Planarization Layer for Organic Electronic Devices

Technical Field The invention relates to organic electronic devices comprising polycycloolefin planarization layers, and more particularly to planarization layers positioned between the substrate and a functional layer e.g. a semiconducting layer, a dielectric layer or an electrode, and further to the use of such a planarization layer in organic electronic devices, and to processes for preparing such polycycloolefin planarization layers and organic electronic devices.

Background

In recent years there has been growing interest in organic electronic (OE) devices, for example field effect transistors for use in display devices and logic capable circuits, or organic photovoltaic (OPV) devices. A conventional organic field effect transistor (OFET) typically includes source, drain and gate electrodes, a semiconducting layer made of an organic semiconductor (OSC) material, and an insulator layer (also referred to as "dielectric" or "gate dielectric"), made of a dielectric material and positioned between the OSC layer and the gate electrode.

A broad range of different substrates can be used for OE devices like OFETs and OPVs. The most common are polymers like polyethylene terephthalate (PET), polyethylene naphthalate (PEN), other polyesters, polyimide, polyacrylate, polycarbonate, polyvinylalcohol, polycycloolefin or polyethersulphone. Thin metal films, paper based substrates, glass and others are also available.

However, the substrates that have hitherto been available often contain defects and contamination from the production process. Therefore, for the purpose of integrity of the thin-film OE devices made on top of them, most of these substrates require an additional planarization or barrier layer in order to provide a smooth and defect-free surface.

Further reasons or functions requiring the application of an intermediate layer between substrate and OSC material include: 1) improving the hardness/scratch resistance of the substrate, 2) providing electrical isolation of the substrate and the OSC layer, 3) providing a barrier to prevent diffusion of metal ions, small molecules, and oligomers from the carrier substrate to OSC, 4) modifying wetting properties of the substrate, and 5) acting as adhesion promoter. Various plastic film substrates are commercially available, like for example PET films of the Melinex® series or PEN films of the Teonex® series, both from DuPont Teijin Films™.

Typical commercially available planarization, hard-coating, or barrier materials include:

1) Silicon dioxide (Si0 ₂ ) or silicon nitride (SiNx) electrical insulators, which are used mainly on top of conducting metal substrates. 2) Organic polymers, such as, acrylic-, melamine- or urethane-based polymers.

3) Organic-inorganic hybrid composites, which are based mainly on the use of metal alkoxide and organosiloxane via sol-gel processing, as disclosed for example in US 5,976,703 or in W. Tanglumlert et al. 'Hard-coating materials for poly(methyl methacrylate) from glycidoxypropyl-trimethoxysilane-modified silatrane via sol-gel process', Surface & Coatings Technology 200 (2006) p.2784.

Nevertheless, to date there has been no planarization material which fulfils all requirements for all the commercially available OE/OPV materials. Two of the major weaknesses of the currently available materials are: 1) a low surface energy, which causes de-wetting of OSC materials during coating, therefore requiring additional pre-treatment, and 2) a high permeation of the available polymers and composites to water. Therefore, the above-mentioned materials are not suitable for many OE/OPV applications unless an additional barrier or surface modification layer is applied.

Moreover, the inventors found that the planarization materials used in

commercially available PET or PEN substrates have turned out not to be fully compatible with recently developed high performance OSC materials, like those of the Lisicon® Series (commercially available from Merck KGaA or Merck

Chemicals Ltd.). Further, poor electrical stability of devices using the Lisicon® Series OSC directly on top of planarised Melinex® and Teonex® has been observed. Therefore, an additional barrier/surface modification layer on top of the existing planarization layer, or a replacement for the planarization layer would be desired.

In general, a planarization material should exhibit one or more of the following characteristics:

1) acting as an insulator,

2) providing a smooth surface (preferably arithmetic average roughness of

absolute values (R _a ) <5 and maximum high of the profile (R _t ) <50),

3) providing for the electrical performance and stability of OFETs compared to the best working example on any other substrate,

4) enabling good between the substrate and electrode metals (preferably 50N/cm or higher),

5) possessing good wetting properties for OSC formulations (preferably a surface energy of the planarization layer >50mN/m),

6) inherent resistance to process chemicals,

7) opticalltransparency in the visible spectrum,

8) deposition using well established industrial processes.

Therefore, there is still a need for improved planarization layers which can be used in OE devices, especially OFETs and OPV cells, which fulfil the above- mentioned requirements.

One aim of the present invention is to provide planarization layers meeting these requirements. Another aim is to provide improved OE/OPV devices comprising such planarization layers. Further aims are immediately evident to the person skilled in the art from the following description.

The inventors of the present invention have found these aims can be achieved by providing planarization layers and OE devices in accordance with the present invention and as claimed hereinafter. Summary of the Invention

The invention relates an organic electronic device comprising a substrate and a functional layer, wherein said functional layer is selected from semiconducting layers, dielectric layers and electrodes, wherein a planarization layer is positioned between the substrate and the functional layer, such that it contacts both the substrate and the fuctional layer, and wherein said planarization layer comprises a polycycloolefinic polymer or said planarization layer comprises a polymer composition comprising a polycycloolefinic polymer.

The invention further relates to a planarization layer in an organic electronic device, wherein said planarization layer comprises a polycycloolefinic polymer or comprises a polymer composition comprising a polycycloolefinic polymer.

Preferably said planarization layer consists of a polycycloolefinic polymer or consists of a polymer composition comprising a polycycloolefinic polymer.

Further preferably, said planarization layer is provided between a substrate and a functional layer of said organic electronic device such that it contacts both the substrate and the fuctional layer. Further preferably the fuctional layer is selected from a semiconducting layer, a dielectric layer and an electrode.

The invention further relates to the use of a planarization layer comprising a polycycloolefinic polymer or comprising a polymer composition comprising a polycycloolefinic polymer in an organic electronic device. The invention further relates to a method of using a polycycloolefinic polymer or a polymer composition comprising a polycycloolefinic polymer in the fabrication of a planarization layer for an organic electronic device.

The polycycloolefinic polymer is preferably a norbornene-type polymer.

The organic electronic device is preferably an Organic Field Effect Transistor (OFET), including an Organic Thin Film Transistor (OTFT) as a subclass, preferably a top gate OFET or bottom gate OFET, an Organic Photovoltaic (OPV) Device or an Organic Sensor. The invention further relates to a product or an assembly comprising an organic electronic device as described above and below. Such product or assembly is preferably an Integrated Circuit (IC), a Radio Frequency Identification (RFID) tag, a security marking or security device containing an RFID tag, a Flat Panel Display (FPD), a backplane of an FPD, or a sensor.

The invention further relates to a process of preparing a top gate OFET or bottom gate OFET as described above and below. Brief Description of the Drawings

Embodiments of the invention are described below with reference to the following drawings. Figure 1 is a schematic representation of a typical top gate OFET device according to prior art;

Figure 2 is a schematic representation of a typical bottom gate OFET device according to prior art;

Figure 3 is a schematic representation of a top gate OFET device in accordance with a preferred embodiment of the present invention;

Figure 4 is a schematic representation of a bottom gate OFET device in accordance with a preferred embodiment of the present invention.

Figure 5 is a transfer curve of a top gate OFET device of Comparison Example 1.

Figure 6 is a transfer curve of a top gate OFET device of Example 1.

Figure 7 is a transfer curve of a top gate OFET device of Comparison Example 2. Figure 8 is a transfer curve of a top gate OFET device of Example 2.

Figure 9 is a transfer curve of a top gate OFET device of Example 3. Detailed Description

Advantageously, the polycycloolefinic or norbornene-type polymers used in the planarization layers of the present invention are tailorable to overcome the drawbacks that have been observed in previously known planarization materials, such as poor electrical stability of the OSC in contact with the planarization layer, low surface energy which causes de-wetting of the OSC material during coating.

Moreover, the planarization layers comprising polycycloolefinic polymers show improved adhesion to the substrate and to electrodes, reduced surface roughness, and improved OSC performance.

The planarization layers comprising polycycloolefinic polymers allow for time-, cost- and material-effective production of OFETs employing organic

semiconductor materials and organic dielectric materials on a large scale.

Further, as will be discussed, the polycycloolefinic or norbornene-type polymers can, in combination with the substrate and/or with functional layers like the organic dielectric layer or the OSC layer, provide improved surface energy, adhesion and structural integrity of such combined layers in comparison with planarization materials of prior art that have been employed in such OFETs.

As used herein, the term "polymer" will be understood to mean a molecule that encompasses a backbone of one or more distinct types of repeating units (the smallest constitutional unit of the molecule) and is inclusive of the commonly known terms "oligomer", "copolymer", "homopolymer" and the like. Further, it will be understood that the term polymer is inclusive of, in addition to the polymer itself, residues from initiators, catalysts and other elements attendant to the synthesis of such a polymer, where such residues are understood as not being covalently incorporated thereto. Further, such residues and other elements, while normally removed during post

polymerization purification processes, are typically mixed or co-mingled with the polymer such that they generally remain with the polymer when it is transferred between vessels or between solvents or dispersion media. As used herein, the terms "orthogonal" and "orthogonality" will be understood to mean chemical orthogonality. For example, an orthogonal solvent means a solvent which, when used in the deposition of a layer of a material dissolved therein on a previously deposited layer, does not dissolve said previously deposited layer.

As used herein, the term "polymer composition" means at least one polymer, and one or more other materials added to the at least one polymer to provide, or to modify, specific properties of the polymer composition and or the at least one polymer therein. It will be understood that a polymer composition is a vehicle for carrying the polymer to a substrate to enable the forming of layers or structures thereon. Exemplary materials include, but are not limited to, solvents, antioxidants, photoinitiators, photosensitizers, crosslinking moieties or agents, reactive diluents, acid scavengers, leveling agents and adhesion promoters. Further, it will be understood that a polymer composition may, in addition to the aforementioned exemplary materials, also encompass a blend of two or more polymers.

As defined herein, the terms "polycycloolefin", "polycyclic olefin", and "norbornene-type" are used interchangeably and refer to addition

polymerizable monomers, or the resulting repeating unit, encompassing at least one norbornene moiety such as shown by either Structure Al or A2, below. The simplest norbornene-type or polycyclic olefin monomer bicyclo[2.2.1]hept-2-ene (Al) is commonly referred to as norbornene.

(Al) (A2)

However, the term "norbornene-type monomer" or " norbornene-type repeating unit", as used herein, is understood to not only mean norbornene itself but also to refer to any substituted norbornene, or substituted and unsubstituted higher cyclic derivatives thereof, for example of Structures B 1 and B2, shown below, wherein m is an integer greater than zero.

