WO2014075300A1 - Composition de polymère organométallique, procédé pour sa préparation et oled fabriquée à partir de celle-ci - Google Patents

Composition de polymère organométallique, procédé pour sa préparation et oled fabriquée à partir de celle-ci Download PDF

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WO2014075300A1
WO2014075300A1 PCT/CN2012/084766 CN2012084766W WO2014075300A1 WO 2014075300 A1 WO2014075300 A1 WO 2014075300A1 CN 2012084766 W CN2012084766 W CN 2012084766W WO 2014075300 A1 WO2014075300 A1 WO 2014075300A1
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substituted
unsubstituted
composition
cycloalkyl
polymer
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PCT/CN2012/084766
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English (en)
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Jessen Jichang FENG
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Dow Global Technologies Llc
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Priority to PCT/CN2012/084766 priority Critical patent/WO2014075300A1/fr
Priority to CN201310574848.0A priority patent/CN103819904A/zh
Priority to TW102141714A priority patent/TW201434975A/zh
Priority to JP2013236487A priority patent/JP2014116599A/ja
Priority to KR1020130138754A priority patent/KR20140063461A/ko
Publication of WO2014075300A1 publication Critical patent/WO2014075300A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/16—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/187—Metal complexes of the iron group metals, i.e. Fe, Co or Ni

Definitions

  • An OLED is a light-emitting diode (LED), in which the emissive electroluminescent layer is a film of an organic compound, which emits light in response to an electric current.
  • a typical OLED has a multi-layer structure, and typically includes an indium tin oxide (ITO) anode, and a metal cathode. Sandwiched between the ITO anode and the metal cathode are several organic layers, such as a hole injection layer (HIL), a hole transfer layer (HTL), an emitting material layer (EML), an electron transfer layer (ETL) and an electron injection layer (EIL).
  • HIL hole injection layer
  • HTL hole transfer layer
  • EML emitting material layer
  • ETL electron transfer layer
  • EIL electron injection layer
  • HIL hole injection layer
  • the most commonly used HIL material is poly(3,4- ethylenedioxythiophene)/poly(styrene sulfonic acid) complex (PEDOT PSS).
  • PEDOT PSS poly(3,4- ethylenedioxythiophene)/poly(styrene sulfonic acid) complex
  • OLED fabricated from PEDOT/PSS show a short life time due to corrosion induced by the high acidity of the PEDOT/PSS.
  • the PEDOT/PSS solution is often aqueous- based. When it is used in an OLED, trace moisture residue in the film may cause corrosion to the electrical circuit and lead to device decay. Thus there is a continuous need for HIL materials, especially non-aqueous HIL compositions, for OLED application.
  • JP2008/111941A discloses an electrochromic device that is characterized by: a pair of electrode structures having transparent electrodes formed on support substrates , which are disposed so that the transparent electrodes face each other via an electrolyte layer.
  • a porous electrode to which an electrochromic coloring material that develops a color by oxidation or reduction is adsorbed is formed on at least one of the transparent electrodes in the pair of electrode structures; and a porous electrode carrying a ferrocene polymer compound having a predetermined structure is formed on the transparent electrode constituting the counter electrode structure.
  • CN178601 OAdiscloses a photochromic ferrocene diarylene compound.
  • the ferrocene diarylene compound is a carrier switch material and can be used as organic luminescent layer of OLED device.
  • references that teach materials useful in electronic devices include WO 2010/082924 (cross-linkable copper phthalocyanine complex), WO 2011/120709 (quadratic planar mononuclear transition metal complexes), WO 2004/041962 (crosslinkable composite of boronic acid or a boronic acid derivative and an organic or organometallic moiety), US 2011/0198666 (p-dopant (Al, Be or Ir) with a matrix polymer, US 2008/073440 (crosslinkable composite of Ir), WO 2003/022008 (organic matrix doped with a metal complex), US 2005/0260444 (macrocyclic ligand coordinated to a metal center), and US 2009/0212280 (organic semiconducting matrix doped with a metal complex n-dopant).
