Progress in Surface Science 81 (2006) 387401 www.elsevier.

com/locate/progsurf

Review

Vacuum coating of plastic optics

Ulrike Schulz *, Norbert Kaiser
Fraunhofer Institute for Applied Optics and Precision Engineering IOF, Albert-Einstein-Str. 7, 07745 Jena, Germany Commissioning editor: A.W. Kleyn

Abstract Vacuum technologies for the deposition of optical interference coatings on polymer substrates, based on long-term experience in glass coating, have been under development for about 20 years. A growing market for precision optical elements and consumer optics moulded from thermoplastic polymers requires antireective properties and hard coatings. Owing to the manifold chemical and physical properties of optical polymers, special eorts are essential for each type of plastic to nd polymer-capable coating conditions. The main focus of this article is on evaluating the state of the art in vacuum-coating processes applied to plastics today, and on discussing specic coating techniques and evaluation procedures. A better understanding of the complex interactions between lowpressure plasmas and the various polymer materials will be a key factor in making durable plastic optics for future applications; achieving this will be a challenge to surface scientists. 2006 Elsevier Ltd. All rights reserved.
Keywords: Plastic optics; Coating on plastics; Vacuum coating; Antireection; Plasma surface modication

Contents 1. 2. 3. 4. 5. 6.
*

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Coatings for plastic optics . . . . . . . . . . . . . . . . . . . . . Trends in vacuum-coating techniques . . . . . . . . . . . . . Wet-chemical coatings . . . . . . . . . . . . . . . . . . . . . . . . Moth-eye structures to achieve antireflection properties. Problems with vacuum coating . . . . . . . . . . . . . . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

388 389 392 393 394 395

Corresponding author. Tel.: +49 3641807344. E-mail addresses: ulrike.schulz@iof.fraunhofer.de, schulz@iof.fraunhofer.de (U. Schulz).

0079-6816/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.progsurf.2006.07.001

388

U. Schulz, N. Kaiser / Progress in Surface Science 81 (2006) 387401

7. 8.

6.1. Interactions between plasmas and polymers . . . . . . . . . . . . . . . . . . . . . . . . . 6.2. Diversity of materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3. Stress in coatings on plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.4. Difficulties with testing procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Challenges to surface scientists . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. . . . . . . .

. . . . . . . .

395 396 396 397 398 398 399 399

1. Introduction Rigid plastic optical components will replace parts made from glass whenever improved properties or lower costs can be achieved with plastic elements. The classical elds of application are eyeglasses and complex-shaped lenses for precision optical systems. In the near future, transparent plastics with optical-grade surfaces will be used on a large scale for covering car instruments and as refractive and diractive elements for optical sensors. In the case of precision optical parts, transparent polymers such as poly-methyl methacrylate (PMMA) and bisphenol-A polycarbonate (PC) have been common for more than 50 years. Moreover, many new materials optimized for optics among them polyamides, polyether sulfones, cycloolen polymers and its copolymers have been developed during the last few years [1]. These thermoplastic polymers can be processed cost-eectively into high-precision forms by injection moulding or hot embossing. A selection of transparent thermoplastics and their properties is shown in Table 1. Coatings can enlarge the area of application of polymer optics. Antireection (AR) properties are required for many precision optical elements and for consumer optical products such as eyeglasses and covers for displays. Another motivation for coating plastics results from the mechanical and chemical properties of organic polymers. Protective coatings increase the resistance of the polymer to abrasion, protect the polymer from chemical attack, or reduce gas ow through or from the polymer. In addition, coatings can be helpful for modifying the surface energy, thereby adjusting the wettability by water or oil [2,3]. When used as substrates for vacuum coating, organic polymers are much more complicated than inorganic glasses. Their various chemical structures can lead to various reactions in contact with chemicals or a plasma. Modern vacuum-coating processes are generally associated with short-wavelength radiation sources. The most signicant threats to the long-term stability of coated plastics are caused by vacuum ultraviolet (VUV) during the deposition process and by environmental factors, including humidity and the ultraviolet radiation in daylight. Both types of threat can result in immediate or slow changes in the bulk or interface properties after coating. Because of the complex dierences between polymer materials, every plastic material requires specic conditions for coating. The focus of this article is on evaluating the state of the art in vacuum-coating processes applied to plastics today. In practice, many coating procedures for polymers were initially adapted from glass-coating processes by empirical variation of parameters. On the other hand, surface scientists have studied the interactions between polymer surfaces and highly energetic radiation for many years [46]. For the generation of a stable interface between a

U. Schulz, N. Kaiser / Progress in Surface Science 81 (2006) 387401

389

Table 1 Properties of transparent thermoplastic materials (from manufacturers published data sheets and Refs. [1,43]) Material Brand name (examples) Plexiglas 7N, 8N Optrez 1310 Makrolon LQ2647 Apec 1897 Topas 5013 Zeonex E48R Zeonex 480R Zeonex 330R Zeonor 1020R Arton FX4727 Apel 5014DP Udel P-1700 Ultrason E2010 Trogamid CX7323 nD (587.6 nm) 1.491 1.512 1.585 1.573 1.533 1.53 1.525 1.509 1.53 1.523 1.543 1.634 1.65 1.516 52 56 23 58 56 56 Abbe value VD 58 54 30 Light transmittance (%), 3 mm 92 93 91 90 92 92 92 92 92 92 90 84 80 89 Deection temperature (C), ASTM D648 95 118 124 172 123 122 123 103 101 110 125 174 208 122a Suitability for vacuum coating Unknown ++ + +++ +++ +++ +++ Unknown Unknown Unknown +++ +++

