微晶硅薄膜的表面粗糙度及其生长机制的X射线掠角反射研究

采用等离子体增强化学气相沉积技术沉积一系列处于不同生长阶段的微晶硅薄膜.通过同步辐射X射线掠角反射技术研究微晶硅薄膜的表面粗糙度随时间等的演化，探讨微晶硅薄膜的生长动力学过程及其生长机制.研究结果表明，在衬底温度为200 ℃，电极间距为2 cm，沉积气压为6.66×1０² Pa，射频功率密度为0.22 W/cm²，氢稀释度分别为99%和98%的沉积条件下，在玻璃衬底上生长的微晶硅薄膜生长指数β分别为0.21±0.01和0.24±0.01.根据KPZ模型，微晶硅薄膜的生长机制为有限扩散生长. 关键词： X射线掠角反射 微晶硅薄膜 表面粗糙度 生长机制     

椭圆偏振技术研究VHF-PECVD高速沉积微晶硅薄膜的异常标度行为

采用VHF-PECVD技术高速沉积了不同生长阶段的微晶硅薄膜,通过椭圆偏振技术研究了生长过程中微晶硅薄膜表面粗糙度的演化.实验结果表明,沉积气压P_g=300 Pa时,β=0.81,其超出标度理论中β最大值为0.5范围,出现异常标度行为.这表明微晶硅薄膜高速生长中还存在其他粗糙化增加的因素,此粗糙化增加的因素与阴影作用有关. 关键词： 微晶硅薄膜 椭偏光谱法 生长机制 表面粗糙度     

Influence of Boron doping on microcrystalline silicon growth

Microcrystalline silicon (μc-Si:H) thin films with and without boron doping are deposited using the radio-frequency plasma-enhanced chemical vapour deposition method. The surface roughness evolutions of the silicon thin films are investigated using ex situ spectroscopic ellipsometry and an atomic force microscope. It is shown that the growth exponent β and the roughness exponent α are about 0.369 and 0.95 for the undoped thin film, respectively. Whereas, for the boron-doped μc-Si:H thin film, β increases to 0.534 and α decreases to 0.46 due to the shadowing effect.     

沉积速率对甚高频等离子体增强化学气相沉积制备微晶硅薄膜生长标度行为的影响

本文采用甚高频等离子体增强化学气相沉积技术制备了沉积速率系列不同生长阶段的微晶硅薄膜,通过椭圆偏振技术研究了生长过程中微晶硅薄膜表面粗糙度的演化.实验结果表明:沉积速率为0.08和0.24nm/s的低速沉积时,硅薄膜表面粗糙度接近,生长指数分别为β=0.21和β=0.20,对应有限扩散生长模式,此时沉积速率对硅薄膜生长影响不大,原因是低速沉积时成膜先驱物有足够时间迁移到能量低的位置;当沉积速率增加到0.66nm/s时,硅薄膜表面粗糙度明显增加,生长指数β=0.81,大于0.5,出现了异常标度行为,与低速沉积的生长模式明显不同,原因是高速沉积时成膜前驱物来不及扩散就被下一层前驱物覆盖,降低了成膜前驱物在薄膜表面的扩散,使表面粗糙度增加和生长指数β增大.β大于0.5的异常标度行为与阴影效应有关.     

The study of amorphous incubation layers during the growth of microcrystalline silicon films under different deposition conditions

<正>The structural un-uniformity of μc-Si:H films prepared using a very high frequency plasma-enhanced chemical vapour deposition method has been investigated by Raman spectroscopy,spectroscopic ellipsometer and atomic force microscopy.It was found that the formation of amorphous incubation layer was caused by the back diffusion of SiH_4 and the amorphous induction of glass surface during the initial ignition process,and growth of the incubation layer can be suppressed and uniformμc-Si:H phase is generated by the application of delayed initial SiH_4 density and silane profiling methods.     

