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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0803—Compounds with Si-C or Si-Si linkages
  • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
  • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
• • 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 potential barriers
• • 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
  • H10K30/451—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a metal-semiconductor-metal [m-s-m] structure
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • 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
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight
  • H10K85/649—Aromatic compounds comprising a hetero atom
  • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
  • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
• • 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 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
• • 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 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]
  • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
• • 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

Definitions

• the present invention relates generally to the field of organic semiconductors and, more particularly, to silylethynylated heteroacenes as well as to formulations and electronic devices made with these compounds.
• Display technology is expected to become a dominant sector of high-tech industry in the future. It is also expected that the flat panel display technology will be revolutionized by the use of organic semiconductors that will allow manufacture of cheap, flexible, lightweight, fully portable flat panel displays with no apparent limits to their size. It is predicted that due to the lower manufacturing cost, organic semiconductor based displays will eventually gain dominance over amorphous silicon based counterparts and the respective market share will grow to $1.6 billion by 2007. To realize these goals, however, significant breakthroughs will have to take place in. the area of organic semiconductor material and device processing.
• OFTs organic thin film transistors
• OTFT process temperatures allow fabrication on a range of surfaces including cloth, paper or lower temperature polymeric substrates.
• Organic semiconductors for use in OTFTs can be broadly divided into two groups as high and low mobility materials.
• High mobility materials have mobility > 0.1 cm 2 /V-s, usefully large carrier energy bandwidth (> 0.1 eV) and weak or sometimes absent temperature activation of mobility.
• most high mobility organic semiconductors have been small molecule materials (with pentacene the most notable example) and most have been deposited by vacuum sublimation or from a solution precursor with a high- temperature (> 150° C) conversion step.
• Low mobility materials have mobility from about 10 "5 - 10 "1 cm 2 /V-s, typically transport carriers by hopping, and have strong temperature activation of mobility.
• Most polymeric organic semiconductors fall into this group and many have the potential advantage that they can be deposited from solution.
• the present invention relates to compounds of formula I
• X is -O-, -S-, -Se- or -NR" 1 -,
• R is cyclic, straight-chain or branched alkyl or alkoxy having 1 to 20, preferably 1 to 8 C-atoms, or aryl having 2-30 C-atoms, all of which are optionally fluorinated or perfluorinated, with SiR ⁇ preferably being trialkylsilyl,
• R' is H, F, Cl, Br, I, CN, straight-chain or branched alkyl or alkoxy having 1 to 20, preferably 1 to 8 C-atoms and optionally being fluorinated or perfluorinated, optionally fluorinated or perfluorinated aryl having 6 to 30 C-atoms, preferably C 6 F 5 , or CO 2 R", with R" being H, optionally fluorinated alkyl having 1 to 20 C-atoms, or optionally fluorinated aryl having 2 to 30, preferably 5 to 20 C- atoms,
• R"' is H or cyclic, straight-chain or branched alkyl with 1 to 10 C- atoms, preferably H, m is O or i , n is O or i .
• the invention further relates to a formulation comprising one or more compounds of formula I, and preferably further comprising one or more organic solvents.
• the invention further relates to electronic devices, in particular transistors, organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic photovoltaic (OPV) devices, integrated circuits (ICs), sensors, radio frequency identification (RFID) tags and solar cells, comprising one or more compounds of formula I or formulations comprising them.
• OFETs organic field effect transistors
• OFTs organic thin film transistors
• OOV organic photovoltaic
• ICs integrated circuits
• RFID radio frequency identification
• Figure 1a and 1b are schematical illustrations of two possible embodiments for the field-effect transistor of the present invention.
• Figure 2a and 2b are schematical representations illustrating two possible embodiments of the photovoltaic apparatus of the present invention.
• novel compounds of the present invention may be broadly described as silylethynylated heteroacenes (anthra(diheterocycles), tetra(diheterocycles) and penta(diheterocycles) compounds).
• Preferred compounds of formula I are selected from the following formulae:
• R, R' and X are as defined above.
• a formulation comprising one or more of the novel compounds of formula I 1 A1 , A2, B1 , B2, C1 or C2 and one or more solvents.
