WO2021040777A1 - Unités d'affichage électro-optiques émissives/non émissives - Google Patents

Unités d'affichage électro-optiques émissives/non émissives Download PDF

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Publication number
WO2021040777A1
WO2021040777A1 PCT/US2020/013050 US2020013050W WO2021040777A1 WO 2021040777 A1 WO2021040777 A1 WO 2021040777A1 US 2020013050 W US2020013050 W US 2020013050W WO 2021040777 A1 WO2021040777 A1 WO 2021040777A1
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WIPO (PCT)
Prior art keywords
electro
optic
layer
pixel
emissive
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PCT/US2020/013050
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English (en)
Inventor
John Rilum
Paul Atkinson
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Chromera, Inc.
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Priority claimed from US16/553,572 external-priority patent/US11467433B2/en
Application filed by Chromera, Inc. filed Critical Chromera, Inc.
Publication of WO2021040777A1 publication Critical patent/WO2021040777A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/0121—Operation of devices; Circuit arrangements, not otherwise provided for in this subclass
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/0102—Constructional details, not otherwise provided for in this subclass
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/02—Materials and properties organic material
    • G02F2202/022—Materials and properties organic material polymeric

Definitions

  • the field of the invention is manufacture and use of electronic displays comprised of electro-optic pixels.
  • the internet of things (IoT) and other emerging markets for inexpensive, and often disposable, intelligent electronic devices are creating demand for smaller, thinner, often flexible, ruggedized, and fit-for-purpose electro-optic displays.
  • Currently known display devices are constructed of multiple pixels, that when viewed together, display a message or symbol to the user.
  • the pixels of these conventional displays are of the same type.
  • a mono-stable display for example will have only mono-stable pixels while a bi-stable display will have only two stable- states, electrically switchable pixels.
  • the pixels of common (non cholesteric) LCDs are mono stable, but each is the same as the others.
  • the pixels of three-color electrophoretic displays are multi-stable, that is they are stable in three states, but the pixels themselves are all the same.
  • an emissive/non-emissive display which is a unitary apparatus constructed such that a wide variety of electro-optic functions are enabled .
  • the emissive/non-emissive display even when having multiple pixels, enables sharing of selected structures among the pixels.
  • there sets of pixels in the display that exhibit different combinations of emissive and non-emissive properties, and advantageously operable properties, such as stability, sequencing, and switching properties, and another set of pixels that are different from the first set.
  • a highly flexible emissive and non-emissive may be construed to satisfy a wide range of display needs.
  • the emissive and non-emissive display may be polymorphic.
  • a polymorphic display which is a unitary apparatus constructed such that a wide variety of electro-optic functions are enabled.
  • the polymorphic display even when having multiple pixels, enables sharing of selected structures among the pixels.
  • a highly flexible polymorphic display may be construed to satisfy a wide range of display need.
  • transition sequencing is an important benefit of polymorphic displays and as described below, of polymorphic pixels.
  • property of transition sequencing is the ability to selectively and dynamically determine and effect a transition sequence, and therefore the operable properties of a polymorphic pixel or polymorphic display, responsive to different electrical signals.
  • electrical signals are generated responsive to various conditions, events and actions etc., such as those common to intelligent display devices described later herein.
  • FIG. l is a diagram showing operable states and corresponding optical states for a display in accordance with the present invention.
  • FIG. 2 is a diagram showing operable states and corresponding optical states for a display in accordance with the present invention.
  • FIG. 3 is a diagram showing operable states and corresponding optical states for a display in accordance with the present invention.
  • FIG. 4 is a diagram showing operable states and corresponding optical states for a display in accordance with the present invention.
  • FIG. 5A is a block representative of a display in accordance with the present invention.
  • FIG. 5B is a block representative of a display in accordance with the present invention.
  • FIG. 6A is a block representative of a display in accordance with the present invention.
  • FIG. 6B is a block representative of a display in accordance with the present invention.
  • FIG. 6C is a block representative of a display in accordance with the present invention.
  • FIG. 6D is a block representative of a display in accordance with the present invention.
  • FIG. 6E is a block representative of a display in accordance with the present invention.
  • FIG. 7 is a diagram showing operable states and corresponding optical states for a display in accordance with the present invention.
  • FIG. 8 is a diagram showing operable states and corresponding optical states for a display in accordance with the present invention.
  • FIG. 9A is a block representative of a display in accordance with the present invention.
  • FIG. 9B is a block representative of a display in accordance with the present invention.
  • FIG.10A is a block representative of a display in accordance with the present invention.
  • FIG. 10B is a block representative of a display in accordance with the present invention.
  • FIG. 11 is a legend to the stippling used in the Figures.
  • FIG. 12A is a block representative of a display in accordance with the present invention.
  • FIG. 12B is a block representative of a display in accordance with the present invention.
  • FIG. 12C is a block representative of a display in accordance with the present invention.
  • FIG. 12D is a block representative of a display in accordance with the present invention.
  • FIG. 13 is a diagram showing operable states and corresponding optical states for a display in accordance with the present invention.
  • FIG. 14 is a block representative of a display in accordance with the present invention.
  • FIG. 15A is a block representative of a display in accordance with the present invention.
  • FIG. 15B is a block representative of a display in accordance with the present invention.
  • FIG. 15C is a block representative of a display in accordance with the present invention.
  • FIG. 15D is a block representative of a display in accordance with the present invention.
  • FIG. 15E is a block representative of a display in accordance with the present invention.
  • FIG. 16A is a block representative of a display in accordance with the present invention.
  • FIG. 16B is a block representative of a display in accordance with the present invention.
  • FIG. 16C is a block representative of a display in accordance with the present invention.
  • FIG. 17 is a diagram showing operable states and corresponding optical states for a display in accordance with the present invention.
  • FIG. 18 is a diagram showing operable states and corresponding optical states for a display in accordance with the present invention.
  • FIG. 19 is a diagram showing operable states and corresponding optical states for a display in accordance with the present invention.
  • FIG. 20A is a block representative of a display in accordance with the present invention.
  • FIG. 20B is a block representative of a display in accordance with the present invention.
  • FIG. 20C is a block representative of a display in accordance with the present invention.
  • Polymorphic displays are unitary apparatus having multiple operable properties. Of particular interest are the operable properties, individually and in combination, of stability, switching and transition sequencing.
  • Polymorphic displays may be constructed to have multiple types of electro-optic display pixels (“pixels”), each type having different operable properties. Polymorphic displays may also be constructed with “polymorphic pixels” described herein, that individually have multiple operable properties, and are independently operable to produce different operating states.
  • the operable properties of a polymorphic display’s pixels determine its possible operating states, e.g. whether the pixel is stable or volatile, switchable or self-switching from one state to another or not switchable once in a previously switched to state, or the transition sequence is forward, forward-only (irreversible), reverse, or branching, or a combination thereof.
  • the optical state of a polymorphic display’s pixel corresponds to the pixel’s operating state[s] according to the pixel’s optical properties.
  • one polymorphic display pixel may be white in a stable, first state, and dark blue in a volatile, second state, and red in a third, stable state.
  • pixels of conventional electro-optic displays are of the same type.
  • a mono-stable display for example will have only mono-stable pixels while a bi stable display will have only two stable, electrically switchable pixels.
  • the pixels of common (non cholesteric) LCDs are mono-stable, but each is the same as the others.
  • the pixels of three- color electrophoretic displays are multi-stable, that is they are stable in three states, but the pixels themselves are all the same.
  • Pixels have at least two optical states according to their optical properties that typically include color perceptible to the human eye.
  • the optical state of the pixel may in general be determined by the resulting optical reflectivity, transmission, or polarization, of the pixel (at a specific wavelength or wavelength range of the illuminating source), whereas for an emissive display it may be determined by the intensity, polarization and spectral composition of the emitted light.
  • the optical state of the pixel may, e.g., be determined by a pseudo-color in the sense of a change in reflectivity at electromagnetic wavelengths outside the human visible range.
  • Pixels may be of various sizes, shapes, patterns and configured to stand alone or in groups (e.g. as segments to create alphanumeric characters, or RGB super pixels). Pixels typically comprise an electro-optic layer with electrodes either in direct contact with, or in close proximity to, the electro-optic layer. Depending on desired operable properties of the display pixels, the composition of their electro-optic layers may comprise for example, electrochromic materials, liquid crystals, electrophoretic particles, electrowetting fluids, electro-liquid powder materials, etc.
  • Display pixels may be categorized according to the operable properties associated with them being mono-stable, bi-stable and multi-stable, and polymorphic. Descriptions of the pixel types are described in general below, and later in detail.
  • Mono-stable pixels have one, stable operating state (and corresponding optical state) and a second, volatile operating state (and corresponding optical state). Mono-stable pixels also have the stability operable properties of being reversible and self-switching. That is, they automatically, or “self’, switch from their volatile operating state to back their stable, first operating state when power to the pixel is terminated (or drops below a threshold necessary to maintain the state).
  • a mono-stable pixel s first, operating state is stable without power.
  • an electrical switching signal is applied to a mono-stable pixel, the pixel transitions from a stable, first operating state to a volatile, second, operating state.
  • the volatile operating state is maintained as long as a maintenance signal is applied to the pixel.
  • the maintenance signal is terminated (for whatever reason) the pixel self-switches from the second operating state back to the first, stable operating state.
  • Examples of mono-stable displays comprised of mono-stable pixels are common LCDs (liquid crystal displays), EPDs (electrophoretic and ECDs (electrochromic displays), and LEDs (light-emitting diodes) and OLEDs (organic light-emitting diodes).
  • FIG. 1 The operable states and corresponding optical states of an exemplary mono-stable pixel 100 are illustrated in FIG. 1
  • the first operating state 111 is stable and switchable, and its corresponding optical state (color) is white.
  • FIG. 11 presents a legend for colors-to-pattems, shapes and symbols used in the other figures.
  • the second operating state 113 is volatile, self-switchable (reversible), and its corresponding optical state is purple. When self-switched (power is terminated to the pixel) the pixel transitions back (reverses) to the stable, first operating state 111, and corresponding optical state (white).
  • FIG. 1 Also illustrates a mono-stable pixel 200 similar to mono-stable pixel 100.
  • Mono-stable pixel 200 however has an optional second volatile, self-switching operating state 216, and a corresponding blue optical state.
  • pixel 200 self-switches from the optional second volatile operating state 216 to the stable, first operating state 212 when power to the pixel is terminated or disrupted.
  • the pixel 200 has the transition sequence property (described later) of branching, that is the property whereby the transition sequence depends on the current state of the pixel and the switching signal.
  • a first switching signal transitions the pixel from its stable, switchable first operating state 212 to a first volatile, self-switchable operable state 214, and a corresponding optical state, in this case purple.
  • a second switching signal (different than the first) transitions the pixel to a second volatile, self-switchable operable state 216, and corresponding optical state, in this case blue.
  • Bi-stable pixels have two stable operating states. Switching between the two, stable operating states is accomplished with an electrical switching signal. Once switched, the operating state (and the corresponding optical state) persists when the power is terminated (without a maintenance signal).
  • Bi-stable pixels may be reversible (e.g. EPDs, conventional ECDs, cholesteric, ferroelectric or zenithal bistable LCDs) or irreversible (as described in US patent No. 9,030,724 Flexible and Printable Electrooptic Devices).
  • EPDs electronic photosensitive diode
  • Conventional bi-stable pixels are electrically switched and are not self-switching (but always switchable).
  • Some pixels characterized as bi stable however, have limited persistence in one or the other optical states. In other words, some bi-stable pixels are self-switching over time. Such pixels, may therefore be more accurately considered mono-stable with limited persistence in the second operating state (the first being unpowered).
  • FIG. 2 The operable states and corresponding optical states of exemplary bi-stable pixels are illustrated in FIG. 2.
  • Pixel 300 has a first operating state 310 that is stable and switchable, and a corresponding optical state (color) that is white.
  • the second operating state 320 is also stable and switchable (and reversible), and its corresponding optical state is red. Note that a maintenance signal is not required for the pixel to remain in the second operating state once switched from the first operating state. Note further that the second operating state is not self switching, and a switching signal is required to switch from the second, stable operating state, and corresponding optical state, back to the first stable operating state.
