# US 11,079,649 B2 · Metal sensitized color changing material

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- Number: US 11,079,649 B2
- Document ID: US11079649B2
- Status: Granted
- Kind: B2
- Application number: 14/884,201
- Filed: 2015-10-15
- Published: 2016-04-21
- Granted: 2021-08-03
- Earliest claimed: 2014-10-15
- Assignees: University of South Florida; United States Department of Energy
- Applicants: University of South Florida
- Inventors: Manoj Kumar Ram; D. Yogi Goswami; Elias K. Stefanakos
- Web page: https://patentgrep.com/patent/US11079649B2

## CPC

- G02F 1/153: Constructional details
- C09K 9/02: Organic tenebrescent materials
- G02B 26/005: {based on electrowetting}
- G02F 1/0018: {Electro-optical materials}
- G02F 1/15165: {Polymers}
- 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
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS

## Abstract

The subject invention pertains to color changeable, film materials comprising a metal substrate layer; a conducting polymer or conducting polymer composite layer; and an electrolyte layer. The conducting polymer or conducting polymer composite layer of the film material is capable of exhibiting changes in one or more optical properties when the film material is in contact with a metal. The subject invention also pertains to methods of preparing conducting polymer films capable of exhibiting changes in optical properties.

## Claims

### Claim 1

A device comprising:
a substrate coated with a substrate metal or a substrate metal oxide, wherein the substrate metal is gold, silver, or platinum and the substrate metal oxide is indium tin oxide or fluorine doped tin oxide, wherein the layer of the substrate metal or the substrate metal oxide is electrically continuous;
an active layer in direct physical contact with a first portion of a top surface of the substrate, wherein the active layer comprises a conducting polymer or a conducting polymer composite layer;
an electrolyte layer in direct physical contact with the active layer; and
a removable contact metal piece,
wherein the electrolyte layer comprises an acidic oxidant or a mixture of an acid and an oxidant;
wherein the active layer changes color and transparency when the electrolyte layer is directly contacted with the removable contact metal piece in the absence of an energy input from an external source; and
wherein the removable contact metal piece comprises copper, low carbon steel, nickel, zinc, iron, indium, tin, aluminum, manganese, cobalt, palladium , lithium, magnesium, sodium, or an alloy thereof,
wherein the removable contact metal piece has a first position in which no other element of the device is in contact with the removable contact metal piece, and a second position in which the electrolyte layer is directly contacted with the removable contact metal piece.

### Claim 2 (depends on 1)

The device of claim 1, wherein the change in color causes a change in the visible color of the active layer.

### Claim 3 (depends on 1)

The device of claim 1, wherein the change in the transparency causes a change in the transparency of the active layer to visible light.

### Claim 4 (depends on 1)

The device of claim 1, wherein the active layer comprises the conducting polymer, and the conducting polymer comprises at least one of a polyaniline, poly(ortho-anisidine), poly(o-toluidine), poly(ethoxy-aniline), a substituted polyanaline, a polypyrrole, a substituted polypyrrole, a polythiophene, polyindole, polycarbazole, and substituted polycarbazole.

### Claim 5 (depends on 1)

The device of claim 1, wherein the active layer comprises the conducting polymer composite, and the conducting polymer composite comprises at least one of polyaniline-rhodamine, polypyrrole-rhodamine, polythiophene-rhodamine, polyaniline and its derivatives with congo red, polypyrrole and its derivatives with congo red, polythiophene and its derivatives with conga red, polyaniline and its derivatives with metal oxides, polypyrrole and its derivatives with metal oxides, polythiophene and its derivatives with metal oxides, and polycarbazole and its derivatives with metal oxides.

### Claim 6 (depends on 1)

The device of claim 1, wherein the substrate is glass, fiber, ceramic, cloth or plastic.

### Claim 7 (depends on 1)

The device of claim 1, wherein the electrolyte layer comprises the acidic oxidant, and the acidic oxidant comprises o-iodoxybenzoic acid, peracetic acid, perboric acid, percaboxylic acid, citric acid, lactic acid, succinic acid, tartaric acid, or any combination thereof.

### Claim 8 (depends on 1)

The device of claim 1, wherein the removable contact metal piece is an alloy comprising at least two of copper, low carbon steel, nickel, zinc, iron, indium, tin, aluminum, manganese , cobalt, palladium, lithium, magnesium, and sodium.

