Modulating microstructure and optical properties of hydrogenated nanocrystalline silicon photovoltaic materials prepared under hydrogen diluted silane PECVD by various DC bias

Hydrogenated nanocrystalline silicon (nc-Si:H) thin films were fabricated by plasma enhanced chemical vapor deposition under the various negative substrate bias voltages with hydrogen as a diluent of silane. The microstructure and optical properties of nc-Si:H thin films were studied by Raman scattering spectroscopy, X-ray diffraction (XRD), transmission electron microscopy, and optical transmission spectroscopy. Raman spectra and XRD pattern reveal that applying negative bias voltages at the moderate level favors the enhancement of crystalline volume fraction, increase of crystallite sizes and decrease of residual stress. We also demonstrated that the negative direct current bias can be used to modulate the volume fraction of voids, refractive index, absorption coefficient, compactness and ordered degree of nc-Si:H films. It is found that the film deposited at −80 V shows not only high crystallinity, size of crystallite, and static index n₀ but also low residual stress and volume fraction of voids. Furthermore, the microstructural evolution mechanism of nc-Si:H thin films prepared at different bias voltages is tentatively explored.     

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采用由脉冲负偏压调节的等离子体增强化学气相沉积方法,以硅烷为源气体,在玻璃基片上沉积得到了多孔二氧化硅薄膜。将反应过程中加在沉积区域的脉冲偏压固定在-350V,当占空比从0.162增大到0.864时,薄膜样品的形貌、成份和结构均不相同。扫描电镜照片表明,组成多孔氧化硅薄膜的颗粒在占空比增大时变得细腻,并且薄膜整体变得多孔且蓬松。拉曼光谱和红外光谱结果显示,薄膜样品中的非晶硅和Si-H键在较高的占空比下减弱甚至消失。占空比升高时氧化硅桥键所占比例持续增加。     

脉冲偏压占空比对多孔氧化硅薄膜性质的影响

采用由脉冲负偏压调节的等离子体增强化学气相沉积方法,以硅烷为源气体,在玻璃基片上沉积得到了多孔二氧化硅薄膜。将反应过程中加在沉积区域的脉冲偏压固定在-350V,当占空比从0.162增大到0.864时,薄膜样品的形貌、成份和结构均不相同。扫描电镜照片表明,组成多孔氧化硅薄膜的颗粒在占空比增大时变得细腻,并且薄膜整体变得多孔且蓬松。拉曼光谱和红外光谱结果显示,薄膜样品中的非晶硅和Si-H键在较高的占空比下减弱甚至消失。占空比升高时氧化硅桥键所占比例持续增加。     

Influence of substrate bias voltage on structure and properties of the CrAlN films deposited by unbalanced magnetron sputtering

The CrAlN films were deposited on silicon and stainless steel substrates by unbalanced magnetron sputtering system. The influence of substrate bias on deposition rate, composition, structure, morphology and properties of the CrAlN films was investigated. The results showed that, with the increase of the substrate bias voltage, the deposition rate decreased accompanied by a change of the preferred orientation of the CrAlN film from (2 2 0) to (2 0 0). The grain size and the average surface roughness of the CrAlN films declined as the bias voltage increases above −100 V. The morphology of the films changed from obviously columnar to dense glass-like structure with the increase of the bias voltage from −50 to −250 V. Meanwhile, the films deposited at moderate bias voltage had better mechanical and tribological properties, while the films deposited at higher bias voltage showed better corrosion resistance. It was found that the corrosion resistance improvement was not only attributed to the low pinhole density of the film, but also to chemical composition of films.     

氮化硅薄膜中纳米非晶硅颗粒的键合结构及光致发光

采用螺旋波等离子体化学气相沉积技术以N₂/SiH₄/H₂为反应气体制备了镶嵌有纳米非晶硅颗粒的氢化氮化硅薄膜,通过改变N₂流量实现了薄膜从红到蓝绿的可调谐光致发光.傅里叶红外透射和紫外-可见光吸收特性分析表明,所生长薄膜具有较高的氢含量,N₂流量增加使氢的键合结构发生变化,非晶硅颗粒尺寸减小,所对应的薄膜的光学带隙逐渐增加和微观结构有序度减小.可调光致发光(PL)主要来源于纳米硅颗粒的量子限制效应发光,随N₂流量增加,PL的谱线展宽并逐渐增强. 关键词： 傅里叶红外透射谱 光吸收谱 纳米硅粒子镶嵌薄膜 光致发光     

Influences of hydrogen dilution on microstructure and optical absorption characteristics of nc-SiO_x:H film

By using the plasma enhanced chemical vapor deposition(PECVD) technique, amorphous silicon oxide films containing nanocrystalline silicon grain(nc-Si O x:H) are deposited, and the bonding configurations and optical absorption properties of the films are investigated. The grain size can be well controlled by varying the hydrogen and oxygen content,and the largest size is obtained when the hydrogen dilution ratio R is 33. The results show that the crystallinity and the grain size of the film first increased and then decreased as R increased. The highest degree of crystallinity is obtained at R = 30.The analyses of bonding characteristics and light absorption characteristics show that the incorporation of hydrogen leads to an increase of overall bonding oxygen content in the film, and the film porosity first increases and then decreases. When R = 30, the film can be more compact, the optical absorption edge of the film is blue shifted, and the film has a lower activation energy.     

