Title of Invention

ELECTRICALLY-CONTROLLABLE DEVICE HAVING VARIABLE OPTICAL AND/OR ENERGY PROPERTIES

Abstract An electrically controllable device having variable optical/energy properties in transmission or in reflection, comprising: at least one carrier substrate provided with a stack of electrochromically functional layers, including at least two electrochromic active layers, separated by an electrolyte, characterized in that the stack is between a lower current lead and an upper current lead, wherein the lower current lead is positioned nearest to the carrier substrate and the upper current lead is positioned furthest from the substrate, and wherein the stack of functional layers is joined to at least one polymer film, having a percentage shrinkage between 0.6 and 2.0% and wherein the substrate is doubly curved.
Full Text ELECTRICALLY CONTROLLABLE DEVICE HAVING
VARIABLE OPTICAL AND/OR ENERGY PROPERTIES
The invention relates to electrically controllable devices having variable
optical and/or energy properties. It relates more particularly to devices that use
electrochromic systems operating in transmission or in reflection.
Examples of electrochromic systems are described in Patents
US-5 239 406 and EP-612 826.
Electrochromic systems have been extensively studied. They are known
to comprise in general two layers of electrochromic materials separated by an
electrolyte and flanked by two electrodes. Each of the electrochromic layers,
under the effect of an electrical supply, can inject charges reversibly, the
change in their oxidation state as a result of these injections/ejections resulting
in a change in their optical and/or thermal properties (for example, in the case of
tungsten oxide, a switch from a blue coloration to a colourless appearance).
It is common practice to classify electrochromic systems in three
categories:
- that in which the electrolyte is in the form of a polymer or a gel, for
example, a protonically conducting polymer such as those described in Patents
EP-253 713 or EP-670 346, or a polymer conducting by lithium ions such as
those described in Patents EP-382 623, EP-518 754 and EP-532 408, the other
layers of the system generally being of an inorganic nature;
- that in which the electrolyte is an essentially inorganic layer. This
category is often referred to by the term "all-solid-state" system - examples of
such may be found in Patents EP-867 752 and EP-831 360, French Patent
Application FR-2 791 147 and French Patent Application FR-2 781 084; and
that in which all the layers are based on polymers, the category then being often
referred to by the term "all-polymer" system.

Many applications have already been envisaged for these systems. They
are employed most generally as glazing for buildings or as glazing for vehicles,
especially as sunroofs, or else, when they operate in reflection and no longer in
transmission, as antidazzle rearview mirrors.
However, for all these applications, owing to their sensitivity to
environmental attack, the electrically controllable devices are not generally
inserted as they are within a substrate, but are protected within a laminated
substrate that also incorporates at least one lamination interlayer, which is
generally a polymer film.
This polymer film may optionally have a solar-protection function for the
purpose of protecting the layers of the electrochromic system from being heated
up by infrared radiation. In another configuration, the solar-protection function is
attached to the layers of the stack of the electrochromic system.
However, and whatever the origin of the solar-protection function, the
reliability of the electrochromic systems, which may for example be expressed
in terms of the durability of the switching of cycles between a colouration state
and a non-colouration state of the active layers, is dependent on the
temperature, and any temperature variation (in particular an increase in
temperature of the active layers as a result of intensive exposure to infrared
radiation (electrochromic roof placed in full sunlight)) results in an increase in
the rate of degradation of the said active layers.
Conventionally, this solar-protection function is performed by an
antireflection coating, which usually consists of a stack of thin interferential
layers, in general an alternation of layers based on a dielectric material or
based on a metal oxide, especially of the metal oxide, nitride or oxynitride type,
having high and low refractive indices.
Although it perfectly fulfils its role of protecting the active layers of the
electrochromic system from infrared radiation, the solar-protection layer, which
is optionally incorporated within the lamination interlayer, must also withstand
the mechanical stresses resulting from the lamination.
These stresses are all the more substantial when the laminated substrate
has a complex profile (a substrate with a large deflexion in at least one

