高氢稀释制备微晶硅薄膜微结构的研究

采用高氢稀硅烷热丝化学气相沉积方法制备氢化微晶硅薄膜.其结构特征用Raman谱，红外透射谱，小角X射线散射等来表征.结果表明微晶硅的大小及在薄膜中的晶态比χ_c随氢稀释度的提高而增加.而从红外谱计算得到氢含量则随氢稀释度的增加而减少.小角X射线散射结果表明薄膜致密度随氢稀释度的增加而增加.结合红外谱和小角X射线散射的结果讨论与比较了不同相结构下硅网络中H的键合状态.认为随着晶化的发生和晶化程度的提高H逐渐移向晶粒表面，在硅薄膜中H的存在形式从以SiH为主向SiH₂ 关键词：     

Growth characteristics of amorphous-layer-free nanocrystalline silicon films fabricated by very high frequency PECVD at 250 ℃

Amorphous-layer-free nanocrystalline silicon films were prepared by a very high frequency plasma enhanced chemical vapor deposition(PECVD) technique using hydrogen-diluted SiH4 at 250 C.The dependence of the crystallinity of the film on the hydrogen dilution ratio and the film thickness was investigated.Raman spectra show that the thickness of the initial amorphous incubation layer on silicon oxide gradually decreases with increasing hydrogen dilution ratio.High-resolution transmission electron microscopy reveals that the initial amorphous incubation layer can be completely eliminated at a hydrogen dilution ratio of 98%,which is lower than that needed for the growth of amorphous-layer-free nanocrystalline silicon using an excitation frequency of 13.56 MHz.More studies on the microstructure evolution of the initial amorphous incubation layer with hydrogen dilution ratios were performed using Fourier-transform infrared spectroscopy.It is suggested that the high hydrogen dilution,as well as the higher plasma excitation frequency,plays an important role in the formation of amorphous-layer-free nanocrystalline silicon films.     

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.      

Features of the structure and defect states in hydrogenated polymorphous silicon films

The structural and electronic properties of thin hydrogenated polymorphous silicon films obtained by plasma-enhanced chemical vapor deposition from hydrogen (H₂) and monosilane (SiH₄) gas mixture have been studied by means of transmission electron microscopy, electron paramagnetic resonance (EPR) spectroscopy, and Raman spectroscopy. It has been established that the studied films consist of the amorphous phase containing silicon nanocrystalline inclusions with the average size on the order of 4–5 nm and the volume fraction of 10%. A signal was observed in the hydrogenated polymorphous silicon films during the EPR investigation that is attributed to the electrons trapped in the conduction band tail of microcrystalline silicon. It has been shown that the introduction of a small fraction of nanocrystals into the amorphous silicon films nonadditively changes the electronic properties of the material.     

氮化硅薄膜中纳米非晶硅颗粒的键合结构及光致发光

采用螺旋波等离子体化学气相沉积技术以N₂/SiH₄/H₂为反应气体制备了镶嵌有纳米非晶硅颗粒的氢化氮化硅薄膜,通过改变N₂流量实现了薄膜从红到蓝绿的可调谐光致发光.傅里叶红外透射和紫外-可见光吸收特性分析表明,所生长薄膜具有较高的氢含量,N₂流量增加使氢的键合结构发生变化,非晶硅颗粒尺寸减小,所对应的薄膜的光学带隙逐渐增加和微观结构有序度减小.可调光致发光(PL)主要来源于纳米硅颗粒的量子限制效应发光,随N₂流量增加,PL的谱线展宽并逐渐增强. 关键词： 傅里叶红外透射谱 光吸收谱 纳米硅粒子镶嵌薄膜 光致发光     

Preparation of hydrogenated microcrystalline silicon films with hot-wire-assisted MWECR-CVD system

