GB2581229A

GB2581229A - Electronic device with improved adhesion between fluorinated dielectric layer and polyolefinic layer and method for producing such electronic device

Info

Publication number: GB2581229A
Application number: GB1915760.1A
Authority: GB
Inventors: Bhintade Rashmi
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2018-11-07
Filing date: 2019-10-30
Publication date: 2020-08-12
Also published as: GB201915760D0

Abstract

An electronic device comprising a fluorinated dielectric layer and a polycycloolefinic e.g. polynorbornene layer adjacent to each other. The polycycloolefic layer comprising fluorinated polycycloolefin with partially of fully fluorinated monomer units. The fluorinated dielectric layer does not comprise and polycycloolefin and adhesion between a fluorinated dielectric layer and the polycycloolefinic layer is at least 1.0N/2.5cm as determined by a 90° peel test. Also shown is a method of producing the electronic device comprising depositing a formulation of polycycloolefinic polymer onto a fluorinated dielectric layer.

Description

Intellectual Property Office Application No. GII1915760.1 RTM Date:29 May 2020 The following terms are registered trade marks and should be read as such wherever they occur in this document:

DECON

Intellectual Property Office is an operating name of the Patent Office www.gov.uk/ipo Electronic Device with Improved Adhesion between Fluorinated Dielectric Layer and Polyolefinic Layer and Method for Producing such Electronic Device

Technical Field

The present application relates to a device with improved adhesion between a fluorinated dielectric layer and a polycycloolefinic layer deposited thereon, ifhe present application also relates to a method for producing an electronic device by depositing a formulation onto a fluorinated dielectric layer, wherein the formulation comprises a polycycloolefin and at least one solvent having specific properties.

Background

In recent years, organic electronic devices, fe, electronic devices wherein at least one of the functional layers comprises a substantial amount of an organic material have been developed for a wide range of potential applications. As example of such functional layers, mention may be made of fluorinated dielectric layers.

One of the major challenges in organic electronic devices is to ensure that the resulting device is based on a "robust" stack, i.e. a sequence of functional layers and optional non-functional layers that adhere well to each other and do not easily delaminate under manufacturing and/or use conditions.

On the other hand, lower adhesion may be an advantage in some device production processes, which in some instances require the deposition of auxiliary processing layers, i.e. layers that aid in the production of the device but are subsequently at least partially removed and thus are not completely or not at all comprised in the finished device.

Generally, such auxiliary processing layers are made of different materials that are different from the materials comprised in the functional layers of a device. This necessitates a significant number of materials that have to be kept in stock, It would therefore be advantageous if at least some of these materials could be used for more than one purpose, for example, that they could be used as processing aid and as functional material. -2 -

Consequently, it is an object of the present application to provide for an improved device, preferably for an improved organic electronic device.

it is also an object of the present application to provide for an improved device, preferably for an improved organic electronic device, being characterized by improved adhesion between layers, particularly between dielectric layers.

It is also an objective of the present application to provide for an improved method of producing such device, preferably such organic electronic device.

Suinman/ The present inventors have now surprisingly found that the above objects may he attained either individually or in any combination by the present process for producing a device and by the device produced by such process.

The present application therefore provides for an electronic device comprising fluorinated dielectric layer and a polycycloolefinic layer adjacent to each other, said polycycloolefinic layer comprising a fluorinated polycycloolefin comprising partially or fully fluorinated monomeric units Ml', wherein the fluorinated dielectric layer does not comprise any polycycloolefin, and adhesion between the fluorinated dielectric layer and the polycycloolefinic layer is at least 1.0 NI/2,5 cm as determined by a 90' peel test.

The present application therefore also provides for a method of producing the electronic device of any one or more of claims 1 to 9, said method comprising the steps of a) providing a fluorinated dielectric layer, and b) depositing a formulation comprising a polycycloolefinic polymer and at least one solvent onto said fluorinated dielectric layer to form a polycyclolefinic layer, wherein said polycycloolefinic polymer comprises partially or fully fluorinated monomeric units, and wherein said at least one solvent has a polar component 5p of the Hansen solubility of at most 4.0 NAPa.

Brief description of the drawings

Figure 1 shows a general schematic representation of an exemplary top gate organic field-effect transistor (OFET).

Detailed description

For the purposes of the present application an asterisk ("*" or "*") is used to denote a linkage to an adjacent unit or group, including for example, in case of a polymer, to an adjacent repeating unit or any other group.

For the purposes of the present application the term "organyl group" is used to denote any organic substituent group, regardless of functional type, having one free valence at a carbon atom (see also International Union of Pure and Applied Chemistry, Compendium of Chemical Terminology, Gold Book, Version 2.3.3, 2012-02-24, page 1040).

For the purposes of the present application the term "organoheteryl group" is used to denote any univalent group comprising carbon, said group thus being organic, but having the free valence at an atom other than carbon (see also International Union of Pure and Applied Chemistry, Compendium of Chemical Terminology, Gold Book, Version 2.3.3, 2012-02-24, page 1039).

For the purposes of the present application the term "carbylgroup" includes both, organyl groups and organoheteryl groups.

For the purposes of the present application the term "hydrocarbyl group" is used to denote univalent groups formed by removing a hydrogen from a hydrocarbon (see also International Union of Pure and Applied Chemistry, Compendium of Chemical Terminology, Gold Book, Version 2.3.3, 2012-02-24, page 694).

For the purposes of the present application the term "hydrocarbylene group" is used to denote divalent groups formed by removing two hydrogen atoms from a hydrocarbon, the free valences of which are not engaged in a double bond (see also International Union of Pure and Applied Chemistry, Compendium of Chemical Terminology, Gold Book, Version 2.3.3, 2012-02-24, page 694). -.4-.

For the purposes of the present application the term "partially fluorinated" is used to denote that one or more hydrogen atoms of a compound, but not all, have been replaced with fluorine.

For the purposes of the present applic.ation the term "fully fluorinated" or "per fluorinated" is used to denote that all hydrogen atoms of a compound have been replaced with fluorine. Such fully fluorinated compounds may also he identified by the prefix "perfluoro".

For the purposes of the present application the term "monomer" is used to denote a substance composed of monomer molecules, and the term "monomer molecule' is used to denote a molecule which can undergo polymerization thereby contributing constitutional units to the essential structure of a macromolecule or polymer (see also international Union of Pure and Applied Chemistry, Compendium of Chemical Terminology, Gold Book, Version 2.3.3, 2012-02-24, page 662).

For the purposes of the present application the term 'constitutional unit" is used to denote an atom or group of atoms (with pendant atoms or groups, if any) comprising a part of the essential structure of a macromolecule, an oligomer molecule, a block or a chain (see also International Union of Pure and Applied Chemistry, Compendium of Chemical Terminology, Gold Book, Version 2.3.3, 2012-02-24, page 326).

For the purposes of the present application the term "hornopolymer" is used to denote a polymer derived from one species of (real, implicit or hypothetical) monomer (see also International Union of Pure and Applied Chemistry, Compendium of Chemical Terminology, Gold Book, Version 2.3.3, 2012-02-24, page 685).

For the purposes of the present application the term "copolymer" is used to denote a polymer derived from more than one species of monomer (see also international Union of Pure and Applied Chemistry, Compendium of Chemical Terminology, Gold Book, Version 2,3.3, 2012-02-24, page 335). -5 -

For the purposes of the present application the term "block polymer" is used to denote a polymer, wherein in the constituent macromolecules adjacent blocks are constitutionally different, i.e. adjacent blocks comprise constitutional units derived from different species of monomer or from the same species of monomer but with a different composition or sequence distribution of constitutional units (see also International Union of Pure and Applied Chemistry, Compendium of Chemical Terminology, Gold Book, Version 2.3.3, 2012-02-24, page 171).

For the purposes of the present application, the term "pendant group" is used to denote an offshoot, neither oligorneric nor polymeric from a chain, particularly from the backbone chain of a polymer (see also International Union of Pure and Applied Chemistry, Compendium of Chemical Terminology, Gold Book, Version 233, 2012-02-24, page 1076).

In general terms the present application provides for an electronic device, preferably an organic electronic device, comprising a fluorinated dielectric layer and a polycycloolefinic layer adjacent to each other. Further, the present application provides for a method for producing such electronic device. The term "adjacent to each other " is used to denote that the two layers are neighboring to each other, i.e. that the polycycloolefinic layer is applied to the surface (or part of the surface) of the fluorinated dielectric layer or vice versa, depending upon the device architecture.

The present inventors have been greatly surprised by the fact that the devices produced in accordance with the present application are characterized by a vastly improved adhesion between the fluorinated dielectric layer and the polycycloolefinic layer.

Thus, the present device comprising fluorinated dielectric layer and a polycycloolefinic layer adjacent to each other is characterized by the adhesion between said fluorinated dielectric layer and said polycycloolefinic layer being at least 1.0 N/2.5 cm, more preferably at least 1.5 N/2.5 cm, even more preferably at least 2.0 N/2.5 cm" even more preferably at least 2.5 N/2.5 cm, and most preferably at least 3.0 N/2.5 cm, determined as described in the test methods. -6 -

FLUORINATED DIELECTRIC LAYER

For the purposes of the present application the term "fluorinated dielectric layer" is used to denote a layer, preferably a layer comprised in an organic electronic device, that comprises one or more fluorinated dielectric materials different from a polycycloolefin in at least 50 wt%, for example in at least 60 wt%, 70 wt%, 80 wt%, 90 wt%, 95 wl%, 96 wt%, 97 w1%, 98 wt%, 99 wt%, 99,5 wt%, 99.6 wt%, 99.7 wt%, 99,8 wt% or 99.9 wt%, with wt% relative to the total weight of said fluorinated dielectric layer, or essentially consists of such one or more fluorinated dielectric materials.

The fluorinated dielectric material is not particularly limited. In general terms, the fluorinated dielectric material comprises, or preferably consists of, a fluoropolyrner comprising or, preferably, consisting of monomeric units derived from partially or fully fluorinated monomers, such monomers not being a cycloolefin, Suitable fluoropolymers may, for example, be homopolymers, random copolymers or block copolymers. Such materials are generally known to the skilled person and can be obtained from various commercial sources.

Suitable examples of partially or fully fluorinated monomers may at each occurrence independently be selected from the group consisting of the following: Group A perfluorinated olefins having from two to eight carbon atoms, such as for example tetrafluorcethylene or hexafluoropropylene; Group B partially fluorinated olefins having fronii two to eight carbon atoms, such as for example vinylidene fluoride (F2C=CH2) vinyl fluoride (FIFC=CH7), 1,2-clifluoroethylene (HFC=CHF) or trifluoroethylene (F2Cri-CFFI); Group C (perfluoroalkyl}ethylenes of formula E12C=CR-C3 F23.1 with a being an integer from 1 to 10, preferably a being 1, 2, 3, 4, 5 or 6, most preferably a being 1, 2, 3 or 4; Group D partially fluorinated olefins, wherein one or more of the hydrogen atoms is independently of each other replaced with one selected from the group consisting of chlorine, bromine or iodine, such as for example ch orotrifluoroethylene (CIFOr-CF2); -7 -Group E perfluorovinylalkylethers of formula F2C=C-0-C,F2a42 with a being an integer from 1 to 10, preferably a being 1, 2, 3, 4, 5 or 6, most preferably a being 1, 2, 3 or 4; Group F partially or fully fluorinated diolefins of formula R1R2C=CR3-0-C(R4)2- (CR82)b-(0),--CR8=CR7R8, with b being 0, 1 or 2; c being 0 or 1; R1, R2, R3, P.4, R8, R8, R7 and R8 being at each occurrence independently selected from the group consisting of H, F, CI, alkyl having from 1 W 5 carbon atoms, and alkyl having from I to 5 carbon atoms with one or more, preferably all, hydrogen atoms substituted by F; and Group G partially or fully fluorinated 5-membered rings comprising at least one double bond, preferably partially or fully fluorinated dihydrofurans or dioxoles, preferably perfluorinated dihydrofurat» or dioxoles.

