WO2014101178A1 - Tetraphenylene ethylene based compound and oled device containing the same - Google Patents

Tetraphenylene ethylene based compound and oled device containing the same Download PDF

Info

Publication number
WO2014101178A1
WO2014101178A1 PCT/CN2012/088034 CN2012088034W WO2014101178A1 WO 2014101178 A1 WO2014101178 A1 WO 2014101178A1 CN 2012088034 W CN2012088034 W CN 2012088034W WO 2014101178 A1 WO2014101178 A1 WO 2014101178A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
layer
hydrocarbon
combinations
electronic device
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2012/088034
Other languages
French (fr)
Inventor
Jean Jing YAN
Xiaofan Ren
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
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 Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Priority to PCT/CN2012/088034 priority Critical patent/WO2014101178A1/en
Priority to TW102146936A priority patent/TW201434802A/en
Priority to KR1020130163804A priority patent/KR20140088017A/en
Priority to JP2013270610A priority patent/JP2014129347A/en
Priority to CN201310743948.1A priority patent/CN104064689A/en
Publication of WO2014101178A1 publication Critical patent/WO2014101178A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/06—Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/58—Naphthylamines; N-substituted derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/40—Benzopyrazines
    • C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • 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
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3

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 shows a short lifetime 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.
  • the present disclosure provides a composition comprising a tetraphenylene ethylene of Structure (I), a tetraphenylene ethylene of Structure (IA), or a combination thereof as shown below.
  • Ri, R 2 , R 3 , and R 4 are the same or different.
  • Each of Ri, R 2 , R 3 , and R 4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; or
  • each of Ri and R 2 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and R 3 and R 4 form a ring structure; or
  • each of R3 and R4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and Ri and R 2 form a ring structure; or
  • Ri and R 2 form a ring structure
  • R 3 and R 4 form a ring structure
  • the present disclosure also provides a film formed from the present composition comprising the tetraphenylene ethylene of Structure (I), the tetraphenylene ethylene of Structure (IA), or a combination thereof.
  • the present disclosure also provides an electronic device comprising at least one component formed the present composition comprising the tetraphenylene ethylene of Structure (I), the tetraphenylene ethylene of Structure (IA), or a combination thereof.
  • An advantage of the present composition is that it can be used in both thermal evaporation and solution processes.
  • Figure 1 is a current-voltage curve for OLED devices in accordance with embodiments of the present disclosure.
  • Figure 2 is a graph showing the luminance efficiency of OLED devices in accordance with embodiments of the present disclosure.
  • Figure 3 is a graph showing the decay of luminance intensity with time for OLED devices in accordance with embodiments of the present disclosure.
  • the present disclosure provides a composition comprising the following: a tetraphenylene ethylene of Structure (I), a tetraphenylene ethylene of Structure (IA), or a combination thereof as shown below.
  • Ri, R 2 , R 3 , and R 4 are the same or different.
  • Each of Ri, R 2 , R 3 , and R 4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof; or
  • each of Ri and R 2 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof; and R 3 and R 4 form a ring structure; or
  • each of R 3 and R 4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof; and Ri and R 2 form a ring structure; or [0020] Ri and R 2 form a ring structure, and R 3 and R 4 form a ring structure.
  • each of Ri and R 2 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof; and R 3 and R 4 form a ring structure.
  • each of R3 and R4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof; and Ri and R 2 form a ring structure.
  • Ri and R 2 form a ring structure
  • R 3 and R 4 form a ring structure
  • the non-identified substituents of Structure (I) and Structure (IA) may be selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof. In an embodiment, the non-identified substituents of Structure (I) and Structure (IA) are hydrogen.
  • a "hydrocarbon,” as used herein, is a compound that contains only hydrogen and carbon.
  • the hydrocarbon contains 1 to 50 carbon atoms.
  • the hydrocarbon can be (i) branched or unbranched, (ii) saturated or unsaturated or aromatic, (iii) cyclic or acyclic, and (iv) any combination if (i)-(iii).
  • the term “hydrocarbon” includes "a hydrocarbylgroup,” (or “hydrocarbonyl group”)which is a hydrocarbon substituent having a valence (typically univalent).
  • the hydrocarbon contains 1 to 30 carbon atoms, or 1 to 24 carbon atoms, or 1 to 20 carbon atoms, or 1 to 12 carbon atoms, or 1 to 6 carbon atoms.
  • a “substituted hydrocarbon,” as used herein, is a hydrocarbon that includes one or more heteroatoms.
  • a “heteroatom” refers to an atom other than carbon or hydrogen.
  • Nonlimiting examples of heteroatoms include: F, CI, Br, N, O, P, B, S, Si, Sb, Al, Sn, As, Se and Ge.
  • An "unsubstituted hydrocarbon” is a hydrocarbon that contains no heteroatoms.
  • a "ring structure,” as used herein, is a ring composed of a hydrocarbon or a substituted hydrocarbon, and the ring structure can be saturated or unsaturated and the ring structure can contain one, or two, or more than two rings.
  • the composition includes a tetraphenylene ethylene (TPE) with the Structure (I) and isomers thereof.
  • TPE tetraphenylene ethylene
  • Structure (I) is provided below.
  • Ri, R 2 , R3, and R 4 are the same or different.
  • Each of R 1 -R 4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof.
  • each of R 1 -R 4 is independently selected from hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and combinations thereof.
  • alkyl group is a straight-chain, branched or unbranched, saturated hydrocarbon radical. Suitable alkyl radicals include, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl (or 2-methylpropyl), hexyl, octyl, etc. In an embodiment, the alkyl group has between 1 and 30, or between 1 and 24, or between 1 and 20, or between 1 and 12, or between 1 and 6 carbon atoms.
  • substituted alkyl group refers to an alkyl group as just described in which the hydrocarbon radical includes one or more heteroatoms.
  • aryl group is an aromatic substituent which may be a single aromatic ring or multiple aromatic rings which are fused together, linked covalently, or linked to a common group such as a methylene moiety or an ethylene moiety.
  • the aromatic ring(s) may include phenyl, naphthyl, anthracenyl, and biphenyl, among others.
  • the aryl group has between 6 and 50, or between 6 and 30, or between 6 and 24, or between 6 and 20, or between 6 and 12 carbon atoms.
  • substituted aryl group refers to an aryl group as just described, in which the aromatic substituent includes one or more heteroatoms.
  • the present composition includes isomers of Structure (I).
  • the TPE of Structure (I) includes a Z-isomer, an E-isomer, and combinations thereof.
  • the Z-isomer has the Structure (I) shown below.
