US20220052277A1 - Self-assembled monolayer for electrode modification and device comprising such self-assembled monolayer - Google Patents

Self-assembled monolayer for electrode modification and device comprising such self-assembled monolayer Download PDF

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US20220052277A1
US20220052277A1 US17/299,698 US201917299698A US2022052277A1 US 20220052277 A1 US20220052277 A1 US 20220052277A1 US 201917299698 A US201917299698 A US 201917299698A US 2022052277 A1 US2022052277 A1 US 2022052277A1
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electronic device
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David Sparrowe
Changsheng Wang
William Mitchell
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Merck Performance Materials Ltd
Merck Performance Materials GmbH
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Merck Patent GmbH
Merck Performance Materials GmbH
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    • H01L51/0094—
    • H—ELECTRICITY
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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
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/80—Constructional details
    • H10K10/82—Electrodes
    • H10K10/84—Ohmic electrodes, e.g. source or drain electrodes
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/30—Organic light-emitting transistors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
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    • H01L51/442—
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/80—Constructional details
    • H10K10/82—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present application relates to a self-assembled monolayer suitable for the modification of electrodes comprised in electronic devices as well as to such electronic devices.
  • the present application also relates to a method for depositing such self-assembled monolayer onto an electrode as well as to the manufacturing of the corresponding devices.
  • Organic electronic materials have established their presence in a wide range of electronic devices, such as organic photodetectors (OPD), organic photovoltaic cells (OPV), organic light emitting diodes (OLEDs) and organic field effect transistors (OFETs), to name a few only. Because they may be deposited onto an underlying substrate by solution processing, organic materials hold the promise of allowing for simplified and highly flexible production, potentially also leading to reduced manufacturing costs.
  • OPD organic photodetectors
  • OLEDs organic light emitting diodes
  • OFETs organic field effect transistors
  • the work function of the electrode materials has to match the energy level of the highest occupied molecular orbital (HOMO) for a p-type organic semiconducting material and of the lowest unoccupied molecular orbital (LUMO) for an n-type organic semiconducting material. Therefore, for a p-type organic electronic device gold, palladium and platinum are suitable electrode materials. Alternatively, silver electrodes have been used in combination with self-assembled monolayers, wherein the self-assembled monolayer brings the work function of the electrode to a level suitable for a p-type organic electronic device.
  • HOMO highest occupied molecular orbital
  • LUMO lowest unoccupied molecular orbital
  • Copper may, for example, be considered as a potential alternative electrode material because of its good conductivity, relatively low cost and relative ease to use in manufacturing processes. In addition, copper is already widely used in the semiconductor industry.
  • copper is chemically quite reactive and also requires surface modification in order to match the work function of the copper electrode to the respective organic semiconducting material.
  • Such surface modification may, for example, be done by plating the copper surface with silver. Unfortunately, this frequently leads to the formation of silver dendrites, consequently rendering the so-produced electronic devices less efficient or even completely useless.
  • molybdenum may also be used, for example, in combination with a self-assembled monolayer thereon formed by the deposition of octadecyltrichlorosilane and phenethyltrichlorosilane, as disclosed by Dong-Jin Yun and Shi-Woo Rhee in Journal of the Electrochemical Society 155(6) H357-H362 (2008).
  • metal oxide electrodes such as for example indium tin oxide (ITO) electrodes
  • ITO indium tin oxide
  • an object of the present application to provide an electrode, which is suitable for use in an organic electronic device, preferably at reduced cost.
  • the present application therefore provides for an organic electronic device comprising an electrode, a self-assembled monolayer on said electrode and an organic semiconducting layer on said self-assembled monolayer, wherein said self-assembled monolayer is formed by depositing the reaction product of a compound of the following formula (I)
  • the present application also provides for a method of producing the organic electronic device of any one or more of claims 1 to 12 , said method comprising the steps of
  • FIG. 1 shows a schematic representation of an exemplary top gate OFET in accordance with the present application.
  • FIG. 2 shows a schematic representation of an exemplary bottom gate OFET in accordance with the present application.
  • organic electronic device refers to an electronic device comprising an organic semiconducting layer, i.e. a semiconducting layer comprising at least 50 wt % (e.g. 60 wt % or 70 wt % or 80 wt % or 90 wt % or 95 wt % or 97 wt % or 99.0 wt % or 99.5 wt % or 99.7 wt % or 99.9 wt %), with wt % relative to the total weight of said semiconducting layer, and preferably consists of one or more organic semiconducting material.
  • the terms “consist of” and “consisting of” do not exclude the presence of impurities, which may normally be present, for example but in no way limited to, impurities resulting from the synthesis of a compound (e.g. an organic semiconducting material) or—in case of metals—trace metals.
  • an asterisk “*” is used to denote a linkage to an adjacent unit or group, including for example, in case of a polymer, to an adjacent repeating unit or any other group. In some instances, where specifically identified as such, the asterisk “*” may also denote a mono-valent chemical group.
  • the present application relates to an organic electronic device.
  • Said organic electronic device comprises an electrode, a self-assembled monolayer and an organic semiconducting layer, wherein the self-assembled monolayer is (or is formed) on the electrode, and wherein the organic semiconducting layer is on (or is deposited onto) the self-assembled monolayer.
  • the organic electronic device comprises an electrode, a self-assembled monolayer and an organic semiconducting layer, with the self-assembled monolayer between the electrode and the organic semiconducting layer.
  • the electrode comprises a metal or an electrically conductive metal oxide or a blend thereof, preferably in at least 50 wt % (for example in at least 60 wt % or 70 wt % or 80 wt % or 90 wt % or 95 wt % or 97 wt % or 99.0 wt % or 99.5 wt % or 99.7 wt % or 99 wt %), with wt % relative to the total weight of said electrode, and most preferably consists of the metal or the electrically conductive metal oxide or a blend thereof.
  • metal as used herein also includes the possibility of a blend of two or more metals.
  • electrically conductive metal oxide as used herein also includes the possibility of a blend of two or more metal oxides and/or the possibility of mixed metal oxides.
  • Said metal is not particularly limited.
  • Metals generally suitable may, for example, be selected from the group consisting of chromium, molybdenum, tungsten, cobalt, rhodium, iridium, nickel, palladium, platinum, gold, silver, and any blend of any of these, with chromium, molybdenum and tungsten being preferred, and molybdenum being most preferred.
  • the electrically conductive metal oxide is selected from the group consisting of indium tin oxide (ITO), molybdenum oxide, tin oxide, and any blend of any of these.
  • the self-assembled monolayer essentially covers the electrode.
  • the term “essentially covers” is used to denote that—depending upon the architecture of the respective organic electronic device—the self-assembled monolayer covers the electrode in such a way that preferably no part of the electrode is in direct physical contact with the organic semiconducting layer; or that the self-assembled monolayer covers the entire surface of the electrode, preferably the entire surface of the electrode facing the organic semiconducting layer; or that the self-assembled monolayer covers the part of the surface of the electrode that is active in the change transfer.
