Charge transporting semi-conducting material and electronic device comprising it

Patent metadata

Field	Value
Publication number	US-10873030-B2
Application number	US-201716078416-A
Country	US
Kind code	B2
Filing date	Feb 22, 2017
Priority date	Feb 22, 2016
Publication date	Dec 22, 2020
Grant date	Dec 22, 2020

Abstract

The present invention relates to a charge transporting semi-conducting material comprising: a) at least one electrical dopant, and b) a branched or cross-linked charge-transporting polymer comprising cyclobutenone cross-linking units of at least one of the general formulae la and/or lb, wherein aa) Pol 1 , Pol 2 , Pol 3 and Pol 4 are independently selected chains of the charge-transporting polymer, bb) X 1 , X 2 , X 3 , and X 4 are independently selected optional spacer units or, independently, represent direct bonding of Pol 1 , Pol 2 , Pol 3 and Pol 4 chains to the cyclobutenone ring, cc) Z 1 , Z 2 , Z 3 , and Z 4 are independently selected from H, halogen or a carbon-containing group; the charge transporting semi-conducting material being obtainable by a process comprising: i) providing a solution containing aaa) at least one precursor charge transporting compound comprising at least one covalently attacked alkenyloxy group having generic formula II wherein X is an optional spacer which is further linked to a charge transporting structural moiety of the precursor charge transporting compound, the dashed line represents the bonding to a charge transporting structural moiety of the precursor charge transporting compound and Z 1 , Z 2 , Z 3 , and Z 4 are independently selected from H, halogen or the carbon-containing group, bbb) at least one electrical dopant, ccc) at least one solvent, ii) depositing the solution on a substrate, iii) removing the solvent, and iv) reacting the alkinyloxy groups to effect crosslinking, preferably by heating, wherein the average number of the alkinyloxy groups per one molecule of the precursor charge transporting compound provided in the step i) is equal to or greater than 2, preferably greater than 2.05, and a process for preparing the same.

First claim

The invention claimed is:

1. Charge transporting semi-conducting material comprising:
a) at least one electrical dopant, and
b) a branched or cross-linked charge-transporting polymer comprising cyclobutenone cross-linking units of at least one of the general formulae Ia and/or Ib,

wherein
aa) Pol 1 , Pol 2 , Pol 3 and Pol 4 are independently selected chains of the charge-transporting polymer,
bb) X 1 , X 2 , X 3 , and X 4 are independently selected optional spacer units or, independently, represent direct bonding of Pol 1 , Pol 2 , Pol 3 and Pol 4 chains to the cyclobutenone ring, and
cc) Z 1 , Z 2 , Z 3 , and Z 4 are independently selected from H, halogen or a carbon-containing group.

2. Charge transporting semi-conducting material according to claim 1 , wherein the electrical dopant is a p-dopant or an n-dopant.

3. Charge transporting semi-conducting material according to claim 1 , wherein the electrical dopant is selected from
(i) [3]-radialene compounds, wherein each bridgehead carbon atom is substituted by a nitrile group, C 6 -C 14 perfluorinated aryl or C 2 -C 14 perfluorinated heteroaryl, wherein up to three fluorine atoms in the perfluorinated substituents may optionally be replaced by groups independently selected from nitrile or trifluoromethyl, and/or
(ii) unsubstituted or substituted oxazolyl, diazolyl and/or thiazolyl radicals.

4. Electronic device comprising a semi-conducting layer comprising the charge transporting semi-conducting material according to claim 1 .

5. A charge transporting semi-conducting material obtained by a process comprising:
i) providing a solution containing
aaa) at least one precursor charge transporting compound comprising at least one covalently attached alkinyloxy group having generic formula II

wherein
X is an optional spacer which is further linked to a charge transporting structural moiety of the precursor charge transporting compound,
the dashed line represents the bonding to a charge transporting structural moiety of the precursor charge transporting compound, and
Z 1 , Z 2 , Z 3 , and Z 4 are independently selected from H, halogen or the carbon-containing group,
bbb) at least one electrical dopant,
ccc) at least one solvent,

ii) depositing the solution on a substrate,
iii) removing the solvent, and
v) reacting the alkinyloxy groups to effect crosslinking,
wherein the average number of the alkinyloxy groups per one molecule of the precursor charge transporting compound provided in the step i) is equal to or greater than 2.

