Si NCs in the SRN. Furthermore, the blue shift of PL peaks accompanied by improved PL intensity after annealing process could be attributed to the effect of improved crystallization as well as nitride passivation in the films. Such multilayer structure should be advantageous for photovoltaic applications as the ultrathin barrier layer allow better electrical conductivity while still able to confine the growth of desired Si NC size for bandgap engineering.     

Crystallization behavior of silicon quantum dots in a silicon nitride matrix

Silicon quantum dot superlattice was fabricated by alternating deposition of silicon rich nitride (SRN) and Si3N4 layers using RF magnetron co-sputtering. Samples were then annealed at temperatures between 800 and 1,100 degrees C and characterized by grazing incident X-ray diffraction (GIXRD), transmission electron microscopy (TEM), Raman spectroscopy, and Fourier transform infrared spectroscopy (FTIR). GIXRD and Raman analyses show that the formation of silicon quantum dots occurs with annealing above 1,100 degrees C for at least 60 minutes. As the annealing time increased the crystallization of silicon quantum dots was also increased. TEM images clearly showed SRN/Si3N4 superlattice structure and silicon quantum dots formation in SRN layers after annealing at 1,100 degrees C for more than 60 minutes. The changes in FTIR transmission spectra observed with annealing condition corresponded to the configuration of Si-N bonds. Crystallization of silicon quantum dots in a silicon nitride matrix started stabilizing after 60 minutes' annealing and approached completion after 120 minutes'. The systematic investigation of silicon quantum dots in a silicon nitride matrix and their properties for solar cell application are presented.     

Light emitting mechanisms dependent on stoichiometry of Si-rich-SiN<Subscript>x</Subscript> films grown by PECVD

Light emission and morphology of silicon-rich silicon nitride films grown by plasma-enhanced chemical vapor deposition were investigated versus film’s stoichiometry. The excess silicon content in the films was controlled varying the NH₃/SiH₄ gas flow ratio from 0.45 up to 1.0. High-temperature annealing was employed to form the silicon quantum dots (QDs) and to enhance the photoluminescence (PL) in visible spectral range. The PL spectrum was found to be complex. The competition of five PL bands leads to the non-monotonous variation of total PL peak position in the range of 1.55–2.95 eV when the Si excess content increases. The shape of PL spectra depends also on an excitation light wavelength. It is shown that for the films fabricated with R ≤ 0.56 and R ≥ 0.67 the dominant contribution into PL spectra is given by native SiN_x defects, whereas in the films obtained with R = 0.59–0.67 the Si-QDs form the main radiative channel. The highest PL intensity is detected in Si-rich SiN_x films grown at R = 0.59–0.67 as well. PL mechanisms are discussed in terms of the contribution of different radiative channels in the light emission process that can show the ways for the optimization of SiN_x light-emitting properties.     

PECVD法氮化硅薄膜的研究

本文采用射频等离子体增强化学气相生长法（ＰＥＣＶＤ），在单晶硅衬底上生长氮化硅薄膜，经Ｘ射线衍射测试发现，在（１００）晶向硅片上生长的氮化硅薄膜为（１０１）晶向的外延生长膜。还用红外吸收光谱拉曼光谱和Ｘ射线光电子能谱测试了β－Ｓｉ３Ｎ４的特性，讨论了它在微电子学中的应用。     

周期性梯度富硅SiNx薄膜的微结构与发光特性

采用磁控共溅射结合快速光热退火技术在单晶硅和石英衬底上制备了含硅量子点的周期性梯度富硅SiN_x薄膜(梯度薄膜)和单层富硅SiN_x薄膜(单层薄膜)。采用Raman光谱、掠入射X射线衍射(GIXRD)、透射电子显微镜(TEM)、傅里叶变换红外(FTIR)光谱和光致发光(PL)光谱分析了薄膜的结构特性、键合特性和发光特性。Raman光谱、GIXRD和TEM结果表明, 梯度薄膜和单层薄膜中的硅量子点晶化率分别为41.7%和39.2%; 梯度薄膜的硅量子点密度是单层薄膜的5.4倍。FTIR光谱结果显示两种薄膜均为富硅氮化硅薄膜, 梯度薄膜的硅含量小于单层薄膜。PL光谱结果表明梯度薄膜中的辐射复合缺陷少于单层薄膜。     

Photoluminescence from intermediate phase silicon structure and nanocrystalline silicon in plasma enhanced chemical vapor deposition grown Si/SiO(2) multilayers

