ETHER-BASED POLYMERS AS PHOTO-CROSSLINKABLE DIELECTRICS

Abstract

Polymers comprising at least one unit of formula (1) wherein n is 0 or 1, m and p are independently from each other 0, 1, 2, 3, 4, 5 or 6, provided that the sum of n, m and p is at least 2, and n and p are not 0 at the same time, Ar.sup.1 and Ar.sup.2 are independently from each other C.sub.6-14-arylene or C.sub.6-14-aryl, which may be substituted with 1 to 4 substituents independently selected from the group consisting of C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl and 5 to 14 membered heteroaryl, and X.sup.1, X.sup.2 and X.sup.3 are independently from each other and at each occurrence O or S, compositions comprising these polymers, and electronic devices comprising a layer formed from the compositions. Preferably, the electronic device is an organic field effect transistor and the layer is the dielectric layer.

##STR00001##

Claims

1: A polymer, comprising: at least one unit of formula (1): ##STR00056## wherein: n is 0 or 1; m and p are independently from each other 0, 1, 2, 3, 4, 5 or 6, provided that the sum of n, m and p is at least 2, and n and p are not 0 at the same time; Ar.sup.1 and Ar.sup.2 are independently from each other a C.sub.6-14-arylene or a C.sub.6-14-aryl, which may be substituted with 1 to 4 substituents independently selected from the group consisting of a C.sub.1-30-alkyl, a C.sub.2-30-alkenyl, a C.sub.2-30-alkynyl, a C.sub.5-8-cycloalkyl, a C.sub.6-14-aryl and a 5 to 14 membered heteroaryl; X.sup.1, X.sup.2 and X.sup.3 are independently from each other and at each occurrence O or S; R.sup.1 and R.sup.2 are independently from each other and at each occurrence selected from the group consisting of a C.sub.1-30-alkyl, a C.sub.2-30-alkenyl, a C.sub.2-30-alkynyl, a C.sub.5-8-cycloalkyl, a C.sub.6-14-aryl and a 5 to 14 membered heteroaryl; C.sub.1-30-alkyl, C.sub.2-30-alkenyl and C.sub.2-30-alkynyl can be substituted with 1 to 5 substituents independently selected from the group consisting of a halogen, CN, a C.sub.5-6-cycloalkyl, a C.sub.6-10-aryl and a 5 to 10 membered heteroaryl; C.sub.5-8-cycloalkyl can be substituted with 1 to 5 substituents independently selected from the group consisting of a halogen, a C.sub.1-10-alkyl, CN, a C.sub.2-10-alkenyl, a C.sub.2-10-alkynyl, a C.sub.6-10-aryl and a 5 to 10 membered heteroaryl; and C.sub.6-14-aryl and 5 to 14 membered heteroaryl can be substituted with 1 to 5 substituents independently selected from the group consisting of a halogen, CN, a C.sub.1-10-alkyl, a C.sub.2-10-alkenyl, a C.sub.2-10-alkynyl and a C.sub.5-6-cycloalkyl.

2: The polymer of claim 1, wherein: n is 0 or 1; and m and p are independently from each other 0, 1, 2, 3 or 4, provided that the sum of n, m and p is at least 2, and n and p are not 0 at the same time.

3: The polymer of claim 1, wherein: n is 0 or 1; and m and p are independently from each other 0, 1, 2, 3 or 4, provided that the sum of n and p is at least 2.

4: The polymer of claim 1, wherein: n is 0 or 1; and m and p are independently from each other 0, 1, 2, 3 or 4, provided that the sum of n and p is at least 3.

5: The polymer of claim 1, wherein: Ar.sup.1 and Ar.sup.2 are independently from each other a phenylene or phenyl, which may be substituted with 1 to 4 substituents independently selected from the group consisting of a C.sub.1-30-alkyl, a C.sub.2-30-alkenyl, a C.sub.2-30-alkynyl, a C.sub.5-8-cycloalkyl, a C.sub.6-14-aryl and a 5 to 14 membered heteroaryl; C.sub.1-30-alkyl, C.sub.2-30-alkenyl and C.sub.2-30-alkynyl can be substituted with 1 to 5 substituents independently selected from the group consisting of a halogen, CN, a C.sub.5-6-cycloalkyl, a C.sub.6-10-aryl, and a 5 to 10 membered heteroaryl; C.sub.5-8-cycloalkyl can be substituted with 1 to 5 substituents independently selected from the group consisting of a halogen, CN, a C.sub.1-10-alkyl, a C.sub.2-10-alkenyl, a C.sub.2-10-alkynyl, a C.sub.6-10-aryl and a 5 to 10 membered heteroaryl; and C.sub.6-14-aryl and 5 to 14 membered heteroaryl can be substituted with 1 to 5 substituents independently selected from the group consisting of a halogen, CN, a C.sub.1-10-alkyl, a C.sub.2-10-alkenyl, a C.sub.2-10-alkynyl and a C.sub.5-6-cycloalkyl.