  • the composition comprises Structure (I), wherein Ri, R 2 , R3, and R4are as defined above.
  • the E-isomer has the Structure (IA) shown below.
  • the composition comprises Structure (IA), wherein Ri, R 2 , R 3 , and R 4 are as defined above.
  • the present composition may comprise from greater than zero, or 1 wt % to 99wt % Z-isomer (Structure I) and from less the 100 wt %, or 99 wt % to 1 wt % E-isomer (Structure IA).
  • the composition comprises from greater than zero,orl wt %, or 10 wt %, or 25 wt %, or 50 wt %, or 75 wt%, or 90 wt%, or 99 wt% Z-isomer; and from less than 100 wt %, or 99 wt %, or 90 wt %, or 75 wt %, or 50 wt %, or 25 wt%, or 10 wt%, or 1 wt% E-isomer. Weight percent is based on total weight of the composition.
  • one, some, or all of Ri through R 4 include one or more aryl groups.
  • each of R1-R4 includes at least one or more aryl groups.
  • Ri and R 2 form a ring structure.
  • each of Ri and R 2 includes an aryl group, and Riand R 2 form a ring structure.
  • R3 and R4 form a ring structure.
  • each of R 3 and R 4 include an aryl group, and R 3 and R 4 form a ring structure.
  • Ri and R 2 form a ring structure, and R 3 and R 4 form another ring structure.
  • each of Riand R 2 includes an aryl group, and Riand R 2 form a ring structure, and each of R 3 and R 4 includes an aryl group, and R 3 and R 4 form a ring structure.
  • each of Rithrough R 4 is a phenyl group.
  • the TPE has the Structure (II) below.
  • each of Ri through R 4 of the TPE is a phenyl group.
  • the TPE is a mixture of Z-isomer (II) and E-isomer ( ⁇ ) as shown below.
  • the TPE of Structure (I), Structure (IA), and combination thereof has an calculated Highest Occupied Molecular Orbital (HOMO) level from -4.30 electron volts, eV) to -5.20 eV, or from -4.3 eV to -4.9 eV.
  • HOMO Highest Occupied Molecular Orbital
  • the TPE of Structure (I), Structure (IA), or combinations thereof has a calculated HOMO level from -4.3 eV to -4.6 eV.
  • the TPE of Structure (I) has a molecular weight (MW) from 700 to 1300 g/mole. In a further embodiment, the TPE of Structure (I) has a molecular weight from 800 to 1200 g/mole.
  • the TPE containing Structure (I), Structure (IA), or combinations thereof has a weight average molecular weight (Mw) from 500 to 1500 g/mole.
  • the composition is a solution.
  • the solution includes an aromatic solvent and the present TPE composition.
  • the TPE has Structure (I), Structure (IA), or a combination thereof.
  • the TPE is dissolved in the solvent.
  • the aromatic solvent is selected from xylene, toluene, benzene, anisole and combinations thereof.
  • the present composition may comprise two or more embodiments disclosed herein. 2.
  • the present disclosure provides a film formed from a composition comprising the following: the TEP of Structure (I), the TEP of Structure (IA), or a combination thereof.
  • the TEP of Structure (I) and the TEP of Structure (IA) can be any respective TEP as described above.
  • the film includes a TEP of Structure (I), a TEP of Structure (IA), or a combination thereof with the structures below.
  • Ri, R 2 , R 3 , and R 4 are the same or different.
  • Each of Ri, R 2 , R 3 , and R 4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; or
  • each of Ri and R 2 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and R 3 and R 4 form a ring structure; or
  • each of R3 and R4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and Ri and R 2 form a ring structure; or
  • Ri and R 2 form a ring structure
  • R 3 and R 4 form a ring structure
  • each of Ri and R 2 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and R 3 and R 4 form a ring structure.
  • each of R 3 and R 4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and Ri and R 2 form a ring structure.
  • Ri and R 2 form a ring structure
  • R 3 and R 4 form a ring structure
  • the film includes at least two layers, Layer A and Layer B.
  • Layer A includes the present TPE composition or is otherwise formed from a composition containing the TPE of Structure (I), the TPE of Structure (IA), or combinations thereof.
  • each of Ri through R 4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof.
  • Layer A is a hole injection layer.
  • the Layer A is a hole injection layer formed from the composition comprising the TEP of Structure (I), the TEP of Structure (IA), or combinations thereof and the composition has a HOMO level from -4.3 eV to -4.6 eV.
  • Layer B is a hole transport layer.
  • the thickness of Layer A is from 5nm to 500nm, or from 5nm to 100 nm, or from 5nm to 50nm
  • the thickness of Layer B is from 5nm to 500nm, or from 5nm to lOOnm, or from 5nm to 50nm.
  • Layer A further comprises a p-type dopant.
  • the p-type dopant is an organometal compound or an organometal salt.
  • the p-type 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 Layer 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.
  • the present film may comprise a combination of two or more embodiments disclosed herein. 3. Electronic Device
  • the present disclosure provides an electronic device comprising at least one component formed from a composition comprising the tetraphenylene ethylene of Structure (I), the tetraphenylene ethylene of Structure (IA), or combinations thereof.
  • the TEP of Structure (I) and the TEP of Structure (IA) can be any respective TEP as described above.
  • the electronic device includes a TEP of Structure (I), a TEP of Structure (IA), or combination thereof with the structures below.
  • Ri, R 2 , R 3 , and R 4 are the same or different.
  • Each of Ri, R 2 , R 3 , and R 4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; or
  • each of Ri and R 2 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and R 3 and R 4 form a ring structure; or
  • each of R 3 and R 4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and Ri and R 2 form a ring structure; or
  • Ri and R 2 form a ring structure
  • R 3 and R 4 form a ring structure
  • each of Ri and R 2 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and R 3 and R 4 form a ring structure.
  • each of R 3 and R 4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and Ri and R 2 form a ring structure. [0077] In an embodiment, Ri and R 2 form a ring structure, and R 3 and R4 form a ring structure.
  • the electronic device includes at least one layer containing the present composition with the TPE of Structure (I), the TPE of Structure (IA), or combinations thereof.
  • the electronic device includes a first electrode.
  • the electronic device includes a second electrode disposed over the first electrode.
  • the electronic device includes an organic layerdisposed between the first electrode and the second electrode.
  • the organic layer includes the present composition comprising the TPE of Structure (I), the TPE of Structure (IA), or combinations thereof.
  • the organic layer is Layer A and Layer A is a hole injection layer.
  • the electronic device includes a second Layer B.
  • Layer B is a hole transport layer.
  • Layer A is in contact with Layer B.
  • the electronic device includes an emitting layer.
  • the thickness of Layer A is from lnm to lOOOnm, or from 2 nm to 500 nm, or from 5 nm to 200 nm.
  • the thickness of Layer B is from 1 nm to 1000 nm, or from 2 nm to 500 nm, or from 5 nm to 200 nm.
  • the electronic device is an OLED (Organic Light Emitting
  • the electronic device includes a first electrode that is an ITO layer.