With regards to Group F, it is preferred that R', R2, Rs, R-S, R6, R7 and R8 are at each occurrence independently selected from the group consisting of H, F, CH3, CH2F, CHF2, and CH; and more preferred that R4, R2, R7 and R8 are F, and Rs, R4, Rs, and R6 are at each occurrence independently F or CF3; and most preferred that RI, R2, R3, R4, Preferred examples of the monomers of Group F are represented by the following formula (I) Fre= 0-CF2-02)b-(0),-CF---,CF2 with b being 0, 1 or 2; c being 0 or 1. Specific examples of the monomers of Group F may be selected from the following formulae (la) and (lb) F2C=CF-O-C12-CF2-0-CF=CF7 (la) F2C.:=CF-O-CF2-CF=CF2 (lb) With regards to Group G, preferred examples are represented by the following formula Op R5, R6, R7 and R8 are all F. -8 -wherein Rth, R11, R12 and R13 are at each occurrence independently selected from the group consisting of F, partially or fully fluorinated alkyl comprising from 1 to 5 carbon atoms and partially or fully fluorinated alkoxy comprising from 1 to 5 carbon atoms, Preferably R1°, R11; R12 and R13 are at each occurrence independentiy F or fully fluorinated alkyl comprising from 1 to 5 carbon atoms.

More preferably; Wu; R12 and R13 are at each occurrence independently F or -CF3. Most preferably, R.1° and R" are -CF3, and R12 and R1-3 are F. The fluoropolymer may comprise the monomeric units derived from the partially or fully fluorinated monomers preferably in at least SO mol%, more preferably in at east 60 mol% or 70 mol% or 80 mol% or 90 mol%, even more preferably in at least 95 mol% or 97 mol% or 99 mol%, still even more preferably in at least 99.5 mol% and most preferably consists of such at least one partially or fully fluorinated monomer, with mol% relative to the total number of repeat units comprised in the fluoropolyrner. The remainder of repeat units comprised in such fluoropolyrner may be derived from any suitable monomer, such as, for example, olefins having one or two double bonds. Exemplary olefins may be selected from the group consisting of ethylene, propylene, butene-1, butene-2, iso-butylene, butadiene, and any mixture of any of these.

The fluoropoi prier may optionally comprise repeat units derived from at least one fluorine-free monomer, i.e. from a monomer that does not comprise any fluorine atom. Suitable examples of the at least one fluorine-free monomer may at each occurrence independently be selected from the group consisting of (i) olefins having from 2 to 8 carbon atoms, suitable examples of which may be selected from the group consisting of ethylene, propylene, butene-1, butene-2, buta-1,3-diene, pentene-1, pentene-2, hexene-1, hexene-2 and octene-1, with ethylene, propylene, butene-1 and hexene-i being preferred; (ii) vinyl monomers, such as vinyl chloride; (iii) acrylate monomers, such as methyl rnethacrylate; and (iv) styrene monomers, such as styrene or methylstyrene.

The respective polymers are obtained by polymerization of one or more of the above monomers by methods well known to the skilled person, for example, by radical polymerization. In general terms, such polymerization is based on rendering an olefin monomer (A) into an alkanecily1 constitutional unit (A') as schematically shown below. R\ /R / \

R

(A) (A') with R denoting any carbyl group.

Preferably the fluoropolymer is an amorphous fluoropolymer. Preferred examples of amorphous fluoropolymers may be selected from the group of polymers comprising, preferably consisting of, a first monomeric unit, at each occurrence independently derived from a monomer of Group E as defined above or a monomer of Group G as defined above, and an optional second monomeric unit, at each occurrence independently derived from a monomer selected from the group consisting of any of Groups A, B, C and D as defined above, and olefins as defined above.

An example of a suitable amorphous fluoropolymer comprises, preferably consists of, monomeric units derived from perfluorinated dioxole and at least one olefin. Said at least one olefin may be selected from the group consisting of monomers of any of Groups A, B. C and D as defined above as well as fluorine-free olefins having from 2 to 8 carbon atoms as defined above.

Another example of a suitable amorphous fluoropolymer comprises, preferably consists of, constitutional units derived from the monomers of Group G, for example of the following formula (II'), and optionally further constitutional units of formula *-CF2i-CF2-4.

-10 -(In Fp-OF / °N 7CF2 0E2 Such fluoropolymers are, for example, commercially available from AGC Chemicals Europe as CytopTM, or from Du Pont de Nemours as TeflonTm AF. Specific examples of suitable and commercially available amorphous fluoropolymers are Cytop 1.0 809M® or Cytop 107M® from AGC Chemicals, Other examples of suitable fluoropolymers are, for example, Teflon AP 1600 or 2400 from DuPont de Nemours

POLYCYCLOOLEEINIC LAYER

The polycycloolefinic layer comprises a fluorinated polycycloolefin, preferably consists of a fluorinated polynorbornene. Said fluorinated polynorbornene may be partially fluorinated or perfluorinated, and is preferably partially fluorinated. Partially fluorinated polycycloolefins may be obtained either by the polycycloolefin comprising, or preferably consisting of, partially fluorinated monomers, or alternatively by the polycycloolefin consisting of non-fluorinated monomers and partially or fully fluorinated monomers.

For the purposes of the present application the term "polynorbornene is used to denote a polymer comprising norbornadiy1 monomeric units of generalized and simplified formula (B') or derivatives thereof obtained by addition polymerization of norbornene monomer of generalized and simplified formula (B) or derivatives thereof.

(B) (W) In case of it being a homopolymer said fluorinated polycycloolefin comprises partially or fully fluorinated pendant groups. in case of it being a copolymer, said fluorinated polycycloolefin comprises partially or fully fluorinated pendant groups as well as non-fluorinated pendant groups, i.e. pendant groups that do not comprise fluorine. Expressed differently, a homopolymer consists of constitutional units M1', and a copolymer of constitutional units M1' and constitutional units M2', with M1' being a constitutional unit comprising a fully or partially fluorinated pendant group, and with M2' being a constitutional unit that does not comprise fluorine. Within any fluorinated polycycloolefin, or M2' or both may at each occurrence be selected independently from one another.

A fluorinated polycycloolefin suitable for the present application may be selected from the group consisting of (i) a homopolymer of general formula -[1/11.7-1,1-, wherein all M1' are the same; (ii) a copolymer of general formula -1_Mri1,,r, wherein Mt is at each occurrence selected independently and wherein at least one M1' differs from the others; (iii) a block copolymer of general formula --[Ml'i-],1-[M21,2-; and (iv) a random copolymer comprising constitutional units and constitutional units MT in random order, and preferably is a random copolymer.

ml and m2 are integers and are selected such that the weight average molecular weight (Mw) of the fluorinated poiycycloolefin is preferably at least 5,000 g/mol or 10,000 g/mol or 20.000 g/mol or 30,000 g/mol or 40.000 g/mol or 50,000 g/mol, and preferably is at most 500,000 g/mol or 450,000 g/mol or 400,000 g/mol or 350,000 g/mol or 300,000 g/mol or 250,000 Wind or 200,000 g/mol or 150,000 g/mol or 100,000 g/mol, determined by PGC as described herein.

Molecular weights of the polycycloolefins may be determined by gel permeation chromatography (GPC) on commercially available equipment, having two Phenomenex Phenogel Linear Column and a Phenogel 106 A Column (ail columns are 10 ttm packed capillary columns) and a refractive index detector, in chlorobenzene at 50QC using commercially available narrow molecular weight standards of polystyrene for calibration.

Preferably said fluorinated polycycloolefin comprises first constitutional unit M1' in at least 20 mol%, preferably in at least 25 mol%, more preferably in at least 30 mol%, even more preferably in at least 35 mol%, still even more preferably in at -12 -least 40 mol%, and most preferably in at least 45 mol%, with mol% *=5p ct to the total number of constitutional units, i.e. the sum of M1' and M2'.

Constitutional units M1' and M2' may, for example, be represented by general formulae (lila') and (111b1), respectively, and are derived by addition polymerization of the respective monomers tyll with general formula (111a) and M2 with general formula (111b) (11a) (R20R2.1C)" (111b) (nib') with d, e, R2u and R21 as defined herein, as well as any substituted norbomene and the respective monomeric unit.

d is an integer from 0 to 5, e.g. 0, 1, 2, 3, 4 or 5. Preferably d is an integer from 0 to 3, e.g. 0, 1, 2 or 3. More preferably d is 0 or 1. Most preferably d is 0, e is an integer of from 0 to 5, e.g. 0, 1, 2, 3,4 or 5. Preferably e is an integer from 0 to 3, e.g. 0, 1, 2 or 3. More preferably e is 0 or 1. Most preferably e is O. 1S2') and Ril may at each occurrence independently be selected from the group consisting of H, F and -CF, and preferably are at each occurrence independently H or F, and most preferably are H Preferred constitutional units Mt and M2' may, for example, be represented by general formulae (IVas) and (1\./b;) and are derived by addition polymerization of the respective monomers M1 of general formula (IVa) and M2 of general formula (IVb) (IVal IVa') (R20R21C), (IVb (IVEY) wherein d, e, 0, R21, R22, R23 and R24 are as defined herein.

Q is selected from the group consisting of -012-, -CI-12-CH2-, -CF2-CF2-and 0.

Preferably Q is selected from the group consisting of -CH,, -CF17-CF12-and 0. Most preferably 0 is -CH7-.

For any monomer M1 and constitutional unit Mr at least one, and preferably only one, of pendant groups W1, R22, R23 and R22' comprises a partially or fully fluorinated group.

Preferably in Ml. and Mr, R22, R23, R24 and R25 are independently of each other hydrogen, fluorine, or *-(R25h -R27 with f being 0 or 1, and R25 and R27 as defined herein. Preferably, only one of R22, R23, R24 and R)s is -(R26),-R22, with f, R26 and R24 R22 as defined herein. It is also possible to two of R22. R23, and R26 together form a cycloalkane ring, which may be partially or fully fluorinated.

Preferably in M1 and MI. R25 is at each occurrence independently selected from the group consisting of -0-(R28),-, -C(=0)-(R23)e -0-C(=0)-(R28), -, -0(=0)0'4R28), -and -R28-with g being 0 or 1 and R22 being at each occurrence independently 14 -selected from the group consisting of -[(CH2)h) -(CHF)ii2HCF2)hs -1 with h = hi + h2 + h3 and h being an integer of from 1 to 10, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. Preferably R28 is at each occurrence independently -(CH2)h-or -(CF2)h-, and more preferably is at each occurrence independently selected from the group consisting of -CH2-, -CH2-CH2-, -CF2-and -CF2-CF2-.

Preferably in Ml. and M1', R21 is at each occurrence dependently selected horn the group consisting of partially or fully fluorinated alkyl haying from 1 to 20, preferably from to 10 carbon atoms; and partially or fully fluorinated aryl haying from 6 to 20, preferably from 6 to 10 carbon atoms, wherein said partially or fully fluorinated aryl may optionally be substituted with CjHkFm with i being an integer of from 1 to 20, preferably from 1 to /0, with i being 1, 2, 3, 4, 6 and 8 being particularly preferred, and k + m = 2i + 1.

Preferred examples of suitable monomers Mi may be selected from the group consisting of the following formulae (V-01.) to (V-14) NBC,IF9 (V-01) NBCH2C5F5 (V-02) NBC6F5 (V-03) NBCH2C512 (V-04) NBCH2C5H4CF3 (V-05) NBalkylC6F5 (V-06) (CH,) C.)bF", a -15 -

CFH

FPCNB (V-7) FHCNB (V-8) FOCHNB (V-9) FPCHNB (V-10) CBPFAcNB (V-11) PPVENB (V-12) D OxoTCNB (V-13) PFBTCNB (V-14) For an monomer M2 and constitutional unit MT pendant. groups R11, R22 n2 and Ftbl do not comprise fluorine.

-16 - 4 23 and -2 22, R, R2 5 Preferably in M2 and M2', R F. are independently of each other hydrogen, or -(R26); -R27 with f being 0 or 1, and R26 and R27 as defined herein. Preferably, only one of F122, R23, R24 and R25 is -(R26)f -R21, with f, R26 and R21 as defined herein. It is also possible to two of R22, R23, R24 and R25 together form a cycloalkane ring.