direction, such as a doubly curved substrate).
The object of the present invention is therefore to alleviate these
drawbacks by proposing an electrically controllable device that incorporates at
least one polymer film that is suitable for complex substrate profiles.
The subject of the invention is therefore an electrically controllable device
haying variable optical/energy properties in transmission or in reflection,
comprising at least one carrier substrate provided with a stack of functional
layers, including at least two electrochromic active layers, separated by an
electrolyte, the said stack being placed between two current leads, namely the
lower current lead and the upper current lead respectively ("lower"
corresponding to the current lead closest to the carrier substrate, as opposed to
the "upper" current lead that is furthest from the said substrate), characterized in
that the stack of functional layers is joined to at least one polymer film, the
percentage shrinkage of which is between 0.6 and 2.0% and preferably
between 0.8 and 1.5%.
By using a flexible polymer film, the electrically controllable system may
be inserted without any risk into a laminated substrate of complex profile.
In preferred embodiments of the invention, one or other of the following
arrangements may furthermore optionally be used:
- the polymer film is a birefringent dielectric multilayer film suitable for
reflecting at least 50% of the light within a spectral band of at least 100 nm in
width;
- the device constitutes a vehicle sunroof, which can be actuated
autonomously, or a vehicle side window or rear window;
- the device constitutes a windscreen or portion of a windscreen;
- the windscreen has a complexity value F of between 0.00215 and
0.00240 and preferably between 0.00219 and 0.00230;
- the device is located in the top part of the windscreen, especially in
the form of one or more bands along the outline of the windscreen;
- the device is located in the central part of the windscreen, especially
in order to prevent a driver being dazzled at night, with the aid of automated

control of its power supply using at least one camera and/or at least one light
sensor;
- the device constitutes a graphical and/or alphanumeric data display
panel, glazing for buildings, a rearview mirror, an aircraft cabin window or
windscreen, or a skylight;
- the device constitutes interior or exterior glazing for buildings, or is
used as a shop showcase or countertop, which may be curved, or is even used
as glazing for the protection of an object of the painting type, as a computer
antidazzle screen, or as glass furniture;
the device operates in transmission or in reflection;
- the device includes at least one transparent, plain or curved, clear or
bulk-tinted substrate, polygonal in shape or at least partly curved;
- the device includes an opaque or opacified substrate;

- the electronic conductivity of at least one of the active layers is
sufficient for replacing the conducting layers with a grid of wires; and
- the conducting wires increase the conductivity of the active layers, in
order to guarantee colouration uniformity.
The invention will be described in greater detail in conjunction with the
appended drawings in which:
- Figure 1 is a schematic view of an electrically controllable device
according to the invention; and
- Figure 2 gives the position of the various points needed to calculate
the complexity factor F.
In the appended drawings, some of the elements may be shown on a
larger or smaller scale than in reality, so as to make the figures easier to
understand.
Figure 1 shows a glass plate 1 provided with a lower conducting
layer 2, with an active stack 3, surmounted by an upper conducting layer 4, with
a first grid of conducting wires 5 or an equivalent device for taking the electric
current above the upper conducting layer and with a second grid of conducting
wires 6 or an equivalent device for taking the electric current below the lower
conducting layer 2. The current leads are either conducting wires if the

electrochromic active layer is sufficiently conducting, or a grid of wires running
over or within a layer forming an electrode, this electrode being made of metal
or being of the TCO (Transparent Conductive Oxide) type made of ITO, F:SnO2
or AI:ZnO, or a single conducting layer.
The conducting wires 5, 6 are metal wires, for example made of tungsten
(or copper), optionally coated with carbon, with a diameter between 10 and
100 urn and preferably between 20 and 50 urn, these being straight or wavy,
and placed on a polymer sheet by a technique known in the wire-heated
windshield field, for example a technique described in Patents EP-785 700,
EP-553 025, EP-506 521 and EP-496 669.
One of these known techniques consists in using a heated press wheel
that presses the wire against the surface of the polymer sheet, this press wheel
being fed with wire from a feed reel via a wire guide device.
The lower conducting layer 2 is a bilayer formed from a 50 nm SiOC first
layer surmounted by a 400 nm F:SnO2 second layer (both layers preferably
deposited in succession by CVD on the float glass before cutting).
Alternatively, it may be a bilayer formed from an approximately 20 nm
optionally doped SiO2-based first layer (said layer being especially doped with
aluminium or boron) surmounted by an approximately 100 to 350 nm ITO
second layer (both layers preferably vacuum-deposited in succession by
magnetically enhanced reactive sputtering in the presence of oxygen, and
optionally hot).
The upper conducting layer is a 100 to 300 nm ITO layer, also deposited
by. magnetically enhanced reactive sputtering on the active stack, or is
produced in a manner similar to the lower conducting layer 2.
The active stack 3 shown in Figure 1 is made of the following:
- a first layer of anodic electrochromic material made of hydrated iridium
oxide lrOxHy 40 to 100 nm in thickness (it may be replaced with a layer of
hydrated nickel oxide) possibly alloyed with other metals;
- a layer of tungsten oxide 100 nm in thickness;
- a second layer of hydrated tantalum oxide or hydrated silicon oxide or
hydrated zirconium oxide 100 nm in thickness; and