Intrinsic hydrogenated microcrystalline silicon (\muc-Si:H) films have been prepared by hot-wire-assisted microwave electron-cyclotron-resonance chemical vapour deposition (HW-MWECR-CVD) under different deposition conditions. Fourier-transform infrared spectra and Raman spectra were measured. Optical band gap was determined by Tauc plots, and experiments of photo-induced degradation were performed. It was observed that hydrogen dilution plays a more essential role than substrate temperature in microcrystalline transformation at low temperatures. Crystalline volume fraction and mean grain size in the films increase with the dilution ratio (R=H₂/(H₂+SiH₄)). With the rise of crystallinity in the films, the optical band gap tends to become narrower while the hydrogen content and photo-induced degradation decrease dramatically. The samples, were identified as \mu c-Si:H films, by calculating the optical band gap. It is considered that hydrogen dilution has an effect on reducing the crystallization activation energy of the material, which promotes the heterogeneous solid-state phase transition characterized by the Johnson--Mehl--Avrami (JMA) equation. The films with the needed structure can be prepared by balancing deposition and crystallization through controlling process parameters.     

氢稀释对纳米晶硅薄膜晶化特性的影响及薄膜生长机理

以SiH₄与H₂作为前驱气体,采用射频等离子增强化学气相沉积技术制备了纳米晶硅薄膜.利用Raman散射和红外吸收光谱等技术,对不同氢稀释比条件下薄膜的微观结构和键合特性进行了研究.结果表明,随着氢稀释比增加,薄膜的晶化率明显提高,而氢稀释比过高时,薄膜晶化率呈现减少趋势.红外吸收光谱分析表明,纳米晶硅薄膜中氢的键合模式与薄膜的晶化特性密切相关.随着氢稀释比增加,薄膜中整体氢含量和SiH₂键合密度明显减少,而在高氢稀释比条件下,氢稀释比增加导致薄膜中SiH₂键合密度和整体氢含量增加.     

用SiCl4/H2气源沉积多晶硅薄膜光照稳定性的研究

对以SiH₄/H₂及SiCl₄/H₂为源气体、采用 等离子体增强化学气相沉积技术制备的非晶硅薄膜和多晶硅薄膜进行了光照稳定性的研究.实验表明，制备的多晶硅薄膜并没有出现 非晶硅中的光致衰减现象，其光电导、暗电导在光照过程中没有下降反而有所上升且电导率 变化快慢受氢稀释度的制约.多晶硅薄膜的光照稳定性可能来源于高的晶化度及Cl元素的存在. 关键词： 多晶硅薄膜 稳恒光电导效应 晶界 光致衰退效应     

氢稀释对多晶硅薄膜结构特性和光学特性的影响

以SiCl₄和H₂为气源，用等离子体增强化学气相沉积技术，在250℃的低温下，研究氢稀释度对多晶硅薄膜结构特性的影响.实验结果表明，对于以SiCl₄和H₂组成的反应源气体，氢对薄膜生长特性的影响有异于SiH₄/H₂，在一定功率下，薄膜的晶化率随氢稀释度的减小而增加，在一定的氢稀释度下薄膜晶化度达到最大值85％；随着氢稀释度的继续减小，薄膜晶化度迅速下降，并逐渐向非晶态结构转变.随氢稀释度的减小，薄膜的光学带隙由 1.5eV减小至约1.2eV，而后增大至1.8eV.沉积速率则随氢稀释度的减小先增加后减小，在无氢条件下，无薄膜形成.在最佳氢稀释度条件下，Cl基是促进晶化度提高，晶粒长大的一个主要因素. 关键词： 多晶硅薄膜 微结构 氢稀释 4')" href="#">SiCl₄     

Photoconductivity and dark conductivity of hydrogenated amorphous silicon

The study of plasma-deposited hydrogenated amorphous silicon films prepared in various deposition systems and under the use of different gases (SiH₄, SiD₄, Si₂H₄) shows a unique correlation between the photoconductivity and the dark conductivity of undoped and lightly doped films grown under optimized conditions. Deviations from his relation occur at high doping levels, in particular for boron doping, as well as upon annealing. They are attributed to an increased density of gap states due to hydrogen depletion.     

