In‐Situ‐Charakterisierung optischer Mehrschichtsysteme in Großflächen‐ Produktionsanlagen

The paper discusses approaches to the insitu analysis of optical multi‐layer coating stacks such as mirror coatings, AR coatings or lowE layer stacks on large‐area substrates in production environments. The stable production of complex layer systems requires in‐situ analysis systems that are able to provide spectral information and optical performance data, but also yield thickness information for individual layers and thus aide the operating staff in detailed analyzing deviations from the production target stack. Solutions incorporating in‐situ optical reflectance, transmittance and ellipsometry measurements wi^th optical data being collected not only for the completed layer stack, but also at intermediate coating stages, are discussed and the accuracy, robustness and stability of different measurement systems and computation strategies are compared.     

PVD‐Schutzschichten für Werkzeuge des Präzisionsblankpressens

PVD protective coatings for precision molding tools Precision glass molding (PGM) is a replicative hot forming process for the production of complex optical components, such as aspherical lenses for digital and mobile phone cameras or optical elements for laser systems. The efficiency and thus also the profitability of the PGM depend on the unit price per pressed component, which correlates primarily with the service lifetime of the pressing tools. To increase tool lifetime, the tool surfaces are coated with protective coatings based on precious metals or carbon using physical vapour deposition (PVD). The PVD coating technology enables the deposition of thin coatings, which also follow more complex surface geometries and achieve a high surface quality. PVD coatings are also commonly used to protect tools from wear and corrosion. This paper presents two chromium‐based nitride hard coatings produced by an industrial PVD unit and investigated for their applicability for PGM. Two different coating architectures were implemented, on the one hand a single coating chromium aluminium nitride (Cr,Al)N coating and on the other hand a nanolaminar CrN/AlN coating with alternating layers of chromium nitride and aluminium nitride. The latter is a coating consisting of hundreds of nano‐layers, only a few nanometers thick. Both coatings, (Cr,Al)N and CrN/AlN, each have a thickness of s ～ 300 nm in order to follow the tool contour as closely as possible. The properties of the coating systems, which are of particular relevance for PGM, are considered. These include on the one hand the adhesion of glass, the roughness and topography of the surface and the adhesion between the coating and the tool material. In addition, the barrier effect of the coatings against diffusion of oxygen was investigated. In order to reproduce the thermal boundary conditions of the PGM, thermocyclic aging tests are performed and their influence on the different properties is described.     

Vacuum ultraviolet coatings of Al protected with MgF(2) prepared both by ion-beam sputtering and by evaporation

Ion-beam sputtering (IBS) and evaporation are the two deposition techniques that have been used to deposit coatings of Al protected with MgF(2) with high reflectance in the vacuum ultraviolet down to 115 nm. Evaporation deposited (ED) Al protected with IBS MgF(2) resulted in a larger (smaller) reflectance below (above) 125 nm than the well-known all-evaporated coatings. A similar comparison is obtained when the Al film is deposited by IBS instead of evaporation. The lower reflectance of the coatings protected with IBS versus ED MgF(2) above 125 nm is because of larger absorption of the former. Both nonprotected IBS Al, as well as IBS Al protected with ED MgF(2), resulted in a band of reflectance loss that was peaked at 127 and 157 nm, respectively. This result was attributed to the excitation of surface plasmons due to the enhancement of surface roughness with large spatial wave vectors in the sputter deposition. This reflectance loss for IBS Al protected with MgF(2) is small at the short (lambda~120 nm) and long (lambda<350 nm) wavelengths investigated. IBS Al protected with ED MgF(2) is thus a promising coating for these two spectral regions. Coatings protected with IBS MgF(2) resulted in a reflectance as high as coatings protected with ED MgF(2) at wavelengths longer than 550 nm, whereas the former had a lower reflectance below this wavelength.     

Optical properties of an optically rough coating from inversion of diffuse reflectance measurements

A method is developed for determining the optical properties of an optically rough coating on an opaque substrate from reflectance measurements. A modified Kubelka-Munk two- flux model is used to calculate the reflectance of the coating as a function of the refractive index, absorption coefficient, scattering coefficient, and thickness. The calculated reflectance is then fitted to measurements using a spectral projected gradient algorithm, allowing the optical properties to be obtained. The technique is applied to titanium dioxide coatings on a titanium substrate. Realistic values of refractive index and absorption coefficients are generally obtained. Quantities that are useful for solar water-splitting applications are calculated, including the depth profile of absorption and the proportion of the incident photon flux absorbed in the coating under solar illumination.     