Poly (methylmethacrylate) Alicyclic acrylate Polycarbonate

Cycloolen polymer

Polysulfone Polyether sulfone Polyamide

a

45

ISO 75-2 (0.45 MPa load).

specic polymer substrate and an evaporated layer, it is essential to understand the basic surface chemistry of the polymer during and after the layer deposition process. Therefore, these issues must be addressed jointly by surface scientists and coating engineers if we are to achieve progress in the development of new coating processes. 2. Coatings for plastic optics Coatings for plastic optics comprise optical interference layers, protective layers, and additional thin lms to manage the interface or to provide additional surface properties. The term optical thin lm indicates coatings with physical thicknesses in the range of a few to several hundreds of nanometers. In the optical sense, a lm is called thin when interference eects can be detected in transmitted or reected light. An arrangement of multiple layers with well-dened refractive indices and thicknesses which provides desired spectral characteristics by means of interference eects is called a coating design. A very important type of coating for optics is antireective layers, which are typically deposited on polymers in the same way as on glass, by vacuum deposition of interference layers [7]. The reduction in reectance due to interference phenomena is a function of the wavelength

390

U. Schulz, N. Kaiser / Progress in Surface Science 81 (2006) 387401

of the incident radiation and of the angle of incidence of the light on the surface. The simplest case in which we can obtain antireective properties from a material with refractive index ns at a dened wavelength k0 is to deposit a thin lm with a lower refractive index ni and with an optical thickness that is one-quarter of the wavelength (a quarter-wave layer). The most frequently used broadband AR coatings for the visible spectral range are adapted from the quarterhalfquarter design, where the rst quarter-wave layer, of medium refractive index, is replaced by parts of high-index and low-index quarter-wave layers followed by a high-index layer two quarter-waves thick (a half-wave layer) and a low-index quarter-wave layer on top. Many other designs for optical interference coatings, such as for dielectric mirrors, lters and beam splitters, are layer stacks that consist of alternating high-index and low-index layers each with an optical thickness of one quarter-wave at a dened design wavelength. For more details of the basics of interference theory, see Refs. [8,9]. The layer stacks used to build up interference coatings typically consist of metal oxides with a dened refractive index and a precise thickness. The low-index material most often used is silica (n = 1.5), whereas the high-index material can be selected from a variety of oxide materials with refractive indices in the range between 1.67 (alumina) and 2.4 (titanium dioxide). The selection of the material is important for the coating of plastics because of eects such as heat emission during evaporation and the absorption of ultraviolet light. At present, not very much information is available from the literature about coating designs specialized for polymer substrates. Some rules derived from our experience during the development of designs for antireective coatings may be valid: The materials and thicknesses of the layers have to be adjusted considering the mechanical and thermal stresses in the lm and the total amount of heat dissipated in the lm during the deposition process. The process parameters for the materials used have to be suitable, to avoid damage to the bulk and interface of the polymer during thin-lm deposition. The thin-lm materials have to be selected in order to achieve protection of the interfaces or the bulk polymer from ultraviolet radiation, depending on the type of polymer substrate. Interfacial zones with changed optical properties due to plasma treatment have to be taken into account in the calculation of the design. Designs should be suitable for integrating additional functions such as improved scratch resistance, barrier functions, antistatic functions or hydrophobic properties. Modern software design tools are available to generate specic broadband antireective designs, taking into account the requirements of an individual polymer and its application eld. An increased total coating thickness in a design may sometimes be acceptable because of the hardening eect obtained together with the optical eect. A prominent example is the AR-hard design type [10,11]. Typical coating designs and their spectral performance are shown in Figs. 1 and 2. These kinds of multilayer system are useful for obtaining antireective properties in the visible spectral range, improved scratch resistance, and water repellency on the surface simultaneously. A combination of a lacquer (i.e. a wet-chemical applied polysiloxane compound) with interference antireective layers is common on eyeglasses, whereas the AR-hard design was developed for thermoplastic optics where lacquering is unfavourable.

U. Schulz, N. Kaiser / Progress in Surface Science 81 (2006) 387401

391

Fig. 1. (a) A common coating for plastic eyeglasses. A four-layer antireective coating and a hydrophobic layer are deposited by vacuum evaporation on top of a lacquered plastic substrate. (b) AR-hard scratch-resistant antireective coating for thermoplastic optical components. All layers are deposited by vacuum deposition. The total thickness can be adjusted between 1 lm and 3 lm according to the hardness requirements.

Fig. 2. Spectral reectance for the designs shown in Fig. 1. The thickness of the eyeglass coating is about 3.3 lm (of which the lacquer accounts for 3 lm); the thickness of the AR-hard system is about 1.2 lm.

