Amorphous to crystalline phase transition in pulsed laser deposited silicon carbide

SiC thin films were grown on Si (1 0 0) substrates by excimer laser ablation of a SiC target in vacuum. The effect of deposition temperature (up to 950 °C), post-deposition annealing and laser energy on the nanostructure, bonding and crystalline properties of the films was studied, in order to elucidate their transition from an amorphous to a crystalline phase. Infra-red spectroscopy shows that growth at temperatures greater than 600 °C produces layers with increasingly uniform environment of the Si-C bonds, while the appearance of large crystallites is detected, by X-ray diffraction, at 800 °C. Electron paramagnetic resonance confirms the presence of clustered paramagnetic centers within the sp² carbon domains. Increasing deposition temperature leads to a decrease of the spin density and to a temperature-dependent component of the EPR linewidth induced by spin hopping. For films grown below 650 °C, post-deposition annealing at 1100 °C reduces the spin density as a result of a more uniform Si-C nanostructure, though large scale crystallization is not observed. For greater deposition temperatures, annealing leads to little changes in the bonding properties, but suppresses the temperature dependent component of the EPR linewidth. These findings are explained by a relaxation of the stress in the layers, through the annealing of the bond angle disorder that inhibits spin hopping processes.     

Research on the boron contamination at the p/i interface of microcrystalline silicon solar cells deposited in a single PECVD chamber

This paper studies boron contamination at the interface between the p and i layers of μ c-Si:H solar cells deposited in a single-chamber PECVD system. The boron depth profile in the i layer was measured by Secondary Ion Mass Spectroscopy. It is found that the mixed-phase μ c-Si:H materials with 40% crystalline volume fraction is easy to be affected by the residual boron in the reactor. The experimental results showed that a 500-nm thick μ c-Si:H covering layer or a 30-seconds of hydrogen plasma treatment can effectively reduce the boron contamination at the p/i interface. However, from viewpoint of cost reduction, the hydrogen plasma treatment is desirable for solar cell manufacture because the substrate is not moved during the hydrogen plasma treatment.     

Defects in thin film silicon at the transition from amorphous to microcrystalline structure

Defects in thin film silicon with different structure all the way from amorphous to microcrystalline were investigated by electron spin resonance with emphasis on amorphous material prepared close to the transition to crystalline growth. Electron beam irradiation and stepwise annealing is used for reversible variation of the defect density over three orders of magnitude. The electron irradiation enhances mainly the native paramagnetic defects. Additional resonances are found as satellites to the central line, which anneal rapidly at temperatures below 100 °C. These features are most pronounced for the amorphous material prepared close to the transition to crystalline growth. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

分步法高速沉积微晶硅薄膜

为提高微晶硅薄膜的纵向结晶性能, 在甚高频等离子体增强化学气相沉积技术的基础上, 采用过渡参数缓变和两步法相结合的方法在普通玻璃衬底上高速沉积薄膜. 当功率密度为2.1 W/cm², 硅烷浓度在6%和9.6%之间变化时, 从薄膜方向和玻璃方向测算的Raman晶化率的差异维持在2%以内. 硅烷浓度为9.6%时, 薄膜沉积速率可达3.43 nm/s, 从薄膜方向和玻璃方向测算的Raman晶化率分别为50%和48%, 差异的相对值仅为4.0%. 合理控制过渡阶段的参数变化, 可使两个方向的Raman晶化率差值下降到一个百分点. 表明采用新方法制备薄膜, 不仅可以抑制非晶孵化层的形成, 改善微晶硅薄膜的纵向结构, 还为制备优质薄膜提供了较宽的参数变化空间. 关键词： 微晶硅薄膜 非晶孵化层 高速沉积 甚高频等离子体增强化学气相沉积     

Si-nanostructures formation in amorphous silicon nitride SiNx:H deposited by remote PECVD

