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.     

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     

相变域硅薄膜材料的光稳定性

采用RF-PECVD技术，通过改变反应气体的硅烷浓度制备了一系列不同晶化率不掺杂的硅薄膜材料，研究了工艺变化对材料结构的影响及材料光电特性同微结构的关系.随后进行了光衰退试验，在分析光照前后光电特性变化规律的基础上，认为材料中的非晶成分是导致材料光电特性衰退的主要原因.在靠近过渡区非晶一侧的硅材料比普通非晶硅稳定，衰退率较少；高晶化率微晶硅材料性能稳定，基本不存在光衰退；在靠近过渡区微晶一侧的硅材料虽然不是完全不衰退，但相比高晶化率硅材料来说更适合制备高效微晶硅电池. 关键词： 射频等离子体增强化学气相沉积 硅薄膜 Staebler-Wronski(SW)效应 稳定性     

微晶硅薄膜的制备及结构和稳定性研究

采用甚高频等离子体增强化学气相沉积技术制备了不同衬底温度的微晶硅薄膜.利用傅里叶变换红外吸收对制备薄膜进行了结构方面的测试分析.结果表明：随衬底温度的升高，材料 中的氢含量总的趋势下降；傅里叶变换红外吸收和二次离子质谱测试结果都显示薄膜中氧含 量随衬底温度的升高而增加（在10¹⁹cm^-3量级）；与高衬底温度相 比，低衬底温度制备的材料易于后氧化，这说明低温制备材料的稳定性不好. 关键词： 甚高频等离子体增强化学气相沉积 微晶硅薄膜 傅里叶变换红外吸收     

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.      

甚高频等离子体增强化学气相沉积制备微晶硅太阳电池的研究

采用甚高频等离子体增强化学气相沉积技术成功地制备了不同硅烷浓度和辉光功率条件下的微晶硅电池.电池的J-V测试结果表明：在实验的硅烷浓度和功率范围内，随硅烷浓度的降低和功率的加大，对应电池的开路电压逐渐变小；硅烷浓度的不同对电池的短路电流密 度有很大的影响，但功率的影响在实验研究的范围内不是很显著.对于微晶硅电池，N层最好 是非晶硅，这是因为一方面可以降低对电流的横向收集效应，另一方面也降低了电池的漏电概率，提高了电池的填充因子. 关键词： 微晶硅太阳电池 甚高频等离子体增强化学气相沉积     

Microstructure of hydrogenated silicon thin films prepared from silane diluted with hydrogen

We report results obtained from FTIR and TEM measurements carried out on silicon thin films deposited by plasma-enhanced chemical vapor deposition (PECVD) from silane diluted with hydrogen. The hydrogen content, the microstructure factor, the mass density and the volume per Si-H vibrating dipoles were determined as a function of the hydrogen dilution. 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). With increasing dilution the transition from amorphous to microcrystalline phase appears faster and the average mass density of the films decreases. The μc-Si:H films are mixed-phase void-rich materials with changing triphasic volume fractions of crystalline and amorphous phases and voids. Different bonding configurations of vibrating Si-H dipoles were observed in the a-Si:H and μc-Si:H. The bonding of hydrogen to silicon in the void- and vacancy-dominated mechanisms of network formation is discussed.     

相变区硅薄膜拉曼和红外光谱分析

采用等离子体增强化学气相沉积(PECVD)技术制备了一系列不同氢稀释率下的硅薄膜,采用拉曼散射光谱和傅里叶红外光谱技术研究了非晶/微晶相变区硅薄膜的微观结构变化,将次晶结构(paracrystalline structure)引入到非晶/微晶相变区硅薄膜结构中,提出了次晶粒体积分数(f_p),用来表征硅薄膜中程有序程度。结果表明,氢稀释率的提高导致硅薄膜经历了从非晶硅到微晶硅的相变过程,在相变区靠近非晶相的一侧,硅薄膜表现出氢含量高、结构致密和中程有序度高等特性,氢在薄膜的生长中主要起到表面钝化作用。在相变区靠近微晶相的一侧,硅薄膜具有氢含量低、晶化率高和界面体积分数小等特性,揭示了氢的刻蚀作用主控了薄膜生长过程。采用扫描电子显微镜对样品薄膜的表面形貌进行分析,验证了拉曼散射光谱和傅里叶红外光谱的分析结果。非晶/微晶相变区尤其是相变区边缘硅薄膜结构特性优良,在太阳能电池应用中适合用作硅基薄膜电池本征层。     

