nc-Si:H/c-Si硅异质结太阳电池中本征硅薄膜钝化层的优化

采用射频等离子体增强化学气相沉积(RF-PECVD)法在低温、低功率的条件下制备了一系列本征硅薄膜, 研究了硅烷浓度(C_S)对薄膜微结构、光电特性及表面钝化性能的影响. 将本征硅薄膜作为钝化层应用到氢化纳米晶硅/晶硅(nc-Si:H/c-Si)硅异质结(SHJ)太阳电池中, 研究了硅烷浓度和薄膜厚度对电池性能的影响. 实验发现: 随着硅烷浓度的降低, 本征硅薄膜的晶化率、氢含量、结构因子、光学带隙和光敏性等都在过渡区急剧变化; 本征硅薄膜的钝化性能由薄膜的氢含量及氢的成键方式决定. 靠近过渡区的薄膜具有较好的致密性和光敏性, 氢含量最高, 带隙态密度低, 且主要以SiH 形式成键, 对硅片表现出优异的钝化性能, 使电池的开路电压大幅提高. 但是, 当薄膜的厚度过小时, 会严重影响其钝化质量. 本实验中, 沉积本征硅薄膜的最优硅烷浓度为6% (摩尔分数), 且当薄膜厚度为~8 nm时, 所制备电池的性能最好. 实验最终获得了开路电压为672 mV, 短路电流密度为35.1 mA·cm^-2, 填充因子为0.73, 效率为17.3%的nc-Si:H/c-Si SHJ太阳电池     

Plasma deposition of silicon nitride-like thin films from organosilicon precursors

Plasmas containing hexamethyldisilazane or hexamethylcyclotrisilazane and nitrogen or ammonia were used to deposit silicon nitride-like films at low substrate temperature (T<60°C). Optical properties (refractive index and absorption coefficient), chemical composition of the deposit and film growth rate were examined with respect to the deposition parameters (rf power, pressure and feed composition). As deposited films from ammonia containing mixtures were silicon nitride-like, contained carbon, and were nearly oxygen free. Furthermore, only Si−N, Si−H, and N−H bonds were identified in as-deposited films. The reactive Si−H bonds progressively transformed into Si−O bonds as the films were exposed to air. Films deposited from highly ammonia-diluted mixtures, high RF power and low pressure showed the highest stability with refractive indices as high as 1.8.     

沉积温度对等离子增强化学气相沉积法制备的SiNx:H薄膜特性的影响

利用Centrotherm公司生产的管式等离子增强化学气相沉积(PECVD)设备在p型抛光硅片表面沉积SiN_x:H薄膜, 研究沉积温度对SiN_x:H薄膜的组成及光学特性、结构及表面钝化特性的影响. 然后采用工业化的单晶硅太阳电池制作设备和工艺制作太阳电池, 研究不同温度制备的薄膜对电池电性能的影响. 测试结果表明: SiN_x:H薄膜的折射率随着沉积温度的升高而变大, 分布在1.926-2.231之间, 这表明Si/N摩尔比随着沉积温度的增加而增加; 当沉积温度增加时, 薄膜中Si－H键和N－H键浓度呈现减小趋势, 而Si－N键浓度逐渐升高, 薄膜致密度增加; 随着沉积温度的升高, SiN_x:H薄膜中的氢析出导致了钝化硅片的有效少子寿命先升高后降低, 并且有效少子寿命出现明显的时间衰减特性. 当沉积温度为450 °C时, 薄膜具有最优的减反射和表面钝化效果. 采用不同温度PECVD制备的5组电池的电性能测试结果也验证了这一结果.     

