Blue–violet photoluminescence from colloidal suspension of nanocrystalline silicon in silicon oxide matrix

We report room temperature visible photoluminescence (PL), detectable by the unaided eye, from colloidal suspension of silicon nanocrystals (nc-Si) prepared by mechanical milling followed by chemical oxidation. The PL bands for samples prepared from Si wafer and Si powder peak at 3.11 and 2.93 eV respectively, under UV excitation, and exhibit a very fast (～ns) PL decay. Invasive oxidation during chemical treatment reduces the size of the nc-Si domains distributed within the amorphous SiO₂ matrix. It is proposed that defects at the interface between nc-Si and amorphous SiO₂ act as the potential emission centers. The origin of blue–violet PL is discussed in relation to the oxide related surface states, non-stoichiometric suboxides, surface species and other defect related states.     

纳米硅薄膜的光致发光特性

用等离子体增强化学汽相淀积法系统制备了发光纳米硅(nc-Si∶H)薄膜.讨论了晶粒尺寸和表面结构对光致发光(PL)谱的影响.用量子限制-发光中心模型解释了nc-Si∶H的PL.研究了PL谱的温度特性.温度从10K上升到250K，PL峰值红移了54meV，且PL强度衰减了两个数量级. 关键词：     

Structural and photo-luminescence properties of nanocrystalline silicon films deposited at low temperature by plasma-enhanced chemical vapor deposition

Nanocrystalline silicon (nc-Si) films were prepared by a plasma-enhanced chemical vapor deposition method at a deposition temperature below 220 °C with different dynamic pressures (P_g), hydrogen flow rates ([H₂]), and RF powers, using SiH₄/H₂/SiF₄ mixtures. We examined the photo-luminescence (PL) spectra and the structural properties. We observed two stronger and weaker PL spectra with a peak energies around E_PL = 1.8 and 2.2-2.3 eV, respectively, suggesting that the first band was related to nanostructure in the films, and another band was associated with SiO-related bonds. The nc-Si films with rather large PL intensity was obtained for high [H₂] and/or low pressure values, However, effects of [H₂] are likely to be different from those of P_g. The average grain size (δ) and the crystalline volume fraction (ρ) at first rapidly increase, and then slowly increase, with increasing P_g. Other parameters exhibited opposite behaviors from those of δ or ρ. These results were discussed in connection with the changes in the PL properties with varying the deposition conditions.     

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     

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.     

Morphological and optical properties changes in nanocrystalline Si (nc-Si) deposited on porous aluminum nanostructures by plasma enhanced chemical vapor deposition for Solar energy applications

Photoluminescence (PL) spectroscopy was used to determine the electrical band gap of nanocrystalline silicon (nc-Si) deposited by plasma enhancement chemical vapor deposition (PECVD) on porous alumina structure by fitting the experimental spectra using a model based on the quantum confinement of electrons in Si nanocrystallites having spherical and cylindrical forms. This model permits to correlate the PL spectra to the microstructure of the porous aluminum silicon layer (PASL) structure. The microstructure of aluminum surface layer and nc-Si films was systematically studied by atomic force microscopy (AFM), transmission electron microscopy (TEM), Raman spectroscopy and X-ray diffraction (XRD). It was found that the structure of the nanocrystalline silicon layer (NSL) is dependent of the porosity (void) of the porous alumina layer (PAL) substrate. This structure was performed in two steps, namely the PAL substrate was prepared using sulfuric acid solution attack on an Al foil and then the silicon was deposited by plasma enhanced chemical vapor deposition (PECVD) on it. The optical constants (n and k as a function of wavelength) of the deposited films were obtained using variable angle spectroscopic ellipsometry (SE) in the UV-vis-NIR regions. The SE spectrum of the porous aluminum silicon layer (PASL) was modeled as a mixture of void, crystalline silicon and aluminum using the Cauchy model approximation. The specific surface area (SSA) was estimated and was found to decrease linearly when porosity increases. Based on this full characterization, it is demonstrated that the optical characteristics of the films are directly correlated to their micro-structural properties.     

发光纳米硅/二氧化硅多层膜的特性与氢气氛退火的影响

利用等离子体增强化学气相沉积法制备了氢化非晶硅/二氧化硅多层膜，通过两步热退火的方法获得了尺寸可控的纳米硅/二氧化硅多层结构，晶粒尺寸约为4nm，在室温下观察到了较强的光致可见发光，其发光峰位于750nm.在此基础上，发现合适的氢气氛退火能有效地提高材料的发光强度.电子顺磁共振实验表明氢气氛退火有效地降低了纳米硅中的非辐射复合中心而导致发光效率的提高.     

