VINYLETHER-BASED POLYMER AS DIELECTRIC

Abstract

The present invention provides polymers comprising units of formula (1) as well as compositions comprising the polymers, processes for the preparation of the polymers, electronic devices comprising the polymers, and processes for the preparation of the electronic devices, and the use of the polymers as dielectric materials.

##STR00001##

Claims

1. Polymers comprising units of formula (1) ##STR00066## wherein X.sup.1 and X.sup.2 are independently O or S, L.sup.1 is a linking group, and R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, O—C.sub.1-30-alkyl, O—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, C(O)—C.sub.1-30-alkyl, C(O)—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, C.sub.5-7-cycloalkyl, C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.b, O—C.sub.5-7-cycloalkyl, O—C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.b, C(O)—C.sub.5-7-cycloalkyl, C(O)—C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.b, C.sub.6-14-aryl, C.sub.6-14-aryl substituted with one or more substituents R.sup.b, O—C.sub.6-14-aryl, O—C.sub.6-14-aryl substituted with one or more substituents R.sup.b, C(O)—C.sub.6-14-aryl, C(O)—C.sub.6-14-aryl substituted with one or more substituents R.sup.b, 5 to 14 membered heteroaryl and 5 to 14 membered heteroaryl substituted with one or more substituents R.sup.b, or R.sup.1 and R.sup.2 together with the C-atoms to which they are attached form a 5 to 6 membered ring or a 5 to 6 membered ring substituted with one or more substituents R.sup.c, and R.sup.3, R.sup.4 and R.sup.5 are independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, O—C.sub.1-30-alkyl, O—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, C(O)—C.sub.1-30-alkyl, C(O)—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, C.sub.5-7-cycloalkyl, C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.b, O—C.sub.5-7-cycloalkyl, O—C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.b, C(O)—C.sub.5-7-cycloalkyl, C(O)—C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.b, C.sub.6-14-aryl, C.sub.6-14-aryl substituted with one or more substituents R.sup.b, O—C.sub.6-14-aryl, O—C.sub.6-14-aryl substituted with one or more substituents R.sup.b, C(O)—C.sub.6-14-aryl, C(O)—C.sub.6-14-aryl substituted with one or more substituents R.sup.b, 5 to 14 membered heteroaryl and 5 to 14 membered heteroaryl substituted with one or more substituents R.sup.b, or R.sup.2 and R.sup.3 together with the C-atoms to which they are attached form a 5 to 6 membered ring or a 5 to 6 membered ring substituted with one or more substituents R.sup.c, and R.sup.1, R.sup.4 and R.sup.5 are independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, O—C.sub.1-30-alkyl, O—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, C(O)—C.sub.1-30-alkyl, C(O)—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, C.sub.5-7-cycloalkyl, C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.b, O—C.sub.5-7-cycloalkyl, O—C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.b, C(O)—C.sub.5-7-cycloalkyl, C(O)—C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.b, C.sub.6-14-aryl, C.sub.6-14-aryl substituted with one or more substituents R.sup.b, O—C.sub.6-14-aryl, O—C.sub.6-14-aryl substituted with one or more substituents R.sup.b, C(O)—C.sub.6-14-aryl, C(O)—C.sub.6-14-aryl substituted with one or more substituents R.sup.b, 5 to 14 membered heteroaryl and 5 to 14 membered heteroaryl substituted with one or more substituents R.sup.b, or R.sup.3 and R.sup.4 together with the C-atoms to which they are attached form a 5 to 6 membered ring or a 5 to 6 membered ring substituted with one or more substituents R.sup.c, and R.sup.1, R.sup.2 and R.sup.5 are independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, O—C.sub.1-30-alkyl, O—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, C(O)—C.sub.1-30-alkyl, C(O)—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, C.sub.5-7-cycloalkyl, C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.b, O—C.sub.5-7-cycloalkyl, O—C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.b, C(O)—C.sub.5-7-cycloalkyl, C(O)—C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.b, C.sub.6-14-aryl, C.sub.6-14-aryl substituted with one or more substituents R.sup.b, O—C.sub.6-14-aryl, O—C.sub.6-14-aryl substituted with one or more substituents R.sup.b, C(O)—C.sub.6-14-aryl, C(O)—C.sub.6-14-aryl substituted with one or more substituents R.sup.b, 5 to 14 membered heteroaryl and 5 to 14 membered heteroaryl substituted with one or more substituents R.sup.b, or R.sup.4 and R.sup.5 together with the C-atoms to which they are attached form a 5 to 6 membered ring or a 5 to 6 membered ring substituted with one or more substituents R.sup.c, and R.sup.1, R.sup.2 and R.sup.3 are independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, O—C.sub.1-30-alkyl, O—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, C(O)—C.sub.1-30-alkyl, C(O)—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, C.sub.5-7-cycloalkyl, C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.b, O—C.sub.5-7-cycloalkyl, O—C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.b, C(O)—C.sub.5-7-cycloalkyl, C(O)—C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.b, C.sub.6-14-aryl, C.sub.6-14-aryl substituted with one or more substituents R.sup.b, O—C.sub.6-14-aryl, O—C.sub.6-14-aryl substituted with one or more substituents R.sup.b, C(O)—C.sub.6-14-aryl, C(O)—C.sub.6-14-aryl substituted with one or more substituents R.sup.b, 5 to 14 membered heteroaryl and 5 to 14 membered heteroaryl substituted with one or more substituents R.sup.b, wherein R.sup.a is at each occurrence selected from the group consisting of O—C.sub.1-20-alkyl, C(O)—C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, O—C.sub.5-6-cycloalkyl, C(O)—C.sub.5-6-cycloalkyl, phenyl, O-phenyl, C(O)-phenyl and 5 to 9 membered heteroaryl, and R.sup.b and R.sup.c are independently and at each occurrence selected from the group consisting of C.sub.1-20-alkyl, O—C.sub.1-20-alkyl, C(O)—C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, O—C.sub.5-6-cycloalkyl, C(O)—C.sub.5-6-cycloalkyl, phenyl, O-phenyl, C(O)-phenyl and 5 to 9 membered heteroaryl.