Toward perfect antireflection coatings. 3. Experimental results obtained with the use of Reststrahlen materials

The equipment and methods used to produce wide-angle antireflection coatings based on Reststrahlen materials are described. The optical constants of the coating materials used in the construction of the multilayers were determined by spectrophotometric ellipsometry and are compared with the literature values. The measured performance of an experimentally produced antireflection coating is compared with the expected calculated performance. The reflectance is low over a wide range of angles, but only in the narrow-wavelength region at which the refractive index of the Reststrahlen material is close to unity.     

Universal antireflection coatings for substrates for the visible spectral region

It is possible to design normal-incidence antireflection coatings that reduce the reflectance of any substrate with a refractive index that lies in the range of 1.48 to 1.75. The performance of such coatings depends on the width of the spectral region over which the reflectance is to be suppressed, on the coating materials used for their construction, and on the overall optical thickness of the layer system. For example, the calculated average spectral reflectance of a set of six different substrates with refractive indices 1.48, 1.55, 1.60, 1.65, 1.70, and 1.75, when coated with a 0.56-μm-thick, eight-layer antireflection coating designed for the 0.40-0.80-μm spectral region, was 0.34%. This is higher than the average reflectance that is attainable with a conventional antireflection coating of similar optical thicknesses designed for a particular refractive index. However, it is an acceptable value for most applications. With the universal type of antireflection coating described, it is thus possible to coat a number of different refractive-index substrates in one deposition run, and this can result in considerable cost and time savings.     

Modeling the image quality of enhanced reflectance x-ray multilayers as a surface power spectral density filter function

Residual surface roughness over the entire range of relevant spatial frequencies must be specified and controlled in many high-performance optical systems. This is particularly true for enhanced reflectance multilayers if both high reflectance and high spatial resolution are desired. If we assume that the interfaces making up a multilayer coating are uncorrelated at high spatial frequencies (microroughness) and perfectly correlated at low spatial and midspatial frequencies, then the multilayer can be thought of as a surface power spectral density (PSD) filter function. Multilayer coatings thus behave as a low-pass spatial frequency filter acting on the substrate PSD, with the exact location and shape of this cutoff being material and process dependent. This concept allows us to apply conventional linear systems techniques to the evaluation of image quality and to the derivation of optical fabrication tolerances for applications utilizing enhanced reflectance x-ray multilayers.     

Realization of High Performance AR‐coatings with Dust‐ and Water‐Repellent Properties

Hydrophobic coatings enable the manufacture of easy‐to‐clean surfaces having dust‐ and water‐repellent properties. In this work, a hydrophobic coating is deposited as a top layer on an antireflective (AR) multilayer system to produce low reflectance optical surfaces at a normal incident angle in the visible spectrum with dust‐ and water‐repellent properties for applications in precision optics. It is shown that the hydrophobic coating can be considered, from an optical point of view, as two adjacent thin layers having specific thicknesses and densities. In fact, the hydrophobic layer is one monolayer comprising molecular chains with anchoring groups responsible for the chemical bond with the substrate material and functional groups responsible for the water‐ and oil‐repellent properties. Their optical constants are determined and included in the final coating design. High performance AR coatings having an average reflectance of 0.14% at 7° incident angle in the 400‐680nm spectral range together with a pleasing purplered reflex color are produced. Coated lenses exhibit an excellent abrasion resistance, environmental stability, resistance to cleaning agents, homogeneity and water repellence with contact angles against water higher than 110°.     

Coatings with graded-reflectance profile: conventional and unconventional characteristics

The main feature of graded optical coatings is a spatial reflectance profile that displays a maximum value at the coating center and goes toward a minimum along the radius according to a predefined law. A number of other requirements for using graded coatings in the laser field have been added to this basic property during the course of time. After a survey of the conventional properties of graded coatings, these additional characteristics are described, and their influence on the coating design and performance is examined.     

Surface morphology, composition and thermal behavior of tungsten-containing anodic spark coatings on aluminium alloy

Anodic spark coatings on aluminium alloy were prepared in aqueous electrolytes with sodium tungstate. The influence of boric acid addition in the electrolyte on the surface morphology, elemental and phase composition of the coatings was investigated. In both cases the coatings contained O, Al and W. The coatings obtained in electrolyte with boric acid and sodium tungstate contain also B at approximately 1 at.%. Scanning electron microscopy indicated that the coatings had three layers: the grey underlayer of anodic alumina, the second black layer of crystalline or amorphous aluminium tungstate agglomerated into fibers and the outer green layer of WO₃. It was proposed that isopoly- and heteropolyanions in the electrolyte used take part in the coating growth.     