  • the self-assembled monolayer is formed by depositing a formulation comprising a compound of the following formula (I)
  • R 2 is an alkyl group having from 1 to 10 carbon atoms.
  • R 2 is an alkyl group having from 1 to 5 carbon atoms.
  • R 2 may be selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl and n-pentyl. It is most preferred that R 2 is iso-propyl.
  • the self-assembled monolayer may actually be formed by depositing the reaction product of the compound of formula (I) and the alcohol of formula R 2 —OH, for example by depositing any one or more of compounds (I-a) to (I-c), preferably of compound (I-c) predominantly or even solely.
  • X is at each occurrence independently halogen, preferably Cl, or an alkoxy group having from 1 to 10 carbon atoms.
  • the alkoxy group is —O—C a H 2a+1 with a being an integer of at least 1 and of at most 10, preferably of at least 1 and of at most 5.
  • Examples of preferred alkoxy groups may be selected from the group consisting of —O—CH 3 , —O—CH 2 —CH 3 , —O—(CH 2 ) 2 —CH 3 , —O—CH(CH 3 ) 2 , —O—(CH 2 ) 3 —CH 3 , —O—C(CH 3 ), and —O—CH 2 —CH(CH 3 ) 2 .
  • a particularly preferred alkoxy group is —O—CH(CH 3 ) 2 .
  • R 1 is at each occurrence independently alkyl having from 1 to 10 carbon atoms, said alkyl being substituted with at least one electron-withdrawing group R A , or aryl having from 6 to 30 aromatic carbon ring atoms, said aryl being substituted with at least one electron-withdrawing group R A .
  • R 1 is at each occurrence independently a group of any one of the following formulae (II-a) or (II-b)
  • R A is an electron withdrawing group.
  • R A is at each occurrence independently selected from the group consisting of —NO 2 , —CN, —F, —Cl, —Br, —I, —OAr 2 , —OR 3 , —COR 3 , —SH, —SR 3 , —OH, —C ⁇ CR 3 , —CH ⁇ CR 3 2 , and alkyl having from 1 to 10 carbon atoms, wherein one or more, preferably all, hydrogen atoms are replaced by F, with Ar 2 and R 3 as defined herein.
  • R A is at each occurrence independently selected from the group consisting of —CN, —F, —Cl, —Br, —I, —OR 3 , and alkyl having from 1 to 10 carbon atoms, wherein one or more, preferably all, hydrogen atoms are replaced by F, with R 3 as defined herein. Even more preferably R A is at each occurrence independently selected from the group consisting of —F, —OR 3 , and alkyl having from 1 to 10 carbon atoms, wherein one or more, preferably all, hydrogen atoms are replaced by F, with R 3 as defined herein. Most preferably R A is F.
  • Ar 2 is an aryl having from 6 to 30 carbon atoms, preferably having from 6 to 20 carbon atoms, and most preferably is phenyl.
  • Ar 2 is substituted with one or more substituent selected from the group consisting of —CN, —F, —Cl, —Br, —I, —OR 3 , and alkyl having from 1 to 10, preferably from 1 to 5, carbon atoms, wherein one or more, preferably all, hydrogen atoms are replaced by F, with R 3 as defined herein.
  • R 3 is an alkyl having from 1 to 10, preferably from 1 to 5, carbon atoms, or alkyl having from 1 to 10, preferably from 1 to 5, carbon atoms, wherein one or more, preferably all, hydrogen atoms are replaced by F.
  • alkyl suitable as R 3 may be selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl and n-pentyl.
  • fluorinated alkyl i.e. alkyl wherein one or more, preferably all, hydrogen atoms are replaced by F
  • suitable as R 3 may be selected from the group consisting of —CF 3 , —C 2 F 5 , -n-C 3 F 7 (i.e. n-propyl), and -n-C 4 F 9 (i.e. n-butyl).
  • Preferred examples of the compound of formula (I) may be selected from the group consisting of the following formulae (I-1) to (I-11)
  • X as defined herein, and e being an integer of at least 1 and at most 10 (for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10).
  • the self-assembled monolayers of the present invention may have a thickness (measured perpendicular to the surface of such layer) from 1 to 10, more preferably from 1 to 5, even more preferably from 1 to 3, and still even more preferably from 1 to 2 molecular layers. Most preferably said thickness is about one molecular layer.
  • the organic semiconducting material is not particularly limited. Any organic semiconducting material may be used, such as for example so-called “small molecules” or polymers.
  • small molecules refers to organic semiconducting compounds that generally have a molecular weight of at most 1000 g mol ⁇ 1 , preferably of at most 500 g mol ⁇ 1 .
  • the organic semiconducting material can either be an n-type or p-type semiconducting material.
  • said organic semiconducting material has a field effect transistor mobility of at least 1 ⁇ 10 ⁇ 5 cm 2 V ⁇ 1 s ⁇ 1 .
  • the organic semiconducting layer is solid.
  • the semiconducting layer comprises, and preferably consists of, one or more, preferably one, organic semiconducting material.
  • said semiconducting material has a transistor mobility of at least 1 ⁇ 10 ⁇ 5 cm 2 V ⁇ 1 s ⁇ 1 and/or the energy level of the highest occupied molecular orbital (HOMO) of the semiconducting material is lower than the lower of the Fermi energy levels of the first and second electrode materials.
  • the semiconducting layer preferably has a thickness of at least 5 nm, more preferably of at least 10 nm, and of at most 20 ⁇ m, more preferably of at most 15 ⁇ m and most preferably of at most 10 ⁇ m.
  • the organic semiconducting material is preferably selected from the group consisting of monomeric compounds (also referred to as “small molecule”), oligomers, polymers or blends of any of these, for example, including but not limited to blends of one or more monomeric compounds, one or more oligomers or one or more polymers. More preferably the organic semiconducting material is a polymer or a blend of polymers. Most preferably the organic semiconducting material is a polymer.
  • organic semiconducting material is not particularly limited.
  • the organic semiconducting material comprises a conjugated system.
  • conjugated system is herein used to denote a molecular entity or a part of a molecular entity, the structure of which may be represented as a system of alternating single and multiple bonds (see also International Union of Pure and Applied Chemistry, Compendium of Chemical Terminology, Gold Book, Version 2.3.3, 2014-02-24, pages 322-323).
  • organic semiconducting material suited for use herein may, for example, be represented by the following formula (V)
  • monomeric unit M and m are as defined herein. At each occurrence M may be selected independently.
  • m may be any integer from 1 to 100,000.
  • m For a monomer or monomeric unit m is 1.
  • oligomer m is at least 2 and at most 10.
  • polymer m is at least 11.
  • the organic semiconducting material comprises one or more aromatic units.
  • M may be an aromatic unit.
