Diketopyrrolopyrrole polymers as organic semiconductors

Abstract

A polymer includes repeating unit(s) of the formula (I). a, b, c, d, e and f are 0, 1, 2, or 3. Ar.sup.1 and Ar.sup.1′ are independently of each other a group of formula (AR1). Ar.sup.2, Ar.sup.2′, Ar.sup.3, Ar.sup.3′, Ar.sup.4 and Ar.sup.4′ are independently of each other a group of formula (AR2). The polymer is preferably a co-polymer. ##STR00001##

Claims

1. A polymer comprising repeating unit(s) of the formula (I): ##STR00086## wherein a, b, c, d, e and f are 0, 1, 2, or 3; Ar.sup.1 and Ar.sup.1′ are independently of each other a group of formula: ##STR00087## Ar.sup.2, Ar.sup.2′, Ar.sup.3, Ar.sup.3′, Ar.sup.4 and Ar.sup.4′ are independently of each other a group of formula: ##STR00088## with the proviso that, if Ar2, Ar2′, Ar3, Ar3′, Ar4 or Ar4′ are a group of formula ##STR00089## R.sup.4 and R.sup.4′ are not both hydrogen; p is 0, 1, 2, 3 or 4; R.sup.1 and R.sup.2 may be the same or different and are selected from hydrogen, a C.sub.1-C.sub.25alkyl group, an alkenyl group, an alkynyl group, which may optionally be substituted by E and/or interrupted by D, an allyl group, which can be substituted one to three times with C.sub.1-C.sub.4alkyl, a cycloalkyl group, which can be substituted one to three times with C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8thioalkoxy, or C.sub.1-C.sub.8alkoxy, or a cycloalkyl group, which can be condensed one or two times by phenyl, which can be substituted one to three times with C.sub.1-C.sub.4alkyl, halogen, nitro or cyano, a cycloalkenyl group, a ketone or aldehyde group, an ester group, a carbamoyl group, a silyl group, a siloxanyl group, Ar.sup.10, or —CR.sup.5R.sup.6—(CH.sub.2).sub.g—Ar.sup.10; wherein R.sup.5 and R.sup.6 are independently from each other hydrogen, fluorine, cyano, or C.sub.1-C.sub.4 alkyl, which can be substituted by fluorine, chlorine or bromine, or phenyl, which can be substituted one to three times with C.sub.1-C.sub.4alkyl, Ar.sup.10 is aryl or heteroaryl, which may optionally be substituted by G, and g is 0, 1, 2, 3 or 4; R.sup.3 may be the same or different within one group and is selected from C.sub.1-C.sub.25alkyl, which may optionally be substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, which may optionally be substituted by G, C.sub.2-C.sub.20heteroaryl, which may optionally be substituted by G, C.sub.1-C.sub.18alkoxy, which may optionally be substituted by E and/or interrupted by D, C.sub.7-C.sub.25aralkyl, wherein aryl of the aralkyl may optionally be substituted by G, or —CO—R.sup.28, or two or more groups R.sup.3 which are in the neighborhood to each other, form a ring; R.sup.4, R.sup.4′, R.sup.7 and R.sup.7′ are independently from each other hydrogen, C.sub.1-C.sub.25alkyl, which may optionally be substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, which may optionally be substituted by G, C.sub.2-C.sub.20heteroaryl, which may optionally be substituted by G, C.sub.1-C.sub.18alkoxy, which may optionally be substituted by E and/or interrupted by D, C.sub.7-C.sub.25aralkyl, wherein aryl of the aralkyl may optionally be substituted by G, or —CO—R.sup.28; or R.sup.4 and R.sup.4′ form a ring; D is —CO—, —COO—, —S—, —SO—, —SO.sub.2—, —O—, —NR.sup.25, —CR.sup.23═CR.sup.24—, or —C≡C—; E is —OR.sup.29, —SR.sup.29, —NR.sup.25R.sup.26, —COR.sup.28, —COOR.sup.27, —CNR.sup.25R.sup.26, —CN, or halogen; G is E, C.sub.1-C.sub.18alkyl, which may be interrupted by D, or C.sub.1-C.sub.18alkoxy which is substituted by E and/or interrupted by D; wherein R.sup.23, R.sup.24, R.sup.25 and R.sup.26 are independently of each other hydrogen, C.sub.6-C.sub.18aryl, C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkyl which is interrupted by an oxygen atom; R.sup.27 and R.sup.28 are independently of each other hydrogen, C.sub.6-C.sub.18aryl, C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkyl which is interrupted by an oxygen atom; R.sup.29 is hydrogen, C.sub.6-C.sub.18aryl, C.sub.6-C.sub.18aryl, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkyl which is interrupted by an oxygen atom; R.sup.109 and R.sup.110 are independently of each other hydrogen, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, C.sub.2-C.sub.20heteroaryl, C.sub.2-C.sub.20heteroaryl which is substituted by G, C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl, C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.18alkoxy which is substituted by E and/or interrupted by D, or C.sub.7-C.sub.25aralkyl; or R.sup.109 and R.sup.110 together form a group of formula ═CR.sup.100R.sup.101; wherein R.sup.100 and R.sup.101 are independently of each other hydrogen, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, C.sub.2-C.sub.20heteroaryl; or C.sub.2-C.sub.20heteroaryl which is substituted by G; or R.sup.109 and R.sup.110 together form a five or six membered ring, which is optionally substituted by C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, C.sub.2-C.sub.20heteroaryl, C.sub.2-C.sub.20heteroaryl which is substituted by G, C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl, C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.18alkoxy which is substituted by E and/or interrupted by D, C.sub.7-C.sub.25aralkyl, or —C(═O)—R.sup.18; R.sup.111 is hydrogen, a C.sub.1-C.sub.25alkyl group, a C.sub.4-C.sub.18cycloalkyl group, a C.sub.1-C.sub.25alkoxy group, in which one or more carbon atoms which are not in neighborhood to each other could be replaced by —O—, —S—, or —C(═O)—O—, and/or wherein one or more hydrogen atoms can be replaced by F, a C.sub.6-C.sub.24aryl group, or a C.sub.6-C.sub.24aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R.sup.111; m can be the same or different at each occurrence and is 0, 1, 2, or 3; X.sup.1 is a hydrogen atom, or a cyano group with the proviso that, if Ar.sup.1 and Ar.sup.1′ are a group of formula ##STR00090## a and d are not 0.