(Bl) (B2)

By the substitution of a norbornene-type monomer with a pendant group, the properties of a polymer formed therefrom can be tailored to fulfill the needs of individual applications. The procedures and methods that have been developed to polymerize functionalized norbornene-type monomers exhibit an outstanding flexibility and tolerance to various moieties and groups of the monomers. In addition to polymerization of monomers with a specific pendant group, monomers having a variety of distinct functionalities can be randomly polymerized to form a final material where the types and ratios of monomers used dictate the overall bulk properties of the resulting polymer.

As used herein, "hydrocarbyl" refers to a radical or group that contains a carbon backbone where each carbon is appropriately substituted with one or more hydrogen atoms. The term "halohydrocarbyl" refers to a hydrocarbyl group where one or more of the hydrogen atoms, but not all, have been replaced by a halogen (F, CI, Br, or I). The term perhalocarbyl refers to a hydrocarbyl group where each hydrogen has been replaced by a halogen. Non-limiting examples of hydrocarbyls, include, but are not limited to a C]- C ₂₅ alkyl, a C ₂ -C ₂₄ alkenyl, a C ₂ -C ₂₄ alkynyl, a C ₅ -C ₂₅ cycloalkyl, a C ₆ -C2 ₄ aryl or a C ₇ -C ₂ 4 aralkyl. Representative alkyl groups include but are not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert- butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and dodecyl. Representative alkenyl groups include but are not limited to vinyl, propenyl, butenyl and hexenyl. Representative alkynyl groups include but are not limited to ethynyl, 1-propynyl, 2-propynyl, 1 butynyl, and 2-butynyl.

Representative cycloalkyl groups include but are not limited to cyclopentyl, cyclohexyl, and cyclooctyl substituents. Representative aryl groups include but are not limited to phenyl, biphenyl, naphthyl, and anthracenyl.

Representative aralkyl groups include but are not limited to benzyl, phenethyl and phenbutyl. The term "halohydrocarbyl" as used herein is inclusive of the hydrocarbyl moieties mentioned above but where there is a degree of halogenation that can range from at least one hydrogen atom being replaced by a halogen atom (e.g., a fluoromethyl group) to where all hydrogen atoms on the hydrocarbyl group have been replaced by a halogen atom (e.g., trifluoromethyl or perfluoromethyl), also referred to as perhalogenation. For example, halogenated alkyl groups that can be useful in embodiments of the present invention can be partially or fully halogenated, alkyl groups of the formula C _a X _2a+ i wherein X is independently a halogen or a hydrogen and a is selected from an integer of 1 to 25. In some embodiments each X is independently selected from hydrogen, chlorine, fluorine bromine and/or iodine. In other embodiments each X is independently either hydrogen or fluorine. Thus, representative halohydrocarbyls and perhalocarbyls are exemplified by the aforementioned exemplary hydrocarbyls where an appropriate number of hydrogen atoms are each replaced with a halogen atom.

In addition, the definition of the terms "hydrocarbyl", "halohydrocarbyl", and "perhalohydrocarbyl", are inclusive of moieties where one or more of the carbons atoms is replaced by a heteroatom selected independently from O, N, P, or Si. Such heteroatom containing moieties can be referred to as, for example, either "heteroatom-hydrocarbyls" or "heterohydrocarbyls", including, among others, ethers, epoxies, glycidyl ethers, alcohols, carboxylic acids, esters, maleimides, amines, imines, amides, phenols, amido-phenols, silanes, siloxanes, phosphines, phosphine oxides,

phosphinites, phosphonites, phosphites, phosphonates, phosphinates, and phosphates.

Further exemplary hydrocarbyls, halohydrocarbyls, and perhalocarbyls, inclusive of heteroatoms, include, but are not limited to, -(CH ₂ ) _n -Ar- (CH ₂ )n-C(CF ₃ ) ₂ -OH, -(CH ₂ ) _n -Ar-(CH ₂ ) _n -OCH ₂ C(CF ₃ ) ₂ -OH,

-(CH ₂ ) _n -C(CF ₃ ) ₂ -OH, -((CH ₂ )i-0-) _k -(CH ₂ )-C(CF3) ₂ -OH,

-(CH ₂ ) _n -C(CF ₃ )(CH ₃ )-OH, -(CH ₂ ) _n -C(0)NHR*, -(CH ₂ )„-C(0)C1, -(CH ₂ )„- C(0)OR*, -(CH ₂ )n-OR*, -(CH ₂ ) _n -OC(0)R* and -(CH ₂ ) _n -C(0)R*, where n independently represents an integer from 0 to 12, i is 2, 3 or 4, k is 1, 2 or 3, Ar is aryl, for example phenyl, and R* independently represents hydrogen, a Ci-Cn alkyl, a CpCn halogenated or perhalogenated alkyl, a C ₂ -Cio alkenyl, a C ₂ -Cio alkynyl, a C5-C12 cycloalkyl, a C ₆ -Ci ₄ aryl, a C ₆ -Ci ₄ halogenated or perhalogenated aryl, a C ₇ -CH aralkyl or a halogenated or perhalogenated C ₇ - Ci ₄ aralkyl.

Exemplary perhalogenated alkyl groups include, but are not limited to, trifluoromethyl, trichloromethyl, -C ₂ F ₅ , -C ₃ F ₇ , -C4F9, -C ₆ F ₁₃ , -C ₇ F ₁₅ , and - Ci iF ₂₃ . Exemplary halogenated or perhalogenated aryl and aralkyl groups include, but are not limited to, groups having the formula -(CH ₂ ) _x -C ₆ FyH _5-y , and -(CH ₂ ) _x -C6F _y ¾ _-y -/?C _z F _q H _2z+1-q , where x, y, q and z are independently selected integers from 0 to 5, 0 to 5, 0 to 9 and 1 to 4, respectively.

Specifically, such exemplary halogenated or perhalogenated aryl groups include, but are not limited to, pentachlorophenyl, pentafluorophenyl, pentafluorobenzyl, 4-trifluoromethylbenzyl, pentafluorophenethyl, pentafluorophenpropyl, and pentafluorophenbutyl.

In a preferred embodiment of the present invention, the norbornene-type polymer incorporates two or more distinct types of repeating units. In another preferred embodiment of the present invention, the norbornene- type polymer incorporates one or more distinct types of repeating units, where at least one such type of repeating unit encompasses pendant crosslinkable groups or moieties that have some degree of latency. By "latency", it is meant that such groups do not crosslink at ambient conditions or during the initial forming of the polymers, but rather crosslink when such reactions are specifically initiated, for example by actinic radiation or heat. Such latent crosslinkable groups are incorporated into the polymer backbone by, for example, providing one or more norbornene-type monomers encompassing such a pendant crosslinkable group, for example, a substituted or unsubstituted maleimide or maleimide containing pendant group, to the polymerization reaction mixture and causing the polymerization thereof. Preferred crosslinkable groups include a group comprising a substituted or unsubstituted maleimide portion, an epoxide portion, a vinyl portion, an acetylene portion, an indenyl portion, a cinnamate portion or a coumarin portion, and more specifically a group selected from a 3-monoalkyl- or 3,4- dialkylmaleimide, epoxy, vinyl, acetylene, cinnamate, indenyl or coumarin group.

In another preferred embodiment the norbornene-type polymer comprises one or more one or more distinct types of repeating units sselected of

Formula I

(I) wherein Z is selected from -CH ₂ -, -CH ₂ -CH ₂ - or -0-, m is an integer from 0 to 5, each of R ¹ , R ² , R ³ and R ⁴ are independently selected from H, a Cj to C ₂₅ hydrocarbyl, a to C ₂₅ halohydrocarbyl or a Ci to C ₂₅ perhalocarbyl group.

The repeating units of Formula I are formed from the corresponding norbornene-type monomers of Formula la where Z, m and R ^{1 "4} are as defined above:

(la)

In the repeating units and monomers of Formula I and la, in a preferred embodiment Z is -CH ₂ - and m is 0, 1 or 2, in another preferred embodiment, Z is -CH ₂ - and m is 0 or 1, and in still another preferred embodiment, Z is - CH ₂ - and m is 0. In another preferred embodiment the planarization layer comprises a polymer composition which comprises a either a single norbornene-type polymer or a blend of two or more different norbornene-type polymers.

Where such polymer composition embodiments encompass a single norbornene-type polymer, such polymer can be a homopolymer, that is to say a polymer encompassing only one type of repeating unit, or a copolymer, that is to say a polymer encompassing two or more distinct types of repeating units. Where such polymer composition embodiments encompass a blend of different polymers, "different" is understood to mean that each of the blended polymers encompasses at least one type of repeating unit, or combination of repeating units, that is distinct from any of the other blended polymers.

In another preferred embodiment of the invention the polymer composition is a blend of two or more different norbornene-type polymers, wherein each epeating units of formula I

wherein Z is selected from -CH ₂ -, -CH ₂ -CH ₂ - or -0-, m is an integer from 0 to 5, each of R ¹ , R ² , R ³ and R ⁴ are independently selected from H, a Ci to C ₂ 5 hydrocarbyl, a Ci to C ₂₅ halohydrocarbyl or a C] to C ₂₅ perhalocarbyl group.

The polymer and polymer composition embodiments of the present invention can advantageously be tailored to provide a distinct set of properties for each of many specific applications. That is to say that different combinations of norbornene-type monomers with several different types of pendant groups can be polymerized to provide norbornene-type polymers having properties that provide for obtaining control over

properties such as flexibility, adhesion, dielectric constant, and solubility in organic solvents, among others. For example, varying the length of an alkyl pendant group can allow control of the polymer's modulus and glass transition temperature (Tg). Also, pendant groups selected from maleimide, cinnamate, coumarin, anhydride, alcohol, ester, and epoxy functional groups can be used to promote crosslinking and to modify solubility characteristics. Polar functional groups, epoxy and triethoxysilyl groups can be used to provide adhesion to metals, silicon, and oxides in adjacent device layers. Fluorinated groups, for example, can be used to effectively modify surface energy, dielectric constant and influence the orthogonality of the solution with respect to other materials.

Thus, in further preferred embodiments of the present invention, in particular for such embodiments where only one of R ^1'4 is different from H, one or more of R ^{1 "4} denote a halogenated or perhalogenated aryl or aralkyl group including, but not limited to those of the formula -(CH ₂ ) _x -C ₆ F _y H _5-y , and -(CH ₂ )x-C ₆ F _y H _4- y-pC _z F _q H _2z+1-q , where x, y, q, and z are independently selected integers from 0 to 5, 0 to 5, 0 to 9, and 1 to 4, respectively, and "p" means "para". Specifically such formulae include, but are not limited to, trifluoromethyl, trichloromethyl, -C ₂ F ₅ , -C ₃ F ₇ , -C ₄ F ₉ , C ₆ F ₁₃ , -C ₇ Fi ₅ , -CuF ₂₃ , pentachlorophenyl, pentafluorophenyl, pentafluorobenzyl, 4- trifluoromethylbenzyl, pentafluorophenylethyl, pentafluorophenpropyl, and pentafluorophenbuty 1.

