Non-aqueous ink compositions containing metallic nanoparticles suitable for use in organic electronics

Patent metadata

Field	Value
Publication number	US-10385229-B2
Application number	US-201615743557-A
Country	US
Kind code	B2
Filing date	Jul 6, 2016
Priority date	Jul 17, 2015
Publication date	Aug 20, 2019
Grant date	Aug 20, 2019

Abstract

Described herein are non-aqueous ink compositions containing a polythiophene having a repeating unit complying with formula (I) described herein, one or more metallic nanoparticles, and a liquid carrier having one or more organic solvents. The present disclosure also concerns the uses of such non-aqueous ink compositions, for example, in organic electronic devices.

First claim

What is claimed is:

1. A non-aqueous ink composition comprising:
(a) a polythiophene comprising a repeating unit complying with formula (I)

wherein R 1 and R 2 are each, independently, H, alkyl, fluoroalkyl, alkoxy, aryloxy, or —O—[Z—O] p —R e ;
wherein
Z is an optionally halogenated hydrocarbylene group,
p is equal to or greater than 1, and
R e is H, alkyl, fluoroalkyl, or aryl; or

wherein R 1 is a sulfonic acid group (—SO 3 H) and R 2 is alkyl, fluoroalkyl, alkoxy, aryloxy, or —O—[Z—O] p —R e ;
wherein Z, p and R e have the same meanings as defined above;
(b) one or more metallic nanoparticles; wherein the amount of the metallic nanoparticles is from 1 wt. % to 90 wt. %, relative to the combined weight of the metallic nanoparticles and the doped polythiophene and undoped polythiophene, and
(c) a liquid carrier comprising one or more organic solvents.

2. The non-aqueous ink composition according to claim 1 , wherein R 1 and R 2 are each, independently, H, fluoroalkyl, or —O[C(R a R b )—C(R c R d )—O] p —R e ; wherein each occurrence of R a , R b , R c , and R d , is each, independently, H, halogen, alkyl, fluoroalkyl, or aryl; R e is H, alkyl, fluoroalkyl, or aryl; p is 1, 2, or 3, or —OR f , wherein R f is alkyl or aryl, or
wherein R 1 is a sulfonic acid group (—SO 3 H) and R 2 is fluoroalkyl, or —O[C(R a R b )—C(R c R d )—O] p —R e , wherein R a , R b , R c , R d , R e , and p have the same meanings as defined above, or —OR f , wherein R f has the same meaning as defined above.

3. The non-aqueous ink composition according to claim 2 , wherein each occurrence of R a , R b , R c , and R d , is each, independently, H, (C 1 -C 8 )alkyl, (C 1 -C 8 )fluoroalkyl, or phenyl; and R e is (C 1 -C 8 )alkyl, (C 1 -C 8 )fluoroalkyl, or phenyl.

4. The non-aqueous ink composition according to claim 1 , wherein R 1 is H and R 2 is other than H or R 1 and R 2 are both other than H.

5. The non-aqueous ink composition according to claim 1 , wherein the repeating unit comprises at least one unit selected from the group consisting of formulae (1-1a) to (I-III) below:

6. The non-aqueous ink composition according to claim 5 , wherein the repeating unit comprises at least one unit selected from the group consisting of formulae (I-II) and (I-III).

7. The non-aqueous ink composition according to claim 1 , wherein the polythiophene comprising a repeating unit complying with formula (I) is doped with a dopant.

8. The non-aqueous ink composition according to claim 7 , wherein the dopant comprises a tetraarylborate.

9. The non-aqueous ink composition according to claim 1 , wherein the one or more metallic nanoparticles comprise a transition metal oxide.

10. The non-aqueous ink composition according to claim 9 , wherein the one or more metallic nanoparticles comprise zirconium oxide (ZrO 2 ), titanium dioxide (TiO 2 ), zinc oxide (ZnO), vanadium(V) oxide (V 2 O 5 ), molybdenum trioxide (MoO 3 ), tungsten trioxide (WO 3 ), or mixtures thereof.