纳米晶硅薄膜中氢含量及键合模式的红外分析

采用传统射频等离子体化学气相沉积技术在100—350℃的衬底温度下高速沉积氢化硅薄膜. 傅里叶变换红外光谱和Raman谱的研究表明,纳米晶硅薄膜中的氢含量和硅氢键合模式与薄膜的晶化特性有密切关系,当薄膜从非晶相向晶相转变时,氢的含量减少了一半以上,硅氢键合模式以SiH₂为主. 随着衬底温度的升高和晶化率的增加,纳米晶硅薄膜中氢的含量以及其结构因子逐渐减少. 关键词： 氢化纳米晶硅薄膜 红外透射谱 氢含量 硅氢键合模式     

氢化非晶硅叠层薄膜对单晶硅表面钝化研究

采用等离子体增强化学气相沉积法生长的单层本征氢化非晶硅薄膜对单晶硅片进行钝化,结果表明增加氢稀释比有利于减少薄膜中的缺陷,增强钝化效果,过量的氢稀释比会导致非晶硅在硅片表面的外延晶化生长,降低钝化效果。退火导致非晶硅晶化程度增加,降低了钝化效果,同时退火提升了薄膜的质量,改变了H键合方式,增强了钝化效果。因此,单层氢化非晶硅只有在合适的氢稀释比和退火温度才可以获得最佳钝化效果。为了提高非晶硅薄膜对硅片的钝化效果,采用具有高低氢稀释比的叠层本征非晶硅薄膜对硅片进行钝化。因此将高氢稀释比沉积的非晶硅薄膜叠层生长于低氢稀释比的薄膜之上,避免非晶硅在硅片表面的外延生长。在退火过程中,高氢稀释比薄膜中的氢扩散到低氢稀释比薄膜中,有效地钝化了非晶硅中和单晶硅表面的悬挂键,改善了非晶硅/硅片的界面质量,叠层钝化后硅片的少子寿命为7.36 ms,隐含开路电压为732 mV。     

激发频率对高氢稀释下纳米晶硅薄膜生长特性的影响

利用等离子体增强化学气相沉积技术,在高氢稀释条件下,研究不同激发频率对纳米晶硅薄膜生长特性的影响.剖面透射电子显微镜(TEM)分析结果显示,不同激发频率下制备的纳米晶硅薄膜晶化区均呈锥状结构生长,但13.56 MHz激发频率下制备的纳米晶硅薄膜最初生长阶段存在非晶态孵化层,即纳米晶硅薄膜的形成经历了由非晶态孵化层到晶态结构层的转变.而高激发频率(40.68 MHz)下硅纳米晶则能直接在非晶态衬底上生长形成.Raman谱和红外吸收谱测量结果表明高激发频率(40.68 MHz)下制备的纳米晶硅薄膜不但具有较高     

Optical and Structural Properties of Ammonia-Free Amorphous Silicon Nitride Thin Films for Photovoltaic Applications

Hydrogenated amorphous silicon nitride (a-SiN_x:H) thin films have been deposited through the green chemistry route using silane (SiH₄) and nitrogen (N₂) as process gases with SiH₄ flow being variable and N₂ flow being constant without the use of pollutant and corrosive ammonia (NH₃) by the plasma-enhanced chemical vapor deposition technique at 13.56 MHz. Fourier transform infrared spectroscopy analysis shows various possible vibrational modes of Si-H, Si-N, and N-H bonds present in the film. Raman spectroscopy is performed on these samples to calculate volume fractions corresponding to amorphous phases present in the a-SiN_x:H films. The refractive index (η) values are calculated using Swanepoel's method, which are in the range of 2.89 to 3.17. The thickness of the deposited films has been evaluated using transmission spectra. Absorption coefficient and band gap (E _g) values are obtained from optical absorption studies. An increase in the E _g and a decrease in the η value have been observed for the samples grown with decreasing SiH₄ flow.     

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.     

In-situ monitoring and control of hydrogenated amorphous silicon–germanium band-gap profiling during plasma deposition process

In-situ germanium content monitoring and its characteristics in SiH₄/GeH₄/H₂ plasmas was studied during hydrogenated amorphous silicon–germanium (a-SiGe:H) film depositions. Since an appropriate band-gap profiling in a-SiGe:H deposition is very important to achieve high efficiency solar cell, the accurate monitoring and control of Ge contents are required. In this work, we found the spectral intensity ratio of silicon atom (288.2 nm) and germanium atom (303.9 nm) emission has strong relation with Ge content in plasmas. In typical, band-gap energy of films was decreased with the increasing of gas flow ratio GeH₄/SiH₄. However, at different total flow rate of GeH₄, the band-gap was different for same gas flow ratio cases because the Ge content in plasmas was changed due to the changes of electron temperature by hydrogen dilution. On the other hand, the emission intensity ratio Ge/Si detected the band-gap variation. Using this method, therefore, we measured and control Ge/Si to make a U-shape band-gap profile which was proved by an ellipsometer and Auger electron spectroscopy depth profile analysis.     

