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 tech-
niques and evaluation procedures. A better understanding of the complex interactions between low-
pressure 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. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
2. Coatings for plastic optics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
3. Trends in vacuum-coating techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
4. Wet-chemical coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
5. Moth-eye structures to achieve antireflection properties. . . . . . . . . . . . . . . . . . . . . . . 394
6. Problems with vacuum coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 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

6.1. Interactions between plasmas and polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . 395

6.2. Diversity of materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
6.3. Stress in coatings on plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
6.4. Difficulties with testing procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
7. Challenges to surface scientists . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
8. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 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 sen-
sors. 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 poly-
amides, polyether sulfones, cycloolen polymers and its copolymers have been developed
during the last few years [1]. These thermoplastic polymers can be processed cost-eec-
tively 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 plas-
tics 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 compli-
cated than inorganic glasses. Their various chemical structures can lead to various reac-
tions 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) dur-
ing the deposition process and by environmental factors, including humidity and the ultra-
violet 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 nD Abbe Light Deection Suitability
(examples) (587.6 nm) value VD transmittance temperature (C), for vacuum
(%), 3 mm ASTM D648 coating
Poly Plexiglas 1.491 58 92 95
(methylmethacrylate) 7N, 8N
Alicyclic acrylate Optrez 1310 1.512 54 93 118 Unknown
Polycarbonate Makrolon 1.585 30 91 124 ++
LQ2647
Apec 1897 1.573 90 172 +
Cycloolen polymer Topas 5013 1.533 58 92 123 +++
Zeonex 1.53 56 92 122 +++
E48R
Zeonex 1.525 56 92 123 +++
480R
Zeonex 1.509 92 103
330R
Zeonor 1.53 92 101 +++
1020R
Arton 1.523 52 92 110 Unknown
FX4727
Apel 1.543 56 90 125 Unknown
5014DP
Polysulfone Udel P-1700 1.634 23 84 174 Unknown
Polyether sulfone Ultrason 1.65 80 208 +++
E2010
Polyamide Trogamid 1.516 45 89 122a +++
CX7323
a
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 sim-
plest 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 quar-
ter-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 (tita-
nium 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 mechan-
ical 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 inter-
faces 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 resis-
tance, 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 top-
coats 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 dip-
coating 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 peruoro-
polyether [13].
Besides transparent coatings, metal layers are required on plastic optics to form front-
surface 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 thermo-
plastics 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 distor-
tion 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 10 6 mbar, the oxide raw materials used to form interference layer stacks are
evaporated thermally by electron-beam guns in a pressure range of about 10 4 mbar. Oxy-
gen 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 refrac-
tive index at the surface, the surface hardness, the colour of the bulk polymer (i.e., yellow-
ing) 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) pro-
cesses 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 plas-
tics is the possibility to produce partly organic coatings with a gradient of hardness and elas-
ticity [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 vac-
uum 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 reac-
tive-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 tempera-
tures 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 coat-
ing 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 con-
ditions 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. How-
ever, 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 antire-
ective 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 sto-
chastic 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 anti-
reective 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 short-
wavelength radiation, which is produced by plasma ion sources, glow-discharge supple-
mentary 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 treat-
ments 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 treat-
ment 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 mate-
rial-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-beam-
evaporated 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 impor-
tance. 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 pro-
cess 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, ten-
sile-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 dif-
ference 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 coat-
ing 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. Calcula-
tion 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 manage-
ment 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 test-
ing, 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 temper-
ature 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 con-
ditions and accelerate the polymer damage processes at the same time. For plastic eye-
glasses, 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 classi-
cation test if applied on a cross-section (EN ISO 2409, ASTM D3002). For coated poly-
mers, 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 con-
trast 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 inhi-
bit 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 dif-
cult 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 mod-
els. 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. Photo-
products of PC could be identied by using chemical derivatization reactions, optical spec-
troscopy (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 Spec-
troscopy (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 com-
pletely 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 prob-
ably 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 dis-
play covers have to pass extended environmental and mechanical tests.
For optical applications, a growing number of miscellaneous polymers have to be com-
bined 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 nanome-
ters. 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 vac-
uum 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 for-
mation 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 prop-
erties. 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 coat-
ing 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.

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