  • the electronic device also includes an HIL Layer, Layer A, containing the present TPE composition with the TPE of Structure (I), the TPE of structure (II), or combinations thereof.
  • the electronic device also includes a HTL Layer, Layer B.
  • the TPE composition of Layer A has a HOMO level that is between the HOMO level for the ITO layer and the HOMO level of the HTL material.
  • the TPE composition of Layer A has a calculated HOMO value from -4.3 eV to -4.6 eV.
  • the present electronic device may comprise a combination of two or more embodiments disclosed herein.
  • 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.
  • 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.
  • 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.
  • HTL Hole transport layer
  • High hole mobility is recommended for OLED devices.
  • 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 (TP AC), N,N-diphenyl- N,N-bis(3-methylphenyl)-l ,l -biphenyl-4,4-diamine (TPD), and N,N '-diphenyl- ⁇ , ⁇ '-bis(l- naphthyl)-(l ,1 '-biphenyl)-4,4'-diamine (NPB).
  • TP AC di(p-tolyl)aminophenyl]cyclohexane
  • TPD N,N '-diphenyl- ⁇ , ⁇ '-bis(l- naphthyl)-(l ,1 '-biphenyl)-4,4'-diamine
  • Solvent A: THF; B: 0.1%FA in water/THF 95/5
  • UV detector Diode Array 254 nm
  • HPLC High Pressure Liquid Chromatography
  • Cyclicvoltammetry (CV):CV for the compounds was carried out on a CHI voltammetric analyzerin a three-electrode cell with a Pt counter electrode, an Hg Hg 2 Cl2reference electrode, and a Platinum plate electrode at a scan rate of lOmV/s with 0.1 M tetrabutylammonium hexafluorophosphateas the supporting electrolyte. Ferrocene was added as the internal standard. The potential values were calculated according to the peak difference of the oxidation peak of the hole injection material and ferrocene standard.
  • Atomic Force Microscope AFM was applied to visualize the surface morphology and determine the surface roughness as well as the film thickness of the spin coated FflL film.
  • the AFM measurement was performed by a tapping mode on a Dimension V instrument produced by Veeco.
  • the amplitude (A) of the vertical deviations was used to calculate the roughness of the surface.
  • the amplitude parameters R a and R q are used to describe the surface roughness.
  • Ra is the arithmetic average of absolute amplitude values
  • Rq is the root mean square of the amplitude values, which are described as:
  • A 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 mixture was centrifuged and the supematant was concentrated and purified on a silica gel column using a mixture of petroleum ether and dichloromethane (2:1) as eluent.
  • the product (3) was a bright yellow powder (60%).
  • the yellow powder was purified by sublimation at 360°C to obtain a pure product, which has a HPLC purity of 99.4%(Z isomer: 55.7%, E isomer:46.7%).
  • Nonlimiting examples of the present TPE with Structure (I), Structure (IA) are provided in Table 2 below. Table 2
  • the HOMO level is calculated by the method described below
  • ITO glass (Sodalime glass: 2 cm*2 cm) was pre-treated by ultrasonicating in soap water, acetone, ethanol and w -propanol in sequence and drying thoroughly in air.
  • the composition (3) was prepared in the synthesis example (above) and was dissolved in anisole with a concentration of 5 mg/mL. Then the solution was spin-coated on clean ITO.
  • the surface roughness of the spin-coated film of compound 3on ITO was characterized by Atomic Force Microscopy (AFM) (shown in Table 4). Compared to the original ITO, which has a surface roughness of 5.3 nm, the surface roughness (R q ) after spin-coating compound 3 on it decreased to 0.5 nm after spin-coating compound 3 on ITO.
  • AFM Atomic Force Microscopy
  • OLEDs were fabricated onto an ITO coated glass substrate that served as the anode, and topped with an aluminum cathode. All organic layers were thermally deposited by chemical vapor deposition in a vacuum chamber with a base pressure of less than 1 x 10 "7 Torr.The deposition rates of organic layers were maintained at 0.1-0.05 nm/s.
  • the aluminum cathode was deposited at 0.5 nra/s.
  • the active area of the OLED device was "3 mm x 3mm," as defined by the shadow mask for cathode deposition.
  • the glass substrate (20mm by 20mm) was available from Samsung Corning with ITO layer thickness of 1500 Angstrom.
  • ITO glass (2 cm x 2 cm) was cleaned as described in the film example above, and treated with oxygen plasma.
  • Compound 3 was prepared in the synthesis example (above), and was dissolved in anisole with a concentration of approximately 20 mg/mL.
  • the solution of compound 3 was spin-coated onto the ITO glass substrates as HIL in glove box.
  • the film was annealed at 80°C for 20 min. Then the film substrates were transferred into a thermal evaporator, under a vacuum of approximately 1 x 10 "7 Torr.
  • HTL1, HTL2, Fl Blue EML Aluminum 8 -Hydroxy quinolinate (Alq 3 ) and Lithium quinolate (Liq) were deposited, in sequence, with a thickness of 5nm, 25nm, 20nm,30nm and 2nm,respectively.
  • the deposition rates of organic layers were maintained at 0.1-0.05 nm/s.
  • the deposition rates of organic layers were maintained at 0.1-0.05 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.
  • composition (3) is vacuum deposited onto ITO instead of being spin-coated.
  • the device structure is as follows:
  • J-V-L current-voltage-brightness
  • KEITHLY 2308 Luminescence meter
  • EL spectra of the OLED devices were collected by a calibrated CCD spectrograph.
  • FIGS 1 -3 and Table 5 show that inventive devicesl and 2 using inventive composition (3) as HIL (either deposited by thermo-evaporation or solution process), exhibit comparable driving voltage and efficiency as comparative examples3 and 4. However, device examples 1 and 2 exhibit better lifetime compared to the comparative examples. After 600 min with a starting luminance of 4000 Cd/m 2 , the luminance of device remains the same (100%) as the beginning for the devices comprising compound 3 applied by evaporation process(Device example 1) and it becomes slightly higher (102.3%) than the beginning for the devices comprising compound 3 applied by solution process (Device example 2). However, for the devices comprising polythiophene (Comparative example 3) and 2-TNATA (Comparative example 4) as HIL, respectively, decreased to 01.3% and 07.3% after the same duration.
  • the Applicant has developed hole-injection material formed from the composition comprising TPE of Structure (I), TPE of structure (IA), or a combination thereof.
  • the present TPE composition is suitable for both thermo-evaporation and solution processes.
  • Devices comprising such material as HIL show comparable driving voltage and efficiency as those using polythiophenes and 2-TNATAas HIL but longer lifetime than those using polythiophenes and 2-TNATAas HIL.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Quinoline Compounds (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Indole Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present disclosure provides a composition, a film containing the composition, and an electronic device containing the composition. The composition comprises a tetraphenylene ethylene of Structure (I), a tetraphenylene ethylene of Structure (IA), or a combination thereof: wherein for each structure (I) and (IA), R1, R2, R3, and R4 are the same or different, and wherein R1, R2, R3 and R4 are each independently selected from the group consisting of hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof.