Preferabiy in M2 and M2'. R26 is at each occurrence independently selected from the group consisting of -0-(R28),-, --C(=0)-(R28), --0-C(=0)-(R28), -, and -R28-with g being 0 or 1 and R28 being at each occurrence independently selected from the group consisting of -(CF12)h-, with h being an integer of from 1 to 10, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. Preferably R-?a is at each occurrence independently -CH-or -CH2-CH2-.

Preferably in M2 and M2', R" is at each occurrence independently selected from the group consisting of alkyl having from 1 to 20, preferably from 1 to 10 carbon atoms; and aryl having from 6 to 20, preferably from 6 to 10 carbon atoms, wherein said aryl may optionally he substituted with CiHk with i being an integer of from 1 to 20, preferably from 1 to 10, with i being 1, 2, 3, 4, 6 and 8 being particularly preferred, and k = 2i + 1.

Preferred examples suitable monomers M2 may be selected from the group consisting of the foil ng formulae (V1-01.) to (V1-40) Methyl H exy I NB (V1-01) MeNB (V1-02) BuNB (V1-03) HexNB (V1-04) 17 - ()GANS (10-05) DecNB (VF-06) PENB (VI-07) TD (1,0-08) Me0AcNB (VI-09) NBXOH (VI-10) NBCH2Gly0Ac (1.0-11) NBCH2Gly0H (VI-12) NBTON (,1-13) NBTODD (VI-14) DCPD (VI-15) CH2CH2OAC CA-12CH,OH (OH2CH20)2Me (CH2CH20)3Me NPCHMNB (V1-21.) DMM1MeNB (Vi-22) D AIE'N 011-23) 18 -6 1 7 7 EONB (1/1-16) tv1GENB -17) AkSiNB (V1-1. , El ArSiNB (11-19) Me MCHMNB (V1-20) 19 -DMMIPrNB DIMMIBuNB (VI-25) DMMIFIxNB (VI-26) Et.PhDM NB (VI-27) MMIIVieNB (VI-28) MINB (VI-29) MIENB (VI-30) -20 -DHNMINB (10-31) Me0C1nnNB (40-32) CinnNB (40-33) EtMe0CinnNB (VI-34) MeCoumNB (VI-35) EtCournNB (VI-36) EtPhIndNB (40-37) PhIndNB (11-38) Si(OC2H5)3

TESNB

PMNB

With regards to formulae (V-01) to (V44) and (VI-01) to (VI-40) it is noted that "Me" means methyl, "Et" means ethyl, "OMe-p" means para-methoxy, "Ph" and "C6H5" mean phenyl, "C61-14" means phenylene, "C6E5" means pentafluorophenyl, "OAc" means acetate, "PFAc" means -0C(0)-C7F15, and for each of the above subformulae having a methylene bridging group (a CH) covalently bonded to both the norbornene ring and a functional group), it will be understood that the methylene bridging group can be replaced by a covalent bond or -(CH2),, and n is an integer from 1 to 6.

It is further noted that the monomers of, for example, formulae (VI-16), (VI-17) and (VI-22) to (VI-30) with reactive pendant groups may be used to induce crosslinking in the fluorinated polycycloolefin.

While each Formula (lila), (Was), (111b), (IW), (IVa), (IVa'), (iVb), (1Vb;), (V-01) to (V- 14) and (VI-01.) to (VI-40) above are depicted without indication of any stereochernistry, it should be noted that generally each of the monomers, unless indicated otherwise, are obtained as diastereomeric mixtures that retain their configuration when converted into repeating units. As the exo-and endo-isomers of such diastereomeric mixtures can have slightly different properties, it should be further understood that preferred embodiments of the present invention are made to take advantage of such differences by using monomers that are either a mixture of isomers that is rich in either the exo-or emio-isomer, or are essentially the pure advantageous isomer.

Examples of norbornene monomers, poiyrners and methods for their synthesis are provided herein and can also be found in US 5,468,819, US 6,538,087, US 2006/0020068 Al, US 2007/0066775 Al and US 2008/01.94740 Al, which are incorporated into this application by reference. Exemplary polymerizations -22 -processes employing Group VIII transition metal catalysts are described in the aforementioned US 2006/0020068 Al.

ELECTRONIC DEVICE

The present inventors have found that organic electronic devices comprising two dielectric layers produced as described herein exhibit improved adhesion between these dielectric layers, i.e. the fluorinated dielectric layer and the polycycloolefinic layer. Thus the present devices comprise such two dielectric layers, preferably adjacent the semiconducting layer.

In general, the electronic device of the present application may be any type of electronic device. For example, the present electronic device may be selected from the group consisting of organic field effect transistors (OFET), thin film transistors (TFT), integrated circuits (IC), logic circuits, capacitors, radio frequency identification (RE-ID) tags, devices or components, organic light emitting diodes (OLED), organic light emitting transistors (OLET), flat panel displays, backlights of displays, organic photovoltaic devices (OPV), organic solar cells (0-SC), photodiodes, laser diodes, photoconductors, organic photodetectors (OPD), electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, charge injection layers, charge transport layers or interlayers in polymer light emitting diodes (PLEDs), Schottky diodes, planarising layers, antistatic films, polymer electrolyte membranes (REM), conducting substrates, conducting patterns, electrode materials in batteries, alignment layers, biosensors, biochips, security markings, security devices, and components or devices for detecting and discriminating DNA sequences. The present organic electronic device may preferably be selected from the group consisting of organic field effect transistors (OFET), organic thin film transistors (OTFT), organic light emitting diodes (OLED), organic light emitting transistors (OLET), organic photovoltaic devices (OPV), organic photodetectors (OPD), organic solar cells, laser diodes, Schottky diodes, photoconductors and photodetectors. More preferably the present organic electronic device is an organic field effect transistor (PFET) or an organic thin film transistor (OTFT).

A preferred example of the present organic electronic device is an organic field effect transistor, preferably comprising a gate electrode, a source electrode, a drain electrode, one or more insulating layers (preferably a gate insulating layer), and an organic semiconducting layer. Optionally an organic field effect transistor may also comprise one or more selected from the group consisting of substrate and charge transport layer. These layers in the OFET device may be arranged in any sequence, provided that the source electrode and the drain electrode are separated from the gate electrode by the insulating layers, the gate electrode and the semiconductor layer both contact the insulating layers, and the source electrode and the drain electrode both contact the semiconducting layer.

The (NET device according to the present invention can be a top gate device or a bottom gate device. Suitable structures of an OFET device are known to the skilled person and are described in the literature, for example in US 2007/0102696 Al.

Though the present invention will be described in more detail in respect to organic field effect transistors and organic Win film transistors, this is in no way intended to be limiting. Correspondingly the present also applies to any other of above listed electronic device comprising a fluorinated dielectric layer and a polycycloolefinic layer adjacent to each other.

Figure 1 shows a general schematic representation of an exemplary top gate organic field-effect transistor (OFET), including source and drain electrodes (2) provided on a substrate (1)" a semiconducting layer (3), a fluorinated dielectric layer (4) as defined above as gate insulator layer provided on the organic semiconducting layer (3), a polycycioolefinic layer (5) provided on the gate insulator layer, and a gate electrode (6). The area or space between the source electrode and the drain electrode is generally denoted as "channel area".

The gate, source and drain electrodes, the insulating layers, and the semiconducting layer in the OFET device may be arranged in any sequence, provided that the source and drain electrode are separated from the gate electrode by the insulating layers, the gate electrode and the semiconductor layer both contact the insulating layers, and the source electrode and the drain electrode both contact the semiconducting layer.

The OFET device can be a top gate device or a bottom gate device. Suitable structures and manufacturing methods of an OFET device are known to the skilled in the art and are described in the literature, for example in US 2007/0102696 Al.

Electrode As used herein, the term electrode is used for an element which is adapted to be electrically contacted and which is adapted to inject negative and/or positive charge carriers into the semiconducting layer and/or which is adapted to extract negative and/or positive charge carriers from the semiconducting layer.

For example, said electrode may be a source electrode and/or a drain electrode in an organic field effect transistor, wherein the source electrode and the drain electrode both contact the semiconducting layer such that a semiconducting channel connects the source and drain electrodes. Preferably, such electrodes are provided on a supporting layer or substrate. Examples of suitable supporting layers or substrates, as they may be referred to in the context of organic electronic devices, are given below.

The electrode material that may be used in the present invention for preparing organic electronic devices is not particularly limited, Suitable electrode materials include electrically conducting organic and inorganic materials, or blends thereof. Exemplary organic electrode materials or blends include polyaniline, polypyrrole, poly(3,4-ethylenedioxythiophene) (PEDOT) or doped conjugated polymers, further dispersions or pastes of graphite, As electrode material inorganic materials are preferred, which are preferably selected from metals and metal oxides. The types of metal and metal oxide that may be used in the present invention also include alloys and any blend of metals, any blend of metal oxides as well as any blend of metals and metal oxides.

Exemplary metals, which are particularly suitable as electrodes in organic electronic devices may be selected from the group consisting of gold (Au), silver (Ag), copper (Cu), aluminum (Al), nickel (Ni), palladium (Pd), platinum (Pt), titanium (Ti), calcium (Ca), molybdenum (Mc), scandium (Sc), and any blend thereof. Of these, gold, copper and silver are particularly preferred, since they bond very well to chalcogenol groups, Le., to groups -OH (hydroxyl), -SH (thiol), -SeH (selenol) and -TeH (tellurol), preferably to -SH. Silver is most preferred, since it is more stable than copper and cheaper than gold. Exemplary alloys, which are particularly suitable as electrodes in organic electronic devices include stainless steel (e.g., 332 stainless steel, 316 stainless steel), alloys of gold, alloys of silver, alloys of copper, alloys of aluminum, alloys of nickel, alloys of palladium, alloys of platinum, alloys of titanium, alloys of calcium, alloys of molybdenum and alloys of scandium.

Exemplary electrically conducting metal oxides include indium tin oxide (ITO), fluorine-doped tin oxide, tin oxide, zinc oxide, aluminum-doped zinc oxide, and any blend thereof.

Semiconducting layer The organic semiconducting layer comprises, preferable consists of, oneo organic semniconducting material as described in the following.

The organic semiconducting material is preferably selected from the group consisting of monomeric compounds (also referred to as "small molecule"), oligomers, polymers or blends of any of these, for example, including but not limited to blends of one or more monomeric compounds, one or more oligomers or one or more polymers. More preferably the organic semiconducting material is a polymer or a blend of polymers. Most preferably the organic semiconducting material is a polymer, The type of organic semiconducting material is not particularly limited. In general the organic semiconducting material comprises a conjugated system. The term "conjugated system" is herein used to denote a molecular entity or a part of a molecular entity whose structure may be represented as a system of alternating single and multiple bonds (see also International Union of Pure and Applied Chemistry, Compendium of Chemical Terminology, Gold Book, Version 2.3.3, 2014-02-24, pages 322-323).

An organic semiconducting material suited for use herein may, for example, be represented by the following formula (VII) -26 -wherein monomeric unit M and m are as defined herein. At each occurrence M may be selected independently.

With regards to formula (VII) m may be any integer from 1 to 100,000. For a monomer or monomeric unit m is 1; For an oligomer m is at least 2 and at most 10. For a polymer m is at least 11.

Preferably, the organic semiconducting material comprises one or more aromatic units. Expressed differently, with regards to formula (VU) M may be an aromatic unit. Such aromatic units preferably comprise two or more, more preferably three or more aromatic rings. Such aromatic rings may, for example, at each occurrence independently be selected from the group consisting of 5-, 6-, 7-and 8-membered aromatic rings, with 5-and 6-membered rings being particularly preferred.

