2
Fig. 6.2 Schematic path of a plane wave incident onto
a single layer with refractive index n
1
. The reection and
transmission coefcients for the amplitudes at the interfaces
m = 1, 2 are denoted by t
m
and r
m
, respectively. A prime
added to the coefcients indicates a transfer of the wave
opposite to the direction of incidence
P
a
r
t
A
6
.
1
Thin Film Optical Coatings 6.1 Theory of Optical Coatings 375
boundary (coefcient t
1
), partially reected back by the
second boundary (coefcient r
1
) and then reaches via the
rst boundary the incident medium with an amplitude
A
1
= E
0
t
1
r
2
t
1
. On its double path through the layer the
considered partial wave also undergoes a phase shift
1
which is dependent on the thickness d
1
and the refractive
index n
1
of the layer:
1
=
2n
1
d
1
cos
1
. (6.2)
In (6.2), the case of an arbitrary angle of incidence
1
in the layer is taken into account, which has to be cal-
culated by Snellius law. On the basis of the preceding
considerations, the amplitude A
1
of the rst partial wave
emerging from the layer can be written as:
A
1
= t
1
t
1
r
2
E
0
exp(i2
1
) . (6.3)
In this notation t
1
indicates the transmission coefcient
for waves passing the rst boundary in the direction
opposite to the incident wave. If this notation is applied
in the same sense to the part of the wave reected back
into the layer by the rst boundary (coefcient r
1
), the
amplitude A
2
of this partial wave after back-reection
by the second boundary and passing the rst boundary
is given by:
A
2
= t
1
t
1
r
2
E
0
exp(i2
1
)r
1
r
2
exp(i2
1
) . (6.4)
In addition to the expression for the rst-order ampli-
tude, the second-order partial wave includes a factor
r
2
r
1
ex p(i2
1
). Obviously, this additional factor ap-
pears for every further order of reection, and therefore,
the amplitudes A
k
of a partial wave of the order k can
be determined:
A
k
= t
1
t
1
r
2
E
0
exp(i2
1
)[r
1
r
2
exp(i2
1
)]
k1
.
(6.5)
To calculate the reectance of the layer, all partial waves
emerging from the layer into the incident medium have
to be added to determine the total amplitude A
tot
of the
reected contributions. This sum can be expressed in
closed form, because the partial waves follow the rule
of a geometric expansion:
A
tot
=
_
r
1
+
t
1
t
1
r
2
exp(i2)
1r
1
r
2
exp(i2)
_
E
0
. (6.6)
Finally, the reection coefcient r
S
of the single layer
is determined by the ratio between the total amplitude
of the reected wave and the amplitude of the incoming
wave
r
s
=
A
tot
A
0
=
r
1
+r
2
exp(i2)
1+r1r
2
exp(i2)
. (6.7)
In this expression, the coefcients r
1
and t
1
have been
replaced by using the following relations, which can be
derived from the conditions of continuity valid for the
amplitude at the boundaries:
t
1
t
1
= (1r
1
)(1r
1
) = (1r
1
)(1+r
1
) = 1r
2
1
.
(6.8)
In view of the fact that only eld intensities but not
amplitudes can be measured, it is worthwhile to convert
the expression for the amplitude reection coefcient
into the corresponding reectivity value:
R
s
=
r
2
1
+2r
1
r
2
cos(2
1
) +r
2
2
1+2r
1
r
2
cos(2
1
) +r
2
1
r
2
2
. (6.9)
In principle, (6.9) provides all the means for the de-
scription of the spectral transfer function for a single
layer also including the cases of an arbitrary angle of
incidence and an absorbing layer material. For this gen-
eral case, the refractive index has to be expressed in its
complex form with n
1
= n
1
+ik
1
, where k
1
denotes the
extinction coefcient of the layer material, and the Fres-
nel formulae as well as Snellius law have to be applied
in their complex form.
In order to get a deeper insight into the fundamen-
tal operating principle of coatings the discussion of
a few special congurations is of particular interest. In
optical thin lm technology the layer thickness D
i
is of-
ten expressed in units of quarter-wave optical thickness
(QWOT) at the design wavelength
Z
:
D
i
=
4n
i
d
i
Z
. (6.10)
If the layer thickness is an integer multiple of 1 QWOT,
the phase shift of a wave with the design wavelength
traveling perpendicularly through the layer corresponds
to multiples of /2. Evaluating (6.9) for a 2 QWOT
of any dielectric material on the basis of the Fresnel
formulae for normal incidence results in:
R
s
=
_
r
1
+r
2
1+r
1
r
2
_
2
,
with
r
1
=
n
0
n
1
n
0
+n
1
, r
2
=
n
1
n
2
n
1
+n
2
,
R
s
=
_
n
0
n
2
n
0
+n
2
_
2
. (6.11)
Apparently, the expression for the reectance is reduced
to the Fresnel formulae for an interface between the inci-
dent mediumand the carrier medium, demonstrating that
P
a
r
t
A
6
.