多晶薄膜表面粗化与生长方式转变

采用原子力显微镜研究了磁控溅射多晶薄膜表面粗化行为对归一化沉积温度T_s/T_m(T_s是沉积温度，T_m是材料熔点)的依赖性与薄膜生长方式转变行为.随着T_s/T_m增加，薄膜表面粗糙度增加，而表征粗糙度随时间演化特征的生长指数β历经了先减小再增加的过程.β对T_s/T_m的依赖关系反映了薄膜生长方式的转变行为，即薄膜生长依次由随机生长方式向表面扩散驱动生长方式与异常标度行为生长方式转变.在低于体扩散控制薄膜生长的温度时，晶界扩散机理导致多晶薄膜的表面粗化的异常标度行为. 关键词： 多晶薄膜 表面粗化 温度 生长     

Dynamic scaling and optical properties of Zn（S,O, OH） thin film grown by chemical bath deposition

The scaling behavior and optical properties of Zn(S, O and OH) thin films deposited on soda-lime glass substrates by chemical bath deposition method were studied by combined roughness measurements, scanning electron microscopy and optical properties measurement. From the scaling behaviour, the value of growth scaling exponent β , 0.38±0.06, was determined. This value indicated that the Zn(S, O, OH) film growth in the heterogeneous process was influenced by the surface diffusion and shadowing effect. Results of the optical properties measurements disclosed that the transmittance of the film was in the region of 70%-88% and the optical properties of the film grown for 40 min were better than those grown under other conditions. The energy band gap of the film deposited with 40 min was around 3.63 eV.     

Atomic force microscopy study of growth kinetics: Scaling in TiN-TiB2 nanocomposite films on Si(1 0 0)

We used the reactive unbalanced close-field dc-magnetron sputtering growth of TiN-TiB₂ on Si(1 0 0) at room temperature to determine if scaling theory provides insight into the kinetic mechanisms of two-phase nanocomposite thin films. Scaling analyses along with height-difference correlation functions of measured atomic force microscopy (AFM) images have shown that the TiN-TiB₂ nanocomposite films with thickness ranging from 70 to 950 nm exhibit a kinetic surface roughening with the roughness increasing with thickness exponentially. The roughness exponent α and growth exponent β are determined to be ∼0.93 and ∼0.25, respectively. The value of dynamic exponent z, calculated by measurement of the lateral correlation length ξ, is ∼3.70, agreeing well with the ratio of α to β. These results indicate that the surface growth behavior of sputter-deposited TiN-TiB₂ thin films follows the classical Family-Vicseck scaling and can be reasonably described by the noisy Mullins diffusion model, at which surface diffusion serves as the smoothing effect and shot noise as the roughening mechanism.     

Growth dynamics of pulsed laser deposited indium oxide thin films: a substrate dependent study

Indium oxide films are deposited by pulsed laser deposition in the presence of oxygen atmosphere, on different substrates, namely GaAs, Si, quartz, and glass. The structural, morphological, and interface characteristics are studied. Cubic In₂O₃ phase is confirmed by high resolution X-ray diffraction measurements. While the films on Si, glass, and quartz substrates are polycrystalline, the films on GaAs exhibit a preferred orientation along (2 2 2) plane. The structure and crystalline nature of the films are also confirmed by Raman spectroscopy. Furthermore, Raman spectra show the appearance of gallium oxide modes arising due to Ga diffusion from the substrate. The morphology of the films deposited on different substrates is studied by atomic force microscopy and rms roughness values are obtained. A two-dimensional power spectral density analysis has been used to calculate the growth exponent (α). A value of α > 1 (α < 1) for films grown on GaAs/Si (quartz/glass) substrates suggests that the growth on crystalline substrates is governed by the linear diffusion model, whereas the growth on amorphous substrates follows the dynamic scaling behaviour. UV-visible study shows a high optical transmittance of >90% and a band gap value of 3.64 and 3.79 eV for the films deposited on quartz and glass substrates, respectively.     

Hydrogen evolution during deposition of microcrystalline silicon by chemical transport

We exposed a freshly deposited boron-doped, hydrogenated amorphous silicon (a-Si:H) layer to hydrogen plasma under conditions of chemical transport. In situ spectroscopic ellipsometry measurements revealed that atomic hydrogen impinging on the film surface behaves differently before and after crystallization. First, the plasma exposure increases hydrogen solubility in the a-Si:H network leading to the formation of a hydrogen-rich subsurface layer. Then, once the crystallization process engages, the excess hydrogen starts to leave the sample. We have attributed this unusual evolution of the excess hydrogen to the grown hydrogenated microcrystalline (μc-Si:H) layer, which gradually prevents the atomic hydrogen from the plasma reaching the μc-Si:H/a-Si:H interface. Consequently, hydrogen solubility, initially increased by the hydrogen plasma, recovers the initial value of an untreated a-Si:H material. To support the theory that the outdiffusion is a consequence and not the cause of the μc-Si:H layer growth, we solved the combined diffusion and trapping equations, which govern hydrogen diffusion into the sample, using appropriate approximations and a specific boundary condition explaining the lack of hydrogen injection during μc-Si:H layer growth.     