These aromatic rings comprised in the organic semiconducting material optionally comprise one or more heteroatoms selected from Se, Te, P, Si, B, As, N, 0 or 5, preferably from Si, N. 0 or S. Further, these aromatic rings may optionally be substituted with alkyl, alkoxy, polyalkoxy, thicalkyl, acyl, aryl or substituted aryl groups, halogen; with fluorine being the preferred halogen, cyano, nitro or an optionally substituted secondary or tertiary aikylamine or arylamine represented by -N(111)(R"), where R' and R" are each independently H, an optionally substituted alkyl or an optionally substituted aryl, alkoxy or polyalkoxy groups are typically employed. Further, where R' and R" is alkyl or aryl these may be optionally fluorinated; The aforementioned aromatic rings can be fused rings or linked to each other by a conjugated linking group such as -C(T1)=C(T7)-; -N=N-, -N=C(R"I)-, where Ti and T2 each independently represent H; Cl, F, -,Ca'N or lower alkyl groups such as CiLl alkyl groups; R"' represents H, optionally substituted alkyl or optionally substituted aryl. Further', where R" is alkyl or aryl, it may he optionally fluorinated.

-27 -Further preferred organic semiconducting materials may be polymers or copolymers wherein the monomeric units M of formula (VII) may at each occurrence be independently selected from the group consisting of formulae (Al) to (A83) and (D1) to (D142)

N

SN N\ /N

N-N N-N (A4)

(A2) (A3) (Al) N.Se,N

P (A8) (AS) R103

NH

\R102R1311R102 (Al2) R102 (A9) (A10) (A11) (A17) (A18) (A21) (A22) R10.

R101 F;04 R102 N,n3 R 107 R"1 R (A15) (A16) (A1.4) R103

N N

N N R102 R102 (A20) (A24) (A19) (A23) (A25) (A26) (A27) (A28)

-29 -(A29) R102 Ek102 (A30) R102 Sc (A34) (AD.1) RR' R101---"(;se (A32) R101 o Se (A35) (A36)

-R1C)2 S,

N N N\ I N N,N, /. ii \ 1' N N p a 0

I

1O1 1 Di 11101 (A39) (A42) R102 \ N (A45) (A40) (A43) R101 [ Rth2 (A46) (A44) (A37) (A41) (A38) (A47) (A48) (A49) (A50) (A51) (A52) lot, N=N (A58)

S (A57) R102 R101 R103 R104 (A53) (A55) (A55)

0 (A61) (A60) (A62) (A63) (A64) -32 -R102 (A70) (A69) (A68) R 'al R102 (A66) (A67) R101 Ri03

S---R1021 R104 (A79) (A74)

N N R102 R103 \\ N"N (A71) oTh R. (A77) R"1 (A78) (A80) (A81) (A73) (A76) (A82) (D8) R101

-34 -(D10) (D5) (D2) R102 103 Ri" (D3) (D4) (D1.1) R102 /Se, 101'Se Se Se (D12) (D13) R102 (015) R.1°1 0 0 Ii (D18) (026) (027) (028) (D21) (020) (023) (024) R131 R1°1 Se \ p 0 R"32 (022) Fro R102 (025) 101 104 (014) (017) (019) r,102 FR'" (029) (030) 0 0 (033) IO2' Ai 03 R102, R10i \ Rio / Se (0J2 -36 -i \ R101 i 102 R

R R104 R10 Si (035) (036) (038) (039) (031) R101 R102 (037) A102

RI° 0 R103 A104 (040) (041) -37 -R104 (D43) R1°2\ (04.4) (D46)

S I' (D47)

_101 R1C2 N / Si (D49) R104 (D48) (D50) N, 1.102 (054)

R NJ

101 102 RwIN,.Rffi2 Si 1 N. R1"/ 04 R10.3/ 04 (D55) (057) (D61) (D56) Rmi (058) R102 193 191 \ R104 (060) (D62) 7"Sie R103/ Ria4 (053) -39 -SP N*

I

-7-"Se (D63) R107 R101 (D69) s (D67) (D64) (D66) (D68) F,103 R1 R104 (D70) R " -40 -R101 (D74) R131 R102 (D76) R \ R102 \ f S Ge S ---, NN,----* \\ 1/ (D78) (D77) (D73) R103 (D75) -41 -R.100 p:07 R103 R102 i 4103 ing 5 03 R10 (D80) R101 *-(D81) R101\ Pr'102 (D82) (D83) -42 -(D84) R101 102

R (D85) (D86) (D87) Ri°2 \

S n4 \ I R1116 (088) R1" 1" \ FR108\ Si, R1" (D90) R103 R104 fi (D91.) ir2

R (D92) r*.

R101/ R1112F R103' \R104 (D93) R132 (D96)

A (097) R103

101 ---4 (094) (0102) -44 -(D98) (D99) RR' R102, (D100) (D95) R'" R'm (D107) (0108) (D109) (0:104) R101,102 1-< (D105) (D106) R103\ "R1" Ge

R Si

-45 -R104 (D11.6) (D117) (D118) _10: R102

N R"3 R103

(D110) 9.1o5 R101) R102 03 R1a4 (0113) R101 (D119) (D120) (D111) (D112) (D114) (D115) (D121) (D122) -46 -R103 R102 (D123) ry03 (D124) (0125) P:" -I\ (D126) RThi\ .$102 \ct. --r-

es"' CRio4 (0129) (0131) (D128) R10 R102 1\

N

(D130) (D132) ** (0141) (0142) -47 -R105,, \ 104 R101 (0133) R!04 RI" R1" 102 irc 1.0

-X *

"4,101 R104 (0135) (11 k 101 R102 (0136) R103 (0137) (0139) (0140) (0138) (0134) N=N -48 -wherein R201 n102, -103 R'°4, Rims, R106 ' and Rws are independently of each other selected from the group consisting of H and 135 as defined herein.

Rs is at each occurrence independently a carbyl group as defined herein and preferably selected from the group consisting of any group RT as defined herein, hydrocarbyl having from 1 to 40 carbon atoms wherein the hydrocarbyl may he further substituted with one or more groups RP, and hydrocarbyl having from 1 to 40 carbon atoms comprising one or more heteroatoms selected from the group consisting of N, 0, 5, P. Si, Se, As, Te or Ge, with N, 0 and S being preferred heteroatoms, wherein the hydrocarbyl may be further substituted with one or more groups RT.

Preferred examples of hydrocarbyl suitable as Rs may at each occurrence be independently selected from phenyl, phenyl substituted with one or more groups R1, alkyl and alkyl substituted with one or more groups R', wherein the alkyl has at least 1, preferably at least 5 and has at most 40, more preferably at most 30 or 25 or 20, even more preferably at most 15 and most preferably at most 12 carbon atoms. It is noted that for example alkyl suitable as Rs also includes fluorinated alkyl, i.e. alkyl wherein one or more hydrogen is replaced by fluorine, and peraiorinated alkyl, i.e. alkyl wherein all of the hydrogen are replaced by fluorine.

Fe is at each occurrence independently selected from the group consisting of F" Br, Cl, -CN, -NC, -NCO, -NCS, -OCN, --SCN, --C(0)NR°R°°, -C(0)X°, --C(0)R°, --NH2, -Nee°, --SH, --SR°, --S03H, -.SOR°, -OH, --OR°, -NO2, --SF3 and -SiR°R°°5°°°. Preferred RT are selected from the group consisting of F, Br, Cl. -CN, -NC, -NCO, --NCS, -OCN, -SCN, -C(0)NR°5°°, -C(0)X°, -C(0)R°, -NH2, -Nee°, -SH" -SR°, -OH, -OR° and -SiR°R°°R°°°. Most preferred 5T is F. Ft°, fe° and Rare are at each occurrence independently of each other selected from the group consisting of H, F and hydrocarbyl having from 1 to 40 carbon atoms.

Said hydrocarbyl preferably has at least 5 carbon atoms. Said hydrocarbyl preferably has at most 30, more preferably at most 25 or 20, even more preferably at most 20, and most preferably, at most 12 carbon atoms. Preferably, R°, R°° and R°°° are at each occurrence independently of each other selected from the group consisting of H, F, alkyl, fluorinated alkyl, alkenyl" alkynyl, phenyl and fluorinated phenyl. More preferably, 11°, R°° and R°°°' are at each occurrence -49 -independently of each other selected from the group consisting of H, F. alkyl, fluorinated, preferably perfluorinated, alkyl, phenyl and fluorinated, preferably perfluorinated, phenyl.

it is noted that for example alkyl suitable as 13°, Rl'a and R" also includes perfluorinated alkyl, i.e. alkyl wherein all of the hydrogen are replaced by fluorine. Examples of suitable alkyls may be selected from the group consisting of methyl, ethyl, m-propyl, iso-propyl, n-butyl, iso-butyl, tert--butyl (or "t-butyl"), pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octaclecyl, nonadecyi and eicosyl (-C20H41).

X° is halogen. Preferably X° is selected from the group consisting of F, Cl and Br.

A hydrocarbyl group comprising a chain of 3 or more carbon atoms and heteroatoms combined may be straight chain, branched and/or cyclic, including Spiro and/or fused rings.

Hydrocarbyl suitable as Rs, Ro, K-00 and/or 13" may be saturated or unsaturated. Examples of saturated hydrocarbyl include alkyl. Examples of unsaturated hydrocarbyl may be selected from the group consisting of alkenyi (including acyclic and cyclic alkenyl)" alkynyl, allyl, alkylclienyl, polyenyl, aryl and heteroaryl.

Preferred hydrocarbyl suitable as R5, R°, fe and/or R°°° include hydrocarbyl comprising one or more heteroatorrs and may for example be selected from the group consisting of alkoxy, alkylcarbonyi, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy, alkylaryloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy.

Preferred examples of aryl and heteroaryl comprise mono-, hi-or tricyclic aromatic or heteroarornatic groups that may also comprise condensed rings.

Especially preferred aryl and heteroaryl groups may be selected from the group consisting of phenyl, phenyl wherein one or more CH groups are replaced by N, naphthalene, fluorene, thiophene, pyrrole, preferably N-pyrrole, furan, pyridine, preferably 2-or 3-pyridine, pyrirridine, pyridazine, pyrazine, triazole, tetrazole, pyrazole, imidazole, isothiazole, thiazole, thiadiazole, isoxazole, oxazole, oxadiazole, thiophene, preferably 2-thiophene, selenophene, preferably 2-selenophene, thieno[3,2-b]thiophene, thieno[2,3-b]thiophene, dithienothiophene, furo[3,2-b]furan, furo[2,3-b]furan, seleno[3,2-b]selenophene, seleno[2,3-b]selenophene, thieno[3,2-b]selenophene, thieno[3,2-blfuran, indole, isoindole, benzo[b]furan, benzo[b]thiophene, benzo[1,2-b;4,5-b]dithiophene, benzo[2,1-h;3,4-bldithiophene, quinole, 2- methylquinole, isoquinole, qui noxa II ne, quinazoline, benzotriazole, benzimidazole, benzothiazole, benzisothiazole, benzisoxazole, benzoxadiazole, benz.oxazole and benzothiadiazole.

Preferred examples of an aikoxy group, i.e. a corresponding alkyl group wherein the terminal CI-12 group is replaced by -0-, can be straight-chain or branched, preferably straight-chain (or linear). Suitable examples of such alkoxy group may be selected from the group consisting of rnethoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy, tetradecoxy, pentadecoxy, hexadecoxy, heptadecoxy and octadecoxy.

Preferred examples of alkenyl, i.e. a corresponding alkyl wherein two adjacent CF-i2 groups are replaced by -CI-1=CH-can be straight-chain or branched. It is preferably straight-chain. Said alkenyl preferably has 2 to 10 carbon atoms. Preferred examples of alkenyl may be selected from the group consisting of vinyl, prop-1-enyl, or prop-2-e.nyl, but-2-enyl or but-3-enyl, pent-1-enyl, pent-2-enyl, pent-3-enyl or pent-4-enyl, hex-1-enyl, hex-2-enyl, hex-3-enyl, hex-4-enyl or hex5-enyl, hept--1--enyl, hept-2-enyl, hept--3-enyi, hept--4-enyl, hept-5--erly1 or hept-6--enyl, oct--1-enyi, oct--2-enyl, oct-3-enyl, oct-4-enyl, oct-5-enyl, oct-6-enyl or oct-7-enyl, non-1-enyl, non-2-enyl, non-3-enyl, non-4-enyl, non-5-enyl, non-6-enyl, non-7-enyl, non-8-enyl, dec-1-enyl, dec-2-enyl, dec-3-enyl, dec-4-enyl, dec-5-enyl, dec-6-enyl, dec-7-enyl, dec-8-enyl and dec-9-enyl.

