Characterization of Optical Materials
Characterization of Optical Materials
Characterization of Optical Materials
INTRODUCTION 1
vi Contents
Contents vii
viii Contents
ix
This Materials Characterization Series attempts to address the needs of the practical
materials user, with an emphasis on the newer areas of surface, interface, and thin
film microcharacterization. The Series is composed of the leading volume, Encyclope-
dia of Materials Characterization, and a set of about 10 subsequent volumes concen-
trating on characterization of individual materials classes.
In the Encyclopedia, 50 brief articles (each 10 to 18 pages in length) are presented
in a standard format designed for ease of reader access, with straightforward tech-
nique descriptions and examples of their practical use. In addition to the articles,
there are one-page summaries for every technique, introductory summaries to group-
ings of related techniques, a complete glossary of acronyms, and a tabular compari-
son of the major features of all 50 techniques.
The 10 volumes in the Series on characterization of particular materials classes
include volumes on silicon processing, metals and alloys, catalytic materials, inte-
grated circuit packaging, etc. Characterization is approached from the materials user’s
point of view. Thus, in general, the format is based on properties, processing steps,
materials classification, etc., rather than on a technique. The emphasis of all volumes
is on surfaces, interfaces, and thin films, but the emphasis varies depending on the
relative importance of these areas for the materials class concerned. Appendixes in
each volume reproduce the relevant one-page summaries from the Encyclopedia and
provide longer summaries for any techniques referred to that are not covered in the
Encyclopedia.
The concept for the Series came from discussion with Marjan Bace of Manning
Publications Company. A gap exists between the way materials characterization is
often presented and the needs of a large segment of the audience—the materials user,
process engineer, manager, or student. In our experience, when, at the end of talks or
courses on analytical techniques, a question is asked on how a particular material (or
processing) characterization problem can be addressed the answer often is that the
speaker is “an expert on the technique, not the materials aspects, and does not have
experience with that particular situation.” This Series is an attempt to bridge this gap
by approaching characterization problems from the side of the materials user rather
than from that of the analytical techniques expert.
We would like to thank Marjan Bace for putting forward the original concept,
Shaun Wilson of Charles Evans and Associates and Yale Strausser of Surface Science
Laboratories for help in further defining the Series, and the Editors of all the indi-
vidual volumes for their efforts to produce practical, materials user based volumes.
Though there have been advances in the materials and in the design and manufactur-
ing of integrated optical devices since this volume was originally published, the basic
principles of the techniques and protocols for analysis and characterization of optical
materials discussed here remain valid. There have, of course, been technical advances
for many of these techniques (ease of use, software, spatial resolution, and extension
of wavelengths into the UV for optical methods). Applications in the new, carbon-
based materials, such as nanotubes and graphene, have developed. After this re-issue
in a form close to the original, it is our intent that updates, covering the advances that
have occurred, will be released as downloads as they become available.
xi
The design and manufacture of advanced optical materials have been driven by a
multidisciplinary approach from which new components and integrated optical
devices have evolved. The diversity of optical materials—including metals, poly-
mers, glasses, ceramics, semiconductors, and composites—provides a challenge to
the analyst charged with characterizing optical surfaces and interfaces and developing
associated structure–property relationships. Analysis of most optical materials must
include not only measurements of optical properties, but a determination of the fun-
damental surface and interfacial material properties as well. For example, correlating
the optical response of a material with its microstructure, residual interfacial stress,
phase purity, and surface-roughness can lead to a refinement of processing methods
in order to secure the optimum material for a particular application.
This volume—one component of the Materials Characterization Series: Surfaces,
Interfaces, Thin Films—focuses on the kind of information derived from the princi-
pal analytical methods currently used to characterize optical materials. This infor-
mation is useful for identifying the key parameters that control the optical response
of a material. The theory and methodology of the analytical methods used for
the surface and interfacial characterization of optical materials are discussed in
the lead volume of the series, Encyclopedia of Materials Characterization, and are
summarized in the appendix of this book. The intent of this volume is not to
discuss instrumental methods in great detail, but to provide the necessary back-
ground information to permit a constructive dialogue to be initiated between the
researcher with a specific problem to address and the technical specialist skilled in
applying a particular method.