- a second layer of cathodic electrochromic material based on tungsten
oxide WO3 370 nm in thickness;
this stack 3 is particularly stable, especially to UV, and operates by
insertion/ejection of lithium ions (Li+) or alternatively H+ ions.
The stack 3, the upper and lower conducting layers and the current leads
embedded in the surface of a polymer sheet f are deposited on the internal face
of a first substrate. The glazing also includes a second substrate, on top of the
polymer sheet. The two substrates and the polymer sheet are joined together by
a known technique - lamination or calendering - or by heating, possibly with
pressure.
The polymer sheet f is a birefringent dielectric multilayer film reflecting at
least 50% of the light in a band at least 100 nm in width within a spectral range
of interest and able to be shaped to a curved substrate by a uniform contraction
effect.
This film is sold under the brand name SRF by 3M and forms a
PET/coPMMA-based multilayer about 50 urn in thickness.
According to one characteristic of this film, it has a substantially greater
degree of contraction than that of other polymer films that also provide a solar-
protection function.
For comparison, the values of the degree of contraction after a heat
treatment at 130°C for 1 hour are given below.
These values should be compared with that of a conventional PET film
sold by Southwall, which incorporates a solar-protection coating.
The contraction values for this PET film are between 0.25% and 0.45%.
The contraction values for the film sold by 3M are between 0.8% and 1.5% for a
standard manufacture, and between 1.6% and 1.9% for a special manufacture
that was developed for the requirements of the invention.
Within the context of the invention, a parameter F has been defined that
makes it possible to characterize the complexity of glazing that incorporates the
polymer film, for example that developed by 3M.
The parameter F is calculated in the following manner:


The reader may refer to the graphic given in Figure 2 for the spatial
positioning of the various points mentioned in the above formula.
This polymer film is incorporated within a laminated substrate, the
complexity value F of which is between 0.00215 and 0.00240 and preferably
between 0.00219 and 0.00230.
The combination of the three parts produces an electrically controllable
device having variable optical and/or energy properties, the electrochromic
material for which is protected from the outside, thereby increasing the lifetime
of the electrically controllable device. The polymer film is particularly suitable for
protecting the layer of functional (for example electrochromic) material from
impacts, especially by chippings which may result in star-shaped shatter marks
of the substrate. It may also be noted that the polymer film constitutes a
moisture barrier, which effectively slows down the rate of deterioration at the
site of impacts caused by chippings.
Moreover, the two glass plates forming the substrates of the electrically
controllable device described above are made of standard, flat clear silica-soda-
lime glass, each having a thickness of about 2 mm, and at least one possibly
being bulk-tinted.
Thus, an illustrative example of the invention is made up as follows:
glass (2.1 mm)/PU (0.76 mm)/polymer film/PL) (0.76 mm)/functional layer/grey
glass (2.1 mm).
When this functional layer is the electrochromic system mentioned
above, measurements give:
> Coloured state:

> Non-coloured state:

In this configuration, the polymer film has dimensions smaller than those
of the substrates between which it is incorporated; the polymer film follows the
screen-printing contours in such a way that the edges of the film are embedded