Optical coatings for deuterium fluoride chemical laser systems

The high-power laser system has brought an interesting challenge to the development of optical coatings. A wide variety of coating specifications that are often contradictory have to be fulfilled. The choices of deposition process as well as coating materials are critical to coating loss, damage threshold, long-term stability, and other optical properties. A number of optical coatings being newly applied to deuterium fluoride laser systems are presented. The 3.8-mum laser reflection coatings with high damage threshold, multichromatic beam splitters, antireflection coatings with widely separated dual-wavelength bands, and 0.55-14-mum wide-band reflective coatings have been developed on substrates such as Si, Mo, fused silica, chemical vapor deposition ZnSe. Superior results have been obtained with ion-assisted deposition and electron-beam evaporation. Approaches to coating design and practical aspects of coating development are also discussed.     

溶胶-凝胶SiO2在变色薄膜中的应用

变色薄膜是一种非常有用的光学产品。用溶胶－凝胶SiO2作为变色薄膜中的介质层（Cr/SiO2/Al）能明显提高产品的质量和生产效率。本文介绍了溶胶－凝胶SiO2薄膜的制作方法，提出了用酸性催化控制SiO2溶胶过程；用网线辊涂布的方法形成薄膜，连同烘烧后处理完成SiO2凝胶过程。文章还对SiO2薄膜的光学特性和在制备变色薄膜中相关条件对整个薄膜性能的影响进行了分析。     

Estimation of the average residual reflectance of broadband antireflection coatings

We deal with optimal two-material antireflection (AR) coatings for the visible and adjacent spectral regions. It has been shown before that, for a given set of input parameters (refractive indices of the substrate, ambient medium and high- and low-index coating materials, and for a given spectral width of the AR coating), such designs consist of one or more clusters of layers of approximately constant optical thickness and number of layers. We show that, through the analysis of many different optimal coatings, it is possible to derive two parameters for a simple empirical expression that relates the residual average reflectance in the AR region to the number of clusters. These parameters are given for all possible combinations of relative spectral bandwidth equal to 2, 3, and 4; low-index to ambient-medium index ratio equal to 1.38 and 1.45; and high-to-low index ratio equal to 1.4, 1.5, and 1.7. The agreement between the numerically and the empirically calculated values of residual average reflectance is excellent. From the information presented the optical thin-film designer can quickly calculate the required number of layers and the overall optical thickness of an AR coating having the desired achievable residual average reflectance.     

Removal of a protective coating on Al by ion etching for high reflectance in the far ultraviolet

The effect of ion etching on the reflectance of Al coatings in the far ultraviolet is investigated. Ion etching of an overlayer grown on Al was performed by applying 100-300 eV Ar(+) ions using an ion gun. Ion etching was employed to remove the oxide naturally grown on an Al film that had been in contact with atmosphere. Ion etching was also used to remove part or all of the protective MgF(2) film on Al. The reflectance at 121.6 nm, H Lyman alpha line of the overlayer-removed Al surface was monitored after protecting it with a MgF(2) layer. Ion etching on both types of coatings resulted in an excellent reflectance value at 121.6 nm, whereas a reflectance loss was observed at longer wavelengths.     

Using Field Measurements to Assess Aging of Self-Cleaning High-Reflectance Paint

Continuous field measurements were used to evaluate the aging of solar reflectance on self-cleaning coatings for roofs in comparison with conventional coatings that have no self-cleaning function. Solar reflectance on self-cleaning coatings decreases by about 6 % per year with annual variations, due to the adhesion of dirt. On the other hand, solar reflectance on conventional coatings greatly decreases, by approximately 18 % within four months of the coating’s application, due to the adhesion of dirt. Then, it gradually recovers at a rate of about 4 % per year, with annual variations, due to degradation of the coating. It is due to degradation of the conventional coating that the difference of solar reflectance between the self-cleaning coating and the conventional coating becomes almost zero in two years. Both the adhesion of dirt and coating degradation by chalking affect the temporal change of solar reflectance with annual variation.     

