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     

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     

Hydrogen-induced-intrinsic transport in undoped microcrystalline silicon

It is demonstrated that microcrystalline silicon (μc-Si:H) of intrinsic character can be produced by post-growth atomic hydrogen treatment. Undoped μc-Si:H films with a dark-conductivity activation energy (E _a) of about 0.20 eV were grown by plasma-enhanced chemical vapor deposition, and then subsequently exposed to an atomic hydrogen plasma. The hydrogen treatment is shown to result in a gradual increase in the E _a with increasing treatment time, followed by saturation at about 0.57 eV, a value observed for truly intrinsic μc-Si:H films. In the saturated state, the dark conductivity is on the order of 10⁻⁷ S/cm. The dark conductivity prefactor is found to follow the Meyer–Neldel rule. It is proposed that charge transport takes place in amorphous-like tissue surrounding the crystalline grains. The results are attributed to the Fermi level shift due to a change in the gap state distribution.     

Improvement of transport properties for polycrystalline silicon prepared by plasma-enhanced chemical vapor deposition

The carrier transport property of polycrystalline silicon (poly-Si:H:F) thin films was studied in relation to film microstructure, impurity, in situ or post-annealing treatments to obtain better carrier transport properties. Poly-Si:H:F films were prepared from SiF₄ and H₂ gas mixtures at temperatures <300 °C. Dark conductivity of the films prepared at high SiF₄/H₂ gas flow ratio (e.g., 60/3 sccm) exhibits a high value for intrinsic silicon and its Fermi level is located near the conduction band edge. The carrier incorporation is suppressed well, either by in situ hydrogen plasma treatment or by post-annealing with high-pressure hot-H₂O vapor. It is confirmed that weak-bonded hydrogen atoms are removed by the hot-H₂O vapor annealing. In addition, evident correlation between impurity concentrations and dark conductivity is not found for these films. It is thought that the carrier incorporation in the films prepared at high SiF₄/H₂ gas flow ratios is related to grain-boundary defects such as weak-bonded hydrogen. By applying hot-H₂O vapor annealing at 310 °C to a 1-μm-thick p-doped (400)-oriented poly-Si:H:F film, Hall mobility was improved from 10 cm²/Vs to 17 cm²/Vs. Received: 7 August 2000 / Accepted: 2 March 2001 / Published online: 20 June 2001     

沉积速率对甚高频等离子体增强化学气相沉积制备微晶硅薄膜生长标度行为的影响

本文采用甚高频等离子体增强化学气相沉积技术制备了沉积速率系列不同生长阶段的微晶硅薄膜,通过椭圆偏振技术研究了生长过程中微晶硅薄膜表面粗糙度的演化.实验结果表明:沉积速率为0.08和0.24nm/s的低速沉积时,硅薄膜表面粗糙度接近,生长指数分别为β=0.21和β=0.20,对应有限扩散生长模式,此时沉积速率对硅薄膜生长影响不大,原因是低速沉积时成膜先驱物有足够时间迁移到能量低的位置;当沉积速率增加到0.66nm/s时,硅薄膜表面粗糙度明显增加,生长指数β=0.81,大于0.5,出现了异常标度行为,与低速沉积的生长模式明显不同,原因是高速沉积时成膜前驱物来不及扩散就被下一层前驱物覆盖,降低了成膜前驱物在薄膜表面的扩散,使表面粗糙度增加和生长指数β增大.β大于0.5的异常标度行为与阴影效应有关.     

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.     

The high deposition of microcrystalline silicon thin film by very high frequency plasma enhanced chemical vapour deposition and the fabrication of solar cells

