IP Library Granted Patent US 7,994,497
Granted Patent B2
US 7,994,497 · App. 12/253,565 · Granted Aug 9, 2011

Poly[bis(ethynyl)heteroacene]s and electronic devices generated therefrom

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Quick Facts
Patent No.
US 7,994,497
App. No.
12/253,565
Granted
Aug 9, 2011
Kind
B2
Abstract

An electronic device comprising a polymer of Formula or Structure (I) wherein R 1 is hydrogen, halogen, a suitable hydrocarbon, or a heteroatom containing group; R 2 is hydrogen, a suitable hydrocarbon, a heteroatom containing group, or a halogen; R 3 and R 4 are independently a suitable hydrocarbon, hydrogen, a heteroatom containing group, or a halogen; Ar is an aromatic component; x, y, a, b, and c represent the number of groups or rings, respectively; Z represents sulfur, oxygen, selenium, or NR wherein R is hydrogen, alkyl, or aryl; and n represents the number of repeating units.

Claims (36)

1. An electronic device comprising a polymer of Formula (I):

wherein R 1 is hydrogen, halogen, cyano, nitro, alkyl, aryl, alkoxy, substituted alkyl, substituted aryl, substituted alkoxy, or trialkylsilyl; R 2 is hydrogen, alkyl, aryl, alkoxy, substituted alkyl, substituted aryl, substituted alkoxy, trialkylsilyl, cyano, nitro, or a halogen; R 3 and R 4 are independently alkyl, aryl, alkoxy, substituted alkyl, substituted aryl, substituted alkoxy, hydrogen, trialkylsilyl, cyano, nitro, or a halogen; Ar is an aromatic component; x and y are independently from zero to about 12; a and b are independently from zero to about 3; c is from 1 to about 4; Z represents sulfur, oxygen, selenium, or NR wherein R is hydrogen, alkyl, or aryl; and n represents the number of repeating units and is 2 or more.

2. A device in accordance with claim 1 wherein Ar is selected from the group consisting of the following structural units which can be optionally substituted with alkyl, aryl, alkoxy, substituted alkyl, substituted aryl, substituted alkoxy, trialkylsilyl, or a halogen

wherein X is selected from the group consisting of C(R′R″), O, S, Se, NR′″, and Si(R′R″), and wherein R′, R″, and R′″ are independently selected from the group consisting of hydrogen, alkyl, or aryl; and Y is a carbon atom or a nitrogen atom.

3. A device in accordance with claim 1 wherein Z is S, Se, or O.

4. A device in accordance with claim 1 wherein R 1 is alkyl.

5. A device in accordance with claim 1 wherein R 1 is aryl.

6. A device in accordance with claim 1 wherein R 1 is trialkylsilyl.

7. A device in accordance with claim 1 wherein R 2 is hydrogen.

8. A device in accordance with claim 1 wherein R 2 is alkyl.

9. A device in accordance with claim 1 wherein R 2 is aryl.

10. A device in accordance with claim 1 wherein R 2 is alkoxy.

11. A device in accordance with claim 1 wherein R 2 is halogen.

12. A device in accordance with claim 1 wherein R 2 is cyano (CN) or nitro (NO 2 ).

13. A device in accordance with claim 1 wherein at least one of R 3 and R 4 is alkyl or alkoxy.

14. A device in accordance with claim 1 wherein at least one of R 3 and R 4 is aryl.

15. A device in accordance with claim 1 wherein at least one of R 1 , R 2 , R 3 and R 4 is cyano or nitro.

16. A device in accordance with claim 1 wherein Z is sulfur.

17. A device in accordance with claim 1 wherein at least one of R 1 , R 2 , R 3 and R 4 is alkyl with from about 1 to about 25 carbon atoms, or aryl with from 6 to about 36 carbon atoms.

18. A device in accordance with claim 1 wherein each x and y independently represents a number of from zero to about 12; and the sum of x and y is from zero to 12.

19. A device in accordance with claim 1 wherein each x and y independently represents a number of from zero to about 12, and the sum of x and y is from zero to about 6.

20. A device in accordance with claim 1 wherein a and b each independently represent a number of from zero to about 3, and the sum of a and b is from zero to about 6.

21. A device in accordance with claim 1 wherein a and b each independently represent a number of from zero to about 2, and the sum of a and b is from zero to about 2.

