Title of Invention

ELECTRODE FOR ELECTROCHEMICAL/ELECTROCONTROLLABLE DEVICES

Abstract An electrochemical/electrocontrollable device having variable optical and/or energetic properties, comprising at least one carrier substrate provided with an electroactive layer or an electroactive layer stack arranged between a so-called "lower" electrode and a so-called "upper" electrode, characterized in that at least one of the lower or upper electrodes comprises at least four layers including at least one metal functional layer having intrinsic electrical conductivity properties, said functional layer being associated with an electrochemical barrier layer of an electrically conductive material which is transparent in the visible range, said electrochemical barrier layer being associated with a humidity protection layer of an electrically conductive material which is transparent in the visible range and said functional layer being associated with a first sublayer of electrically conductive material which is transparent in the visible range.
Full Text ELECTRODE FOR ELECTROCHEMICAL/ELECTROCONTROLLABLE
DEVICES
The present invention relates to an electrochemical
and/or electrocontrollable device of the glazing type
which has variable optical and/or energetic properties,
or a photovoltaic device, or alternatively an
electroluminescent device.
Specifically, there is nowadays an increased demand for
so-called "intelligent" glazing which can adapt to the
users' requirements.
There is also an increased demand for photovoltaic
glazing, which makes it possible to convert solar
energy into electrical energy, as well as for
electroluminescent glazing which has advantageous
applications in display equipment and as surfaces for
illumination.
As regards "intelligent" glazing, this may involve
controlling the delivery of sunlight through glazing
fitted on the exterior of buildings or vehicles such as
automobiles, trains or aircraft. The purpose is to be
able to limit excessive heating inside the
cockpits/rooms, but only in case of strong sunshine.
It may also involve controlling the degree of vision
through glazing, particularly in order to darken it,
render it diffusing or prevent any vision when so
desired. This may relate to glazing fitted in rooms,
trains, aircraft or fitted as automobile side windows.
It also relates to the mirrors used as wing mirrors in
order to avoid the driver being suddenly dazzled, or
signaling panels so that messages appear when this is
necessary or intermittently in order to attract more
attention. Glazing which can be rendered diffusing at
will may be used when so desired, for instance in
projection screens.

- 2 -
As a variant, it may involve generating light by the
glazing in order to control the level of luminosity or
the color generated.
There are various electrocontrollable systems allowing
these types of aspect/thermal property modifications.
In order to modulate the light transmission or light
absorption by glazing, there are so-called viologen
systems such as those described in Patents US-5 239 406
and EP-612 826.
In order to modulate the light transmission and/or
thermal transmission of glazing, there are also so-
called electrochromic systems. As is known, these
generally comprise two electrochromic material layers
separated by an electrolyte layer and framed by .two
electrically conductive layers. Each of these
electrochromic material layers can reversibly insert
cations and electrons, the modification of their
oxidation state due to these insertions/deinsertions
leading to a change in its optical and/or thermal
properties. In particular, their absorption and/or
their reflection at visible and/or infrared wavelengths
can be modified.
It is customary to divide electrochromic systems into
three categories:
that in which the electrolyte is in the form of a
polymer or a gel; for example, a polymer with protonic
conduction such as those described in Patents
EP-253 713 or EP-670 346, or a polymer with lithium ion
conduction such as those described in Patents
EP-382 623, EP-518 754 and EP-532 408; the other layers
of the system are generally of inorganic nature,