Amorphous silicon carbonitride thin‐film coatings produced by remote nitrogen microwave plasma chemical vapour deposition using organosilicon precursor

Amorphous silicon carbonitride (a‐SiCN) films were produced by remote nitrogen plasma chemical vapour deposition (RP‐CVD) from bis(dimethylamino)methylsilane precursor. The effect of substrate temperature (T _S) on the kinetics of RP‐CVD, chemical structure, surface morphology and some properties of the resulting films is reported. The T _S dependence of film growth rate implies that RP‐CVD is an adsorption‐controlled process. Fourier transform infrared spectroscopic examination revealed that an increase in T _S from 30 to 400°C involves the elimination of organic moieties from the film and the formation of Si─C and Si─N network structure. The films were characterized in terms of their surface roughness and basic physical and optical properties, such as density and refractive index, respectively. Reasonably good relationships between the structural parameters represented by relative integrated intensity of infrared absorption bands from the Si─C and Si─N bonds (controlled by T _S) and the film properties are determined. Due to their small surface roughness, high density and high refractive index, the a‐SiCN films produced at T _S ≥ 350°C would seem to be useful protective coatings for metals and optical devices.     

Ellipsometric characterization of inhomogeneous non‐stoichiometric silicon nitride films

Variable‐angle spectroscopic ellipsometry is employed for the optical characterization of non‐stoichiometric silicon nitride thin films exhibiting inhomogeneity formed by refractive index and extinction index changes through the film thickness. For all the film samples, the best fit of the experimental data is achieved if, in addition to the inhomogeneity, an overlayer or roughness of the upper boundary is included. However, distinguishing of these two defects is found not to be possible. The influence of working gas ratio, deposition temperature and on/off time on the film properties is studied. The refractive index and extinction coefficient is found to increase with increasing working gas ratio and less significantly with decreasing deposition temperature. It is also found that the inhomogeneity increases with decreasing deposition temperature, and the deposition rate of the films decreases with increasing working gas ratio. The influence of the on/off time on the film properties is practically unimportant. Copyright © 2013 John Wiley & Sons, Ltd.     

Room-temperature ferromagnetism in silicon oxide/silicon nitride composite films

Room-temperature ferromagnetism has been observed in silicon oxide/silicon nitride composite films formed on Si substrates at different substrate temperatures, and the ferromagnetic properties of the samples have been found to depend on the silicon nitride content of the films. It is proposed that the ferromagnetism is related to the interface states between the silicon oxide particles and silicon nitride particles. The saturation magnetization (M_S) reached its maximum value in the film produced at a substrate temperature of 400 °C. A further study on the magnetic properties of the film has been carried out using first-principles calculations based on the density functional theory. The calculations suggest that the magnetic moments of the film originate from N 2p and Si 2p states in the vicinity of the hetoro-interface.     

不同基底对TiO2和SiO2薄膜的光学性能的影响

采用溶胶-凝胶法分别在K9玻璃、单晶硅和石英玻璃基底上制备了纳米TiO₂和SiO₂薄膜。利用SEM、UV-Vis及反射式椭圆偏振光谱仪对薄膜的微观结构及光学特性进行了表征和分析。结果表明:3种基底中, 单晶硅基底上TiO₂和SiO₂薄膜折射率最大;在非晶态K9玻璃和石英玻璃基底上TiO₂薄膜折射率和透光率差异较大;SiO₂薄膜在非晶态基底上折射率、透光率相近;3种基底上薄膜的折射率和消光系数都有随波长增大而减小的趋势, 同时Cauchy模型能较好的描述单晶硅基底上两种薄膜在400~800 nm波段的光学性能。     

不同基底对TiO2和SiO2薄膜的光学性能的影响

采用溶胶-凝胶法分别在K9玻璃、单晶硅和石英玻璃基底上制备了纳米TiO₂和SiO₂薄膜。利用SEM、UV-Vis及反射式椭圆偏振光谱仪对薄膜的微观结构及光学特性进行了表征和分析。结果表明：3种基底中, 单晶硅基底上TiO₂和SiO₂薄膜折射率最大;在非晶态K9玻璃和石英玻璃基底上TiO₂薄膜折射率和透光率差异较大;SiO₂薄膜在非晶态基底上折射率、透光率相近;3种基底上薄膜的折射率和消光系数都有随波长增大而减小的趋势, 同时Cauchy模型能较好的描述单晶硅基底上两种薄膜在400~800 nm波段的光学性能。     

