EP3987588A1 - Formulierung aus einem organischen halbleitermaterial vom typ p und einem halbleitermaterial vom typ n - Google Patents

Formulierung aus einem organischen halbleitermaterial vom typ p und einem halbleitermaterial vom typ n

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Publication number
EP3987588A1
EP3987588A1 EP20733629.8A EP20733629A EP3987588A1 EP 3987588 A1 EP3987588 A1 EP 3987588A1 EP 20733629 A EP20733629 A EP 20733629A EP 3987588 A1 EP3987588 A1 EP 3987588A1
Authority
EP
European Patent Office
Prior art keywords
solvent
formulation
type
polymer
organic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20733629.8A
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English (en)
French (fr)
Inventor
Alex LHEUREUX
Emeline Saracco
Benjamin BOUTHINON
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Isorg SA
Original Assignee
Isorg SA
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Filing date
Publication date
Application filed by Isorg SA filed Critical Isorg SA
Publication of EP3987588A1 publication Critical patent/EP3987588A1/de
Pending legal-status Critical Current

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Classifications

    • 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
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • 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
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • 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
    • H10K2102/301—Details of OLEDs
    • H10K2102/361—Temperature
    • 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
    • H10K30/50—Photovoltaic [PV] devices
    • 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

  • a formulation comprising a p-type organic semiconductor material and an n-type semiconductor material
  • the present description relates generally to formulations comprising an organic semiconductor (OSC), as well as inks for the preparation of organic electronic devices, as well as to methods of preparing organic electronic devices using such formulations.
  • OSC organic semiconductor
  • organic semiconductors (OSC, acronym for organic semiconductor) have aroused keen interest in academia and industry.
  • OPDs organic photodiodes
  • OLEDs organic light-emitting diodes
  • OLEDs organic light-emitting diodes
  • OCVs organic photovoltaic cells
  • inorganic semiconductors can be applied by relatively simple and inexpensive deposition and coating methods, including spin coating or spin coating methods. coating.
  • the inks and the formulations to be applied by such processes generally require a viscosity specific to the process used.
  • the adjustment of the viscosity of the ink is complicated by the fact that it depends on a number of variables, such as the nature of the components of the ink, for example the molecular weight of the organic semiconductor compound or the nature of the ink. solvent, as well as the respective concentrations of the components.
  • semiconductor organic compounds are frequently designed to maximize their electronic properties, such as the mobility of charge carriers without considering solubility, thus limiting the choice of potential solvents.
  • an object of one embodiment is to at least partially overcome the drawbacks of inks comprising an organic semiconductor compound described above.
  • An object of an embodiment is for the viscosity of the ink to be adapted to the deposition process used.
  • One embodiment provides for a formulation comprising:
  • a p-type organic semiconductor polymer comprising a conjugated aryl compound, a conjugated heteroaryl compound or a mixture of at least two of these compounds;
  • an n-type semiconductor material comprising fullerene, substituted fullerene or a mixture of at least two of these compounds
  • the concentration of the p-type organic semiconductor polymer being between 4 mg / mL and 8 mg / mL per milliliter of solvent and the concentration of the n-type organic semiconductor material being between 10 mg / mL and 14 mg / mL per milliliter of solvent.
  • the solvent comprises a first non-aqueous solvent having a first boiling point of between 140 ° C and 200 ° C and a second non-aqueous solvent, different from the first solvent, and having a point of d 'boiling above 200 ° C.
  • the first solvent comprises toluene, o-xylene, m-xylene or p-xylene, trimethylbenzene, tetralin, anisole, alkylanisoles, naphthalene, tetrahydronaphthalene , Alkylnaphthalene or a mixture of at least two of these solvents and the second solvent comprises acetophenone, dimethoxybenzene, benzyl benzoate, alkylnaphthalene or a mixture of at least two of these solvents.
  • the proportion of the second solvent is preferably from 1% to 5% relative to the total weight of the first and second solvents.
  • the formulation has a viscosity of between 3 mPa.s and 7 mPa.s.
  • the p-type semiconductor polymer comprises aryl groups and thiophene groups.
  • the n-type semiconductor material is PCBM-C 6 o ⁇
  • the first solvent is o-xylene and the second solvent is acetophenone.
  • One embodiment provides for the use of a formulation as defined above, as coating or printing ink for the preparation of optoelectronic devices.
  • An embodiment also provides a method of preparing a formulation as defined above, comprising the mixture of the organic semiconductor polymer of type p and of the semiconductor material of type n in the form of powders, the addition of the solvent not aqueous mixture to obtain the formulation, heating the formulation and filtering the formulation.
  • the semiconductor organic polymer of type pa has a target molecular weight and is obtained by mixing a first powder of the polymer with a first molecular weight greater than the target molecular weight and a second powder of the same polymer with a second molecular weight lower than the target molecular weight.
  • the step of heating the formulation comprises heating the formulation from 30 min to 2 h at a temperature between 50 ° C and 70 ° C.
  • the filtering step is carried out by passing the formulation through a filter, the pore size of which is between 0.2 ⁇ m and 1 ⁇ m.