Especial./ preferred alkenyl groups are C2_C2-1_ k_nyl, C4-C7-3E-alkenyl, C5-C7-4-alkenyl, C5-C2-5-alkenyl and C-/-6-alkenyl, in particular C2-C2-1E-alkenyl, C1-C7-3Ealkenyi and Cs-C2-4-alkenyi. Examples of particularly preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyi, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 42-hexenyl, 4E-hexertyl, 47-heptenyi, 5-hexenyl, 6-heptenyl and the like. Alkenyl groups having up to 5 C atoms are generally preferred.

Preferred examples of oxaalkyi, i.e. a corresponding alkyl wherein one non-terminal CH2 group is replaced by -0-, can be straight-chain or branched, preferably straight chain. Specific examples of oxaalkyl may be selected from the group consisting of 2-oxapropyl (=methoxymethyl), 2-(=ethoxyrnethyl) or 3-oxabutyl (r2-methoxyethyl), 2-, 3-, or 4-oxapentyl, 2-, 3-, 4-, or 5-oxahexyl, 2-, 3-, 4-, 5-, or 6-oxabeptyl, 2-, 3-, 4-, 5-, 6-or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7-or 8-oxanonyl and 2-, 3-, 4-, 5-, 6-,7-, 8-or 9-oxadecyl.

Preferred examples of carbonyloxy and oxycarbonyl, i.e. a corresponding alkyl wherein one CH2 group is replaced by --0-and one of the * hereto adjacent CH2 groups is replaced by -C(0)-. may be selected from the group consisting of acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyioxymethyl, propionyloxyrnethyl, butyryloxymethyl, pentanoyloxyrnethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxy-carbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonypethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxycarbonyflethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl, and 4-(methoxycarbonyI)-butyl.

Preferred examples of th calkyl, i,e. where one CH2 group is replaced by -3-, may be straight--chain or branched, preferably straight-chain. Suitable examples may be selected from the group consisting of thlomethyl (-SCH3), 1-thioethyl (-SCH2CF12,), 1-thiopropyl (-SCH2CH2CH3), 1-(thiobutyl), 1-(thiopentyl), 1-(thiohexyl), 1-(thloheptyl), 1-(thiooctyl), 1.-(thiononyl), 1.-(thiodecyl), 1-(thioundecyl) and 1-(th iododecyl).

A fluoroalkyl group is preferably perfluoroalkyl C1f-2k], wherein i is an integer from 1 to 13, in particular CF3, 0,F, C31:7, C4F9, CsFit, C6f33, C2F16 or C2F17, very preferably C6F33, or partially fluorinated alkyl, in particular 1,1-difluoroalkyl, all of which are straight-chain or branched.

Alkyl, alkoxy, aikenyl, oxaalkyl, thioalkyl, carbonyl and carhonyloxy groups can be achiral or chiral groups. Particularly preferred chiral groups are 2-butyl (=1--52 methylpropyl), 2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, 2-butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 7-decylnonadecyl, in particular 2-rnethylbutyl, 2-rnethylbutoxy, 2-rnethylpentoxy, 3-rnethylpentoxy, 2-ethyl-hexoxy, 1-methylhexoxy, 2-octyloxy, 2-oxa-3-rnethylbutyl, 3-oxa-4-methyl- pentyl, 4-methylhexyl, 2-butyloctyl, 2-hexyldecyl, 2-octylclodecyl, 7-decylnonadecyl, 3,8-dirnethyloctyl, 2-hexyl, 2-octyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-meth-oxyoctoxy, 6-rnethyloctoxy, 6-inethyloctanoyloxy, 5-methylheptyloxycarbonyl, 2-methylbutyryloxy, 3-methylyaleroyloxy, 4-methylhexancyloxy, 2-chloropropionyloxy, 2-chlorc-3-methylbutyryloxy, 2-chloro-4-methyl-yaleryl-oxy, 2-chloro-3-rnethylyaleryloxy, 2-methyl-3-oxapentyl, 2-methyl-3-oxa-hexyl, 1-methoxypropy1-2-oxy, 1-ethoxypropy1-2-oxy, 1-oropoxypropy1-2-oxy, butoxypropy1-2-oxy, 2-fluorooctyloxy, 2-fluorodecyloxy, 1,1,1-trifluoro-2-octyloxy, 1,1,1-trifluoro-2-octyl, 2-fluoromethyloctyloxy for example. Most preferred is 2-ethylhexyl.

Preferred achiral branched groups are isopropyl, isobutyl (=methylpropyl), isopentyl (=3-methylbutyl), tert-butyl, isopropoxy, 2-methyl-propoxy and 3-methyibutoxy.

In a preferred embodiment, the organyl groups are independently of each other selected from primary, secondary or tertiary alkyl or alkoxy with 1 to 30 C atoms, wherein one or more H atoms are optionally replaced by F, or aryl, aryloxy, he.teroaryl or heteroaryloxy that is optionally alkylateci or a lkoxylated and has 4 to 30 ring atoms. Very preferred groups of this type are selected from the group consisting of the following formulae ALK-ALK ALK ALK ALK--"'" ALK

ALK

ALK ALK ALK r

ALK ALK ALK

ALK

wherein "ALV denotes optionally fluorinated, preferably linear, alkyl or alkoxy with 1 to 20, preferably 1 to 12 C-atoms, in case of tertiary groups very preferably 1 to 9 C atoms, and the dashed line denotes the link to the ring to which these groups are attached. Especially preferred among these groups are those wherein ail ALK subgroups are identical.

Further, in some preferred embodiments in accordance with the present invention, the organic semiconducting materials are polymers or copolymers that encompass one or more repeating units, e.g. M in formula (I), selected from thiophene-2,5-diyl, 3-substituted thiophene-2,5-diyl, optionally substituted thieno[2,3-b]thiophene-2,5-diyl, optionally substituted thieno[3,2-b]thiophene2,5-diyl, selenophene-2,5-diyl, or 3-substituted selenophe.ne-2,5-diyl.

Preferred examples of organic semiconducting materials comprise one or more monomeric units selected from the group consisting of formulae (Al) to (A83) and one or more monomeric units selected from the group consisting of formulae (DI.) to (D142).

Further preferred examples of organic semiconductor materials that can be used in this invention include compounds, oligomers and derivatives of compounds selected from the group consisting of conjugated hydrocarbon polymers such as polyacene, polyphenylene, poly(phe.nylene vinyiene), polyfluorene including oligomers of those conjugated hydrocarbon polymers; condensed aromatic hydrocarbons, such as, tetracene, chrysene, pentacene, pyrene, pc.,rylene, coronene, or soluble, substituted derivatives of these; oligomeric pa ra substituted phenylenes such as p-quaterphenyl (p-4P), p-quinquephenyl (p-5P), p-sexiphenyl (p-E,P), or soluble substituted derivatives of these; conjugated heterocyclic polymers such as poly(3-substituted thiophene), poly(3,4-bisubstituted thiophene), optionally substituted polythieno[2,3-b]thlophene, optionally substituted polythieno[3,2-b]thiophene, poly(3-substituted selenophene), polybenzothiophene, polyisothianapthene, poly(N-substituted pyrrole), poly(3-substituted pyrrole), poly(3,4-bisubstituted pyrrole), polyfuran, polypyridine, poly- 1,3,4-oxacliazoles, polyisothianaphthene, poly(N-substituted poly(2-substituted aniline), poly(3-substituted aniline), poly(2,3-bisubstituted aniline), polyazulene, polypyrene.; pyrazoline compounds; polyselenophene; polybenzofuran; polyindole; polypyridazine; benzidine compounds; stilbene compounds; triazines; substituted metallo-or metal-free porphines, phthalocya nines, fluorophthalocyanines, naphthalocyanines or fluoro,naphthalocyanines; C50 and C73 fullerenes; N,NI-dialkyl, substituted dialkyl, diaryl or substituted diaryl-1,4,5,8.-naphthalenetetracarboxylic diimide and fluoro derivatives; N,AP-dialkyl, substituted dialkyl, diaryl or substituted diaryl perylenetetracarboxylicdiimide; bathophenanthroline; dipheno,quinones; oxaciiazoles; 11,11,12,12--tetracyanonaptho-2,6.-quinodimethane; cc,a!--bis(di-thienc43,2--b2',3'--dithiophene); 2,8--dialkyl, substituted dialkyl, diaryl or substituted diaryl anthradithiophene; 2,2'-bisbenzo[1,2-b:4,5--bldithiophene.

Where a liquid deposition technique of the OSC is desired, compounds from the above list and derivatives thereof are limited to those that are soluble in an appropriate solvent or mixture of appropriate solvents.

Other preferred examples of organic semiconducting materials may be selected from the group consisting of substituted oligoacenes, such as pentacene, tetracene or anthracene, or heterocyclic derivatives thereof.

Bis(trialkylsilylethynyi) oligoacenes or bis(trialkylsilylethynyl) heteroacenes, as disclosed for example in US 6,690,029 or WO 2005/055248 Al or US 7,385,221, are also useful.

Further preferred organic semiconducting materials are selected from the group consisting of small molecules or monomers of the tetra-heteroaryl indacenod thiophene-based structural unit as disclosed in WO 2016/015804 Al, and polymers or copolymers comprising one or more repeating units thereof.

Also preferred organic semiconducting materials may be selected from the group of small molecules or monomers or polymers comprising a 2,7-(9,91)spirobifluorene moiety, optionally substituted and preferably substituted with amino groups. Such spirobifluorenes are, for example, disclosed in WO 97/39045. Examples of spirobifiuorenes suitable for use as monomeric unit M of formula (VII) may be selected from the group consisting of formulae (VI-1) to (VI-7) VI-2) (V1-5) (VI-6) wherein each of the hydrogen atoms may independently of any other be as defined herein in respect to Rim and each asterisk "s" independently may denote a bond to neighboring moiety (for example in a polymer) or may denote a bond to a group as defined above for R101 (for example in a compound of formula (V-a) or (V-b)). In respect to formulae (VI-1) to (VI-7) preferred substituents, including the ones for "*", may be selected from the group consisting of alkyl having from 1 to 20 carbon atoms; aryl having from 6 to 20 carbon atoms, said aryl being optionally substituted with alkyl or alkoxy having from 1 to 20, preferably 1 to 10 carbon atoms; and NR11UR111 with Rul) and Rui being independently of each other selected from the group consisting of alkyl having from 1 to 20 carbon atoms, aryl having from 6 to 20 carbon atoms, said aryl being optionally substituted with alkyl or alkoxy having from 1 to 20, preferably 1 to 10 carbon atoms, most preferably R110 and R111 being independently of each other selected from methyl, ethyl, npropyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, methoxy, ethoxy, n-propoxy, iso-propoxy n-butoxy, iso-butoxy,.tert-butoxy, and pentoxy.

-56 -In a one aspect the present semiconducting material may, for example, be a small molecule, i.e. a compound comprising one (i.e. m = 1) structural unit of formula (VII) and two inert chemical groups W and W. Such a small molecule may for example be represented by formula (I-a) W-M-Rb (V-a) wherein M is as defined herein and fr and Rb are inert chemical groups. Such inert chemical groups W and Rh may independently of each other be selected from the group consisting of hydrogen, fluorine, alkyl having from 1 to 10 carbon atoms, alkyl having from 1 to 10 carbon atoms wherein one or more, for example all, hydrogen has been replaced with fluorine, aromatic ring systems of from S to 30 carbon atoms and aromatic ring systems of from 5 to 30 carbon atoms wherein one or more hydrogen atom may independently of any other be replaced by fluorine or alkyl having from 1 to 10 carbon atoms.

