Solution-based metal induced crystallization of a-Si

This paper investigates a simplified metal induced crystallization (MIC) of a-Si, named solution-based MIC (S-MIC). The nickel inducing source was formed on a-Si from salt solution dissolved in de-ionized water or ethanol. a-Si thin film was deposited with low pressure chemical vapour deposition or plasma enhanced chemical vapour deposition as precursor material for MIC. It finds that the content of nickel source formed on a-Si can be controlled by solution concentration and dipping time. The dependence of crystallization rate of a-Si on annealing time illustrated that the linear density of nickel source was another critical factor that affects the crystallization of a-Si, besides the diffusion of nickel disilicide. The highest electron Hall mobility of thus prepared S-MIC poly-Si is 45.6cm²/(V.s). By using this S-MIC poly-Si, thin film transistors and display scan drivers were made, and their characteristics are presented.     

硅锗量子阱结构在硅异质结太阳电池中应用的数值模拟

利用半导体工艺和器件仿真软件silvaco TCAD(Technology Computer Aided Design),模拟研究了采用硅/硅锗合金(silicon/silicon germanium alloy,Si/Si_(1-x)Ge_x)量子阱结构作为吸收层的薄膜晶体硅异质结太阳电池各项性能.模拟结果显示,长波波段光学吸收随锗含量的增加而增加,而开路电压则因Si_(1-x)Ge_x)层带隙的降低而下降.锗含量为0.25时,短路电流密度的增加补偿了开路电压的衰减,效率提升0.2%.氢化非晶硅/晶体硅(a-Si:H/c-Si)界面空穴密度以及Si_(1-x)Ge_x)量子阱的体空穴载流子浓度制约着空穴费米能级的位置,进而影响到开路电压的大小.随着锗含量增加,a-Si:H/c-Si界面缺陷对开压的影响降低,Si_(1-x)Ge_x)量子阱的体缺陷对开压的影响则相应增加.高效率含Si_(1-x)Ge_x)量子阱结构的硅异质结太阳电池的制备需要a-Si:H/c-Si界面缺陷的良好钝化以及高质量Si_(1-x)Ge_x)量子阱的生长.     

载流子选择性接触:高效硅太阳电池的选择

太阳电池可看成由光子吸收层和接触层两个基本单元组成,接触层是高复合活性金属界面和光子吸收层之间的区域.为了进一步提高硅太阳电池的转换效率,关键是降低光子吸收层和接触之间的复合损失.近年来,载流子选择性接触引起了光伏界的研究兴趣,其被认为是接近硅太阳电池效率理论极限的最后的障碍之一.本文分析了三种类型的载流子选择性接触:在光子吸收层与金属界面之间引入薄的重掺杂层,即所谓的发射极或背面场;利用两种材料之间的导带或价带对齐;利用高功函数的金属氧化物与晶硅接触从而在晶硅中感应能带弯曲.基于一维太阳电池模拟软件wx AMPS,模拟了扩散同质结硅太阳电池[结构为(p~+)c-Si/(n)c-Si/(n~+)c-Si]、非晶硅薄膜硅异质结太阳电池[结构为(p~+)a-Si/(i)a-Si/(n)c-Si/(i)a-Si/(n~+)a-Si]和氧化物薄膜硅异质结太阳电池[结构为(n)MoO_x/(n)c-Si/(n)TiO_x]暗态下的能带结构和载流子浓度的空间分布,其中c-Si为晶硅;a-Si为非晶硅;(i),(n)和(p)分别表示本征、n型掺杂和p型掺杂.模拟结果表明:载流子选择性接触的核心是在接触处晶硅表面附近形成载流子浓度空间分布的不对称进而使得电导率的不对称,形成了对电子的高阻和空穴的低阻或者对空穴的高阻和电子的低阻,从而让空穴轻松通过同时阻挡电子,或者让电子轻松通过同时阻挡空穴,形成空穴选择性接触或者电子选择性接触.     

Hydrogen evolution during deposition of microcrystalline silicon by chemical transport

We exposed a freshly deposited boron-doped, hydrogenated amorphous silicon (a-Si:H) layer to hydrogen plasma under conditions of chemical transport. In situ spectroscopic ellipsometry measurements revealed that atomic hydrogen impinging on the film surface behaves differently before and after crystallization. First, the plasma exposure increases hydrogen solubility in the a-Si:H network leading to the formation of a hydrogen-rich subsurface layer. Then, once the crystallization process engages, the excess hydrogen starts to leave the sample. We have attributed this unusual evolution of the excess hydrogen to the grown hydrogenated microcrystalline (μc-Si:H) layer, which gradually prevents the atomic hydrogen from the plasma reaching the μc-Si:H/a-Si:H interface. Consequently, hydrogen solubility, initially increased by the hydrogen plasma, recovers the initial value of an untreated a-Si:H material. To support the theory that the outdiffusion is a consequence and not the cause of the μc-Si:H layer growth, we solved the combined diffusion and trapping equations, which govern hydrogen diffusion into the sample, using appropriate approximations and a specific boundary condition explaining the lack of hydrogen injection during μc-Si:H layer growth.     