6: The polymer of claim 1, wherein: Ar.sup.1 and Ar.sup.2 are independently from each other a phenylene or phenyl, which may be substituted with 1 to 4 substituents independently selected from the group consisting of a C.sub.1-20-alkyl, a C.sub.2-20-alkenyl and a C.sub.2-20-alkynyl; and C.sub.1-20-alkyl, C.sub.2-20-alkenyl and C.sub.2-20-alkynyl can be substituted with 1 to 5 substituents independently selected from the group consisting of a halogen, CN, a C.sub.5-6-cycloalkyl, a C.sub.6-10-aryl and a 5 to 10 membered heteroaryl.

7: The polymer of claim 1, wherein Ar.sup.1 and Ar.sup.2 are independently from each other an unsubstituted phenylene or phenyl.

8: The polymer of claim 1, wherein: at least one of n, m and p is not 0; and X.sup.1, X.sup.2 and X.sup.3 are O.

9: The polymer of claim 1, wherein: R.sup.1 and R.sup.2 are independently from each other and at each occurrence selected from the group consisting of a C.sub.1-20-alkyl, a C.sub.2-20-alkenyl, a C.sub.2-20-alkynyl and phenyl; C.sub.1-20-alkyl, C.sub.2-20-alkenyl and C.sub.2-20-alkynyl can be substituted with 1 to 5 substituents independently selected from the group consisting of a halogen, CN, a C.sub.5-6-cycloalkyl, a C.sub.6-10-aryl and a 5 to 10 membered heteroaryl; and phenyl can be substituted with 1 to 5 substituents independently selected from the group consisting of a halogen, CN, a C.sub.1-10-alkyl, a C.sub.2-10-alkenyl, a C.sub.2-10-alkynyl and a C.sub.5-6-cycloalkyl.

10: The polymer of claim 1, wherein: R.sup.1 and R.sup.2 are independently from each other and at each occurrence selected from the group consisting of a C.sub.1-10-alkyl and phenyl; C.sub.1-10-alkyl can be substituted with 1 to 5 substituents independently selected from the group consisting of a halogen and phenyl; and phenyl can be substituted with 1 to 5 substituents independently selected from the group consisting of a halogen and C.sub.1-6-alkyl.

11: The polymer of claim 1, wherein: at least one of m and p is not 0; R.sup.1 and R.sup.2 are a C.sub.1-6-alkyl; and C.sub.1-6-alkyl can be substituted with 1 to 3 of a halogen.

12: The polymer of claim 1, which is a copolymer comprising: at least one unit of formula (1): ##STR00057## and at least one unit of formula (10): ##STR00058## wherein: n is 0 or 1; m and p are independently from each other 0, 1, 2, 3, 4, 5 or 6, provided that the sum of n, m and p is at least 2, and n and p are not 0 at the same time; q is 0, 1, 2, 3, 4, 5 or 6; Ar.sup.1, Ar.sup.2 and Ar.sup.3 are independently from each other a C.sub.6-14-arylene or a C.sub.6-14-aryl, which may be substituted with 1 to 4 substituents independently selected from the group consisting of a C.sub.1-30-alkyl, a C.sub.2-30-alkenyl, a C.sub.2-30-alkynyl, a C.sub.5-8-cycloalkyl, a C.sub.6-14-aryl and a 5 to 14 membered heteroaryl; X.sup.1, X.sup.2, X.sup.3, and X.sup.4 are independently from each other and at each occurrence O or S; R.sup.1, R.sup.2 and R.sup.3 are independently from each other and at each occurrence selected from the group consisting of a C.sub.1-30-alkyl, a C.sub.2-30-alkenyl, a C.sub.2-30-alkynyl, a C.sub.5-8-cycloalkyl, a C.sub.6-14-aryl and a 5 to 14 membered heteroaryl; C.sub.1-30-alkyl, C.sub.2-30-alkenyl and C.sub.2-30-alkynyl can be substituted with 1 to 5 substituents independently selected from the group consisting of a halogen, CN, a C.sub.5-6-cycloalkyl, a C.sub.6-10-aryl and a 5 to 10 membered heteroaryl; C.sub.5-8-cycloalkyl can be substituted with 1 to 5 substituents independently selected from the group consisting of a halogen, CN, a C.sub.1-10-alkyl, a C.sub.2-10-alkenyl, a C.sub.2-10-alkynyl, a C.sub.6-10-aryl and a 5 to 10 membered heteroaryl, and C.sub.6-14-aryl and 5 to 14 membered heteroaryl can be substituted with 1 to 5 substituents independently selected from the group consisting of a halogen, CN, a C.sub.1-10-alkyl, a C.sub.2-10-alkenyl, a C.sub.2-10-alkynyl and a C.sub.5-6-cycloalkyl.

13: A composition, comprising: the polymer of claim 1 and a solvent.

14: The composition of claim 13, further comprising: a crosslinker.

