Title of Invention

A SUBSTRATE COATED WITH AT LEAST ONE DIELECTRIC THIN-FILM LAYER

Abstract The invention relates to a substrate coated with at least one dielectric thin-film layer deposited by magnetically enhanced sputtering or reactive sputtering in the presence of oxygen and/or nitrogen, with exposure to at least one ion beam coming from an ion source, wherein said dielectric layer exposed to the ion beam is crystallized, wherein said dielectric layer has a crystallinity of greater than 90% and an RMS roughness of less than 1.5 nm.
Full Text The present invention relates to the field of dielectric-based thin-film coatings,
especially of the metal oxide, nitride or oxynitride type, which are deposited on
transparent substrates, especially glass substrates, using a vacuum deposition
technique.
The invention relates to a coated substrate, to a manufacturing process, to an
installation for manufacturing and for applying the substrate and/or the process for
producing glazing assemblies, especially double-glazing or laminated glazing
assemblies, comprising at least one substrate according to the invention.
For the purpose of manufacturing what are called " functional" glazing
assemblies, the usual practice is to deposit, on at least one of the substrates of which
they are composed, a thin-film layer or a thin-film multilayer, so as to give the glazing
assemblies optical (for example antireflection) properties, properties in the infrared
(low emissivity) and/or electrical conduction properties. Layers based on an oxide
and/or nitride dielectric are frequently used, for example on either side of a silver
layer or a doped metal oxide layer, or as an interferential layer in multilayers in which
low- and high-refractive index dielectrics alternate.
Layers deposited by sputtering are reputed to be somewhat less chemically
and mechanically resistant than layers deposited by pyrolithic deposition. Thus, the
experimental technique of ion-beam-assisted deposition has been developed in
which a layer is bombarded with an ion beam, for example an oxygen or argon ion
beam, which makes it possible to increase the density of the layer and its adhesion to
the carrier substrate. This technique has for a long time been applicable only to very
small sized substrates, owing to the problems posed in particular in terms of
convergence between, on the one hand, the ion beam coming from a very localized
source and, on the other hand, the particles resulting from the evaporation or
sputtering of the target.
Document EP 601 928 discloses a sequential treatment of the deposited layer,
by firstly depositing a layer in a sputtering chamber and then bombarding this
dielectric layer after it has been deposited with a " low energy" ion beam coming
from a point source, with an energy allowing the sputtering of the layer under the

impact of the ions of the beam to be limited, typically of less than 500 eV and around
one hundred eV.
This treatment is aimed essentially at increasing the physical and/or chemical
durability of the layer, by densification of the layer, and makes it possible to achieve a
lower surface roughness of the layer, favoring the subsequent" layering " of a layer
subsequently deposited on top of it.
However, this treatment has the drawback of only being able to be carried out
on a fully deposited layer.
Another drawback of this treatment is that it allows only densification of the
layer thus treated and this densification causes an increase in the refractive index of
the layer thus treated. The layers thus treated therefore cannot replace the untreated
layers, because of their different optical properties, and mean that the multilayer
systems, in which the material must be included, have to be completely redefined.
In addition, this treatment is not optimized for being carried out on a large
substrate, for example for the production of an architectural glazing assembly.
Furthermore, this process is not at all compatible with the sputtering process,
especially magnetically enhanced sputtering and preferably reactive sputtering in the
presence of oxygen and/or nitrogen, especially because of the very different working
pressures : at the time of this invention, the ion sources operated at pressures 10 to
100 times lower than the pressures used in the processes for sputtering, especially
magnetically enhanced sputtering and preferably reactive sputtering in the presence
of oxygen and/or nitrogen.
More recently, ion sources have been developed that are more compatible
with processes for depositing thin films by sputtering, in particular by solving the
problem of convergence of the particle beams and by improving the matching
between the size and the geometry, on the one hand, of the cathode and, on the
other hand, of the ion source. These systems, known as " linear sources", are
described for example in documents US 6 214 183 or US 6 454 910.
Document WO 02/46491 describes the use of a source of this type for
producing a functional silver oxide layer by sputtering using a silver target with
bombardment by an oxygen ion beam. The ion beam is used to densify the silver
material and convert it into a layer containing silver oxide. As a result of the
densification, the silver oxide layer is capable of absorbing and/or reflecting a
significant amount of the UV.