11. The non-aqueous ink composition according to claim 9 , wherein the metallic nanoparticles comprise one or more organic capping groups.

12. A process for forming a hole-carrying film, the process comprising:
1) coating a substrate with a non-aqueous ink composition according to claim 1 ; and
2) annealing the coating on the substrate, thereby forming the hole-carrying film.

13. A hole-carrying film formed by the process according to claim 12 .

14. The hole-carrying film according to claim 13 , wherein the film has a transmittance of at least 85% of light having a wavelength of about 380-800 nm.

15. The hole-carrying film according to claim 13 , wherein the film has a thickness of from 5 nm to 500 nm.

16. A device comprising the hole-carrying film according to claim 13 , wherein the device is an OLED, OPV, transistor, capacitor, sensor, transducer, drug release device, electrochromic device, or battery device.

17. The device according to claim 16 , wherein the device is an OLED, OPV, transistor, capacitor, sensor, transducer, drug release device, electrochromic device, or battery device.

18. The process according to claim 12 , wherein the annealing temperature is from 25° C. to 300° C.

19. The non-aqueous ink composition according to claim 1 , wherein the total amount of water present in the liquid carrier is from 0 to 5% wt.

20. The non-aqueous ink composition according to claim 1 , wherein the liquid carrier consists of one or more organic solvents.

21. The non-aqueous ink composition according to claim 1 , wherein the liquid carrier consists of two or more organic solvents.

22. A non-aqueous ink composition comprising:
(a) a polythiophene comprising a repeating unit complying with formula (I)

wherein R 1 and R 2 are each, independently, H, alkyl, fluoroalkyl, alkoxy, aryloxy, or —O—[Z—O] p —R e ;
wherein
Z is an optionally halogenated hydrocarbylene group,
p is equal to or greater than 1, and
R e is H, alkyl, fluoroalkyl, or aryl; or

wherein R 1 is a sulfonic acid group (—SO 3 H) and R 2 is alkyl, fluoroalkyl, alkoxy, aryloxy, or —O—[Z—O] p —R e ;
wherein Z, p and R e have the same meanings as defined above;
(b) one or more metallic nanoparticles; wherein the one or more metallic nanoparticles comprise a transition metal oxide and wherein the metallic nanoparticles comprise one or more organic capping groups; and
(c) a liquid carrier comprising one or more organic solvents.

23. A non-aqueous ink composition comprising:
(a) a polythiophene comprising a repeating unit complying with formula (I)

wherein R 1 and R 2 are each, independently, H, alkyl, fluoroalkyl, alkoxy, aryloxy, or —O—[Z—O] p —R e ;
wherein
Z is an optionally halogenated hydrocarbylene group,
p is equal to or greater than 1, and
R e is H, alkyl, fluoroalkyl, or aryl; or

wherein R 1 is a sulfonic acid group (—SO 3 H) and R 2 is alkyl, fluoroalkyl, alkoxy, aryloxy, or —O—[Z—O] p —R e ;
wherein Z, p and R e have the same meanings as defined above;
(b) one or more metallic nanoparticles; wherein the total amount of water present in the liquid carrier is from 0 to 5% wt, and
(c) a liquid carrier comprising one or more organic solvents.

Assignees

• Nissan Chemical Ind Ltd

Inventors

• Wang Jing
• Li Sergey B
• Difalco Laura
• Decampo Floryan
• Chen Shilei

Classifications

• C09D165/00

  Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C09D107/00 - C09D157/00, C09D161/00 take precedence); Coating compositions based on derivatives of such polymers · CPC title

• C09D11/106

  containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds · CPC title

• C08K2003/2258

  of tungsten · CPC title

• C08K2003/2255

  of molybdenum · CPC title

• C08K2003/2244

  of zirconium · CPC title