15: A process for preparing an electronic device containing a layer formed from the composition of claim 13, the process comprising: applying the composition on a pre-cursor of the electronic device in order to form the layer.

16: An electronic device obtainable by the process of claim 15.

17: An article, comprising: the polymer of claim 1, wherein the article is selected from the group consisting of a dielectric layer, a resist layer, an insulating layer, a passivation layer, a planarization layer, an encapsulation layer and a coating layer.

Description

[0193] FIG. 1 shows the drain current I.sub.ds in relation to the gate voltage V.sub.gs (transfer curve) for a top-gate, bottom-contact (TGBC) field effect transistor comprising polymer PB as dielectric material at a source voltage V.sub.ds of −3V (triangle), respectively, −30V (square) is shown in FIG. 1.

[0194] FIG. 2 shows the drain current I.sub.ds in relation to the gate voltage V.sub.gs (transfer curve) for a top-gate, bottom-contact (TGBC) field effect transistor comprising polymer Pe as dielectric material at a source voltage V.sub.ds of −5V (triangle), respectively, −30V (square).

EXAMPLES

Example 1

Preparation of Compound 2a

[0195] ##STR00041##

Preparation of Compound 3a

[0196] 4-nitrobenzaldehyde (30.0 g, 198.5 mmol, 1 eq.), Cu(OAc).sub.2 hydrate (0.05 eq.), Cs.sub.2CO.sub.3 (2 eq.) and compound 4a (2 eq.) were dissolve in DMF (450 mL) under inert atmosphere (N.sub.2). Then, the reaction mixture was stirred at 100° C. for 4 hrs. The reaction mixture was diluted with ethyl acetate, filtered over a Buchner funnel, washed with aqueous NaOH (1×20 mL) and water (1×20 mL). The organic phases were gathered, dried over MgSO.sub.4 and evaporated under reduced pressure. Purification was performed by column chromatography, employing hexane/DCM (7:3) as eluent giving compound 3a as a yellow oil (86% yield). .sup.1H-NMR (400 MHz, CDCl.sub.3), δ (ppm): 9.94 (s, 1H), 7.87 (m, 2H), 7.26 (m, 2H), 7.11-7.06 (m, 4H). m/z (EI)=(M+H).sup.+=283.

Preparation of Compound 2a

[0197] Methyltriphenylphosphonium bromide (148 g, 3.4 eq) was dissolved in anhydrous THF (500 mL) under N.sub.2 and the resulting solution was cooled to −40° C. Potassium tert-butoxide (6 eq) was then added and the reaction mixture was stirred for 30 mins. Compound 3a (1 eq) dissolved in anhydrous THF (200 mL) was subsequently added and the reaction mixture was stirred for 3 hrs at −40° C., and then warmed to room temperature. The reaction mixture was filtered over a Buchner funnel and the solvent removed under reduced pressure. Column chromatography was employed to purify compound 2a using hexane/DCM (9:1) as the eluent. Compound 2a was obtained in 84% as colourless oil. .sup.1H-NMR (400 MHz, CDCl.sub.3), δ (ppm): 7.40 (d, J=8.8 Hz, 2H), 7.15 (d, J=12.8 Hz, 2H), 7.02-6.96 (m, 4H), 6.70 (dd, J=20 Hz, J.sub.1=12.4 Hz, 1H), 5.68 (d, J=20 Hz, 1H), 5.22 (d, J=12.4 Hz, 1H). m/z (EI)=(M+H).sup.+=281.

Example 2

Preparation of Compound 2b

[0198] ##STR00042##

Preparation of Compound 3b

[0199] Compound 3b was prepared in analogy to compound 3a in example 1, but using compound 4b instead of compound 4a. Purification was performed by column chromatography, employing hexane/ethyl acetate (5:1) as eluent giving compound 3b as orange solid (48% yield). .sup.1H-NMR (400 MHz, CDCl.sub.3), δ (ppm): 9.88 (s, 1H), 7.80 (d, 2H), 7.02 (m, 4H), 6.95 (d, 2H), 3.81 (s, 3H). Data are in agreement with those reported in the literature Tetrahedron 2013, 69, 6884.

Preparation of Compound 2b

[0200] Compound 2b was prepared in analogy to compound 2a in example 1, but using compound 3b instead of compound 3a. Purification was performed by column chromatography, employing hexane/ethyl acetate (5:1) as eluent giving compound 2a as white solid (72% yield). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2), δ (ppm): 7.35 (d, J=8.8 Hz, 2H), 6.97 (d, J=9.2 Hz, 2H), 6.88 (m, 4H), 6.67 (dd, J=17.6 Hz, J.sub.1=11.2 Hz, 1H), 5.65 (d, J=17.6 Hz, 1H), 5.17 (d, J=11.2 Hz, 1H), 3.79 (s, 3H). m/z (EI)=(M+H).sup.+=226.3.