  • One embodiment also provides for an optoelectronic device prepared from a formulation as defined above.
  • the optoelectronic device is chosen from organic photodiodes, organic light-emitting diodes, and organic photovoltaic cells.
  • FIG. 1 represents, in the form of a block diagram, an embodiment of a method for manufacturing a semiconductor layer comprising a p-type organic semiconductor material and an n-type semiconductor material;
  • Figure 2 is a sectional view, partial and schematic, of an embodiment of an optical sensor.
  • the terms “ink” and “formulation” are used to denote a composition comprising at least one p-type organic semiconductor material, an n-type semiconductor material and at least one solvent.
  • organic semiconductor material is used to denote a semiconductor material comprising at least one organic semiconductor compound. Therefore, such an organic semiconductor material can also include one or more inorganic semiconductor compounds.
  • the molecular weight is given in number average molecular weight Mn or mass average molecular weight Mw, and is determined by gel permeation chromatography (GCP, acronym for gel permeation chromatography) against a standard polystyrene in eluents such as tetrahydrofuran, trichloromethane, chlorobenzene or 1, 2, 4-trichlorobenzene. Unless otherwise indicated, chlorobenzene is used as a solvent for the measurements.
  • GCP gel permeation chromatography
  • Mw molecular weight distribution
  • PDI polydispersity index
  • degree of polymerization also called total number of repeating units
  • the expression “repeating unit” or “repeating unit” denotes a monomer unit forming the backbone of the polymer compound and is a structural unit of which at least one is present in the polymer compound.
  • the term "n-valent heterocyclic group” (where n is 1 or 2) denotes a group which is prepared by removing n hydrogen atom (s) from a heterocyclic compound (particularly, an aromatic heterocyclic compound) and in which these fractions form bonds with other atoms.
  • heterocyclic compound denotes an organic compound having a cyclic structure, which contains in the ring not only carbon atoms, but also a heteroatom such as an oxygen atom, a sulfur atom, a carbon atom. nitrogen, a phosphorus atom or a boron atom among the elements forming the ring.
  • the formulation according to the present application comprises: a) at least one n-type organic semiconductor material and at least one p-type organic semiconductor material; b) at least one solvent; c) optionally at least one polymer in the form of particles; and d) optionally at least one conductive additive.
  • the formulation may comprise one or more p-type organic semiconductor compounds and one or more n-type semiconductor compounds.
  • the semiconductor compound (s), preferably the p-type organic semiconductor compound (s), can for example also be one or more photoactive compounds.
  • photoactive compound is used to refer to a compound which helps convert incoming light into electrical energy.
  • the p-type organic semiconductor compound (s) can be a polymer, an oligomer or a small molecule, and can be represented by the following formula (I):
  • the p-type organic semiconductor compound (s) are each a polymer.
  • the groups R 1 and R 2 are carbyl groups, preferably chosen from the group consisting of alkyl groups having from 1 to 20 carbon atoms, partially or fully fluorinated alkyl groups having from 1 to 20 carbon atoms , phenyl and phenyl groups substituted by alkyl groups having 1 to 20 carbon atoms or partially or fully fluorinated alkyl groups having 1 to 20 carbon atoms.
  • Examples of p-type organic semiconductor compounds can be conjugated aryl and heteroaryl compounds, for example an aromatic compound, preferably containing two or more, and more preferably at least three, aromatic rings.
  • Preferred examples of p-type organic semiconductor compounds comprise aromatic rings chosen from 5, 6 or 7-membered aromatic rings, more preferably chosen from 5 or 6-membered aromatic rings.
  • Each of the aromatic rings of the p-type organic semiconductor compound can optionally contain one or more heteroatoms chosen from Se, Te, P, Si, B, As, N, O or S, generally from N, O or S.
  • aromatic rings may be optionally substituted with alkyl, alkoxy, polyalkoxy, thioalkyl, acyl, aryl or substituted aryl groups, a halogen group, in particular fluorine, cyano, nitro, or a secondary alkylamine or arylamine. or optionally substituted tertiary, represented by -N (R 3 ) (R 4 ), where R 3 and R 4 are each independently H, alkyl aryl, optionally substituted alkoxy or an optionally substituted polyalkoxy group.
  • R 3 and R 4 are an alkyl or aryl group, these can optionally be fluorinated.
  • N C (R '"), where Ti and T2 each independently represent H, Cl, F, -CN or lower alkyl groups such as alkyl groups having 1 to 4 carbon atoms, R'" representing H, a an optionally substituted alkyl group or an optionally substituted aryl group. Further, when R '"is an alkyl or aryl group, it may be fluorinated.