In situ spectromicroscopic study of nickel induced lateral crystallization of amorphous silicon thin film using SPESM

Scanning photoelectron spectromicroscopy (SPESM) has been used to study nickel metal induced lateral crystallization (Ni-MILC) of amorphous silicon (a-Si) thin films, produced by in situ annealing of vacuum deposited Ni patterned films on a-Si. The spatial variations in the chemical composition of the Ni-MILC of a-Si were directly imaged. High-resolution photoemission spectra of both Si 2p and Ni 3p core levels and valence band were used to evaluate morphological changes and chemical interactions. Our direct spectromicroscopic characterization clearly shows that the Ni-MILC process in UHV leads to the lower crystallization temperature and a faster crystallization speed of a-Si, and a poly-Si film with high-crystallinity can be obtained. A unified mechanism for the enhanced growth rate of the high-crystallinity poly-Si film produced by Ni-MILC in UHV is proposed.     

薄膜硅/晶体硅异质结电池中本征硅薄膜钝化层的性质及光发射谱研究

本文采用甚高频等离子体化学气相沉积技术 (VHF-PECVD) 制备薄膜硅/晶体硅异质结电池中的本征硅薄膜钝化层, 光发射谱 (OES) 测量技术研究了硅薄膜沉积过程中等离子体发光谱随时间的变化. 结果表明: 在实验优化条件下等离子体发光谱很快达到稳定 (大约25 s), 并且SiH^*/H_α^* 的比值随时间变化较小, 避免了生长过程中硅薄膜结构的不均匀性, 这主要是SiH₄没有完全耗尽避免了SiH₄的反向扩散. 进一步研究了沉积参数对稳态发光谱和硅薄膜性质的影响, 结果表明: 随着硅烷浓度增加, H_α^*峰强度减小, SiH^*峰强度增加, 薄膜从微晶转变成非晶, 非晶硅薄膜钝化效果好; 随着沉积气压增大, H_α^*和 SiH^*峰强度先增加后减小, 高气压下H_α^*和 SiH^*峰强度下降主要是反应前驱物的聚合形成高聚合物, 不利于形成高质量的硅薄膜, 因此钝化效果下降; 随着反应功率密度增加, H_α^*和 SiH^*峰强度增大, 当功率密度为150 mW/cm² 趋于饱和, 硅薄膜的致密度和钝化效果也开始下降, 50 mW/cm²的低功率密度下硅薄膜钝化效果差可能是由于原子H 浓度低, 不能完全钝化单晶硅表面的悬挂键. 关键词： 薄膜硅 异质结 光发射谱 钝化     

Electric-field-enhanced metal-induced crystallization of hydrogenated amorphous silicon at room temperature

A novel simple method of crystallization of hydrogenated amorphous silicon (a-Si:H) thin films is described. Namely, we studied a metal-induced crystallization enhanced by a dc electric field in sandwich p⁺–i–n⁺structures. The samples were fabricated from wide-bandgap a-Si:H with high hydrogen content (13–51 at. % H). Macroscopic islands of a-Si:H (up to ∼1 mm in diameter) in the region between upper (CrNi) and lower (ITO) contacts crystallize instantaneously when a sufficiently high dc electric field (≳10⁵ V cm^-1) is applied. The crystallization sets in at room temperature and ambient atmosphere and is spatially selective. A proposed microscopic mechanism of such an easy macroscopic crystallization consists in easy diffusion of Ni and/or Ni silicides (representing nucleation sites) through a dense network of voids in hydrogen-rich a-Si:H. Received: 30 November 2000 / Accepted: 3 May 2001 / Published online: 27 June 2001     

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).     

Nickel induced lateral crystallization behavior of amorphous silicon films

Nickel induced lateral crystallization of amorphous silicon with and without electric field has been studied. Dendritic silicon growth behavior is observed, with crystallites of a few hundred nanometers in width and up to a few microns in length. The behavior can be understood from the preferential epitaxial growth of silicon from the (1 1 1) facets of the NiSi₂ precipitate, which forms during the early stage of the annealing process. The dendritic growth fronts are different with and without electric field in the nickel induced lateral crystallization process. Electric field is found to be beneficial in increasing the lateral crystallization rate and improving the film crystallinity. Joule heating plays an important role as well to enhance the lateral crystallization.     