Example 3

Preparation of Compound 2c

[0201] ##STR00043##

Preparation of Compound 3c

[0202] Compound 3c was prepared in analogy to compound 3a in example 1, but using compound 4c instead of compound 4a. Purification was performed by column chromatography, employing hexane/ethyl acetate (5:1) as eluent giving compound 3c as orange oil (77% yield). .sup.1H-NMR (400 MHz, CDCl.sub.3), δ (ppm): 9.88 (s, 1H), 7.79 (m, 2H), 7.20 (m, 1H), 7.07 (m, 1H), 6.96 (m, 4H), 3.77 (s, 3H). m/z (EI)=(M+H).sup.+=229.

Preparation of Compound 2c

[0203] Compound 2c was prepared in analogy to compound 2a in example 1, but using compound 3c instead of compound 3a. Column chromatography was employed to purify compound 2c using hexane/ethyl acetate (5:1) as the eluent. Compound 2c was obtained in 40% yield as yellow solid. .sup.1H-NMR (400 MHz, CDCl.sub.3), δ (ppm): 7.35 (m, 2H), 7.15 (m, 1H), 7.3-6.90 (5H), 6.68 (dd, J=17.6 Hz, J.sub.1=10.8 Hz, 1H), 5.65 (d, J=17.6 Hz, 1H), 5.16 (d, J=10.38 Hz, 1H), 3.82 (s, 3H). m/z (EI)=(M+H).sup.+=227.

Example 4

Preparation of Compound 2d

[0204] ##STR00044##

Preparation of Compound 3d

[0205] Compound 3d was prepared in analogy to compound 3a in example 1, but using compound 4d instead of compound 4a. Purification was performed by column chromatography, employing hexane/ethyl acetate (5:1) as eluent giving compound 3d as a yellow oil (30% yield). .sup.1H-NMR (400 MHz, CDCl.sub.3), δ (ppm): 9.87 (s, 1H), 7.77 (m, 2H), 7.16 (m, 1H), 6.95 (m, 2H), 6.65 (m, 2H), 3.75 (s, 6H). m/z (EI)=(M+H).sup.+=259.1

Preparation of Compound 2d

[0206] Compound 2d was prepared in analogy to compound 2a in example 1, but using compound 3d instead of compound 3a. Column chromatography was employed to purify compound 2d using hexane/ethyl acetate (5:1) as the eluent. Compound 2d was obtained in 81% yield as pale yellow solid. .sup.1H-NMR (400 MHz, CDCl.sub.3), δ (ppm): 7.30 (d, J=10 Hz, 2H), 7.15 (t, J=8.4 Hz, 1H), 6.81 (d, J=8.4 Hz, 2H), 6.66 (m, 3H), 5.60 (d, J=18 Hz, 1H), 5.11 (d, J=12 Hz, 1H), 3.77 (s, 6H). m/z (EI)=(M+H).sup.+=257.1

Example 5

Preparation of Compound 2e

[0207] ##STR00045##

Preparation of Compound 3e

[0208] Compound 3e was prepared in analogy to compound 3a in example 1, but using compound 4e instead of compound 4a. Purification was performed by column chromatography, employing hexane/ethyl acetate (5:1) as eluent giving compound 3e as a yellow solid (50% yield). .sup.1H-NMR (400 MHz, CDCl.sub.3), δ (ppm): 9.92 (s, 1H), 7.85 (d, J=8.8 Hz, 2H), 7.06 (d, J=8.8 Hz, 2H), 6.33 (s, 2H), 3.85 (s, 3H), 3.81 (s, 6H). m/z (EI)=(M+H).sup.+=289.1

Preparation of Compound 2e

[0209] Compound 2e was prepared in analogy to compound 2a in example 1, but using compound 3e instead of compound 3a. Column chromatography was employed to purify compound 2e using hexane/ethyl acetate (5:1) as the eluent. Compound 2e was obtained in 66% yield as pale yellow oil. .sup.1H-NMR (400 MHz, CDCl.sub.3), δ (ppm): 7.37 (d, J=6.8 Hz, 2H), 6.96 (d, J=6.8 Hz, 2H), 6.69 (dd, J=17 Hz, J.sub.1=11 Hz, 1H), 6.27 (s, 2H), 5.67 (d, J=17 Hz, 1H), 5.20 (d, J=11 Hz, 1H), 3.83 (s, 3H), 3.78 (s, 6H). m/z (EI)=(M+H).sup.+=287.1