The object of the present invention is to remedy the drawbacks of the prior art
and to provide novel thin-film materials that can be used to coat transparent
substrates of the glass type, novel deposition processes and novel installations.
The invention relies on the fact that it is possible to deposit thin-film layers
made of a dielectric, especially an oxide and/or nitride, with exposure to an ion beam
by controlling the conditions so that the material of the final layer has a better degree
of crystallization, much greater than the degree of crystallization of the material
deposited conventionally, that is to say without subjecting the layer to at least one ion
beam.
In this regard, the subject of the invention is a substrate, especially a glass
substrate, as claimed in claim 1. The substrate according to the invention is coated
with at least one dielectric thin-film layer deposited by sputtering, especially
magnetically enhanced sputtering and preferably reactive sputtering in the presence
of oxygen and/or nitrogen, with exposure to at least one ion beam coming from an ion
source, and the deposited dielectric layer exposed to the ion beam is crystallized.
The term " crystallized" is understood to mean that at least 30% of the
constituent material of the dielectric layer exposed to the ion beam is crystallized and
that the size of the crystallites can be detected by X-ray diffraction, i.e. they have a
diameter of greater than a few nanometers.
The ion beam used to implement the present invention is what is called a
" high-energy" beam, typically having an energy ranging from around several
hundred eV to several thousand eV.
Advantageously, the parameters are controlled in such a way that the
dielectric layer deposited on the substrate by sputtering with exposure to the ion
beam has a very low roughness.
The term " very low roughness" is understood to mean that the dielectric layer
exposed to the ion beam has a roughness at least 20%, and preferably at least 50%,
less than that of the same dielectric layer not exposed to the ion beam.
The dielectric layer exposed to the ion beam may thus have a roughness of
less than 0.1 nm for a thickness of 10 nm.
Advantageously, the parameters may also be controlled in such a way that the
layer has an index very much less or very much greater than the index of a layer
deposited without an ion beam, but which may also be close to the index of a layer
deposited without an ion beam.

Within the meaning of the present description, the term " close" implies an
index that differs from the reference value by at most around 5%.
The invention also makes it possible to create an index gradient in the
deposited layer.
In a variant, said layer thus has an index gradient adjusted according to the
parameters of the ion source.
Advantageously, for at least some of the dielectric materials that can be
deposited, whatever the index modification produced, the density of the dielectric
layer deposited on the substrate by sputtering with exposure to the ion beam may be
maintained with a similar or identical value.
Within the meaning of the present description, a " similar" density value differs
from the reference value by at most around 10%.
The invention applies in particular to the production of a dielectric layer made
of a metal oxide or silicon oxide, whether stoichiometric or nonstoichiometric, or
made of a metal nitride or oxynitride or silicon nitride or oxynitride.
In particular, the dielectric layer may be made of an oxide of at least one
element taken from silicon, zinc, tantalum, titanium, tin, aluminum, zirconium,
niobium, indium, cerium, and tungsten. Among mixed oxides that can be envisioned,
mention may in particular be made of indium tin oxide (ITO).
The layer may be obtained from a cathode made of a doped metal, that is to
say one containing a minor element: as an illustration, it is common practice to use
cathodes made of zinc containing a minor proportion of another metal, such as
aluminum or gallium. In the present description, the term " zinc oxide " is understood
to mean a zinc oxide possibly containing a minor proportion of another metal. The
same applies to the other oxides mentioned.
For example, a zinc oxide layer deposited according to the invention may have
a degree of crystallinity of greater than 90% and especially greater Jiari_9§%_ajid an
RMS roughness of less than 1.5 nm and especially around 1 nm.
This zinc oxide layer deposited according to the invention may have a
refractive index that can be adjusted to a value of less than or equal to 1.95,
especially around 1.35 to 1.95. Its density may be maintained at a value close to
5.3 g/cm3 and especially at a value of around 5.3± 0.2 g/cm3, identical to the density
of a ZnO layer deposited at low pressure, which is around 5.3 g/cm3 .
Zinc oxide layers having a refractive index adjusted to a value of less than
1.88 and similar to this value may be obtained by setting the sputtering conditions

