磁控溅射制备氧化硅薄膜生长速率

氧化硅薄膜是半导体工业中常见的薄膜材料,通常采用化学气相沉积方法制备。但是这种制备方法存在缺欠。采用磁控溅射的方法首先在石英衬底上制备了氧化硅薄膜。研究了射频功率、氧气含量和溅射压强对氧化硅薄膜沉积速率的影响。发现沉积速率随着射频功率的增加而增加;随着氧气含量的增加,先减小后增大;当溅射压强在0.4~0.8 Pa之间变化时,沉积速率变化很小,当溅射压强超过0.8 Pa时沉积速率迅速下降。讨论了不同生长条件下造成氧化硅薄膜生长速率变化的原因。     

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.     

甚高频高速沉积微晶硅薄膜的研究

采用甚高频化学气相沉积(VHF-PECVD)技术制备了系列微晶硅(μc-Si:H)薄膜样品,重点研究了硅烷浓度、功率密度、沉积气压和气体总流量对薄膜沉积速率和结晶状态的影响,绘制了沉积气压和功率密度双因素相图. 以0.75nm/s的高速沉积了器件质量级的微晶硅薄膜,并以该沉积速率制备出了效率为5.5%的单结微晶硅薄膜电池. 关键词： 微晶硅薄膜 高速沉积 甚高频化学气相沉积     

Sputtering of the magnetron diode target in the presence of an external ion beam

The effect of an external ion beam on the plasma and target of a dc magnetron sputtering system in the course of reactive deposition of films is investigated. A combined experimental setup consisting of a magnetron diode and a hall-current ion source is constructed. The influence of a fast ion beam on the discharge current formation, the target emission characteristics, and the target etching rate is considered. It is shown that the ion assistance expands the operating range of the magnetron diode, increases the deposition rate, and substantially shortens the target training time. At the same time, it practically does not affect the ionization processes in the plasma.     

高压PECVD技术沉积硅基薄膜过程中硅烷状态的研究

采用高压射频等离子体增强化学气相沉积(RF-PECVD)方法在不同功率下制备了一系列硅薄膜材料，研究了材料晶化率和生长速度随功率变化的规律， 进而研究PECVD方法沉积硅薄膜过程中的硅烷反应状态，并提出可以根据硅烷耗尽程度的不同将硅烷反应状态分为未耗尽、耗尽和过耗尽三种.然后，对不同硅烷反应状态下的材料结构、光电性能以及相应的电池进行了研究，并指出适合于太阳电池本征层的高质量微晶硅材料应该沉积在硅烷耗尽状态. 关键词： 耗尽状态 微晶硅 光发射谱     

The microstructure and optical properties of crystallized hydrogenated silicon films prepared by very high frequency glow discharge

A series of nc-Si:H films with different crystalline volume fractions have been deposited by very high frequency glow discharge in a plasma with a silane concentration [SiH₄]/([SiH₄] + [H₂]) varying from 2% to 10%. The nc-Si:H films have been characterized by Raman spectroscopy, XRD diffraction, and UV-vis-near infrared spectrophotometer. The deposition rate increases nearly linear with increasing the silane concentration while the crystalline volume fraction decrease from 58% to 12%. The refractive index and the absorption of the samples were obtained through a modified four-layer-medium transmission model based on the envelope method. It was found that the refractive indices and absorption coefficient increase with increasing silane concentration. Compared to the films deposited using conventional RF-PECVD with excitation frequency of 13.56 MHz, the samples prepared by very high frequency glow discharge have higher absorption coefficients, which is due to its better compactness and lower defect density.     

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.     

A magnetron sputtering technique to prepare a-C:H films: Effect of substrate bias

Amorphous hydrogenated carbon (a-C:H) films were deposited by magnetron sputtering with a mixture gas of Ar and CH₄. The a-C:H films deposited by this method have relatively low internal stress (<1 GPa) compared to some films deposited by conventional deposition process. The effects of substrate bias voltage on microstructure, surface morphology and mechanical properties of the films were investigated by various techniques. It has been found that the polymer-like structure is dominated at low bias voltage (−100 V), while the diamond-like structure with the highest hardness and internal stress is the main feature of the a-C:H films deposited under high bias voltage (−300 V). With increasing the bias voltage further, the feature of diamond-like structure decreases associating with the increase of graphitization. The frictional test shows that the friction coefficient and wear rate of the a-C:H films are depended strongly on structure and mechanical properties, which were ultimately influenced by the deposition method and bias voltage.     

Investigation of the microstructure and optical properties of hydrogenated polymorphous silicon films prepared with pure silane

The dependences of microstructure and optical properties of hydrogenated polymorphous silicon (pm-Si:H) films on total gas pressure were studied. Instead of using high diluted silane in H₂, pure silane was used as the source gas. The films were grown by the radio-frequency plasma-enhanced chemical vapour deposition method. Fourier-transform infrared spectrometry was used to characterize the presence of Si _m H _n clusters in pm-Si:H film deposited on KBr substrate. Atomic force microscopy (AFM) analysis characterized the morphology of the pm-Si:H films and X-ray diffraction at grazing incidence angle (XRDGI) microstructure analysis also confirmed the existence of Si _m H _n nanocrystalline clusters in pm-Si:H. The thickness and optical constants of the films were measured by spectra ellipsometry as well as scanning electron microscopy. Derived using the Tauc relation, the dependence of optical bandgap, E_g , and coefficient, B, on the pressure during deposition process is discussed. The influence of inter-electrode distance on growth rate and surface smooth was analyzed using AFM.     

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.     

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     

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.     

