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Thin lms are generally used to improve thesurfacepropertiesofsolids.

Transmission, reec-tion, absorption, hardness, abrasion resistance,corrosion,


permeation and electrical behaviourare only some of the properties of a bulk
mate-rial surface that can be improved by using a thinlm. Nanotechnology
also is based on thin lmtechnology.

Thin Film Deposition is the technology of applying a very thin film of


material between a few nanometers to about 100 micrometers, or
the thickness of a few atoms onto a substrate surface to be
coated, or onto a previously deposited coating to form layers.

Thin lms are used if no low-priced bulkmaterial that corresponds to the


required speci-cations of the material exists.Examples from optics are:
changes of reec-tion or tting of the transmission of glass bodies;micro-,
nano- and opto-electronics are based onthin lm technology.Thin lm
technologies are divided into PVD(physical vapour deposition) and CVD
(chemicalvapour deposition) processes.PVD processes include:

High-vacuum evaporation

Cathodic sputtering

Ion plating

Ion implantation

Ion beam mixing

Plasma diffusion methods and pulse implanta-tion

Plasma spraying.

Physical vapor deposition (PVD) describes a variety of vacuum deposition


methods which can be used to produce thin lms and coatings. PVD is
characterized by a process in which the material goes from a condensed
phase to a vapor phase and then back to a thin lm condensed phase. The
most common PVD processes are sputtering and evaporation. PVD is used in
the manufacture of items which require thin lms for mechanical, optical,
chemical or electronic functions.

Advantages

PVD coatings are sometimes harder and more corrosion resistant than
coatings applied by the electroplating process. Most coatings have high
temperature and good impact strength, excellent abrasion resistance and are
so durable that protective topcoats are almost never necessary.

Ability to utilize virtually any type of inorganic and some organic coating
materials on an equally diverse group of substrates and surfaces using a wide
variety of nishes.

More environmentally friendly than traditional coating processes such as


electroplating and painting.[citation needed]

More than one technique can be used to deposit a given lm.

Disadvantages

Specic technologies can impose constraints; for example, line-of-sight


transfer is typical of most PVD coating techniques, however there are
methods that allow full coverage of complex geometries.

Some PVD technologies typically operate at very high temperatures and


vacuums, requiring special attention by operating personnel.

Requires a cooling water system to dissipate large heat loads.

Optical Coating: Materials and Deposition


Technology
Optical coatings are deposited as thin-lm multilayers of a variety of
materials using specic deposition techniques. Coatings are applied to optical
components that are intended for use at wavelength regions between UV and
far-IR. The materials and processes used to make these coatings are
described here and in the attendant materials data tables.

General material categories and deposition processes

In Table 1, the chemical categories of the materials that are used for optical
coating are segregated by spectral region; overlap exists between all regions.
Table 2 lists the materials typically used in those spectral regions. These pure
(unmixed) compounds represent selections distilled from dozens of potential
materials according to required thin-lm layer properties such as
transparency, mechanical properties, environmental durability and ease of
deposition.

With the exception of the uoride compounds and lanthanum titanate, these
materials are typically deposited by e-beam evaporation or by sputtering
from targets. Fluoride compounds and many of the oxide compounds can,
alternatively, be evaporated from resistance-heated sources. Because of
chemical, stress and process incompatibilities, layers from the oxide and
uoride chemical classes are generally not combined in a coating. The
exception is with UV coatings where layers are thin and the material selection
of transparent materials is small. Multicomponent materials have been
developed to achieve improvements in one or more thin-lm layer properties
over the single-element precursor. Examples are doped uorides and oxides
and mixtures of two or more similar materials. Mixed and doped starting
materials can be obtained, or modications can be accomplished during
evaporation or sputtering from separate sources of materials. Layers of
uorides and suldes (selenides) are combined in LWIR coatings.