For eyeglasses and display covers, so-called easy-to-clean functions are required in addition. Antireective coatings with reduced dust attraction (antistatic properties) can be achieved easily by replacing small parts of the high-index material in an optical layer stack with electrically conductive indium tin oxide [12]. Hydrophobic and oleophobic topcoats should make it easier to remove fatty ngerprints. The state-of-the-art technique is the use of vacuum evaporation of organic precursors from a ceramic target and then dipcoating procedures on top of the AR-coated surface. The layer on top of the AR coating, just a few nanometers thick, typically consists of uoroalkyl silanes (FAS) or a peruoropolyether [13]. Besides transparent coatings, metal layers are required on plastic optics to form frontsurface and back-surface mirrors and beam splitters. A good metallic lm will completely reect or absorb the incident light if it is about 100 nm thick, whereas thinner lms are partially transparent. Aluminium and silver are the best reector materials in the visible,

392

U. Schulz, N. Kaiser / Progress in Surface Science 81 (2006) 387401

and gold is a good reector in the infrared range. The typical materials used to protect metal layers on polymer substrates from atmospheric corrosion are SiO2 and organically modied compounds of it [14]. One of the most popular applications of metallized thermoplastics is in injection-moulded reectors for automotive headlights. 3. Trends in vacuum-coating techniques Naturally, coating on plastics has to be done at temperatures below their heat distortion temperature. For most thermoplastics this means a temperature limit of about 120 C. Without substrate heating, only porous coatings would be obtained from most thin-lm materials. Moreover, these coatings would probably show poor adhesion because of insucient substrate activation. Unstable optical properties during the life of the optical part have to be reckoned with, owing to water uptake depending on the environmental conditions. Nevertheless, physical vapour deposition on plastics without substrate heating is still a common method of producing metallic reectors and is sometimes used for basic AR coatings that do not have to pass severe environmental tests. During the last decade, important innovations have been made in coating plastics. An alternative method of providing energy to a growing layer is the use of a low-pressure plasma emitted by a plasma source or an ion source. A currently well-established coating system for plastics is plasma ion-assisted deposition (plasma-IAD) using an advanced plasma source (Fig. 3) [15,16]. After pumping down the pressure inside of the box-coater to about 106 mbar, the oxide raw materials used to form interference layer stacks are evaporated thermally by electron-beam guns in a pressure range of about 104 mbar. Oxygen can be added to obtain a dened oxide stoichiometry. The thicknesses of layers can be controlled with nanometer precision by use of an oscillating-quartz-crystal monitor or by in-line monitoring of the transmission or reection. The growing layers are bombarded with argon ions emitted by an ion source, where the energy of the ions is between 70 eV and 150 eV. Properties such as the surface energy, the adhesion of the coating, the refractive index at the surface, the surface hardness, the colour of the bulk polymer (i.e., yellowing) and the surface topography can be inuenced by the parameters of this ion source [17]. Plastic optics with interference coatings produced by plasma-IAD are available

Fig. 3. Plasma ion-assisted deposition system with electron beam gun and advanced plasma source (APS) (Leybold Optics).

U. Schulz, N. Kaiser / Progress in Surface Science 81 (2006) 387401

393

Fig. 4. Principal features of an assembly for plasma-impulsed chemical vapour deposition (PICVD) developed by SCHOTT HiCotec.

now from a growing number of German companies, namely Jenoptik Polymer Systems, Fresnel Optics and Fuji Magnetics. Another well-established process for thermoplastics has been developed by the German company SCHOTT HiCotec [18]. In the plasma-impulsed chemical vapour deposition (PICVD) process, the gaseous precursor is decomposed by a pulsed microwave plasma (Fig. 4). PICVD and similar plasma-enhanced chemical vapour deposition (PECVD) processes are particularly suitable for coating small-sized 3D substrates and are already used in the industrial coating of light reectors and eyeglasses. A special advantage of coating plastics is the possibility to produce partly organic coatings with a gradient of hardness and elasticity [19]. An example is provided by abrasion-resistant organically modied silica layers on polycarbonate. To obtain these, silane or siloxane precursors are injected into the vacuum chamber and polymerized by applying a microwave or radio-frequency plasma [20 23]. Such a process is in use as part of the EXATEC 900 polycarbonate glazing system [24]. Because of the comparatively high emission of heat and radiation, the sputtering of dielectrics can be critical for plastic substrates. Nevertheless, sputter deposition processes for AR coatings can be preceded by lacquering or by a PECVD process step that deposits an initial protective layer [25,26]. Some new concepts use the advantage of high thickness precision in the production of AR layers on eyeglasses and hard-coated polycarbonate. Among these are closed-eld magnetron sputtering [27] and reactive pulse magnetron sputtering (PMS) using the unipolar sputtering mode [28]. The advantages of reactive-pulse-sputtered coatings are short deposition times and the potential for large-scale production. Sputtering is also a basic technology in web coaters for exible substrates. In that case, undesired heating of the polymer can be prevented by cooling the web over a drum [29,30]. Metal sputter-coating systems are well established in the manufacturing of reectors for car lights and indoor lighting [31]. 4. Wet-chemical coatings Wet-chemical coatings can be deposited by dip coating or spin coating on rigid at or slightly curved substrates. Injection-moulded parts of complex form are not suitable for