- 3 -
that in which the electrolyte is an essentially
inorganic layer. This category is often referred to by
the term "all solid" system, and examples of it can be
found in Patents EP-867 752, EP-831 360, Patents
WO.00/57243 and WO.00/71777,
that in which all the layers are based on polymers,
which category is often referred to by the term "all
polymer" system.
There are also systems referred to as "optical valves".
These are films comprising a polymer matrix, generally
crosslinked, in which micro-droplets are dispersed
containing particles which are capable of being placed
along a privileged direction under the action of a
magnetic or electric field. For instance, Patent
WO.93/09460 discloses an optical valve comprising a
polyorganosilane matrix and particles of the polyiodide
type which intercept the light much less when a voltage
is applied to the film.
So-called liquid crystal systems with a functionality
similar to the previous ones may also be mentioned.
These are based on the use of a film placed between two
conductive layers and based on a polymer in which
droplets of liquid crystals are arranged, in particular
nematic liquid crystals with a positive dielectric
anisotropy. When a voltage is applied to the film, the
liquid crystals become oriented along a privileged
axis, which allows vision. When there is no voltage,
without alignment of the crystals, the film becomes
diffusing and prevents vision. Examples of such films
are described particularly in European Patent
EP-0 238 164 and American Patents US-4 435 047,
US-4 806 922, US-4 732 456. When laminated and
incorporated between two glass substrates, this type of
film is marketed by Saint-Gobain Vitrage under the
brand name "Priva-Lite".

- 4 -
It is moreover possible to use all the liquid crystal
devices known by the terms "NCAP" (Nematic
Curvilinearly Aligned Phases) or "PDLC" (Polymer
Dispersed Liquid Crystal) .
It is also possible to use cholesteric liquid crystal
polymers, such as those described in . Patent
WO.92/19695.
As regards electroluminescent systems, these comprise
an organic or inorganic electroluminescent materia], or
material stack supplied with electricity by electrodes.
A common feature of all these systems together is the
need to be equipped with current feeds, which supply
electrodes generally in the form of two electrically
conductive layers on either side of the layer or
various active layer (s) of the system.
These electrically conductive layers (which may in fact
be a stack of layers) commonly comprise a layer based
on indium oxide, generally tin-doped indium oxide
better known by the abbreviation ITO. They may also be
layers based on tin oxide doped for example with
antimony, or based on zinc oxide doped for example with
aluminum (or a mixture based on at least two of these
oxides).
Document WO93/05438, for example, discloses an
electrically conductive layer consisting of a thin
metal layer based in particular on silver, copper,
aluminum, which is associated with a layer based on a
metallic blocker such as, for example, iron, zirconium,
titanium, tungsten. This stack of the TCO type
(transparent conductive oxide) is intended to be
integrated in an electrochemical device of the
electrochromic type, inside which the metallic blocker
layer constitutes a barrier to diffusion of the Li+

- 5 -
ions between one of the active layers and the metal
layer.
Furthermore, W094/15247 discloses an electrically
conductive layer with a structure similar to that
previously described, which is supplemented with a
layer based on a transparent conductive oxide such as,
for example, zinc oxide or tin-doped indium oxide.
US5510173 and US5763063 moreover disclose a stack
structure with energetic control incorporating a layer
of silver or copper advantageously alloyed with a noble
metal, for which protection in respect of corrosion is
obtained by coating with a bilayer based on In2O3 and
ITO or ZnO2/In2O3 and ITO. In the case of using ZnO2,
application as an electrode is impossible owing to the
insulating character of this oxide.
Furthermore, Patent US6870656 describes a reflective
electrode structure incorporating a layer based on an
electrochemically stable alloy of silver and gold.
For every electrically conductive layer structure
described above, its electrochemical stability is
obtained only when this electrically conductive layer
is alloyed.
ITO layers have been studied in particular. They can be
easily deposited by magnetic field assisted cathodic
sputtering, either from an oxide target (unreactive
sputtering) or from a target based on indium and tin
(reactive sputtering in the presence of an oxidizing
agent such as oxygen). In order to present a sufficient
electrical conductivity for the application and in
order to be electrochemically robust, however, they
require the application of a heat treatment step in
situ or for finishing (often above 300°C).

