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.     

硅薄膜沉积过程中等离子发光基团的一维空间分布研究

使用光发射谱(OES)对甚高频等离子增强化学气相沉积(VHF-PECVD)技术沉积硅薄膜时的等离子体发光基团的空间分布进行了在线监测和研究. 研究表明：等离子体的不同发光基团都存在着一个中间强度较大的区域和两边电极附近的暗区;增大硅烷浓度和提高辉光功率都会增大SiH^*峰强度;硼烷的加入,使得SiH^*和Hα^*峰强度增大,但硼烷流量变化的影响很小;硼烷流量增大,材料的晶化率下降,而I_{［Hα^*］关键词： 甚高频等离子增强化学气相沉积 等离子体 发光基团 空间分布}     

射频激发热丝化学气相沉积制备硅薄膜过程中光发射谱的研究

采用射频(rf)激发,在热丝化学气相沉积(HWCVD)制备微晶硅薄膜的过程中产生发光基元,测量了rf激发HWCVD (rf-HWCVD)的光发射谱,比较了相同工艺条件下rf-HWCVD和等离子体增强CVD(PECVD)的光发射谱,分析了rf功率、热丝温度和沉积气压对rf-HWCVD光发射谱的影响.结果表明,在射频功率<0.1W/cm²时,rf-HWCVD发射光谱反映了HWCVD高的气体分解效率和高浓度原子氢的特点,能够解释气压变化与微晶硅薄膜微结构的关系,是研究HWCVD气相过程的有 关键词： HWCVD OES 微晶硅     

高速沉积微晶硅薄膜光发射谱的研究

采用PR650光谱光度计对高速沉积微晶硅薄膜的生长过程进行了在线监测研究,并对所对应的材料进行了Raman谱和红外吸收谱(FTIR)的测试.结果表明：能反映材料晶化程度的I_［SiH^*］/I_［Hβ^*］比值在沉积时间为100 s之内有下降的趋势,且反应气体总流量T_fl越小下降趋势越明显,这与拉曼散射光谱对材料的结构测试结果一致;沉积5 min时I 关键词： 高速沉积 微晶硅薄膜 电子温度     

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.     

VHF等离子体光发射谱(OES)的在线监测

采用光发射谱(OES)测量技术，对不同制备条件下的甚高频(VHF)等离子体辉光进行了在线监 测.实验表明，VHF等离子体中特征发光峰(Si，SiH,H_α,H^*_β 等)的强度较常规的射 频(RF)等离子体明显增强，并且在制备μc-Si：H的工艺条件下(H稀释度R(H₂/S iH₄)=23 )，随激发频率的增加而增大，这些发光峰的变化趋势与材料沉积速率的变化规律较相似.Si H峰等的强度随气压的变化则因硅烷H稀释度及功率的不同而异：高H稀释(R=23)时，SiH峰强 度在低辉光功率下随反应气压的增大单调下降，在高辉光功率下随气压的变化呈现类高斯规 律；低H稀释(R=5．7)时， SiH峰随气压的变化基本上是单调下降的，下降速率也与功率有 关，这些结果表明，VHF-PECVD制备μc-Si：H和a-Si：H的反应动力学过程存在较大差异.此 外，随着激发功率的增大，Si，SiH峰都先迅速增大然后趋于饱和，并且随着H稀释率的增大 ，将更快呈现饱和现象.通过对OES结果的分析与讨论可知，VHF-PECVD技术沉积硅基薄膜可 以有效提高沉积速率，而且，硅基薄膜的沉积速率的进一步提高需要综合考虑H稀释度、气 压和功率等的匹配与优化. 关键词： 甚高频等离子体化学气相沉积 氢化硅薄膜 光发射谱     