  • Pixel 400 is also bi-stable however unlike the pixel 300 in the previous example, once switched from the first stable, switchable operable state 430 to the second, stable operable state 440, pixel 400 is non-switchable (not switchable or self-switching). In the second operable state, pixel 400 is irreversible and permanent. It cannot be switched (transitioned from the second operable state to the first) and has the stability property of being non-switchable and a transition sequence property of being irreversible.
  • bi-stable pixels In addition to bi-stable pixels there are a few types of multi-stable pixels, typically having three, stable states.
  • One example are the pixels in three-color, electrophoretic displays. Each pixel contains three distinct particle types (e.g., pigment or dye particle) corresponding to different colors. Note however that as with conventional mono-stable and bi-stable displays, the operable properties of the pixels are the same.
  • the operable states of a multi-state pixel 500 are illustrated in FIG. 3.
  • pixel 500 is stable, switchable (forward-only, irreversibly) with a corresponding optical state (color) that is white.
  • the second operating state 520 is also stable and switchable, with a corresponding optical state (color) that is blue.
  • the transition sequence is forward-only to the third operating state 530. It cannot be switched to the first stable operating state from the second stable operating state.
  • the third operating state 530 is also stable and switchable, and has a corresponding optical state (color) that is red.
  • the transition sequence therefore comprises three inter-state transitions (described later), one which is forward- only and irreversible, and two that are forward-only, reversible and repeatable.
  • Polymorphic pixels may be constructed to have various combinations of operable properties.
  • Polymorphic pixels have at least two stable operating states, an unpowered, first state and at least one other stable state which may for example be irreversible and permanent as previously described. They also have one or more volatile operating states.
  • FIG. 4 illustrates the operable states of a polymorphic pixel 600.
  • the pixel has two stable operating states 610 and 630 and one volatile operating state 620.
  • Pixel 600 also has two transition sequence branches 601 and 602. The transition sequence branch is selected with a switching signal that determines the next operating state.
  • Branch 601 comprises a first operating state 620 that is stable, switchable with a corresponding optical state (color) that is white.
  • Branch 601 also comprises a second operating state 620 that is volatile, self-switching with a corresponding optical state (color) that is red.
  • pixel 600 Upon termination or disruption of a maintenance signal, pixel 600 will self-switch and transition from the volatile, self-switching state 620 to the previous operating state 620.
  • Branch 601 comprises two inter-state transitions which are both reversible and repeatable, until and unless, transition sequence branch 602 is selected with a switching signal that transitions to operating state 630.
  • Branch 602 comprises the same first operating state 620 as branch 601, however unlike branch 601 it has a second operating state 630 that is irreversible and permanent.
  • branch 602 comprises only one inter state transition, a forward, irreversible transition from operating state 620 to operating state 630. Once switched (transitioned) along branch 602 to operating state 630 by an appropriate switching signal, the pixel is no longer switchable (non-switchable). In total the transition sequence property for pixel 600 includes three inter-state transitions (two repeatable, and one irreversible).
  • FIG. 7 illustrates the operable states of another exemplary polymorphic pixel 900.
  • the pixel in this case has two stable operating states 905 and 908 (and two corresponding optical states, white and black respectively).
  • Pixel 900 also has two volatile operating states 906 and 910 (and two corresponding optical states, red and purple respectively).
  • polymorphic pixel 900 has four possible operating states and corresponding optical states (red, white, black and purple).
  • polymorphic pixel 900 has a transition sequence comprising two branches 902 and 903. The branch selected depends on the switching signals and the prior operating states of the pixel.
  • the transition sequence along branch 902 consists of a stable, switchable first operating state and a volatile, self-switching second operating state. Branch 902 is reversible and repeatable until the pixel is operably switched to branch 903.
  • the transition sequence along branch 903 consists of the same first operating state 905, stable, switchable with a corresponding optical state (color) that is white.
  • Branch 903 also comprises a stable, switchable second operating state 908 with a corresponding optical state (color) that is black.
  • the transition sequence from 905 to 908 is not reversible (irreversible) and is therefore not repeatable. From operating state 908 the transition sequence is only forward to operating state 910.
  • the third operating state 910 along branch 903 is volatile, self-switching with a corresponding optical state (color) of purple. The inter-state transitions between operating states 908 and 910 are therefore reversible and repeatable.
  • the transition sequence along the entire branch 903 from operating state 905 to operating state 910 includes both forward, irreversible transitions and forward, reversible transitions. Note that the once the polymorphic pixel 900 is switched and transitions to branch 903 (from operating state 905 to operating 908) it cannot be switched, transition to branch 902 and operating state 908. The polymorphic pixel 900 can however effect different operating states along branch 902 and then switch be switched, transition to branch 903.
  • An operable property of pixels is transition sequencing, that is, the property of being able to transition between multiple, different operating states in sequences that include forward, forward-only (irreversible), reverse (reversible), repeatable and non-repeatable and combinations thereof.
  • a transition sequence is comprised of inter-state transitions, that is transitions between two consecutive operable states of a pixel. Exemplary transition sequences are described below and illustrated in embodiments 100, 200, 300, 400, 500, 600, 900, and 1000. Transition sequencing also includes branching. Branching is the property of being able generate different sequences of inter-state transitions from a particular operable state of the pixel. A branch is created by effecting one of a plurality of transitions according to different electrical signals.
  • Embodiment 200 illustrates simple transition sequence including branching for a mono-stable pixel. Of particular interest are complex transitional sequences for polymorphic pixels including branching properties such as those illustrated in embodiments 900 and 1000.
  • polymorphic displays introduce the ability to electrically switch (with a switching signal) or self-switch (by terminating a maintenance signal) the operating state from one to another operating state that is other than the previous one.
  • transition sequencing property of polymorphic pixels can be produced using a variety of different polymers and combinations of them, e.g. with mixtures combining more than one type, or depositing more than one layer of them within the polymorphic pixel.
  • transition sequencing is an important benefit of polymorphic displays and as described below, of polymorphic pixels.
  • property of transition sequencing is the ability to selectively and dynamically determine and effect a transition sequence, and therefore the operable properties of a polymorphic pixel or polymorphic display, responsive to different electrical signals.
  • electrical signals are generated responsive to various conditions, events and actions etc., such as those common to intelligent display devices described later herein.
  • a polymorphic display is an electro-optic display comprising a single polymorphic pixel. More typically however, a polymorphic display is a unitary apparatus constructed having at least two pixels, the pixels having at least some of the following elements in common: structure, materials, circuitry, and optionally a display driver IC. As previously described, the display pixels may be of different types according to their operable properties.
  • the structure of a polymorphic display determines its physical form. The structure comprises for example, substrates, spacers, matrices, separators, spacers, barriers, sealants, transparent/viewing surfaces (e.g. ‘windows’) etc.
  • a polymorphic display’s structure complements that of the electro-optic materials, other materials (e.g. adhesives) and electrical circuitry (including electrodes).
  • the electro-optic layers of different pixel types e.g. electrochromics, LCDs, EPDs etc.
  • electrochromics, LCDs, EPDs etc. are often constructed with materials that are fluid or semi-solid and therefore that depend on various structures to hold them. And importantly, to reliably couple to the electrical circuitry.
  • a polymorphic display’s electro-optic layer, and the pixels of which they are made, may share common materials. Such materials may for example be constructed as a single, continuous layer across multiple pixels, such as the electrolyte illustrated in FIG. 5 A and 10A. Alternatively, a material (e.g. the electro-optic material 710 of FIG. 5A and 1310 and 1320 of FIG. 10A) may be common to some but not all the pixels, and may be constructed as discrete, spatially separated elements within same physical layer (or the same manufacturing process). Such patterning advantageously allowing for other common materials to be interspersed among them.
  • a pixel comprises an electro-optic layer with electrodes either in direct contact with, or in close proximity to, the electro-optic layer.
  • the electrodes are configured for applying electrical signals to the pixels individually or in groups and are typically formed on common structure (e.g. flexible substrates or layers).
  • the electrodes may be configured in various ways including vertical (e.g. on the top and bottom surfaces of an electro optic layer, interdigitated (both electrodes are on the same layer), or combinations of both.
  • the electrodes on the side or sides of the electro-optic layer facing the viewing surface or surfaces are transparent e.g. ITO or transparent, conductive silver-inks patterned on PET.
  • the pixel electrodes may be exposed for connection to circuitry of another device such as an intelligent display device describe herein.
  • the electrodes may also be coupled to additional circuitry and components (e.g. display driver IC, backplane etc.) constructed as part of the polymorphic display apparatus (e.g. using common structure), for pixel addressing, signal management/noise reduction, visible verification (such as that described in US patent applications 14,927,098 Symbol Verification for an Intelligent Label Device, and 15/368,622 Optically Determining Messages on a Display) etc.
  • additional circuitry and components e.g. display driver IC, backplane etc.
  • additional circuitry and components e.g. display driver IC, backplane etc.
  • visible verification such as that described in US patent applications 14,927,098 Symbol Verification for an Intelligent Label Device, and 15/368,622 Optically Determining Messages on a Display
  • exemplary display pixels 700, 800 and 1100 are configured with electrodes on the surfaces of the electro-optic layer (e.g. front and back).
  • FIG. 10A and 10B is an exemplary four-pixel structure employing interdigitated electrodes and different, patterned material layers to create pixels having different operable (and associated optical) properties. The viewing perspective is from the back of the structure. Note that the illustrations are intended only to focus on certain elements of a polymorphic display and not completed devices. Note further, the common material layers of which some are patterned and some continuous across the pixels.
  • the first layer 1200 of the four-pixel structure (viewed from the back) is a transparent substrate 1230 having interdigitated electrode 1220 and four companion electrodes 1210 (of which only one is numbered). Electrode 1220 is common to the four companion electrodes, all of which are collectively part of the display circuitry. Each of the interdigitated patterns are the foundation for four individual pixels. Structure 1300 shows layer 1200 with printed (or otherwise deposited) polymer 1310 and a different polymer 1320. Polymer 1310 spans two pairs of interdigitated electrodes so the corresponding pixels will have the same operable properties. Polymer 1310 covers a single electrode pair and the corresponding pixel will have operable properties different from the other three.
  • Structure 1400 shows layer 1300 with a printed (or otherwise deposited) opaque electrolyte 1410.
  • Electrolyte 1410 is an opaque EC mix.
  • all three of the pixels with polymer layers will have the properties of being volatile, self-switchable.
  • the fourth interdigitated electrode pair (the one without a polymer layer) will have the properties of being stable, switchable, irreversible and permanent.
  • Structure 1500 is the same as structure 1400 with a transparent EC mix instead of the opaque EC mix 1410.
  • This integrated, process friendly structure comprises four separately operable pixels, three having the
  • a signal protocol is used by the processor to manage the different switching signals and maintenance signals according to the types of pixels which comprise the polymorphic display.
  • the signal protocol provides the timing, duration, pattern (e.g. pulse shape, sequence), frequency, voltage or current, polarity etc. required by the processor to generate the appropriate signals.
  • a switching signal is an electrical signal applied to a pixel for setting the operating states of the pixel (e.g. for switching from one operating state to another).
  • a maintenance signal is an electrical signal applied to a pixel in a volatile state (self switching) to maintain its current operating state.
  • the maintenance signal is often different from the switching signal that switched the pixel to the current volatile operating state that is maintained by the maintenance signal.
  • An intelligence display device is an apparatus comprising a polymorphic display, and some or all of electronics, a power apparatus and appropriate to the application, a communication apparatus, sensors, and actuators.
  • An intelligent display device is typically a unitary apparatus configured to be coupled or combined with a good or its packaging. Often, but not always, the intelligent display device is low cost, often disposable, low power and small in size. In some applications, though the intelligent display device is significantly larger and designed to present high-content messages or messages to be read by humans or machines at a distance. Exemplary configurations include labels, patches, tags, smart-cards, loyalty cards, packaging, containers, seals, caps, documents, test/sensing/monitoring devices, terminals, electronic-shelf labels, free standing displays, electronics devices etc. [0092] Electronics
  • intelligent display device includes electronic functions, for example, processor, memory, clock/timer, security, verification, communications and sensors, etc. that may be integrated into a single electronic device or implemented with discrete components.
