Organic semiconductor doping process

Patent metadata

Field	Value
Publication number	US-9929343-B2
Application number	US-201414894187-A
Country	US
Kind code	B2
Filing date	May 30, 2014
Priority date	May 30, 2013
Publication date	Mar 27, 2018
Grant date	Mar 27, 2018

Abstract

The present invention relates to the doping of organic semiconductors and processes for producing layers of p-doped organic semiconductors. Disclosed is a process for p-doping organic semiconductors comprising treating the organic semiconductor with an oxidized salt of the organic semiconductor. A process for producing a layer of a p-doped organic semiconductor comprising producing a p-doped organic semiconductor by treating the organic semiconductor with an oxidized salt of the organic semiconductor; disposing a composition comprising a solvent and the p-doped organic semiconductor on a substrate; and removing the solvent is also described. Also disclosed is a process for producing a layer of a p-doped organic semiconductor comprising: disposing a composition comprising a solvent, the organic semiconductor and a protic ionic liquid on a substrate; and removing the solvent. A process for producing a semiconductor device comprising a process for doping an organic semiconductor according to the invention is also described. Finally, a high purity p-dopant composition is described.

First claim

The invention claimed is:

1. A process for producing a p-doped organic semiconductor comprising treating an organic semiconductor with a protic ionic liquid,
wherein the organic semiconductor comprises a compound of formula (Vb)

and wherein each R 1 is the same or different and is a group selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 1-8 alkoxy, hydroxyl, mono-C 1-8 alkylamino, di-C 1-8 alkylamino, amino, halide, cyano, nitro, and thiol; and
wherein the protic ionic liquid is not 1-ethyl-3-methylimidazolium-TFSI or 1-butyl-3-methylimidazolium-TFSI.

2. The process according to claim 1 wherein the protic ionic liquid is a compound of formula PA wherein P is a cation selected from H + , H 3 O + , an ammonium cation, an imidazolium cation, a pyridinium cation, a pyrrolidonium cation or an indolium cation; and wherein A is ClO 4 − , NO 3 − or an anion of formula (i), (ii), (iii) or (iv)

wherein each X is the same or different and is an electron withdrawing group, optionally wherein X is CF 3 or CF 2 CF 3 , or wherein A is bis(trifluoromethanesulfonyl)imide, bis(pentafluoroethanesulfonyl)imide, bis(perfluoropropanesulfonyl)imide, trifluoroacetate, or trifluoromethanesulfonate.

3. The process according to claim 2 wherein P is a cation selected from H + , H 3 O + , NR 4 + , NHR 3 + , NH 2 R 2 + , NH 3 R + or NH 4 + ,

wherein R is independently selected from C 1-8 alkyl, C 2-8 alkenyl or aryl; and
wherein R a , R b , and R c are independently selected from H, C 1-8 -alkyl, C 2-8 -alkenyl or aryl, and at least one of R a , R b , and R c is H.

4. The process according to claim 1 wherein the protic ionic liquid is selected from H-TFSI, 1-alkyl-3-methylimidazolium-TFSI, H-BETI, 1-alkyl-3-methylimidazolium-BETI, 1-methyl-3-methylimidazolium-TFSI, and 1-propyl-3-methylimidazolium-TFSI.

5. The process according to claim 1 wherein the amount of the protic ionic liquid is from 0.01 to 50 mol % relative to the amount of the organic semiconductor.

6. A process according to claim 1 wherein the amount of the protic ionic liquid is from 5 to 30 mol % relative to the amount of the organic semiconductor.

7. A process for producing a layer of a p-doped organic semiconductor comprising disposing on a substrate an organic semiconductor and a protic ionic liquid,
wherein the organic semiconductor comprises a compound of formula (Vb)

and wherein each R 1 is the same or different and is a group selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 1-8 alkoxy, hydroxyl, mono-C 1-8 alkylamino, di-C 1-8 alkylamino, amino, halide, cyano, nitro, and thiol; and
wherein the protic ionic liquid is not 1-ethyl-3-methylimidazolium-TFSI or 1-butyl-3-methylimidazolium-TFSI.