Amorphous Si/SiO(2) multilayers (MLs) on silicon wafers were fabricated in a plasma enhanced chemical vapor deposition system via cycles of silicon deposition and plasma oxidation. The structural and optical properties of the MLs were characterized using transmission electron microscopy, Raman scattering and room temperature photoluminescence (PL) measurements. Intermediate phase silicon structure (IPSS), which is intermediate in order between the continuous random network amorphous phase and the well ordered crystalline phase, was found in the a-Si sublayers around the crystallization onset temperature. Red-near infrared wavelength region PL from recombination via structural defects inside the IPSS and Si = O at the surface of both nanocrystal Si (nc-Si) and IPSS was observed. In the samples with IPSS and nc-Si coexisting, the IPSS was found to be about five times more efficient as regards PL than nc-Si.     

Si-rich a-SiC:H thin films: Structural and optical transformations during thermal annealing

Amorphous hydrogenated silicon-rich silicon carbide (a-Si_0.8C_0.2:H) thin films were prepared by plasma enhanced chemical vapour deposition and were thermally annealed in a conventional resistance heated furnace at annealing temperatures up to 1100 °C. The annealing temperatures were varied and the samples were characterised with Auger electron spectroscopy, glancing incidence X-ray diffraction, Raman spectroscopy, Fourier transformed infrared spectroscopy, transmission electron microscopy and photoluminescence (PL) spectroscopy. As-deposited a-Si_0.8C_0.2:H thin films contain a large amount of hydrogen and are amorphous. When annealing the films, the onset of Si crystallisation appears at 700 °C. For higher annealing temperatures, we observed SiC crystallites in addition to the Si nanocrystals (NCs). The crystallisation of SiC correlates with the occurrence of a strong PL band, which is strongly reduced after hydrogen passivation. Thus PL signal originates from the SiC matrix. Si NCs exhibit no PL yield due to their inhomogeneous size distribution.     

Highly Porous Silicon Membranes Fabricated from Silicon Nitride/Silicon Stacks

Nanopore formation in silicon films has previously been demonstrated using rapid thermal crystallization of ultrathin (15 nm) amorphous Si films sandwiched between nm‐thick SiO₂ layers. In this work, the silicon dioxide barrier layers are replaced with silicon nitride, resulting in nanoporous silicon films with unprecedented pore density and novel morphology. Four different thin film stack systems including silicon nitride/silicon/silicon nitride (NSN), silicon dioxide/silicon/silicon nitride (OSN), silicon nitride/silicon/silicon dioxide (NSO), and silicon dioxide/silicon/silicon dioxide (OSO) are tested under different annealing temperatures. Generally the pore size, pore density, and porosity positively correlate with the annealing temperature for all four systems. The NSN system yields substantially higher porosity and pore density than the OSO system, with the OSN and NSO stack characteristics fallings between these extremes. The higher porosity of the Si membrane in the NSN stack is primarily due to the pore formation enhancement in the Si film. It is hypothesized that this could result from the interfacial energy difference between the silicon/silicon nitride and silicon/silicon dioxide, which influences the Si crystallization process.     

Optical properties of nano-silicon

We investigated the optical properties of silicon clusters and Si nanocrystallites using photolumine-scence (PL) and Raman scattering technique. Broad luminescence band in the red region was observed from Si-doped SiO₂ thin films deposited by co-sputtering of Si and SiO₂ onp-type Si (100) substrates, annealed in Ar and O₂ atmosphere. Nanocrystalline Si particles fabricated by pulsed plasma processing technique showed infrared luminescence from as grown film at room temperature. Raman spectra from these films consisted of broad band superimposed on a sharp line near 516 cm⁻¹ whose intensity, frequency, and width depend on the particle sizes arising from the phonon confinement in the nanocrystalline silicon. We also performed PL, Raman and resonantly excited PL measurements on porous silicon film to compare the optical properties of Si nanostructures grown by different techniques. An extensive computer simulation using empirical pseudo-potential method was carried out for 5–18 atoms Si clusters and the calculated gap energies were close to our PL data. Paper presented at the 5th IUMRS ICA98, October 1998, Bangalore.     