The formation of silicon nanoclusters embedded in amorphous silicon nitride (SiN_x:H) can be of great interest for optoelectronic devices such as solar cells. Here amorphous SiN_x:H layers have been deposited by remote microwave-assisted chemical vapor deposition at 300 °C substrate temperature and with different ammonia [NH₃]/silane [SiH₄] gas flow ratios (R=0.5−5). Post-thermal annealing was carried out at 700 °C during 30 min to form the silicon nanoclusters. The composition of the layers was determined by Rutherford back scattering (RBS) and elastic recoil detection analysis (ERDA). Fourier transform infrared spectroscopy (FTIR) showed that the densities of SiH (2160 cm⁻¹) and NH (3330 cm⁻¹) molecules are reduced after thermal annealing for SiN:H films deposited at flow gas ratio R>1.5. Breaking the SiH bonding provide Si atoms in excess in the bulk of the layer, which can nucleate and form Si nanostructures. The analysis of the photoluminescence (PL) spectra for different stoichiometric layers showed a strong dependence of the peak characteristics (position, intensity, etc.) on the gas flow ratio. On the other hand, transmission electron microscopy (TEM) analysis proves the presence of silicon nanoclusters embedded in the films deposited at a gas flow ratio of R=2 and annealed at 700 °C (30 min).     

Formation mechanism of incubation layers in the initial stage of microcrystalline silicon growth by PECVD

The incubation layers in microcrystalline silicon films (\muc-Si:H) are studied in detail. The incubation layers in \muc-Si:H films are investigated by bifacial Raman spectra, and the results indicate that either decreasing silane concentration (SC) or increasing plasma power can reduce the thickness of incubation layer. The analysis of the in-situ diagnosis by plasma optical emission spectrum (OES) shows that the emission intensities of the SiH*(412\,nm) and H_\al (656nm) lines are time-dependent, thus SiH*/H_\al ratio is of temporal evolution. The variation of SiH*/H_\al ratio can indicate the variation in relative concentration of precursor and atomic hydrogen in the plasma. And the atomic hydrogen plays a crucial role in the formation of \muc-Si:H; thus, with the plasma excited, the temporal-evolution SiH*/H_\al ratio has a great influence on the formation of an incubation layer in the initial growth stage. The fact that decreasing the SC or increasing the plasma power can decrease the SiH*/H_\al ratio is used to explain why the thickness of incubation layer can reduce with decreasing the SC or increasing the plasma power.     

Amorphous silicon waveguides grown by PECVD on an Indium Tin Oxide buried contact

Low-loss hydrogenated amorphous silicon (α-Si:H) waveguides were realized by plasma enhanced chemical vapour deposition (PECVD) on a transparent conductive oxide (TCO) layer which is intended to provide the buried contact in active devices, e.g. switches and modulators. In particular we propose a technological solution to overcome both the strong reduction in optical transmittance due to the very high extinction coefficient of metal contacts and, at the same time, the optical scattering induced by the texturization effect induced in α-Si:H films grown on TCO. The realized waveguides were characterized in terms of propagation losses at 1550 nm and surface roughness. The experimental performances have been compared to those obtained through calculations using an optical simulation package. The results are found to be in agreement with the experimental data.     

微晶硅薄膜晶体管稳定性研究

对有源区处于结构过渡区的微晶硅底栅薄膜晶体管，测试其偏压衰退特性时，观察到一种“自恢复”的衰退现象.当栅和源漏同时施加10 V的偏压时，测试其源-漏电流随时间的变化，发现源-漏电流先衰减、而后又开始恢复上升的反常现象.而当采用栅压为10 V、源-漏之间施加零偏压的模式时，源-漏电流随时间呈先是几乎指数式下降、随之是衰退速度减缓的正常衰退趋势.就此现象进行了初步探讨. 关键词： 过渡区硅材料 微晶硅薄膜晶体管 稳定性 自恢复衰退     

Laser annealing study of PECVD deposited hydrogenated amorphous silicon carbon alloy films

The influence of carbon content on the crystallization process has been investigated for the excimer laser annealed hydrogenated amorphous silicon carbon alloy films deposited by Plasma Enhanced Chemical Vapour Deposition (PECVD) technique, using silane methane gas mixture diluted in helium, as well as for the hydrogenated microcrystalline silicon carbon alloy films prepared by PECVD from silane methane gas mixture highly diluted in hydrogen, for comparison. The study demonstrates clearly that the increase in the carbon content prevents the crystallization process in the hydrogen diluted samples while the crystallization process is enhanced in the laser annealing of amorphous samples because of the increase in the absorbed laser energy density that occurs for the amorphous films with the higher carbon content. This, in turn, facilitates the crystallization for the laser annealed samples with higher carbon content, resulting in the formation of SiC crystallites along with Si crystallites.     