  • Preferred examples of p-type organic semiconductor compounds suitable for the present application include compounds, oligomers and derivatives of compounds selected from the group consisting of polymers of conjugated hydrocarbons such as polyacene, polyphenylene, poly (phenylene vinylene), polyfluorene, including the oligomers of these polymers of conjugated hydrocarbons; condensed aromatic hydrocarbons, such as tetracene, chrysene, pentacene, pyrene, perylene, coronene or their soluble substituted derivatives; para phenylenes substituted with oligomers such as p-quaterphenyl (p-4P), p-quinquephenyl (p-5P), p-sexiphenyl (p-6P), or their soluble substituted derivatives; conjugated heterocyclic polymers such as poly (3-substituted thiophenes), poly (3,4-bisubstituted thiophenes), optionally substituted polythien
  • the p-type organic semiconductor compounds are polymers or copolymers which comprise one or more repeating units chosen from thiophene-2, 5-diyl, thiophene -2, 5-substituted 3-diyl, thieno [2, 3-b] thiophene-2, 5-diyl optionally substituted, thieno [3, 2-b] thiophene-2, 5-diyl optionally substituted, selenophene -2, 5-diyl or selenophene-2, 5-diyl substituted in 3.
  • p-type organic semiconductor compounds are copolymers comprising one or more electron acceptor units and one or more electron donor units.
  • the 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, preferably disubstituted in 4,8, and further comprising one or more aryl or heteroaryl units selected from group A and group B, preferably comprising at least one unit from group A and at least one unit from group B, group A consisting of aryl or heteroaryl groups having electron donor properties and group B consisting of aryl or heteroaryl groups having electron acceptor properties.
  • the group A consists of selenophene-2, 5-diyl, thiophene-2, 5-diyl, thieno [3, 2-b] thiophene-2, 5-diyl, thieno [2, 3-b] thiophene -2, 5-diyl, selenopheno [3, 2-b] selenophene-2, 5-diyl, selenopheno [2, 3-b] selenophene-2, 5-diyl, selenopheno [3, 2-b] thiophene-2 , 5-diyl, selenopheno [2, 3-b] thiophene-2, 5-diyl, benzo [1, 2-b: 4, 5-b '] dithiophene-
  • Group B consists of benzo [2,1,3] thiadiazole-4, 7-diyl, 5, 6-dialkyl-benzo [2,1,3] thiadiazole-4, 7-diyle, le 5, 6-dialkoxybenzo [2, 1,3] thiadiazol-4, 7-diyl, benzo [2,1,3] selenadiazol-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- dicyano, 1,
  • the p-type organic semiconductor compounds are substituted oligoacenes.
  • oligoacenes can, for example, be selected from the group consisting of pentacene, tetracene or anthracene, and their heterocyclic derivatives.
  • n-type semiconductor compounds examples include inorganic compounds and organic compounds.
  • the n-type semiconductor compound can for example be an inorganic semiconductor compound chosen from the group comprising zinc oxide (ZnO x) , zinc-tin oxide (ZTO), titanium oxide (TiO x) , molybdenum oxide (MoO x) , nickel oxide (NiO x) , cadmium selenide (CdSe) and mixtures of at least two of these compounds.
  • ZnO x zinc oxide
  • ZTO zinc-tin oxide
  • TiO x titanium oxide
  • MoO x molybdenum oxide
  • NiO x nickel oxide
  • CdSe cadmium selenide
  • the n-type semiconductor compound can, for example, be an organic compound chosen from the group consisting of graphene, fullerene, substituted fullerene and any mixture of at least two of these compounds.
  • suitable fullerenes and substituted fullerenes can be chosen from the group consisting of indene-C 6 o _ bisadduct such as ICBA, or methano-C 6 o fullerene derived from the acid methyl ester ( 6, 6) -phenyl-butyric acid, also known as "PCBM-C60" or "C60PCBM", as described for example in G. Yu, J. Gao, JC Hummelen, F. Wudl, AJ Heeger, Science 1995 , flight.
  • n-type semiconductor compounds are described in the publication by Zhang et al entitled “Nonfullerene Acceptor Molecules for Bulk Heteroj unction Organic Solar Cells” (Chemical Reviews, 2018 Apr 11; 118 (7): 3447- 3507. doi: 10.1021 / acs. Chemrev.7b00535. Epub 2018 Mar 20).
  • the p-type organic semiconductor compound is mixed with an n-type semiconductor such as a fullerene or a substituted fullerene, such as for example PCBM-C 60 , PCBM-C70, PCBM-Cei, PCBM-C 71 , bis-PCBM-C 6i , bis-PCBM-C 7i , ICMA-C60 (1% 4 '-dihydronaphto [2% 3': 1, 2] [5,6] fullerene-C 6 o), ICBA- C 6 cv OQDM-C 6O (1% 4 '-dihydronaphto [2', 3 ': 1, 9] [5, 6] fullerene-C 6 o _ lh), bis-oQDM-C 6 cv graphene or an oxide metallic, for example ZnO x , TiO x , ZTO, MoO x , NiO x or quantum dots for example in PbS, CdSe or
  • the present formulation comprises polymer particles, said polymer particles having a diameter of at most 2 ⁇ m.
  • said polymer particles have a diameter of at most 1.5 ⁇ m, more preferably at most 1.0 ⁇ m, or 0.9 ⁇ m, or 0.8 mpi, or 0.7 mpi, or 0.6 mpi, and even more preferably at most 0.5 mpi.
  • said polymer particles have a diameter of at least 10 nm, more preferably at least 15 nm and even more preferably at least 20 nm.