Further still, some preferred embodiments of the present invention, in particular for such embodiments where only one of R ^1"4 is different from H, encompass a group that is different from H that is a polar group having a terminal hydroxy, carboxy or oligoethyleneoxy moiety, for example a terminal hydroxyalkyl, alkylcarbonyloxy (for example, acetyl), hydroxy- oligoethyleneoxy, alkyloxy-oligoethyleneoxy or alkylcarbonyloxy- oligoethyleneoxy moiety, where "oligoethyleneoxy" is understood to mean - (CH ₂ CH ₂ 0)s- with s being 1, 2 or 3; for example l-(bicyclo[2.2.1]hept-5-en- 2-yl)-2,5,8,l l-tetraoxadodecane (NBTODD) where s is 3 and 5-((2-(2- methoxyethoxy)ethoxy)methyl) bicyclo[2.2.1]hept-2-ene (NBTON) where s is 2.

Further still, other preferred embodiments of the present invention, in particular for such embodiments where only one of R ^1"4 is different from H, encompass a group that is different from H that is a group having a pendant silyl group, for example a silyl group represented by -(CH ₂ ) _n -SiR ⁹ 3 where n is an integer from 0 to 12, and each R independently represents halogen selected from the group consisting of chlorine, fluorine, bromine and iodine, linear or branched (Ci to C ₂ o)alkyl, linear or branched (Ci to C ₂ o)alkoxy, substituted or unsubstituted (C ₆ to C ₂ o)aryloxy, linear or branched (Ci to C ₂ o)alkyl carbonyloxy, substituted or unsubstituted (C ₆ to C ₂₀ )aryl; linear or branched (Ci to C ₂ o) dialkylamido; substituted or unsubstituted (C ₆ -C2 ₀ ) diarylamido; substituted or unsubstituted (Ci-C ₂ o)alkylarylamido.

Yet further still, for such embodiments where only one of R is different from H, preferred embodiments encompass a group that is either a photoreactive or a crosslinkable group. Preferred photoreactive or crosslinkable groups encompass a linking portion L and a functional portion Fp. Preferably L denotes or comprises a group selected from Q- Ci ₂ alkyls, aralkyls, aryls or hetero atom analogs. Further preferably Fp denotes or comprises one or more of a maleimide, a 3-monoalkyl- or 3,4- dialkylmaleimide, epoxy, vinyl, acetylenic, cinnamate, indenyl or coumarin moiety, which is capable of a crosslinking or 2+2 crosslinking reaction.

As used herein, the phrase "photoreactive and/or crosslinkable", when used to describe certain pendant groups, will be understood to mean a group that is reactive to actinic radiation and as a result of that reactivity enters into a crosslinking reaction, or a group that is not reactive to actinic radiation but can, in the presence of a crosslinking activator, enter into a crosslinking reaction.

Preferred repeating units that encompass a pendant photoreactive or crosslinkable group that are representative of Formula I are formed during polymerization from norbornene-type monomers that include, but are not limited to, those selected from the following formulae:

P2

where n is an integer from 1 to 8, Q ¹ and Q ² are each independently from one another -H or -CH ₃ , and R' is -H or -OCH ₃ .

Further preferred repeating units of Formula I such as described above are derived from one or more norbornene-type monomers represented by the following structural formulae 1 through 5 below:

For structural formulae 1-5 above, m is an integer from 0 to 3, A is a connecting, spacer or bridging group selected from (CZ ₂ ) _n , (CH ₂ ) _n - (CH=CH) _p -(CH ₂ ) _n , (CH ₂ )„-O-(CH ₂ ) _n , (CH ₂ ) _n -C ₆ Q ₄ -(CH ₂ ) _n , and for structure 1 additionally selected from (CH ₂ ) _n -0 and C(0)-0; R is selected from H, CZ ₃ , (CZ ₂ ) _n CZ ₃ , OH, O-(O)CCH ₃ , (CH ₂ CH ₂ O) _n CH ₃ , (CH ₂ ) _n -C ₆ Q ₅ , cinnamate or p-methoxy-cinnamate, coumarin, phenyl-3-indene, epoxide, C≡C-Si(C ₂ H ₅ ) ₃ or C≡C-Si(i-C ₂ Hs) ₃ , each n is independently an integer from 0 to 12, p is an integer from 1-6, C ₆ Q ₄ and C Q ₅ denote benzene that is substituted with Q, Q is independently H, F, CH ₃ , CF ₃ or OCH ₃ , Z is independently H or F, with the proviso that -A-R does not contain an -O-O- (peroxy) linkage, and R" is independently H or CH ₃ .

Further preferred repeating units of Formula I such as described above are formed from one or more norbornene-type monomers that include, but are not limited to, those selected from the following formulae:

1

PCT/EP2013/000255

17

-20-

where "Me" means methyl, "Et" means ethyl, "OMe-p" means para-methoxy, "Ph" and "C ₆ H ₅ " mean phenyl, means phenylene, "C ₆ F ₅ " means pentafluorophenyl, in subformulae 9 and 11 "OAc" means acetate, in sub- formula 25 "PFAc" means -OC(0)-C ₇ Fi ₅ , and for each of the above subformulae having a methylene bridging group (a C¾ covalently bonded to both the norbornene ring and a functional group), including but not limited to 11-14, 16, 18, 19 and 54, it will be understood that the methylene bridging group can be replaced by a covalent bond or -(CH ₂ ) _b - as in formula 20, and b is an integer from 1 to 6.

It will be further noted that while 55 specific examples are provided above, other monomers in accordance with embodiments of the present invention are inclusive of monomers represented by formula la where at least one of R ¹ , R ² , R ³ and R ⁴ are hydrocarbyls, halohydrocarbyls, and perhalocarbyls, inclusive of heteroatoms, that include -(CH ₂ ) _n -Ar-(CH ₂ ) _n -C(CF ₃ ) ₂ -OH, - (CH ₂ ) _n -Ar-(CH ₂ ) _n -OCH ₂ C(CF ₃ ) ₂ -OH, -(CH ₂ ) _n -C(CF ₃ ) ₂ -OH, -((CH ₂ )j-0-) _k - (CH ₂ )-C(CF ₃ ) ₂ -OH, -(CH ₂ ) _n -C(CF ₃ )(CH ₃ )-OH, (CH ₂ ) _n -C(0)NHR*, (CH ₂ ) _n - C(0)C1, -(CH ₂ ) _n -C(0)OR*, (CH ₂ ) _n -OR*, -(CH ₂ ) _n -OC(0)R* and -(CH ₂ ) _n - C(0)R*, where n independently represents an integer from 0 to 12, i is 2, 3 or 4, k is 1, 2 or 3, Ar is aryl, for example phenyl, and R* independently represents hydrogen, a Ci-Cn alkyl, a Ci-Cn halogenated or perhalogenated alkyl, a C ₂ -Cio alkenyl, a C ₂ -Ci ₀ alkynyl, a C ₅ -C ₁₂ cycloalkyl, a C ₆ -C ₁₄ aryl, a C ₆ -Ci ₄ halogenated or perhalogenated aryl, a C ₇ -C ₁₄ aralkyl or a

halogenated or perhalogenated C ₇ -Cj ₄ aralkyl. Exemplary perhalogenated alkyl groups include, but are not limited to, trifluoromethyl, trichloromethyl, -C ₂ F ₅ , -C ₃ F ₇ , -C ₄ F9,-C ₇ F ₁₅ , and -CnF ₂₃ . Exemplary halogenated or perhalogenated aryl and aralkyl groups include, but are not limited groups having the formula -(CH ₂ ) _x- C ₆ F _y H _5-y , and -(CH ₂ ) _x -C ₆ F _y H4 _-y - C _z F _q H _2z+1-q , where x, y, q, and z are independently selected integers from 0 to 5, 0 to 5, 0 to 9, and 1 to 4, respectively. Specifically, such exemplary halogenated and perhalogenated aryl groups include, but are not limited to,

pentachlorophenyl, pentafluorophenyl, pentafluorobenzyl, 4- trifluoromethylbenzyl, pentafluorophenylethyl, pentafluorophenpropyl, and pentafluorophenbutyl.

While Formula I and la, as well as each of the subformulae and generic formulae provided above are depicted without indication of any

stereochemistry, 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 expand 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 endo- isomer, or are essentially the pure

advantageous isomer. Another preferred embodiment of the present invention is directed to polymers of Formula I that comprise repeating units where one of R ^1"4 , for example R ¹ , is a fluorinated or perfluorinated alkyl, aryl or aralkyl group as described above and the others of R ^1"4 are H. Preferably R ¹ is selected from one of the above subformulae 15-26 and more preferably from subformulae 15, 16, 17, 18, 19 or 20 (NBC ₄ F ₉ , NBCH ₂ C ₆ F ₅ , NBC ₆ F ₅ , NBCH ₂ C ₆ H ₃ F ₂ , NBCH ₂ C ₆ H ₄ CF ₃ , and NBalkylC ₆ F ₅ ).

Another preferred embodiment of the present invention is directed to polymers of Formula I that have repeating units where one of R ¹ - ⁴ , for example R ¹ , is a photoreactive or crosslinkable group as described above and the others of R ^1"4 are H. Preferably R ¹ is a group as shown in one of the above subformulae 27-50 and more preferably as shown in subformulae 34, 35, 36, 37 and 38 (DMMIMeNB, DMMIEtNB, DMMIPrNB, DMMIBuNB and DMMIHxNB).

Another preferred embodiment of the present invention is directed to polymers of Formula I that have repeating units where one of R ^1'4 , for example R ¹ , is a pendant silyl group represented by— (CH ₂ ) _n -SiR ⁹ ₃ where n is an integer from 0 to 12, R ⁹ independently represents halogen selected from the group consisting of chlorine, fluorine, bromine and iodine, linear or branched (Cj to C ₂₀ )alkyl, linear or branched (Ci to C ₂₀ )alkoxy, substituted or unsubstituted (C ₆ to C ₂ o)aryl, linear or branched {C _\ to C ₂₀ )alkyl carbonyloxy, substituted or unsubstituted (C ₆ to C ₂ o)aryloxy; linear or branched (C _\ to C ₂₀ ) dialkylamido; substituted or unsubstituted (C ₆ -C ₂₀ ) diarylamido; substituted or unsubstituted (C]-C ₂ o)alkylarylamido..

