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.     

Effect of ZnO film deposition methods on the photovoltaic properties of ZnO–Cu2O heterojunction devices

The effect of ZnO film depositions using various film deposition methods such as magnetron sputtering (MSP), pulsed laser deposition (PLD) and vacuum arc plasma evaporation (VAPE) on the photovoltaic properties of ZnO–Cu₂O heterojunction solar cells is described in this report. In addition, the relationship between the resulting photovoltaic properties and the film deposition conditions such as supply power and substrate arrangement was investigated in Al-doped ZnO (AZO)–Cu₂O heterojunction devices fabricated using AZO thin films prepared by d.c. magnetron sputtering (d.c.MSP) or r.f. magnetron sputtering (r.f.MSP). The results showed that the measured photovoltaic properties of devices fabricated with films deposited on substrates oriented perpendicular to the target were better than those of devices fabricated with films deposited on substrates oriented parallel to the target. It was also found that ZnO film depositions under conditions where a relatively weaker oxidizing atmosphere was used yield better properties than films derived from MSP, which utilizes a high-density and high-energy plasma. Using VAPE and PLD, for example, high efficiencies of 1.52 and 1.42%, respectively, were obtained under AM2 solar illumination in devices fabricated at a substrate temperature around 200 °C.     

The effect of the deposition method on the optical properties of SiO2 thin films

Three films of SiO₂ deposited by three different methods (chemical vapor deposition, electron beam evaporation and r.f. sputtering) were studied to show the effect of the method of preparation on the optical constants of the films. Of the three studied films, the film prepared by electron beam gun deposition showed refractive index values (n) close to the bulk material in the spectral range 300–850 nm. No values for the absorption constant (k) were determined except for the film prepared by r.f. sputtering, which showed higher k values due to the non-stoichiometric structure of the film.     

Metal/dielectric transmission interference filters with low reflectance. 2. Experimental results

The successful fabrication of metal/dielectric multilayer filters requires not only accurate control of the individual layer thicknesses, but also a good knowledge of the optical constants of the materials used in the filters. In the case of metal films, it is also essential to know whether any transition layers are formed at the interfaces and, if so, how their thicknesses and optical constants depend on the deposition conditions. An automatic, real-time process control, magnetron sputtering deposition system was modified to permit the manufacture of metal/dielectric filters using optical monitoring techniques. To illustrate the performance of this system, two bandpass filters, a short-wavelength pass filter, and a neutral density filter were produced, all having a low reflectance for light incident on one side. The metal layers used in these filters consisted of either Ni or Ag. TheAg films could be protected from the O(2) plasma using thin Ni or Si films. Good agreement was obtained between the calculated and measured spectral transmittance and reflectance curves.     

Investigation of the interfacial structure of ultra-thin platinum film deposited by cathodic–arc

Ultra-thin films are of interest in the production of X-ray mirrors that use a multilayer structure. The most commonly used deposition techniques are dc magnetron sputtering and electron beam evaporation; this paper presents results of cathodic–arc deposition. Ultra thin films of platinum with nominal thicknesses in the range 15–65 Å were deposited on silicon substrates and the film structure investigated using X-ray reflectivity and X-ray photoelectron spectroscopy. It has been found that the structure of the deposited films consists of three layers—the platinum film, a silicon oxide layer and a platinum silicide layer. In contrast to dc magnetron and electron beam deposited films, the silicide layer of cathodic–arc deposited films have a higher density and greater thickness, which is attributed to the higher energy process of this deposition technique. These attributes of the cathodic–arc deposited films suggest that the deposition technique is not suitable for production of mirrors of materials that react with each other, but for materials that do not the deposition technique is potentially more favourable than that of e-beam and magnetron sputtering.     

Post-nucleation phenomena in the Volmer-Weber mode of epitaxy

Two commonly used methods of depositing a thin film in vacuum are evaporation and sputtering. Evaporation has the advantage of rapid deposition in relatively high vacuum for non-refractory materials. Evaporated films are, however, liable to be weakly bonded to the substrate, because of the low arrival energy of the evaporant, unless effects such as chemical bonding occur. Sputtered films generally bond strongly but sputtering is a much slower deposition process than evaporation so that there may be a high density of contaminating inclusions. As charging also affects the sputtering process special techniques such as r.f. sputtering must be employed for insulating targets.A saddle-field ion source has been developed which operates with cold cathodes and without a magnetic field at pressures compatible with evaporation. Evaporated films deposited in the presence of a beam from this source exhibit the bonding properties of sputtered films. The beam contains a high proportion of energetic neutrals so that the method can be applied to both insulating and conducting substrates. The ion source is compact and can be installed generally in existing vacuum equipment. The source geometry can be varied to ensure that the area covered by the beam matches the deposition area.     

