This is a continuation, of applicaton Ser. No. 409,829 filed 10/26/73, now abandoned.

BACKGROUND OF INVENTION

This invention relates to electro-optical devices whose electromagnetic radiation absorption characteristics can be selectively altered by influence of a suitably controlled electric field. More particularly, this invention is directed to a sandwich type cell in which two layers of electrochromic material are separated by solid, semi-solid or liquid ion conducting media and which has a means to illuminate the imaging area.

In commonly assigned, copending U.S. applications, Ser. No. 41,153, Ser. No. 41,154, and Ser. No. 41,155, all filed May 25, 1970, and U.S. Pat. No. 3,521,941 and 3,578,843; Ser. No. 41,153, abandoned and refiled as Ser. No. 211,857, Dec. 23, 1971, abandoned and refiled as Ser. No. 361,760, May 18, 1973, now U.S Pat. No. 3,879,108; Ser. No. 41,154 abandoned and refiled Apr. 13, 1972, now pending; Ser. No. 41,155, now U.S. Pat. No. 3,708,220; there are described electro-optical devices exhibiting a phenomenon known as persistent electrochromism wherein electromagnetic radiation absorption characteristic of a persistent electrochromic material is altered under the influence of an electric field. Such devices were employed in sandwich arrangement between two electrodes. Coloration was induced by charging the electrochromic film negative with respect to the counter-electrode, employing an external potential. The counter-electrode can be the same as the persistent electrochromic material or different.

By reversing the original polarity of the field or by applying a new field, it was also possible to cancel, erase or bleach the visible coloration.

These steps of color inductionand erasure are defined as cycling.

Although the devices described in the prior applications are effective to change their electromagnetic radiation transmitting properties under the influence of an electric field, and have extremely good visibility over a wide range of lighting conditions, including high ambient light, they operate by light absorbtion and are therefore not viewable in the dark.

It is therefore an object of this invention to provide an electrochromic imaging device viewable in darkness.

A further object is to provide an electrochromic device having means for illuminating the display area.

These and other objects of the invention will become apparent as the description thereof proceeds.

SUMMARY OF THE INVENTION

The image display device is formed in a sandwich arrangement of an electrochromic layer as an imaging area and a counter-electrode with a spacing of a conducting medium, e.g. an electrolyte, between the areas. Means are provided for supplying electric current to the counter-electrode layer. Any conventional means is suitable. A particularly advantageous means for electrical connection is to deposit the electrochromic imaging layer and counter-electrode on a conductive surface, such as NESA glass. It is particularly advantageous to incorporate an electrochromic material with the counter-electrode which is identical to that used for the imaging area. This provides greater compatability between imaging area and counter-electrode, and allows the device to operate on lower voltage.

In the present invention, a means of illumination is provided at one edge of the transparent substrate on which the image is produced.

Prior EC information displays normally employ ambient light to display information as the display is light absorbing rather than light emitting. In total darkness, the display is not readable. The invention makes use of the novel light absorbing characteristic of the EC film against the light colored, diffusing and reflecting background produced by the ion conducting medium to produce an illuminated, high contrast display at a minimum of light energy expended. Attempts to edge light other reflective displays such as liquid crystal types have not been successful as the nature of the structure causes the transparent conducting circuit to the image to become visible. Edge lighting the EC display of the invention helps to hide the transparent circuit to the image and imparts a good appearance under light or dark ambient conditions. The illumination means may be any suitable means, and the illumination is transmitted through the image substrate thereby illuminating the entire area. Any image formed is clearly visible by the absorbed light and the contrast with the illuminated background.

The foregoing and other features, objects and advantages of the present invention will become more apparent from the following detailed description.

DETAILED DESCRIPTION OF INVENTION

As used herein, a "persistent electrochromic material" is defined as a material responsive to the application of an electric field of a given polarity to change from a first persistent state in which it is essentially non-absorptive of electromagnetic radiation in a given wavelength region, to a second persistent state in which it is absorptive of electromagnetic radiation in the given wavelength region, and once in said second state, is responsive to the application of an electric field of the opposite polarity to return to its first state. Certain of such materials can also be responsive to a short circuiting condition, in the absence of an electric field, so as to return to the initial state.

By "persistent" is meant the ability of the material to remain in the absorptive state to which it is changed, after removal of the electric field, as distinguished from a substantially instantaneous reversion to the initial state, as in the case of the Franz-Keldysh effect.

