Azide-based crosslinking agents

Abstract

The present invention provides compounds of formula ##STR00001##
a process for their preparation, a solution comprising these compounds, a process for the preparation of a device using the solution, devices obtainable by the process and the use of the bis-azide-type compounds as cross-linkers.

Claims

1. Compounds of formula ##STR00065## wherein a is 0, 1 or 2, b is 1, 2, 3 or 4, c is 0 or 1, d is 0, 1, 2, 3 or 4, e is 0, 1 or 2, x is 0, 1 or 2, y is 0, 1 or 2, z is 0, 1 or 2, w is 0, 1 or 2, n is 0 or 1, Ar.sup.1 and Ar.sup.2 are independently from each other and at each occurrence, selected from an aromatic or heteroaromatic moiety, each of which is optionally substituted with one or more substituent R.sup.a selected from the group consisting of C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 12 membered heteroaryl, COOR.sup.10, CONR.sup.10R.sup.11, COR.sup.10, SO.sub.3R.sup.10, CN, NO.sub.2, halogen, OR.sup.10, SR.sup.10, NR.sup.10R.sup.11, OCOR.sup.10 and NR.sup.10COR.sup.11, wherein R.sup.10 and R.sup.11 are independently from each other and at each occurrence, selected from H, C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or 5 to 12 membered heteroaryl, and C.sub.1-20-alkyl and C.sub.5-8-cycloalkyl are each optionally substituted with one or more substituents R.sup.aa at each occurrence, R.sup.aa selected from the group consisting of phenyl, COOR.sup.12, CONR.sup.12R.sup.13, COR.sup.12, SO.sub.3R.sup.12, CN, NO.sub.2, halogen, OR.sup.12, SR.sup.12, NR.sup.11R.sup.12, OCOR.sup.12 and NR.sup.12COR.sup.13, and C.sub.6-14-aryl and 5 to 12 membered heteroaryl are each optionally substituted with one or more substituent R.sup.ab at each occurrence, R.sup.ab selected from the group consisting of C.sub.1-10-alkyl, cyclopentyl, cyclohexyl, COOR.sup.12, CONR.sup.12R.sup.13, COR.sup.12, SO.sub.3R.sup.12, CN, NO.sub.2, halogen, OR.sup.12, SR.sup.12, NR.sup.12R.sup.13, OCOR.sup.12 and NR.sup.12COR.sup.13, wherein R.sup.12 and R.sup.13 are independently from each other and at each occurrence, selected from C.sub.1-10-alkyl, cyclopentyl, cyclohexyl or phenyl, and at least two adjacent Ar.sup.1, at least two adjacent Ar.sup.2, and/or Ar.sup.1 and Ar.sup.2, both connected to L.sup.2 or if c=0 to each other, can be additionally linked by one or more L.sup.a, wherein L.sup.a is a C.sub.1-4-alkylene that is optionally substituted with one or more C.sub.1-10-alkyl, and one or more CH.sub.2 groups of C.sub.1-4-alkylene can be replaced by C═O, (C═O)O, (C═O)NR.sup.60, SO.sub.2—NR.sup.60, NR.sup.60, NR.sup.60R.sup.61, O or S, wherein R.sup.60 and R.sup.61 are independently from each other and at each occurrence a C.sub.1-10-alkyl, L.sup.1 and L.sup.3 are independently from each other and at each occurrence ##STR00066##  wherein R.sup.3 and R.sup.4 are independently from each other and at each occurrence, selected from H, C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 12 membered heteroaryl, COOR.sup.20, CONR.sup.20R.sup.21, COR.sup.20, SO.sub.3R.sup.20, CN, NO.sub.2, or halogen, wherein R.sup.20 and R.sup.21 are independently from each other and at each occurrence, selected from H, C.sub.1-20-alkyl and C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or 5 to 12 membered heteroaryl, and C.sub.1-20-alkyl and C.sub.5-8-cycloalkyl are each optionally substituted with one or more substituents R.sup.b at each occurrence, R.sup.b selected from the group consisting of phenyl, COOR.sup.22, CONR.sup.22R.sup.23, COR.sup.22, SO.sub.3R.sup.22, CN, NO.sub.2, halogen, OR.sup.22, SR.sup.22, NR.sup.22R.sup.23, OCOR.sup.22 and NR.sup.22COR.sup.23, and C.sub.6-14-aryl and 5 to 12 membered heteroaryl are each optionally substituted with one or more substituent R.sup.c at each occurrence, R.sup.c selected from the group consisting of C.sub.1-10-alkyl, cyclopentyl, cyclohexyl, COOR.sup.22, CONR.sup.22R.sup.23, COR.sup.22, SO.sub.3R.sup.22, CN, NO.sub.2, halogen, OR.sup.22, SR.sup.22, NR.sup.22R.sup.23, OCOR.sup.22 and NR.sup.22COR.sup.23, wherein R.sup.22 and R.sup.23 are independently from each other and at each occurrence, selected from C.sub.1-10-alkyl, cyclopentyl, cyclohexyl or phenyl, or, if L.sup.1 or L.sup.3 are ##STR00067## R.sup.3 and R.sup.4 together with the C-atoms to which they are attached form a 5 to 7-membered non-aromatic ring system A, L.sup.2 is a linking moiety selected from the group consisting of C.sub.1-10-alkylene, C.sub.2-10-alkenylene, C.sub.5-8-cycloalkylene, C.sub.1-4-alkylene-C.sub.5-8-cycloalkylene-C.sub.1-4-alkylene, C.sub.1-4-alkylene-phenylene-C.sub.1-4-alkylene, C.sub.2-4-alkenylene-C.sub.5-8-cycloalkylene-C.sub.2-4-alkenylene and C.sub.2-4-alkenylene-phenylene-C.sub.2-4-alkenylene, optionally substituted with one or more substituent R.sup.f at each occurrence selected from the group consisting of C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 12 membered heteroaryl, COOR.sup.40, CONR.sup.40R.sup.41, COR.sup.40, SO.sub.3R.sup.40, CN, NO.sub.2, halogen, OR.sup.40, SR.sup.40, NR.sup.40R.sup.41, OCOR.sup.40 and NR.sup.40COR.sup.41, wherein R.sup.40 and R.sup.41 are independently from each other and at each occurrence H, C.sub.1-10-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or 5 to 12 membered heteroaryl, wherein C.sub.1-20-alkyl and C.sub.5-8-cycloalkyl are each optionally substituted with one or more substituents R.sup.fa at each occurrence, R.sup.fa selected from the group consisting of phenyl, COOR.sup.42, CONR.sup.42R.sup.43, COR.sup.42, SO.sub.3R.sup.42, CN, NO.sub.2, halogen, OR.sup.42, SR.sup.42NR.sup.42R.sup.43, OCOR.sup.42 and NR.sup.42COR.sup.43, wherein C.sub.6-14-aryl and 5 to 12 membered heteroaryl are each optionally substituted with one or more substituent R.sup.fb at each occurrence, R.sup.fa selected from the group consisting of C.sub.1-10-alkyl, cyclopentyl, cyclohexyl, COOR.sup.42, CONR.sup.42R.sup.43, COR.sup.42, SO.sub.3R.sup.42, CN, NO.sub.2, halogen, OR.sup.42, NR.sup.42R.sup.43, OCOR.sup.42 and NR.sup.42COR.sup.43, wherein R.sup.42 and R.sup.43 are independently from each other and at each occurrence selected from C.sub.1-10-alkyl, cyclopentyl, cyclohexyl or phenyl, and wherein one or more CH.sub.2 groups of C.sub.1-10-alkylene, C.sub.1-4-alkylene, C.sub.2-10-alkenylene, C.sub.2-4-alkenylene and/or C.sub.5-8-cycloalkylene can be replaced by C═O, (C═O)O, (C═O)NR.sup.50, SO.sub.2—NR.sup.50, NR.sup.50, NR.sup.50R.sup.51, O or S, wherein R.sup.50 and R.sup.51 are independently from each other and at each occurrence C.sub.1-10-alkyl, and R.sup.1 and R.sup.2 are independently from each other and at each occurrence, selected from H, C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 12 membered heteroaryl, COOR.sup.30, CONR.sup.30R.sup.31, COR.sup.30, SO.sub.3R.sup.30, CN, NO.sub.2, halogen, OR.sup.30, SR.sup.30, NR.sup.30R.sup.31, OCOR.sup.30 or NR.sup.30COR.sup.31, wherein R.sup.30 and R.sup.31 are independently from each other and at each occurrence, selected from H, C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or 5 to 12 membered heteroaryl, and C.sub.1-20-alkyl and C.sub.5-8-cycloalkyl are each optionally substituted with one or more substituents R.sup.d at each occurrence, R.sup.d selected from the group consisting of phenyl, COOR.sup.32, CONR.sup.32R.sup.33, COR.sup.32, SO.sub.3R.sup.32, CN, NO.sub.2, halogen, OR.sup.32, SR.sup.32, NR.sup.32N.sup.33, OCOR.sup.32 and NR.sup.32COR.sup.33, and C.sub.6-14-aryl and 5 to 12 membered heteroaryl are each optionally substituted with one or more substituent R.sup.e at each occurrence, R.sup.e selected from the group consisting of C.sub.1-10-alkyl, cyclopentyl, cyclohexyl, COOR.sup.32, CONR.sup.32R.sup.33, COR.sup.32, SO.sub.3R.sup.32, CN, NO.sub.2, halogen, OR.sup.32, SR.sup.32, NR.sup.32R.sup.33, OCOR.sup.32 and NR.sup.32COR.sup.33, wherein R.sup.32 and R.sup.33 are independently from each other and at each occurrence, selected from C.sub.1-10-alkyl, cyclopentyl, cyclohexyl or phenyl.

