US009030724B2
`
`(12) United States Patent
`Agrawal et al.
`
`(10) Patent No.:
`45) Date of Patent:
`
`US 9,030,724 B2
`MaV 12, 2015
`y A,
`
`(54) FLEXIBLE AND PRINTABLE
`ELECTROOPTIC DEVICES
`
`(75) Inventors: Anoop Agrawal, Tucson, AZ (US);
`John P. Cronin, Tucson, AZ (US); Lori
`ERA. A. sy",
`arlos L. Tonazzi, Tucson, AZ (US)
`(73) Assignee: Chromera, Inc., Poway, CA (US)
`
`(*) Notice:
`
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 694 days.
`
`(21) Appl. No.:
`
`13/002,275
`
`(22) PCT Filed:
`
`Jul. 2, 2009
`
`(86). PCT No.:
`S371 (c)(1),
`(2), (4) Date:
`
`PCT/US2O09/049644
`
`Dec. 30, 2010
`
`(87) PCT Pub. No.: WO2010/003138
`PCT Pub. Date: Jan. 7, 2010
`
`(65)
`
`Prior Publication Data
`US 2011 FOO96388A1
`Apr. 28, 2011
`O
`O
`Related U.S. Application Data
`(60) Provisional application No. 61/078.328, filed on Jul. 3,
`2008, provisional application No. 61/087,796, filed on
`Aug. 11, 2008, provisional application No.
`61/109,691, filed on Oct. 30, 2008, provisional
`application No. 61/156,932, filed on Mar. 3, 2009,
`provisional application No. 61/168,421, filed on Apr.
`10, 2009, provisional application No. 61/187,619,
`filed on Jun. 16, 2009.
`
`
`
`(2006.01)
`(2006.01)
`(2006.01)
`
`(51) Int. Cl.
`GO2F I/53
`GO2F I/5
`GO2F 1/163
`(52) U.S. Cl.
`CPC ............ G02F 1/1506 (2013.01); G02F 1/1508
`(2013.01); G02F1/1533 (2013.01); G02F
`1/163 (2013.01); G02F 2001/1515 (2013.01);
`Y10T 29/49 155 (2013.01)
`(58) Field of Classification Search
`USPC .................................................. 359/265 275
`See application file for complete search history.
`
`(56)
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`5,253,100 A * 10/1993 Yang et al. .................... 359,266
`2002.0005977 A1* 1 2002 Guarret al. ....
`... 359,265
`2003/0227664 A1* 12/2003 Agrawal et al. ...
`... 359,269
`2007/0139756 A1* 6/2007 Agrawal et al. ............... 359,265
`* cited by examiner
`
`Primary Examiner — Evelyn A. Lester
`
`ABSTRACT
`(57)
`This invention discloses how electrooptic devices including
`electrochromic devices that can be fabricated as tags or
`labels; and further the materials used, device structures and
`how these can be processed by printing technologies and on
`flexible Substrates. In addition, Systems using displays of
`Such devices and their integration with other components are
`described for forming labels and tags, etc., that may be actu
`ated wirelessly or powered with low voltage and low capacity
`batteries.
`
`25 Claims, 26 Drawing Sheets
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`US 9,030,724 B2
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`1.
`FLEXBLE AND PRINTABLE
`ELECTROOPTIC DEVICES
`
`2
`ing display applications, new materials, or new ways of using
`the existing materials is required. In addition, these displays
`and their integration into labels and tags should be done so
`that they can be produced at low cost. Some of the low cost
`processing methods are use of printing processes, particularly
`high speed processes such as roll to roll processes for flexible
`Substrates or continuous process to print on rigid substrates.
`The materials and concepts discussed here may be used for
`any EC application, but as demonstrated in several examples
`these would be particularly suitable for low cost displays.
`Since these displays comprise several layers of different
`materials, printing means that at least one of the layers is
`deposited using printing methods. Typically at least one of the
`electrodes or an electrolyte is printed. In particular, materials
`and material combinations that change their optical state by
`polymerization and their use in the EC devices will be dis
`closed. In addition, the metal layers when formed or removed
`also result in high contrast. Use of these materials will also be
`disclosed. EC device structures, processes to fabricate these
`devices and their integration with other components at a sys
`tems level for manufacturing of complete labels and tags
`along with their applications will be disclosed.
