WO2016126209A1 - Matériaux polymériques conducteurs électriques à dopage de type p pour couches d'injection de trous et d'extraction de trous - Google Patents

Matériaux polymériques conducteurs électriques à dopage de type p pour couches d'injection de trous et d'extraction de trous Download PDF

Info

Publication number
WO2016126209A1
WO2016126209A1 PCT/SG2016/050058 SG2016050058W WO2016126209A1 WO 2016126209 A1 WO2016126209 A1 WO 2016126209A1 SG 2016050058 W SG2016050058 W SG 2016050058W WO 2016126209 A1 WO2016126209 A1 WO 2016126209A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
oligomer
doped
diyl
phenyl
Prior art date
Application number
PCT/SG2016/050058
Other languages
English (en)
Inventor
Lay-Lay Chua
Kian-Hoon Peter Ho
Rui-Qi Png
Chun-Yi Mervin ANG
Kim Kian Choo
Guan-Yu Cindy TANG
Original Assignee
National University Of Singapore
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by National University Of Singapore filed Critical National University Of Singapore
Publication of WO2016126209A1 publication Critical patent/WO2016126209A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • 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
    • H10K71/30—Doping active layers, e.g. electron transporting layers
    • 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
    • H10K85/115—Polyfluorene; Derivatives thereof
    • 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
    • H10K85/151—Copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/124—Copolymers alternating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/145—Side-chains containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/145—Side-chains containing sulfur
    • C08G2261/1452—Side-chains containing sulfur containing sulfonyl or sulfonate-groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/146—Side-chains containing halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
    • C08G2261/3162—Arylamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C08G2261/512—Hole transport
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/59—Stability
    • C08G2261/592—Stability against heat
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/79—Post-treatment doping
    • C08G2261/792—Post-treatment doping with low-molecular weight dopants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/92—TFT applications
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/30—Devices controlled by radiation
    • 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]
    • H10K50/17—Carrier injection layers