Carbon coatings on silica glass optical fibers studied by reflectance Fourier-transform infrared spectroscopy and focused ion beam scanning electron microscopy

Carbon coatings applied on optical fibers via chemical vapor deposition were characterized by a resistance technique, focused ion beam/scanning electron microscopy (FIB/SEM), and reflectance Fourier-transform infrared spectroscopy (FTIR). The resistance technique measures the thickness of carbon film by measuring the resistance over a section of optical fiber, and backing out the film thickness. The FIB/SEM system was used to remove a cross section of the optical fiber and carbon coating and using a scanning transmission electron detector the thickness was measured. The FTIR approach is based on the fact that the wavelength of the light in the mid-infrared region (~ 10 μm) is significantly larger than the typical thickness of the carbon coatings (< 0.1 μm) which makes the coating “semi-transparent” to the infrared light. Carbon coating deposition results in significant transformations of the band profiles of silica in the reflectance spectra that were found to correlate with the carbon coating thickness for films ranging from 0.7 nm to 54.6 nm. The observed transformations of the reflectance spectra were explained within the framework of Fresnel reflection of light from a dual-layer sample. The advantage of this approach is a much higher spatial resolution in comparison with many other known methods and can be performed more quickly than many direct measurement techniques.     

溶胶-凝胶法在PMMA上制备SiO2-Al2O3涂层过程的研究

采用溶胶－凝胶法，以无机盐ＡｌＣｌ３．６Ｈ２Ｏ、醇盐ＴＥＯＳ及自制偶联剂为原料，在ＰＭＭＡ上制备抗磨涂层，选择出得到高质量涂膜的合适组分及工艺。研究了膜形成的基本规律。     

Interfacial study of magnesium-containing fluoridated hydroxyapatite coatings

Magnesium-containing fluoridated hydroxyapatite (Mg_xFHA) coatings have been developed to improve the biological performances of fluoridated hydroxyapatite (FHA) coatings. The coatings are deposited on Ti6Al4V substrates via a sol-gel process. The interface between the coating and substrate is characterized by scanning electron microscopy, glow discharge optical emission spectroscopy and X-ray photoelectron spectroscopy for coating thickness, elemental distribution and chemical states. Pull-off test is used to evaluate the adhesion strength. The results show that the interdiffusion of elements happens at the coating/substrate interface. The incorporation of Mg ions into FHA coatings enhances the pull-off adhesion strength between the coating and the substrate, but no significant difference is observed with different Mg concentrations.     

Morphology of Al2O3 scales on doped CoCrAl coatings

Adhesion between surface scale and protective coating is an essential requirement of a material possessing good overall oxidation resistance. Poor adhesion can lead to exfoliation of the oxide in response to thermal cycling or mechanically applied stresses, resulting in enhanced oxidation rates. Marked improvements in scale-substrate adhesion can be obtained by means of the formation of protrusions of oxide growing into the substrate. These act to key the protective scale to the surface and are more effective when a uniform distribution of small oxide pegs can be achieved. Thus the structure of the coating, the type of “rare earth addition” and its concentration are all important and this has been examined using electron beam physical-vapor-deposited CoCrAl coatings containing various elemental additions. The coatings were subjected to both isothermal and cyclic oxidation in the temperature range 1000–1200°C. The coating-scale interface and the development of pegs growing into the coating was examined in detail by dissolving away the underlying metal and coating using a bromine-methanol solution. The distribution of the pegs provides a good qualitative assessment of the oxide scale adherence. Results are compared with earlier studies on cast CoCrAl alloys containing various additions.     

Thermally grown oxide scales on γ-TiAl coated with thermal protection systems

Abstract

Thermal barrier coatings (TBCs) of yttria partially stabilized zirconia were deposited on gamma TiAl samples using electron-beam physical vapour deposition. The specimens were coated with intermetallic Ti –Al – Cr layers and CrAlYN/CrN nanoscale multilayer coatings. The lifetime of the TBC systems was determined performing cyclic oxidation tests in air at temperatures between 850 and 950–C. The TBC systems with Ti –Al – Cr and CrAlYN/CrN layers did not fail at 850 and 900–C during the maximum exposure time period of 1000 cycles of 1 h dwell time at high temperature. No spallation of the thermal barrier coatings was observed. As revealed by post-oxidation microstructural analysis, the protective coatings were severely degraded when exposed at 900–C, resulting in growth of mixed oxides on the substrate. Underneath the thermal barrier coating an outer oxide scale with a columnar structure was observed, consisting of rutile and α-Al₂O₃. Energy-dispersive X-ray spectroscopy analysis revealed zirconia and chromia being dissolved in the outer oxide scale. The columnar structure and the presence of zirconia indicated an effect of the TBC on the morphology of the outer oxide scale. The zirconia top coat exhibited an excellent adherence to this oxide scale formed on the protective layers when degraded, and at defects like cracks. When thermally cycled at 950–C, the TBC system on specimens coated with Ti –Al – Cr failed by spallation of the thermally grown mixed oxides, whereas the thermal barrier coating was well adherent to the outer oxide scale at this temperature, too.