Example 6

Preparation of Compound 2f

[0210] ##STR00046##

Preparation of Compound 6a

[0211] (4-Formylphenyl)boronic acid (8a) (0.4 g, 2.6 mmol), 3,4,5-trimethoxy bromobenzene (7a) (0.5 g, 2.0 mmol) and tetra-n-butylammonium bromide (0.1 g, 0.4 mmol) were dissolved in toluene (5 mL) and a K.sub.2CO.sub.3 aqueous solution (5N, 1.6 mL) was subsequently added. The bilayer mixture was degassed with N.sub.2 and finally tetrakis(triphenylphosphine)palladium (0.1 g, 0.1 mmol) was added under inert atmosphere. The reaction mixture was heated at 100° C. overnight. The reaction mixture was extracted with DCM (2×25 ml). The combined organic fractions were anhydrified over MgSO.sub.4 and evaporated under reduced pressure. Crude compound 6a was purified by chromatography column, employing hexanes/ethyl acetate as the eluent. Compound 6a was obtained in 85% yield as a colorless oil. .sup.1H-NMR (400 MHz, CDCl.sub.3), δ (ppm): 10.06 (s, 1H), 7.94 (d, J=8 Hz, 2H), 7.71 (d, J=8 Hz, 2H), 6.82 (s, 2H), 3.94 (s, 6H), 3.91 (s, 3H).

Preparation of Compound 2f

[0212] Methyltriphenylphosphonium bromide (2.4 g, 6.8 mmol) was dissolved in anhydrous THF (15 mL) under N.sub.2 and the reaction mixture was cooled to −40° C. Potassium tert butoxide (1.3 g, 12 mmol) was then added and the solution turned dark. After stirring for 30 mins compound 6a (0.5 g, 2.0 mmol) in 5 mL of THF was added and the reaction mixture was allowed to warm up to room temperature, while being stirred overnight. The reaction mixture was filtered over a Buchner funnel, the solvent was removed under reduced pressure and the crude compound 2f was purified by column chromatography over silica gel employing hexane/ethyl acetate (8/2) as the eluent. Compound 2f was obtained in 76% yield as a white solid. .sup.1H-NMR (400 MHz, CDCl.sub.3), δ (ppm): 7.50 (d, J=8 Hz, 2H), 7.47 (d, J=8 Hz, 2H), 6.78 (s, 2H), 6.75 (dd, J=17 Hz, J.sub.2=11 Hz, 1H, overlapping with singlet at 6.78), 5.79 (d, J=17 Hz, 1H), 5.27 (d, J=11 Hz, 1H), 3.92 (s, 6H), 3.89 (s, 3H). m/z (EI)=(M+H).sup.+=271.1.

Example 7

Preparation of Polymer Pa

[0213] ##STR00047##

[0214] Compound 2a (1 g, 4.7 mmol) was heated at 125° C. under nitrogen atmosphere in neat conditions. After overnight heating, the polymer formed was dissolved in toluene and precipitated by pouring this solution into methanol to give a white solid. The isolated polymer was re-dissolved in THF and precipitated again by pouring this solution into methanol. The precipitation process was repeated once more. Polymer Pa was obtained in 53% yield. Mw 151000 Da. Polydispersity (PDI) 2.5. Tg 62° C. Relative permittivity (at 1 kHz, 25° C.) 2.7.

Example 8

Preparation of Polymer Pb

[0215] ##STR00048##

[0216] Compound 2b (1 g, 4.4 mmol) and 1,1′-azobis(cyclohexanecarbonitrile) (10 mg, 0.04 mmol, 1% eq) were dissolved in anhydrous toluene (3 mL). The solution was degassed by three cycles of freeze-pump-thaw. The reaction mixture was stirred at 80° C. under nitrogen atmosphere for 2 days. The reaction mixture diluted with toluene under ambient conditions, and the diluted reaction mixture was poured into methanol to precipitate the polymer. The isolated polymer was re-dissolved in THF and precipitated again by pouring the solution into methanol. The precipitation process was repeated once more. Polymer Pb was obtained in 60% yield as white solid. Mw 70000 Da. Polydispersity (PDI) 2.1. Tg 80° C. Relative permittivity (at 1 kHz, 25° C.) 3.2.

Example 9

Preparation of Polymer Pc

[0217] ##STR00049##

[0218] Compound 2c (1 g, 4.4 mmol) and 1,1′-azobis(cyclohexanecarbonitrile) (10 mg, 0.04 mmol, 1% eq) were dissolved in anhydrous toluene (3 mL). The solution was degassed by three cycles of freeze-pump-thaw. The reaction mixture was stirred at 80° C. under nitrogen atmosphere for 2 days. The reaction mixture diluted with toluene under ambient conditions, and the diluted reaction mixture was poured into methanol to precipitate the polymer. The isolated polymer was re-dissolved in THF and precipitated again by pouring the solution into methanol. The precipitation process was repeated once more. Polymer Pc was obtained in 33% yield as white solid. Mw 129000 Da. Polydispersity (PDI) 2.2. Tg 97° C. Relative permittivity (at 1 kHz, 25° C.) 3.1.