22. A device in accordance with claim 1 wherein n is a number of from 2 to about 5,000.

23. A device in accordance with claim 1 wherein n is a number of from 2 to about 1,000.

24. A device in accordance with claim 1 wherein n is a number of from about 10 to about 100.

25. A thin film transistor comprised of a substrate, a gate electrode, a gate dielectric layer, a source electrode and a drain electrode, and in contact with the source/drain electrodes and the gate dielectric layer a semiconductor layer of Formula (I):

wherein R 1 is hydrogen, halogen, cyano, nitro, alkyl, aryl, alkoxy, substituted alkyl, substituted aryl, substituted alkoxy, or trialkylsilyl; R 2 is hydrogen, alkyl, aryl, alkoxy, substituted alkyl, substituted aryl, substituted alkoxy, trialkylsilyl, cyano, nitro, or a halogen; R 3 and R 4 are independently alkyl, aryl, alkoxy, substituted alkyl, substituted aryl, substituted alkoxy, hydrogen, trialkylsilyl, cyano, nitro, or a halogen; Ar is an aromatic component; x and y are independently from zero to about 12; a and b are independently from zero to about 3; c is from 1 to about 4; Z represents sulfur, oxygen, selenium, or NR wherein R is hydrogen, alkyl, or aryl; and n represents the number of repeating units and is 2 or more.

26. A device in accordance with claim 25 wherein Ar is thienylene or phenylene.

27. A device in accordance with claim 25 said semiconductor is poly[bis(ethynyl)heteroacene] of the following formulas

wherein R 5 is alkyl, aryl, substituted aryl, or trialkylsilyl; and wherein n is from 2 to about 2,000.

28. A device in accordance with claim 25 wherein said substrate is a plastic sheet of a polyester, a polycarbonate, or a polyimide; said gate source and drain electrodes are each independently comprised of silver, gold, nickel, aluminum, chromium, platinum, or indium titanium oxide, or a conductive polymer, and said gate dielectric layer is comprised of inorganic nitrides or oxides, or organic polymers, silicon nitride, silicon oxide; and wherein said polymer is a poly[bis(ethynyl)heteroacene] and is deposited by solution processes of spin coating, stamp printing, screen printing, or jet printing.

29. A device in accordance with claim 25 wherein alkyl and alkoxy contain from 1 to about 20 carbon atoms, and aryl contains from 6 to about 36 carbon atoms.

30. A device in accordance with claim 25 wherein each x and y is from zero to about 12, each a and b is from zero to about 3, R is alkyl, and n is from 10 to about 200.

31. A polymer of Formula (I):

wherein R 1 is hydrogen, halogen, cyano, nitro, alkyl, aryl, alkoxy, substituted alkyl, substituted aryl, substituted alkoxy, or trialkylsilyl; R 2 is hydrogen, alkyl, aryl, alkoxy, substituted alkyl, substituted aryl, substituted alkoxy, trialkylsilyl, cyano, nitro, or a halogen; R 3 and R 4 are independently alkyl, aryl, alkoxy, substituted alkyl, substituted aryl, substituted alkoxy, hydrogen, trialkylsilyl, cyano, nitro, or a halogen; Ar is an aromatic component; x and y are independently from zero to about 12; a and b are independently from zero to about 3; c is from 1 to about 4; Z represents sulfur, oxygen, selenium, or NR wherein R is hydrogen, alkyl, or aryl; and n represents the number of repeating units and is 2 or more.

Assignments (9)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 6, 2025
From: XEROX CORPORATION
To: GENESEE VALLEY INNOVATIONS, LLC
Reel/Frame 073842/0479 →
SECOND LIEN NOTES PATENT SECURITY AGREEMENT Recorded Jul 2, 2025
From: XEROX CORPORATION
To: U.S. BANK TRUST COMPANY, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 071785/0550 →
FIRST LIEN NOTES PATENT SECURITY AGREEMENT Recorded Apr 11, 2025
From: XEROX CORPORATION
To: U.S. BANK TRUST COMPANY, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 070824/0001 →
SECURITY INTEREST Recorded Feb 13, 2024
From: XEROX CORPORATION
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 066741/0001 →
TERMINATION AND RELEASE OF SECURITY INTEREST IN PATENTS RECORDED AT RF 064760/0389 Recorded Feb 13, 2024
From: CITIBANK, N.A., AS COLLATERAL AGENT
To: XEROX CORPORATION
Reel/Frame 068261/0001 →
SECURITY INTEREST Recorded Nov 20, 2023
From: XEROX CORPORATION
To: JEFFERIES FINANCE LLC, AS COLLATERAL AGENT
Reel/Frame 065628/0019 →
SECURITY INTEREST Recorded Jun 22, 2023
From: XEROX CORPORATION
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 064760/0389 →
RELEASE OF SECURITY INTEREST IN PATENTS AT R/F 062740/0214 Recorded May 18, 2023
From: CITIBANK, N.A., AS AGENT
To: XEROX CORPORATION
Reel/Frame 063694/0122 →
SECURITY INTEREST Recorded Nov 10, 2022
From: XEROX CORPORATION
To: CITIBANK, N.A., AS AGENT
Reel/Frame 062740/0214 →