2. The polymers of claim 1, wherein X.sup.1 and X.sup.2 are O.

3. The polymers of claim 1, wherein L.sup.1 is a linking group which is C.sub.1-30-alkylene.

4. The polymers of any of claim 1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, O—C.sub.1-30-alkyl, O—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, C(O)—C.sub.1-30-alkyl, and C(O)—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, or R.sup.1 and R.sup.2 together with the C-atoms to which they are attached form a 5 to 6 membered aromatic ring or a 5 to 6 membered aromatic ring substituted with one or more substituents R.sup.c, and R.sup.3, R.sup.4 and R.sup.5 are independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, O—C.sub.1-30-alkyl, O—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, C(O)—C.sub.1-30-alkyl, and C(O)—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, or R.sup.2 and R.sup.3 together with the C-atoms to which they are attached form a 5 to 6 membered aromatic ring or a 5 to 6 membered aromatic ring substituted with one or more substituents R.sup.c, and R.sup.1, R.sup.4 and R.sup.5 are independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, O—C.sub.1-30-alkyl, O—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, C(O)—C.sub.1-30-alkyl, and C(O)—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, or R.sup.3 and R.sup.4 together with the C-atoms to which they are attached form a 5 to 6 membered aromatic ring or a 5 to 6 membered aromatic ring substituted with one or more substituents R.sup.c, and R.sup.1, R.sup.2 and R.sup.5 are independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, O—C.sub.1-30-alkyl, O—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, C(O)—C.sub.1-30-alkyl, C(O)—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, or R.sup.4 and R.sup.5 together with the C-atoms to which they are attached form a 5 to 6 membered aromatic ring or a 5 to 6 membered aromatic ring substituted with one or more substituents R.sup.c, and R.sup.1, R.sup.2 and R.sup.3 are independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, O—C.sub.1-30-alkyl, O—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, C(O)—C.sub.1-30-alkyl, C(O)—C.sub.1-30-alkyl substituted with one or more substituents R.sup.a, wherein R.sup.a is at each occurrence selected from the group consisting of O—C.sub.1-20-alkyl, C(O)—C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, O—C.sub.5-6-cycloalkyl, C(O)—C.sub.5-6-cycloalkyl, phenyl, O-phenyl, and C(O)-phenyl, and R.sup.c is at each occurrence selected from the group consisting of C.sub.1-20-alkyl, O—C.sub.1-20-alkyl, C(O)—C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, O—C.sub.5-6-cycloalkyl, C(O)—C.sub.5-6-cycloalkyl, phenyl, O-phenyl, and C(O)-phenyl.