  • aromatic units preferably comprise two or more, more preferably three or more aromatic rings.
  • aromatic rings may, for example, at each occurrence independently be selected from the group consisting of 5-, 6-, 7- and 8-membered aromatic rings, with 5- and 6-membered rings being particularly preferred.
  • aromatic rings comprised in the organic semiconducting material optionally comprise one or more heteroatoms selected from Se, Te, P, Si, B, As, N, O or S, preferably from Si, N, O or S. Further, these aromatic rings may optionally be substituted with alkyl, alkoxy, polyalkoxy, thioalkyl, acyl, aryl or substituted aryl groups, halogen, with fluorine being the preferred halogen, cyano, nitro or an optionally substituted secondary or tertiary alkylamine or arylamine represented by —N(R′)(R′′), where R′ and R′′ are each independently H, an optionally substituted alkyl or an optionally substituted aryl, alkoxy or polyalkoxy groups are typically employed. Further, where R′ and R′′ is alkyl or aryl these may be optionally fluorinated.
  • organic semiconducting materials may be polymers or copolymers wherein the monomeric units M of formula (V) may at each occurrence be independently selected from the group consisting of formulae (A1) to (A83) and (D1) to (D142)
  • R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 and R 108 are independently of each other selected from the group consisting of H and R S as defined herein.
  • R S is at each occurrence independently a carbyl group as defined herein and preferably selected from the group consisting of any group R T as defined herein, hydrocarbyl having from 1 to 40 carbon atoms wherein the hydrocarbyl may be further substituted with one or more groups R T , and hydrocarbyl having from 1 to 40 carbon atoms comprising one or more heteroatoms selected from the group consisting of N, O, S, P, Si, Se, As, Te or Ge, with N, O and S being preferred heteroatoms, wherein the hydrocarbyl may be further substituted with one or more groups R T .
  • hydrocarbyl suitable as R S may at each occurrence be independently selected from phenyl, phenyl substituted with one or more groups R T , alkyl and alkyl substituted with one or more groups R T , wherein the alkyl has at least 1, preferably at least 5 and has at most 40, more preferably at most 30 or 25 or 20, even more preferably at most 15 and most preferably at most 12 carbon atoms.
  • alkyl suitable as R S also includes fluorinated alkyl, i.e. alkyl wherein one or more hydrogen is replaced by fluorine, and perfluorinated alkyl, i.e. alkyl wherein all of the hydrogen are replaced by fluorine.
  • R T is at each occurrence independently selected from the group consisting of F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR 0 R 00 , —C(O)X 0 , —C(O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —OR 0 , —NO 2 , —SF 5 and —SiR 0 R 00 R 000 .
  • Preferred R T are selected from the group consisting of F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR 0 R 00 , —C(O)X 0 , —C(O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —OH, —OR 0 and —SiR 0 R 00 R 000 .
  • Most preferred R T is F.
  • R 0 , R 00 and R 000 are at each occurrence independently of each other selected from the group consisting of H, F and hydrocarbyl having from 1 to 40 carbon atoms.
  • Said hydrocarbyl preferably has at least 5 carbon atoms.
  • Said hydrocarbyl preferably has at most 30, more preferably at most 25 or 20, even more preferably at most 20, and most preferably at most 12 carbon atoms.
  • R 0 , R 00 and R 000 are at each occurrence independently of each other selected from the group consisting of H, F, alkyl, fluorinated alkyl, alkenyl, alkynyl, phenyl and fluorinated phenyl.
  • R 0 , R 00 and R 000 are at each occurrence independently of each other selected from the group consisting of H, F, alkyl, fluorinated, preferably perfluorinated, alkyl, phenyl and fluorinated, preferably perfluorinated, phenyl.
  • alkyl suitable as R 0 , R 00 and R 000 also includes perfluorinated alkyl, i.e. alkyl wherein all of the hydrogen are replaced by fluorine.
  • suitable alkyls may be selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl (or “t-butyl”), pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl (—C 20 H 41 ).
  • X 0 is halogen.
  • X 0 is selected from the group consisting of F, Cl and Br.
  • a hydrocarbyl group comprising a chain of 3 or more carbon atoms and heteroatoms combined may be straight chain, branched and/or cyclic, including spiro and/or fused rings.
  • Hydrocarbyl suitable as R S , R 0 , R 00 and/or R 000 may be saturated or unsaturated.
  • saturated hydrocarbyl include alkyl.
  • unsaturated hydrocarbyl may be selected from the group consisting of alkenyl (including acyclic and cyclic alkenyl), alkynyl, allyl, alkyldienyl, polyenyl, aryl and heteroaryl.
  • Preferred hydrocarbyl suitable as R S , R 0 , R 00 and/or R 000 include hydrocarbyl comprising one or more heteroatoms and may for example be selected from the group consisting of alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy, alkylaryloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy.
  • aryl and heteroaryl comprise mono-, bi- or tricyclic aromatic or heteroaromatic groups that may also comprise condensed rings.
  • aryl and heteroaryl groups may be selected from the group consisting of phenyl, phenyl wherein one or more CH groups are replaced by N, naphthalene, fluorene, thiophene, pyrrole, preferably N-pyrrole, furan, pyridine, preferably 2- or 3-pyridine, pyrimidine, pyridazine, pyrazine, triazole, tetrazole, pyrazole, imidazole, isothiazole, thiazole, thiadiazole, isoxazole, oxazole, oxadiazole, thiophene, preferably 2-thiophene, selenophene, preferably 2-selenophene, thieno[3,2-b]thiophene, thieno[2,3-b]thiophene, dithienothiophene, furo[3,2-b]furan, furo[2,3-b]furan, sel
  • alkoxy group i.e. a corresponding alkyl group wherein the terminal CH 2 group is replaced by —O—
  • alkoxy group can be straight-chain or branched, preferably straight-chain (or linear).
  • Suitable examples of such alkoxy group may be selected from the group consisting of methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy, tetradecoxy, pentadecoxy, hexadecoxy, heptadecoxy and octadecoxy.
  • alkenyl i.e. a corresponding alkyl wherein two adjacent CH 2 groups are replaced by —CH ⁇ CH— can be straight-chain or branched. It is preferably straight-chain.
  • Said alkenyl preferably has 2 to 10 carbon atoms.
  • alkenyl may be selected from the group consisting of vinyl, prop-1-enyl, or prop-2-enyl, but-1-enyl, but-2-enyl or but-3-enyl, pent-1-enyl, pent-2-enyl, pent-3-enyl or pent-4-enyl, hex-1-enyl, hex-2-enyl, hex-3-enyl, hex-4-enyl or hex-5-enyl, hept-1-enyl, hept-2-enyl, hept-3-enyl, hept-4-enyl, hept-5-enyl or hept-6-enyl, oct-1-enyl, oct-2-enyl, oct-3-enyl, oct-4-enyl, oct-5-enyl, oct-6-enyl or oct-7-enyl
  • alkenyl groups are C 2 -C 7 -1E-alkenyl, C 4 -C 7 -3E-alkenyl, C 5 -C 7 -4-alkenyl, C 6 -C 7 -5-alkenyl and C 7 -6-alkenyl, in particular C 2 -C 7 -1E-alkenyl, C 4 -C 7 -3E-alkenyl and C 5 -C 7 -4-alkenyl.
  • alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like.
  • Alkenyl groups having up to 5 C atoms are generally preferred.
  • oxaalkyl i.e. a corresponding alkyl wherein one non-terminal CH 2 group is replaced by —O—
  • oxaalkyl can be straight-chain or branched, preferably straight chain.
  • Preferred examples of carbonyloxy and oxycarbonyl i.e. a corresponding alkyl wherein one CH 2 group is replaced by —O— and one of the thereto adjacent CH 2 groups is replaced by —C(O)—.
  • Preferred examples of thioalkyl may be straight-chain or branched, preferably straight-chain. Suitable examples may be selected from the group consisting of thiomethyl (—SCH 3 ), 1-thioethyl (—SCH 2 CH 3 ), 1-thiopropyl (—SCH 2 CH 2 CH 3 ), 1-(thiobutyl), 1-(thiopentyl), 1-(thiohexyl), 1-(thioheptyl), 1-(thiooctyl), 1-(thiononyl), 1-(thiodecyl), 1-(thioundecyl) and 1-(thiododecyl).
  • a fluoroalkyl group is preferably perfluoroalkyl C i F 2i+1 , wherein i is an integer from 1 to 15, in particular CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , C 6 F 13 , C 7 F 15 or C 8 F 17 , very preferably C 6 F 13 , or partially fluorinated alkyl, in particular 1,1-difluoroalkyl, all of which are straight-chain or branched.
  • the organyl groups are independently of each other selected from primary, secondary or tertiary alkyl or alkoxy with 1 to 30 C atoms, wherein one or more H atoms are optionally replaced by F, or aryl, aryloxy, heteroaryl or heteroaryloxy that is optionally alkylated or alkoxylated and has 4 to 30 ring atoms.
  • Very preferred groups of this type are selected from the group consisting of the following formulae
  • ALK denotes optionally fluorinated, preferably linear, alkyl or alkoxy with 1 to 20, preferably 1 to 12 C-atoms, in case of tertiary groups very preferably 1 to 9 C atoms, and the dashed line denotes the link to the ring to which these groups are attached.
  • tertiary groups very preferably 1 to 9 C atoms
  • the dashed line denotes the link to the ring to which these groups are attached.
  • Especially preferred among these groups are those wherein all ALK subgroups are identical.
  • the organic semiconducting materials are polymers or copolymers that encompass one or more repeating units, e.g. M in formula (I), selected from thiophene-2,5-diyl, 3-substituted thiophene-2,5-diyl, optionally substituted thieno[2,3-b]thiophene-2,5-diyl, optionally substituted thieno[3,2-b]thiophene-2,5-diyl, selenophene-2,5-diyl, or 3-substituted selenophene-2,5-diyl.
  • M in formula (I) selected from thiophene-2,5-diyl, 3-substituted thiophene-2,5-diyl, optionally substituted thieno[2,3-b]thiophene-2,5-diyl, optionally substituted thieno[3,2-b]thiophene-2,5-d
  • organic semiconducting materials comprise one or more monomeric units selected from the group consisting of formulae (A1) to (A83) and one or more monomeric units selected from the group consisting of formulae (D1) to (D142).
  • organic semiconductor materials that can be used in this invention include compounds, oligomers and derivatives of compounds selected from the group consisting of conjugated hydrocarbon polymers such as polyacene, polyphenylene, poly(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
  • organic semiconducting materials may be selected from the group consisting of substituted oligoacenes, such as pentacene, tetracene or anthracene, or heterocyclic derivatives thereof.
  • substituted 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 also useful.
  • organic semiconducting materials are selected from the group consisting of small molecules or monomers of the tetra-heteroaryl indacenodithiophene-based structural unit as disclosed in WO 2016/015804 A1, and polymers or copolymers comprising one or more repeating units thereof.
  • organic semiconducting materials may be selected from the group of small molecules or monomers or polymers comprising a 2,7-(9,9′)spirobifluorene moiety, optionally substituted and preferably substituted with amino groups.
  • spirobifluorenes are, for example, disclosed in WO 97/39045.
  • Examples of spirobifluorenes suitable for use as monomeric unit M of formula (V) may be selected from the group consisting of formulae (VI-1) to (VI-7)
  • each of the hydrogen atoms may independently of any other be as defined herein in respect to R 101 and each asterisk “*” independently may denote a bond to neighboring moiety (for example in a polymer) or may denote a bond to a group as defined above for R 101 (for example in a compound of formula (V-a) or (V-b)).
  • preferred substituents including the ones for “*”, may be selected from the group consisting of alkyl having from 1 to 20 carbon atoms; aryl having from 6 to 20 carbon atoms, said aryl being optionally substituted with alkyl or alkoxy having from 1 to 20, preferably 1 to 10 carbon atoms; and NR 110 R 111 with R 110 and R 111 being independently of each other selected from the group consisting of alkyl having from 1 to 20 carbon atoms, aryl having from 6 to 20 carbon atoms, said aryl being optionally substituted with alkyl or alkoxy having from 1 to 20, preferably 1 to 10 carbon atoms, most preferably R 110 and R 111 being independently of each other selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, methoxy, ethoxy, n-
  • a small molecule may for example be represented by formula (I-a)
  • R a and R b are inert chemical groups.
  • Such inert chemical groups R a and R b may independently of each other be selected from the group consisting of hydrogen, fluorine, alkyl having from 1 to 10 carbon atoms, alkyl having from 1 to 10 carbon atoms wherein one or more, for example all, hydrogen has been replaced with fluorine, aromatic ring systems of from 5 to 30 carbon atoms and aromatic ring systems of from 5 to 30 carbon atoms wherein one or more hydrogen atom may independently of any other be replaced by fluorine or alkyl having from 1 to 10 carbon atoms.
  • Further preferred p-type 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[1,2-b:4,5-b′]dithiophene-2,5-diyl units that are preferably 4,8-disubstituted by one or more groups R as defined above, and further comprising one or more aryl or heteroaryl units selected from Group A and Group B, preferably comprising at least one unit of Group A and at least one unit of Group B, wherein Group A consists of aryl or heteroaryl groups having electron donor properties and Group B consists of aryl or heteroaryl groups having electron acceptor properties, and preferably Group A consists of selenophene-2,5-diyl, thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, thieno[2,3-b]thiophene
  • Group B consists of benzo[2,1,3]thiadiazole-4,7-diyl, 5,6-dialkyl-benzo[2,1,3]thiadiazole-4,7-diyl, 5,6-dialkoxybenzo[2,1,3]thiadiazole-4,7-diyl, benzo[2,1,3]selenadiazole-4,7-diyl, 5,6-dialkoxy-benzo[2,1,3]selenadiazole-4,7-diyl, benzo[1,2,5]thiadiazole-4,7,diyl, benzo[1,2,5]selenadiazole-4,7,diyl, benzo[2,1,3]oxadiazole-4,7-diyl, 5,6-dialkoxybenzo[2,1,3]oxadiazole-4,7-diyl, 2H-benzotriazole-4,7-diyl, 2,3-dicyano-1,4-phenylene, 2,5-
  • 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 also useful.
