US20130207091A1 - Planarization layer for organic electronic devices - Google Patents

Planarization layer for organic electronic devices Download PDF

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US20130207091A1
US20130207091A1 US13/767,435 US201313767435A US2013207091A1 US 20130207091 A1 US20130207091 A1 US 20130207091A1 US 201313767435 A US201313767435 A US 201313767435A US 2013207091 A1 US2013207091 A1 US 2013207091A1
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layer
electronic device
organic electronic
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polymer
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Piotr Wierzchowiec
Pawel Miskiewicz
Tomas Backlund
Li Wei Tan
Paul Craig Brookes
Irina Afonina
Larry F. Rhodes
Andrew Bell
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Merck Patent GmbH
Promerus LLC
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Merck Patent GmbH
Promerus LLC
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Priority to US13/767,435 priority Critical patent/US20130207091A1/en
Assigned to PROMERUS LLC, MERCK PATENT GMBH reassignment PROMERUS LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AFONINA, IRINA, BACKLUND, TOMAS, TAN, LI W., WIERZCHOWIEC, PIOTR, BELL, ANDREW, RHODES, LARRY F., BROOKES, PAUL C., MISKIEWICZ, PAWEL
Publication of US20130207091A1 publication Critical patent/US20130207091A1/en
Priority to US14/936,923 priority patent/US9490439B2/en
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    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • H01L51/0001—
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/191—Deposition of organic active material characterised by provisions for the orientation or alignment of the layer to be deposited
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • H10K77/10—Substrates, e.g. flexible substrates
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
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    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/464—Lateral top-gate IGFETs comprising only a single gate
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    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
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    • Y02E10/549—Organic PV cells
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • Embodiments in accordance with the present invention relate 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.
  • a functional layer e.g. a semiconducting layer, a dielectric layer or an electrode
  • a conventional organic field effect transistor 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.
  • OSC organic semiconductor
  • gate dielectric insulator layer
  • 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.
  • 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.
  • 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 FilmsTM
  • Typical commercially available planarization, hard-coating, or barrier materials include:
  • Silicon dioxide (SiO 2 ) or silicon nitride (SiNX) electrical insulators which are used mainly on top of conducting metal substrates.
  • Organic polymers such as, acrylic-, melamine- or urethane-based polymers.
  • 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 U.S. Pat. No. 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.
  • 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 advantageous.
  • planarization material should exhibit one or more of the following characteristics:
  • 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.
  • Embodiments in accordance with the present invention encompass an organic electronic device overlying a substrate, the substrate having a planarization layer provided between the substrate and a functional layer, where the planarization layer encompasses a polycycloolefinic polymer and the functional layer is one of a semiconducting layer, a dielectric layer or an electrode.
  • Some embodiments in accordance with the present invention are also directed to the use of the aforementioned planarization layer in an organic electronic device. Still further, some embodiments are directed to a method of using a polycycloolefinic polymer in the fabrication of a planarization layer for an organic electronic device.
  • the aforementioned polycycloolefinic polymer is for example a norbornene-type polymer.
  • the aforementioned organic electronic device is for example an Organic Field Effect Transistor (OFET), which is inclusive of an Organic Thin Film Transistor (OTFT), a top gate OFET, a bottom gate OFET, an Organic Photovoltaic (OPV) Device or an Organic Sensor.
  • OFET Organic Field Effect Transistor
  • OTFT Organic Thin Film Transistor
  • OOV Organic Photovoltaic
  • Embodiments of the present invention are also inclusive of a product or an assembly encompassing an organic electronic device as described above and below.
  • Such product or assembly being 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.
  • IC Integrated Circuit
  • RFID Radio Frequency Identification
  • FPD Flat Panel Display
  • FPD Flat Panel Display
  • backplane of an FPD or a sensor.
  • FIG. 1 is a schematic representation of a top gate OFET device according to prior art
  • FIG. 2 is a schematic representation of a bottom gate OFET device according to prior art
  • FIG. 3 is a schematic representation of a top gate OFET device in accordance with an embodiment of the present invention.
  • FIG. 4 is a schematic representation of a bottom gate OFET device in accordance with an embodiment of the present invention.
  • FIG. 5 is a transfer curve of the top gate OFET device of Comparison Example 1;
  • FIG. 6 is a transfer curve of the top gate OFET device of Example 1.