Table 2 also segregates materials according to their mean high-,


intermediate- and low-refractive indices within the spectral ranges of greatest
usefulness, as limited by absorption. Refractive index is a property of key
importance in multilayer coating designs for AR, edge lters, dichroic
reectors, polarizers, laser reectors and spectral lters.
Deposition and growth of thin lms of these materials to build optical
coatings is accomplished by one of the many variations of two main physical
vapor deposition (PVD) processes: evaporation and sputtering. Deposition of
lms of metal oxide compounds by evaporation or by sputtering can proceed
from a preparation of the compound as the starting material or from the base
metal and subsequent reactive oxidization to the nal desired composition.
The nonoxide materials in Table 1 generally start and end with similar
compositions. The data tables that follow this article provide suggested
deposition parameters.

Coating deposition process technology

Process outline: The components of the deposition process, from


performance requirement to nished product, are diagrammed in Figure 1. It
is evident from the descriptions of the process components that material
science and deposition technology play complex interdependent roles in
successfully producing optical coatings. It is important to understand the
individual components and their interactions.
The components of coating materials technology.

Figure 1. The components of coating materials technology.

Design and engineering considerations: When presented with the spectral


and environmental requirements and the substrate material to be coated, the
coating engineer decides on the coating materials and the deposition process
and monitoring technique. A thin-lm design is generated that includes the
wavelength dependencies of the optical constants, refractive index and
extinction coefficient, determined for the materals and deposition process
parameters. Predicted performance is evaluated with respect to spectral
coverage, incidence angle, surface shape, substrate temperature constraints,
mechanical durability and verication measurement. The starting form of the
coating material and its preparation are selected based on deposition
technique and thin-lm design. Some materials require preconditioning to
prepare for smooth deposition at a constant rate and consistent composition.
The deposition process operational parameters, previously determined for
each material, are programmed into the deposition controller along with the
coating design. Deposition parameters coupled with material behavior
determine the physical microstructural properties of the thin-lm layer. Those
lm properties in turn determine the optical, mechanical and environmental
properties of each deposited layer.

Materials selections: The materials that will be used in the design are
selected according to the spectral criteria of Tables 1 and 2, as well as
durability requirements and deposition process. Coating materials are
preprocessed and formed to provide controlled vaporization behavior and to
insure that the physical and optical properties of the deposited lm are
consistent from run to run. The optimum lm composition, physical structure,
and the vaporization behavior throughout the deposition process are strongly
dependent on the preparation of the starting material. Furthermore, the
different chemical compositions outlined in Table 1 and the specic
compounds listed in Table 2 require individual preparations and forms. More
detailed discussions are available on the CERAC Web site.1

Oxide compounds: Oxide lms can be deposited from an evaporant source


or sputtered using oxide or metallic targets. Evaporable metal oxide
compounds are supplied in several forms and preparations depending on the
particular compound. Typical physical forms are sintered or melted pieces,
broken crystals, hot-or cold-pressed tablets, or pre-melted, preformed e-beam
pocket cones. Cold-pressed and sintered preparations of tablets and pellets of
various sizes are made from powder that might be combined with a binder
and hot pressed in a vacuum or in an inert atmosphere. Compressed density
(>95 %) is desired to minimize volume porosity from which water vapor or
gas can be released upon heating. Some oxides adsorb surface water; others
form hydrates that dissociate with heat. Both types of inclusions can result in
the release of water vapor or other trapped gas and generate particulates or
cause pressure variations. Fluoride compounds adsorb atmospheric water
and experience the same problems and must be gently outgassed.

