Doping methods for hole injection and transport layers

Patent metadata

Field	Value
Publication number	US-9978473-B2
Application number	US-201213573676-A
Country	US
Kind code	B2
Filing date	Oct 3, 2012
Priority date	Oct 4, 2011
Publication date	May 22, 2018
Grant date	May 22, 2018

Abstract

A method including combining at least one first compound in a neutral form with at least one ionic dopant in a first solvent system to provide a first doped reaction product, isolating the first doped reaction product in solid form, and combining the isolated first doped reaction product with at least one conjugated polymer in neutral form in a second solvent system to form a second doped reaction product including an oxidized form of the conjugated polymer a neutral form of the first compound is described. Advantages include better stability, ease of use, and lower metal content. Applications include organic electronic devices including OLEDs.

First claim

What is claimed is:

1. A method comprising:
providing a hole transporting compound, wherein the hole transporting compound is an arylamine compound, which has a neutral form and an oxidized form, wherein the molecular weight of the hole transporting compound is less than 1,000 g/mole;
providing at least one ionic dopant comprising a cation and an anion,
combining the hole transport compound in a neutral form with the at least one ionic dopant comprising at least one cation and at least one anion in a first solvent system to provide the first doped reaction product, wherein the combination produces a neutral form of the cation, and wherein the first doped reaction product comprises the oxidized form of the hole transporting compound and the anion;
isolating the first doped reaction product in solid form, including removing the neutral form of the cation from the first doped reaction product;
providing at least one conjugated polymer which has a neutral form and an oxidized form,
combining the first doped reaction product with the at least one conjugated polymer in neutral form in a second solvent system to form a second doped reaction product comprising an oxidized form of the conjugated polymer and the anion; wherein doping produces a neutral form of the hole transporting compound.

2. The method of claim 1 , wherein the first doped reaction product is in solid form.

3. The method of claim 1 , wherein the anion is an arylborate anion.

4. The method of claim 1 , wherein the anion is represented by at least one of:

wherein independently, each of R 1 to R 10 is H, an alkyl, a perfluoroalkyl (C1-C10), a polyether, F, Cl, Br, I, CN, an optionally substituted phenyl, or an optionally substituted naphthyl; “A” is boron, gallium, phosphorous, antimony, SO 3 or CO 2 ; X is F, Cl, Br, I or CN; n is 0 to 6; and m is ≤6−n.

5. The method of claim 1 , wherein the conjugated polymer is a polythiophene.

6. The method of claim 1 , wherein the conjugated polymer comprises a regioregular polythiophene.

7. The method of claim 1 , wherein the hole transporting compound is 9,9-dimethyl-N2,N7-diphenyl-N2,N7-di-m-tolyl-9H-fluorene-2,7-diamine or N 1 ,N 4 -bis(4-methoxyphenyl)-N 1 ,N 4 -diphenylbenzene-1,4-diamine.

8. The method of claim 1 , wherein the hole transporting compound has a hole mobility of at least about 0.001 cm 2 /Vs.

9. The method of claim 1 , wherein the hole transporting compound has a molecular weight of less than 750 g/mole.

10. The method of claim 1 , wherein the hole transporting compound has work function of at least −4.7 eV.

11. The method of claim 1 , wherein the hole transporting compound has a work function which is larger than the work function of the conjugated polymer.

12. The method of claim 1 , wherein the cation of the ionic dopant is an oxidized species of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Ta, W, Re, Os, Ir, Pt, or Au; and the anion of the ionic dopant is represented by at least one of the following structures:

wherein independently, each of R 1 to R 10 is H, an alkyl, a perfluoroalkyl (C1-C10), a polyether, F, Cl, Br, I, CN, an optionally substituted phenyl, or an optionally substituted naphthyl; “A” is boron, gallium, phosphorous, antimony, SO 3 or CO 2 ; X is F, Cl, Br, I or CN; n is 0 to 6; and m is ≤6−n.

13. The method of claim 1 , wherein the cation is silver.

14. The method of claim 1 , wherein the cation is silver and the anion is an arylborate anion.

15. The method of claim 1 , wherein the ionic dopant is silver tetrakis(pentafluorophenyl) borate, silver tetrakis(2-(1,3,4,5,6,7-heptafluoro)naphthyl)borate, or a combination thereof.

16. The method of claim 1 , wherein the combining of the hole transport compound in neutral form with the at least one cation and at least one anion in a first solvent is carried out at a temperature of less than about 50° C.

17. The method of claim 1 , wherein the first solvent system comprises at least 90 wt. % organic solvent.

18. The method of claim 1 , wherein the removing the neutral form of the cation comprises removing zero valent metal from the first solution with use of silver powder after forming the first doped reaction product.

19. The method of claim 1 , wherein the isolating the first doped reaction product in solid form is carried out with use of halogenated solvent.

20. The method of claim 1 , wherein the isolated first doped reaction product has a work function larger, more negative than −4.7 eV.

21. The method of claim 1 , wherein the difference in work function between the conjugated polymer and the isolated first doped reaction product is at least 0.3 eV.

22. The method of claim 1 , wherein the conjugated polymer comprises at least one polythiophene comprising an alkoxy substituent at either the 3-position, the 4-position or both.

23. The method of claim 1 , wherein the conjugated polymer has a number average molecular weight of at least 5,000 g/mole.

24. The method of claim 1 , wherein the second solvent system comprises at least one aromatic hydrocarbon solvent and at least one nitrile solvent.

25. The method of claim 1 , wherein an ink is formulated from the second doped reaction product, and the ink further comprises at least one matrix material.

26. The method of claim 1 , wherein an ink is formulated from the second doped reaction product, and the ink further comprises at least one matrix material comprising at least one copolymer which comprises arylamine side groups and para-hydroxyphenyl side groups.

27. The method of claim 1 , wherein an ink is formulated from the second doped reaction product, and the ink further comprises at least one matrix material comprising at least one copolymer which comprises fused aromatic side groups and para-hydroxyphenyl side groups.

28. The method of claim 1 , wherein the cation is silver, and wherein the amount of silver in the first doped reaction product is less than 500 ppm.

29. The method of claim 1 , wherein the ionic dopant is a silver arylborate dopant and the conjugated polymer is a polythiophene.

30. The method of claim 1 , wherein, the ionic dopant is a silver arylborate dopant, and the conjugated polymer is a poly(alkoxythiophene), and wherein the work function of the isolated first doped reaction product is larger, more negative than the work function of the conjugated polymer.

31. A method, comprising:
providing at least one hole transporting compound which has a neutral form and an oxidized form, wherein the hole transporting compound is an arylamine compound,
providing at least one ionic dopant comprising a cation and an anion,
combining the at least one hole transporting compound in a neutral form with the at least one ionic dopant comprising at least one cation and at least one anion in

Assignees

• Nissan Chemical Ind Ltd

Inventors

• Seshadri Venkataramanan
• Chopra Neetu

Classifications

• C08F212/26 Primary

  Nitrogen · CPC title

• C08F212/22

  Oxygen · CPC title

• C09K2211/1483

  containing nitrogen and sulfur as heteroatoms · CPC title

• C09K2211/1433

  bridged by heteroatoms, e.g. N, P, Si or B · CPC title

• C08F226/06

  by a heterocyclic ring containing nitrogen · CPC title