WO2009082157A2 - Aryl amine derivative and organic electroluminescence device using the same - Google Patents

Aryl amine derivative and organic electroluminescence device using the same Download PDF

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Publication number
WO2009082157A2
WO2009082157A2 PCT/KR2008/007608 KR2008007608W WO2009082157A2 WO 2009082157 A2 WO2009082157 A2 WO 2009082157A2 KR 2008007608 W KR2008007608 W KR 2008007608W WO 2009082157 A2 WO2009082157 A2 WO 2009082157A2
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group
biphenyl
naphthyl
amine derivative
aryl amine
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WO2009082157A3 (en
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Jung Sub Lee
Kyoung Soo Kim
Tae Hyung Kim
Ho Cheol Park
Sang-Do Lee
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Doosan Corp
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Doosan Corp
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    • 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
    • C07C211/61—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 with at least one of the condensed ring systems formed by three or more 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
    • C07C211/54—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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • 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
    • 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
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
    • C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
    • C07C2603/50—Pyrenes; Hydrogenated pyrenes

Definitions

  • the present invention relates to a novel aryl amine derivative and an organic electroluminescent device using the same.
  • organic electroluminescence refers to the phenomenon in which electric energy is converted into light energy by means of an organic substance. That is, if a voltage is applied between an anode and a cathode when an organic layer is disposed between both the electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer. Then, the injected holes and electrons are recombined to form excitons, and light is emitted when the excitons drop to the ground state.
  • the organic layer As a way to provide a more efficient organic electroluminescent device (OELD) , research has been actively pursued to form an organic layer in the device in a multilayer structure instead of a monolayer structure.
  • the organic layer In most organic electroluminescent devices in use, which have a structure in which an organic layer and electrodes are deposited, the organic layer generally has a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer
  • an organic layer in an organic electroluminescent device is formed in a multilayer structure in this way is that interfaces between electrodes and an organic material are stabilized, or holes and electrons having a large difference in mobility in an organic material can be effectively transported to a light emitting layer by using suitable hole transport and electron transport materials, and luminous efficiency can be improved by balancing the densities of holes and electrons in the light emitting layer. Accordingly, it can be said that hole injection, hole transport, electron injection, and electron transport layers play important roles in an organic electroluminescent device.
  • Organic electroluminescent devices comprising an organic material have been extensively studied since C. W. Tang et al. of the Eastman Kodak Co. developed an organic electroluminescent device by a vacuum deposition method in 1987.
  • An organic photoconductive material that has been developed as a hole transport material has many advantages, such as low cost, flexible processability, and pollution-free, and various compounds have been proposed as the organic photoconductive material.
  • Examples of such compounds include an oxadiazole derivative, an oxazole derivative, a hydrazone derivative, a triarylpyrazoline derivative, an aryl amine derivative, a stylbene derivatives, etc.
  • the aryl amine derivative such as 4, 4' , 4"-tris [N, N- (1- naphthyDphenylamino] triphenylamine ( 1-TNATA) , 4, 4' , 4"-tris [N, N- (m-tolyl)phenylamino] triphenylamine (MTDATA), 4, 4' -bis [N- (1- naphthyl) -N-phenylamino] biphenyl ( ⁇ -NPD) , or 4, 4' -bis [N- (m- tolyl) -N-phenylamino] biphenyl (TPD), is widely used as a hole transport material or a hole injection material.
  • the conventional hole transport material is disadvantageous in that its stability and durability are insufficient.
  • the film is whitened due to crystallization or agglomeration when left for about two weeks because ⁇ -NPD is originally a crystalline compound.
  • 2,7- bis (dinaphthylamino) -9, 9-dimethylfluorene that is a fluorene derivative having a dimethyl group at 9, 9-position, 2,7-bis(N,N- diphenylamino) -9, 9-diphenylfluorene that is a fluorene derivative having diphenyl group at 9, 9-position, and the like are highly crystalline materials, and thus have the same problem as mentioned above. Consequently, when they are applied to an organic film device, such as an organic electroluminescent device, there is a problem in that short-circuiting and dark-spot formation are highly probable. Therefore, there is a need to develop a hole transport material that is excellent in hole transport capability and film stability, and has high glass transition temperature (T 9 ) .
  • the present invention has been made in view of the above-mentioned problems, and the present invention provides an organic electroluminescent device having improved luminous efficiency, luminance, power efficiency, and thermal stability (i.e. heat resistance) by developing a novel synthesized aryl amine derivative comprising a tetrahydropyrene core and applying the developed aryl amine derivative to the organic electroluminescent device.
  • Ar 1 to Ar 4 , X 1 , and X 2 are each independently a
  • C 5 -C 30 aromatic ring group that is an aromatic ring group substituted or unsubstituted by at least one kind selected from the group consisting of a Ci-C 30 alkyl group, a C 2 -C 30 alkenyl group , a C 2 -C 30 al kynyl group, a C 5 -C 3O aryl group, a Cs-C 3O heteroaryl group, a Cs-C 30 aryloxy group, a Ci-C 30 alkyloxy group, a C 5 -C 30 arylamino group, a C 5 -C 30 diarylamino group, a C 6 -C 30 arylalkyl group, a C 3 -C 30 cycloalkyl group, a C 3 -C 3 O heterocycloalkyl group, and a halogen atom;
  • R 1 to R 11 are each independently selected from the group consisting of a hydrogen atom, a Ci-C 30 alkyl group, a C 2 -C 30 alkenyl group, a C 2 -C 30 alkynyl group, a C 5 -C 30 aryl group, a C 5 -C 30 heteroaryl group, a C 5 -C 30 aryloxy group, a Ci-C 30 alkyloxy group, a C 5 -C 30 arylamino group, a C 5 -C 30 diarylamino group, a C 6 -C 30 arylal kyl group , a C 3 -C 30 cycloal kyl group , a C 3 -C 30 heterocycloalkyl group, and a halogen atom; and n and m are each independently an integer of 0 to 2 .
  • the Ci-C 30 alkyl group, the C 2 -C 3O alkenyl group, the C 2 -C 3 O alkynyl group, the C 5 -C 30 aryl group, the C 5 -C 30 heteroaryl group, the C 5 -C 30 aryloxy group, the Ci-C 30 alkyloxy group, the C 5 -C 30 arylamino group, the C 5 -C 30 diarylamino group, the C 6 -C 30 arylalkyl group, the C 3 -C 30 cycloalkyl group, and the C 3 -C 30 heterocycloalkyl group in Ar 1 to Ar 4 , X 1 , X 2 , and R 1 to R 11 may be each independently further substituted or unsubstituted by at least one kind of substituent selected from the group consisting of halogen, an amino group, a nitrile group, a nitro group, a Ci-C 40 alkyl group, a C 2 -C 40
  • an organic electroluminescent device comprising (i) an anode; (ii) a cathode; and (iii) one or more organic layers between the anode and the cathode, at least one of the one or more organic layers comprising the above aryl amine derivative represented by Formula 1.
  • the organic layer comprising the above aryl amine derivative represented by Formula 1 comprises a hole transport layer.
  • the aryl amine derivative represented by Formula 1 according to the present invention can ensure the stability of a material by an increased glass transition temperature (T 9 ) .
  • T 9 glass transition temperature
  • the stability, luminous efficiency, luminance, and power efficiency of an organic electroluminescent device can be improved.