(especially the oxygen content of the atmosphere) so as to deviate slightly from the
stoichiometry of the intended oxide so as to compensate for the impact of the ion
bombardment.
The dielectric layer may also be made of silicon nitride or oxynitride. Such
nitride dielectric layers may be obtained by setting the sputtering conditions
(especially the nitrogen content of the atmosphere) so as to deviate slightly from the
stoichiometry of the intended nitride, so as to compensate for the impact of the ion
bombardment.
In general, the ion beam has the effect of improving the mechanical properties
of the dielectric layer.
As a result of the ion bombardment, quantities of one or more bombarded
species are introduced into the layer, in a proportion that depends on the nature of
the gas mixture at the source and on the source/cathode/substrate configuration. As
an illustration, a layer deposited under bombardment by an argon ion beam may
include argon with a content of around 0.2 to 0.6 at%, especially about 0.45 at%.
Generating the ion beam via an ion source that uses soft iron cathodes or
cathodes of any other material, especially paramagnetic material, which are eroded
during the process, may be responsible for the presence of traces of iron in the
deposited layer. It has been confirmed that iron present with a content of less than
3 at% or less is acceptable as it does not degrade the properties, especially optical or
electrical properties, of the layer. Advantageously, the deposition parameters
(especially the substrate transport speed) are adjusted so as to have an iron content
of less than 1 at%.
By preserving the usual optical properties, it is very easy to incorporate the
dielectric layers thus obtained into multilayers known for manufacturing what are
called " functional" glazing assemblies, in particular using a silver-based metal
functional layer.
Specific multilayers may be designed that incorporate a dielectric of index
adjusted to a different value from the standard value.
Thus, the subject of the invention is a substrate coated with a multilayer in
which a silver layer is deposited on top of said dielectric layer exposed to the ion
beam. Another dielectric layer may then be deposited on top of this silver layer.
This configuration proves to be particularly advantageous when the lower
dielectric layer is based on zinc oxide and/or tin oxide as they give rise to particularly
well oriented growth of the silver layer on the oxide layer, with improved final

properties. It is known that the presence of a zinc oxide layer beneath the silver has
an appreciable influence on the quality of said silver layer. The formation of the silver
layer on the zinc oxide layer deposited according to the invention results in a quite
remarkable improvement.
In fact it is observed that the silver layer thus formed is better crystallized with
an increase of 15 to 40% in the crystalline phase (diffraction from (111) planes)
compared with the amorphous phase.
In this regard, the subject of the invention is also a process according to the

invention for improving the crystallization of a silver layer deposited on a dielectric
layer, especially on a dielectric layer based on zinc oxide, in which said dielectric
layer is deposited on the substrate by sputtering, especially magnetically enhanced
sputtering and preferably reactive sputtering in the presence of oxygen and/or
nitrogen, with exposure to at least one ion beam, preferably coming from a linear
source. According to this process, at least one functional layer, especially one based
on silver, is deposited on said dielectric layer and said functional layer undergoes a
crystallization step. The size of the crystallites of the silver layer can therefore be
increased by around 15 to 40%, especially 30 to 40% (diffraction from (111) planes).
This is manifested by a reduction in the resistivity of the silver (which is directly
related to the energy emissivity properties) or a reduction in the surface resistance
R□ by at least 10%, for the same silver thickness, with an R□ value of less than 6 Ω /
□, or even less than 2.1 Ω / □, especially around 1.9Ω/□.
These substrates are thus particularly advantageous for producing low-
emissivity or solar-controlled glazing assemblies, or else translucent elements with a
high electrical conductivity, such as the screens for electromagnetic shielding of
plasma display devices.
In these substrates, another dielectric layer may be placed on top of the silver
layer. It may be chosen based on the abovementioned oxides or nitrides or
oxynitrides. The other layer itself may or may not be deposited with exposure to an
ion beam.
The multilayer may include at least two silver layers or even three or four silver
layers.
Examples of multilayers that can be produced according to the invention
comprise the following sequences of layers :