  • the electronics will also typically include display driver circuitry configured to store and process appropriate data and algorithms (e.g. a signal protocol), temperature compensation etc.to generate the electricals to the polymorphic display and pixels it comprises.
  • the display driver circuitry may be advantageously configured with the processor and memory or one or more separate components. And further, the display driver circuitry may be configured as part of the polymorphic display or as part of the electronic functions of the intelligent display device, or, distributed between the two.
  • the intelligent display device includes one or more power apparatus for powering the electrical functions in the intelligent label including a polymorphic display.
  • Exemplary power apparatus include internal energy storage such as batteries or charged capacitors, wired interfaces capable of receiving electrical energy, wireless energy harvesters, or a combination thereof.
  • the energy harvester for example, may produce electric energy from light (e.g. solar cell), RF energy (e.g., antenna/rectifier), thermal energy (e.g., thermopile), or shock and vibration (e.g. strain gauges, nanogenerators, MEMS devices) that the intelligent label device is subject to.
  • the intelligent display device also has electronics that enable wireless or wired communication to or from the intelligent label.
  • Exemplary wireless communication apparatus includes those that support Wi-Fi, Bluetooth, BLE, RFID (e.g. RAIN or NFC), ZigBee and other local area wireless networks, low power wide area (LPWN) and cellular and other wide area networks.
  • Intelligent display devices may include support for portable memory chips, cards, sticks and other portable memory storage devices.
  • An intelligent display device may have one or more sensors sensing the inside or outside environment (outside or inside the intelligent display device), the polymorphic display or other components or systems of the intelligent display device.
  • exemplary sensors include a temperature sensor, a humidity sensor, and altitude sensor, a pressure sensor, an optical sensor, a vibration sensor (including a shock sensor), a humidity sensor, biological or a chemical sensor (including a gas sensor, a pH sensor), a magnetic sensor, a smoke sensor, a radiation sensor etc.
  • an intelligent display device may have one or more actuators.
  • Actuators activate, deactivate or otherwise effect control over electrical functions in the intelligent display device in response to external or internal stimulus, e.g. mechanical action, sensor input, electrical or wireless signals etc.
  • Actuators may be used to activate different electrical functions at different times, e.g. when an item is shipped (the package is sealed) or when an item is received (the package is opened).
  • Actuators may also minimize power consumption, and thereby maximizing the shelf- life/operating life of intelligent display devices having internal power apparatus, by activating electronics only when appropriate to the application. Actuators, in cooperation with timers/clocks may also be used to establish the time/date an event occurs.
  • Exemplary actuators include mechanical switches (e.g. the open or close an electrical circuit), electro-optic, electrochemical, electro-mechanical and electro-acoustic devices, wired connectors (for receiving electrical signals), wireless receivers (for harvesting RF energy, receiving RF signals) etc., and are described in US patent 9,471,862 An Intelligent Label Device and Method.
  • FIG. 5A shows an exemplary configuration of a polymorphic display 700 comprising two pixels, each having different operable properties, in side view and front view. For illustration purposes, only two pixels are shown although it is to be understood that a polymorphic display may comprise many such pixels.
  • the right pixel 701 is bi-stable, having a bi-stable, permanent and irreversible second operating state (such as 200 in FIG. 2), whereas the left pixel 702 is mono-stable and self-switchable (such as 100 in FIG. 1).
  • bi-stable pixel 701 In regard to bi-stable pixel 701, detailed embodiments of bi-stable, permanent and irreversible display devices and pixels, are disclosed in US patent 9,030,724 Flexible and Printable Electrooptic Devices. For simplicity, only the key aspects pertaining to the configuration and function of such pixels within a polymorphic display are described herein and presented in 700 in FIG. 5A.
  • Exemplary embodiment 700 consists of an electro-optic layer 703 further including an electropolymerizable monomer, an electrolyte (e.g. ionic liquid), and (optionally) highly reflective particles (e.g. TiO?) collectively, here and throughout, referred to as an “EC mix” (“electrochromic mixture”).
  • the EC mix as illustrated is of a substantially uniform composition.
  • the electro-optic layer 703, in this example, the EC mixture, is sandwiched between a pair of electrodes; a front electrode 704 and a back electrode 705.
  • the front electrode is at least partially transparent (e.g. ITO) and configured on a substantially transparent substrate 706 (e.g., glass, plastic, etc.) and is advantageously sealed with a barrier/protective layer.
  • the back electrode 705 and back substrate/barrier 709 may both either be transparent (for front and back side viewing of the display) or opaque (front side only viewing).
  • Mono-stable pixel 702 uses a conjugated (conductive) polymer film 710 that can switch reversibly between two distinctly different operable states when the polymer is in contact with an electrolyte (such as the one contained in the EC mix 703).
  • the operable states correspond to a conductive (oxidized chemical) state and an insulating (neutral or reduced chemical) state according to the presence of a switching signal followed by a maintenance signal, or the termination or disruption of the maintenance signal.
  • the pixel 702 transitions from a stable, first state to a volatile second state. The pixel remains in the volatile second state for the duration of the maintenance signal.
  • the maintenance signal is terminated (or disrupted for any reason) the pixel self switches (transitions back) to the stable, first state.
  • the EC mix 703 of pixel 701 comprises an electrolyte that can function as the electrolyte for pixel 702.
  • the monomer and other materials in the EC mix do not prevent the electrolyte from use in both pixels.
  • the two pixels can have in common electrode 705, top and bottom substrates 706, 709, and barrier/protective layer 707. Additionally, they can share a common, patterned electrode layer (and manufacturing process) comprising the pixel’s respective front electrodes 704 and 711. They can also share mask layer 708 described below. Not shown is the structure that would encapsulate the entire apparatus (e.g. the side barrier/protective structure) and the appropriate display driver circuitry with connections to the pixel electrodes.
  • polymorphic display 700 is a unitary apparatus comprising two pixels, each a different type according to their respective operable properties (bi-stable, permanent and irreversible, and mono-stable), and further that have in common, structure, materials and circuitry.
  • the two pixels 701 and 702 share a single, common electrolyte layer.
  • the switching voltages for the polymer films in the mono-stable pixel 702 are typically significantly lower (near IV) than that typically required for electropolymerization (near 3 V) in the bi-stable pixel 701. This provides an upper threshold means to keep the monomer in the EC mix from electropolymerizing yet allowing the self-switching polymer 710 to switch between operating states by applying a switching signal followed by applying and then terminating maintenance signal across the common back electrode layer 705 and the front electrode 711.
  • the front electrodes, 704 and 711, for the two operable pixel types of the polymorphic display 700 can be made of different (transparent conductor) materials, it is preferably made of the same material by patterning a single front electrode layer deposited onto the single substrate 706. Depending on the locations of the address lines/circuitry to the pixel electrodes of the display (not shown in FIG. 5A), while providing a high display contrast (dark background of the pixel openings), it may be advantageous to mask certain areas by an opaque, light absorbing material 708.
  • One group of electrochromic polymers are switchable from a stable, un-powered operating state corresponding to an oxidized chemical state, and a corresponding clear optical state, to a volatile, self-switching operating state corresponding to a neutral chemical state, and a corresponding colored optical state, and self-switching back to the stable, un-powered operating state and corresponding oxidized chemical state, and corresponding clear optical state.
  • Exemplary polymers of this type include dioxythiophenes (e.g. certain XDOT, such as PProDOT, PEDOT).
  • Another group of electrochromic polymers are switchable from a stable, un-powered operating state corresponding to a neutral chemical state, and a corresponding first, colored optical state, to a volatile, self-switching operating state corresponding to an oxidized chemical state, and corresponding second, colored or predominately clear optical state, and self-switching back to the stable, un-powered operating state and corresponding neutral chemical state, and corresponding first, colored optical state.
  • Exemplary polymers of this type include thiophene based polymers (e.g. poly(methylthiophene)).
  • viologen can be adsorbed by a porous material, such as nanoparticle-based TiCE, to form an active layer (e.g. in place of the polymer layer 710), or added to the EC mix 703, and may additionally function or co-function as the electrolyte.
  • an optional layer also known as a charge storage layer
  • a complementary conducting polymer material 714 on the counter (back) electrode 705, to facilitate the self-switching process and/or to add additional material layers to protect the counter (back) electrode 705 from the electrolyte 703.
  • polymers include anodically coloring polymers, such as XDOPs (dioxypyrroles) or alternating copolymers of XDOT and carbazoles such as PEDOT-NMe(Cbz), and cathodically coloring polymer such as XDOTs such as PEDOT or PProDOT, which self-switch to an oxidized state.
  • Cathodic materials may also be deposited to protect a bare counter electrode including derivatives of bipyridinium, such as viologen, and anthraquinone and its derivatives in solution.
  • An opaque or reflective (e.g. TiCE additive) EC mix may mask the electrochromic characteristics of the above materials, or they may be intentionally included in the resulting optical states as seen from the front side or back side (for a two-sided display).
  • Self-switching polymer films are typically prepared by spray casting 5mg/mL polymer solutions in toluene. When cured, the deposited layer may become a film less than sub micron thick.
  • Self-switching polymers may be deposited onto the electrode using a variety of methods including: spray, spin, or drop casting neutral electrochromic polymer solutions; printing technology such as inkjet printing; dip casting from solution; and oxidative chemical vapor deposition of conducting polymer films or electrochemical deposition.
  • the properties of self-switching polymer films may further be manipulated through a chemical defunctionalization step rendering the film less soluble, allowing for deposition of additional layers such as the layer of EC mix 703.
  • an individual pixel of the polymorphic display 700 is switched by an electrical signal applied to its corresponding electrode pair (704 and 705 or 711 and 705).
  • both the states of the bi-stable pixel 701 and the mono-stable pixel 702 are stable and each having a first, white optical state, 712 and 713, as determined by the reflective TiCE of the EC mix and the transmissive property of the electrochromic polymer layer 710.
  • the corresponding voltages across each respective electrode pair is 0V (715 and 716).
  • FIG. 5B illustrates the respective optical states 718, 720 of the polymorphic display 700 after application of respective independent switching signals.
  • the switching signal for irreversibly transitioning the bi-stable pixel 701 into an irreversible and permanent operating state can be accomplished through a variety of switching protocols such as those disclosed in US patent 9,030,724 Flexible and Printable Electrooptic Devices and US provisional patent application 14/797,141 Device and Method to Fix a Message on a Display, including e.g. applying a voltage above a certain threshold (as indicated by 719 of e.g. 3 V) for a defined time duration (e.g., 2s).
  • the anode typically is the (front) electrode 704 such that the polymerized monomer 717 is (anodically) formed on or at the electrode, displacing the (white) EC mix and further providing a substantial change of color (e.g. from white to dark blue) as observed from the viewing side.
  • the operable (and optical) state will remain as it is permanent and irreversible.
  • the switching signal for reversibly transitioning the mono-stable pixel 702 into a volatile operating state can be accomplished by, for example, applying a voltage above a certain threshold (as indicated by 721 of e.g. IV) for a defined time duration (e.g., Is).
  • a certain threshold as indicated by 721 of e.g. IV
  • a defined time duration e.g., Is.
  • the cathode is the front electrode 711 in case of electrochromic polymers providing chemically neutral (reduced) volatile states (as shown in FIG. 5B) and oxidized stable states (as shown in FIG.
  • a maintenance signal is applied with the same effective polarity as the switching signal, in order for pixel to maintain its current state. Upon termination or disruption of the maintenance signal the volatile state will self-switch back to its original white state (713 in FIG.
  • polymorphic functionality is achieved in a single pixel, called a polymorphic pixel.
  • a polymorphic pixel multiple (two or more) polymorphic pixels with the same operable properties can also form a polymorphic display, as discussed above.
  • FIG. 6A illustrates an exemplary embodiment 800 of a polymorphic pixel 801, in side view and front view.
  • the pixel 801 follows the same vertical structure configuration as that of pixel 702 shown in FIG. 5A, and will thus not be described in detail except wherein there are differences that pertain to the polymorphic functionality.