On-line reoptimization of filter designs for multivariate optical elements

An automated method for producing multivariate optical element (MOE) interference filters that are robust to errors in the reactive magnetron sputtering process is described. Reactive magnetron sputtering produces films of excellent thickness and uniformity. However, small changes in the thickness of individual layers can have severe adverse effects on the predictive ability of the MOE. Adaptive reoptimization of the filter design during the deposition process can maintain the predictive ability of the final filter by changing the thickness of the undeposited layers to compensate for the errors in deposition. The merit function used, the standard error of calibration, is fundamentally different from the standard spectrum matching. This new merit function allows large changes in the transmission spectrum of the filter to maintain performance.     

Deposition and spectral performance of an inhomogeneous broadband wide-angular antireflective coating

Gradient index coatings and optical filters are a challenge for fabrication. In a round-robin experiment, basically the same hybrid antireflection coating for the visible spectral region, combining homogeneous refractive index layers of pure materials and linear gradient refractive index layers of material mixtures, has been deposited. The experiment involved three different deposition techniques: electron-beam evaporation, ion-beam sputtering, and radio frequency magnetron sputtering. The material combinations used by these techniques were Nb(2)O(5)/SiO(2), TiO(2)/SiO(2), and Ta(2)O(5)/SiO(2), respectively. The spectral performances of samples coated on one side and on both sides have been compared to the corresponding theoretical spectra of the designed profile. Also, the reproducibility of results for each process is verified. Finally, it is shown that ion-beam sputtering gave the best results in terms of deviation from the theoretical performance and reproducibility.     

Characterization and cytocompatibility of carbon films

Carbon layers on polyethyleneterephtalate (PET) backing were prepared by 3 different deposition methods as evaporation, sputtering and photo induced chemical vapor deposition. UV-Vis, Raman spectroscopy, Rutherford backscattering techniques, goniometry and electrical resistance measurement were used for the characterization of the layers. Surface morphology of the layers was determined by AFM technique and the thickness was determined by SEM and profilometry. Adhesion and proliferation of 3T3 cells by method in vitro were studied. It was found that the properties of the deposited carbon layer depend on the deposition method. The layers prepared by sputtering are composed from oxidized amorphous carbon in the form of disordered graphite. Contact angle of deposited carbon layers decreases in comparison to pristine PET. The electrical resistance of carbon layer also decreases, a dramatic decrease being observed especially after carbon flash evaporation. The carbon deposition has no significant influence on surface roughness, but the surface morphology is strongly influenced. Adhesion of 3T3 fibroblast didn't show any significant difference between PET, sputtered and CVD layers. Proliferation of 3T3 fibroblast has shows differences due to the surface morphology and also wettability of the surface which is linked to the chemical composition.     

Influence of film thickness and annealing atmosphere on the structural, optical and luminescence properties of nanocrystalline TiO2 thin films prepared by RF magnetron sputtering

TiO₂ thin films were deposited onto quartz substrates by RF magnetron sputtering. Inorder to investigate the effect of film thickness on the structural and optical properties, films were deposited for different time durations, and post-annealed at 873 K. The influence of annealing atmosphere (air/oxygen) on the film properties was also investigated. The films were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–vis spectroscopy and photoluminescence (PL) spectroscopy. Films deposited at different time durations are amorphous-like in nature. From XRD patterns it can be inferred that deposition for longer duration is essential for achieving crystallisation in TiO₂ thin films prepared by RF magnetron sputtering. The films exhibited good adherence to the substrate and are crack free as revealed by SEM images. Film thickness was found to increase with increase in sputtering time. The optical band gap of the films was found to decrease with increase in film thickness, which is consistant with XRD observations. Film thickness did not show any significant variation when annealed in both air and oxygen. Defect related PL emission in the visible region (blue) was observed in all the investigated films, which suggests the application of these films in optoelectronic display devices.     

