衬底温度对柔性硫化锌薄膜结构与光学性能的影响北大核心CSCD

本文利用射频磁控溅射薄膜沉积技术在柔性聚酰亚胺(PI)、氧化铟锡(ITO)玻璃及石英玻璃衬底上制备了透明硫化锌(ZnS)薄膜。通过改变生长过程中的衬底温度,全面系统地研究了衬底温度对柔性和刚性ZnS薄膜的晶体结构、光透过率、光学常数以及表面性能影响的规律。研究表明升高衬底温度有利于形成ZnS薄膜(111)晶面的择优取向生长。不同衬底温度条件下制备的柔性和刚性ZnS薄膜在可见光波长范围内的平均光透过率均大于80%;在红外波长范围的平均光透过率达到85%。柔性ZnS薄膜在400 nm-890 nm波长范围内的光学折射率为2.21-2.56。刚性ZnS薄膜的光学折射率随着衬底温度的升高有所增加,当衬底温度为300℃时,刚性ZnS薄膜在890 nm波长处的折射率达到2.26。柔性ZnS薄膜厚度及表面粗糙度均随着衬底温度的升高而降低,当衬底温度为300℃时,柔性ZnS薄膜表面均方根粗糙度达到最小值2.99 nm。为实现高性能柔性ZnS光电器件,应控制生长柔性ZnS薄膜的衬底温度在200℃-300℃,以获得最优化的器件性能。     

ZnS薄膜的水浴法制备及其光学性能

以酒石酸和柠檬酸钠为络合剂,采用水浴法(CBD)制备ZnS薄膜.利用X射线衍射(XRD)、X射线能谱仪(EDAX)、扫描电镜(SEM)、紫外-可见分光光度计(UV-vis)研究ZnS薄膜的结构、成分、形貌及光学性能.利用透射光谱计算了ZnS薄膜的光学禁带宽度.结果表明:ZnS薄膜呈立方相晶体结构,水浴沉积时间为3h的ZnS薄膜原子比Zn∶S为1∶0.85,薄膜表面均一致密,在可见光区有着好的透射性能,在300～800 nm的光谱范围内平均透射率达到80.8%,光学禁带宽度为3.78eV,适合作为太阳能电池过渡层.     

蒸发速率对ZnS薄膜性能的影响

为了研究蒸发速率对ZnS薄膜的折射率、表面形貌和应力等性能的影响,本文采用电子束蒸发技术进行了ZnS薄膜的制备。首先在K9玻璃基片上镀制薄膜,采用分光光度计进行透射率曲线的测试,利用光谱反演法得出薄膜的折射率,采用原子力显微镜表征了样品的表面形貌。最后在聚酰亚胺基底上镀制薄膜,利用Stoney公式计算出薄膜的应力。结果表明,随着蒸发速率的增加,薄膜折射率先增大后减小,在2000nm波长处薄膜的折射率最大值为2.21,最小值为2.07。蒸发速率越大,薄膜样品表面结构越疏松。不同蒸发速率下制备的薄膜均呈现压应力,增大蒸发速率可以显著降低薄膜应力。ZnS薄膜的性能受蒸发速率影响显著,蒸发速率为1.5nm/s时折射率可达到最大值,蒸发速率为2.5nm/s时薄膜应力最小。     

实时测量器件中光学薄膜厚度的新方法研究

从薄膜光学理论出发，阐述了利用光学反射比实时测量特种器件中光学薄膜厚度的原理，介绍了测试仪器，分析了测试结果。在已知基底的折射率、光学薄膜的折射率、消光系数及入射光波长的情况下，可计算出光学薄膜的反射比随厚度变化的理论曲线，实验曲线与理论曲线相比较，可实时获得薄膜的厚度信息，这对控制薄膜工艺很有益处。     

实时测量器件中光学薄膜厚度的新方法研究

从薄膜光学理论出发，阐述了利用光学反射比实时测量特种器件中光学薄膜厚度的原理，介绍了测试仪器，分析了测试结果。在已知基底的折射率，光学薄膜的折射率，消光系数及入射光波长的情况下，可计算出光学薄膜的反射比随厚度变化的理论曲线，实验曲线与理论曲线相比较，可实时获得薄膜的厚度信息，这对控制薄膜工艺很有益处。     