in the screen-printing points. This configuration makes it possible to achieve
even higher curving complexity values (F).
The invention applies in the same way to curved and/or toughened glass
substrates.
Likewise, at least one of the glass substrates may be bulk-tinted,
especially tinted blue or green, grey, bronze or brown.
The substrates used in the invention may also be based on a polymer
(PMMA, PC, etc.). It should also be noted that the substrates may have very
varied geometrical shapes: they may be in the form of a square or rectangle,
but also in the form of any polygon or at least partly curved profile, defined by
rounded or undulating contours (round, oval, "waves", etc.).
Moreover, at least one of the two glass substrates (on that face which is
not provided with the electrochromic or equivalent system) may be covered with
a coating having another functionality (this other functionality possibly being, for
example, a solar-protection stack, an antifouling stack or the like). As regards
the solar-protection stack, this may be a stack of thin layers deposited by
sputtering and including at least one silver layer. It is thus possible to have
combinations of the following types:
- glass/electrochromic system/solar-protection layers/glass;
- glass/electrochromic system/glass/thermoplastic/glass;
- glass/electrochromic system/thermoplastic/glass; and
- glass/thermoplastic/electrochromic system/thermoplastic/glass.
The solar-protection coating may also be deposited, not on one of the
glass substrates, but on a sheet of flexible polymer of the PET (poly(ethylene
terephthalate)) type.
For examples of solar-protection coatings, the reader may refer to
Patents EP 826 641, EP 844 219, EP 847 965, W099/45415 and
EP 1010 677.
The device forming the subject of the invention described above may
also be incorporated into a three-glass "substrate", the latter being
advantageously used for the production of glazing that meets the safety
requirements.

Moreover, it may be noted that the electrically controllable device as
described above has the advantage of being transparent to electromagnetic
waves.
Thus, these electrically controllable devices incorporating electrochromic
and solar-protection functionalities are being increasingly used in the motor-
vehicle field, which often requires transparency to electromagnetic waves
(mobile telephones, various types of remote control, automatic payment
systems at motorway toll barriers, etc.).

WE CLAIM:
1. An electrically controllable device having variable optical/energy properties
in transmission or in reflection, comprising:
at least one carrier substrate provided with a stack of electrochromically
functional layers, including at least two electrochromic active layers,
separated by an electrolyte, characterized in that the stack is between a
lower current lead and an upper current lead, wherein the lower current
lead is positioned nearest to the carrier substrate and the upper current
lead is positioned furthest from the substrate, and
wherein the stack of functional layers is joined to at least one polymer film,
having a percentage shrinkage between 0.6 and 2.0% and
wherein the substrate is doubly curved.
2. The electrically controllable device as claimed in claim 1, wherein the
polymer film is a birefringent dielectric multilayer film suitable for reflecting at
least 50% of the light within a spectral band of at least 100 nm in width.
3. The electrically controllable device as claimed in claim 1, which constitutes
a vehicle sunroof, which can be actuated autonomously, or a vehicle side
window or a rear window.
4. The electrically controllable device as claimed in claim 1, which constitutes
a windscreen or a portion of a windscreen.
5. The electrically controllable device as claimed in claim 4, which is located
in the top part of the windscreen.

6. The electrically controllable device as claimed in claim 4, which is located in
the central part of the windscreen, with the aid of automated control of its power
supply using at least one camera and/or at least one light sensor.
7. The electrically controllable device as claimed in claim 1, which constitutes a
graphical and/or alphanumeric data display panel, glazing for buildings, a
rearview mirror, an aircraft cabin window or windscreen, or a skylight.
8. The electrically controllable device as claimed in claim 1, which constitutes:
interior or exterior glazing for buildings; a shop showcase or countertop, which
may be curved; glazing for the protection of an object of the painting type;
a computer antidazzle screen; or glass furniture.

9. The electrically controllable device as claimed in claim 1, which operates in
transmission or in reflection.
10. The electrically controllable device as claimed in claim 1, wherein at least one
carrier is transparent, or tinted and wherein at least one carrier is curved
polygonal, or partly curved.
11. The electrically controllable device as claimed in claim 1, which includes an
opaque or opacified substrate.
12. The electrically controllable device as claimed in claim 1, wherein an
electronic conductivity of at least one of the active layers is sufficient for replacing
the conducting layers with a grid of wires.

13. The electrically controllable device as claimed in claim 12, wherein the
conducting wires increase the conductivity of the active layers, in order to
guarantee colouration uniformity.
14. The electrically controllable device as claimed in claim 1, wherein the
percentage shrinkage of the polymer film is between 0.8 and 1.5%.
15. The electrically controllable device as claimed in claim 5, which is located in
the form of one or more bands along the outline of the windscreen.
16. The electrically controllable device as claimed in claim 1, wherein the stack of
electrochromically functional layers comprises
a first layer of anodic electrochromic material comprising hydrated iridium oxide
or hydrated nickel oxide, which can include one or more other metals,
a layer of tungsten oxide;
a layer of hydrated tantalum oxide or hydrated silicon oxide or hydrated
zirconium oxide; and
a layer of cathodic electrochromic material based on tungsten oxide.
17. The electrically controllable device as claimed in claim 1, wherein the
polymer film is a planar or substantially planar film contacting only one surface of
a lower conducting layer.
18. The electrically controllable device as claimed in claim 1, wherein the
polymer film has dimensions smaller than those of the layers between which the
polymer film is positioned.

