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WO2018037230A1 - Dérivés de pyridyl-éthylènedioxy-thiophène en tant que matériau conducteur transparent - Google Patents

Dérivés de pyridyl-éthylènedioxy-thiophène en tant que matériau conducteur transparent Download PDF

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Publication number
WO2018037230A1
WO2018037230A1 PCT/GB2017/052487 GB2017052487W WO2018037230A1 WO 2018037230 A1 WO2018037230 A1 WO 2018037230A1 GB 2017052487 W GB2017052487 W GB 2017052487W WO 2018037230 A1 WO2018037230 A1 WO 2018037230A1
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molecule
film
group
solution
electron
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Peter Skabara
Joseph Cameron
Neil FINDLAY
Anto Regis INIGO
Rupert Taylor
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University of Strathclyde
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University of Strathclyde
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • 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
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
    • 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
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/155—Hole transporting layers comprising dopants
    • 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 is directed to the field of organic electronics, in particular transparent conductive materials for use in optoelectronics.
  • Transparent conductive films are employed in multiple electronics applications such as liquid crystal displays, OLEDs, touchscreens and photovoltaics, where a highly conductive material that does not block light is required.
  • Transparent conducting metal- oxides particularly indium tin oxide (ITO) are the most widely used materials due to their high conductivity and low visible light absorption coefficient when deposited as thin films.
  • ITO indium tin oxide
  • Some materials are currently employed to form transparent conductive films, such as conductive polymers, metallic nanowires, carbon nanotubes or graphene.
  • Organic materials are widely available and present advantages over their inorganic counterparts such as low-cost processing, mechanical flexibility and the possibility to tune their properties through structural modification or different processing techniques.
  • Solution processable functional organic materials can be easily deposited on multiple surfaces, (including flexible substrates) by means of a variety of simple deposition techniques, leading to low-cost, lightweight and even flexible organic electronic devices.
  • Printing processes of organic materials have been optimised to achieve high throughput and low temperature fabrication of large area flexible electronics.
  • organic materials have limitations in electronic applications due to lower carrier densities and charge mobilities than established inorganic transparent conductive materials.
  • PEDOT:PSS a composite of poly(3,4-ethylenedioxythiophene) (PEDOT) with polystyrene sulfonic acid (PSS), is currently the go-to material for applications in solution-processed organic electronics where a highly conductive yet transparent material is needed. It is employed in a wide range of applications such as antistatic coatings for plastic films in electronic packaging and photographic films, counter- electrodes in capacitors, transparent and flexible electrodes in electronic applications such as touch screens, transparent electrodes and/or hole injection layers in OLEDs for displays and lighting applications, hole transport layers and/or transparent electrodes in organic solar cells.
  • the PSS groups are inherently acidic and hygroscopic. Upon exposure to air, water can be absorbed onto films comprising PEDOT:PSS and generating an aqueous acidic environment. This acidity is detrimental for device performance as it can cause degradation of adjacent layers of organic functional materials and/or etching of Indium Tin Oxide (ITO) electrodes, which are commonly used in organic electronic applications. ITO electrodes are very sensitive to acidity, leading to diffusion of oxygen out of the ITO electrode into the active polymer layer of the device. This hinders the performance of organic electronic devices and reduces their stability in atmospheric conditions. 1 It is amongst the objects of the present invention to provide novel transparent conductive materials for electronic applications.
  • ITO Indium Tin Oxide
  • the present invention is based on the development of novel compounds for transparent conductive coatings.
  • a molecule for use as a conductive coating the molecule having the structure:
  • R may be present or absent. When present R may be selected from the group comprising an alkyl chain, an oligoether chain, an aliphatic alcohol and/or an amine functionality or combinations thereof; Xi-X 4 may be selected from the group comprising
  • Y may be selected from the group comprising H, an electron-donating carbocyclic aromatic ring, an electron-donating aromatic heterocycle, an electron-withdrawing aromatic carbocyclic ring and/or an electron-withdrawing aromatic heterocycle; and wherein R is presnet, A " is present and may be any suitable counter ion.
  • the R substituents may comprise an alkyl group, such as a linear and/or branched alkyl chain.
  • Linear alkyl chains have the general formula C n H 2 n + i .
  • Linear alkyl chains may have a number of carbon atoms (n) ranging from 1 to 20.
  • linear alkyl chains may comprise C 3 H 7 , C 4 H 9 , CsHn , C 6 H 13 , C 7 H 15 , C 8 H 17 , C 9 H 19 , C 10 H 21 , C 12 H 25 , C 16 H 33 and/or C 18 H 37 .
  • Branched alkyl chains are isomers of linear alkyl chains with general formula C n H 2n+ i in which the alkane has alkyl substituents along its chain.