  • the (optional) complementary conducting polymer material 714 is not shown and the EC mix 703, which together with the conducting polymer layer 710 form the electro-optic layer, initially will be assumed to contain highly reflective particles (e.g. TiCE) as an additive to the otherwise natively transmissive (clear) EC mix.
  • highly reflective particles e.g. TiCE
  • the polymer layer 710 is assumed be self- switchable, comprising an initial stable, clear optical state and a corresponding oxidized chemical state, switchable to a volatile red optical state with a corresponding reduced chemical state.
  • a polymer which such characteristics includes, e.g., poly ⁇ 3,4-di(2- ethylhexyl oxy)thi ophene-co-3 , 4-di (m ethoxy )thi ophene ⁇ .
  • the initial (i.e., before any application of an electrical signal to its front 711 and back 705 electrodes) operable state 905 of pixel 801 is stable with a corresponding white optical state 804 (FIG. 6A), as determined by reflected light from the Ti0 2 particles of the EC mix 703 transmitted through the clear polymer layer 710.
  • a switching signal (along branch 902) as indicated by 806 in FIG. 6B
  • the operable state of the pixel switches to a volatile state 906 with a corresponding red optical state 807.
  • this optical state will remain for the duration of the maintenance signal, after which it will self-switch back to its operable state 905.
  • the pixel 801 will remain in a self-switchable state along branch 902 as long as the switching signal level does not exceed the threshold (e.g. 3 V) for electrochemical polymerization of the monomer in the EC mix 703. If, however, the applied voltage reaches the threshold voltage, with the front electrode 711 being the anode, the monomer polymerizes 802 (FIG. 6C) onto (or near) the self-switchable polymer layer 710. Note that during the switching the polymer layer 710 is in an oxidized chemical state, clear optical state, and electrically conductive state, which facilitates the polymerization process.
  • the threshold e.g. 3 V
  • the operable state of the pixel switches irreversibly to a stable state 908 with a corresponding, e.g., dark blue optical state 809.
  • This optical state is determined by the color of the polymerized layer 802. Note that after the switching is complete, the self-switchable polymer layer will remain in a clear state.
  • the pixel is now in a mono-stable and self-switchable operable state, as further applying a switching signal 811 (FIG. 6D) with a continued maintenance signal results in a volatile state 910 with red color of the self-switchable polymer layer 721.
  • the resulting optical state 812 will generally be a combination of 721 (here, red) and 802 (here, dark blue). For instance, and in this particular case, if layer 721 is relatively thick, the optical state will be a predominantly red color; if layer 721 is relatively thin (i.e.
  • the optical state will closely match the dark blue color of layer 802; or, if 721 has a thickness somewhere in the middle, the color may be a compound purple. Again, after removal of the maintenance signal, indicated by 813 in FIG. 6E the pixel will self-switch back to operable state 908 (and corresponding optical state 809).
  • the reflective Ti0 2 particles are not included in the EC mix 703 resulting in a transmissive (clear) optical property. This alters the optical state of the initial operable state 904, depending on the reflective properties of the back electrode 705.
  • the back electrode 705 is presumed light absorbing (e.g. carbon black) resulting in an initial optical state of black as illustrated by 1001 of the operable states of this embodiment 1000 in FIG. 8.
  • the operable and optical states of the other states along branches 1002 and 1003 are the same as those illustrated and discussed in FIG. 7, 902 and 903, respectively (here assuming, for simplicity, that layers 721 and 802 are largely reflective, and the yellow tint of the EC mix 703 does not contribute).
  • this particular embodiment enables additional operable states by analogously polymerizing the monomer of the EC mix onto (or near) the back electrode by applying an opposite polarity of the switching signal onto the pair of electrodes.
  • additional operable states are shown along an extended branch indicated by 1005, as well as, an additional third branch 1004, with operable states as indicated.
  • the volatile optical states 1006 and 1008 are the same as 906, and that the stable optical states of 1010 and 1011 are virtually the same as 908 (ignoring any effect of viewing through the transmissive EC mix).
  • the reflective Ti0 2 particles are again not included in the EC mix 703, but an inert dye (here assumed yellow) is added resulting in a corresponding yellow tint of the EC mix.
  • the back electrode 705 is presumed light reflective.
  • the concentration of the dye is such that light will be reflected through a double pass of the pixel stack yielding, in this case, an initial yellow optical state 1001.
  • states 1010 and 1011 which will have a new optical state of green, resulting from the dark blue polymerized layer on the back electrode viewed through the yellow tinted EC mix.
  • this configuration can exhibit five different optical states, three stable states and two volatile states, with a variety of operable properties including irreversible and mono-stable states.
  • FIG. 9A illustrates another exemplary embodiment 1100 of a polymorphic pixel 1101 with a non-switchable operating state, in side view and front view.
  • the pixel 1101 follows the same vertical structure configuration as that of pixel 801 shown in FIG. 6 A, and will thus not be described in detail except wherein there are differences that pertain to the polymorphic functionality.
  • the reflective T1O2 particles are not included in the EC mix 703 resulting in a transmissive (clear) optical property.
  • the polymer layer 1102 is again assumed be self-switchable, comprising an initial stable, clear optical state and a corresponding oxidized chemical state, switchable to a volatile red optical state with a corresponding reduced chemical state.
  • the self-switching polymer layer 1102 is present on the back electrode 705 (as opposed to the front electrode 711 as in FIG. 6A).
  • the back electrode 705 is reflective or transparent with an additional diffuse reflective layer behind it (not shown in FIG. 9A).
  • the initial (i.e., before any application of an electrical signal to its front 711 and back 705 electrodes) operable state 610 of pixel 1101 is stable with a corresponding white optical state 1103, as determined by reflected light from back electrode 705.
  • the operable state of the pixel switches to a volatile state 620 with a corresponding red optical state 1106.
  • this optical state will remain for the duration of the maintenance signal, after which it will self-switch back to its initial operable state 610.
  • the pixel 1101 will remain in a self-switchable state along branch 601 as long as the switching signal level does not exceed the threshold (e.g. 3 V) for electrochemical polymerization of the monomer in the EC mix 703. If, however, the applied voltage reaches the threshold voltage, with the back electrode 705 being the anode, the monomer polymerizes 1108 (FIG. 9C) onto (or near) the self-switchable polymer layer 1102. Note, again, that during the switching the polymer layer 1102 is in an oxidized chemical state, clear optical state, and electrically conductive state, which facilitates the polymerization process.
  • the threshold e.g. 3 V
  • the operable state of the pixel switches irreversibly to a stable state 630 with a corresponding, e.g., dark blue optical state 1109.
  • This optical state 630 is determined by the color of the polymerized layer 1102 as the EC mix 703 is transmissive. Note, again, that after the switching is complete, the self-switchable polymer layer will remain in a clear state. However, in contrast to Example 1 above, this operable state does not allow for any further switching affecting the corresponding optical state 1109, thus it is in an operable state which is non-switchable.
  • the electrode layers for switching the electro-optic layers have been focused on non-pattemed configurations with either transparent or opaque optical properties.
  • an interdigitated pair of electrodes Such configurations enable a single patterned electrode layer instead of two separate non-patterned electrode layers simplifying the manufacturing process of polymorphic pixels and displays. Furthermore, this allows for two activation surfaces per interdigitated electrode pair in a single layer with a multitude of operable states.
  • an interdigitated transparent electrode structure e.g. ITO
  • ITO interdigitated transparent electrode structure
  • FIG. 10A shows (in a back side view) a conceptual electrode layout 1200 consisting of four pairs of interdigitated electrodes (corresponding to four pixels of the completed polymorphic display).
  • one digitated electrode of each of the four pairs is (optionally) connected to a common electrode connection 1220.
  • a common electrode connection 1220 can be addressed using the common electrode 1220 and a pixel specific digitated electrode (e.g. 1210).
  • the interdigitated electrode layer is deposited (e.g. directly printed or by patterning of a uniform film using, e.g. photolithography or laser ablation) onto a substrate 1230 (outlined).
  • This process is further followed by deposition (e.g. printing) of one or more self switching polymers (all in the same layer), such as shown in 1300 by a first self-switching polymer 1310 and a second self-switching polymer 1320. Note that the deposition can continuously span of more than one electrode pair (such as in the case of 1310).
  • the widths and separation of the electrode digits are optimized with respect to the particular properties of the self-switching polymer (e.g. thickness) and switching protocol.
  • the self-switching polymer e.g. thickness
  • switching protocol e.g. switching protocol
  • the EC mix layer can be deposited (e.g. by a further printing process), as shown by layer 1410 in FIG. 10B.
  • the EC mix is opaque (white, containing Ti0 2 particles), however, it may also be transparent (without Ti0 2 particles) as shown in 1500 by layer 1510.
  • the EC mix can also be deposited onto select pixels using different EC mix compositions (e.g. a different monomer polymerizing to a unique color).
  • some pixels may only have an electrolyte printed on top (i.e. no EC mix).
  • the above examples disclose embodiments of polymorphic displays and pixels with various operable states corresponding to optical states determined by reflective properties of the pixels.
  • the method and means can advantageously be extended to transmissive and/or polarization properties.
  • the self-switching polymer or polymerized monomer layers can be designed (with appropriate activation protocols) such that the transmitted light through (the colored layers in) the pixels determine the optical state.
  • both the back electrode and substrate are at least partially transmissive as well.
  • electrochromic materials could be combined with a liquid crystal material to from an electro optic layer capable of generating both polarization and color changes to transmitted light through the layer (with corresponding operable states).
  • polarizers in front and behind the electro-optic layer e.g. on the outer surface of front (and back, if transmissive) substrate or cover layer, could, e.g., convert the polarization changes to light intensity changes.
  • the above exemplary embodiments primarily working in the visible wavelength range.
  • the embodiments of the current invention also include wavelength outside of the human visible range (e.g. machine reading).
  • electrochromic polymers typically exhibit significant reflectivity changes in the IR wavelengths between the oxidized (conductive) and reduced (non-conductive) states, these materials can thus also be utilized for generating operable state changes outside of the visible range for polymorphic pixels and displays.
  • FIG. 12A-D illustrates another embodiment of the current invention in side view and front view, in which the pixels of a polymorphic display 1600 operates in a shutter mode (i.e., a means for either transmitting or reflecting/absorbing light).
  • a shutter mode i.e., a means for either transmitting or reflecting/absorbing light.
  • the EC Mix 703 spanning both the right pixel 1601, with a bi-stable, permanent and irreversible second operating state, and the left pixel 1602, which is monostable and self-switchable, is predominantly transparent (i.e., without any Ti02 in the EC Mix).
  • the complementary conducting polymer material 714 can be patterned appropriately to all or a set of pixels of the polymorphic display. Additionally, the material may be pixel specific according to the intended properties of the corresponding pixel. As presented in FIG. 5A, embodiment 1600 additionally comprises a fixed-image layer 1603 containing fixed-images 1604 (here a “smiley face”) and 1605 (here a “check mark”), which both can be revealed or obscured to the viewing side depending on the transmissive properties of the respective pixels 1601 and 1602. Note that here the polymorphic display is illustrated functionally as an indicator with two pixels large enough to each contain a legible image.
  • the image layer may contain one or more images (also referred to herein as messages) and a polymorphic display may comprise multiple fixed- image layers.
  • fixed-image layer 1603 may include only discrete images (such as 1604 and 1605) with no (printing) layer material in-between, as shown in FIGS. 12A-D.
  • the fixed-images, 1604 and 1605 may e.g. be printed or otherwise constructed or placed directly onto substrate 709 or onto a separate thin substrate or film (not shown) which subsequently is adhered to substrate 709.
  • the back electrode 705 of this embodiment shown in FIG. 12A is transparent such that a fixed-image located on the back-side of the back electrode may be seen from the viewing side.
  • the fixed-image may also be printed or placed directly onto the front side (not shown) of an optionally opaque back electrode 705, for instance, with the fixed-images printed using conductive ink of a favorably different color than the opaque electrode to provide image contrast. In either case the fixed- images may also be printed in full color. Additionally, the fixed image may also be printed or placed directly on the front side of the optional complementary conductive polymer material 714 shown in FIG. 5A), advantageously with an image construction and material which provide for sufficient image contrast and ion conductivity (e.g., porous, containing small holes).