394

U. Schulz, N. Kaiser / Progress in Surface Science 81 (2006) 387401

this deposition method. In coating polymers, it is essential to avoid using high temperatures for curing or using radiation-induced cross-linking reactions for hardening. Some typical materials used to improve the abrasion resistance of thermoplastics are organically modied silanes. Silicate-based inorganicorganic hybrid polymers (ORMOCERs) have attracted considerable attention owing to their optical and mechanical properties [32]. The synthesis of these polymers includes a chemical modication of organic components so that they attach covalently to the inorganic network. The development of antireective coatings using wet-chemical processes has mainly been related to single-layer and two-layer systems, such as an antistatic two-layer AR coating consisting of a solgel alkoxide polymeric material and a colloidal indium tin oxide material [33]. The preparation of multilayers by the solgel process is complex, because the deposition and hardening steps have to be repeated many times. The requirement for high precision in the layer thickness, in the nanometer range, calls for clean-room conditions with well-controlled temperature and humidity. The basic research in this eld is focused on the liquid coating precursors rather than on the kind of polymer substrate or the coating design [34]. The technological details are probably the main challenge in each specic case of application of this technique. Only a few examples of the practical application of wet-chemical antireective systems on plastic substrates are described on the World Wide Web, among them multilayer AR coatings on PMMA produced by Nagase & Co. Ltd. and by YTC America Inc. [35,36]. 5. Moth-eye structures to achieve antireection properties Antireection is the most important optical function that is obtained by coating. However, for plastic substrates the application of surface structures instead of antireection coatings is an interesting alternative. Sub-wavelength surface structures with antireective properties are called moth-eye structures because they were rst observed in nature on the eyes of night-ying moths [37]. These antireective structures create a gradient of the eective refractive index from the substrate side to the air side. The conditions for antireective behaviour in the visible spectral range can be fullled if small-sized features (<300 nm) with a depth of several hundred nanometers are produced. The rst technical solutions were generated using an interference pattern at the intersection of two coherent beams of light from a laser. Today, master structures with surface areas up to about 0.5 m2 can be generated by a holographic optical process, and eorts are in progress to increase this area [38]. The outstanding etching behaviour of PMMA can be used to generate a stochastic antireective structure directly on the polymer surface [39,40]. A self-organized structure grows within a few minutes if the surface is bombarded in vacuum with ions from an Ar/O2 plasma (Fig. 5). A special advantage of this type of antireective structure is the low sensitivity of the antireective performance to variation of the angle of incidence of the light (Fig. 6). Thus, this procedure can be applied with favourable results to curved surfaces. Stochastic structures suitable for antireective behaviour can also be generated directly on a hot-embossing tool by anodic oxidation of aluminium directly on the tool [41], or by depositing a very rough PVD coating [42]. The basic disadvantage of all of these antireective structures is their mechanical weakness. The surfaces have to be handled very carefully, and it is practically impossible to clean them. Antireective surface structures on polymers may, however, potentially be inexpensive because they can be replicated by

U. Schulz, N. Kaiser / Progress in Surface Science 81 (2006) 387401

395

Fig. 5. Scanning electron microscopy image of ion-etched stochastic antireective structures on PMMA [40].

Fig. 6. Transmission of light at normal incidence and at 45 of a PMMA sample with ion-etched antireective structure compared with the untreated polymer.

embossing. Cost issues will promote their industrial application on protected or built-in optical components. 6. Problems with vacuum coating 6.1. Interactions between plasmas and polymers Modern vacuum-coating processes are generally associated with a plasma and shortwavelength radiation, which is produced by plasma ion sources, glow-discharge supplementary equipment and electron beam evaporators. High-energy ions, radicals and short-wavelength radiation have enough energy to break chemical bonds in polymers and thereby initiate chemical modication. For most plastic materials, their interaction