  • the aryl amine derivative according to the present invention can significantly contribute to an improvement in the hole transport capability of an organic electroluminescent device, and particularly such an improved hole transport capability is very effective to maximize the performance of a full-color organic EL panel .
  • the aryl amine derivative represented by Formula 1 is a compound comprising a tetrahydropyrene core, amine groups (-NAr 1 Ar 2 and -NAr 3 Ar 4 ) each independently substituted at 2 and 7 positions of the tetrahydropyrene, and aromatic ring groups (X 1 and X 2 ) each independently substituted or unsubstituted between the tetrahydropyrene core and the amine groups (-NAr 1 Ar 2 and -NAr 3 Ar 4 ) .
  • Ar 1 to Ar 4 , X 1 , and X 2 are each independently a
  • C 5 -C 30 aromatic ring group that is preferably, but not limited to, a monovalent or divalent group selected from the group consisting of benzene, biphenyl, terphenyl, naphthalene, anthracene, triphenylamine, phenanthrene, pyrene, fluorene, and xanthene .
  • the aryl amine derivative represented by Formula 1 may be expressed by compounds presented below in Tables 1 to 3. However, the following compounds in Tables 1 to 3 are illustrative merely, and the aryl amine derivative represented by Formula 1 according to the present invention is not limited thereto.
  • HT-155 4, 4-biphenyl 4-biphenyl 3-biphenyl HT-156 4, 4-biphenyl 4-biphenyl HT-157 4, 4-biphenyl 4-biphenyl 2-p-terphenyl HT-158 1, 5-naphthyl 1-naphthyl 1-naphthyl HT-159 1, 5-naphthyl 1-naphthyl 2-naphthyl HT-160 1, 5-naphthyl 1-naphthyl 9-phenanthryl HT-161 1, 5-naphthyl 1-naphthyl 1-pyrenyl HT-162 1, 5-naphthyl 1-naphthyl phenyl HT-163 1, 5-naphthyl 1-naphthyl 2-biphenyl HT-164 1, 5-naphthyl 1-naphthyl 3-
  • S-group that is S-I to S-47
  • S-I to S-47 corresponds to non-limitative examples of amine substituents (-NAr 1 Ar 2 and - NAr 3 Ar 4 ) in Formula 1.
  • -NAr 1 Ar 2 and -NAr 3 Ar 4 may be each independently selected from, but not limited to, the following S- group, that is, S-I to S-47.
  • the organic electroluminescent device comprises (i) an anode, (ii) a cathode, and
  • the aryl amine derivative represented by Formula 1 may be a mixture of at least two kinds of aryl amine derivatives represented by Formula 1.
  • the aryl amine derivative represented by Formula 1 may be included as a hole transport material in the organic electroluminescent device to thereby improve the luminous efficiency, luminance, power efficiency, and thermal stability of the organic electroluminescent device.
  • the organic layer comprising the aryl amine derivative represented by Formula 1 is preferably a hole transport layer.
  • the organic layers other than the organic layer comprising the aryl amine derivative of the present invention may be a hole injection layer, a hole transport layer, a light emitting layer, and/or an electron transport layer.
  • a non-limitative example of the organic electroluminescent device according to the present invention may have a structure in which, for example, a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are laminated in sequence, and the hole transport layer of them comprises the aryl amine derivative represented by Formula 1.
  • An electron injection layer may be disposed on the electron transport layer.
  • the organic electroluminescent device according to the present invention may further comprise an insulating layer or adhesive layer that is inserted at the interfaces of the electrodes and the organic layers respectively.
  • the organic layer comprising the aryl amine derivative represented by Formula 1 may be formed by a vacuum deposition method or solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, thermal transfer, and the like.
  • the organic electroluminescent device according to the present invention may be manufactured by forming the organic layers and the electrodes by use of materials and methods well known in the art, except that at least one of the organic layers is formed in such a manner as to comprise the aryl amine derivative of the present invention.
  • a silicon wafer for example, a silicon wafer, a quartz or glass plate, a metal plate, a plastic film or sheet, etc. may be used as a substrate.
  • anode material examples include, but are not limited to, metal, such as vanadium, chrome, copper, zinc, and gold, or alloy thereof; metal oxide, such as zinc oxide, indium oxide, indium tin oxide (ITO) , and indium zinc oxide (IZO) ; ZnO; Al or SnO 2 ; a combination of metal, such as Sb, and oxide; conductive polymer, such as polythiophene, poly (3-methylthiophene) , poly [3, 4- (ethylene-1, 2-dioxy) thiophene] (PEDT), polypyrrole, and polyaniline; and carbon black.
  • metal such as vanadium, chrome, copper, zinc, and gold, or alloy thereof
  • metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO) , and indium zinc oxide (IZO)
  • ZnO zinc oxide
  • Al or SnO 2 a combination of metal, such as Sb, and oxide
  • conductive polymer such as polythiophene, poly
  • Examples of a cathode material include, but are not limited to, metal, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloy thereof; and a material having a multilayer structure, such as LiF/Al or LiO 2 ZAl. Further, there is no particular limitation on the materials of the hole injection, light emitting, electron transport, and electron injection layers, and they may be formed using conventional materials. Reference will now be made in detail to exemplary embodiments of the present invention. However, the following examples are illustrative merely, and the scope of the present invention is not limited thereto.
  • An OELD was manufactured by the following method: A glass substrate, on which an ITO (indium tin oxide) film was coated to a thickness of 1500A, was ultrasonically cleaned with distilled water. On completion of the cleaning with distilled water, the substrate was ultrasonically cleaned with a solvent, such as isopropyl alcohol, acetone, or methanol, was dried, and then was delivered to a plasma cleaner. In the plasma cleaner, the substrate was cleaned using oxygen plasma for 5 minutes, and then was delivered to a vacuum deposition apparatus.
  • a solvent such as isopropyl alcohol, acetone, or methanol
  • DS-205 Doosan, Korea was thermally vacuum-deposited to a thickness of 800A on the so-prepared ITO (anode) to form a hole injection layer, and the aryl amine derivative represented by Formula 1-5 (HT-I) was vacuum-deposited to a thickness of 150A on the hole injection layer to form a hole transport layer.
  • DS-H45 the aryl amine derivative represented by Formula 1-5
  • An OELD was manufactured in the same manner as in Example 1, except that the aryl amine derivative represented by Formula 1-1 (HT-2), obtained in Preparation Example 2, was used as the hole transport material, instead of the aryl amine derivative represented by Formula 1-5 (HT-I) , obtained in Preparation Example 1.
  • HT-2 aryl amine derivative represented by Formula 1-1
  • HT-I aryl amine derivative represented by Formula 1-5
  • An OELD was manufactured in the same manner as in Example 1, except that the aryl amine derivative represented by Formula 1-14 (HT-3) , obtained in Preparation Example 3, was used as the hole transport material, instead of the aryl amine derivative represented by Formula 1-5 (HT-I) , obtained in Preparation Example 1.
  • Example 1 had a luminance of 608cd/m 2 and thus exhibited a luminous efficiency of 6.1cd/A at a current density of lOmA/cm 2 and a voltage of 5.2V
  • Example 2 had a luminance of 618cd/m 2 and thus exhibited a luminous efficiency of 6.5cd/A at a current density of lOmA/cm 2 and a voltage of 5.3V
  • Example 3 had a luminance of 602cd/m 2 and thus exhibited a luminous efficiency of 6.1cd/A at a current density of lOmA/cm 2 and a voltage of 5.5V
  • Example 4 had a luminance of 609cd/m 2 and thus exhibited a luminous efficiency of ⁇ .Ocd/A at a current density of lOmA/cm 2 and a voltage of 5.7V.