  • organic semiconducting materials are selected from the group consisting of small molecules or monomers of the tetra-heteroaryl indacenodithiophene-based structural unit as disclosed in WO 2016/015804 A1, and polymers or copolymers comprising one or more repeating units thereof, such as, for example, one of the following polymers (P-1) to (P-3):
  • the present organic semiconducting material may also comprise other components, such as, for example, a fullerene or modified fullerene.
  • a fullerene or modified fullerene In such blends of polymer and fullerene the ratio polymer:fullerene is preferably from 5:1 to 1:5 by weight, more preferably from 1:1 to 1:3 by weight, most preferably 1:1 to 1:2 by weight.
  • Suitable fullerenes may, for example, be indene-C 60 -fullerene bis-adduct like ICBA, or a (6,6)-phenyl-butyric acid methyl ester derivatized methano C 60 fullerene, also known as “PCBM-C 60 ” or “C 60 PCBM”, as disclosed for example in G. Yu, J.
  • Organic semiconducting materials may be purchased from commercial sources, such as SigmaAldrich or Merck KGaA (Darmstadt, Germany), or may be synthesized according to published syntheses.
  • the present semiconducting material may be an oligomer or a polymer as defined above.
  • oligomers and polymers may be synthesized according to or in analogy to methods that are known to the skilled person and are described in the literature from monomers as described in the following.
  • Monomers that are suitable for the synthesis of the present oligomers and polymers may be selected from compounds comprising a structural unit of formula (I) and at least one reactive chemical group R C which may be selected from the group consisting of Cl, Br, I, O-tosylate, O-triflate, O-mesylate, O-nonaflate, —SiMe 2 F, —SiMeF 2 , —O—SO 2 Z 1 , —B(OZ 2 ) 2 , —CZ 3 ⁇ C(Z 3 ) 2 , —C ⁇ CH, —C ⁇ CSi(Z 1 ) 3 , —ZnX 00 and —Sn(Z 4 ) 3 , preferably —B(OZ 2 ) 2 or —Sn(Z 4 ) 3 , wherein X 00 is as defined herein, and Z 1 , Z 2 , Z 3 and Z 4 are selected from the group consisting of alkyl and aryl, preferably al
  • R C and R d are reactive chemical groups as defined above in respect to R C .
  • Such monomers may generally be prepared according to methods well known to the person skilled in the art.
  • X 00 is halogen.
  • X 00 is selected from the group consisting of F, Cl and Br.
  • Preferred aryl-aryl coupling and polymerisation methods used in the processes described herein may, for example, be one or more of Yamamoto coupling, Kumada coupling, Negishi coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling, C—H activation coupling, Ullmann coupling and Buchwald coupling.
  • Yamamoto coupling is described for example in WO 00/53656 A1.
  • Negishi coupling is described for example in J. Chem. Soc., Chem. Commun., 1977, 683-684.
  • Yamamoto coupling is described for example in T. Yamamoto et al., Prog. Polym.
  • Stille coupling is described for example in Z. Bao et al., J. Am. Chem. Soc., 1995, 117, 12426-12435.
  • monomers having two reactive halide groups are preferably used.
  • Suzuki coupling compounds of formula (I-b) having two reactive boronic acid or boronic acid ester groups or two reactive halide groups are preferably used.
  • Stille coupling monomers having two reactive stannane groups or two reactive halide groups are preferably used.
  • Negishi coupling monomers having two reactive organozinc groups or two reactive halide groups are preferably used.
  • Preferred catalysts are selected from Pd(0) complexes or Pd(II) salts.
  • Preferred Pd(0) complexes are those bearing at least one phosphine ligand, for example Pd(Ph 3 P) 4 .
  • Another preferred phosphine ligand is tris(ortho-tolyl)phosphine, for example Pd(o-Tol 3 P) 4 .
  • Preferred Pd(II) salts include palladium acetate, for example Pd(OAc) 2 .
  • the Pd(0) complex can be prepared by mixing a Pd(0) dibenzylideneacetone complex, for example tris(dibenzyl-ideneacetone)dipalladium(0), bis(dibenzylideneacetone)-palladium(0), or Pd(II) salts e.g. palladium acetate, with a phosphine ligand, for example triphenylphosphine, tris(ortho-tolyl)phosphine or tri(tert-butyl)phosphine.
  • a Pd(0) dibenzylideneacetone complex for example tris(dibenzyl-ideneacetone)dipalladium(0), bis(dibenzylideneacetone)-palladium(0), or Pd(II) salts e.g. palladium acetate
  • a phosphine ligand for example triphenylphosphine, tris(ortho-tolyl)phosphin
  • Suzuki polymerisation is performed in the presence of a base, for example sodium carbonate, potassium carbonate, lithium hydroxide, potassium phosphate or an organic base such as tetraethylammonium carbonate or tetraethylammonium hydroxide.
  • a base for example sodium carbonate, potassium carbonate, lithium hydroxide, potassium phosphate or an organic base such as tetraethylammonium carbonate or tetraethylammonium hydroxide.
  • Yamamoto polymerisation employs a Ni(0) complex, for example bis(1,5-cyclooctadienyl)nickel(0).
  • Suzuki and Stille polymerisation may be used to prepare homopolymers as well as statistical, alternating and block random copolymers.
  • Statistical or block copolymers can be prepared for example from the above monomers of formula (I-b), wherein one of the reactive groups is halogen and the other reactive group is a boronic acid, boronic acid derivative group or and alkylstannane.
  • the synthesis of statistical, alternating and block copolymers is described in detail for example in WO 03/048225 A2 or WO 2005/014688 A2.
  • leaving groups of formula —O—SO 2 Z 1 can be used wherein Z 1 is as described above.
  • Particular examples of such leaving groups are tosylate, mesylate and triflate.
  • some embodiments of the present invention employ organic semiconducting compositions that include one or more organic binders.
  • the binder which is typically a polymer, may comprise either an insulating binder or a semiconducting binder, or mixtures thereof, may be referred to herein as the organic binder, the polymeric binder, or simply the binder.
  • Preferred binders according to the present invention are materials of low permittivity, that is, those having a permittivity ⁇ of 3.3 or less.
  • the organic binder preferably has a permittivity ⁇ of 3.0 or less, more preferably 2.9 or less.
