Title of Invention

AN ELECTROCHEMICAL SYSTEM

Abstract Electrochromic system comprising at least one substrate of organic nature (S1, S2), at least one electronically conductive layer (2, 4), at least one layer of organic varnish (10) lying between the electronically conductive layer and the substrate, and at least one active layer, characterized in that it includes a barrier layer (11), based on silicon nitride, oxide or oxynitride, or based on aluminum nitride or oxide or oxynitride or on a mixture of at least two of these compounds, mixed Si/A1 nitrides or oxynitrides, in-terposed between the organic varnish layer and the electronically conductive layer.
Full Text

ELECTROCHEMICAL SYSTEM ON A PLASTIC
The present invention relates to the field of
electrochemical devices comprising at least one active
species, in particular to the field of electrochromic
devices. These electrochemical devices are used
especially for manufacturing glazing whose light and/or
energy transmission or light and/or energy reflection
can be modulated by means of an electric current.
Taking the particular example of electrochromic
systems, it will be recalled that these comprise, in a
known manner, at least one anodic-coloration or
cathodic-coloration species having two coloration
states corresponding to two oxidation states, one of
the states generally being transparent.
Many electrochromic systems are constructed on the
following "five-layer" model: TC1 / EC1 / EL / EC2 /
TC2, in which TC1 and TC2 are electronically conductive
materials, EC1 and EC2 are electrochromic materials
capable of reversibly and simultaneously inserting
cations and electrons, and EL is an electrolyte
material that is both an electronic insulator and an
ionic conductor. The electronic conductors are
connected to an external power supply and by applying a
suitable potential difference between the two
electronic conductors the color of the system can be
changed. Under the effect of the potential difference,
depending on the system considered, the oxidation
states are reversed or else the ions are extracted from
one electrochromic material and inserted into the other
electrochromic material, passing through the
electrolyte material. The electronic conductors and the
external power circuit which allow the transport of
electrons ensure electrical neutrality of the entire
system. The electrochromic system is generally
deposited on a support, which may or may not be
transparent, and organic or mineral in nature, which is
then called a substrate. In certain cases, two

substrates may be used - either each possesses part of
the electrochromic system and the complete system is
obtained by joining the two substrates together, or one
substrate has the entire electrochromic system and the
other one is designed to protect the system.
When the electrochromic system is intended to work in
transmission, the electroconductive materials are
generally transparent oxides, the electronic conduction
of which has been increased by doping, such as the
materials In2O3:Sn, In2O3:Sb, Zn0:Al or SnO2:F. Tin-doped
indium oxide (In2O3: Sn or ITO) is frequently chosen for
its high electronic conductivity properties and its low
light absorption. When the system is intended to work
in reflection, one of the electroconductive materials
may be of metallic type.
One of the electrochromic materials most used and most
studied is tungsten oxide, which switches from a blue
color to transparent depending on its charge insertion
state. This is a cathodic coloration electrochromic
material, that is to say its colored state corresponds
to the inserted (or reduced) state and its bleached
state corresponds to the extracted (or oxidized) state.
During construction of a five-layer electrochromic
system it is common practice to combine it with an
anodic coloration electrochromic material, such as
nickel oxide or iridium oxide, the coloration mechanism
of which is complementary. This results in an
enhancement in the light contrast of the system. It has
also been proposed to use a material that is optically
neutral in the oxidization states in question, such as
for example cerium oxide. All the abovementioned
materials are of inorganic type, but it is also
possible to combine organic materials, such as
viologens (bipyridium salts), 5,10-dihydrophenazines,
1,4-phenylenediamines, benzidines, metallocenes,
Prussian blues or electronically conductive polymers
(polythiophene, polypyrrole, polyaniline etc.) or

metallopolymers, with inorganic electrochromic
materials, or even to use only organic electrochromic
materials.
When a multilayer structure based essentially on
organic materials is used, the five-layer structure may
be simplified to a three-layer structure, namely
TC1/AC/TC2, within which the active "layer" AC is in
the form of a polymer matrix, a gel or a liquid. The
layer AC then comprises, in one of the same medium, all
the necessary electroactive materials, namely in
particular the anodic-coloration and cathodic-
coloration species and optionally ionic salts having an
electrolyte function, which are dissolved in a solvent
of the propylene carbonate type. Furthermore, the layer
AC may also contain one or more polymers and additives.
The interpenetrating network polymer systems described
in application FR 2 857 759 are also constructed on
this three-layer model. Moreover, simple systems
conventionally called "viologen" systems, in which
cathodic-coloration species, of the type comprising
bipyridinium salts (namely viologen materials) and
anodic-coloration species (for example phenazines) are
dissolved in a liquid or a gel based for example on
propylene carbonate are also three-layer systems.
Irrespective of the envisioned structure, provision is
made for these electrochemical systems to be deposited
on a substrate having an organic glass function,
conventionally based on PMMA (polymethyl methacrylate) ,
PC (polycarbonate) PET (polyethylene terephthalate),
PEN (polyethylene naphthoate) or COC (cycloolefin
copolymer).
Now, the deposition of the abovementioned
electrochemical structures on a substrate of
essentially organic nature poses a number of problems
which the present invention is intended to remedy.