Description

TETRAPHENYLENE ETHYLENE BASED COMPOUND
AND OLED DEVICE CONTAINING THE SAME
BACKGROUND
[0001] An OLED (organic light-emitting diode) 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). To facilitate hole injection, and achieve a smooth surface, a hole injection layer (HIL), located between an ITO anode and a hole transfer layer, is often desired. The most commonly used HIL material is poly(3,4- ethylenedioxythiophene)/poly(styrene sulfonic acid) complex (PEDOT/PSS). However, OLED fabricated from PEDOT PSS shows a short lifetime due to corrosion, induced by the high acidity of the PEDOT/PSS. In addition, 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.
[0002] Conventional multilayered OLED devices are produced by way of thermal deposition. Thermal deposition, however, has drawbacks. Thermal deposition requires thermal evaporation under high vacuum which increases fabrication complexity and makes the utilization of the expensive OLED materials very inefficient (typically less than 20%). Additionally, pixelation using evaporation masks limits the scalability and resolution of the OLED device.
[0003] Solution processes, such as such as ink-jet printing and nozzle printing, are becoming viable alternatives to thermal deposition production techniques for OLED devices. Unfortunately, conventional OLED materials, such as N,N'-Di-[(l-naphthalenyl)-N,N'- diphenyl]-l,l'-biphenyl)-4,4'-diamine (NPB) and 4,4',4'-Tris[2- naphthyl(phenyl)amino]triphenylamine (2-TNATA), are not suitable for the solution process due to poor film morphology and crystallization upon spin-casting. [0004] A need therefore exists for OLED materials that can be used in solution processes for the production of OLED devices. A need further exists for OLED materials that can be used in both thermal deposition and solution processes for the production of OLED devices.
SUMMARY
[0005] The present disclosure provides a composition comprising a tetraphenylene ethylene of Structure (I), a tetraphenylene ethylene of Structure (IA), or a combination thereof as shown below.
Figure imgf000003_0001
[0006] For each structure (I) and (IA), Ri, R2, R3, and R4 are the same or different. Each of Ri, R2, R3, and R4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; or
[0007] each of Ri and R2 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and R3 and R4 form a ring structure; or
[0008] each of R3 and R4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and Ri and R2 form a ring structure; or
[0009] Ri and R2 form a ring structure, and R3 and R4 form a ring structure.
[0010] The present disclosure also provides a film formed from the present composition comprising the tetraphenylene ethylene of Structure (I), the tetraphenylene ethylene of Structure (IA), or a combination thereof.
[0011] The present disclosure also provides an electronic device comprising at least one component formed the present composition comprising the tetraphenylene ethylene of Structure (I), the tetraphenylene ethylene of Structure (IA), or a combination thereof. [0012] An advantage of the present composition is that it can be used in both thermal evaporation and solution processes.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Figure 1 is a current-voltage curve for OLED devices in accordance with embodiments of the present disclosure.
[0014] Figure 2 is a graph showing the luminance efficiency of OLED devices in accordance with embodiments of the present disclosure.
[0015] Figure 3 is a graph showing the decay of luminance intensity with time for OLED devices in accordance with embodiments of the present disclosure.
DETAILED DESCRIPTION
1. Composition
[0016] The present disclosure provides a composition comprising the following: a tetraphenylene ethylene of Structure (I), a tetraphenylene ethylene of Structure (IA), or a combination thereof as shown below.
Figure imgf000004_0001
[0017] For each structure (I) and (IA), Ri, R2, R3, and R4 are the same or different. Each of Ri, R2, R3, and R4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof; or
[0018] each of Ri and R2is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof; and R3 and R4 form a ring structure; or
[0019] each of R3 and R4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof; and Ri and R2 form a ring structure; or [0020] Ri and R2 form a ring structure, and R3 and R4 form a ring structure.
[0021] In an embodiment, each of Ri and R2is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof; and R3 and R4 form a ring structure.
[0022] In an embodiment, each of R3 and R4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof; and Ri and R2 form a ring structure.
[0023] In an embodiment, Ri and R2 form a ring structure, and R3 and R4 form a ring structure.
[0024] The non-identified substituents of Structure (I) and Structure (IA) may be selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, or a combination thereof. In an embodiment, the non-identified substituents of Structure (I) and Structure (IA) are hydrogen.
[0025] A "hydrocarbon," as used herein, is a compound that contains only hydrogen and carbon. The hydrocarbon contains 1 to 50 carbon atoms. The hydrocarbon can be (i) branched or unbranched, (ii) saturated or unsaturated or aromatic, (iii) cyclic or acyclic, and (iv) any combination if (i)-(iii). The term "hydrocarbon" includes "a hydrocarbylgroup," (or "hydrocarbonyl group")which is a hydrocarbon substituent having a valence (typically univalent). In an embodiment, the hydrocarbon contains 1 to 30 carbon atoms, or 1 to 24 carbon atoms, or 1 to 20 carbon atoms, or 1 to 12 carbon atoms, or 1 to 6 carbon atoms.
[0026] A "substituted hydrocarbon," as used herein, is a hydrocarbon that includes one or more heteroatoms. A "heteroatom" refers to an atom other than carbon or hydrogen. Nonlimiting examples of heteroatoms include: F, CI, Br, N, O, P, B, S, Si, Sb, Al, Sn, As, Se and Ge.
[0027] An "unsubstituted hydrocarbon" is a hydrocarbon that contains no heteroatoms.
[0028] A "ring structure," as used herein, is a ring composed of a hydrocarbon or a substituted hydrocarbon, and the ring structure can be saturated or unsaturated and the ring structure can contain one, or two, or more than two rings.
[0029] In an embodiment, the composition includes a tetraphenylene ethylene (TPE) with the Structure (I) and isomers thereof. Structure (I) is provided below.
(I)
Figure imgf000006_0001
[0030] Ri, R2, R3, and R4 are the same or different. Each of R1-R4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof.
[0031] In an embodiment, each of R1-R4 is independently selected from hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and combinations thereof.
[0032] An "alkyl group" is a straight-chain, branched or unbranched, saturated hydrocarbon radical. Suitable alkyl radicals include, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl (or 2-methylpropyl), hexyl, octyl, etc. In an embodiment, the alkyl group has between 1 and 30, or between 1 and 24, or between 1 and 20, or between 1 and 12, or between 1 and 6 carbon atoms.
[0033] The term "substituted alkyl group," as used herein, refers to an alkyl group as just described in which the hydrocarbon radical includes one or more heteroatoms.
[0034] An "aryl group" is an aromatic substituent which may be a single aromatic ring or multiple aromatic rings which are fused together, linked covalently, or linked to a common group such as a methylene moiety or an ethylene moiety. The aromatic ring(s) may include phenyl, naphthyl, anthracenyl, and biphenyl, among others. In particular embodiments, the aryl group has between 6 and 50, or between 6 and 30, or between 6 and 24, or between 6 and 20, or between 6 and 12 carbon atoms.
[0035] The term "substituted aryl group," as used herein, refers to an aryl group as just described, in which the aromatic substituent includes one or more heteroatoms.
[0036] In an embodiment, the present composition includes isomers of Structure (I). The TPE of Structure (I) includes a Z-isomer, an E-isomer, and combinations thereof. [0037] The Z-isomer has the Structure (I) shown below. In an embodiment, the composition comprises Structure (I), wherein Ri, R2, R3, and R4are as defined above.