396

U. Schulz, N. Kaiser / Progress in Surface Science 81 (2006) 387401

with plasma emissions is an essential factor for good adhesion properties. Plasma treatments typically produce polar groups on polymer surfaces. Wettability is therefore always improved to various degrees [43]. The improvement of adhesion by plasma treatment has been attributed variously to this improved wettability, to surface cross-linking and to interfacial diusion. If poor coating adhesion is observed after a plasma treatment because of a cohesive fracture in the bulk, the main problem may be the weak boundary layer formed in the polymer during the treatment. Correct identication of the locus of failure is of great importance therefore. If the fracture occurs cohesively in a thin bulk layer near the interface, eort should be directed towards strengthening this weak boundary layer rather than increasing the interfacial attraction. Taking into account the very short treatment times that are sucient for the activation of most polymer surfaces and the danger of formation of weakly bonded layers, all treatments should be as short as possible. 6.2. Diversity of materials In contrast to optical glass, a variety of surface compositions are characteristic of the polymers used in optics. As already mentioned, the dierent behaviours of the manifold polymer materials in contact with a plasma have to be considered. Some further material-specic properties with more or less inuence on vacuum processes are the thermal characteristics of the material (e.g., heat distortion temperature and thermal expansion coecient) and the degassing behaviour (reversible water absorption). Electron-beamevaporated oxide layers deposited with plasma ion assistance show the best adhesion on certain types of polycycloolens, polyamides and polyether sulfones [44]. Boat-evaporated oxide layers, deposited without the inuence of radiation or plasma emissions, exhibit excellent layer adhesion on most plastic substrates (see Table 1). It has to be emphasized that the question of whether or not damage occurs in the plasma is essential in determining coating quality and lifetime, whereas water absorption, for example, is of minor importance. Excellent adhesion properties have been observed for several types of polyamides and for polyether sulfone, although all of these polymers contain high amounts of water. The most critical optical polymer for coating is PMMA because of its tendency to form weakly bonded layers of degradation products after contact with a plasma [45]. In a process suggested recently, a VUV protective layer is deposited without the presence of any plasma. On this base layer, further optical layers can be deposited by applying plasma assistance [46]. In addition, polycarbonate (Makrolon and Lexan) shows complicated interactions with plasmas. Some plasma conditions are described as being helpful in improving the adhesion properties [4749], but unfavourable results are possible as well. For outdoor applications, coatings have to provide UV-protective properties to prevent later ablation of the coating. This is a special challenge for vacuum coating, because the absorption characteristics of typical evaporation materials are not sucient to lter out the critical wavelengths between 350 nm and 400 nm. 6.3. Stress in coatings on plastics Stress can adversely aect the interface between a coating and a polymer and initiate cracking or ablation of a thin lm. The mechanical stress in a coating depends mainly on the deposition parameters, especially the ion bombardment energy and the deposition rate [50]. In the case of plasma-IAD, most coatings show a compressive stress that

U. Schulz, N. Kaiser / Progress in Surface Science 81 (2006) 387401

397

increases with ion bombardment energy. Although coatings have a compressive stress, tensile-stress cracking may occur during ion-assisted deposition of oxide layers. On polymers, an additional component of thermal stress has to be taken into account because of the difference in thermal expansion between organic substrates and inorganic thin lms [51]. The evaporation of high-index oxides causes a much stronger temperature increase in a plastic substrate than does the evaporation of the low-index component silica. The temperature of the substrate is inuenced by emissions from the ion source, too. Therefore, the deposition rate and ion energy in ion-assisted processes have to be carefully optimized, and the coating design should contain high-index layers that are as thin as possible. The investigation of the development of thermal stresses during lm deposition on a polymer substrate requires an in situ measurement of the substrate temperature. Calculation of stress gradients can be helpful in understanding the various cracking mechanisms of coatings on polymers during environmental tests and in discovering the weakest points in coating designs. It is obvious that suitable coating designs and temperature management during lm deposition are essential factors for obtaining coatings with a tailored environmental stability. 6.4. Diculties with testing procedures The diversity of polymer materials, combined with the broad range of applications, makes it dicult to dene generally applicable standards for coated plastics. Lifetime testing, including adhesion tests, plays a more important role than in the case of coated glass, because of the higher risk of interface damage and crack formation. Test procedures should preferably be dened so as to emulate the stresses occurring during the actual application. Besides the common climatic test conditions (e.g., high humidity and temperature cycling according to ISO 9022 or MIL-C-675), outdoor applications require testing for resistance to solar radiation. It is dicult to nd test conditions that simulate real conditions and accelerate the polymer damage processes at the same time. For plastic eyeglasses, the Weathering-QUV test (ASTM D4329, D4587, ISO 4892) is very commonly used. But this test tends to apply a dose of UV radiation which is much stronger than occurs naturally. Even for the denition of test procedures, polymer-specic reactions have to be taken into account. The adhesion of coatings to plastics is normally tested with a tape-peel test, which can be carried out as a pass/fail test (EN ISO 9211, ASTM D1876), or as a six-step classication test if applied on a cross-section (EN ISO 2409, ASTM D3002). For coated polymers, it is suggested that one should inspect the tested sample area with a microscope to identify the location of failure in the interface, which may be either in a near-surface region or in the bulk polymer. A more quantitative adhesion test is lacking at present. The pull test (MIL 883, ASTM D4541, EN ISO 4624) cannot be used, because there is no glue available to x the stud onto the sample without any chemical interaction with the polymer. In addition, abrasion resistance is of considerable importance for many plastic optical components, and yet extremely dicult to dene in any terms. Abrasion resistance is a combination of factors such as hardness, packing density, elasticity, adhesion and others. On polymer surfaces, a thin inorganic lm may act like an eggshell. In particular, the results of scratch tests that use a spiky scratch pin are dependent more on the hardness of the polymer substrate than on the hardness of the coating. Various standard tests