Electroluminescence microspectroscopy of silicon nanocrystals obtained by Si(+) ion implantation in SiO(2)

Room-temperature electroluminescence (EL) has been measured at both macroscopic and microscopic levels from metal-oxide-semiconductor devices containing silicon nanocrystals (Si-nc) embedded in silicon dioxide (SiO(2)) obtained by high-temperature annealing (1050 and 1100?°C) after Si(+) ion implantation. It is found that spatially integrated (macroscopic) EL is dominated by a near-infrared band centered where the photoluminescence (PL) band of Si-nc (from 700 to 1000?nm) is located. However, on a microscopic scale, EL emission is inhomogeneous, the sample surface exhibiting many visible spots of micron-order diameter. EL spectra from a microscopic surface of ～1?μm(2)(μEL) on visible spots have revealed dominant contributions between ～550 and ～650?nm, attributed to oxide defects. These spectral features rapidly decrease with distance from a bright spot, while lower-intensity near-infrared contributions (750-950?nm) remain unaffected up to relatively large distances before eventually becoming extinct. The macroscopic EL measurements can be explained as a superposition of the μEL and PL spectra. A luminescent mechanism is proposed in which charge carriers mostly tunnel through high-defect-density channels in the oxide, yielding bright visible spots, while Si-nc in these channels and their surroundings contribute to the luminescence by hosting electron-hole recombinations (EL) and/or exhibiting PL due to optical excitation from the nearby visible EL spot.     

Evaluation of the radiative recombination mechanism in Si nanocrystals embedded in Silica matrix

We report measurements of the temperature dependence of photoluminescence (PL) life-time and efficiency of Si nanocrystals (Si-Nc) embedded in silica matrix. We use a practical technique based on lock-in acquisition that allows us to simultaneously evaluate, at each emission-energy, intensity and decay-time of the detected signal. Samples are prepared by Silicon-ion implantation in a SiO2 layer followed by thermal annealing. The implantation dose of Si ions ranges between 2 x 10(16) cm-2 and 2 x 10(17) cm(-2). Intensity of Si-Nc PL shows the characteristic rising by increasing the temperature up to approximately 100 K followed by a flattening or a weak reduction up to room temperature. This behaviour reveals a population of radiative states built up by a thermally activated process. Similarly, the measured PL decay-rate is not constant with temperature but shows evidence of a thermal activation. By measuring on different samples the activation energies Ea involved in the temperature dependence of PL intensity and decay time we verify that in all these processes Ea is a decreasing function of implantation dose (i.e., of crystallite size). This result is consistent with models connecting radiative recombination to excitons confined inside Si-Nc, in seeming contrast with the common attribution of PL of non-passivated Si-Nc to the recombination from surface/interface states. To verify the consistency of this statement, we have compared our experimental data with the predictions of quantum confinement theory obtaining an excellent agreement.     

Infrared and raman spectroscopic studies of optically transparent zirconia (ZrO2) films deposited by plasma-assisted reactive pulsed laser deposition

Plasma-assisted pulsed laser deposited zirconia (ZrO(2)) films were studied by Fourier transform infrared (FT-IR) and Raman spectroscopy for structural characterization and thermal stability in combination with optical characterization by spectroscopic ellipsometry and optical transmission measurements. Only the monoclinic ZrO(2) phase was positively identified from the infrared and Raman spectra of the as-deposited ZrO(2) films, which show excellent optical transparency from the ultraviolet to the near infrared as revealed by optical characterization. The as-deposited ZrO(2) films are free of any SiO(x) interfacial layer when deposited on silicon. The prepared ZrO(2) films exhibit good thermal stability in their structural, optical, and interfacial properties up to 900 °C. Upon annealing above 1100 °C, a silicon oxide interfacial layer forms due to the oxidation of the silicon substrate surface by the oxygen diffused from the oxide film to the silicon substrate at high temperatures.     

The structure of Si-SiO2 layers with high excess Si content prepared by magnetron sputtering

Si-SiO₂ layers with high excess Si content prepared by magnetron co-sputtering of Si and SiO₂ and subsequently annealed were studied by electron paramagnetic resonance and photoluminescence methods. It was shown that adding oxygen during the deposition run or aging in air of as-deposited films influences the characteristics of the oxide layer surrounding the silicon crystallites. It was found that for layers with more than 55 vol.% of excess silicon the silicon crystallites are oriented. After high-temperature annealing not all the excess silicon was in crystalline form but part of it was in the amorphous phase. The depth distribution of the crystallites was found to be homogeneous while the distribution of amorphous silicon has a maximum around the middle of the layer.