5. The polymers of claim 4, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are independently selected from the group consisting of H, C.sub.1-10-alkyl and O—C.sub.1-10-alkyl, or R.sup.1 and R.sup.2 together with the C-atoms to which they are attached form an aromatic 6-membered aromatic ring, which is ##STR00067## wherein the C-atoms marked with * are the C-atoms to which R.sup.1 and R.sup.2 are attached, and R.sup.3, R.sup.4 and R.sup.5 are independently selected from the group consisting of H, C.sub.1-10-alkyl and O—C.sub.1-10-alkyl, or R.sup.2 and R.sup.3 together with the C-atoms to which they are attached form an aromatic 6-membered aromatic ring, which is ##STR00068## wherein the C-atoms marked with * are the C-atoms to which R.sup.2 and R.sup.3 are attached, and R.sup.1, R.sup.4 and R.sup.5 are independently selected from the group consisting of H, C.sub.1-10-alkyl and O—C.sub.1-10-alkyl, or R.sup.3 and R.sup.4 together with the C-atoms to which they are attached form an aromatic 6-membered aromatic ring, which is ##STR00069## wherein the C-atoms marked with * are the C-atoms to which R.sup.3 and R.sup.4 are attached, and R.sup.1, R.sup.2 and R.sup.5 are independently selected from the group consisting of H, C.sub.1-10-alkyl and O—C.sub.1-10-alkyl, or R.sup.4 and R.sup.5 together with the C-atoms to which they are attached form an aromatic 6-membered aromatic ring, which is ##STR00070## wherein the C-atoms marked with * are the C-atoms to which R.sup.4 and R.sup.5 are attached, and R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of H, C.sub.1-10-alkyl and O—C.sub.1-10-alkyl.

6. The polymers of claim 1 also comprising units of formula (2) ##STR00071## wherein X.sup.3 is independently O or S, L.sup.2 is a covalent bond or a linking group, R.sup.6 is independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.1-30-alkyl substituted with one or more substituents R.sup.d, C.sub.5-7-cycloalkyl, C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.e, C.sub.6-14-aryl, C.sub.6-14-aryl substituted with one or more substituents R.sup.e, 5 to 14 membered heteroaryl and 5 to 14 membered heteroaryl substituted with one or more substituents R.sup.e, wherein R.sup.d is at each occurrence selected from the group consisting of O—C.sub.1-20-alkyl, C(O)—C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, O—C.sub.5-6-cycloalkyl, C(O)—C.sub.5-6-cycloalkyl, phenyl, O-phenyl, C(O)-phenyl and 5 to 9 membered heteroaryl, and R.sup.e is at each occurrence selected from the group consisting of C.sub.1-20-alkyl, O—C.sub.1-20-alkyl, C(O)—C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, O—C.sub.5-6-cycloalkyl, C(O)—C.sub.5-6-cycloalkyl, phenyl, O-phenyl, C(O)-phenyl and 5 to 9 membered heteroaryl.

7. The polymers of claim 6, wherein X.sup.3 is O.

8. The polymers of claim 6, wherein L.sup.2 is a covalent bond or a linking group, which is phenylene.

9. The polymers of claim 6, wherein R.sup.6 is independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.1-30-alkyl substituted with one or more substituents R.sup.d, C.sub.5-7-cycloalkyl, and C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.e, wherein R.sup.d is at each occurrence selected from the group consisting of O—C.sub.1-20-alkyl, C(O)—C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, O—C.sub.5-6-cycloalkyl, C(O)—C.sub.5-6-cycloalkyl, phenyl, and O-phenyl, C(O)-phenyl, and R.sup.e is at each occurrence selected from the group consisting of C.sub.1-20-alkyl, O—C.sub.1-20-alkyl, C(O)—C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, O—C.sub.5-6-cycloalkyl, C(O)—C.sub.5-6-cycloalkyl, phenyl, O-phenyl, and C(O)-phenyl.

10. The polymers of claim 9, wherein R.sup.6 is independently selected from the group consisting of H, C.sub.1-10-alkyl and C.sub.5-7-cycloalkyl.

11. The polymer of claim 6 comprising at least 80 mol % units of formula (1) and (2) based on the mols of all repeating units of the polymer.

12. A process for the preparation of the polymers of claim 1 comprising units of formula (1) ##STR00072## wherein X.sup.1 and X.sup.2, L.sup.1 and R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as defined in claim 1, which process comprises the step of polymerizing monomers including the compound of formula (3) ##STR00073## wherein X.sup.1, X.sup.2, L.sup.1, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as defined for a compound of formula (1), in order to yield the polymers of claim 1.