Definitions

  • p-Doped electrically conductive polymers are ⁇ -conjugated organic polymers that have been p-doped to an electrically conductive state. This is achieved using a p-dopant, which is a strong oxidant or a strong acid, to introduce mobile positive charges, called holes, into the conjugated segments of the polymer. These holes need to be counterbalanced by anions in the material, called "counter- anions". Because the holes are charged and are mobile, the material is capable of conducting electricity, often having an electrical conductivity between 10 ⁇ 6 to 10 2 Scm -1 .
  • Some p-doped polymers can be processed from solution into layers which have an ability to also inject holes into and extract holes from some semiconductors.
  • the layers performing these functions are called hole-injection layers (HILs) and hole-extraction layers (HELs) respectively.
  • the semiconductors may be an organic material, or an inorganic material including, for example, quantum dots, nanowires, fullerenes, carbon nanotubes, graphene, 2D materials and soft inorganic crystals for example perovskites.
  • the resultant semiconductor devices include, for example, diodes, light-emitting diodes, field-effect transistors and solar cells.
  • the workfunction of the HIL and HEL plays a key role in determining its efficiency for hole injection and extraction respectively.
  • the workfunction (WF) is the difference in energy between the Fermi level and the vacuum level of the material. Workfunctions larger than about 5.0 eV are referred to as "high"
  • the contact between the HIL and the semiconductor layer should have a low hole-injection resistance.
  • An ideal hole contact would have negligible hole-injection resistance compared to the resistance in the bulk of the
  • Such a contact is called an ohmic hole contact.
  • Forming ohmic contacts is crucial to achieving high device efficiency and reliability, and is thus a fundamental objective in device technology.
  • the HIL needs to be able to inject the required high density of holes into the semiconductor layer, so that the applied voltage is used primarily to transport them across the bulk of the semiconductor. This often requires the HIL to have a sufficiently large WF that approaches or exceeds the ionization potential (I p ) of the semiconductor. In contrast, a non-ohmic hole contact demands a significant electric field to inject holes across the interface. This not only lowers device efficiency, but also degrades device reliability and stability. Similar considerations also apply to the hole-extraction contact.
  • the counter-anions should preferably be immobilized within the HIL (or HEL) so that they cannot diffuse into the adjacent semiconductor layer. If the counter- anions can migrate through the semiconductor, the holes would also migrate, and this would degrade the hole-doping profile, which is the variation of hole density with location in the semiconductor. Stability of the doping profiles correlates to the stability of the device characteristics. The doping profile should not degrade during processing, storage and operation of the device.
  • the present invention is concerned with providing a new class of p-doped polymers. More specifically, the present invention is concerned with providing design and strategy for achieving p-doped materials with high workfunctions greater than about 5.0 eV, preferably ultrahigh WFs greater than about 5.2 eV, and up to about 6.2 eV.
  • the present invention provides a class of p-doped materials comprising triarylaminium moieties and covalently-attached counter-anions, and optionally further comprising one or more noncovalently attached cations, and their undoped precursors, that can give the desired high workfunction, electrical, processing and stability characteristics.
  • These materials can provide ohmic hole injection and extraction contacts to semiconductor materials with deeper I p (i.e., I p greater than about 5.0 eV) than previously possible, up to the workfunction of the p-doped material. Furthermore, they are sufficiently stable under ambient conditions for processing devices.
  • the invention provides a material comprising a p-doped electrically-conductive polymer or oligomer comprising one or more triarylaminium moieties, and one or more counter-anions covalently bonded to said polymer or oligomer, or to a second polymer or oligomer, wherein the one or more triarylaminium moieties optionally comprises one or more heteroatoms, and wherein the polymer is p-doped to a density of about 0.1 to about 1 hole per triarylamine moiety, and the polymer is capable of forming a film having a workf unction of from about 5.0 eV to about 6.2 eV.
  • the triarylaminium moieties form a fully conjugated polymer, a partially conjugated polymer, or pendant groups on a polymer.
  • the triarylamine moieties prior to doping, are selected from optionally substituted N,N-diphenyl(N-phenyl)amine-4,4'-diyl, optionally substituted 9-phenylcarbazole-3,6-diyl, optionally substituted 9- phenylphenoxazine-3,7-diyl, optionally substituted 10-phenylphenothiazine-5-oxide-3,7-diyl, optionally substituted N,N'-diphenylene(N,N'-diphenyl)-l,4-phenylenediamine, or optionally substituted N,N'-diphenylene(N,N'-diphenyl)4,4'-diphenylenediamine, wherein substitutions are one or more selected from hydrogen, alkyl, cycloalkyl, phenyl, substituted phenyl, alkoxy, phenoxy, substituted phenoxy,
  • one or more co-monomers of the polymer or oligomer comprise fluorene, indenofluorene, phenylene, arylene vinylene, thiophene, azole, quinoxaline, benzothiadiazole, oxadiazole, thiophene, arylamine or bisphenol-A; or optionally substituted fluorene, indenofluorene, phenylene, arylene vinylene, thiophene, azole, quinoxaline, benzothiadiazole, oxadiazole, thiophene, arylamine or bisphenol-A.
  • the counter-anions are selected from sulfonate, fluoroalkylsulfonate, trifluoromethylsulfonylimide, fluoroalkylsulfonylimide, carboxylate, fluoroalkylcarboxylate, phosphonate, fluoroalkylphosphonate, phosphate, sulfate, or a combination thereof.
  • These can be covalently attached to the triarylamine polymer or oligomer, on the triarylamine moieties or the co-monomer moieties; or on a second polymer or oligomer optionally comprising one or more triarylaminium moieties.
  • the material further comprises one or more non-covalently attached cations, wherein the cations are selected from Li + , Na + , K + , Cs + , NH 4 + , R 4 N + where R is Ci-Ci 2 alkyl or phenyl, R 3 S + where R is Ci-Ci 2 alkyl or phenyl, R tP "1" where R is Ci-Ci 2 alkyl or phenyl, or an aromatic heterocycle-containing cation.
  • the aromatic heterocycle cations are preferably selected from pyridinium, imidazolium, pyrrolium or pyrylium.
  • the polymer or oligomer, prior to doping is selected from
  • n is at least 5, preferably at least 10; where m is at least 5, preferably at least 10; where M + are non-covalently attached cations.
  • the holes are fully self-compensated by the covalently-bonded counter- anions .
  • the material may possess any one or more of the following characteristics: (i) the undoped precursor has p-dopable ⁇ - conjugated segments that have I p larger than about 5.0 eV and up to about 6.2 eV; (ii) the material is p-doped to an electrically-conductive state with electrical conductivity greater than about 10 ⁇ 5 S cm -1 to provide sufficient conductance across the layer thickness and WF greater than about 5.0 eV; (iii) counter-anions to charge-balance the holes are covalently bonded to the triarylaminium polymer or oligomer, or a second polymer or oligomer; (iv) the material has non-covalently attached cations which can be selected to give the desired solvent processability characteristics; and/or (v) the material has suitable solvent processing characteristics compatible with the presence of underlying layers, and with the deposition of overlayers, so that layers of these materials can be fabricated into devices.
  • the material may be obtained from one or more of the following steps: (i) the undoped precursor is doped using a strong oxidant, and the oxidant by-product subsequently removed from the material so that the holes are counter-balanced by the bonded anions; (ii) the undoped precursor is pre-doped in solution and purified to give processable p-doped solutions wherein the holes are substantially counter-balanced by the bonded anions; (iii) the undoped precursor is post-doped after film-formation and purified to give the final p-doped state in which the holes are substantially counter-balanced by the bonded anions.
  • the invention provides a composition comprising the material of the first aspect and a polymer diluent.
  • the invention provides a method of making the material of the first aspect, the method comprising p-doping a polymer or oligomer with a p-dopant, followed by removing excess ions via a solvent, wherein the p-dopant is a one-electron oxidant with a formal oxidation potential larger than about 0.8 V.
  • the invention provides a layer comprising a p-doped electrically-conductive polymer or oligomer comprising one or more triarylaminium moieties, wherein the polymer or oligomer is in the form of a layer, and one or more counter- anions covalently bonded to said polymer or oligomer, or to a second polymer or oligomer, wherein the workfunction of the layer is from about 5.0 eV to about 6.2 eV.
  • the invention provides a layer comprising a p-doped electrically- conductive polymer or oligomer comprising one or more triarylaminium moieties, wherein the polymer or oligomer is in the form of a layer, and one or more counter-anions covalently bonded to said polymer or oligomer or to a second polymer or oligomer, wherein the layer is capable of hole-injection into or hole-extraction from a semiconductor having a ionization potential of at least about 5.0 eV, and preferably at least about 5.2 eV.
  • the holes are fully self-compensated by the covalently-bonded counter-anions .
  • the invention provides a method of fabricating the layers of the fourth and/or fifth aspect, the method comprising depositing a solution of the p-doped polymer or oligomer, or depositing a solution of the undoped polymer or oligomer, to form a layer, followed by p-doping with a p-dopant, and removing excess ions.