Example 10

Preparation of Polymer Pd

[0219] ##STR00050##

[0220] Compound 2d (3 g, 11.7 mmol) and 1,1′-azobis(cyclohexanecarbonitrile) (12 mg, 0.05 mmol, 1% eq), were dissolved in anhydrous toluene (7 mL). The solution was degassed by three cycles of freeze-pump-thaw. The reaction mixture was stirred at 80° C. under nitrogen atmosphere for 2 days. The reaction mixture diluted with toluene under ambient conditions, and the diluted reaction mixture was poured into methanol to precipitate the polymer. The isolated polymer was re-dissolved in THF and precipitated again by pouring the solution into methanol. The precipitation process was repeated once more. Polymer Pd was obtained in 37% yield as white solid. Mw 176000 Da. Polydispersity (PDI) 2.2. Tg 1480C. Relative permittivity (at 1 kHz, 25° C.) 3.6.

Example 11

Preparation of Polymer Pe

[0221] ##STR00051##

[0222] Compound 2e (1 g, 4.5 mmol) and 1,1′-azobis(cyclohexanecarbonitrile) (8 mg, 0.03 mmol 1% eq) were dissolved in anhydrous toluene (3 mL). The solution was degassed by three cycles of freeze-pump-thaw. The reaction mixture was stirred at 80° C. under nitrogen atmosphere for 2 days. The reaction mixture diluted with toluene under ambient conditions, and the diluted reaction mixture was poured into methanol to precipitate the polymer. The isolated polymer was re-dissolved in THF and precipitated again by pouring the solution into methanol. The precipitation process was repeated once more. Polymer Pe was obtained in 85% yield as white solid. Mw 220000 Da. Polydispersity (PDI) 2.1. Tg 104° C. Relative permittivity (at 1 kHz, 25° C.) 3.7.

Example 12

Preparation of Polymer Pf

[0223] ##STR00052##

[0224] Compound 2f (5 g, 18 mmol) and dicumyl peroxide (50 mg, 0.18 mmol), were dissolved in anhydrous toluene (11 mL). The solution was degassed by three cycles of freeze-pump-thaw. The reaction mixture was stirred at 95° C. under nitrogen atmosphere for 2 days. The reaction mixture diluted with toluene under ambient conditions, and the diluted reaction mixture was poured into methanol to precipitate the polymer. The isolated polymer was re-dissolved in THF and precipitated again by pouring the solution into methanol. The precipitation process was repeated once more. Polymer Pf was obtained in 93% yield as white solid. Mw 114000 Da. Polydispersity (PDI) 2.5. Tg 145° C. Relative permittivity (at 1 kHz, 25° C.) 3.6.

Example 13

Preparation of Polymer Pg

[0225] ##STR00053##

[0226] Compound 9a (1.1 g, 7.9 mmol), compound 2c (1.2 g, 5.3 mmol) and dicumyl peroxide (36 mg, 0.13 mmol, 1% eq) were dissolved in anhydrous toluene (6 mL). The solution was degassed by three cycles of freeze-pump-thaw. The reaction mixture was stirred at 95° C. under nitrogen atmosphere for 2 days. The reaction mixture diluted with toluene under ambient conditions, and the diluted reaction mixture was poured into methanol to precipitate the polymer. The isolated polymer was re-dissolved in THF and precipitated again by pouring the solution into methanol. The precipitation process was repeated once more. Random polymer Pg was obtained in 44% yield as white solid. Mw 137000 Da. Polydispersity (PDI) 2.4. Tg 102° C. Relative permittivity (at 1 kHz, 25° C.) 3.3.

Example 14

Preparation of Polymer Ph

[0227] ##STR00054##

[0228] Compound 9a (1.2 g, 8.7 mmol), compound 2d (1.5 g, 5.8 mmol) and dicumyl peroxide (39 mg, 0.14 mmol, 1% eq) were dissolved in anhydrous toluene (6 mL). The solution was degassed by three cycles of freeze-pump-thaw. The reaction mixture was stirred at 95° C. under nitrogen atmosphere overnight. The reaction mixture diluted with toluene under ambient conditions, and the diluted reaction mixture was poured into methanol to precipitate the polymer. The isolated polymer was re-dissolved in THF and precipitated again by pouring the solution into methanol. The precipitation process was repeated once more. Random polymer Ph was obtained in 48% yield as white solid. Mw 115000 Da. Polydispersity (PDI) 2.1. Tg 138° C. Relative permittivity (at 1 kHz, 25° C.) 3.4.

Example 15

Preparation of Polymer Pi

[0229] ##STR00055##

[0230] Compound 9a (0.8 g, 6.3 mmol), compound 2e (1.2 g, 4.2 mmol) and 1,1′-azobis(cyclohexanecarbonitrile) (25 mg, 0.10 mmol, 1% eq) were dissolved in anhydrous toluene (6 mL). The solution was degassed by three cycles of freeze-pump-thaw. The reaction mixture was stirred at 95° C. under nitrogen atmosphere overnight. The reaction mixture diluted with toluene under ambient conditions, and the diluted reaction mixture was poured into methanol to precipitate the polymer. The isolated polymer was re-dissolved in THF and precipitated again by pouring the solution into methanol. The precipitation process was repeated once more. Random polymer Pi was obtained in 42% yield as white solid. Mw 140000 Da. Polydispersity (PDI) 1.9. Tg 107° C. Relative permittivity (at 1 kHz, 25° C.) 3.0.