... ZnO (i) / Ag/oxide such as ZnO ...
... Si3N4 / ZnO (i) / Ag / oxide such as ZnO ...
... Si3N4/ZnO (i) / Ag / Si3N4 / (optionally an oxide) ...
... Si3N4 / ZnO (i) / Ag / Si3N4/ ZnO (i)/ Ag / Si3N4 ...
... Si3N4 / ZnO (i) / Ag / Si3N4 / ZnO (i)/ Ag / Si3N4 / (oxide)...
where (i) indicates that the layer is exposed to the ion beam and where a blocking
metal layer may be inserted above and/or below at least one silver layer.
The substrate used could also be made of a plastic, especially a transparent
plastic.
The subject of the invention is also a process for manufacturing a substrate as
described above, i.e. a process for depositing a multilayer, in which at least one
dielectric layer is deposited on the substrate by sputtering, especially magnetically
enhanced sputtering and preferably reactive sputtering in the presence of oxygen
and/or nitrogen, in a sputtering chamber, with exposure to at least one ion beam
coming from an ion source. In the process according to the invention, the ion beam is
created from a linear source and the refractive index of said dielectric layer exposed
to the ion beam may be adjusted according to the parameters of the ion source.
The refractive index of the dielectric layer exposed to the ion beam may be
decreased or increased relative to the index of this layer deposited without an ion
beam.
Advantageously, for at least some of the dielectric materials to be deposited,
whatever the index modification produced, the density of the dielectric layer
deposited on the substrate by sputtering with exposure to the ion beam is
maintained.
Exposure to the ion beam takes place in the sputtering chamber
simultaneously with and/or sequentially after the deposition of the layer by sputtering.
The expression " simultaneously with" is understood to mean that the
constituent material of the dielectric thin-film layer is subjected to the effects of the
ion beam while it is yet to be completely deposited, that is to say that it has not yet
reached its final thickness.
The term " sequentially after" is understood to mean that the constituent
material of the dielectric thin-film layer is subjected to the effects of the ion beam
when the layer has been completely deposited, that is to say after it has reached its
final thickness.

In the variant with exposure simultaneously with deposition, the position of the
ion source(s) is preferably optimized so that the maximum density of sputtered
particles coming from the target is juxtaposed with the ion beam(s).
Preferably, to produce an oxide-based dielectric layer, an oxygen ion beam is
created with an atmosphere containing very largely oxygen, especially 100% oxygen,
at the ion source, whereas the atmosphere at the sputtering cathode is preferably
composed of 100% argon.
In this variant, exposure to the ion beam takes place simultaneously with the
deposition of the layer by sputtering. For this purpose, it is unnecessary to limit the
ion energy as in the prior art; on the contrary, an ion beam with an energy between
200 and 2000 eV or even between 500 and 5000 eV, especially between 500 and
3000 eV, is advantageously created.
The ion beam may be directed onto the substrate and/or onto the sputtering
cathode, especially along a direction or at a non-zero angle with the surface of the
substrate and/or of the cathode respectively, such that the ion beam juxtaposes with
the flux of neutral species ejected from the target by sputtering.
This angle may be around 10 to 80° relative to the normal to the substrate,
measured for example vertically in line with the center of the cathode, and vertically
in line with the axis of the cathode when it is cylindrical.
In the case of direct flux on the target, the ion beam coming from the source
juxtaposes with the " racetrack " of the target created by the sputtering, that is to say
the centers of the two beams, coming from the cathode and from the ion source
respectively, meet at the surface of the substrate.
Advantageously, the ion beam may also be used outside the racetrack and
directed toward the cathode, in order to increase the degree of use of the target
(ablation). The ion beam can therefore be directed onto the sputtering cathode at an
angle of ± 10 to 80° relative to the normal to the substrate passing through the center
of the cathode, and especially through the axis of the cathode when it is cylindrical.
The source/substrate distance, in a sequential or simultaneous configuration,
is from 5 to 25 cm, preferably 10 ± 5 cm.
The ion source may be positioned before or after the sputtering cathode along
the direction in which the substrate runs (i.e. the angle between the ion source and
the cathode or the substrate is respectively negative or positive relative to the normal
to the substrate passing through the center of the cathode).