Role of amorphous silicon domains of Er^3＋ emission in the Er—doped hydrogenated amorphous silicon suboxide film

An investigation on the correlation between amorphous Si (a-Si) domains and Er^{3+} emission in the Er-doped hydrogenated amorphous silicon suboxide (a-Si:O:H) film is presented. On one hand, a-Si domains provide sufficient carriers for Er^{3+} carrier-mediated excitation which has been proved to be the highest excitation path for Er^{3+} ion; on the other hand, hydrogen diffusion from a-Si domains to amorphous silicon oxide (a-SiO_x) matrix during annealing has been found and this possibly decreases the number of nonradiative centres around Er^{3+} ions. This study provides a better understanding of the role of a-Si domains on Er^{3+} emission in a-Si:O:H films.     

Quantum confinement in amorphous silicon quantum dots embedded in silicon nitride

Amorphous silicon quantum dots (a-Si QDs) were grown in a silicon nitride film by plasma enhanced chemical vapor deposition. Transmission electron micrographs clearly demonstrated that a-Si QDs were formed in the silicon nitride. Photoluminescence and optical absorption energy measurement of a-Si QDs with various sizes revealed that tuning of the photoluminescence emission from 2.0 to 2.76 eV is possible by controlling the size of the a-Si QD. Analysis also showed that the photoluminescence peak energy E was related to the size of the a-Si QD, a (nm) by E(eV) = 1.56+2.40/a(2), which is a clear evidence for the quantum confinement effect in a-Si QDs.     

Effects of irradiation conditions on the lateral grain growth during laser crystallization of amorphous silicon films on borosilicate glass substrates

The effects of preheating laser power and pulse laser energy on the size and crystallinity of laterally grown grains by dual-laser crystallization of amorphous silicon (a-Si) films on borosilicate glass substrates were investigated. Plasma-enhanced chemical vapor deposition was adopted for the deposition of the a-Si films in order to reduce the process temperature and thus the diffusion of metal impurities from the glass substrate to the deposited a-Si films. It was found that the preheating laser power is critical in enhancing grain size, whereas the pulse laser energy is closely related to crystal quality. It is demonstrated that by properly adjusting the process conditions, laterally grown grains of 50-μm size could be obtained.     

硅异质结太阳电池的物理机制和优化设计

硅异质结太阳电池是一种由非晶硅薄膜层沉积于晶硅吸收层构成的高效低成本的光伏器件,是一种具有大面积规模化生产潜力的光伏产品.异质结界面钝化品质、发射极的掺杂浓度和厚度以及透明导电层的功函数是影响硅异质结太阳电池性能的主要因素.针对这些影响因素已经有大量的研究工作在全世界范围内展开,并且有诸多研究小组提出了器件效率限制因素背后的物理机制.洞悉物理机制可为今后优化设计高性能的器件提供准则.因此及时总结硅异质结太阳电池的物理机制和优化设计非常必要.本文主要讨论了晶硅表面钝化、发射极掺杂层和透明导电层之间的功函数失配以及由此形成的肖特基势垒;讨论了屏蔽由功函数失配引起的能带弯曲所需的特征长度,即屏蔽长度;介绍了硅异质结太阳电池优化设计的数值模拟和实践;总结了硅异质结太阳电池的研究现状和发展前景.     

铝诱导非晶硅薄膜的场致低温快速晶化及其结构表征

铝诱导非晶硅薄膜晶化可以降低退火温度、缩短退火时间，是制备多晶硅薄膜的一种重要方法.在此基础上，通过在退火过程中加入电场加速了界面处硅、铝原子间的互扩散，实现了非晶硅薄膜的快速低温晶化.实验结果表明，外加电场，退火温度为400℃，退火时间为60min时，薄膜的晶化率大于60％；退火温度为450℃退火时间为30min时，薄膜已经呈现明显的晶化现象；退火温度为500℃退火时间为15min时，薄膜的x射线多晶峰强度与非晶峰强度之比为未加电场的3—4倍. 关键词： 非晶硅薄膜 多晶硅薄膜 外加电场     

