nc-Si/SiO2多层膜的制备及蓝光发射

在等离子体增强化学气相淀积(PECVD)系统中，采用a-Si∶H层淀积与原位等离子体氧化相结合的逐层生长的方法成功制备出a-Si∶H/SiO2多层膜 (ML)；利用限制性结晶原理通过两步退火处理使a-Si∶H层晶化获得尺寸可控的nc-Si/SiO2 ML，并观察到室温下的蓝光发射；结合Raman散射和剖面透射电子显微镜技术分析了nc-Si/SiO2 ML的结构特性；通过对晶化样品光致发光谱和紫外-可见光吸收谱的研究，探讨了蓝光发射的起源. 关键词： 纳米硅多层膜 等离子体氧化 蓝光发射 热退火     

Nanocrystalline silicon films prepared by laser—induced crystallization

The excimer laser-induced crystallization technique has been used to investigate the preparation of nanocrystalline silicon (nc-Si) from amorphous silicon ($\al$-Si) thin films on silicon or glass substrates. The $\al$-Si films without hydrogen grown by pulsed-laser deposition are chosen as precursor to avoid the problem of hydrogen effluence during annealing. Analyses have been performed by scanning electron microscopy, atomic force microscopy, Raman scattering spectroscopy and high-resolution transmission--electron microscopy. Experimental results show that silicon nanocrystals can be formed through laser annealing. The growth characters of nc-Si are strongly dependent on the laser energy density. It is shown that the volume of the molten silicon predominates essentially the grain size of nc-Si, and the surface tension of the crystallized silicon is responsible for the mechanism of nc-Si growth.     

低温铝诱导晶化制备纳米晶硅薄膜的物相和光学性能研究

采用射频磁控溅射镀膜系统,在玻璃衬底上制备了非晶硅(α-Si)/铝(Al)复合薄膜,结合氮气(N₂)气氛中低温快速光热退火制备了纳米晶硅(nc-Si)薄膜;利用光学显微镜、共焦光学显微仪、X射线衍射(XRD)仪、拉曼散射光谱(Raman)仪和紫外-可见光-近红外分光光度计(UV-VIS-NIR)对纳米晶硅薄膜的表面形貌、物相及光学性能进行了表征,研究了退火工艺对薄膜性能的影响。结果表明： 300 ℃,25 min光热退火可使α-Si/Al膜晶化为纳米晶硅薄膜,晶化率为15.56%,晶粒尺寸为1.75 nm;退火温度从300 ℃逐渐升高到400 ℃,纳米晶硅薄膜晶粒尺寸、晶化率、带隙逐渐增加,表面均匀性、晶格畸变量逐渐减小;退火温度从400 ℃逐渐升高到500 ℃,纳米晶硅薄膜的晶粒尺寸、晶化率继续增加,带隙则逐渐降低;采用纳米晶硅薄膜的吸光模型验证了所制备的纳米晶硅薄膜的光学特性,其光学带隙的变化趋势与吸光模型得出的结果一致。     

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.     

溅射气氛和退火方式对硅纳米晶的形成及发光特性的影响

利用磁控溅射技术溅射硅靶,通过调节溅射气氛在硅衬底上生长了SiO/SiO₂超晶格,热退火处理后超晶格中的SiO发生相分离得到硅纳米晶。通过比较不同退火方式对于硅纳米晶的形成的影响发现,管式炉退火处理的样品给出非常强的室温光致发光,其发光峰的峰位随着硅纳米晶尺寸的增大而红移,且管式炉退火比快速热退火更有利于硅纳米晶的形成。     

激光限制结晶技术制备nc-Si/SiO2多层膜

在等离子体增强化学气相淀积系统中，采用aSi:H层淀积和原位等离子体氧化相结合的逐层生长技术制备了aSi:H/SiO_2多层膜.在激光诱导限制结晶原理基础上，使用KrF准分子脉冲激光为辐照源，对aSi:H/SiO_2多层膜进行辐照，使纳米级厚度的aSi:H子层晶化.Raman散射谱和电子衍射谱的结果表明，经过激光辐照后纳米Si颗粒在原始的aSi:H子层内形成，晶粒尺寸可以根据aSi:H层的厚度精确控制.还研究了样品的光致发光（PL）特性以及激光辐照能量密度对PL性质的影响. 关键词： 脉冲激光 多层膜 限制结晶     

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.     