This paper reports that the intrinsic microcrystalline silicon ($\mu $c-Si:H) films are prepared with plasma enhanced chemical vapour deposition from silane/hydrogen mixtures at 200\du\ with the aim to increase the deposition rate. An increase of the deposition rate to 0.88\,nm/s is obtained by using a plasma excitation frequency of 75\,MHz. This increase is obtained by the combination of a higher deposition pressure, an increased silane concentration, and higher discharge powers. In addition, the transient behaviour, which can decrease the film crystallinity, could be prevented by filling the background gas with Hchemical vapour deposition, plasma deposition, solar cells, crystallinityProgram supported by the State Key Development Program for Basic Research of China (Grant No 2006CB202601), and Basic Research Project of Henan Province in China (Grant No 072300410140).7280N, 7830G, 8115HThis paper reports that the intrinsic microcrystalline silicon ($\mu $c-Si:H) films are prepared with plasma enhanced chemical vapour deposition from silane/hydrogen mixtures at 200\du\ with the aim to increase the deposition rate. An increase of the deposition rate to 0.88\,nm/s is obtained by using a plasma excitation frequency of 75\,MHz. This increase is obtained by the combination of a higher deposition pressure, an increased silane concentration, and higher discharge powers. In addition, the transient behaviour, which can decrease the film crystallinity, could be prevented by filling the background gas with Hchemical vapour deposition, plasma deposition, solar cells, crystallinityProgram supported by the State Key Development Program for Basic Research of China (Grant No 2006CB202601), and Basic Research Project of Henan Province in China (Grant No 072300410140).7280N, 7830G, 8115HThis paper reports that the intrinsic microcrystalline silicon ($\mu $c-Si:H) films are prepared with plasma enhanced chemical vapour deposition from silane/hydrogen mixtures at 200\du\ with the aim to increase the deposition rate. An increase of the deposition rate to 0.88\,nm/s is obtained by using a plasma excitation frequency of 75\,MHz. This increase is obtained by the combination of a higher deposition pressure, an increased silane concentration, and higher discharge powers. In addition, the transient behaviour, which can decrease the film crystallinity, could be prevented by filling the background gas with Hchemical vapour deposition, plasma deposition, solar cells, crystallinityProgram supported by the State Key Development Program for Basic Research of China (Grant No 2006CB202601), and Basic Research Project of Henan Province in China (Grant No 072300410140).7280N, 7830G, 8115HThis paper reports that the intrinsic microcrystalline silicon ($\mu $c-Si:H) films are prepared with plasma enhanced chemical vapour deposition from silane/hydrogen mixtures at 200\du\ with the aim to increase the deposition rate. An increase of the deposition rate to 0.88\,nm/s is obtained by using a plasma excitation frequency of 75\,MHz. This increase is obtained by the combination of a higher deposition pressure, an increased silane concentration, and higher discharge powers. In addition, the transient behaviour, which can decrease the film crystallinity, could be prevented by filling the background gas with Hchemical vapour deposition, plasma deposition, solar cells, crystallinityProgram supported by the State Key Development Program for Basic Research of China (Grant No 2006CB202601), and Basic Research Project of Henan Province in China (Grant No 072300410140).7280N, 7830G, 8115HThis paper reports that the intrinsic microcrystalline silicon ($\mu $c-Si:H) films are prepared with plasma enhanced chemical vapour deposition from silane/hydrogen mixtures at 200\du\ with the aim to increase the deposition rate. An increase of the deposition rate to 0.88\,nm/s is obtained by using a plasma excitation frequency of 75\,MHz. This increase is obtained by the combination of a higher deposition pressure, an increased silane concentration, and higher discharge powers. In addition, the transient behaviour, which can decrease the film crystallinity, could be prevented by filling the background gas with H$_{2}$ prior to plasma ignition, and selecting proper discharging time after silane flow injection. Material prepared under these conditions at a deposition rate of 0.78\,nm/s maintains higher crystallinity and fine electronic properties. By H-plasma treatment before i-layer deposition, single junction $\mu $c-Si:H solar cells with 5.5{\%} efficiency are fabricated.     

Dimensional evolution of silicon nanowires synthesized by Au–Si island-catalyzed chemical vapor deposition

This study explores the nucleation and morphological evolution of silicon nanowires (Si-NWs) on Si (0 0 1) and (1 1 1) substrates synthesized using nanoscale Au–Si island-catalyzed rapid thermal chemical vapor deposition. The Au–Si islands are formed by Au thin film (1.2–3.0 nm) deposition at room temperature followed by annealing at 700 °C, which are employed as a liquid-droplet catalysis during the growth of the Si-NWs. The Si-NWs are grown by exposing the substrates with Au–Si islands to a mixture of gasses SiH₄ and H₂. The growth temperatures and the pressures are 500–600 °C and 0.1–1.0 Torr, respectively. We found a critical thickness of the Au film for Si-NWs nucleation at a given growth condition. Also, we observed that the dimensional evolution of the NWs significantly depends on the growth pressure and temperature. The resulting NWs are 30–100 nm in diameter and 0.4–12.0 μm in length. For Si (0 0 1) substrates 80% of the NWs are aligned along the 1 1 1 direction which are 30° and 60° with respect to the substrate surface while for Si (1 1 1) most of the NWs are aligned vertically along the 1 1 1 direction. In particular, we observed that there appears to be two types of NWs; one with a straight and another with a tapered shape. The morphological and dimensional evolution of the Si-NWs is significantly related to atomic diffusion kinetics and energetics in the vapor–liquid–solid processes.     