  • Comparative Example 1 had a luminance of 560cd/m 2 and thus exhibited a luminous efficiency of
  • the inventive materials have an effect of reducing a driving voltage as compared to existing NPB because material stability ensured by their increased glass transition temperature (T 9 ) contributes to device stability, and additionally can also improve luminous efficiency.

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Abstract

Disclosed are a novel aryl amine derivative and an organic electroluminescent device using the same. More specially, the aryl amine derivative is a compound comprising a tetrahydropyrene core, amine groups (-NAr1Ar2 and -NAr3Ar4) each independently substituted at 2 and 7 positions of the tetrahydropyrene, and aromatic ring groups (X1 and X2) each independently substituted or unsubstituted between the tetrahydropyrene core and the amine groups (-NAr1Ar2 and -NAr3Ar4). Further, provided is an organic electroluminescent device comprising (i) an anode, (ii) a cathode, and (iii) one or more organic layers between the anode and the cathode, at least one of the one or more organic layers comprising the aryl amine derivative. Preferably, the organic layer comprising the aryl amine derivative is a hole transport layer.

Description

ARYL AMINE DERIVATIVE AND ORGANIC ELECTROLUMINESCENCE DEVICE
USING THE SAME
Technical Field The present invention relates to a novel aryl amine derivative and an organic electroluminescent device using the same.
Background Art As generally know in the art, organic electroluminescence refers to the phenomenon in which electric energy is converted into light energy by means of an organic substance. That is, if a voltage is applied between an anode and a cathode when an organic layer is disposed between both the electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer. Then, the injected holes and electrons are recombined to form excitons, and light is emitted when the excitons drop to the ground state.
As a way to provide a more efficient organic electroluminescent device (OELD) , research has been actively pursued to form an organic layer in the device in a multilayer structure instead of a monolayer structure. In most organic electroluminescent devices in use, which have a structure in which an organic layer and electrodes are deposited, the organic layer generally has a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer
The reason why an organic layer in an organic electroluminescent device is formed in a multilayer structure in this way is that interfaces between electrodes and an organic material are stabilized, or holes and electrons having a large difference in mobility in an organic material can be effectively transported to a light emitting layer by using suitable hole transport and electron transport materials, and luminous efficiency can be improved by balancing the densities of holes and electrons in the light emitting layer. Accordingly, it can be said that hole injection, hole transport, electron injection, and electron transport layers play important roles in an organic electroluminescent device.
Organic electroluminescent devices comprising an organic material have been extensively studied since C. W. Tang et al. of the Eastman Kodak Co. developed an organic electroluminescent device by a vacuum deposition method in 1987.
An organic photoconductive material that has been developed as a hole transport material has many advantages, such as low cost, flexible processability, and pollution-free, and various compounds have been proposed as the organic photoconductive material. Examples of such compounds include an oxadiazole derivative, an oxazole derivative, a hydrazone derivative, a triarylpyrazoline derivative, an aryl amine derivative, a stylbene derivatives, etc. Among others, the aryl amine derivative, such as 4, 4' , 4"-tris [N, N- (1- naphthyDphenylamino] triphenylamine ( 1-TNATA) , 4, 4' , 4"-tris [N, N- (m-tolyl)phenylamino] triphenylamine (MTDATA), 4, 4' -bis [N- (1- naphthyl) -N-phenylamino] biphenyl (α-NPD) , or 4, 4' -bis [N- (m- tolyl) -N-phenylamino] biphenyl (TPD), is widely used as a hole transport material or a hole injection material. However, the conventional hole transport material is disadvantageous in that its stability and durability are insufficient. For example, in the case of an α-NPD film formed by a vacuum deposition method, the film is whitened due to crystallization or agglomeration when left for about two weeks because α-NPD is originally a crystalline compound. Also, 2,7- bis (dinaphthylamino) -9, 9-dimethylfluorene that is a fluorene derivative having a dimethyl group at 9, 9-position, 2,7-bis(N,N- diphenylamino) -9, 9-diphenylfluorene that is a fluorene derivative having diphenyl group at 9, 9-position, and the like are highly crystalline materials, and thus have the same problem as mentioned above. Consequently, when they are applied to an organic film device, such as an organic electroluminescent device, there is a problem in that short-circuiting and dark-spot formation are highly probable. Therefore, there is a need to develop a hole transport material that is excellent in hole transport capability and film stability, and has high glass transition temperature (T9) .
Disclosure Technical Problem
Therefore, the present invention has been made in view of the above-mentioned problems, and the present invention provides an organic electroluminescent device having improved luminous efficiency, luminance, power efficiency, and thermal stability (i.e. heat resistance) by developing a novel synthesized aryl amine derivative comprising a tetrahydropyrene core and applying the developed aryl amine derivative to the organic electroluminescent device.
Technical Solution
In accordance with an aspect of the present invention, there is provided an aryl amine derivative represented by the following Formula 1: [Formula 1]
Figure imgf000004_0001
In Formula 1, Ar1 to Ar4, X1, and X2 are each independently a
C5-C30 aromatic ring group that is an aromatic ring group substituted or unsubstituted by at least one kind selected from the group consisting of a Ci-C30 alkyl group, a C2-C30 alkenyl group , a C2-C30 al kynyl group, a C5-C3O aryl group, a Cs-C3O heteroaryl group, a Cs-C30 aryloxy group, a Ci-C30 alkyloxy group, a C5-C30 arylamino group, a C5-C30 diarylamino group, a C6-C30 arylalkyl group, a C3-C30 cycloalkyl group, a C3-C3O heterocycloalkyl group, and a halogen atom;
R1 to R11 are each independently selected from the group consisting of a hydrogen atom, a Ci-C30 alkyl group, a C2-C30 alkenyl group, a C2-C30 alkynyl group, a C5-C30 aryl group, a C5-C30 heteroaryl group, a C5-C30 aryloxy group, a Ci-C30 alkyloxy group, a C5-C30 arylamino group, a C5-C30 diarylamino group, a C6-C30 arylal kyl group , a C3-C30 cycloal kyl group , a C3-C30 heterocycloalkyl group, and a halogen atom; and n and m are each independently an integer of 0 to 2 . Here, the Ci-C30 alkyl group, the C2-C3O alkenyl group, the C2-C3O alkynyl group, the C5-C30 aryl group, the C5-C30 heteroaryl group, the C5-C30 aryloxy group, the Ci-C30 alkyloxy group, the C5-C30 arylamino group, the C5-C30 diarylamino group, the C6-C30 arylalkyl group, the C3-C30 cycloalkyl group, and the C3-C30 heterocycloalkyl group in Ar1 to Ar4, X1, X2, and R1 to R11 may be each independently further substituted or unsubstituted by at least one kind of substituent selected from the group consisting of halogen, an amino group, a nitrile group, a nitro group, a Ci-C40 alkyl group, a C2-C40 alkenyl group, a Ci-C40 alkoxy group, a C3-C40 cycloalkyl group, a C2-C40 heterocycloalkyl group, a C5-C40 aryl group, and a C4-C40 heteroaryl group.