Evolution of infrared spectra and optical emission spectra in hydrogenated silicon thin films prepared by VHF-PECVD

A series of hydrogenated silicon thin films with varying silane concentrations have been deposited by using very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) method. The deposition process and the silicon thin films are studied by using optical emission spectroscopy (OES) and Fourier transfer infrared (FTIR) spectroscopy, respectively. The results show that when the silane concentration changes from 10% to 1%, the peak frequency of the Si—H stretching mode shifts from 2000 cm ^{- 1} to 2100 cm ^{- 1}, while the peak frequency of the Si—H wagging—rocking mode shifts from 650 cm ^{- 1} to 620 cm ^{- 1}. At the same time the SiH^*/H_α intensity ratio in the plasma decreases gradually. The evolution of the infrared spectra and the optical emission spectra demonstrates a morphological phase transition from amorphous silicon (a-Si:H) to microcrystalline silicon (μc-Si:H). The structural evolution and the μc-Si:H formation have been analyzed based on the variation of H_α and SiH^* intensities in the plasma. The role of oxygen impurity during the plasma process and in the silicon films is also discussed in this study.     

太阳电池用本征微晶硅材料的制备及其结构研究

采用VHF-PECVD技术制备了系列不同硅烷浓度和反应气压的微晶硅薄膜.运用拉曼散射光谱和 x射线衍射对制备的材料进行了结构分析.在实验研究的范围内，制备材料的晶化程度随硅烷 浓度的增加而降低.XRD的测试结果表明：制备的微晶硅材料均体现了(220)方向择优.应用在 电池的有源层中，制备出了效率达7.1%的单结微晶硅太阳电池，电池的结构是glass/ZnO/p( μc-Si:H)/i(μc-Si:H)/n(a-Si:H/Al)，没有ZnO背反射电极，有源层的厚度仅为1.2μm. 关键词： 本征微晶硅薄膜 拉曼光谱 x射线衍射     

Kinetic mechanisms of initiating hydrogen-oxygen mixture combustion through the excitation of electronic degrees of freedom of molecular oxygen by laser radiation

Kinetic mechanisms resulting in the enhancement of combustion of H₂+O₂ mixtures when O₂ molecules are excited to the a ¹Δ_g and b ¹Σ _g ⁺ states with laser radiation (λ=1.268 and 0.762 μm) are analyzed. It is shown that the excitation of O₂ molecules by the laser radiation leads to the appearance of new O, H, and OH formation channels; promotes the ignition of the starting mixture; and reduces the self-ignition temperature. With initial pressures in the range P ₀=10³–10⁴ Pa, the self-ignition temperature can be reduced to 300 K even at relatively low energies of the laser radiation with λ=0.762 μm.     

Effects of gas temperature on optical and transport properties of a-Si:H films deposited by PECVD

Effects of silane temperature (T _g) before glow-discharge on the optical and transport properties of hydrogenated amorphous silicon (a-Si:H) thin films were investigated. The optical measurements show that the refractive index increases with increasing T _g. The transport characterizations show that when T _g increases, the dark conductivity increases. However, the temperature coefficient of resistance decreases. In addition, after holding at 130°C for 20 h, the resistance variation, ΔR/R, of the films deposited at T _g = room temperature (10.8%) is much larger than those deposited at silane temperatures of 80°C (3%) and 160°C (2%). This can be attributed to different rates of defect creation in a-Si:H films caused by various T _g.     

Study of structural and optical properties of ZnO films grown by pulsed laser deposition

Wurtzite zinc oxides films (ZnO) were deposited on silicon (0 0 1) and corning glass substrates using the pulsed laser deposition technique. The laser fluence, target-substrate distance, substrate temperature of 300 °C were fixed while varying oxygen pressures from 2 to 500 Pa were used. It is observed that the structural properties of ZnO films depend strongly on the oxygen pressure and the substrate nature. The film crystallinity improves with decreasing oxygen pressure. At high oxygen pressure, the films are randomly oriented, whereas, at low oxygen pressures they are well oriented along [0 0 1] axis for Si substrates and along [1 0 3] axis for glass substrates. A honeycomb structure is obtained at low oxygen pressures, whereas microcrystalline structures were obtained at high oxygen pressures. The effect of oxygen pressure on film transparency, band gap E_g and Urbach energies was investigated.     