Example 16

Preparation of a Top-Gate, Bottom-Contact Field Effect Transistor Comprising Polymer Pb as Dielectric Material

[0231] Gold was sputtered onto PET substrate to form approximately 40 nm thick gold source/drain electrodes. A 0.75% (weight/weight) solution of the diketopyrrolopyrrole (DPP)-thiophenepolymer 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 (1,000 rpm, 30 seconds). The wet organic semiconducting layer was dried at 90° C. on a hot plate for 60 seconds. A solution of 100 mg/ml of polymer Pb, prepared as described in example 8, in butyl acetate, containing 4% by weight of a 2,7-bis[2-(4-azido-2,3,5,6-tetrafluoro-phenyl)ethynyl]-9,9-dihexyl-fluorene as crosslinker based on the weight of polymer Pb, was filtered through a 0.45 micrometer filter. The solution was spin-coated (1500 rpm, 30 seconds) on the semiconducting layer. The wet dielectric layer was pre-baked at 90° C. for 2 minutes and subsequently UV-cured by irradiating at 365 nm with a dosage of ˜60mJ/cm.sup.2 under ambient conditions. Gate electrodes of gold (thickness approximately 80 nm) were evaporated through a shadow mask on the dielectric layer.

[0232] The top gate, bottom contact (TGBC) field effect transistor was measured by using a Keithley 4200-SCS semiconductor characterization system.

[0233] 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 at a source voltage V.sub.ds of −3V (triangle), respectively, −30V (square) is shown in FIG. 1.

[0234] The charge-carrier mobility was extracted in the saturation regime from the slope of the square root drain current I.sub.ds.sup.1/2 versus gate-source voltage V.sub.gs. The threshold voltage V.sub.on was obtained using the following equation: μ=2I.sub.ds/{(W/L)Ci(V.sub.gs−V.sub.on).sup.2}, wherein Ci is the capacitance per unit of the dielectric layer.

[0235] The average values of the charge carrier mobility μ, the I.sub.on/I.sub.off ratio and the onset voltage V.sub.on for the organic field effect transistor are given in table 1.

TABLE-US-00001 TABLE 1 charge carrier mobility V.sub.on Ig @ −30 V Polymer [cm.sup.2/Vs] I.sub.on/I.sub.off [V] [A] Pb 0.132 8.15E+05 3 3.15E−07

Example 17

[0236] Preparation of Capacitor Comprising a Dielectric Layer Formed from Polymers Pb

[0237] A solution of 60 mg/ml of polymer Pb, prepared as described in example 8, in butyl acetate 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 (1000 rpm, 30 seconds). The wet dielectric layer was dried at 90° C. for 2 minutes on a hot plate to obtain a ˜400 nm thick layer. 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).

[0238] The capacitor obtained was characterized in the following way: The relative permittivity was deduced from the capacitance measured with Agilent E4980A Precision LCR Meter (signal amplitude 1 V).

[0239] The results are depicted in table 2.

TABLE-US-00002 TABLE 2 Frequency [Hz] Relative permittivity 40 3.16 4000 3.18 1000000 3.16

Example 18

[0240] Stability of the Cured Dielectric Layer Formed from Polymer Pb Towards Solvent Dissolution

[0241] Crosslinking test was performed by utilizing a dielectric solution of 80 mg/ml polymer Pb, prepared as described in example 8, in butyl acetate containing 4% by weight a 2,7-bis[2-(4-azido-2,3,5,6-tetrafluoro-phenyl)ethynyl]-9,9-dihexyl-fluorene as crosslinker based on the weight of polymer Pb. The solution 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 dielectric layer was pre-baked at 90° C. for 2 minutes on a hotplate to obtain a ˜500 nm thick film. The dielectric layer was exposed to 365 nm UV radiation under ambient conditions by employing a dosage of ˜60mJ/cm.sup.2. Post baking was done at 90° C. for 2 min on hotplate. Dielectric layer was developed by immersing the dielectric layer into butyl acetate for 1 minute followed by nitrogen blowing and drying 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). The average film retention ratio was 97%.

Example 19

Preparation of a Top-Gate, Bottom-Contact Field Effect Transistor Comprising Polymer Pe as Dielectric Material

[0242] Gold was sputtered onto PET substrate to form approximately 40 nm thick gold source/drain electrodes. A 0.75% (weight/weight) solution of the diketopyrrolopyrrole semiconducting polymer of example 1 of WO 2013/083506 in toluene was filtered through a 0.45 micrometer polytetrafluoroethylene (PTFE) filter and then applied by spin coating (1,200 rpm, 30 seconds). The wet organic semiconducting layer was dried at 90° C. on a hot plate for 60 seconds. A solution of 100 mg/ml of polymer Pe, prepared as described in example 11, in mixture of propylene glycol monomethyl ether acetate (PGMEA) and butylacetate (BuAc) (70/30), containing 3% by weight of 2,7-bis[2-(4-azido-2,3,5,6-tetrafluoro-phenyl)ethynyl]-9,9-dihexyl-fluorene as crosslinker based on the weight of polymer Pe, was filtered through a 0.45 micrometer filter.

