# US 10,873,030 B2 · Charge transporting semi-conducting material and electronic device comprising it > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,873,030 B2 - Document ID: US10873030B2 - Status: Granted - Kind: B2 - Application number: 16/078,416 - Filed: 2017-02-22 - Published: 2019-02-21 - Granted: 2020-12-22 - Earliest claimed: 2016-02-22 - Assignees: Novaled GmbH - Applicants: Novaled GmbH - Inventors: Kay Lederer; Steffen Runge; Jan Blochwitz-Nimoth; Felix Limberg; Hartmut Krüger - Web page: https://patentgrep.com/patent/US10873030B2 ## CPC - H10K 85/151: {Copolymers} - C08F 226/02: by a single or double bond to nitrogen - C08F 226/12: N-Vinylcarbazole - H10K 71/164: {using vacuum deposition} - H10K 71/30: Doping active layers, e.g. electron transporting layers - H10K 71/40: Thermal treatment, e.g. annealing in the presence of a solvent vapour - H10K 85/141: {comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE} - H10K 85/146: {poly N-vinylcarbazol; Derivatives thereof} - H10K 50/14: Carrier transporting layers - H10K 50/155: comprising dopants - H10K 71/12: using liquid deposition, e.g. spin coating - H10K 2102/351: {Thickness} - H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## 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) Pol1, Pol2, Pol3 and Pol4 are independently selected chains of the charge-transporting polymer, bb) X1, X2, X3, and X4 are independently selected optional spacer units or, independently, represent direct bonding of Pol1, Pol2, Pol3 and Pol4 chains to the cyclobutenone ring, cc) Z1, Z2, Z3, and Z4 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 Z1, Z2, Z3, and Z4 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. ## Claims ### Claim 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) Pol1, Pol2, Pol3 and Pol4 are independently selected chains of the charge-transporting polymer, bb) X1, X2, X3, and X4 are independently selected optional spacer units or, independently, represent direct bonding of Pol1, Pol2, Pol3 and Pol4 chains to the cyclobutenone ring, and cc) Z1, Z2, Z3, and Z4 are independently selected from H, halogen or a carbon-containing group. ### Claim 2 (depends on 1) Charge transporting semi-conducting material according to claim 1, wherein the electrical dopant is a p-dopant or an n-dopant. ### Claim 3 (depends on 1) 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, C6-C14 perfluorinated aryl or C2-C14 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. ### Claim 4 (depends on 1) Electronic device comprising a semi-conducting layer comprising the charge transporting semi-conducting material according to claim 1. ### Claim 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 Z1, Z2, Z3, and Z4 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. ### Claim 6 (depends on 5) 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. ### Claim 7 (depends on 5) 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. ### Claim 8 (depends on 5) Charge transporting semi-conducting material according to claim 5, wherein the charge transporting structural moiety is comprised in a carbocyclic or heterocyclic structural moiety. ### Claim 9 (depends on 8) Charge transporting semi-conducting material according to claim 8, wherein the charge transporting structural moiety comprises an aromatic system of delocalized electrons. ### Claim 10 (depends on 9) 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. ### Claim 11 (depends on 5) Charge transporting semi-conducting material according to claim 5, wherein the charge transporting structural moiety comprises at least one trivalent nitrogen atom. ### Claim 12 (depends on 11) 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. ### Claim 13 (depends on 5) 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. ### Claim 14 (depends on 6) 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. ### Claim 15 (depends on 5) 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. ### Claim 16 (depends on 5) Charge transporting semi-conducting material according to claim 5, wherein the reacting of the alkinyloxy groups to effect crosslinking comprises heating. ### Claim 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 Z1, Z2, Z3, and Z4 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. ### Claim 18 (depends on 17) 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. ### Claim 19 (depends on 17) Process according to claim 17, wherein the reacting of the alkinyloxy groups to effect crosslinking comprises heating. ### Claim 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 Z1, Z2, Z3, and Z4 are independently hydrogen, halogen or a carbon-containing group, b) at least one electrical dopant, and c) at least one solvent. ### Claim 21 (depends on 20) Solution according to claim 20, wherein the solvent comprises at least 1 wt % of a nitrile compound.