  • the invention provides a device comprising the layers of the fourth and/or fifth aspect.
  • FIG. 1 shows UV-Vis-NIR spectra of undoped mTFF-F3S0 3 Na (dotted line) and self-compensated p-doped mTFF-F3S0 3 Na (solid line).
  • FIG. 2 shows I-V characteristics of OLED pixels with device geometry of ITO/ HIL/ 86 nm 9,9-dioctylfluorene/ 120 nm Al, using a self-compensated /?-doped HIL produced according to the present invention illustrated in Example 4a.
  • FIG. 3 shows I-V characteristics of OLED pixels with device geometry of ITO/ HIL/ 86 nm F9,9-dioctylfluorene/ 120 nm Al, using a prior art HIL (PEDT:PSSH).
  • FIG. 4 shows I-V characteristics of an OLED pixel with device geometry of ITO/ HIL/ 80 nm 9,9-bis(p-octylphenyl) fluorene/ 120 nm Ag, using a self-compensated /?-doped HIL produced according to the present invention illustrated in Example 4d.
  • FIG. 5 shows I-V characteristics of an OLED pixel with device geometry of ITO/ HIL/ 80 nm 9,9-bis(p-octylphenyl) fluorene/ 120 nm Ag, using different HILs, including a prior art HIL (PEDT:PSSH) and a self-compensated /?-doped HIL produced according to the present invention illustrated in Example 4e.
  • HILs including a prior art HIL (PEDT:PSSH) and a self-compensated /?-doped HIL produced according to the present invention illustrated in Example 4e.
  • FIG. 6 shows a schematic of an organic field effect transistor with a monolayer of self-compensated /?-doped HIL assembled on the Au electrode, produced according to the present invention illustrated in Example 4h.
  • FIG. 7 shows the transfer characteristics of the transistors based on a prior art structure and a structure with a self-compensated /?-doped HIL. Drain voltage is stepped from 0 to -20 V in -2.5 V steps.
  • Scheme la depicts synthesis of an alternating copolymer of N,N-diphenyl(N-(m- trifluoromethyl)phenyl)amine-4,4'-diyl and disodium 9,9-bis(3-sulfonatopropyl)fluorene-2,7- diyl (mTFF- F3S0 3 Na).
  • Scheme lb depicts synthesis of an alternating copolymer of N,N-diphenyl(N-(p- sec-butyl)phenyl)amine-4,4'-diyl and disodium 9,9-bis(3-sulfonatopropyl)fluorene-2,7-diyl (TFB-F3S0 3 Na).
  • Scheme lc depicts synthesis of an alternating copolymer of N,N-diphenyl(N-(p- sec-butyl)phenyl)amine-4,4'-diyl and bis(tetramethyammonium) 9,9-bis(3- sulfonatopropyl)fluorene-2,7-diyl (TFB -F3 S 0 3 TMA) .
  • Scheme Id depicts synthesis of an alternating copolymer of N,N-diphenyl(N-(p- methoxy)phenyl)amine-4,4'-diyl and disodium 9,9-bis(3-sulfonatopropyl)fluorene-2,7-diyl (TFOMe-F3S0 3 Na).
  • Scheme le depicts synthesis of an alternating copolymer of N,N-diphenyl(N- phenyl)amine-4,4'-diyl with different substituents on the pendant N-phenyl ring and disodium 9,9-bis(3-sulfonatotetrafluoroethyl)fluorene-2,7-diyl (TAAx-F2fS0 3 Na).
  • Scheme lg depicts synthesis of an alternating copolymer of N,N-diphenyl(N-(m- trifluoromethyl)phenyl)amine-4,4'-diyl and dicesium 9,9-bis(3- trifluoromethanesulfonylimidopropyl)fluorene-2,7-diyl (mTFF-F3TFSICs).
  • the present invention is concerned with providing a new class of p-doped polymers. More specifically, the present invention is concerned with providing design and strategy for achieving p-doped materials with high workfunctions greater than about 5.0 eV, preferably ultrahigh workfunctions greater than about 5.2 eV, and up to about 6.2 eV.
  • the present invention provides high workfunction p-doped electrically-conductive materials comprising triarylaminium moieties with covalently-attached counter- anions, and their undoped precursors.
  • the IUPAC name for aminium (common name) is ammoniumyl.
  • the common name aminium will be used throughout this document.
  • the materials comprise polymers and/or oligomers. Polymers are macromolecules of relatively high molecular weights of more than 5 kDa, with typically more than ten identical or dissimilar monomer units bonded together. Oligomers are macromolecules of relatively low molecular weights of 5 kDa or less, with typically at least two and up to ten identical or dissimilar monomer units bonded together.
  • the materials are p-doped to give holes on the triarylaminium moieties. These materials are surprisingly stable in the p-doped state even for ultrahigh workfunctions between about 5.2 and about 6.2 eV, where oxidation of water becomes thermodynamically favorable.
  • These holes are furthermore counterbalanced by anions covalently-bonded to the material.
  • the counter- anion may be bonded to the polymer and/ or oligomer containing the triarylaminium units, or may be bonded to another polymer and/or oligomer provided specifically for the counter- anions.
  • the bonded counter-anions have severely restricted diffusion, which limits the possibility for degradation or scrambling of the desired doping profile during processing, storage and device operation. This stabilizes its hole- injection and extraction characteristics.
  • the bonded counter-anions are present in excess, wherein the excess is counter-balanced by one or a plurality of associated but non-bonded cations, which are referred to as spectator cations.
  • the material comprises the p-doped electrically-conductive material with bonded counter-anions and one or a plurality of non- bonded spectator cations.
  • the incorporation of spectator cations may be advantageous to modify the solvent processing (e.g., solubility and viscosity) characteristics of the material.
  • non-bonded spectator cations does not result in instability of the doping profile unlike the case with non-bonded counter-anions. This is because the non- bonded anions can diffuse or migrate together with the holes as neutral entities, thereby facilitating hole transfer to an adjacent undoped region, whereas the non-bonded cations cannot diffuse or migrate together with the holes as neutral entities.
  • one or a plurality of polymer diluents may be advantageously incorporated to give a composition that comprises the p-doped electrically-conductive material with bonded counter-anions and optionally with one or a plurality of non-bonded spectator cations, and one or a plurality of polymer diluents.
  • the incorporation of polymer diluents may be advantageous to modify the hole density, injection characteristics and absorption characteristics of the composition.
  • a strong oxidant also called p-dopant
  • an ion removal process is applied to remove excess ion pairs and enforce self-compensation.
  • These two steps may be performed on the undoped precursor material in solution to generate the self-compensated p-doped material in solution. This is called solution-state doping method.
  • the p-doped materials can then be deposited and patterned on the desired substrate by spin-casting, inkjet printing, doctor blading, self-assembly or other suitable methods.
  • the two steps may be performed on films of the undoped precursor material that has been deposited and patterned on the substrate by a suitable method described above, including a layer-by-layer polyelectrolyte assembly.
  • a layer-by-layer polyelectrolyte assembly a polycation and polyanion are alternately assembled by adsorption on the substrate to build the film.
  • a photolithography patterning method may be used.
  • the film may contain photocrosslinkable moieties which are activated by light illuminated through a mask to pattern the film.
  • the film may be patterned by etching or dissolving away areas exposed by a photoresist mask layer that has first been fabricated on the film. The film is then exposed to the p-dopant in solution and then to a suitable pure solvent to accomplish the ion-removal step. This is called film-state doping method.
  • the undoped precursor material comprises triarylamine units. These moieties may be a part of the polymer backbone or may be present as a pendant unit attached to a polymer backbone.
  • polymer structure If the triarylamine moiety is part of the polymer backbone, it may form a fully-conjugated polymer optionally with other repeating units. These include oxygen, sulphur, aromatic, and/or heteroaromatic units, such as fluorene, indenofluorene, phenylene, arylene vinylene, thiophene, azole, quinoxaline, benzothiadiazole, oxadiazole, thiophene, and arylamine.
  • oxygen, sulphur, aromatic, and/or heteroaromatic units such as fluorene, indenofluorene, phenylene, arylene vinylene, thiophene, azole, quinoxaline, benzothiadiazole, oxadiazole, thiophene, and arylamine.
  • An example of a fully-conjugated copolymer formed with another repeating unit is the polymer represented by the two repeating units N,N-diphenyl(N- phenyl)amine-4,4'-diyl and 9,9-dialkylfluorene-2,7-diyl.
  • the triarylamine moiety may form a partly-conjugated polymer that is interrupted along its backbone by non-conjugating units.
  • Such units include bisphenol-A, methacrylate, siloxane, and meta-linked benzene.
  • An example of a partly-conjugated polymer copolymer is the polymer formed by the two repeating units N,N-diphenyl(N- phenyl) amine-4,4'-diyl and bisphenol-A.
  • the triarylamine moiety could be a pendant group attached to a polymer backbone.
  • polymer backbones include poly(methacrylate), and vinyl polymers. The choice is determined by the desired, molecular packing, processing characteristics and the electronic levels of the material, in particular its I p .
  • the polymer molecular weight can be about 8 kDa to about 200 kDa, and more preferably about 30 kDa to about 200 kDa.
  • Triarylamine moiety refers to a trivalent amine unit that is trisubstituted with three identical or dissimilar aromatic units. These units may not be linked other than through the nitrogen atom, as exemplified by the prototype N,N- diphenyl(N-phenyl)amine-4,4'-diyl. Optionally, these units may be linked, as exemplified by the prototype 9-phenylcarbazole-3,6-diyl. Linking the units will planarize a portion of the moiety, and beneficially improve stability during device operation, and alter the I p of the resultant material.
