Formation of conjugated polymers for solid-state devices

• US 9,680,102 B2
• Filed: 10/10/2014
• Issued: 06/13/2017
• Est. Priority Date: 03/25/2010
• Status: Active Grant

• Current Assignee: University of Connecticut (State of Connecticut)
• Original Assignee: University of Connecticut (State of Connecticut)
• Inventors: Sotzing, Gregory Allen, Invernale, Michael A.
• Primary Examiner(s): Pham, Long
• Application Number:
  US14/511,450
• Publication Number:
  US 20160056382A1
• Time in Patent Office: 977 Days
• CPC Class Codes: C08G 2261/3223 containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
• CPC Class Codes: C08G 2261/44 Electrochemical polymerisation, i.e. oxidative or reductive coupling
• CPC Class Codes: C08G 2261/54 electrochromatic
• CPC Class Codes: C25B 3/00 Electrolytic production of organic compounds
• CPC Class Codes: G02F 1/15165 Polymers
• CPC Class Codes: G02F 2001/164 the electrolyte is made of polymers
• CPC Class Codes: H10K 10/46 Field-effect transistors, e.g. organic thin-film transistors [OTFT] H10K10/43 takes precedence
• CPC Class Codes: H10K 30/00 Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation integrated devices or assemblies of multiple devices H10K39/00, H10K65/00; electrolytic light-sensitive devices H01G9/20
• CPC Class Codes: H10K 50/11 characterised by the electroluminescent [EL] layers
• CPC Class Codes: H10K 71/125 using electrolytic deposition e.g. in-situ electropolymerisation
• CPC Class Codes: H10K 85/10 Organic polymers or oligomers
• CPC Class Codes: H10K 85/1135 Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
• CPC Class Codes: Y02E 10/549 Organic PV cells

Abstract

Disclosed herein is a facile process for the formation of conjugated polymers inside or outside assembled solid-state devices. One process generally involves applying a voltage to a device comprising at least two electrodes, a combination of an electrolyte composition and a electroactive monomer disposed between the electrodes, and a potential source in electrical connection with the at least two electrodes; wherein the applying voltage polymerizes the electroactive monomer into a conjugated polymer. Also disclosed are electrochromic articles prepared from the process and solid-state devices comprising a composite of an electrolyte composition and a conjugated polymer.

Claims

1. A method of forming a solid-state device, comprising:

providing a gel electrolyte precursor and an electroactive monomer disposed between at least two electrodes to form a device,

applying a voltage to the device to polymerize the electroactive monomer in the presence of the gel electrolyte precursor to form a conjugated polymer, and

crosslinking the gel electrolyte precursor to form a crosslinked gel electrolyte composition to form a solid-state device comprising a composite comprising conjugated polymer and crosslinked gel electrolyte composition.

2. The method of claim 1, wherein the crosslinked gel electrolyte composition comprises a lithium, sodium, or potassium salt, or an ionic liquid.

3. The method of claim 1, wherein the device further comprises a reference electrode.

4. The method of claim 1, wherein the electroactive monomer is thiophene, substituted thiophene, carbazole, 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, acetylene, phenylene, substituted phenylene, naphthalene, substituted naphthalene, biphenyl and terphenyl and their substituted versions, phenylene vinylene (e.g., p-phenylene vinylene), substituted phenylene vinylene, aniline, substituted aniline, indole, substituted indole, or a combination thereof.

5. The method of claim 1, wherein the electroactive monomer is

6. The method of claim 1, wherein the combination of gel electrolyte precursor and an electroactive monomer further comprises a conducting oligomer, a conducting precursor polymer, a viologen, or a combination thereof.

7. The method of claim 1, further comprising patterning the device using

a blocking material;

direct patterning;

lithography;

individually addressable electrodes;

or

directed polymerization by the selective application of voltage.

8. The method of claim 1, wherein an electrochemical atomic force microscope (AFM) tip is used as an external working electrode to supply the voltage for the applying.

19. A solid-state device prepared by the method of claim 1.

9. A solid-state device, comprising:

at least two electrodes; and

a composite disposed between the at least two electrodes, the composite comprising a conjugated polymer and a crosslinked gel electrolyte composition;

wherein the solid-state device is formed by

providing a gel electrolyte precursor and an electroactive monomer disposed between at least two electrodes to form a device,

applying a voltage to the device to polymerize the electroactive monomer in the presence of the gel electrolyte precursor to form a conjugated polymer, and

crosslinking the gel electrolyte precursor to form a crosslinked gel electrolyte composition to form the solid-state device comprising a composite comprising conjugated polymer and crosslinked gel electrolyte composition, wherein the conjugated polymer is not formed as a discrete film.

10. The solid-state device of claim 9, wherein the crosslinked gel electrolyte composition comprises a lithium, sodium, or potassium salt, or an ionic liquid.

11. The solid-state device of claim 9, further comprising a layer disposed on the composite, the layer comprising

a second electrolyte composition, or

a second composite comprising the second electrolyte composition and a second conjugated polymer formed by in situ polymerization of a second electroactive monomer in a second combination comprising the second electrolyte composition and second electroactive monomer.

12. The solid-state device of claim 9, wherein the electroactive monomer is thiophene, substituted thiophene, carbazole, 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, acetylene, phenylene, substituted phenylene, naphthalene, substituted naphthalene, biphenyl and terphenyl and their substituted versions, phenylene vinylene (e.g., p-phenylene vinylene), substituted phenylene vinylene, aniline, substituted aniline, indole, substituted indole, or a combination thereof.

13. The solid-state device of claim 9, wherein the electroactive monomer is

14. The solid-state device of claim 9, wherein the providing a gel electrolyte precursor and an electroactive monomer further comprises providing a conducting oligomer, a conducting precursor polymer, a viologen, or a combination thereof.

15. The solid-state device of claim 9, wherein the at least two electrodes are indium-doped tin oxide (ITO) coated substrates.

16. The solid-state device of claim 9, further comprising a reference electrode.

17. The solid-state device of claim 9, further comprising a potential source in electrical connection with the at least two electrodes.

18. The solid-state device of claim 9, wherein the device is an electrochromic device, an organic thin-film transistor, an organic light-emitting diode, or an organic photovoltaic cell.