In accordance with another aspect of the present invention, there is an organic electroluminescent device (OELD) comprising (i) an anode; (ii) a cathode; and (iii) one or more organic layers between the anode and the cathode, at least one of the one or more organic layers comprising the above aryl amine derivative represented by Formula 1.
Preferably, in the above organic electroluminescent device, the organic layer comprising the above aryl amine derivative represented by Formula 1 comprises a hole transport layer.
Advantageous Effects The aryl amine derivative represented by Formula 1 according to the present invention can ensure the stability of a material by an increased glass transition temperature (T9) . Thus, when the aryl amine derivative according to the present invention is employed as a hole transport material, the stability, luminous efficiency, luminance, and power efficiency of an organic electroluminescent device can be improved. In the long run, the aryl amine derivative according to the present invention can significantly contribute to an improvement in the hole transport capability of an organic electroluminescent device, and particularly such an improved hole transport capability is very effective to maximize the performance of a full-color organic EL panel .
Best Mode The aryl amine derivative represented by Formula 1 according to the present invention is a compound comprising a tetrahydropyrene core, amine groups (-NAr1Ar2 and -NAr3Ar4) each independently substituted at 2 and 7 positions of the tetrahydropyrene, and aromatic ring groups (X1 and X2) each independently substituted or unsubstituted between the tetrahydropyrene core and the amine groups (-NAr1Ar2 and -NAr3Ar4) .
In Formula 1, Ar1 to Ar4, X1, and X2 are each independently a
C5-C30 aromatic ring group that is preferably, but not limited to, a monovalent or divalent group selected from the group consisting of benzene, biphenyl, terphenyl, naphthalene, anthracene, triphenylamine, phenanthrene, pyrene, fluorene, and xanthene .
More specially, the aryl amine derivative represented by Formula 1 may be expressed by compounds presented below in Tables 1 to 3. However, the following compounds in Tables 1 to 3 are illustrative merely, and the aryl amine derivative represented by Formula 1 according to the present invention is not limited thereto.
Table 1
Compound Ar1 Ar2 Ar3 Ar4
HT-I 1-naphthyl 1-naphthyl 1-naphthyl 1-naphthyl
HT-2 1-naphthyl 1-naphthyl 2-naphthyl 2-naphthyl
HT-3 1-naphthyl 1-naphthyl 9-phenanthryl 2-naphthyl
HT-4 1-naphthyl 1-naphthyl 1-pyrenyl 2-naphthyl
HT-5 1-naphthyl 1-naphthyl phenyl 2-biphenyl
HT-6 1-naphthyl 1-naphthyl 2-biphenyl 2-biphenyl
HT-7 1-naphthyl 1-naphthyl 3-biphenyl 2-biphenyl
HT-8 1-naphthyl 1-naphthyl 4-biphenyl 2-biphenyl
HT-9 1-naphthyl 1-naphthyl 2-p-terphenyl 4-biphenyl
HT-10 2-naphthyl 2-naphthyl 1-naphthyl 4-biphenyl
HT-Il 2-naphthyl 2-naphthyl 2-naphthyl 4-biphenyl
HT-12 2-naphthyl 2-naphthyl 9-phenanthryl 4-biphenyl
HT-13 2-naphthyl 2-naphthyl 1-pyrenyl 4-biphenyl
HT-14 2-naphthyl 2-naphthyl phenyl 3-biphenyl
HT-15 2-naphthyl 2-naphthyl 2-biphenyl 3-biphenyl
HT-16 2-naphthyl 2-naphthyl 3-biphenyl 3-biphenyl
HT-17 2-naphthyl 2-naphthyl 4-biphenyl 3-biphenyl
HT-18 2-naphthyl 2-naphthyl 2-p-terphenyl 3-biphenyl
HT-19 9-phenanthryl 9-phenanthryl 1-naphthyl 9-phenanthryl
HT-20 9-phenanthryl 9-phenanthryl 2-naphthyl 9-phenanthryl
HT-21 9-phenanthryl 9-phenanthryl 9-phenanthryl 1-pyrenyl
HT-22 9-phenanthryl 9-phenanthryl 1-pyrenyl 9-phenanthryl
HT-23 9-phenanthryl 9-phenanthryl phenyl 9-phenanthryl
HT-24 9-phenanthryl 9-phenanthryl 2-biphenyl 1-pyrenyl
HT-25 9-phenanthryl 9-phenanthryl 3-biphenyl 1-pyrenyl
HT-26 9-phenanthryl 9-phenanthryl 4-biphenyl 1-pyrenyl
HT-27 9-phenanthryl 9-phenanthryl 2-p-terphenyl l~pyrenyl HT-28 1-pyrenyl 1-pyrenyl 1-naphthyl 9-phenanthryl HT-29 1-pyrenyl 1-pyrenyl 2-naphthyl 9-phenanthryl HT-30 1-pyrenyl 1-pyrenyl 9-phenanthryl 9-phenanthryl HT-31 1-pyrenyl 1-pyrenyl 1-pyrenyl 1-pyrenyl HT-32 1-pyrenyl 1-pyrenyl phenyl 1-pyrenyl HT-33 1-pyrenyl 1-pyrenyl 2-biphenyl 1-pyrenyl HT-34 1-pyrenyl 1-pyrenyl 3-biphenyl 1-pyrenyl HT-35 1-pyrenyl 1-pyrenyl 4-biphenyl phenyl HT-36 1-pyrenyl 1-pyrenyl 2-p-terphenyl phenyl HT-37 phenyl phenyl 1-naphthyl phenyl HT-38 phenyl phenyl 2-naphthyl phenyl HT-39 phenyl phenyl 9-phenanthryl phenyl HT-40 phenyl phenyl 1-pyrenyl 4-biphenyl HT-41 phenyl phenyl phenyl 4-biphenyl HT-42 phenyl phenyl 2-biphenyl 4-biphenyl HT-43 phenyl phenyl 3-biphenyl 4-biphenyl HT-44 phenyl phenyl 4-biphenyl 4-biphenyl HT-45 phenyl phenyl 2-p-terphenyl 3-biphenyl HT-46 2-biphenyl 2-biphenyl 1-naphthyl 3-biphenyl HT-47 2-biphenyl 2-biphenyl 2-naphthyl 3-biphenyl HT-48 2-biphenyl 2-biphenyl 9-phenanthryl 3-biphenyl HT-49 2-biphenyl 2-biphenyl 1-pyrenyl 3-biphenyl HT-50 2-biphenyl 2-biphenyl phenyl 3-biphenyl HT-51 4-biphenyl 2-biphenyl 2-biphenyl 2-biphenyl HT-52 4-biphenyl 2-biphenyl 3-biphenyl 3-biphenyl HT-53 4-biphenyl 2-biphenyl 4-biphenyl 3-biphenyl HT-54 4-biphenyl 2-biphenyl 2-p-terphenyl 3-biphenyl HT-55 4-biphenyl 3-biphenyl 1-naphthyl 3-biphenyl HT-56 4-biphenyl 3-biphenyl 2-naphthyl 3-biphenyl HT-57 4-biphenyl 3-biphenyl 9-phenanthryl 9-phenanthryl HT-58 4-biphenyl 3-biphenyl 1-pyrenyl 1-pyrenyl