采用热丝辅助的新型微波电子回旋共振法制备高质量的氢化非晶硅薄膜

采用热丝辅助的新型微波电子回旋共振法制备了高质量的氢化非晶硅薄膜。在制备过程中，热丝对改进薄膜微结构，提高稳定性及光电特性方面起到了重要的作用。实验结果表明：在薄膜的微结构中，硅氢二键含量显著减少并出现了少量微晶相，其有利于改善薄膜的稳定性；在薄膜的光电特性方面，薄膜的沉积速率及光敏性分别达到了2.0nm/s和4.71*105以上。     

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.     

Use of optical emission spectroscopy to investigate the process of fabrication ofa-Si:H films in a combined silane-containing discharge

The results of investigations carried out with the aid of optical emission spectroscopy and concerned with the process of deposition of amorphous hydrogenated silicon (a-Si:H) films in a combined discharge are presented. Correlations between the intensities of emission lines and bands and the rate of the deposition of films were established. To control the quality of films, it is proposed to record changes in the intensity of the atomic hydrogen line (H_β) during the deposition of a-Si:H. A comparison of plasma radiation spectra for different types of discharge was made. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 423–426, July–August, 2000.     

Role of the hydrogen in the light-induced defects in undoped hydrogenated amorphous silicon

We have investigated the effect of the deposition temperature (i.e. the hydrogen content) on the light-induced effects in undoped hydrogenated amorphous silicon (a-Si:H). Combined junction capacitance-temperature (C-T), ESR and IR absorption measurements are carried out in both the dark annealed state (A) and the saturated light-soaked state (B), as well as after partial annealing of the samples, starting from state B. The experimental results indicate that the films deposited at the highest substrate temperature (i.e. the lowest H content) exhibit a completely different behaviour from those deposited at lower substrate temperature (i.e. with higher H concentration), when the samples are left for long times at room temperature in the dark after partial annealing. These results are discussed in detail in relation to the different models proposed to explain the light-induced effects in a-Si:H.     

Properties of a-Si:N:H films beneficial for silicon solar cells applications

Amorphous silicon-nitride thin films a-Si:N:H were obtained by plasma enhanced chemical vapour deposition (PECVD) method from SiH₄+NH₃ at 13.56 MHz. The process parameters were chosen to obtain the films of properties suitable for optoelectronic and mechanical applications. FTIR analysis of a-Si:N:H films indicated the presence of numerous hydrogen bonds (Si-H and N-H) which passivate structural defects in multicrystalline silicon and react with impurities. The morpho-logical investigations show that the films are homogeneous. The deposition of a-Si:N:H layers leads to the decrease in friction coefficient of used substrates. Optical properties were optimised to obtain the films of low effective reflectivity, large energy gap E_g from 2.4 to 2.9 eV and refractive index in the range of 1.9 to 2.2. Reduction of friction coefficient for monocrystalline silicon after covering with a-Si:N:H films was observed: from 0.25 to 0.18 for 500 cycles.     

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.     

Effect of hydrogen on hardness of amorphous silicon

A comparative study of hardness of thin films of hydrogenated amorphous silicon (a-Si:H) and hydrogen-free amorphous silicon (a-Si) was carried out to reveal the role of hydrogen in the plastic properties of amorphous silicon. In addition, the effect of hydrogen on hardness was established by changing hydrogen concentration in the material using post-deposition processing of the samples. The hydrogen concentration in a-Si:H was decreased by thermal annealing. In a-Si hydrogen was introduced by plasma hydrogenation. The values of hardness of the as-prepared a-Si and a-Si:H films were determined by nanoindentation using depth profiling. Low-depth indentation was applied to evaluate the effect of post-hydrogenation. The results obtained show that the presence of hydrogen in the amorphous silicon network leads to the increase in hardness. The conducted experiments demonstrate that plasma hydrogenation can be used as an effective tool to increase the hardness of amorphous silicon. Hardness of a-Si:H of about 12.3–12.7 GPa is as high as of crystalline silicon, suggesting a-Si:H can be a substitute for crystalline silicon in some MEMS.     

Pulsed laser deposition of photosensitive a-Si thin films

Si films have been fabricated by pulsed KrF excimer laser deposition (PLD) through the use of various Si targets and deposition conditions. The deposits consisted of droplets and homogeneous films, which were assigned to be crystalline and amorphous silicon, respectively, by the micro Raman scattering measurements. Not only the crystalline but also the amorphous Si part scarcely (<1 atomic %) contained hydrogen regardless of whether or not the films are prepared in the presence of H₂ gas. Conditions were explored to reduce the droplet formation and to produce photosensitive films. Amorphous Si films with photosensitivity (C_ph/C_d) exceeding 10³ were obtained, and they exhibited high stability against light soaking. Thus, PLD is a promising method to fabricate photosensitive and photostable a-Si films.     