  • Examples of branched alkyl chains comprise, but are not limited to 2-ethylhexyl, 3- ethylhexyl, 4-ethylhexyl.
  • the R substituents may comprise a linear and/or branched alkyl chain functionalised with a polar substituent.
  • the R substituents may comprise linear or branched oligoethers, linear or branched alcohols and/or linear or branched amines.
  • Oligoethers may have the formula n , wherein n may be selected from 1 to 10 repeat units.
  • R substituents may comprise a branched oligoether comprising a linear alkyl functionality with oligoether substituents along the chain.
  • branched alkyl chains functionalised with oligoether functionalities comprise, but are not limited to
  • Aliphatic alcohol substituents have a general formula (CnH 2 n + i-x)(OH) x and may comprise a linear or branched alkyl chain as defined above with one or more hydroxyl substituent.
  • alcohols envisaged herein may comprise, but are not limited to C1 H2OH, C 2 H 4 OH, C 3 H 6 OH, C 5 H 10 OH, C 5 H 9 (OH) 2 , C 6 H 12 OH, C 7 H 14 OH, C 8 H 16 OH, C 6 H (OH) 2 , C 6 H 10 (OH) 3 ,C 9 H 16 (OH) 3 , and the like.
  • Amine substituents may comprise primary, secondary or tertiary amines.
  • Aliphatic primary amine substituents have a general formula -C n H 2n (NH 2 ).
  • Aliphatic secondary amine substituents have a general formula -NH(C n H 2n+ i ).
  • Aliphatic tertiary amine substituents have a general formula -N(C n H 2n+ i ) (C m H 2m+1 ).
  • Amines envisaged herein may comprise any length of alkyl chain chains.
  • the alkyl chains of the amine substituents may be linear or branched.
  • Amine substituents may one or more amine substituent.
  • Amines envisaged herein may comprise any number of amine substituents, for example 1 , 2, 3 and the like. Examples of amine substituents may comprise, but are not limited to
  • electron-donating groups may comprise, but are not limited to
  • electron-withdrawing groups may comprise, but are not limited to o O O O O O O
  • electron donating aromatic carbocyclic rings comprise, but are not limited to aryl units, such as phenylene or fluorene moieties with or without electron donating substituents.
  • electron donating carbocyclic aromatic rings comprise, but are not limited to:
  • Examples of electron withdrawing aromatic carbocyclic aromatic rings comprise, but are not limited to aryl units substituted with electron-withdrawing groups, such as cyanobenzene or nitrobenzene.
  • electron donating aromatic heterocycles comprise, but are not limited to:
  • electron withdrawing heterocycles comprise, but are not limited to:
  • Some electron withdrawing heterocycles may be attached to the molecules described herein on more than one position.
  • a may be attached at the 2-, 3- and/or 4- positions;
  • b may be attached at the 2-, 3- and/or 5- positions;
  • c may be attached at the 2- and 5- positions,
  • d and e may be attached at the 4- and 7- positions,
  • f may be attached at the 2, 5, 8 and 1 1 positions and
  • g may be attached at the 4 and 10 positions.
  • suitable counterions may comprise, but are not limited to F “ ,CI “ , Br “ , , PF 6 -, BF 4 " , SbF 6 " TsO " , MsO " .
  • the molecule has the general structure shown in Figure 1 , wherein XrX 4 are H, Y is H, R is a linear alkyl chain and A " is Br " or .
  • the molecule has the general structure shown in Figure 1 , wherein XrX 4 are H, Y is H, R is a branched alkyl chain and A " is Br “ or I " .
  • the molecule has the general structure shown in Figure 1 , wherein X X 4 are H, Y is H, R is an oligoether chain, such as and A " is Br “ or I " .
  • the molecule has the general structure shown in Figure 1 , wherein XrX 4 are H, Y is H, R is an alcohol or an amine functionality and A " is Br " or I " .
  • the alcohol may be a linear or a branched alcohol.
  • the alcohol may be a primary alcohol.
  • the alcohol may be a secondary alcohol.
  • the alcohol may be a tertiary alcohol.
  • the amine may be a linear amine.
  • the amine may be a branched amine.
  • the amine may be primary, secondary or tertiary.
  • the molecules described herein may be small molecule organic semiconductors.
  • Small molecule organic semiconductors may have a molecular weight lower than 1000.
  • Small molecule organic semiconductors may comprise a low number of conjugated monomers.
  • Small molecule organic semiconductors may comprise between 2 and 20 conjugated monomers.
  • the molecules described herein may comprise between three and six conjugated monomers.
  • the molecules described herein may be heterocyclic oli
  • the molecules may be monodisperse.
  • the molecules may comprise a core comprising a bisEDOT unit and a pyridine unit.