1
376 Part A Basic Principles and Materials
the single 2 QWOT layer has no inuence on the spec-
tral transmittance of the structure. For the case of a layer
with a thickness of 1 QWOT at the design wavelength,
(6.9) can be written in the form:
R
s
=
_
n
2
n
0
n
2
1
n
2
n
0
+n
2
1
_
2
. (6.12)
The reectance of the single layer on the substrate can
be totally suppressed if the condition n
2
1
= n
0
n
2
is ful-
lled. For a further illustration of the effects typical
for a single dielectric layer, corresponding reectance
spectra are depicted for different refractive indices in
Fig. 6.3. Considering the reectance values at the de-
sign wavelength
Z
the cases n
2
1
=n
2
(zero reectance),
n
1
< n
2
(reectance lower than the reectance of the
uncoated substrate), n
1
= n
2
(reectance equal to the
reectance of the uncoated substrate), and n
1
>n
2
(re-
ectance higher than the reectance of the uncoated
substrate) can be distinguished. As a function of the
wavelength, a cyclic behavior of the spectra with a period
of one octave can be observed, which shows common
points of tangency at the reectance level of the bare sub-
strate. These points can be attributed to the wavelength
positions, where the layer thickness is according to an
even multiple of QWOT resulting in the special con-
dition described by (6.9). Thus, on one hand, a single
1 QWOT layer of a material matched to the refractive
index of the substrate can be employed as an antire-
ective coating. On the other hand, a layer with a high
index of refraction is suitable for an enhancement of
the reectance to a certain limit given by the availabil-
ity of high-refracting materials. Actually, single-layer
coatings can still be found nowadays on many opti-
cal components for laser applications, where only one
wavelength has to be controlled.
In principle, the outlined theoretical approach for
the single layer can also be transferred to the calcula-
tion of multilayer systems. However, considering the
enormous number of partial waves, which increases ex-
ponentially with the number of layers in a stack, the
resulting equations become extremely complicated and
difcult to handle. For example, the expression for the
reectance of a three-layer system would already ll
one printed page of this book. Therefore, the idea of
a formalism assigning a matrix to each layer of the de-
sign was a substantial step forward to an understanding
of thin lm design. This so-called matrix formalism,
which was born in the 1940s, can be deduced on the
basis of the boundary conditions of the electric and
magnetic eld at the interfaces between the layers in
TiO
2
: n
1
= 2.25
HfO
2
: n
1
= 1.95 Al
2
O
3
:n
1
=1.62
MgF
2
: n
1
=1.38
Y
2
O
3
: n
1
=1.76
R (%)
Wavelength (nm)
400 1400
24
21
18
15
12
9
6
3
0
600 800 1000 1200
LZH
Fig. 6.3 Spectra calculated for a 1 QWOT single layer
(
Z
= 1000 nm) of different materials on a the surface of
a Nd:YAGrod (n
2
=1.78, ambient refractive index n
0
=1).
The refractive indices are typical values for e-beam depo-
sition of the corresponding deposition materials: MgF
2
:
n
1
= 1.38, Al
2
O
3
: n
1
= 1.62, Y
2
O
3
: n
1
= 1.76, HfO
2
:
n
1
= 1.95, TiO
2
: n
1
= 2.25. The line corresponds to the
reectivity of the uncoated substrate material
a system [6.58]. Besides the clear representation of
each layer by a single matrix M
i
, this approach offers
a second major advantage which is related to a con-
secutive multiplication of these single-layer matrices to
calculate the transfer function of a multilayer system.
Thus, considering a stack, which is formed by a num-
ber K of single layers with layer 1 located at the rst
interface in respect to the incoming wave, the transfer
matrix M
S
of the entire stack can just be determined by
the following multiplication:
M
S
= M
1
M
2
M
3
. . . M
i
M
i+1
. . . M
K
. (6.13)
The elements of the single-layer matrix M
i
can be de-
rived fromthe boundary conditions in the layer structure
relating the electric (E
i1
) and magnetic (H
i1
) eld
strength at the front face to the eld strength values (E
i
and H
i
) at the rear face of the layer:
_
E
i1
H
i1
_
= M
i
_
E
i
H
i
_
=
_
cos
i
i
n
i
sin
i
in
i
sin
i
cos
i
__
E
i
H
i
_
. (6.14)
In this formalism, the matrix elements M
ij
contain the
refractive index n
i
of the layer and the phase shift
i
,
which are exclusively parameters of the layer number i.
For a calculation of the reection coefcient r
SK
of
the entire structure comprising also the substrate (index
P
a
r
t
A
6
.
1
Thin Film Optical Coatings 6.1 Theory of Optical Coatings 377
of refraction n
T
) and the ambient medium (index of
refraction n
0
), again the ratios of the amplitudes have to
be considered:
r
SK
=
n
0
M
11
+in
0
n
T
M
12
iM
21
n
T
M
22
n
0
M
11
+in
0
n
T
M
12
+iM
21
+n
T
M
22
(6.15)
In order to demonstrate the elegance of the matrix for-
malism, the reectance of a high-reecting dielectric
mirror will be considered in the following. The standard
design of such a mirror is a periodical 1 QWOT stack
(see also Fig. 6.1) of two coating materials with a highn
H
and a lowindex of refraction n
L
. For an efcient descrip-
tion of the designs, a notation in capital letters, which
indicate a 1 QWOT layer of a certain layer material, is
often used in optical thin lm technology. For example,
a mirror stack with 11 layers in the described structure is
represented by the sequence HLHLHLHLHLH (H: re-
fractive index n
H
L: refractive index n
L
) or even more
condensed by (HL)
5
H. For the more general case of N
layer pairs (design: (HL)
N
H) the matrix M
DM
of the
dielectric mirror can be expressed by:
M
DM
=
_
0 i/n
H
in
H
0
__
0 i/n
L
in
L
0
_
_
0 i/n
H
in
H
0
_
. . .