  • FIG. 7 is a transfer curve of the top gate OFET device of Comparison Example 2.
  • FIG. 8 is a transfer curve of the top gate OFET device of Example 2.
  • FIG. 9 is a transfer curve of the top gate OFET device of Example 3.
  • 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.
  • planarization layers comprising polycycloolefinic polymers show improved adhesion to the substrate and to electrodes, reduced surface roughness, and improved OSC performance.
  • 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.
  • 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.
  • 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.
  • orthogonal and “orthogonality” will be understood to mean chemical orthogonality.
  • 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.
  • 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.
  • 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.
  • a polymer composition may, in addition to the aforementioned exemplary materials, also encompass a blend of two or more polymers.
  • polycycloolefin 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 A1 or A2, below.
  • the simplest norbornene-type or polycyclic olefin monomer bicyclo[2.2.1]hept-2-ene (A1) is commonly referred to as norbornene.
  • 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 B1 and B2, shown below, wherein m is an integer greater than zero.
  • 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.
  • 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.
  • hydrocarbyl refers to a radical or group that contains a carbon backbone where each carbon is appropriately substituted with one or more hydrogen atoms.
  • halohydrocarbyl refers to a hydrocarbyl group where one or more of the hydrogen atoms, but not all, have been replaced by a halogen (F, Cl, Br, or I).
  • 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 1 -C 25 alkyl, a C 2 -C 24 alkenyl, a C 2 -C 24 alkynyl, a C 5 -C 25 cycloalkyl, a C 6 -C 24 aryl or a C 7 -C 24 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.
  • 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.
  • perhalohydrocarbyl is inclusive of the hydrocarbyl moieties mentioned above but where all the hydrogen atom being replaced by a halogen atom.
  • 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+1 wherein X is independently a halogen or a hydrogen and a is selected from an integer of 1 to 25.
  • each X is independently selected from hydrogen, chlorine, fluorine bromine and/or iodine.
  • each X is independently either hydrogen or fluorine.
  • 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.
  • hydrocarbyl halohydrocarbyl
  • 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.
  • 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.
  • 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 ) 1 —O—) k —(CH 2 )—C(CF 3 ) 2 —OH, —(CH 2 ) n —C(CF 3 )(CH 3 )—OH, —(CH 2 ) n —C(O)NHR*, —(CH 2 ) n —C(O)Cl, —(CH 2 ) n —C(O)OR*, —(CH 2 )
  • Exemplary perhalogenated alkyl groups 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 F 15 , and —C 11 F 23 .
  • Exemplary halogenated or perhalogenated aryl and aralkyl groups include, but are not limited to, groups having the formula —(CH 2 ) x —C 6 F y H 5 ⁇ y , and —(CH 2 ) x —C 6 F y H 4 ⁇ y ⁇ p 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.
  • such exemplary halogenated or perhalogenated aryl groups include, but are not limited to, pentachlorophenyl, pentafluorophenyl, pentafluorobenzyl, 4-trifluoromethylbenzyl, pentafluorophenethyl, pentafluorophenpropyl, and pentafluorophenbutyl.
  • the norbornene-type polymer incorporates two or more distinct types of repeating units.
  • 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.
  • 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.
  • crosslinkable groups encompass 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.
  • R 1 , R 2 , R 3 and R 4 are independently selected from H, a C 1 to C 25 hydrocarbyl, a C 1 to C 25 halohydrocarbyl or a C 1 to C 25 perhalocarbyl group.
  • the repeating units of Formula I are formed from the corresponding norbornene-type monomers of Formula Ia where Z, m and R 1 -R 4 are as defined above:
  • Z is —CH 2 — and m is 0, 1 or 2.
  • Z is —CH 2 — and m is 0 or 1
  • Z is —CH 2 — and m is 0.
  • Some embodiments of the invention encompass an organic electronic device overlying a substrate, the substrate having a planarization layer provided between the substrate and a functional layer, where the planarization layer encompasses a polymer composition that comprises a polycycloolefinic polymer, and the functional layer is one of a semiconducting layer, a dielectric layer or an electrode.
  • Polymer composition embodiments in accordance with the invention encompass either a single norbornene-type polymer or a blend of two or more different norbornene-type polymers.
  • 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.
  • “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.