2. Compounds of claim 1, wherein n=0, and the compound of formula (1) is of formula ##STR00068## wherein R.sup.1, R.sup.2, x, y, z, w, L.sup.1, Ar.sup.1, L.sup.2, Ar.sup.2, L.sup.3, a, b, c, d and e are as depicted in claim 1.

3. The compounds of claim 1, wherein Ar.sup.1 and Ar.sup.2 are independently from each other and at each occurrence, selected from an aromatic or heteroaromatic moiety, each of which is optionally substituted substituted with one or more substituent R.sup.a selected from the group consisting of C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 12 membered heteroaryl, COOR.sup.10, CONR.sup.10R.sup.11, COR.sup.10, SO.sub.3R.sup.10, CN, NO.sub.2, halogen, OR.sup.10, NR.sup.10R.sup.11, OCOR.sup.10 and NR.sup.10COR.sup.11, wherein R.sup.10 and R.sup.11 are independently from each other and at each occurrence, selected from H, C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or 5 to 12 membered heteroaryl, and at least two adjacent Ar.sup.1, at least two adjacent Ar.sup.2, and/or Ar.sup.1 and Ar.sup.2, both connected to L.sup.2 or if c=0 to each other, can be additionally linked by one or more L.sup.a, and L.sup.1 and L.sup.3 are independently from each other and at each occurrence ##STR00069## wherein R.sup.3 and R.sup.4 are independently from each other and at each occurrence H, C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 12 membered heteroaryl, COOR.sup.20, CONR.sup.20R.sup.21, COR.sup.20, SO.sub.3R.sup.20, CN, NO.sub.2, or halogen, wherein R.sup.20 and R.sup.21 are independently from each other and at each occurrence H, C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or 5 to 12 membered heteroaryl, or, if L.sup.1 or L.sup.3 are ##STR00070## R.sup.3 and R.sup.4 together with the C-atoms to which they are attached form a 5 to 7-membered non-aromatic ring system A.