  • devices fabricated with monodisperse materials usually present more reproducible outputs than devices fabricated with polymers presenting polydispersity.
  • the molecules described herein may be pure.
  • devices prepared with pure organic materials can be more stable than devices prepared with materials comprising impurities, since these impurities can lead to degradation of the organic materials.
  • the molecules described herein may present chemical diversity.
  • the molecules described herein may present functionalisation sites in their molecular structure.
  • the molecules described herein may present a functionalisation site at the 1 - position of the pyridine (i.e. the N position). This functionalisation site is named R in the general molecular structure of the molecules.
  • the molecules described herein present functionalisation sites at the 2- 3-, 5- and/or 6- positions of the pyridine unit. These functionalisation sites are named Xi-X 4 in the general molecular structure of the molecules.
  • the molecules described herein may present a functionalisation site at the a position of the terminal EDOT unit. This functionalisation site is named Y in the general molecular structure of the molecules.
  • the molecules described herein may be functionalised by adding substitutents at the functionalisation sites of the molecules. Beneficially, the presence of functionalisation sites in the molecular structure enables tuneability of the molecules described. Therefore, advantageously the molecules described herein may be tunable.
  • the molecules described herein may be capable of structural modifications to tailor their properties to each target application.
  • the R substituent of the molecules may be changed to adjust the solubility of the molecules in different solvents.
  • the R substituent of the molecules may be changed to tune the morphology and/or molecular packing of films of the molecules.
  • the R, X and/or Y substituents of the molecules may be changed to alter the bandgap of the molecules. For example, adding a conjugated monomer at the Y functionalisation site may lead to a reduction of the bandgap of the molecules through extension of the conjugation length.
  • the Highest Occupied Molecular Orbital (HOMO) and Lowest Occupied Molecular Orbital (LUMO) energy levels of the molecules described herein may be tuned by adding electron donating and/or electron withdrawing groups to the functionalisation sites of the molecules. Electron donating groups may increase the HOMO energy level of the molecules. Electron withdrawing groups may decrease the LUMO energy level of the molecules.
  • the molecules and/or materials, such as the conductive films described herein may be transparent in the ultraviolet-visible (UV-Vis) light spectral region (from 190 to 750 nm). Transparent materials allow a percentage of incident light in a certain spectral region (transmittance %) to pass through them.
  • UV-Vis ultraviolet-visible
  • Transparent materials allow a percentage of incident light in a certain spectral region (transmittance %) to pass through them.
  • the molecules and/or materials made with molecules of the present invention are >50%, such as >60%, 70%, 80% or more transparent, as readily tested by the skilled reader.
  • the physical, chemical and/or electrical properties of the molecules described herein may be modified by chemical functionalisation of the molecules.
  • the physical, chemical and/or electrical properties of the molecules described herein may be fine-tuned for each required application via functionalisation of their chemical structure, as described above.
  • the physical and/or electrical properties of the molecules described herein may be modified by physical processing.
  • the physical and/or electrical properties of the molecules described herein may be modified by solvent treatment, solvent vapour annealing, thermal annealing, plasma pre- treatment of the substrate, encapsulation, deposition method, molecular self-assembly and the like.
  • the molecules described herein may present tunable conductivity, tunable electronic levels and/or tunable processability in different solvent mediums.
  • the molecules described herein may be soluble in common organic solvents.
  • the molecules described herein may be soluble in methanol, ethanol, acetone, acetonitrile, chloroform, dichloromethane, carbon tetrachloride, chlorobenzene, cyclohexane, diethyl ether, ethyl acetate, hexane, toluene, dimethyl sulfoxide (DMSO), tetrahydrofuran and the like.
  • the molecules described herein may be soluble in water-miscible alcohols. The solubility of the molecules in different solvents may be modified by structural modification.
  • the solubility of the molecule in a solvent may be altered by changing the R substituent of the pyridine.
  • the solubility of the molecules in each solvent may be tailored by choosing an R substituent of the pyridine capable of solubilising the molecule in that solvent.
  • the molecules described herein may be soluble in common organic solvents such as dichloromethane and chloroform.
  • the molecules described herein may be solution processable.
  • devices comprising the molecules described herein may be fabricated by solution processing techniques such as electrodeposition, spin coating, drop casting, dip coating, doctor blading, spray coating, ink-jet printing, Langmuir-Blodgett, nanoimprint lithography, microcontact printing, and/or roll-to-roll printing techniques such as gravure printing, offset printing and/or flexographic printing.
  • solution processing techniques such as electrodeposition, spin coating, drop casting, dip coating, doctor blading, spray coating, ink-jet printing, Langmuir-Blodgett, nanoimprint lithography, microcontact printing, and/or roll-to-roll printing techniques such as gravure printing, offset printing and/or flexographic printing.