13. A process of claim 12 for the preparation of the polymers comprising units of formula (1) and (2) ##STR00074## wherein X.sup.1, X.sup.2, L.sup.1, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as defined in claim 12, and X.sup.3 is independently O or S, L.sup.2 is a covalent bond or a linking group, R.sup.6 is independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.1-30-alkyl substituted with one or more substituents R.sup.d, C.sub.5-7-cycloalkyl, C.sub.5-7-cycloalkyl substituted with one or more substituents R.sup.e, C.sub.6-14-aryl, C.sub.6-14-aryl substituted with one or more substituents R.sup.e, 5 to 14 membered heteroaryl and 5 to 14 membered heteroaryl substituted with one or more substituents R.sup.e, wherein R.sup.d is at each occurrence selected from the group consisting of O—C.sub.1-20-alkyl, C(O)—C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, O—C.sub.5-6-cycloalkyl, C(O)—C.sub.5-6-cycloalkyl, phenyl, O-phenyl, C(O)-phenyl and 5 to 9 membered heteroaryl, and R.sup.e is at each occurrence selected from the group consisting of C.sub.1-20-alkyl, O—C.sub.1-20-alkyl, C(O)—C.sub.1-20-alkyl, C.sub.5-6-cycloalkyl, O—C.sub.5-6-cycloalkyl, C(O)—C.sub.5-6-cycloalkyl, phenyl, O-phenyl, C(O)-phenyl and 5 to 9 membered heteroaryl, which process comprises the step of polymerizing monomers including a compound of formula (3) and a compound of formula (4) ##STR00075## wherein X.sup.1, X.sup.2, L.sup.1, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as defined for a unit of formula (1), and X.sup.3, L.sup.2 and R.sup.6 are as defined for a unit of formula (2), in order to yield the polymers comprising units of formula (1) and (2).

14. A composition comprising at least one polymer of claim 1 and a solvent.

15. The composition of claim 14, also comprising a crosslinking agent.

16. An electronic device comprising a layer i) comprising the polymers of claim 1, or ii) formed from the composition comprising the above mentioned polymers and a solvent.

17. The electronic device of claim 16, which is a field effect transistor.

18. A process for the preparation of the field effect transistor of claim 17, which comprises the steps of applying the composition on a precursor of the field effect transistor, removing the solvent of the composition and forming a dielectric layer.

19. Use of the polymers of claim 1 as dielectric material.

Description

[0126] FIGS. 1 to 7 show the drain current I.sub.d in relation to the gate-source voltage V.sub.gs (transfer curve) for the top-gate, bottom-contact (TGBC) field effect transistor of example 4 comprising Pa (FIG. 1), Pb (FIG. 2), Pc (FIG. 3), Pd (FIG. 4), Pe (FIG. 5), Pf (FIG. 6) and Pg (FIG. 7), respectively, as dielectric material at a drain-source voltage V.sub.ds of −30V. The solid black line curve shows the drain current plotted on a logarithmic scale (left y-axis). The solid dark grey line shows the square root of drain current plotted on a linear scale (right y-axis). In addition, FIGS. 1 to 7 show the gate current plotted on a logarithmic scale (left y-axis) as light-grey, dotted line.

[0127] FIG. 8 shows the drain current plotted on a linear scale (left y-axis) for the top-gate, bottom-contact (TGBC) field effect transistor of example 4 comprising Pa, and for the top-gate, bottom-contact (TGBC) field effect transistor of comparative example 1 comprising polystyrene.

EXAMPLES

Example 1a

Preparation of Polymer Pa

[0128] ##STR00056##

[0129] In a three-neck bottom flask, compound 3a, prepared as describes in example 2a, (2 g, 9.3 mmol) and vinylbutyl ether (4a) (0.23 g 2.3 mmol) were dissolved in dichloromethane (10 mL) together with catalytic amount of ethyl acetate (0.1 mL). The solution was then cooled to −40° C. by means of an acetonitrile/dry ice bath. To the cooled solution, SnCl.sub.4 (0.5% mol) and BF.sub.3 in 1M DCM solution (0.5% mol) were subsequently added, keeping the temperature at −40° C. After stirring for 5 to 6 hrs, polymer Pa was precipitated in .sup.iPrOH. The obtained white solid was filtered, dried and precipitated two more times in .sup.iPrOH by dissolving it in the minimal amount of toluene. Polymer Pa was obtained in quantitative yield as white solid that was then characterized by gel permeation chromatography and H.sup.1-NMR. δ ppm, CCl.sub.2D.sub.2: 7.7-6.8 (m, broad); 4.2-3.5 (m, broad); 3.5-3.2 (m, broad); 2.0-1.2 (m, broad); 0.7-0.95 (m, broad). Mn=312000 g/mol, Mz=837000 g/mol. PDI=2.7.

Example 1b

Preparation of Polymer Pb

[0130] ##STR00057##

[0131] In a three-neck bottom flask, compound 3a, prepared as described in example 2a, (2.0 g, 9 mmol) and methoxystyrene (4b) (0.42 g, 3 mmol) were dissolved in dichloromethane (10 mL) together with catalytic amount of ethyl acetate (0.1 mL). The solution was then cooled to −40° C. by means of an acetonitrile/dry ice bath. To the cooled solution, SnCl.sub.4 (0.5% mol) and BF.sub.3 in 1M DCM solution (0.5% mol) were subsequently added, keeping the temperature at −40° C. After stirring for 6 hrs, polymer Pb was precipitated in .sup.iPrOH. The obtained white solid was filtered, dried and precipitated two more times in .sup.iPrOH by dissolving it in the minimal amount of toluene. Polymer Pb was obtained in 95% yield as white solid that was then characterized by gel permeation chromatography and H.sup.1-NMR (δ ppm, CCl.sub.2D.sub.2: 7.8-6.3 (m, broad); 4.1-3.5 (m, broad); 2.0-1.2 (m, broad). Mn=29000 g/mol, Mz=98000 g/mol. PDI=2.0.