  • the invention provides a composition comprising at least one dopant, and a polymer comprising at least one unit selected from Structure I:
  • M is selected from Fe, Co, or Ni
  • Ri, R 2 , R3 and R4 are each independently selected from hydrogen; deuterium; halogen; substituted or unsubstitutedCi-Ci 6 alkyl; substituted or unsubstituted C 6 -Ci 6 aryl; substituted or unsubstituted C 3 -Ci 6 cycloalkyl; substituted or unsubstituted 5- to 7-membered heterocycloalkyl; substituted or unsubstituted C 6 -Ci 6 aryl fused with one or more cycloalkyl; 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubstituted aromatic rings or C 3 -Ci 6 cycloalkyl fused with one or more substituted or unsubstituted aromatic rings; substituted or unsubstituted Ci-Ci6silyl, cyano, nitro, or hydroxy;
  • n is greater than or equal to 1 ;
  • x is from 0 to 4; and y is from 0 to 4.
  • the invention also provides a film comprising at least two layers, Layer A and Layer B, wherein Layer A is formed from a Composition A comprising a polymer comprising at least one unit selected from Structure I:
  • Ri, R 2 , R3 and R4 are each independently selected from hydrogen; deuterium; halogen; substituted or unsubstitutedCi-Ci 6 alkyl; substituted or unsubstituted C 6 -Ci 6 aryl; substituted or unsubstituted C 3 -Ci 6 cycloalkyl; substituted or unsubstituted 5- to 7-membered heterocycloalkyl; substituted or unsubstituted C 6 -Ci 6 aryl fused with one or more cycloalkyl; 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubstituted aromatic rings or C 3 -Ci 6 cycloalkyl fused with one or more substituted or unsubstituted aromatic rings; substituted or unsubstituted Ci-Ci6silyl, cyano, nitro, or hydroxy;
  • n is greater than or equal to 1 ;
  • x is from 0 to 4.
  • y is from 0 to 4.
  • the invention also provides an electronic device comprising at least one component formed from a Composition A comprising a polymer comprising at least one unit selected from Structure I:
  • Ri, R 2 , R3 and R4 are each independently selected from hydrogen; deuterium; halogen; substituted or unsubstitutedCi-Ci6 alkyl; substituted or unsubstituted C 6 -Ci 6 aryl; substituted or unsubstituted C 3 -Ci 6 cycloalkyl; substituted or unsubstituted 5- to 7-membered heterocycloalkyl; substituted or unsubstituted C 6 -Ci 6 aryl fused with one or more cycloalkyl; 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubstituted aromatic rings or C3-C16 cycloalkyl fused with one or more substituted or unsubstituted aromatic rings; substituted or unsubstituted Ci-Ci 6 silyl, cyano, nitro, or hydroxy;
  • n is greater than or equal to 1 ;
  • x is from 0 to 4.
  • y is from 0 to 4.
  • Figure 1 is the H 1 NMR of polymeric ferrocenylmethylphenylsilane (PFMPS) in
  • Figure 2 is the cyclic voltammetry curve of PFMPS solubilized in dimethylformamide (DMF)with 0.1 molar tetrabutylammonium hexafluorophosphate as the supporting electrolyte.
  • Figure 3 are the current-voltage curves of OLED Example 1 (PFMPS), OLED Example 2 (PFMPS+10% dopant), and Comparative example (polythiophene) in OLED.
  • Figure 4 are the luminescence efficiency curves of OLED Example 1 (PFMPS), OLED Example 2 (PFMPS+10% dopant), and Comparative example (polythiophene) in OLED.
  • Figure 5 are the luminescence decay curves of OLED Example 1 (PFMPS), OLED Example 2 (PFMPS+10% dopant), and Comparative example (polythiophene) in OLED.
  • HIL materials developed to date for OLED applications are largely limited to organic materials.
  • polymers with ferrocene in the main chain have been developed and used as HIL material. Surprisingly, these polymers have been found to be useful as HIL material, and OLED incorporating these polymers as HE. material exhibit good electroluminescent performance.