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.     

The effect of applied negative bias voltage on the structure of Ti-doped a-C:H films deposited by FCVA

Ti-doped hydrogenated diamond-like carbon (DLC) films were deposited on Si(1 0 0) substrates by a filtered cathodic vacuum arc (FCVA) method using Ar and CH₄ as the feedstock. The composition and microstructure of the films were investigated by Raman spectroscopy, X-ray photoelectron spectroscopy and IR spectroscopy. The internal stress was determined by the radius of curvature technique. The influence of the bias voltage on the microstructure of the as-deposited films was investigated. It was found that the graphite-like bonds was dominated in the Ti-doped DLC film deposited at 0 V bias voltage. When bias voltage was increased to −150 V, more diamond-like bond were produced and the sp³ content in film reached the maximum value, after which it decreased and more graphite-like bonds feature produced with further increase of the negative bias voltage. The compressive internal in the Ti-doped DLC films also exhibited a maximum value at −150 V bias voltage. IR results indicated that CH bonded intensity reduced, and H atoms bonded with C atoms were substituted for the Ti atoms as the negative bias voltage increasing. All the composition and microstructure change can be explained by considering the plasma conditions and the effect of negative bias voltage applied to the substrate.     

氧离子导体La1.9Y0.1Mo2O9细晶粒陶瓷的制备和电学性质研究

采用溶胶凝胶法合成的La_1.9Y_0.1Mo₂O₉纳米晶粉体, 结合微波烧结技术制备出不同晶粒度的La_1.9Y_0.1Mo₂O₉块体样品. 利用X射线衍射仪(XRD)、高分辨透射显微镜(HRTEM)、场扫描显微镜(SEM)对粉体及陶瓷块体的物相、 形貌进行了表征, 利用交流阻抗谱仪测试了样品不同温度下的电导率. 实验结果表明, 掺Y的La_1.9Y_0.1Mo₂O₉能将高温立方β 相稳定到室温; 块体样品致密均匀, 平均晶粒度范围在60 nm–4 μm之间; 致密度高的样品表现出高的电导率, 其中900 ℃烧结样品的电导率600 ℃时高达0.026 S/cm, 比固相反应法制备的La_1.9Y_0.1Mo₂O₉样品高出约1倍. 总结认为样品的致密性对电导率影响较大, 是通过影响晶界电导率来影响总电导率的, 样品的晶粒度(在60 nm–4 μm范围内)对电导率的影响还不能确定. 关键词： 氧离子导体 1.9Y_0.1Mo₂O₉')" href="#">La_1.9Y_0.1Mo₂O₉ 细晶粒陶瓷 微波烧结     

Tunable Ba0.5Sr0.5TiO3 film bulk acoustic resonators using SiO2/Mo Bragg reflectors

Tunable and switchable Ba 0.5 Sr 0.5 TiO 3 film bulk acoustic resonators（FBARs） based on SiO 2 /Mo Bragg reflectors are explored,which can withstand high temperature for the deposition of Ba x Sr 1 x TiO 3（BST） films at 800 C.The dc bias-dependent resonance may be attributed to the piezoelectricity of the BST film induced by an electrostrictive effect.The series resonant frequency is strongly dc bias-dependent and shifts downwards with dc bias increasing,while the parallel resonant frequency is only weakly dc bias-dependent and slightly shifts upwards at low dc bias（ 45 V） while downwards at higher dc bias.The calculated relative tunability of shifts at series resonance frequency is around 2.3% and the electromechanical coupling coefficient is up to approximately 8.09% at 60-V dc bias,which can be comparable to AlN FBARs.This suggests that a high-quality tunable BST FBAR device can be achieved through the use of molybdenum（Mo） as the high acoustic impedance layer in a Bragg reflector,which not only provides excellent acoustic isolation from the substrate,but also improves the crystallinity of BST films withstanding higher deposition temperature.     