Electrochromic Materials

The materials which form the electrochromic materials of the device in general are electrical insulators or semiconductors. Thus are excluded those metals, metal alloys, and other metal-containing compounds which are relatively good electrical conductors.

The persistent electrochromic materials are further characterized as inorganic substances which are solid under the conditions of use, whether as pure elements, alloys, or chemical compounds, containing at least one element of variable oxidation state, that is, at least one element of the Periodic System which can exist in more than one oxidation state in addition to zero. The term "oxidation state" as employed herein is defined in "Inorganic Chemistry," T. Moeller, John Wiley and Sons, Inc., New York, 1952.

These include materials containing a transition metal element (including Lanthanide and Actinide series elements), and materials containing non-alkali metal elements such as copper. Preferred materials of this class are films of transition metal compounds in which the transition metal may exist in any oxidation state from +2 to +8. Examples of these are: transition metal oxides, transition metal oxysulfides, transition metal halides, selenides, tellurides, chromates, molybdates, tungstates, vanadates, niobates, tantalates, titanates, stannates, and the like. Particularly preferred are films of metal stannates, oxides and sulfides of the metals of Groups (IV)B, (V)B and (VI)B of the Periodic System, and Lanthanide series metal oxides and sulfides. Examples of such are copper stannate, tungsten oxide, cerium oxide, cobalt tungstate, metal molybdates, metal titanates, metal niobates, and the like.

Additional examples of such compounds are the following oxides: MO oxides, e.g. MnO, NiO, CoO, etc.; M₂ O₃ oxides, e.g., Cr₂ O₃, Fe₂ O₃, Y₂ O₃, Yb₂ O₃, V₂ O₃, Ti₂ O₃, Mn₂ O₃, etc.; MO₂ oxides, e.g., TiO₂, MnO₂, ThO₂ , etc.; M₃ O₄ oxides, e.g., Co₃ ThO₂, etc.; 4, Mn₃ O₄, Fe₃ O₄, etc.; MO₃ oxides, e.g., CrO₃, UO₃, etc.; M₂ O₅ oxides, e.g., V₂ O₅, Nb₂ O₅, Ta₂ O₅ etc.; M₄ O₆ oxides; M₂ O₇ oxides, e.g., V₂ O₅, Nb₂ O₅, Ta₂ O₅, etc.; M₄ O₆ oxides; M₂ O₇ oxides such as M₂ O₇ ; complex oxides such as those of the formula XYO₂ (X and Y being different metals), e.g., LiNiO₂, etc.; XYO₃ oxides, e.g., LiMnO₃, FeTiO₃, MnTiO₃, CoTiO₃, NiTiO₃, LiNbO₃ , LiTaO₃, NaWO₃ etc.; XYO₄ oxides, e.g., MgWO₄, CdWO₄, NiWO₄, etc.; XY₂ O₆, e.g., CaNb₂ O₆ ("Niobite" oxides); X₂ Y₂ O₆, e.g., Na₂ Nb₂ O₆ : Spinel structure oxides, i.e., of the formula X₂ YO₄, e.g., Na₂ MoO₄, NaWO₄, Ag₂ MoO₄, Cu₂ MoO₄, Li₂ MoO₄, Li₂ WO₄, Sr₂ TiO₄, Ca₂ MnO₄, etc.; XY₂ O₄, e.g., FeCr₂ O₄, TiZn₂ O₄, etc.; X₂ YO₅ oxides, e.g., Fe₂ TiO₅, Al₂ TiO₅, etc.; and X₃ Y₃ O (ternary) oxides, e.g., Mo₃ Fe₃ O, W₃ Fe₃ O, X₃ Ti₃ O (where X is Mn, Fe, Co, etc.). For a discussion of some complex oxides, see Advanced Inorganic Chemistry, Cotten and Wilkinson, p. 51, (1966), Interscience Publishers, Inc., New York and Progress in Inorganic Chem., Vol. 1, 465 (1959) Interscience Publishers, Inc., New York. Also included are nitrides, and the sulfides corresponding to the above oxides. Hydrates of certain metal oxides may also be used, e.g., WO₃ .H₂ O, WO₃ .2H₂ O, MoO₃ .H₂ O and MoO₃ .2H₂ O.

A particularly advantageous aspect in the present invention is the use of two separate layers of identical electrochromic materials one layer being employed in the counterelectrode for the other layer. A preferred embodiment consists of tungsten oxide as the electrochromic color electrode and tungsten oxide and graphite as the counter-electrode.