This book consists of two major sections, an introductory chapter, and an exten-
sive appendix, which summarizes the analytical methods pertinent to the character-
ization of optical materials. The book covers both crystalline and amorphous mate-
rials—with applications from the far infrared (∼1 mm wavelength) to the vacuum
ultraviolet (∼100 nm wavelength) regions of the spectrum—and presents a succinct
discussion of the type of information obtainable using various key surface character-
ization methods. The extensive list of references for each chapter may be consulted
to gain a more thorough understanding of a particular subject area.
The topics covered and organization of this volume grew from a number of
discussions with Marjan Bace of Manning Publications Company, who persuaded
me to consider editing a text on the surface and interfacial characterization of
optical materials. His direction and advice were greatly appreciated. I wish to
express my gratitude to all contributing authors, who took time from their busy
schedules to participate in writing this volume. I hope the readers will find our
xii
Gregory J. Exarhos
Preface xiii
xiv
Introduction
gregory j. exarhos
2 INTRODUCTION
INTRODUCTION 3
4 INTRODUCTION
References
INTRODUCTION 5
Contents
1.1 Introduction
1.2 What Surface Roughness Is
1.3 How Surface Roughness Affects Optical Measurements
1.4 How Surface Roughness and Scattering Are Measured
1.5 Characterization of Selected Surfaces
1.6 Future Directions
1.1 Introduction
Surface roughness can take many forms. Often it consists of tiny scratches in ran-
dom directions remaining after polishing, but it can also be the grooved structure
produced by diamond-turning a metal mirror, the grain relief on a polished metal
mirror such as molybdenum, the distinct random machining marks left on a finished
metal part to give it a diffuse patina, the tiny parallel grooves on a glass surface that
has been precision-ground, or even a few large scratches or pits (digs) sometimes
caused by improper handling. Some materials such as ceramics or silicon carbide
contain voids, while others—including aluminum or beryllium—have hard inclu-
sions in their bulk; all these things can appear on the surface. Optical or magnetic
films applied to surfaces can add additional roughness. With modern deposition
techniques, optical dielectric films such as silicon dioxide, titanium dioxide, zinc
sulfide, and magnesium fluoride are generally extremely smooth and contour the
surfaces onto which they are deposited. However, silver, gold, and copper films, in
particular, tend to be slightly lumpy, adding a fraction of a nanometer roughness to
the surface. Other metal films such as aluminum, platinum, nickel, and rhodium are
smoother since they are finer-grained. Magnetic films applied to aluminum or plas-
tic surfaces and used to store information in dense arrays are generally quite rough
compared with optical films. Optically black materials that absorb or scatter light are
even rougher. These coatings have steep slopes and contain tiny holes acting as light
traps because of multiple scattering.
The processing of a material can greatly affect its surface roughness. Here we
give two examples, first a metal reflector and then a polished glass surface. For the
metal reflector, consider a piece of polycrystalline copper such as oxygen-free, high-
purity copper. This material can be cut to shape, rough finished, and then given a
matte finish with a fine grade of sandpaper or emery paper. In this case, the surface
looks slightly dull and contains a large number of scratches oriented in all direc-
tions. Alternately, the final finish can be made with a precision grinding wheel that
produces tiny parallel grooves. The surface looks burnished, but there are colored
bands produced by diffraction from the grooves when the piece is viewed at certain
angles. If the copper surface is optically polished on a pitch lap with a fine grade of
abrasive in a liquid slurry, a smooth, shiny surface can be produced that contains
tiny randomly oriented scratches and, sometimes, imbedded polishing compound.