I)
Figure imgf000007_0001
[0038] The E-isomer has the Structure (IA) shown below. In an embodiment, the composition comprises Structure (IA), wherein Ri, R2, R3, and R4are as defined above.
(IA)
Figure imgf000007_0002
[0039] The present composition may comprise from greater than zero, or 1 wt % to 99wt % Z-isomer (Structure I) and from less the 100 wt %, or 99 wt % to 1 wt % E-isomer (Structure IA).
[0040] In an embodiment, the composition comprises from greater than zero,orl wt %, or 10 wt %, or 25 wt %, or 50 wt %, or 75 wt%, or 90 wt%, or 99 wt% Z-isomer; and from less than 100 wt %, or 99 wt %, or 90 wt %, or 75 wt %, or 50 wt %, or 25 wt%, or 10 wt%, or 1 wt% E-isomer. Weight percent is based on total weight of the composition. [0041] In an embodiment, one, some, or all of Ri through R4 include one or more aryl groups. In a further embodiment, each of R1-R4 includes at least one or more aryl groups.
[0042] In an embodiment, Ri and R2form a ring structure. In a further embodiment, each of Ri and R2 includes an aryl group, and Riand R2 form a ring structure.
[0043] In an embodiment, R3 and R4 form a ring structure. In a further embodiment, each of R3 and R4 include an aryl group, and R3 and R4 form a ring structure.
[0044] In an embodiment, Ri and R2 form a ring structure, and R3 and R4 form another ring structure. In a further embodiment, each of Riand R2 includes an aryl group, and Riand R2 form a ring structure, and each of R3 and R4 includes an aryl group, and R3 and R4 form a ring structure.
[0045] In an embodiment, each of Rithrough R4 is a phenyl group. In a further embodiment, the TPE has the Structure (II) below.
(Π)
Figure imgf000008_0001
[0046] In an embodiment, each of Ri through R4 of the TPE is a phenyl group. In a further embodiment, the TPE is a mixture of Z-isomer (II) and E-isomer (ΠΑ) as shown below.
Figure imgf000009_0001
(Π) (ΠΑ).
[0047] In an embodiment, the TPE of Structure (I), Structure (IA), and combination thereof, has an calculated Highest Occupied Molecular Orbital (HOMO) level from -4.30 electron volts, eV) to -5.20 eV, or from -4.3 eV to -4.9 eV.
[0048] In an embodiment, the TPE of Structure (I), Structure (IA), or combinations thereof has a calculated HOMO level from -4.3 eV to -4.6 eV.
[0049] In an embodiment, the TPE of Structure (I) has a molecular weight (MW) from 700 to 1300 g/mole. In a further embodiment, the TPE of Structure (I) has a molecular weight from 800 to 1200 g/mole.
[0050] In an embodiment the TPE containing Structure (I), Structure (IA), or combinations thereof has a weight average molecular weight (Mw) from 500 to 1500 g/mole.
[0051] In an embodiment, the composition is a solution. The solution includes an aromatic solvent and the present TPE composition. The TPE has Structure (I), Structure (IA), or a combination thereof. The TPE is dissolved in the solvent. In one embodiment, the aromatic solvent is selected from xylene, toluene, benzene, anisole and combinations thereof.
[0052] The present composition may comprise two or more embodiments disclosed herein. 2. Film
[0053] The present disclosure provides a film formed from a composition comprising the following: the TEP of Structure (I), the TEP of Structure (IA), or a combination thereof. The TEP of Structure (I) and the TEP of Structure (IA) can be any respective TEP as described above. In particular, the film includes a TEP of Structure (I), a TEP of Structure (IA), or a combination thereof with the structures below.
Figure imgf000010_0001
[0054] For each structure (I) and Structure (IA), Ri, R2, R3, and R4 are the same or different. Each of Ri, R2, R3, and R4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; or
[0055] each of Ri and R2is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and R3 and R4 form a ring structure; or
[0056] each of R3 and R4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and Ri and R2 form a ring structure; or
[0057] Ri and R2 form a ring structure, and R3 and R4 form a ring structure.
[0058] In an embodiment, each of Ri and R2is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and R3 and R4 form a ring structure.
[0059] In an embodiment, each of R3 and R4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and Ri and R2 form a ring structure.
[0060] In an embodiment, Ri and R2 form a ring structure, and R3 and R4 form a ring structure.
[0061] In an embodiment, the film includes at least two layers, Layer A and Layer B. Layer A includes the present TPE composition or is otherwise formed from a composition containing the TPE of Structure (I), the TPE of Structure (IA), or combinations thereof. In a further embodiment, each of Ri through R4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof. [0062] In an embodiment, Layer A is a hole injection layer. In an further embodiment, the Layer A is a hole injection layer formed from the composition comprising the TEP of Structure (I), the TEP of Structure (IA), or combinations thereof and the composition has a HOMO level from -4.3 eV to -4.6 eV.
[0063] In an embodiment, Layer B is a hole transport layer.
[0064] In an embodiment, the thickness of Layer A is from 5nm to 500nm, or from 5nm to 100 nm, or from 5nm to 50nm, and the thickness of Layer B is from 5nm to 500nm, or from 5nm to lOOnm, or from 5nm to 50nm.
[0065] In an embodiment, Layer A further comprises a p-type dopant. In a further embodiment, the p-type dopant is an organometal compound or an organometal salt.
[0066] In an embodiment, the p-type dopant is an organometal salt comprising at least one phenyl group. In a further embodiment, the anion component of the salt comprises a boron atom. In another further embodiment, the organometal salt has a structure selected from one of the following:
Figure imgf000011_0001
[0068] In an embodiment, the amount of dopant in Layer 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.
[0069] The present film may comprise a combination of two or more embodiments disclosed herein. 3. Electronic Device
[0070] The present disclosure provides an electronic device comprising at least one component formed from a composition comprising the tetraphenylene ethylene of Structure (I), the tetraphenylene ethylene of Structure (IA), or combinations thereof. The TEP of Structure (I) and the TEP of Structure (IA) can be any respective TEP as described above. In particular, the electronic device includes a TEP of Structure (I), a TEP of Structure (IA), or combination thereof with the structures below.
Figure imgf000012_0001
[0071] For each structure (I) and Structure (IA), Ri, R2, R3, and R4 are the same or different. Each of Ri, R2, R3, and R4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; or
[0072] each of Ri and R2is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and R3 and R4 form a ring structure; or
[0073] each of R3 and R4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and Ri and R2 form a ring structure; or
[0074] Ri and R2 form a ring structure, and R3 and R4 form a ring structure.
[0075] In an embodiment, each of Ri and R2is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and R3 and R4 form a ring structure.
[0076] In an embodiment, each of R3 and R4 is independently selected from hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and Ri and R2 form a ring structure. [0077] In an embodiment, Ri and R2 form a ring structure, and R3 and R4 form a ring structure.
[0078] In an embodiment, the electronic device includes at least one layer containing the present composition with the TPE of Structure (I), the TPE of Structure (IA), or combinations thereof.
[0079] In an embodiment, the electronic device includes a first electrode.
[0080] In an embodiment, the electronic device includes a second electrode disposed over the first electrode.
[0081] In an embodiment, the electronic device includes an organic layerdisposed between the first electrode and the second electrode. The organic layer includes the present composition comprising the TPE of Structure (I), the TPE of Structure (IA), or combinations thereof.
[0082] In an embodiment, the organic layer is Layer A and Layer A is a hole injection layer.
[0083] In an embodiment, the electronic device includes a second Layer B.
