Highly conductive polymer film compositions from nanoparticle induced phase segregation of counterion templates from conducting polymers

• US 10,005,914 B2
• Filed: 04/22/2016
• Issued: 06/26/2018
• Est. Priority Date: 04/23/2015
• Status: Active Grant

• Current Assignee: University of Connecticut (State of Connecticut)
• Original Assignee: University of Connecticut (State of Connecticut)
• Inventors: Sotzing, Gregory Allen
• Primary Examiner(s): Kopec, Mark
• Assistant Examiner(s): Thomas, Jaison P
• Application Number:
  US15/135,894
• Publication Number:
  US 20160312044A1
• Time in Patent Office: 795 Days
• CPC Class Codes: B05D 1/005 Spin coating
• CPC Class Codes: B05D 1/02 performed by spraying
• CPC Class Codes: B05D 1/18 performed by dipping
• CPC Class Codes: B05D 1/30 performed by gravity only, i.e. flow coating
• CPC Class Codes: B05D 3/142 Pretreatment
• CPC Class Codes: C09D 5/24 Electrically-conducting paints conductive materials H01B1/00
• CPC Class Codes: H01B 1/122 Ionic conductors
• CPC Class Codes: H01B 1/127 comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
• CPC Class Codes: H01B 1/128 comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes

Abstract

Disclosed are conductive polymer film structures comprising an insulating substrate comprising nucleophile derivatized nanoparticles located at the surface of the insulating substrate; and a conducting polymer:template polymer coating disposed on at least a portion of a surface of the insulating substrate through which a chemical bond forms between at least one anion of the template polymer and nucleophile derivatized nanoparticles located at the surface of the insulating substrate.

Claims

1. A conductive polymer film structure, comprising

an insulating substrate comprising nucleophile derivatized nanoparticles located at the surface of the insulating substrate;

and

a conducting polymer;

template polymer coating disposed on at least a portion of a surface of the insulating substrate through which a chemical bond forms between at least one anion of the template polymer and nucleophile derivatized nanoparticles located at the surface of the insulating substrate.

2. The conductive polymer film structure of claim 1, wherein the insulating substrate is polyacrylic, polyamide, polycarbonate, polyether, polyester, polyethylene, polyimide, polyurethane, polyester-polyurethane copolymer, polyurea, polythiourea, polysiloxane, polyisoprene, polybutadiene, polyethylene oxide, polylactic acid, blends thereof, or copolymers thereof.

3. The conductive polymer film structure of claim 1, wherein the nucleophile derivatized nanoparticles is silicon dioxide (SiO₂), titanium dioxide (TiO₂), aluminum oxide, calcium oxide, amine functionalized nanoparticles, or a combination thereof.

4. The conductive polymer film structure of claim 1, wherein the nanoparticles have a particle size of about 1 nanometer (nm) to about 1000 nm.

5. The conductive polymer film structure of claim 1, wherein the nanoparticles are present in the insulating substrate in an amount of about 0.05 to about 5 wt % based on the total weight of the insulating substrate.

6. The conductive polymer film structure of claim 1, wherein the insulating substrate has a thickness of about 100 nm to about 5 mm.

7. The conductive polymer film structure of claim 1, wherein the conducting polymer of the conducting polymer:

template polymer comprises units of a conducting monomer wherein the conducting monomer is thiophene, substituted thiophene, 3,4-ethylenedioxythiophene, thieno[3,4-b]thiophene, substituted thieno[3,4-b]thiophene, dithieno[3,4-b;

3′

,4′

-d]thiophene, thieno[3,4-b]furan, substituted thieno[3,4-b]furan, bithiophene, substituted bithiophene, pyrrole, substituted pyrrole, phenylene, substituted phenylene, naphthalene, substituted naphthalene, biphenyl and terphenyl and their substituted versions, phenylene vinylene, substituted phenylene vinylene, aniline, substituted aniline, a monomer of any one of structures (I)-(XXIX);

8. The conductive polymer film structure of claim 1, wherein the template polymer comprises sulfonic acid groups, phosphoric acid groups, or a combination thereof.

9. The conductive polymer film structure of claim 1, wherein the conducting polymer:

template polymer coating is a film/sheet or a pattern.

10. The conductive polymer film structure of claim 1, wherein the conducting polymer:

template polymer coating has a thickness of about 40 nm to about 1 micrometer.

11. The conductive polymer film structure of claim 1, further comprising an additional substrate, wherein the insulating substrate is disposed on a surface of the additional substrate.

12. The conductive polymer film structure of claim 11, wherein the additional substrate is reflective.

13. The conductive polymer film structure of claim 1, having one or more of the following:

photopic transmittance >

80%;

sheet resistance of about 5 to about 20 ohm/cm²; and

conductivity greater than 5000 S/cm.

14. The conductive polymer film structure of claim 1, wherein the conducting polymer:

template polymer is PEDOT;

PSS.

15. An article comprising the conductive polymer film structure of claim 1.

16. The article of claim 15, wherein the article is a display, a touchscreen, a photovoltaic, a resistive heated window, resistive heated mirrors, a see-through display, a transistor, a see-through circuitry element, or a reflective device.

17. A method of making a conductive polymer film structure, comprising

forming a conducting polymer:

template polymer coating on at least a portion of a surface of an insulating substrate,

wherein the insulating substrate comprises nanoparticles located at the surface of the insulating substrate,

optionally where the insulating substrate is plasma treated before the forming a conducting polymer;

template polymer coating.

18. The method of claim 17, wherein the conducting polymer:

template polymer coating is formed using a casting process, tape casting, flow coating, spray coating, spin coating, ink jetting, dip coating, or a combination thereof.

19. An article comprising the conductive polymer film structure prepared by the method of claim 17.

20. The article of claim 19, wherein the article is a display, a touchscreen, a photovoltaic, a resistive heated window, resistive heated mirrors, a see-through display, a transistor, a see-through circuitry element, or a reflective device.