- 6 -
It is an object of the invention to be able to obtain
an electrochemically robust assembly of electrically
conductive layers for constituting the electrodes of
electrochemical/electrocontrollable systems of the
types previously described (electrochromic,
photovoltaic, electroluminescent, etc.) it is a
further aim to achieve this object with less cost and
by avoiding the heat treatment steps, and without
radically changing the known configurations of
electrochromic systems which concern the invention. A
more general object is to develop superior electrodes
on an essentially transparent substrate (glass or
polymeric material).
The invention relates to an electrochemical/
electrocontrollable device having variable optical
and/or energetic properties, comprising at least one
carrier substrate provided with an electroactive layer
or an electraactiye layer stack arranged between a so-
called "lower" electrode and a so-called "upper"
electrode. According to the invention, at least one of
the lower or upper electrodes comprises at least four
layers including at least one metal functional, layer
having intrinsic electrical conductivity properties,
said functional layer being associated with an
electrochemical barrier layer of an electrically
conductive material which is transparent in the visible
range, said electrochemical barrier layer being
associated with a humidity protection layer of an
electrically conductive material which is transparent
in the visible range and said functional layer being
associated with a first sublayer of electrically
conductive material which is transparent in the visible
range.
Owing to this particular stack structure, a transparent
electrode exhibiting an electrochemical stability
compatible with electrocontrollable systems while
having properties of high electrical conductivity can

- 7 -
be obtained with less cost, and without resorting to a
thermal finishing treatment. It is moreover to be noted
that electrochemical systems with this type of stack
structure have similar characteristics on the lower
electrode and optionally on the upper electrode, in
terms of coloration speed and homogeneity, as those
using conventional electrodes of the prior art (main.'l y
based on indium oxide, optionally doped). It is
furthermore to be noted that the electrode obtained in
this way is electrically conductive both in its
thickness and over its surface.
In preferred embodiments of the invention, one and/or
other of the following provisions may optionally be
furthermore employed:
- the first sublayer is identical in nature to the
electrochemical barrier layer,
- the electrochemical barrier layer is based on zinc
oxide or a mixed oxide of zinc doped with another
metal selected from the following family of
metals: Al, Ga, B, Sc,
- the zinc oxide is of the ZnOx type with x less
than 1, preferably lying between 0.88 and 0.98, in
particular between 0.90 and 0.95,
- the functional layer is based on a pure material
selected from silver or Cu or Zn or Al or Au or
based on an alloy of this material containing in
particular Al, Pt, Cu, Zn, Cd, In, Bo, Si, Zr, Mo,
Ni, Li, Cr, Ga, Ge, Mg, Mn, Co, Sn, the humidity
barrier layer being based on indium oxide doped in
particular with tin, or tin oxide doped in
particular with antimony,
- the first sublayer is associated with a second
sublayer similar to the humidity barrier layer.

- 8 -
In the context of the invention, the term "lower"
electrode is intended to mean the electrode which lies
closer to the carrier substrate taken as a reference,
on which at least some of the active layers are
deposited (for example all the active layers in an "all
solid" electrochromic system). The "upper" electrode is
the one deposited on the other side, with respect to
the same reference substrate.
Advantageously, the upper and/or lower electrode
according to the invention has an electrical
resistivity of between 10.10-4 and 9.10-5 ohm. cm, which
makes its use as an electrode perfectly satisfactory.
Preferably, in particular in order to achieve this
level of resistivity, it has a total thickness of
between 160 and 320 nm.
The electrode remains transparent in these thickness
ranges, that is to say it exhibits low absorption of
light in the visible range. Nevertheless, it is not
unfeasible to have much thicker layers (particularly in
the case when the electroactive system of the
electrochromic type functions in reflection rather than
in transmission) or thinner layers (particularly when
they are associated with another type of conductive
layer, for example metallic, in the electrode).
As mentioned above, the invention may be applied to
various types of electrochemical or electrocontrollable
systems. It more particularly concerns electrochromic
systems, particularly "all solid" or "all solid on
polymer" or "all polymer" systems, or alternatively
liquid crystal or viologen systems, or even
electroluminescent systems.
The electrochromic systems or glazing to which the
invention may be applied are described in the patents