  • Aromatic units may contain only carbon atoms in the molecular framework. Optionally, they may also contain heteroatoms including oxygen, nitrogen or sulfur or other atoms, as exemplified by the prototypes 9-phenylphenoxazine-3,7- diyl and 10-phenylphenothiazine-5-oxide-3,7-diyl. Heteroatoms may beneficially reduce the chemical reactivity of the rings, the stability during device operation, and I p of the resultant material.
  • the triarylamine moiety may also be in the form of "dimers” and higher multimers, as exemplified by the prototypes N,N-diphenylene(N,N'-diphenyl)-l,4- phenylenediamine and N,N'-diphenylene(N,N'-diphenyl)4,4'-diphenylenediamine moieties.
  • dimers and higher multimers may beneficially reduce the chemical reactivity of the rings, improve stability during device operation, and alter the I p of the resultant material.
  • aromatic units could bear one or more substitutions in place of hydrogen, for example alkyl, cycloalkyl, phenyl and substituted phenyl groups to improve processability for intended application; alkoxy, phenoxy or substituted phenoxy groups to improve processability and downshift I p ; alkylthio, phenylthio or substituted phenylthio groups to improve processability and downshift I p ; fluorine, cyano, nitro, alkylketo, trichloromethyl or trifluoromethyl groups to improve processability and upshift I p .
  • substitutions in place of hydrogen for example alkyl, cycloalkyl, phenyl and substituted phenyl groups to improve processability for intended application; alkoxy, phenoxy or substituted phenoxy groups to improve processability and downshift I p ; alkylthio, phenylthio or substituted phenylthio groups to improve processability and downshift I p ; fluorine,
  • the I p of the undoped precursor material could be varied between about 4.8 eV and about 6.5 eV, preferably between about 5.0 and about 6.2 eV, more preferably between about 5.2 and about 6.2 eV.
  • the alkyl part can comprise 1 to 10 carbons atoms.
  • Examples of straight-chain and branched-chain alkyl groups having 1-4 carbon atoms are methyl, ethyl, n-propyl, iso- propyl, n-butyl, and t-butyl.
  • Substitutions in particular at the p-position may be beneficial to block undesired reactivity when the polymer is p-doped.
  • the I p of the material can be tuned between about 4.8 eV and about 6.5 eV, preferably between about 5.0 and about 6.2 eV, more preferably between about 5.2 eV to about 6.2 eV, as illustrated here with two families of materials.
  • the I p values of polymers for the following substitutions on the N-phenyl ring are: p- methoxy 5.3 eV, p-sec-butyl 5.5 eV, m-trifluoromethyl 5.8 eV, p-trifluoromethyl 6.3 eV.
  • the workfunctions obtained for the corresponding heavily-p-doped polymer with 0.8 holes per repeat unit is 5.2 eV, 5.5 eV, 5.7 eV and 5.8 eV respectively, using hexafluoroantimonate as a model counter- anion.
  • a larger model counter-anion, tetrakis( 1,3,5- trifluromethylbenzene)borate the corresponding workfunction increases by 0.3 eV to reach 6.1 eV for the last mentioned polymer.
  • a larger anion or an anion spaced further away from the hole tends to increase workfunction.
  • the I p values of polymers for the following substitutions on the N-phenyl ring are: p-sec-butyl 5.5 eV, m-trifluoromethyl 6.1 eV, p-trifluoromethyl 6.4 eV.
  • the workfunctions obtained for the corresponding heavily- p-doped polymer with 0.8 holes per repeat unit is 5.5 eV, 5.8 eV and 6.0 eV respectively, using tetrakis(l,3,5-trifluoromethylbenzene)borate as model counter-anion.
  • the workfunction of the doped material depends on I p of the undoped precursor material, it depends in addition on the doping level, the counter-anion and any spectator cation present.
  • the workfunction of the p-doped material increases greatly with doping level.
  • the regime of strong doping for example from about 0.2 holes to about 1 hole per amine repeat unit, it increases only slightly with doping level.
  • the trend in the workfunction of a heavily-p-doped polymer can be controlled through the energy of the singly occupied molecular orbital that is influenced by the I p of the polymer, although it is additionally influenced by counter-anion, and spectator cation if any.
  • the I p can be measured by ultraviolet photoemission spectroscopy following standard procedures of measuring the kinetic energies at the Fermi level and the low-energy cutoff of the sample to determine the vacuum level, and then extrapolating the photoemission onset to define the I p , as described for example in: Hwang J.H., Wan A., Kahn A. Mater. Sci. Eng. R 64 (2009) pp.1. All ionization potentials and workfunctions in this document were measured this way.
  • Other ways to measure I p includes cyclic voltammetry, which may be complicated by counter-ion effects, and an ambient photoemission technique often called AC2.
  • the electrical conductivity can be measured by standard four-probe force-sense measurements.
  • the suitability of the doping level used in the HIL/ HEL can be directly assessed in the device configuration by capacitance-voltage measurements as a function of dc bias and frequency.
  • the capacitance is preferably constant up to 10 MHz and substantially independent of bias between -3 and +3 V.
  • ohmicity of contact The extent to which an ohmic hole contact is achieved can be evaluated from the current-voltage characteristics of a set of hole-only diodes fabricated with the HIL/ HEL, and then modelling the characteristics to determine whether the current is space-charge-limited and/or to determine the hole density at the contact.
  • An ohmic contact is one that is substantially ohmic, yielding a current density preferably at least one-third of the expected space-charge-limited current density. Usually such an ohmic contact has a hole density of at least 2x10 11 holes per cm 2.
  • a non-ohmic contact may yield current density less than one-tenth of the expected space-charge-limited current density.
  • the covalently-bonded anion is one or a plurality selected from the group of anions well known in organic chemistry. Examples include sulfonate, fluoroalkylsulfonate, trifluoromethylsulfonylimide, fluoroalkylsulfonylimide, carboxylate, fluoroalkylcarboxylate, and phosphonate, fluoroalkylphosphonates, sulfate, phosphate.
  • the anion is more preferably selected from the group of weakly nucleophilic anions. Examples include sulfonate, fluoroalkylsulfonate, trifluoromethylsulfonylimide, fluoroalkylsulfonylimide,
  • fluoroalkylcarboxylate phosphonate, fluoroalkylphosphonates, sulfate, phosphate and a combination thereof.
  • Oxidative stability The anion needs to have good oxidative stability. Oxidative stability is the ability of the said chemical moiety to resist electrochemical oxidation. This can be assessed by the electrode potential for oxidation of the chemical moiety. The anion should not undergo electrochemical oxidation up to an electrode potential of 2 V vs standard hydrogen electrode (SHE). For good oxidative stability, the anion should preferably be hydrophobic to avoid physisorption of water.
  • the anion preferably has low nucleophilicity.
  • Nucleophilicity is the tendency of the said chemical moiety to take part in nucleophilic (i.e., formal electron pair donation) reactions. This can be inferred from the rate of nucleophilic reactions on model targets, such as Malachite, tropylium, benzhydrylium or other aromatic carbocations. See for example: March's Advanced Organic Chemistry: Reactions,
  • the anions preferably are of similar or lower
  • nucleophilicity as compared to sulfonate or phosphonate.
  • the anions preferably are derived from acids with similar or more negative pKa values less than -1 in 1,2-dichloroethane.
  • a suitable anion is a sulfonate covalently bonded to a polymer or through a (Ci-C 8 )-alkyl or (Ci-C 8 )-perfluoroalkyl chain, a phosphonate bonded to a polymer or through a (Ci-C 8 )-alkyl or (Ci-C 8 )-perfluoroalkyl chain, or a carboxylate bonded to a polymer through a (Ci-C 8 )-perfluoroalkyl chain.
  • Anion attachment The anion is covalently attached to a material directly or through a short spacer chain, such as an alkyl chain, i.e., -(CH 2 ) X - where x is 1-8, preferably 2-4; a perfluoroalkyl chain, e.g., -(CF 2 ) X - where x is 1-8, preferably 2-4; an alkoxy chain - (OCH 2 CH 2 ) x -, where x is 1-3, preferably 1-2; or a perfluoro alkoxy chain -(OCF 2 CF 2 ) x -, where x is 1-3, preferably 1-2.
  • the material may be the one that contains the triarylamine moiety, or a separate polymer provided by the purpose of attaching the anion. Examples of such a polymer include vinyl polymers, such as polystyrenesulfonate.
  • side chains can be, for example, alkyl, perfluoroalkyl or alkoxyl; or optionally substituted alkyl, perfluoroalkyl or alkoxyl, wherein the substituent is a polar group such as alkoxy, phenoxy, cyano, alkylketo, alkoxycarbonyl, or alkoxycarbonyloxy.
  • the p- doped material is not fully self -compensated. This means that free anions need to be present.
  • the holes in the self-compensated p-doped material cannot significantly diffuse or migrate through the material. This is because all the counter-anions are immobilized. There are no other excess anions that can diffuse or migrate together with the holes. Without hereby being limited by theory, this is key to achieving a stable doping level that does not degrade during processing, storage or device operation.
  • the spectator ions can advantageously be employed to impart solvent processability to the undoped precursor material. This may be beneficial for solution- state doping.
  • the spectator ions may further impart solvent processability to the fully- or heavily- p-doped polymer, depending on its choice.
  • the desired anionic groups can be provided on the polymer by pre- or post-functionalization, depending on ease of synthesis and purification, and the characteristics of the resultant materials.
  • the anion group can be incorporated into the monomer which is then polymerized. Alternatively it can be functionalized into the polymer post-polymerization using a suitable chemistry.
  • the one or a plurality of spectator cations may preferably be selected from the group of cations.