HT-59 4-biphenyl 3-biphenyl phenyl phenyl HT-60 3-biphenyl 3-biphenyl 2-biphenyl 2-biphenyl HT-61 3-biphenyl 3-biphenyl 3-biphenyl 3-biphenyl HT-62 3-biphenyl 3-biphenyl 4-biphenyl 3-biphenyl HT-63 3-biphenyl 3-biphenyl 2-p-terpheny 3-biphenyll HT-64 4-biphenyl 4-biphenyl 1-naphthyl 2-biphenyl HT-65 4-biphenyl 4-biphenyl 2-naphthyl 2-biphenyl HT-66 4-biphenyl 4-biphenyl 9-phenanthryl 4-biphenyl HT-67 4-biphenyl 4-biphenyl 1-pyrenyl 4-biphenyl HT-68 4-biphenyl 4-biphenyl phenyl 9-phenanthryl HT-69 4-biphenyl 4-biphenyl 2-biphenyl 9-phenanthryl HT-70 4-biphenyl 4-biphenyl 3-biphenyl 1-pyrenyl HT-71 4-biphenyl 4-biphenyl 4-biphenyl 1-pyrenyl HT-72 4-biphenyl 4-biphenyl 2-p-terphenyl phenyl HT-73 1-naphthyl 1-naphthyl 1-naphthyl phenyl HT-74 1-naphthyl 1-naphthyl 2-naphthyl 2-naphthyl HT-75 1-naphthyl 1-naphthyl 9-phenanthryl 2-naphthyl HT-76 1-naphthyl 1-naphthyl 1-pyrenyl 1-naphthyl HT-77 1-naphthyl 1-naphthyl phenyl 1-naphthyl HT-78 1-naphthyl 1-naphthyl 2-biphenyl 1-naphthyl HT-79 1-naphthyl 1-naphthyl 3-biphenyl 3-biphenyl HT-80 1-naphthyl 1-naphthyl 4-biphenyl 2-biphenyl HT-81 1-naphthyl 1-naphthyl 2-p-terphenyl 4--biphenyl HT-82 2-naphthyl 2-naphthyl 1-naphthyl 9-phenanthryl HT-83 2-naphthyl 2-naphthyl 2-naphthyl phenyl HT-84 2-naphthyl 2-naphthyl 9-phenanthryl 2-naphthyl HT-85 2-naphthyl 2-naphthyl 1-pyrenyl 1-naphthyl
Table2
Compound X1 Ar1, Ar2 Ar3, Ar4
HT-86 2,4-biphenyl 2-biphenyl 2-biphenyl
HT-87 2, 4-biphenyl 2-biphenyl 3-biphenyl
HT-88 2, 4-biphenyl 2-biphenyl 4-biρhenyl
HT-89 2, 4-biphenyl 2-biphenyl 2-p-terphenyl
HT-90 3, 4-biphenyl 3-biphenyl 1-naρhthyl
HT-91 3, 4-biphenyl 3-biphenyl 2-naphthyl HT-92 3, 4-biphenyl 3-biphenyl 9-phenanthryl
HT-93 3, 4-biphenyl 3-biphenyl 1-pyrenyl
HT-94 3, 4-biphenyl 3-biphenyl phenyl
HT-95 3, 4-biphenyl 3-biphenyl 2-biphenyl
HT-96 3, 4-biphenyl 3-biphenyl 3-biphenyl
HT-97 3, 4-biphenyl 3-biphenyl 4-biphenyl
HT-98 3, 4-biphenyl 3-biphenyl 2-p-terphenyl
HT-99 4, 4-biphenyl 4-biphenyl 1-naphthyl
HT-100 4, 4-biphenyl 4-biphenyl 2-naphthyl
HT-101 4, 4-biphenyl 4-biphenyl 9-phenanthryl
HT-102 4, 4-biphenyl 4-biphenyl 1-pyrenyl
HT-103 4 , 4-biphenyl 4-biphenyl phenyl
HT-104 4, 4-biphenyl 4-biphenyl 2-biphenyl
HT-105 4, 4-biphenyl 4-biphenyl 3-biphenyl
HT-106 4, 4-biphenyl 4-biphenyl 4-biphenyl
HT-107 4, 4-biphenyl 4-biphenyl 2-p-terphenyl
HT-108 1, 5-naphthyl 1-naphthyl 1-naphthyl
HT-109 1, 5-naphthyl 1-naphthyl 2-naphthyl
HT-IlO 1, 5-naphthyl 1-naphthyl 9-phenanthryl
HT-111 1, 5-naphthyl 1-naphthyl 1-pyrenyl
HT-112 1, 5-naphthyl 1-naphthyl phenyl
HT-113 1, 5-naphthyl 1-naphthyl 2-biphenyl
HT-114 1, 5-naphthyl 1-naphthyl 3-biphenyl
HT-115 1, 5-naphthyl 1-naphthyl 4-biphenyl
HT-116 1, 5-naphthyl 1-naphthyl 2-p-terphenyl
HT-117 2, 6-naphthyl 2-naphthyl 1-naphthyl
HT-118 2, 6-naphthyl 2-naphthyl 2-naphthyl
HT-119 2, 6-naphthyl 2-naphthyl 9-phenanthryl
HT-120 2, 6-naphthyl 2-naphthyl 1-pyrenyl
HT-121 2, 6-naphthyl 2-naphthyl phenyl
HT-122 2, 6-naphthyl 2-naphthyl 2-biphenyl
HT-123 2, 6-naphthyl 2-naphthyl 3-biphenyl
HT-124 2, 6-naphthyl 2-naphthyl 4-biphenyl HT-125 2, 6-naphthyl 2-naphthyl 2-p-terphenyl
HT-126 4, 4-biphenyl 1-naphthyl 4-biphenyl
HT-127 4, 4-biphenyl 2-naphthyl 4-biphenyl
HT-128 4, 4-biphenyl 9-phenanthryl 9-phenanthryl
HT-129 4, 4-biphenyl 9-phenanthryl 1-pyrenyl
HT-130 4 , 4-biphenyl 9-phenanthryl phenyl
HT-131 4, 4-biphenyl 9-phenanthryl 2-biphenyl
HT-132 4, 4-biphenyl 9-phenanthryl 3-biphenyl
HT-133 4, 4-biphenyl 9-phenanthryl 4-biphenyl
HT-134 4, 4-biphenyl 9-phenanthryl 2-p-terphenyl
HT-135 4, 4-biphenyl 1-pyrenyl 1-naphthyl
Table 3
Compound X1, X2 Ar1, Ar2 Ar3, Ar4
HT-136 2, 4-biphenyl 2-biphenyl 2-biphenyl
HT-137 2, 4-biphenyl 2-biphenyl 3-biphenyl
HT-138 2, 4-biphenyl 2-biphenyl 4-biphenyl
HT-139 2, 4-biphenyl 2-biphenyl 2-p-terphenyl
HT-140 3, 4-biphenyl 3-biphenyl 1-naphthyl
HT-141 3, 4-biphenyl 3-biphenyl 2-naphthyl
HT-142 3, 4-biphenyl 3-biphenyl 9-phenanthryl
HT-143 3, 4-biphenyl 3-biphenyl 1-pyrenyl
HT-144 3, 4-biphenyl 3-biphenyl phenyl
HT-145 3, 4-biphenyl 3-biphenyl 2-biphenyl
HT-146 3, 4-biphenyl 3-biphenyl 3-biphenyl
HT-147 3, 4-biphenyl 3-biphenyl 4-biphenyl
HT-148 3, 4-biphenyl 3-biphenyl 2-p-terphenyl
HT-149 4, 4-biphenyl 4-biphenyl 1-naphthyl
HT-150 4, 4-biphenyl 4-biphenyl 2-naphthyl
HT-151 4, 4-biphenyl 4-biphenyl 9-phenanthryl
HT-152 4, 4-biphenyl 4-biphenyl 1-pyrenyl
HT-153 4, 4-biphenyl 4-biphenyl phenyl
HT-154 4, 4-biphenyl 4-biphenyl 2-biphenyl
HT-155 4, 4-biphenyl 4-biphenyl 3-biphenyl HT-156 4, 4-biphenyl 4-biphenyl 4-biphenyl HT-157 4, 4-biphenyl 4-biphenyl 2-p-terphenyl HT-158 1, 5-naphthyl 1-naphthyl 1-naphthyl HT-159 1, 5-naphthyl 1-naphthyl 2-naphthyl HT-160 1, 5-naphthyl 1-naphthyl 9-phenanthryl HT-161 1, 5-naphthyl 1-naphthyl 1-pyrenyl HT-162 1, 5-naphthyl 1-naphthyl phenyl HT-163 1, 5-naphthyl 1-naphthyl 2-biphenyl HT-164 1, 5-naphthyl 1-naphthyl 3-biphenyl HT-165 1, 5-naphthyl 1-naphthyl 4-biphenyl HT-166 1, 5-naphthyl 1-naphthyl 2-p-terphenyl HT-167 2, β-naphthyl 2-naphthyl 1-naphthyl HT-168 2, 6-naphthyl 2-naphthyl 2-naphthyl HT-169 2, 6-naphthyl 2-naphthyl 9-phenanthryl HT-170 2, β-naphthyl 2-naphthyl 1-pyrenyl HT-171 2, 6-naphthyl 2-naphthyl phenyl HT-172 2, β-naphthyl 2-naphthyl 2-biphenyl HT-173 2, 6-naphthyl 2-naphthyl 3-biphenyl HT-174 2, 6-naphthyl 2-naphthyl 4-biphenyl HT-175 2, 6-naphthyl 2-naphthyl 2-p-terphenyl HT-176 4, 4-biphenyl 1-naphthyl 4-biphenyl HT-177 4, 4-biphenyl 2-naphthyl 4-biphenyl HT-178 4, 4-biphenyl 9-phenanthryl 9-phenanthryl HT-179 4, 4-biphenyl 9-phenanthryl 1-pyrenyl HT-180 4, 4-biphenyl 9-phenanthryl phenyl HT-181 4, 4-biphenyl 9-phenanthryl 2-biphenyl HT-182 4, 4-biphenyl 9-phenanthryl 3-biphenyl HT-183 4, 4-biphenyl 9-phenanthryl 4-biphenyl HT-184 4, 4-biphenyl 9-phenanthryl 2-p-terphenyl HT-185 4, 4-biphenyl 1-pyrenyl 1-naphthyl