- 9 -
cited above. They may comprise at least one carrier
substrate and a stack of functional layers successively
comprising at least a first electrically conductive
layer, an electrochemically active layer capable of
reversibly inserting ions such as H+, Li+, OH
respectively of the anodic or cathodic electrochromic
material type, an electrolyte layer, a second
electrochemically active layer capable of reversibly
inserting ions such as H+, Li+, OH" respectively of.the
cathodic or anodic electrochromic material type, and a
second electrically conductive layer (the term "layer"
is to be understood as meaning a single layer or a
stack of a plurality of continuous or discontinuous
layers).
The invention also relates to the incorporation of the
electrochemical devices described in the preamble of
the present application in glazing, which functions in
reflection (mirror) or in transmission. The term
"glazing" is to be understood in the broad sense, and
covers any essentially transparent material made of
glass and/or polymeric material (such as polycarbonate
PC or polymethyl methacrylate PMMA). The carrier
substrates and/or counter-substrates, that is to say
the substrates framing the active system, may be rigid,
flexible or semi-flexible.
If the glazing functions in reflection, it may in
particular be used as an interior mirror or as a wing
mirror.
The invention also relates to the various applications
which may be found for these devices, glazing or
mirrors: this may involve making glazing for buildings,
particularly exterior glazing, interior partitions or
glazed doors. It may also involve windows, roofs or
interior partitions for means of transport such as
trains, aircraft, automobiles, boats. It may also
involve visualization or display screens such as

- 10 -
projection screens, television or computer screens,
touch-sensitive screens. They may also be used to make
spectacles or camera lenses, or alternatively to
protect solar panels. They may also be used as energy
storage devices of the battery, fuel cell type,
batteries and cells themselves.
The invention will now be described in more detail with
the aid of nonlimiting examples and figures:
- Figure 1: a schematic view in section of an
electrochromic cell using an electrode according
to the invention,
- Figure 2 illustrates for various configurations of
electrodes according to the invention their
electrochemical protection.
Figure 1 is deliberately very schematic and is not
necessarily to scale, in order to make it easier to
read: it represents a section of an "all • solid"
electrochromic device according to the teachings of the
invention, successively comprising:
- a substrate of clear silica-soda-lime glass 1 with
a thickness of 2.1 mm,
- a lower electrode 2 comprising a layer stack of
the ITO/ZnO:Al/Ag/ZnO:Al/ITO type with respective
thicknesses 15 to 20 nm for ITO/60 to 80 nm for
ZnO:Al/3 to 15 nm for silver/60 to 80- nm for
ZnO:Al/15 to 20 nm for ITO,

- an upper electrode 4 based on ITO or SnC>2:F,
- an electrochromic system 3 whose structure is
described below,

- 11 -
- a PU sheet 7 making it possible to laminate the
glass 1 with another glass 8 having the same
characteristics as the glass 1. Optionally, the
face of the glass 8 turned toward the PU sheet 7
is provided with a stack of thin layers having a
solar protection function. This stack may in
particular comprise two silver layers intercalated
with dielectric layers, in .a manner which is
known.
The electrochromic system 3 comprises:
- a first anodic electrochromic material layer EC1
of (hydrated) iridium oxide measuring 40 to 100 nm
or hydrated nickel oxide measuring 40 to 400 nm,
optionally alloyed with other metals (as a
variant, this layer may be replaced by an anodic
electrochromic material layer of nickel oxide
measuring 100 to 300 nm, optionally alloyed with
other metals),
- a layer of tungsten oxide measuring 100 nm,
- a second layer of hydrated tantalum oxide or
hydrated silicon oxide or hydrated zirconium oxide
measuring 100 nm, these last two layers forming a
layer with an electrolyte function EL,
- a second layer of cathodic electrochromic material
EC2 based on tungsten oxide WO3 measuring 370 nm.
All these layers were deposited by magnetic field
assisted cathodic sputtering.
The electrochromic device described above constitutes
Example 1.