• the solvents are preferably organic solvents, very preferably selected from alkylated and/or fluorinated or chlorinated benzenes like toluene, xylene and the like, anisole or its alkylated and/or fluorinated derivatives, tetralin, indane, decalin, N,N-dimethylaniline, N-methylpyrrolidone, N 1 N- dimethylformamide or pyridine.
• a transistor in accordance with yet another aspect of the present invention preferably comprises a gate electrode, a semiconductor constructed from the novel compounds or formulations of the present invention, an insulator between the gate electrode and the semiconductor, a source electrode and a drain electrode.
• a photovoltaic device preferably comprises a transparent anode, a semiconductor constructed from the novel compounds or formulations of the present invention, an n-type material and a cathode.
• Suitable methods and materials for preparing electronic devices like transistors and photovoltaic devices and their components, like for example the gate, source or drain electrode, cathode, anode or n-type material (electron transporter), are known to the person skilled in the art and are described in the literature, for example in WO 02/45184 A1 , WO 03/052841 A1 , WO 2004/013922 A2 and the references cited therein.
• - X is -O-, -Se- or -NH-
• R 1 is F, Cl, Br or COOH, very preferably F, Cl or Br, most preferably F,
• R is straight-chain or branched alkyl having 1 to 8 C atoms, preferably methyl, ethyl, propyl which is n-propyl or isopropyl, or butyl which is n- butyl, sec-butyl, isobutyl or tert-butyl, .
• R'" is H,
• R 1 is selected from optionally fluorinated or perfluorinated aryl having 6 to 30 C-atoms, preferably CeF 5 , F, Cl, Br, I, CN and CO 2 R", very preferably from F, Cl and Br.
• silylethynylated heteroacenes are usually prepared as a mixture of isomers.
• Formulae Ai and A 2 represent the two isomers of anthra (diheterocycles).
• Formulae Bi and B 2 represent the two isomers of tetra (diheterocycles).
• Formulae C 1 and C 2 represent the two isomers of penta (diheterocycles).
• the novel compounds of the present invention include both the mixture of the isomers of formulae A1 , A2; B1 , B2; or C1 , C2 and the pure isomers A1. A2, B1. B2, C1 or C2.
• the isomers A1 , A2, B1 , B2, C1 or C2 may be purified from the mixture of isomers of formulae A1 , A2; B1 , B2; or C1 , C2 by methods known to those skilled in the art including but not limited to high-performance liquid chromatography (HPLC).
• HPLC high-performance liquid chromatography
• novel compounds of the present invention can be prepared by a relatively simple and straightforward method. Specifically, the silylethynylated heteroacenes are easily made by the addition of an alkynyllithium to the corresponding acenequinone, followed by reductive workup with either HI or tin (II) chloride:
• acenequinone is very easily prepared by a 4-fold aldol condensation between a dialdehyde and commercially-available 1 ,4-cyclohexanedione:
• the "R” group of these dialdehydes is typically installed by the following sequence:
• heterocyclic dialdehyde for all of these materials is the heterocyclic dialdehyde.
• Many of these heterocyclic dialdehydes are known in the literature, and some are even commercially available:
• Thiophene 2,3-dialdehyde is commercially available from Aldrich and Acros chemical.
• Furan 2,3-dialdehyde is prepared as described in Zaluski, M. C; Robba, M.; Bondale, M. Bull. Chim. Soc. Fr. 1970, 4, 1445.
• heterocyclic dialdehydes can be prepared by the same methods outlined for the synthesis of the furan and selenophene compounds. The following synthesis and examples are prepared to further illustrate the invention, but it is not to be considered as limited thereto.
• a number of useful electronic devices may be constructed from the novel compounds of the present invention.
• a typical field effect transistor (FET) according to the present invention (10) is illustrated in Figure 1a.
• the FET (10) is comprised of a gate electrode (12) of a type known in the art, an insulator or gate dielectric (14) also of a type known in the art and a semiconductor (16) in the form of a thin layer or film of the compounds of the present invention.
• the FET (10) includes a conductive source electrode (18) and a drain electrode (20) both operatively connected to the semiconductor (16).