4. The compounds of claim 1, wherein L.sup.2 is selected from the group consisting of C.sub.1-10-alkylene, C.sub.2-10-alkenylene, C.sub.5-8-cycloalkylene, each of which is optionally substituted with one or more substituent R.sup.f R.sup.1 and R.sup.2 are independently from each other and at each occurrence H, C.sub.1-20-alkyl, C.sub.6-14-aryl, COOR.sup.30, CONR.sup.30R.sup.31, COR.sup.30, SO.sub.3R.sup.30, CN, NO.sub.2, halogen, OR.sup.30, SR.sup.30, or NR.sup.30R.sup.31, wherein R.sup.30 and R.sup.31 are independently from each other and at each occurrence H, C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or 5 to 12 membered heteroaryl.

5. The compounds of claim 1, wherein a and e are the same and are 0 or 1, b is 1, 2 or 3, c is 0 or 1, and d is 0, 1, 2 or 3, x and y are the same and are 0, 1 or 2, and z and w are the same and are 0, 1 or 2, Ar.sup.1 and Ar.sup.2 are independently from each other and at each occurrence a C.sub.6-14-aromatic or a 5 to 12 membered heteroaromatic moiety, which can be substituted with one or more substituent R.sup.a selected from the group consisting of C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 12 membered heteroaryl, COOR.sup.10, CONR.sup.10R.sup.11, COR.sup.10, SO.sub.3R.sup.10, CN, NO.sub.2, halogen, OR.sup.10, SR.sup.10, NR.sup.10R.sup.11, OCOR.sup.10 and NR.sup.10COR.sup.11, wherein R.sup.10 and R.sup.11 are independently from each other and at each occurrence H, C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or 5 to 12 membered heteroaryl, wherein at least two adjacent Ar.sup.1, at least two adjacent Ar.sup.2, and/or Ar.sup.1 and Ar.sup.2, both connected to L.sup.2 or if c=0 to each other, can be additionally linked by one or more L.sup.a, wherein L.sup.a is a linking moiety B, L.sup.1 and L.sup.3 are the same and are ##STR00071##  wherein R.sup.3 and R.sup.4 are independently from each other and at each occurrence H, C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 12 membered heteroaryl, COOR.sup.20, CONR.sup.20R.sup.21, COR.sup.20, SO.sub.3R.sup.20, CN, NO.sub.2 or halogen, wherein R.sup.20 and R.sup.21 are independently from each other and at each occurrence H, C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or 5 to 12 membered heteroaryl, L.sup.2 is a linking moiety A, wherein the linking moiety A is selected from the group consisting of C.sub.1-10-alkylene, C.sub.2-10-alkenylene, C.sub.5-8-cycloalkylene, C.sub.1-4-alkylene-C.sub.5-8-cycloalkylene-C.sub.1-4-alkylene, C.sub.1-4-alkylene-phenylene-C.sub.1-4-alkylene, C.sub.2-4-alkenylene-C.sub.5-8-cycloalkylene-C.sub.2-4-alkenylene and C.sub.2-4-alkenylene-phenylene-C.sub.2-4-alkenylene, which can be substituted with one or more substitutent R.sup.f at each occurrence selected from the group consisting of C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 12 membered heteroaryl, COOR.sup.40, CONR.sup.40R.sup.41, COR.sup.40, SO.sub.3R.sup.40, CN, NO.sub.2, halogen, OR.sup.40, NR.sup.40R.sup.41, OCOR.sup.40 and NR.sup.40COR.sup.41, wherein R.sup.40 and R.sup.41 are independently from each other and at each occurrence H, C.sub.1-10-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or 5 to 12 membered heteroaryl, and one or more CH.sub.2 groups of C.sub.1-10-alkylene, C.sub.1-4-alkylene, C.sub.2-10-alkenylene, C.sub.2-4-alkenylene and/or C.sub.5-8-cycloalkylene can be replaced by C═O, (C═O)O, (C═O)NR.sup.50, SO.sub.2—NR.sup.50, NR.sup.50, NR.sup.50R.sup.51, O or S, wherein R.sup.50 and R.sup.51 are independently from each other and at each occurrence C.sub.1-10-alkyl, and R.sup.1 and R.sup.2 are the same and are H, C.sub.1-20-alkyl or C.sub.5-8-cycloalkyl.

6. The compounds of claim 5, wherein a and e are the same and are 0 or 1, b is 1, c is 0 or 1, and d is 0 or 1, x and y are the same and are 0 or 1, and z and w are the same and are 1 or 2, Ar.sup.1 and Ar.sup.2 are the same and are a C.sub.6-14-aromatic or a 5 to 12 membered heteroaromatic moiety, which can be substituted with one or more substituent R.sup.a selected from the group consisting of C.sub.1-20-alkyl and OR.sup.10, wherein R.sup.10 is independently from each other and at each occurrence C.sub.1-20-alkyl, and wherein Ar.sup.1 and Ar.sup.2, both connected to L.sup.2 or if c=0 to each other, can be additionally linked by one or more L.sup.a, wherein L.sup.a is a linking moiety B, wherein the linking moiety B is C.sub.1-4-alkylene, which can be substituted with one or more C.sub.1-10-alkyl, L.sup.1 and L.sup.3 are the same and are ##STR00072##  wherein R.sup.3 and R.sup.4 are independently from each other and at each occurrence H, C.sub.1-20-alkyl, COOR.sup.20, CONR.sup.20R.sup.21, COR.sup.20, SO.sub.3R.sup.20, CN, NO.sub.2 or halogen, wherein R.sup.20 and R.sup.21 are independently from each other and at each occurrence H or C.sub.1-20-alkyl, L.sup.2 is selected from the group consisting of C.sub.1-10-alkylene, C.sub.2-10-alkenylene, C.sub.5-8-cycloalkylene, C.sub.1-4-alkylene-C.sub.5-8-cycloalkylene-C.sub.1-4-alkylene, C.sub.1-4-alkylene-phenylene-C.sub.1-4-alkylene, C.sub.2-4-alkenylene-C.sub.5-8-cycloalkylene-C.sub.2-4-alkenylene and C.sub.2-4-alkenylene-phenylene-C.sub.2-4-alkenylene, wherein one or more CH.sub.2 groups of C.sub.1-10alkylene, C.sub.1-4-alkylene, C.sub.2-10-alkenylene, C.sub.2-4-alkenylene acid/or C.sub.5-8-cycloalkylene can be replaced by C═O, (C═O)O, (C═O)NR.sup.50, SO.sub.2—NR.sup.50, NR.sup.50, NR.sup.50R.sup.51, O or S, wherein R.sup.50 and R.sup.51 are independently from each other and at each occurrence C.sub.1-10-alkyl, and R.sup.1 and R.sup.2 are the same and are branched C.sub.3-6-alkyl.