After polishing, the surface can be chemically etched to remove the subsurface
damage generated by the polishing operation. Orange peel (waviness) is introduced
by preferential etching of the grains and uneven etching of the entire surface. A
grid of straight lines reflected from the surface appears wavy. Single-point diamond
turning can produce a shiny surface with a minimum of subsurface damage. On the
surface are closely spaced grooves made by the cutting diamond as well as coarser
and deeper grooves caused by vibrations between the machine, tool, and surface;
also, large grains in the material form a mottled surface structure (see Figure 1.1).
If aluminum, stainless steel, or beryllium had been considered, alloying material
in the form of tiny hard particles dispersed throughout the material produce tiny
bumps or pullouts (holes) in a polished surface. These increase the scattering level
and, of course, the measured surface roughness.
In the second example, a piece of optical glass, which could be a window, beam
splitter, filter, or witness sample, is first cut to shape by sawing or grinding. In some
cases, glass can be molded to a size slightly larger than that of the finished shape
and then fine-ground. The ground surface has a matte finish. Progressively finer
grades of abrasive in water are used when the part is ground against an iron lap
to bring the shape closer to the finished shape; the matte finish appears smoother.
After the final grinding operation, polishing begins with a pitch lap and a fine
abrasive mixed with water to make a slurry. Tiny surface asperities are polished flat
but pits remain, giving the surface a gray appearance. As more material is removed,
the pits gradually disappear, the grayness diminishes, and tiny scratches appear, ori-
ented in all directions according to the random motion of the polishing machine.
Figure 1.2 Dimensions of various types of surface features. The height scale
is ~1000 times smaller than the lateral scale.
All surface roughness scatters light. The character of the roughness—heights and
spatial wavelengths—determines the intensity of the scattering and its angular dis-
tribution. As an example, an aluminum-coated glass mirror normally scatters ∼0.1%
of the light that it reflects. In other words, the ratio between the total scattered light
and the total reflected light (specular reflectance plus scattering) is 0.1%. This surface
would have a roughness of ∼1.6 nm rms.
If we use this roughness as a ballpark figure, the total reflectance at normal
incidence of an opaque mirror is reduced by about 0.1%. If light is reflected at
nonnormal incidence, the specular reflectance is higher and the scattering losses
lower. The transmission of a transparent piece of glass is also reduced by scattering
from both surfaces.
If intensities are being measured, surface roughness scatters light out of the beam.
However, if polarization properties are being measured, the effect of the surface rough-
ness on a beam of plane polarized, circularly polarized, or elliptically polarized light
at nonnormal incidence as in an ellipsometer or polarimeter6 is negligible if the
amount of surface roughness is small (i.e., the surface appears shiny).7, 8 If the sur-
face is so rough that multiple scattering occurs, the ellipsometric and polarimetric
parameters are affected.9
Transmission measurements that depend on measuring an angle of deviation,
as, for example, when determining the refractive index of a glass by measuring the
angle of minimum deviation, are unaffected by surface roughness as long as it is
small enough not to distort the slit image being observed. Striae, bubbles, and other
types of inhomogeneities in the bulk of the glass are more serious problems in this
type of measurement.
In waveguides where light is traveling within an optical fiber, surface roughness
greatly affects the amount of light unintentionally coupled out of the fiber. In fact,
this principle is used in the total internal reflection microscopy (TIRM)10 technique
to observe surface imperfections (see Section 1.5).
A wide variety of methods are available for measuring surface roughness and the
light scattering the roughness produces.2 These methods can be grouped into those
that give pictures of surfaces (and sometimes quantitative information) and those
that yield quantitative statistical information about the surfaces. Figure 1.4 shows
a diagram of measurement techniques that are suitable for various types of rough
surfaces. This figure is similar to Figure 1.3 except that the measurement techniques
have been added to the types of surface roughness. The various techniques are dis-
cussed in this section.