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     

H2， He混合稀释生长微晶硅锗薄膜

采用H₂,He混合气体稀释等离子辅助反应热化学气相沉积法生长微晶硅锗薄膜,并在生长过程中对等离子体进行光发射光谱在线监测.结果表明：混合气体稀释法可以有效提高等离子体中的原子氢数目,降低等离子体中的电子温度;用XRD和光暗电导率表征样品的微结构和光电特性时发现,通过优化混合稀释气体中He和H₂气体的比例,能够减少薄膜中的缺陷态,促进薄膜<220>择优取向生长,有效改善微晶硅锗薄膜结构,提高光电吸收性能. 关键词： 化学气相沉积 微晶硅锗薄膜 光发射光谱 X射线衍射     

Preparation of thin Si:H films in an inductively coupled plasma reactor and analysis of their surface roughness

An important concern in the deposition of Si:H films is to obtain smooth surfaces. Herein, we deposit the thin Si:H films using Ar-diluted SiH₄ as feedstock gas in an inductively coupled plasma reactor. And we carry a real-time monitor on the deposition process by using optical emission spectrum technology in the vicinity of substrate and diagnose the Ar plasma radial distribution by Langmuir probe. Surface detecting by AFM and surface profilometry in large scale shows that the thin Si:H films have small surface roughness. Distributions of both the ion density and the electron temperature are homogeneous at h = 0.5 cm. Based on these experimental results, it can be proposed inductively coupled plasma reactor is fit to deposit the thin film in large scale. Also, Ar can affect the reaction process and improve the thin Si:H films characteristics.     

Evolution of microcrystalline growth pattern by ultraviolet spectroscopic ellipsometry on Si:H films prepared by Hot-Wire CVD

Ultra-violet spectroscopic ellipsometry has been applied successfully to determine the evolution of μc-Si:H film structure, including incubation layer, bulk layer and the growth zone and surface over-layer, their individual thickness and composition. In view of the availability of a significantly high atomic H density in H₂-diluted SiH₄ ensemble in Hot-Wire CVD, microcrystallization seems to be achieved easily at a low substrate temperature. Atomic H induced etching at the growing network has been identified as instrumental in controlling the microcrystallization in Si:H. Sharp elimination of the incubation layer as well as surface roughness and significant improvement in the overall crystallinity was obtained on increase in H₂ dilution to SiH₄. A H₂ dilution limited sharp transition from an amorphous dominated (a+μc)-Si mixed phase to a virtually amorphous free μc-Si phase has been identified. However, enhanced atomic H reactivity at the growth zone beyond the attainment of the amorphous free bulk and the surface layer induces porosity in the network and a gradual deviation from crystallinity.     

激光等离子体淀积硅膜

本工作研究了低温、低压下硅薄膜的激光淀积过程,获得均匀性好,平方厘米量级的多晶和非晶态薄膜。仔细测量了淀积过程的最佳条件,在380℃基片温度做得多晶膜。利用有共振吸收的光学击穿以及气体被击穿后产生爆炸波导致高能Si原子产生的模型,讨论了激光等离子体CVD动力学过程。发现TEACO₂激光击穿SiH₄,以及诱发的爆炸波对硅膜生长有重要作用。理论算得的硅膜生长面积和晶态结构与实验定性符合。 关键词：     

Influence of H2O/DEZ ratio on LPCVD ZnO:B films for application in a-Si:H/μc-Si:H tandem solar cells

In this study, boron doped zinc oxide (ZnO:B) films were prepared at different water to diethyl zinc (H₂O/DEZ) flow ratios from 0.6 to 1.4 by a low pressure chemical vapor deposition (LPCVD) technique. It is found that the morphology of ZnO:B films varies from small leaf-like to pyramidal surface structures with the increasing H₂O/DEZ flow ratio. The rough ZnO:B films deposited at a relatively H₂O/DEZ flow ratio such as 1.2 or 1.4 show a high haze value of up to 28 % at 600 nm and $\mathrm{a} (11\overline{2}0)$ preferential crystallographic orientation. All ZnO:B films were applied in hydrogenated amorphous silicon/microcrystalline silicon tandem solar cells (a-Si:H/μc-Si:H) as front electrodes. The efficiency of the solar cells increases with the increasing H₂O/DEZ flow ratio, which is attributed to a high spectral response mainly in the long-wavelength range and the consequent enhancement of short-circuit current. A high-efficiency a-Si:H/μc-Si:H tandem solar cell of 10 % was achieved. The H₂O/DEZ ratio is an important process parameter to tune the material properties of LPCVD ZnO:B films and the performances of corresponding silicon thin film solar cells.     