7. The compounds of claim 6, wherein x and y are the same and are 0, z and w are the same and are 2, Ar.sup.1 and Ar.sup.2 are the same and are ##STR00073## which can be substituted with one or more substituent R.sup.a selected from the group consisting of C.sub.1-10-alkyl and OR.sup.10, wherein R.sup.10 is independently from each other and at each occurrence C.sub.1-10-alkyl, and wherein Ar.sup.1 and Ar.sup.2, both connected to L.sup.2 or if c=0 to each other, can be additionally linked by one or more L.sup.a, wherein L.sup.a is a linking moiety B, wherein the linking moiety B is methylene substituted with one or more C.sub.1-10-alkyl, L.sup.1 and L.sup.3 are the same and are ##STR00074##  wherein R.sup.3 and R.sup.4 are H, and L.sup.2 is C.sub.1-10-alkylene, wherein one or more CH.sub.2 groups of C.sub.1-10-alkylene can be replaced by C═O, (C═O)O, (C═O)NR.sup.50, SO.sub.2—NR.sup.50, NR.sup.50, NR.sup.50R.sup.51, O or S, wherein R.sup.50 and R.sup.51 are independently from each other and at each occurrence C.sub.1-10-alkyl.

8. A process for the preparation of the compounds of formula ##STR00075## of claim 1, which process comprises the step of reacting a compound of formula ##STR00076## wherein a, b, c, d, e, x, y, z, w, Ar.sup.1, Ar.sup.2, L.sup.1, L.sup.3, L.sup.2, R.sup.1 and R.sup.2 are as depicted for the compound of formula (1), with M.sup.m+(N.sub.3.sup.−).sub.m, wherein m is 1, 2 or 3, and M is a metal.

9. A solution comprising one or more compounds of formula (1) of claim 1, one or more polymers and one or more solvents.

10. The solution of claim 9, wherein the one or more polymers are dielectric polymers.

11. The solution of claim 10, wherein the one or more polymers are styrene-based polymers.

12. A process for the preparation of a device which process comprises the steps of (i) depositing the solution of claim 9 on a support in order to form a layer, and (ii) exposing the layer of step (i) to radiation in order to form a polymer layer.

13. The process of claim 12, wherein the device is an electronic device.

14. The process of claim 13, wherein the radiation of step (ii) has a wavelength in the range of 300 to 450 nm.

15. A device obtainable by the process of claim 12.

16. A polymer prepared with a compound of claim 1 as a cross-linker.

17. The compounds of claim 2, wherein R.sup.1 and R.sup.2 are independently from each other and at each occurrence H, C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 12 membered heteroaryl, COOR.sup.30, CONR.sup.30R.sup.31, COR.sup.30, SO.sub.3R.sup.30, CN, NO.sub.2, halogen, OR.sup.30, SR.sup.30, NR.sup.30R.sup.31, OCOR.sup.30 or NR.sup.30 COR.sup.31, wherein R.sup.30 and R.sup.31 are independently from each other and at each occurrence H, C.sub.1-20-alkyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or 5 to 12 membered heteroaryl.

Description

(1) FIG. 1 shows the drain current I.sub.ds in relation to the gate voltage V.sub.gs (transfer curve) for the top-gate, bottom-contact (TGBC) field effect transistor of example 6 comprising a dielectric layer formed from Formulation B at a source voltage V.sub.ds of −3V (triangle), respectively, −30V (square).

(2) FIG. 2 shows the drain current I.sub.ds in relation to the drain voltage V.sub.ds (output curve) for the top-gate, bottom-contact (TGBC) field effect transistor of example 6 comprising a dielectric layer formed from Formulation B at a gate voltage V.sub.gs of 5V, 0 V, −5 V, −10 V, −15 V, −20V, −25V and −30 V.

(3) FIG. 3 shows the drain current I.sub.ds in relation to the gate voltage V.sub.gs (transfer curve) for the top-gate, bottom-contact (TGBC) field effect transistor of example 7 comprising a dielectric layer formed from Formulation C at a source voltage V.sub.ds of −3V (triangle), respectively, −30V (square).

(4) FIG. 4 shows the drain current I.sub.ds in relation to the drain voltage V.sub.ds (output curve) for the top-gate, bottom-contact (TGBC) field effect transistor of example 7 comprising a dielectric layer formed from Formulation C at a gate voltage V.sub.gs of 5V, 0 V, −5 V, −10 V, −15 V, −20V, −25V and −30 V.

(5) FIG. 5 shows the drain current I.sub.ds in relation to the gate voltage V.sub.gs (transfer curve) for the top-gate, bottom-contact (TGBC) field effect transistor of example 8 comprising a semiconducting layer formed from Formulation E at a source voltage V.sub.ds of −3V (triangle), respectively, −30V (square).

(6) FIG. 6 shows the drain current I.sub.ds in relation to the drain voltage V.sub.ds (output curve) for the top-gate, bottom-contact (TGBC) field effect transistor of example 8 comprising a semiconducting layer formed from Formulation E at a gate voltage V.sub.gs of 5V, 0 V, −5 V, −10 V, −15 V, −20V, −25V and −30 V.

(7) FIG. 7 shows a microscope image of the photo-patterned dielectric layer of example 9 formed from Formulation C taken using an Axio Imager Microscope.

(8) FIG. 8 shows a microscope image of the photo-patterned semiconductor layer of example 10 formed from Formulation D taken using an Axio Imager Microscope.