Thus, the inventors have firstly noticed that
constituents of the composition of the abovementioned
layer AC, which have been deposited directly on a
surface portion of the substrate of organic nature,
could prematurely age the latter following chemical
etching. Moreover, the organic substrate does not
always allow the functionality of the layer AC.
Furthermore, the interaction with the substrate may
degrade the functionality of the layer AC.
The inventors have also made the following observation:
The layer TC1 or TC2, of essentially mineral nature,
which is necessary for the operation of the
electrochemical system to be all-solid or all-polymer
(it allows passage of the current needed to switch from
a colored state to a bleached state, or vice versa),
poses problems at the interface with the organic
substrate. This is because TC1 or TC2, generally based
on ITO albeit thick in order to obtain the required
resistivity (less than 5 ohms per square), requires
deposition at high temperature (several hundred degrees
Celsius) in order to improve its crystalinity. This is
possible when the substrate having a glass function is
inorganic (made of glass) but is very difficult to
envision when the substrate is organic.
The object of the present invention is to alleviate the
drawbacks by proposing a modification to the substrate
of organic nature in order to make it compatible with
an electrochemical multilayer stack structure.
For this purpose, the subject of the invention is an
electrochemical system comprising at least one
substrate of organic nature, at least one
electronically conductive layer and at least one active
species, characterized in that it includes at least one
organic layer lying between the electronically
conductive layer and the substrate, a barrier layer,

based on silicon nitride, oxide or oxynitride, or based
on aluminum nitride or oxide or oxynitride or on a
mixture of at least two of these compounds (mixed Si/Al
nitrides or oxynitrides) said barrier layer being
interposed between the varnish layer and the
electronically conductive layer.
By using a layer at the interface between the substrate
and the electronically conductive layer, it is possible
on the one hand, to improve the adhesion between the
substrate and the electronically conductive layer (by
compensating for the differences in stresses and in
expansion between the substrate and the electronically
conductive layer) and, on the other hand, to limit
chemical attack of the substrate by the components of
the AC system.
In other preferred embodiments of the invention, one or
more of the following arrangements may optionally also
be employed:
the substrate comprises PMMA;
the substrate is drawn PMMA;
the organic layer is a polysiloxane-based
varnish;
the organic layer has a thickness between
0.5 urn and 10 µm and preferably from 1 to 3 µm;
the electronically conductive layer is of the
metallic type or of the TCO (transparent conductive
oxide) type made of ITO, SnO2:F, ZnO:Al, or a
multilayer of the TCO/metal/TCO type, this metal being
chosen especially from silver, gold, platinum and
copper, or a multilayer of the NiCr/metal/NiCr type,
the metal also being chosen especially from silver,
gold, platinum and copper;
the barrier layer has a thickness of 50 nm to
500 nm and preferably 100 nm to 300 nm;
the three-layer system with the
electrochemically active central layer AC comprises in
one and the same medium, anodic-coloration and

cathodic-coloration electroactive materials, one or
more solvents, optionally one or more polymers and
optionally one or more ionic salts acting, if
necessary, as electrolyte;
the anodic-coloration species are organic
compounds such as phenazine derivatives, for example
5,10-dihydrophenazine, 1,4-phenylenediamine, benzidine,
metallocene, phenothiazine and carbazole;
the cathodic-coloration species are organic
compounds such as derivatives of viologen (a
bipyridinium salt) such as methyl viologen
tetrafluoroborates, octyl viologen tetrafluoroborates,
or quinone or polythiophene;
the solvents may be dimethyl sulfoxide, N,N-
dimethylformamide, propylene carbonate, ethylene
carbonate, N-methylpyrolidinone, y-butyrolactone, ionic
liquids, ethylene glycols, alcohols, ketones and
nitriles;
the polymers may be polyethers, polyesters,
polyamides, polyimides, polycarbonates,
polymethacrylates, polyacrylates, polyacetates,
polysilanes, polysiloxanes and celluloses;
the ionic salts are for example lithium
perchlorate, trifluoromethanesulfonate (triflate)
salts, trifluoromethanesulfonylimide salts, ammonium
salts or ionic liquids;
the layer AC has a thickness of 50 µm to 500 µm
and preferably 150 µm to 300 µm;
the active species is in the form of an
electrochemically active layer comprising at least one
of the following compounds: tungsten (W) oxide, niobium
(Nb) oxide, tin (Sn) oxide, bismuth (Bi) oxide,
vanadium (V) oxide, nickel (Ni) oxide, iridium (Ir)
oxide, antimony (Sb) oxide or tantalum (Ta) oxide, by
itself or as a mixture, and optionally including an
additional metal such as titanium, tantalum or rhenium;
and
the system further includes a layer having an
electrolytic function, chosen from silicon nitride