Silicon oxynitride thin films synthesised by the reactive gas pulsing process using rectangular pulses

Silicon oxynitride thin films were synthesised by the reactive gas pulsing process using an argon, oxygen and nitrogen gas mixture from a semiconductor Si target. Argon and nitrogen were introduced at a constant mass flow rate, whereas oxygen gas was periodically supplied using a rectangular pulsed flow rate. The O₂ injection time T_ON (or duty cycle α) was the only varied parameter. The influences of this parameter on the discharge behaviour, on the Si target voltage, and on the resulting chemical composition of the films were investigated. The temporal evolution of the total pressure exhibits exponential shape differing from the rectangular oxygen pulse shape, due to the response time of the gas flowmeter and to the progressive oxidation of the target and the chamber walls. During the T_ON time, the preferential adsorption of the introduced O₂ induces a decay in Si target voltage. Reversion to the nitrided mode is still possible as soon as the O₂ injection is stopped. The elemental analyses assessed by secondary neutral mass spectrometry (SNMS) showed that the O/N ratio within silicon oxynitride films linearly depends on the T_ON time. Increasing the duty cycle α over a certain value results in an oxidised steady state formation during the T_ON time. This formation was observed by real time measurements of the emission lines ratio I(O^*)/I(Ar^*) indicative of the O₂ partial pressure and confirmed by the time derivative of the target voltage. During the T_OFF time, the alternation with the nitrided mode becomes impossible, leading to the specific synthesis of stoichiometric SiO₂ films.     

Similarities between amorphous and microcrystalline forms of hydrogenated silicon from periodic DFT modelling: coupled Si–H vibrations in (SiH)X groups,X = 2–4

Microstructure factor (MF) is one of the most important properties of hydrogenated silicon (HS) used in industry. It is expressed via vibrational intensities of low stretching modes (LSM) of Si–H and high stretching modes (HSM) of SiH₂/SiH₃ bonds, i.e. MF = I_HSM/(I_LSM + I_HSM). Mixed character of HSM due to Si–H contributions (together with SiH₂/SiH₃ ones) is confirmed by vibrational analysis of Si–H valence bonds in a 120Si:18H model of amorphous HS at the Perdew-Burke-Ernzerhof (PBE)/projector augmented wave (PAW)level. Comparison with precedent solutions for di- and poly-vacancies in microcrystalline HS shows that the redistribution of its Si–H modes between HSM and LSM bands depends on the extent of perturbation of the vacancies. This relation between the HSM/LSM repartition and HS distortion explains possible MF dependence from short or medium range ordering and its link with crystallisation kinetics.     

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：     

Doping properties of microcrystalline silicon prepared by mercury sensitized photochemical vapor deposition

Conductivity of photo-CVD microcrystalline silicon (c-Si:H) in wide range of dopant gas concentration (10^–53/SiH₄, B₂H₆/SiH₄<10^–2) is investigated. As compared with a-Si:H, the conductivity of the film is improved more than two orders of magnitude by microcrystallization for a wide range of dopant concentration at a deposition temperature of as low as 150°C. This indicates the suitability of photo-CVD for low temperature processing. A conductivity minimum is found at a doping ratio of about B₂H₆/SiH₄=1×10^–5.     