Topical meeting on optical interference coatings (OIC'2001): manufacturing problem

Measurements are presented of the experimental filters submitted to the first optical thin-film manufacturing problem posed in conjunction with the Topical Meeting on Optical Interference Coatings, in which the object was to produce multilayers with spectral transmittance and reflectance curves that were as close as possible to the target values that were specified in the 400- to 600-nm spectral region. No limit was set on the overall thickness of the solutions or the number of layers used in their construction. The participants were free to use the coating materials of their choice. Six different groups submitted a total of 11 different filters for evaluation. Three different physical vapor deposition processes were used for the manufacture of the coatings: magnetron sputtering, ion-beam sputtering, and plasma-ion-assisted, electron-beam gun evaporation. The solutions ranged in metric thickness from 758 to 4226 nm and consisted of between 8 and 27 layers. For all but two of the samples submitted, the average rms departure of the measured transmittances and reflectances from the target values in the spectral region of interest was between 0.98% and 1.55%.     

Effect of substrate temperature and annealing treatment on the electrical and optical properties of silver-based multilayer coating electrodes

Multilayer coatings consisting of thin silver layers sandwiched between layers of transparent conducting metal oxides are investigated from the view point of low-resistance electrodes for use in flat panel displays, solar cells, etc. ZnO/Ag/ZnO multilayer films were prepared on glass substrates by simultaneous RF magnetron sputtering of ZnO and dc magnetron sputtering of Ag. Optimization of the deposition conditions of both ZnO layers and metallic layers were performed for better electrical and optical properties. The structural, electrical and optical properties of the films (deposited at room temperature, different substrate temperature and annealed at different conditions) were characterized with various techniques. We could not produce high-quality transparent conductive electrodes simply by annealing at various temperatures. However, improved electrical properties and a considerable shift in the transmittance curves was observed after heat treatment. The experimental results show that the electrical resistivity of as-grown films can be decreased to 10^− 5 Ω cm level with post-annealing at 400 °C for 2 h in vacuum atmosphere. After heat treatment, the sheet resistance was reduced as much as 20% which was due to the increased grain size of Ag film. The samples heat treated at 200-400 °C under vacuum or nitrogen atmosphere showed the best electrical properties. The key to the superior electrical and optical properties of the multilayer is the optimization of growth conditions of the silver layer by careful control of the oxide properties and the use of appropriate annealing temperature and atmosphere.     

A comparative study of the UV optical and structural properties of SiO2, Al2O3, and HfO2 single layers deposited by reactive evaporation, ion-assisted deposition and plasma ion-assisted deposition

Growing requirements for the optical and environmental stability, as well as the radiation resistance against high-power laser radiation, especially for optical interference coatings used in the ultraviolet spectral range, have to be met by new, optimised, thin-film deposition technologies. For applications in the UV spectral range, the number of useful oxide thin film materials is very limited due to the higher absorption at wavelengths near to the electronic bandgap of the materials. Applying ion-assisted processes offers the ability to grow dense and stable films, but in each case careful optimisation of the deposition process (evaporation rate, substrate temperature, bombarding gas, ion energy and ion current density) has to achieve a balance between densification of the layers and the absorption. High-quality coatings and multilayer interference systems with SiO₂ as the low-index material can be deposited by various physical vapour deposition technologies, including reactive e-beam evaporation, ion-assisted deposition and plasma ion-assisted deposition. In order to improve the degradation stability of dielectric mirrors for use in UV free-electron laser optical cavities, a comparative study of the properties of SiO₂, Al₂O₃ and HfO₂ single layers was performed, and was addressed to grow very dense films with minimum absorption in the spectral range from 200 to 300 nm. The films were deposited by low-loss reactive electron-beam evaporation, by ion-assisted deposition using a ‘Mark II’ ion source, and by plasma ion-assisted deposition using the advanced plasma source. Optical and structural properties of the samples were studied by spectral photometry, infrared spectroscopy, X-ray diffraction and reflectometry, as well as by investigation of the surface morphology. The interaction of UV radiation with photon energy values close to the bandgap was studied. For HfO₂ single layers, laser-induced damage thresholds at 248 nm were determined in the 1-on-1 and 1000-on-1 test modes as a function of the deposition technology and film thickness.     

Mechanical stress and thermal-elastic properties of oxide coatings for use in the deep-ultraviolet spectral region

Mechanical stress and the structures of SiO2, Al2O3, and HfO2 single oxide layers and of high-reflection multilayer coatings deposited by reactive evaporation, plasma ion-assisted deposition, and ion-beam sputtering have been studied. The stress was related to the microstructure and to the incorporation of water by means of infrared spectroscopy. From the slopes of measured stress-temperature curves of these coatings deposited onto two substrate materials (silicon and fused silica), the biaxial moduli and the thermal expansion coefficients of the films were estimated.     