  • the molecules described herein may present a neutral pH.
  • the molecules may not be acidic.
  • the molecules may present non-acidic and/or pH neutral functionalities.
  • the performance of devices fabricated with the molecules described herein may be superior to the performance of devices fabricated with other currently used acidic materials, such as PEDOT:PSS, due to the lack of acidic functionalities in the structure of the molecules.
  • Acidity of a layer, such as the hole injection layer, hole transport layer and/or electrode layer can deteriorate other layers in the device, leading to contamination and decrease in device performance.
  • the molecules described herein may be precursors to a conductive material.
  • the molecules described herein may form a conductive material in solution.
  • solubilised molecules described herein may be doped in solution to form a conductive material.
  • the doped conductive material may be a doped dimer of the molecules described herein.
  • a doped dimer of the molecules described herein may be a conductive material.
  • a film of the conductive material described herein may be deposited from solution.
  • the conductive material described herein may be formed by doping the molecules described herein in solution.
  • the conductivity of the conductive material may be raised, for example by several orders of magnitude, by chemical or electrochemical doping.
  • P- doping involves oxidation of the molecules and/or conductive material
  • n-doping involves reduction of the molecules and/or conductive material.
  • Doping the molecules and/or conductive material described herein may involve the partial oxidation or reduction of the molecules and/or conductive material, each oxidation state exhibiting its own characteristic reduction potential.
  • the molecules and/or the conductive material described herein may be chemically doped in solution with a dopant.
  • Suitable dopants may comprise, but are not limited to NOBF 4 , NOPF 6 , NOSbF 6 , FeCI 3 , F 4 TCNQ, AsF 5 , DDQ, nitrosonium salts, chloranil, TNF and TCNE.
  • the molecules and/or the conductive material described herein may be electrochemically doped in solution.
  • a transparent conductive film or coating may be obtainable by preparing a solution through dissolving a molecule described herein or a functionally active derivative thereof in a solvent, forming a conductive material by doping the solution for example with a suitable dopant and depositing a film of conductive material from the solution.
  • Solvents suitable for dissolving a molecule described herein may comprise, but are not limited to methanol, ethanol, acetone, acetonitrile, chloroform, dichloromethane, carbon tetrachloride, chlorobenzene, cyclohexane, diethyl ether, ethyl acetate, hexane, toluene, dimethyl sulfoxide (DMSO), tetrahydrofuran and water.
  • DMSO dimethyl sulfoxide
  • Doping the solution may comprise electrochemically doping the solution or chemically doping the solution.
  • Chemically doping the solution may comprise of adding a dopant selected from the group comprising of NOPF 6 , NOSbF 6 , F 4 TCNQ, AsF 5 , DDQ, nitrosonium salts, chloranil, TNF and TCNE.
  • chemically doping the solution may comprise adding nitrosonium salts, NOPF 6 or NOSbF 6 .
  • Chemical dopants may be added to the solution in any suitable concentration.
  • chemically doping the solution may comprise adding chemical dopants to the solution in a range of about 0.5 to about 10 molar equivalents.
  • Chemically doping the solution may comprise adding chemical dopants to the solution in a range of about 1 to about 5 molar equivalents. Chemically doping the solution may compise adding 2.5 molar equivalents of a chemical dopant, such as nitrosonium salts, NOPF 6 or NOSbF 6 to the solution.
  • a chemical dopant such as nitrosonium salts, NOPF 6 or NOSbF 6
  • Depositing a film of conductive material from the solution may be performed by any suitable solution processing technique.
  • suitable solution processing techniques may comprise, but are not limited to electrodeposition, spin coating, drop casting, dip coating, doctor blading, spray coating, ink-jet printing, Langmuir-Blodgett, nanoimprint lithography, microcontact printing, and/or roll-to-roll printing techniques such as gravure printing, offset printing and/or flexographic printing.
  • the film of conductive material is made by drop casting.
  • a film described herein may present controllable levels of doping while controlling the degree of transparency and film morphology. The concentration of dopant in a film of the conductive material described herein may be modified to tune the conductivity of the film.
  • Changing the doping levels in a film of the conductive material may affect the transmittance of the film and the film morphology.
  • the transmittance and morphology of the film may be optimised for each concentration of dopant in the film, for example by drop casting the film, adding solvent additives and the like.
  • films of the molecules and/or conductive material described herein may present a doping level of 2.5 molar equivalents of NOPF 6 or NOSbF 6 . Controlled levels of doping are crucial for ensuring successful conductivity of the layer.
  • Layers and/or films of the molecules and/or conductive material of the present invention may present reproducible controlled levels of doping that can be adjusted depending on the application, while maintaining a smooth and uniform morphology.