  • the organic binder has a permittivity ⁇ 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.
  • the use of binders with a permittivity ⁇ of greater than 3.3 may lead to a reduction in the OSC layer mobility in an electronic device, for example, in an OFET.
  • high permittivity binders could also result in increased current hysteresis of the device, which is undesirable.
  • 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.
  • 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.
  • 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 (V) 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 present organic electronic device may optionally comprise one or more substrates.
  • substrate is not particularly limited and may be any suitable material that is inert under use conditions. Examples of such materials are glass and polymeric materials.
  • Preferred polymeric material include but are not limited to alkyd resins, allyl esters, benzocyclobutenes, butadiene-styrene, cellulose, cellulose acetate, epoxide, epoxy polymers, ethylene-chlorotrifluoro ethylene copolymers, ethylene-tetra-fluoroethylene copolymers, fiber glass enhanced polymers, fluorocarbon polymers, hexafluoropropylenevinylidene-fluoride copolymer, high density polyethylene, parylene, polyamide, polyimide, polyaramid, polydimethylsiloxane, polyethersulphone, polyethylene, polyethylenenaphthalate, polyethyleneterephthalate, polyketone, polymethylmethacrylate, polypropylene, polyst
  • the substrate can be any suitable material, for example a polymeric material, metal or glass material coated with one or more of the above listed materials or coated with one or more metal, such as for example titanium. It will be understood that in forming such a substrate, methods such as extruding, stretching, rubbing or photochemical techniques can be employed to provide a homogeneous surface for device fabrication as well as to provide pre-alignment of an organic semiconductor material in order to enhance carrier mobility therein.
  • the substrate can be a polymeric material, metal or glass coated with one or more of the above polymeric materials.
  • a suitable substrate may, for example, be transparent or semi-transparent.
  • a suitable substrate may, for example, also be flexible or non-flexible.
  • Said substrate may, for example, serve as support and preferably be adjacent to a first electrode layer.
  • Said substrate may, for example, also serve as support for the planarization layer holding the first electrode layer.
  • a substrate may be introduced into the electronic device between or adjacent to any layer and placed such that it serves best to support the device and/or be best placed with regards to manufacturing requirements.
  • the present organic electronic device may optionally comprise further layers acting as charge transport layers.
  • Exemplary charge transport layers may act as hole transporting layer and/or electron blocking layer, or electron transporting layer and/or hole blocking layer. Generally—if present—such layers are between the electrodes and the organic semiconducting layer.
  • Suitable materials for a hole transporting and/or electron blocking layer may be selected from the group consisting of metal oxides, like for example, zinc tin oxide (ZTO), MoOx, NiOx, a conjugated polymer electrolyte, like for example PEDOT:PSS, a conjugated polymer, like for example polytriarylamine (PTAA), an organic compound, like for example N,N′-diphenyl-N,N′-bis(I-naphthyl)(1,1′-biphenyl)-4,4′diamine (NPB), N,N′-diphenyl-N,N′-(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine (TPD).
  • metal oxides like for example, zinc tin oxide (ZTO), MoOx, NiOx, a conjugated polymer electrolyte, like for example PEDOT:PSS, a conjugated polymer, like for example polytriarylamine (PTAA),
  • Suitable materials for a hole blocking and/or electron transporting layer may be selected from the group consisting of metal oxides, such as for example, ZnOx, TiOx, a salt, like for example LiF, NaF, CsF, a conjugated polymer electrolyte, like for example poly[3-(6-trimethylammoniumhexyl)thiophene], poly(9,9-bis(2-ethylhexyl)-fluorene]-b-poly[3-(6-trimethylammoniumhexyl)thiophene], or poly[(9,9-bis(3′-(N,N-dimethyl-amino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctyl-fluorene)] or an organic compound, like for example tris(8-quinolinolato)-aluminium(III) (Alq 3 ), 4,7-diphenyl-1,10
  • the present organic electronic device may, for example, be selected from the group consisting of organic field effect transistors (OFET), organic thin film transistors (OTFT), organic light emitting diodes (OLED), organic light emitting transistors (OLET), organic photovoltaic devices (OPV), organic photodetectors (OPD), organic solar cells, laser diodes, Schottky diodes, photoconductors and photodetectors.
  • OFET organic field effect transistors
  • OLED organic thin film transistors
  • OLED organic light emitting diodes
  • OLET organic light emitting transistors
  • OLED organic light emitting transistors
  • OLET organic photovoltaic devices
  • OPD organic photodetectors
  • organic solar cells laser diodes
  • PFET organic field effect transistor
  • OFT organic thin film transistor
  • a preferred example of the present organic electronic device is an organic field effect transistor, preferably comprising a gate electrode, a source electrode, a drain electrode, an insulating layer (preferably a gate insulating layer), and an organic semiconducting layer.
  • an organic field effect transistor may also comprise one or more selected from the group consisting of substrate and charge transport layer.
  • the OFET device according to the present invention can be a top gate device or a bottom gate device.
  • Suitable structures of an OFET device are known to the skilled person and are described in the literature, for example in US 2007/0102696 A1.
  • FIG. 1 shows a schematic representation of a typical top gate OFET according to the present invention, including source (S) and drain (D) electrodes (2) provided on a substrate (I), a self-assembled monolayer (3) formed by depositing a compound of formula (I) as defined herein provided on the S/D electrodes, a layer of organic semiconducting material (4) provided on the S/D electrodes and the self-assembled monolayer (3), a layer of dielectric material (5) as gate insulator layer provided on the organic semiconducting layer (4), a gate electrode (6) provided on the gate insulator layer (5), and an optional passivation or protection layer (7) provided on the gate electrode (6) to shield it from further layers or devices that may be provided later or to protect it from environmental influence.
  • the area between the source and drain electrodes (2), indicated by the double arrow, is the channel area.
  • FIG. 2 shows a schematic representation of a typical bottom gate-bottom contact OFET according to the present invention, including a gate electrode (6) provided on a substrate (I), a layer of dielectric material (5) (gate insulator layer) provided on the gate electrode (4), source (S) and drain (D) electrodes (2) provided on the gate insulator layer (6), a self-assembled monolayer (3) formed by depositing a compound of formula (I) as defined herein provided on the S/D electrodes, a layer of an organic semiconducting material (4) provided on the S/D electrodes and the self-assembled monolayer (3), and an optional protection or passivation layer (7) provided on the organic semiconducting layer (4) to shield it from further layers or devices that may be later provided or protect it from environmental influences.
  • a gate electrode (6) provided on a substrate (I)
  • a layer of dielectric material (5) gate insulator layer
  • source (S) and drain (D) electrodes (2) provided on the gate insulator layer (6)
  • the dielectric material for the gate insulator layer is preferably a solution processable material.