The following S-group, that is S-I to S-47, corresponds to non-limitative examples of amine substituents (-NAr1Ar2 and - NAr3Ar4) in Formula 1. Thus, -NAr1Ar2 and -NAr3Ar4 may be each independently selected from, but not limited to, the following S- group, that is, S-I to S-47.
Figure imgf000013_0001
S-2 S-3
S-1 S-4
Figure imgf000013_0002
S-12 S-13 S- 14
Figure imgf000013_0003
S-17
S-15 S-16
Figure imgf000013_0004
S-18 S-19 S-20
Figure imgf000014_0001
S-21 S-22 S-23
Figure imgf000014_0002
S-24 S-25 S-26
Figure imgf000014_0003
S-27 S-28 S-29
Figure imgf000014_0004
S-33 S-34 S-35
Figure imgf000014_0005
S-36 S-37 S-38
Figure imgf000014_0006
S-39 S-40 S-41
Figure imgf000015_0001
Figure imgf000015_0002
S-45 S-46
S-47
Also, typical examples of the aryl amine derivative represented by Formula 1 according to the present invention are as follows but not limited to: [Formula 1-1]
Figure imgf000015_0003
Figure imgf000016_0001
[Formula 1-7]
Figure imgf000016_0002
[Formula 1-8]
Figure imgf000017_0001
; Formula 1-9]
Figure imgf000017_0002
[Formula 1-11]
Figure imgf000017_0003
Figure imgf000018_0001
[Formula 1-15]
Figure imgf000018_0002
[Formula 1-16]
Figure imgf000018_0003
[Formula 1-17]
Figure imgf000019_0001
[Formula 1-19]
Figure imgf000019_0002
[Formula 1-21]
Figure imgf000019_0003
[Formula 1-22;
Figure imgf000020_0001
[Formula 1-24]
Figure imgf000020_0002
Further, the organic electroluminescent device according to the present invention comprises (i) an anode, (ii) a cathode, and
(iii) one or more organic layers between the anode and the cathode, and is characterized in that at least one of the one or more organic layers comprises the above aryl amine derivative represented by Formula 1.
Here, the aryl amine derivative represented by Formula 1 may be a mixture of at least two kinds of aryl amine derivatives represented by Formula 1.
Also, the aryl amine derivative represented by Formula 1 may be included as a hole transport material in the organic electroluminescent device to thereby improve the luminous efficiency, luminance, power efficiency, and thermal stability of the organic electroluminescent device.
Hole injection and transport materials may suffer from a lack of electrons while holes are created in a molecule, and thus the stability of the molecule may be reduced. However, the aryl amine derivative represented by Formula 1 is rich in electrons due to non-covalent electron pairs of amine existing in a molecule. Thus, when the aryl amine derivative represented by Formula 1 is used as a hole transport material, the non-covalent electron pairs of amine in the aryl amine derivative can reduce the instability of a molecule, which is caused by the creation of holes in the molecule, so that the overall molecular stability does not deteriorate. Thus, the organic layer comprising the aryl amine derivative represented by Formula 1 is preferably a hole transport layer. Further, in the organic electroluminescent device according to the present invention, the organic layers other than the organic layer comprising the aryl amine derivative of the present invention may be a hole injection layer, a hole transport layer, a light emitting layer, and/or an electron transport layer. More specially, a non-limitative example of the organic electroluminescent device according to the present invention may have a structure in which, for example, a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are laminated in sequence, and the hole transport layer of them comprises the aryl amine derivative represented by Formula 1. An electron injection layer may be disposed on the electron transport layer.
In addition to the structure in which an anode, one or more organic layers, and a cathode are laminated in sequence, the organic electroluminescent device according to the present invention may further comprise an insulating layer or adhesive layer that is inserted at the interfaces of the electrodes and the organic layers respectively. In the organic electroluminescent device according to the present invention, the organic layer comprising the aryl amine derivative represented by Formula 1 may be formed by a vacuum deposition method or solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, thermal transfer, and the like.
The organic electroluminescent device according to the present invention may be manufactured by forming the organic layers and the electrodes by use of materials and methods well known in the art, except that at least one of the organic layers is formed in such a manner as to comprise the aryl amine derivative of the present invention.
For example, a silicon wafer, a quartz or glass plate, a metal plate, a plastic film or sheet, etc. may be used as a substrate.