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     

The Effect of Substrate Temperature on the Properties of Nanostructured Silicon Carbide Films Deposited by Hypersonic Plasma Particle Deposition

Nanostructured silicon carbide films have been deposited on molybdenum substrates by hypersonic plasma particle deposition. In this process a thermal plasma with injected reactants (SiCl₄ and CH₄) is expanded through a nozzle leading to the nucleation of ultrafine particles. Particles entrained in the supersonic flow are then inertially deposited in vacuum onto a temperature-controlled substrate, leading to the formation of a consolidated film. In the experiments reported, the deposition substrate temperature T_s has ranged from 250°C to 700°C, and the effect of T_s on film morphology, composition, and mechanical properties has been studied. Examination of the films by scanning electron microscopy has shown that the grain sizes in the films did not vary significantly with T_s. Micro-X-ray diffraction analysis of the deposits has shown that amorphous films are deposited at low T_s, while crystalline films are formed at high T_s. Rutherford backscattering spectrometry has indicated that the films are largely stoichiometric silicon carbide with small amounts of chlorine. The chlorine content decreases from 8% to 1.5% when the deposition temperature is raised from 450°C to 700°C. Nanoindentation and microindentation tests have been performed on as-deposited films to measure hardness, Young's modulus and to evaluate adhesion strength. The tests show that film adhesion, hardness and Young's modulus increase with increasing T_s. These results taken together demonstrate that in HPPD, as in vapor deposition processes, the substrate temperature may be used to control film properties, and that better quality films are obtained at higher substrate temperatures, i.e. T_s700°C.     

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.     

Effect of Ar in the source gas on the microstructure and optoelectronic properties of microcrystalline silicon films deposited by plasma-enhanced CVD

Hydrogenated microcrystalline silicon films have been prepared by plasma-enhanced chemical vapor deposition technique using silane diluted in H₂ or H₂ + Ar. The microstructures for silicon films have been evaluated by Raman scattering spectroscopy, X-ray diffraction and Fourier-transform infrared spectroscopy. Optical characterization has been done by UV-vis spectroscopy. It is found that the addition of Ar in diluent gases efficiently improves the deposition rate and crystallinity due to an enhanced dissociation of the source gas and the energy of deexcitation of Ar* released within the growth zone. Meanwhile, the enhanced crystallinity and the reducing of hydrogen ion bombardment with increasing Ar dilution lead to the polymerization and also a bad passivation of the hydrogen which cause the widening of the optical gap and increase of defect states in the μc-Si films. The absorption coefficient and dark conductivity are found to decrease basically with increasing Ar dilution corresponding to the widening optical gap and more defects. That the activation energy increases with increasing Ar dilution or decreasing hydrogen dilution is due to the fact that more defect states lead to a pulling down of the Fermi level.     

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.     

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     

衬底温度和硼掺杂对p型氢化微晶硅薄膜结构和电学特性的影响

以B₂H₆为掺杂剂,采用射频等离子体增强化学气相沉积技术在玻璃衬底上制备p型氢化微晶硅薄膜.研究了衬底温度和硼烷掺杂比对薄膜的微结构和暗电导率的影响.结果表明：在较高的衬底温度下很低的硼烷掺杂比即可导致薄膜非晶化;在实验范围内,随着衬底温度升高薄膜的晶化率单调下降,暗电导率先缓慢增加然后迅速下降,变化趋势与硼烷掺杂比的影响极为相似.最后着重讨论了p型氢化微晶硅薄膜的生长机理. 关键词： p型氢化微晶硅薄膜 衬底温度 晶化率 电导率     