Effect of hydrogen on surface texturing and crystallization of a-Si:H thin film irradiated by excimer laser

Hydrogenated amorphous silicon (a-Si:H) thin films have been considered for use in solar cell applications because of their significantly reduced cost compared to crystalline bulk silicon. However, their overall efficiency and stability are lower than that of their bulk crystalline counterpart. Limited work has been performed on simultaneously solving the efficiency and stability issues of a-Si:H. Previous work has shown that surface texturing and crystallization on a-Si:H thin film can be achieved through a single-step laser processing, which can potentially alleviate the disadvantages of a-Si:H in solar cell applications. In this study, hydrogenated and dehydrogenated amorphous silicon thin films deposited on glass substrates were irradiated by KrF excimer laser pulses and the effect of hydrogen on surface morphologies and microstructures is discussed. Sharp spikes are focused only on hydrogenated films, and the large-grained and fine-grained regions caused by two crystallization processes are also induced by presence of hydrogen. Enhanced light absorptance is observed due to light trapping based on surface geometry changes of a-Si:H films, while the formation of a mixture of nanocrystalline silicon and original amorphous silicon after crystallization suggests that the overall material stability can potentially improve. The relationship between crystallinity, fluence and number of pulses is also investigated. Furthermore, a step-by-step crystallization process is introduced to prevent the hydrogen from diffusing out in order to reduce the defect density, and the relationship between residue hydrogen concentration, fluence and step width is discussed. Finally, the combined effects show that the single-step process of surface texturing and step-by-step crystallization induced by excimer laser processing are promising for a-Si:H thin-film solar cell applications.     

Aluminium-induced crystallization of amorphous silicon films deposited by DC magnetron sputtering on glasses

Amorphous silicon (a-Si) and hydrogenated amorphous silicon (a-Si:H) films were deposited by DC magnetron sputtering technique with argon and hydrogen plasma mixture on Al deposited by thermal evaporation on glass substrates. The a-Si/Al and a-Si:H/Al thin films were annealed at different temperatures ranging from 250 to 550 °C during 4 h in vacuum-sealed bulb. The effects of annealing temperature on optical, structural and morphological properties of as-grown as well as the vacuum-annealed a-Si/Al and a-Si:H/Al thin films are presented in this contribution. The averaged transmittance of a-Si:H/Al film increases upon increasing the annealing temperature. XRD measurements clearly evidence that crystallization is initiated at 450 °C. The number and intensity of diffraction peaks appearing in the diffraction patterns are more important in a-Si:H/Al than that in a-Si/Al layers. Results show that a-Si:H films deposited on Al/glass crystallize above 450 °C and present better crystallization than the a-Si layers. The presence of hydrogen induces an improvement of structural properties of poly-Si prepared by aluminium-induced crystallization (AIC).     

沉积压力对氢化非晶硅薄膜特性的影响

采用等离子增强化学气相沉积(PECVD)系统,以乙硅烷和氢气为气源,普通钠钙玻璃为衬底制备了氢化非晶硅(a-Si∶H)薄膜,研究了沉积压力对非晶硅薄膜的沉积速率、光学带隙以及结构因子的影响。采用台阶仪、紫外可见分光光度计、傅里叶变换红外光谱仪和扫描电子显微镜等手段分别表征了a-Si∶H薄膜的沉积速率,光学带隙、结构因子和表面形貌。结果表明： 随着沉积压力的增加,沉积速率呈现先上升后下降的趋势,光学带隙不断下降。当沉积压力小于210 Pa时,以SiH键存在的H原子较多,而以SiH₂或SiH₃等形式存在的H较少; 当沉积压力大于210 Pa时,以SiH₂,(SiH₂)_n或SiH₃等形式存在的H较多。通过结构因子的计算,发现沉积压力在110～210 Pa的范围内沉积的薄膜质量较好。     

Control of epitaxial growth at a-Si:H/c-Si heterointerface by the working pressure in PECVD

The epitaxial-Si(epi-Si) growth on the crystalline Si(c-Si) wafer could be tailored by the working pressure in plasmaenhanced chemical vapor deposition(PECVD).It has been systematically confirmed that the epitaxial growth at the hydrogenated amorphous silicon(a-Si:H)/c-Si interface is suppressed at high pressure(hp) and occurs at low pressure(1p).The hp a-Si:H,as a purely amorphous layer,is incorporated in the 1p-epi-Si/c-Si interface.We find that:(i) the epitaxial growth can also occur at a-Si:H coated c-Si wafer as long as this amorphous layer is thin enough;(ii) with the increase of the inserted hp layer thickness,lp epi-Si at the interface is suppressed,and the fraction of a-Si:H in the thin films increases and that of c-Si decreases,corresponding to the increasing minority carrier lifetime of the sample.Not only the epitaxial results,but also the quality of the thin films at hp also surpasses that at lp,leading to the longer minority carrier lifetime of the hp sample than the lp one although they have the same amorphous phase.     