  • composition embodiments of the invention encompass a blend of two or more different norbornene-type polymers, wherein each polymer comprises one or more distinct types of repeating units of formula I
  • R 1 , R 2 , R 3 and R 4 are independently selected from H, a C 1 to C 25 hydrocarbyl, a C 1 to C 25 halohydrocarbyl or a C 1 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.
  • 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 ⁇ p 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, and “p” means “para”.
  • 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 F 15 , —C 11 F 23 , pentachlorophenyl, pentafluorophenyl, pentafluorobenzyl, 4-trifluoromethylbenzyl, pentafluorophenylethyl, pentafluorophenpropyl, and pentafluorophenbutyl.
  • some 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 O) s — with s being 1, 2 or 3; for example 1-(bicyclo[2.2.1]hept-5-en-2-yl)-2,5,8,11-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.
  • NBTODD 1-(bicyclo
  • R 1-4 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 9 independently represents halogen selected from the group consisting of chlorine, fluorine, bromine and iodine, linear or branched (C 1 to C 20 )alkyl, linear or branched (C 1 to C 20 )alkoxy, substituted or unsubstituted (C 6 to C 20 )aryl, linear or branched (C 1 to C 20 )alkyl carbonyloxy, substituted or unsubstituted (C 6 to C 20 )aryloxy; linear or branched (C 1 to C 20 ) dialkylamido; substituted or unsubstituted (C 6 -C 20 ) diaryla
  • Photoreactive or crosslinkable groups encompass a linking portion L and a functional portion Fp.
  • L denotes or comprises a group selected from C 1 -C 12 alkyls, aralkyls, aryls or hetero atom analogs.
  • Fp denotes or comprises one or more of a maleimide, a 3-monoalkyl- or 3,4-dialkylmaleimide, epoxy, vinyl, acetyl, cinnamate, indenyl or coumarin moiety, which is capable of a crosslinking or 2+2 crosslinking reaction.
  • 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.
  • Exemplary 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:
  • n is an integer from 1 to 8
  • Q 1 and Q 2 are each independently from one another —H or —CH 3
  • R′ is —H or —OCH 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 ) n —O—(CH 2 ) n , (CH 2 ) n —C 6 Q 4 -(CH 2 ) n , and for structure 1 additionally selected from (CH 2 ) n —O and C(O)—O;
  • 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 )
  • repeating units represented by Formula I are formed from one or more norbornene-type monomers that include, but are not limited to, those selected from the following formulae:
  • 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 ) i —O—) b —(CH 2 )—C(CF 3 ) 2 —OH, —(CH 2 ) n —C(CF 3 )(CH 3 )—OH, (CH 2 ) n —C(CF 3 )—OH, (CH 2 ) n —C(CF 3 )—OH, (CH 2 ) n —C(CH 3 )—
  • Exemplary perhalogenated alkyl groups include, but are not limited to, trifluoromethyl, trichloromethyl, —C 2 F 5 , —C 3 F 7 , —C 4 F 9 , —C 7 F 15 , and —C 11 F 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 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.
  • such exemplary halogenated and perhalogenated aryl groups include, but are not limited to, pentachlorophenyl, pentafluorophenyl, pentafluorobenzyl, 4-trifluoromethylbenzyl, pentafluorophenylethyl, pentafluorophenpropyl, and pentafluorophenbutyl.
  • R 1 is selected from one of the above subformulae 15-26 and in one embodiment 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 ).
  • R 1 is a group as shown in one of the above subformulae 27-50 and as shown in subformulae 34, 35, 36, 37 and 38 (DMMIMeNB, DMMIEtNB, DMMIPrNB, DMMIBuNB and DMMIHxNB).
  • R 1 is a pendant silyl group represented by —(CH 2 ) n —SiR 93 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 (C 1 to C 20 )alkyl, linear or branched (C 1 to C 20 )alkoxy, substituted or unsubstituted (C 6 to C 20 )aryl, linear or branched (C 1 to C 20 )alkyl carbonyloxy, substituted or unsubstituted (C 6 to C 20 )aryloxy; linear or branched (C 1 to C 20 ) dialkylamido; substituted or unsubstituted (C 6 -C 20 ) diarylamido; substituted or unsubstituted (C 1 -C 20 )
  • 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.