`
`25
`
`SUMMARY OF THE PRESENT INVENTION
`
`RELATED APPLICATIONACLAIM OF PRIORITY
`
`This application is a national stage application under 35
`U.S.C. S371 of, and claims priority from, International Appli
`cation No. PCT/US09/49644, filed 2 Jul. 2009, which is a
`PCT Application and is related to and claims priority of
`provisional application Ser. Nos. 61/078.328, filed on Jul. 3,
`2008: 61/087,796, filed Aug. 11, 2008: 61/109,691 filed on
`Oct. 30, 2008: 61/156,932 filed on Mar. 3, 2009, 61/168,421
`filed on Apr. 10, 2009 and 61/187,619 filed Jun. 16, 2009, and
`PCT application PCT/US09/49644 filed on Jul. 2, 2009, all of
`which applications are incorporated by reference herein.
`
`10
`
`15
`
`FIELD OF THE INVENTION
`
`The present invention relates to novel electrochromic
`materials, and devices formed by these materials and the
`applications of these electrochromic devices. Particularly
`preferred applications of these devices, are in the area of
`flexible displays and/or those where these are processed by
`printing methods. These displays are usually assembled or
`processed so that these are part of other electronic flexible
`and/or printed products Such as electronic labels and tags.
`This invention also discloses electronic biodegradable labels
`and tags.
`
`BACKGROUND OF THE INVENTION
`
`30
`
`Electrooptic devices which change their optical state/dis
`played information upon application of voltage, such as elec
`trochromic (EC) devices, can be used for a variety of appli
`cations, for example automotive mirrors, energy efficient
`glazing, displays, eye-wear and optical filters, to name a few.
`The device construction and the materials used have to be
`adapted to each application so that the device performance is
`most Suitable for the intended application. An emerging area
`for EC applications are displays with wide ranging attributes
`and cost structures. As an example for use in displays, this
`technology is being developed for those applications where
`the tablet or the screen is refreshed at video speeds or able to
`exhibit color images. In Such applications, reversibility and
`rapid change of color is required. An advantage of EC dis
`plays is their wide viewing angle and the visibility is not
`impaired under bright lights. On the other side of the spec
`trum, highly inexpensive displays and indicators are required
`that may be produced for product labels and tags which are
`disposable or replaced periodically. These displays may
`require irreversible information to be displayed or have lim
`ited cyclability. Irreversible means that the display or the
`indicator change the state or show the information when they
`are activated the first time. Limited cyclability is usually
`about 10,000 cycles or less. This information may fade away
`after a few seconds or may last alongtime giving permanence
`to the image (bistable state). Further, many of the tags and
`labels for Such uses may not have an onboard power Source
`and thus may have to be activated by power derived from
`other components located on the same tag or the label. Such
`power may be derived from a radio frequency coupling of an
`antenna on the tag, an optical coupling with a source or
`ambient light, mechanical coupling to a motion or vibration,
`or a Sonar source, etc. In all cases the power to activate the
`display is limited. Since EC devices are able to react at low
`potentials (typically less than 3V), power is not lost in upcon
`Verting the Voltage. To meet a demand for many of the emerg
`
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`In accordance with the purposes of the present invention, as
`embodied and broadly described herein, the invention pro
`vides materials, methods of forming and applications of elec
`trochromic devices. These methods can be advantageously
`used to form displays which can be made at low cost for many
`applications such as labels and tags.
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`FIG. 1: Shows the schematic of the structure of an EC
`device formed using this invention;
`FIG. 2: Shows the schematics of the structure of another
`EC device formed using this invention;
`FIG.3a: Shows schematics of an EC device fabricated by
`the inventive method;
`FIG.3b: Shows schematics of an EC device (top and front
`view) fabricated by the inventive method;
`FIG. 3c: Shows schematics of an EC device fabricated by
`the inventive method;
`FIG. 4: Shows schematics of an EC device fabricated by
`the inventive method;
`FIG. 5: Shows schematics of an EC device fabricated by
`the inventive method;
`FIG. 6a Shows schematics of an EC device fabricated by
`the inventive method;
`FIG. 6b Shows schematics of an EC device fabricated by
`the inventive method;
`FIG. 7 Shows schematics of an EC device fabricated by the
`inventive method;
`FIG. 8 Shows schematics of an EC device fabricated by the
`inventive method;
`FIG. 9 Schematics of a two electrode interdigited display
`pattern showing characters.