2. The polymer according to claim 1, wherein R.sup.1 and R.sup.2 are independently from each other hydrogen; C.sub.1-C.sub.25alkyl, which can optionally be interrupted by one or more oxygen atoms; C.sub.5-C.sub.12cycloalkyl, which can be substituted one to three times with C.sub.1-C.sub.8alkyl and/or C.sub.1-C.sub.8alkoxy; or C.sub.5-C.sub.12cycloalkyl, which can be condensed one or two times by phenyl, which can be substituted one to three times with C.sub.1-C.sub.4alkyl, halogen, nitro or cyano; phenyl or 1- or 2-naphthyl which can be substituted one to three times with C.sub.1-C.sub.8alkyl and/or C.sub.1-C.sub.8alkoxy, or —CR.sup.5R.sup.6—(CH.sub.2).sub.g—Ar.sup.10 wherein R.sup.5 and R.sup.6 are each hydrogen, Ar.sup.10 is phenyl or 1- or 2-naphthyl, which can be substituted one to three times with C.sub.1-C.sub.8alkyl and/or C.sub.1-C.sub.8alkoxy, and g is 0 or 1.

3. The polymer according to claim 1, wherein the polymer is a co-polymer comprising repeating units of formula: ##STR00091## wherein A is a repeating unit of formula I, —COM.sup.1- is selected from repeating units of formula: ##STR00092## wherein R.sup.7 and R.sup.7′ are as defined in formula I, R.sup.44 and R.sup.41 are each hydrogen, C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy, and R.sup.45 is hydrogen, C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, wherein D and E are as defined in formula I, and —COM.sup.2- is a group of formula: ##STR00093## wherein R.sup.116 and R.sup.117 are independently of each other hydrogen, C.sub.1-C.sub.18alkyl, which can optionally be interrupted by an oxygen atom, or C.sub.1-C.sub.18alkoxy, which can optionally be interrupted by an oxygen atom, R.sup.119 and R.sup.120 are independently of each other hydrogen, C.sub.1-C.sub.18alkyl, which can optionally be interrupted by an oxygen atom, or R.sup.119 and R.sup.120 together form a group of formula ═CR.sup.100R.sup.101, wherein R.sup.100 and R.sup.101 are independently of each other hydrogen, C.sub.1-C.sub.18alkyl, or R.sup.119 and R.sup.120 together form a five or six membered ring, which optionally can be substituted by C.sub.1-C.sub.18alkyl.

4. The polymer according to claim 3, wherein the polymer is a co-polymer of formula: ##STR00094## and optionally, ##STR00095## wherein the order of the unit ##STR00096## and the unit ##STR00097## is arbitrary in the repeating unit (ACOM2), and the order of the unit ##STR00098## and the unit ##STR00099## is arbitrary in the repeating unit (COM12), is 1, p is 0 or 1, r is 0 or 1, s is 0 or 1, a molar amount of the repeating unit (ACOM2) is from 0.005 to 1 and a molar amount of the repeating unit (COM12) is from 0.995 to 0, with respect to a total of repeating units included in the polymer.

5. The polymer according to claim 1, wherein Ar.sup.1 and Ar.sup.1′ are the same and are a group of formula: ##STR00100## and Ar.sup.2, Ar.sup.2′, Ar.sup.3, Ar.sup.3′, Ar.sup.4 and Ar.sup.4′ are independently of each other a group of formula: ##STR00101## wherein p stands for 0, 1, or 2, R.sup.3 may be the same or different within one group and is selected from C.sub.1-C.sub.25alkyl, which may optionally be substituted by E and/or interrupted by D, or C.sub.1-C.sub.18alkoxy, which may optionally be substituted by E and/or interrupted by D, R.sup.4 is C.sub.6-C.sub.25alkyl, which may optionally be substituted by E and/or interrupted by D, C.sub.6-C.sub.14aryl, which may optionally be substituted by G, C.sub.1-C.sub.25alkoxy, which may optionally be substituted by E and/or interrupted by D, or C.sub.7-C.sub.15aralkyl, wherein aryl of the aralkyl may optionally be substituted by G, D is —CO—, —COO—, —S—, —SO—, —SO.sub.2—, —O—, —NR.sup.25—, wherein R.sup.25 is C.sub.1-C.sub.12alkyl, E is —OR.sup.29; —SR.sup.29; —NR.sup.25R.sup.25; —COR.sup.28; —COOR.sup.27; —CONR.sup.25R.sup.25; or —CN, and G is —OR.sup.29; —SR.sup.29; —NR.sup.25R.sup.25; —COR.sup.28; —COOR.sup.27; —CONR.sup.25R.sup.25; —CN, or C.sub.1-C.sub.18alkyl, wherein R.sup.25, R.sup.27, R.sup.28 and R.sup.29 are independently of each other C.sub.1-C.sub.12alkyl.