  • fixed images may also include “dynamic” images that are generated after manufacture of the polymorphic display (at a preferable point during the switching cycle). For instance, with a patterned back electrode 705 (e.g., interdigitated pair per Example 4 or segmented) a desired image could be generated by polymerization of EC mix 703 onto the corresponding electrode pattern (by respective application of an activation signal across the interdigitated pair of electrodes or back segmented and front electrodes).
  • a patterned back electrode 705 e.g., interdigitated pair per Example 4 or segmented
  • a desired image could be generated by polymerization of EC mix 703 onto the corresponding electrode pattern (by respective application of an activation signal across the interdigitated pair of electrodes or back segmented and front electrodes).
  • the self-switching polymer 1606 is different than those previously discussed in Example 7, in that its stable (non- powered) state is colored (e.g. black or blue), whereas its volatile state is transparent or clear (here, for example, in the human visible wavelength range).
  • Exemplary polymers with such characteristic include anodically coloring conductive polymers with low oxidation potentials, such as, PBEDOT-NMeCbz and PProDOP-NPrS.
  • FIG. 12A illustrates the initial state of the polymorphic display 1600 prior to any application of switching signals across electrodes 704 and 705 of pixel 1601 and 711 and 705 of pixel 1602.
  • the vertical structure of pixel 1601 is transparent allowing fixed-image 1604 (“smiley face”) to be seen 1607 from the viewing side (indicated by 1607 in the front view of FIG. 5 A).
  • the self-switchable polymer of pixel 1602 however is colored (and favorably also opaque) in its unpowered stable state, thus the fixed-image 1605 of pixel 1602 is obscured or hidden from the viewing side (indicated by 1608 in the front view of FIG. 5A).
  • a resulting transparent state of the self switching polymer layer 1607 reveals fixed-image 1605 (“check mark”), as shown by 1610 in FIG. 12B.
  • the fixed-mage 1605 will remain visible for the duration of the maintenance signal (e.g. indicating that device is operating).
  • pixel 1601 is switched by applying a voltage above a certain threshold (e.g. +3V), such that the polymerized monomer layer 1611 is formed at the front electrode 704 of pixel 1601.
  • This switching signal can for instance be in response to an event, e.g., the temperature of the display itself or the good the polymorphic display is attached to, exceeded a set threshold.
  • the polymerized monomer layer 1611 is colored (e.g. dark blue), and advantageously opaque, fixed-image 1604 is now hidden in a permanently and irreversibly hidden or obscured, as indicated by 1612 in FIG. 12C.
  • the self-switchable polymer reverts back to its stable colored state 1606, resulting in both fixed-images being hidden, as indicated by 1608 and 1612 in FIG. 12D.
  • electrochromic conductive polymers which are mono-stable and self-switchable and could be used as layer with either a transparent (clear) state in the stable state (e.g., 710 in FIG. 5A) or self-erasing state (as indicated by 1609 in FIG. 12B).
  • a transparent (clear) state in the stable state e.g., 710 in FIG. 5A
  • self-erasing state as indicated by 1609 in FIG. 12B
  • Such polymers provide for expanded shutter mode functionality. Specifically, the operable states of such a pixel 1700 as shown in FIG. 13, exhibit a first colored stable state 1740 as deposited (e.g.
  • the first stable state for a spray cast film of a disubstituted poly(propylenedioxythiophene) PProDOT(CH 2 0EtHx) 2 ⁇ Macromolecules , 2004, 37 (20), pp 7559-7569] (prior to power being applied for the first time) is red 1740
  • the second stable state corresponding to an oxidized chemical state is transparent (or clear) 1760
  • the third volatile state corresponding to a neutral (reduced) chemical state (after a second switching signal followed by a maintenance signal is applied) is blue 1780.
  • the third state is achievable through a phenomenon called “doping induced order” where the expulsion of the electrolyte allows a reorganization of the polymer backbone to a lower energy state.
  • Such an exemplary three-state polymer could advantageously be applied as layer 1606 of pixel 1602 of the polymorphic display shutter structure 1600 in FIG. 12A.
  • pixel 1602 could provide augmented indication (or message), that the display (and associated good) has never been powered up or activated by indication of a stable red state, which is irreversibly switchable to a second clear and stable state (revealing image 1605), followed immediately by a second switching signal transitioning to the third volatile blue state (indicating the power is on). If the maintenance signal in this state is subsequently terminated (for instance, when power is no longer available), it self-switches back to the second clear state revealing image 1605 (which, in this case, may indicate a “no power” symbol).
  • polymers with such characteristics can, for example, also be utilized as material layer 710 of pixel 702 in FIG. 5 A or of pixel 801 in FIG. 6A, to provide for bistable, irreversibly switchable, and self-switchable operable properties in conjunction with appropriately selected switching signals and signal protocol.
  • polymorphic display embodiment 1800 it may be desirable to contain the EC mix or electrolyte material by means of compartments within a common structure as illustrated by polymorphic display embodiment 1800 in FIG. 14. This is, in particular, applicable for cases in which the EC mix or electrolyte is characterized by a relatively high viscosity (e.g., after deposition or printing). However, it is also advantageously utilized for polymorphic displays for which individual pixels require different types of electrolytes (for optimized electrochromic functionality) or comprise distinct electro-optic materials.
  • Such electro-optic materials may comprise any material that can affect reflected, transmitted, or emitted electro-magnetic radiation (e.g., amplitude, intensity, polarization, and/or wavelength) based on an electric input (e.g. switching) signal.
  • electro-optic materials may comprise any material that can affect reflected, transmitted, or emitted electro-magnetic radiation (e.g., amplitude, intensity, polarization, and/or wavelength) based on an electric input (e.g. switching) signal.
  • electro-optic materials examples include liquid crystals (e.g., cholesteric and ferroelectric), electrophoretic (particle systems), electrochromic materials, electrowetting fluids, electro-liquid powder materials, plasmonic nanostructures, optical interference stacks (including those switched by microelectromechanical systems), photonic crystals, and phosphorescent materials, as well as, emissive materials such as LED materials, OLED (and other electroluminescent) materials, quantum dot materials (photo-emissive or electro-emissive), or any combination thereof.
  • emissive materials such as LED materials, OLED (and other electroluminescent) materials, quantum dot materials (photo-emissive or electro-emissive), or any combination thereof.
  • emissive materials such as LED materials, OLED (and other electroluminescent) materials, quantum dot materials (photo-emissive or electro-emissive), or any combination thereof.
  • emissive materials such as LED materials, OLED (and other electroluminescent) materials, quantum dot materials
  • Embodiment 1800 is similar to embodiment 1600 in FIG. 12A without the fixed- image layer 1603, and will not be explained in detail expect where there are differences.
  • the key difference of embodiment 1800 as compared to embodiment 1600 is the integration of a compartmentalized structure (vertically) spanning the front transparent substrate 706 and the back (here common) electrode 705, thus providing containment of the EC mix 703 of pixel 1801
  • the thickness of the containment wall 1806 in-between pixels may be different (e.g. thinner as shown) as compared to those containing edge pixels of the polymorphic display (here 1804 and 1805).
  • the thicknesses and aspect ratios of the walls are favorably optimized taking into account the compartmentalized structure material (e.g., flexible polymer), rigidity (or viscosity) of the EC mic 703 and electrolyte 1803, flexibility of the display, as well as, functionality and lateral fill factor of the pixels.
  • the compartmentalized structure material be made opaque (e.g. by adding a light absorbing dye or ink particles) to enhance the image quality of the completed polymorphic display.
  • the compartmentalized structure may, for instance, be fabricated from a solid uniform film by accordingly removing material (e.g. by laser ablation), before it is applied (with e.g. an adhesive) to the front substrate 706 or back substrate 709 (with transparent of opaque conductive layer 705), or generated in place by a photolithographic process.
  • material e.g. by laser ablation
  • an adhesive e.g. an adhesive
  • the compartmentalized structure may be generated through an embossing process, e.g., by embossing a thermoplastic or photopolymer layer onto conductor layer 705 supported by back substrate 709, with subsequent filling/sealing of the electro-optic material, and attachment to the front substrate 706 (with pixelated transparent conductors).
  • embossing e.g., by embossing a thermoplastic or photopolymer layer onto conductor layer 705 supported by back substrate 709, with subsequent filling/sealing of the electro-optic material, and attachment to the front substrate 706 (with pixelated transparent conductors).
  • Such a structure would enable switching of polymorphic display pixels based on, for example, electro optic materials that respond to an electric field including, e.g., electrophoretic and liquid crystal materials.
  • back electrode 705 e.g.
  • electro-optic materials requiring low resistive interface to its corresponding electrodes would not switch.
  • electrochromic functionality can be achieved by substituting the front pixel electrode (e.g. 704 or 711) with a pair of interdigitated electrodes (as illustrated in Example 4).
  • FIG. 15A illustrates an embodiment 1900 of such a polymorphic display in its pre-powered state, in side and front views, with two (indicator) pixels comprising a bi-stable electrophoretic right pixel 1901 and a monostable and self-switchable left pixel 1902.
  • the left pixel is functionally similar to pixel 702 illustrated in FIG. 5A, thus only differences will be highlighted.
  • the optional complementary conductive polymer material 714 is not shown.
  • the electrolyte 1803 e.g., ionic liquid
  • pixel 1902 is similar to that of 1802 of embodiment 1800, discussed in Example 6 , with containment walls 1804 and 1806.
  • the indicator output 1912 of pixel 1902 is black, as shown in FIG. 15A.
  • the right pixel 1901 comprises an electrophoretic microencapsulated electro-optic layer of spheres 1920 filled with suspension fluid containing two types of oppositely charged ink particles, white 1921 and black 1922. These particles move in response to an applied electric field between electrodes 704 and 705, such that white ink particles 1921 remain stable at the front surface after application of a switching signal applied to the electrodes (of a specific polarity), whereas the black ink particles 1922 (of opposite charge) remain stable at the back of the electro-optic layer as shown in FIG. 15 A.
  • the resulting indicator output 1911 of pixel 1901 is white.
  • FIG. 15B pixel 1902 is switched (analogously to pixel 1602 in FIG. 12B) to its volatile state (e.g. indicating the display is powered up), resulting in a clear state of polymer layer 1609 and a white state of the indicator output 1914 (here assuming, for example, that electrolyte includes a Ti0 2 coloring additive).
  • the state of indicator will self-switch back to output 1912, as shown in FIG.
  • pixel 1901 can favorably indicate the occurrence of an event (e.g., the temperature of the display or associated good exceeds a set limit) by switching the state of the electrophoretic electro-optical layer such that the black ink particles are now instead at the viewing side, corresponding to a black stable state of the indicator output 1915 as shown in FIG. 15D.
  • an event e.g., the temperature of the display or associated good exceeds a set limit
  • pixel 1902 reverts back to black indicator output state 1912 with the bi-stable indicator output remaining black, as indicated by 1915 in FIG. 15E.
  • both pixels are reversible.
  • electrophoretic microencapsulated electro-optic layers are formed in roll- to-roll processes onto a non-pattemed electrode layer on a support substrate. This allows for prefabrication of the electrophoretic electro-optic layer of pixel 1901 of embodiment 1900 onto back substrate 709 with the non-pattered electrode layer 705 using an adhesive 1915.
  • the compartmentalized structure may also be formed onto front substrate 706 facilitating alignment to pixelated electrodes (704 and 711).
  • the electrophoretic electro-optic layer is attached electrode 704 and substrate 706 by a transparent adhesive 1925, whereas the pre-filled electrolyte material 1803 is sealed by the adhesively attached compartmentalized structure.
  • the thickness of the compartmentalized structures 1806 and 1804 (defining the thickness of electrolyte material 1803) may be different than that of the electrophoretic electro-optic layer of pixel 1901, and the structure wall 1806 may be optional.
  • exemplary embodiment 1900 of FIG. 15 A there are many variations of exemplary embodiment 1900 of FIG. 15 A.