  • said polymer particles comprise a polymer which exhibits crosslinking, ie a polymer with a certain degree of crosslinking.
  • the polymer is suitable for forming a stable dispersion.
  • stable dispersion of polymer particles denotes a dispersion of polymer particles in the solvent (s) as defined above, said polymer particles remaining dispersed for at least 24 hours, from preferably for at least 48 hours after being dispersed in the solvent (s).
  • the polymer particles preferably comprise at least 50% by weight, or 60% by weight, or 70% by weight, or 80% by weight, or 90% by weight, or 95% by weight, or 97% by weight, or 99% by weight of a crosslinkable polymer relative to the total weight of the polymer particles, or preferably consists of such a crosslinkable polymer.
  • crosslinkable polymers that can be used in the present application can be for example chosen from the group consisting of polystyrene, polyacrylic acid, polytethacrylic acid, poly (methyl methacrylate), epoxy resins , polyesters, vinyl polymers, or any mixture of at least two of these compounds, of which polystyrene and polyacrylic acid are preferred, and polystyrene is most preferred.
  • the crosslinkable or already crosslinked polymers are generally known to those skilled in the art and can be obtained from commercial sources, such as, for example, from Spherotech Inc., Lake Forest, IL, USA or from Sigma-Aldrich.
  • the polymer included in the polymer particles has a number average molecular weight Mn (as determined, for example, by GPC) of at least 50,000 g / mol, preferably of at least 100,000 g / mol, more preferably at least 150,000 g / mol, and even more preferably at least 200,000 g / mol.
  • the polymer comprised in the polymer particles has a number average molecular weight Mn (as determined, for example, by GPC) of at most 2,000,000 g / mol, preferably of at most 1,500,000 g / mol, and more preferably at most 1,000,000 g / mol.
  • the polymer particles of the present invention are not soluble in the solvents included in the present formulation.
  • the formulation further comprises at least one conductive additive chosen from the group consisting of volatile compounds and / or not capable of reacting chemically with organic semiconductor materials (OSC).
  • OSC organic semiconductor materials
  • they are chosen from compounds which have no permanent doping effect on the OSC material (for example by oxidizing or by reacting chemically with the OSC material), or from volatile compounds, or both. Therefore, according to one embodiment, the formulation does not contain additives, such as, for example, oxidants or protonic or Lewis acids, which react with the OSC material to form ionic products.
  • the formulation does not contain additives which are not volatile and which cannot be removed from the solid OSC material after processing. If additives are used, capable of electrically doping the OSC material, such as carboxylic acids, they should preferably be chosen from volatile compounds so that they can be removed from the OSC film after its deposition.
  • conductive additives such as, for example, oxidants, Lewis acids, inorganic protic acids or non-volatile protic carboxylic acids.
  • the total concentration of these additives in the formulation should then preferably be less than 0.5%, more preferably less than 0.1%, even more preferably less than 0.01% by weight.
  • the formulation does not contain dopants selected from this group.
  • the conductive additives are chosen so as not to permanently boost the OSC, and / or they are removed from the OSC material after treatment (in which the treatment means consist for example of depositing the OSC material. OSC material on a substrate or to form a layer or film thereof) and / or they are present at a sufficiently low concentration to avoid a significant effect on the properties of the OSC material, caused for example by permanent doping. More preferably, the conductive additives are not chemically bonded to the OSC material or to the film or layer comprising it.
  • the preferred conductive additives are chosen from the group consisting of compounds which neither oxidize the OSC material nor react chemically with the OSC material.
  • the terms "oxidize” and “chemically react” used above and below refer to possible oxidation or further chemical reaction of the conductive additive with the OSC material under the conditions used for the manufacture, storage, transport and / or use of the formulation and the OE device.
  • volatile conductive additives are chosen from the group consisting of volatile compounds.
  • volatile as used in this specification means that the additive can be removed from the OSC material by evaporation, after the OSC material has been deposited on a substrate or an OE device, under conditions (such as temperature and / or reduced pressure) which does not significantly damage the OSC material or the OE device.
  • this means that the additive has a boiling point or a sublimation temperature of less than 300 ° C, more preferably greater than 135 ° C, even more preferably greater than 120 ° C, at the pressure used, very preferably at atmospheric pressure (1013 hPa). Evaporation can also be accelerated, for example by applying heat and / or reduced pressure.
  • the suitable and preferred conductive additives which do not oxidize or do not react chemically with the OSC material are chosen from the group consisting of soluble organic salts, such as for example permanent quaternary ammonium or phosphonium salts, Imidazolium or other heterocyclic salts, in which the anion is for example chosen from the group consisting of halides, sulphates, acetate, formate, tetrafluoroborate, hexafluorophosphate, methanesulphonate, triflate
  • tetraalkyl ammonium mixed tetraaryl ammonium or tetraalkylarylammonium ions
  • the alkyl or aryl groups may be the same or different from each other, in addition to heterocyclic ammonium salts (e.g. ionic liquids), protonated alkyl or aryl ammonium salts or other nitrogen-based salts such as dilauryl salts ammonium.