(Si3N4) , molybdenum oxide (MoO3) , tantalum oxide (Ta2O5) ,
antimony oxide (Sb2O5) , nickel oxide (NiOx) , tin oxide
(SnO2) , zirconium oxide (ZrO2) , aluminum oxide (A12O3) ,
silicon oxide (SiO2) , niobium oxide (Nb2O5) , chromium
oxide (Cr2O3) , cobalt oxide (Co3O4) , titanium oxide
(TiO2) , zinc oxide (ZnO) optionally alloyed with
aluminum, tin zinc oxide (SnZnOx), vanadium oxide
(V2O5) , at least one of these oxides being optionally
hydrogenated or nitrided.
Within the context of the invention, a simplified
configuration of the transparent substrate / TC1 /
layer AC / TC2 / transparent substrate type (three-
layer system) in which the material of the layer AC is
partitioned between two organic substrates may be used.
Moreover, in an "all-solid" (five-layer system)
configuration, the manufacture is simplified since it
is possible to deposit all of the layers of the system,
one after another, on a single carrier substrate.
Furthermore, the device is lightened since it is no
longer essential to have two carrier substrates. The
invention also relates to applications of the
electrochemical device relating to electrochromic
glazing. In this case, it is advantageous to provide
for the substrate or substrates of the device to be
transparent, made of plastic, when the glazing is
intended to operate in variable light transmission.
When the glazing is intended to operate in variable
light transmission, with a device provided with one or
two transparent substrates, it can be mounted as
multiple glazing, especially double glazing, with
another transparent substrate and/or laminated glazing.
Returning to the electrochromic glazing application,
the glazing may advantageously be employed as
architectural glazing, automotive glazing, glazing for
industrial/public transport vehicles, glazing for land
transport vehicles, for aircraft (particularly as

windows), river-going or sea-going craft, rear-view or
other mirrors, or as optical elements, such as camera
objectives, or else as the front face or element to be
placed on or near the front face of display screens for
computers or televisions.
The organic substrates are made of light or dark
plastic, of flat or curved shape, and are extremely
lightweight compared with inorganic glass substrates.
Their thickness may vary between 0.6 mm and 19 mm,
depending on the expectations and requirements of the
end users. The substrates may be partially coated with
an opaque material, in particular around the periphery,
especially for aesthetic reasons. The substrate may
also have a specific functionality (arising from a
stack of at least one layer of the solar-control,
antireflection, low-E, hydrophobic, hydrophilic or
other type), and in this case the electrochromic
glazing combines the functions provided by each element
so as to meet the requirements of the users.
A polymer interlayer is used here for the purpose of
joining together the two substrates using the
lamination procedure commonly used in the automobile or
building world so as to end up with a safety or comfort
product: anti-ejection or bulletproof safety for use in
the transport and anti-break-in field (shatterproof
glass) for use in the building field, or providing,
thanks to this lamination interlayer, an acoustic,
solar-protection or coloration functionality. The
lamination operation is also favorable in the sense
that it isolates the functional stack from chemical or
mechanical attack. The interlayer is preferably chosen
based on ethylene/vinyl acetate (EVA) or its
copolymers. It may also be made of polyurethane (PU) ,
polyvinyl butyral (PVB), a multi-component or single-
component resin that is thermally crosslinkable (epoxy
or PU) or UV-crosslinkable (epoxy or acrylic resin).
The lamination interlayer is generally transparent, but

it may be completely or partially colored in order to
meet the wishes of the users.
The isolation of the multilayer stack from the outside
is generally supplemented by systems of seals placed
along the edges of the substrates,or even partly
inside the substrates.
The lamination interlayer may also include additional
functions, such as the inclusion of a solar-protection
function provided for example by' a plastic film
comprising ITO/metal/ITO multilayers or a film composed
of a stack of organic layers.
The invention also relates to the process for
manufacturing the device according to the invention, in
which it is possible to deposit the layers of the
functional multilayer stack (TC1/EC1/EL/EC2/TC2) by a
vacuum technique, of the sputtering type, optionally
magnetron or magnetically enhanced sputtering, by
thermal evaporation or electron-beam evaporation, by
laser ablation, by CVD (Chemical Vapor Deposition),
optionally plasma-enhanced or microwave-enhanced CVD.
The active layer AC may be deposited by an atmospheric
pressure technique especially by the deposition of
layers by sol-gel synthesis, particularly dip coating,
spray coating or laminar flow coating. In the case of
simplified viologen-type systems, it may be
advantageous to use a system for injecting the AC
medium between the two substrates. The layers TC1 and
TC2 are deposited by a technique similar to that for
the five-layer stack structure.
In fact, it is particularly advantageous here to use a
vacuum deposition technique, especially of the
sputtering type, as it allows very fine control of the
characteristics of the layer constituting the
electrolyte (deposition rate, density, structure, etc.)

Further advantageous details and characteristics of the
invention will emerge from the description given below
with reference to the appended drawings which show:
figure 1 is a front view of the subject of the
invention;
figure 2 is a sectional view of AA of figure 1,
illustrating an embodiment of the invention employing
an electrochemical system of essentially inorganic
nature also called an "all-solid" system
(conventionally a five-layer system);
figure 3 is a sectional view of BB of figure 1,
illustrating an embodiment of the invention employing
an electrochemical system of essentially inorganic
nature;
figure 4 is a sectional view of AA of figure 1,
illustrating one embodiment of the invention employing
an electrochemical system of essentially organic
nature;
figure 5 is a sectional view of BB of figure 1,
illustrating one embodiment of the invention employing
an electrochemical system of essentially organic
nature;
figure 6a and 6b illustrate, respectively, an
image of the surface and a roughness curve obtained
(along the AA axis) of the bare PMMA on which no
solvent has been deposited;
figures 7a and 7b illustrate, respectively, a
surface image and a roughness curve obtained (along the
AA axis) of the bare PMMA on which a drop of propylene
carbonate has been deposited;
figures 8a and 8b illustrate, respectively, a
surface image and a roughness curve obtained (along the
AA axis) of the PMMA coated with an organic varnish on
which no solvent has been deposited; and
figures 9a and 9b illustrate, respectively, a
surface image and a roughness curve obtained (along the
AA axis) of the PMMA coated with an organic varnish on
which a drop of propylene carbonate has been deposited.