`FIG. 10 Shows schematics of a device with electrolyte in
`channels;
`FIG. 11 Shows a transmission change of an EC device
`when colored and bleached
`FIG. 12 Shows schematics of layout of a display and other
`components on a tag or a label;
`FIG. 13 Shows cross-section of a display that may be used
`as a label or a tag;
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`FIG. 14: Shows a schematics of a label or a tag that uses
`several indicators;
`FIG. 15: Shows cross-section of a display that may be used
`as a label or a tag;
`FIG.16: Shows cross-section of a display that may be used
`as a label or a tag;
`FIG. 17: Schematics of electrodes for electrooptic device
`and connections scheme to various tag components on a
`substrate;
`FIG. 18: Schematics of integration of various components
`on the tag substrate shown in FIG. 17:
`FIG. 19: Schematics of various components on the tag
`substrate shown in FIG. 18;
`FIG. 20a: Schematics of various components on the tag
`substrate shown in FIG. 18, top view:
`FIG. 20b: Schematics of various components on the tag
`substrate shown in FIG. 18, bottom view:
`FIG. 21a-c: Schematics of the electronics component used
`for the assembly in FIG. 18;
`FIG. 22: Schematics of connections for placement of an
`electrooptic device and connections scheme to various tag
`components on a Substrate;
`FIG. 23: Schematics of the electrode and partial connection
`scheme for an electrooptic device to be connected to the tag
`shown in FIG. 22.
`FIG. 24a-d: Schematics of formation of the electrooptic
`device to be connected to the tag shown in FIG. 22.
`FIG.25a, b. Schematics of an overview of the display ele
`ment from FIG. 24 integrated with the tag substrate of FIG.
`22, top and bottom views.
`FIG. 26a,b; Schematics showing details of connections
`and components of the display element from FIG. 24 inte
`grated with the tag substrate of FIG.22, top and bottom views
`FIG. 27: Shows a card incorporating display according to
`the invention;
`FIGS. 28a–f Schematics of an indicative device and a
`processing sequence for its formation;
`FIG. 29: Shows a schematics of a system that uses a dis
`play;
`FIG. 30: Shows a schematics of a system that uses a dis
`play;
`FIG.31: Schematics of a wireless powered display system
`constructed using this invention.
`
`DETAILED DESCRIPTION
`
`This invention discloses fabrication of low cost, low power
`electrochromic displays and their applications in integrating
`them in a variety of ways. Although the invention illustrates
`most of the novelty using EC materials and devices, however,
`in Some cases other electrooptic materials and technologies,
`Such as liquid crystals, electrophoretic and others may also be
`used. In particular, the applications targeted are tickets (for
`events, games, transportation, lotteries etc.), tags, labels, etc.
`that can be used as product labels, Supermarket shelf price
`labels, security labels, cards (e.g., gift cards, other limited use
`greeting cards, credit and debit cards), medical applications
`Such as status of a patch or a wound, etc. These labels may be
`used for office products such as to label documents, folders,
`binders, etc. One may activate these products wirelessly, and
`depending on the user selectivity, displays on specific office
`products may be activated which may be easy to identify
`visually for the task at hand. All of these applications are
`collectively called as “tags and labels’. These labels may
`comprise of integrated sensors, or a sensor feed may be pro
`vided to them. These sensors may be looking at/for changes in
`type or value of pH, color, optical absorption, fluorescence,
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`weight, permeability, moisture, electrical resistance, capaci
`tance, impedance, mechanical modulus, magnetic suscepti
`bility, Volume, time, temperature, pressure, gas, enzymes,
`other chemicals, etc. These displays may be irreversible, that
`is, once activated they can form an image which stays there
`for a period of time, which may be considered permanent
`relative to the product life. As an example, for inventory
`control, an area on the label applied to the product package
`may change color via a stimulus when it is close to expiration.