  • the invention provides a composition comprising at least one dopant, and a polymer comprising at least one unit selected from Structure I:
  • M is selected from Fe, Co, or Ni
  • Ri, R 2 , R3 and R4 are each independently selected from hydrogen; deuterium; halogen; substituted or unsubstitutedCi-Ci 6 alkyl; substituted or unsubstituted C 6 -Ci 6 aryl; substituted or unsubstituted C 3 -Ci 6 cycloalkyl; substituted or unsubstituted 5- to 7-membered heterocycloalkyl; substituted or unsubstituted C 6 -Ci 6 aryl fused with one or more cycloalkyl; 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubstituted aromatic rings or C 3 -Ci 6 cycloalkyl fused with one or more substituted or unsubstituted aromatic rings; substituted or unsubstituted Ci-Ci6silyl, cyano, nitro, or hydroxy;
  • n is greater than or equal to 1 ;
  • x is from 0 to 4.
  • y is from 0 to 4.
  • An inventive composition may comprise a combination of two or more embodiments described herein.
  • the dopant is a P-type dopant.
  • M in Structure I is Fe.
  • n of Structure I is from 1 to 1,000,000, or from 1 to 10,000 or from 1 to 1,000.
  • x and y of Structure I are both zero.
  • the halogen of at least one of, or at least two of, or at least three of, or all ofRi, R 2 , R3 and R4of Structure I is fluoride.
  • the amount of polymer in the composition is from oneweight percent (wt%) to 99wt%, or from 50wt% to 99wt%, or from 70wt% to 99wt%, based upon the weight of the composition.
  • the composition consists essentially of the polymer of Structure I and a P-type dopant.
  • the dopant is an organometal compound or an organometal salt.
  • the dopant of the composition is an organometal salt comprising at least one phenyl group.
  • the dopant is an organometal salt comprising at least one phenyl group.
  • the anion component of the salt comprises a boron atom.
  • the organometal salt has a structure selected from one of the following
  • the organometal salt has the structure:
  • the amount of dopant in the composition is from 1 weight percent (wt%) to 99wt%, or from lwt% to 50wt%, or from lwt% to 30wt%, based upon the weight of the composition.
  • the amount of polymer in the composition is from 70 wt% to 99 wt%, and the amount of P-type dopant in the composition is from 1 wt% to 30 wt%, both based on the weight of the composition.
  • An inventive composition may comprise a combination of two or more embodiments described herein.
  • the invention also provides a film comprising at least one layer formed from an inventive composition of one or more embodiments described herein.
  • the invention also provides an electronic device comprising at least one component formed from an inventive composition of one or more embodiments described herein.
  • the invention also provides, in a second aspect, a film comprising at least two layers, A and B, wherein Layer A is formed from a Composition A comprising a polymer comprising at least one unit selected from Structure I:
  • Ri, R 2 , R3 and R4 are each independently selected from hydrogen; deuterium; halogen; substituted or unsubstitutedCi-Ci6 alkyl; substituted or unsubstituted C 6 -Ci 6 aryl; substituted or unsubstituted C 3 -Ci 6 cycloalkyl; substituted or unsubstituted 5- to 7-membered heterocycloalkyl; substituted or unsubstituted C 6 -Ci 6 aryl fused with one or more cycloalkyl; 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubstituted aromatic rings or C 3 -Ci 6 cycloalkyl fused with one or more substituted or unsubstituted aromatic rings; substituted or unsubstituted Ci-Ci 6 silyl, cyano, nitro, or hydroxy;
  • n is greater than or equal to 1 ;
  • x is from 0 to 4.
  • y is from 0 to 4.
  • An inventive film may comprises a combination of two or more embodiments described herein.
  • Layer B is a hole transport layer.
  • Composition A comprises from 1 to 99 weight percent (wt%) of at least one polymer comprising at least unit selected from Structure I, based on the weight of the composition. In a further embodiment Composition A comprises from 50 to 99wt% of at least one polymer comprising at least unit selected from Structure I, based on the weight of the composition. In a further embodiment, Composition A comprises from 70to 99wt% of at least one polymer comprising at least unit selected from Structure I, based on the weight of the composition.