In the appended drawings, certain elements have been
shown on a larger or smaller scale than in reality, so
as to make the figures easier to understand.
The example illustrated by figures 1, 2 and 3 relates
to electrochromic glazing 1. It comprises in
succession, from the outside to the inside of the
passenger compartment, two plastic substrates S1, S2,
made of drawn PMMA, or made of PC or COC, for example
2.1 mm and 2.1 mm in thickness respectively.
The substrates S1 and S2 are of the same size and their
dimensions are 150 mm * 150 mm.
The substrate S1 shown in figures 2 and 3 includes, on
face 2, a thin-film multilayer stack of the all-solid
(five-layer) electrochromic type. The substrate S1 is
laminated to the substrate S2 via a thermoplastic sheet
F1 made of polyurethane (PU) of 0.8 mm thickness (it
may be replaced with a sheet of ethylene/vinyl acetate
(EVA) or polyvinyl butyral (PVB)).
It may be seen in the figures that the current
collector layers 2 and/or 4 (TC1 and/or TC2 layers for
example) are not in direct contact with the substrates
S1 and/or S2.
At least one organic layer 10 (visible in figures 2 and
3) is interposed between the substrate and the
electronically conductive layer, improving the adhesion
of the TC1 and/or TC2 layer to the substrate and
preventing the substrate from being chemically attacked
by the layer AC, which is of an organic nature, while
the electronically conductive layer is of essentially
mineral nature.
This organic layer 10 is a varnish based on
polysiloxanes. These polysiloxanes are prepared from

commercially available silanes (for example from Sigma-
Aldrich-Fluka) preferably from tetraethoxysilane
(TEOS), methyltrimethoxysilane (MTMS) or phenyl
trimethoxysilane (PMTS), with a thickness of between
0.5 µm and 10 urn, preferably 1 to 3 µm.
The organic layer 10 may also be covered with an
inorganic layer 11 (shown in figures 2 and 3, 4 and 5),
the layer 11 being for example Si3N4 if a barrier layer
is needed or an SiOx layer formed by PECVD (plasma-
enhanced chemical vapor deposition).
The electrochromic thin-film multilayer comprises an
active multilayer 3 placed between two electronically
conductive materials, also called current collectors 2
and 4. The collector 2 is intended to be in contact
with face 2.
The collectors 2 and 4 and the active multilayer 3 may
be either substantially of the same size and shape, or
substantially of different size and shape, and it will
be understood therefore that the path of the collectors
2 and 4 will be tailored according to the
configuration. Moreover, the dimensions of the
substrates, in particular S1, may be essentially
greater than those of 2, 4 and 3. The collectors 2
and/or 4 may also be in the form of a grid or network
of wires or the like.
The collectors 2 and 4 are of the metallic type or of
the TCO (Transparent Conductive Oxide) type made of
ITO, SnO2:F or ZnO:Al, or they may be a multilayer of
the TCO/metal/TCO type, this metal being selected in
particular from silver, gold, platinum and copper. They
may also be a multilayer of the NiCr/metal/NiCr type,
the metal again being selected in particular from
silver, gold, platinum and copper.

Depending on the configuration, they may be omitted,
and in this case current leads are directly in contact
with the active multilayer 3.
The glazing 1 incorporates current leads 8, 9 which
control the active system via a power supply. These
current leads are of the type used for heated windows
(namely shims, wires or the like).
A preferred embodiment of the collector 2 is one formed
by depositing, on face 2, a doped (especially aluminum-
doped or boron-doped) or undoped bilayer consisting of
a SiO2-based first layer about 20 nm in thickness
followed by an ITO second layer of about 100 to 600 nm
in thickness (the two layers preferably being deposited
in succession, in a vacuum, by reactive magnetron
sputtering in the presence of oxygen).
Another embodiment of the collector 2 is one formed by
depositing, on face 2, a monolayer consisting of ITO
about 100 to 600 nm in thickness (a layer preferably
deposited, in a vacuum, by reactive magnetron
sputtering in the presence of oxygen).
The collector 4 is a 100 to 500 nm ITO layer also
deposited by reactive magnetron sputtering on the
active multilayer.
The active multilayer 3 shown in figures 2 and 3 is
made up as follows:
• a 100 to 300 nm layer of anodic electrochromic
material made of nickel oxide, possibly alloyed with
other metals. As a variant (not shown in the figures),
the layer of anodic material is based on a 40 to 100 nm
layer of iridium oxide;
• a 100 nm layer of tungsten oxide;
• a 100 nm layer of hydrated tantalum oxide or
hydrated silica oxide or hydrated zirconium oxide, or a
mixture of these oxides; and