Use of Neural Network to Control a Refractive Index of SiN Film Deposited by Plasma Enhanced Chemical Vapor Deposition

Refractive index of silicon nitride film deposited in a plasma enhanced chemical deposition system is modeled by using neural network. The deposition process was characterized with a full factorial experiment. Additional 12 experiments were conducted to test model appropriateness. Predicted model behaviors were in good agreement with actual measurements. Deposition mechanisms were qualitatively examined especially with respect to the pressure. Possible interactions between the pressure and other factors (SiH₄, NH₃, radio frequency (RF) power, and substrate temperature) were examined on the basis of SiH/NH bond ratio. The refractive index increased with increasing either SiH₄ flow rate or RF power. In contrast, the refractive index decreased with increasing NH₃ flow rate. Little interactions between the pressure and RF power were observed. Pressure effect on the refractive index was quite different depending on the level of SiH₄ flow rate or substrate temperature. In general, increasing the pressure increased the refractive index. Meanwhile, the refractive index was insensitive to parameter variations at relatively high pressures. The most complex interaction occurred as the pressure interacted with the temperature. Useful clues to control the refractive index were revealed from the predictive model.     

Preparation of SiBN films deposited by MOCVD

SiBN films were prepared by the MOCVD method using triethylsilane and triethylboron as source materials. The SiBN films were a mixture of boron nitride and silicon nitride determined by IR spectra. The relationship between the ratio of mixture and the preparation condition is clarified. The ratio of silicon nitride to boron nitride in the films was proportional to the ratio of triethylsilane to triethylboron under a large excess of ammonia flow condition. The reaction temperature also influenced the ratio of boron nitride and silicon nitride in the films. The deposition rate of the film increased up to 800°C with a maximum at 1000°C, and decreased up to 1300°C with small value. The crystallinity of SiBN films was very poor because the crystal growth was obstructed.     

Spectroscopic and electrical properties of SiO2 films prepared by simple and cost effective sol-gel process

Amorphous SiO2 thin films were prepared on glass and silicon substrates by cost effective sol-gel method. Tetra ethyl ortho silicate (TEOS) was used as the precursor material, ethanol as solvent and concentrated HCl as a catalyst. The films were characterized at different annealing temperatures. The optical transmittance was slightly increased with increase of annealing temperature. The refractive index was found to be 1.484 at 550 nm. The formation of SiO2 film was analyzed from FT-IR spectra. The MOS capacitors were designed using silicon (100) substrates. The current-voltage (I-V), capacitance-voltage (C-V) and dissipation-voltage (D-V) measurements were taken for all the annealed films deposited on Si (100). The variation of current density, resistivity and dielectric constant of SiO2 films with different annealing temperatures was investigated and discussed for its usage in applications like MOS capacitor. The results revealed the decrease of dielectric constant and increase of resistivity of SiO2 films with increasing annealing temperature.     

Tuning the optical properties of mesoporous TiO2 films by nanoscale engineering

The optical properties of spin-coated titanium dioxide films have been tuned by introducing mesoscale pores into the inorganic matrix. Differently sized pores were templated using Pluronic triblock copolymers as surfactants in the sol-gel precursor solutions and adjusted by varying the process parameters, such as the polymer concentration, annealing temperature, and time. The change in refractive index observed for different mesoporous anatase films annealed at 350, 400, or 450 °C directly correlates with changes in the pore size. Additionally, the index of refraction is influenced by the film thickness and the density of pores within the films. The band gap of these films is blue-shifted, presumably due to stress the introduction of pores exerts on the inorganic matrix. This study focused on elucidating the effect different templating materials (Pluronic F127 and P123) have on the pore size of the final mesoporous titania film and on understanding the relation of varying the polymer concentration (taking P123 as an example) in the sol-gel solution to the pore density and size in the resultant titania film. Titania thin film samples or corresponding titanium dioxide powders were characterized by X-ray diffraction, cross-section transmission electron microscopy, nitrogen adsorption, ellipsometery, UV/vis spectrometry, and other techniques to understand the interplay between mesoporosity and optical properties.     