The chemical state of the starting material might be fully oxidized or be


reduced to a suboxide. The reduced state often melts and is conductive; both
properties are desirable for e-gun vaporization. Materials that evaporate from
the melt have a lower tendency of ejecting microparticulates and spatter
(large projectiles) that can result in optical scatter and pinhole creation. When
the melt is electrically conducting, e-beam deection and defocus due to
localized charging are eliminated. The reduced forms are gray or black in
color vs. white for the fully oxidized insulating material. Reoxidization is
achieved in several ways. The rst is deposition onto a substrate held at
temperature >200 C, providing an excess of oxygen. The second method is
to produce oxygen ions in a reactive plasma process. The third popular
technique is to use an ion assist (IAD) source that produces energetic Ar and
O ions. If the activation/reactive energies are insufficient to produce a
nonabsorbing lm, postbaking in air at a high temperature (>300 C) might
be required.

Referring to the tables, we see that the low-index oxide common to all oxide
coating combinations is SiO2. The companion high-index materials for visible
through SW wavelengths are titania or tantala. A successful replacement for
tantala, Ta2O5, is lanthanum titanate LaTiO3. As prepared, this material is
actually a complex chemical compound. Compared to pure tantala, LaTiO3
has the desirable properties of requiring lower evaporation temperature
producing denser lm layers of lower stress with nearly the same index. Its IR
transparency extends to ~8 m.

Titanium dioxide, TiO2, is a favorite visible-range material because of its high


refractive index. It nds wide application in AR coatings in the ophthalmic
industry. Numerous deposition techniques involving different oxidation states
of the starting preparations have been studied. To avoid the presence of
multiple and unstable crystalline states in the deposited coating, and
evaporation difficulties, the starting material composition should be Ti3O5.
This suboxide composition melts, enabling smooth, reproducible deposition.
Another high-index alternative to titania and tantala is niobia. Oxides of the
three materials can be deposited by sputtering the metal.

Some oxide compounds, and all uoride compounds, melt before reaching
evaporation temperature; others, such as silica, alumina and refractory oxide
compounds (hafnia and zirconia), evaporate from a fused vitreous surface or
sublimate (SiO). If the material retains its granular form rather than forming a
melt, heat transfer among the grains or pieces is inefficient, and the
concentration of heat at sharp boundaries such as dust, voids or trapped
water sites can result in the explosive emanation of particles and pressure
bursts. Extended preconditioning with a sweeping electron beam can reduce
these problems.
Avoiding problems: Particulate showering and spatter and pressure bursts
are common problems encountered when evaporating oxide compounds.
When the starting material is not properly preconditioned or is of
nonoptimum composition, particle emanation can range in intensity from
occasional bursts to continuous showering. Particles ranging in size from
nanometer to multiple-micrometer can be embedded in the layer and cause
light scatter or voids (pinholes) when removed by abrasion. Particulates are
often the initiation sites for laser damage and water penetration, and that
failure mechanism is as important as absorption in the lm in limiting the
damage threshold. Included particulates become points of mechanical stress
concentration and initiation sites for failures such as crazing and cracking.
With underdense starting materials, pressure variation from the release of
trapped gases during lm layer growth can contribute to inhomogeneity of
optical properties as well as upsetting the crystal monitor.

A technique that coating technicians apply to reduce these problems is to


create a dense melt by repeated charging of the crucible and melting down to
a dense mass. This procedure is wasteful of time and resources, and an
improved preparation of many oxide compounds has been introduced:
premelted cones that t the e-beam pocket.

Refractory oxides require evaporation temperatures that range from 1000 C


to >2500 C to transition from solid to vapor state (see data tables).
Materials with evaporation temperatures >2000 C are tantala, zirconia,
hafnia, alumina, yttria and scandia. These materials do not form a melted
pool from which evaporation can precede but instead a melted/fused spot
essentially a point source and the focused electron beam succeeds in
eroding a hole whose vapor distribution pattern changes with hole depth.
Rapid sweeping of the e-beam should be used to broaden the pattern area,
and will reduce thickness and rate nonuniformities. These problems are
virtually nonexistent with sputter deposition because of the larger source and
higher pressures.