Among the methods that give pictures of surfaces are microscopes ranging from
optical microscopes, scanning electron microscopes, and transmission electron
microscopes to scanning probe microscopes. These latter instruments can be used
to produce topographic maps of surfaces on an atomic scale, both laterally and ver-
tically.11, 12 If the surface is conducting, a scanning tunneling microscope (STM)
can be used to produce a topographic map of the electron density. Most optical
surfaces are nonconducting, and maps and profiles of the surface topography can
be obtained by using an atomic force microscope (AFM). Some of the scanning-
probe microscopes are now commercially available (from Digital Instruments, Inc.,
Park Scientific Instruments, and WYKO Corporation). The transmission elec-
tron microscope (TEM) and a newer scanning transmission electron microscope
(STEM) are excellent for giving pictures of thin film surfaces or their cross sec-
tions. However, a surface replica must be made and shadowed at a suitable oblique
angle in order to show the roughness structure on a film surface. Cross sectioning a
film is even more difficult. The scanning electron microscope (SEM) requires steep
surface slopes to produce an image with good contrast, and much effort and exper-
tise are required to show the shallow but distinct structure on a diamond-turned
metal surface.
A differential interference contrast or Nomarski (light) microscope2, 13–15 is far
superior to an SEM for observing roughness structure on smooth surfaces using
Quantity Reference
Instrument Type Principle Measured Surface
Bauer 100 Optical Reflection of two Curvature No
noncontact light beams
rms roughness, power spectral density function, and other statistical properties
of surfaces. The relation between scattering and the various statistical quantities
depends on an assumption about the form of the surface roughness. If it consists
of tiny polishing marks that are uniformly distributed over an isotropic surface, the
roughness heights are small compared to the wavelength, and the lateral dimensions
of the surface roughness are much larger than the wavelength, then scalar and vector
scattering theories provide relations between the scattering and surface statistics.
The TIS from an opaque surface can be calculated from a simple relation obtained
from scalar scattering theory. For light incident normally on the surface, the expres-
sion is17, 18
TIS ≈ (4πδ/λ)2 (1.1)
where δ is the rms roughness and λ is the wavelength. This equation has been shown
to predict correctly the scattering from an aluminized polished glass sample having
a roughness of about 3 nm rms in the wavelength range from ∼0.4 to 1.0 µm.17 At
present, there are no commercially available instruments for measuring TIS.
The expression for angle-resolved scattering derived from vector scattering theory
is more complicated19–21 and includes wavelength scaling (proportional to λ–4),
cosine of the angle of incidence, cosine squared of the scattering angle, functions
Tables 1.2 shows examples of six surfaces or groups of surfaces along with suggested
ways of characterizing them. All of the materials in the first group (aluminum-
coated glass mirror, diamond-turned copper mirror, and polished molybdenum
mirror) are opaque and highly reflecting; they can all be characterized by using
the same techniques, which have been discussed above. The surfaces can first be
inspected in a Nomarski microscope to see whether they contain isolated defects
that would affect the measurements or whether they require cleaning. If the dia-
mond-turned copper mirror was turned on-center, it would have a small defect at
that point that would affect profile or scattering measurements. The surfaces can be
In the future, the STM, AFM, and other atomic probes will be used more to enable
us to better understand surface roughness on an atomic scale and relate it to light
scattering. There will be more long-scan profilers that have better lateral resolution
and can measure surface heights in the waviness regime. Measurements made by
these instruments will be used to improve the methods for making optical surfaces.
Subsurface damage and anisotropic grain structure will be studied both from theo-
retical and from experimental points of view in order for us to better understand
their effects on optical scattering and to minimize the scattering as much as possible.
Finally, more theoretical work should be done for us to better understand the lack of
wavelength scaling of the TIS and ARS into the ultraviolet and vacuum ultraviolet
and into the infrared spectral regions.
References
REFERENCES 25