  • a film of the conductive material described herein may present a transmittance comparable to ITO and PEDOT:PSS in the UV-Vis light spectral region. Films of the conductive material described herein may present transmittance of up to 90% at 100 nm thickness in the visible light spectral region. Films of the conductive material described herein may present transmittance in the region of 30%-90% in the UV-Vis light spectral region. For example, films of the conductive material described herein may present transmittance up to 60% in the UV-Vis light spectral region.
  • a film of the conductive material described herein may present a conductivity between 4.0 x 10 ⁇ 7 and 1 S/cm after doping.
  • a film of the conductive material described herein may present conductivity of up to 1000 S/cm after doping.
  • the conductivity of films of the conductive material described herein may be optimised, for example by using different dopants and/or dopant concentrations.
  • a film of the conductive material described herein may be used as a conductive layer in an organic electronic device.
  • a film of the conductive material described herein may be used as a transparent conductive standalone electrode in an organic electronic device.
  • a film of the conductive material described herein may be used as a charge transport layer in an organic electronic device.
  • a film of the conductive material described herein may be used as a hole injection layer in an organic electronic device.
  • a film of the conductive material described herein may be used as a transparent electrode and/or interlayer electrode in organic photovoltaics (OPVs) (also known as organic solar cells), organic light emitting diodes (OLEDs), and the like.
  • OOVs organic photovoltaics
  • OLEDs organic light emitting diodes
  • a film of the conductive material described herein may have applications in display technologies, solar light harvesting, mobile and computer devices and/or lighting applications.
  • a method of tuning the properties of the molecules described herein comprising altering the substituents of the molecules.
  • Altering the substituents may comprise of chemically modifying one or more of the R, XrX 4 and/or Y substituents of the molecule.
  • Altering the substituents may comprise choosing substituents tailored to the desired application.
  • R substituents may be chosen to provide solubility in different solvents and/or to provide the required molecular packing to achieve a smooth film morphology. As such, the solubility of the molecules can be tailored to the solvent required for each specific application.
  • XrX 4 and/or Y substituents may be chosen to alter the bandgap of the molecule.
  • the bandgap of the molecules can be tailored to the required application.
  • the HOMO and/or LUMO energy levels of the molecules may be tuned to match the HOMO and/or LUMO levels of adjacent functional layers and/or electrodes.
  • a transparent conductive coating comprising a film of a transparent conductive material described herein.
  • a transparent standalone electrode comprising a film of a conductive material described herein.
  • an organic electronic device comprising a film of a conductive material described herein.
  • the organic electronic device may be a thin film organic electronic device.
  • thin film organic electronic devices may be prepared by depositing a film of the conductive transparent material described herein on a transparent substrate, such as ITO or glass, and depositing electrodes on the film.
  • the conductive transparent material is deposited by a drop casting technique known in the art and described herein.
  • the organic electronic device may be an organic photovoltaic (OPV).
  • the organic electronic device may be an organic light emitting diode OLED.
  • the organic electronic device may be an electrochromic device.
  • electrochromic devices may be prepared by using a transparent standalone electrode of the fifth aspect as a working electrode to electrochemically deposit an electrochromic material on the electrode.
  • Figure 1 shows a top view of a thin film device comprising a film described herein, the device is used for electrical, surface and thickness measurements.
  • Figure 2 shows current-voltage (IV) characteristics for thin film devices fabricated using the following compounds: (a) 4b, (b) 4a, (c) 4f, (d) 4h, (e) 4i and (f) 4k.
  • Figure 3 shows AFM images for the surface of the most conductive thin film devices containing the following compounds: (a) 4b, (b) 4a, (c) 4f, (d) 4h, (e) 4i and (f) 4k.
  • Figure 4 shows a view of the light beam (green dotted line) on the substrate in UV/Vis spectrophotometer.
  • Figure 5 shows the transmittance of thin films taken at different points in the film and the subsequent average value.
  • Figure 6 shows current-voltage (IV) characteristics for thin film devices fabricated using compound 4r with dopants (a) NOPF 6 and (b) NOSbF 6
  • Figure 7 shows AFM surface images of compound 4r films cast from solutions doped with (a) NOSbF 6 and (b) NOPF 6 .
  • Figure 8 shows the transmittance of thin films of compound 4r doped with NOPF 6 (1 ) and NOSbF 6 (2) taken at different points in the film and the subsequent average value.