Controlling nanostructural growth: A growth structure problem common to


oxide and uoride lms is that of low packing density. Apart from a small
number of exceptions (SiO and alumina), thin lms tend to grow with a
columnar nanostructure unless special measures are adopted. The energy
and chemical environments present during growth determine the nature and
scale of the structure. When low energy is present, for example at low
substrate temperature, the arriving adatoms do not have sufficient mobility
energy to nucleate continuous coverage on the surface. Lacking surface
mobility, isolated islands nucleate nanocrystallites that then grow in
thickness. Subsequent self-shadowing results in the growth of an open
structure of columns that have greater diameters at the substrate surface
and taper with height. Vapor incidence at large angles can also increase
columnar spacing and exaggerate these problems. The porous structure is
not only mechanically weak and soft, but is permeable to moisture.
Adsorption of water on the walls of the columns increases the effective
optical index and also changes intrinsic stress; both properties are unstable
to humid and arid exposure. Spectral shifting and stress-induced failure under
varying humidity conditions are evidence of underdense layers.

Film density can increase to near bulklike values by increasing the growth
energy of the adatoms or by changing the material composition to discourage
singular growth dynamics. In preference to resorting to very high substrate
temperatures to eliminate optical and mechanical instabilities, IAD is used to
apply high energy to the lm. In this technique, ions of oxygen and argon
impact the growing lm transferring high kinetic energies, ~100s eV. Greater
surface mobility and high momentum transfer result in high packing density.

The second method for discouraging low packing density is to introduce an


impurity content whose species occupy the spaces and the unsatised
bonds normally accompanying nanocrystallites, thereby interfering with
crystalline growth and resulting in an amorphous, dense structure. The
additive should be mutually solvent with the host material and possess other
favorable chemical properties. A number of oxide (and uoride) mixtures
have been engineered and are available commercially.1,2

Materials that require high vaporization temperatures, such as the refractory


oxides, often form multiple crystalline phases. This can occur in the e-gun
pocket where the temperature difference between areas can exceed several
hundred degrees so that melting and recrystallization occur nonuniformly.
The presence in the source of multiple oxidation states and crystal
morphologies affects composition and evaporation temperature after
repeated evaporations from the same source. The forms possess different
refractive indices, stress levels and evaporation temperatures. Therefore, it
will be impossible to achieve repeatable results in subsequent production
runs without renewing the composition of the evaporation skin layer. This
behavior is characteristic of titanium oxide, zirconia and other oxide
materials. Critical applications such as wideband AR coatings require that the
index of the rst thin layer (high index) be repeatable.

Multicomponent materials: The higher evaporation temperature oxide


compounds, zirconia, hafnia and scandia, are transparent into the UV, as
noted, but these materials present evaporation and optical problems. A
refractive index gradient that varies with lm thickness can exist in the lm
layer. Other oxide compounds, in pure form, suffer inconsistent evaporation
behavior. The lm itself might contain multiple crystalline states that can
transform at high temperature, causing the optical and mechanical properties
of the lm to be unstable.

Mixed materials composed of a host oxide and small percentage of a similar


oxide compound have been introduced to improve on evaporation
consistency. In addition, the mixed materials promote the growth of dense
lm layer structures because the incorporation of the additive discourages
the growth of multiple crystalline phases. Instead, a matrix of ne crystallites
is assumed to form that is effectively pseudo amorphous. The result is
stable properties under exposure to high temperature or high energy laser
irradiation. Binary and tertiary mixtures have been engineered that exhibit
improved hardness and tribological properties along with transparency.1
Lanthanum titanate is a material that provides improved properties, as
discussed above.