[0243] The solution was spin-coated (2000 rpm, 30 seconds) on the semiconducting layer. The wet dielectric layer was pre-baked at 90° C. for 2 minutes and subsequently UV-cured by irradiating at 365 nm with a dosage of ˜100mJ/cm.sup.2 under ambient conditions. Afterwards, the device was wetted with a solution of PGMEA/BuAc (70/30) for 1 minute to develop the dielectric and spin-coated dry at (2000 rpm, 1 min) followed by a post-bake of 5 minutes at 90° C. on a hot plate. Gate electrodes of gold (thickness approximately 80 nm) were evaporated through a shadow mask on the dielectric layer.

[0244] The top gate, bottom contact (TGBC) field effect transistor was measured by using a Keithley 2612B sourcemeter.

[0245] 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 at a source voltage V.sub.ds of −5V (triangle), respectively, −30V (square) is shown in FIG. 2.

[0246] The charge-carrier mobility was extracted in the saturation regime from the slope of the square root drain current I.sub.ds.sup.1/2 versus gate-source voltage V.sub.gs. The threshold voltage V.sub.on was obtained using the following equation: μ=2I.sub.ds/{(W/L)Ci(V.sub.gs−V.sub.on).sup.2}, wherein Ci is the capacitance per unit of the dielectric layer and W/L is 25. The thickness of the dielectric has been measured by a profilometer to 468 nm.

[0247] The average values of the charge carrier mobility μ, the I.sub.on/I.sub.off ratio and the onset voltage V.sub.on for the organic field effect transistor are given in table 3.

TABLE-US-00003 TABLE 3 charge carrier mobility V.sub.on Ig @ −30 V Polymer [cm.sup.2/Vs] I.sub.on/I.sub.off [V] [A] Pe 0.27 1.7E+05 −0.5 2E7

Example 20

Preparation of a Capacitor Comprising Polymer Pe as Dielectric Material

[0248] A solution of 100 mg/ml of polymer Pe, prepared as described in example 11, in PGMEA/BuAc (70/30) 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 (2000 rpm, 30 seconds). The wet dielectric layer was dried at 90° C. for 2 minutes to obtain a 550 nm thick layer. Gold electrodes (area=3.0 mm.sup.2) were then vacuum-deposited through a shadow mask on the dielectric layer at <1×10.sup.−5 mbar

[0249] The capacitor obtained was characterized in the following way: The relative permittivity was deduced from the capacitance measured with Agilent 4284A Precision LCR Meter (signal amplitude 1 V).

[0250] The results are depicted in table 4.

TABLE-US-00004 TABLE 4 Frequency [Hz] Relative permittivity 20 3.57 100 3.55 100000 3.45

Example 21

[0251] Stability of the Cured Dielectric Layer Formed from Polymer Pe Towards Solvent Dissolution

[0252] Crosslinking test was performed by utilizing a dielectric solution of 40 mg/ml polymer Pe (Mw 130′000) in butyl acetate containing 4% by weight a 2,7-bis[2-(4-azido-2,3,5,6-tetrafluorophenyl)ethynyl]-9,9-dihexyl-fluorene as crosslinker based on the weight of polymer Pe. The solution 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 pre-baked at 90° C. for 2 minutes on a hotplate to obtain a 520 nm thick film. A shadow mask was aligned on top of the dielectric layer before curing using 365 nm (radiation dosage 60 mJ/cm2) in ambient conditions, in the presence of oxygen. 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. 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). The average film retention ratio was 94%.

Comparative Example 1

[0253] Stability of a Cured Dielectric Layer Formed from Polystyrene Towards Solvent Dissolution

[0254] Crosslinking test was performed by utilizing a dielectric solution of 40 mg/ml polystyrene (Mw˜2,000,000, supplied by Pressure Chemicals) in butyl acetate containing 4% by weight a 2,7-bis[2-(4-azido-2,3,5,6-tetrafluoro-phenyl)ethynyl]-9,9-dihexyl-fluorene as crosslinker based on the weight of polystyrene. The solution 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 pre-baked at 90° C. for 2 minutes on a hotplate to obtain a 520 nm thick film. A shadow mask was aligned on top of the dielectric layer before curing using 365 nm (radiation dosage 60 mJ/cm2) in ambient conditions, in the presence of oxygen. 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. 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). The average film retention ratio was 50%.

[0255] Example 21 and Comparative Example 1 show that the stability of the cured dielectric layer formed from polymer Pe towards solvent dissolution is higher than the stability of the cured dielectric layer from polystyrene (Mw˜2,000,000, supplied by Pressure Chemicals) towards solvent dissolution when the polymer is applied, cured and developed under ambient conditions.