  • R 1 is a group as shown in one of the above subformulae 9-14, and generally of subformula 9 (MeOAcNB).
  • Another 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.
  • 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 F 9 , NBCH 2 C 6 F 5 , NBC 6 F 5 , NBCH 2 C 6 F 2 , NBCH 2 C 6 H 4 CF 3 , NBalkylC 6 F 5 ), and a second type of repeating unit selected from subformulae 34, 35, 36, 37 and 38 (DMMIMeNB, DMMIEtNB, DMMIPrNB, DMMIBuNB, DMMIHxNB).
  • Another 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.
  • 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, DMMIHxNB), and a second type of repeating unit selected from subformulae 53 and 54 (TMSNB, TESNB).
  • Another 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.
  • 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, DMMIHxNB), and a third type of repeating unit selected from subformula 16 (NBCH 2 C 6 F 5 ).
  • Another 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 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.
  • 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.
  • 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 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 embodiment the ratio of such first and second type of repeat units is from 80:20 to 20:80. In still another embodiment the ratio of such first and second type of repeat units is from 60:40 to 40:60. In yet another embodiment the ratio of such first and second type of repeat units is from 55:45 to 45:55.
  • Another 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 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).
  • the polymer embodiments of the present invention are formed having a weight average molecular weight (M w ) that is appropriate to their use.
  • M w weight average molecular weight
  • 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.
  • the polymer has a M w of at least 30,000, while in another embodiment the polymer has a M w of at least 60,000.
  • the upper limit of the polymer's M w is up to 400,000, while in another embodiment the upper limit of the polymer's M w is up to 250,000.
  • 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 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, units formed by monomers selected from subformulae 27-50.
  • the polymer 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.
  • actinic radiation may be employed to image-wise expose 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 2 .
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • crosslinking can be achieved by exposure to UV radiation.
  • the crosslinkable group of the crosslinker is 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 a group that 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.
  • the crosslinker is selected of formula III1 or III2
  • X′ is O, S, NH or a single bond
  • A′′ is a single bond or a connecting, spacer or bridging group, which is for example selected from (CZ 2 ) n , (CH 2 ) n —(CH ⁇ CH) p —(CH 2 ) n , (CH 2 ) n —O—(CH 2 ) n , (CH 2 ) n —C 6 Q 10 -(CH 2 ) n , 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 Q 10 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 III1 at least one of X′ and the two groups A′′ is not a single bond.
  • P is selected from a maleimide group, a 3-monoalkyl-maleimide group, a 3,4-dialkylmaleimide group, an epoxy group, a vinyl group, an acetylene group, an indenyl group, a cinnamate group 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 compounds of formula III1 are selected from formula C1:
  • the crosslinkers are selected from DMMI-butyl-DMMI, DMMI-pentyl-DMMI and DMMI-hexyl-DMMI, wherein “DMMI” means 3,4-dimethylmaleimide.
  • the spacer group A′′ denotes linear C 1 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, Cl, Br, I, or CN, wherein optionally one or more non-adjacent CH 2 groups are replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR 18 —, —SiR 18 R 19 —, —C(O)—, —C(O)O—, —OC(O)—, —OC(O)—O—, —S—C(O)—, —C(O)—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
  • Suitable groups A′′ are —(CH 2 ) n —, —(CH 2 CH 2 O) n —, —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 —O) n —, 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 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.
  • crosslinkers like those of formula C1 is disclosed for example in U.S. Pat. No. 3,622,321 which is incorporated by reference into this application.
  • 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 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 functional layer provided onto the planarization layer is a semiconducting or dielectric layer.
  • Suitable adhesion promoters are selected of formula IV
  • 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
  • P is a crosslinkable group, preferably as defined in formula III1 above.
  • G is a group of the formula —SiR 12 R 13 R 14 , or a group of the formula —NH—SiR 12 R 13 R 14 , wherein R 12 , R 13 and R 14 are each independently selected from halogen, silazane, C 1 -C 12 -alkoxy, C 1 -C 12 -alkylamino, optionally substituted C 5 -C 20 -aryloxy and optionally substituted C 2 -C 20 -heteroaryloxy, and wherein one or two of R 12 , R 13 and R 14 may also denote C 1 -C 12 -alkyl, optionally substituted C 5 -C 20 -aryl or optionally substituted C 2 -C 20 -heteroaryl.