Quantum emission efficiency of nanocrystalline and amorphous Si quantum dots

The paper presents the comparison of emission efficiencies for crystalline Si quantum dots (QDs) and amorphous Si nanoclusters (QDs) embedded in hydrogenated amorphous (a-Si:H) films grown by the hot wire-CVD method (HW-CVD) at the variation of technological parameters. The correlations between the intensities of different PL bands and the volumes of Si nanocrystals (nc-Si:H) and/or an amorphous (a-Si:H) phase have been revealed using X-ray diffraction (XRD) and photoluminescence (PL) methods. These correlations permit to discuss the PL mechanisms in a-Si:H films with embedded nc-Si QDs. The QD parameters of nc-Si:H and a-Si:H QDs have been estimated from PL results and have been compared (for nc-Si QDs) with the parameters obtained by the XRD method. Using PL and XRD results the relations between quantum emission efficiencies for crystalline (η_cr) and amorphous (η_am) QDs have been estimated and discussed for all studied QD samples. It is revealed that a-Si:H films prepared by HW-CVD with the variation of wire temperatures are characterized by better passivation of nonradiative recombination centers in comparison with the films prepared at the variation of substrate temperatures or oxygen flows.     

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。     

Modulating microstructure and optical properties of hydrogenated nanocrystalline silicon photovoltaic materials prepared under hydrogen diluted silane PECVD by various DC bias

Hydrogenated nanocrystalline silicon (nc-Si:H) thin films were fabricated by plasma enhanced chemical vapor deposition under the various negative substrate bias voltages with hydrogen as a diluent of silane. The microstructure and optical properties of nc-Si:H thin films were studied by Raman scattering spectroscopy, X-ray diffraction (XRD), transmission electron microscopy, and optical transmission spectroscopy. Raman spectra and XRD pattern reveal that applying negative bias voltages at the moderate level favors the enhancement of crystalline volume fraction, increase of crystallite sizes and decrease of residual stress. We also demonstrated that the negative direct current bias can be used to modulate the volume fraction of voids, refractive index, absorption coefficient, compactness and ordered degree of nc-Si:H films. It is found that the film deposited at −80 V shows not only high crystallinity, size of crystallite, and static index n₀ but also low residual stress and volume fraction of voids. Furthermore, the microstructural evolution mechanism of nc-Si:H thin films prepared at different bias voltages is tentatively explored.     

磷掺杂纳米硅薄膜的研制

用PECVD薄膜沉积方法,成功地制备了磷掺杂纳米硅(nc-Si:H(P))薄膜.用扫描隧道电镜(STM)、Raman散射、傅里叶变换红外吸收(FTIR)谱、电子自旋共振(ESR)、共振核反应(RNR)技术对掺磷纳米硅进行了结构分析,确认了样品的微结构为纳米相结构.掺磷后膜中纳米晶粒的平均尺寸d减小,一般在25—45nm之间,且排列更加有序.掺磷nc-Si:H膜具有较高的光吸收系数,光学带隙在173—178eV之间,和本征nc-Si:H相同.掺杂nc-Si:H薄膜电导率在10^-1关键词：     

Structural and optical properties study of nanocrystalline Si (nc-Si) thin films deposited on porous aluminum by plasma enhanced chemical vapor deposition

In this paper we report detail investigation and correlation between micro-structural and optical properties of nanocrystalline silicon (nc-Si) deposited by plasma enhancement chemical vapor deposition (PECVD) on porous aluminum structure. The influence of the microstructure of the nc-Si thin films on their optical properties was investigated through an extensive characterization. The effect of anodisation currents on the microstructure of aluminum surface layer and nc-Si films was systematically studied by atomic force microscopy (AFM) and transmission electron microscopy (TEM), Raman spectroscopy and X-ray diffraction (XRD). The optical constants (n and k as a function of wavelength) of the films were obtained using variable angle spectroscopic ellipsometry (SE) in the UV-vis-NIR regions. The silicon layer (SL) was modeled as a mixture of void, crystalline silicon and aluminum using the Bruggeman approximation. Based on this full characterization, it is demonstrated that the optical characteristics of the films are directly correlated to their micro-structural properties. A very bright photoluminescence (PL) was obtained and find to depend on anodisation current.     