• a layer of cathodic electrochromic material based
on hydrated tungsten oxide with a thickness of 200 to
500 nm, preferably 300 to 400 nm, for example about
37 0 nm.
The active multilayer 3 may be incized over all or part
of its periphery with grooves produced by mechanical
means or by laser etching, possibly using a pulsed
laser. This is done so as to limit the peripheral
electrical leakage, as described in French application
FR-2 781 084.
The glazing unit shown in figures 1, 2 and 3 also
incorporates (but not shown in the figures) a first
peripheral seal in contact with faces 2 and 3, this
first seal being designed to form a barrier to external
chemical attack.
A second peripheral seal is in contact with the edge of
SI, the edge of S2 and face 4 so as to form: a barrier,
and a means of mounting with the transport means, to
provide a seal between the inside and the outside, to
form an attractive feature, and to form means for the
incorporation of reinforcing elements.
According to other alternative embodiments of the
invention, the "all-solid" active multilayer 3 may be
replaced with other families of polymer type
electrochromic materials.
In the configuration shown in figures 4 and 5, the
electrochromic system (with three or five layers) is
assembled directly between two substrates S1 and S2.
This is a configuration of the following type:
S1/organic layer (10)/inorganic layer (11)/TC1 (2)/
active medium (3)/ TC2(4)/ inorganic layer (11') /
organic layer (10')/ substrate S2.

The active medium 3 may consist of 3 polymer layers in
a first variant or a mixed multilayer stack consisting
of inorganic layers and polymers in a second variant,
or else a single medium consisting of viologens and
phenazines dissolved so as to have a typical
concentration of 3 ˟ 10-2M for example in propylene
carbonate, and in which a tetrabutylammonium
tetrafluoroborate salt may be added with a
concentration of 5 ˟ 10"2M in order to form the
electrolyte support.
These embodiments incorporate the same collectors 2 and
4 described above in the case of the all-solid-type
electrochemical systems.
However, they differ by the fact that they do not
require a lamination interlayer f1 for assembling the
organic substrates S1 and S2.
Thus, according to a first example illustrated in
figure 4, a first part formed from a layer of
electrochromic material, or otherwise called the active
layer, made of poly (3,4-ethylenedioxythiophene) from 10
to 10 000 nm, preferably 50 to 500 nm, in thickness on
a PET substrate coated with an ITO layer - as a
variant, it may be one of the derivatives of this
polymer - is deposited by known liquid deposition
techniques (spray coating, dip coating, spin coating or
flow coating) or else by electrodeposition, on a
substrate coated with its current collector, this
current collector possibly being a lower or upper
conducting layer forming the electrode (anode or
cathode) optionally provided with wires or the like.
Whatever the polymer constituting this active layer,
this polymer is particularly stable, especially under
UV, and operates by insertion/extraction of lithium
ions (Li+) or alternatively of H+ ions.

A second part acting as electrolyte, and formed from a
layer with a thickness of between 50 nm and 2000 µm,
and preferably between 50 nm and 1000 µm, is deposited
by a known liquid deposition technique (spray coating,
dip coating, spin coating or flow coating) between the
first and third parts on the first part, or else by
injection. This second part is based on a
polyoxyalkylene, especially polyoxyethylene. As a
variant, it may be a mineral-type electrolyte based for
example on hydrated tantalum oxide, zirconium oxide or
silicon oxide.
This second electrolyte part deposited on the layer of
active electrochromic material, which is itself
supported by the organic substrate, including its
organic varnish layer, is then coated with a third
part, the constitution of which is similar to the first
part, namely this third part is made up of a substrate,
coated with a current collector, this current collector
itself being covered with an active layer.
A second example corresponds to glazing operating by
proton transfer. This consists of:
• a first organic substrate S1 made of drawn
PMMA, for example 1, 4 mm in thickness; then
• a varnish layer 10;
• a first 300 nm TCO-type electronically
conductive layer 2;
• an 185 nm first layer of anodic
electrochromic material made of nickel oxide NiOxHy (it
could be replaced with a 55 nm layer of hydrated
iridium oxide);
• an electrolyte made up of a 70 nm first layer
of hydrated tantalum oxide, a 100 micron second layer
of a POE-H3PO4 polyoxyethylene/phosphoric acid solid
solution, or alternatively a PEI-H3PO4
polyethyleneimine/phosphoric acid solid solution;
• a 350 nm second layer of cathodic
electrochromic material based on tungsten oxide;

• a second 300 nm TCO-type electronically
conducting layer 4;
• A varnish layer 10; and then
• A second organic substrate S2, identical to
the first.
In this example, there is therefore a bilayer
electrolyte based on a polymer normally used in this
type of glazing, which is "lined" with a layer of
hydrated tantalum oxide that is sufficiently conducting
not to impair proton transfer via the polymer and that
protects the back electrode made of anodic
electrochromic material from direct contact with the
latter, the intrinsic acidity of which would be
prejudicial thereto.
Instead of the hydrated Ta2O5 layer, a layer of the
hydrated Sb2O5 or TaWOx type may be used.
It is also possible to provide a three-layer
electrolyte, with two hydrated oxide layers, either
with one of them on each side of the polymer layer, or
with the two layers superposed one on the other on the
side facing the layer of anodic electrochromic
material.
According to yet another alternative embodiment, a
barrier layer 11 is intended to be provided between the
organic layer and the electronically conductive layer
TC1 and/or TC2 (to be seen in particular in figure 3
and in figure 4) based on a nitride, oxide, oxynitride
or carbide, chosen from silicon and aluminum or based
on aluminum nitride or oxynitride or carbide or on a
mixture of at least two of these compounds (mixed Si/A1
nitrides or oxynitrides) ; this barrier layer has a
thickness of 50 nm to 500 nm and preferably from 100 nm
to 300 nm.