Example 1c

Preparation of Polymer Pc

[0132] ##STR00058##

[0133] In a three-neck bottom flask, compound 3a, prepared as described in example 2a, (1.5 g, 7 mmol) and methoxystyrene (4b) (0.94 g 7 mmol) were dissolved in dichloromethane (10 mL) together with catalytic amount of ethyl acetate (0.1 mL). The solution was then cooled to −40° C. by means of an acetonitrile/dry ice bath. To the cooled solution, SnCl.sub.4 (0.5% mol) and BF.sub.3 in 1M DCM solution (0.5% mol) were subsequently added, keeping the temperature at −40° C. After stirring for 6 hrs, polymer Pc was precipitated in .sup.iPrOH. The obtained white solid was filtered, dried and precipitated two more times in .sup.iPrOH by dissolving it in the minimal amount of toluene. Polymer Pc was obtained in 95% yield as white solid that was then characterized by gel permeation chromatography and H.sup.1-NMR. .sup.1H-NMR δ ppm, CCl.sub.2D.sub.2: 7.8-6.3 (m, broad); 4.1-3.8 (m, broad); 3.8-3.5 (m, broad); 2.0-1.2 (m, broad). Mn=43000 g/mol, Mz=117000 g/mol. PDI=1.7

Example 1d

Preparation of Dielectric Polymer Pd

[0134] ##STR00059##

[0135] In a three-neck bottom flask, compound 3b, prepared as described in example 2b, (1.0 g, 5 mmol) and methoxystyrene (4b) (1.34 g 5 mmol) were dissolved in dichloromethane (10 mL) together with catalytic amount of ethyl acetate (0.1 mL). The solution was then cooled to −40° C. by means of an acetonitrile/dry ice bath. To the cooled solution, SnCl.sub.4 (0.5% mol) and BF.sub.3 in 1M DCM solution (0.5% mol) were subsequently added, keeping the temperature at −40° C. After stirring for 6 hrs, polymer Pd was precipitated in .sup.iPrOH. The obtained white solid was filtered, dried and precipitated two more times in .sup.iPrOH by dissolving it in the minimal amount of toluene. Polymer Pd was obtained in 67% yield as white solid that was then characterized by gel permeation chromatography and H.sup.1-NMR. .sup.1H-NMR δ ppm, CCl.sub.2D.sub.2: 7.1-6.9 (m, broad); 6.8-6.3 (m, broad); 4.0-3.5 (m, broad); 2.7-2.8 (m, broad); 2.0-1.2 (m, broad); 1.2-1.1 (m, broad). Mn=14000 g/mol, Mz=44000 g/mol. PDI=1.9.

Example 1e

Preparation of Polymer Pe

[0136] ##STR00060##

[0137] In a three-neck bottom flask, compound 3b, prepared as described in example 2b, (1.03 g, 0.5 mmol) and cyclohexylvinylether (4c) (0.65 g 10 mmol) were dissolved in dichloromethane (10 mL) together with catalytic amount of ethyl acetate (0.1 mL). The solution was then cooled to −40° C. by means of an acetonitrile/dry ice bath. To the cooled solution, SnCl.sub.4 (0.5% mol) and BF.sub.3 in 1M DCM solution (0.5% mol) were subsequently added, keeping the temperature at −40° C. After stirring for 6 hrs, polymer Pe was precipitated in .sup.iPrOH. The obtained white solid was filtered, dried and precipitated two more times in .sup.iPrOH by dissolving it in the minimal amount of toluene. Polymer Pe was obtained in quantitative yield as white solid that was then characterized by gel permeation chromatography and H.sup.1-NMR. .sup.1H-NMR δ ppm, CCl.sub.2D.sub.2: 7.1-6.9 (m, broad); 6.8-6.6 (m, broad); 4.0-3.4 (m, broad); 3.3-3.2 (m, broad); 2.8-2.7 (m, broad); 1.9-1.3 (m, broad); 1.3-1.1 (m, broad). Mn=25000 g/mol, Mz=125000 g/mol. PDI=2.4.