  • Other preferred conductive additives are selected from the group consisting of alkali metal salts such as bis (trifluoromethylsulfonyl) imide alkali metal salts or inorganic salts.
  • Very preferred organic salts are, for example, tetra-n-butylammonium chloride, tetraoctylammonium bromide, benzyltridecylammonium sulfate, benzene, diphenyl didodecylammonium hexafluorophosphate, N-methyl-N-trioctylammonium bis (triofluoryl )omethylsulfate imide or a mixture of at least two of these compounds.
  • Suitable and preferred volatile organic salts are, for example, ammonium acetates, formates, triflates or methanesulfonates, such as trimethylammonium acetate, triethylammonium acetate, dihexylammonium methanesulfonate, octylammonium formate, DBN ( 1, 5-diazabicyclo [4.3.0] non-5-ene) acetate or their mixtures or their precursors.
  • ammonium acetates formates, triflates or methanesulfonates, such as trimethylammonium acetate, triethylammonium acetate, dihexylammonium methanesulfonate, octylammonium formate, DBN ( 1, 5-diazabicyclo [4.3.0] non-5-ene) acetate or their mixtures or their precursors.
  • a preferred additive of this type is for example a mixture of tributylamine and trifluoroacetic acid, which yields tributylammonium trifluoroacetate in the formulation, or a mixture of a short chain trialkylamine (preferably with a boiling point below 200 ° C, more preferably less than 135 ° C) and a volatile organic acid (preferably with a boiling point greater than 200 ° C, more preferably greater than 135 ° C and a pKa value equal to or greater than the value of pKa of acetic acid).
  • Additional preferred conductive additives are alcohols, preferably volatile alcohols, volatile carboxylic acids and organic amines, preferably volatile organic amines, more preferably alkylamines.
  • Suitable and preferred alcohols or volatile alcohols are for example isopropyl alcohol, isobutanol (2-butanol), hexanol, methanol or ethanol
  • Suitable and preferred volatile carboxylic acids are for example those having a boiling point below 135 ° C, more preferably below 120 ° C (at atmospheric pressure), such as for example formic acid, acetic acid, di- or trifluoroacetic acid.
  • Other carboxylic acids such as propionic or higher acids, di- or trichloroacetic acid or methanesulfonic acid, are also acceptable and can be used if their concentration is chosen low enough to avoid significant doping of the OSC material, and is preferably greater than 0% and less than 0.5%, more preferably less than 0.25%, even more preferably less than 0.1% by weight.
  • Suitable and preferred organic amines or volatile organic amines are alkyl amines, for example primary or secondary alkyl amines, such as n-dibutylamine, ethanolamine or octylamine.
  • conductive additives which are not removed from the OSC material after the deposition of the OSC layer, such as eg. soluble organic salts or non-volatile alcohols or amines as mentioned above, some of these compounds can also have a permanent doping effect even if they do not oxidize or react with the OSC layer, for example example by trapping charges passing through the device. Therefore, the concentration of these additives should be kept low enough so that the performance of the device is not significantly affected.
  • the maximum tolerable concentration for each of these additives in the formulation can be chosen depending on its ability to continuously boost the OSC material.
  • conductive additives chosen from soluble organic salts their concentration in the formulation is preferably from 1 ppm to 2% by weight, more preferably from 50 ppm to 0.6% by weight, even more preferably from 50 ppm to 0.1% by weight.
  • conductive additives chosen from volatile organic salts their concentration in the formulation is preferably from 1 ppm to 2% by weight, more preferably from 50 ppm to 0.6% by weight, even more preferably from 50 ppm to 0.1% by weight.
  • conductive additives chosen from alcohols or volatile alcohols
  • their concentration in the formulation is preferably from 1% to 20%, more preferably from 2% to 20%, even more preferably from 5% to 10% by weight.
  • conductive additives chosen from volatile carboxylic acids
  • their concentration in the formulation is preferably 0.001% or more, more preferably 0.01% or more, and preferably 2% or less, more preferably 1% or less, even more preferably less than 0.5% (all the percentages being by weight).
  • conductive additives chosen from amines and volatile amines, their concentration in the formulation is preferably 0.001% or more, more preferably 0.01% or more, and preferably 2% or less, more preferably 1% or less, again more preferably less than 0.5% (all the percentages being by weight).
  • Conductive additives such as iodine and iodine compounds can also be used, such as for example IBr, iodine in the +3 oxidation state or other mild oxidants which can be removed from the solid OSC film, for example for example by heating and / or under vacuum at the drying stage, so as not to spike the solid film OSC.
  • these additives are preferably used in a concentration ranging from more than 0 to less than 0.5%, preferably less than 0.1%, more preferably less than 0.05% by weight.
  • the formulation comprises one to five conductive additives, more preferably one, two or three conductive additives, even more preferably a conductive additive.
  • the conductivity of the formulation of the present invention is preferably from 10 4 S / m to 10 10 S / m, more preferably from 10 5 S / m to 10 9 S / m, more preferably from 2 * 10 6 S / m to 10 9 S / m, more preferably from 10 7 S / m to 10 8 S / m.