Optical absorption in PECVD deposited thin hydrogenated silicon in light of ordering effects

We report results obtained from measurements of optical transmittance spectra carried out on a series of silicon thin films deposited by plasma-enhanced chemical vapour deposition (PECVD) from silane diluted with hydrogen. Hydrogen dilution of silane results in an inhomogeneous growth during which the material evolves from amorphous hydrogenated silicon (a-Si:H) to microcrystalline hydrogenated silicon (μc-Si:H). Spectral refractive indices and absorption coefficients were determined from transmittance spectra. The spectral absorption coefficients were used to determine the Tauc optical band gap energy, the B factor of the Tauc plots, E ₀₄ (energy at which the absorption coefficient is equal to 10⁴ cm⁻¹), and the Urbach energy as a function of the hydrogen dilution. The results were correlated with microstructure, namely volume fractions of the amorphous and crystalline phase with voids, and with the grain size.      

Influence of ignition condition on the growth of silicon thin films using plasma enhanced chemical vapour deposition

The influences of the plasma ignition condition in plasma enhanced chemical vapour deposition (PECVD) on the interfaces and the microstructures of hydrogenated microcrystalline Si (μc-Si:H) thin films are investigated. The plasma ignition condition is modified by varying the ratio of SiH₄ to H₂ (R_H). For plasma ignited with a constant gas ratio, the time-resolved optical emission spectroscopy presents a low value of the emission intensity ratio of Hα to SiH^* (I_Hα/I_SiH^*) at the initial stage, which leads to a thick amorphous incubation layer. For the ignition condition with a profiling R_H, the higher I_Hα/I_SiH^* values are realized. By optimizing the R_H modulation, a uniform crystallinity along the growth direction and a denser μ c-Si:H film can be obtained. However, an excessively high I_Hα/I_SiH^* may damage the interface properties, which is indicated by capacitance-voltage (C-V) measurements. Well controlling the ignition condition is critically important for the applications of Si thin films.     

Photoluminescence of a-Si:H films grown by plasma-enhanced chemical vapor deposition and doped with erbium from the metallorganic compound Er(HFA)3·DME

Using standard low-temperature (<300 °C) plasma-enhanced chemical vapor deposition (PE CVD) technology, films of a Si(Er): H were obtained that emitted light in the neighborhood of 1.54 μm at room temperature. The Er source was the specially synthesized fluorine-containing metallorganic complex Er(HFA)₃·DME where HFA=CF₃C(O)CHC(O)CF₃ and DME=CH₃OCH₂CH₂OCH₃, which possesses a low transition temperature to the gas phase (of order 100 °C) at working pressures (0.1–0.5 Torr) for the PE CVD method. Distinctive features of the photoluminescence spectrum of a-Si(Er):H were investigated in the range 0.5–1.7 μm for T=77 and 300 K. The presence of photoconductivity in the synthesized films is evidence of their satisfactory electronic quality. Fiz. Tverd. Tela (St. Petersburg) 40, 1433–1436 (August 1998)     

HW-MWECR-CVD法制备氢化微晶硅薄膜及其微结构研究

用热丝辅助微波电子回旋共振化学气相沉积方法制备出高晶化体积分数的氢化微晶硅(μc-Si:H)薄膜.拉曼散射和X射线衍射技术对样品的微观结构测量分析表明，当反应气体中SiH₄浓度在3.6%—50%之间大范围变化时，μc-Si:H薄膜均具有高的晶化体积分数.进一步的分析表明，在SiH₄浓度较大时制备的薄膜，其结构以非晶-微晶的过渡相为主.薄膜易于晶化或生长为过渡相的主要原因是微波电子回旋共振使SiH₄气体高度分解，等离子体高度电离. 关键词： 微波电子回旋共振化学气相沉积 氢化微晶硅薄膜 拉曼散射 X射线衍射     

氧分压对Mg掺杂ZnO薄膜结晶质量和光学特性的影响

利用脉冲激光沉积技术,通过改变沉积过程中的氧气压力,在蓝宝石(0001)基片上制备了一系列ZnMgO合金.通过X射线衍射、反射和透射光谱以及室温和变温荧光光谱,对薄膜的结构和光学性能进行了系统地表征,分析了工作气压对ZnMgO合金薄膜的结晶质量及光学特性的影响.研究结果表明:随着沉积环境中氧气压力的增大,ZnMgO薄膜的结晶质量下降,富氧环境下,与蓝宝石晶格平行的ZnO晶粒的出现是导致薄膜结晶质量下降的主要原因;相对于本征ZnO,不同氧气环境下沉积的ZnMgO薄膜的紫外荧光峰均出现了不同程度的蓝移.随着工 关键词： ZnO Mg掺杂 脉冲激光沉积 薄膜生长 光学特性