Photoluminescence studies on nanostructured cadmium sulfide thin films prepared by chemical bath deposition method and annealed at different temperatures

Nanostructured cadmium sulfide (CdS) thin films have been prepared by chemical bath deposition (CBD) method and after post deposition annealing of the thin films at different temperatures, photoluminescence (PL) property has been studied. The effects of various photoexcitation wavelengths on the PL behaviour of different annealed films of CdS were studied by recording the PL spectra. The intensity of PL, the profile of the PL spectra and the effects of photoexcitation wavelength depend drastically on the temperature of the post deposition annealing of the thin films. The XRD patterns of the films show the presence of both the hexagonal and cubic phases (mixed phases). The emission peak arises from the surface defects of the CdS nanocrystalline thin films. Significant modification in the surface morphology of the CdS films upon annealing has been observed from the FESEM images. The morphology of the thin films is expected to influence the PL behaviour of the CdS thin films. The quantum size effect and size dependant PL have been observed.     

热丝法制备纳米晶硅薄膜结构及沉积机制的研究

用热丝法制备了纳米晶硅薄膜．通过Raman散射谱及X射线谱，系统地研究了沉积气压P_g、高H₂稀释及衬底与钨丝之间距离对沉积速率、纳米硅薄膜的形成和结构等的影响．计算了沉积过程中的温度场分布．讨论了沉积过程中反应基元的输运和相关的气相反应，以及H在薄膜生长中的作用，由此分析了沉积参量对薄膜结构的影响，得到了与实验相一致的结果． 关键词：     

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。     

纳米硅薄膜的生长动力学与计算机模拟

氢化纳米硅(nc-Si:H)薄膜由于其具有奇异的结构和独特的性质,而引起广泛的关注.本文在等离子体增强化学气相淀积(PECVD)系统中,以高纯H₂高度稀释SiH₄为反应气体源,在射频和直流双重功率源的激励下制备成功具有纳米结构的nc-Si:H薄膜.利用高分辨率电子显微镜(HREM)、Raman散射谱(RSS)、扫描隧道电子显微镜(STM)等实验技术对nc-Si:H薄膜样品作了研究.基于对薄膜制备过程的动力学分析,提出nc-Si:H薄膜的分形生长模型:扩散与反应限 关键词：     

Excitation of Intra-4f Shell Luminescence of Rare Earth Ions (Er3+ and Yb3+) by the Energy Transfer from Si Nanocrystals

Photoluminescence (PL) properties of SiO₂ films containing Si nanocrystals (nc-Si) and Er³⁺ (Yb³⁺) were studied. PL peaks attributable to the recombination of electron–hole pairs in nc-Si (1.5eV) and the intra-4f shell transition of Er³⁺ (0.81eV) (Yb³⁺ (1.26eV)) were observed simultaneously at room temperature. Correlation of the two peaks was studied as a function of nanocrystalline size. It was found that the intensity of the Er³⁺-related (Yb³⁺-related) peak increases drastically as the size of nc-Si decreases. Temperature dependence of PL spectra was studied. In the case of Yb-doped samples, temperature quenching of the PL became small as the size decreased, while in the case of Er-doped samples, no remarkable temperature dependence was observed. Two major features of the quantum size effects of nc-Si, i.e., the band-gap widening and the increase in the PL efficiency with decreasing the size, are thought to contribute to the improvement of room temperature PL efficiency of Er³⁺ (Yb³⁺).     

ZnO-Si不同退火条件对生长ZnSe薄膜的影响

研究了作为缓冲层的ZnO薄膜在不同的退火时间、退火温度下退火对Si衬底上生长ZnSe膜质量的影响。当溅射有ZnO膜的Si(111)衬底的退火条件变化时，从X射线衍射谱（XRD）和光致发光谱（PL）中可见，ZnSe(111)膜的晶体质量有较大的变化。变温的PL谱表明，Si衬底上生长的具有ZnO缓冲层的ZnSe膜的近带边发射峰起源于自由激子发射。     

Electrical and deep levels characteristics of ZnO/Si heterostructure by MOCVD deposition

ZnO films have been prepared on p-type Si substrates by metal-organic chemical vapour deposition （MOCVD） at different total gas flow rates. The current versus voltage and temperature （I - V - T） characteristics, the deep-level transient spectroscopy （DLTS） and the photoluminescence （PL） spectra of the samples were measured. DLTS shows two deep-level centres of E1 （Ec-0.13±0.02eV） and E2 （Ec-0.43±0.05eV） in sample 1202a, which has a ZnO/p-Si heterostructure. A deep level at Ec-0.13±0.01 eV was also obtained from the I -T characteristics. It was considered to be the same as E1 obtained from DLTS measurement. The emission related to this deep level center was detected by PL spectra. In addition, the energy location and the relative trap density of E1 was varied when the total gas flow rate was changed.     

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.