  • the conductivity is determined using a parameter analyzer.
  • the sample to be tested is placed in a cell of known dimensions.
  • a cell constant is determined from these dimensions.
  • the analyzer is then used to record the current flowing as the voltage is swept from -1 V to 1 V or 0 V to 2 V, as appropriate.
  • the data recorded for a standard solution is ohmic In this case, the resistance can be learned by taking the gradient of this ohmic line. By dividing this resistance by the cell constant, we get the resistivity, the converse of which is the conductivity.
  • the solvent included in the formulation of the present description can be one or more non-aqueous solvents.
  • the solvent is an organic solvent or a mixture of two or more organic solvents.
  • the solvent used in the ink composition is preferably a solvent capable of uniformly dissolving or dispersing solid components in the ink composition.
  • solvents examples include chlorinated solvents such as chloroform, methylene chloride, 1, 2-dichloroethane, 1, 1, 2-trichloroethane, chlorobenzene and o-dichlorobenzene, based solvents.
  • ether such as tetrahydrofuran, methyltetrahydrofuran, dimethyltetrahydrofuran, dioxane and anisole
  • aromatic hydrocarbon solvents such as toluene, o-xylene, m-xylene, p-xylene, benzaldehyde, tetralin (1, 2, 3, 4-tetrahydronaphthaline) and 1, 3-dimethoxybenzene
  • aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, trimethylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane
  • ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, methylhexanone, benzophenone and acetophenone
  • ester solvents
  • the concentration of the p-type organic semiconductor material and the n-type semiconductor material in the formulation is between 0.1% and 10% by weight.
  • aromatic hydrocarbon solvents ether solvents, aliphatic hydrocarbon solvents, ester solvents and ketone solvents are preferred, as this confers good solubility, characteristics. viscosity and uniformity in film formation of the formulation.
  • 3-heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2-decanone, dicyclohexylcenone, acetophenone and benzophenone are preferred.
  • Two or more solvents are preferably used in combination, two or three solvents are preferably used in combination and two solvents are particularly preferably used in combination, because the film-forming properties and the characteristics of the device are improved.
  • the first solvent also called the main solvent
  • the second solvent also called co-solvent
  • the two solvents preferably dissolve 1% by weight or more of an aromatic polymer at 60 ° C and in particular one of the two solvents preferably dissolves 1% by weight or more of an aromatic polymer at 25 ° C, because good viscosity is obtained.
  • the first solvent is then preferably toluene, o-xylene, m-xylene, p-xylene, trimethylbenzene, tetralin, anisole, alkylanisoles, naphthalene, tetrahydronaphthalene, 1 ' alkylnaphthalene or a mixture of at least two of these solvents.
  • the second solvent is preferably acetophenone, dimethoxybenzene, benzyl benzoate, alkylnaphthalene or a mixture of at least two of these solvents.
  • the proportion of the solvent having the highest boiling point among the combined solvents is preferably from 1% to 30% by weight, more preferably from 2% to 20 % by weight, even more preferably from 2% to 15%, relative to the total weight of the solvents, since good viscosity and film-forming properties are obtained.
  • the concentration of the p-type organic semiconductor material is between 4 mg / mL and 25 mg / mL per mL of solvent.
  • the concentration of the p-type organic semiconductor material is less than 10% by weight of the solution.
  • the proportion between the p-type organic semiconductor material and the n-type organic semiconductor material ranges from 1: 1 to 1: 2 by weight.
  • the solvent In the case where a volatile additive is used, the solvent must be chosen so as to be able to be evaporated from the semiconductor layer comprising the semiconductor materials deposited at the same time as the additive, preferably during the same step of treatment.
  • the treatment temperature used to remove the solvent and the volatile additive must be chosen so as not to damage the semiconductor layer.
  • the deposition treatment temperature is between room temperature and 135 ° C and more preferably between 60 ° C and 110 ° C.
  • the present application further relates to a method for preparing a layer comprising a p-type organic semiconductor material and an n-type organic material as defined above.
  • FIG. 1 illustrates, in the form of a block diagram, an embodiment of a method of manufacturing such a layer.
  • Said method comprising the steps of a) providing a formulation comprising a p-type organic semiconductor material, an n-type organic material, at least one solvent and optionally additives, b) depositing the formulation on a substrate and c ) essentially removing the solvent.
  • step b) of the present process is carried out by spin coating or by coating.
  • Step c) can be carried out by heating the formulation once deposited, by placing the formulation in a chamber at sub-atmospheric pressure in order to carry out evaporation under vacuum, or by combining heating and evaporation under vacuum.
  • Steps b) and c) can be at least partially confused.
  • the solvent comprises a first solvent and a second solvent as described above
  • the heating temperature in step c) can be higher than the boiling point of the first solvent and lower than the boiling point of the second solvent.
  • the heating temperature in step c) may be lower than the boiling point of the first solvent and of the boiling point. of the second solvent. The first solvent, having the lower boiling point, will nevertheless evaporate faster than the second solvent.
  • Step c) can be carried out at atmospheric pressure or under vacuum.