Example 1f

Preparation of Polymer Pf

[0138] ##STR00061##

[0139] In a three-neck bottom flask, compound 3c, prepared as described in example 2c, (1.0 g, 5 mmol) and methoxystyrene (4b)(1.34 g 5 mmol) were dissolved in dichloromethane (10 mL) together with catalytic amount of ethyl acetate (0.1 mL). The solution was then cooled to −40° C. by the means of an acetonitrile/dry ice bath. To the cooled solution, SnCl.sub.4 (0.5% mol) and BF.sub.3 in 1M DCM solution (0.5% mol) were subsequently added, keeping the temperature at −40° C. After stirring for 6 hrs, polymer Pf was precipitated in .sup.iPrOH. The obtained white solid was filtered, dried and precipitated two more times in .sup.iPrOH by dissolving it in the minimal amount of toluene. Polymer Pf was obtained in quantitative yield as white solid that was then characterized by gel permeation chromatography and H.sup.1-NMR. .sup.1H-NMR δ ppm, CCl.sub.2D.sub.2: 6.8-6.6 (m, broad); 3.9-3.6 (m, broad); 1.9-1.6 (m, broad). Mn=28000 g/mol, Mz=98000 g/mol, PDI=1.9.

Example 1g

Preparation of Polymer Pg

[0140] ##STR00062##

[0141] In a three-neck bottom flask, compound 3a, (12.0 g, 56 mmol), prepared as described in example 2a, was dissolved in dry dichloromethane (50 mL) together with catalytic amount of ethyl acetate (0.1 mL). The solution was then cooled to −40° C. by the means of an acetonitrile/dry ice bath. To the cooled solution, SnCl.sub.4 (0.56 mol) and BF.sub.3 in 1M DCM solution (0.56 mol) were subsequently added, keeping the temperature at −40° C. After stirring for 6 hrs, polymer Pg was precipitated in .sup.iPrOH (250 mL). The obtained white solid was filtered, dried and precipitated two more times in .sup.iPrOH by dissolving it in the minimal amount of toluene. The polymer was obtained in 88% yield (10.6 g) as pale gray solid that was then characterized by gel permeation chromatography and 1H-NMR. Mn=50K, Mz=622 k, PDI=3.5 .sup.1H-NMR (δ ppm, CCl.sub.2D.sub.2: 77-7.3 (m, broad); 6.9-67 (m, broad); 4.1-3.6 (m, broad); 2.0-1.6 (m, broad).

Example 2a

Preparation of Compound 3a

[0142] ##STR00063##

[0143] Compound 8a (0.2 mol) was dissolved in dimethyl formamide (100 mL) together with K.sub.2CO.sub.3 (57.5 g, 0.4 mol) and compound 9a (27.1 g, 0.25 mol). The reaction mixture was heated at 80° C. overnight. Water was added to the cooled solution until the precipitation of the solid monomer was induced or a phase separation of the liquid from water was performed. Yield: 92% Recrystallization from cyclohexane yielded a pale gay powder. .sup.1H-NMR δ ppm, CCl.sub.2D.sub.2: 7.77-7.72 (m, 3H), 7.43 (td, 1H, δ.sub.1=7 Hz, δ.sub.2=1 Hz), 7.33 (td, 1H, δ.sub.1=7 Hz, δ.sub.2=1 Hz), 7.17-7.14 (m, 2H), 6.55 (dd, 1H, δ.sub.1=MHz, δ.sub.2=7 Hz), 4.09-4.06 (m, 2H), 4.24 (d, 1H, δ.sub.1=2 Hz), 4.33-4.27 (m, 3H).

Example 2b

Preparation of Compound 3b

[0144] ##STR00064##

[0145] Compound 8b (0.2 mol) was dissolved in dimethyl formamide (100 mL) together with K.sub.2CO.sub.3 (57.5 g, 0.4 mol) and compound 9a (27.1 g, 0.25 mol). The reaction mixture was heated at 80° C. overnight. Water was added to the cooled solution until the precipitation of the solid monomer was induced or a phase separation of the liquid from water was performed. Yield: 89%. The crude was distilled (2.2 10.sup.−1 mbar, T=110° C.) yielding a colorless oil. .sup.1H-NMR δ ppm, CCl.sub.2D.sub.2: 7.13 (d, 2H, δ.sub.1=8 Hz), 6.83 (d, 2H, δ.sub.1=8 Hz), 6.52 (dd, 1H, δ.sub.1=MHz, δ.sub.2=7 Hz), 4.23 (dd, 1H, δ.sub.1=MHz, δ.sub.2=2 Hz), 4.15-4.13 (m, 2H), 4.07 (dd, 1H, δ.sub.1=7 Hz, δ.sub.2=2 Hz), 4.00-3.98 (m, 2H), 2.84 (seq, 1H, δ.sub.1=4 Hz), 1.20 (d, 6H, δ.sub.1=4 Hz).