[0084] In an embodiment, Layer B is a hole transport layer.
[0085] In an embodiment, Layer A is in contact with Layer B.
[0086] In an embodiment, the electronic device includes an emitting layer.
[0087] In an embodiment, the thickness of Layer A is from lnm to lOOOnm, or from 2 nm to 500 nm, or from 5 nm to 200 nm. The thickness of Layer B is from 1 nm to 1000 nm, or from 2 nm to 500 nm, or from 5 nm to 200 nm.
[0088] In an embodiment, the electronic device is an OLED (Organic Light Emitting
Device).
[0089] In an embodiment, the electronic device includes a first electrode that is an ITO layer. The electronic device also includes an HIL Layer, Layer A, containing the present TPE composition with the TPE of Structure (I), the TPE of structure (II), or combinations thereof. The electronic device also includes a HTL Layer, Layer B. The TPE composition of Layer A has a HOMO level that is between the HOMO level for the ITO layer and the HOMO level of the HTL material. In an embodiment, the TPE composition of Layer A has a calculated HOMO value from -4.3 eV to -4.6 eV.
[0090] The present electronic device may comprise a combination of two or more embodiments disclosed herein.
DEFINITIONS [0091] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are by weight. For purposes of United States patent practice, the contents of any referenced patent, patent application or publication are incorporated by reference in their entirety (or its equivalent U.S. version is so incorporated by reference) especially with respect to the disclosure of synthetic techniques, definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure), and general knowledge in the art.
[0092] The terms "comprising," "including," "having," and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. In order to avoid any doubt, all 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. In contrast, the term, "consisting essentially of excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term "consisting of excludes any component, step or procedure not specifically delineated or listed.
[0093] "Dopant" and like terms, refer 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.
[0094] "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. For Fluorescent dopants, 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. For Phosphorescent dopants, the assisting host materials should have high triplet energy to confine triplets of the dopant.
[0095] "Hole transport layer (HTL)," and like terms, refers to a layer made from a material, which transports holes. High hole mobility is recommended for OLED devices. 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. Examples of HTL compounds include, but are not limited to, di(p-tolyl)aminophenyl]cyclohexane (TP AC), N,N-diphenyl- N,N-bis(3-methylphenyl)-l ,l -biphenyl-4,4-diamine (TPD), and N,N '-diphenyl-Ν,Ν '-bis(l- naphthyl)-(l ,1 '-biphenyl)-4,4'-diamine (NPB).
[0096] Some embodiments of the present disclosure will now be described in detail in the following Examples.
EXAMPLES
1. Materials
[0097] The materials used in the following examples are shown in Table 1.
Table 1 : Materials Used in the Examples
Figure imgf000015_0001
Figure imgf000016_0001
A.R. - Analytical Reagent
*SCRC = Sinopharm Chemical Reagent Co., Ltd.
2. Characterization
[0098] Nuclear Magnetic Resonance ( H and 13C NMR): The samples were dissolved in proper deuterated solvent with a concentration of 10 mg/mL. The NMR spectra were recorded on a Varian Mercury Plus 400 MHz spectrometer. Chemical shifts are reported versus tetramethylsilane.
[0099] Liquid Chromatography/Mass Spectrometry (LC/MS):
Sample was dissolved in THF at around 1 mg/mL. \ iL solution was injected for LC/MS analysis.
Instrument: Agilent 1220 HPLC/ G6224A TOF mass spectrometer
Column: Agilent eclipse-C18 4.6*50mm, 1.7μπι
Column oven temperature: 30°C
Solvent: A: THF; B: 0.1%FA in water/THF 95/5
Gradient: 0-6 min 40-80% A, hold for 9 min
Flow: 0.3 mL/min
UV detector: Diode Array 254 nm
MS condition:
Capillary Voltage: 3900 kV (Neg), 3500 kV (Pos)
Mode: Neg and Pos
Scan: 100-2000 amu
Rate: l s/scan
Desolvation temperature: 300°C [00100] High Pressure Liquid Chromatography (HPLC): Approximately 50 mg of the sample is weighed then is diluted with 10 g tetrahydrofuran. The sample solution is filtrated through a 0.45 μιτι syringe filter and 5 μΐ of the filtrate is injected to HPLC system.
Parameter Parameter Value
Injection volume 5 μΐ,
Instrument Agilent 1200 HPLC
Column Agilent Zorbax C8 4.6*250mm, 5 urn
Temperature 40°C Detector DAD=330 nm, ref=470 nm
Mobile Phase Eluent A: Water(0.1 % FA); Eluent B : THF
Time A% B% Flow Rate(mL/min)
0.0 42 58 1
40 35 65 1
47 34 66 1
48 10 90 1
[00101] Cyclicvoltammetry (CV):CV for the compounds was carried out on a CHI voltammetric analyzerin a three-electrode cell with a Pt counter electrode, an Hg Hg2Cl2reference electrode, and a Platinum plate electrode at a scan rate of lOmV/s with 0.1 M tetrabutylammonium hexafluorophosphateas the supporting electrolyte. Ferrocene was added as the internal standard. The potential values were calculated according to the peak difference of the oxidation peak of the hole injection material and ferrocene standard.
[00102] Atomic Force Microscope (AFM):AFM was applied to visualize the surface morphology and determine the surface roughness as well as the film thickness of the spin coated FflL film. The AFM measurement was performed by a tapping mode on a Dimension V instrument produced by Veeco.
[00103] The amplitude (A) of the vertical deviations was used to calculate the roughness of the surface. The amplitude parameters Ra and Rq are used 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:
Figure imgf000017_0001
where A; is the amplitude (height or depth) of a pixel i (means a point on the surface) in the AFM image, and n is the total number of pixels in the image.
[00104] To determine the thickness of the spin coated film, 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.
3. Synthesis of Tetraphenylene Ethylene-Type Materials
[00105] A. Synthesis of 1 ,2-bis(4-bromophenyl)-l ,2-diphenylethenes(l)
Figure imgf000018_0001
Br
1
Scheme 1
[00106] 4-Bromobenzophenone (5 g, 19.2 mmol) and zinc dust (2.5 g, 38.2 mmol) was placed into a 250 mL two-necked round-bottom flask equipped with a reflux condenser. After evacuation under vacuum and flushing with dry nitrogen three times, 100 mL of THF was added. The mixture was cooled to 0-5°C in ice-water bath, and 2.1 mL (19.2 mmol) of TiCl4 was added slowly using a syringe. The mixture was slowly warmed to room temperature, and after stirring for 0.5 hour, it was refluxed for 12 hours. After cooling down to room temperature, the reaction mixture was poured into ice water and extracted three times with dichloromethane. The solvent was evaporated under vacuum and the residue was washed with ethanol to yield a white powder(yield 70%).
1H-NMR(CDC13, 400 MHz): 7.19-7.25 (m, 3H), 7.06-7.13(m, 7H), 6.96-7.03(m, 5H), 6.85- 6.90(m, 3H).
[00107] B. S nthesisoj 1 ,2-bis[4-(N-phenyl)aminophenylJ-l ,2-diphenylethenes (2)
Figure imgf000018_0002
Scheme 2
[00108] Under an atmosphere of nitrogen, a 250 ml 3 -neck round bottom flask was charged with (1) (4.90 g, 10 mmol), Pd2(dba)3 (0.549 g, 0.6 mmol), t-BuOK(4.49 g, 40 mmol)and BINAP (0.747 g, 1.2 mmol). After evacuation under vacuum and flushing with dry nitrogen three times, aniline (2.32 g, 25 mmol) and 60 mL anhydrous toluene was added using a syringe sequentially. The mixture was heated to 80°C overnight and allowed to cool to room temperature. The mixture was centrifuged and the supematant was concentrated and purified on a silica gel column using a mixture of petroleum ether and ethyl acetate (10:1) as eluent. The product (2) was a pale yellow powder (yield 40%). 1H-NMR(d6-DMSO, 400 MHz), <5(TMS, ppm): 8.10-8.18 (d, 2H), 7.15-7.23 (m, 6 H), 7.05- 7.15(m, 4H), 6.95-7.07(m, 6H), 6.75-6.88 (m, 10 H).
[00109] C. Synthesis of l,2-bis(4-{N,N-[4-(N,N-diphenylamino)phenyl]phenyl}amino)- 1 ,2-diphenylethenes (3)
Scheme 3