  • the dielectric that is in direct contact with the semiconductor are preferably organic dielectric materials having a dielectric constant from 1.0 to 5.0, very preferably from 1.8 to 4.0 (“low k materials”), as disclosed for example in US 2007/0102696 A1 or U.S. Pat. No. 7,095,044.
  • the dielectric constant is not restricted, but preferably is fairly high in order to increase the device's capacitance.
  • the gate insulator layer is deposited, e.g. by spin-coating, doctor blading, wire bar coating, spray or dip coating or other known methods, from a formulation comprising an insulator material and one or more solvents with one or more fluoro atoms (fluorosolvents), preferably a perfluorosolvent.
  • fluorosolvents e.g. FC75® (available from Acros, catalogue number 12380).
  • fluoropolymers and fluorosolvents are known in prior art, like for example the perfluoropolymers Teflon AF® 1600 or 2400 (from DuPont) or Fluoropel® (from Cytonix) or the perfluorosolvent FC 43® (Acros, No. 12377).
  • organic dielectric materials having a dielectric constant from 1.0 to 5.0, very preferably from 1.8 to 4.0 (“low k materials”), as disclosed for example in US 2007/0102696 A1 or U.S. Pat. No. 7,095,044.
  • the present transistor device may also be a complementary organic thin film transistor (CTFT) comprising a layer of a p-type semiconductor material as well as a layer of an n-type semiconductor material.
  • CTFT complementary organic thin film transistor
  • the present application also relates to a method for producing the present organic electronic device as described above, said method comprising the steps of
  • the formulation may, for example, be deposited onto the electrode by vacuum or vapor deposition methods or by liquid coating methods.
  • exemplary deposition methods include physical vapor deposition (PVD), chemical vapor deposition (CVD), sublimation or liquid coating methods.
  • Liquid coating methods are preferred. Particularly preferred are solvent-based liquid coating methods.
  • solvent-based liquid coating a formulation, which comprises the compound of formula (I) as defined herein and an alcohol of formula R 2 —OH as defined herein (or the respective reaction product(s) of the compound of formula (I) as defined herein and an alcohol of formula R 2 —OH as defined herein), is deposited onto the metal surface or the metal oxide surface.
  • the solvent may be at least partially evaporated.
  • Preferred solvent-based liquid coating methods include, without limitation, dip coating, spin coating, ink jet printing, letter-press printing, screen printing, doctor blade coating, roller printing, reverse-roller printing, offset lithography printing, flexographic printing, gravure printing, web printing, spray coating, brush coating and pad printing.
  • the formulation may comprise one or more further suitable solvent.
  • suitable solvents may, for example, be selected from the group consisting of alcohols different from R 2 —OH as defined herein, ethers, ketones, aromatic hydrocarbons and any mixture of any of these.
  • Suitable ethers may have a linear or a cyclic structure and may for example be selected from the group consisting of diethylether, tetrahydrofuran (THF), butyl phenyl ether, methyl ethyl ether and 4-methylanisole.
  • Suitable ketones may for example be selected from the group consisting of acetone, 2-heptanone and cyclohexanone.
  • Suitable aromatic hydrocarbons may for example be selected from the group consisting of toluene, mesitylene, o-xylene, m-xylene, p-xylene, cyclohexylbenzene and halogenated aromatic hydrocarbons.
  • halogenated aromatic hydrocarbons are chlorobenzene, dichlorobenzene and trichlorobenzene as well as any mixture of any of these.
  • the compound of formula (I) is present in (or expressed differently, is initially added to) the formulation or solution in from 0.01 wt % to 10 wt %, preferably from 0.01 wt % to 5 wt %, and most preferably from 0.05 wt % to 2 wt %, with wt % being relative to the total weight of the formulation or solution.
  • the metal or metal oxide may be applied to the substrate by any of the conventional methods.
  • the methods may for example be selected from vacuum deposition, vapor deposition and liquid coating.
  • Exemplary deposition methods include physical vapor deposition (PVD), chemical vapor deposition (CVD), sublimation or liquid coating methods. Such methods form part of the general knowledge in the field and are well known to the skilled person.
  • the metal or metal oxide surface is preferably subjected to a washing step.
  • a preferred washing step comprises an acidic washing with a acid or a blend of acids, said acids being organic or inorganic acids. Examples of suitable acids are acetic acid, citric acid or hydrochloric acid.
  • the metal or metal oxide surface may be subjected to a plasma treatment step.
  • the washing step and the SAM treatment are combined into a single step.
  • this combined step may be carried out by applying a formulation in accordance with the present invention to the metal or metal oxide surface, said formulation comprising a precursor compound as defined above and an acid as defined above.
  • washing step and the SAM treatment may be carried out sequentially in two separate steps.
  • the soaking time i.e. the time during which the formulation is applied to the metal or metal oxide surface, is preferably at least 5 s and at most 72 h.
  • the deposition of individual functional layers in the preparation of the present electronic devices is carried out using solution processing techniques.
  • This can be done for example by applying a formulation, preferably a solution, comprising the organic semiconducting material or the dielectric material and further comprising one or more organic solvents, onto the previously deposited layer, followed by evaporation of the solvent(s).
  • Preferred deposition techniques include, without limitation, dip coating, spin 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.
  • Very preferred solution deposition techniques are spin coating, flexographic printing and inkjet printing.
  • the dielectric material for the gate insulator layer is preferably an organic material. It is preferred that the dielectric layer is solution coated which allows ambient processing, but could also be deposited by various vacuum deposition techniques. When the dielectric is being patterned, it may perform the function of interlayer insulation or act as gate insulator for an OFET. Preferred deposition techniques include, without limitation, dip coating, spin 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. Ink-jet printing is particularly preferred as it allows high resolution layers and devices to be prepared.
  • the dielectric material could be cross-linked or cured to achieve better resistance to solvents and/or structural integrity and/or to improve patterning (photolithography).
  • Preferred gate insulators are those that provide a low permittivity interface to the organic semiconductor.
  • Suitable solvents are selected from solvents including but not limited to hydrocarbon solvents, aromatic solvents, cycloaliphatic cyclic ethers, cyclic ethers, acetates, esters, lactones, ketones, amides, cyclic carbonates or multi-component mixtures of the above.
  • solvents examples include cyclohexanone, mesitylene, xylene, 2-heptanone, toluene, tetrahydrofuran, MEK (methyl ethyl ketone), MAK (2-heptanone), cyclohexanone, 4-methylanisole, butyl-phenyl ether and cyclohexylbenzene, very preferably MAK, butyl phenyl ether or cyclohexylbenzene.
  • the total concentration of the respective functional material (organic semiconducting material or gate dielectric material) in the formulation is preferably from 0.1 to 30 wt %, preferably from 0.1 to 5 wt %, relative to the total weight of the formulation (i.e. functional material(s) and solvent(s)).
  • organic ketone solvents with a high boiling point are advantageous for use in solutions for inkjet and flexographic printing.