稳定、优质nc-Si/a-Si:H薄膜的研制和特性分析

利用等离子体增强化学气相沉积技术研制出了优质稳定的氢化非晶-纳米晶两相结构硅薄膜.薄膜的光电导率相对于器件质量的非晶硅有两个数量级的提高；光敏性也较好，光、暗电导比可以达到１０⁴，此外薄膜的光电导谱具有更宽的长波光谱响应.更为重要 的是薄膜的光致退化效应远小于典型的非晶硅薄膜，在光强为５０ｍW／ｃｍ²的卤钨灯光 照２４h后，光电导的衰退小于１０％.这种薄膜优良的光电性能源于薄膜中的非晶母体的存在使其在 光学跃迁中的动量选择定则发生松弛，因而具有大的光学吸收系数和 关键词： 非晶硅 微结构 光致变化     

Properties of a-Si:H films deposited by RF magnetron sputtering at 95 °C

In this work we have investigated the dependence of optical and electrical properties of RF sputtered undoped a-Si:H films and B or P doped a-Si:H films on hydrogen flow rate (F_H). Low deposition temperature of 95 °C was used, a process compatible with low-cost plastic substrates. FTIR spectroscopy and ESR measurements were used for the investigation of Si-H_x bonding configurations, and concentrations of hydrogen and dangling bonds. We found that there is a strong correlation between the total hydrogen concentration, the dangling bonds density and the optoelectronic properties of the films. The best photosensitivity value was found to be 1.4 × 10⁴ for the undoped films. The dark conductivity (σ_D) of the doped layers varied from 5.9 × 10⁻⁸ to 6.5 × 10⁻⁶ (Ω cm)⁻¹ for different ratios F_Ar/F_H. These variations are attributed to both the different B and P concentrations in the films (according to SIMS measurements) and the enhanced disorder of the films introduced by the large number of inactive impurities. The B doping efficiency is lower compared to the P one. A small photovoltaic effect is also observed in n-i-p solar cells fabricated on polyimide (PI) substrates having ITO as antireflective coating, with an efficiency of 1.54%.     

键合氢对GDa—Si:H薄膜光致发光性质的影响

测量了在不同衬底温度下制备的GDa-Si:H膜的光致发光谱和光吸收谱。实验发现键合氢含量的增加导致光致发光峰强度、发光峰能量、发光带半宽度、Stokes位移和热淬灭的增大。由此导出:(1)键合氢不仅能消除无辐射复合中心,而且能产生辐射复合中心;(2)随着键合氢含量的增加电子-声子相互作用增强,带尾宽度缓慢变窄。 关键词：     

Transport and stability studies on high band gap a-Si:H films prepared by argon dilution

Device quality hydrogenated amorphous silicon films (a-Si:H) are deposited at a high deposition rate (4–5 Å/s) using a mixture of argon and hydrogen-diluted silane. The films exhibit good opto-electronic properties and show less degradation upon light soaking. Light-induced changes in conductivity could be annealed at much lower temperature. The presence of Ar^* and atomic hydrogen in plasma replaces the weak Si-Si bonds, which are responsible for light-induced degradation by strong Si-Si bonds. This results in the improved stability of the films.     

a-Si:H/a-SiNx:H超晶格薄膜光致发光性质的研究

本文报道了a-Si:H/a-SiNx:H超晶格薄膜光致发光某些性质的研究。实验发现,这种超晶格薄膜光致发光的强度和峰值能量随交替层a-Si:H厚度,测量温度及光照时间等而变化。同时还发现,在阴、阳两极上,利用GD法沉积的样品,发光强度和峰值能量也有所不同。文中对这些实验结果作了初步解释。     

Nuclear magnetic resonance investigation of H, H2 and dopants in hydrogenated amorphous silicon and related materials

Nuclear magnetic resonance has been successfully applied to the study of the microstructure of hydrogenated amorphous silicon and related materials. It has been used to determine the local bonding and structural environment of the host atoms, the hydrogen, and the dopants. First, we review some of these NMR experimental results on the hydrogen microstructure in hydrogentaed amorphous semiconductors and compare the results on plasma deposited hydrogenated amorphous silicon (a-Si:H), remote hydrogen plasma deposited a-Si:H, thermally annealed a-Si:H, doped a-Si:H, microcrystalline Si and amorphous (Si, Ge):H alloys. A common feature is that these materials exhibit a heterogeneous distribution of hydrogen bonded to the semiconductor lattice in dilute and clustered phases. In addition, the lattice contains voids of varying number and size that contain non-bonded molecular hydrogen whose quantity is altered by deposition conditions and thermal treatment. Second, we review some aspects of the local bonding structure of dopants in a-Si:H. A significant fraction of the dopants are found to be in dopant-hydrogen clusters similar to those proposed to explain hydrogen passivation in crystalline silicon. Implications of the determined local structure on the doping efficiency are discussed.     

氢化非晶硅薄膜中氢含量及键合模式的红外分析

Fourier红外透射(FTIR)谱技术是研究氢化非晶硅（a-Si∶H）薄膜中氢的含量（CH）及硅—氢键合模式（Si-Hn）最有效的手段.对用等离子体化学气相沉积（PCVD）方法在不同的衬底温度（Ts）下制备出的氢化非晶硅薄膜，通过红外透射光谱的基线拟合、高斯拟合分析，得到了薄膜中的氢含量，硅氢键合模式及其组分，并分析了这些参量随衬底温度变化的规律.