[00110] Under an atmosphere of nitrogen, a 250 ml 3-neck round bottom flaskwas charged with (2) (1.54 g, 3 mmol), Pd2(dba)3 (0.137 g, 0.15 mmol) and t-BuOK (1.35 g, 12 mmol). After evacuation under vacuum and flushing with dry nitrogen three times, P(t-Bu)3 solution in toluene (100 mg/mL) (0.9 mL, 0.45 mmol) and 20 mL anhydrous toluene was added using a syringe sequentially. The mixture was heated to 80°C overnight and allowed to cool to room temperature. The mixture was centrifuged and the supematant was concentrated and purified on a silica gel column using a mixture of petroleum ether and dichloromethane (2:1) as eluent. The product (3) was a bright yellow powder (60%). The yellow powder was purified by sublimation at 360°C to obtain a pure product, which has a HPLC purity of 99.4%(Z isomer: 55.7%, E isomer:46.7%).
Figure imgf000019_0002
400 MHz), <5(TMS, ppm): 6.5-7.5 (m)
13C-NMR(CD2C12, 100 MHz), <5(ppm): 122.27, 122.41, 123.78, 123.95, 125.34, 125.46, 126.34, 127.62, 129.20, 131.46, 132.21
HRMS(ESI, m/z):\ 001 ^(M+H*)
[00111] Nonlimiting examples of the present TPE with Structure (I), Structure (IA) are provided in Table 2 below. Table 2
Figure imgf000020_0001
Table 2 (Cont'd)
Figure imgf000021_0001
Table 2 (Cont'd)
Figure imgf000022_0001
Table 2 (Cont'd)
Figure imgf000023_0001
Table 2 (Cont'd)
Figure imgf000024_0001
1 The HOMO level is calculated by the method described below
4. HOMO Level
[00112] Calculation of HOMO
[00113] Density Functional calculations were carried out using Gaussian 09 set of programs. The ground-state geometry of each molecule was optimized using the hybrid B3LYP functional with 6-3 lg (d) basis set, from which the HOMO molecular orbital values in electron volts (eV) were extracted. [00114] The geometry of each molecule at neutral and triplet state was optimized with the same method and basis set as that in ground-state calculation, from this and the ground-state calculation, the triplet energy was calculated from the energy difference between the neutral triplet and ground-state energy.
[00115] A procedure described in literature (J. Phys. Chem. A, 2003, 107, 5241-5251) was applied to calculate the reorganization energy of each molecule which is an indicator of electron and hole mobility.
[00116] Table 3 below compares the HOMO level for Example 1 (from Table 2) to the HOMO level for other tetraphenylene ethylene compounds (Inv - inventive and Comp = comparative).
Table 3 : Calculated HOMO levels of materials
Figure imgf000025_0001
Table 3 (Cont'd)
Figure imgf000026_0001
lrrhe HOMO level calculated by the method described above
INV = Inventive Example
COMP = Comparative Sample 5. Film
[00117] ITO glass (Sodalime glass: 2 cm*2 cm) was pre-treated by ultrasonicating in soap water, acetone, ethanol and w -propanol in sequence and drying thoroughly in air. The composition (3)was prepared in the synthesis example (above) and was dissolved in anisole with a concentration of 5 mg/mL. Then the solution was spin-coated on clean ITO. The surface roughness of the spin-coated film of compound 3on ITO was characterized by Atomic Force Microscopy (AFM) (shown in Table 4). Compared to the original ITO, which has a surface roughness of 5.3 nm, the surface roughness (Rq) after spin-coating compound 3 on it decreased to 0.5 nm after spin-coating compound 3 on ITO.
Table 4: Surface roughness before and after spin-coating of Compound 3 on ITO
Figure imgf000027_0001
6. Device examples
A. Device example 1
[00118] All organic materials were purified by sublimation before deposition. OLEDs were fabricated onto an ITO coated glass substrate that served as the anode, and topped with an aluminum cathode. All organic layers were thermally deposited by chemical vapor deposition in a vacuum chamber with a base pressure of less than 1 x 10"7Torr.The deposition rates of organic layers were maintained at 0.1-0.05 nm/s. The aluminum cathode was deposited at 0.5 nra/s. The active area of the OLED device was "3 mm x 3mm," as defined by the shadow mask for cathode deposition. The glass substrate (20mm by 20mm) was available from Samsung Corning with ITO layer thickness of 1500 Angstrom.
[00119] ITO glass (2 cm x 2 cm) was cleaned as described in the film example above, and treated with oxygen plasma. Compound 3 was prepared in the synthesis example (above), and was dissolved in anisole with a concentration of approximately 20 mg/mL. The solution of compound 3 was spin-coated onto the ITO glass substrates as HIL in glove box. The film was annealed at 80°C for 20 min. Then the film substrates were transferred into a thermal evaporator, under a vacuum of approximately 1 x 10"7 Torr. The following layers: HTL1, HTL2, Fl Blue EML, Aluminum 8 -Hydroxy quinolinate (Alq3) and Lithium quinolate (Liq)were deposited, in sequence, with a thickness of 5nm, 25nm, 20nm,30nm and 2nm,respectively. The deposition rates of organic layers were maintained at 0.1-0.05 nm/s. The deposition rates of organic layers were maintained at 0.1-0.05 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.
[00120] Finally the device was sealed with epoxy before testing. The device structure is as follows:
Compound3(40 nm)/HTLl (5 nm) HTL2 (25 nm)/Fl Blue ML(20 nm)/
Alq3(30 nm) /Liq(2 nm)
B. Device example 2
[00121] The procedure is the same as described in device example 1 , except that composition (3) is vacuum deposited onto ITO instead of being spin-coated. The device structure is as follows:
Compound3 (40 nm)/HTLl (5 nm) HTL2 (25 nm)/Fl Blue ML(20 nm)/
Alq3(30 nm) /Liq(2 nm)
C Comparative sample 3— Device
[00122] The procedure is the same as described in device example 1 except that 2-TNATA is vacuum deposited as HIL instead of Compound 3.
D. Comparative Sample 4— Device
[00123] The procedure is the same as described in device example 1 , except that polythiophene (Plextronics Co.) is spin-coated as HIL instead of Compound 3.
E. Testing
[00124] The current-voltage-brightness (J-V-L) characterizations for the OLED were performed with a source measurement unit (KEITHLY 238) Luminescence meter (MINOLTA CS-100A). EL spectra of the OLED devices were collected by a calibrated CCD spectrograph.
[00125] Current- Voltage curves, luminescence efficiency curves, and luminescence decay curves of inventive device examples 1 and 2, and comparative samples 3 and 4 are shown in Figures 1, 2 and 3, respectively. The data of driving voltage (at 1000 Cd^2),current efficiency (at 1OOOCdr2) and lifetime (4000Cdr2, after 600 min) for these devices are compiled in Table 5. Table 5: Comparison of driving voltage, current efficiency and lifetime of devices using (3), polythiophenes and 2-TNATA as HIL
V Cd/A CIE Lifetime
@1000Cd/ @1000Cd @1000Cd/ 4000Cd/m2,
m" /m;i m" 600min
Comnositio III )( Evaporated ) 4 4 5 0 1 51 1 51 ] 0( ) 0
Composition (3)(Spin-coated) 4.6 6.6 149/153 102.3
PoK tln( "iphene 4 3 6 4 148 1 72 01 3
2-TNATA 4.1 5.8 148,145 97.3 [00126] Figures 1 -3 and Table 5 show that inventive devicesl and 2 using inventive composition (3) as HIL (either deposited by thermo-evaporation or solution process), exhibit comparable driving voltage and efficiency as comparative examples3 and 4. However, device examples 1 and 2 exhibit better lifetime compared to the comparative examples. After 600 min with a starting luminance of 4000 Cd/m2, the luminance of device remains the same (100%) as the beginning for the devices comprising compound 3 applied by evaporation process(Device example 1) and it becomes slightly higher (102.3%) than the beginning for the devices comprising compound 3 applied by solution process (Device example 2). However, for the devices comprising polythiophene (Comparative example 3) and 2-TNATA (Comparative example 4) as HIL, respectively, decreased to 01.3% and 07.3% after the same duration.
[00127] In this disclosure, the Applicant has developed hole-injection material formed from the composition comprising TPE of Structure (I), TPE of structure (IA), or a combination thereof. The present TPE composition is suitable for both thermo-evaporation and solution processes. Devices comprising such material as HIL show comparable driving voltage and efficiency as those using polythiophenes and 2-TNATAas HIL but longer lifetime than those using polythiophenes and 2-TNATAas HIL.
[00128] It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.