  • M of Structure I of the polymer of Composition A is Fe.
  • n of Structure I of the polymer of Composition A is from 1 to 1 ,000, and both x and y of Structure I of the polymer of Composition A are zero.
  • Layer A is in contact with Layer B.
  • the film further comprises an emitting layer.
  • the thickness of Layer A is from 5nm to 500nm, or from5nm to lOOnm, or from 5 nm to 50nm
  • the thickness of Layer B is from 5nm to 500nm, or from 5nm to lOOnm, or from 5nmto 50nm.
  • Composition A further comprises a P-type dopant.
  • the dopant is an organometal compound or an organometal salt.
  • the dopant is an organometal salt comprising at least one phenyl group.
  • the anion component of the salt comprises a boron atom.
  • the organometal salt has a structure selected from one of the following:
  • the amount of dopant in Composition A is from 1 weight percent (wt%) to 99 wt%, or from 1 wt% to 50 wt%, or from 1 wt% to 30wt%, based upon the weight of the composition.
  • An inventive film may comprise a combination of two or more embodiments described herein.
  • the invention also provides, in a third aspect, an electronic device comprising at least one component formed from a Composition A comprising a polymer comprising at least one unit selected from Structu
  • M is selected from Fe, Co, or Ni
  • Ri, R 2 , R3 and R4 are each independently selected from hydrogen; deuterium; halogen; substituted or unsubstitutedCi-Ci6 alkyl; substituted or unsubstituted C6-Ci6aryl; substituted or unsubstituted C 3 -Ci 6 cycloalkyl; substituted or unsubstituted 5- to 7-membered heterocycloalkyl; substituted or unsubstituted C 6 -Ci 6 aryl fused with one or more cycloalkyl; 5- to 7-membered heterocycloalkyl fused with one or more substituted or unsubstituted aromatic rings or C 3 -Ci 6 cycloalkyl fused with one or more substituted or unsubstituted aromatic rings; substituted or unsubstituted Ci-Ci 6 silyl, cyano, nitro, or hydroxy;
  • n is greater than or equal to 1 ;
  • x is from 0 to 4.
  • y is from 0 to 4.
  • An inventive electronic device may comprises a combination of two or more embodiments described herein.
  • Composition A further comprises a P-type dopant.
  • the dopant is an organometal compound or an organometal salt.
  • the dopant is an organometal salt comprising at least one phenyl group.
  • the anion component of the salt comprises a boron atom.
  • the organometal salt has a structure selected from one of the following:
  • the organometal salt has the structure:
  • the amount of dopant in Composition A is from 1 weight percent (wt%) to 99 wt%, or from 1 wt% to 50 wt%, or from 1 wt% to 30wt%, based upon the weight of the composition.
  • M of Structure I of the polymer of Composition A is Fe.
  • n of Structure I of the polymer of Composition A is from 1 to
  • the electronic device further comprises a first electrode.
  • the electronic device further comprises a second electrode disposed over the first electrode.
  • the electronic device further comprises an organic layer disposed between the first and second electrodes.
  • the at least one component, formed from Composition A, of the electronic device is an organic layer, which is disposed between the first and second electrodes.
  • the electronic device further comprises a second Layer B.
  • Layer B is a hole transport layer.
  • Layer A is in contact with Layer B.
  • the electronic device further comprises an emitting layer.
  • the thickness of Layer A is from 5 nm to 50 nm
  • the thickness of Layer B is from 5 nm to 50 nm.
  • the electronic device is an OLED (Organic Light Emitting Device).
  • inventive composition may comprise a combination of two or more embodiments as described herein.
  • inventive film may comprise a combination of two or more embodiments as described herein.
  • inventive electronic device may comprise a combination of two or more embodiments as described herein.
  • polymer comprising at least one unit selected from Structure I:
  • M, Ri, R 2 , R3, R4 and R 5 , n, x and y are defined above (see Summary of Invention).