椭偏透射法测量氢化非晶硅薄膜厚度和光学参数

针对多角度椭偏测量透明基片上薄膜厚度和光学参数时基片背面非相干反射光的影响问题,报道了利用椭偏透射谱测量等离子增强化学气相沉积法(PECVD)制备的a-Si:H薄膜厚度和光学参数的方法,分析了基片温度T_s和辉光放电前气体温度T_g的影响.研究表明,用椭偏透射法测量的a-Si:H薄膜厚度值与扫描电镜(SEM)测得的值相当,推导得到的光学参数与其他研究者得到的结果一致.该方法可用于生长在透明基片上的其他非晶或多晶薄膜. 关键词： 椭偏测量 透射法 光学参数 氢化非晶硅薄膜     

Fabrication of high growth rate solar-cell-quality μc-Si:H thin films by VHF-PECVD

Several series of Si:H films were fabricated by the very high frequency plasma enhanced chemical vapour deposition (VHF-PECVD) at different substrate temperatures (T_s) and silane concentration (SC=[SiH_4]/[SiH_4+H_2]%). The results of Raman spectroscopy showed structural evolution of the Si:H films with the variation of T_s and SC. The results of x-ray diffraction (XRD) measurements indicated that T_s also influences the crystal orientation of the Si:H films. The modulation effect of T_s on crystalline volume fraction (X_c) is more evident for the high SC, which shows different trend compared to low SC. In addition, the growth rate of the films also showed a regular change with the variation of SC and T_s. Different samples in the series showed a similar increase in dark conductivity and a decrease in photosensitivity with increasing T_s and decreasing SC. Device-quality microcrystalline silicon materials were deposited at a high growth rate, characterized by relatively low dark conductivity and relatively high photosensitivity in a certain crystalline range. The microcrystalline silicon solar cell with a conversion efficiency of 4.55% has been prepared by VHF-PECVD.     

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     

Electronic structure and defect states of transition films from amorphous to microcrystalline silicon studied by surface photovoltage spectroscopy

In this paper, surface photovoltage spectroscopy (SPS) is used to determine the electronic structure of the hydrogenated transition Si films. All samples are prepared by using helicon wave plasma-enhanced chemical vapour deposition technique, the films exhibit a transition from the amorphous phase to the microcrystalline phase with increasing temperature. The film deposited at lower substrate temperature has the amorphous-like electronic structure with two types of dominant defect states corresponding to the occupied Si dangling bond states (D⁰/D^- and the empty Si dangling states (D⁺). At higher substrate temperature, the crystallinity of the deposited films increases, while their band gap energy decreases. Meanwhile, two types of additional defect states is incorporate into the films as compared with the amorphous counterpart, which is attributed to the interface defect states between the microcrystalline Si grains and the amorphous matrix. The relative SPS intensity of these two kinds of defect states in samples deposited above 300\du increases first and decreases afterwards, which may be interpreted as a result of the competition between hydrogen release and crystalline grain size increment with increasing substrate temperature.     

非晶硅太阳电池BZO/p-a-SiC:H接触特性改善的研究

采用重掺杂的p型微晶硅来改善前电极掺硼氧化锌 (ZnO:B) 和窗口层p型非晶硅碳 (p-a-SiC) 之间的非欧姆接触特性. 通过优化插入层p型微晶硅的沉积参数 (氢稀释比H₂/SiH₄、硼掺杂比B₂H₆/SiH₄) 获得了较薄厚度下 (20 nm) 暗电导率高达4.2 S/cm的p型微晶硅材料. 在本征层厚度约为150 nm, 仅采用Al背反射电极的情况下,获得了效率6.37%的非晶硅顶电池(V_oc=911 mV, FF=71.7%, J_sc=9.73 mA/cm²), 开路电压V_oc和填充因子FF均较无插入层的电池有大幅提升. 关键词： 氧化锌 p型微晶硅 非晶硅顶电池 非欧姆接触