  • P is 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 selected from (CZ 2 ) n , (CH 2 ) n —(CH ⁇ CH) p —(CH 2 ) n , (CH 2 )—O, (CH 2 ) n —O—(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(O)—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 Q 4 is phenyl that is substituted with Q, C 6 Q 10 is cyclohexyl that is substituted with Q, Q is independently H, F, CH 3 , CF 3 or OCH 3 .
  • Suitable adhesion promoters are selected from formula A1:
  • R 12 , R 13 R 14 , and A′′ are as defined above, and R 10 and R 11 are each independently H or a C 1 -C 6 alkyl group.
  • Suitable compounds of formula A1 are for example 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.
  • 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.
  • 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.
  • FETs field effect transistors
  • OFETs organic field effect transistors
  • TFT thin film transistors
  • OTFTs organic thin film transistors
  • FIG. 1 and FIG. 2 depict schematic representations of top and bottom gate organic field effect transistors, respectively, according to prior art.
  • the OFET device of FIG. 1 and FIG. 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 ).
  • FIG. 3 is a schematic and exemplary representation of a top gate OFET device in accordance with one 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 FIG. 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
  • FIG. 4 is a schematic and exemplary representation of a bottom gate OFET device in accordance with an 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 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 FIG. 4 , 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 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
  • Deposition and/or forming of the layers and structures of the OFET embodiments in accordance with the present invention are performed using solution processing techniques where such techniques are possible.
  • a formulation or composition of a material typically a solution encompassing one or more organic solvents
  • a formulation or composition of a material can be deposited or formed using 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.
  • an organic semiconductor material and 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 can be employed.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • the polymer 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.
  • 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 2 .
  • 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.
  • 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.
  • 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 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.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • the thickness of a functional layer for example a gate dielectric or organic semiconductor layer, in some electronic device embodiments according to the present invention is from 0.001 (in case of a monolayer) to 10 ⁇ m; In other embodiments such thickness ranges from 0.001 nm to 1 ⁇ m, and in still other 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.
  • polymeric 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,
  • the substrate is a polymer film of a polymer selected from the group consisting of polyesters, polyimides, polyarylates, polycycloolefins, polycarbonates and polyethersulphones.
  • 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 FilmsTM may be used.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • 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 1 ⁇ 10 ⁇ 5 cm 2 V ⁇ 1 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.
  • OSCs can be deposited by any liquid coating technique, for example ink-jet deposition or via PVD or CVD techniques.
  • the semiconducting layer that is formed can be a composite of two or more of the same or different types of organic semiconductors.
  • a p-type OSC material may, for example, be mixed with an n-type material to achieve a doping effect of the layer.
  • multilayer organic semiconductor layers are used.
  • 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.
  • the OSC contains aromatic rings selected from 5-, 6- or 7-membered aromatic rings, while in other 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.
  • 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 15 and R 16 is alkyl or aryl these may be optionally fluorinated.
  • 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
  • conjugated hydrocarbon polymers such as poly
  • 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]thiophene-2,5-diyl, optionally substituted thieno[3,2-b]thiophene-2,5-diyl, selenophene-2,5-diyl, or 3-substituted selenophene-2,5-diyl.
  • Copolymers of this embodiment are for example copolymers comprising one or more benzo[1,2-b:4,5-b′]dithiophene-2,5-diyl units that are 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, 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 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, selenoph
  • the OSC materials are substituted oligoacenes such as pentacene, tetracene or anthracene, or heterocyclic derivatives thereof.
  • oligoacenes such as pentacene, tetracene or anthracene, or heterocyclic derivatives thereof.
  • Bis(trialkylsilylethynyl)oligoacenes or bis(trialkylsilylethynyl)heteroacenes as disclosed for example in U.S. Pat. No. 6,690,029 or WO 2005/055248 A1 or U.S. Pat. No. 7,385,221, are incorporated by reference into this application, are also useful.
  • 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 c of 3.3 or less.
  • the organic binder preferably has a permittivity c of 3.0 or less, more preferably 2.9 or less.
  • the organic binder has a permittivity c 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 c 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.
  • a suitable organic binders include polystyrene, or polymers or copolymers of styrene and ⁇ -methyl styrene, or copolymers including styrene, ⁇ -methylstyrene and butadiene may suitably be used. Further examples of suitable binders are disclosed for example in US 2007/0102696 A1 is incorporated by reference into this application.