- 12 -
Example 2 is given below; it is a structure known from
the prior art and for which both the lower and upper
electrodes are based on ITO or Sn02:F.
EXAMPLE 2 (comparative = standard EC)
The electrochromic glazing EC has an identical
composition to Example 1, except that
- the lower electrode 2 is based on ITO (tin-doped
indium oxide) measuring 500 nm, deposited hot
(350°C).
As a variant, the upper electrode comprises other
conductive elements: this may in particular involve
associating the electrode with a layer more conductive
than it, and/or with a plurality of conductive strips
or wires. Reference will be made to the cited Patent
WO00/57243 for more details about the implementation of
such multi-component electrodes. A preferred embodiment
of this type of electrode consists in a network of
conductive wires, encrusted on the surface of a polymer
sheet (which may then protect the active system and/or
allow lamination of the glass-type carrier substrate
with another glass in the case of fabricating
electroactive glazing, for example of the
electrochromic type), being applied onto the ITO layer.
Comparative tests were then carried out on the two
electrochromic cells of Examples 1 and 2.
The most reliable validation of the TCOs consists .in
carrying out a durability test of the electrochromic
cells by exposure to 80°C in the colored state. In this
context, the parameters representative of the
degradation of the glazing EC are the change in the
switching time (Vcom) and the contrast
(TLuncolored/TLuncolored).

- 13 -

Time (h) V com (s) Contrast
Example 2 (std EC) 0 6 6.5

1500 12 4.6
Example 1 0 5 7.1

1500 15 5
The table above indicates that the switching time
(Vcom) and the contrast experience a similar change on
the standard sample (with the 500 nm lower electrode of
hot ITO) and on the sample incorporating the multilayer
TCO. The use of the multilayer TCO is therefore
perfectly compatible with use in electrochromic
glazing.
Optical measurement

colored state uncolored state
Optical
measurement TL RL a* b* TL RL a* b*
Example 2
(std EC) 56.3 8.74 -3 8.5 8.6 9.49 -7 -16.2
Example 1 32.5 29.4 -7.1 8.5 4.6 2 6.6 -9.5 -11.8
The optical results show (for a TCO incorporating an Ag
layer with a thickness of 12 nm) a- loss of TL as well
as an increase in the reflection. This greater light
absorption is perfectly acceptable for the automobile
roof application, where the TL level expected by the
customer is at most 40%.
Other examples illustrating other embodiments of the
invention are given below.
Example 3
According to a variant of the invention forming the
subject matter of Example 3, it substantially repeats
the structure of the stack in Figure 1 except as

- 14 -
regards the nature of the lower electrode 2 and upper
electrode 4. Specifically, both of them comprise a
layer stack of the ITO/ZnO:Al/Ag/ZnO:Al/ITO type with
respective thicknesses 15 to 20 nm for ITO/60 to 80 nm
for ZnO:Al/3 to 15 nm for silver/60 to 80 nm for
ZnO:Al/15 to 20 nm for ITO. This configuration makes it
possible to obviate the wire network, the conduction of
the TCO being equivalent to that of the ITO + wire
assembly.
Other exemplary embodiments of the invention are given
below. The following table collates the electrical and
optical characteristics of different multilayer TCOs
complying with various applications.

Multiple layer Rsq Ttot
(nm) p(Q.cm) TL RL Abs
IT02o/ZnO:Al6o/Ag12/ZnO:Al6o/IT020 4.6 172 7.91 E-05 49.6 39.9 10.5
IT015/ZnO:Al6o/Ag12/ZnO:Al6o/IT015 5.3 162 8.58 E-05 54 31.9 14 .1
ITO20/ZnO:Al60/Ag6/ZnO:Al60/ITO20 14 168 2.3 E-04 65.3 25.4 9.3
IT020/ZnO:Al60/Ag3/ZnO:Al6o/IT02o 60 165 9.9 E-04 65.1 12.6 22.3
IT020/ZnO:Al13o/Ag3/ZnO:Al13o/IT02o 25 303 7.57 E-04 57.5 14.8 27.7
In the table above: Ttot: total thickness, p: effective
resistivity of the stack and Rsq. = p/Ttot in Q/square.
Furthermore, TL: light transmission in %, RL: light
reflection, Abs = 100-RL-TL.
The inventors have found that the electrochemical
protection of the barrier layer is determined by the
thickness of the electrochemical barrier layer. The
inventors have thus been able to determine that a
minimum thickness of 60 nm ZnO:Al is necessary in order
to protect the Ag. This is illustrated in Figure 2
where a TCO comprising 12 nm of Ag experiences an
oxidation cycle with the aid of a so-called "three
electrode" setup having a working electrode (TCO
studied), a reference electrode (saturated calomel