6. The polymer according to claim 1 wherein ##STR00102## may be the same or different, and are a group of formula: ##STR00103## wherein indicates the bond to the diketopyrrolopyrrole skeleton, R.sup.4 and R.sup.4′ are each C.sub.6-C.sub.25alkyl, which may optionally be substituted by E and/or interrupted by D, C.sub.6-C.sub.14aryl, which may optionally be substituted by G, C.sub.1-C.sub.25alkoxy, which may optionally be substituted by E and/or interrupted by D, or C.sub.7-C.sub.15aralkyl, wherein aryl of the aralkyl may optionally be substituted by G, D is —CO—, —COO—, —S—, —SO—, —SO.sub.2—, —O—, —NR.sup.25—, wherein R.sup.25 is C.sub.1-C.sub.12alkyl, E is —OR.sup.29; —SR.sup.29; —NR.sup.25R.sup.25; —COR.sup.28; —COOR.sup.27; —CONR.sup.25R.sup.25; or —CN, and G is —OR.sup.29; —SR.sup.29; —NR.sup.25R.sup.25; —COR.sup.28; —COOR.sup.27; —CONR.sup.25R.sup.25; —CN, or C.sub.1-C.sub.18alkyl, wherein R.sup.25, R.sup.27, R.sup.28 and R.sup.29 are independently of each other C.sub.1-C.sub.12alkyl.

7. The polymer according to claim 1, wherein the polymer comprises repeating units of the formula: ##STR00104## wherein a, b, c, d, e, f, R.sup.1, R.sup.2, Ar.sup.1, Ar.sup.1′, Ar.sup.2, Ar.sup.2′, Ar.sup.3, Ar.sup.3′, Ar.sup.4 and Ar.sup.4′ are as defined in formula I, h is 1, and Ar.sup.5 is a group of formula: ##STR00105## wherein R.sup.7 and R.sup.7′ are as defined in formula I.

8. The polymer according to claim 1, comprising repeating units of the formula: ##STR00106## ##STR00107## ##STR00108## wherein R.sup.1 and R.sup.2 are independently from each other C.sub.1-C.sub.25alkyl, R.sup.3 and R.sup.3′ are independently from each other C.sub.6-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen atoms, R.sup.4 and R.sup.4′ are independently from each other C.sub.6-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen atoms, and R.sup.7 and R.sup.7′ are independently from each other C.sub.6-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen atoms.

9. A semiconductor device, comprising the polymer according to claim 1.

10. The semiconductor device according to claim 9, which is a solar cell, comprising in this order: (a) a cathode, (b) optionally a transition layer, (c) a photoactive layer, (d) optionally a smoothing layer, (e) an anode, (f) a substrate, wherein the photoactive layer comprises the polymer.

11. The semiconductor device according to claim 1, which is a thin film transistor device comprising: a plurality of electrically conducting gate electrodes disposed on a substrate; a gate insulator layer disposed on the electrically conducting gate electrodes; a plurality of sets of electrically conductive source and drain electrodes disposed on the gate insulator layer such that each of the sets is in alignment with each of the gate electrodes; an organic semiconductor layer disposed in the channel between source and drain electrodes on the gate insulator layer substantially overlapping the gate electrodes; wherein the organic semiconductor layer comprises the polymer, or a mixture containing the polymer.

12. A process for the preparation of an organic semiconductor device according to claim 9, the process comprising applying a solution and/or dispersion of the polymer in an organic solvent to a substrate and removing the solvent.