In a variant of the invention, an ion beam is created in the sputtering chamber
using a linear ion source simultaneously with the deposition of the layer by sputtering,
and then the deposited layer undergoes an additional treatment with at least one
other ion beam.
The present invention will be more clearly understood on reading the
detailed description below of illustrative but non-limiting examples and from figure 1
appended hereto, which illustrates a longitudinal sectional view of an installation
according to the invention.
To manufacture " functional" glazing assemblies (solar-controlled glazing,
low-emissivity glazing, heated windows, etc.), it is usual practice to deposit a thin-film
multilayer comprising at least one functional layer on a substrate.
When this functional layer (or these functional layers) is (or are) especially
based on silver, it is necessary to deposit a silver layer (thickness between 8 and
15 nm) whose normal emissivity and/or electronic resistivity are minimal.
To do this, it is known that the silver layer must be deposited on an oxide
sublayer which is :
(i) made of perfectly crystallized zinc (wurtzite phase) with a preferred
orientation formed by the basal planes ((0002) planes) parallel to the substrate ; and
(ii) perfectly smooth (minimal roughness).
The current technical solutions for depositing the zinc oxide do not allow
both these characteristics to be obtained.
For example:
- the solutions for crystallizing zinc oxide (by heating the substrate,
increasing the cathode power, increasing the thickness and increasing the oxygen
content) result in an increase in the roughness of the layer, which leads to an
appreciable degradation in the performance of the silver layer deposited on top ; and
- the solutions for depositing a zinc oxide which is smooth or has a low
roughness (low-pressure deposition, deposition on a very small thickness) result in
partial amorphization of the silver layer, which impairs the quality of the
heteroepitaxial growth of the silver on the ZnO.
Within the context of the invention, it has been observed, surprisingly, that
the deposition in particular of zinc oxide, but also of many other dielectrics, assisted
by an ion beam coming from a linear source makes it possible, under certain
conditions, to deposit a highly crystallized layer with an extremely low roughness.
This considerably improves the quality of the epitaxially grown silver layer on the

subjacent dielectric and therefore both the optical and mechanical properties of the
multilayers.
Control Example 1
In this example, a zinc oxide layer 40 nm in thickness was applied to a glass
substrate using an installation (10) illustrated in figure 1.
The deposition installation comprised a vacuum sputtering chamber (2)
through which the substrate (1) ran along conveying means (not illustrated here),
along the direction and in the sense illustrated by the arrow F.
The installation (2) included a magnetically enhanced sputtering system (5).
This system comprised at least one cylindrical rotating cathode (but it could also have
been a flat cathode), extending approximately over the entire width of the substrate,
the axis of the cathode being placed approximately parallel to the substrate. This
sputtering system (5) was placed at a height H5 of 265 mm above the substrate.
The material extracted from the cathode of the sputtering system was directed
onto the substrate approximately as a beam (6).
The installation (2) also included a linear ion source (4) emitting an ion
beam (3), which also extended approximately over the entire width of the substrate.
This linear ion source (4) was positioned at a distance L4 of 170 mm from the
cathode axis, in front of the cathode with regard to the direction in which the
substrate runs, at a height H4 of 120 mm above the substrate.
The ion beam (3) was directed at an angle A relative to the vertical to the
substrate passing through the axis of the cathode.
This deposition was carried out using a known sputtering technique on the
substrate (1) running through a sputtering chamber (2) past a rotating cathode,
based on Zn containing about 2% by weight of aluminum in an atmosphere
containing argon and oxygen. The run speed was at least 1 m/min.
The deposition conditions given in Table 1a below were adapted so as to
create a slightly substoichiometric zinc oxide layer with an index of 1.88 (whereas a
stoichiometric ZnO layer has an index of 1.93 - 1.95).
This layer was analyzed by X-ray reflectometry in order to determine its
density and thickness, and by X-ray diffraction in order to determine its crystallinity.
The spectrum revealed a peak at 29 = 34° typical of (0002) ZnO. The size of the

crystallites was deduced from the diffraction spectrum using the conventional
Scherrer formula and using the fundamental parameters.
The light transmission through the substrate, the light reflection from the
substrate and the resistance per square were also measured. The measured values
are given in Table 1b below.
Example 1
In this example, a zinc oxide layer 40 nm in thickness was applied according to
the invention to a glass substrate.
This deposition was carried out by sputtering onto the substrate, which ran
through the same sputtering chamber as in Control Example 1, in an atmosphere at
the sputtering cathode containing only argon. A linear ion source placed in the
sputtering chamber was used to create, simultaneously with the sputtering, an ion
beam using an atmosphere at the source composed of 100% oxygen. The source
was inclined so as to direct the beam onto the substrate at an angle of 30°.
The modified deposition conditions made it possible to produce a zinc oxide
layer having an index of 1.88, the density of which was identical to that of the control
material.
The optical properties were barely affected by exposure to the ion beam.
The X-ray diffraction spectrum revealed a very intense ZnO (0002) peak
showing, for constant ZnO thickness, an increase in the amount of ZnO that
crystallized and/or a more pronounced orientation.
An iron constant of less than 1 at% was measured by SIMS.
Rutherford backscattering spectroscopy measurements showed that the ZnO
layer contained 0.45 at% argon.