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     

Excimer-laser-assisted RF glow-discharge deposition of amorphous and microcrystalline silicon thin films

We combine the deposition of Hydrogenated amorphous Silicon (a-Si:H) by rf glow discharge with XeCl-excimer laser irradiation of the growing surface in order to obtain different kinds of silicon films in the same deposition system. In-situ UV-visible ellipsometry allows us to measure the optical properties of the films as the laser fluence is increased from 0 up to 180 mJ/cm² in separate depositions. For fixed glow-discharge conditions and a substrate temperature of 250° C we observe dramatic changes in the film structure as the laser fluence is increased. With respect to a reference a-Si:H film (no laser irradiation) we observe at low laser fluences (15–60 mJ/cm²) that the film remains amorphous but demonstrates enchanced surface roughness and bulk porosity. At intermediate fluences (80–165 m/Jcm²), we obtain an amorphous film with an enhanced density with respect to the reference film. Finally, at high fluences (165–180 mJ/cm²), we obtain microcrystalline films. The in-situ ellipsometry measurements are complemented by ex-situ measurements of the dark conductivity, X-ray diffraction, and Elastic Recoil Detection Analysis (ERDA). Simulation of the temperature profiles for different film thicknesses and for three laser fluences indicates that crystallization occurs if the surface temperature reaches the melting point of a-Si:H ( 1420 K). The effects of laser treatment on the film properties are discussed by taking into account the photonic and thermal effects of laser irradiation.Presented at LASERION 93, Munich, June 21–23, 1993     

Polycrystalline silicon films obtained by hot-wire chemical vapour deposition

Silicon films were deposited at moderate substrate temperatures (280–500° C) from pure silane and a silane-hydrogen mixture (10% SiH₄, 90% H₂) in a hotwire CVD reactor. The morphology, structure and composition of the samples were studied with scanning electron microscopy, transmission electron microscopy, transmission electron diffraction, X-ray diffraction, Raman spectroscopy and secondary ion mass spectrometry. The sample deposited at 500° C with pure silane has an amorphous structure, whereas the samples obtained from silane diluted in hydrogen have a polycrystalline structure, even that grown at the lowest temperature (280° C). Polycrystalline samples have a columnar structure with 0.3–1 m crystallite sizes with preferential orientation in [220] direction. Deposition rates depend on the filament-substrate distance and range from 9.5 to 37 Å/s for the polycrystalline samples. The high quality of the polycrystalline samples obtained makes the hot-wire technique very promising. Moreover, it is expected to be easily scaled up for applications to large-area optoelectronic devices and to photovoltaic solar cells.     

等离子体增强化学气相沉积法实现硅纳米线掺硼

用等离子体增强化学气相沉积(PECVD)方法成功实现硅纳米线的掺B.选用Si片作衬底，硅烷 （SiH4）作硅源，硼烷（B2H6）作掺杂气体， Au作催化剂，生长温度440℃.基于气-液-固(VLS)机制，探讨了掺B硅纳米线可能的生长机制.PECVD法化学成分配比更灵活，更容易实现纳米线掺杂，进一步有望生长硅纳米线pn结，为研制纳米量级器件提供技术基础. 关键词： 硅纳米线 化学气相沉积 纳米器件     

Monitoring of the growth of microcrystalline silicon by plasma‐enhanced chemical vapor deposition using in‐situ Raman spectroscopy

Raman spectra of microcrystalline silicon layers have been recorded in‐situ during growth. The spectra have been collected under realistic conditions for solar cell deposition. To enable these measurements an electrode with an optical feed through has been developed. By using a metallic grid to shield the feed through it is possible to achieve homogeneous deposition of µc‐Si:H at a sufficient optical transmission. In‐situ Raman measurements were carried out during the deposition of a layer with an intentionally introduced gradient in crystallinity that was seen in‐situ as well in reference measurements performed on the same layer ex‐situ. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Hydrogen evolution in amorphous silicon carbide

The influence of the hydrogen content and its evolution in the annealing treatments of the structural properties of hydrogenated amorphous silicon carbide (a-SiC:H) prepared by plasma enhanced chemical vapour deposition under different deposition conditions have been studied. The results indicate how strongly hydrogen affects the presence of defects in the amorphous network of the samples.     

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.     

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     

Analysis of heating effect on the process of high deposition rate microcrystalline silicon

A possible heating effect on the process of high deposition rate microcrystalline silicon has been studied.It includes the discharge time-accumulating heating effect,discharge power,inter-electrode distance,and total gas flow rate induced heating effect.It is found that the heating effects mentioned above are in some ways quite similar to and in other ways very different from each other.However,all of them will directly or indirectly cause the increase of the substrate surface temperature during the process of depositing microcrystalline silicon thin films,which will affect the properties of the materials with increasing time.This phenomenon is very serious for the high deposition rate of microcrystalline silicon thin films because of the high input power and the relatively small inter-electrode distance needed.Through analysis of the heating effects occurring in the process of depositing microcrystalline silicon,it is proposed that the discharge power and the heating temperature should be as low as possible,and the total gas flow rate and the inter-electrode distance should be suitable so that device-grade high quality deposition rate microcrystalline silicon thin films can be fabricated.     

Infrared characterization of silicon dioxide films obtained by chemical vapour deposition

Summary In this work we report new FTIR absorbance measurements due to Si−O stretching bond, Si−O−Si and O−Si−O bending bonds of silicon dioxide amorphous films. We compare the optical results obtained from films grown by APCVD, LPCVD, PACVD and thermal oxidation techniques. The effect of thermal annealing on optical obsorbance structures has been studied. To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

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.