Further preferred p-type °Ks are copolymers comprising electron acceptor and electron donor units. Preferred copolymers of this preferred embodiment are for example copolymers comprising one or more benzo[1,2-b:4,5-b]dithiophene-2,5-diyl units that are preferably 4,8-disubstituted by one or more groups R as defined above, and further comprising one or more aryl or heteroaryl units selected from Group A and Group B, preferably comprising at least one unit of Group A and at least one unit of Group B. wherein Group A consists of aryl or heteroaryl groups having electron donor properties and Group B consists of aryl or heteroaryl groups having electron acceptor properties, and preferably Group A consists of selenophene-2,5-diyl, thiophene-2,5-diyl, thieno[3,2- b]thiophene-2,5-diyl, thienc[2,3-b]thioohene-2,5-diyl, selenopheno[3,2-b]selenophene-2,5-diyl, selenopheno[2,3-b]selenophene-2,5*diyl, selenopheno[3,2-b]thiophene-2,5-diyl, selenopheno[2,3-b]thiophene-2,5-cliyl, benzo[1,2-b:4,5-b]dithiophene-2,6-diyl, 2,2-dithiophene, 2,2-diselenophene, 4H-cyclopenta[2,1-b:3,4-b]dithiophene-2,6- diyl, 2,7-di-thien-2-yl-carbazole, 2,7-di-thien-2-yl-fluorene, indaceno[1,2-b:5,6- b]dithiophene-2,7-diyl, benzo[1",2":4,5;4",5":4',5]bis(silolo[3,2-b:3',2- blthiophene)-2,7-diyl, 2,7-di4hien-2-yl-indaceno[1,2-b:5,6-Mdithiophene, 2,7-di-thien-2-yl-benzo[1",2":4,524",5":4',51bistsilolo[3,2-b:3', 2'-bithiophene)-2,7-diyl, and 2,7-di-thien-2-yl-phenanthro[1,10,9,8-cid"e,f,g]carbazole, all of which are 57 -optionally substituted by one or more, preferably one or two groups R as defined above, and Group B consists of benzo[2,1,3]thiacliazole-4,7-cliyl, 5,6-dialkyl-benzo[2,1,3]thiadiazole-4,7-diyi, 5,6-dialkoxyberno[2,1,3]thiadiazole-4,7-diyi, benzo[2,1,3]selenadiazole-4,7-diyi, 5,6-dialkoxy-benzo[2,1,3]selenadiazole-4,7-diyl, benzo[1,2,5]thiadiazole-4,7,diyl, benzo[1,2,5]selenadiazole-4,7,diyi, benzo[2,1.,3]oxadiazole-4,7-diyl, 5,6-dialkox.ybento[2,1,3]oxadiazole-4,7-diyl, 2Hbenzotriazole-4,7-thyl, 2,3-dicyano-1,4-phenylene, 2,5-dicyano,1,4-phenyiene, 2,3- difluro-1,4-phenylene, 2,5-difluoro-i,4-phenylene, 2,3,5,6-tetrafluoro-1,4- 1.0 phenylene, 3,4-difluorothiophene-2,5-diyl, thieno[3,4-b]pyrazine-2,5-diyl, quinoxaline-5,8-diyl, thieno[3,4-b]thiophene-4,6-diyl, thieno[3,4-b]thiophene-6,4-diyl, and 3,6-pyrrolo[3,4-c]pyrrole-1,4-dione, all of which are optionally substituted by one or more, preferably one or two groups R as defined above.

In other preferred embodiments of the present invention, the OSC materials are substituted oligoacenes such as pentacene, tetracene or anthracene, or heterocyclic derivatives thereof. Bis(triallwisilylethynyi) oligoacenes or bis(trialkylsilylethynyl) heteroacenes, as disclosed for example in US 6,690,029 or WO 2005/055248 Al or US 7,385,221., are also useful.

Further preferred organic semiconducting materials are selected from the group consisting of small molecules or monomers of the tetra-heteroaryl indacenod thiophene-based structural unit as disclosed in WO 2016;015804 Al, and polymers or copolymers comprising one or more repeating units thereof, such as, for example, one of the following polymers (P-1) to (P-3): (P-1) (P-2) (P-3) Depending upon the intended application the present organic semiconducting material may also comprise other components, such as, for example, a fullerene or modified fullerene, the ratio polymer: fuilerene is preferably from 5:1 to 1:5 by weight, more preferably from 1:1 to 1:3 by weight, most preferably 1:1 to 1:2 by weight. Suitable fullerenes may, for example, be indene-C60-fullerene bis-adduct like ICRA, or a (6,6)-phenyl-butyric acid methyl ester deriyatizecl methane C60 fullerene, also known as "PCBM-C60"or "C60PCBM", as disclosed for example in G. Yu, J. Gao, J.C. Hurnmeien, F. Wudl, A..I. Heeger, Science 1995, Vol. 270, p. 1789 ff and haying the structure shown below, or structural analogous compounds with e.g. a C61 fullerene group, a C70 fullerene group, or a C71 fullerene group, or an organic polymer (see for example Coakley, K. M. and McGehee, M. D. Chem. Mater. 2004, 16, 4533).

-59 -C60PCBM Such organic semiconducting materials may be purchased from commercial sources, such as SigmaAldrich or Merck KGaA (Darmstadt, Germany), or may be synthesized according to published syntheses.

In a further aspect the present semiconducting material may be an oligomer or a polymer as defined above. Such oligomers and polymers may be synthesized according to or in analogy to methods that are known to the skilled person and are described in the literature from monomers as described in the following.

Monomers that are suitable for the synthesis of the present oligorners and polymers may be.selected from compounds comprising a structural unit of formula (I) and at least one reactive chemical group R which may be selected from the group consisting of Cl, Br, I, 04osylate, 0-triflate, 0-rnesylate, 0- nonaflate, -SiMe2F, -SiMeF2, -0-502Z1, -B(072)2, --C73=C(Z3)2, -C=CSi(Z1)3, -ZnX0° and -Sn(Z4h, preferably -B(OZ2)2 or -Sn(Z4)3, wherein XGO is as defined herein, and Z1, Z2, Z3 and Z" are selected from the group consisting of alkyl and aryl, preferably alkyl having from 1 to 10 carbon atoms, each being optionally substituted with R° as defined herein, and two groups 72 may also together form a cyclic group. Alternatively such a monomer may comprise two reactive chemical groups and is, for example, represented by formula (V-b) Rc-Pyl-Rd wherein M is as defined herein and Fe and RI are reactive chemical groups as defined above in respect to R'. Such monomers may generally be prepared according to methods weli known to the person skilled in the art.

-60 -X00 is halogen. Preferably X(3° is selected from the group consisting of F, Cl and Br. Most preferably Xcl° is Br.

Preferred aryl-aryl coupling and polymerisation methods used in the processes described herein may, for example, be one or more of Yamamoto coupling, Kumada coupling, Negishi coupling, Suzuki coupling, Stifle coupling, Scnogashira coupling, Heck coupling, C-H activation coupling, Ullmann coupling and Buchwald coupling, Especially preferred are Suzuki coupling, Negishi coupling, Stifle coupling and Yamamoto coupling. Suzuki coupling is described for example in WO 00/53656 Al. Negishi coupling is described for example in J. Chem Soc., Chem. Commun., 1977, 683-684. Yamamoto coupling is described for example in T. Yamamoto etal., Prog. Pa/yin. Sci., 1993, 17, 1153-1205, or WO 2004/022626 Al, and Stile coupling is described for example in Z. Bao et al., J. Am. Chem. Soc., 1095, 117, 12426-42435. For example, when using Yamamoto coupling, monomers having two reactive halide groups are preferably used. When using Suzuki coupling, compounds of formula (l-b) having two reactive boronic acid or boronic acid ester groups or two reactive halide groups are preferably used. When using Stille coupling, monomers having two reactive stannane groups or two reactive halide groups are preferably used. When using Negishi coupling, monomers having two reactive organozinc groups or two reactive halide groups are preferably used.

Preferred catalysts, especially for Suzuki, Negishi or Stille coupling, are selected from Pd(0) complexes or Pd(II) salts, Preferred Pd(0) complexes are those bearing at least one phosphine ligand, for example Pd(Ph3P)4. Another preferred phosphine ligand is tris(ortho-tolyl)phosphine, for example Pd(o-Tol3P)4. Preferred Pd(II) salts include palladium acetate, for example Pc1(0Ac)2. Alternatively the Pd(0) complex can be prepared by mixing a Pd(0) dibenzylideneacetone complex, for example tris(dihenzyl-ideneacetone)dipalladium(0), bis(dibenzylideneacetone)-palladium(0), or Pd(II) salts e.g. palladium acetate, with a phosphine ligand, for example triphenylphosphine, tris(ortho-tolyl)phosphine or tri(tert-butyl)phosphine. Suzuki polymerisation is performed in the presence of a base, for example sodium carbonate, potassium carbonate, lithium hydroxide, potassium phosphate or an organic base such as tetraethylammonium carbonate or tetraethylarnmoniurn hydroxide. Yamamoto polymerisation employs a Ni(0) complex, for example his(1,5-cyclooctadienyl)nickel(0).

-61 - Suzuki and StiIle polymerisation may be used to prepare homopolymers as well as statistical, alternating and block random copolymers. Statistical or block copolymers can be prepared for example from the above monomers of formula (I-S b), wherein one of the reactive groups is halogen and the other reactive group is a boronic acid, boronic acid derivative group or and alkylstannane. The synthesis of statistical, alternating and block copolymers is described in detail for example in WO 03/048225 A2 or WO 2005/014688 A2.

As alternatives to halogens as described above, leaving groups of formula -0-S027.1 can be used wherein Z1 is as described above. Particular examples of such leaving groups are tosylate, mesylate and triflate.

Binder Where appropriate and needed, for example, to adjust the rheological properties as described for example in WO 2005/055248 Al, some embodiments of the present invention employ organic semiconducting compositions that include one or more organic binders.

The binder, which is typically a polymer, may comprise either an insulating binder or a semiconducting binder, or mixtures thereof may be referred to herein as the organic binder, the polymeric binder, or simply the binder.

Preferred binders are materials of low permittivity, that is, those having a permittivity s of 3.3 or less, The organic binder preferably has a permittivity of 3.0 or less, more preferably 2.9 or less. Preferably the organic binder has a permittivity e of 1.7 or more. It is especially preferred that the permittivity of the binder is in the range from 2.0 to 2.9. Whilst not wishing to be bound by any particular theory it is believed that the use of binders with a permittivity e of greater than 3.3, may lead to a reduction in the 0.5.0 layer mobility in an electronic device, for example an OFET. In addition, high permittivity binders could also result in increased current hysteresis of the device, which is undesirable.

Examples of suitable organic binders include polystyrene, or polymers or copolymers of styrene and a-methyl styrene; or copolymers including styrene, a- -62 -methylstyrene and butadiene may suitably be used. Further examples of suitable binders are disclosed for example in US 2007/0102696 Al.

In one type of preferred embodiment, the organic binder is one in which at least 95%, more preferably at least 98% and especially all of the atoms consist of hydrogen, fluorine and carbon atoms.

The binder is preferably capable of forming a film, more preferably a flexible film.

The binder can also be selected from crosslinkable binders such as acrylates, epoxies, vinylethers, and thiolenes, preferably having a sufficiently low permittivity, very preferably of 3.3 or less. The binder can also be mesogenic or liquid crystalline.

In another preferred embodiment the binder is a semiconducting binder, which contains conjugated bonds, especially conjugated double bonds and/or aromatic rings. Suitable and preferred binders are for example polytriarylamines as disclosed for example in US 6,630,566.

The proportions of binder to OSC is typically 20:1 to 1:20 by weight, preferably 10:1 to 1:10 more preferably 5:1 to 1:5, still more preferably 3:1 to 1:3 further preferably 2:1 to 1:2 and especially 1:1. Dilution of the compound of formula 1 in the binder has been found to have little or no detrimental effect on the charge mobility, in contrast to what would have been expected from the prior art.