`Such a product can then be easily identified by the store
`personnel and removed. In some cases, the label should be
`reversible so that the image can be updated periodically and
`Some may even require holding the image without further
`power consumption. An example of this may be a price label
`on the Supermarket shelf. Applications such as cards (bus or
`train passes, School lunch cards, store gift cards, etc.) may
`have a display that is periodically updated when one takes
`them near an emitting source, and then the image needs to be
`retained without power until the card is used next or for any
`desired time. Thus there are many examples where wireless
`communication Such as by optical, Sonar or radio frequency
`communication, will energize these displays and the associ
`ated electronics. The power may also come from onboard
`sources such as a battery or solar cell. Although the preferred
`mode is wireless activation, this invention may also be used
`with wired displays. Examples of these applications and some
`of the devices suggested for these may be found in U.S. Pat.
`No. 7.286,061 (conditional access for antitheft of optical
`media) and patent applications UA2008011 1675 (observable
`properties triggered upon interrogation of RFIDS for tracking
`systems); UA200801 00455 (a tag with an antenna and a chip
`showing a persistent image after interrogation for inventory
`control); UA20080170287 (a security device to provide a
`visual alert); UA20070114621 (wirelessly powered flexible
`tag); UA20070114365 (antitheft optical shutter activated by
`RF); PCT applications WO08022972 (EC indicator for prod
`uct authentication) and WO08022966 (EC indicator). Print
`ing of several components on flexible Substrates including
`displays or indicators along with connectors, sensors, logic
`and power electronics on a Substrate to reduce cost is com
`monly known theme as included in many publications, e.g. a
`few examples are Aperturen 2005 publication from Acreo AB
`(located in Krista, Sweden) (http://www.acreo.se/upload/
`Publications/Aperturen/Aperturen2005-02.pdf), US patent
`applications UA2007/0143774, UA2007/0128760 and PCT
`application WO08/115591. All of these also anticipate a com
`mon layer or material that is common to several components.
`However, none of these address the issue of biodegradation or
`matching the mechanical properties of the various layers so
`that flexible devices with high durability can be obtained.
`Flexibility usually refers to products made on stock (or sub
`strate) that is processed in a roll to roll configuration where
`the stock has to be flexed around the rollers in the processing
`equipment, or where flexibility or bending is needed from the
`product during its use.
`Specifically, in a variety of consumer and industrial prod
`ucts/processes that are using radio frequency (RF) wireless
`technology to read information on tags or labels on product
`packaging, passports, payment cards, inventory control,
`product tracking, animal control, etc. These tags comprise of
`an antenna coupled to a radio frequency chip. When this tag is
`wirelessly coupled by radio frequency via an authorized
`Source, the chip on the tag is energized and the information
`stored on this chip may be read. The emitter or the source is
`usually a part of the network and can wirelessly communicate
`with the chip. In the emerging applications the RF chips may
`have an added functionality where the chips are further con
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`5
`nected to additional devices to activate an action from the
`power derived from the antenna energization. This could be a
`display, a Sound buZZer, or a mechanical lock, etc. Many Such
`applications have been described in the patent literature. Such
`as US patent applications 2007/0,114,621; 2008/0,100.455;
`and U.S. Pat. Nos. 7,227,445; 7,273,181. The wireless cou
`pling to the chip via the antenna on the tag can also provide
`power to turn on the display (passive). Alternatively, a battery
`on the tag (active) may be used to accomplish this. However,
`in some cases the latter approach may make the product more
`expensive and disposal may be an issue, thus passive
`approach is preferred. Alternatively wireless energy harvest
`ing devices, such as a Solar cell may be located on the tag
`which may also be formed by a printing process. Other wire
`less power devices that can be used harvest power from vibra
`tions, Sound, RF power, etc. Some of the emerging devices
`based on these principles are from Adaptive Energy (Hamp
`ton, Va.) that uses a piezoelectric sensor to convert power
`from vibrations, or from Powercast (Pittsburgh, Pa.) that uses
`a sensor for power harvesting from RF radiation. These
`devices may interface with batteries to recharge them, or
`charge a capacitor. One may be print specific components,
`Such as the capacitor, battery or even the entire power har
`vesting system. Depending upon a desired response based on
`the dialogue between the chip and the interrogating source,
`the display may be energized. Since this coupling may last for
`a few seconds, in some cases it is desired for the display to be
`persistent or show the information for a long time without
`consuming power. As an example, cafeteria food card, store
`gift card, train or bus card may show the amount remaining
`when one swipes the card in a reader or walks by a booth with
`an emitting source for wirelessly coupling to the card (i.e., the
`antenna and the chip on the card). This information may have
`to remain displayed for a few seconds for some applications
`while for others it should be displayed for several days or
`weeks. This action may also require erasure or updating of
`any past information that is being displayed. A label on a
`package at a store checkout can interact wirelessly with the
`terminal, which can then communicate through a network to
`verify the product authenticity, and turn on an EC indicator
`permanently. In another application on inventory control, a
`wireless communication system in a Supermarket can interact
`with any of the desired or all of the product labels on the
`product package, and then turn an indicator on the package
`label if it is expired, or is recalled, or needs to go on sale, etc.