• the insulator (14) may, for example, be a dielectric or metal oxide or even an insulating polymer like poly(methylmethacrylate).
• the conducting source and drain electrodes (18), (20) may be metals known in the art to be useful as electrodes, heavily doped semiconductors such as silicon or even a conducting polymer.
• the FET illustrated in Figure 1a is known as a bottom-gate, top-contact configuration.
• An alternative embodiment of the FET (10) of the present invention is illustrated in Figure 1b. This configuration is known as a bottom-gate, bottom-contact configuration.
• FIG. 1c Another alternative embodiment of the FET (10) of the present invention is illustrated in Figure 1c.
• This configuration is known as a top-gate configuration, and is comprised of a substrate (22) of a type known in the art, a conductive source electrode (18) and a drain electrode (20), both operatively connected to a semiconductor (16) in the form of a thin layer or film of the compounds of the present invention, an insulator or gate dielectric (14) of a type known in the art, and a gate electrode (12) also of a type known in the art.
• the gate electrode (12), source electrode (18) and drain electrode (20) may again be any sort of conductor: gold, silver, aluminum, platinum, heavily-doped silicon or an organic conducting polymer.
• the insulator or gate dielectric (14) can be an oxide such as aluminum oxide or silicone oxide or an insulating polymer such as poly(methylmethacrylate). In either configuration the compound of the present invention may be applied either by solution or vapor methods to form the semiconductor (16).
• the semiconductor (16) comprises one or more organic binders, preferably polymeric binders, as described for example in WO 2005/055248 A1 , to adjust the Theological properties, preferably in a proportion of binder to semiconductor from 20:1 to 1 :20, preferably 10:1 to 1 :10, more preferably 5:1 to 1 :5 by weight.
• the binder polymers may also be semiconducting.
• a typical photovoltaic apparatus according to the present invention (22) is illustrated in Figure 2a.
• the photovoltaic apparatus (22) comprises a transparent conductive electrode or anode (24), a semiconductor (26) in the form of a thin layer or film of the compound of the present invention and a bottom electrode or cathode (28).
• a layer (30) of n-type material is provided between the semiconductor (26) and the cathode (28).
• the semiconductor (26) comprises the compound of the present invention blended with an n-type material.
• the compounds of the present invention are typically used as the hole transporter (the "p-type” material).
• This material must be used in conjunction (i.e. as a blend) with with an n-type material, defined as any electron-accepting compound.
• n-type or acceptor materials are fullerenes like C60, or solubilized derivatives thereof, or perylene diimides like PTCBI (3,4,9, 10-perylenetetracarboxylic bisbenzimidazole).
• the photovoltaic apparatus (22) can typically be constructed in the two ways illustrated in Figures 2a and 2b.
• the p- type compound and the n-type compound are both deposited from vapor or solution in sequential steps, leading to a single heterojunction interface.
• the p-type material and the n-type material may be mixed and deposited from solution on the anode prior to deposition of the cathode material.
• the p-type and n- type materials phase segregate, leading to multiple heterojunctions in the bulk.
• the anode material typically has a high work function and is transparent (ITO or (10) oxide on glass or plastic).
• the cathode (28) is a low work function conductor, and is typically reflective to improve efficiency (aluminum, silver or an indium-gallium eutectic).
• the anode layer can be pre-coated with a commercial conducting polymer like PEDOT (poly(3,4-ethylenedioxythiophene)) or a blend of PEDOTPSS (poly(styrenesulfonate)) in order to improve charge injection efficiency.
• PEDOT poly(3,4-ethylenedioxythiophene)
• PEDOTPSS poly(styrenesulfonate
• n-BuLi (19.5 ml, 47,9 mmol, 2.6 M in hexanes) was added dropwise and the mixture was stirred for 2 hr.
• the above quinone mixture (3.87 g) was added and stirring W as continued overnight, followed by the addition of anhydrous THF (20 ml) and additional stirring for 2 d.
• Water (2 ml) and a solution of SnCI 2 - H 2 O (10.0 g, 44 mmol) in 10 % HCI (20 ml) was added and the solution was stirred for 2 hr.
• DCM 100 ml was then added and the organic layer was separated, dried over MgSO 4 , and rinsed through a thin pad of silica (DCM).