Correlation between optical properties and Si nanocrystal formation of Si-rich Si oxide films prepared by plasma-enhanced chemical vapor deposition

We have investigated the phase separation and silicon nanocrystal (Si NC) formation in correlation with the optical properties of Si suboxide (SiO_x, 0 < x < 2) films by thermal annealing in high vacuum. The SiO_x films were deposited by plasma-enhanced chemical vapor deposition at different nitrous oxide/silane (N₂O/SiH₄) flow ratios. The as-deposited films show increased Si concentration with decreasing N₂O/SiH₄ flow ratio, while the deposition rate and surface roughness have strong correlations with the flow ratio in the N₂O/SiH₄ reaction. After thermal annealing at temperatures above 1000 °C, Fourier transform infrared spectroscopy, Raman spectroscopy, and transmission electron microscopy manifest the progressive phase separation and continuous growth of crystalline-Si (c-Si) NCs in the SiO_x films with increasing annealing temperature. We observe a transition from multiple-peak to single peak of the strong red-range photoluminescence (PL) with increasing Si concentration and annealing temperature. The appearance of the single peak in the PL is closely related to the c-Si NC formation. The PL also redshifts from ∼1.9 to 1.4 eV with increasing Si concentration and annealing temperature (i.e., increasing NC size). The good agreements of the PL evolution with NC formation and the PL peak energy with NC size distribution support the quantum confinement model.     

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.     

Preferential etching of Si–Si bond in the microcrystalline silicon germanium

Hydrogenated microcrystalline silicon germanium (μc-Si_1?xGe_x:H) films were investigated as a bottom cell absorber in multi-junction solar cells. μc-Si_1?xGe_x:H films were prepared using very high frequency (VHF, 60 MHz) plasma enhanced chemical vapor deposition (PECVD) systems working pressure of about 1.5 Torr. The precursor flow rates were carefully controlled to determine the phase transition point and to improve the crystallinity of μc-Si_1?xGe_x:H. A relatively high plasma power was necessary to have the high hydrogen (H₂) dilution. Raman spectroscopy study showed transition steps from amorphous to microstructure morphology as hydrogen dilution increasing. Crystallite Si–Ge and Ge–Ge bonds were occurred at relatively higher H₂ dilution compare to crystallite Si–Si bond. The rapidly increased Ge content as increasing the H₂ dilution is believed mainly due to the different decomposition rate of silane (SiH₄) and germane (GeH₄). The other reason of high Ge content even at the low GeH₄ precursor flow rate is probably due to the preferential etching of silicon atom by H₂. The preferential etching of Si–H possibly occurred in very highly concentrated H₂ plasma due to the preferential attachment of Si–H. The compositions of μc-Si_1?xGe_x:H films measured using RBS were Si_0.83Ge_0.17, Si_0.67Ge_0.33 and Si_0.59Ge_0.41 at H₂/SiH₄ flow rate of 60, 80 and 100, respectively. μc-Si_1?xGe_x:H films showed the dark (σ_d) and photo conductivity (σ_p) of about 10^?7 and 10^?5 S/cm, respectively and photo response (σ_p/σ_d) was about 10². This study will present the comprehensive evaluation of crystallization behavior of μc-Si_1?xGe_x:H films.     

类富勒烯纳米晶CNx薄膜及其场致电子发射特性

利用微波等离子体增强化学气相沉积技术制备出了CN_x薄膜,并利用x射线光电子能谱、x射线衍射、扫描电子显微镜和Raman光谱等测试手段对所制备的CN_x薄膜的微结构和成分进行了分析.研究了其场致电子发射特性.发现薄膜的结构和场发射特性与反应系中的甲烷、氮气及氢气的流量比有关,当甲烷、氢气及氮气流量比为8/50/50 sccm时,制备的薄膜具有弯曲层状的纳米石墨晶体结构（类富勒烯结构）和很好的场发射特性.场发射阈值电场降低至1.1V/μm.当电场为5.9V/μm时,平 关键词： 类富勒烯 x薄膜')" href="#">CN_x薄膜 场致电子发射 微波等离子体增强化学气相沉积