Another preferred embodiment of the present invention is directed to polymers of Formula I that have repeating units where one of R ^1"4 , for example R ¹ , is a polar group having a hydroxy, carboxy, acetoxy or oligoethyleneoxy moiety as described above and the others of R ^{1 "4} denote H. Preferably R ¹ is a group as shown in one of the above subformulae 9-14, and more preferably of subformula 9 (MeOAcNB).

Another preferred embodiment of the present invention is directed to a polymer having a first type of repeating unit selected from fluorinated repeating units as described above and a second type of repeating unit selected from crosslinkable repeating units, also as described above.

Preferred polymers of this embodiment include polymers having a first type of repeating unit selected from subformulae 15, 16, 17, 18, 19 and 20

(NBC ₄ F9, NBCH ₂ C ₆ F ₅ , NBC ₆ F ₅ , NBCH ₂ C ₆ F ₂ , NBCH ₂ C ₆ H ₄ CF ₃ , and

NBalkylC ₆ F5), and a second type of repeating unit selected from

subformulae 34, 35, 36, 37 and 38 (DMMIMeNB, DMMIEtNB,

DMMIPrNB, DMMIBuNB and DMMIHxNB). Another preferred embodiment of the present invention is directed to a polymer having a first type of repeating unit selected from crosslinkable repeating units as described above and a second type of repeating unit selected from repeating units having a pendant silyl group, also as described above. Preferred polymers of this embodiment include polymers having a first type of repeating unit selected from subformulae 34, 35, 36, 37 and 38 (DMMIMeNB, DMMIEtNB, DMMIPrNB, DMMIBuNB and DMMIHxNB), and a second type of repeating unit selected from subformulae 53 and 54 (TMSNB, TESNB). Another preferred embodiment of the present invention is directed to a polymer having a first type of repeating unit selected from fluorinated repeating units as described above, a second type of repeating unit selected from crosslinkable repeating units, also as described above and a third type of repeating unit selected from polar repeating units, again as described above. Preferred polymers of this embodiment include polymers having a first repeating unit of subformula 9 (MeOAcNB), a second type of repeating unit selected from subformulae 34, 35, 36, 37, or 38

(DMMIMeNB, DMMIEtNB, DMMIPrNB, DMMIBuNB and

DMMIHxNB), and a third type of repeating unit selected from subformula 16 (NBCH ₂ C ₆ F ₅ ). Another preferred embodiment of the present invention is directed to a polymer having more than three different types of repeating units in accordance with Formula I. Another preferred embodiment of the present invention is directed to a polymer blend of a first polymer having a first type of repeating unit in accordance with Formula I, and a second polymer having, at least, a first type of repeating unit and a second type of repeating unit in accordance with Formula I that is distinct from the first type.

Alternatively such polymer blends can encompass the aforementioned second polymer mixed with an alternative first polymer having two or more distinct types of repeat units in accordance with Formula I. Further preferably, such polymer blends can encompass the aforementioned alternative first polymer mixed with an alternative second polymer having three distinct types of repeat units in accordance with Formula I. Another preferred embodiment of the present invention is directed to a polymer having a first and a second distinct type of repeat units in accordance with Formula I where the ratio of such first and second type of repeat units is from 95:5 to 5:95. In another preferred embodiment the ratio of such first and second type of repeat units is from 80:20 to 20: 80. In still another preferred embodiment the ratio of such first and second type of repeat units is from 60:40 to 40:60. In yet another preferred embodiment the ratio of such first and second type of repeat units is from 55:45 to 45:55. Another preferred embodiment of the present invention encompasses a polymer blend of one or more polymers each having at least one type of repeat unit in accordance with Formula I and one or more polymers having repeat units that are different from norbornene-type repeat units. These other polymers are preferably selected from polymers including but not limited to poly(methyl methacrylate) (PMMA), polystyrene (PS), poly-4- vinylphenol, polyvinylpyrrolidone, or combinations thereof, like PMMA-PS and -polyacrylonitrile (PAN).

Examples of suitable and preferred norbornene monomers, polymers and methods for their synthesis are provided herein and can also be found in US 5,468,819 B2, US 6,538,087 B2, US 2006/0020068 Al, US 2007/0066775 Al, US 2008/0194740 A 1, PCT/EP201 1/004281, US Ser.No.13/223,784, PCT/EP201 1/004282, US 6,723,486 B2, US 6,455,650 B2 and US

Ser.No.13/223,884, which are incorporated into this application by reference. For example, exemplary polymerizations processes employing Group VIII transition metal catalysts are described in the aforementioned US

2006/0020068 Al .

The polymer embodiments of the present invention are formed having a weight average molecular weight (M _w ) that is appropriate to their use.

Generally, a M _w from 5,000 to 500,000 is found appropriate for some embodiments, while for other embodiments other M _w ranges can be advantageous. For example, in a preferred embodiment, the polymer has a M _w of at least 30,000, while in another preferred embodiment the polymer has a M _w of at least 60,000. In another preferred embodiment, the upper limit of the polymer's M _w is up to 400,000, while in another preferred embodiment the upper limit of the polymer's M _w is up to 250,000. It will be understood that since an appropriate M _w is a function of the desired physical properties in the cured polymer, films, layers or structures derived therefrom, it is a design choice and thus any M _w within the ranges provided above is within the scope of the present invention.

In a preferred embodiment of the present invention, a crosslinkable or crosslinked polymer is used. It has been found that such a crosslinkable or crosslinked polymer can serve to improve one or more properties selected from structural integrity, durability, mechanical resistivity and solvent resistivity of the gate dielectric layer and the electronic device. Suitable and preferred crosslinkable polymers are for example those having one or more repeating units of Formula I wherein one or more of R denotes a crosslinkable group, very preferably units formed by monomers selected from subformulae 27-50.

For crosslinking, the polymer, generally after deposition thereof, is exposed to electron beam or electromagnetic (actinic) radiation such as X- ray, UV or visible radiation, or heated if it contains thermally crosslinkable groups. For example, actinic radiation may be employed to image-wise expose the polymer using a wavelength of from 1 1 nm to 700 nm, such as from 200 to 700 nm. A dose of actinic radiation for exposure is generally from 25 to 15,000 m J/cm . Suitable radiation sources include mercury, mercury/xenon, mercury/halogen and xenon lamps, argon or xenon laser sources, x-ray. Such exposure to actinic radiation causes crosslinking in exposed regions. Although other repeating unit pendant groups that crosslink can be provided, generally such crosslinking is provided by repeating units that encompass a maleimide pendant group, that is to say one of R ¹ to R ⁴ is a substituted or unsubstituted maleimide moiety. If it is desired to use a light source having a wavelength outside of the photo- absorption band of the maleimide group, a radiation sensitive

photosensitizer can be added. If the polymer contains thermally

crosslinkable groups, optionally an initiator may be added to initiate the crosslinking reaction, for example in case the crosslinking reaction is not initiated thermally.

In a preferred embodiment, the planarization layer is post exposure baked at a temperature from 70°C to 130°C, for example for a period of from 1 to 10 minutes. Post exposure bake can be used to further promote crosslinking of crosslinkable moieties within exposed portions of the polymer.

In another preferred embodiment, the crosslinkable polymer composition comprises a stabilizer material or moiety to prevent spontaneous

crosslinking and improve shelf life of the polymer composition. Suitable stabilizers are antioxidants such as catechol or phenol derivatives that optionally contain one or more bulky alkyl groups, for example t-butyl groups, in ortho-position to the phenolic OH group.

In order to improve the processing of the functional layers and the integrity of the electronic device, it is desirable to decrease the time needed for the process while keeping or improving the physical properties of the layers being formed. This can be maintained where subsequent layers and solvents used in forming such layers are orthogonal and thus do not dissolve each other. Where such orthogonality is difficult to obtain, crosslinking, typically UV crosslinking, a first functional layer to make such first layer insoluble with respect to the polymer composition of a second functional layer will prevent any influence of the properties of either layer on the other layer. Shortening the time needed for the processing can be done for example by tuning the coating process, while decreasing the time needed for UV crosslinking can be achieved both by chemical adjustment of the polymer or by changes in the process.

However, chemical modifications of polymers are limited, because the UV sensitivity is related to certain properties of the polymer, and for example changes towards increased UV sensitivity may decrease the solubility. Changing the process, for example, by using higher power UV, could increase the possibility of creating an ozone atmosphere and thus cause undesired changes in the surface of the polymer.

Therefore, in a preferred embodiment of the present invention the polymer composition comprises one or more crosslinker additives. Such additives comprise two or more functional groups that are capable of reacting with the pendant crosslinkable groups of the polycycloolefinic polymer. It will also be understood that the use of such crosslinker additives can also enhance the crosslinking of the aforementioned polymer.

In one embodiment of this invention, crosslinking can be achieved by exposure to UV radiation.

The crosslinkable group of the crosslinker is preferably selected from a maleimide, 3-monoalkyl-maleimide, 3,4-dialkylmaleimide, epoxy, vinyl, acetylene, indenyl, cinnamate or coumarin group, or a group that comprises a substituted or unsubstituted maleimide portion, epoxide portion, vinyl portion, acetylene portion, indenyl portion, cinnamate portion or coumarin portion. Very preferably the crosslinker is selected of formula III 1 or III2

P-A"-X ^* -A"-P III1

H _4-C C(A"-P) _C III2 wherein X' is O, S, NH or a single bond, A" is a single bond or a connecting, spacer or bridging group, which is preferably selected from (CZ ₂ ) _n ,

(CH ₂ ) _n -(CH=CH) _p -(CH ₂ ) _n , (CH ₂ ) _n -0-(CH ₂ )n, (CH ₂ ) _n -C ₆ Q ₁₀ -(CH ₂ )„, and C(O), where each n is independently an integer from 0 to 12, p is an integer from 1-6, Z is independently H or F, C ₆ Qio is cyclohexyl that is substituted with Q, Q is independently H, F, CH ₃ , CF ₃ , or OCH ₃ , P is a crosslinkable group, and c is 2, 3, or 4, and where in formula IIIl at least one of X' and the two groups A" is not a single bond. P is preferably selected from a maleimide, a 3-monoalkyl-maleimide, a 3,4- dialkylmaleimide, an epoxy, a vinyl, an acetylene, an indenyl, a cinnamate or a coumarin group, or comprises a substituted or unsubstituted maleimide portion, an epoxide portion, a vinyl portion, an acetylene portion, an indenyl portion, a cinnamate portion or a coumarin portion.

Suitable and preferred compounds are selected from formula CI :

wherein R ¹⁰ and R ¹¹ are independently of each other H or a Ci-C ₆ alkyl group, and A" is as defined in formula IIIl. Especially preferred crosslinkers are selected from DMMI-butyl-DMMI, DMMI-pentyl-DMMI and DMMI- hexyl-DMMI, wherein "DMMI" means 3,4-dimethylmaleimide.