  • essentially removing the solvent is used to indicate that at least 50% by weight, preferably at least 60% by weight or 70% by weight, more preferably at least 80% by weight, or 90% by weight, even more preferably at least 92% by weight, or 94% by weight, or 96% by weight, or 98% by weight, in particular at least 99% by weight, or at least 99.5% by weight of the solvent are removed, the percentage by weight being relative to the weight of the solvent in the formulation provided in step a).
  • the formulation used preferably has a viscosity at 20 ° C. of at least 1 mPa.s.
  • the solution has a viscosity at 20 ° C of at most 100 mPa.s, more preferably at most 50 mPa.s and even more preferably at most 30 mPa.s.
  • the solution used preferably has a viscosity of between 4 cPo (4 mPa.s) and 15 cPo (15 mPa.s).
  • the temperature for preparing the formulation, in particular in step a) is between 20 ° C and 90 ° C, preferably between 50 ° C and 70 ° C.
  • step a) for preparing the formulation comprises the mixture of powders corresponding to the p-type semiconductor organic material, to the n-type semiconductor organic material and optionally to additives (step a1), addition of solvent (step a2) and stirring and heating (step a3).
  • Step a1 can be carried out by mixing a powder of the p-type semiconductor organic material and a powder of the n-type semiconductor organic material.
  • the p-type semiconductor organic material is a polymer characterized by a target molecular weight and is obtained by mixing the polymer, for example in powder form, with a first molecular weight greater than the target molecular weight and the same polymer, for example in powder form, with a second molecular weight lower than the target molecular weight.
  • step a3 comprises heating the formulation for 3 h to 24 h, preferably for 6 h to 15 h.
  • the mixtures and formulations of polymers according to the present invention may further comprise one or more other components or additives chosen, for example, from surfactant compounds, lubricating agents, wetting agents, dispersing agents, hydrophobic agents, adhesive agents, flow improvers, defoamers, de-aerating agents, diluents reactive or not, dyes, pigments, stabilizers, nanoparticles or inhibitors.
  • surfactant compounds for example, from surfactant compounds, lubricating agents, wetting agents, dispersing agents, hydrophobic agents, adhesive agents, flow improvers, defoamers, de-aerating agents, diluents reactive or not, dyes, pigments, stabilizers, nanoparticles or inhibitors.
  • Step a) of manufacturing the formulation can comprise the storage (step a4) of the formulation obtained in step a3.
  • the manufacturing step a) further comprises a step a5 of heating the formulation prior to step b), for example from 30 min to 2 h , at a temperature between 50 ° C and 70 ° C, optionally with stirring, followed by a filtering step.
  • the filtering step is preferably carried out after the reheating step.
  • the filtering step can be carried out by passing the formulation through a filter.
  • the filter can be based on cellulose acetate, polytetrafluoroethylene (PFTE), poly (vinylidene fluoride) (PVDF), regenerated cellulose or glass fibers.
  • the pore size of the filter may be between 0.2 ⁇ m and 1 ⁇ m, preferably equal to about 0.45 ⁇ m.
  • the present application also relates to an optoelectronic device comprising a layer which comprises a p-type semiconductor organic material and an n-type semiconductor material as defined above.
  • the preferred devices are OPDs, OLEDs and OPVs.
  • OPDs devices OLEDs and OPVs
  • BHJ mass heterojunction OPD devices
  • the present OPV or OPD device may preferably comprise, between the active layer and the first or the second electrode, one or more additional buffer layers serving as hole transport layer and / or electron blocking layer, which comprise a material such as a metal oxide, such as for example ZTO, MoO x , NiO x , a conjugated polymer electrolyte, such as for example PEDOT: PSS, a conjugated polymer, such as for example polytriarylamine (PTAA), an organic compound, such as for example N, N '-diphenyl-N, N' -Bis (1-naphthyl ) (1, 1 '-biphenyl) - 4,4'-diamine (NPB), N, NT-diphenyl-N, N' - (3-methylphenyl) - 1, lT-biphenyl-4, 4T-diamine (TPD ), or else as a hole blocking layer and / or electron transport layer, comprising a material such as a metal
  • the polymer: fullerene ratio is from 1: 1 to 1: 2 by weight.
  • a polymeric binder can also be included, from 5% to 95% by weight. Examples of the binder include polystyrene (PS), polypropylene (PP), and polymethyl methacrylate (PMMA).
  • FIG. 2 is a partial and schematic sectional view of a first embodiment of an OPD device 10.