Nickel-disilicide-assisted excimer laser crystallization of amorphous silicon

Polycrystalline silicon (poly-Si) thin film has been prepared by means of nickel-disilicide (NiSi多晶硅 受激准分子激光器结晶 结晶化 界面晶粒生长polycrystalline silicon, excimer laser crystallization,Ni-disilicide, Ni-metal-induced lateral crystallization, two-interface grain growthProject supported by the National High Technology Development Program of China (Grant No 2002AA303250) and by the National Natural Science Foundation of China (Grant No 60576056).9/7/2005 12:00:00 AM3/6/2006 12:00:00 AMPolycrystalline silicon （poly-Si） thin film has been prepared by means of nickel-disilicide （NiSi2） assisted excimer laser crystallization （ELC）. The process to prepare a sample includes two steps. One step consists of the formation of NiSi2 precipitates by heat-treating the dehydrogenated amorphous silicon （a-Si） coated with a thin layer of Ni. And the other step consists of the formation of poly-Si grains by means of ELC. According to the test results of scanning electron microscopy （SEM）, another grain growth model named two-interface grain growth has been proposed to contrast with the conventional Ni-metal-induced lateral crystallization （Ni-MILC） model and the ELC model. That is, an additional grain growth interface other than that in conventional ELC is formed, which consists of NiSi2 precipitates and a-Si. The processes for grain growth according to various excimer laser energy densities delivered to the a-Si film have been discussed. It is discovered that grains with needle shape and most of a uniform orientation are formed which grow up with NiSi2 precipitates as seeds. The reason for the formation of such grains which are different from that of Ni-MILC without migration of Ni atoms is not clear. Our model and analysis point out a method to prepare grains with needle shape and mostly of a uniform orientation. If such grains are utilized to make thin-film transistor, its characteristics may be improved.     

Dynamics of hydrogen in hydrogenated amorphous silicon

The problem of hydrogen diffusion in hydrogenated amorphous silicon (a-Si:H) is studied semiclassically. It is found that the local hydrogen concentration fluctuations-induced extra potential wells, if intense enough, lead to the localized electronic states in a-Si:H. These localized states are metastable. The trapping of electrons and holes in these states leads to the electrical degradation of the material. These states also act as recombination centers for photo-generated carriers (electrons and holes) which in turn may excite a hydrogen atom from a nearby Si-H bond and breaks the weak (strained) Si-Si bond thereby apparently enhancing the hydrogen diffusion and increasing the light-induced dangling bonds.     

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.     

On the modeling of hydrogen diffusion processes and complex formation in p-type crystalline silicon

Deuterium diffusion profiles in p-type silicon doped with boron (10¹⁷–10¹⁹ cm^-3) and aluminum (10¹⁸ cm^-3) are simulated with an improved version of a previously reported model. The new approach, based on the observation of experimental profiles, excludes H₂ molecule formation and leads to a reduced fit parameters model. The different diffusion coefficients and activation energies of H⁰ and H⁺ species are determined and discussed in the light of available data. The dissociation energies of BH and AlH complexes are also calculated and found to be in good agreement with the corresponding reported values in the literature.     

Enhanced metal-induced-crystallization of hydrogenated amorphous silicon by electric field

This article demonstrates that metal-induced crystallization of PECVD grown amorphous silicon can be enhanced by the application of an external electrical field. Results from the observation of the Si(111) XRD peak height of the thermally annealed Si/Al/glass structure show that at very high vertical electric field (up to 7000 V/cm) no enhancement on aluminum induced crystallization of a-Si is found, whereas a clear enhancement of crystallization can be observed for the horizontal electric field as low as 100 V/cm. Mechanisms are proposed to explain such an observation, and it is suggested that the vertical Al/Si interdifussion process is prolonged under horizontal electric fields because of the presence of electron-collision caused by Al or AlSi_x ions, which allows more nucleation to take place. PACS 61.10.Kw; 81.10.Jt; 81.40.-z     

Modeling of silicon-nanocrystal formation in amorphous silicon/silicon dioxide multilayer structure

The formation process of silicon-nanocrystals （Si-NCs） in the amorphous silicon/silicon dioxide （a-Si/SiO2） multilayer structure during thermal annealing is theoretically studied with a modified model based on the Gibbs free energy variation. In this model, the concept of average effective interfacial free energy variation is introduced and the whole formation process consisting of nucleation and subsequent growth is considered. The calculating results indicate that there is a lower limit of the silicon layer thickness for forming Si-NCs in a-Si/SiO2 multilayer, and the oxide interfaces cannot constrain their lateral growth. Furthermore, by comparing the results for a-Si/SiO2 and a-Si/SiNx multilayers, it is found that the constraint on the crystal growth from the dielectric interfaces depends on the difference between interfacial free energies.