基片温度对SiNx薄膜结晶状态及机械性能的影响

利用微波电子回旋共振增强磁控反应溅射法在不同基片温度下制备无氢SiN_x薄膜.通过傅里叶变换红外光谱、透射电子显微镜、台阶仪、纳米硬度仪等表征技术,研究了基片温度对SiN_x薄膜结晶状态、晶粒尺寸、晶体取向等结晶性能以及薄膜的生长速率、硬度等机械性能的影响,并探讨了薄膜结晶性能与机械性能之间的关系.研究结果表明,在基片温度低于300℃时制备的SiN_x薄膜以非晶状态存在,硬度值仅为18GPa左右;基片温度 关键词： x')" href="#">SiN_x 磁控溅射 微观结构 硬度     

Effect of Substrate Bias on Microstructures of Zirconia Thin Films Deposited by Cathodic Vacuum Arc

Zirconium oxide （Zr02） thin films are deposited at room temperature by cathodic arc at substrate biases of 0 V, -60 V and -120 V, respectively. The crystal structure, composition, morphology, and deposition rate of the as-deposited thin films are systematically investigated by x-ray diffraction, x-ray photoelectron spectroscopy （XPS） as well as scanning electron microscopy. The results show that the crystal structure, morphology and deposition rate of the films all are dependant on substrate bias. With the increase of bias voltage from 0 V to -120 V, the zirconium oxide thin film grown on silicon wafer first exhibits monoclinic lattice and tetragonal lattice, further evolves monoclinic phase with the preferred orientation along the （-111） and （-222） directions at -60 V and finally along nearly one observed preferred （002） direction under -120 V. In addition, the variations of morphology with bias voltage are correlated to changes of the film structure. The results of XPS demonstrate that Zr elements are almost oxidized completely in the films achieved under -120 V bias.     

溅射工艺参数对硅薄膜微结构影响的Raman分析

为了解决碳化硅难以进行光学加工的问题,该文采用射频磁控溅射方法,在碳化硅反射镜坯体上沉积与碳化硅具有相近热膨胀系数且易于进行光学加工的硅薄膜。利用拉曼光谱(Raman)对衬底温度、射频功率、衬底偏压等溅射工艺条件对硅膜微结构的影响进行了分析。研究发现：随着衬底温度的升高,薄膜的晶化率先增大后减小;衬底偏压的增加不利于薄膜有序结构的形成;射频功率对薄膜微结构的影响比较复杂,随着功率的升高,薄膜晶粒尺寸减小,晶化率降低,当射频功率进一步升高时,薄膜中有序团簇尺寸和晶化率逐渐升高。但过高的射频功率反而不利于薄膜的晶化。     

Nucleation of diamond on silicon wafers using C60 in the hot filament chemical vapour deposition system

Scanning electron microscopy and Raman shifts were used to study the process of diamond nucleation and growth using C60 in the hot filament chemical vapour deposition (HFCVD) system.The process of nucleation and growth of diamond films on silicon wafer using C60 as intermediate layer in HFCVD system is described.In order to increase the density of diamond nuclei on the wafers,it is not necessary to use negative bias.The UV-light pre-treatment is not beneficial for improving the diamond nucleation.The multi-layers of C60 molecules,but not a monolayer,can increase the density of diamond nuclei in the presence of H atoms.     

Development of rf plasma sputtered Al2O3-TiO2 multilayer broad band antireflecting coatings and its correlation with plasma parameters

TiO₂/Al₂O₃/TiO₂/Al₂O₃ multilayer structures were obtained at different oxygen:argon gas ratios of 20:80, 30:70, 50:50 and 60:40 sccm and constant rf power of 200 W using reactive magnetron sputtering. Grain size and elemental distribution in the films were studied from AFM image and XPS spectra respectively. The deposited grain size increased with increasing oxygen:argon gas ratio. The optical band gap, refractive index, extinction coefficient were calculated from UV-vis transmittance and reflectance spectra. It was observed that the value of refractive index, extinction coefficient and band gap increased with increasing oxygen. These variations are due to the defects levels generated by the heterostructure and explained by the PL spectrum. The antireflecting (AR) efficiency of the films was estimated from the reflectance spectra of the films. Broad band antireflecting coating for the visible range was achieved by varying oxygen content in the film. The plasma chemistry controlled the antireflecting property by the interface interdiffusion of atoms during layer transition in multilayer deposition. The in situ investigation of the plasma chemistry was performed using optical emission spectroscopy. The plasma parameters were estimated and correlated with the characteristics of the films.     