`The information on the display has to remain on for suffi
`ciently long so that the store employees are able to get to them
`and take properaction. Thus, these labels have to be low cost
`So as not to excessively increase the cost of products, tags, etc.
`Further, the display materials and processes used have to be
`compatible with packaging materials and systems and be
`non-toxic to the environment when disposed. Many of the
`preferred electrolytic compositions comprising ionic liquids
`do not interact with common packaging materials such as
`paper, polyvinyl chloride, polystyrene, polycarbonate, poly
`ester, acrylic and polyolefins and do not vaporize. It is also
`preferred that one is able to use polymeric materials as coat
`ings or Substrates or as part of active devices that decompose
`in the landfills or in an industrial compostable facility. This is
`important as such products will be made and disposed in large
`numbers. The materials that biodegrade in soils are those that
`show substantial degradation within 180 days in a land fill.
`Example of the materials (for clear or opaque Substrates or
`other layers as described in this disclosure) that are biode
`gradable are conventional polymers with additives that make
`these biodegradable (e.g., see Eco-PureTM additives that pro
`mote biodegradability in polymers when added in a concen
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`tration of about 1%, available from Biotech Environmental
`LLC in Albuquerque, N. Mex.) or those polymers that biode
`grade themselves. Polymers for the former category are poly
`ethylene, polypropylene, polyester, polystyrene, polycarbon
`ate, and many others including addition to any layer in the
`device. Examples of the latter category are polylactic acid
`based polymers which includes various crystallinity grades
`varied by changing the proportion of D and L. lactic acid units
`(e.g. sold by Natureworks LLC, Minnetonka, Minn.), poly
`hydroxyalkanoate, poly-ecaprolactone, and polyesters such
`as poly(butylene adipate terephthalate) (sold as Ecoflex from
`BASF, Germany). Examples of additives to promote biodeg
`radation in a variety of polymers are provided in published
`US patent application 200801 03232, which is included
`herein by reference. More on biodegradability requirements
`and regulatory standards is contained in many standards Such
`as ASTM D5338, ASTMD6400, ISO 14855, ISO 16929, ISO
`17088, ISO 20200 and EN 13432 (European Norm). Biode
`gradability for the purposes of this disclosure is defined as a
`material meeting any of the above regulatory standards. It is
`preferred that the biodegradable materials meet at least one of
`these standards. In some cases the self biodegradable poly
`mers may have high permeability to moisture. These may be
`coated with polyolefins, wherein these polyolefins may com
`prise biodegradation promoting additives. Those polymers
`derived from bio feed stock may also be used (e.g., polyols
`used in polyesters and urethanes which are derived from
`plants and seeds such as corn, Soyabean, castor, linseed),
`however, the preferred materials are those that biodegrade
`regardless of their source. Paper includes cardboard, fabrics,
`or other paper-like structures Such as mats, non-woven webs,
`etc which includes natural and manmade polymers including
`those that biodegrade. Even these materials could be made to
`biodegrade faster in specific landfill environments when addi
`tives such as those described above are added.