单室沉积高效非晶硅/微晶硅叠层太阳电池的研究

采用甚高频等离子体增强化学气相沉积技术,在前期单室沉积的微晶硅薄膜太阳电池和非晶硅/微晶硅叠层太阳电池研究的基础上,通过对微晶硅底电池本征层硅烷浓度的优化,获得了初始效率达到11.02%(电池面积1.0 cm²)的非晶硅/微晶硅叠层太阳电池.同时,100 cm²的非晶硅/微晶硅叠层太阳电池的组件效率也达到了9.04%. 关键词： 非晶硅/微晶硅叠层电池 单室 甚高频     

VHF-PECVD低温制备微晶硅薄膜的拉曼散射光谱和光发射谱研究

采用拉曼散射光谱和PR650光谱光度计对VHF-PECVD制备的微晶硅薄膜进行了结构表征和在线监测研究.结果表明：功率对材料的晶化率（χc）有一定的调节作用，硅烷浓度大，微调作用更明显；SiH*的强度只能在一定的范围内表征材料的沉积速率，功率大相应的速率反而下降；I［Hα*］/I［SiH*］强度比值反映了材料晶化程度，此结果和拉曼散射光谱测试结果显示出一致性；I［Hβ*］/I［Hα*］的强度比表明氢等离子体中的电子温度随功率的增大而逐渐降低. 关键词： 甚高频等离子体增强化学气相沉积 微晶硅 拉曼散射谱 光发射谱     

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.      

The interfacial reaction between ITO and silicon nitride deposited by PECVD in fringe field switching device

In fringe field switching (FFS) device, the distance (l) between electrodes should be smaller than the cell gap (d) to generate fringe field. In order to increase the transmittance, common and pixel electrodes which are separated with the insulator should be transparent conductive materials. When the silicon-nitride by plasma enhanced chemical vapor deposition using SiH₄ gas is deposited on ITO in FFS device, the radical containing hydrogen causes the reduction of the indium-oxide to metallic indium on the film surface and finally the decrease of transmittance in visible range. To prohibit the reduction of In, the reduction of SiH₄ flow rate is needed. Therefore we suggest the two-step process in depositing the SiN_x consisting of a buffer-SiN_x layer and a bulk-SiN_x layer.     

微晶硅薄膜的结构及光学性质的研究

借助RF-PECVD辅助RTP技术，采用高沉积气压的技术路线制备了优质的微晶硅薄膜，并利用拉曼光谱、反射谱和透射谱分别研究了微晶硅的晶化率和光学性质.实验中发现微晶硅的吸收边出现了相对红移，此相对红移可归结于薄膜晶化率的提高和带尾态密度的降低. 关键词： 微晶硅 拉曼光谱 快速热处理 红移     

Use of neural network method to characterize pressure controlled charge density of silicon nitride films deposited by PECVD

A prediction model of charge density of silicon nitride (SiN) films was constructed by using a generalized regression neural network (GRNN). The SiN film was deposited by a plasma enhanced chemical vapor deposition (PECVD) system and the deposition process was characterized by means of a statistical experiment. The prediction performance of GRNN was optimized by using a genetic algorithm (GA) and yielded an improved prediction of about 63% over statistical regression model. The optimized model was utilized to qualitatively investigate the effect of process parameters under various pressures. A refractive index model was effectively utilized to validate charge density variations. For the variations in process parameters, charge density was strongly dependent on [N-H]. Effects of NH₃ or SiH₄ flow rates were significant only under high collision rate. Effect of pressure-induced collision rate was noticeable only at higher NH₃ flow rate or lower SiH₄ flow rate.     