13. A monomer of the formula (X): ##STR00109## wherein a, b, c, d, e and f are 0, 1, 2, or 3; Ar.sup.1 and Ar.sup.1′ are independently of each other a group of formula: ##STR00110## Ar.sup.2, Ar.sup.2′, Ar.sup.3, Ar.sup.3′, Ar.sup.4 and Ar.sup.4′ are independently of each other a group of formula: ##STR00111## with the proviso that, if Ar2, Ar2′, Ar3, Ar3′, Ar4 or Ar4′ are a group of formula ##STR00112## R.sup.4 and R.sup.4′ are not both hydrogen; p is 0, 1, 2, 3 or 4; R.sup.1 and R.sup.2 may be the same or different and are selected from hydrogen, a C.sub.1-C.sub.25alkyl group, an alkenyl group, an alkynyl group, which may optionally be substituted by E and/or interrupted by D, an allyl group, which can be substituted one to three times with C.sub.1-C.sub.4alkyl, a cycloalkyl group, which can be substituted one to three times with C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8thioalkoxy, or C.sub.1-C.sub.8alkoxy, or a cycloalkyl group, which can be condensed one or two times by phenyl, which can be substituted one to three times with C.sub.1-C.sub.4alkyl, halogen, nitro or cyano, a cycloalkenyl group, a ketone or aldehyde group, an ester group, a carbamoyl group, a silyl group, a siloxanyl group, Ar.sup.10, or —CR.sup.5R.sup.6—(CH.sub.2).sub.g—Ar.sup.10; wherein R.sup.5 and R.sup.6 are independently from each other hydrogen, fluorine, cyano, or C.sub.1-C.sub.4 alkyl, which can be substituted by fluorine, chlorine or bromine, or phenyl, which can be substituted one to three times with C.sub.1-C.sub.4alkyl, Ar.sup.10 is aryl or heteroaryl, which may optionally be substituted by G, and g is 0, 1, 2, 3 or 4; R.sup.3 may be the same or different within one group and is selected from C.sub.1-C.sub.25alkyl, which may optionally be substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, which may optionally be substituted by G, C.sub.2-C.sub.20heteroaryl, which may optionally be substituted by G, C.sub.1-C.sub.18alkoxy, which may optionally be substituted by E and/or interrupted by D, C.sub.7-C.sub.25aralkyl, wherein aryl of the aralkyl may optionally be substituted by G, or —CO—R.sup.28, or two or more groups R.sup.3 which are in the neighborhood to each other, form a ring; R.sup.4, R.sup.4′, R.sup.7 and R.sup.7′ are independently from each other hydrogen, C.sub.1-C.sub.25alkyl, which may optionally be substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, which may optionally be substituted by G, C.sub.2-C.sub.20heteroaryl, which may optionally be substituted by G, C.sub.1-C.sub.18alkoxy, which may optionally be substituted by E and/or interrupted by D, C.sub.7-C.sub.25aralkyl, wherein aryl of the aralkyl may optionally be substituted by G, or —CO—R.sup.28; or R.sup.4 and R.sup.4′ form a ring; D is —CO—, —COO—, —S—, —SO—, —SO.sub.2—, —O—, —NR.sup.25—, —CR.sup.23═CR.sup.24—, or —C≡C—; E is —OR.sup.29, —SR.sup.29, —NR.sup.25R.sup.26, —COR.sup.28, —COOR.sup.27, —CNR.sup.25R.sup.26, —CN, or halogen; G is E, C.sub.1-C.sub.18alkyl, which may be interrupted by D, or C.sub.1-C.sub.18alkoxy which is substituted by E and/or interrupted by D; wherein R.sup.23, R.sup.24, R.sup.25 and R.sup.26 are independently of each other hydrogen, C.sub.6-C.sub.18aryl, C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkyl which is interrupted by an oxygen atom; R.sup.27 and R.sup.28 are independently of each other hydrogen, C.sub.6-C.sub.18aryl, C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkyl which is interrupted by an oxygen atom; R.sup.29 is hydrogen, C.sub.6-C.sub.18aryl, C.sub.6-C.sub.18aryl, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkyl which is interrupted by an oxygen atom; R.sup.109 and R.sup.110 are independently of each other hydrogen, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, C.sub.2-C.sub.20heteroaryl, C.sub.2-C.sub.20heteroaryl which is substituted by G, C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl, C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.18alkoxy which is substituted by E and/or interrupted by D, or C.sub.7-C.sub.25aralkyl; or R.sup.109 and R.sup.110 together form a group of formula ═CR.sup.100R.sup.101; wherein R.sup.100 and R.sup.101 are independently of each other hydrogen, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, C.sub.2-C.sub.20heteroaryl; or C.sub.2-C.sub.20heteroaryl which is substituted by G; or R.sup.109 and R.sup.110 together form a five or six membered ring, which is optionally substituted by C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, C.sub.2-C.sub.20heteroaryl, C.sub.2-C.sub.20heteroaryl which is substituted by G, C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl, C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.18alkoxy which is substituted by E and/or interrupted by D, C.sub.7-C.sub.25aralkyl, or —C(O)—R.sup.18; R.sup.111 is hydrogen, a C.sub.1-C.sub.25alkyl group, a C.sub.4-C.sub.18cycloalkyl group, a C.sub.1-C.sub.25alkoxy group, in which one or more carbon atoms which are not in neighborhood to each other could be replaced by —O—, —S—, or —C(═O)—O—, and/or wherein one or more hydrogen atoms can be replaced by F, a C.sub.6-C.sub.24aryl group, or a C.sub.6-C.sub.24aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R.sup.111; m can be the same or different at each occurrence and is 0, 1, 2, or 3; X.sup.1 is a hydrogen atom, or a cyano group with the proviso that, if Ar.sup.1 and Ar.sup.1′ are a group of formula ##STR00113## a and d are not 0; and X is ZnX.sup.12, wherein X.sup.12 is a halogen atom; —SnR.sup.207R.sup.208R.sup.209, wherein R.sup.207, R.sup.208 and R.sup.209 are identical or different and are hydrogen or C.sub.1-C.sub.6alkyl, wherein two radicals among R.sup.207, R.sup.208 and R.sup.209 optionally form a common ring and R.sup.207, R.sup.208 and R.sup.209 are optionally branched or unbranched; or OS(O).sub.2CF.sub.3, —OS(O).sub.2-aryl, —OS(O).sub.2CH.sub.3, —B(OH).sub.2, —B(OY.sup.1).sub.2, ##STR00114## —BF.sub.4Na, or —BF.sub.4K, wherein Y.sup.1 is independently in each occurrence a C.sub.1-C.sub.10alkyl group and Y.sup.2 is independently in each occurrence —CY.sup.3Y.sup.4—CY.sup.5Y.sup.6— or —CY.sup.7Y.sup.8—CY.sup.9Y.sup.10—CY.sup.11Y.sup.12—, wherein Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Y.sup.7, Y.sup.8, Y.sup.9, Y.sup.10, Y.sup.11 and Y.sup.12 are independently of each other hydrogen or a C.sub.1-C.sub.10alkyl group.