The spacer group A" preferably denotes linear Ci to C ₃₀ alkylene or branched C ₃ to C ₃₀ alkylene or cyclic C ₅ to C ₃₀ alkylene, each of which is unsubstituted or mono- or polysubstituted by F, CI, Br, I ,or CN, wherein optionally one or more non-adjacent CH ₂ groups are replaced, in each case independently from one another, by -0-, -S-, -NH-, -NR ¹⁸ -, -SiR ¹⁸ R ¹⁹ -, - C(O)-, -C(0)0-, -OC(O)-, -OC(0)-0-, -S-C(O)-, -C(0)-S-, -CH=CH- or - C≡C- in such a manner that O and/or S atoms are not linked directly to one another, R ¹⁸ and R ¹⁹ are independently of each other H , methyl, ethyl or a C ₃ to Ci 2 linear or branched alkyl group. Preferred groups A" are -(CH ₂ ) _r -, -(CH ₂ CH ₂ 0) _s -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ -S- CH ₂ CH ₂ - or -CH ₂ CH ₂ -NH-CH ₂ CH ₂ - or -(SiR ¹⁸ R ¹⁹ -0) , with r being an integer from 2 to 12, s being 1, 2 or 3 and R ¹⁸ and R ¹⁹ having the meanings given above.

Further preferred groups A" are selected from methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylene-thioethylene, ethylene-N-methyl- iminoethylene, 1-methylalkylene, ethenylene, propenylene, and butenylene.

The synthesis of crosslinkers like those of formula CI is disclosed for example in US 3,622,321.

In another preferred embodiment the polymer composition used for preparation of the planarization layer comprises a crosslinkable

polycycloolefinic polymer and a reactive adhesion promoter. The reactive adhesion promoter comprises a first functional group that is capable of crosslinking with the pendant crosslinkable group in the crosslinkable polycycloolefinic polymer, and a second functional group which is a surface-active group that is capable of interactions, for example chemical bonding, with the functional layer provided onto the planarization layer. The adhesion promoter may be used especially if the the functional layer provided onto the planarization layer is a semiconducting or dielectric layer.

Preferably the adhesion promoter is a compound of formula IV G-A"-P IV wherein G is a surface-active group, preferably a silane or silazane group, A" is a single bond or a connecting, spacer or bridging group, preferably as defined in formula III1 above, and P is a crosslinkable group, preferably as defined in formula III1 above. G is preferably a group of the formula -SiR ¹² R ¹³ R ¹⁴ , or a group of the formula -NH-SiR ^I2 R ¹³ R ¹⁴ , wherein R ¹² , R ¹³ and R ¹⁴ are each independently selected from halogen, silazane, Ci-Ci ₂ -alkoxy, CrCn-alkylamino, optionally substituted C ₅ -C ₂ o-aryloxy and optionally substituted C ₂ -C ₂ o- heteroaryloxy, and wherein one or two of R ¹² , R ¹³ and R ¹⁴ may also denote

C]-Ci ₂ -alkyl, optionally substituted C ₅ -C ₂ o-aryl or optionally substituted C ₂ - C ₂ o-heteroaryl.

P is preferably selected from a maleimide, a 3-monoalkyl-maleimide, a 3,4- dialkylmaleimide, an epoxy, a vinyl, an acetyl, an indenyl, a cinnamate or a coumarin group, or comprises a substituted or unsubstituted maleimide portion, an epoxide portion, a vinyl portion, an acetyl portion, an indenyl portion, a cinnamate portion or a coumarin portion. A" is preferably selected from (CZ ₂ )„, (CH ₂ ) _n -(CH=CH) _p -(CH ₂ ) _n , (CH ₂ ) _n -0, (CH ₂ ) _n -0-(CH ₂ ) _n , (CH ₂ ) _n -C ₆ Q ₄ -(CH ₂ ) _n , (CH ₂ ) _n -C ₆ Q ₁₀ -(CH ₂ ) _n and C(0)-0, where each n is independently an integer from 0 to 12, p is an integer from 1-6, Z is independently H or F, C ₆ Q ₄ is phenyl that is substituted with Q, C ₆ Qio is cyclohexyl that is substituted with Q, Q is independently H, F, CH ₃ , CF ₃ or OCH ₃ .

Preferred adhesion promoters are selected from formula Al :

where R ¹² , R ¹³ R ¹⁴ , and A" are as defined above, and R ¹⁰ and R ¹¹ are each independently H or a Ci-C ₆ alkyl group. Especially preferred are DMMI-propyl- Si(OEt) ₃ , DMMI-butyl-Si(OEt) ₃ , DMMI-butyl-Si(OMe) ₃ , DMMI-hexyl- Si(OMe) ₃ , wherein "DMMI" means 3,4-dimethylmaleimide. Preferably the polymer compositions generally encompass, in addition to one or more polymer components, a casting solvent optionally having orthogonal solubility properties with respect to the insulating layer material and the OSC layer, an optional cross-linking agent, an optional reactive solvent, an optional UV sensitizer, and an optional thermal sensitizer. The present invention also relates to an electronic device having or being obtained through the use of a polymer composition according to the present invention.

Such electronic devices include, among others, field effect transistors (FETs) and organic field effect transistors (OFETs), thin film transistors (TFT) and organic thin film transistors (OTFTs), which can be top gate or bottom gate transistors. For example, transistors made through the use of a polymer composition according to the present invention are depicted schematically in Figures 3 and 4.

Figure 1 and Figure 2 depict schematic representations of top and bottom gate organic field effect transistors, respectively, according to prior art. Thus the OFET device of Figure 1 and Figure 2 include substrate (10), source and drain electrodes (20), organic semiconductor layer (30), gate dielectric layer (40), gate electrode (50), and an optional passivation layer (60).

Figure 3 is a schematic and exemplary representation of a top gate OFET device in accordance with a first preferred embodiment of the present invention. Such OFET device includes substrate (10), planarization layer (70), which is derived from a polymer composition encompassing a polycycloolefinic polymer or blend of polycycloolefinic polymer as described above and below, source and drain electrodes (20), organic semiconductor layer (30), gate electrode (50), gate dielectric layer (40), and optional layer (60), which is for example a layer having one or more of insulating, protecting, stabilizing and adhesive function, and which is disposed overlying gate electrode (50) and gate dielectric layer (40).

Another subject of the present invention is a process for preparing a top gate OFET device, for example as illustrated in Figure 3, by a) depositing a layer of planarization material (70), which comprises a polycycloolefinic polymer or a polymer blend or polymer composition comprising a polycycloolefinic polymer as described above and below, on a substrate (10), b) forming source and drain electrodes (20) on at least a portion of planarization layer (70) as depicted, c) depositing a layer of organic semiconductor material (30) over the previously deposited planarization layer (70) and source and drain electrodes (20), d) depositing a layer of dielectric material (40) on organic semiconductor layer (30), e) forming gate electrode (50) on at least a portion of dielectric layer (40) as depicted, and f) optionally depositing layer (60), which is for example an insulating and/or protection and/or stabilizing and/or adhesive layer, on the gate electrode (50) and portions of dielectric layer (40).

Figure 4 is a schematic and exemplary representation of a bottom gate OFET device in accordance with a third preferred embodiment of the present invention. Such OFET device includes substrate (10), planarization layer (70), which is derived from a polymer composition encompassing a polycycloolefmic polymer or blend of polycycloolefmic polymer as described above and below, source and drain electrodes (20), organic semiconductor layer (30), gate electrode (50), gate dielectric layer (40), and optional second insulator layer (60), which is a passivation or protection layer to shield the source and drain electrodes (20) from further layers or devices provided on top of the device.

Another subject of the present invention is a process for preparing a bottom gate OFET device, for example as illustrated in Figure 4, by a) depositing a layer of planarization material (70), which comprises a polycycloolefmic polymer or a polymer blend or polymer composition comprising a polycycloolefmic polymer as described above and below, on a substrate (10), b) forming gate electrode (50) on at least a portion of planarization layer (70) as depicted, c) depositing a layer of dielectric material (40) over the previously deposited planarization layer (70) and gate electrode (50), d) depositing a layer of organic semiconductor material (30) on dielectric layer (40), e) forming source and drain electrodes (20) on at least a portion of organic semiconductor layer (40) as depicted, and f) optionally depositing layer (60), which is for example an insulating and/or protection and/or stabilizing and/or adhesive layer, on the source and drain electrodes (20) and portions of organic semiconductor layer (30).

The aforementioned processes for preparing a transistor are another subject of the present invention.

Deposition and/or forming of the layers and structures of the OFET embodiments in accordance with the present invention are preferably performed using solution processing techniques where such techniques are possible. For example a formulation or composition of a material, typically a solution encompassing one or more organic solvents, can be deposited or formed using preferred techniques that include, but are not limited to, dip coating, spin coating, slot die coating, ink jet printing, letter-press printing, screen printing, doctor blade coating, roller printing, reverse-roller printing, offset lithography printing, flexographic printing, web printing, spray coating, brush coating, or pad printing, followed by the evaporation of the solvent employed to form such a solution. For example, an organic semiconductor materialand an organic dielectric material can each be deposited or formed by spin coating, flexographic printing, and inkjet printing techniques in an order appropriate to the device being formed. Slot die coating is most preferred.

Specifically, where planarization layer (70) is deposited by solution processing and employing a solution of one or more of the polymer or polymer blends as described above and below in one or more organic solvents, such solvents are preferably selected from, but not limited to, organic ketones such as methyl ethyl ketone (MEK), 2-heptanone (MAK), cyclohexanone, cyclopentanone, and ethers such as butyl-phenyl ether, 4-methylanisole and aromatic hydrocarbons such as cyclohexylbenzene, or mixtures thereof. Preferably, the total concentration of the polymer material in the formulation is from 0.1 - 25 wt. % although other concentrations can also be appropriate. Organic ketone solvents with a high boiling point have been found to be especially suitable and preferred solvents where inkjet and flexographic printing techniques are employed. The planarization layer (70) should be applied with an appropriate thickness to provide sufficient wetting and adhesion for any additional layers coated thereon while not negatively affecting device performance. While the appropriate thickness of planarization layer (70) used in fabricating a device is a function of the specific device being made and the ultimate use of such a device, among other things, as general guidelines it has been found that a preferred thickness in the range of from 0.1 to 10 microns . It will be understood, however, that other thickness ranges may be appropriate and thus are within the scope of the present invention. In some preferred embodiments of the present invention, a crosslinkable or crosslinked polymer is used as the planarization layer material or as a component thereof. It has been found that such a crosslinkable or crosslinked polymer can serve to improve one or more properties selected from structural integrity, durability and solvent resistance of the planarization layer and the electronic device. Very suitable and preferred crosslinkable polymers are for example those having one or more repeating units of Formula I wherein one or more of R ^1"4 denotes a crosslinkable group, very preferably units of subformulae 27-50.