  • the organic binder is one in which at least 95%, in an other embodiment at least 98% and another embodiment when 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.
  • 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.
  • 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 U.S. Pat. No. 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.
  • 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).
  • Teonex Q65FA® PEN film (available from DuPont Teijin FilmsTM) 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.
  • 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.
  • Lisicon M001® available from Merck Chemicals Ltd.
  • the OSC formulation was then printed as a 5 ⁇ 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 3 /m 2 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 ⁇ m thick.
  • 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 FIG. 5 .
  • Teonex Q65FA® film (available from DuPont Teijin FilmsTM) was washed in methanol.
  • 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.
  • M001 available from Merck Chemicals Ltd.
  • OSC Lisicon S1200-Series® formulation as used in Comparison Example 1 was then printed as a 5 ⁇ 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 3 /m 2 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 approximately 1 ⁇ m thick.
  • 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 FIG. 6 .
  • 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 FIG. 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.
  • the surface roughness of the substrates of Comparison Example 1 and Example 1 was measured by Atomic Force Microscopy (AFM).
  • the surface roughness of the Teonex Q65FA® substrate as used in Comparison Example 1 is 0.6 nm (Ra) and 20 nm (Rt), whereas the surface roughness of the same substrate coated with a layer of pDMMIBuNB as used in Example 1, is 0.2 nm (Ra) and 5 nm (Rt) for pDMMIBuNB layer.
  • the surface energy of the Teonex Q65FA® substrate as used in Comparison Example 1 is 32 mN/m (without plasma treatment), whereas the surface energy of the same substrate coated with a layer of pDMMIBuNB as used in Example 1, is 50 mN/m respectively.
  • the substrate of Comparison Example 1 needs further plasma treatment to increase surface energy.
  • 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.
  • pDMMIBuNB is resistant to plasma treatment, which is commonly applied after a photolithographic process in order to remove post-process residues.
  • Melinex ST506® film (available from DuPont Teijin FilmsTM) 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.
  • 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.
  • Lisicon M001® available from Merck Chemicals Ltd.
  • OSC Lisicon S1200-Series® formulation as used in Comparison Example 1 was then printed as a 5 ⁇ 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 3 /m 2 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 ⁇ m thick.
  • 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 FIG. 7 .
  • Melinex ST506® film (available from DuPont Teijin FilmsTM) was washed in methanol.
  • 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.
  • Lisicon M001® available from Merck Chemicals Ltd.
  • OSC Lisicon S1200-Series® formulation as used in Comparison Example 1 was then printed as a 5 ⁇ 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 3 /m 2 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 ⁇ m thick.
  • 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 FIG. 8 .
  • 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 FIG. 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 particularly important to ensure applicability of the transistors.
  • the surface roughness of the substrates of Comparison Example 2 and Example 2 was measured by Atomic Force Microscope.
  • 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 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 (R t ) for pDMMIBuNB layer.
  • the surface energy of the Melinex ST506® substrate as used in Comparison Example 2 is 33 mN/m, whereas the surface energy of the same substrate coated with a layer of pDMMIBuNB as used in Example 2, is 50 mN/m respectively.
  • the substrate of Comparison Example 2 needs further plasma treatment to increase surface energy.
  • 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.
  • pDMMIBuNB is resistant to plasma treatment, which is commonly applied after a photolithographic process in order to remove post-process residues.
  • 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.
  • Melinex ST506® film (available from DuPont Teijin FilmsTM) was washed in methanol.
  • 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.
  • Lisicon M001® available from Merck Chemicals Ltd.
  • OSC Lisicon S1200-Series® formulation as used in Comparison Example 1 was then printed as a 5 ⁇ 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 3 /m 2 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 ⁇ m thick.
  • 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 FIG. 9 .
  • 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 FIG. 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 particularly important to ensure applicability of the transistors.
  • 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.
  • 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 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.
  • the surface energy of the Melinex ST506® substrate as used in Comparison Example 2 is 33 mN/m, whereas 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.
  • the substrate of Comparison Example 2 needs further plasma treatment to increase surface energy.
  • 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.
  • 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 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.
  • 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.
  • TES triethoxysilyl

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