- 15 -
electrode) and a counter-electrode (glass -! 500 nm I TO)
which are immersed in an H3P04 liquid electrolyte
(orthophosphoric acid).
According to another alternative embodiment intended
particularly for use with an electrocontrollable system
of the electroluminescent type:
Distinction is made between a first family, in which
the organic electroluminescent material of the thin
layer consists of evaporated molecules (ODELs) such as,
for example, A1Q3 (tris(8-hydroxyquinone) aluminum),
DPVBi (4,4'-(diphenyl vinylene biphenyl)), DMQA
(dimethyl quinacridone) or DCM (4-(dicyanomethylene)-2-
methyl-6-(4-dimethylaminostyryl)-4H-pyran). In this
case, additional layers promoting the transport of
electrical carriers (holes and electrons) are
associated on each of the faces of the thin layer,
these additional layers respectively being referred to
as "HTL" and "ETL" for "hole transporting layer" and
"electron transporting layer". In order to improve the
injection of the holes into the HTL layer, it is
furthermore associated with a layer referred to as
"HIL" for "hole injection layer" consisting, for
example, of copper or zinc phthalocyanine,
A second family, in which the organic
electroluminescent material of the thin layer consists
of polymers (pLEDs) such as, for example, PPV for
poly(para-phenylene vinylene), PPP (poly(para-
phenylene)), DO-PPP (poly(2-decyloxy-l,4-phenylene)),
MEH-PPV (poly [2- (2'-ethylhexyloxy)-5-methoxy-l, 4-
phenylene vinylene]), CN-PPV (po1y[2,5-bis(hexyloxy)-
1, 4-phenylene-(1-cyanovinylene)]) or PDAFs
(poly(dialkylfluorenes)), the polymer layer likewise
being associated with a layer which promotes the
injection of holes (HIL), consisting for example of
PEDT/PSS (poly(3,4-ethylene-dioxythiophene)/poly (4-
styrene sulfonate)),

- 16 -
A third family, in which the inorganic electro-
luminescent material of the thin layer consists of a
thin layer of a luminophore, for example sulfides such
as for example ZnS:Mn or SrS:Ce or oxides such as
Zn2Si04:Mn, Zn2Ge04:Mn or Zn2Ga204:Mn. In this case, an
insulating layer made from a dielectric materia] ,
conventionally for example Si3N4, BaTi03 or Al203/Ti02,
is associated with each of the faces of the
electroluminescent thin layer,
A fourth family, in which the inorganic
electroluminescent layer consists of a thick layer of a
luminophore such as, for example, ZnS:Mn or ZnS:Cu,
this layer being associated with an insulating layer of
dielectric material, for example BaTi03, these layers
generally being produced by screen printing.
Whatever the type of electroluminescent system, organic
or inorganic, in thin or thick layers, the layer stack
comprising in particular the electroluminescent layer
is associated on either side of the insulating layers
HTL, ETL, HIL with two electrodes (a cathode and an
anode in the case of organic systems).
These electrodes are similar to those already envisaged
for electrocontrollable systems of the electrochromic
type as described above.
It may nevertheless be necessary to. render one of these
electrodes reflective and, to this end, the thickness
of the functional layer with electrical conductivity
properties is'increased. The thicknesses of each- of the
layers forming the stack for the two types of electrode
are given below:
Electrode El: 15 to 20 nm for ITO/60 to 80 nm for
ZnO:Al/6 to 12 nm for silver/60 to 80 nm for ZnO:Al/15
to 20 nm for ITO.