For crosslinking, the polymer, generally after deposition thereof, is exposed to electron beam or electromagnetic (actinic) radiation such as X-ray, UV or visible radiation, or heated if it contains thermally crosslinkable groups. For example, actinic radiation may be employed to image the polymer using a wavelength of from 11 nm to 700 nm, such as from 200 to 700 nm. A dose of actinic radiation for exposure is generally from 25 to 15,000 mJ/cm . Suitable radiation sources include mercury, mercury/xenon, mercury/halogen and xenon lamps, argon or xenon laser sources, or X-ray. Such exposure to actinic radiation is to cause crosslinking in exposed regions. Although other repeating unit pendant groups that crosslink can be provided, generally such crosslinking is provided by repeating units that encompass a maleimide pendant group, that is to say one of R to R ⁴ is a substituted or unsubstituted maleimide moiety. If it is desired to use a light source having a wavelength outside of the photo-absorption band of the maleimide group, a radiation sensitive photosensitizer can be added. If the polymer contains thermally crosslinkable groups, optionally an initiator may be added to initiate the crosslinking reaction, for example in case the crosslinking reaction is not initiated thermally.

In a preferred embodiment, the planarization layer is post exposure baked at a temperature from 70°C to 130°C, for example for a period of from 1 to 10 minutes. Post exposure bake can be used to further promote crosslinking of crosslinkable moieties within exposed portions of the polymer.

The other components or functional layers of the electronic device, like the substrate, the gate and source and drain electrodes, and organic semiconductor layer, can be selected from standard materials, and can be manufactured and applied to the device by standard methods. Suitable materials and manufacturing methods for these components and layers are known to a person skilled in the art and are described in the literature. Exemplary deposition methods include the liquid coating methods previously described as well as chemical vapor deposition (CVD) or physical vapor deposition methodologies.

Generally the thickness of a functional layer, for example a gate dielectric or organic semiconductor layer, in some preferred electronic device embodiments according to the present invention is from 0.001 (in case of a monolayer) to 10 μπι; In other preferred embodiments such thickness ranges from 0.001 to 1 um, and in still other preferred embodiments from 5 nm to 500 nm, although other thicknesses or ranges of thickness are contemplated and thus are within the scope of the present invention.

Various substrates may be used for the fabrication of the electronic device embodiments of the present invention. For example glass or polymeric materials are most often used. Preferred materials include, but are not limited to, alkyd resins, allyl esters, benzocyclobutenes, butadiene-styrene, cellulose, cellulose acetate, epoxy polymers, ethylene-chlorotrifluoro ethylene copolymers, ethylene- tetra-fluoroethylene copolymers, fiber glass enhanced thermoplastic, fluorocarbon polymers, hexafluoropropylenevinylidene-fluoride copolymer, polyethylene, parylene, polyamide, polyimide, polyaramid, polydimethylsiloxane,

polyethersulphone, polyethylenenaphthalate, polyethyleneterephthalate, polyketone, polymethylmethacrylate, polypropylene, polystyrene, polysulphone, polytetrafluoroethylene, polyurethanes, polyvinylchloride, polycycloolefin, silicone rubbers, and silicones, where polyethyleneterephthalate, polyimide, polycycloolefin and polyethylenenaphthalate materials have been found most appropriate. Additionally, for some embodiments of the present invention the substrate can be any thermoplastic, metal or glass material coated with one or more of the above listed materials.

Preferably the substrate is a polymer film of a polymer selected from the group consisting of polyesters, polyimides, polyarylates, polycycloolefins,

polycarbonates and polyethersulphones.

Especially preferred are polyester substrates, most preferably polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), for example PET films of the Melinex® series or PEN films of the Teonex® series, both from DuPont Teijin Films™ may be used. The latter do already include a thin plananzation coating on top.

Thus, an preferred embodiment of the present invention relates to an electronic device comprising a substrate which does already include a plananzation coating, and wherein a plananzation layer comprising a polycycloolefinic polymer or polymer composition as described above and below is deposited onto said planarization coating. Another embodiment of the present invention relates to an electronic device comprising a substrate which does not include a planarization coating, and wherein a planarization layer comprising a polycycloolefinic polymer or polymer composition as described above and below is deposited onto said substrate. The gate, source and drain electrodes of the OFET device embodiments in accordance with the present invention can be deposited or formed by liquid coating, such as spray-, dip-, web- or spin-coating, or by vacuum deposition methods, including but not limited to physical vapor deposition (PVD), chemical vapor deposition (CVD) or thermal evaporation. Suitable electrode materials and deposition methods are known to the person skilled in the art. Suitable electrode materials include, without limitation, inorganic or organic materials, or composites of the two. Exemplary electrode materials include polyaniline, polypyrrole, poly(3,4-ethylene-dioxythiophene) (PEDOT) or doped conjugated polymers, further dispersions or pastes of graphite or graphene or particles of metal such as Au, Ag, Cu, Al, Ni or their mixtures as well as sputter coated or evaporated metals such as Cu, Cr, Pt/Pd, Ag, Au or metal oxides such as indium tin oxide (ITO), F-doped ITO or Al-doped ZnO. Organometallic precursors may also be used and deposited from a liquid phase. The organic semiconductor materials and methods for applying the organic semiconductor layer for OFET embodiments in accordance with the present invention can be selected from standard materials and methods known to the person skilled in the art, and are described in the literature. The organic semiconductor can be an n- or p- type OSC, which can be deposited by PVD, CVD or solution deposition methods. Effective OSCs exhibit a FET mobility of greater than lxlO ^"5 cmV's ^"1 . OSC embodiments in accordance with the present invention can be either OFETs where the OSC is used as the active channel material, OPV devices where the OSC is used as charge carrier material, or organic rectifying diodes (ORDs) where the OSC is a layer element of such a diode. OSCs for such embodiments can be deposited by any of the previously discussed deposition methods, but as they are generally deposited or formed as blanket layers, solvent coated methods such as spray-, dip-, web- or spin-coating, or printing methods such as ink-jet printing, flexo printing or gravure printing, are typically employed to allow for ambient temperature processing. However, OSCs can be deposited by any liquid coating technique, for example ink-jet deposition or via PVD or CVD techniques.

For some preferred OFET embodiments, the semiconducting layer that is formed can be a composite of two or more of the same or different types of organic semiconductors. For example, a p-type OSC material may, for example, be mixed with an n-type material to achieve a doping effect of the layer. In some preferred embodiments of the invention, multilayer organic semiconductor layers are used. For example an intrinsic organic semiconductor layer can be deposited near the gate dielectric interface and a highly doped region can additionally be coated adjacent to such an intrinsic layer.

The OSC material employed for electronic device embodiments in accordance with the present invention can be any conjugated molecule, for example an aromatic molecule containing preferably two or more, very preferably at least three aromatic rings. In some preferred embodiments of the present invention, the OSC contains aromatic rings selected from 5-, 6- or 7-membered aromatic rings, while in other preferred embodiments the OSC contains aromatic rings selected from 5- or 6-membered aromatic rings. The OSC material may be a monomer, oligomer or polymer, including mixtures, dispersions and blends of one or more of monomers, oligomers or polymers.

Each of the aromatic rings of the OSC optionally contains one or more hetero atoms selected from Se, Te, P, Si, B, As, N, O or S, generally from N, O or S. Further, the aromatic rings may be optionally substituted with alkyl, alkoxy, polyalkoxy, thioalkyl, acyl, aryl or substituted aryl groups, halogen, where fluorine, cyano, nitro or an optionally substituted secondary or tertiary alkylamine or arylamine represented by -N(R ¹⁵ )(R ¹⁶ ), where R ¹⁵ and R ¹⁶ are each

independently H, an optionally substituted alkyl or an optionally substituted aryl, alkoxy or polyalkoxy groups are typically employed. Further, where R ^1S and R ¹⁶ is alkyl or aryl these may be optionally fluorinated.

The aforementioned aromatic rings can be fused rings or linked with a conjugated linking group such as -C(T,)=C(T ₂ )-, -C≡C-, -N(R'")-, -N=N-, (R"')=N-, - N=C(R'")-, where Ti and T ₂ each independently represent H, CI, F, -C≡N or lower alkyl groups such as C alkyl groups; R'" represents H, optionally substituted alkyl or optionally substituted aryl. Further, where R ^m is alkyl or aryl can be fluorinated.

In some preferred electronic device embodiments of the present invention, OSC materials that can be used include compounds, oligomers and derivatives of compounds selected from the group consisting of conjugated hydrocarbon polymers such as polyacene, polyphenylene, poly(phenylene vinylene), polyfluorene including oligomers of those conjugated hydrocarbon polymers; condensed aromatic hydrocarbons, such as, tetracene, chrysene, pentacene, pyrene, perylene, coronene, or soluble, substituted derivatives of these; oligomeric para substituted phenylenes such as p-quaterphenyl (p-4P), p-quinquephenyl (p- 5P), p-sexiphenyl (p-6P), 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]thiophene, 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-l,3,4-oxadiazoles, polyisothianaphthene, poly(N-substituted aniline), 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, phthalocyanines, fluorophthalocyanines, naphthalocyanines or fluoronaphthalocyanines; C ₆ o and C ₇₀ fullerenes; N,N'-dialkyl, substituted dialkyl, diaryl or substituted diaryl-l,4,5,8-naphthalenetetracarboxylic diimide and fluoro derivatives; N,N -dialkyl, substituted dialkyl, diaryl or substituted diaryl 3,4,9,10- perylenetetracarboxylicdiimide; bathophenanthroline; diphenoquinones; 1,3,4- oxadiazoles; 11,11,12,12-tetracyanonaptho-2,6-quinodimethane;

a,a'-bis(dithieno[3,2-b2',3'-d]thiophene); 2,8-dialkyl, substituted dialkyl, diaryl or substituted diaryl anthradithiophene; 2,2'-bibenzo[l ,2-b:4,5-b']dithiophene.

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.