三元体系化学水浴法制备ZnS薄膜结晶性能的研究

太阳薄膜电池ZnS缓冲层一般以氨水为主络合剂、水合肼为辅助络合剂二元络合体系化学水浴法制备。实验发现以氨水为主络合剂、水合肼和柠檬酸为辅助络合荆三元体系制备的ZnS薄膜质量明显要比氨水、水合肼二元体系的ZnS薄膜好。薄膜表面更加光亮、平整，光透过率能得到明显提高。从实验现象和测试结果来看，随柠檬酸浓度增加，在反应溶液中无定形态白色沉淀明显减少，ZnS薄膜结晶性能也得到明显提高，ZnS薄膜光透过率升高。柠檬酸浓度为0．15mol／L时，薄膜光透过率达到85％左右，完全满足太阳能电池的要求；继续增加柠檬酸的量，薄膜光透过率趋于一致，光透过率略有回落。     

硫化法在金属箔片衬底上制备ZnS薄膜研究

采用铝箔作为衬底材料,用溅射Zn薄膜再硫化的两步法制备ZnS薄膜,对薄膜进行XRD、EDS和SEM测试,分析硫化温度对薄膜特性的影响。实验结果表明,硫化温度400℃可确保Zn与S反应生成ZnS,薄膜择优取向为(111)晶面。提高硫化温度可增大(111)衍射峰的强度和晶粒尺寸,即提高ZnS薄膜的结晶度。所制备薄膜的组分接近ZnS化学计量比,且表现出贫Zn和富S特性,说明已发生充分的硫化反应。薄膜表面平滑且无裂纹,由致密排列的晶粒组成。实验结果说明采用硫化法在铝箔衬底上制备ZnS薄膜的可行性。     

化学水浴中氨浓度对沉积ZnS薄膜的影响

用化学水浴法在玻璃衬底上沉积ZnS薄膜。采用XRD、SEM、nkd-薄膜分析系统对薄膜的形貌、结构和光学性能进行了分析，结果表明：当氨浓度〈1．50mol／L，可获得白点较少、平整性较好的非晶ZnS薄膜，在红移方向上很长的波段内透过率较好，可达95％以上，禁带宽度为3．81eV，折射率随波长的增加而减小，从2．32变化到1．92。有关化学水浴ZnS薄膜折射率的报道极少；当氨浓度〉1．50mol／L时，薄膜白点增多，易龟裂和剥落，结构是立方闪锌矿。     

ZnS薄膜沉积过程的基材效应

采用热蒸发及离子束辅助沉积技术制备了单层ZnS薄膜,研究了Si、Ge、K9及石英玻璃基材对薄膜沉积速率及光学特性的影响。采用椭偏法拟合了薄膜的厚度和折射率,分析了不同基材上沉积薄膜的色散特性。研究结果表明,薄膜的生长存在明显的基材效应,无论室温沉积、基温200℃,还是采用离子束辅助沉积,石英基材上均具有最高的沉积速率。室温沉积时,4种基材上薄膜的沉积速率差为3.3 nm/min,加热进一步扩大了这种差异(5.2 nm/min),而离子束辅助则在一定程度上缩小了这种差异(1.86 nm/min)。在室温下,石英基材上沉积的ZnS薄膜具有最低的折射率,其他几种基材上折射率差异不大。加热会使Si、Ge及K9玻璃上的折射率差异变大,与石英玻璃上薄膜折射率差异减小,离子源的使用则进一步缩小了这种差异。透射率光谱测试证实了这一结果。     

化学水浴法制备ZnS薄膜及其光学性能

以酒石酸与柠檬酸钠为络合剂,采用化学水浴法(CBD)沉积ZnS薄膜.利用X射线衍射仪(XRD)、X射线能谱仪(EDAX)、扫描电镜(SEM)、紫外-可见分光光度计(UV-Vis)研究ZnS薄膜的结构、组成、形貌及光学性能,利用透射光谱计算ZnS薄膜的光学禁带宽度(Eg).结果表明:ZnS薄膜呈立方相晶体结构,经过300℃熟处理1h的ZnS薄膜原子比为Zn:S=1:0.85,表面均一致密,在可见光区的平均透射率达到80%,光学禁带宽度为3.74ev,适合作为太阳能电池过渡层.     