Examples of an anode material include, but are not limited to, metal, such as vanadium, chrome, copper, zinc, and gold, or alloy thereof; metal oxide, such as zinc oxide, indium oxide, indium tin oxide (ITO) , and indium zinc oxide (IZO) ; ZnO; Al or SnO2; a combination of metal, such as Sb, and oxide; conductive polymer, such as polythiophene, poly (3-methylthiophene) , poly [3, 4- (ethylene-1, 2-dioxy) thiophene] (PEDT), polypyrrole, and polyaniline; and carbon black. Examples of a cathode material include, but are not limited to, metal, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloy thereof; and a material having a multilayer structure, such as LiF/Al or LiO2ZAl. Further, there is no particular limitation on the materials of the hole injection, light emitting, electron transport, and electron injection layers, and they may be formed using conventional materials. Reference will now be made in detail to exemplary embodiments of the present invention. However, the following examples are illustrative merely, and the scope of the present invention is not limited thereto.
[Preparation Example 1] Preparation of Aryl Amine Derivative Represented by Formula 1-5 (HT-I)
Preparation Example 1-1: Preparation of 4,5,9,10- tetrahydropyrene
[Reaction Scheme 1]
Figure imgf000023_0001
1Og of pyrene was put into a flask, 500ml of ethyl acetate and 5g of Raney nickel were added thereto, and then the mixture solution was stirred under N2 at room temperature for 3 days. The reaction solution was filtered, the solvent was removed from the filtrate, and then the residual solid was dried. The dried solid was put into a flask, 250ml of ethanol and 0.15g of Pd/C were added thereto, and then the mixture solution was reacted at a pressure of 45psi H2 for 6 days. The reaction solution was filtered, the solvent was removed from the filtrate, and then the residual solid was dried to obtain 8g of tetrahydropyrene.
GC-Mass (theoretical value: 206.11g/mol, measured value: 206g/mol)
Preparation Example 1-2: Preparation of 2,7-dibromo- 4,5,9, 10-tetrahydropyrene
[Reaction Scheme 2]
Figure imgf000023_0002
5g of tetrahydropyrene obtained in Preparation Example 1-1 was put into a flask, 100ml of distilled water was added thereto, to which 3.5ml of Br2(2.1eq, 0.05mol) was further added slowly, and then the mixture solution was stirred at room temperature for 2 days. After completion of the reaction, the reaction solution was filtered, and then the filtrate was washed several times with distilled water. The washed filtrate was purified using a sublimator to obtain 5.7g of dibromo-tetrahydropyrene (yield 65%) .
GC-Mass (theoretical value: 364.07g/mol, measured value: 364g/mol)
Preparation Example 1-3: Preparation of bis (biphenyl) amine
[Reaction Scheme 3]
Figure imgf000024_0001
5g of 4-aminobiphenyl (leq, 0.029mol) and 7.4g of A- bromobiphenyl (l.leq, 0.0319mol) were dissolved in 200ml of toluene in a flask. 0.06g of Pd2(dba)3 (0.03eq, 0.87mmol), 3.7g of Na(t-Bu)O (l.leq, 0.0319mol), and 0.2g of P(t-Bu)3 (O.Oβeq, 1.74mmol) were added to the mixture solution respectively, and then the resultant mixture solution was heated and stirred for 12 hours. After completion of the reaction, the reaction solution was filtered through celite, and then 7.5g of 4,4'- bis (biphenyl) amine was obtained from the filtrate through column chromatography (yield 81%) .
GC-Mass (theoretical value: 321.15g/mol, measured value: 320g/mol)
Preparation Example 1-4 : Preparation of Aryl Amine Derivative represented by Formula 1-5
[Reaction Scheme 4]
Figure imgf000024_0002
5g of dibromo-tetrahydropyrene (leq, 0.0137mol) obtained in Preparation Example 1-2 and 9.64g of 4, 4' -bis (biphenyl) amine (2.2eq, 0.03mol) obtained in Preparation Example 1-3 were dissolved in 200ml of toluene in a flask. 0.37g of Pd2(dba)3 (0.03eq, 0.4mol), 3.8g of Na(t-Bu)0 (2.2eq, 0.03mol), and 0. Ig of P(t-Bu)3 (O.Oβeq, 0.8mmol) were added to the mixture solution respectively, and then the resultant mixture solution was heated and stirred for 12 hours. After completion of the reaction, the reaction solution was filtered through celite, and then 8.3g of aryl amine derivative represented by Formula 1-5 (HT-I) was obtained from the filtrate through column chromatography (yield 72%) .
Tg: 2090C
1H-NMR: 7.75 (t, IH), 7.46 (t, IH), 7.48 (d, IH), 6.52(t, IH) , 6.2(m, IH) , 2.95 (d, 2H) .
[Preparation Example 2] Preparation of Aryl Amine Derivative Represented by Formula 1-1 (HT-2)
[Reaction Scheme 5]
Figure imgf000025_0001
5g of dibromo-tetrahydropyrene (leq, 0.0137mol) obtained in Preparation Example 1-2 and 6.6g of N-phenylnaphthalene-1-amine (2.2eq, 0.03mol) were dissolved in 200ml of toluene in a flask. 0.37g of Pd2(dba)3 (0.03eq, 0.4mol), 3.8g of Na(t-Bu)O (2.2eq, 0.03mol), and 0. Ig of P(t-Bu)3 (O.Oβeq, 0.8mmol) were added to the mixture solution respectively, and then the resultant mixture solution was heated and stirred for 12 hours. After completion of the reaction, the reaction solution was filtered through celite, and then 6.6g of aryl amine derivative represented by Formula 1-1 (HT-2) was obtained from the filtrate through column chromatography (yield 76%) . Tg: 1840C
1H-NMR: 7.61 (t, IH), 7.48 (t, IH), 7.44 (t, IH), 7.16(m, 2H), 7.01(t, 2H), β.55(t, IH), 6.2(t, IH), 2.98(d, 2H).
[Preparation Example 3] Preparation of Aryl Amine Derivative Represented by Formula 1-14 (HT-3)
Preparation Example 3-1: Preparation of N^ phenylbiphenylamine
[Reaction Scheme 6]
Figure imgf000026_0001
1Og of aniline (leq, O.lmol) 27.5g of 4-bromobiphenyl
(l.leq, O.llmol) were dissolved in 150ml of toluene in a flask.
0.27g of Pd2(dba)3 (0.03eq, 3mmol) , 10.5g of Na(t-Bu)O (l.leq,
O.llmol), and 0. Ig of P(t-Bu)3 (O.Oβeq, O.βmmol) were added to the mixture solution respectively, and then the resultant mixture solution was heated and stirred for 12 hours. After completion of the reaction, the reaction solution was filtered through celite, and then 22.1g of N-phenylbiphenyl-4-amine was obtained from the filtrate through column chromatography (yield 84%) .
GC-Mass (theoretical value: 245.12g/mol, measured value: 245g/mol)
Preparation Example 3-2 : Preparation of N- (biphenyl-4-yl) - 7-bromo-N-phenyl-4 ,5,9, lO-tetrahydropyrene-2-amine [Reaction Scheme 7]
Figure imgf000026_0002
5g of dibromo-tetrahydropyrene (leq, 0.0137mol) obtained in Preparation Example 1-2 and 3.36g of N-phenylbiphenyl-4-amine (l.leq, 0.014mol) obtained in Preparation Example 3-1 were dissolved in 150ml of toluene in a flask. 0.37g of Pd2(dba)3 (0.03eq, 4mmol) , 1.4g of Na(t-Bu)0 (l.leq, 0.014mol), and O.lβg of P(t-Bu)3 (O.Oβeq, 0.8nπmol) were added to the mixture solution respectively, and then the resultant mixture solution was heated and stirred for 12 hours. After completion of the reaction, the reaction solution was filtered through celite, and then 7.24g of N- (biphenyl-4-yl) -7-bromo-N-phenyl-4, 5, 9, 10-tetrahydropyrene-2- amine was obtained from the filtrate through column chromatography (yield 82%) .