Example 2c

Preparation of Compound 3c

[0146] ##STR00065##

[0147] Compound 8c (0.2 mol) was dissolved in dimethyl formamide (100 mL) together with K.sub.2CO.sub.3 (57.5 g, 0.4 mol) and compound 9a (27.1 g, 0.25 mol). The reaction mixture was heated at 80° C. overnight. Water was added to the cooled solution until the precipitation of the solid monomer was induced or a phase separation of the liquid from water was performed. Yield: 90%. The crude was used without any further purification. .sup.1H-NMR δ ppm, CCl.sub.2D.sub.2: 6.85-6.80 (m, 4H), 6.53 (dd, 1H, δ.sub.1=14 Hz, δ.sub.2=6 Hz), 4.23 (d, 1H, δ.sub.1=MHz), 4.13-4.11 (m, 2H), 4.04 (d, 1H, δ.sub.1=6 Hz), 3.99-3.98 (m, 2H), 3.73 (s, 3H).

Example 3

Preparation of Capacitors Comprising Polymers Pa, Pb, Pc, Pd, Pe, Pf and Pg, Respectively

[0148] Compositions comprising polymer Pa, Pb, Pc, Pd, Pe, Pf and Pg, respectively, and a solvent as listed in table 1 were filtered with a 0.7 μm filter. The composition comprising polymer Pa was applied on a glass substrate covered with a conductive indium tin oxide (ITO) layer by spin coating under the conditions mentioned in table 1. The compositions comprising polymer Pb, Pc, Pd, Pe, Pf and Pg, respectively, were applied on a PET substrate with lithographically patterned gold electrodes by spin-coating under the conditions mentioned in table 1. The wet films obtained were baked at 90° C. for 30 minutes on a hot plate to obtain polymer layers with a thickness as indicated in table 1. Gold top-electrodes (area see table 1) were then vacuum-deposited through a shadow mask on the polymer layers at a pressure of below 1×10.sup.−5 mbar.

TABLE-US-00001 TABLE 1 Spin coating Composition Spin- Layer Polymer speed Spin thickness Area Polymer [wt %].sup.a Solvent [rpm] time [s] [nm] [mm.sup.2] Pa 10 butyl acetate 1500 30 489 2.9 Pb 10 butyl acetate 1500 30 560 1.4 Pc 12 butyl acetate 1500 30 450 1.4 Pd 8 butyl acetate 1200 30 319 1.4 Pe 8 butyl acetate 1500 30 407 1.4 Pf 10 butyl acetate 1500 30 473 1.4 Pg 12 PGMEA/CP.sup.b 1500 30 357 1.4 9/1 .sup.abased on the weight of the composition. .sup.bPropylene glycol methyl ether acetate/cyclopentanone.

[0149] The capacitors obtained were characterized by measuring the complex capacitance with a LCR meter Agilent 4284A (signal amplitude 1 V) to obtain the relative permittivity K=K′+iK″, where the K′ is the dielectric constant and K″ is a measure of the dielectric loss.

[0150] K′ is calculated by the following equation:

K′=C×d/(A×epsilon.sub.0)

with C is the capacitance measured by the LCR meter, d the thickness of the dielectric layer, A the area of the capacitor and epsilon.sub.0 is the vacuum permittivity (8,85E-12 F/m).

[0151] K″ is calculated by:

K″=tan(delta)×K′

with tan (delta) measured by the LCR meter.

TABLE-US-00002 TABLE 2 K′ K′ K″ K″ Polymer (20 Hz) (100 kHz) (20 Hz) (100 kHz) Pa 3.15 2.9 0.08 0.05 Pb 3.23 3.09 0.08 0.03 Pc 3.59 3.36 0.08 0.04 Pd 3.32 3.22 0.07 0.03 Pe 3.15 2.86 0.10 0.01 Pf 3.91 3.63 0.13 0.02 Pg 3.11 3.06 0.01 0.01

Example 4

Preparation of a Top-Gate, Bottom-Contact (TGBC) Field Effect Transistors Comprising Polymers Pa, Pb, Pc, Pd, Pe, Pf and Pg, Respectively, as Dielectric Material

[0152] Gold was sputtered onto PET substrate to form approximately 40 nm thick gold source/drain electrodes. A 1% (weight/weight) solution of the diketopyrrolopyrrole semiconducting polymer of example 1 of WO2013/083506 in mesitylene was filtered through a 0.45 micrometer polytetrafluoroethylene (PTFE) filter and then applied by spin coating (1,000 rpm, 60 seconds). The wet organic semiconducting layer was dried at 120° C. on a hot plate for 60 seconds. Compositions comprising a dielectric polymer and a solvent as listed in table 3 were filtered with 0.7 μm filter and applied on the semiconductor by spin coating under the conditions mentioned in table 3. The wet dielectric layers were baked at 90° C. for 30 minutes after coating to obtain polymer layers with a thickness as indicated in table 3. Gate electrodes of gold (thickness approximately 70 nm) were evaporated through a shadow mask on the dielectric layer.