398

U. Schulz, N. Kaiser / Progress in Surface Science 81 (2006) 387401

involve a pad that is drawn under a controlled load for a given number of strokes. The scratching media used include soft cloths, rubber and steel wool. But most tests suer from the fact that they do not deliver a measurable value of abrasion resistance. The best way to evaluate the mechanical properties is to try to simulate the application situation as well as possible. The result will be dependent not only on the physical properties of the coating but also on the kind of polymer substrate. 7. Challenges to surface scientists The main problem for plastic optics is to ensure a permanently good adhesion of the coating so that it works under given application conditions for a dened lifetime. In contrast to glass optics, the surface and interface chemistry of the specic kind of polymer plays the most important role in achieving this. For every polymer, its specic interaction with the plasma inside the vacuum chamber inuences the surface chemistry and can inhibit or improve the adhesion properties. There are reactive radicals, high-energy electrons and photons present, as well as ions and atoms from the evaporated oxides, which react in various ways with the surface. For a practical coating process, it is impossible or very difcult to separate the eects that occur under the low-pressure plasma conditions used. Moreover, the engineers who develop the vacuum technology are not in a position to carry out such detailed chemical studies. Therefore, it is the task of surface scientists to study these interactions under dened conditions in detail, and to develop corresponding models. This has to be done for each plastic material needed for optical applications. As a favourable example, the basic work on bisphenol-A polycarbonate by Rivaton et al. should be mentioned here [52,53]. The photochemical and thermal behaviour of PC in air and in vacuum was studied by applying dened irradiation conditions. Photoproducts of PC could be identied by using chemical derivatization reactions, optical spectroscopy (UV-VIS and FTIR), HPLC and Size Exclusion Chromatography (SEC). Very helpful details from this work could be used to identify the mechanism of adhesion loss on coated polycarbonate caused by specic low-pressure plasma conditions or by ex situ UV irradiation. In addition, some interactions between plasma and PMMA are now well understood as a result of surface spectroscopic studies using X-ray Photoelectron Spectroscopy (XPS), Ion Scattering Spectroscopy (ISS), Secondary Ion Mass Spectroscopy (SIMS) and FTIR spectroscopy [45,5456]. However, the practical situation in relation to producing coatings with high adhesion that will be maintained over a long time is still unsatisfactory. In addition, the chemical mechanism behind the formation of deep surface structures on PMMA under specic ion bombardment conditions has not yet been completely discovered, although such processes are already being applied in industry. For other polymers, including many polycycloolens and polyamides, basic studies of interface eects which determine the adhesion properties and their long-term changes would probably increase the reliability of those polymers. The surface modications which occur under low pressure conditions have to be simulated in irradiation experiments and studied with analytical methods as mentioned above for PC and PMMA. 8. Summary The introduction of easy-to-form polymer materials is now becoming important for achieving cost savings in the production of complex-shaped, high-end precision optical

U. Schulz, N. Kaiser / Progress in Surface Science 81 (2006) 387401

399

components and of consumer electronics and automobile parts. This replacement of glass by plastics is a challenge also for modern vacuum and plasma techniques. At present there is a demand for techniques to manufacture multifunctional optical interference coatings on rigid plastic components in mass production. A combination of antireective properties with high abrasion resistance is most important. Coated parts such as eyeglasses and display covers have to pass extended environmental and mechanical tests. For optical applications, a growing number of miscellaneous polymers have to be combined with naturally incompatible, brittle, inorganic thin-lm materials. Vacuum-coating processes are the most appropriate techniques at present for producing high-end optical interference coatings that need a thickness precision in the range of one or two nanometers. The fundamental features of present-day coating technologies are the application of ion assistance in evaporation processes, and the possibility to use low-temperature plasmas in chemical vapour deposition processes. The low-pressure plasma present in modern vacuum processes provides the possibility to activate substrate surfaces, to densify growing layers and to adjust mechanical and thermal lm stresses. However, eects such as the formation of weak boundary layers and yellowing have to be taken into consideration. Basic research is required to understand the manifold interactions between the surface and the plasma. Substrate-specic vacuum processes are under development for various types of plastic materials. Polymer materials that do not decompose on surfaces during vacuum-coating processes, such as cycloolen polymers, will probably replace PMMA, in particular, for precision optical applications where coating is required. In the case of PMMA, plasma degradation processes oer an interesting alternative means to achieve antireective properties. Antireective surface structures can be prepared by direct ion etching of PMMA and by other techniques. To avoid problems with handling and cleaning, plants with coating capabilities should be located next to the manufacturers of the polymer parts (e.g., injection-moulding companies). Furthermore, eorts have to be made to correct the lack of experience concerning the lifetime properties and environmental stability of coated plastics. Acknowledgements This research was supported by the German Federal Ministry of Education and Research (BMBF), under Grant No. FKZ 03N3118. References
[1] K. Minami, Optical plastics, in: S. Ba umer (Ed.), Handbook of Plastic Optics, Wiley-VCH, Frankfurt, 2005, pp. 109147. [2] H. Chatham, Review: Oxygen diusion barrier properties of transparent oxide coatings on polymeric substrates, Surf. Coat. Technol. 78 (1996) 19. [3] M.F. Samson, Ophthalmic lens coatings, Surf. Coat. Technol. 81 (1996) 7986. [4] A. Holla nder, R. Wilken, J. Behnisch, Subsurface chemistry in the plasma treatment of polymers, Surf. Coat. Technol. 116119 (1999) 788791. [5] E.M. Liston, L. Martinu, M.R. Wertheimer, Plasma surface modication of polymers for improved adhesion: A critical review, J. Adhesion Sci. Technol. 7 (1993) 10911127. [6] A. Licciardello, M.E. Fragalla, G. Foti, G. Compagnini, O. Puglisi, Ion beam eects on the surface and on the bulk of thin lms of polymethylmethacrylate, Nucl. Instrum. Meth. Phys. Res. B 116 (1996) 168 172.