  • the polymer may comprise two or more embodiments as described herein.
  • Ri of Structure I is one of the following: hydrogen; deuterium; halogen; substituted or unsubstitutedCi-Ci 6 alkyl; substituted or unsubstituted C 6 - Ci 6 aryl; substituted or unsubstituted C 3 -Ci 6 cycloalkyl; substituted or unsubstituted 5- to 7-membered heterocycloalkyl; or hydroxy.
  • Ri of Structure I is one of the following: hydrogen; halogen; substituted or unsubstitutedCi-Ci 6 alkyl; substituted or unsubstituted C 6 -Ci 6 aryl.
  • R 2 of Structure I is one of the following: hydrogen; deuterium; halogen; substituted or unsubstitutedCi-Ci 6 alkyl; substituted or unsubstituted C 6 - Ci 6 aryl; substituted or unsubstituted C 3 -Ci 6 cycloalkyl; substituted or unsubstituted 5- to 7-membered heterocycloalkyl; or hydroxy.
  • R 2 of Structure I is one of the following: hydrogen; halogen; substituted or unsubstitutedCi-Ci 6 alkyl; substituted or unsubstituted C 6 -Ci 6 aryl.
  • R 3 of Structure I is one of the following: hydrogen; deuterium; halogen; substituted or unsubstitutedCi-Ci 6 alkyl; substituted or unsubstituted C 6 - Ci 6 aryl; substituted or unsubstituted C 3 -Ci 6 cycloalkyl; substituted or unsubstituted 5- to 7-membered heterocycloalkyl; or hydroxy.
  • R 3 of Structure I is one of the following: hydrogen; halogen; substituted or unsubstitutedCi-Ci 6 alkyl; substituted or unsubstituted C 6 -Ci 6 aryl.
  • R 4 of Structure I is one of the following: hydrogen; deuterium; halogen; substituted or unsubstitutedCi-Ci6alkyl; substituted or unsubstituted Ce- Ci 6 aryl; substituted or unsubstituted C 3 -Ci 6 cycloalkyl; substituted or unsubstituted 5- to 7-membered heterocycloalkyl; or hydroxy.
  • R 4 of Structure I is one of the following: hydrogen; halogen; substituted or unsubstitutedCi-Ci 6 alkyl; substituted or unsubstituted C 6 -Ci 6 aryl.
  • n is from 1 to 1,000,000, further from 1 to 100,000, further from 1 to 10,000, and further from 1 to 1000.
  • x is 0, or 1, or 2, or 3, or 4.
  • x is 0.
  • y is 0, or 1, or 2, or 3, or 4.
  • y is 0.
  • the polymer comprises at least one unit selected from the following:
  • Me is methyl
  • M, Ri, R 2 , R 3 , R 4 , x, y and n are as previously described.
  • the polymer of comprises at list one unit selected from the following:
  • Me is methyl
  • M, Ri, R 2 , R 3 , R 4 , x, y and n are as previously described.
  • the polymer comprises at least one unit selected from the following:
  • Me is methyl and n is from 1 to 1,000,000, further from 1 to 100,000, further from 1 to 10,000, and further from 1 to 1000.
  • the polymer comprises at least one structure selected from the following:
  • Me is methyl and n is from 1 to 1,000,000, further from 1 to 100,000, further from 1 to 10,000, and further from 1 to 1000.
  • the polymer comprises at least one of the following structures ,or combinations thereof
  • Me is methyl and n is from 1 to 1 ,000,000, further from 1 to 100,000, further from 1 to 10,000, and further from 1 to 1000.
  • M is preferably Fe
  • n is preferably from 1 to 1,000
  • x and y are preferably both zero.
  • Polymer and like terms mean a compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term polymer thus embraces the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure and within the bulk polymer), and the term interpolymer as defined below.
  • the polymer may contain trace amounts of residual catalyst residues.
  • Interpolymer and like terms mean a polymer prepared by the polymerization of at least two different types of monomers.