  • cations include Li + , Na + , K + , Cs + ; ammonium and substituted ammonium R 4 N + where R is preferably C1-C12 alkyl or phenyl, including N,N- dimethylmorpholinium; sulfonium R 3 S + where R is C1-C12 alkyl or phenyl; phosphonium R tP "1" where R is preferably C1-C12 alkyl or phenyl; aromatic heterocycle cations including pyridinium, imidazolium, pyrrolium, pyrylium, including their substituted analogues.
  • imidazolium examples include N-butyl-N-methylimidazolium (often denoted bmim), N- hexyl-N-methylimidazolium (hmim) and N-octyl-N-methylimidazolium (omim).
  • the spectator cation can be chosen to help solubilize the p-doped polymer in the desired processing solvent.
  • the nature and number density of these cations modify the morphology and coulombic interactions within the ionic clusters comprising counter-anions, holes and spectator cations in the p-doped material.
  • the spectator cation can provide enthalpic and entropic contributions to solvation energetics, and hence a degree-of- freedom to improve solubility of the material.
  • imidazolium tend to introduce a richer solubilization behavior owing to the presence of a solubilizing alkyl side chain on the cation.
  • Insertion of spectator cations typically have the covalently-bonded anions counterbalanced by H + , Na + or K + in the undoped precursor material, depending on the chemical process used.
  • H + covalently-bonded anions counterbalanced by H + , Na + or K + in the undoped precursor material, depending on the chemical process used.
  • Several ways are available to exchange the desired spectator cation or cations into the material before p-doping. These include: (i) dialysis, (ii) ion-exchange resin, or (iii) metathesis.
  • the material is dissolved in a suitable solvent and kept on one side of a suitable dialysis membrane.
  • a suitable salt of the target cation or cations is dissolved into a suitable solvent and placed either on the same side or opposite side of the membrane.
  • the membrane may be made, for example, of cellulose or polyethersulfone.
  • the dialysate is refreshed and gradually replaced with pure solvent. In this way, ion exchange takes place and excess ions are removed from the material.
  • the material may be purified by dialysis until the desired ionic purity is obtained, for example sub-1% ionic impurities.
  • the desired cation is first inserted in the usual way into a suitable ion-exchange resin, which is then placed in contact with the material in solution for the ion exchange to take place.
  • the material is mixed with a suitable salt of the target cation to precipitate an insoluble salt.
  • a suitable salt of the target cation such as a bromide or an iodide
  • the one or a plurality of polymer diluents may preferably be selected from the group of polymers that can have favorable interaction with the p-doped material, subject to the requirements of oxidative stability and low nucleophilicity.
  • examples of such polymers include polyelectrolytes, such as poly(styrenesulfonate salts).
  • p-doping has to be accomplished using a p-dopant that has a much higher reduction potential than a proton or acid.
  • the formal reduction potential E° of an oxidant measures the thermodynamic ability of the oxidant to transfer holes to oxidize another material.
  • a dopant that has a higher E° value is a stronger dopant.
  • the E value of a proton in aqueous solution is 0.0 V vs SHE.
  • p-Dopant A suitable p-dopant is selected from the group of electron-transfer oxidants, more preferably from the group of one-electron oxidants.
  • one-electron dopants include (indicative E° values in bracket): tris(p-nitrophenyl) aminium salts (1.84 V), tris(2,4-dibromophenyl)aminium salts (1.78 V), tris(p-cyanophenyl)aminium (1.72 V), nitronium salts (1.6 eV), thianthrenium salts (1.49 V), nitrosonium salts (1.42 V), tris(p- bromophenyl) aminium salts (1.34 V), tri(p-methylphenyl) aminium salts (1.04 V) and tris(p- methoxyphenyl) aminium salts (0.80 V).
  • Suitable salts include those of the non-nucleophilic anions, such as hexafluoroantimonate, hexachloroantimonate, perfluoroalkylsulfonate and
  • the anion is selected based on the following
  • the p-dopant selected should be one that is just sufficiently strong to p-dope the polymer under the selected conditions of solution- state doping or film- state doping.
  • Nitrosonium and tris(p-bromophenyl)aminium salts are suitable for polymers with Ip in the range of about 5.2 to about 6.5 eV for both solution- state doping and film-state doping.
  • Another suitable p-dopant is tetraalkylammonium persulfate.
  • the desired doping level is between about 0.1 hole per repeat unit to about 1.0 hole per repeat unit, more preferably between about 0.4 hole per repeat unit to about 0.8 hole per repeat unit. This can be checked using X-ray photoemission spectroscopy of the Nls core level by quantifying the fraction of photoemission intensity attributed to the p-doped triarylamine moiety (binding energy vs vacuum level, approximately 406.0 eV) compared to the total photoemission intensity including that of the undoped triarylamine moiety (approximately 404.5 eV).
  • this can be checked using UV-Vis spectroscopy by quantifying the fractional loss in the absorption band intensity of the ⁇ ⁇ ⁇ * band at about 3.0-3.5 eV, and rise in the p-doped band intensities between 0.5-3.0 eV.
  • this can be checked using Hall measurements.
  • the doping can be monitored in situ by UV-Vis spectroscopy for both solution- state and film-state doping to adjust the concentration of the p-dopant until the desired doping level is achieved.
  • the purity of the resultant self-compensated p-doped material can be quantified by infrared vibration spectroscopy through the absorption band intensities of the undesired ions.
  • purification can be achieved by immersing the film in a suitable wash solvent.
  • Moderately polar solvents such as acetonitrile, and solvent mixtures of a highly polar solvent such as nitromethane, propylene carbonate, and a non-polar solvent such as dioxane are suitable for this purpose.
  • solvents with dielectric constants above 20 may be considered for materials with high anion density.
  • fewer solvents are available due to the restrictions on oxidative stability and purity of the solvents.
  • solvents with dielectric constants above 20 and oxidative potential above 2.5 V vs SHE may be considered: acetonitrile, methoxyacetonitrile, propylene carbonate, ethylene carbonate, nitromethane.
  • solvents with dielectric constants above 20 may be considered for materials with low anion density.
  • the solvent or solvent mixture selected should have the appropriate volatility (boiling point) for the film deposition method chosen.
  • an acidity modifier may be added to the solvent to regulate the proton activity and/or the conjugate anion activity of the solvent or other electroactive species in the solvent to stabilize the p-doped material in the solvent.
  • the p-doped materials can be applied as HILs in diodes, including light-emitting diodes and photoconductive diodes, and field-effect transistors.
  • the HIL is fabricated to a thickness of about 5 to about 100 nm, preferably about 30 to about 50 nm, over an anode which may be made, for example, of a metal or a transparent conducting oxide.
  • the HIL may be deposited directly in the doped form or in the undoped precursor form and then doped.
  • the HIL may be patterned by photolithography or other methods.
  • the light-emitting semiconductor layer or a plurality of light-emitting semiconductor layers may be deposited over the HIL.
  • one or a plurality of buffer interlayers may be deposited over the HIL before depositing the light-emitting semiconductor layer.
  • the cathode is then deposited, which may be made, for example, of a metal or composite layered structure including LiF.
  • one or a plurality of buffer interlayers may be deposited over the semiconductor layer before depositing the cathode.
  • the buffer interlayers may perform roles including confinement of opposite carriers, confinement of excitons and assistance to carrier injection.
  • the light-emitting organic semiconductor layer is fabricated in the reverse sequence.
  • the HIL is fabricated to a thickness of about 5 to about 100 nm, preferably about 5 to about 20 nm, over an electrode array which may be made, for example, of a metal or a transparent conducting oxide.
  • the HIL is preferably aligned to the electrode array by photolithography or self-organization.
  • the HIL may be deposited directly in the doped form or in the undoped precursor form and then doped.
  • the film may contain photocrosslinkable moieties which are activated by light illuminated through a mask to pattern the film.
  • the film may be patterned by etching or dissolving away areas exposed by a photoresist mask layer that has first been fabricated on the film.
  • the HIL is self-aligned to the electrode array by chemical interactions. This process, also called self- assembly, typically limits the HIL thickness to 1-5 nm.
  • the semiconductor is then deposited over the HIL, followed by one or a plurality of gate dielectric layers, and a patterned gate electrode.
  • the semiconductor layer may be patterned by photolithography.
  • the field effect transistors may be fabricated in the reverse sequence. In this case, an oxygen-plasma or a reductant may be used to pattern the HIL.
  • the p-doped materials can be applied as HELs in photodiodes.
  • the HEL is fabricated to a thickness of about 5 to about 100 nm, preferably about 30 to about 50 nm, over a hole-collecting electrode which may be made, for example, of a metal or a transparent conducting oxide.
  • the HEL may be deposited directly in the doped form or in the undoped precursor form and then doped.
  • the HIL may be patterned by photolithography or other methods.
  • the light-absorbing photoactive semiconductor layer or a plurality of photoactive semiconductor layers may be deposited over the HIL.
  • the electron-collecting electrode is then deposited, which may be made, for example, of a metal or a transparent conducting oxide.