`It is important to realize that the substrates used for printed
`and flexible displays, not only house the display but also the
`electronics including antennas if used. Thus the biodegrada
`tion is an important topic for the entire flexible and/or printed
`electronic labels and tags which would be made in large
`numbers and disposed. These include electronic RFID tags
`and labels. Ifflexible and/or printed electronics is going to be
`produced in large quantities and then disposed, then the entire
`product or most of it needs to be biodegradable. As an
`example flexible solar cells and many products need to be
`stable to photodegradation but then biodegrade when dis
`posed. One can use the above principles of making biode
`gradable products for any printed and/or flexible electronics
`product even if it does not have a display. Also encapsulation
`layers, connectors, antennas, sealing adhesives, all of the
`layers that use polymers can be made of biodegradable matri
`ces or additives added to do so. This can be done for both
`thermosets and thermoplastics. There may be minor compo
`nents and coatings that may not degrade readily, but prefer
`ably more than 50% weight of the product and more prefer
`ably more than 80% weight of the product and most
`preferably greater than 98% of the product weight of flexible
`and/or printed electronics can be designed to biodegrade.
`This would be a better option as compared to recyclability due
`to the difficulty of disassembly of various materials as many
`of these are present as coatings and adhesives. Since biodeg
`radation usually kicks in landfills where there are microbes
`present, some of the materials may be optionally recycled if
`they are not disposed in the landfill. One may use these
`principles of using additives for Substrates and other layers
`for electrooptic (EO) devices that may use polymeric sub
`strates and polymeric layers including electrolytes, adhesives
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`and conductors. Some examples of products that can be made
`biodegradable are EC windows and EC automotive mirrors
`(see PCT application serial number PCT/US09/32491 filed
`on Jan. 29, 2009, which is included herein by reference),
`non-emissive polymeric displays for electronic books and
`readers, electronic billboards, light emitting diodes for light
`ing and displays, flexible Solar cells, electroluminescent dis
`plays, etc.
`Since the indicators and displays of this invention may be
`printed, they may also be printed on the Surface of any product
`whether it is conductive or nonconductive without making a
`separate label. They can be used for labels and indicators for
`a wide variety of consumer products and packages and are
`durable in performance. Further, for those labels where the
`power source is only RF activation, the displays have to
`function under low power environments where both the volt
`age and the current output of the chips on the tags are limited.
`These displays should be preferably energized at lower than
`5V, preferably lower than 2.5 V. The average current con
`sumed should be less than 20 mA, preferably lower than 3 mA
`during the period in which the displays are powered. Further,
`it is also preferred that the displays be powered in less than 10
`s, and preferably inless than 2 S. The persistence time (i.e., the
`time for which the information is displayed after the power is
`removed) may be tunable based on the composition of the
`electrolyte or the electrode from about a few seconds to
`forever. Forever or permanent is always relative to the prod
`uct/package life. Typically, this is from weeks to several
`years. If electrochromic displays are used that are part of an
`active matrix pixel system, then it is preferred that the thresh
`old voltage be below 1.5V, so that power can be transmitted
`below this voltage to the pixels without activating the con
`nectOrS.
`Display Materials and Devices
`The EC display devices may comprise of several layers,
`sometimes the EC material (or electrooptic material) is
`located on an electrode as a separate layer from the electro
`lyte, and sometimes EC material may be both in the electro
`lyte and in additional layers, and yet in other cases it may
`solely reside in the electrolyte. Since one of the primary
`40
`objective of the invention is low cost products, it is preferred
`to reduce the number of layers in an EC device, thus those EC
`devices where the EC material is resident only in electrolytes
`and additional electrochemically active layers are not used
`and are most preferred device constructions. Redox materi
`als/species are those that undergo electrochemical oxidation
`and reduction upon device activation, and these may be
`reversible or irreversible. Cathodic redox undergo reduction
`at the cathode and the anodic redox undergo oxidation at the
`anode. In addition, it is preferred that all of the layers are
`printed sequentially until the device is complete.
`The electrolytes that are deposited by printing should
`become solid after deposition. This may be due to the removal
`of a solvent, cooling or by further reaction (e.g. polymeriza
`tion and/or crosslinking). The electrolytes may be hydro
`philic or hydrophobic (latter are preferred). For hydrophilic
`electrolytes those systems are preferred where the device
`performance is not dependent too much on water content,
`otherwise the performance of this device will change when
`subjected to different environmental conditions.
`One method to create the EC displays with long persistence
`or permanent image is by using those materials as redox
`agents that become colored upon polymerization. These are
`particularly Suitable