掺硼p型非晶硅薄膜的制备及光学性能的表征

以高氢稀释的硅烷(SiH₄ )为反应气体,硼烷(B₂H₆)为掺杂气体,利用RF-PECVD方法,在玻璃衬底上制备出掺硼的氢化非晶硅(a-Si:H)薄膜,研究了硼掺杂量对氢化非晶硅(a-Si:H)薄膜的光学性能的影响.利用NKD-7000 W光学薄膜分析系统测试薄膜的透射谱和反射谱,并利用该系统的软件拟合得出薄膜的折射率、消光系数、吸收系数等光学性能参数,利用Tauc法计算掺硼的非晶硅薄膜的光学带隙.实验结果表明,随着硼掺杂量的增加,掺杂非晶硅薄膜样品在同一波长处的折射率先增大后减小,而且每一样品均随着入射光波长的增加而减小,在波长500 nm处的折射率均达到4.3以上;薄膜的消光系数和吸收系数随着硼掺杂量的增大而增大,在500 nm处的吸收系数可高达1.5×10⁵cm^-1.在实验的硼掺杂范围内,光学带隙从1.81 eV变化到1.71 eV.     

Influence of Mn incorporation on the structural and optical properties of sol gel derived ZnO film

Undoped and manganese doped ZnO (ZnO:Mn) films were prepared by sol gel method using spin coating technique. The effect of Mn incorporation on the structural and optical properties of the ZnO film has been investigated. The crystalline structure and orientation of the films have been investigated by using their X-ray diffraction spectra. The films exhibit a polycrystalline structure. Mn incorporation led to substantial changes in the structural characteristics of the ZnO film. The scanning electron microscopy (SEM) images of the films showed that the surface morphology of the ZnO film was affected by the Mn incorporation. The transparency of the ZnO film decreased with the Mn incorporation. The optical band gap and Urbach energy values of the ZnO and ZnO:Mn films were found to be 3.22, 3.19 eV and 0.10, 0.23 eV, respectively. The optical constants of these films, such as refractive index, extinction coefficient and optical dielectric constants were determined using transmittance and reflectance spectra. The refractive index dispersion curve of the films obeys the single oscillator model with dispersion parameters. The oscillator energy, E _o , and dispersion energy, E _d, of the films were determined 5.30 and 16.26 eV for ZnO film and 5.80 and 12.14 eV for ZnO:Mn film, respectively.     

Deposition of SiO2-Like Films by HMDSN/O2 Plasmas at Low Pressure in a MMP-DECR Reactor

The effects of process parameters such as O₂/HMDSN (hexamethyldisilazane) ratio, microwave discharge power and deposition pressure on the growth rate, chemical bonding nature, and refractive index of thin films deposited by microwave plasma from HMDSN with oxygen, have been investigated. The plasma was created in a Microwave Multipolar reactor excited by Distributed Electron Cyclotron Resonance. The films were deposited at room temperature and characterized by Fourier Transform Infrared spectroscopy and ellipsometry. Growth rate increased with the discharge power P or the deposition pressure but decreased significantly with increasing O₂/HMDSN ratio. A large change in the film composition was observed when the O₂/HMDSN ratio was varied: films deposited with only HMDSN precursor are polymer-like but as the O₂/HMDSN ratio increased, organic groups decreased. For relative pressure values over 70%, deposited films are SiO₂-like with refractive index values close to those found for thermal silicon dioxide.     