  • one or a plurality of buffer interlayers may be deposited over the HEL layer before the photoactive layer.
  • one or a plurality of buffer interlayers may be deposited over the photoactive layer before the electron-collecting electrode.
  • the buffer interlayers may perform roles including confinement of opposite carriers and assistance to carrier extraction.
  • the photovoltaic is fabricated in the reverse sequence.
  • a first cell incorporating a HEL is fabricated followed by a second cell incorporating an identical or dissimilar HEL.
  • Examples la through le as outlined below are for synthesis of model polymers from the corresponding monomers to give various copolymers containing N,N-diphenyl(N- phenyl)amine-4,4'-diyl but with different substituents on the pendant N-phenyl ring, different covalently-bonded counter-anion and different spectator cation to illustrate the generality of the concept.
  • Example la Synthesis of an alternating copolymer of N,N-diphenyl(N-(m- trifluoromethyl)phenyl)amine-4,4'-diyl and disodium 9,9-bis(3-sulfonatopropyl)fluorene-2,7- diyl (mTFF- F3S0 3 Na) (See Scheme la).
  • the reactant solution was further degassed (15 min).
  • the reaction vial was loaded into a Biotage microwave synthesizer and rapidly heated to the selected polymerization condition (130°C, 15 min).
  • the polymer was extracted into methanol, concentrated on rotavap, precipitated in acetone and collected on a 2- ⁇ nylon filter.
  • the polymer was then washed with water until the washing was neutral (pH « 7), redissolved in hot methanol (10 mg /mL), filtered through 2- ⁇ nylon syringe filter, and concentrated on rotavap.
  • the polymer was finally precipitated in toluene and collected on a 2- ⁇ nylon filter.
  • the product was vigorously agitated in a saturated sodium
  • Example lb Synthesis of an alternating copolymer of N,N-diphenyl(N-(p-sec- butyl)phenyl)amine-4,4'-diyl and disodium 9,9-bis(3-sulfonatopropyl)fluorene-2,7-diyl (TFB-F3S0 3 Na) (See Scheme lb).
  • TFB-F3S0 3 Na 9,9-bis(3-sulfonatopropyl)fluorene-2,7-diyl
  • Example lc Synthesis of an alternating copolymer of N,N-diphenyl(N-(p-sec- butyl)phenyl)amine-4,4'-diyl and bis(tetramethyammonium) 9,9-bis(3- sulfonatopropyl)fluorene-2,7-diyl (TFB -F3 S O 3 TMA) (See Scheme lc).
  • Example Id Synthesis of an alternating copolymer of N,N-diphenyl(N-(p- methoxy)phenyl)amine-4,4'-diyl and disodium 9,9-bis(3-sulfonatopropyl)fluorene-2,7-diyl (TFOMe-F3S0 3 Na) (See Scheme Id).
  • Example le Synthesis of an alternating copolymer of N,N-diphenyl(N- phenyl)amine-4,4'-diyl with different substituents on the pendant N-phenyl ring and disodium 9,9-bis(3-sulfonatotetrafluoroethyl)fluorene-2,7-diyl (TAAx-F2fS0 3 Na) (See Scheme le).
  • Sodium 2-Sulfonatotetrafluoroethyl ionic side-chains attached to the fluorene monomer can be synthesized by a 2-step process involving: (1) S 2 Nucleophilic substitution of perfluoro -bromide side chains; (2) sulfinatodehalogenation method which converts the perfluorobromide to a sulfinate salt. This was followed by an oxidation using hydrogen peroxide to give perfluoro- sulfonated fluorene monomer.
  • step (1) KOH is employed as a base to remove the 9-proton on fluorene.
  • 1- bromo-2-iodotetrafluoroethane (2.5 equiv) and DMSO is added dropwise into the reaction mixture, warmed to 50°C for 6 h, cooled to room temperature and then quenched with water, and DCM added to extract the aqueous layer. The extract is then dried and concentrated on a rotary evaporator.
  • step (2) Na 2 S 2 0 4 (2.2 equiv) is added under Ar to a mixture of bis(l-bromo- tetrafluoroethyl)fluorene (1.0 equiv) in a degassed aqueous ACN (2 H 2 0: 1 ACN), and NaHC0 3 , and the reaction mixture heated (70°C, 3 h). The two-phase mixture is then extracted with ethyl acetate. The extracts are dried and concentrated on rotavap.
  • the sulfinite salt obtained is then washed with hexane and isopropanol, redissolved in aqueous ACN solution (3 H 2 0: 5 ACN) and then reacted with H 2 0 2 (22°C, 24 h), whereupon the sulfinite salt is completely oxidised to the sulfonate to give the title diBr-F2S0 3 Na monomer.
  • the reaction mixture is then concentrated, washed with hexane and evaporated to yield the monomer, which is then purified by recrystallization.
  • Example If Synthesis of an alternating copolymer comprising one unit of N,N- diphenyl(N-phenyl)amine-4,4'-diyl with alkoxysulfonate side chain and three units of 9,9- bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-9H-fluorene-2,7-diyl (TFOC3S0 3 Na-3FEG) (See Scheme If).
  • the reactant solution was further degassed (15 min).
  • the reaction vial was loaded into a Biotage microwave synthesizer and rapidly heated to the selected polymerization condition (130°C, 15 min).
  • the polymer was precipitated in acetone and collected on a 2- ⁇ nylon filter.
  • the polymer was then washed with water until the washing was neutral (pH « 7), redissolved in hot DMF (20 mg /mL), filtered through 0.45- ⁇ nylon syringe filter.
  • the polymer was finally reprecipitated in acetone and collected on a 2- ⁇ nylon filter.
  • the product was vigorously agitated in a saturated sodium diethyldithiocarbamate solution (20 h) to extract Pd catalyst residues.
  • Example lg Synthesis of an alternating copolymer of N,N-diphenyl(N-(m- trifluoromethyl)phenyl)amine-4,4'-diyl and dicesium 9,9-bis(3- trifluoromethanesulfonylimidopropyl)fluorene-2,7-diyl (mTFF-F3TFSICs)(See Scheme lg)
  • the conversion to a trifluoromethanesulfonylimide was a three-step process which firstly involved the chlorination of sulfonated polymers e.g. mTFF-F3S0 3 Na using oxalyl chloride (10 eq) in THF.
  • the sulfonated polymers were first suspended in THF before addition of chlorinating agent. Addition of oxalyl chloride solubilized the polymer suspension in THF.
  • the reaction mixture is left to stir at room temperature for 12 h in N 2 . After removing the excess chlorinating agents by vacuum under N 2 protection,
  • trifluoromethansulfonamide (10 eq) was dissolved and added to the THF solution. The reaction mixture was again left to stir at room temperature for 12 hours. Upon end of reaction, the polymer was precipitated in MeOH. Finally, the polymer is dissolved in DMSO and converted to the ionic dicesium form by neutralization with cesium acetate. The final mTFF-F3TFSICs polymer is precipitated in THF and recovered by filtration on a 2- ⁇ nylon filter. The rate of conversion to trifluoromethanesulfonylimide was confirmed by X-ray photoelectron spectroscopy.
  • Example 2 Synthesis of post-phosphonated alternating copolymers of N,N- diphenyl(N-(mtrifluoromethyl) phenyl)amine-4,4'-diyl and 9,9-dioctylfluorene-2,7-diyl (P03Na 2 -mTFF-F8).
  • 1,3,5-trioxane (173 ⁇ L, 0.385 mmol) was dissolved in anhydrous chloroform to give a clear solution (200 mg/mL) of Chlorotrimethylsilane (146 ⁇ L, 1.15 mmol) and SnCl 4 (45 ⁇ L, 0.385 mmol) were added to the polymer solution at room temperature in N 2 glovebag. The reaction was terminated at 12 h and 24 h to give a degree of substitution per repeat unit of 1.0 and 1.8 respectively. The product was precipitated in a MeOH: H 2 0 mixture (10: 1 vol/vol), and collected on centrifuge at 10,000 rev per min (8700 g, 15 min).
  • the centrifugate was redissolved in chloroform (2.0 mL) and precipitated with MeOH. This step was repeated thrice.
  • the chloromethylated polymer was then dried in a dessicator to remove all solvents. 1H NMR confirmed the presence and concentration of the desired -CH 2 C1 group.
  • the chloromethylated polymer (30 mg) was dissolved in mesitylene (6.0 mL) to give a clear solution (5 mg/mL). Triethyl phosphite (1.0 mL, 6.19 mmol) was added, and the mixture heated in an oven (165°C, N2, 16 h), then precipitated in MeOH.
  • Example 3 Cation exchange of undoped polymer.
  • Cellulose dialysis tubings (Sigma, D0405), cut into strips of 14-16 cm in length, were soaked in a beaker of Millipore water for 30mins. After 30mins, the dialysis tubings were rinsed with Millipore water.
  • Each dialysis tubing was filled with approximately 10 mL of solution.
  • the dialysis tubings 2 in each beaker containing 500 mL of Millipore water and a stirrer bar, was dialyzed for 2 h at a rotation of 80 rev per min. Subsequently, at every 4 h interval, the Millipore water was replaced. This was repeated thrice.
  • the cation exchange process was complete with mTFF-F3S0 3 P(Ph) 4 collected as the final product.
  • mTFF-F3S0 3 P(Ph) 4 polymer dissolved in MeOH was rotavap to remove the MeOH, leaving behind the solid mTFF-F3S0 3 P(Ph) 4 .
  • mTFF-F3S0 3 P(Ph) 4 was dried completely in a vacuum oven heated to 120°C, and subsequently stored in an inert nitrogen environment.
  • Example 4 Solution- state doping and film-state post-doping of different triarylamine polymers to give self-compensated p-doped films.
  • Examples 4a through 4h as outlined below exemplify the solution- state doping and film-state post-doping of different triarylamine polymers to give self-compensated p- doped films with high workfunctions and illustrate the generality of the concept.
  • Example 4a Film-state post-doping of a layer-by-layer assembled film of the alternating phosphonated and trimethylammonionated copolymers of N,N-diphenyl(N-(p-sec- butyl)phenyl)amine-4,4'-diyl and 9,9- dioctylfluorene-2,7-diyl (P0 3 Na 2 -mTFF-F8/ NMe 3 Br- mTFF-F8) with a nitronium salt.
  • Example 2a The P0 3 Na 2 -mTFF-F8 product of Example 2a was assembled alternately with the trimethylammonionated derivative made analogously to Example 2a onto ITO-glass treated with a monolayer of poly(styrenesulfonic acid). Each assembled monolayer of the polymer increases the film thickness by 2.0 nm.
  • the polyelectrolyte monolayer (PEM) assembly was then p-doped simply by contact with a p-dopant solution of nitronium hexafluoroantimonate. Solvent was contacted with the p-doped polymer film to remove excess ions.
  • Example 4b Solution- state doping of an alternating copolymer of N,N- diphenyl(N-(mtrifluoromethyl) phenyl)amine-4,4'-diyl and disodium 9,9-bis(3- sulfonatopropyl)fluorene-2,7-diyl (mTFF-F3S0 3 Na) with a tris(p-bromophenyl)aminium salt.