  • Figure 9 shows an example of current voltage (IV) characteristics from film of 4r doped with NOSbF 6
  • Figure 10 shows example of current voltage (IV) characteristics from film of compound 4 doped with NOSbF 6
  • Figure 1 1 shows Current density-voltage-luminance characteristics of OLEDs fabricated using Poly[2-methoxy-5-(2-ethylhexyloxy)-1 ,4-phenylenevinylene] (MEH- PPV) emissive layer and with device architectures (a) ITO/HTL 1/MEH-PPV/Ca/AI; (b) ITO/HTL 2/MEH-PPV/Ca/AI; (c) ITO/HTL 3/MEH-PPV/Ca/AI; (d) ITO/HTL 4/MEH- PPV/Ca/AI; (e) ITO/HTL 5/MEH-PPV/Ca/AI; (f) ITO/HTL 6/MEH-PPV/Ca/AI
  • Figure 12 shows Current density-voltage-luminance characteristics of OLED with device architecture ITO/HTL 3/Green 2/Ca/AI
  • the compounds are small molecules with a bis-EDOT coupled to a pyridine with different solubilising moieties at the 1 -position of the pyridine.
  • the molecules are soluble in common organic solvents including but not limited to chloroform, toluene, acetonitrile, chlorobenzene, dimethyl sulfoxide, ethylene glycol, dichloromethane and tetrahydrofuran.
  • These small molecules are conductive, transparent and soluble in common solvents, but they do not comprise any acidic functionalities. This is advantageous since acidity can be detrimental for device performance and longevity as adjacent layers of the device can be damaged in an acidic environment.
  • 3,4-Ethylenedioxythiophene (10.0 g, 7.51 ml, 70.35 mmol, 1 .0 equiv.) was dissolved in anhydrous THF (150 ml) and cooled to -80 °C, where n-butyllithium (freshly titrated at 2.29 M in hexanes, 21 .95 ml, 73.16 mmol, 1 .04 equiv.) was added slowly. On complete addition, the reaction mixture was warmed to 0 °C in an ice/salt bath and stirred for 2 h under Ar.
  • reaction mixture was quenched by addition of water (200 ml) and brine (50 ml), then extracted with dichloromethane (150 ml, then 2 ⁇ 100 ml). The organic layers were combined, dried over MgS0 4 then filtered.
  • 4-Bromopyridine hydrochloride (3.66 g, 18.82 mmol, 1.5 equiv.) was added to a 100 ml conical flask and dissolved in distilled water (50 ml). To this, and equimolar solution of potassium carbonate (2.60 g, 18.82 mmol, 1 .5 equiv. in 50 ml of distilled water) was added, and the aqueous solution extracted with diethyl ether (3 ⁇ 30 ml). The organic extracts were combined, dried (MgS0 4 ), filtered and concentrated to a slightly pink oil, which was then re-dissolved in anhydrous toluene (40 ml).
  • Glass substrates were cleaned using deionised water, acetone and propan-2-ol with ultra-sonication and dried over a stream of compressed air before being subject to UV- ozone treatment for 2 minutes.
  • FIG. 1 A layout of the structure of the thin films used for conductivity testing is shown in Figure 1 .
  • the previously prepared solution comprising one of the molecules 4a, 4b, 4f, 4h, 4i or 4k, was used to spin-coat the glass substrates at a spin speed of 2000 rpm and the coated substrates were annealed at ⁇ ⁇ 00°C for 20 minutes. After annealing the substrates, the sides of the substrates were cleaned to reveal glass to improve metal contacts.
  • the substrates were placed in a sample holder with shadow mask for the deposition four pairs of Al electrodes (dimensions: 1 .5 mm ⁇ 4 mm). The holder and mask were placed in the evaporation chamber and 70 nm thick Al electrodes were deposited at 1 ⁇ 10 ⁇ 6 mbar. Once the chamber had returned to atmospheric pressure, the substrates were removed and conductive silver paint was applied to the outside edges of the electrodes to improve the contacts and the paint was allowed to dry for 20 minutes. Drop casted films
  • FIG. 1 A schematic diagram of devices fabricated with the molecules described herein is shown in Figure 1 .
  • Thin film devices comprising a film of the conductive material described herein were prepared on glass substrates of 15 x 15 mm.
  • the red bar shows the active device area where the resistivities were measured.
  • Figure 2 shows current-voltage (IV) plots for each film tested.
  • the resistivity (p) is then calculated using this value and the inverse of the resistivity is the conductivity ( ⁇ ).
  • Table 1 shows the results of conductivity measurements performed on devices fabricated with molecules described herein and data on theRSM roughness (which is an indication of the uniformity of the film) of the films shown in Figure 3.
  • RRMS root mean square roughness
  • AFM atomic force microscopy
  • UV-Vis transmission spectroscopy was performed on samples using a standard UV-Vis spectrometer. Since the measurement is limited by the shape and dimensions of the light spot, transmission spectra were recorded in the middle of the samples, away from the location of the top electrodes. Samples processed with same conditions as above were used to measure transmission on locations of the film other than the top electrodes. The areas where the spectra are recorded are divided by the black dotted line shown in Figure 4 into the left, centre and right regions which are used to characterise transmittance across the film.