提高微晶硅薄膜太阳电池效率的研究

采用甚高频等离子体增强化学气相沉积技术制备了系列微晶硅薄膜太阳电池，指出了气体总流量和背反射电极的类型对电池性能参数的影响.电池的I-V测试结果表明：随反应气体总流量的增加，对应电池的短路电流密度、开路电压和填充因子都有很大程度的提高，结果使得电池的光电转换效率得以提高.另外，ZnO/Ag/Al背反射电极能明显提高电池的短路电流密度，进而也提高了电池的光电转换效率.对气体总流量和背反射电极类型影响电池效率的原因进行了分析. 关键词： 微晶硅薄膜太阳电池 气体流量 ZnO/Ag/Al背反射电极     

沉积温度对微晶硅薄膜结构特性的影响

采用PECVD技术，在玻璃衬底上沉积μc-Si:H薄膜. 用拉曼光谱、SEM和UV分光光度计对不同沉积温度下沉积的薄膜的结构特性进行分析. 研究发现：沉积温度较低时，随着沉积温度的升高，薄膜的晶化率增加；当沉积温度超过某一温度值时，随着温度的进一步升高，薄膜的晶化率降低. 这时，表面反应由表面扩散限制转变为流量控制. 该温度值随着硅烷含量的降低而降低. 关键词： 氢化微晶硅薄膜 拉曼散射谱 晶化率 UV分光光度计     

电子束蒸发法制备ZrO2薄膜的相变模型分析

 用电子束蒸发方法制备了纯的ZrO₂薄膜和含Y₂O₃摩尔分数为7%和13%的ZrO₂薄膜,即YSZ薄膜,通过测定薄膜的损伤阈值来验证温度诱导相变模型;并用X射线衍射（XRD）来测定ZrO₂和YSZ镀膜材料和薄膜的结构特征。结果表明：ZrO₂镀膜材料和薄膜室温下都表现为单斜相,YSZ镀膜材料和薄膜室温下都以立方相存在;YSZ薄膜的损伤阈值远高于ZrO₂薄膜的损伤阈值,这是因为添加Y₂O₃后的YSZ材料的相比较稳定,在蒸发过程中不会发生相变,而ZrO₂材料则发生相变,产生缺陷,缺陷在激光作用下成为吸收中心和初始破坏点,导致ZrO₂薄膜的损伤阈值降低。     

超薄高速率单结微晶硅薄膜电池及其叠层电池

采用甚高频等离子体增强化学气相沉积技术, 基于优化表面形貌及光电特性的溅射后腐蚀ZnO:Al衬底, 将通过调控工艺参数获得的器件质量级高速微晶硅(μupc-Si:H )材料(沉积速率达10.57 Å/s)应用到微晶硅单结电池中, 获得了初始效率达7.49%的高速率超薄微晶硅单结太阳电池(本征层厚度为1.1 μm). 并提出插入n型微晶硅和p型微晶硅的隧穿复合结, 实现了非晶硅顶电池和微晶硅底电池之间的低损电连接, 由此获得了初始效率高达12.03% (V_oc=1.48 eV, J_sc=11.67 mA/cm², FF=69.59%)的非晶硅/微晶硅超薄双结叠层电池(总厚度为1.48 μm), 为实现低成本生产太阳电池奠定了基础.     

A fast method to diagnose phase transition from amorphous to microcrystalline silicon

A series of hydrogenated silicon thin films were prepared by the radio frequency plasma enhanced chemical vapor deposition method (RF-PECVD) with various silane concentrations. The influence of silane concentration on structural and electrical characteristics of these films was investigated to study the phase transition region from amorphous to microcrystalline phase. At the same time, optical emission spectra (OES) from the plasma during the deposition process were monitored to get information about the plasma properties, Raman spectra were measured to study the structural characteristics of the deposited films. The combinatorial analysis of OES and Raman spectra results demonstrated that the OES can be used as a fast method to diagnose phase transition from amorphous to microcrystalline silicon. At last the physical mechanism, why both OES and Raman can be used to diagnose the phase transition, was analyzed theoretically.