14. A process for preparing the polymer according to claim 3, the process comprising reacting a dibromide of formula Br-A-Br with an equimolar amount of a diboronic acid or diboronate of formula: ##STR00115## under the catalytic action of Pd and triphenylphosphine, wherein X.sup.11 is independently in each occurrence —B(OH).sub.2, —B(OY.sup.1).sub.2 or ##STR00116## wherein Y.sup.1 is independently in each occurrence a C.sub.1-C.sub.10alkyl group and Y.sup.2 is independently in each occurrence —CY.sup.3Y.sup.4—CY.sup.5Y.sup.6—, or —CY.sup.7Y.sup.8—CY.sup.9Y.sup.10—CY.sup.11Y.sup.12—, wherein Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Y.sup.7, Y.sup.8, Y.sup.9, Y.sup.10, Y.sup.11 and Y.sup.12 are independently of each other hydrogen or a C.sub.1-C.sub.10alkyl group.

Description

EXAMPLES

Example 1

(1) ##STR00068##

(2) a) A solution of 4.5 g of DPP 1, 6.23 g of K.sub.2CO.sub.3 and 8.68 g of 1-bromo-2-ethyl-hexyl in 60 ml of N-methyl-pyrrolidone (NMP) is heated to 140° C. for 6 h. The mixture is washed with water and extracted with dichloromethane. The organic phase is then dried and filtered on a double layer of silica gel and Hyflo® (CAS 91053-39-3; Fluka 56678) before it is concentrated. The residue is dissolved in 100 ml of chloroform, cooled down to 0° C. and 2 equivalents of N-bromosuccinimide are then added portion wise over a period of 1 h. After the reaction has been completed, the mixture is washed with water. The organic phase is extracted, dried and concentrated. The compound is then purified over a silica gel column to give 1.90 g of a violet powder of DPP 2.

(3) ##STR00069##

(4) b) A solution of 500 mg of the dibrominated DPP 2, 990 mg of the tin derivative and 85 mg of Pd(PPh.sub.3).sub.4 in 30 ml of dry toluene is refluxed overnight under inert conditions. After cooling down, the mixture is filtrated on a double layer silica gel/Hyflo®, concentrated and precipitated with methanol. The precipitate is filtrated and rinsed with methanol to give 530 mg of a blue solid of DPP 3.

(5) ##STR00070##

(6) c) A solution of 2.55 g of the corresponding monomer 3 in chlorobenzene is degassed with argon over 15 min at 50° C. Then 1.6 g of FeCl.sub.3 are added in nitromethane and the mixture is stirred while degassing for 4 hours at 50° C. The solution is then poured into methanol and the blue precipitate is then filtrated and washed with methanol. The solid is then purified by soxhlet extraction, using methanol and hexane to purify and chloroform to extract 2 g of the polymer fraction (4).

(7) M.sub.w=13301

(8) Fe content=75 ppm

(9) Photophysical Properties:

(10) UV spectra of spin coated films on glass substrates are made from hot chlorobenzene solutions and annealed at different temperatures:

(11) TABLE-US-00001 Annealing Conditions UV/Vis-absorption Room temperature 680 nm 20 minutes at 100° C. 720 nm, 800 nm 20 minutes at 150° C. 720 nm, 800 nm

(12) Growing of the band at 800 nm shows the appearance of strong aggregation behaviour while annealing.

Application Example 1a

DPP-Polymers Based Field-Effect Transistors

(13) a) Experimental:

(14) Bottom-gate thin-film transistor (TFT) structures with p-Si gate were used for all experiments. A high-quality thermal SiO.sub.2 layer served as gate-insulator of C.sub.i=32.6 nF/cm.sup.2 capacitance per unit area. Source and drain electrodes were patterned by photolithography directly on the gate-oxide (bottom-contact configuration). On each substrate 16 transistors are present with Au source/drain electrodes defining channels of different length. Prior to the deposition of the organic semiconductor the SiO.sub.2 surface was derivatized with hexamethyldisilazane (HMDS) or octadecyltrichlorosilane (OTS). The films are prepared either by spin casting or drop casting the polymer obtained in example 1 in different solvents. The transistor behaviour is measured on an automated tester elaborated by CSEM, Transistor Prober TP-10.

(15) b) Transistor Performance:

(16) The thin-film transistors showed clear p-type transistor behavior. From a linear fit to the square root of the saturated transfer characteristics a field-effect mobility of 0.15 cm.sup.2/Vs could be determined. The transistors showed a threshold voltage of about 0 V to 5 V. The transistors showed good on/off current ratios of 10.sup.4 to 10.sup.7.

(17) Annealing of the sample results in a drastic increase of the performances (especially mobility), which can be correlated to a better aggregation of the polymer in the solid state. Testing of a set of OFETs after 2 months exposed in air conditions shows remarkable stability as the mobility is almost constant. The on/off ratio, which usually suffers the most, is only reduced by a factor of 10.