_
0 i/n
H
in
H
0
_
. ,, .
(2N+1) matrices
(6.16)
Obviously, the single matrices for the 1 QWOT-layer
reduce to simple expressions containing solely the re-
fractive index of the materials for this special case
of normal incidence. Executing the matrix multipli-
cation, applying (6.15) and calculating the reectance
R
DM
=r
DM
r
DM
results in:
R
DM
14n
0
n
T
n
2N
L
n
2(N+1)
H
. (6.17)
This expression is an approximation for a large number
N of QWOT-layer pairs, which is typical for practical
systems involving 10 to 40 layer pairs. An interpreta-
tion of this estimation (6.17) indicates that the contrast
(n
L
/n
H
) between the indices of refraction governs the
number of layer pairs necessary to achieve a dened re-
ectance value. A high contrast does not only reduce
the number of layer pairs, but also results in a more ex-
tended reection band in the spectrum of the QWOT
stack (Fig. 6.4). In Fig. 6.5 the development of the re-
ectance spectrum is illustrated for the QWOT stack
dened in Fig. 6.4 for different angles of incidence.
The shift of the spectra towards shorter wavelength
can be explained on the basis of a reduction of the
phase difference between the partial waves in the layer
structure. For arbitrary angles of incidence the spectra
of p- and s-polarization have to be considered sepa-
rately in the matrix formalism resulting in a broader
reectance band for the s-polarization compared to the
p-polarization. These effects have to be taken into ac-
count if a dielectric mirror designed for normal incidence
is operated under arbitrary angles of incidence in an
application.
Besides the described high-reecting stacks, antire-
ective coatings are often applied in laser technology
to reduce reection losses of windows, laser rods, or
lenses. Compared to the mirror designs, antireective
(AR) coatings are regularly built only of a few lay-
ers, but often of more than two materials, especially
to accomplish the demands of lowest residual reec-
tivity for a broad spectral range. For laser technology
with its dominant single-wavelength applications and
challenging specications concerning the losses and the
power-handling capability of the coatings, single layers
or two-layer AR coatings are mainly employed. On the
basis of two layers, a total suppression of the Fresnel
reection of most substrate materials can be accom-
plished for one wavelength. Such coatings, which are
often called V-coatings according to the shape of their
Re(k)
Im(k)
UV
IR
k
Vacuum
Vis
Fig. 6.4 Reectance spectra calculated for 1 QWOT stacks (
Z
=
1064 nm) of different high-refracting materials in conjunction with
SiO
2
(n
L
= 1.46) as the low-index material on a quartz surface
(n
T
= 1.46, refractive index of the ambient n
0
= 1). The refractive
indices of the high-index layers are typical values for electron-beam
deposition of the corresponding deposition materials: Al
2
O
3
: n
H
=
1.62 (green), CeO
2
: n
H
=1.80 (blue), HfO
2
: n
H
= 1.95 (magenta),
TiO
2
: n
H
=2.25 (black). The number of layer pairs is kept constant
at N = 6 for all depicted spectra
P
a
r
t
A
6
.
1
378 Part A Basic Principles and Materials
s
p
R (%)
Wavelength (nm)
800 1600
100
90
80
70
60
50
40
30
20
10
0
880 960 1040 1120 1200 1280 1360 1440 1520
45
LZH
Normal
incidence
Fig. 6.5 Reectance spectra calculated for 1 QWOT stack with
parameters according to Fig. 6.4 and TiO
2
(n
H
= 2.25) as the
high-index material. Besides the spectrum for normal incidence,
the reectance is depicted for an angle of incidence of 45
. For
arbitrary angles of incidence, s- and p-components have to be
distinguished
spectra, offer the advantage of lowest total thickness
providing minimum losses and highest laser-induced
damage thresholds [6.9].
In regard to the important role of losses and stabil-
ity of coating systems for laser technology, the designs
are often also optimized with respect to the distribution
of the electrical eld strength in the structure. In view
of the fact that the matrices associate the eld strength
values at different positions in the layer system, the cal-
culation of the eld strength distribution can be readily
accomplished using the matrix method. Moreover, an
implementation of the formalisms into modern computer
algorithms, which allow for the calculation of all trans-
fer parameters including many other important aspects
in laser technology, such as absorbance, phase shift or
group delay dispersion, is an uncomplicated task. In the
course of the rapid development of computer technology,
extensive software tools are available nowadays, which
even allowfor an inverse synthesis of multilayer designs.
As input parameters of these modern optimization tools
the desired spectral characteristics can be entered, and
appropriate design solutions are developed on the basis
of sophisticated algorithms. In summary, the challenges
of optical thin lm technology are no longer concen-
trated on the theoretical modeling and the calculation
of designs. Present and future problems are coupled to
the reproducible and precise production of coatings with
high optical quality and environmental stability.