氢稀释对FTS沉积a-Si:H薄膜结构特性的影响

采用对靶磁控反应溅射技术,以氢气作为反应气体在不同的氢稀释比条件下制备了氢化非晶硅薄膜.利用台阶仪、傅里叶红外透射光谱、Raman谱和紫外-可见光透射谱测量研究了不同氢稀释比对氢化非晶硅薄膜生长速率和结构特性的影响.分析结果发现,利用对靶磁控溅射技术能够实现低温快速沉积高质量氢化非晶硅薄膜的制备.随着氢稀释比不断增加,薄膜沉积速率呈现先减小后增大的趋势.傅里叶红外透射光谱表明,氢化非晶硅薄膜中氢含量先增大后变小.而Raman谱和紫外-可见光透射谱分析发现,氢稀释比的增加使氢化非晶硅薄膜有序度和光学带隙均先增大后减小.可见,此技术通过改变氢稀释比R能够实现氢化非晶硅薄膜结构的有效控制.     

氢稀释对高速生长纳米晶硅薄膜晶化特性的影响

以SiH₄与H₂为气源,采用射频等离子体增强化学气相沉积技术,在较高的压强(230Pa)下,研究氢稀释率对纳米晶硅薄膜的生长速率和晶化特性的影响. 实验表明,薄膜的晶化率,晶粒尺寸随着氢稀释率的提高而增加,当氢稀释率为99%,薄膜的晶化率接近70%. 而沉积速率却随着氢稀释率的减小而增加,当氢稀释率从99%减小到95%时,薄膜的沉积速率由0.3nm/s 增加至0.8nm/s. 关键词： 纳米晶硅薄膜 氢稀释 晶化率 硅烷     

Study of hydrogenated amorphous silicon nitride films prepared by RF magnetron sputtering

Hydrogenated amorphous silicon nitride films have been deposited by the rf magnetron sputtering method with non-stoichiometric and stoichiometric compositions using a poly-Si target and a mixture of Ar, H₂ and N₂ as the sputtering gas. Data on optical and infrared absorption, electrical conductivity, breakdown voltage, capacitance measurements and thermal evolution of hydrogen have been presented as a function of nitrogen concentration in the films, especially in the stoichiometric region of composition. Attempts have been made to identify the roles of hydrogen and nitrogen in determining the electrical and optical properties and thermal stability exhibited by the films. Properties relevant for device application of the material have been shown to be comparable to those obtained by glow discharge or electron cyclotron resonance plasma chemical vapour deposition methods of deposition. RF magnetron sputtering has therefore been suggested as a viable alternative to the more widely adopted CVD methods for device applications of silicon nitride, where the use of hazardous process gases can be avoided.     

Effects of high hydrogen dilution ratio on optical properties of hydrogenated nanocrystalline silicon thin films

Hydrogenated nanocrystalline silicon thin films were prepared by plasma enhanced vapor deposition technique. In our experiment, hydrogen dilution ratio R_H was changed mainly, while the other parameters, such as the radio frequency power, the direct current bias value, the chamber pressure, the total gas flow and the substrate temperature were kept constant. The film's surface topography was gained by AFM. The chemical bond was confirmed by Fourier transform infrared spectra. The optical properties were characterized by transmission spectra. To consider absorption peak of stretching vibration mode of SiH₃ at 2140 cm⁻¹ and to reduce the calculation error, a hydrogen content calculation method was proposed. Effects of hydrogen dilution ratio on the deposition rate v and hydrogen content C_H were investigated. The bonding mode and the force constants k of chemical bond, the structural factor f in films were changed by high hydrogen dilution ratio, which gave rise to the shift of absorption peak of infrared stretching mode and the decrease of optical band gap E_g.