TABLE-US-00003 TABLE 3 Composition Spin coating Layer Polymer Spin-speed Spin time thickness Polymer [wt %].sup.a Solvent [rpm] [s] [nm] Pa 12 butyl acetate 1500 30 525 Pb 10 butyl acetate 1500 30 543 Pc 12 butyl acetate 1500 30 546 Pd 8 butyl acetate 1200 30 390 Pe 8 butyl acetate 1500 30 510 Pf 10 butyl acetate 1500 30 515 Pg 12 PGMEA/CP 1200 30 477 9/1 .sup.abased on the weight of the composition. .sup.bPropylene glycol methyl ether acetate/cyclopentanone.

[0153] The top-gate, bottom-contact (TGBC) field effect transistors were measured by using a Keithley semiconductor characterization system.

[0154] The drain current I.sub.d in relation to the gate-source voltage V.sub.gs (transfer curve) for the top-gate, bottom-contact (TGBC) field effect transistors at a drain-source voltage V.sub.ds of −30 V is shown in FIG. 1 (for Pa), FIG. 2 (for Pb), FIG. 3 (for Pc), Figured (for Pd), FIG. 5 (for Pe), FIG. 6 (for Pf), and FIG. 7 (for Pg) respectively. The solid black line curve shows the drain current plotted on a logarithmic scale (left y-axis). The solid dark grey line shows the square root of drain current plotted on a linear scale (right y-axis). In addition, FIGS. 1 to 7 show the gate current plotted on a logarithmic scale (left y-axis) as light-grey, dotted line.

[0155] The charge-carrier mobility μ was calculated by using the following equation:

μ=m.sup.2×2L/(C.sub.G×W) with C.sub.G=K′×epsilon.sub.0/d

wherein m is the slope of the square root drain current I.sub.d.sup.1/2 extracted by a linear fit to the square root of the drain current in the transfer curves of FIGS. 1 to 7, L=10 μm is the channel length of the transistor, W=250 μm is the channel width of the transistor, and C.sub.G is the area normalized capacitance, with epsilon.sub.0 is the vacuum permittivity of 8.85×10.sup.−12 F//m, K′ is the dielectric constant of the respective material measured at 20 Hz (see table 2) and d is the thickness of the dielectric polymer on top of the organic semiconductor (see table 3).

[0156] The threshold voltage Vth was calculated by using the following equation

Vth=−1×m/b

[0157] Wherein m is the slope of the square root drain current I.sub.ds.sup.1/2 extracted from the transfer curves, and b is the y-axis intersection of the fitted curve.

[0158] The Ion/Ioff ratio was calculated by using the following equation:

Ion/Ioff=I.sub.D max/I.sub.D min

[0159] The average values of the charge-carrier mobility μ, the I.sub.on/I.sub.off ratio and the threshold voltage V.sub.th for the organic field effect transistor taken from at least 10 TFTs are given in table 4.

TABLE-US-00004 TABLE 4 charge carrier mobility μ V.sub.th Polymer [cm.sup.2/Vs] I.sub.on/I.sub.off [V] Pa 0.69 6E4 1 Pb 0.56 6E4 1 Pc 0.47 3E4 1 Pd 0.47 1E5 0.5 Pe 0.56 7E5 0 Pf 0.44 1E5 0.5 Pg 0.52 1E5 0.5

Comparative Example 1

Preparation of a Top-Gate, Bottom-Contact (TGBC) Field Effect Transistors Comprising Polystyrene as Dielectric Material

[0160] A top-gate, bottom contact (TGBC) field effect transistor was prepared in analogy to example 4, but comprising polystyrene (MW 2,000,000 g/mol) instead of Pa as dielectric material, and measured by using a Keithley semiconductor characterization system in analogy to example 4.

[0161] FIG. 8 shows the of drain current plotted on a linear scale (left y-axis) for the transistor of example 4 comprising Pa as dielectric material and of the transistor of comparative example 1 comprising polystyrene as dielectric material.

[0162] FIG. 8 shows that a higher drain current can be achieved using the field effect transistor of example 4 comprising Pa as dielectric material at a specific gate-source voltage (operational voltage) compared to using the field effect transistor comprising polystyrene as dielectric material. Or in other words, a specific drain current can be achieved using the field effect transistor of example 4 comprising Pa as dielectric material at a lower specific gate-source voltage (operational voltage) compared to using the field effect transistor comprising polystyrene as dielectric material.