The stability of high refractive index polymer materials for high-density planar optical circuits

Owing to the structural flexibility, easy processing and fabrication capabilities, polymers are being increasingly attractive for a variety of optical applications. In order to increase the integration density of such optical circuits, higher index contrasts and, thus, polymers with considerably higher refractive index are essentially needed. An organometallic polymer and a conventional epoxy material are combined to form a compatible high index material. When cured at elevated temperatures, the organometallic polymer decomposes to form a highly dispersed metal oxide phase that imparts high index properties to the polymer films. These hybrid high refractive index polymer films must be stable in patterning of optical waveguide structure for photonic manufacturing. In this paper, we report the stability and optical characterization study of a modified organometallic high refractive index polymer film in manufacturing of optical waveguide devices.     

高折射率有机/无机纳米杂化透明膜层材料的制备与性质研究

采用溶胶-凝胶法,将钛酸酯和硅烷偶联剂(KH-560)进行共水解,经涂膜、固化,制备了一系列含有无机二氧化钛纳米相的无机/有机杂化膜层材料,通过不同方法对杂化膜层的微结构、光学、机械和热性质进行了表征.结果表明,所得到的有机/无机纳米复合膜层,在可见光范围内的透过率均在90%以上,同时具有较好的耐热性和较高的折射率(nd=1.47~1.73),并且膜层与基材的附着性好,铅笔硬度达到4~5H.     

On the break-in and passivation phenomena in polypyrrole/sulfate films

The influence of different divalent cations (M²⁺) on the electrochemical charging/discharging process of polypyrrole/sulfate (PPy/SO₄) films has been investigated. In principle, two different types of M²⁺ were found: (a) cations that cause the break-in phenomenon in the PPy film during electrochemical cycling with a gradual increase of film electroactivity and (b) cations in whose solutions the PPy film remains mainly electroinactive. Certain correlations have been drawn between several physico-chemical properties of the investigated cations and the break-in and passivation phenomena. The break-in and passivation phenomena were found to be influenced by the size and deformability of the cation hydration shell, ion covalent index and softness, as well as by the pH value of the test solution.     

Covalent molecular assembly of multilayer dendrimer ultrathin films in supercritical medium

Ultrathin films containing dendrimers are fabricated on amine- and anhydride-derivatized silicon dioxide surface through alternate layer-by-layer (LbL) assembly of pyromellitic dianhydride (PMDA) and poly(amidoamine) (PAMAM) dendrimer in supercritical carbon dioxide (SCCO2) with interlayer linkage established by covalent bonds. X-ray photoelectron and UV-visible absorption spectroscopies, atomic force microscopy (AFM), and ellipsometry were employed to study the interfacial chemistry, growth, morphology, and thickness of the assembled film. XPS analysis suggests that the PMDA/PAMAM interlayer covalent bond is established to completion, and functional surfaces for immobilization of the next layer are available after deposition of each layer. UV-visible absorption and ellipsometry revealed layer-by-layer growth of the film. The functional property film as a porous matrix was manifested in the reduction of the refractive index upon introduction of the dendrimer.     

Sintering Anomaly in Silica-Titania Sol-Gel Films

Sol-gel processing has been successfully applied to the preparation of silica-titania planar waveguides for integrated optics. In order to achieve low loss guides, proper densification is essential. A series of single layer silica-titania films were deposited by spin-coating on Si substrates from precursor sols prepared by mixing tetraethylorthosilicate (TEOS) with titanium tetra-iso-propoxide (TPOT). The thermal densification behavior of these thin gel films was followed by measuring their refractive index, by ellipsometry, as a function of the temperature, between 300–900°C and the heating time; an anomalous sintering behavior was found, consisting of a rapid initial rise in film density (calculated from the refractive index) at any heat-treatment temperature, followed by a pronounced minimum at times of the order of 3 minutes, after which the density slowly increased until the maximum plateau value, reached at each temperature.In order to explain the above sintering anomaly, a detailed compositional and structural characterization was performed on the films by infrared spectroscopy (IR) and X-ray photoemission spectroscopy (XPS). A redistribution of the Ti⁴⁺ ions within the film thickness was detected, which may in part explain the observed anomaly and has implications regarding the possible occurrence of phase separation during film sintering.