400

U. Schulz, N. Kaiser / Progress in Surface Science 81 (2006) 387401

[7] U. Schulz, Review of modern techniques to generate antireective properties on thermoplastic polymers, Appl. Opt. 45 (2006) 16081618. [8] A. Macleod, Thin-Film Optical Filters, Institute of Physics Publishing, Bristol, 2001. [9] R. Willey, Practical Design and Production of Thin Films, Marcel Dekker, Basel, 2002. [10] U. Schulz, U. Schallenberg, N. Kaiser, Reection-reducing coating, WIPO PCT publication WO0204374, 17 January 2002. [11] U. Schulz, U.B. Schallenberg, N. Kaiser, Symmetrical periods in antireective coatings for plastic optics, Appl. Opt. 42 (2003) 13461351. [12] D. Bohling, M. Coda, R. Blacker, R. Gove, Development of intrinsically conductive antireection coatings for the ophthalmic industry, in: Proc. 43rd Ann. Tech. Conf. Society of Vacuum Coaters, 2000, pp. 222229. [13] Y. Takahashi, K. Shinde, Optical antireection element, European Patent EP1387187A1, 04 February 2004. [14] Dombrowski, M. Friz, Manufacturing of water-repellent coating on optical substrate, European Patent EP0770699B2, 03 April 2002. [15] A. Zo ller, R. Go tzelmann, K. Matl, W. Klug, H. Hagedorn, Plasma ion assisted deposition: A powerful technology for the production of optical coatings, Proc. SPIE 3133 (1992) 196204. [16] S. Mohan, M.G. Krishna, A review of ion beam assisted deposition of optical thin lms, Vacuum 46 (1995) 645659. [17] P. Munzert, U. Schulz, N. Kaiser, Transparent thermoplastic polymers in plasma assisted coating processes, Surf. Coat. Technol. 173174 (2003) 10481052. [18] M. Kuhr, S. Bauer, U. Rothhaar, D. Wol, Coatings on plastics with the PICVD technology, Thin Solid Films 442 (2003) 107116. [19] D. Poitras, L. Martinu, Interphase in plasma-deposited lms on plastics: Eect on the spectral properties of optical lters, Appl. Opt. 39 (2000) 11681173. k, L. Zaj c , V. Burs , M. Valtr, J. Houdkova , V. Per , Plasma deposition a kova ina, A. Mackova [20] P. Dvor kova of diamond-like protective coating with silicon oxide content, in: Proc. 46th Ann. Tech. Conf. Society of Vacuum Coaters, 2003, pp. 16. ` che, Y. Se gui, M.R. Wertheimer, Studies of the earliest stages of plasma[21] G. Dennler, A. Houdayer, M. Latre enhanced chemical vapor deposition of SiO2 on polymeric substrates, Thin Solid Films 382 (2001) 13. villon, Study of the mechanical behavior of [22] A. Hofrichter, A. Constantinescu, S. Benayoun, P. Bulkin, B. Dre plasma-deposited silica lms on polycarbonate and steel, J. Vac. Sci. Technol. 18 (2000) 20122016. [23] T. Schmauder, K.D. Nauenburg, K. Kruse, G. Ickes, Hard coating by plasma CVD on polycarbonate for automotive and optical applications, in: M.A. Aegerter (Ed.), Proc. 5th Int. Conf. Coatings on Glass, Buchdruckerei GmbH, Blieskastel, 2004, pp. 841848. [24] Available from: <http://www.exatec.de/en/advancedtechnologies.aspx>. [25] R. Beckmann, K.D. Nauenburg, T. Naumann, U. Patz, G. Ickes, H. Hagedorn, J. Snyder, A new high-rate deposition process for scratch- and wipe-resistant coatings for optical and decorative plastic parts, in: Proc. 44th Ann. Tech. Conf. Society of Vacuum Coaters, 2001, pp. 288294. [26] Available from: <http://www.singulus.com>. [27] D.R. Gibson, J.M. Walls, I. Brinkley, E.M. Waddell, Flexible and high throughput deposition of multilayer optical coatings using closed eld magnetron sputtering, in: Proc. 47th Ann. Tech. Conf. Society of Vacuum Coaters, 2004, pp. 377382. [28] J.C. Weber, U. Schulz, H. Bartzsch, P. Frach, N. Kaiser, Deposition of broadband antireection coatings on plastic substrates by evaporation and reactive pulse magnetron sputtering, in: Proc. SPIE, vol. 5963, in press. Available from: <http://bookstore.spie.org/index.cfm?fuseaction=DetailVolume&productid=602550>. [29] Available from: <http://www.ardenne-at.com>. [30] S. Schiller, V. Kirchho, N. Schiller, H. Morgner, PVD coating of plastic webs and sheets with high rates on large areas, Surf. Coat. Technol. 125 (2000) 354360. [31] H. Gru nwald, W. Dicken, K.D. Nauenburg, R. Adam, J. Bartella, T. Gebele, S. Mitzla, U. Patz, J. Snyder, in: K.L. Mittal (Ed.), Metallized Plastics 7: Fundamental and Applied Aspects, VSP BV, Utrecht, 2001. [32] G. Schottner, K. Rose, U. Posset, Scratch and abrasion resistant coatings on plastic lenses state of the art, current developments and perspectives, J. SolGel Sci. Technol. 27 (2003) 7179. [33] S.-S. Park, H. Zheng, Composition and method for a coating providing anti-reective and anti-static properties, US Patent No. 6372354B1, 16 April 2002. [34] D. Chen, Anti-reection (AR) coatings made by solgel processes: A review, Solar Energy Mater. Solar Cells 68 (2001) 313336. [35] Available from: <http://www.nagase.co.jp/english/index.html>.