8. The process according to claim 7 wherein the process comprises
(a) disposing on a substrate a solvent, an organic semiconductor and a protic ionic liquid; and
(b) removing the solvent.

9. The process according to claim 8 wherein the process comprises
(a) disposing on a substrate a composition comprising a solvent, an organic semiconductor and a protic ionic liquid; and
(b) removing the solvent.

10. The process according to claim 7 wherein the organic semiconductor comprises 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenyl-amine)-9,9′-Spirobifluorene (Spiro-OMeTAD).

11. The process according to claim 7 wherein the protic ionic liquid is selected from H-TFSI, 1-alkyl-3-methylimidazolium-TFSI, H-BETI, 1-alkyl-3-methylimidazolium-BETI, 1-methyl-3-methylimidazolium-TFSI, and 1-propyl-3-methylimidazolium-TFSI

12. The process according to claim 9 wherein the process further comprises producing the composition comprising the solvent, the organic semiconductor and the protic ionic liquid by treating a composition comprising the organic semiconductor and a first solvent with a composition comprising the protic ionic liquid and a second solvent.

13. The process according to claim 12 wherein the first solvent is chlorobenzene and the second solvent is acetonitrile.

14. The process according to claim 9 wherein the composition disposed on the substrate further comprises LiTFSI and/or tert-butyl pyridine.

15. The process according to claim 14 wherein the composition comprises from 1 to 40 mol % LiTFSI and from 50 to 150 mol % tert-butyl pyridine relative to the amount of the organic semiconductor.

16. The process according to claim 8 wherein the solvent comprises acetonitrile and/or chlorobenzene.

17. The process according to claim 7 wherein the substrate comprises an electrode material or a semiconductor material or a mesoporous layer of a semiconductor material or a mesoporous layer of a dielectric material.

18. The layer of a p-doped organic semiconductor produced according to the process of claim 7 .

19. A layer of a p-doped organic semiconductor, wherein the layer comprises an organic semiconductor and a protic ionic liquid, and
the organic semiconductor comprises a compound of formula (Vb)

and wherein each R 1 is the same or different and is a group selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 1-8 alkoxy, hydroxyl, mono-C 1-8 alkylamino, di-C 1-8 alkylamino, amino, halide, cyano, nitro, and thiol; and
wherein the protic ionic liquid is not 1-ethyl-3-methylimidazolium-TFSI or 1-butyl-3-methylimidazolium-TFSI.

20. The layer according to claim 19 wherein the organic semiconductor comprises 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenyl-amine)-9,9′-Spirobifluorene (Spiro-OMeTAD) and/or wherein the protic ionic liquid is selected from H-TFSI, 1-alkyl-3-methylimidazolium-TFSI, H-BETI, and 1-alkyl-3-methylimidazolium-BETI, 1-methyl-3-methylimidazolium-TFSI, and 1-propyl-3-methylimidazolium-TFSI

21. A process for producing a semiconductor device comprising
a step of producing a p-doped organic semiconductor by a process comprising treating an organic semiconductor with a protic ionic liquid; or
a step of producing a layer of a p-doped organic semiconductor by a process comprising disposing on a substrate an organic semiconductor and a protic ionic liquid,
wherein the organic semiconductor comprises a compound of formula (Vb)

and wherein each R 1 is the same or different and is a group selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 1-8 alkoxy, hydroxyl, mono-C 1-8 alkylamino, di-C 1-8 alkylamino, amino, halide, cyano, nitro, and thiol; and
wherein the protic ionic liquid is not 1-ethyl-3-methylimidazolium-TFSI or 1-butyl-3-methylimidazolium-TFSI.

22. The process according to claim 21 wherein the process further

Assignees

• Isis Innovation
• Univ Oxford Innovation Ltd

Inventors

• Snaith Henry
• Leijtens Tomas
• Abate Antonio
• Sellinger Alan

Classifications

• H01G9/2013

  the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide · CPC title

• H01G9/2059

  comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution · CPC title

• Y02E10/549

  Organic PV cells · CPC title

• H01L2251/305

  Electricity · mapped topic

• H01L51/005

  Electricity · mapped topic