6.2 Production of Optical Coatings
Looking back, the production of optical coatings ex-
hibits a long and successful technical history. Besides the
already mentioned early aging and etching experiments
of Fraunhofer and Taylor, in 1852 Grove described the
sputtering effect, as it was later called, in a gas discharge
apparatus [6.10]. In 1857, Faraday vaporized gold wires
by high electrical currents and studied the optical prop-
erties of the deposited material, although he was mainly
interested in the nest particles [6.11]. Wright reported
in 1877 on the production of transparent metallic lms
by the electrical discharge in exhausted tubes [6.12]. In
1884, Edison led an application for a patent, which
described thermal evaporation within a vacuum ves-
sel as well as arc vaporization to plate one material
with another and was granted in 1894 (Fig. 6.6) [6.13].
In the following decades, a multitude of publications
documented the development of industrial production
methods for optical coatings, starting with single layers
and resulting in increasingly complex multilayer sys-
tems [6.14, 15]. Within the scope of the present article,
a short overview of the most common production tech-
niques for optical thin lmlters fromthe basics to some
of the latest developments will be given. Further infor-
mation about optical coating technology can be found in
a variety of comprehensive technical books [6.9,1619].
Concerning the industrial production, there are fun-
damental demands on the deposition process, although
their priorities depend on the specic applications. High
reproducibility of the optical properties of the thin lms
is needed, as well as of the mechanical characteristics.
Large areas have to be coated homogeneously, using
high deposition rates with simultaneous realization of
a precise layer thickness determination and termina-
tion. Furthermore, a high level of automation, a short
process time, and inexpensive, nontoxic deposition ma-
terials are economically relevant. With regard to the thin
lm material choice, specic requirements also have
to be fullled [6.20]. Dielectrics for use in multilayer
coatings have to be transparent in the spectral region de-
sired by the specic application. Therefore, besides an
appropriate refractive index contrast, a low extinction
coefcient has to be realized. In addition, an adequate
P
a
r
t
A
6
.
2
Thin Film Optical Coatings 6.2 Production of Optical Coatings 379
Fig. 6.6 Illustration from Edisons patent Art of Plating
One Material with Another, granted in 1894 [6.13]. The
conductive coating material is vaporized within a vacuum
chamber by a continuous arc between the electrodes (a). For
coating mirrors, Edison placed glass plates on the inner side
of the apparatus. Furthermore, the patent describes thermal
evaporation by resistive heating
mechanical and environmental stability must be ensured.
Finally, the materials have to be technically controllable
within the chosen deposition process, and have to ex-
hibit the potential to form amorphous, compact thin lm
microstructures. In the visible and near-infrared spec-
tral region, these requirements are covered best by the
material class of oxides. Common examples are the
low-refractive-index materials SiO
2
or Al
2
O
3
and the
high-refractive-index metal oxides Ta
2
O
5
, Nb
2
O
5
, or
TiO
2
. Going down to the ultraviolet and vacuum ultra-
violet wavelength ranges, the oxides are complemented
and successively replaced by uorides, e.g., AlF
3
, MgF
2
,
and LaF
3
. In contrast, the mid- and far-infrared spectral
region is the domain of materials such as Ge, Si, ZnSe,
ZnS, and the radioactive ThF
4
, which is still in use,
mainly for high power CO
2
laser optics.
6.2.1 Thermal Evaporation
Within the most common deposition processes for op-
tics, thin lms are produced under vacuum conditions.
In general, these processes are divided into two clas-
sication groups: on the one hand, the physical vapor
deposition (PVD), comprising thermal vaporization as
well as sputtering, and, on the other hand, chemical
vapor deposition (CVD).
One of the basic ways to realize PVD is thermal
evaporation of the thin lm material by direct or indi-
rect heating of the deposition material within a vacuum
chamber. The evaporated material condenses on the
substrates to be coated, which are usually located on
a rotating spherical calotte above the evaporator. If the
uniformity of the layer thickness distribution across the
calotte does not full the requirements on the basis of
the given geometrical set up, additional masks are used.
Under vacuum conditions, the evaporation rate exhibits
a strong dependency on the temperature, and is mainly
determined by the temperature-dependent equilibrium
vapor pressure p
2mk
B
T
, (6.18)
with
dN
e
/dt number of evaporating atoms per time unit,
A
e
surface area of the evaporation source,
e
evaporation coefcient (sticking coefcient for
vapor atoms onto the surface),
p
= p
0
e
L
0
k
B
T
, (6.19)
where p
0
is a constant factor and L
0
is the latent heat of
evaporation per atom or molecule.
With the focus on technical aspects, a variety of
evaporation sources has been developed. In practice,
unwanted contamination effects of the lms with con-
tact material from the evaporation source, as well as
its signicant corrosion, can occur due to chemical re-
actions at the required high temperatures. Furthermore,
high evaporation temperatures between some hundred
to several thousand Kelvin have to be reached within the
evaporation source.
P
a
r
t
A
6
.
2
380 Part A Basic Principles and Materials
An elementary, but not often used, method is the
sublimation of a conducting material by direct current
heating. This technique is not applicable to many ma-
terials; potential examples are C, Cr, Fe, Ni, Rh, and
Ti. An early developed and widely applied way to real-
ize thermal evaporation is indirect heating of the coating
material by a resistively heated reservoir. The charac-
teristic shape of the reservoir gave this process variant
its name: boat evaporation. Evaporation boats are made
of conducting high-temperature resistant materials, e.g.