(9) FIG. 9 shows the bottom-gate, bottom-contact design of a field effect transistor (FET) device.

(10) FIG. 10 shows the top-gate, bottom-contact design of a field effect transistor (FET) device.

(11) FIG. 11 shows the film retention ratio (d1/d2) in correlation to the applied dosage of radiation for a polymer dielectric layer formed from formulation C.

EXAMPLE 1

(12) Preparation of Compound 1a

(13) ##STR00061##
Preparation of Compound 2a

(14) A mixture of 2,7-dibromo-9,9-dihexyl-9H-fluorene (3a) (492 mg, 1.00 mmol), 2,3,4,5,6,-pentafluorostyrene (4Aa/4Ba) (524 mg, 2.7 mmol), P(o-tolyl).sub.3 (12 mg, 0.04 mmol) and Pd(OAc).sub.2 (4.5 mg, 0.02 mmol) in triethylamine (0.87 mL) was heated at 90° C. for 1 day under N.sub.2. The reaction mixture was cooled to room temperature and extracted with dichloromethane (3×15 mL), The organic layer was finally washed with water (3×30 mL). The organic phase was then dried over MgSO.sub.4 and evaporated under reduced pressure. The crude product was purified by column chromatography using hexane as the eluent to yield compound 2a as pale yellow solid (370 mg, 64%).

(15) Preparation of Compound 1a

(16) A mixture of NaN.sub.3 (73 mg, 1.1 mmol) and compound 2a (367 mg, 0.5 mmol) in DMF (9.0 mL) and water (1.4 mL) was heated at 90° C. until no more starting material was monitored by TLC.

(17) The reaction mixture was cooled to room temperature, diluted with water, extracted with ethyl acetate and washed with water (3×30 mL). The organic layer was dried over MgSO.sub.4 and the solvent removed under reduced pressure. The solid was purified by column chromatography (dichloromethane:hexane 5:95) to yield compound 1a as orange solid (115 mg, 35%). λ.sub.max=386 and 408 nm.

EXAMPLE 2

Preparation of Compound 1b

(18) ##STR00062##
Preparation of Compound 2b

(19) A mixture of 2,5-dibromothiophene (3b) (1.0 g, 4.1 mmol), 2,3,4,5,6-pentafluorophenylboronic acid (5Aa/5Ba) (2.1 g, 10.3 mmol), Pd(PPh.sub.3).sub.4 (763 mg, 0.7 mmol), Ag.sub.2O (1.9 g, 8.2 mmol) and K.sub.3PO.sub.4 trihydrate (7.025 g) in DMF (30 mL) was stirred at 85° C., overnight. The mixture was then filtered through Celite, poured into water and extracted with dichloromethane (3×25 mL). The combined organic layers were washed with water (3 times), dried over MgSO.sub.4 and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using hexane as eluent to yield compound 2b as white powder (767 mg, 45%).

(20) Preparation of Compound 1b

(21) A mixture of NaN.sub.3 (171 mg, 2.6 mmol) and compound 2b (500 mg, 1.2 mmol) in DMF (20 mL) and water (3 mL) was heated at 90° C. The reaction was monitored by TLC. The mixture was cooled to room temperature, diluted with water, extracted with ethyl acetate and washed with water (3×25 mL). The extract was dried over MgSO.sub.4 and the solvent removed under reduced pressure. The crude product was purified by column chromatography with gradient elution (hexane to hexane/dichloromethane 75:25) to yield compound 1b as a brownish-orange solid (382 mg, 69%). λ.sub.max=386 nm.

EXAMPLE 3

(22) Preparation of Compound 1c

(23) ##STR00063##
Preparation of Compound 3c

(24) A mixture of 2-bromo-3-hexylthiophene (9Aa/9Ba) (3.0 mL, 14.8 mmol) and succinyl chloride (8a) (0.73 mL, 6.4 mmol) in anhydrous DCM (5 mL) was added dropwise to a cooled (0° C.) suspension of AlCl.sub.3 (2.1 g, 15.5 mmol) in anhydrous DCM (5 mL). The reaction mixture was then stirred at room temperature for 2.5 h and finally refluxed for 30 mins. The reaction mixture was poured into ice followed by addition of concentrated HCl and stirred for 1 h. The aqueous layer was extracted with DCM (3×30 mL), washed with HCl solution (10%), water, and saturated NaHCO.sub.3 solution. Finally, the organic layer was dried over Na.sub.2SO.sub.4 and the solvent removed under reduced pressure. The crude solid was purifies by washing with hot ethanol giving compound 3c as orange solid (0.87 g, yield: 30%).

(25) Preparation of Compound 2c

(26) A mixture of compound 3c (0.6 g, 1.0 mmol), 2,3,4,5,6-pentafluorostyrene (4Aa/4Ba) (0.4 mL, 2.7 mmol, Pd(OAc).sub.2 (6 mg, 0.02 mmol) and tri(o-tolyl)phosphine (0.015 g, 0.05 mmol) in triethylamine (1.18 mL, 8.50 mmol) and DMF (3 mL) was heated at 90° C. overnight. The reaction was monitored by TLC and LC/MS and heated until no more starting material was observed. Triethylamine was removed under reduced pressure and the reaction mixture was extracted with DCM (3×30 mL). The organic layer was washed with water (100 mL) and brine (100 mL), dried over MgSO.sub.4 and the solvent removed under reduced pressure. The crude was purified by column chromatography using hexane/DCM (1:1) as eluent giving compound 2c as orange solid (0.17 g, yield 26%).