6. Charge transporting semi-conducting material according to claim 5 , wherein the precursor charge transporting compound is a precursor charge transporting oligomer or a precursor charge transporting small molecule.

7. Charge transporting semi-conducting material according to claim 5 , wherein the precursor charge transporting compound is a charge transporting polymer which comprises ethylene building units substituted with at least one pending side group comprising at least one charge transporting structural moiety which comprises a conjugated system of at least 4 delocalized electrons.

8. Charge transporting semi-conducting material according to claim 5 , wherein the charge transporting structural moiety is comprised in a carbocyclic or heterocyclic structural moiety.

9. Charge transporting semi-conducting material according to claim 8 , wherein the charge transporting structural moiety comprises an aromatic system of delocalized electrons.

10. Charge transporting semi-conducting material according to claim 9 , wherein the charge transporting structural moiety comprises at least two rings which are independently selected from aromatic and heteroaromatic rings.

11. Charge transporting semi-conducting material according to claim 5 , wherein the charge transporting structural moiety comprises at least one trivalent nitrogen atom.

12. Charge transporting semi-conducting material according to claim 11 , wherein the trivalent nitrogen atom is substituted with three carbocyclic or heterocyclic rings which are independently selected from aromatic and heteroaromatic rings.

13. Charge transporting semi-conducting material according to claim 5 , wherein the charge transporting structural moiety is selected from the group consisting of

wherein the dashed line represents the covalent bond to the rest of the charge transporting polymer.

14. Crosslinked charge transporting polymer which is formed from the precursor charge transporting oligomer and/or from the precursor charge transporting small molecule as defined in claim 6 .

15. Charge transporting semi-conducting material according to claim 5 , wherein the average number of the alkinyloxy groups per one molecule of the precursor charge transporting compound provided in the step i) is equal to or greater than 2.05.

16. Charge transporting semi-conducting material according to claim 5 , wherein the reacting of the alkinyloxy groups to effect crosslinking comprises heating.

17. Process for preparing a charge transporting semi-conducting material, the process comprising:
i) providing a solution containing
a) a precursor charge-transporting compound comprising at least one covalently attached alkinyloxy group having formula II

wherein
X is the optional spacer which is further linked to a charge transporting structural moiety of the precursor charge transporting compound,
the dashed line represents the bonding to the charge transporting structural moiety of the precursor charge transporting compound and
Z 1 , Z 2 , Z 3 , and Z 4 are independently hydrogen, halogen or a carbon-containing group,
b) at least one electrical dopant,
c) at least one solvent,

ii) depositing the solution on a substrate,
iii) removing the solvent, and
iv) reacting the alkinyloxy groups to effect crosslinking,
wherein the average number of the substituted alkinyloxy groups having formula II per molecule in the precursor charge transporting compound is equal to or greater than 2.

18. Process according to claim 17 , wherein the average number of the alkinyloxy groups per one molecule of the precursor charge transporting compound provided in the step i) is equal to or greater than 2.05.

19. Process according to claim 17 , wherein the reacting of the alkinyloxy groups to effect crosslinking comprises heating.

20. Solution comprising:
a) a precursor charge-transporting compound comprising at least one covalently attached alkinyloxy group having formula II

wherein
X is the optional spacer which is further linked to a charge transporting structural moiety of the precursor charge transporting compound,
the dashed line represents the bonding to the charge transporting structural moiety of the precursor charge transporting compound and

Assignees

• Novaled Gmbh

Inventors

• Lederer Kay
• Runge Steffen
• Blochwitz-Nimoth Jan
• Limberg Felix
• KRüGER HARTMUT

Classifications

• H10K71/40

  Thermal treatment, e.g. annealing in the presence of a solvent vapour · CPC title

• H10K85/146

  poly N-vinylcarbazol; Derivatives thereof · CPC title

• H10K85/151 Primary

  Copolymers · CPC title

• H10K85/6572

  comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole · CPC title

• H10K85/631

  Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine · CPC title