Example 2
In this example, a glass substrate was coated with the following multilayer:
10 nm ZnO /19.5 nm Ag /10 nm ZnO,
where the lower zinc oxide layer was obtained as in Example 1 with exposure to an
ion beam.
As in Example 1, the lower layer was produced by adapting the residence time
of the substrate in the chamber in order to reduce the thickness of the oxide layer to
10 nm.
The substrate was then made to run past a silver cathode in an atmosphere
composed of 100% argon and then once again past a zinc cathode in an
argon/oxygen atmosphere under the conditions of Control Example 1.
This multilayer was analyzed by X-ray diffraction in order to determine its state
of crystallization. The spectrum revealed a peak at 29 = 34° typical of ZnO, and a
peak at 29 = 38° typical of silver. The size of the silver crystallites was determined
from the diffraction spectrum using the conventional Scherrer formula and using the
fundamental parameters.
The light transmission through the substrate, the light reflection from the
substrate and the surface resistance were also measured.
The results are given in Table 2 below.
These properties are compared with those of a Control Example 2 in which the
lower zinc oxide layer was produced without exposure to the ion beam.
The comparison reveals that the crystallization of the silver layer is
considerably improved when the subjacent zinc oxide layer is produced with
exposure to the ion beam, this being manifested by a lower surface resistance, i.e. an
improved conductivity.


Control Example 3
In this example, the following multilayer was produced on a glass substrate :

in which the lower zinc oxide layer was obtained as in Example 1 with exposure to an
ion beam.
The zinc oxide layer was produced as in Example 1 by adapting the residence
time of the substrate in the chamber in order to reduce the thickness of the oxide
layer to 8 nm.
Next, the substrate was made to run past a silver cathode in an atmosphere
composed of 100% argon.
The optical and performance properties of Control Example 3 as single glazing
(SG) and as double glazing (4/15/4 DG with the internal cavity composed of 90% Ar)
are given in Table 3 below.
Example 3
The same deposition conditions as those of Control Example 3 were used,
except that a linear ion source was placed in the sputtering chamber and was used to
create, simultaneously with the sputtering, an ion beam during production of the zinc-
oxide-based layer, with an atmosphere at the source composed of 100% oxygen.
The source was inclined so as to direct the beam onto the substrate at an angle of
30° and was positioned at a distance of about 14 cm from the substrate.
These modified deposition conditions made it possible to produce a zinc oxide
layer having an index substantially identical to that of the control layer.
The optical and performance properties of Example 3 as single glazing (SG)
and as double glazing (4/15/4 DG, the internal cavity of which was composed of 90%
Ar) are also given in Table 3 below.


As may be seen, the optical properties are barely affected by exposure to the
ion beam, but the thermal properties are substantially improved, since a gain of 10%
is obtained in terms of resistance per square (R) and in normal emissivity (en).
Control Example 4
A multilayer having the following layer thickness (in nanometers) was
produced on a glass substrate, corresponding to the multilayer sold by Saint-Gobain
Glass France under the brand name PLANISTAR :

The optical and performance properties of Control Example 4 as double
glazing (4/15/4, with the internal cavity composed of 90 % Ar) are given in Table 4
below.
Example 4
A multilayer having the same thicknesses as Control Example 4 was produced
under the same conditions as those of Control Example 4, except that a linear ion
source was placed in the sputtering chamber and used to create, simultaneously with
the sputtering, an ion beam during production of each zinc-oxide-based layer directly
subjacent to each silver-based functional layer.
The atmosphere at the source was composed of 100% oxygen. The source
was inclined so as to direct the beam onto the substrate at an angle of 30° and was
positioned at a distance of about 14 cm from the substrate. The energy of the ion
beam was, for each pass, around 1000 eV. The pressure inside the chamber was 0.1
ubar during the first pass and 4.3 ubar during the second pass, for a target power of
5.5 kW during the first pass and 10 kW during the second pass.

These modified deposition conditions made it possible to produce a zinc oxide
layer having an index substantially identical to that of the control layer.
The optical and performance properties of Example 4 as double glazing
(4/15/4 the internal cavity of which was composed of 90 % Ar) are also given in Table
4 below.
As may be seen, the optical properties are barely affected by exposure to the
ion beam, but the thermal properties are greatly improved, since again a gain of
about 10% is obtained in terms of resistance per square (R).