Charge storage characteristics of hydrogenated nanocrystalline silicon film prepared by rapid thermal annealing

The early stages of hydrogenated nanocrystalline silicon (nc-Si:H) films deposited by plasma-enhanced chemical vapour deposition were characterized by atomic force microscopy. To increase the density of nanocrystals in the nc-Si:H films, the films were annealed by rapid thermal annealing (RTA) at different temperatures and then analysed by Raman spectroscopy. It was found that the recrystallization process of the film was optimal at around 1000℃. The effects of different RTA conditions on charge storage were characterized by capacitance--voltage measurement. Experimental results show that nc-Si:H films obtained by RTA have good charge storage characteristics for nonvolatile memory.     

Ce3+注入对不同尺寸的nc-Si/SiO2 超晶格发光特性的影响

通过电子束蒸发方法以及高温退火处理,得到nc-Si/SiO₂超晶格。将样品分别注入剂量为2.0×10¹⁴ cm^-2和2.0×10¹⁵ cm^-2的Ce³⁺,再对其进行二次退火处理,获得多组样品。通过对样品光致发光光谱的分析发现,样品发光强度的变化不仅受到Ce³⁺注入剂量的影响,而且也受到nc-Si颗粒大小的影响。在相同注入计量和相同的二次退火处理温度下,nc-Si颗粒较大的样品经Ce³⁺注入后其发光强度增强较为明显。     

掺铒硅基材料发光的新途径

关键词：     

The charge storage of the nc—Si layer

Sandwiched structures (a-SiN_x/a-Si/a-SiN_x) have been fabricated by the plasma enhanced chemical vapour deposition technique. A Si nanocrystal (nc-Si) layer was formed by crystallization of an a-Si layer according to the constrained crystallization principle after quasi-static thermal annealing at 1100℃ for 30 min. Transmission electron microscopy (TEM) and Raman scattering spectroscopy clearly demonstrated that nc-Si grains were formed in the as-deposited a-Si layer after annealing. The density of nc-Si grains is about 10¹¹cm^-2 as shown by TEM photographs. Using capacitance－voltage (C－V) measurements we investigated the electrical characteristics of the sandwiched structures. The charge storage phenomenon of the nc-Si layer was observed from the shift of flat-band voltage (V_FB) in C－V curves at a high frequency (1 MHz). We estimated the density of nc-Si grains to be about 10¹¹cm^-2 from the shift value of V_FB, which is in agreement with the result of TEM photographs. At the same time, we found that the shift of V_FB increased with the increase of the applied constant dc voltage or the thickness of the nc-Si layer.     

The origin of blue photoluminescence from nc-Si/SiO2 multilayers

Intensive blue photoluminescence (PL) was observed at room temperature from the nanocrystalline-Si/SiO$_{2}$ (nc-Si/SiO$_{2})$ multilayers (MLs) obtained by thermal annealing of SiO/SiO$_{2}$\,MLs for the first time. By controlling the size of nc-Si formed in SiO sublayer from 3.5 to 1.5 nm, the PL peak blueshifts from 457 to 411 nm. Combining the analysis of TEM, Raman and absorption measurement, this paper attributes the blue PL to multiple luminescent centres at the interface of nc-Si and SiO$_{2}$.     

Annealing effects on residual stress of HfO2/SiO2 multilayers

HfO2/SiO2 multilayer films were deposited on BK7 glass substrates by electron beam evaporation method.The effects of annealing at the temperature between 200 and 400℃ on residual stresses have been studied.It is found that the residual stress of as-deposited HfO2/SiO2 multilayers is compressive.It becomes tensile after annealing at 200℃,and then the value of tensile stress increases as annealing temperature increases.And cracks appear in the film because tensile stress is too large when the sample is annealed at 400℃.At the same time,the crystallite size increases and interplanar distance decreases with the increase of annealing temperature.The variation of residual stresses is corresponding with the evolution of structures.     

Resonant Tunnelling and Storage of Electrons in Si Nanocrystals within a-SiNx/nc-Si/a-SiNx Structures

The a-SiNx/nanocrystalline silicon （nc-Si）/a-SiNx sandwiched structures with asymmetric double-barrier are fabricated in a plasma enhanced chemical vapour deposition （PECVD） system on p-type Si substrates. The nc-Si layer in thickness 5nm is fabricated from a hydrogen-diluted silane gas by the layer-by-layer deposition technique. The thicknesses of tunnel and control SiNx layers are 3nm and 20nm, respectively. Frequency-dependent capacitance spectroscopy is used to study the electron tunnelling and the storage in the sandwiched structures. Distinct frequency-dependent capacitance peaks due to electrons tunnelling into the nc-Si dots and capacitance-voltage （C - V） hysteresis characteristic due to electrons storage in the nc-Si dots are observed with the same sample. Moreover, conductance peaks have also been observed at the same voltage region by conductance-voltage （G - V） measurements. The experimental results demonstrate that electrons can be loaded onto nc-Si dots via resonant tunnelling and can be stored in our a-SiNx/nc-Si/a-SiNx structures.     