Substrate and other lavers The present organic electronic device may optionally comprise one or more substrate. Such substrate is not particularly limited and may be any suitable material that is inert under use conditions, Examples of such materials are glass and polymeric materials. Preferred polymeric material include but are not limited to alkyd resins, allyl esters, benzocyclobutenes, butadiene-styrene, cellulose, cellulose acetate, epoxide, epoxy polymers, ethylene-chlorotrifluoro ethylene copolymers, ethylene-tetra-fluoroethylene copolymers, fiber glass enhanced polymers, fluorocarbon polymers, hexafluoropropyiene-vinylidene fluoride copolymer, high density polyethylene, parylene, polyamide, polyimide, polyaramid, polydirnethylsiloxane, polyethersulphone, polyethylene, polyethylenenaphthalate, polyethylenetere phthalate, polyketone, polyrnethylmethacrylate, polypropylene, polystyrene, polysulphone, polytetrafluoroethylene, polyurethanes, polyvinylchloride, polycycloolefin, silicone rubbers, and silicones. Of these poiyethyleneterepht Mate, polyirnide, polycycloolefin and polyethylenenaphthalate materials are more preferred. Additionally, for some embodiments of the present invention the substrate can be any suitable material, for example a polymeric material, metal or glass material coated with one or more of the above listed materials or coated with one or more metal, such as for example titanium. It vvill be understood that in forming such a substrate, methods such as extruding, stretching, rubbing or photochemical techniques can be employed to provide a homogeneous surface for device fabrication as well as to provide pre-alignment of an organic semiconductor material in order to enhance carrier mobility therein. Alternatively, the substrate can be a polymeric material, metal or glass coated with one or more of the above polymeric materials.

A suitable substrate may, for example, be transparent or semi-transparent. A suitable substrate may, for example, also be flexible or non-flexible.

Said substrate may, for example, serve as support and preferably be adjacent to a first electrode layer and opposite the second electrode layer.

Additionally the present organic electronic device may optionally comprise further layers acting as charge transport layers. Exemplary charge transport layers may act as hole transporting layer and/or electron blocking layer, or electron transporting layer and/or hole blocking layer. Generally ---if present --such layers are between the electrodes and the organic semiconducting layer.

Suitable materials for a hole transporting and/or electron blocking layer may be selected from the group consisting of metal oxides, like for example, ZTO, IVIo0x, NiO, a conjugated polymer electrolyte, like for example PEDOT:PSS, a conjugated polymer, like for example polytriarylamine (PTAA), an organic compound, like for example N,1\15-ciiphenyl-N,N1-bis(1-naphthyl)(1,1'-bipheny1)-4,41diamine. (NPB), N,Nl-diphenyl-N,NT-(3-rnethylpheny1)-1,1r-biphenyl-4,4r-diamine (TPD).

-64 -Suitable materials for a hole blocking and/or electron transporting layer may be selected from the group consisting of metal oxides, like for example, ZnO,, TiO,, a salt, like for example LiF, NaF, CsF, a conjugated polymer electrolyte, like for example poly[3-(6-trimethylarnmoniurnhexylithiophenel, poly19,9-bis(2-ethylhexyli-fluorenej-b-poly[3- (6-trimethylammoniumhexyGthiophene], or poly[(9,9-bis(3"-(N,N-climethyl-amino)propyl)-2,7-fluorenej-alt-2,7-(9, 9-clioctylfluorene)ll or an organic compound, like for example tris(8-quinolinolato)alurniniurn(III) (Alq3), 4,7-dipheny1-1,10-phenanthroline.

PRODUCTION METHOD

The present application also provides for a method of producing such electronic device, said method comprising the steps of a) providing a fluorinated dielectric layer as defined herein, and b) depositing a polycycloolefinic formulation onto said fluorinated dielectric layer to form a polycycloolefinic layer, said polycycloolefinic formulation comprising at least one solvent and at least one fluorinated polycycloolefin as defined herein.

Said at least one solvent has a polar component op of the Hansen solubility of at most 4.0 MPa, preferably of at most 3.8 MPa. It is noted that for a formulation comprising two or more solvents, the solvents together, i.e. the blend of solvents, needs to have a polar component 6p of the Hansen solubility of at most 4.0 MPa, preferably of at most 3.8 MPa.

The Hansen Solubility Parameters can be determined using the Hansen Solubility Parameters in Practice (F1SPiP) program (2'd edition) as supplied by Hansen and Abbot et al., and may also be obtained from CM. 1-lansen, Hansen Solubility Parameters, A User's Handbook, Second edition, CRC Press, 2007.

Preferably, suitable solvents may be selected from the group consisting of aryl compounds as defined in the following, esters as further defined in the following, ketones as further defined in the following, ethers as further defined in the following, and any blend of any of these. More preferably, suitable solvents may be selected from the group consisting of aryl compounds as further defined in the following, ketones as further defined in the following, ethers as further defined in the following, and any blend of any of these. Most preferably, a suitable solvent may be selected from the group consisting of ketones as further defined in the following.

Preferabiy, aryl compounds suitable as the at least one solvent may, for example, be selected from the group consisting of 1,2,3,4-tetrahydronaphthalene (tetralin), 1,2,3,4-letramethylbenzene, 1,2,3,5-tetrarnethylbenzene, 1,2,31rirnethylbenzene, 1,2,4,5--tetrarnethylbenzene, 1,2,4-trichlorobenzene, 1,2,4-trimethylbenzene, 1,3,3-trimethy1-2-methyleneindole, 1,3-diisopropylbenzene, 1,4-diisopropylbenzene, 1,5-dimethyltetralin, 1-rnethylindane, 2,6-diisopropyl naphthalene, 2,6-dimethylnaphthalene, 3-isopropylbiphenyl, 5-decanolide, 5-tertbutyl-m-xylene, a-pinene, butylbenzene, cyclohexylbenzene, decahydronaphthalene, diphenyl ether, ethylbenzene, gamma-terpinene, hexylbenzene, isoarnylbenzerie, iso-butylbenzene, isochroman, isopropylbenzene (cumene), ni-cymene, mesitylene, m-xylene, n-butylbenzene, n-propyibenzene, otliethylbenzenes, o-ethyltoluene, o-xylene, pentylbenzene, p-ethyltoluene, pisopropyitoluene (p-cyrnene), p-xylene, sec-butylbenzene, t-butylbenzene, and toluene.

Preferred esters suitable as the at least one solvent may be represented by the following formula (S-1) 1-13C-(0-12)51-Q=0)-0-(0-12)52-CH3 wherein s1 + s2 5, for example, 5, 6, 7, 8, 9 or 10. Preferably 51 + s2 20.

Examples of preferred ketones are n-butyl acetate and iso-butyl acetate.

Preferred ketones suitable as the at least one solvent may be represented by he following formula (5-2) 1-f3C-(CH2),3-C(=0)-(0-12)sii-C1-13 (S-2) wherein s3 + s4;? 8, preferably s3 + s4:? 9, and most preferably s3 + s4 10.

Preferably + s2 20. Most preferred are 2-decanone and 3-decanone.

-66 -Preferred ethers suitable as the at ieast one solvent may be selected from the group consisting of 1,4-dioxane and ethers represented by the following formula (S-3) wherein R3:3 and R3' may at each occurrence independently be selected from the group consisting of alkyl having from 1 to 20, preferably from 1 to 15, and most preferably from 1 to 10 carbon atoms. Such alkyl may, for example, be selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, so-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl.

The layers comprised in the present devices may be produced by standard methods that are well known to the skilled person, for example, by depositing a formulation comprising the respective material and one or more solvents.

Preferred deposition methods may be selected from liquid coating techniques. Examples of such liquid coating techniques ma be selected, without limitation, from the group consisting of dip coating, spin coating, ink jet printing, nozzle printing, letter-press printing, screen printing, gravure printing, doctor blade coating, roller printing, reverse-roller printing, offset lithography printing, dry offset lithography printing, .Flexographic printing, web printing, spray coating, curtain coating, brush coating, slot dye coating or pad printing.

ink jet printing is particularly preferred when high resolution layers and devices need to be prepared. Selected formulations of the present invention may be applied to prefabricated device substrates by ink jet printing or rnicrodispensing. Preferably industrial piezoelectric print heads such as but not limited to those supplied by Aprion, Hitachi-Koki, inklet Technology, On Target Technology, Picojet, Spectra, Trident, Xaar may be used to apply the organic semiconductor layer to a substrate. Additionally semi-industrial heads such as those manufactured by Brother, Epson, Konica, Seiko Instruments Toshiba TEC or single nozzle rnicrodispensers such as those produced by Microdrop and Microfab may be used.

In order to be applied by ink jet printing or rnicrod spensing, the respective materials first need to be dissolved in a suitable solvent. Solvents must not have any detrimental effect on the chosen deposition equipment, particularly the print head. Additionally, solvents should have boiling points >100°C, preferably >140°C and more preferably >150°C in order to prevent operability problems caused by the solution drying out inside the print head. Apart from the solvents mentioned above, suitable solvents include substituted and non-substituted xylene derivatives, di-C1"2-alkyl formarnide, substituted and non--substituted anisoles and other phenol-ether derivatives, substituted heterocycles such as substituted pyridines, pyrazines, pyrimidines, pyrrolidinones, substituted and non-substituted iy,N-di-C2-alkyianilines and other fluorinated or chlorinated aromatics.

Examples of preferred solvents suitable" for example, for depositing a formulation comprising a semiconducting material, may be selected from the group consisting or aliphatic hydrocarbons, chlorinated hydrocarbons, aromatic hydrocarbons, ketones, ethers and mixtures thereof. Additional solvents which can be used include 1,2,4-trimethylbenzene, 1,2,3,4-tetra-methyl benzene, pentylbenzene, mesitylene, cumene, cymene., cyclohexylbenzene, diethylhenzene, tetralin, decaiin, 2,6-lutidine, 2-fluoro-m-xylene., 3-fluoro-o-xylene, 2- chlorobenzotrifluoride, N,N-dimethylformamide, 2-chloro-6-fluorotoluene" 2- fluoroanisole, anisole, 2,3-clirnethylpyrazine, 4-fluoroanisole, 3-fluoroanisole, 3- trifluoro-methylanisc.fle, 2-methylanisole., phe.netol, 4-rnethylanisole, 3-methylanisole, 4-fluoro-3-methylanisole, 2-fluorobenzonitrile, 4-fluoroveratrol, 2,6-dirnethylanisole, 3-4Iuorobenzo-nitrile, 2,5-dimethylanisole, 2,4-dimethylanisole, benzonitrile, 3,5-dimethyl-anisole, N,N-dimethylaniline, ethyl benzoate, 1-fluoro-3,5-dimethoxy-benzene, 1-rnethylnaphthalene, N-methylpyrrolidinone, 3-fluorobenzo-trifluoride, benzotrifluoride, dioxane, trifluoromethoxy-benzene, 4-fluorobenzotrifluoride, 3-fluoropyridine, toluene, 2-fluorc-toluene" 2-fluarobenzotrifluoride, 3-fluorotoluene, 4-isopropylbiphenyl, phenyl ether, pyridine, 4-fluorotoluene, 2,5-difluorotoluene, 1-chloro-2,4- lorobenzene, 2-fluoropyridine, 3-chlorofluoro-benzene, 1-chloro-2,5-difluorobenzene, 4-chlorofluorobenzene, chloro-benzene, o-dichlorobenzene, 2-chlorofluorobenzene, p-xylene, m-xylene, o-xylene or mixture of o--, me, and p-isomers. Solvents with relatively low polarity are generally preferred. For inkjet printing solvents and solvent mixtures with high boiling temperatures are preferred. For spin coating alkylatecl benzenes like xylene and toluene are preferred.

Examples of especially preferred solvents include, without limitation, clichloromethane, trichlorornethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisoie, morpholine; toluene, o-xylene, m-xylerie, p-xylene, 1,4-dioxane, acetone, methylethylketone, 1,2-dichloroethane, 1.4,11richloroethane, 1,1,2,21c2trachloroethane, ethyl acetate, n--butyl acetate, N,N-dimethylformamide, dimethylacetarnide, dimethylsulfoxide, tetraline, decaline, indane, methyl benzoate, ethyl benzoate, mesitylene and/or mixtures thereof.

The concentration of compounds in the formulation is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight; with % by weight given relative to the total weight of the formulation. Optionally, the formulation may also comprise one or more binders to adjust the theological properties, as described for example in WO 2005/055248 Al.