As a variant, this barrier layer may be composed of
several inorganic layers, chosen from those mentioned
above, or an alternation of organic and inorganic
layers, the organic layer being chosen from
polysiloxanes, polysilanes, polyacrylates,
polyacetates, polyesters, and celluloses.
According to yet another variant, the barrier layer may
be made from tin oxide, zinc oxide, titanium oxide,
chromium oxide, copper oxide, germanium oxide, indium
oxide, iridium oxide, antimony oxide, tantalum oxide,
zirconium oxide or a compound of the SiOxCyHz or TiOxCyHz
type.
A third example (illustrated in general by figures 1 to
3, except as regards the organic layer 10, which is
absent) corresponds to a "five-layer" system using an
organic substrate of the PMMA slab type with a
thickness of 4 mm, which has undergone as a sole
treatment an RBS washing before the metal oxide layers
are deposited. It consists of:
a first 4 mm organic substrate S1, for
example made of drawn PMMA;
of an ITO-based TCO layer 2 was deposited
with a thicknes s of 500 nm;
of an EC1/EL/EC2 multilayer (forming the
system 3) judiciously chosen from the abovementioned
oxide layers were deposited;
of an ITO-based TCO layer 4;
of a second 4 mm organic substrate S2, for
example made of drawn PMMA.
The substrate S1 made of drawn PMMA on which the
abovementioned multilayer was deposited is then
laminated, to S2 at the same time as the connections
are placed thereon, by means of an interlayer f1 made
of PU and an inorganic glass back pane.

The cell thus obtained is then cycled between -2 V and
1 V so as to color and bleach it. Irrespective of the
times for coming to equilibrium at a given potential (2
min, 10 min or 60 min), the measured light transmission
levels at the two potentials are close to 50%. The cell
is therefore non-functional and many cracks are
observed, with the naked eye, at the multilayer, these
being the sign of poor adhesion between the organic
substrate and the electronically conductive and/or
electroactive layers.
A fourth example (illustrated by figures 1-3)
corresponds to a "five-layer" system using an organic
substrate of the type consisting of a PMMA slab 4 mm in
thickness on which a polysiloxane-based organic varnish
layer 10 was deposited by flow coating. Precisely the
same metal oxide layers as those described in the third
example were then deposited on the PMMA slab + the
polysiloxane-based varnish, keeping the same deposition
conditions as those used in the third example. The
assembly of the cell by laminations with a PU
interlayer as well as the positioning of the
connections also remain identical to those of the third
example.
The cell thus obtained is then cycled between -2 V and
1 V so as so color and bleach it. The cell thus
switches from a dark blue color to a brownish-gray
color, and the light transmission values, measured
after equilibrium times of 2 minutes, vary from 2% to
50%. The functionality of this cell produced on the
PMMA slab + siloxane-based varnish 10 is completely
satisfactory, with a contrast of 25 and with no
cracking being observed, whether with the naked eye or
with a microscope.
A fifth example illustrates, within the context of the
invention, the protection that the organic varnish on a
polymer substrate such as PMMA provides. Drops of

propylene carbonate (about 2 ml) were deposited on 3
PMMA-based substrates:
- bare PMMA;
PMMA + organic (polysiloxane-based) varnish;
PMMA + organic (polysiloxane-based) varnish +
ITO layer.
After several hours at room temperature, the propylene
carbonate reacted with the bare PMMA, whereas no
reaction was observed on the other two substrates.
After wiping, the propylene carbonate drop leaves a
trace on the bare PMMA - this trace corresponds to a
swollen area, with an overall increase in thickness of
about 6 microns relative to the area that was not in
contact with the propylene carbonate.
In addition, on the bare PMMA and on the PMMA + organic
varnish, the areas on which propylene carbonate drops
had been deposited were analyzed using a profilometer
and compared with the areas that had never been in
contact with propylene carbonate. Figures 6a to 9a show
the surface images and the roughness curves thus
obtained (figures 6a to 9b). The surfaces shown in
figures 6a and 7b are very different and in addition,
the average distance PV (the distance between the top
of the peaks and the bottom of the valleys) of the
roughness curves passes from 0.1 to 0.54 microns
between the bare PMMA, on which no solvent was
deposited, and the bare PMMA on which a drop of
propylene carbonate was deposited. This corresponds to
deeper grooves on the bare PMMA in contact with
propylene carbonate than on the bare PMMA that was
never in contact with propylene carbonate. However, the
surface images in figures 8a and 9a are similar and the
average distance PV is identical in the case of the
PMMA + organic varnish area on which a drop of PMMA was
deposited and on the PMMA + organic varnish area on
which no solvent was deposited.