  • the OSC or dielectric material is spun for example between 1000 and 2000 rpm for a period of for example 30 seconds to give a layer with a preferred layer thickness between about 100 nm and about 2000 nm for the dielectric and about 5 nm to about 300 nm for the semiconductor.
  • the film can be heated at an elevated temperature to remove all residual volatile solvents.
  • the dielectric material layer is annealed after exposure to radiation, for example at a temperature from 70° C. to 130° C., for example for a period of from 1 to 30 minutes, preferably from 1 to 10 minutes.
  • the annealing step at elevated temperature can be used to complete the cross-linking reaction that was induced by the exposure of the cross-linkable groups of the dielectric material to photoradiation.
  • a washing step or a drying step or both are performed.
  • said process may additionally comprise the following steps, preferably in such sequence, of
  • the process may further comprise the steps of
  • step (d) the process may further comprise the step of
  • Further layers may be deposited by standard methods, which are well known in the industry. Liquid coating of devices is more desirable than vacuum deposition techniques. Solution deposition methods are especially preferred. Preferred deposition techniques include, without limitation, dip coating, spin coating, inkjet printing, nozzle printing, letter-press printing, screen printing, gravure printing, doctor blade coating, roller printing, reverse-roller printing, offset lithography printing, dry offset lithography printing, flexographic printing, web printing, spray coating, curtain coating, brush coating, slot dye coating or pad printing.
  • the gate insulator layer is deposited, e.g. by spin-coating, doctor blading, wire bar coating, spray or dip coating or other known methods, from a formulation comprising an insulator material and one or more solvents with one or more fluoro atoms (fluorosolvents), preferably a perfluorosolvent.
  • fluorosolvents e.g. FC75® (available from Acros, catalogue number 12380).
  • fluoropolymers and fluorosolvents are known in prior art, like for example the perfluoropolymers Teflon AF® 1600 or 2400 (from DuPont) or Fluoropel® (from Cytonix) or the perfluorosolvent FC 43® (Acros, No. 12377).
  • F 5 C 6 —SiCl 3 is sensitive to hydrolysis and therefore is best stored in an environment free of humidity or residual water in solvents.
  • V d W ⁇ C i L ⁇ ⁇ s ⁇ a ⁇ t ⁇ ( V g - V 0 ) ( eq . ⁇ 1 )
  • V 0 Turn-on voltage
  • ITO Indium tin oxide
  • ITO Indium tin oxide
  • a solution of F 5 C 6 —SiCl 3 in iso-propanol ( i Pr—OH) such solution thus—without wishing to be bound by theory—probably predominantly comprising F 5 C 6 —Si(O— i Pr) 3 as active species, thereby forming the self-assembled monolayer.
  • Excess solution was spun off, following by rinsing with iso-propanol.
  • Onto the resulting self-assembled monolayer was then deposited a layer of an organic semiconducting material comprising derivatives of indacenodithiophene and benzothiadiazole.
  • Example 2 The preparation of Example 2 was repeated with the difference that for the preparation of the self-assembled monolayer para-chlorobenzene phosphate (see formula (III) below) in iso-propanol, instead of the F 5 C 6 —SiCl 3 in iso-propanol, was used.
US17/299,698 2018-12-04 2019-11-14 Self-assembled monolayer for electrode modification and device comprising such self-assembled monolayer Pending US20220052277A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120319097A1 (en) * 2010-02-25 2012-12-20 Merck Patent Gesellschaft Mit Beschrankter Haftung Electrode treatment process for organic electronic devices
US20140147628A1 (en) * 2012-11-28 2014-05-29 Shin-Etsu Chemical Co., Ltd. Surface Modifier For Transparent Oxide Electrode, Surface-Modified Transparent Oxide Electrode, And Method For Producing Surface-Modified Transparent Oxide Electrode

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19614971A1 (de) 1996-04-17 1997-10-23 Hoechst Ag Polymere mit Spiroatomen und ihre Verwendung als Elektrolumineszenzmaterialien
GB9726810D0 (en) 1997-12-19 1998-02-18 Zeneca Ltd Compounds composition & use
DE60035970T2 (de) 1999-03-05 2008-05-15 Cambridge Display Technology Ltd. Polymerherstellung
GB0028867D0 (en) 2000-11-28 2001-01-10 Avecia Ltd Field effect translators,methods for the manufacture thereof and materials therefor
GB2371248A (en) * 2000-12-04 2002-07-24 Seiko Epson Corp Fabrication of self-assembled monolayers
US6690029B1 (en) 2001-08-24 2004-02-10 University Of Kentucky Research Foundation Substituted pentacenes and electronic devices made with substituted pentacenes
DE10159946A1 (de) 2001-12-06 2003-06-18 Covion Organic Semiconductors Prozess zur Herstellung von Aryl-Aryl gekoppelten Verbindungen
JP2004047176A (ja) 2002-07-09 2004-02-12 Sharp Corp 有機エレクトロルミネッセンス素子
DE10241814A1 (de) 2002-09-06 2004-03-25 Covion Organic Semiconductors Gmbh Prozeß zur Herstellung von Aryl-Aryl gekoppelten Verbindungen
DE10337077A1 (de) 2003-08-12 2005-03-10 Covion Organic Semiconductors Konjugierte Copolymere, deren Darstellung und Verwendung
JP2005085731A (ja) 2003-09-11 2005-03-31 Seiko Epson Corp 有機エレクトロルミネッセンス装置、及び有機エレクトロルミネッセンス装置の製造方法、並びに電子機器
EP1687830B1 (fr) 2003-11-28 2010-07-28 Merck Patent GmbH Ameliorations apportees a des couches semiconductrices organiques
US7385221B1 (en) 2005-03-08 2008-06-10 University Of Kentucky Research Foundation Silylethynylated heteroacenes and electronic devices made therewith
DE102009012163A1 (de) * 2009-03-06 2010-09-09 Siemens Aktiengesellschaft Monolagen organischer Verbindungen auf Metalloxidoberflächen oder oxidhaltigen Metalloberflächen und damit hergestelltes Bauelement auf Basis organischer Elektronik
DE102011077961A1 (de) * 2011-06-22 2012-12-27 Siemens Aktiengesellschaft Schwachlichtdetektion mit organischem fotosensitivem Bauteil
US9914742B2 (en) 2014-07-29 2018-03-13 Merck Patent Gmbh Tetra-heteroaryl indacenodithiophene-based polycyclic polymers and their use

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120319097A1 (en) * 2010-02-25 2012-12-20 Merck Patent Gesellschaft Mit Beschrankter Haftung Electrode treatment process for organic electronic devices
US20140147628A1 (en) * 2012-11-28 2014-05-29 Shin-Etsu Chemical Co., Ltd. Surface Modifier For Transparent Oxide Electrode, Surface-Modified Transparent Oxide Electrode, And Method For Producing Surface-Modified Transparent Oxide Electrode

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