W, Mo, Ta, or C, in addition partially equipped with
a ceramic insert (liner). Obviously, the maximum evap-
oration temperature is limited by the melting point of
the boat material. In a slightly modied alternative, the
boat is reduced to a lament, wetted by molten material,
which is kept in place by surface tension. However, due
to the thermal inertia of the boat and the molten coat-
ing material, a nearly real-time rate control is difcult
to realize. Furthermore, the melting can exhibit disad-
vantageous spatter behavior, leading to coating defects.
This effect can be partially suppressed by equipping the
boats with perforated caps or chimney constructions.
Another technical possibility to melt conductive ma-
terials is the application of induction heating. While
inductive heaters are frequently used for large molten
masses, e.g., in the eld of crystal growth, this solution
is rarely used for the deposition of optical coatings.
Today, the most common thermal evaporation
method in the industrial production of optical coat-
ings is the direct heating of the coating material within
a crucible by an electron beam (Fig. 6.7). The character-
istic parameters of the electron beam, which is directed
by magnetic elds into the water-cooled crucibles, are
an acceleration voltage of 610 kV and currents of
0.11.5 A. In order to achieve uniform evaporation, the
electron beam can be swept across the coating material
by deection coils, optionally combined with a rotat-
ing crucible. In addition, multi-crucible electron-beam
sources allow the sequential evaporation of different
coating materials within one process; otherwise the de-
position plants are equipped with two or more sources.
Compared to boat evaporation, the electron-beam heat-
ing technique offers important advantages. Due to its
high power densities, high-melting-point materials can
be evaporated and, furthermore, the cooled crucible
prevents contamination. With regard to rate control,
electron-beamsources benet froma lowinertia in com-
bination with the high reliability of todays technical
solutions. However, it must be pointed out that high
local temperatures may lead to decomposition, if chem-
ical compounds are used as coating materials. In the case
Coating
material
Crucible
Heating
voltage
Acceleration
voltage
Deflection
coils
Electron beam
Anode Cathode
Fig. 6.7 Electron-beam evaporation source. The electrons
are accelerated by a potential difference of several kV and
are directed by a magnetic eld into the water-cooled cru-
cible. Additional deection coils allow for the beam to
write adapted patterns on the material to achieve uniform
evaporation
of oxides, an additional oxygen inlet can overcome this
problem. In common deposition systems, stoichiometric
lms can be attained applying a typical oxygen partial
pressure range of 1 to 310
2
Pa. Thermal evaporation
in the presence of reactive gases such as oxygen, nitro-
gen, or even uorine is sometimes referred to as reactive
evaporation.
Regarding the layer properties, thin lms pro-
duced by thermal evaporation exhibit characteristic
microstructures depending on the individual process pa-
rameters. The typical thermal energies below 0.3 eV of
the condensing particles result in packing densities lower
than the density values of the corresponding bulk mater-
ials. As a consequence of limited surface mobility of the
condensing particles and shadowing effects, a colum-
nar growth containing microstructural voids is most
common for evaporated lms [6.23, 24]. Derived from
experimental studies, approved structure zone models
have been developed that describe characteristic zones
depending on the ratio between the substrate tempera-
ture and the melting point of the coating material [6.25].
Usually, the process parameters are optimized to achieve
maximized packing densities to minimize voids, which
results in the need for an additional substrate heating,
typically in the range of 300
+
Coating
material
Insulated substrate holder
(neg. self-bias potential)
Plasma beam
Plasma
source
Fig. 6.8 Schematic diagram of a reactive low-voltage ion plating
(RLVIP) system. An argon discharge is directed from a plasma
source into the crucible of an electron-beamevaporator. The ionized
coating material and a part of the argon ions are accelerated towards
the substrates by the self-bias voltage of the electrically insulated
substrate holder
P
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.
2
382 Part A Basic Principles and Materials
may lead to ion-induced stoichiometry defects by the
preferential sputtering effect, which results from differ-
ent sputtering efciencies of the single components of
a compound [6.31]. In the case of the widely used metal
oxides, the preferential sputtering of oxygen atoms re-
sults in an oxygen deciency and consequently, in an
increase of the optical absorption losses [6.32]. In prac-
tice, ion energies covering the range of several 10 eV
to several 100 eV are applied within typical IAD pro-
cesses. The usual ion-source operating media are inert
or reactive gases, in the latter case, in particular, oxy-
gen to assist oxide coatings. Consequently, besides the
densication effect, the stoichiometry of oxides benets
from the reactive ions, resulting in homogeneous layers
with reduced optical losses.
Concerning the IADprocess environment, some cen-
tral demands on the ion source can be stated. High ion
currents at low ion energies are needed, and the ion
current distribution across the calotte has to be exten-
sive and homogeneous. The ion source must exhibit
a high stability and reliability, even at long process
times. An independent control of ion current and en-
ergy within a wide parameter eld is also advantageous.
Furthermore, contamination of the growing layers by
material originating from the ion source has to be
avoided. And nally, options for reactive gases that can
Substrate holder drive Vacuum chamber
Substrates
Ion
source
Evaporation
source (e-beam)
Fig. 6.9 Principle arrangement of an ion-assisted deposi-
tion (IAD) process. Besides the electron-beamevaporators,
an ion source is implemented in the vacuum chamber. The
substrates are exposed to the low-energy ion beam, which
results in an additional energy transfer into the growing
layer
be used, low levels of maintenance, and low operating
costs are relevant. Nowadays, a variety of gridded and
grid less ion sources, fullling nearly all these require-
ments for standard IAD applications, are commercially
available [6.33, 34].