  • the non-patterned electrode layer would require the non-patterned electrode layer to be transparent, it would allow the back patterned electrode layer, as well as, the (optionally conductive) adhesive 1925 to be opaque.
  • the self-switching conducting polymer layer could be either printed on the front prefabricated electrode layer or on the back patterned electrode layer. The latter case would preferably include a transparent electrode material 1803, as the polymer layer is viewed through the electrolyte.
  • electrophoretic electro-optic materials may also comprise a multitude of stable states (e.g., a number of stable distinguishable grey levels); or contain three or more types of ink particles and/or a colored suspension fluid with corresponding stable color states.
  • Example 8 (Pixels Constructed with Different Redox and Electrolyte Layers)
  • electro-polymerizable monomer layers are polymerized in-situ , i.e. within the display device.
  • One preferred embodiment is a polymorphic display comprising different sets of pixels, each comprising different redox layers and a shared electrolytic layer that spans multiple pixels - and can provide independent pixel switching.
  • Independent switching is achieved for example with a polymorphic display comprising a permanent and irreversible pixel (constructed with an electropolymerizable monomer layer) and a self-switchable pixel (constructed with a conductive polymer layer), where the two pixels share a common electrolytic layer, even if the respective switching voltage levels are comparable and/or their ranges are overlapping (i.e., not highly non linear with distinct threshold voltages).
  • redox materials for redox layers are those that are solid in the temperature range of interest of the display device (e.g. operating and storage temperature ranges), in contrast to those that form liquids (of various viscosities) suitable for single-layer EC mixtures.
  • the electro polymerizable monomers (and subsequently polymerized monomers) are preferably insoluble in the electrolyte, which improves compatibility with a large range of electrolytes (e.g. ionic liquids). For example, hydrophobic monomers would be less likely to dissolve/disperse in polar ionic liquid.
  • Electro-polymerizable monomers including macromonomers and oligomers
  • electro-polymerizable monomers that are characterized by relatively high molecular weight, e.g. benzophenone, benzothiadiazoles, carbazoles, fused aromatic ring systems, fluorenone, and further specifically fluorinated monomers (and compounds), as they tend to aggregate together to form solid layers.
  • Electro-polymerizable monomers that oxidize at relatively high potentials are also advantageous as these are less susceptible to oxidation and therefore more stable in (pre- switched) display devices and thus reducing or eliminating the need for high-performance device barrier layers/encapsulation.
  • a electro-polymerizable monomer layer may be deposited onto the electrode layer (e.g. 704 or 705 of of pixel 701 in FIG. 5 A) using a variety of methods (similar to the conductive polymer layer for self-switchable pixel, see e.g. 710 of pixel 702 in FIG. 5 A), including spray casting, screen or inkjet printing, gravure coating, etc. These deposition methods may further be solution based (solvent assisted) using either polar or non-polar solvent depending on the monomer’s properties, and include other additives such as polystyrene (to increase viscosity) or adhesion promotors (e.g.
  • exemplary solvents include cyclopentyl methyl ether (CPME), 2-methyltetrahydrofuran, dihydrolevoglucosenone (cyrene), acetonitrile, etc.
  • electro-polymerizable monomer layers may be patterned onto (partially or substantially conforming to) a pixelated electrode, or deposited as a continuous (shared) layer across multiple pixel electrodes (favorably with sufficient spacing between neighbor pixel electrodes).
  • Deposited (and patterned) electro- polymerizable monomer layers may have pixel-specific monomer properties to achieve pixel particular optical states (e.g. colors) and/or pixel specific modalities for polymorphic displays.
  • the redox layer may also contain multiple electropolymerizable monomers to achieve a broader spectrum of optical states, e.g. by blending the monomers in different ratios to form a single solid layer, forming multiple solid sub-layers each with a different polymerizable monomer, or any combination thereof.
  • the multiple monomers may also comprise dissimilar (e.g. distinct or overlapping but shifted ranges of) polymerization activation thresholds to achieve different optical states by application of distinct switching signals/protocols (e.g. voltage levels, durations, etc.) to the addressing electrodes.
  • the electrolyte layer may include solid polymer electrolytes, gel polymer electrolytes, and polyelectrolytes, with green alternatives in gel polymer electrolytes based on e.g. cellulose or lignin, or ionic liquids.
  • the electrolyte may also be deposited using a variety of printing techniques, as previously discussed, and may be a liquid (favorably contained) or (highly) viscous layer (with increased mechanical and interfacial stability by additives including, e.g. zeolites, A1 2 0 3 , MgO, or Si0 2 ), or advantageously made semi-solid or solid with appropriate additives (e.g. thermally or UV curable monomers, microbeads, etc.) to form fully solid device stacks (including the electrode materials).
  • the electrolyte layer may additionally include colorants (e.g., pigments, dyes, or Ti0 2 ).
  • Solid electro-polymerizable monomer layers can provide for a multitude of operable properties for polymorphic display pixels and polymorphic pixels.
  • the polymodal properties and modalities include a first stable state, corresponding to a first optical state (e.g. a first color) as deposited.
  • the first state is irreversibly switchable to a second state (by oxidatively electropolymerizing the solid monomer layer), corresponding to a second optical state (e.g. a second color), which may be either stable or volatile depending on the properties of the monomer.
  • the polymerized (oxidized) monomer may further be switchable to a volatile third state (i.e., analogous to the operable states 1700 shown in FIG. 13), corresponding to a third optical state (e.g. a third color), and remain in this (reduced polymerized) state for the duration of the maintenance signal (as discussed above).
  • a volatile third state i.e., analogous to the operable states 1700 shown in FIG. 13
  • a third optical state e.g. a third color
  • the respective optical states i.e. first, second, and third colors of the solid EC layer (either the monomer or the electropolymerized monomer) may correspond to a transparent, lightly colored semi-transparent, or colored opaque state, which may be non-reflective (absorptive), semi-reflective, or reflective.
  • the pixel color may be different than the monomer layer depending on properties of the layer(s) viewable behind the redox layer (e.g. through intentional color blending by means of a colored electrolyte and/or back electrode/substrate or reflective interference stack effects).
  • the third optical state may also be indistinguishable from that of the second state (e.g. for a wavelength or within a wavelength range).
  • a single electro-polymerizable monomer layer may also be deposited on the back (counter) electrode of a pixel (e.g., instead of the self-switching polymer layer 1102 of polymorphic pixel 1101 in FIG. 9 A), or layers of the same or different monomer properties on each electrode (with the completed display device viewable from one or both sides), to achieve different polymorphic modalities.
  • an irreversible switching modality can be achieved with a separate electro-polymerizable monomer layer in conjunction with an adjacent electrolyte layer, an EC mix layer (e.g., 703 of embodiment 1100 in FIG.
  • electrolyte layer which includes polymerizable monomers
  • electrolyte layer could also be used as the electrolyte layer to achieve additional irreversible transitions, e.g. with the electro- polymerizable monomer layer and the in-mix monomer layer activated at different polymerization thresholds.
  • FIG. 16A shows an exemplary configuration of a polymorphic display 2000 comprising two pixels, each having different operable properties, in side view and front view.
  • the right pixel 2001 comprising a solid monomer (redox) layer 2011, is bi-stable with both self-switchable and irreversibly switchable operable properties (such as 1700 in FIG. 13), whereas the left pixel 2002 is mono-stable and self-switchable (such as 100 in FIG. 1).
  • redox solid monomer
  • pixel 2002 (and pixel 2001) comprises a shared electrolyte (without a monomer) which is colored yellow (e.g. ionic liquid with an appropriate pigment or dye).
  • the self- switchable redox layer comprising a conductive polymer 2010 is green in its volatile state and substantially transparent in its stable state [e.g. a spray cast film of ECP-G Chem. Mater. 2012, 24, 255-268] FIG.
  • FIG. 16A shows pixel 2002 prior to application of a switching signal (to pixel electrode 711 and common electrode 705), with the pixel having a transparent conductive polymer layer 2010, and a corresponding yellow optical state 2013.
  • FIG. 16B shows pixel 2002 after application of a switching signal (and application of a maintenance signal), resulting in a green polymer layer 2021, and a corresponding green optical state 2020. The pixel remains in its volatile state until the maintenance signal is terminated, at which point it self-switches back to its yellow stable state 2013 as shown in FIG. 16C.
  • this exemplary embodiment comprises a redox layer comprising a solid electro-polymerizable monomer 2011 of fluorenone-thienylene vilylene [TVF] (((2,7-bis(5-[(E)- l,2bis(3-octylthien-2-yl)ethylene])-fluoren-9-one) [“Solution versus solid-state electropolymerization of regioregular conjugated fluorenone-thienylene vinylene macromonomers — voltammetric and spectroelectrochemical investigations”, R.
  • TVF fluorenone-thienylene vilylene
  • This exemplary electro-polymerizable monomer 2011 is red in its first stable state (prior to power being applied for the first time), with the pixel 2001 having a corresponding red optical state 2012 as shown in FIG. 16A.
  • This operable state is irreversibly switchable, by applying a switching signal across pixel electrodes 704 and 705, to a second stable state, corresponding to a light blue in color (2018 in FIG. 16B).
  • the change in the operable state and optical state (color) occurs by solid-state electropolymerization of the solid TVF monomer in conjunction with the shared electrolyte layer 2003 of pixel 2001.
  • the light blue polymerized layer 2018 is partially transparent (and reflective) and color blends with the yellow electrolyte layer 2013 to yield an approximately green optical state 2019.
  • the composite color of the optical state 2019 can be tuned, e.g. by selection of monomer layer 2011 thickness, concentration and selection of electrolyte colorant, or activation protocol (e.g. duration of activation signal). For example, it may be desirable to color match the composite optical state 2019 to the optical state 2020 of the volatile state of self-switching pixel 2002.
  • the polymerized layer switches to a volatile third state, which is orange/red 2014 ,with a corresponding orange/red optical state 2015 of pixel 2001, as shown in FIG.
  • pixel 2002 could be constructed as pixel 2001 but with a solid monomer comprising a different modality of e.g. a volatile second state and a stable third state.
  • pixel 2002 could be constructed as a display with pixel 2002 having the same modalities as (polymorphic) pixel 2001, however, with a second monomer having different optical properties in one or more states of those corresponding to pixel 2001.
  • pixel 2001 comprises a solid electropolymerizable monomer (redox) layer 2011 in combination with an electrolyte layer 2003 which may be a liquid, semi-solid or solid
  • redox layer 2011 may contain a liquid monomer in a mix (e.g. an EC mix as above) or form a gel or semi-solid layer (e.g. by adding for example zeolites, AI2O3, MgO, or S1O2, or polymer such as polystyrene to the mix, or providing a porous or a printed microscale structure for the layer).
  • E/N-E displays are unitary apparatuses that have a plurality of pixels that include at least one emissive pixel and one non-emissive pixel, and that are configured as an electro-optic layer with electrodes on the surface of the electro optic device.
  • E/N-E displays wherein at least two of the plurality of pixels have different operating properties; i.e. that are polymorphic.
  • E/N-E displays provide many benefits with compact form factors (e.g. thickness, surface area, shape), fit-for-purpose designs (e.g. optical effects and operable properties) and constructions, ease of fabrication (e.g., printing, spray casting, coating, roll-to-roll manufacturing), message integrity, robustness and durability, and lower net-integrated cost into intelligent display devices.
  • Emissive pixels particularly in combination with non-emissive pixels, advantageously draw a user’s attention (e.g. alert/alarm), or provide focus to what’s important, e.g. a particular item, good, or package, or change in condi tion/state of the good.
  • emissive pixel(s) may convey specific messages where the presentation conveys information through color, brightness, or emissive pattern (e.g. flashing, blinking scrolling, radial, fading in/out etc.).
  • the emissive characteristics can enhance the perceptibility of a displayed message, e.g. through increased contrast, colors, particularly in predominantly dark environments.
  • E/N-E displays improve outcomes that depend on local user actions and transactions that depend on them.
  • the emissive light is typically within the human visible spectrum range (intended for a human user), however, it may also be tuned to other wavelengths (e.g. IR or UV) for machine detection.
  • Emissive pixels may further be enhanced with symbols (similarly to non-emissive pixels 1601 and 1602 in FIG. 12B), shapes, patterns, or alphanumeric characters.