Claims

1. A composition comprising:
a tetraphenylene ethylene of Structure (I), a tetraphenylene ethylene of Structure (IA), or a combination thereof:
Figure imgf000030_0001
wherein for each structure (I) and (IA), Ri, R2, R3, and R4 are the same or different, and wherein each of Ri, R2, R3, and R4 is independently selected from the group consisting of hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; or
wherein each of Ri and R2 is independently selected from the group consisting of hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and R3 and R4 form a ring structure; or
wherein each R3 and R4 IS independently selected from the group consisting of hydrogen, a hydrocarbon, a substituted hydrocarbon, and combinations thereof; and Ri and R2 form a ring structure; or
wherein Ri and R2 form a ring structure, and R3 and R4 form a ring structure.
2. The composition of claim 1, comprising isomers of Structure (I) selected from the group consisting of Z-isomer, E-isomer, and combinations thereof.
3. The composition of claim 1, wherein each of Ri through R4 comprises at least one aryl group.
4. The composition of claim 1, wherein each of Ri through R4 is a phenyl group.
5. The composition of claim 1, wherein the tetraphenylene ethylene of Structure (I), the tetraphenylene ethylene of structure (IA), or a combination thereof has a calculated HOMO level from -4.3 eV to -4.6 eV.
6. The composition of claim 1, wherein the tetraphenylene ethylene of Structure (I) has a molecular weight from 700 g/mole to 1300 g/mole.
7. The composition of claim 1, further comprising an aromatic solvent.
8. The composition of claim 7, wherein the aromatic solvent is selected from the group consisting of xylene, toluene, benzene, anisole and combinations thereof.
9. A film comprising at least two layers, Layer A and Layer B, and wherein layer A is formed from the composition of claim 1.
10. The film of claim 9, wherein Layer A is a hole injection layer.
11. The film of claim 10 wherein the composition has a calculated HOMO level from -4.3 eV to -4.6 eV.
12. The film of claim 9, wherein Layer B is a hole transport layer.
13. An electronic device comprising at least one component formed from the composition of claim 1.
14. The electronic device of claim 13, further comprising a first electrode.
15. The electronic device of all of claims 13-14, further comprising a second electrode disposed over the first electrode.
16. The electronic device of claim 13, wherein the component comprises the composition as an organic layer, the organic layer disposed between a first electrode and a second electrode.
17. The electronic device of claim 13, wherein the component is a hole injection layer comprising the composition.
18. The electronic device of claim 17, wherein the composition has a calculated HOMO level from -4.3 eV to -4.6 eV.
PCT/CN2012/088034 2012-12-31 2012-12-31 Tetraphenylene ethylene based compound and oled device containing the same Ceased WO2014101178A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
PCT/CN2012/088034 WO2014101178A1 (en) 2012-12-31 2012-12-31 Tetraphenylene ethylene based compound and oled device containing the same
TW102146936A TW201434802A (en) 2012-12-31 2013-12-18 Tetrastyrene-based compound and OLED device containing the same
KR1020130163804A KR20140088017A (en) 2012-12-31 2013-12-26 Tetraphenylene ethylene based compound and oled device containing the same
JP2013270610A JP2014129347A (en) 2012-12-31 2013-12-27 Tetraphenylene ethylene based compound and oled device containing the same
CN201310743948.1A CN104064689A (en) 2012-12-31 2013-12-30 Composition based on tetraphenylethylene and OLED device containing composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2012/088034 WO2014101178A1 (en) 2012-12-31 2012-12-31 Tetraphenylene ethylene based compound and oled device containing the same

Publications (1)

Publication Number Publication Date
WO2014101178A1 true WO2014101178A1 (en) 2014-07-03

Family

ID=51019782

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2012/088034 Ceased WO2014101178A1 (en) 2012-12-31 2012-12-31 Tetraphenylene ethylene based compound and oled device containing the same

Country Status (4)

Country Link
JP (1) JP2014129347A (en)
KR (1) KR20140088017A (en)
TW (1) TW201434802A (en)
WO (1) WO2014101178A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112920057A (en) * 2019-12-06 2021-06-08 三星显示有限公司 Organic electroluminescent device and amine compound for organic electroluminescent device

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104119861B (en) * 2013-04-27 2016-03-09 广东阿格蕾雅光电材料有限公司 organic electronic material
EP3457524B1 (en) 2014-06-06 2020-03-25 IHI Corporation Power-transmitting device, power-receiving device, and wireless power supply system
KR102622078B1 (en) * 2018-12-13 2024-01-05 엘지디스플레이 주식회사 Organic light emitting diode and organic light emitting device haivng the diode

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101928559A (en) * 2010-07-07 2010-12-29 中山大学 Aggregation-induced luminescent material containing triphenylethylene and tetraphenylethylene structures and its synthesis method and application
CN102190627A (en) * 2010-12-10 2011-09-21 吉林大学 9,10-phenanthroimidazole derivatives and use thereof as electroluminescent materials

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101928559A (en) * 2010-07-07 2010-12-29 中山大学 Aggregation-induced luminescent material containing triphenylethylene and tetraphenylethylene structures and its synthesis method and application
CN102190627A (en) * 2010-12-10 2011-09-21 吉林大学 9,10-phenanthroimidazole derivatives and use thereof as electroluminescent materials

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112920057A (en) * 2019-12-06 2021-06-08 三星显示有限公司 Organic electroluminescent device and amine compound for organic electroluminescent device
US20210175436A1 (en) * 2019-12-06 2021-06-10 Samsung Display Co., Ltd. Organic electroluminescence device and amine compound for organic electroluminescence device
EP3831807A3 (en) * 2019-12-06 2021-07-07 Samsung Display Co., Ltd. Organic electroluminescence device and amine compound for organic electroluminescence device
CN112920057B (en) * 2019-12-06 2024-02-09 三星显示有限公司 Organic electroluminescent device and amine compound used in organic electroluminescent device
US12439820B2 (en) * 2019-12-06 2025-10-07 Samsung Display Co., Ltd. Organic electroluminescence device and amine compound for organic electroluminescence device

Also Published As

Publication number Publication date
KR20140088017A (en) 2014-07-09
JP2014129347A (en) 2014-07-10
TW201434802A (en) 2014-09-16

Similar Documents

Publication Publication Date Title
US11793069B2 (en) Electron-accepting compound and composition for charge-transporting film, and luminescent element using same
TWI584513B (en) Display
US7972541B2 (en) Doped organic semiconductor material
CN104067400B (en) Organic electronic device
EP3055891B1 (en) Semiconducting material comprising a phosphine oxide matrix and metal salt
EP2887412B1 (en) Semiconducting material
KR101582707B1 (en) Electroactive materials
KR20150002740A (en) Use of a semiconducting compound in an organic light emitting device
Kumar et al. Solution-processable naphthalene and phenyl substituted carbazole core based hole transporting materials for efficient organic light-emitting diodes
KR20130114569A (en) Organic semiconducting material and electronic component
CN101326261A (en) Organic Electroluminescent Devices
TW201536757A (en) Compounds for organic light emitting device and organic light emitting devices having the same
Xia et al. Robust and highly efficient blue light-emitting hosts based on indene-substituted anthracene
KR102669989B1 (en) Phospepine matrix compounds for semiconducting materials
CN105859507A (en) Organic photoelectric material and use thereof
WO2014101178A1 (en) Tetraphenylene ethylene based compound and oled device containing the same
WO2010063609A2 (en) Hole injection material
CN104064689A (en) Composition based on tetraphenylethylene and OLED device containing composition
CN106549103B (en) Only electronics organic semiconductor diodes device
WO2017080445A1 (en) Organic electron transfer material
KR100812173B1 (en) Organic light emitting compound and display device comprising the same
CN118119205A (en) An organic electroluminescent device
HK1212094B (en) Semiconducting material

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: 12890825

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: 12890825

Country of ref document: EP

Kind code of ref document: A1