In the following, the positive effects of ion-induced
layer densication are illustrated briey. With regard to
the microstructure, the aforementioned structure zone
models for thermally evaporated lms have been ex-
tended to integrate the dense structures resulting from
ion-assisted deposition processes [6.35]. As the mi-
crostructural densication by the ions counteracts the
void development of the columnar growth, the high op-
tical losses attributed to adsorbed water can be prevented
by applying IADconcepts. In Fig. 6.10, the optical losses
of a SiO
2
single layer deposited with a thermal evapo-
ration process are compared to those of a SiO
2
single
layer produced within an ion-assisted deposition pro-
cess. The plotted extinction coefcients are calculated
from spectrophotometric transmittance and reectance
measurements and indicate optical losses in the range
between 10% and 20% for the thermally deposited
layer. Using spectrophotometric measurements, no wa-
ter could be detected in the IAD coating. Besides the
reduction of absorption losses, another positive effect
of the dense and water-free microstructure is the drastic
increase in thermal spectral stability of the coatings. Ion-
assisted deposition can reduce the relative wavelength
shift /(
C [6.36].
Furthermore, ion-assisted deposition offers the pos-
sibility to tune the mechanical intrinsic stress of a coating
from tensile to compressive stress, which can improve
the layer adherence and the dimensional accuracy of
critical optical components [6.3739]. And nally, the
implemented ion source enables options for substrate
precleaning process steps.
6.2.3 Sputtering
Sputtering represents an established and versatile class
of energetic vacuumdeposition processes, applying con-
densing particles with signicantly higher energies than
those resulting from thermal evaporation methods. Its
basic principle, derived from the early gas discharge ex-
periments in the 19th century, is depicted in Fig. 6.11.
Within a vacuum chamber at a pressure of about 1 Pa,
a glow discharge is maintained by a direct-current (DC)
voltage in the kV range between the anode, carrying
the substrates to be coated, and the cathode. The cath-
P
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6
.
2
Thin Film Optical Coatings 6.2 Production of Optical Coatings 383
Extinction Coefficient k
Wavelength (m)
2.25 4.00
0.05
0.04
0.03
0.02
0.01
0.00
2.50 2.75 3.00 3.25 3.50 3.75
Fig. 6.10 Comparison of the optical losses of SiO
2
single
layers: thermal evaporation versus ion-assisted deposition
(absorption band of adsorbed water). The optical losses
are calculated frommeasured spectrophotometric transmit-
tance and reectance data
ode consists of the coating material which has to be
electrically conductive (target). In the discharge area,
positive working gas ions, e.g., argon ions, are generated
by impact ionization and accelerated towards the target.
Ions impinging on a solid surface, besides other interac-
tions, eject atoms, molecules, and clusters by collision
cascades. This effect is called sputtering; its efciency
depends on the target material and microstructure as
well as on the species, the energy, and the angle of in-
cidence of the ions. Within the depicted DC discharge
process, the particles sputtered from the target condense
on the substrates and form a layer. As a consequence
of the high kinetic energies of the adatoms in a typical
range of several eV (maximum energy of several tens
of eV), sputtered coatings exhibit a higher density in
comparison to evaporated thin lms.
A way to overcome the DC sputtering limitation to
conductive targets was found in the technology of radio-
frequency (RF) sputtering. In a common set up, the DC
electrodes shown in Fig. 6.11 are converted to RF cou-
pling electrodes. Choosing a geometrical arrangement
in which the surface area of the substrate electrode ex-
ceeds the area of the target electrode, a DCpotential with
a negative target electrode results from the self-bias ef-
fect. Due to this DC potential, the sputtering occurs on
the target, and not on the substrate electrode [6.40].
Today, magnetron sputtering is an important sputter-
ing technology for the industrial production of optical
coatings. The term magnetron is derived from a mag-
netic eld, crossing the electric eld of a DC discharge,
Dark
space shield
Vacuum
chamber
Cathode
Target
Substrates
Anode
Working gas
Ion
Coating
material
Plasma
Fig. 6.11 Schematic diagram of a direct-current sputtering
process. A glow discharge is driven by a DC voltage in the
kV range. Coating material is sputtered from the target on
the cathode and is deposited on the substrates positioned at
the anode
and conning the plasma within the region in front of
the target (Fig. 6.12). Resulting from the increased de-
gree of ionization, a signicantly higher deposition rate
provides a reduction in process time. Furthermore, the
layer quality benets from the less intensive interaction
with the plasma as well as from the reduced pressure,
in the range of 10
1
Pa. However, the application of the
DC magnetron source within a reactive process envi-
ronment is linked to some limiting complications. The
reactive gas interacts with the target material and the
generated compounds form an insulating layer on the
target surface, an effect called target poisoning. Due to
the differences in sputtering efciency of metals and, for
example, oxides or nitrides, the deposition rate decreases
strongly while the target is poisoned. Also a modication
of the discharge conditions is attributed to the formation
of an insulating layer, which can lead to arcs or even a ter-
mination of the discharge. Besides the poisoning of the
target cathode, the whole chamber, acting as an anode, is
covered successively by the insulating compound the
so-called disappearing anode. To overcome these limita-
tions, the magnetron process can be driven in a transition
mode between the metallic and the non-metallic mode.