Refractive index profile modelling of dielectric inhomogeneous coatings using effective medium theories

The coatings having refractive index changing with the thickness present interesting optical performance, improved mechanical properties and smaller light scattering in comparison with classical multilayer stacks. Lot of theoretical work and experimental advances have been done for designing and production of mixture layers with such particular performances. The effective refractive index of the mixture coatings can be calculated by the use of effective medium theories. The refractive index profile characterization of inhomogeneous films that are mixtures of SiO₂ and Nb₂O₅ is presented. The composition is linearly changed through the thickness of the layers. Ex-situ spectrophotometric measurements, i.e. reflectance and transmittance at different incidence angles, are used for the precise characterization of the refractive index profiles. Linear, Maxwell-Garnet, Bruggeman and Lorentz-Lorenz effective medium theories are applied and quality and differences of the results are studied and analyzed. It is shown that the Lorentz-Lorenz model is the most appropriate for the given mixture, suggesting components are well mixed and there are no separated phases.     

Variable refractive index optical coatings

The discrete and restricted values of refractive index of the bulk optical materials at present available are a serious limitation on the usefulness of these materials for optical coatings. This limitation can be overcome by utilizing the atom-by-atom condensation feature of the growth of vapour-deposited thin films, which allows the homogeneous mixing of different materials irrespective of their solubility restrictions. We have used this feature of co-deposition of different materials to form mixed optical materials of variable refractive index, the variation being determined by the composition of the source material. Measurements of the optical constants of these films, prepared by co-evaporation of mixtures of ZnS and MgF₂ of various compositions, have been made. The refractive index of the mixed films is found to be in good agreement with the values predicted on the basis of the Lorentz-Lorentz theory. In addition, the optical equivalence of alternate layers of ZnS and MgF₂ with step thicknesses ranging from 5 to 250 Å has been studied. For step thicknesses less than 100 Å, the optical properties of the composite films are equivalent to those for the homogeneously mixed films. For larger step thicknesses, considerable and complicated interference effects are observed. Thus, variable refractive index composite films can be prepared by (a) co-deposition and (b) deposition of alternate discrete layers of different materials as long as the step thickness does not exceed about 100 Å. Furthermore, these techniques of obtaining optical films of mixed materials can be extended to any combination of materials and therefore they open up a new field in materials technology.     

追踪算法在纳米晶粒薄膜散射研究中的应用

本文通过光线追踪算法结合基于麦克斯韦方程解的蒙特卡洛方法,模拟了光在梯度折射率指数硅/非晶硅(C-Si/a-Si)复合薄膜中的传播情况.文中将梯度折射率指数薄膜考虑成多层均匀折射率薄膜的叠加,每一层的折射率由该层所在位置决定.通过对透射、反射光子在梯度折射率指数薄膜中运动的统计研究,讨论梯度折射率指数薄膜的减反射性能.模拟结果获得了薄膜中粒子的浓度、粒子直径大小以及折射率梯度变化对薄膜反射率的影响规律,这有助于低反射率薄膜的设计,以期解决目前较为引人关注的镀膜玻璃光污染问题.     

Equivalent refractive index of multilayer films of different materials

The variation of the equivalent refractive index with composition of multilayer films of ZnS-MgF₂-SiO, ZnS-Na₃AlF₆ and Ge-ZnS, prepared by depositing alternate layers of different materials, has been investigated. It has been established that, for small step thicknesses (much less than the wavelength of light to be used for measurements) of each layer, the composite multilayer films are optically equivalent to homogeneously mixed films of the same materials of corresponding relative compositions. Further, the results show that the indices of the multilayer films of ZnS-MgF₂-SiO and ZnS-Na₃AlF₆ are in good agreement with the values predicted on the basis of the Lorentz-Lorenz theory. The refractive index of Ge-ZnS multilayer films is in agreement with the Drude theory. Our studies also show that the refractive index of a multilayer film composed of three materials, two of which react chemically in the molten and vapour states, as, for example, ZnS and SiO in ZnS-MgF₂-SiO films, is equivalent to that expected theoretically for a homogeneously mixed film of the same materials. The controlled and predictable equivalent behaviour of multilayer films suggests their use to produce variable refractive index optical coatings by selecting any number of materials which may or may not react with each other chemically.     