Further, in some very preferred embodiments in accordance with the present invention, the OSC materials are polymers or copolymers that encompass one or more repeating units selected from thiophene-2,5-diyl, 3-substituted thiophene- 2,5-diyl, optionally substituted thieno[2,3-b]tbiophene-2,5-diyl, optionally substituted thieno[3,2-b]thiophene-2,5-diyl, selenophene-2,5-diyl, or 3-substituted selenophene-2,5-diyl. Further preferred p-type OSCs are copolymers comprising electron acceptor and electron donor units. Preferred copolymers of this preferred embodiment are for example copolymers comprising one or more benzo[l,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, thieno[2,3-b]thiophene-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-diyl, benzo[l,2-b:4,5-b']dithiophene-2,6-diyl, 2,2-dithiophene, 2,2-diselenophene, ditWeno[3,2-6:2^3'-£i]silole-5,5-diyl, 4H-cyclopenta[2,l-b:3,4-0']dithiophene-2,6- diyl, 2,7-di-thien-2-yl-carbazole, 2,7-di-thien-2-yl-fluorene, indaceno[l,2-b:5,6- b']dithiophene-2,7-diyl, benzo[l",2":4,5;4",5":4 ^, ,5']bis(silolo[3,2-b:3',2'- b']thiophene)-2,7-diyl, 2,7-di-thien-2-yl-indaceno[l ,2-b:5,6-b']dithiophene, 2,7-di- thien-2-yl-benzo[1 2":4,5;4 5^4\5 ^, ^

and 2,7-di-thien-2-yl-phenanthro[l,10,9,8-c,i/,e^]carbazole, all of which are optionally substituted by one or more, preferably one or two groups R as defined above, and

Group B consists of benzo[2,l,3]thiadiazole-4,7-diyl, 5,6-dialkyl- benzo[2,l,3]thiadiazole-4,7-diyl, 5,6-dialkoxybenzo[2,l,3]thiadiazole-4,7-diyl, benzo[2,l,3]selenadiazole-4,7-diyl, 5,6-dialkoxy-benzo[2,l,3]selenadiazole-4,7- diyl, benzo[l ,2,5]thiadiazole-4,7,diyl, benzo[l ,2,5]selenadiazole-4,7,diyl, benzo[2,l,3]oxadiazole-4,7-diyl, 5,6-dialkoxybenzo[2,l,3]oxadiazole-4,7-diyl, 2H-benzotriazole-4,7-diyl, 2,3-dicyano-l,4-phenylene, 2,5-dicyano,l,4- phenylene, 2,3-difluro- 1 ,4-phenylene, 2,5-difluoro-l ,4-phenylene, 2,3,5,6- tetrafluoro- 1 ,4-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, 3,6- pyrrolo[3,4-c]pyrrole-l,4-dione, all of which are optionally substituted by one or more, preferably one or two groups R as defined above.

In other very preferred embodiments of the present invention, the OSC materials are substituted oligoacenes such as pentacene, tetracene or anthracene, or heterocyclic derivatives thereof. Bis(trialkylsilylethynyl) 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.

Where appropriate and needed to adjust the rheological properties as described for example in WO 2005/055248 Al, some embodiments of the present invention employ OSC 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 according to the present invention are materials of low permittivity, that is, those having a permittivity ε of 3.3 or less. The organic binder preferably has a permittivity ε of 3.0 or less, more preferably 2.9 or less.

Preferably the organic binder has a permittivity ε at 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 ε of greater than 3.3, may lead to a reduction in the OSC 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 a suitable orgamc binders include polystyrene, or polymers or copolymers of styrene and a-methyl styrene, or copolymers including styrene, a- 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 I 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. Unless the context clearly indicates otherwise, as used herein plural forms of the terms herein are to be construed as including the singular form and vice versa.

It will be appreciated that variations to the foregoing embodiments of the invention can be made while still falling within the scope of the invention. Each feature disclosed in this specification, unless stated otherwise, may be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

All of the features disclosed in this specification may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. In particular, the features of the invention are applicable to all aspects of the invention and may be used in any combination. Likewise, features described in non-essential combinations may be used separately (not in combination).

The invention will now be described in more detail by reference to the following examples, which are illustrative only and do not limit the scope of the invention.

Above and below, unless stated otherwise percentages are per cent by weight and temperatures are given in degrees Celsius (°C). The values of the dielectric constant□ ("permittivity") refer to values taken at 1000 Hz and 20°C. Unless stated otherwise, the values of the surface energy refer to those calculated from contact angle measurement of the polymers according to the method described in D. K. Owens, R. C. Wendt, "Estimation of the surface free energy of polymers", Journal of Applied Polymer Science, Vol. 13, 1741-1747, 1969 or "Surface and Interfacial Tension: Measurement, Theory, and Applications (Surfactant Science Series Volume 119)" by Stanley Hartland (Editor), Taylor & Francis Ltd; 2004 (ISBN: 0-8247-5034-9), chapter 7, p.: 375: "Contact Angle and Surface Tension Measurement" by Kenji Katoh).

Comparison Example 1 - Top Gate OFET with Teonex® PEN film as substrate Teonex Q65FA® PEN film (available from DuPont Teijin Films™) was washed in methanol and treated with argon plasma for 3 min (microwave plasma generator, power: 100 W, argon flow: 500 ml/min) in order to increase surface energy of the substrate.

60 run thick gold source drain electrodes were evaporated directly onto the PEN substrate with a parallel plate geometry of 20 μπι wide by 1mm long.

The electrodes were treated with Lisicon M001® (available from Merck

Chemicals Ltd.) by spin coating from isopropyl alcohol and evaporating the excess off on a hot plate at 70°C for 2 min.

An OSC Lisicon S1200-series® formulation was used (available from Merck Chemicals Ltd.).

The OSC formulation was then printed as a 5 x 5 cm wide area block on the array of source/drain electrodes on the film as described above using a RK Flexiproof 100 flexographic pnnting with a 8 cm /m loaded anilox and a Cyrel HiQS flexo mat running at 70 m/min speed. The printed OSC layer was then annealed at 70°C for 5 min.

A dielectric layer of fluoro-polymer Lisicon D139® (9% solids available from Merck Chemicals Ltd.) was spun on top of the OSC layer on the device and annealed at 70°C for 8 min to give a dry dielectric film of approximately 1 μιη thick.

Finally a 40nm thick gold gate electrode array of evaporated on top of the dielectric layer in such a way that it covered the existing source drain electrode structures.

The initial transfer curve was recorder at bias voltage of -5 V. Then the device was electrically stressed for 15 h using source/gate voltage of -40 V and the second transfer curve was recorded directly after the stress. The transfer characteristics are shown in Figure 5. Example 1- Top Gate OFET with a Teonex® film covered by a polynorbomene planarization layer according to the invention as substrate

Teonex Q65FA® film (available from DuPont Teijin Films™) was washed in methanol. A layer of the polymer poly(DMMIBuNB) (hereinafter abbreviated as

"pDMMIBuNB"), which is a homopolymer of the monomer of formula (37), having a molecular weight Mw = 100,000, was formed by depositing a solution of the polymer (17.5% TS in MAK with added 0.5% l-chloro-4-propoxy-9H- thioxanthen-9-one w/w) onto the Teonex film via spin coating (1500 rpm, 30 s) followed by 8 min baking at 70°C and 4 min UV exposure (UVA 0.011 W/cm ² , peak at 365 nm).

Approximately 60 nm thick gold source drain electrodes were evaporated onto the polynorbomene layer with a parallel plate geometry of 20 μπι wide by 1 mm long.

The electrodes were treated with M001 (available from Merck Chemicals Ltd.) by spin coating from isopropyl alcohol and evaporating the excess off on a hot plate at 70°C for 2 min. The same OSC Lisicon S1200-series ® formulation as used in Comparison Example 1 was then printed as a 5 x 5 cm wide area block on the array of source/drain electrodes on the film as described above using a RK Flexiproof 100 flexographic printing with a 8 cm /m loaded anilox and a Cyrel HiQS flexo mat running at 70m/min speed. The printed OSC layer was then annealed at 70°C for 5 min.

A dielectric layer of fluoro-polymer Lisicon D139 ® (9% solids available from Merck Chemicals Ltd.) was spun on top of the OSC layer on the device and annealed at 70°C for 8 min to give a dry dielectric film approximately 1 μηι thick.

Finally a 40nm thick gold gate electrode array is evaporated on top of the dielectric layer in such a way that it covered the existing source drain electrode structures. The initial transfer curve was recorder at bias voltage of -5 V. Then the device was electrically stressed for 15 h using source/gate voltage of -40 V and the second transfer curve was recorded directly after the stress. The transfer characteristics are shown in Figure 6.

From Figure 6 it can be seen that in the OFET device of Example 1, the layer of pDMMIBuNB on top of Teonex Q65FA ® film improves stability of the electrical parameters, in comparison to the OFET device of Comparison Example 1 without the additional pDMMIBuNB layer (see Figure 5). Stability of the source - drain current in the 'ON' state (under negative gate bias in case of using p-type semiconductors) and limited threshold voltage shift after application of negative gate bias stress (-40 V) are particularly important to ensure applicability of the transistors.

Such an improved long term stability of those parameters was observed for the devices containg the planarization layer of pDMMIBuNB, compared to devices without the layer of pDMMIBuNB. The surface roughness of the substrates of Comparison Example 1 and Example 1 was measured by Atomic Force Microscopy (AFM).

As a result the surface roughness of the Teonex Q65FA® substrate as used in Comparison Example 1 is 0.6 nm (R _a ) and 20 nm (¾), whereas the the surface roughness of the same substrate coated with a layer of pDMMIBuNB as used in Example 1 , is 0.2 nm (Rg) and 5 nm (¾) for pDMMIBuNB layer.

This shows that the surface roughness was significantly reduced after application of the planarization layer of pDMMIBuNB.

Surface energy measurements using the Owens- Wendt method were carried out for the substrates of Comparison Example 1 and Example 1.

As a result the surface energy of the Teonex Q65FA® substrate as used in Comparison Example 1 is 32 mN/m (without plasma treatment), whereas the the surface energy of the same substrate coated with a layer of pDMMIBuNB as used in Example 1, is 50 raN/m respectively.

Since de-wetting may occur at low surface energies < 40 mN/m, the substrate of Comparison Example 1 needs further plasma treatment to increase surface energy.

In contrast thereto, a surface modification of the pDMMIBuNB layer prior to the OSC deposition, for example in order to improve surface energy and wetting, is not required. Nevertheless, pDMMIBuNB is resistant to plasma treatment, which is commonly applied after a photolithographic process in order to remove post- process residues.

Comparison Example 2 - Top Gate OFET with Melinex® film as substrate

Melinex ST506® film (available from DuPont Teijin Films™) was washed in methanol and treated with argon plasma for 3 min (microwave plasma generator, power: 100 W, argon flow: 500 ml/min) in order to increase surface energy of the substrate.

Approximately 60 nm thick gold source drain electrodes were evaporated onto the directly onto the PEN substrate layer with a parallel plate geometry of 20 μπι wide by 1 mm long.

The electrodes were treated with Lisicon M001® (available from Merck

Chemicals Ltd.) by spin coating from isopropyl alcohol and evaporating the excess off on a hot plate at 70°C for 2 min.

The same OSC Lisicon S1200-series® formulation as used in Comparison Example 1 was then printed as a 5 x 5 cm wide area block on the array of source/drain electrodes on the film as described above using a RK Flexiproof 100 flexographic printing with a 8 cm /m loaded anilox and a Cyrel HiQS flexo mat running at 70 m/min speed. The printed OSC layer was then annealed at 70°C for 5 min.