However, as this transition mode exhibits considerable
instability, a complex active process control has to be im-
plemented to stabilize the relevant parameters, e.g., on
the basis of lambda probes for reactive oxygen [6.41].
A second technological approach is the sequential
processing concept, in which the magnetron sources
work in the metallic mode. Separated from the mag-
netrons, plasma sources provide a subsequent treatment
of deposited sublayers, consisting of a few monolayers,
P
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2
384 Part A Basic Principles and Materials
Cathode Target
Substrates
Anode
Working
gas
Coating material Plasma
Vacuum chamber Bias voltage
(optional)
N S N
Magnetic
field
Fig. 6.12 Basic principle of the magnetron sputtering pro-
cess. A magnetic eld, crossing the electric eld of a DC
discharge, connes the plasma within a region in front of
the target. An optional bias voltage applied to the sub-
strate holder allows for an additional energy input into the
growing layer
with activated reactive gases. In technical implementa-
tion, the magnetron and plasma sources are often located
in a circular geometry with a fast rotating cylindrical
substrate holder in its center [6.42, 43].
Important advances have been achieved on the ba-
sis of dual-magnetron (also called twin-magnetron)
congurations, applying medium-frequency voltages
in a typical range of 20100 kHz [6.44]. In a dual-
magnetron arrangement, both target electrodes working
alternately as the cathode and anode, preventing elec-
trostatic charging as well as the disappearing anode
effect, mentioned above. Furthermore, improvements
have been made by operating magnetrons in pulse mode,
since the limiting thermal load on the target is decreased
by this technique.
Nowadays, inline magnetron sputter systems are
standard for the large-area deposition in the application
elds of architectural glass, photovoltaic, and displays,
whereas sequential processing concepts in combination
with dual magnetrons are currently nding their way
into precision optics.
6.2.4 Ion-Beam Sputtering
Ion-beam sputtering (IBS) represents its own class of
sputtering deposition technology, applicable for the
highest-quality optics. The basic principle of an ion-
beam sputtering process is illustrated schematically in
Fig. 6.13 [6.45]. Within a vacuum chamber, a separated
ion source is directed to the target, which is consequently
not in contact with the ion-generating plasma. The set
up provides a rotating substrate holder for the condens-
ing thin lms in the geometrically preferred direction of
the sputtered particles. Under typical process conditions,
argon ions with kinetic energies in the rage of 1 kV are
employed for sputtering, while an additional reactive-
gas inlet provides an option for depositing compound
layers from metallic targets. In some cases, a second ion
source is directed to the substrates, and allows for as-
sistance of the growing layer (compare IAD) as well as
precleaning of the substrates.
In comparison to the described DC approach,
alternating-current (AC) and magnetron sputtering
processes, ion-beam sputtering offers a variety of ad-
vantages. A low working pressure (reactive 10
2
Pa,
nonreactive 10
3
Pa) in combination with the absence
of interactions between the substrates and the plasma
result in high-quality thin lms with minimum contam-
ination and defects. However, the decisive factor for the
excellent optical and mechanical lm quality in ion-
beam sputtering is the high energy (up to 100 eV) of the
layer-forming particles. IBS coatings are dense, amor-
phous, and suitable for ultra-low-loss components, as
total optical losses in the range of 1 ppm are achiev-
able [6.46]. Furthermore, ion-beam sputtering is an
extremely stable process, which allows for a high de-
gree of automation. Also, energy and current density of
the sputtering ions can be adjusted independently within
a wide range.
Nevertheless, ion-beam sputtering is less often used
in the industrial mass production of optical coatings.
This niche position results from distinct economic dis-
advantages, namely a low deposition rate and technical
difculties in coating larger areas homogeneously. Com-
pared to thermal evaporation or magnetron sputtering
processes for precision optics, typical IBS deposition
rates are 10 times lower (in the range 0.5 /s instead of
0.5 nm/s). Major current market segments for ion beam
sputtering include high-end precision optics for special
applications, mainly in the research and science sector,
e.g. complex chirped mirrors for femtosecond lasers as
well as next-generation lithography [6.47, 48].
6.2.5 Chemical Vapor Deposition (CVD)
Similar to the PVD processes described above, chem-
ical vapor deposition offers a range of process variants.
All CVD processes share the basic principle that the
deposited layer is a product of a chemical reaction of
gaseous reactants (precursors) [6.49]. This reaction is
activated within various process types by different kinds
of energy input, covering thermal, plasma, and radiation-
P
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.
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Thin Film Optical Coatings 6.2 Production of Optical Coatings 385
Substrate holder
Gas
inlet
Ion
source
Targets
Fig. 6.13 Schematic illustration of the ion-beam sputtering
process. A separate ion source is directed to a target, the
sputtered particles condense on the rotating substrates. Au-
tomatically changeable targets allow for the production of
multilayer coatings
induced CVD. Except for the coating material, all further
reaction products have to be gaseous, as they have to be
exhausted from the process chamber. Chemical vapor
deposition is widely applied in hard coatings for wear-
protection purposes, besides being the most widely used
deposition method in the semiconductor industry. In the
production of optical coatings, CVD processes still play
a minor role in comparison with PVD technologies.