  • E/N-E displays as well as E/N- E display devices and intelligent E/N-E display devices (both described below), may be flexible, semi-flexible, semi-rigid or rigid.
  • E/N-E display may be fabricated as standalone structures, or combined with a wide variety of substrates, and advantageously with switching circuitry and other components. Such devices are referred to herein as E/N-E display devices.
  • a substrate may be comprised, individually or in combination, of a variety of inorganic materials (e.g., many plastics, ceramics, or metals (e.g. foils), organic and biodegradable materials such as cellulose, hemp, certain plastics or other materials common to paper, card stock, packaging, fabric, wood, paperboard etc.
  • a substrate may be semi- or substantially transparent to enable viewing of the underlying E/N-E display.
  • an intelligent E/N-E display device is an apparatus comprising an E/N-E display and some or all of electronics, a power apparatus and appropriate to the application, a communication apparatus, sensors, and actuators.
  • An intelligent E/N-E display device is typically a unitary apparatus configured to be coupled or combined with a good or its packaging. Often, but not always, the intelligent display device is low cost, often disposable, low power and small in size. In some applications, though the intelligent display device is significantly larger and designed to present high-content messages or messages to be read by humans, animals or machines at a distance.
  • Exemplary E/N- E intelligent display devices include single use, multi-use, reusable/disposable items including labels, tags, patches (e.g.
  • E/N-E indicators/displays may be configured to be inserted, ejected, replaceable, or swappable.
  • the emissive and non-emissive properties of intelligent E/N-E display devices are managed to generate messages based on different combinations of emissive and non-emissive states according to internal rules or instructions (or external communications). And further, according to signals generated by actuators, or sensed or monitored conditions such as: temperature, humidity, pressure, shock/vibration, the presence of certain chemicals or biologies, electrical, magnetic, RF, light, sound or other forms of electromagnetic energy, ‘touch’ (resistive, surface capacitive, projected capacitive, surface acoustic wave and infrared sensors etc.), etc., location, proximity, motion, time, wireless communications, or combinations thereof.
  • actuators or sensed or monitored conditions such as: temperature, humidity, pressure, shock/vibration, the presence of certain chemicals or biologies, electrical, magnetic, RF, light, sound or other forms of electromagnetic energy, ‘touch’ (resistive, surface capacitive, projected capacitive, surface acoustic wave and infrared sensors etc.
  • signal circuitry for E/N-E displays and devices controls the emissive output of E/N-E pixels according to an appropriate signal protocol (e.g. colors/patterns/intensity, output e.g. stable or fluctuating, continuous or pulsed/patterned, spectral range or bandwidth).
  • the signal protocol may also determine the switching and maintenance signal according to the duration, pattern, and initiation and decay of the emissive light from E/N-E pixels (in responsive to changes in the signals).
  • the signal protocol may also adjust the switching and maintenance signals according to the output of an ambient light sensor (and/or other environmental sensors such as temperature and humidity).
  • An exemplary intelligent E/N-E display device e.g.
  • an intelligent label comprises a two indicator electro-optic E/N-E display comprised of one emissive “warning” indicator and one “fail-safe” non-emissive indicator.
  • both indicators are mono-stable.
  • the emissive warning indicator draws the attention of users and communicates a sense of immediacy - the need to act, for example in response to change in a monitored condition of a good.
  • it’s effectiveness may be diminished if the emissive pixel is ‘always on’ (e.g. continuously emitting, flashing etc.).
  • the power is disrupted or terminated (e.g.
  • the emissive indicator will convey a false-positive message. In other words, the emissive pixel will not emit or flash even though the condition of the good has changed.
  • the companion non-emissive “fail-safe” indicator solves that problem.
  • the non- emissive indicator is switched to an optical state that communicates the device is working. That optical state (and corresponding message - “the device is working”) is maintained as long as a maintenance signal is applied. If for whatever reason power is disrupted or terminated, the non- emissive indicator automatically self-switches to a different (unpowered) optical state that communicates the device is not working correctly - “it failed”.
  • Emissive pixels are generally, mono-stable (non-emissive in its initial state, volatile in the switched emissive state), self-switching and reversible.
  • An emissive pixel may, however, have one or more emissive states. And further, it may also have multiple non-emissive states and different operable properties (e.g. switching, stability or transition sequencing).
  • Such “E/N-E pixels” may operate as emissive pixels, non-emissive pixels or hybrid pixels, the latter having different emissive and non-emissive properties [modes] depending on the switching protocol.
  • An E/N-E pixel for example, may be switchable between emissive and non-emissive modes.
  • an E/N-E display may comprise: one E/N-E pixel plus either one emissive pixel or one non-emissive pixel, or two E/N-E pixels. Or in its simplest configuration, an E/N-E display can comprise a single E/N-E pixel where its emissive and non-emissive modes are independently switchable.
  • a light-emitting (emissive) electrochemical pixel is constructed as electro-optic layer (or portion thereof) that comprises an electroluminescent compound within an electrolyte configured to be in direct contact with or in close proximity to a pair of electrodes (of which at least one is semi- or substantially transparent).
  • the electro-optic layer of an emissive (and non-emissive) pixel may comprise a single or a multitude of distinct or blended sub-layers with a pair of electrodes proximate the surfaces of the electro-optic layer.
  • the light emitted from an emissive or E/N-E pixel is generated within the electro-optic layer, without the requirement of an electrode interposed between the surfaces of the electro-optic layer (thus without the need for a backlight).
  • the electroluminescent compound may e.g. comprise small molecules (e.g. ion transition metal complex - iTMC with or without an electrolyte), electroluminescent polymers, or a blend thereof.
  • the electroluminescent compound (or luminophore) may constitute a major portion (e.g. wt %) of the active layer (common for light-emitting electrochemical cells (LECs)), or the electrolyte may constitute the major portion (common for electrochemiluminesce devices (ECLDs)).
  • the emissive electrochemical pixel may favorably comprise an electro-optic layer of a substantially uniform mixture of electrolyte and electroluminescent compound or have multi sublayers.
  • a bi-layer construction may comprise separate (semi-) solid electroluminescent and electrolyte layers with, e.g., the electrolyte layer being patterned (e.g. fine lines) onto an electrode (e.g. front), and the electroluminescent layer making contact with the patterned electrolyte layer, as well as, both the electrodes.
  • Light emission from such emissive electrochemical pixels occurs after application of a suitable drive signal (i.e., switching signal and continued maintenance signal) to its pair of corresponding electrodes and is typically omnidirectional (e.g. favorable for double sided displays).
  • a suitable drive signal i.e., switching signal and continued maintenance signal
  • predominantly directional light emission can be achieved by absorptive or preferably reflective layers at/or adjacent to the back electrode (presuming a substantially semi- or substantially transparent front electrode) and/or alternatively by providing a focusing layer (e.g. a micro lens array stamped, molded, etched etc. on a separate substrate or part of the display device substrate) at the front of the display.
  • a focusing layer e.g. a micro lens array stamped, molded, etched etc. on a separate substrate or part of the display device substrate
  • Such as focusing layer (or a separate cover layer) may also be colored, tinted or patterned.
  • the light emission may originate near or at the middle of the active (single mixture) layer (e.g. typically for LECs), or may originate proximate the electrode(s). In case of a bi-layer construction (discussed above), the light emission may also occur in the electroluminescent layer at or proximate the edges (sides) of patterned electrolyte layer. It should be noted that although the above description pertains to a vertical stack configuration (with separate and vertically spaced electrode layers), the same principles can be applied to structures with a single electrode layer containing pair(s) of electrodes (e.g. arranged as interdigitated electrode pairs such as those show in embodiment 1200 of FIG. 10 A).
  • the drive signal for a light-emitting electrochemical pixel may consist of a DC voltage differential (for example in the 2-6V range typically for LECs) but may also consist of an AC signal (e.g. 2-5V range at less than lkFIz), or a combination thereof.
  • the electro-optic layer (or sublayers) of a light- emitting electrochemical pixel comprises only an electroluminescent compound and an electrolyte
  • additional materials may be included to provide structure (rigidity, flexibility), provide structure (rigidity, flexibility), facilitate manufacturing processes, e.g., solvents for facilitating printing or spray casting of electro-optic (sub) layers, such as propylene carbonate, ethyl acetate, acetonitrile, tetrahydrofuran, 1 4-dioxane, toluene, N,Ndimethylformamide (DMF), chloroform, polyalkylene glycol and mixtures thereof.
  • solvents for facilitating printing or spray casting of electro-optic (sub) layers such as propylene carbonate, ethyl acetate, acetonitrile, tetrahydrofuran, 1 4-dioxane, toluene, N,Ndimethylformamide (DMF), chloroform, poly
  • solvents such as propylene carbonate act as plasticizers and are advantageous to include in the final device.
  • additives that improve performance include MWCNTs and poly(ABTS).
  • electron transport and hole transport polymers and compounds can be blended with the electroluminescent material to improve quantum efficiencies (e.g. poly(vinylcarbazole) and l,3-bis[2-(4-tert-butylphenyl) -1,3,4- oxadiazo-5-yl]benzene (OXD-7)).
  • PMMA polycaprolactone
  • PEO polyethylene oxide
  • biological binders such as gellan gum, carboxymethyl cellulose, sodium hyaluronate, xanthum gum, pectin, heparin, DNA, sulfated cellulose, dextran sulfonate, guar gum, and agarose.
  • the formation of a solid matrix is achieved by UV radiation when employing acrylates such as dipropylene glycol diacrylate (DPGDA) which are activated with a photoinitiator such as, e.g., DMPAP.
  • DPGDA dipropylene glycol diacrylate
  • a photoinitiator such as, e.g., DMPAP.
  • Such materials advantageously provide a sufficient electrochromic operating window to activate and sustain the light emission appropriate to the application.
  • the electroluminescent material may further be complemented by fl orescent or phosphorescent materials, or materials displaying thermally activated delay fluorescence (TADP) or photoluminescence.
  • the operable mode of an emissive pixel can be extended by adding an electrochromic (reversible) self-switching material such as viologen (or other bipyridum derivate) to a substantially uniform mix of the electroluminescent electro-optic layer, or by including an electrochromic conducting polymer on, for instance, the front electrode.
  • an electrochromic (reversible) self-switching material such as viologen (or other bipyridum derivate)
  • Such constructions can, for instance as illustrated by the operable states 2100 in FIG.
  • the operable mode of an emissive pixel can alternatively be extended to include an irreversible switching transition, by adding, for example, an electropolymerizable monomer to a substantially uniform mix of the electroluminescent electro-optic layer (e.g., an EC mix and EE mix).
  • an electropolymerizable monomer e.g., an EC mix and EE mix.
  • Such a construction favorably comprising an electro-polymerization voltage threshold of the monomer which is higher than the activation voltage threshold for light emission from the electroluminescent compound can, for instance (as illustrated by the operable states 2200 in FIG.
  • a mono-stable, non-emissive 1st state 2220 (before applying any switching or maintenance signal), a volatile emissive 2nd state 2240 (maintained with a maintenance signal) when switched with a 1st protocol (e.g. relatively low voltage), a stable non-emissive 3rd state 2260 when switched with a 2nd protocol (e.g. relatively high voltage), which is irreversible to the 1st state 2220 and to the 2nd state 2240, and (optionally) switchable with a 3rd protocol (e.g. opposite polarity) to a volatile, non-emissive 4th state 2280, which self-switches back to the 3rd state 2260 upon termination of its maintenance signal.
  • a 1st protocol e.g. relatively low voltage
  • a stable non-emissive 3rd state 2260 when switched with a 2nd protocol (e.g. relatively high voltage)
  • 3rd protocol e.g. opposite polarity
  • the operable mode of an emissive pixel can also include an irreversible switching transition by including, for example, an electropolymerizable monomer layer or a polymer layer with operable states as shown in FIG.13, as a sublayer of the electro optic layer.
  • Such constructions can, for instance as illustrated by the operable states 2300 in FIG. 19, provide the operable states of a mono-stable, non-emissive 1st state 2310, which can irreversibly switch (with a 1st protocol) to a stable, non-emissive 2nd state 2320.