离子束辅助工艺中APS源偏转电压对HfO2薄膜性能的影响

 基于Leybold APS1104镀膜系统,采用离子束辅助反应沉积技术,以金属Hf粒为初始镀膜材料,APS源偏转电压为50~140 V范围内,在［100］单晶硅片和紫外石英（JGS1）基板上制备了HfO₂单层膜。分别利用Lambda 900分光光度计、X射线光电子能谱仪、X射线衍射仪以及原子力显微镜对HfO2薄膜的光谱性能、表面及纵向化学成分、晶相结构以及表面粗糙度进行了分析。结果表明：当APS源偏转电压在120~140 V及50~90 V两个范围内变化时,HfO2薄膜的紫外短波光学损耗随着偏转电压的降低而减小,而为110~90 V时紫外短波光学损耗对偏转电压的变化不敏感;偏转电压在50~140 V的范围内时,制备的HfO₂薄膜表面及纵向化学成分无明显变化;当偏转电压为100 V时,HfO₂薄膜晶粒尺寸及表面粗糙度分别达到最大值26.2 nm及5.79 nm,其后,随着偏转电压的降低,二者均逐渐减小。     

负偏压热灯丝CVD金刚石膜核化和早期生长的研究

利用扫描电子显微镜、Raman谱和X射线光电子能谱，研究了Si衬底上热灯丝CVD金刚石膜的核化和早期生长.在-300V和100mA条件下预处理15min，镜面抛光的Si(100)表面上金刚石核密度超过了10⁹cm^-2，但是核的分布极不均匀且可分为三个区域：A区，边缘处以锥体为主；B区，位于边和中心之间过渡区是纳米金刚石；C区，中心处有SiC层.无偏压下生长4h后，A区形成许多大而弧立的金刚石颗粒，B区成为织构金刚石膜，而C区变为含有大量缺陷的连续金刚石膜.衬底负 关键词：     

Effect of Bias Voltage on Microstructure and Mechanical Properties of Nanocomposite ZrCN Films Deposited by Filtered Cathodic Vacuum Arc

Nanocomposite ZrCN films consisting of nanocrystalline ZrCN grains embedded in nitrogen-doped amorphous carbon film are deposited by filtered cathodic vacuum arc technology under different bias voltages ranging from 50to 400 V.The influence of bias voltage on the characterization and the mechanical properties of the ZrCN films are investigated by x-ray diffraction,x-ray photoelectron spectroscopy,scanning electron microscopy,transmission electron microscopy,Raman spectroscopy and nano-indentation.The bias voltage has a subtle effect on the ZrCN grain size,which is around 9.5 nm and keeps almost constant.A slight increase of the bias voltage induces a relatively high sp~3 fraction about 40%in N-doped amorphous C films but leads to the graphitization of the films under a higher voltage.The best mechanical property of the ZrCN film with the hardness of 41 GPa is obtained under the bias voltage of 200 V,indicating the positive effect of slight increase of ion bombardment on the hardness of the films.     

金刚石薄膜负偏压形核的边缘效应

 在微波等离子体化学气相沉积装置中，研究了金刚石薄膜在Si (100)面上的负偏压形核行为，结果表明，偏压大小对金刚石的形核均匀性有显著影响，而甲烷浓度主要影响形核时间，对金刚石的最大核密度影响不大。在硅片尺寸小于钼支撑架时，形核行为存在明显的边缘效应，即在偏压值低于-150 V时，硅片边缘金刚石核密度急剧降低，远低于硅片中央；在甲烷浓度比较低时，硅片边缘核密度要高于中间。研究表明，造成这种现象的主要原因是硅片下的钼支撑架发射电子所致，过量的原子H对金刚石的形核是不利的。     

Si-nanostructures formation in amorphous silicon nitride SiNx:H deposited by remote PECVD

The formation of silicon nanoclusters embedded in amorphous silicon nitride (SiN_x:H) can be of great interest for optoelectronic devices such as solar cells. Here amorphous SiN_x:H layers have been deposited by remote microwave-assisted chemical vapor deposition at 300 °C substrate temperature and with different ammonia [NH₃]/silane [SiH₄] gas flow ratios (R=0.5−5). Post-thermal annealing was carried out at 700 °C during 30 min to form the silicon nanoclusters. The composition of the layers was determined by Rutherford back scattering (RBS) and elastic recoil detection analysis (ERDA). Fourier transform infrared spectroscopy (FTIR) showed that the densities of SiH (2160 cm⁻¹) and NH (3330 cm⁻¹) molecules are reduced after thermal annealing for SiN:H films deposited at flow gas ratio R>1.5. Breaking the SiH bonding provide Si atoms in excess in the bulk of the layer, which can nucleate and form Si nanostructures. The analysis of the photoluminescence (PL) spectra for different stoichiometric layers showed a strong dependence of the peak characteristics (position, intensity, etc.) on the gas flow ratio. On the other hand, transmission electron microscopy (TEM) analysis proves the presence of silicon nanoclusters embedded in the films deposited at a gas flow ratio of R=2 and annealed at 700 °C (30 min).