  • mTFF-F3S0 3 Na 75 mg, 98.1 ⁇ was weighed into a vial and baked on a hotplate (140°C, 30 min) in a nitrogen (N 2 )-filled glovebox to completely dry the polymer. Anhydrous nitromethane (10 mL) was added to give a suspension.
  • Tris(p-bromophenyl)aminium hexachloroantimonate (420 mg, 514.4 ⁇ 8, weighed in N 2 ) was mixed with anhydrous propylene carbonate (10.3 mL) to give a dark-blue solution (50 mM). This p-dopant solution should be freshly prepared before use.
  • the p-dopant solution was added gradually (10 mL) whereupon most of the solids have dissolved.
  • the polymer solution turned from clear to brown-blue.
  • the mixture was centrifuged at 3000 rev per min (780 g, 3 min) to collect the supernatant.
  • Anhydrous diethyl ether 60 mL was added to the supernatant to precipitate the crude self-compensated p-doped polymer.
  • the mixture was centrifuged (3000 rev per min, 780 g, 3 min) and the supernatant discarded.
  • Anhydrous nitromethane (3.6 mL) was added to redissolve the precipitate to give a dark red solution.
  • the solution was filtered through a 5- ⁇ nylon syringe filter to remove any undissolved solids.
  • the solution could be spun-cast at 2000 rev per min to give deep red films of thicknesses 85-105 nm.
  • This solution could be diluted with anhydrous nitromethane (2.4 mL).
  • the solution could be spun-cast at 2000 rev per min to give deep red films of thicknesses 30-35 nm.
  • UV-Vis spectroscopy indicated a doping density of 0.8 hole per amine unit.
  • Infrared spectroscopy indicated the hexachloroantimonate impurity was satisfactorily removed.
  • X-ray photoemission spectroscopy indicated the hexachloroantimonate impurity was satisfactorily removed.
  • Example 4c Solution-state doping of an alternating copolymer of N,N- diphenyl(N-(p-sec-butyl)phenyl)amine-4,4'-diyl and bis(tetraphenylphosphonium)-9,9-bis(3- sulfonatopropyl)fluorene-2,7-diyl (TFB-F3S0 3 P(Ph) 4 ) with a nitrosonium salt.
  • TFB-F3S0 3 P(Ph) 4 was dissolved in anhydrous propylene carbonate to give a clear solution (30 mM, by repeat unit).
  • Nitrosonium hexafluoroantimonate was dissolved in anhydrous propylene carbonate to give a dark blue solution (30 mM).
  • the nitrosonium hexafluoroantimonate solution was added gradually to the polymer solution (2.0 equiv) to give a dark red solution.
  • the crude p-doped polymer product was precipitated with anhydrous diethyl ether (3 vol), and recovered on centrifuge at 6,000 rev per min (3100 g, 5 min). The precipitate was then dissolved in y-butyrolactone to give a dark red solution (60 mM, by repeat unit).
  • Example 4d Solution- state doping of an alternating copolymer of N,N- diphenyl(N-(m-trifluoromethyl) phenyl)amine-4,4'-diyl and disodium 9,9-bis(3- sulfonatopropyl)fluorene-2,7-diyl (mTFF-F3S0 3 Na)
  • Nitrosonium hexafluoroantimonate (9.42 mg, 35.4 ⁇ , weighed in N 2 ) was dissolved with anhydrous nitromethane (1.18 mL) to give a colourless solution (30 mM). This p-dopant solution should be freshly prepared before use.
  • nitromethane diethyl ether (80 ⁇ ⁇ per square cm of film) was contacted with the polymer film (10 s) and spun off at 6000 rev per min. This step was repeated once more.
  • UV-Vis spectroscopy indicated a doping density of 0.8 hole per amine unit.
  • Infrared spectroscopy indicated the hexachloroantimonate impurity was satisfactorily removed.
  • X-ray photoemission spectroscopy indicated the hexachloroantimonate impurity was satisfactorily removed.
  • Example 4e Film-state post-doping of an alternating copolymer of N,N- diphenyl(N-(mtrifluoromethyl) phenyl)amine-4,4'-diyl and disodium 9,9-bis(3- sulfonatopropyl)fluorene-2,7-diyl (mTFF-F3S0 3 Na) with a tris(p-bromophenyl)aminium salt.
  • mTFF-F3 S 0 3 Na polymer ( 13 mg, 17.0 ⁇ s) and MeOH (2.0 mL) were mixed to obtain a clear 6.5 mg/ mL solution.
  • This solution was spin-cast at 6,000 rev per min to give a film of thickness 20-25 nm, which was baked on a hotplate (140°C, 15 min) in a nitrogen (N 2 )-filled glovebox to remove residual solvent including water.
  • Tris(p-bromophenyl)aminium hexachloroantimonate (0.94 mg, weighed in N 2 ) was mixed with anhydrous nitromethane (190 ⁇ L) and anhydrous diethyl ether (580 ⁇ L) to give a solution of 1.5 mM of the p-dopant in a 1:3 vol/vol nitromethane : diethyl ether in N 2 glove box. This p-dopant solution should be freshly prepared before use.
  • Step 1 Film-state p-doping.
  • the p-dopant solution (50 ⁇ L per square cm of film) was contacted with the polymer film (30 s) and spun off at 6,000 rev per min, in the N 2 glovebox.
  • the polymer film turned from pale yellow to red.
  • Step 2 Excess ion removal.
  • Example 4f Film-state post-doping of an alternating copolymer of N,N- diphenyl(N-(m-trifluoromethyl) phenyl)amine-4,4'-diyl and disodium 9,9-bis(3- sulfonatopropyl)fluorene-2,7-diyl (mTFF-F3S0 3 Na) mixed with a polymer diluent poly-4- vinylphenol (PVP) and doped with a nitrosonium salt.
  • mTFF-F3S0 3 Na alternating copolymer of N,N- diphenyl(N-(m-trifluoromethyl) phenyl)amine-4,4'-diyl and disodium 9,9-bis(3- sulfonatopropyl)fluorene-2,7-diyl
  • PVP polymer diluent poly-4- vinylphenol
  • mTFF-F3S0 3 Na polymer (2.25 mg) and MeOH ( 1.0 mL) were mixed to obtain a clear 2.25 mg/ mL solution.
  • PVP polymer (6.75 mg) and MeOH (2.0 mL) were mixed to obtain a clear 3.38 mg/ mL solution.
  • Both solutions were mixed together to give a 3mg/ml 1 :3 w/w mTFF-F3S0 3 Na:PVP solution in MeOH.
  • This solution was spin-cast at 2,000 rev per min to give a film of thickness 20-25 nm, which was baked on a hotplate (220°C, 15 min) in a nitrogen (N2)-filled glovebox to remove residual solvent including water.
  • Step 1 Film-state p-doping.
  • Step 2 Excess ion removal.
  • Example 4g Film-state post-doping of an alternating copolymer of N,N- diphenyl(N-(mtrifluoromethyl) phenyl)amine-4,4'-diyl and disodium 9,9-bis(3- sulfonatopropyl)fluorene-2,7-diyl (mTFF-F3S0 3 Na) with a nitrosonium salt.
  • mTFF-F3S0 3 Na polymer (10 mg, 13.0 ⁇ ) and MeOH (2.0 mL) were mixed to obtain a clear 5 mg/ mL solution.
  • Example 4h Film-state post-doping of a monolayer of an alternating copolymer of N,N-diphenyl(N-(mtrifluoromethyl) phenyl)amine-4,4'-diyl and disodium 9,9-bis(3- sulfonatopropyl)fluorene-2,7-diyl (mTFF-F3S0 3 Na) with a tris(p-bromophenyl)aminium salt.
  • mTFF-F3S0 3 Na polymer (10 mg, 13.0 ⁇ ) and dimethyl sulfoxide (2.0 mL) were mixed to obtain a clear 5 mg/ mL solution.
  • a monolayer of the polymer is self- assembled onto an Au-patterned substrate by contacting the polymer solution (50 ⁇ ⁇ per square cm of substrate) for 1 min before flood-wash with clean DMSO and spun-off at 6000 rev per min. The film was annealed at 220°C (hotplate) for 5 min in glovebox.
  • Tris(p-bromophenyl)aminium hexachloroantimonate (0.8 mg, weighed in N 2 ) was mixed with acetonitrile (980 ⁇ ) to give a solution of 1 mM of the p-dopant. This p-dopant solution should be freshly prepared before use.
  • Step 1 Film-state p-doping.
  • Step 2 Excess ion removal.
  • the dopant solution was flood-wash with clean acetonitrile and spun-off at 6000 rev per min.
  • Example 5 Improved device performances.
  • Examples 5a through 5d as outlined below illustrate the improvements in hole- injection and hole-extraction performance achieved over conventional HILs and HELs.
  • Example 5a Hole injection from ⁇ through the p-doped HIL
  • the self-compensated p-doped triarylaminium PEM assembly (See FIG. 2) provided more than three orders of magnitude improvement in hole current density injected into 9,9-dioctylfluorene compared to the reference 1: 16 PEDT:PSSH (See FIG. 3).
  • Example 5b Hole injection from ITO through the self-compensated solution- state pre-doped alternating copolymer of N,N-diphenyl(N-(m-trifluoromethyl)phenyl)amine- 4,4'-diyl and disodium 9,9-bis(3- sulfonatopropyl)fluorene-2,7-diyl (mTFF-F3S0 3 Na).
  • the reference device with PEDT:PSSH as the HIL gave a turn on voltage at 3.7V and an injection current density of 10-4 Acm-2.
  • the self-compensated p-doped mTFF- F3S0 3 Na give more than three orders of magnitude of hole current density higher than the reference PEDT:PSSH (See FIG. 4).
  • Example 5c Hole injection from ITO through the self-compensated film-state post-doped alternating copolymer of N,N-diphenyl(N-(m-trifluoromethyl)phenyl)amine-4,4'- diyl and disodium 9,9-bis(3-sulfonatopropyl)fluorene-2,7-diyl (mTFF-F3S0 3 Na).
  • the self-compensated p-doped mTFF-F3S0 3 Na give more than three orders of magnitude of hole current density higher than standard 1:6 PEDT:PSSH (See FIG. 5).
  • Example 5d p-Type top-gate bottom-contact organic field effect transistors.
  • s-d electrodes were deposited through a shadow mask on a glass substrate to provide a channel length of 100 ⁇ and a channel width of 3 mm.
  • the substrate was cleaned by UV-ozone.
  • a monolayer of mTFF-F3S0 3 Na polymer is self-assembled onto Au s-d described above in Example 4h.
  • 50-nm-thick DPPT2-T films from chlorobenzene solution were spin-cast over the s-d electrodes in the glovebox. The films were annealed at 100°C (hotplate) for 3 min in glovebox. Poly(methyl methacrylate)
  • ambipolar FETs can be differentiated into p- channel FETs (see FIG 7).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne des matériaux conducteurs électriques à dopage de type P à haut travail d'extraction comprenant un ou plusieurs groupes caractéristiques triarylaminium contrebalancés par des anions en liaison covalente, et comprenant facultativement aussi un ou plusieurs cations à liaison non covalente. Ces matériaux peuvent être utilisés en tant que couches d'injection de trous et d'extraction de trous pour fournir des contacts ohmiques à des semi-conducteurs avec des potentiels d'ionisation plus profonds que ce qui était possible auparavant, pouvant atteindre le travail d'extraction du matériau.
PCT/SG2016/050058 2015-02-03 2016-02-03 Matériaux polymériques conducteurs électriques à dopage de type p pour couches d'injection de trous et d'extraction de trous WO2016126209A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201562111330P 2015-02-03 2015-02-03
US62/111,330 2015-02-03