  • the stable non-emissive state 2320 can further transition to a volatile emissive 3rd state 2340 (maintained with a maintenance signal) when switched with a 2nd protocol (e.g. polarity) along a first branch 2301, or a volatile non-emissive 4th state 2360 (maintained with a maintenance signal) when switched with a 3rd protocol (e.g. opposite polarity) along a second branch 2302, with both the 3rd and 4th states self-switching back to the 2nd state 2320 upon termination of their respective maintenance signal.
  • a volatile emissive 3rd state 2340 maintained with a maintenance signal
  • a 2nd protocol e.g. polarity
  • a volatile non-emissive 4th state 2360 maintained with a maintenance signal
  • both the 3rd and 4th states self-switching back to the 2nd state 2320 upon termination of their respective maintenance signal.
  • the pixel first needs to go through its first (irreversible) transition before
  • the ability of a pixel to operate as an emissive pixel may be considered an operable property.
  • E/N-E displays comprising at least one emissive and one non-emissive pixel, can span a multitude of pixel types, modalities, and combinations. A few exemplary configurations will now be discussed that include various E/N-E pixel modalities.
  • these structures include only two pixels, wherein one is emissive (i.e., includes at least one state that is emissive), and the other is non-emissive.
  • these exemplary configurations each comprise a shared electro-optic layer (further comprising one or more sublayers) sandwiched between two electrode layers in a vertical structure.
  • FIG. 20A shows an exemplary configuration of an E/N-E display 2400 comprising two pixels, each having different operable properties, in side view and front view.
  • the left non- emissive pixel 2402 comprising a polymer (redox) layer 2010, is mono-stable and self- switchable having switchable operable properties.
  • Pixel 2402 is similar to pixel 2002 of FIG. 16A, thus only differences will be discussed. Specifically, instead of having an (yellow) electrolyte 2003, it comprises an electroluminescent electrolyte mixture (EE mix) 2403 and a back electrode 2405, both shared with right pixel 2401.
  • EE mix electroluminescent electrolyte mixture
  • the emissive right pixel 2401 is mono stable with a self-switching modality and an emissive volatile state, and comprises an electroluminescent electrolyte mixture (“EE mix”) 2403 as an electro-optic layer, sandwiched between front electrode 704 with additional hole-transport layer 2411 and back electrode 2405.
  • the EE mix of pixel 2403 comprises an emissive conjugated polymer “Super Yellow” (Livilux PDY-132, Merck), and an electrolyte (e.g. L1CF3SO3), and a suitable binder/matrix (e.g. PEO), with a largely clear to slightly yellow transparent (non-emissive) property.
  • the front electrode 704 (at least semi-transparent), typically acting as the anode for emission, may be made of ITO as previously noted, but could also comprise AZO, Ag-wire, carbon nanotubes, graphene, etc.
  • the hole-transport layer 2411 to facilitate the emissive properties comprises a conductive polymer (here PEDOT:PSS).
  • the back electrode 2504, typically acting as the cathode for emission, is reflective and may also be made of ITO (e.g. for dual side emission), however, preferably Al, Ca, Ba, Ag, Au, or a combination (e.g. alloy) thereof.
  • common pixel electrode layer 2405 may also be pixelated with pixel specific material composition.
  • the EE mix layer 2403 including suitable additives (discussed above), as well as, other layers in the pixel stack, are advantageously formulated to facility layer deposition (e.g. slot-die, spray coating/casting, etc.) or printing (e.g. gravure, off-set, screen, ink-jet, etc.) in sheet-to-sheet (S2S) or roll-to-roll (R2R) processes.
  • the various layers, which may comprise pixel specific compositions may be consecutively be built up on a single substrate (e.g. 706) and finalized with an encapsulation layer(s), or by dividing the layers onto the front (e.g. 706) and back (e.g. 709) substrate and later combining them.
  • An individual layer or a sub-stack of layers may also be built up on a carrier substrate, with subsequent detachment and integration with an adjoining layer of the final stack configuration.
  • light emitting shapes, symbols, patterns, alphanumeric characters may also be included, e.g. by patterning mask layer 708, the hole transport layer 2411, the back electrode 2405, the electro-optic layer (or sublayers) itself, or any combination thereof.
  • the mask layer may further be “color” matched to the non-emissive stable off-state of the missive pixel.
  • the mask may also consist of a non-emissive materials that are electrically addressable to dynamically generate the mask information (e.g. symbol), e.g. with an electrochromic, electrophoretic (shutter mode), or LCD layer.
  • FIG. 20A shows pixel 2402 prior to application of a switching signal (to pixel electrode 711 and common electrode 2405), with the pixel having a transparent conductive polymer layer 2010, and a corresponding (slightly) yellow optical state 2013 (due to the EE mix 2403).
  • FIG. 20B shows pixel 2402 after application of a switching signal (and application of a maintenance signal), resulting in a green polymer layer 2021, and a corresponding green optical state 2020. The pixel remains in its volatile state until the maintenance signal is terminated, at which point it self-switches back to its yellow stable state 2013 as shown in FIG. 16C.
  • FIG. 20A shows emissive pixel 2401 prior to application of a switching signal (to pixel electrode 704 and common electrode 2405), with the pixel having a transparent hole-transport layer 2411 (i.e., stable reduced state of PEDOT:PSS), corresponding to (slightly) yellow optical state 2012 (due to the EE mix 2403), and stable operable state 2120 of FIG. 17.
  • a switching signal to pixel electrode 704 and common electrode 2405
  • FIG. 20A shows emissive pixel 2401 prior to application of a switching signal (to pixel electrode 704 and common electrode 2405), with the pixel having a transparent hole-transport layer 2411 (i.e., stable reduced state of PEDOT:PSS), corresponding to (slightly) yellow optical state 2012 (due to the EE mix 2403), and stable operable state 2120 of FIG. 17.
  • FIG. 20A shows emissive pixel 2401 prior to application of a switching signal (to pixel electrode 704 and common electrode 2405), with the
  • 20B shows pixel 2401 after application of a switching signal (and application of a maintenance signal), resulting in light 2421 being emitted from EE mix layer 2403, corresponding to emissive optical state 2419, and operable emissive state 2140 of FIG. 17.
  • the pixel remains in its volatile state until the maintenance signal is terminated, at which point it self switches back to its yellow stable state 2012 as shown in FIG. 20 A (and stable operable state 2120 of FIG. 17).
  • the switching and maintenance signals may in this case consist of DC voltage (e.g. 5 V) across anode 704 and cathode 2405.
  • the double-arrow simplistically denotes light 2421 from the emissive EE mix layer, although the light originates from the electroluminescent material (“Super Yellow”) located within the in-situ formed p-n junction in the EE mix layer (advantageously near the vertical middle, extending laterally and bound by the pixelated electrode 704).
  • Super Yellow electroluminescent material
  • other emissive colors than the relatively wide spectrum emission from Super Yellow can be achieved, with other electroluminescent materials, or blends thereof.
  • different optical states i.e. emitted wavelength(s) or ranges
  • optical state specific driving protocols e.g. the voltage levels of the maintenance signals.
  • Stable pixel 2401 in FIG. 20 A may also be switched (and maintained) along branch 2102 (in Fig. 17) upon applying a second protocol (e.g. comprising IV DC with opposite polarity to that of branch 2101) to a non- emissive volatile state 2160.
  • a second protocol e.g. comprising IV DC with opposite polarity to that of branch 2101
  • the PEDOT:PSS layer is reduced resulting in a blue layer 2414 corresponding to a blue optical state 2415 (shown in FIG. 20C).
  • the maintenance signal pixel 2401 Upon termination of the maintenance signal pixel 2401 self-switches to back to the initial stable state 2120 (in FIG. 17), and corresponding optical state 2012 as also shown in FIG. 20A.
  • the self-switchable non-emissive operable property of pixel 2401 may alternatively be “switched off’ (i.e. removing branch 2102) by preventing electrochromic reactions in hole transport layer (PEDOT:PSS), e.g., by adding a buffer layer in-between the hole-transport layer 2010 and the EE mix 2403, e.g. of ZnO, CdO or SiC).
  • PDOT:PSS hole transport layer
  • the conducting polymer layer may be considered part on the electrode, as opposed to part of the electro-optic layer.
  • emissive pixel is identical to emissive pixel 2401 of FIGs. 20A-C with the exception that hole-transport layer 2411 is replaced with either a solid electropolymerizable monomer layer (e.g. as discussed in Example 8) or a polymer layer (e.g. poly(propylenedioxythiophene) as discussed in Example 5), with both having self-switchable and irreversibly switchable operable states as illustrated in FIG.13.
  • the first state 2310 (of FIG. 19) is stable (as deposited before any switching signal is applied) with a corresponding optical state (e.g. red in case of the exemplary polymer).
  • the layer Upon applying a switching signal the layer irreversibly switches to second stable (substantially transmissive) state 2320 with a corresponding optical state of (slightly) yellow, similar to pixel 2401 in FIG. 20A.
  • the second stable state is provided by a (stable) polymerized and oxidized layer.
  • Such an oxidized (and conductive) polymer layer may favorably act as hole-transport layer for further reversible switching to the volatile and emissive state 2340 along branch 2301, similar to pixel 2401 in FIG. 20B. Furthermore, it may also be further switched to non-emissive volatile state 2360 along branch 2302 with a corresponding optical state of blue (for the polymer case; orange/red for the monomer case), similar to pixel 2401 in FIG. 20C.
  • E/N-E displays are their total thickness: preferably less than 10 microns, more preferably less than 5 microns, most preferably less than 1 micron.

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Control Of Indicators Other Than Cathode Ray Tubes (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

L'invention concerne une unité d'affichage électro-optique émissive/non-émissive qui est un appareil unitaire construit de façon à permettre diverses fonctions électro-optiques. L'unité d'affichage électro-optique émissive/non-émissive, même lorsqu'elle possède de multiples pixels, permet un partage de structures sélectionnées parmi les pixels. Lors d'une construction à pixels multiples, il existe des ensembles de pixels de l'unité d'affichage qui présentent différentes combinaisons de propriétés émissives et non-émissives, telles que des propriétés de stabilité, de séquençage et de commutation, et un autre ensemble de pixels qui sont différents de ceux du premier ensemble. De cette manière, il est possible de construire une unité d'affichage émissive/non-émissive hautement flexible pour satisfaire une large gamme de besoins d'affichage. L'unité d'affichage émissive et non émissive peut être polymorphe.
PCT/US2020/013050 2019-08-28 2020-01-10 Unités d'affichage électro-optiques émissives/non émissives WO2021040777A1 (fr)

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US16/553,572 US11467433B2 (en) 2017-02-06 2019-08-28 Polymorphic electro-optic displays

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US20170103697A1 (en) * 2015-10-12 2017-04-13 Semiconductor Energy Laboratory Co., Ltd. Display device and driving method of the same
US20180357952A1 (en) * 2017-06-12 2018-12-13 Motorola Mobility Llc Organic Light Emitting Diode Display with Transparent Pixel Portion and Corresponding Devices
US20190049807A1 (en) * 2017-02-06 2019-02-14 Chromera, Inc. Polymorphic electro-optic displays

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Publication number Priority date Publication date Assignee Title
US20050093784A1 (en) * 2003-10-31 2005-05-05 Seiko Epson Corporation Electro-optical device, method of manufacturing the same, and electronic apparatus
US20070075935A1 (en) * 2005-09-30 2007-04-05 Ralph Mesmer Flat-panel display with hybrid imaging technology
US20090243961A1 (en) * 2008-03-27 2009-10-01 Epson Imaging Devices Corporation Electro-optical device and electronic apparatus
US20150155340A1 (en) * 2013-12-02 2015-06-04 Electronics And Telecommunications Research Institute Dual-mode pixels including emissive and reflective devices, and dual-mode display using the pixels
US20170103697A1 (en) * 2015-10-12 2017-04-13 Semiconductor Energy Laboratory Co., Ltd. Display device and driving method of the same
US20190049807A1 (en) * 2017-02-06 2019-02-14 Chromera, Inc. Polymorphic electro-optic displays
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