Preferred solvents for depositing a material by ink jet printing may comprise a benzene derivative which has a benzene ring substituted by one or more substituents wherein the total number of carbon atoms among the one or more substituents is at least three. For example, the benzene derivative may be substituted with a propyl group or three methyl groups, in either case there being at least three carbon atoms in total. Such a solvent enables an ink jet fluid to be formed comprising the solvent with the material, which reduces or prevents clogging of the jets and separation of the components during spraying. The solvent(s) may include those selected from the following list of examples: clodecylbenzene, 1-methyl-44ert-butylbenzene, terpineol, limonene, isodurene, terpinolene, cyrnene, diethylbenzene. The solvent may be a solvent mixture, that is a combination of two or more solvents, each solvent preferably having a boiling point >100T, more preferably >140°C. Such solvent(s) also enhance film formation in the layer deposited and reduce defects in the layer.

The ink jet fluid (that is mixture of solvent; binder and semiconducting compound) preferably has a viscosity at 20°C of 1-100 rnPa;s, more preferably 1-50 rnPa.s and most preferably 1-20 mPa.s.

The present formulations may additionally comprise one or more further components or additives selected for example from surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents which may be reactive or non-reactive, auxiliaries, colourants, dyes or pigments, sensitizers, stabilizers, nanoparticles or inhibitors.

The following examples are intended to illustrate the advantages of the present invention in a non-limiting way.

Examples

The polynorbornenes used herein were obtained from Promerus, Brecksville, Ohio, USA. All other materials, such as fluorinated dielectric material and solvents, were obtained from SigmaAldrich.

Example 1

Samples for determining the adhesion of the polynorbornene to the fluorinated dielectric were prepared as follows: A 30 pm thick layer of Cytop® fluorinated dielectric material was deposited onto a suitable substrate by spin coating at 1500 rpm for 30 s. Then a formulation of a polynorbornene with a p luori nated alkyl pendant group in solvent was applied onto the:fluorinated dielectric material by spin coating at 1500 rpm for 30s and dried at 100It for 2 min on a hotplate.

The so-obtained samples were then subjected to a 90' pee: test: an adhesive tape was applied to the top surface of the sample and held at a 90' angle by a clamp connected to 3 load cell. The test system was programmed to first adjust the slack between tape and test sample to as dose as possible to 900 and then move the sample holder at a preset speed whilst peeling the tape off the substrate. During movement of the sample holder the tape was maintained essentially perpendicular to the test sample. The force required to peed off the top layer was recorded as a function of distance and plotted as peel strength vs. distance.

-70 -Results are summarized in Table I with adhesion reported in N/inch (corresponding to N/2.5 cm).

Table I

Solvent 2-decanone 3-decanone methyl benzoate methyl amyl ketone Adhesion [N/inch] >3 >3 <0.2 < 0.2

Example 2

A top gate OFET device may be prepared as folio s.

A substrate glass is pre-cleaned with 5% Decon-90 in aqueous for 30 min at 70°C followed by DI water rinsing for 5 times, ultrasonic treatment in DI water for 5 min, followed by methanol rinsing for 5 min and spin drying.

Source-drain gold electrodes (40 nm thickness) are formed by shadow deposition of Au using thermal evaporation technique, followed by the deposition of an organic semiconductor formulation by spin-coating at 1500 rpm for 60s and subsequent annealing on a hotplate at 100°C for 2 min, A 30 p.m thick layer of fluorinated dielectric material is deposited thereon by spin coating at 1500 rpm for 30 s, on top of which a polynorbornene formulation is applied by spin coating at 1500 rpm for 30 s and dried at 100°C for 2 min on a hotplate Finally, a 40 nrn layer of gold gate electrode is deposited by the male p0 ration.

The transfer characteristics may then be recorded, for example, by using a transfer measurement system at a bias voltage of --5 V (linear region) and --60V (saturation region),

Claims

-71 -Claims 1. Electronic device comprising a fluorinated dielectric layer and a polycycloolefinic layer adjacent to each other, said polycycloolefinic layer comprising a fluorinated polycycloolefin comprising partially or fully fluorinated monomeric units MIT, wherein the fluorinated dielectric layer does not comprise any polycycloolefin, and adhesion between the fluorinated dielectric layer and the polycycloolefinic layer is at least 1.0 N/2.5 cm as determined by a 90' peel test.
2. Electronic device according to claim 1, wherein the adhesion between the fluorinated dielectric layer and the polymeric layer is at least 1.5 N/2.5 cm.
Electronic device according to claim 1 or claim 2, wherein the fluorinated dielectric layer comprises one or more fluoroelectric materials in at least 50 wt%, relative to the total weight of the fluorinated dielectric layer.
4. Electronic device according any one or more of claims 1 to 3, wherein the fluorinated dielectric material comprises a fluoropolymer comprising monomeric units derived from partially or fully fluorinated monomers, such monomers not being a cycloolefin.
5. Electronic device according claim 1 or claim 2, wherein the fluorinated dielectric layer comprises one or more fluorinated dielectric material being a fluoropolymer comprising monomeric units derived from partially or fully fluorinated monomers selected from any one of the following groups A to G Group A perfluorinated olefins having from two to eight carbon atoms, such as for example tetrafluoroethylene or hexafluoropropylene; Group B partially fluorinated olefins having from two to eight carbon atoms, such as for example vinylidene fluoride (F2G,--:CE12) vinyl fluoride (-IFC-,CH2), 1,2-difluoroethylene (1-1E-C=CFIF) or trifluoroethylene (F2C=CF1-1); Group C (perfluoroallcyljethylenes of formula H2C--,-CH-C,F2an with a being an integer from 1 to 10, preferably a being 1, 2, 3,4, 5 or 6, most preferably a being 1, 2, 3 or 4; Group D partially fluorinated olefins, wherein one or more of the hydrogen atoms is independently of each other replaced with one selected from the group consisting of chlorine, bromine or iodine, such as for example chlorotrifluoroethylene (CIFC=CF2); Group E perfluorovinylalkylethers of formula F2C=C-0-C,F2,-.,1 with a being an integer from 1 to 10, preferably a being 1, 2, 3, 4, 5 or G., most preferably a being 1, 2, 3 01 4; Group F partially or fully fluorinated diolefins of formula RIRIC=CR3-0-C(R4)2-(CRs2)E,--(0),-CR6=CRIRs, with b being 0, 1 or 2; c being 0 or 1; R1, R2, R3, R4, R5, R6, RI and 133 being at each occurrence independently selected from the group consisting of H, F, Cl, alkyl having from 1 to 5 carbon atoms, and alkyl having from 1 to 5 carbon atoms with one or more, preferably all, hydrogen atoms substituted by F; and Group G partially or fully fluorinated 5-membered rings comprising at least one double bond, preferably partially or fully fluorinated dihydrofurans or dioxoles, preferably perfluorinated dihyclrofurans or dioxoles.
6. Electronic device according to any one or more of claims 1 to 5, wherein the polycycleolefin is a polynorbornene.
7. Electronic device according to any one or more of claims 1 to 6 wherein the polycycloolefin comprises partially or fully fluorinated monomers Mll selected from the group consisting of the following formulae (V-01) to (V-14) NBC4F-0 (V-0) NBCH2C6F5 (V-02) NBC8E5 (V-03) NBCH2C6F2 (V-4) NBCH2C6H4CF3 (V-5) NBa lky1C6F5 (V-6) FPCNB (V-7) FFICNB (V-8) FOCH NB (V-9) FPCHNB (V-10) CaPFAcNB (V-11) PPVENB (V-12) 1-1 C2F5 (CH2)p C6F5 0,CH2CH2C4F9 2k CF CF2F1 CH,CHCF,Fi 0e-CF2 z003F7..."CFF1 D OxoTCNB (V-13) PFBTCNB V-14) -74 -F2 C. .0 CF ".CF2CF-CF3 F 6F3 --FF F C F-2
8 Electronic device according to any one or more of claims-1 to 7, wherein the polycycloolefin further comprising constitutional units MT, with MT being a constitutional unit that does not comprise fluorine.
9. Electronic device according to any one or more of claims 1 to 18, wherein the polycycloolefin further comprises constitutional units MT derived from monomers selected from the group consisting of the following formulae (VI- 01) to (VI-40) NB (V1-01) Methyl fivieNB (V1-02) aButyl Hexyl Octyl BuNB (VI-03) HexNB (VI-04) OctNB (V1-05) (VI-08'TDfvle0AcNB (VI-09) NBX0H (VI-10) NBCF1261y0Ac (VI-11) DecNB (VI-06) PENB (VI-07) N BC -OH (VI-12) NBTON (VI-13) NBTODD (VI 14) DCPD (VI-15) EONB (VI-15) CFLCH OAc 0 2 H2O1-1701-1 o,,(CH2C,H20)2Me 0,40E-120E120)3Me 76 -SiEt3 SiEt, MGENB (VI-17) AkSiNB (VI-18) ArSiNB (VI-19) MCHMNB (VI-20) NPCHMNB -21 DMMIMeNB (V22) DMMIEtNB (VI-23) EtPhDMM1NB (V1-27) -77 -DMM1PrNB (V1-24) DMM1BuNB (V1-25) DMMIENNB (V1-26) MM1MeNB (V1-28) MiNB (V1-29) M1ENB 30)DHNMINBC6H40Mel Me0Cir,nNB (VI-32) CinnNB (VI-33) EtMe0CinnNB MeCoumNB (VI-35) Et Co urn NB (V1-3) EtPnIndNB 37) -79 -10. 1.1. 12. 13Electronic apparatus comprising one or more electronic devices of any one or more of claims 1 to 9.Method of producing the electronic device of any one more of claims 1 to 9, said method comprising the steps of a) providing a fluorinated dielectric layer, and b) depositing a formulation comprising a polycycloolefinic polymer and at least one solvent onto said fluorinated dielectric layer to form a polycyclolefinic layer, wherein said polycycloolefinic polymer comprises partially or fully fluorinated monomeric units, and wherein said at least one solvent has a polar component 6p of the Hansen solubility of at most 4.0 MPa.Method according to claim 11, wherein the solvent has a polar component Op of the Hansen solubility of at most 3.8 MPa.Method according to claim 11 or claim 12, wherein the at least one solvent is selected from the group consisting of (i) aryl compounds selected from the group consisting of 1,2,3,4-tetrahydronaphthalene (tetralin), 1,2,3,4-tetramethylbenzene, tetramethylbenzene, 1,2,3-trimethylbenzene, 1,2,4,5-tetrarnethylbenaene, 1,2,4-trichlorobenzene, 1,2,4-trimethylbenzene, 1,3,3-trimethy1-2-methyleneindole, 1,3-diisopropylbenzene, 1,4-PhIndNB (V1-38 TESNE3 (V1-39) PM NB (V1-40) cliisopropylbenzene, 1,5-dimethyltetralin, 1-met. I ndane, 2,6- diisopropyl naphthalene, 2,6-dimethylnaphthalene, 3-isopropylbiphenyl, 5-decanolicle, 5-tert-butyl-m-xylene, a-pinene, butylbenzene, cyclohexylbenzene, decahydro-naphthalene, diphenyl ether, ethylbenzene, gamma terpinene, hexylbenzene, iso- arnylbenzene, iso-butylbenzene, isochroman, isopropylbenzene (currene), m-cyrnene, rnesitylene, m-xylene, n-butylbenzene, n-propylbenzene, o-diethylbenzenes, o-ethyltoluene, o-xylene, pentylbenzene, p-ethyltoluene, p-isopropyltoluene (p-cymene), p-xylene, sec-butylbenzene, t-butylbenzene, and toluene; 00 esters represented by the following formula (5-1) 1-13C-(CF12)51-C(=0)-0-(0-12)s2-CH3 (S4) wherein s1 + s2:2 5, for example, 5,6, 7, 3,9 or 10; (iii) ketones represented by the following formula (5-2) 15 (-13C--(CH2),3-C(-0)4012),,i-C1-13 S-wherein s3 + s4 8; (iv) ethers selected from the group consisting of 1,4-clioxane and ethers represented by the following formula R"--0-8" wherein 83° and R31 may at each occurrence independently be selected from the group consisting of alkyl having from 1 to 20 carbon atoms; and any blend of any of these.Method according to any one or more of claims 11 to 13, wherein the solvent is 2-decanone or 3-deca none.(v) 25