Chemical vapor deposition distinguishes two layer-
forming mechanisms. In heterogeneous nucleation, the
coating material is generated on the substrate surface. In
homogeneous nucleation, the chemical reaction produc-
ing the coating material takes place above the substrate
surface. Subsequently, the reaction product diffuses to
the surface of the substrate, where the lm is formed.
Since coatings produced by homogeneous CVD pro-
cesses in most cases are less dense and exhibit a lower
layer quality than coatings by heterogeneous CVD pro-
cesses, the latter variant is standard. However, some
process concepts combine both types by applying a ho-
mogeneous gas-phase reaction to produce a reactant for
the nal heterogeneous layer-forming reaction. In all
cases, complex gas dynamics have to be controlled by
adaptation of the gas inlets, and a balanced ow and
pressure control.
The classic way to perform chemical vapor deposi-
tion is by thermal activation of the reactions by heating
of the substrates. Most of these reactions require high
temperatures, typically exceeding 450
C, which are
incompatible with optical coatings on substrates for
precision optics or on plastics. As an example, in the
semiconductor industry the pyrolysis of silane is used to
deposit silicon (g: gaseous, s: solid):
SiH
4
(g)
600700
C
Si(s) +2H
2
(g) . (6.20)
Applying additional oxygen, silica coatings can be pro-
duced:
SiH
4
(g) +O
2
(g)
450
C
SiO
2
(s) +2H
2
(g) . (6.21)
Thermally activated chemical vapor deposition pro-
cesses are driven at atmospheric pressure (APCVD)
or, more commonly today, in low-pressure reactors
at a typical pressure range of 10
1
10
3
Pa (LPCVD).
Atmospheric-pressure CVD offers higher deposition
rates than LPCVD, which, in contrast, provides higher
uniformity and a better covering of nonplanar geomet-
rical shapes.
Another way of energy input is used in plasma-
enhanced chemical vapor deposition (PECVD), a pro-
cess variant rapidly gaining importance in many
applications [6.50]. The PECVDtechnique offers the ad-
vantage of much lower process temperatures than those
needed in thermally activated CVD. As a result of the
applied DC, RF or microwave plasma excitation, the
gaseous precursors can react while the substrate temper-
ature stays below300
i
phase shift of a plane wave in layer number i
Table 6.2 Selected quality parameters of optical coating systems for laser applications (Types: HR: high-reecting mirror,
AR: antireective coating, th: thermal evaporation, IBS: ion-beam sputtering)
Laser,
wavelength
Type Absorption
ISO 11551
Total scattering
ISO 13696
Laser-induced damage
threshold, ISO 11254
157 nm, F
2
-excimer HR/th 14% 14%
193 nm, ArF-excimer AR/th 0.72.5% 0.20.5% 12 J/cm
2
(1on1, 20 ns)
HR/th 0.42.0% 0.22.5% 24 J/cm
2
(1on1, 20 ns)
248 nm, KrF-excimer AR/th < 0.025% 10 J/cm
2
(1on1, 30 ns)
HR/th < 500 ppm < 0.2% > 20 J/cm
2
(1on1, 30 ns)
HR/IBS < 0.1% > 3 J/cm
2
(1on1, 30 ns)
633 nm, HeNe Laser HR/th < 30 ppm <30 ppm -
HR/IBS < 5 ppm <5 ppm -
1.064 m, Nd:YAG AR/th < 20 ppm < 100 ppm > 60 J/cm
2
(12 ns, 0.25 mm)
HR/th < 50 ppm < 100 ppm > 100 J/cm
2
(12 ns, 0.25 mm)
HR/IBS < 1 ppm < 1 ppm > 80 J/cm
2
(12 ns, 0.25 mm)
10.6 m, CO
2
-Laser AR/th < 0.16% - > 20 J/cm
2
(100 ns, 1.4 mm)
> 2 kJ/cm
2
(1.2 ms, 250 m)
> 3 kW/mm (100 m)
HR/th < 0.10% - > 25 J/cm
2
(100 ns, 1.4 mm)
> 2 kJ/cm
2
(1.2 ms, 250 m)
d
i
thickness of the layer number i
n
i
refractive index of the layer number i
i
angle of incidence in the layer number i
A
0
amplitude of the partial wave of order zero
A
1
amplitude of the partial wave, order one
A
2
amplitude of the partial wave, order two
t
1
, t
1
transmission coefcients of the ambientlayer
interface
r
1
, r
1
reection coefcients of the ambientlayer in-
terface
r
2
reection coefcient at the layersubstrate in-
terface
A
k
amplitude of the partial wave of order k
r
S
reection coefcient of a single layer
M
i
matrix of layer i
E
i
, H
i
electric eld strength, magnetic eld strength
at the rear plane interface of layer i
M
S
composite matrix of a layer stack of K single
layers
r
SK
reection coefcient of a layer stack of K single
layers
n
0
index of refraction of the ambient medium
D
i
lm thickness expressed in units of QWOT
QWOT quarter-wave optical thickness; the unit for the
thickness of the layer
Z
design wavelength
n
H
refractive index of a high-index material
n
L
refractive index of a low-index material
R
S
reectance of a QWOT stack
P
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.
4
Thin Film Optical Coatings References 393
PVD physical vapor deposition
CVD chemical vapor deposition
dN
e
/dt number of evaporating atoms per unit time
A
e
surface area of the evaporation source
e
evaporation coefcient
p