While the general mechanism of persistent electrochromism is unknown, the coloration is observed to occur at the negatively charged electrochromic layer. Generally, the phenomenon of persistent electrochromism is believed to involve cation transport such as hydrogen or lithium ions to the negative electrode where color centers form in the electrochromic image layer as a result of charge compensating electron flow.

When the persistent electrochromic materials are employed as films, thickness desirably will be in the range of from about 0.1-100 microns. However, since a small potential will provide an enormous field strength across very thin films, the latter, i.e., 0.1-10 microns, are preferred over thicker ones. Optimum thickness will also be determined by the nature of the particular compound being laid down as a film and by the film-forming method since the particular compound and film-forming method may place physical (e.g., nonuniform film surface) and economic limitations on manufacture of the devices.

The films may be laid down on any substrate which, relative to the film, is electrically conducting. The electrically conductive material may be coated on another suitable substrate material including glass, wood, paper, plastics, plaster, and the like, including transparent, translucent, opaque or other optical quality materials. A preferred embodiment in the instant device would employ at least one transparent electrode.

When tungsten oxide is employed as the electrochromic imaging material and an electric field is applied between the electrodes, a blue coloration of the previously transparent electrochromic layer occurs, i.e., the persistent electrochromic layer becomes absorptive of electromagnetic radiation over a band initially encompassing the red end of the visible spectrum, thereby rendering the imaging layer blue in appearance. Prior to the application of the electric field, the electrochromic imaging layer was essentailly non-absorbent and thus transparent.

Spacing Layer

A semi-solid ion conductive gel may be employed. One embodiment comprises in combination sulfuric acid and a gelling material for the acid. Any gelling agent which is compatible with the other components is suitable. Particularly advantageous gelling agents are polyvinyl alcohol, polyacrylamide, sodium silicate, cabo-sil, and the like.

A preferred embodiment employs H₂ SO₄ in combination with polyvinyl alcohol. The properties of this gel may be varied in advantageous manner by employing polyvinyl alcohol of various molecular weights, differing sulfuric acid concentration and different polyvinyl alcohol to acid ratios. Thereby, gels can be produced to give a specific conductivity in the range of from about 0.10 to 0.60 ohm.sup.^-1 cm.sup.^-1.

A distinct advantage of the above mentioned gels is their high ionic conductivity and good chemical stability. We have found that both requirements are unexpectedly met by gels in the preferred conductivity range of 0.20 - 0.40 ohm.sup.^-1 cm¹¹⁶ 1.

Other materials may be incorporated into the gel to vary the physical properties of the gel such as viscosity and vapor pressure. Thus, the composition may optionally include organic solvents such as dimethyl formamide, acetonitrile, proprionitrile, butyrolacetone and glycerin.

Further, the gels used in the instant invention may be made opaque with, for example, stable, white or colored pigments such as TiO₂ or TiO₂ doped with Ni, Sb for use in certain electrochromic display device applications. A fluid layer containing an acid may also be used in place of the gel, as disclosed in copending, commonly assigned application Ser. No. 41,154, filed May 25, 1970.

The spacing layer may also be made ionically conductive by a semi-solid material such as a paste, grease or gel containing some ionically conducting materials. The dispersing medium may be one selected from a group consisting of an ionically conductive paste, grease or gel. A preferred embodiment in the present invention comprises the use of a conductive lithium stearate grease containing dispersed therein propylene carbonate and p-toluene sulfonic acid. The semisoild medium can contain one or more salts selected from Group IA and IIA alkali or alkaline earth materials. Smaller ions such as lithium and sodium are preferred to larger ions as potassium and rubidium since ionic mobility in the electrochromic layer may be a limiting factor. The significant improvements in electrode reversibility and reproducibility and the important advantage of long term stability of operation by use of these gels were unexpected. This is a significant advantage in applications requiring long term service stability. Thus, alpha numeric character presentation and data display devices, wherein the service requirement is stated in years and/or millions of cycles, have become commercially feasible.

In addition, the spacing layer may be an inorganic or other solid material as disclosed in United States Patent No. 3,578,843, e.g. silicon oxide.

Additive Compounds

Compounds may be added to the electrolyte spacing layer such as those used in the imaging layer. Preferably, the additive compound is the same as that of the imaging layer. WO₃ for example, is an effective additive when using a WO₃ imaging layer. The additives are used in an amount to form a 50 to 100% saturated solution.