  • the generic term interpolymer thus includes copolymers (employed to refer to polymers prepared from two different types of monomers), and polymers prepared from more than two different types of monomers.
  • compositions claimed through use of the term “comprising” may include any additional additive, adjuvant or compound, whether polymeric or otherwise, unless stated to the contrary.
  • HTL Hole transport layer
  • HTL Hole transport layer
  • the HTL is used to help block passage of electrons transported by the emitting layer. Small electron affinity is typically required to block electrons.
  • the HTL should desirably have larger triplets to block exciton migrations from an adjacent EML layer.
  • HTL compounds include, but are not limited to, di(p-tolyl)aminophenyl]cyclohexane (TPAC), N,N-diphenyl-N,N-bis(3- methylphenyl)-l,l-biphenyl-4,4-diamine (TPD), and N,N '-diphenyl- ⁇ , ⁇ '-bis(l-naphthyl)- (1,1 '-biphenyl)-4,4'-diamine (NPB).
  • TPAC di(p-tolyl)aminophenyl]cyclohexane
  • TPD N,N-diphenyl-N,N-bis(3- methylphenyl)-l,l-biphenyl-4,4-diamine
  • NPB N,N '-diphenyl- ⁇ , ⁇ '-bis(l-naphthyl)- (1,1 '-biphenyl)-4,4'
  • Emitting layer and like terms mean a layer which consists of host and dopant.
  • the host material could be bipolar or unipolar, and may be used alone or by combination of two or more host materials.
  • the opto-electrical properties of the host material may differ to which type of dopant(Phosphorescent or Fluorescent) is used.
  • the assisting host materials should have good spectral overlap between adsorption of the dopant and emission of the host to induce good Foester transfer to dopants.
  • the assisting host materials should have high triplet energy to confine triplets of the dopant.
  • Dopant refers to an electron acceptor or a donator that increases the conductivity of an organic layer of an organic electronic device, when added to the organic layer as an additive.
  • Organic semiconductors may likewise be influenced, with regard to their electrical conductivity, by doping.
  • Such organic semiconducting matrix materials may be made up either of compounds with electron-donor properties or of compounds with electron -acceptor properties.
  • P-type dopant refers to anelectron acceptor that increases the conductivity of an organic layer of an organic electronic device, when added to the organic layer as an additive.
  • Organic semiconductors may likewise be strongly influenced, with regard to their electrical conductivity, by doping.
  • Such organic semiconducting matrix materials may be made up of either compounds with good electron-donor properties or compounds with good electron -acceptor properties.
  • strong electron acceptors such as tetracyanoquinonedimethane (TCNQ) or 2,3,5,6- tetrafluorotetracyano-l ,4-benzoquinonedimethane (F4TCNQ) have become well known. By electron transfer processes, these produce so-called holes in electron donor-like base materials.
  • Butyllithium (16 mL, 2.3 M) in n-hexane was added dropwise to 3 g (16mmol) of ferrocene dissolved in 20 mL of hexane, followed by 3 mL (20 mol) of TMEDA. The reaction was allowed to proceed overnight, ca. 16 h. Then the product was filtered off, washed with 3*100 mL of hexane under ⁇ atmosphere. The ⁇ , ⁇ -dilithioferrocene-TMEDA complex was used in the next step without further purification.
  • FMPS (l .OOg) was heated in an evacuated, sealed Pyrex tube at 200°C for one hour. After the initial melt, an increase in viscosity was immediately observed, and after 30minutes the tube contents were immobile.
  • the polymer product was dissolved in tetrahydrofuran(THF) (10 mL). The polymer solution was then added dropwise to stirred methanol (200 mL) and the precipitated polymer was collected by filtration, re-dissolved in THF (30 mL), and re-precipitated into methanol (200 mL). Then the precipitated polymer was further purified by Soxhlet extraction using methanol for 48hours.
  • Cyclic voltammetry was performed on a CFfl 760D electrochemical work station at room temperature, with a conventional three-electrode configuration consisting of an Pt plate (diameter: 2mm) working electrode, a Pt wire counter electrode, and a Hg Hg2+ reference electrode. DMF was used as solvent and the supporting electrolyte was 0.1 M tetrabutylammonium hexafluorophosphate.