Example 5
The following multilayer was deposited : glass/Si3N4/ZnO (25 nm)/Ag (9 nm)
and then the crystallographic characteristics of the zinc oxide and the electrical
properties of the silver layer were measured. In addition, the RMS roughness of a
ZnO(25 nm) glass not coated with silver and produced under the same conditions as
previously was evaluated. The angle of inclination A of the ion source relative to the
substrate was 30°. The measured values are given in Table 5 below.


It may therefore be observed, surprisingly, that deposition of ZnO assisted by
an ion beam makes it possible in the above multilayer to reduce the roughness of the
layer thus deposited.
Example 6
TiO2 monolayers were deposited on the glass with and without assistance by
an ion source and then the roughness was measured by simulation of the optical
properties (dispersion relationship) and by X-ray reflectometry. The angle of
inclination A of the ion source relative to the substrate was 20°. The measured values
are given in Table 6 below.

The present invention has been described in the foregoing by way of example.
Of course, a person skilled in the art would be capable of producing various
alternative embodiments of the invention without thereby departing from the scope of
the patent as defined by the claims.

WE CLAIM
1. A substrate coated with at least one dielectric thin-film layer deposited by
magnetically enhanced sputtering or reactive sputtering in the presence of
oxygen and/or nitrogen, with exposure to at least one ion beam coming
from an ion source, wherein said dielectric layer exposed to the ion beam
is crystallized, wherein said dielectric layer has a crystallinity of greater
than 90% and an RMS roughness of less than 1.5 nm.
2. The substrate as claimed in claim 1, wherein said dielectric layer
deposited on the substrate by sputtering with exposure to the ion beam
has an RMS roughness of less than 1 nm.
3. The substrate as claimed in claim 1, wherein the dielectric layer exposed
to the ion beam has a roughness at least 20% less than that of the same
dielectric layer not exposed to the ion beam.
4. The substrate as claimed in claim 1, wherein said dielectric layer
comprises a metal oxide or silicon oxide, which may be stoichiometric or
nonstoichiometric, or comprises a metal nitride or oxynitride or silicon
nitride or oxynitride.
5. The substrate as claimed in claim 1, wherein said dielectric layer
comprises an oxide of at least one element selected from the group
consisting of silicon, zinc, tantalum, titanium, tin, aluminum, zirconium,
niobium, indium, cerium, and tungsten.

6. The substrate as claimed in claim 5, wherein the layer comprises zinc
oxide and has a refractive index of less than or equal to 1.95.
7. The substrate as claimed in claim 5, wherein the layer comprises zinc
oxide and has a degree of crystallinity of greater than 95%.
8. The substrate as claimed in claim 1, wherein said dielectric layer
comprises silicon nitride or oxynitride.
9. The substrate as claimed in claim 1, wherein said layer has an argon
content of around 0.2 to 0.6 at%.
10.The substrate as claimed in claim 1, wherein said layer has an iron
content of less than or equal to 3 at%.
11.The substrate as claimed in claim 1, wherein said substrate is coated with
a multilayer in which a silver layer is placed on top of said dielectric layer
exposed to the ion beam.
12.The substrate as claimed in claim 11, wherein another dielectric layer is
placed on top of the silver layer.
13.The substrate as claimed in claim 11, wherein the multiplayer includes at
least two silver layers.

14.The substrate as claimed in claim 11, wherein said substrate has a surface
resistance R of less than 6 Ω / □.
15.The substrate as claimed in claim 1, wherein the substrate is glass.
16.The substrate as claimed in claim 1, wherein said dielectric layer has a
crystallinity of greater than 95%.
17.The substrate as claimed in claim 16, wherein said dielectric layer has an
RMS roughness of less than 1 nm.
18.The substrate as claimed in claim 1, wherein the at least one ion beam
comes from a linear ion source.
19. A glazing assembly, in particular one of a double glazing assembly and a
laminated glazing assembly, comprising at least one substrate as claimed
in claim 1.


The invention relates to a substrate coated with at least one dielectric thin-film
layer deposited by magnetically enhanced sputtering or reactive sputtering in the
presence of oxygen and/or nitrogen, with exposure to at least one ion beam
coming from an ion source, wherein said dielectric layer exposed to the ion beam
is crystallized, wherein said dielectric layer has a crystallinity of greater than 90%
and an RMS roughness of less than 1.5 nm.