Publications (1)

Publication Number Publication Date
WO2016126209A1 true WO2016126209A1 (fr) 2016-08-11

Family

ID=56564425

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SG2016/050058 WO2016126209A1 (fr) 2015-02-03 2016-02-03 Matériaux polymériques conducteurs électriques à dopage de type p pour couches d'injection de trous et d'extraction de trous

Country Status (1)

Country Link
WO (1) WO2016126209A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020065926A1 (fr) * 2018-09-28 2020-04-02 日立化成株式会社 Matériau électronique organique et son utilisation
WO2020130934A1 (fr) * 2018-12-21 2020-06-25 National University Of Singapore Matériaux organiques électroconducteurs dopés par n
WO2020193757A1 (fr) * 2019-03-28 2020-10-01 Universität Zu Köln Électrode poreuse et son procédé de préparation
CN113823752A (zh) * 2021-09-18 2021-12-21 京东方科技集团股份有限公司 空穴注入材料、电致发光器件和显示装置
JP7385453B2 (ja) 2018-12-25 2023-11-22 住友化学株式会社 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080146744A1 (en) * 1999-04-06 2008-06-19 Cambridge Display Technology Limited Method For Doping A Polymer
US8569752B2 (en) * 2004-10-11 2013-10-29 Cambridge Display Technology Limited Polar semiconductor hole transporting material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080146744A1 (en) * 1999-04-06 2008-06-19 Cambridge Display Technology Limited Method For Doping A Polymer
US8569752B2 (en) * 2004-10-11 2013-10-29 Cambridge Display Technology Limited Polar semiconductor hole transporting material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
SHI ET AL.: "Anionic triphenylamine- and fluorene-based conjugated polyelectrolyte as a hole-transporting material for polymer light-emitting diodes.", POLYM. INT., vol. 58, 2009, pages 373 - 379 *
SHI ET AL.: "Synthesis of novel triphenylamine-based conjugated polyelectrolytes and their application as hole-transport layers in polymeric light emitting diodes.", J. MATER. CHEM., vol. 16, 2006, pages 2387 - 2394 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020065926A1 (fr) * 2018-09-28 2020-04-02 日立化成株式会社 Matériau électronique organique et son utilisation
JPWO2020065926A1 (ja) * 2018-09-28 2021-09-16 昭和電工マテリアルズ株式会社 有機エレクトロニクス材料及びその利用
JP7103424B2 (ja) 2018-09-28 2022-07-20 昭和電工マテリアルズ株式会社 有機エレクトロニクス材料及びその利用
WO2020130934A1 (fr) * 2018-12-21 2020-06-25 National University Of Singapore Matériaux organiques électroconducteurs dopés par n
JP7385453B2 (ja) 2018-12-25 2023-11-22 住友化学株式会社 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法
WO2020193757A1 (fr) * 2019-03-28 2020-10-01 Universität Zu Köln Électrode poreuse et son procédé de préparation
CN113823752A (zh) * 2021-09-18 2021-12-21 京东方科技集团股份有限公司 空穴注入材料、电致发光器件和显示装置
CN113823752B (zh) * 2021-09-18 2023-09-01 京东方科技集团股份有限公司 空穴注入材料、电致发光器件和显示装置

Similar Documents

Publication Publication Date Title
US10763438B2 (en) n-Doped electrically conductive polymeric material
WO2016126209A1 (fr) Matériaux polymériques conducteurs électriques à dopage de type p pour couches d'injection de trous et d'extraction de trous
Takeda et al. An air-stable low-bandgap n-type organic polymer semiconductor exhibiting selective solubility in perfluorinated solvents
Borrelli et al. Bilayer heterojunction polymer solar cells using unsubstituted polythiophene via oxidative chemical vapor deposition
Ratcliff et al. Work function control of hole-selective polymer/ITO anode contacts: an electrochemical doping study
KR101777779B1 (ko) P-도핑된 공액 저분자 전해질 및 이를 이용한 유기전자소자
EP3331041B1 (fr) Cellule solaire
KR20140019778A (ko) 유기 반도체
WO2016100313A1 (fr) Compositions contenant des matériaux porteurs de trous et des fluoropolymères et leurs utilisations
Zhao et al. Application of biuret, dicyandiamide, or urea as a cathode buffer layer toward the efficiency enhancement of polymer solar cells
KR101449775B1 (ko) 초순수 완전-플루오르화 산 중합체로 제조된 전기 전도성 중합체의 조성물
Kim et al. Impact of incorporating nitrogen atoms in naphthalenediimide-based polymer acceptors on the charge generation, device performance, and stability of all-polymer solar cells
Wang et al. End-capping effect of quinoxalino [2, 3-b′] porphyrin on donor–acceptor copolymer and improved performance of polymer solar cells
Yang et al. Universal hole transporting material via mutual doping for conventional, inverted, and blade-coated large-area organic solar cells
Cheng et al. Multi-chlorine-substituted self-assembled molecules as anode interlayers: tuning surface properties and humidity stability for organic photovoltaics
Galindo et al. Investigation of the polymer-salt interactions in polymeric light emitting electrochemical cells: Electronic structure calculations and experimental studies
TW201348284A (zh) 載子傳遞材料以及電子元件
Lu et al. Conjugated polymers containing sulfonic acid fluorene unit for achieving multiple interfacial modifications in fullerene-free organic solar cells
Sun et al. Design, synthesis, and characterization of a novel c‐donor‐nc‐bridge‐c‐acceptor type block copolymer for optoelectronic applications
KR101709199B1 (ko) 싸이오펜 중합체 조성물, 및 이를 포함하는 유기광전자소자
KR101684636B1 (ko) P-도핑된 공액 고분자 전해질 및 이를 이용한 유기전자소자
JP2018503985A (ja) 低コンタクト抵抗を有する有機電界効果トランジスタ
US9793479B2 (en) Methods for fabricating devices including photovoltaic devices
US20220059769A1 (en) n-Doped Electrically Conductive Organic Materials
Hong et al. A Solution-Processed Cathode Interfacial Layer Facilitates Efficient Energy Level Alignment in Organic Photovoltaics

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16746918

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16746918

Country of ref document: EP

Kind code of ref document: A1