  • Figure 5 shows the % transmittance of light at the wavelength of highest absorption ( max)- There are three values which have been combined to give an average to ensure the whole surface is taken into consideration. The higher the value for transmittance, the more suitable for the material is for a role in a device. Low transmittance means light will be absorbed from emission of an OLED device (i.e., self-absorption) or from the incident light on an OPV device, reducing OLED brightness or light intensity reaching the OPV active layer, respectively. As shown in Figure 5, transmittances of over 50 % were obtained with some of the molecules tested.
  • the experimental results are comparable to experimental data obtained from devices prepared as described above with commercially available PEDOT:PSS (Heraeus, CleviosTM P VP AL 4083), the conductivity of which was measured to be 0.005 S cm “1 with a RMS roughness of 1 nm, thickness of 65 nm and a transmittance of 83% at the wavelength of maximum absorbance.
  • the conductivity achieved with some of the molecules described herein was up to four times greater than that of PEDOT:PSS and although the transmittance was somewhat lower than that of PEDOT:PSS, this can be attributed to the thickness and roughness of the films, which has to be experimentally optimised.
  • the thickness of films of the molecules described herein has to be optimised without compromising conductivity in order to improve transparency of the films.
  • Table 2 shows data of conductivity measurements performed on drop-casted films of compound 4r doped with NOSbF 6 and with NOPF 6 and as well as thickness and roughness data obtained on those films (see also Figure 6). AFM images of those films are presented on Figure 7.
  • Films comprising compound 4r chemically doped with NOSbF 6 present higher conductivity and lower surface roughness than films of compound 4r chemically doped with NOPF 6 , the films having similar thickness. Additionally, films comprising of compound 4r chemically doped with NOSbF 6 exhibited transmittances of greater than 75% (see figure 8).
  • thinner films of compound 4r present comparatively greater conductivities and lower surface roughness.
  • the increased conductivity is likely due to the greater uniformity of the drop-cast films.
  • NOSbF 6 (12.6 mg, 2.5 eq) in anhydrous acetonitrile (0.5 ml) was added to Compound 4r (10 mg, 1 eq) in anhydrous acetonitrile (0.5 ml) before being left to stir for 16 hours.
  • the ITO substrate was coated by spin-coating at 2000 rpm and the film was annealed at 120 °C for 20 minutes. The sides of the substrates were cleaned to reveal glass to improve metal contacts. The substrates were placed in a sample holder with shadow mask for the deposition four pairs of Al electrodes (dimensions: 1 .5 mm ⁇ 4 mm).
  • NOSbF 6 (1 .4 mg, 2.5 eq) in anhydrous acetonitrile (0.1 ml) was added to a solution of compound 4 (0.8 mg, 1 eq) in anhydrous acetonitrile (0.1 ml).
  • the solution was diluted with anhydrous DMSO (0.8 ml).
  • a glass substrate was coated using 4 drops of the solution and left to dry for 16 hours. The sides of the substrates were cleaned to reveal glass to improve metal contacts.
  • the substrates were placed in a sample holder with shadow mask for the deposition four pairs of Al electrodes (dimensions: 1 .5 mm ⁇ 4 mm).
  • ITO Indium tin oxide
  • NOPF 6 (8.2 mg, 2.5 eq) in anhydrous acetonitrile (0.5 ml) was added to Compound 4r (10 mg, 1 eq) in anhydrous acetonitrile (0.5 ml) before being left to stir for 16 hours.
  • the ITO substrate was coated by spin-coating at 2000 rpm and the film was annealed at 120 °C for 20 minutes.
  • NOPF 6 (8.2 mg, 2.5 eq) in anhydrous acetonitrile (0.45 ml) was added to Compound 4r (10 mg, 1 eq) in anhydrous acetonitrile (0.45 ml) before dilution with anhydrous DMSO (0.1 ml). The solution was then left to stir for 16 hours.
  • the ITO substrate was coated by spin-coating at 2000 rpm and the film was annealed at 120 °C for 20 minutes.
  • NOSbF 6 (12.6 mg, 2.5 eq) in anhydrous acetonitrile (0.5 ml) was added to Compound 4r (10 mg, 1 eq) in anhydrous acetonitrile (0.5 ml) before being left to stir for 16 hours.
  • the ITO substrate was coated by spin-coating at 2000 rpm and the film was annealed at 120 °C for 20 minutes.
  • NOSbF 6 (12.6 mg, 2.5 eq) in anhydrous acetonitrile (0.45 ml) was added to Compound 4r (10 mg, 1 eq) in anhydrous acetonitrile (0.45 ml) before dilution with anhydrous DMSO (0.1 ml). The solution was then left to stir for 16 hours.