Documents:

02689-kolnp-2005-abstract.pdf

02689-kolnp-2005-claims.pdf

02689-kolnp-2005-description complete.pdf

02689-kolnp-2005-drawings.pdf

02689-kolnp-2005-form 1.pdf

02689-kolnp-2005-form 2.pdf

02689-kolnp-2005-form 3.pdf

02689-kolnp-2005-form 5.pdf

02689-kolnp-2005-international publication.pdf

2689-KOLNP-2005-ABSTRACT 1.1.pdf

2689-KOLNP-2005-AMANDED CLAIMS.pdf

2689-KOLNP-2005-CORRESPONDENCE 1.1.pdf

2689-kolnp-2005-correspondence.pdf

2689-kolnp-2005-correspondence1.2.pdf

2689-KOLNP-2005-DESCRIPTION (COMPLETE) 1.1.pdf

2689-KOLNP-2005-DRAWINGS.pdf

2689-KOLNP-2005-EXAMINATION REPORT REPLY RECIEVED.pdf

2689-kolnp-2005-examination report.pdf

2689-KOLNP-2005-FORM 1-1.1.pdf

2689-kolnp-2005-form 1.pdf

2689-kolnp-2005-form 18.1.pdf

2689-kolnp-2005-form 18.pdf

2689-KOLNP-2005-FORM 2-1.1.pdf

2689-KOLNP-2005-FORM 3-1.1.pdf

2689-kolnp-2005-form 3.2.pdf

2689-kolnp-2005-form 3.pdf

2689-kolnp-2005-form 5.1.pdf

2689-kolnp-2005-form 5.pdf

2689-KOLNP-2005-FORM-27.pdf

2689-kolnp-2005-gpa.pdf

2689-kolnp-2005-gpa1.1.pdf

2689-kolnp-2005-granted-abstract.pdf

2689-kolnp-2005-granted-claims.pdf

2689-kolnp-2005-granted-description (complete).pdf

2689-kolnp-2005-granted-drawings.pdf

2689-kolnp-2005-granted-form 1.pdf

2689-kolnp-2005-granted-form 2.pdf

2689-kolnp-2005-granted-specification.pdf

2689-kolnp-2005-intenational publication.pdf

2689-kolnp-2005-international preliminary examinary report.pdf

2689-kolnp-2005-international search report.pdf

2689-KOLNP-2005-OTHERS.pdf

2689-kolnp-2005-others1.1.pdf

2689-kolnp-2005-pct request form.pdf

2689-KOLNP-2005-PETITON UNDER RULE 137.pdf

2689-kolnp-2005-reply to examination report.pdf

2689-KOLNP-2005-TRANSLATED COPY OF PRIORITY DOCUMENT.pdf

abstract-02689-kolnp-2005.jpg


Patent Number 248711
Indian Patent Application Number 2689/KOLNP/2005
PG Journal Number 32/2011
Publication Date 12-Aug-2011
Grant Date 09-Aug-2011
Date of Filing 23-Dec-2005
Name of Patentee SAINT-GOBAIN GLASS FRANCE
Applicant Address "LES MIROIRS"-18 AVENUE D’ALSACE, F-92400 COURBEVOIE
Inventors:
# Inventor's Name Inventor's Address
1 FISCHER, KLAUS ADOLFKOLPING STRASSE 10 D-52477 ALSDORF
2 BAUBET, CAROLE BOXGRABEN 24-26, D-52064 AACHEN
3 HOFRICHTER, ALFRED RETHELSTRASSE 1, D-52062 AACHEN
4 LOERGEN, MARCUS BLEIBTREUSTRASSE 16 D-10623 BERLIN
5 GIRON, JEAN-CHRISTOPHE VAALSER STRASSE 136 D-52074 AACHEN
6 NADAUD, NICOLAS 63, AVENUE PASTEUR, F-94250 GENTILLY
7 MATITMAN, ERIC 20 RUE OUDRY, F-75013 PARIS
8 ROUSSEAU, JEAN-PAUL 26, RUE DE 1'EST, F-92100 BOULOGNE
9 JANSEN, MANFRED WIELANDSTRASSE 35, D-52511 GEILENKIRCHEN
PCT International Classification Number C03C 17/00
PCT International Application Number PCT/FR04/001651
PCT International Filing date 2004-06-28
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 03/07847 2003-06-27 France