High mutual solubility exists among refractory oxide compounds namely


Al2O3, In2O3, MgO, Y2O3, ZrO2, TiO2 and Sc2O3. The additive proportion is
~10 wt percent. Some examples of available mixtures are TiO2-ZrO2, ZrO2-
MgO, ZnS-CeF3. Zirconia is used in laser coatings as the high-index layer.
However it suffers from high mechanical stress, inhomogeneous index prole,
and low laser damage tolerance. Mixing with 25 percent yttria results in a
threefold increase in damage threshold and improved physical properties.
Similar results have been reported with hafnia. Adding MgO to zirconia
stabilizes the crystalline state to cubic; adding alumina to zirconia constrains
the tetragonal state. In these cases, the nanostructure is not amorphous, but
is a stable crystalline state. Composing a ternary combination of these
compounds results in an amorphous state. The index of mixtures is lower
than that for the pure high index component alone.
By varying the relative proportions of a compatible pair of high- and low-
index materials, any intermediate index can be deposited to produce an
index value that is not available in a single material. Coevaporation,
cosputtering and alternating deposition of two sources are techniques used.

Fluoride coating materials: The evaporation or sputtering of nonabsorbing


lm layers of oxide compounds requires oxidation to the desired composition
by introducing activated oxygen in a reactive process. Fluoride and
semiconductor layer deposition proceed without the need to supply
components; in fact high vacuum is required to limit gas incorporation in
uoride lm layers. Fluorides retain their chemical composition upon
evaporation unless excessively high power is applied. It is advisable to
operate at a minimum e-beam voltage.

Fluoride compounds are evaporated from a melted or sublimating surface.


The uorides that sublime are prepared by vacuum hot pressing followed by
sizing. Melting material forms are crushed premelted or crystalline stock that
has been rened by remelting and recrystallization. Fluoride bonds are
stronger than oxide bonds so dissociation does not occur with thermal
evaporation; however, IAD energies are sufficient to break those bonds and
permit partial substitution of oxygen and the generation of oxyouride
compositions. Such compositions are highly absorbing in the UV, however,
resulting in lower laser damage thresholds than achieved with pure oxide or
uoride compounds. For this reason, e-beam and resistance heated sources
are used without IAD for laser applications.

Many uoride compounds absorb water and must be dehydrated by gentle


heating during the melt preparation. Magnesium uoride provides the lowest
index available over UV to SWIR wavelengths and evaporation material is
prepared by precipitation from solution. Substrate temperatures >250 C are
required for the deposition of lms with packing density >90 percent. The
nanostructure consists of large columns with high void volume. Residual
water absorption bands can be detected in the SWIR (~2.9 m) to MWIR (6.2
m) regions even for depositions made at high temperatures. The quantity of
the volatile component of the absorbed water that resides within the pores
changes between humid and arid conditions, causing the index of the lm to
vary. Yttrium uoride, transparent beyond the 10-m wavelength, and other
uoride lms also exhibit water bands and index variation. The water bands
in ytterbium uoride, YbF3, are shallower than those in YF3.
Fluoride lms typically grow with high tensile stress nature that limits their
maximum physical thickness. The coarse growth structure is also responsible
for high light scatter from the rough column ends at the lm surface. By
admixing small quantities of other uorides, stress, water absorption, and
roughness problems associated with the coarse nanostructure are reduced or
eliminated. Fluoride mixtures have been in use for many years, some
specically engineered to be nonradioactive replacements for thorium
uoride in IR coating designs. The specic uoride mixtures that produce
dense, amorphous and stable lms are CERAC CIROM IRX, IRB and YBaF.1

II-VI compounds: Optical coatings that operate to wavelengths ~5 m can


be built from the oxide and uoride materials that we have discussed. Beyond
~5 m, oxide compounds begin to absorb so sulde and selenide
compositions must be substituted along with semiconductors, as shown in
Table 2. A handful of uorides are also useable up to the limit imposed by
thickness-dependent tensile stress level.

The low-index components for MWIR to LWIR coatings, ZnS and ZnSe, sublime
and dissociate when evaporated. The starting materials are produced in a
CVD process from the reaction of gases. The condensed solids are crushed
and sized or pressed into desired working shapes. If substrate surface and
chamber atmosphere conditions are favorable, the dissociated components
will recombine with correct chemical composition at the substrate and
produce nonabsorbing dense lms. While e-beam is a useable evaporation
technique, a heated baffled box source is preferred because in the nearly
isothermal evaporation environment created, there are fewer hot spots that
can produce unrecoverable composition deviations.