(27) Preparation of Compound 1c

(28) Compound 2c (150 mg, 0.2 mmol) was dissolved in DMF (3.50 mL) and sodium azide (90 mg, 1.5 mmol) in water (0.50 mL) was subsequently added. The reaction mixture was heated at 90° C. for 3 h and monitored by TLC. Water was added to the reaction mixture which was extracted with ethyl acetate (3×25 mL) and dried over MgSO.sub.4. After removing the solvent under reduced pressure, the crude product was purified by column chromatography DCM/methanol (10:1) as eluent. Finally, compound 1c was precipitated in hexane obtaining a red precipitate. The solid was filtered on a Buchner filter in to yield compound 1c in 20% yield. λ.sub.max=405 nm

EXAMPLE 4

(29) Preparation of Compound 1d

(30) ##STR00064##
Preparation of Compound 7a

(31) A solution of ethynyltrimethylsilane (0.60 mL, 4.25 mmol) in triethylamine (8 mL) was slowly added to a solution of compound 3d (1.0 g, 1.93 mmol), (PPh.sub.3).sub.2PdCl.sub.2 (0.068 g, 0.10 mmol), and copper iodide (0.02 g, 0.10 mmol) in triethylamine (20 mL). The resulting mixture was heated at 70° C., overnight. The reaction was monitored by TLC using hexanes as the eluent. Work up: triethylamine was evaporated under reduced pressure and the residue was purified by column chromatography over silica gel, giving compound 7a as yellow solid in 95% yield (0.97 g, 1.8 mmol).

(32) Preparation of Compound 6a

(33) A 20% KOH aqueous solution (2.50 mL) was diluted with methanol (10 mL) and added to a solution of compound 7a (0.97 g, 1.75 mmol) in THF (18 mL). The reaction mixture was then stirred at room temperature until no more starting material was observed by TLC (eluent hexanes). The crude reaction mixture was extracted with hexane (3×15 mL) and the organic phase was washed with water (1×25 mL), and dried over Na.sub.2SO.sub.4. After removing the solvent under reduced pressure, the residue was then purified by column chromatography using hexanes as the eluent, giving compound 6a as yellow oil in quantitative yield (0.7 g, 1.8 mmol) that was directly used in the following step without any further purification.

(34) Preparation of Compound 2d

(35) A solution of compound 6a (0.20 g, 0.50 mmol) in triethylamine (1 mL) was slowly added to a solution of bromo-pentafluorobenzene (4Aa/4Ba) (0.14 mL, 1.09 mmol), (PPh.sub.3).sub.2PdCl.sub.2 (0.017 g, 0.02 mmol), and copper iodide (0.005 g, 0.02 mmol) in triethylamine (11 mL). The reaction mixture was then heated at 70° C. overnight and monitored by TLC. Work up: triethylamine was removed under reduced pressure and the residue was purified by column chromatography over silica gel (eluent hexanes), giving compound 2d as white solid in 59% yield (0.21 g, 0.29 mmol).

(36) Preparation of Compound 1d

(37) Sodium azide (0.15 g, 2.30 mmol) in water (1 mL) was added to a DMF solution (5 mL) of compound 2d (0.21 g, 0.29 mmol) and the mixture heated at 90° C. for 3 hrs. Workup: water was added to the reaction mixture which was subsequently extracted with ethyl acetate (3×10 mL). The organic phase were gathered and dried over MgSO.sub.4. After removing the solvent under reduced pressure the residue was purified by column chromatography over silica gel (eluent hexanes), giving compound 1d as yellow solid in 50% yield (0.11 g, 0.15 mmol). λ.sub.max=365 nm.

EXAMPLE 5

(38) Preparation of Formulations A, B, C, D and E

(39) Formulation A is a solution of 40 mg/ml polystyrene (Mw˜2,000,000, supplied by Pressure Chemicals) in butyl acetate/toluene (23/2 by volume) containing in addition 2% by weight of compound 1b based on the weight of polystyrene. Compound 1b is prepared as described in example 2.

(40) Formulation B is a solution of 40 mg/ml polystyrene (Mw˜2,000,000, supplied by Pressure Chemicals) in butyl acetate containing in addition 4% by weight of compound 1a based on the weight of polystyrene. Compound 1a is prepared as described in example 1.

(41) Formulation C is a solution of 40 mg/ml polystyrene (Mw˜2,000,000, supplied by Pressure Chemicals) in butyl acetate containing in addition 4% by weight of compound 1d based on the weight of polystyrene. Compound 1d is prepared as described in example 4.

(42) Formulation D is a solution of 20 mg/ml of the diketopyrrolopyrrole (DPP)-thiophene-polymer of example 1 of WO 2010/049321 in toluene containing in addition 4% by weight of compound 1b based on the weight of the diketopyrrolopyrrole (DPP)-thiophene-polymer. Compound 1b is prepared as described in example 2.

(43) Formulation E is a solution of 0.75% by weight of the diketopyrrolopyrrole (DPP)-thiophene-polymer of example 1 of WO 2010/049321 in toluene containing in addition 4% by weight of compound 1b based on the weight of diketopyrrolopyrrole (DPP)-thiophene-polymer. Compound 1b is prepared as described in example 2.

(44) Formulations A to E were prepared by mixing polystyrene and the diketrroloolopyrrole (DPP)-thiophene-polymer, respectively, and the crosslinker in the solvent at room temperature.

EXAMPLE 6

(45) Preparation of a Top-Gate, Bottom Contact Field Effect Transistor (FET) Device Comprising a Dielectric Layer Formed from Formulation B

(46) Gold was deposited by thermal evaporation through a shadow mask onto a glass substrate to form an approximately 60 nm thick film of source/drain electrodes (channel length: 50 μm, channel width: 500 μm). A 0.75% by weight solution of the diketopyrrolopyrrole (DPP)-thiophene-polymer of example 1 of WO 2010/049321 in toluene was filtered through a 0.45 micrometer polytetrafluoroethylene (PTFE) filter and then applied by spin coating (1000 rpm, 30 seconds). The wet semiconducting layer was dried at 90° C. on a hot plate for 30 seconds. Formulation B described in example 5 was filtered through a 0.45 micrometer filter and then applied by spin coating (3000 rpm, 30 seconds). The wet dielectric layer was pre-baked at 90° C. for 2 minutes on a hot plate to obtain a 520 nm thick layer. The polymer dielectric layer was UV-cured using 365 nm (radiation dosage 960 mJ/cm.sup.2) at 90° C. Gate electrodes of gold (thickness approximately 80 nm) were evaporated through a shadow mask on the dielectric layer.