U. Schulz, N. Kaiser / Progress in Surface Science 81 (2006) 387401

401

[36] Available from: <http://www.ytca.com>. [37] S.J. Wilson, M.C. Hutley, The optical properties of moth eye antireection surfaces, Opt. Acta 29 (1982) 9931009. [38] A. Gombert, W. Glaubitt, K. Rose, J. Dreibholz, B. Bla si, A. Heinzel, D. Sporn, W. Do ll, V. Wittwer, Subwavelength-structured antireective surfaces on glass, Thin Solid Films 351 (1999) 7378. [39] P. Munzert, H. Uhlig, M. Scheler, U. Schulz, N. Kaiser, Method for reducing boundary surface reection of plastic substrates and substrate modied in such manner and use thereof, WIPO PCT publication WO04024805C1, 13 May 2004. [40] A. Kaless, U. Schulz, P. Munzert, N. Kaiser, NANO-motheye antireection pattern by plasma treatment of polymers, Surf. Coat. Technol. 200 (14) (2005) 5861. [41] T. Sawitowski, N. Beyer, F. Schulz, Bio-inspired anti-reective surfaces by imprinting processes, in: H.-J. Fecht, M. Werner (Eds.), The NanoMicro Interface, Wiley-VCH, Weinheim, 2004, pp. 263280. [42] F. Burmeister, W. Doell, W., G. Kleer, Method for producing a tool which can be used to create structures in the sub-micrometer range, European Patent EP1307604B1, 06 May 2004. [43] F. Garbassi, M. Morra, E. Occhiello, Polymer Surfaces, Wiley-VCH, Weinheim, 1998. [44] U. Schulz, Coating on plastics, in: S. Ba umer (Ed.), Handbook of Plastic Optics, Wiley-VCH, Frankfurt, 2005, pp. 149180. [45] O. Chiantore, L. Trossarelli, M. Lazzari, Photooxidative degradation of acrylic and methacrylic polymers, Polymer 41 (2000) 16571668. [46] P. Munzert, M. Scheler, U. Schulz, N. Kaiser, Optical coating system for radiation-sensitive plastic substrates comprises a protective oxide layer with high absorbance at short wavelengths and opticallyfunctional outer layers, German Patent DE10201492A1, 31 July 2003. villon, J. Klemberg-Sapieha, L. Martinu, F. Poncin-Epaillard, A. Schalchi, [47] S. Vallon, A. Hofrichter, B. Dre J. Benattar, Adhesion mechanism of silica layers on plasma-treated polymers. I. Polycarbonate, J. Adhes. Sci. Technol. 10 (12) (1996) 12871311. [48] F. Sarto, M. Alvisi, E. Melissano, A. Rizzo, S. Scaglione, L. Vasanelli, Adhesion enhancement of optical coatings on plastic substrate via ion treatment, Thin Solid Films 346 (1999) 196201. [49] A. Bergeron, D. Poitras, L. Martinu, Interphase in plasma-deposited silicon nitride optical lms on polycarbonate: in situ ellipsometric characterization, Opt. Eng. 39 (2000) 825831. [50] M.F. Doerner, W.D. Nix, Stresses and deformation processes in thin lms on substrates, CRC Crit. Rev. Solid State Mater. Sci. 14 (3) (1988) 225268. [51] U. Schulz, N. Kaiser, Thermal stress in antireective coatings on polymer substrates, in: Proc. 46th Ann. Tech. Conf. Society of Vacuum Coaters, 2003, pp. 419424. [52] A. Rivaton, Recent advances in bisphenol-A polycarbonate photodegradation, Polym. Degrad. Stab. 49 (1995) 163179. [53] A. Rivaton, B. Mailhot, J. Soulestin, H. Varghese, J.L. Gardette, Comparison of the photochemical and thermal degradation of bisphenol-A polycarbonate and trimethylcyclohexane-polycarbonate, Polym. Degrad. Stab. 75 (2002) 1733. [54] T.J. Hook, J.A. Gardella, L. Salvati, H2O/Ar plasma-modied polymethylmethacrylates, J. Mater. Res. 2 (1) (1987) 117131. , G. Foti, G. Compagnini, O. Puglisi, Ion beam eects on the surface and on [55] A. Licciardello, M.E. Fragala the bulk of thin lms of polymethylmethacrylate, Nucl. Instrum. Meth. Phys. Res. B 116 (1996) 168172. [56] U. Schulz, P. Munzert, N. Kaiser, Surface modication of PMMA by DC glow discharge and microwave plasma treatment for the improvement of coating adhesion, Surf. Coat. Technol. 142144 (2001) 507511.