Multilayer antireflective and protective coatings comprising amorphous diamond and amorphous hydrogenated germanium carbide for ZnS optical elements

To effectively protect and improve the transmittance of ZnS optical elements in the far infrared band, combined amorphous diamond (a-D) and amorphous hydrogenated germanium carbide (a-Ge_1−xC_x:H) films have been developed. The optical interference coatings were designed according to the layer optics theory. The a-D films, of which refractive index and film thickness were controlled by changing substrate bias and deposition time respectively, were deposited by filtered cathodic vacuum arc technology. The a-Ge_1−xC_x:H films were prepared by radio frequency sputtering technology. During this process their refractive index was modulated by changing the gas flow rate ratio and their film thickness was controlled by the flow rate ratio and deposition time. It has been shown that the combined films are superexcellent antireflective and protective coatings for ZnS optical elements.     

大口径溶胶-凝胶光学膜层提拉制备工艺控制

大口径溶胶-凝胶化学膜的光学性能指标主要由膜层厚度和折射率决定,提拉法制备工艺的关键技术就是对这两个参数进行精确控制。通过优化胶体制备工艺,并利用椭圆偏振法测量化学膜膜厚及折射率变化情况,获得了提拉速度模型,并进行了实验验证,为大口径化学膜高性能指标提供了技术和工艺保证。     

激光倍频三波长减反射膜

提出Nd:YAG激光二倍频,三倍频和主激光三波长同时实现减反射膜系设计方法。该方法成功地设计出不同折射率基片SiO_2,LiNiO_3和K_9玻璃在350nm, 530nm,1060nm三个波长带剩余反射率小于0.02％的减反射膜。文中给出设计理论和实例。并用所设计的膜系进行镀制实验,得到较好的结果。对实测曲线与计算曲线不一致性进行了分析。     

Advanced key technologies for magnetron sputtering and PECVD of inorganic and hybrid transparent coatings

Besides classical multilayer systems with alternating low and high refractive indices, reactive pulse magnetron sputtering processes offer various possibilities of depositing gradient films with continuously varying refractive index. Using nanoscale film growth control it is possible to achieve optical filter systems with a defined dependency of refractive index on film thickness, e.g. by sputtering a silicon target in a time variant mixture of oxygen and nitrogen. Also reactive co-sputtering of different target materials such as silicon and tantalum in oxygen is suitable as well. Rugate filters made from SiO_xN_y or Si_xTa_yO_z gradient refractive index profiles find their application in spectroscopy, laser optics and solar concentrator systems.Furthermore polymer substrates are increasingly relevant for the application of optical coatings due to their mechanical and economical advantages. Magnetron PECVD (magPECVD) using HMDSO as precursor allows to deposit carbon containing films with polymer-like properties. Results show the suitability of these coatings as hard coatings or matching layers. Multifunctional coatings with antireflective and scratch-resistant properties were deposited on polymer substrates using a combined magPECVD and sputter deposition process.     

A note on the use of ellipsometry for studying the kinetics of formation of self-assembled monolayers

Ellipsometry is currently one of the most important techniques for characterization of the deposition and growth mode of ultra thin organic films. However, it is well known that for thicknesses normally encountered in organic monolayer films, as would occur for example in self-assembled monolayers, ellipsometry cannot be used to simultaneously determine the thickness and refractive index of the monolayer film. Current practice is to assume a reasonable value for the film refractive index and calculate an effective ‘ellipsometric thickness’. This communication seeks to show that the alternative approach of assuming a thickness for the monolayer (determined by the length of the molecule) and calculating the effective film refractive index lends itself to easier and more meaningful physical interpretation. The Lorentz-Lorenz formula is then used to transform the effective refractive index into a surface coverage and hence to an effective mass coverage. The methodology advanced is applied to the kinetics of formation of a self-assembled monolayer of a well-studied molecule, octadecanethiol on Au.