(47) The characteristics of the top gate, bottom contact field effect transistor (FET) device were measured with a Keithley 4200-SCS semiconductor characterization system. The drain current I.sub.ds in relation to the gate voltage V.sub.gs (transfer curve) for the device comprising a dielectric layer formed from Formulation B at a source voltage V.sub.ds of −3V (triangle), respectively, −30V (square) is shown in FIG. 1. The drain current I.sub.ds in relation to the drain voltage V.sub.ds (output curve) for the device comprising a dielectric layer formed from Formulation B at a gate voltage V.sub.gs of 5V, 0 V, −5 V, −10 V, −15 V, −20V, −25V and −30 V is shown in FIG. 2.

(48) The results are depicted in table 1.

(49) TABLE-US-00001 TABLE 1 dielectric layer Mean mobility Mean Mean V.sub.on Ig formed from [cm.sup.2/Vs] I.sub.on/I.sub.off [V] [@ 30 V] Formulation B 0.135 1.13E+04 2 3.31E−08

EXAMPLE 7

(50) Preparation of a Top-Gate, Bottom Contact Field Effect Transistor (FET) Device Comprising a Dielectric Layer Formed from Formulation C

(51) Gold was deposited by thermal evaporation through shadow mask onto glass substrate to form an approximately 60 nm thick film of source/drain electrodes (channel length: 50 μm, channel width: 500 μm). A 0.75% by weight solution of the diketopyrrolopyrrole (DPP)-thiophene-polymer of example 1 of WO 2010/049321 in toluene was filtered through a 0.45 micrometer polytetrafluoroethylene (PTFE) filter and then applied by spin coating (1000 rpm, 30 seconds). The wet semiconducting layer was dried at 90° C. on a hot plate for 30 seconds. Formulation C described in example 5 was filtered through a 0.45 micrometer filter and then applied by spin coating (3500 rpm, 30 seconds). The wet dielectric layer was pre-baked at 90° C. for 2 minutes on a hot plate to obtain a 520 nm thick layer. The dielectric layer was UV-cured using 365 nm (radiation dosage 1120 mJ/cm.sup.2) at 100° C. with nitrogen flow. Gate electrodes of gold (thickness approximately 80 nm) were evaporated through a shadow mask on the dielectric layer.

(52) The characteristics of the top gate, bottom contact field effect transistor (FET) device were measured with a Keithley 4200-SCS semiconductor characterization system. The drain current I.sub.ds in relation to the gate voltage V.sub.gs (transfer curve) for the device comprising a dielectric layer formed from Formulation C at a source voltage V.sub.ds of −3V (triangle), respectively, −30V (square) is shown in FIG. 3. The drain current I.sub.ds in relation to the drain voltage V.sub.ds (output curve) for the device comprising a dielectric layer formed from Formulation C at a gate voltage V.sub.gs of 5V, 0 V, −5 V, −10 V, −15 V, −20V, −25V and −30 V is shown in FIG. 4.

(53) The results are depicted in table 2,

(54) TABLE-US-00002 TABLE 2 dielectric layer Mean mobility Mean Mean V.sub.on Ig formed from [cm.sup.2/Vs] I.sub.on/I.sub.off [V] [@ 30 V] Formulation C 0.20 3.16E+04 1 8.67E−09

EXAMPLE 8

(55) Preparation of a Top-Gate, Bottom Contact Polymer Field Effect Transistor (FET) Device Comprising a Polymer Semiconducting Layer Formed from Formulation E

(56) Gold was deposited by thermal evaporation through shadow mask onto glass substrate to form an approximately 60 nm thick film of source/drain electrodes (channel length: 50 μm, channel width: 500 μm). Formulation E was applied by spin coating (1000 rpm, 30 seconds). The wet polymer semiconducting layer was dried at 90° C. on a hot plate for 30 seconds, and then UV-cured using 365 nm (radiation dosage 2400 mJ/cm.sup.2) at 90° C. A 4.0% by weight solution of polystyrene supplied by Pressure Chemicals in butyl acetate was applied by spin coating (3000 rpm, 30 seconds), and dried at 90° C. for 30 seconds. Gate electrodes of gold (thickness approximately 80 nm) were evaporated through a shadow mask on the dielectric layer.

(57) The characteristics of the top gate, bottom contact field effect transistor (FET) device were measured with a Keithley 4200-SCS semiconductor characterization system. The drain current I.sub.ds in relation to the gate voltage V.sub.gs (transfer curve) for the device comprising a semiconducting layer formed from Formulation E at a source voltage V.sub.ds of −3V (triangle), respectively, −30V (square) is shown in FIG. 5. The drain current I.sub.ds in relation to the drain voltage V.sub.ds (output curve) for polymer device comprising a semiconducting layer formed from Formulation E at a gate voltage V.sub.gs of 5V, 0 V, −5 V, −10 V, −15 V, −20V, −25V and −30 V is shown in FIG. 6.

(58) The results are depicted in table 3.

(59) TABLE-US-00003 TABLE 3 semiconducting Mean mobility Mean Mean V.sub.on Ig layer formed from [cm.sup.2/Vs] I.sub.on/I.sub.off [V] [@ 30 V] Formulation E 0.028 4.82E+03 2 4.47E−10

EXAMPLE 9

(60) Photo-Patterning of a Polymer Dielectric Layer Formed from Formulation C on Top of a Polymer Semiconducting Layer

(61) A 0.75% by weight solution of the diketopyrrolopyrrole (DPP)-thiophene-polymer of example 1 of WO 2010/049321 in toluene was filtered through a 0.45 micrometer polytetrafluoroethylene (PTFE) filter and applied to a clean silicon dioxide substrate by spin coating (1,500 rpm, 30 seconds). The wet polymer semiconducting layer was dried at 90° C. on a hot plate for 30 seconds. Formulation C, described in example 5, was filtered through a 0.45 micrometer filter and then applied on top of the polymer semiconducting layer by spin coating (3,500 rpm, 30 seconds). The wet polymer dielectric layer was pre-baked at 90° C. for 2 minutes on a hot plate to obtain a 520 nm thick layer. A shadow mask was aligned on top of the dielectric layer before curing using 365 nm (radiation dosage 60 mJ/cm.sup.2) with nitrogen flow. The cured film was developed by immersing the film into butyl acetate for 1 minute followed by blowing with nitrogen and heating at 90° C. for 5 minutes.