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.     

Electromechanical Behavior of Al/Al2O3 Multilayers on Flexible Substrates: Insights from In Situ Film Stress and Resistance Measurements

A series of Al and Al/Al₂O₃ thin-film multilayer structures on flexible polymer substrates are fabricated with a unique deposition chamber combining magnetron sputtering (Al) and atomic layer deposition (ALD, Al₂O₃, nominal thickness 2.4–9.4 nm) without breaking vacuum and thoroughly characterized using transmission electron microscopy (TEM). The electromechanical behavior of the multilayers and Al reference films is investigated in tension with in situ X-ray diffraction (XRD) and four-point probe resistance measurements. All films exhibit excellent interfacial adhesion, with no delamination in the investigated strain range (12%). For the first time, an adhesion-promoting naturally forming amorphous interlayer is confirmed for thin films sputter deposited onto polymers under laboratory conditions. The evolution of Al film stresses and electrical resistance reveal changes in the deformation behavior as a function of oxide thickness. Strengthening of Al is observed with increasing oxide thickness. Significant embrittlement can be avoided for oxide layer thicknesses ≤2.4 nm.     

Thin tristearin deposits as solid hydrogen-rich layers for neutron metrology

Layers of solid material with a relatively high, constant content of hydrogen that is stable over a long period of time are needed for recoil proton telescopes and for precise determination of the cross-section ratio of ²³⁵U(n,f)/H(n,n). Thin layers of tristearin, a material that is relatively rich in hydrogen, have been prepared with an areal density of 0.05 up to 0.5 mg cm⁻² by evaporation in high vacuum. The surface quality was studied by AFM (atomic force microscopy). The thickness of the layers was estimated by several methods and its homogeneity was determined using an optical profilometer. The hydrogen amount in the deposited layer was estimated by combustion analyses.     

Humidity sensitivity of optical structures prepared by r.f.-biased r.f. sputtering

In an attempt to produce optical structures with a lower humidity sensitivity than that of structures deposited by conventional evaporation, we used r.f.-biased r.f. sputtering for the preparation of coatings. The sensitivity was effectively reduced owing to the high density of bias-sputtered films which are subjected to controlled ion bombardment during their growth. Our experiments suggest that neither rate monitoring nor optical monitoring is necessary, at least not in the preparation of simple structures with few layers, if glow discharge sputtering processes comprising r.f. substrate biasing in diode, triode or magnetron set-ups are used to deposit the coatings.     

Wavefront control of SiO2-based ultraviolet narrow-bandpass filters prepared by plasma ion-assisted deposition

Metal oxide layers produced by plasma ion-assisted deposition are extensively used for complex optical coatings due to the availability of materials, the high packing density of films, and the smooth surfaces. Stringent optical surface figure specifications necessary for both laser optics and precision optics require film stress to be well-controlled and surface deformation to be corrected or compensated. SiO(2)- based single-cavity UV narrow-bandpass filters were prepared by plasma ion-assisted deposition. The correlation between film stress, refractive index, deposition parameters, and postdeposition annealing was established. The film stress was calculated based on interferometric surface deformation. The refractive index and film thickness were determined by means of variable angle spectroscopic ellipsometry. The center wavelength of the filters was obtained through spectral transmission measurement. The results suggest that the wavefront distortion of the multilayer coatings is dominated by the compressive stress of the SiO(2) layers and can be controlled and corrected by the amount of plasma ion momentum transfer, substrate temperature, postdeposition annealing, and stress compensation via backside SiO(2) coating. Based on the understanding of the mechanical and optical properties, the wavefront correction technique enables us to satisfy stringent surface figure specifications.     

真空蒸镀红荧烯薄膜及其形貌分析

红荧烯(rubrene)即5,6,11,12-四苯基并四苯,是一种重要的小分子有机半导体材料,可以用以制备红荧烯有机场效应管和太阳能光伏器件。本文首先对传统的热蒸发真空系统进行改造,使之能蒸镀有机薄膜。在一定的蒸发温度下,经过不同蒸镀时间蒸镀红荧烯薄膜,蒸镀时间分别为5,6,7,8 h,获得了具有多晶结构的红荧烯薄膜,并对其形貌进行了分析。结果表明非晶结构的红荧烯薄膜首先在硅衬底上生长,非晶红荧烯薄膜生长至一定厚度后,多晶结构的红荧烯从其中形成。