FABRICATION AND CHARACTERIZATION OF THE SIZE-CONTROLLED AND PATTERNED nc-Si DOTS

A new method of phase-modulated excimer laser crystallization is adopted to fabricate the patterned nanometer-sized crystalline silicon (nc-Si) dots within the sandwiched structure (a-SiN_x:H/a-Si:H/a-SiN_x:H) films. The results of transmission electron microscopy, electron diffraction and Raman scattering show the ultra-thin and single-layer nc-Si films were patterned in the lateral direction and the size of crystallites is controlled by the thickness of as-deposited a-Si film in the longitudinal direction. The effects of the laser energy density on the structures of the samples and the crystallization mechanism are discussed.     

Optical properties investigation of [nc-Si:SiO2/SiO2]30 periodic multilayer films

The optical properties of 30-layer [nc-Si:SiO₂/SiO₂]₃₀ periodic films have been studied. The films were prepared by alternately evaporating SiO and SiO₂ onto Si(100) substrates, followed by annealing at 1100?^°C. Spectroscopic ellipsometry spectrum analysis was used to determine the optical constants of the samples via the Forouhi?CBloomer model. The optical bandgap of a single periodic film is calculated. The photoluminescence (PL) spectra of three samples with different thicknesses clearly show that there are two physical origins of the PL process.     

GaAs/SiO_2超晶格的制备和Raman光谱研究

我们采用射频磁控溅射方法在 p- Si衬底上成功地制备出四周期的非晶 Ga As/Si O2超晶格 ,并取得其高分辨率电镜像。以 80 0℃快速退火方法使超晶格中非晶的 Ga As层局部晶化 ,利用 Raman散射谱研究了其结构变化。     

High temperature reaction and defect chemistry at the Si/SiO2 interface

The generation of structural and electrical defects in Si/SiO₂ structures upon high temperature annealing by the oxide decomposition reaction Si+SiO₂→2SiO ↑ has been studied using scanning electron microscopy (SEM) and ramped current-voltage measurements. The SiO decomposition is nucleated at crystalline defects in the substrate and results in the formation of voids in the oxide. The voids grow laterally with annealing time, independent of the nature of the defect. Prior to the formation of physical voids in the oxide, defects become electrically active, leading to low field dielectric breakdown. The breakdown degradation is prevented when the O₂ pressure in the annealing ambient is sufficient to reverse the decomposition reaction by reoxidizing the SiO product at the interface.     

Photoluminescence properties of SiNx/Si amorphous multilayer structures grown by plasma-enhanced chemical vapor deposition

Very thin (nanometric) silicon layers were grown in between silicon nitride barriers by SiH₂Cl₂/H₂/NH₃ plasma-enhanced chemical vapor deposition (PECVD). The multilayer structures were deposited onto fused silica and silicon substrates. Deposition conditions were selected to favor Si cluster formation of different sizes in between the barriers of silicon nitride. The samples were thermally treated in an inert atmosphere for 1 h at 500 °C for dehydrogenation. Room-temperature photoluminescence (RT-PL) and optical transmission in different ranges were used to evaluate the optical properties of the structures. UV-VIS absorption spectra present two band edges. These band edges are well fitted by the Tauc model typically used for amorphous materials. RT-PL spectra are characterized by strong broad bands, which have a blue shift as a function of the deposition time of the silicon layer, even for as-grown samples. The broad luminescence could be associated with the confinement effect in the silicon clusters. After annealing of the samples, the PL bands red shift. This is probably due to the thermal decomposition of N-H bonds with further effusion of hydrogen and better nitrogen passivation of the nc-Si/SiN_x interfaces.     

Effect of microwave annealing on silicon dioxide/silicon carbide structures

The methods of atomic force microscopy and optical absorption spectroscopy are applied to study the effect of microwave treatment on the properties of SiO₂/SiC structures obtained by rapid thermal annealing and conventional thermal oxidation in steam. From the variation of the sample optical density with total time of microwave treatment, it is concluded that the structures prepared by rapid thermal annealing are more stable against microwave radiation. It is shown that long-term microwave treatment flattens the oxide film surface at the nanolevel regardless of the method of silicon carbide oxidation.