  • AFM was applied to visualize the surface morphology and determine the surface roughness of the spin coated FflL film.
  • the AFM measurement was performed by a tapping mode on a Dimension V instrument produced by Veeco.
  • the deflection of the cantilever also generated a depth profile (or height profile) to show the vertical deviations along the surface in the nanometer range.
  • the amplitude (A) of the vertical deviations was used to calculate the roughness of the surface.
  • Ra and Rq are the most commonly used amplitude parameters to describe the surface roughness. Ra is the arithmetic average of absolute amplitude values and Rq is the root mean square of the amplitude values, which are described as:
  • Ai is the amplitude (height or depth) of a pixel i (means a point on the surface) in the AFM image
  • n is the total number of pixels in the image.
  • part of the film was removed from the ITO substrate by a sharp blade, and then scanned by the cantilever. The thickness of the film was revealed by the gap between the two sections.
  • the surface roughness of the spin-coated PFMPS on ITO was characterized by AFM. The average roughness is reported in Table 2. After the spin-coated PFMPS on ITO, the roughness was improved from 5.3 nanometer (nm) to 1.02 nm of Rq.
  • the HOMO (Highest Occupied Molecular Orbital) level was tested using cyclic voltammetry method.
  • the CV-curve of PFMPS in DMF solution is shown in Figure 2. From the oxidation peak, the HOMO can be estimated to be -5.1—5.2 electron volts (eV). IV. Composition
  • a composition was prepared by blending under ambient conditions (23 °C, atmospheric pressure) 1 grams (g) of PFMPS and O.lg of TriphenylMethyltetrakis-(pentafluorophenyl)- borate (P-dopant)
  • HTL1 , HTL2, Fl Blue EML, ETL and Lithium quinolate (Liq) were deposited in sequence with a thickness of 5nm, 25nm, 20nm,30nm and lnm,respectively.
  • the deposition rates of organic layers were maintained at 0.05 to 0.1 nm/s.
  • the aluminum cathode was deposited at 0.5nm/s.
  • the active area of the OLED was 3 mm by 3 mm, as defined by the shadow mask for cathode deposition.
  • the glass substrate (20 mm by 20 mm) was available from Samsung Coming with ITO layer thickness of 1500 Angstrom (A).
  • OLED OLED(reported in Table 3) were hermetically sealed prior to testing.
  • the OLED have the following common structure: HIL (400A ⁇ 20A) HTL1 (50 A) HTL2 (250 A)/F1 Blue EML(200A)/Alq3(300A)/Liq(10A).
  • the turn-on voltage (Voltage at l OOOnit) of PFMPS is close to Comparative example based on polythiophene; the life time (600min) of PFMPS is longer than that of Comparative example based on polythiophene; current efficiency of PFMPS is the same with Comparative example based on polythiophene after doping with P-dopant.
  • OLED performance based on PFMPS is comparable or even better than Comparative Example based on polythiophene.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention porte sur une composition comprenant au moins un dopant et un polymère comprenant au moins un motif choisi parmi les structures I, dans lesquelles M est choisi parmi Fe, Co ou Ni; R1, R2, R3 et R4 sont chacun indépendamment choisis parmi l'atome d'hydrogène, l'atome de deutérium, un atome d'halogène, un groupe alkyle en C1-C16 substitué ou non substitué, un groupe aryle en C6-C16 substitué ou non substitué, un groupe cycloalkyle en C3-C16 substitué ou non substitué, un groupe hétérocycloalkyle à 5 à 7 chaînons substitué ou non substitué, un groupe aryle en C6-C16 substitué ou non substitué condensé avec un ou plusieurs groupes cycloalkyle, un groupe hétérocycloalkyle à 5 à 7 chaînons condensé avec un ou plusieurs noyaux aromatiques substitués ou non substitués ou un groupe cycloalkyle en C3-C16 condensé avec un ou plusieurs noyaux aromatiques substitués ou non substitués, un groupe silyle en C1-C16 substitué ou non substitué, un groupe cyano, un groupe nitro ou un groupe hydroxy; n est supérieur ou égal à 1; x va de 0 à 4; et y va de 0 à 4. Ces polymères, avec et sans dopant, sont utiles dans la préparation de films et de dispositifs électroniques, tels que des diodes électroluminescentes organiques (OLED).