WE CLAIM
1. Electrochromic system comprising at least one substrate of organic nature
(S1, S2), at least one electronically conductive layer (2, 4), at least one
layer of organic varnish (10) lying between the electronically conductive
layer and the substrate, and at least one active layer, characterized in that
it includes a barrier layer (11), based on silicon nitride, oxide or oxynitride,
or based on aluminum nitride or oxide or oxynitride or on a mixture of at
least two of these compounds, mixed Si/A1 nitrides or oxynitrides, in-
terposed between the organic varnish layer and the electronically
conductive layer.
2. System as claimed in Claim 1, wherein the substrate comprises PMMA.
3. System as claimed in Claim 1, wherein the substrate is drawn PMMA.
4. System as claimed in one of the preceding claims, wherein the organic
varnish layer is a layer of polysiloxane-based varnish.
5. System as claimed in Claim 4, wherein the organic varnish layer has a
thickness between 0.5 µm and 10 µm and preferably from 1 to 3 µm.
6. System as claimed in one of the preceding claims, wherein the
electronically conductive layer is of the metallic type or of the transparent
conductive oxide (TCO) type made of ITO, SnO2: F, ZnO: Al, or a

multilayer of the TCO/metal/TCO type, this metal being chosen especially
from silver, gold, platinum and copper, or a multilayer of the NiCr/metal/
NiCr type, the metal also being chosen especially from silver; gold,
platinum and copper.
7. System as claimed in the preceding claim, wherein the barrier layer has a
thickness of 50 nm to 500 nm and preferably 100 nm to 300 nm.
8. System as claimed in any one of the preceding claims, wherein the active
layer AC comprises in one and the same medium, anodic-col-oration and
cathodic-coloration electroactive materials, one or more solvents,
optionally one or more polymers and optionally one or more ionic salts act-
ing as electrolyte.
9. System as claimed in the preceding claim, wherein the anodic-coloration
materials are organic compounds such as phenazine derivatives, for
example 5,10-dihydrophenazine, 1,4-phenylen-ediamine, benzidine,
metallocene, phenothiazine and carbazole.
10. System as claimed in Claim 8, wherein the cathodic-coloration materials
are organic compounds such as derivatives of viologen (a bipyridinium
salt) such as methyl viologen tetrafluoroborates, octyl viologen
tetrafluoroborates, or quinone or polythiophene.

11. System as claimed in Claim 8, wherein the solvents are dimethyl sulfoxide,
N,N-dimethylfor-mamide, propylene carbonate, ethylene carbonate, N-
methylpyrolidinone, y-butyrolactone, ionic liquids, ethylene glycols,
alcohols, ketones and nitriles.
12. System as claimed in Claim 8, wherein the polymers are polyethers,
polyesters, polyamides, polyimides, polycarbonates, polymethacr-ylates,
polyacrylates, polyacetates, polysilanes, polysiloxanes and celluloses.
13. System as claimed in Claim 8, wherein the ionic salts are lithium
perchlorate, trifluoromethanesulfonate (triflate) salts,
trifluoromethanesulfo-nylimide salts, ammonium salts or ionic liquids.
14. System as claimed in Claim 8, wherein the active layer AC has a thickness
of 50 µm to 500 µm and preferably 150 µm to 300 µm.
15. System as claimed in any one of Claims 1 to 7, wherein the active layer is
in the form of an electrochemically active layer comprising at least one of
the following compounds: tungsten (W) oxide, niobium (Nb) oxide, tin
(Sn) oxide, bismuth (Bi) oxide, vanadium (V) oxide, nickel (Ni) oxide,
iridium (Ir) oxide, antimony (Sb) oxide or tantalum (Ta) oxide, by itself or
as a mixture, and optionally including an additional metal such as titanium,
tantalum or rhenium.
16. System as claimed in any of Claims 1 to 7, wherein it further comprises a
layer having an electrolytic function, chosen from silicon nitride (Si3N4),

molybdenum oxide (Moth), tantalum oxide (Ta205), antimony oxide
(Sb205), nickel oxide (NiOx), tin oxide (SnO2), zirconium oxide (ZrO2),
aluminum oxide (AI203), silicon oxide (SiO2), niobium oxide (Nb205),
chromium oxide (Cr203), cobalt oxide (Co304), titanium oxide (TiO2), zinc
oxide (ZnO) optionally alloyed with aluminum, tin zinc oxide (SnZnOx),
vanadium oxide (V205), at least one of these oxides being optionally
hydrogenated or nitrided, the electrochemically active material and the
materials having an electrolytic function are included in one and the same
medium.
17. Electrochromic glazing, wherein it comprises the electrochromic system as
claimed in one of the preceding claims, having in particular a variable light
and/or energy transmission and/or reflection, with the transparent or
partially transparent substrate or at least some of the transparent or par-
tially transparent substrates, made of a plastic, preferably mounted as
multiple and/or laminated glazing or as double glazing.
18. Electrochromic glazing, comprising the electrochromic system as claimed
in one of Claims 1 to 16, wherein it is combined with at least one other
layer suitable for providing said glazing with an additional functionality
(solar-control, low-E, hydrophobic, hydrophilic or antireflection
functionality).
19. Process for manufacturing the electrochromic system as claimed in one of
Claims 1 to 16, wherein at least one of the layers of the electro-
chromicsystem is deposited by a vacuum technique, of the sputtering

type, optionally magnetron or magnetically enhanced sputtering, by
thermal evaporation or electron-beam evaporation, by laser ablation, by
CVD, optionally plasma-enhanced or microwave-enhanced CVD, or by an
atmospheric-pressure technique, especially by the deposition of layers by
sol-gel synthesis, particularly dip coating, spray coating or laminar flow
coating.