Application Example 1b

DPP-Polymer Based Bulk Heterojunction Solar Cell

(18) a) Experimental:

(19) The solar cell has the following structure: Al electrode/LiF layer/organic layer, including polymer of the invention/[poly(3,4-ethylenedioxy-thiophene) (PEDOT)/poly(styrenesulfonic acid) (PSS)]/ITO electrode/glass substrate. The solar cells are made by spin-coating a layer of PEDOT-PSS on a pre-patterned ITO on glass substrate. Then a 1:4 mixture of the polymer of example 1 (0.5% by weight): [60]PCBM (a substituted C.sub.60 fullerene:

(20) ##STR00071##
is spin coated (organic layer). LiF and Al are sublimed under high vacuum through a shadow-mask.

(21) b) Solar Cell Performance:

(22) The solar cell is measured under a solar light simulator. Then with the External Quantum Efficiency (EQE) graph the current is estimated under AM1.5 conditions.

(23) This leads to value of J.sub.sc=4.1 mA/cm.sup.2, FF=0.539 and V.sub.oc=0.733 V for an estimated overall efficiency of 1.62% measured before annealing. After 10 min at 100° C. the estimated efficiency grows to 2%. After optimisation of the morphology of the active layer by varying the deposition solvent, the polymer/[60]PCBM ratio etc. the performance of the device can be pushed up to 3.06% (J.sub.sc=9.5 mA/cm.sup.2, FF=0.46 and V.sub.oc=0.7 V).

Example 2

(24) ##STR00072##

(25) A solution of 25 g of DPP 1, 46.07 g of K.sub.2CO.sub.3 and 75 g of 1-bromo-2-hexyl-decyl in 300 ml of N-methyl-pyrrolidone (NMP) is heated to 140° C. for 6 h. The mixture is washed with water and extracted with dichloromethane. The organic phase is then dried and filtered on a double layer of silica gel and Hyflo® before it is concentrated. The residue is dissolved in 100 ml of chloroform, cooled down to 0° C. and 2 equivalents of N-bromosuccinimide are then added portion wise over a period of 1 h. After the reaction has been completed, the mixture is washed with water. The organic phase is extracted, dried and concentrated. The compound is then purified over a silica gel column to give 19 g of a violet powder of DPP 5.

(26) ##STR00073##

(27) b) A solution of 18.5 g of the dibrominated DPP 5, 27.47 g of the tin derivative and 2.36 g of Pd(PPh.sub.3).sub.4 in 250 ml of dry toluene is refluxed overnight under inert conditions. After cooling down, the mixture is purified on a silica gel column (CHCl.sub.3/hexane 3/7) to give 20.2 g of a blue solid of DPP 6.

(28) ##STR00074##

(29) c) A solution of 10 g of the DPP derivative 6 is dissolved in 300 ml of chloroform, cooled down to 0° C. and 2 equivalents of N-bromosuccinimide are then added portion wise over a period of 1 h. After the reaction is completed, the mixture is washed with water. The organic phase is extracted, dried, concentrated and precipitated with methanol. The precipitate is filtrated and rinsed with methanol to give 10 g of a blue solid of DPP 7.

(30) ##STR00075##

(31) In a shlenk tube, a solution of 240 mg of Ni(COD).sub.2 and 140 mg bipyridine in 10 ml of toluene is degassed for 15 min. 1 g of the corresponding dibrominated monomer 7 is added to this solution and then the mixture is heated to 80° C. and stirred vigorously overnight. The solution is poured on 100 ml of a 1/1/1 methanol/HCl/acetone mixture and stirred for 1 h. The precipitate is then filtrated, dissolved in CHCl.sub.3 and stirred vigorously at 60° C. with an aqueous solution of ethylenediaminetetraacetic acid (EDTA) tetrasodium salt for one additional hour. The organic phase is washed with water, concentrated and precipitated in methanol. The residue is purified by soxhlet extraction using methanol and hexane and the polymer is then extracted with CHCl.sub.3 to give 250 mg of purple fibres.

(32) M.sub.w=77465

(33) Ni content=65 ppm

(34) Solubility>10% by weight in toluene

(35) Photophysical Properties:

(36) UV of spin coated film on glass substrate is made from a hot chlorobenzene solution and annealed at different temperatures:

(37) TABLE-US-00002 Annealing Conditions UV/Vis-absorption Room temperature 680 nm 20 minutes at 100° C. 720 nm, 800 nm

(38) Growing of the band at 800 nm shows the appearance of strong aggregation behaviour while annealing.

Application Example 2a

DPP-Polymers Based Field-Effect Transistors

(39) a) Experimental:

(40) Application Example 1a is repeated, except that instead of the polymer obtained in example 1 the polymer obtained in example 2 is used.

(41) b) Transistor Performance:

(42) The thin-film transistors showed clear p-type transistor behavior. From a linear fit to the square root of the saturated transfer characteristics a field-effect mobility up to 0.013 cm.sup.2Ns could be determined. The transistors showed a threshold voltage of about 0 V to 4 V. The transistors showed good on/off current ratios of 10.sup.5 to 10.sup.7. Testing of a set of OFETs after 7 days exposed in air conditions shows remarkable stability as the mobility is almost constant even better, on/off ratio which usually suffers the most is only reduced by a factor of 5. This compound shows an electron mobility up to 10.sup.−3 cm.sup.2Ns on the normal setup. After optimisation of this setup using top contact transistors, the ambi-polarity of this polymer is even more pronounced with similar mobilites for holes and electrons up to 0.1 cm.sup.2Ns.