• Solvent was concentrated to a volume of 10 ml, then diluted with hexanes (200 ml), and rinsed onto a thick pad of silica.
• the silica was rinsed with hexanes (600 ml), then hexanes: DCM (1 :1 ) to elute the product mixture, and solvent was removed from this second fraction.
• hexanes: ethyl acetate (9:1 ) 0.82 g of the desired tetradithiophene were isolated. The tetradithiophene was recrystallized from acetone to yield dark-blue needles.
• Step 1 5-bromo-thiophene-2,3-dicarbaldehyde. 2,3-Bis(1 ,3-dioxolan-2-yl)thiophene (13.51 g, 59.2 mmol) was dissolved in
• Step 2 2,8-dibromoanthra[2,3-b:6,7-b']dithiophene-5,11-dione and 2,8-dibromoanthra[2,3-b:7,6-b']dithiophene-5,11-dione.
• Step 3 2,8-dibromo-5,11-bis(triethylsilylethynyl)anthra[2,3-b:6,7-b'] dithiophene and 2,8-dibromo-5,11-bis(triethylsilylethynyl)anthra[2,3- b:7,6-b']dithiophene.
• the compounds of the present invention demonstrate remarkable physical
• the silyl acetylene unit substituted on the inner aromatic ring serves two important purposes. First it lends solubility to the molecule, allowing processing by simple, solution-based methods. Secondly and perhaps more importantly, this functional group causes the molecules to self-assemble into ⁇ -stacked arrays that are critical to improved device performance. More specifically, this molecular arrangement leads to improved conductivity, reduced band gap and field effect transistors (FETs) devices with a hole mobility of 0.001 to more than 1.0 cm 2 A/s.
• FETs field effect transistors
• a field effect transistor as shown in Figure 1a was provided.
• the substrate for the field-effect transistor consisted of a heavily-doped Si wafer with thermally grown oxide layer (370 ran), serving as gate electrode and
• the triethylsilyl anthradithiophene derivative of Example 1 formed a 5 uniform film of excellent quality yielding hole mobility of 1.0 cm 2 /Vs with excellent on/off current ratio (10 7 ). The performance of this material is likely due to the close ⁇ -stacked interactions in the crystal.
• the triethylsilyl anthradithiophene derivative adopts a 2-D ⁇ -stacking arrangement with a ⁇ -face separation of approximately 3.25 A.
• the triethylsilyl 0 anthradithiophene derivative was also characterized by a ⁇ -overlap of 1.57 A 2 and a lateral slip of 2.75, 1.76 A. All measurements were performed in air at room temperature and the mobility was calculated from the saturation currents. 5
• a field effect transistor as shown in Figure 1c was provided as follows: On a glass substrate patterned Au source and drain electrodes were provided by shadow masking. A self assembling monolayer of pentafluorobenzene- thiol (electrode injection layer) was spincoated onto the Au electrodes and washed with IPA. A semiconductor formulation was prepared by dissolving the difluoro triethylsilyl anthradithiophene derivative of Example 5 in a concentration of 2 wt.% in 4-methyl anisole. The semiconductor solution was then spincoated onto the substrate at 500 rpm for 18 seconds followed by 2000rpm for 60s at room temperature in air and the solvent was evaporated.
• the insulator material (Cytop® 809M, available from Asahi Glass) was mixed 3 parts to 2 parts of perfluorosolvent (FC75, Acros catalogue number 12380) and then spincoated onto the semiconductor giving a thickness of approximately 1 ⁇ m and the solvent was evaporated.
• FC75 perfluorosolvent
• the transistor sample was mounted in a sample holder. Microprobe connections were made to the gate, drain and source electrodes using Karl Suss PH 100 miniature probe-heads. These were linked to a Hewlett-Packard 4155B parameter analyser. The drain voltage was set to -5 V and the gate voltage was scanned from +20 to -60 V and back to +20 V in 1 V steps. The field effect mobility values were calculated from the gradient of the ISD (source-drain current) vs. V G (gate voltage) characteristic in the linear regime (Lin mob) and the saturation regime (Sat mob). All measurements were performed in air at room temperature. The results are summarized below:

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