The high-index component of a LWIR multilayer AR, bandpass, or edge lter is


usually germanium, with index = 4, and is evaporated from an e-gun melt.
Procedure to obtain nonabsorbing lms includes the elimination of oxygen
and operation at a deposition rate and a substrate temperature that prevents
the formation of an oxide. Silicon can be used for SWIR lms, but it is difficult
to avoid the formation of a silicon oxide whose evaporation temperature is
much higher than that of the metal, and consequently produces spatter.

Semiconductor materials: Thin-lm photovoltaic solar cells using materials


alternative to silicon are being produced. Power-generating efficiency is
available that is competitive with that achieved by amorphous thin-lm
silicon. Thin-lm layers of direct bandgap semiconductors such as CdTe, CdS
and ZnS and multicompositions, Cu(In,Ga)Se2 (CIGS) and CuInSe2 (CIS) or
CuInSSe (CISS) are used to construct the absorber layers in PV cells on glass
or exible substrates. Multijunction cells can be constructed by varying the
bandgaps of the semiconductors to extend their spectral sensitivity.
Evaporation of CdS and ZnS layers is well established technology.
Coevaporation or sputtering is used to deposit the CIGS layer (for example).
Layers of PV CdS, ZnTe or CdTe can also be grown from a chemical bath in
another construction process. The transparent conducting layer is applied
over or under the absorber semiconducting layer within the stack that makes
up the cell, depending on its character, i.e., its donor function.

Transparent conducting oxides: Solar cells of all compositions and


constructions require a transparent conducting layer as one electrode.
Transparent conductors (TCO) are based on the addition to a transparent
oxide of a few percent of a cation or anion donor carrier that is responsible for
electrical conduction. A variety of TCO materials have been developed; ITO,
indium-doped tin oxide, has the longest history and widest application. ITO is
being replaced by compositions that are less expensive than indium-
containing material. Spray pyrolized SnO2 and SnO2:F are alternates to ITO
for solar cell electrodes, as are Cd2SnO4 and Zn2SnO4. Zinc oxide-based
formulations and reacted targets of these materials are receiving attention
currently. Al:doped ZnO (AZO) is among the TCOs being developed, along
with IZO (indium-doped) and GZO (gallium-doped). AZO is deposited by DC
sputtering from a target that contains 2 to 4 percent aluminum. Another
formulation is Al2O3:ZnO. AZO lms are more transparent than ITO lms, but
less conductive, and material costs are one-third to one-fth of those for ITO.
Lower conductivity is not an issue with transparent electrodes on solar cells.
Deposition on cold substrates and easier patterning procedures are further
advantages of AZO over ITO.

Sputtering materials: Sputter deposition has the advantages of


reproducibility of results and simple process automation. Optical lms can be
deposited from a metal target by oxidizing/nitriding sputtered metal ions to
deposit an oxide or nitride lm layer of the desired composition. DC
magnetron sputtering is the technique used with metal targets that are
electrically conducting. Oxide (insulating) targets can be sputtered by RF, but
the rate is lower. Many variations in the sputter technique have been
developed. Practically any material alloy, mixture, pure metal, ceramic,
oxide, nitride, boride, carbide, etc., can be supplied as a target. Fluorides
and suldes (selenides) are rarely traditionally sputtered because of the
hazardous nature of the components and difficulty in maintaining
composition.

Metals: Metal oxide and nitride compounds for optical applications can be
deposited by admitting the appropriate reactive gas to the sputtering plasma.
Similarly, metal carbide and boride compounds used in tribological coatings
can be sputter deposited. High deposition rates are achieved by DC
magnetron sputtering. Aluminum, gold and silver can be thermally or e-beam
evaporated.

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