Example 3

(43) ##STR00076##

(44) a) A solution of 25 g of DPP 1, 46.07 g of K.sub.2CO.sub.3 and 55 g of 1-bromo-2-butyl-hexyl in 300 ml of N-methyl-pyrrolidone (NMP) is heated to 140° C. for 6 h. The mixture is washed with water and extracted with dichloromethane. The organic phase is then dried and filtered on a double layer of silica gel and Hyflo® before it is concentrated. The residue is dissolved in 100 ml of chloroform, cooled down to 0° C. and 2 equivalents of N-bromosuccinimide are then added portion wise over a period of 1 h. After the reaction has been completed, the mixture is washed with water. The organic phase is extracted, dried and concentrated. The compound is then purified over a silica gel column to give 9.5 g of a violet powder of DPP 8.

(45) ##STR00077##

(46) b) A solution of 2.24 g of the dibrominated DPP 8, 4.11 g of the tin derivative and 351 mg of Pd(PPh.sub.3).sub.4 in 50 ml of dry toluene is refluxed overnight under inert conditions. After cooling down, the mixture is purified on a silica gel column (CHCl.sub.3/hexane 3/7) to give 2.37 g of a blue solid of DPP 9.

(47) ##STR00078##

(48) c) A solution of 1.27 g of the DPP derivative 9 is dissolved in 60 ml of chloroform, cooled down to 0° C. and 2 equivalents of N-bromosuccinimide are then added portion wise over a period of 1 h. After the reaction is completed, the mixture is washed with water. The organic phase is extracted, dried, concentrated and precipitated with methanol. The precipitate is filtrated and rinsed with methanol to give 1.32 g of a blue solid of DPP 10.

(49) ##STR00079##

(50) d) In a Schlenk tube, a solution of 244 mg of Ni(COD).sub.2 and 142 mg bipyridine in 10 ml of toluene is degassed for 15 min. 1 g of the corresponding dibrominated monomer 10 is added to this solution and then the mixture is heated to 80° C. and stirred vigorously overnight. The solution is poured on 100 ml of a 1/1/1 methanol/HCl/acetone mixture and stirred for 1 h. The precipitate is then filtrated, dissolved in CHCl.sub.3 and stirred vigorously at 60° C. with an aqueous solution of ethylenediaminetetraacetic acid (EDTA) tetrasodium salt for one additional hour. The organic phase is washed with water, concentrated and precipitated in methanol. The residue is purified by soxhlet extraction using methanol and hexane and the polymer is then extracted with CHCl.sub.3 to give 650 mg of purple fibres.

(51) M.sub.w=30000

(52) Ni content=52 ppm

(53) Solubility=0.5% by weight in CHCl.sub.3

(54) Photophysical Properties:

(55) UV of spin coated film on glass substrate is made from a hot chlorobenzene solution and annealed at different temperatures:

(56) TABLE-US-00003 Annealing Conditions UV/Vis-absorption Room temperature 720 nm, 810 nm

(57) The band at 810 nm is attributed to the aggregation behaviour.

Application Example 3

DPP-Polymers Based Field-Effect Transistors

(58) a) Experimental:

(59) Application Example 1a is repeated, except that instead of the polymer obtained in example 1 the polymer obtained in example 3 is used.

(60) b) Transistor Performance:

(61) The thin-film transistors showed clear p-type transistor behaviour. From a linear fit to the square root of the saturated transfer characteristics a field-effect mobility up to 0.1 cm.sup.2/Vs could be determined. The transistors showed a threshold voltage of about 6 V. The transistors showed good on/off current ratios of 10.sup.4 to 10.sup.5.

Example 4

(62) ##STR00080##

(63) a) A solution of 3.5 g of DPP 11, 3.04 g of K.sub.2CO.sub.3 and 4.13 g of 1-bromo-2-hexyl-decyl in 60 ml of N-methyl-pyrrolidone (NMP) is heated to 140° C. for 6 h. The mixture is washed with water and extracted with dichloromethane. The organic phase is then dried and filtered on a double layer of silica gel and Hyflo® before it is concentrated. The residue is dissolved in 100 ml of chloroform, cooled down to 0° C. and 2 equivalents of N-bromosuccinimide are then added portion wise over a period of 1 h. After the reaction has been completed, the mixture is washed with water. The organic phase is extracted, dried and concentrated. The compound is then purified over a silica gel column to give 1.7 g of a violet powder of DPP 12.

(64) ##STR00081##

(65) b) A solution of 1.6 g of the dibrominated DPP 12, 0.65 g of the tin derivative and 150 mg of Pd(PPh.sub.3).sub.4 in 60 ml of dry toluene is refluxed overnight under inert conditions. After cooling down, the mixture is purified on a silica gel column (CHCl.sub.3/hexane 3/7) to give 1.27 g of a blue solid of DPP 13.