ABSTRACT


An Electrochromic system
Electrochromic system comprising at least one substrate of organic nature (S1,
S2), at least one electronically conductive layer (2, 4), at least one layer of
organic varnish (10) lying between the electronically conductive layer and the
substrate, and at least one active layer, characterized in that it includes a barrier
layer (11), based on silicon nitride, oxide or oxynitride, or based on aluminum
nitride or oxide or oxynitride or on a mixture of at least two of these compounds,
mixed Si/A1 nitrides or oxynitrides, in-terposed between the organic varnish
layer and the electronically conductive layer.

Documents:

01776-kolnp-2008-abstract.pdf

01776-kolnp-2008-claims.pdf

01776-kolnp-2008-correspondence others.pdf

01776-kolnp-2008-description complete.pdf

01776-kolnp-2008-drawings.pdf

01776-kolnp-2008-form 1.pdf

01776-kolnp-2008-form 2.pdf

01776-kolnp-2008-form 3.pdf

01776-kolnp-2008-form 5.pdf

01776-kolnp-2008-gpa.pdf

01776-kolnp-2008-international publication.pdf

01776-kolnp-2008-international search report.pdf

01776-kolnp-2008-pct request form.pdf

1776-KOLNP-2008-(05-02-2013)-ABSTRACT.pdf

1776-KOLNP-2008-(05-02-2013)-ANNEXURE TO FORM 3.pdf

1776-KOLNP-2008-(05-02-2013)-CLAIMS.pdf

1776-KOLNP-2008-(05-02-2013)-CORRESPONDENCE.pdf

1776-KOLNP-2008-(05-02-2013)-FORM 1.pdf

1776-KOLNP-2008-(05-02-2013)-FORM 2.pdf

1776-KOLNP-2008-(05-02-2013)-OTHERS.pdf

1776-KOLNP-2008-(26-11-2012)-CORRESPONDENCE.pdf

1776-KOLNP-2008-CANCELLED PAGES.pdf

1776-KOLNP-2008-CORRESPONDENCE OTHERS 1.1.pdf

1776-KOLNP-2008-CORRESPONDENCE.pdf

1776-KOLNP-2008-EXAMINATION REPORT.pdf

1776-KOLNP-2008-FORM 18.pdf

1776-KOLNP-2008-GPA.pdf

1776-KOLNP-2008-GRANTED-ABSTRACT.pdf

1776-KOLNP-2008-GRANTED-CLAIMS.pdf

1776-KOLNP-2008-GRANTED-DESCRIPTION (COMPLETE).pdf

1776-KOLNP-2008-GRANTED-DRAWINGS.pdf

1776-KOLNP-2008-GRANTED-FORM 1.pdf

1776-KOLNP-2008-GRANTED-FORM 2.pdf

1776-KOLNP-2008-GRANTED-FORM 3.pdf

1776-KOLNP-2008-GRANTED-FORM 5.pdf

1776-KOLNP-2008-GRANTED-SPECIFICATION-COMPLETE.pdf

1776-KOLNP-2008-INTERNATIONAL PUBLICATION.pdf

1776-KOLNP-2008-INTERNATIONAL SEARCH REPORT & OTHERS.pdf

1776-KOLNP-2008-OTHERS.pdf

1776-KOLNP-2008-PRIORITY DOCUMENT-1.1.pdf

1776-KOLNP-2008-PRIORITY DOCUMENT.pdf

1776-KOLNP-2008-REPLY TO EXAMINATION REPORT.pdf

1776-KOLNP-2008-TRANSLATED COPY OF PRIORITY DOCUMENT.pdf

abstract-1776-kolnp-2008.jpg


Patent Number 257701
Indian Patent Application Number 1776/KOLNP/2008
PG Journal Number 44/2013
Publication Date 01-Nov-2013
Grant Date 29-Oct-2013
Date of Filing 02-May-2008
Name of Patentee SAINT-GOBAIN GLASS FRANCE
Applicant Address 18 AVENUE D'ALSACE F-92400 COURBEVOIE
Inventors:
# Inventor's Name Inventor's Address
1 PIROUX, FABIENNE 112 AVENUE DU PRESIDENT WILSON APPT A - 51 93210 LA PLAINE SAINT DENIS
2 VALENTIN, EMMANUEL 53 AVENUE GENERAL LECLERC 94420 LE PLESSIS TREVISE
3 DUBRENAT, SAMUEL 174 BOULEVARD BERTHIER 75017 PARIS
4 CHAUSSADE, PIERRE 8 ALLEE DU VERGER 45100 ORLEANS
5 RIGAL, FRANCOISE 7, RUE DES GRANDS CHAMPS 45600 SULLY SUR LOIRE
6 MATHEY, GREGOIRE 35 AVENUE ALBERT VIGER 45110 CHATEAUNEUF SUR LOIRE
PCT International Classification Number G02F 1/15
PCT International Application Number PCT/FR2006/051169
PCT International Filing date 2006-11-14
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 0553476 2005-11-16 France