  • the device 10 comprises the following layers (in order from bottom to top): optionally a substrate 12; - An electrode 14 with high output work, preferably comprising a metal oxide, such as for example ITO, serving as anode;
  • a metal oxide such as for example ITO
  • a conductive polymer layer 16 or hole transport layer preferably comprising an organic polymer or a mixture of polymers, for example PEDOT: PSS (poly (3, 4-ethylenedioxythiophene): poly (styrene-sulfonate)) or TBD (N, N '-dyphenyl-NN' -bis (3-methylphenyl) -1, 1 'biphenyl- 4, 4' -diamine) or NBD (N, N '-dyphenyl-NN' Bis (1-naphthylphenyl) - 1,4 'biphenyl-4,4' -diamine);
  • PEDOT PSS (poly (3, 4-ethylenedioxythiophene): poly (styrene-sulfonate)) or TBD (N, N '-dyphenyl-NN' -bis (3-methylphenyl) -1, 1 'biphenyl- 4, 4' -diamine)
  • a layer 20 having electron transport properties comprising for example LiF
  • an electrode 22 with low output work preferably comprising a metal such as for example aluminum, serving as cathode,
  • At least one of the electrodes preferably the anode, is transparent to visible light.
  • a second embodiment corresponding to a preferred OPD device according to the invention is an inverted OPD device and comprises the following layers (from bottom to top):
  • a metal or metal oxide electrode with high output work comprising for example ITO, serving as cathode; a layer having hole blocking properties, preferably comprising a metal oxide such as TiO x , ZnO x , PEI, PEIE;
  • an active layer comprising a p-type and n-type organic semiconductor, located between the electrodes, which may exist for example in the form of a p-type / n-type bilayer or in the form of separate p-type and n-type layers , or in the form of a mixture or of p-type and n-type semiconductors, forming a BHJ;
  • a conductive polymer layer or a hole transport layer preferably comprising an organic polymer or mixture of polymers, for example PEDOT: PSS, or TBD, or NBD; and
  • an electrode comprising a metal with high output work such as, for example, silver, serving as an anode
  • At least one of the electrodes preferably the cathode, is transparent to visible light.
  • the materials according to the invention can be used in OLEDs, for example as an active display material in flat panel display applications, or as backlighting for a screen display. flat, such as a liquid crystal display.
  • OLEDs are made using multi-layered structures.
  • An emission layer is generally sandwiched between one or more electron transport and / or hole transport layers. By applying an electric voltage, the electrons and the holes as charge carriers move towards the emission layer where their recombination leads to the excitation and therefore to the luminescence of the phosphor units contained in the emission layer.
  • the compounds, materials and films of the invention can be used in the emission layer, corresponding to their electrical and / or optical properties. In addition, their use in the emission layer is particularly advantageous if the compounds, materials and films according to the invention themselves exhibit electroluminescent properties or comprise electroluminescent groups or compounds.
  • the materials according to this invention in particular those exhibiting photoluminescent properties, can be used as materials for light sources, for example in display devices, as described in documents EP 0 889,350 or by C. Weder et al., Science, 1998, 279, 835-837.
  • Formulations have been produced.
  • a p-type polymer which may include thiophene and aryl type structural units and as described in US Pat. No. 9,601,695, was used.
  • a first solution was carried out.
  • a powder of the p- type polymer was mixed with a powder of PC ⁇ O BM.
  • First and second solvents were added to the powder mixture.
  • the first solvent was o-xylene.
  • the proportion of the first solvent was 97% by weight relative to the total weight of the first and second solvents.
  • the second solvent was acetophenone.
  • the proportion of the second solvent was of 3% by weight relative to the total weight of the first and second solvents.
  • the concentration of the polymer in the solution was approximately 6 g / L.
  • the concentration of PC O BM in the solution was about 12 g / L.
  • the viscosity of the first solution was measured and was equal to approximately 5 cPo
  • a layer of the first solution was deposited by coating
  • a second solution was carried out.
  • a powder of the p- type polymer was mixed with a powder of PC ⁇ O BM.
  • a solvent was added to the powder mixture.
  • the solvent was 1, 2, 3, 4-tetrahydronaphthalene.
  • the concentration of the polymer in the solution was about 10 g / L.
  • the concentration of PC O BM in the solution was about 20 g / L.
  • the viscosity of the second solution was measured and was about 10 cP.
  • a layer of the second solution was deposited by coating.
  • a third solution was carried out.
  • a powder of the p- type polymer was mixed with a powder of PC ⁇ O BM.
  • First and second solvents were added to the powder mixture.
  • the first solvent was 1, 2, 4-trimethylbenzene.
  • the proportion of the first solvent was 90% by weight relative to the total weight of the first and second solvents.
  • the second solvent was 1, 3-dimethoxybenzene.
  • the proportion of the second solvent was 10% by weight relative to the total weight of the first and second solvents.
  • the concentration of the polymer in the solution was approximately 15 g / L.
  • the concentration of PC O BM in the solution was approximately 26.25 g / L.
  • the viscosity of the first solution was measured and was equal to about 8 cPo (8 mPa.s).

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EP20733629.8A 2019-06-24 2020-06-22 Formulierung aus einem organischen halbleitermaterial vom typ p und einem halbleitermaterial vom typ n Pending EP3987588A1 (de)

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FR1906822A FR3097686B1 (fr) 2019-06-24 2019-06-24 Formulation comprenant un matériau semiconducteur organique de type p et un matériau semiconducteur de type n
PCT/EP2020/067381 WO2020260214A1 (fr) 2019-06-24 2020-06-22 Formulation comprenant un materiau semiconducteur organique de type p et un materiau semiconducteur de type n

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