(62) A microscope image of the photo-patterned polymer dielectric layer formed from Formulation C taken using an Axio Imager Microscope is shown in FIG. 7.

EXAMPLE 10

(63) Photo-Patterning of a Semiconductor Layer Formed from Formulation D

(64) Formulation D, described in example 5, was filtered through a 0.45 micrometer filter and then applied on top of the silicon dioxide substrate by spin coating (1,500 rpm, 30 seconds). A shadow mask was aligned on top of the semiconducting layer before curing using 365 nm (radiation dosage 2400 mJ/cm.sup.2) at 90° C. The cured film was developed by immersing the film into toluene for 1 minute followed by blowing with nitrogen and heating on a 90° C. hotplate for 5 minutes.

(65) A microscope image of the photo-patterned semiconductor layer formed from Formulation D taken using an Axio Imager Microscope is shown in FIG. 8.

EXAMPLE 11

(66) Stability of the Cured Dielectric Layer Formed from Formulation A, Respectively, Formulation C Towards Solvent Dissolution

(67) Formulation A, respectively, Formulation C, both described in example 5, was filtered through a 0.45 micrometer polytetrafluoroethylene (PTFE) filter and coated on a clean silicon dioxide substrate by spin coating (3500 rpm, 30 s). The wet dielectric layer was heated at 90° C. for 2 minutes on the hotplate to obtain 550 nm thick film. The dielectric layer formed from Formulation A was UV-cured using 365 nm (radiation dosage 960 mJ/cm2) at 90° C. The dielectric layer formed from Formulation C was UV-cured using 365 nm (radiation dosage 1120 mJ/cm2) with nitrogen flow at 100° C. Development of the dielectric layer was done by immersing the dielectric layer into butyl acetate for 1 minute followed by heating at 90° C. for 5 minutes. The thickness of the dielectric layer was measured after curing before development (d1) and after development (d2) using Veeco Dektak 150 to obtain the film retention ratio (d2/d1).

(68) The results are depicted in table 4.

(69) TABLE-US-00004 TABLE 4 dielectric layer formed from Formulation A Formulation C Average Film Retention Ratio [%] 94 99

EXAMPLE 12

(70) Stability of the Cured Semiconducting Layer Formed from Formulation D Towards Solvent Dissolution

(71) Formulation D described in example 5, was filtered through a 0.45 micrometer polytetrafluoroethylene (PTFE) filter and coated on a clean silicon dioxide substrate by spin coating (1500 rpm, 30 s). The wet polymer semiconducting layer was heated at 90° C. for 2 minutes on the hotplate, cooled to 60° C., and then the polymer semiconducting layer was UV-cured using 365 nm (radiation dosage ca. 2400 mJ/cm.sup.2) at 90° C. Development of the polymer semiconducting layer was done by immersing the layer into toluene for 1 minute followed by heating at 90° C. for 5 minutes. The thickness of the polymer semiconducting layer was measured after curing before development (d1) and after development (d2) using Veeco Dektak 150 to obtain the film retention ratio (d2/d1).

(72) The results are depicted in table 5.

(73) TABLE-US-00005 TABLE 5 semiconducting layer formed from Formulation D Average Film Retention Ratio [%] 80

EXAMPLE 13

(74) Preparation of Capacitor Comprising a Dielectric Layer Formed from Formulation C

(75) Formulation C, described in example 5, was filtered through a 0.45 micrometer filter and applied on a clean glass substrate pre-coated with indium tin oxide (ITO) electrodes by spin coating (3500 rpm, 30 seconds). The wet dielectric layer was pre-baked at 90° C. for 2 minutes on a hot plate to obtain a 500 nm thick layer. The dielectric layer was UV-cured using 365 nm (radiation dosage 1120 mJ/cm.sup.2) at 100° C. with nitrogen flow. Gold electrodes (area=0.785 mm.sup.2) were then vacuum-deposited through a shadow mask on the dielectric layer at <1×10.sup.−6 Torr (1.3×10.sup.−4 Pa).

(76) The capacitor thus obtained was characterized in the following way: The relative permittivity was deduced from the complex capacity measured with an Agilent E4980A Precision LCR Meter (signal amplitude 1 V).

(77) The results are depicted in table 6.

(78) TABLE-US-00006 TABLE 6 Relative permittivity of capacitor Frequency comprising a dielectric layer formed from [Hz] pure polystyrene Formulation C 40 2.65 2.44 4000 2.50 2.51 1000000 2.49 2.51

(79) As can be derived from table 6 the dielectric constant is unaffected by the addition of compound 1d.

EXAMPLE 14

(80) Evaluation of the Effect of the Radiation Dosage on the Cured Polymer Layer

(81) Formulation C, described in example 5, was filtered through a 0.45 micrometer filter and applied on a silicon dioxide substrate by spin coating (3500 rpm, 30 seconds). The wet dielectric layer was pre-baked at 90° C. for 2 minutes on a hot plate to obtain a 550 nm thick layer. The dielectric layer was UV-cured using 365 nm with different radiation dosages using nitrogen flow. Development of the dielectric layer was done by immersing the dielectric layer into butyl acetate for 1 minute followed by heating at 90° C. for 5 minutes. The thickness of the dielectric layer was measured after curing before development (d1) and after development (d2) using Veeco Dektak 150 to obtain the film retention ratio (d2/d1).

(82) The film retention ratio (d1/d2) in correlation to the applied dosage of radiation for a dielectric layer formed from formulation C is depicted in FIG. 11.

(83) FIG. 11 shows that the applied radiation dosage can be reduced to 20 mJ/cm.sup.2, and the film retention ratio is still retained above 90%.