Formation of conjugated polymers for solid-state devices

Patent metadata

Field	Value
Publication number	US-9680102-B2
Application number	US-201414511450-A
Country	US
Kind code	B2
Filing date	Oct 10, 2014
Priority date	Mar 25, 2010
Publication date	Jun 13, 2017
Grant date	Jun 13, 2017

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.

First claim

What is claimed is:

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

wherein
each occurrence of Q 1 is independently S, O, or Se;
Q 2 is S, O, or N—R 2 ;
each occurrence of Q 3 is independently CH or N;
Q 4 is C(R 1 ) 2 , S, O, or N—R 2 ;
each occurrence of Q 5 is independently CH 2 , S, or O;
each occurrence of R 1 is independently hydrogen, C 1 -C 12 alkyl, C 1 -C 12 alkyl-OH, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 haloalkoxy, aryl, —C 1 -C 6 alkyl-O—C 1 -C 6 alkyl, or —C 1 -C 6 alkyl-O-aryl;
R 2 is hydrogen or C 1 -C 6 alkyl;
each occurrence of R 3 , R 4 , R 5 , and R 6 independently is hydrogen; optionally substituted C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, aryl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, aryloxy, —C 1 -C 10 alkyl-O—C 1 -C 10 alkyl, —C 1 -C 10 alkyl-O-aryl, —C 1 -C 10 alkyl-aryl; or hydroxyl;
each occurrence of R 7 is an electron withdrawing group;
each occurrence of R 8 is independently hydrogen, C 1 -C 6 alkyl, or cyano;
each occurrence of R 9 is independently C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 haloalkoxy, aryl, —C 1 -C 6 alkyl-O—C 1 -C 6 alkyl, —C 1 -C 6 alkyl-O-aryl, or N—R 2 ;
each occurrence of R 10 is independently C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, aryl, —C 1 -C 6 alkyl-O—C 1 -C 6 alkyl, or —C 1 -C 6 alkyl-O-aryl;
E is O or C(R 7 ) 2 ;

represents an aryl;

is C 2 , C 4 , or C 6 alkenylene, an aryl or heteroaryl; and
g is 0, 1, 2, or 3.

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.

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

wherein
each occurrence of Q 1 is independently S, O, or Se;
Q 2 is S, O, or N—R 2 ;
each occurrence of Q 3 is independently CH or N;
Q 4 is C(R 1 ) 2 , S, O, or N—R 2 ;
each occurrence of Q 5 is independently CH 2 , S, or O;
each occurrence of R 1 is independently hydrogen, C 1 -C 12 alkyl, C 1 -C 12 alkyl-OH, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 haloalkoxy, aryl, —C 1 -C 6 alkyl-O—C 1 -C 6 alkyl, or —C 1 -C 6 alkyl-O-aryl;
R 2 is hydrogen or C 1 -C 6 alkyl;
each occurrence of R 3 , R 4 , R 5 , and R 6 independently is hydrogen; optionally substituted C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, aryl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, aryloxy, —C 1

Assignees

• Univ Connecticut
• Univ Connecticut

Inventors

• Sotzing Gregory Allen
• Invernale Michael A

Classifications

• H01L51/5012

  Electricity · mapped topic

• C08G2261/3223

  containing one or more sulfur atoms as the only heteroatom, e.g. thiophene · CPC title

• G02F2001/1515

  Physics · mapped topic

• H01L51/42

  Electricity · mapped topic

• G02F1/15

  based on an electrochromic effect · CPC title