A dielectric layer of fluoro-polymer Lisicon D139® (9% solids available from Merck Chemicals Ltd.) was spun on top of the OSC layer on the device and annealed at 70°C for 8 min to give a dry dielectric film of approximately 1 μιη thick.

Finally a 40 nm thick gold gate electrode array is evaporated on top of the dielectric layer in such a way that it covered the existing source drain electrode structures.

The initial transfer curve was recorder at bias voltage of -5 V. Then the device was electrically stressed for 2 h using source/gate voltage of 30 V and the second transfer curve was recorded directly after the stress.

The transfer characteristics are shown in Figure 7.

Example 2- Top Gate OFET device with a Melinex® film covered by a polvnorbornene planarization layer according to the invention as substrate

Melinex ST506® film (available from DuPont Teijin Films™) was washed in methanol. A layer of the norbornene polymer pBuDMMINB (17.5% TS in MAK with added 0.5% l-chloro-4-propoxy-9H-thioxanthen-9-one w/w) was deposited onto the Melinex film via spin coating (1500 rpm, 30 s) followed by 8 min baking at 70°C and 4 min UV exposure (UVA 0.011 W/cm ² , peak at 365 nm).

Approximately 60 nm thick gold source drain electrodes were evaporated onto the polynorbomene layer with a parallel plate geometry of 20 μπι wide by 1 mm long.

The electrodes were treated with Lisicon M001® (available from Merck

Chemicals Ltd.) by spin coating from isopropyl alcohol and evaporating the excess off on a hot plate at 70°C for 2 min. The same OSC Lisicon S1200-series® formulation as used in Comparison Example 1 was then printed as a 5 x 5 cm wide area block on the array of source/drain electrodes on the film as described above using a RK Flexiproof 100 flexographic printing with a 8cm /m loaded anilox and a Cyrel HiQS flexo mat running at 70 m/min speed. The printed OSC layer was then annealed at 70°C for 5 min. A dielectric layer of fluoro-polymer Lisicon D139® (9% solids available from Merck Chemicals Ltd.) was spun on top of the OSC layer on the device and annealed at 70°C for 8 min to give a dry dielectric film of approximately 1 μπι thick.

Finally a 40 nm thick gold gate electrode array is evaporated on top of the dielectric layer in such a way that it covered the existing source drain electrode structures.

The initial transfer curve was recorder at bias voltage of -5 V. Then the device was electrically stressed for 80 h using source/gate voltage of 30 V and the second transfer curve was recorded directly after the stress.

The transfer characteristics are shown in Figure 8.

From Figure 8 it can be seen that in the OFET device of Example 2, the layer of pDMMIBuNB on top of Melinex ST506® film improves stability of the electrical parameters, in comparison to the OFET device of Comparison Example 2 without the additional pDMMIBuNB layer (see Figure 7). Stability of the source - drain current in the 'ON' state (under negative gate bias in case of using p-type semiconductors) and limited threshold voltage shift after application of positive gate bias stress (30 V) are particulary important to ensure applicability of the transistors.

Such an improved long term stability of those parameters was observed for the devices containg the planarization layer of pDMMIBuNB, compared to devices without the layer of pDMMIBuNB.

The surface roughness of the substrates of Comparison Example 2 and Example 2 was measured by Atomic Force Microscope.

As a result the surface roughness of the Melinex ST506 ® substrate as used in Comparison Example 2 is 0.6 nm (R _a ) and 20 nm (R _t ), whereas the the surface roughness of the same substrate coated with a layer of pDMMIBuNB as used in Example 2, is 0.2 nm (R _a ) and 5 nm (¾) for pDMMIBuNB layer. This shows that the surface roughness was significantly reduced after application of the planarization layer of pDMMIBuNB.

Surface energy measurements using the Owens- Wendt method were carried out for the substrates of Comparison Example 2 and Example 2.

As a result the surface energy of the Melinex ST506® substrate as used in

Comparison Example 2 is 33 mN/m, whereas the the surface energy of the same substrate coated with a layer of pDMMIBuNB as used in Example 2, is 50 mN/m respectively.

Since de-wetting may occur at low surface energies < 40 mN/m, the substrate of Comparison Example 2 needs further plasma treatment to increase surface energy. In contrast thereto, a surface modification of the pDMMIBuNB layer prior to the OSC deposition, for example in order to improve surface energy and wetting, is not required. Nevertheless, pDMMIBuNB is resistant to plasma treatment, which is commonly applied after a photolithographic process in order to remove post- process residues. The adhesion of Au gold to the substrates of Comparison Example 2 and Example 2 was measured by Mecmesin MultiTest 1-i (50 N cell) using 90° peel test. For that purpose both subtrates were covered by approximately 60 nm layers of gold and 25 mm wide tape with 20 N adhesion to gold was applied to peel a stipe of gold from the substrates.

As a result the adhesion of gold to the Melinex ST506 ® substrate as used in Comparison Example 2 is less or equal to 0.5N whereas the adhesion of gold to the same substrate coated with a layer of pDMMIBuNB as used in Example 2, is 16 N.

Example 3 - Top Gate OFET device with a Melinex® film covered by a polvnorbomene planarization layer according to the invention as substrate

Melinex ST506® film (available from DuPont Teijin Films™) was washed in methanol. A layer of the norbornene polymer poly(DMMIBuNB/TESNB) which is a co-polymer of the monomer DMMIBuNB of the formula (37) and the monomer TESNB of the formula (53) in the ratio: 9:1, dissolved in MAK to the concentration of 17.5% TS) was deposited onto the Melinex film via spin coating (1500 rpm, 30 s) followed by 8 min baking at 70°C and 5 min UV exposure (UVA 0.011 W/cm ² , peak at 365 nm).

Approximately 60 nm thick gold source drain electrodes were evaporated onto the polynorbomene layer with a parallel plate geometry of 20 μπι wide by 1 mm long.

The electrodes were treated with Lisicon M001® (available from Merck

Chemicals Ltd.) by spin coating from isopropyl alcohol and evaporating the excess off on a hot plate at 70°C for 2 min.

The same OSC Lisicon S1200-series® formulation as used in Comparison Example 1 was then printed as a 5 x 5 cm wide area block on the array of source/drain electrodes on the film as described above using a RK Flexiproof 100 flexographic printing with a 8 cm /m loaded anilox and a Cyrel HiQS flexo mat running at 70 m/min speed. The printed OSC layer was then annealed at 70°C for 5 min. A dielectric layer of fluoro-polymer Lisicon Dl 39® (9% solids available from Merck Chemicals Ltd.) was spun on top of the OSC layer on the device and annealed at 70°C for 8 min to give a dry dielectric film of approximately 1 μιη thick. Finally a 40 nm thick gold gate electrode array is evaporated on top of the dielectric layer in such a way that it covered the existing source drain electrode structures.

The initial transfer curve was recorder at bias voltage of -5 V. Then the device was electrically stressed for 80 h using source/gate voltage of 30 V and the second transfer curve was recorded directly after the stress.

The transfer characteristics are shown in Figure 9. From Figure 9 it can be seen that in the OFET device of Example 3, the layer of poly(DMMIBuNB/TESNB) on top of Melinex ST506® film improves stability of the electrical parameters, in comparison to the OFET device of Comparison Example 3 without the additional poly(DMMIBuNB/TESNB) layer (see Figure 7). Stability of the source - drain current in the 'ON' state (under negative gate bias in case of using p-type semiconductors) and limited threshold voltage shift after application of positive gate bias stress (30V) are parti culary important to ensure applicability of the transistors.

Such an improved long term stability of those parameters was observed for the devices containg the planarization layer of poly(DMMIBuNBATESNB), compared to devices without the layer of poly(DMMIBuNB/TESNB).

Furthermore, the OFET device of Example 3 shows a decreased source - drain current in the 'OFF' state (under positive gate bias in case of using p-type semiconductors) by over one order of magnitude for non-patterned OSC layer (where OSC layer covers the whole area of a substrate and there is significant current leakage between the neighbouring devices through the OSC layer).

The surface roughness of the substrates of Comparison Example 2 and Example 3 was measured by Atomic Force Microscopy.

As a result the surface roughness of the Melinex ST506 ® substrate as used in Comparison Example 2 (without plasma treatment) is 0.6 nm (R _a ) and 20 nm (R _t ), whereas the the surface roughness of the same substrate coated with a layer of poly(DMMIBuNB/TESNB) as used in Example 3, is 0.2 nm (R _a ) and 5 nm (R _t ) for poly(DMMIBuNB/TESNB) layer.

This shows that the surface roughness was significantly reduced after application of the planarization layer of poly(DMMIBuNB/TESNB). Surface energy measurements using the Owens- Wendt method were carried out for the substrates of Comparison Example 2 and Example 3.

As a result the surface energy of the Melinex ST506® substrate as used in

Comparison Example 2 is 33 mN/m, whereas the the surface energy of the same substrate coated with a layer of poly(DMMIBuNB TESNB) as used in Example 3, is 51 mN/m respectively. Since de-wetting may occur at low surface energies < 40 mN/m, the substrate of Comparison Example 2 needs further plasma treatment to increase surface energy. In contrast thereto, a surface modification of the poly(DMMIBuNB/TESNB) layer prior to the OSC deposition, for example in order to improve surface energy and wetting, is not required. Nevertheless, poly(DMMIBuNB/TESNB) is resistant to plasma treatment, which is commonly applied after a photolithographic process in order to remove post-process residues. The adhesion of Au gold to the substrates of Comparison Example 2 and Example 3 was measured by Mecmesin MultiTest 1-i (50 N cell) using 90° peel test. For that purpose both subtrates were covered by approximately 60 nm layers of gold and 25 mm wide tape with 20 N adhesion to gold was applied to peel a stipe of gold from the substrates.

As a result the adhesion of gold to the Melinex ST506 ® substrate as used in Comparison Example 2 is less or equal to 0.5N, whereas the adhesion of gold to the same substrate coated with a layer of poly(DMMIBuNB/TESNB) as used in Example 2, is >20 N.

The results of Example 1, 2 and 3 demonstrate that a substrate coated with a polynorbornene planarization layer provides largely improved stability of OFETs compared to a prior art substrate as used in Comparison Example 2, which is considered as a benchmark. Low surface roughness and high surface energy of polynorbornene layers are also beneficial for simplification of the OFET manufacturing process. Additionally, specific substituents, on the polynorbornene backbone, like triethoxysilyl (TES) as in formula (53), provide large increase of adhesion to metals like gold, which eliminate the need for additional adhesion layers between the planarization materials and the electrodes.