PCT/CN2012/084766 2012-11-16 2012-11-16 Composition de polymère organométallique, procédé pour sa préparation et oled fabriquée à partir de celle-ci WO2014075300A1 (fr)

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PCT/CN2012/084766 WO2014075300A1 (fr) 2012-11-16 2012-11-16 Composition de polymère organométallique, procédé pour sa préparation et oled fabriquée à partir de celle-ci
CN201310574848.0A CN103819904A (zh) 2012-11-16 2013-11-15 有机金属聚合物组合物，制备它的方法，和由其制造的有机发光二极管
TW102141714A TW201434975A (zh) 2012-11-16 2013-11-15 有機金屬聚合物組成物、其製備方法以及由其製造之ｏｌｅｄ（二）
JP2013236487A JP2014116599A (ja) 2012-11-16 2013-11-15 有機金属ポリマー組成物、それを調製するための方法、およびそれから製作したｏｌｅｄ
KR1020130138754A KR20140063461A (ko) 2012-11-16 2013-11-15 유기금속 중합체 조성물, 그의 제조 방법, 및 그로부터 제작된 ｏｌｅｄ

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US9478758B1 (en) 2015-05-08 2016-10-25 Universal Display Corporation Organic electroluminescent materials and devices
WO2019048316A1 (fr) * 2017-09-07 2019-03-14 Johannes Gutenberg-Universität Mainz Procédé de préparation de ferrocène, de ruthénocène et d'osmocène substitués ainsi que des matières préparées selon ce procédé
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CHET C. ET AL: "SMALL MOLECULE CHEMISORPTION ON INDIUM-TIM OXIDE SURFACE:ENHANCING PROBE MOLECULE ELECTRON-TRANSFER RATES AND PERFORMANCE OF ORGANIC LIGHT-EMITTING DIODES", J.PHYS.CHEM.B, vol. 110, 2006, pages 25191 - 25202 *
NABAVIZADEH S.M. ET AL: "ASSEMBLY OF CYCLOMETALATED PLATINUM(II) COMPLEXES VIA 1,1-BIS(DIPHENYLPHOSPHINO)FERROCENE LIGAND: KINETICS AND MECHANISMS", ORGANOMETALLICS, vol. 30, 16 February 2011 (2011-02-16), pages 1466 - 1477 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9478758B1 (en) 2015-05-08 2016-10-25 Universal Display Corporation Organic electroluminescent materials and devices
US11522150B2 (en) 2017-02-20 2022-12-06 Novaled Gmbh Electronic device, method for preparing the same and display device comprising the same
US11539014B2 (en) 2017-02-20 2022-12-27 Novaled Gmbh Electronic semiconducting device, method for preparing the electronic semiconducting device and compound
US11825667B2 (en) 2017-02-20 2023-11-21 Novaled Gmbh Electronic semiconducting device and method for preparing the electronic semiconducting device
EP3364475B1 (fr) * 2017-02-20 2024-05-29 Novaled GmbH Dispositif elelctronique procede de fabrication et compose
US12022672B2 (en) 2017-02-20 2024-06-25 Novaled Gmbh Electronic semiconducting device, method for preparing the electronic semiconducting device and compound
WO2019048316A1 (fr) * 2017-09-07 2019-03-14 Johannes Gutenberg-Universität Mainz Procédé de préparation de ferrocène, de ruthénocène et d'osmocène substitués ainsi que des matières préparées selon ce procédé
CN113646916A (zh) * 2019-02-06 2021-11-12 诺瓦尔德股份有限公司 制备有机半导体层的方法、用于该方法的组合物以及有机电子器件

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