- 17 -
Electrode E2: 15 to 20 nm for ITO/60 to 80 nm for
ZnO:Al/40 nm minimum for silver/60 to 80 nm for
ZnO:Al/15 to 20 nm for ITO.
This electrode structure according to the invention is
integrated within a stack of the electroluminescent
type according to the following configuration:
El/(Si3N4 (300nm)/luminophore (500nm)/Si3N4 (300nm))/E2
The invention- also relates to the substrate provided
with at least one electrode of the type described
above, independently of the electrical/electrochemical
device in which it is incorporated or intended to be
incorporated, as well as the lower or upper electrode
per se.

- 18 -
Patent claims
1. An electrochemical/electrocontrollable device
having variable optical and/or energetic properties,
comprising at least one carrier substrate provided with
an electroactive layer or an electroactive layer stack
arranged between a so-called "lower" electrode and a
so-called "upper" electrode, characterized in that at
least one of the lower or upper electrodes comprises at
least four layers including at least one metal
functional layer having intrinsic electrical
conductivity properties, said functional layer being
associated with an electrochemical barrier layer of an
electrically conductive material which is transparent
in the visible range, said electrochemical barrier
layer being associated with a humidity protection layer
of an electrically conductive material which is
transparent in the visible range and said functional
layer being associated with a first sublayer of
electrically conductive material which is transparent
in the visible range, the functional layer being based
on a pure material selected from silver or Cu or Zn or
Al or Au.
2. The electrochemical device as claimed in claim
1, characterized in that the first sublayer is
identical in nature to the electrochemical barrier
layer.
3. The electrochemical device as claimed in claim
1 or claim 2, characterized in that the electrochemical
barrier layer, is based on zinc oxide or a mixed oxide
of zinc doped with another metal selected from the
following family of metals: Al, Ga, B, Sc.
4. The electrochemical device as claimed in any
one of the preceding claims, characterized in that the
zinc oxide is of the ZnOx type with x less than 1 ,

- 19 -
preferably lying between 0.88 and 0.98, in particular
between 0.90 and 0.95.
5. The electrochemical device as claimed in any
one of the preceding claims, characterized in that the
humidity barrier layer is based on indium oxide doped
in particular with tin, or tin oxide doped in
particular with antimony.
6. The electrochemical device as claimed in any
one of the preceding claims, characterized in that the
first sublayer is associated with a second sublayer
similar to the humidity barrier layer.
7. The device as claimed in any one of the
preceding claims, characterized in that besides the
layer based on doped indium oxide (5) , the upper
electrode (4) also comprises at least one other
electrically conductive layer and/or a plurality of
conductive strips or conductive wires (6).
8. The device as claimed in any one of the
preceding claims, characterized in that it is an
electrochromic system, in particular an "all solid"
electrochromic system or an "all. solid on polymer"
electrochromic system or an "all polymer"
electrochromic system, a liquid crystal system or a
viologen system, or an electroluminescent system.'
9. An electrode intended to be integrated within
the electrochemical device as claimed in any one of
claims 1 to 8, characterized in that it comprises a
layer stack of the ITO/ZnO:Al/Ag/ZnO:Al/ITO type.
10. The electrode as claimed in claim 9,
characterized in that the thickness of the silver layer
lies between 3 and 15 nm, preferably between 6 and 12
nm.