### Claim 9 (depends on 1)

The device of claim 1, wherein the active layer further comprises nanoparticles of TiO2, WO3, MnO2, SnO2, In2O3, TiO2—WO3, TiO2—MnO2, or TiO2—SnO2.

### Claim 10 (depends on 1)

The device of claim 1, wherein the electrolyte layer comprises a first side surface and a second side surface opposite from the first side surface,
wherein substrate comprises a first side surface and a second side surface opposite from the first side surface, and
wherein the first side surface of the electrolyte layer is coplanar with the first side surface of the substrate.

### Claim 11 (depends on 10)

The device of claim 10, wherein the active layer further comprises a second side surface opposite from the first side surface, and
wherein the second surface side surface of the electrolyte layer is coplanar with the second side surface of the substrate and the second side surface of the active layer.

### Claim 12 (depends on 1)

The device of claim 1, wherein the removable contact metal piece releases electrons when the removable contact metal piece is oxidized by the acidic oxidant or the mixture of an acid and an oxidant, the released electrons along with the presence of hydrogen ions or metal ions causing the changes in color and transparency of the active layer.

### Claim 13 (depends on 1)

The device of claim 1 wherein:
the electrolyte layer is in direct physical contact with a top surface of the active layer.

### Claim 14 (depends on 1)

The device of claim 1 wherein:
the electrolyte layer is in direct physical contact with a top surface and a first side surface of the active layer and in contact with a second portion of the top surface of the substrate different from the first portion of the top surface of the substrate.

### Claim 15

A method for changing color and transparency of a conducting polymer film, the method comprising:
a) providing a device comprising:
i) a substrate coated with a substrate metal or a substrate metal oxide, wherein the substrate metal is gold, silver, or platinum and the substrate metal oxide is indium tin oxide or fluorine doped tin oxide, wherein the layer of the substrate metal or the substrate metal oxide is electrically continuous;
ii) an active layer in direct physical contact with a first portion of a top surface of the substrate, wherein the active layer comprises a conducting polymer or a conducting polymer composite layer; and
iii) an electrolyte layer in direct physical contact with the active layer wherein the electrolyte layer comprises an acidic oxidant or a mixture of an acid and an oxidant; and
b) changing the color and transparency of the active layer in the absence of an energy input from an external source by directly contacting a removable contact metal piece with the electrolyte layer of the device, wherein the removable contact metal piece comprises copper, low carbon steel, nickel, zinc, iron, indium, tin, aluminum, manganese, cobalt, palladium, lithium, magnesium, sodium, or an alloy thereof,
wherein the removable contact metal piece has a first position in which no other element of the device is in contact with the removable contact metal piece, and a second position in which the electrolyte layer is directly contacted with the removable contact metal piece.

### Claim 16 (depends on 15)

The method of claim 15, wherein the active layer further comprises nanoparticles of TiO2, WO3, MnO2, SnO2, In2O3, TiO2—WO3, TiO2—MnO2, or TiO2—SnO2.

### Claim 17 (depends on 15)

The method of claim 15, wherein the electrolyte layer comprises a gel electrolyte.

### Claim 18 (depends on 15)

The method of claim 15, wherein the electrolyte layer comprises a liquid electrolyte.

### Claim 19 (depends on 15)

The method of claim 15, wherein the electrolyte layer comprises a non-aqueous electrolyte.

### Claim 20 (depends on 15)

The method of claim 15, wherein the electrolyte layer comprises a solid electrolyte.

### Claim 21 (depends on 15)

The method of claim 15, wherein the electrolyte layer comprises a first side surface and a second side surface opposite from the first side surface,
wherein substrate comprises a first side surface and a second side surface opposite from the first side surface, and
wherein the first side surface of the electrolyte layer is coplanar with the first side surface of the substrate.

### Claim 22 (depends on 21)

The method of claim 21, wherein the active layer further comprises a second side surface opposite from the first side surface, and
wherein the second surface side surface of the electrolyte layer is coplanar with the second side surface of the substrate and the second side surface of the active layer.

### Claim 23 (depends on 15)

The method of claim 15, wherein the removable contact metal piece releases electrons when the removable contact metal piece is oxidized by the acidic oxidant or the mixture of an acid and an oxidant, the released electrons along with the presence of hydrogen ions or metal ions causing the changes in color and transparency of the active layer.