(66) ##STR00082##

(67) c) A solution of 1.27 g of the DPP derivative 13 is dissolved in 50 ml of chloroform, cooled down to 0° C. and 2 equivalents of N-bromosuccinimide are then added portion wise over a period of 1 h. After the reaction is completed, the mixture is washed with water. The organic phase is extracted, dried, concentrated and precipitated with methanol. The precipitate is filtrated and rinsed with methanol to give 1.22 g of a blue solid of DPP 14.

(68) ##STR00083##

(69) d) In a Schlenk tube, a solution of 292 mg of Ni(COD).sub.2 and 170 mg bipyridine in 10 ml of toluene is degassed for 15 min. 1.2 g of the corresponding dibrominated monomer 14 is added to this solution and then the mixture is heated to 65° C. and stirred vigorously for 41 h. The solution is poured on 100 ml of a 1/1/1 methanol/HCl/acetone mixture and stirred for 1 h. The precipitate is then filtrated, dissolved in CHCl.sub.3 and stirred vigorously at 60° C. with an aqueous solution of ethylenediaminetetraacetic acid (EDTA) tetrasodium salt for one additional hour. The organic phase is washed with water, concentrated and precipitated in methanol. The residue is purified by soxhlet extraction using methanol and hexane and the polymer is then extracted with CHCl.sub.3 to give 730 mg of purple fibres.

(70) M.sub.w=30000

(71) Ni content=14 ppm

(72) Solubility=0.5% by weight in CHCl.sub.3

(73) Photophysical Properties:

(74) UV of spin coated film on glass substrate is made from a hot chlorobenzene solution and annealed at different temperatures:

(75) TABLE-US-00004 Annealing Conditions UV/Vis-absorption Room temperature 720 nm, 800 nm

(76) The band at 800 nm is attributed to the aggregation behaviour.

Application Example 4

DPP-Polymers Based Field-Effect Transistors

(77) a) Experimental:

(78) Application Example 1a is repeated, except that instead of the polymer obtained in example 1 the polymer obtained in example 4 is used.

(79) b) Transistor Performance:

(80) The thin-film transistors showed clear p-type transistor behaviour. From a linear fit to the square root of the saturated transfer characteristics a field-effect mobility up to 0.013 cm.sup.2Ns could be determined. The transistors showed a threshold voltage of about 4 V to 8 V. The transistors showed good on/off current ratios of 10.sup.4 to 10.sup.5. Testing of a set of OFETs after 2 months exposed in air conditions shows remarkable stability as the mobility is even better (up to 0.028 cm.sup.2/Vs), on/off ratio which usually suffer the most is also increased by a factor of 5 to 10 and threshold voltage in the range of 0 V to 4 V.

Example 5

(81) ##STR00084##

(82) In a three neck-flask, a degassed solution of 5 g of 7, 1.185 g of 1,4-benzenediboronic acid bis(pinacol) ester, 3.773 g of K.sub.3PO.sub.4, 88.5 mg of sPhos (2-dicyclohexylphosphino-2′,6′-dimethoxyphenybiphenyl) and 80.6 mg of palladium acetate in 60 ml of toluene, 20 nil of dioxane and 10 ml of water are heated to 90° C. and stirred vigorously overnight. An excess of bromobenzene is then added and after 2 hours at the same temperature an excess of phenylboronic acid pinacol ester is then added to end cap the polymer. After 2 hours to complete the end-capping, 100 mL of NaCN (1% by weight) in water is added and the mixture is stirred at 90° C. for 3 hours. The organic phase is extracted and precipitated in methanol. The residue is redissolved in tolueneand resubmitted to NaCN treatment and the organic phase is precipitated in methanol. The residue is purified by soxhlet extraction using acetone and Et.sub.2O and the polymer is then extracted with CHCl.sub.3 to give 2.5 g of purple fibres.

(83) M.sub.w=27000

(84) Pd content=30 ppm

(85) Solubility=1% by weight in CHCl.sub.3

(86) Photophysical Properties:

(87) UV of spin coated film on glass substrate is made from a hot chlorobenzene solution and annealed at different temperatures:

(88) TABLE-US-00005 Annealing Conditions UV/Vis-absorption Room temperature 630 nm, 680 nm

(89) The band at 680 nm is attributed to the aggregation behaviour.

Example 6

(90) ##STR00085##

(91) 1 g of 7, 82 mg of Pd(PPh.sub.3).sub.4 (10 mol %) and 13.5 mg of copper iodide (10 mol %) are dissolved in diethylamine, (0.85 ml) and THF (2 ml) in a dry, nitrogen flushed flask. The flask is then set under vacuum, flushed with nitrogen, this is repeated three times. 328 mg of the diacetylenique derivative is then added, the flask is sealed under nitrogen, heated up to 85° C. and stirred over night. The reaction mixture is dissolved in 50 ml CHCl.sub.3, triturated in 500 ml MeOH, and filtrated. This action is repeated once. The solid is then purified via soxhlet extraction using MeOH, acetone and heptane and the polymer is then extracted with CHCl.sub.3 to give 0.5 g of purple fibres.

(92) M.sub.w=38000

(93) Solubility=0.5% by weight in CHCl.sub.3

(94) Photophysical Properties:

(95) UV of spin coated film on glass substrate is made from a hot chlorobenzene solution and annealed at different temperatures:

(96) TABLE-US-00006 Annealing Conditions UV/Vis-absorption Room temperature 650 nm, 700 nm

(97) The band at 700 nm is attributed to the aggregation behaviour.