Documents:

02664-kolnp-2005-abstract.pdf

02664-kolnp-2005-claims.pdf

02664-kolnp-2005-description complete.pdf

02664-kolnp-2005-drawings.pdf

02664-kolnp-2005-form 1.pdf

02664-kolnp-2005-form 2.pdf

02664-kolnp-2005-form 3.pdf

02664-kolnp-2005-form 5.pdf

02664-kolnp-2005-international publication.pdf

2664-KOLNP-2005-ABSTRACT 1.1.pdf

2664-KOLNP-2005-ABSTRACT 1.2.pdf

2664-KOLNP-2005-AMANDED CLAIMS.pdf

2664-KOLNP-2005-AMANDED PAGES OF SPECIFICATION.pdf

2664-KOLNP-2005-CANCELLED PAGES.pdf

2664-KOLNP-2005-CLAIMS 1.1.pdf

2664-kolnp-2005-correspondence-1.1.pdf

2664-kolnp-2005-correspondence.pdf

2664-KOLNP-2005-DESCRIPTION (COMPLETE) 1.1.pdf

2664-KOLNP-2005-DESCRIPTION (COMPLETE) 1.2.pdf

2664-KOLNP-2005-DRAWINGS 1.1.pdf

2664-KOLNP-2005-DRAWINGS 1.2.pdf

2664-KOLNP-2005-EXAMINATION REPORT REPLY RECIEVED 1.1.pdf

2664-kolnp-2005-examination report.pdf

2664-KOLNP-2005-FORM 1.1.1.pdf

2664-kolnp-2005-form 18-1.1.pdf

2664-kolnp-2005-form 18.pdf

2664-KOLNP-2005-FORM 2 1.2.pdf

2664-KOLNP-2005-FORM 2.1.1.pdf

2664-KOLNP-2005-FORM 3 1.2.pdf

2664-KOLNP-2005-FORM 3.1.1.pdf

2664-kolnp-2005-form 3.pdf

2664-KOLNP-2005-FORM 5.1.1.pdf

2664-kolnp-2005-form 5.pdf

2664-KOLNP-2005-FORM-27.pdf

2664-kolnp-2005-gpa-1.1.pdf

2664-kolnp-2005-gpa.pdf

2664-kolnp-2005-granted-abstract.pdf

2664-kolnp-2005-granted-claims.pdf

2664-kolnp-2005-granted-description (complete).pdf

2664-kolnp-2005-granted-drawings.pdf

2664-kolnp-2005-granted-form 1.pdf

2664-kolnp-2005-granted-form 2.pdf

2664-kolnp-2005-granted-specification.pdf

2664-kolnp-2005-international preliminary examination report.pdf

2664-kolnp-2005-international search report.pdf

2664-KOLNP-2005-OTHERS.pdf

2664-KOLNP-2005-PA.pdf

2664-kolnp-2005-pct request form.pdf

2664-KOLNP-2005-PETITION UNDER RULE 137.pdf

2664-kolnp-2005-priority document.pdf

2664-KOLNP-2005-REPLY TO EXAMINATION REPORT.pdf

2664-kolnp-2005-translated copy of priority document.pdf


Patent Number 247388
Indian Patent Application Number 2664/KOLNP/2005
PG Journal Number 14/2011
Publication Date 08-Apr-2011
Grant Date 04-Apr-2011
Date of Filing 22-Dec-2005
Name of Patentee SAINT-GOBAIN GLASS FRANCE
Applicant Address 18 AVENUE D'ALSACE F-92400 COURBEVOIE
Inventors:
# Inventor's Name Inventor's Address
1 VAN DER MEULEN, UWE IM SIEF 17 52385 NIDEGGEN-SCHMIDT
2 BECK, FRANZ MATAREST 2 52078 AACHEN
3 PENDER DAVID HAHNERSTRASSE 73 52076 AACHEN
4 GIRON, JEAN-CHRISTOPHE VAALSER STRASSE 136 52074 AACHEN
PCT International Classification Number G02F 1/15
PCT International Application Number PCT/FR2004/001774
PCT International Filing date 2004-07-07
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 03/08385 2003-07-09 France