Counter Electrode

As previously indicated, the counter-electrode may be any electrically conductive material. Particularly advantageous is a layer of electrochromic material, as described previously. It is also advantageous to use the same electrochromic material for the imaging area and counter-electrode. A mixture of graphite and an electrochromic material, or graphite along may be used as the counter-electrode. Other metallic counter-electrodes are disclosed in copending application, Ser. No. 41,154.

The invention may be further understood by reference to the drawings in which

FIG. 1 is a cross section of the electrochromic display device,

FIG. 2 is a front view of a single digital segment in an electrochromic digital display,

FIG. 3 is a cross sectional view of the segment of FIG. 2, taken along the lines A--A,

FIG. 4 is a front view of a linear digital display according to the invention.

As shown in FIG. 1, a conventional EC information display having transparent EC electrode, light colored, pigmented ion conducting medium layer 2 and opaque counter-electrode 3, is combined with a light source 4 so that light is introduced at the edge of the EC electrode glass and by internal reflections and refractions illuminates the entire display. The light may also be introduced through the front or back faces of the EC electrode outboard of the EC image and similarly the entire display may be illuminated. The light source may be electric powered such as, incandescent lamp, fluorescent, LED and electroluminescent or chemiluminescent or radiation activated phosphorescence. The EC electrode 1 forms the viewing surface and has a transparent or translucent substrate 5, e.g. glass, with a conductive layer 6, e.g. tin oxide, and an electrochromic layer 7. The counter electrode 3 is also a composite of a conductive layer 8 on a substrate 9, and a counter-electrode material 10 such as carbon, tungsten oxide, or a mixture thereof. A suitable substrate for the viewing area and counter-electrode is NESA glass, which is glass having a thin transparent layer of tin oxide.

A light 4 provides illumination by introducing light at the edge of substrate 5, which passes through the entire substrate.

When battery 11 is connected to make counter-electrode 3 negative, EC electrode layer 7 colors. When the connections are reversed, EC layer 7 erases (or bleaches).

In FIGS. 2, 3 and 4 are shown electrochromic devices with the EC layer 7 in the form of a plurality of segments which may be selectively activated to show numbers. FIG. 2 shows the number 4.

The invention should be usefully applied in EC displays for watches, clocks, calculators, telephone displays, automobile dashboards, instrument indicators and advertising displays.

Used in reflective applications the displays may be expected to be competitive with light emitting devices under conditions or darkness while retaining the inherent good readability under conditions of bright lighting.

The following specific examples are given to illustrate the invention further and to show specific embodiments and modes of practice of the invention and are not intended to be limitative.

EXAMPLE 1

Graphite on Substrate Counter-Electrode

A counter-electrode was prepared as follows: Dixon Crucible Co. Graphokote No. 120 was brushed on a clean substrate on NESA glass. While the Graphokote 120 film was still wet, WO₃ powder was sprinkled onto the surface. Air drying for 1/2 hour at 25° C. and baking at 300° C. for 1/2 hour followed. The WO₃ particles became embedded in the graphite film as the electrode was air dried at 25° C. The electrode was cooled to 25° C. and soaked in a solution of glycerin-sulfuric acid 10:1 by volume for 24 hours minimum, rinsed with acetone and baked at 90° C. for 1/2 hour to dry. The resulting deposit was composed of approximately 0.5 gm/cm² WO₃ on 2.0 mg./cm² Graphokote 120.

EXAMPLE 2

An electrochromic device was constructed from two NESA glass plates. One conductive NESA plate was coated with a 0.5 micron thick evaporated film of tungsten oxide. The other NESA plate was a counter-electrode as in Example 1. The glass plates so formed were pressed together with the electrochromic and graphite films facing each other but separated by a 0.6 mm. thick sealing ring and spacer which retained an ionically conductive paste consisting of a TiO₂ pigment in a 1:10 ratio of concentrated sulfuric acid and glycerin. This paste was saturated with WO₃. This was accomplished by adding a surplus of WO₃ to the glycerin and sulfuric acid mixture and storing for several days at 50° C. The saturated solution was then poured off leaving the solids behind. The solution was then mixed with the TiO₂ pigment. An incandescent light was placed at the edge of the image area. The image was colored, and was clearly visible in darkness. This device was cycled from color to clear and back to color at an applied potential of 1.1 volts D.C. with half cycles of 100 milliseconds. The device underwent 8,000,000 cycles of switching at 60 cycles per minute without observable deterioration.