  • the ITO substrate was coated by spin-coating at 2000 rpm and the film was annealed at 120 °C for 20 minutes.
  • MEH-PPV concentration: 4 mg ml "1 in toluene
  • MEH-PPV concentration: 4 mg ml "1 in toluene
  • the film was then annealed at 80 °C for 20 minutes.
  • Calcium (40 nm) and aluminium (40 nm) electrodes were deposited by thermal evaporation at 1 ⁇ 10 ⁇ 6 mbar and active area of 4 mm ⁇ 1 .5 mm was obtained by using a shadow mask.
  • Current-Voltage-Luminance data was measured in the glovebox in a light-tight box. See Figure 1 1 and Table 5.
  • ITO Indium tin oxide
  • HTL 3 had previously been prepared by dissolving compound 4r (10 mg, 1 eq) in anhydrous acetonitrile (0.5 ml) and NOPF 6 (8.2 mg, 2.5 eq) in a separate vial with anhydrous acetonitrile (0.5 ml.
  • the NOPF6 solution was added to 4r solution and the resulting solution was stirred overnight.
  • the solution was deposited onto the ITO substrate by spin-coating at 2000 rpm for 60 seconds before annealing at 100 °C for 20 minutes.
  • Compound Green 2 was deposited according to a previous procedure (J. Mater. Chem. C. 2016 4 3774-3780). Calcium (40 nm) and aluminium (40 nm) electrodes were deposited by thermal evaporation at 1 ⁇ 10 ⁇ 6 mbar and active area of 4 mm x 1 .5 mm was obtained by using a shadow mask. Current-Voltage-Luminance data was measured in the glovebox in a light-tight box. See Figure 12 and Table 6.

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Abstract

L'invention concerne une molécule destinée à être utilisée en tant que revêtement conducteur, la molécule comprenant des fonctionnalités PH neutres ou sensiblement neutres et présentant une diversité chimique, une transparence dans le spectre UV-Vis et une solubilité dans des solvants organiques communs. L'invention concerne également un film préparé à partir d'une solution d'une molécule décrite ici, un procédé de réglage des propriétés d'une molécule décrite ici, une électrode transparente et un dispositif électronique organique comprenant une molécule décrite ici.
PCT/GB2017/052487 2016-08-24 2017-08-23 Dérivés de pyridyl-éthylènedioxy-thiophène en tant que matériau conducteur transparent Ceased WO2018037230A1 (fr)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
US20070128465A1 (en) * 2005-12-05 2007-06-07 General Electric Company Transparent electrode for organic electronic devices
JP2015056360A (ja) * 2013-09-13 2015-03-23 山本化成株式会社 アミン化合物、これを含む増感色素、半導体電極及び光電変換素子
WO2016006512A1 (fr) * 2014-07-07 2016-01-14 富士フイルム株式会社 Élément de conversion photoélectrique, cellule solaire à pigment photosensible, colorant à complexe métallique, solution de colorant, et composé de terpyridine ou son produit d'estérification

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Publication number Priority date Publication date Assignee Title
US20070128465A1 (en) * 2005-12-05 2007-06-07 General Electric Company Transparent electrode for organic electronic devices
JP2015056360A (ja) * 2013-09-13 2015-03-23 山本化成株式会社 アミン化合物、これを含む増感色素、半導体電極及び光電変換素子
WO2016006512A1 (fr) * 2014-07-07 2016-01-14 富士フイルム株式会社 Élément de conversion photoélectrique, cellule solaire à pigment photosensible, colorant à complexe métallique, solution de colorant, et composé de terpyridine ou son produit d'estérification

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G. A. SOTZING; J. R. REYNOLDS; P. J. STEEL, ADV. MATER., vol. 9, 1997, pages 726
JOSHUA R. FARRELL ET AL: "Electrochromic Polymer Films Containing Re(I) and Pt(II) Metal Centers", INORGANIC CHEMISTRY, vol. 46, no. 17, 1 August 2007 (2007-08-01), EASTON, US, pages 6840 - 6842, XP055410241, ISSN: 0020-1669, DOI: 10.1021/ic700635h *
LAURE FILLAUD ET AL: "Synthesis of [pi]-Conjugated 2,2:6',2''-Terpyridine-Substituted Oligomers Based on 3,4-Ethylenedioxythiophene", ORGANIC LETTERS , 14(23), 6012-6015 CODEN: ORLEF7; ISSN: 1523-7052, vol. 15, no. 5, 1 March 2013 (2013-03-01), pages 1028 - 1031, XP055410245, ISSN: 1523-7060, DOI: 10.1021/ol303512f *
M.P. DE JONG; L. J. VAN IJZENDOORN; M. J. A. DE VOIGT, APPLIED PHYSICS LETTERS, vol. 77, 2000, pages 14

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