- 20 -
11. The electrode as claimed in claim 9,
characterized in that the thickness of the silver layer
lies between 30 and 50 nm.
12. The electrode as claimed in claim 9,
characterized in that the thickness of the ZnO layer
lies between 60 and 150 nm.
13. The electrode as claimed in claim 9,
characterized in that the thickness of the ITO layer
lies between 10 and 30 nm, preferably between 15 and 20
nm.
14. Glazing, characterized in that it incorporates
the device as claimed in one of claims 1 to 8.
15. A mirror, in particular wing mirror,
characterized in that it incorporates the device as
claimed in one of claims 1 to 8 with a functional layer
thickness of at least 40 nm.
16. Use of the device as claimed in one of claims 1
to 8 or the glazing as claimed in claim 14 to make
glazing for buildings, glazing fitted in interior
partitions or windows or roofs or fitted in means of
transport such as an aircraft, trains, automobiles,
boats, visualization/display screens such as computer
or television screens or projection screens, touch-
sensitive screens, for making spectacles or camera
lenses or solar panel protection, or surfaces for
illumination.
17. A method for obtaining the device as claimed in
one of claims 1 to 8, characterized in that at least
one of the layers forming the lower or upper electrode
is deposited by magnetic field assisted cathodic
sputtering, in particular at room temperature.


An electrochemical/electrocontrollable device having variable optical and/or energetic properties, comprising at least one carrier substrate provided with an electroactive layer or an electroactive layer stack arranged between a so-called "lower" electrode and a so-called "upper" electrode, characterized in that at least one of the lower or upper electrodes comprises at least four layers including at least one metal functional layer having intrinsic electrical conductivity properties, said functional layer being associated with an electrochemical barrier layer of an electrically conductive material which is transparent
in the visible range, said electrochemical barrier layer being associated with a humidity protection layer of an electrically conductive material which is transparent in the visible range and said functional layer being associated with a first sublayer of electrically conductive material which is transparent in the visible range.

Documents:

04543-kolnp-2007-abstract.pdf

04543-kolnp-2007-claims.pdf

04543-kolnp-2007-correspondence others.pdf

04543-kolnp-2007-description complete.pdf

04543-kolnp-2007-drawings.pdf

04543-kolnp-2007-form 1.pdf

04543-kolnp-2007-form 2.pdf

04543-kolnp-2007-form 3.pdf

04543-kolnp-2007-form 5.pdf

04543-kolnp-2007-gpa.pdf

04543-kolnp-2007-international publication.pdf

04543-kolnp-2007-international search report.pdf

04543-kolnp-2007-pct request form.pdf

4543-KOLNP-2007-(01-03-2013)-ABSTRACT.pdf

4543-KOLNP-2007-(01-03-2013)-ANNEXURE TO FORM-3.pdf

4543-KOLNP-2007-(01-03-2013)-CLAIMS.pdf

4543-KOLNP-2007-(01-03-2013)-CORRESPONDENCE.pdf

4543-KOLNP-2007-(01-03-2013)-DESCRIPTION (COMPLETE).pdf

4543-KOLNP-2007-(01-03-2013)-DRAWINGS.pdf

4543-KOLNP-2007-(01-03-2013)-FORM-1.pdf

4543-KOLNP-2007-(01-03-2013)-FORM-2.pdf

4543-KOLNP-2007-(01-03-2013)-OTHERS.pdf

4543-KOLNP-2007-CORRESPONDENCE OTHERS 1.2.pdf

4543-kolnp-2007-form-18.pdf

4543-KOLNP-2007-OTHERS 1.1.pdf

4543-KOLNP-2007-PRIORITY DOCUMENT.pdf


Patent Number 258765
Indian Patent Application Number 4543/KOLNP/2007
PG Journal Number 06/2014
Publication Date 07-Feb-2014
Grant Date 05-Feb-2014
Date of Filing 26-Nov-2007
Name of Patentee SAINT-GOBAIN GLASS FRANCE
Applicant Address 18 AVENUE D'ALSACE F-92400 COURBEVOIE
Inventors:
# Inventor's Name Inventor's Address
1 DUBRENAT, SAMUEL 174, BOULEVARD BERTHIER F-75017 PARIS
2 FANTON, XAVIER 38, BOULEVARD CHARLES FLOQUET, F-93600 AULNAY SOUS BOIS
3 VELENTIN, EMMANUEL 53, AVENUE GENERAL LECLERC, F-94420 LE PLESSIS TREVISE
PCT International Classification Number G02F 1/155
PCT International Application Number PCT/FR2006/050465
PCT International Filing date 2006-05-22
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 0551391 2005-05-27 France