On the determination of energy fluxes at plasma–surface processes

A summary is given of different methods for the determination of the energy influx and its influence on the thermal balance and energetic conditions of substrate surfaces during plasma processing. The discussed mechanisms include heat radiation and kinetic and potential energy of charged particles and sputtered neutrals. For a few examples such as magnetron sputtering of a-C:H films, sputter deposition of aluminum on microparticles, and titanium deposition in a hollow-cathode arc evaporation device the energetic balance of substrates during plasma processing is presented. Received: 6 July 2000 / Accepted: 12 December 2000 / Published online: 3 April 2001     

Magnetron sputtering of YBaCuO target: Effects of discharge voltage and deposition rate variation

The time variations of the discharge voltage and YBaCuO film deposition rate in an on-axis magnetron sputterer are studied. In the case of an YBaCuO ceramic target, the discharge voltage and the rate of superconducting phase deposition decrease with time, exponentially approaching a quasi-steady regime. At a pressure of 100 Pa, a decrease in the magnetic field induction near the target from 1200 to 600 G leads to a rise in the discharge voltage by 25–30% and increases the deposition rate more than twofold. The deposited films offer high electrophysical parameters, as demonstrated with a high-frequency circuit: the intrinsic Q factor of the circuit at 64.5 MHz is found to be 2.7 × 10⁵.     

FTIR法研究BCN薄膜的内应力

采用射频磁控溅射技术,用六角氮化硼和石墨为溅射靶,以氩气(Ar)和氮气(N₂)为工作气体,在Si(100)衬底上制备出硼碳氮(BCN)薄膜。利用傅里叶变换红外光谱(FTIR)考察了不同沉积参数(溅射功率为80～130 W、衬底温度为300～500 ℃、沉积时间为1～4 h)条件下制备的薄膜样品。实验结果表明,所制备薄膜均实现了原子级化合。并且沉积参数对BCN薄膜的生长和内应力有很大影响,适当改变沉积参数能有效释放BCN薄膜的内应力。在固定其他条件只改变一个沉积参数的情况下,得到制备具有较小内应力的硼碳氮薄膜的最佳沉积条件：溅射功率为80 W、衬底温度为400 ℃、沉积时间为2 h。     

Development of protective metal coatings on aluminum by magnetron sputtering

Depositions of copper and titanium coatings on aluminum foils and polished aluminum plates for thier protection against corrosion in alkaline media were performed. The coatings were deposited in three different types of magnetron sputtering systems: a direct current (DC) magnetron discharge, a high current impulse magnetron discharge, and a DC magnetron discharge with melted cathode. Only aluminum foils coated with copper films obtained by combined ion-plasma technology, which included preliminarily sputtering of the aluminum surface with an ion beam, deposition of a dense interlayer in the DC magnetron discharge with ion assistance of initial stage of deposition, and deposition of additional layer in the magnetron discharge with melted cathode, were resistant against 30 wt % NaOH solution.     

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.     

高功率脉冲磁控溅射的阶段性放电特征

本文从放电靶电流出发,采用一种新的研究方法,即将靶电流分解为多个代表具体放电特性的特征参数,全面而系统的研究了不同的工作气压条件下,靶电流各特征参数随靶电压的增加而进行的演化.结果发现高功率脉冲磁控溅射技术(HPPMS)放电靶电流在靶电压由低向高增加的过程中,出现靶电流峰值和平台值的交替变化,体现出明显的阶段性放电特征,且不同的放电阶段在不同气压下出现一定的移动,会在测量范围内出现某些放电阶段的缺失.本文还通过等离子体发射光谱对HPPMS放电靶前等离子体测量发现五个不同的放电阶段分别主要对应氩原子、铬原子、氩离子、铬离子和氩、铬高价离子的放电,但不同的放电条件下相邻的阶段会出现一定程度的交叠.     

激发频率对VHF-PECVD制备微晶硅材料性能的影响

采用甚高频等离子增强化学气相沉积(VHF-PECVD)的方法制备了硅烷浓度分别为6％和7％， 随激发频率变化(40—70MHz)的氢化微晶硅(μc-Si∶H)薄膜材料.研究了材料的电学特性、 结构特性、沉积速率与激发频率之间的关系.结果发现材料的光敏性随频率的增加先降低后 提高，晶化率和沉积速率的变化趋势与之相反；在晶化率最高点，材料在(220)的晶向衍射 峰最高.并从光发射谱的角度研究了材料结构和沉积速率随频率变化的原因. 关键词： 甚高频等离子增强化学气相沉积 本征微晶硅 激发频率     

Surface passivation of crystalline silicon by sputter deposited hydrogenated amorphous silicon

This letter shows that intrinsic hydrogenated amorphous silicon (a‐Si:H) films deposited by RF magnetron sputtering can provide outstanding passivation of crystalline silicon surfaces, similar to that achieved by plasma enhanced chemical vapour deposition (PECVD). By using a 2% hydrogen and 98% argon gas mixture as the plasma source, 1.5 Ω cm n‐type FZ silicon wafers coated with sputtered a‐Si:H films achieved an effective lifetime of 3.5 ms, comparable to the 3 ms achieved by PECVD (RF and microwave dual‐mode). This is despite the fact that Fourier transform infrared spectroscopy measurements show that sputtering and PECVD deposited films have very different chemical bonding configurations. We have found that film thickness and deposition temperature have a significant impact on the passivation results. Self‐annealing and hydrogen plasma treatment during deposition are likely driving forces for the observed changes in surface passivation. These experimental results open the way for the application of sputtered a‐Si:H to silicon heterojunction solar cells. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)