Preparation Example 3-3 : Preparation of Aryl Amine Derivative Represented by Formula 1-14 [Reaction Scheme 8]
Figure imgf000027_0001
7g of N- (biphenyl-4-yl) -7-bromo-N-phenyl-4, 5, 9,10- tetrahydropyrene-2-amine (leq, 0.013mol) obtained in Preparation Example 3-2 and 5.2g of 4- (biphenyl-4- yl (phenyl) amino) phenylboronic acid (l.leq, 0.014mol) were dissolved in 150ml of toluene in a flask. 0.3g of Pd (PPh3) 4 (0.02eq, 0.4mmol) and 60ml of 2M K2CO3 solution were added to the mixture solution respectively, and then the resultant mixture solution was heated and stirred for 12 hours. After completion of the reaction, the reaction solution was filtered through celite, the filtrate was extracted with MC, and then 8.8g of aryl amine derivative represented by Formula 1-14 (HT-3) was obtained from the filtrate through column chromatography (yield 88.4%).
Tg: 192°C
1H-NMR: 7.75 (t, IH), 7.46 (t, IH), 7.48 (d, IH), 6.52(t, IH), 6.2 (m, IH), 2.95 (d, 2H), 7.61 (t, IH), 7.48 (t, IH), 7.44 (t, IH), 7.16(m, 2H), 7.01(t, 2H), 6.55(t, IH), 6.2(t, IH), 2.98 (d, 2H) .
[Preparation Example 4] Preparation of Aryl Amine Derivative Represented by Formula 1-17 (HT-4)
Preparation Example 4-1 : Preparation of N- (4-bromophenyl) - N-phenylnaphthalene-1-amine [Reaction Scheme 9]
Figure imgf000028_0001
1Og of N-phenylnaphthalene-1-amine (leq, 0.046mol) and 14.3g of l-bromo-4-iodobenzene (l.leq, 0.05mol) were dissolved in 150ml of toluene in a flask. 0.27g of Pd2(dba)3 (0.03eq, 3mmol) , 10.5g of Na(t-Bu)O (l.leq, 0.05mol), and O.lg of P(t-Bu)3 (O.Oβeq, O.βmmol) were added to the mixture solution respectively, and then the resultant mixture solution was heated and stirred for 12 hours. After completion of the reaction, the reaction solution was filtered through celite, and then 13.4g of N- (4-bromophenyl) - N-phenylnaphthalene-1-amine was obtained from the filtrate through column chromatography (yield 80.4%).
GC-Mass (theoretical value: 373.05g/mol, measured value: 373g/mol) Preparation Example 4-2 : Preparation of 4- (naphthalene-1- yl (phenyl) amino) phenylboronic acid [Reaction Scheme 10]
Figure imgf000028_0002
5g of N- (4-bromophenyl) -N-phenylnaphthalene-1-amine (leq, 0.013mol) obtained in Preparation Example 4-1 was dissolved 100ml of THF in a flask. 1.03g of n-BuLi (1.2eq, O.Olβmol) was slowly drip-added to the mixture solution at a temperature of 78 °C. The resultant mixture solution was stirred for 30 minutes, and then 1.47g of methyl borate (1.5eq, 0.0195mol) was slowly drip-added thereto at the same temperature. After completion of the addition, the temperature of the mixture solution was elevated to room temperature, and then the mixture solution was stirred for 2 hours. On completion of the reaction, 50ml of IN HCl was added to the reaction solution, and then the reaction solution was stirred. White solid produced in the reaction flask was filtered, washed with hexane, and then dried to obtain 3. βg of A- (naphthalene-1-yl (phenyl) amino) phenylboronic acid (yield 82%).
Preparation Example 4-3 : Preparation of Aryl Amine Derivative Represented by Formula 1-17 [Reaction Scheme 11]
Figure imgf000029_0001
7g of N-(biphenyl-4-yl)-7-bromo-N-phenyl-4,5,9,10- tetrahydropyrene-2-amine (leq, 0.013mol) obtained in Preparation Example 3-2 and A. IAq of 4- (naphthalene-1- yl (phenyl) amino) phenylboronic acid (l.leq, 0.014mol) were dissolved in 150ml of toluene in a flask. 0.3g of Pd (PPh3) 4 (0.02eq, 0.4mmol) and 60ml of 2M K2CO3 solution were added to the mixture solution respectively, and then the resultant mixture solution was heated and stirred for 12 hours. After completion of the reaction, the reaction solution was filtered through celite, the filtrate was extracted with MC, and then 9.07g of aryl amine derivative represented by Formula 1-17 (HT-4) was obtained from the filtrate through column chromatography (yield 88.4%). Tg: 2050C
1H-NMR: 7.61 (t, IH), 7.48 (m, 2H), 7.44 (m, 6H), 7.22 (t, 2H), 7.16(m, 2H), 6.56(t, IH), 2.95 (d, 2H). [Example 1] Manufacture of organic electroluminescent device (OELD) by Use of Aryl Amine Derivative Obtained in Preparation Example 1 (HT-I)
An OELD was manufactured by the following method: A glass substrate, on which an ITO (indium tin oxide) film was coated to a thickness of 1500A, was ultrasonically cleaned with distilled water. On completion of the cleaning with distilled water, the substrate was ultrasonically cleaned with a solvent, such as isopropyl alcohol, acetone, or methanol, was dried, and then was delivered to a plasma cleaner. In the plasma cleaner, the substrate was cleaned using oxygen plasma for 5 minutes, and then was delivered to a vacuum deposition apparatus.
DS-205 (Doosan, Korea) was thermally vacuum-deposited to a thickness of 800A on the so-prepared ITO (anode) to form a hole injection layer, and the aryl amine derivative represented by Formula 1-5 (HT-I) was vacuum-deposited to a thickness of 150A on the hole injection layer to form a hole transport layer. DS-H45
(Doosan, Korea) and DS-405 (Doosan, Korea) were vacuum-deposited to a thickness of 3OθA on the hole transport layer to form a light emitting layer. Alq3 was vacuum-deposited to a thickness of 25θA on the light emitting layer to form an electron transport layer. Subsequently, LiF was deposited to a thickness of IOA on the electron transport layer to form an electron injection layer, and finally aluminum (cathode) was deposited to a thickness of
2000A to manufacture an OELD having a structure shown below in Table 4.
Table 4
Figure imgf000030_0001
[Example 2] Manufacture of OELD by Use of Aryl Amine Derivative Obtained in Preparation Example 2 (HT-2)
An OELD was manufactured in the same manner as in Example 1, except that the aryl amine derivative represented by Formula 1-1 (HT-2), obtained in Preparation Example 2, was used as the hole transport material, instead of the aryl amine derivative represented by Formula 1-5 (HT-I) , obtained in Preparation Example 1.
[Example 3] Manufacture of OELD by Use of Aryl Amine Derivative Obtained in Preparation Example 3 (HT-3)
An OELD was manufactured in the same manner as in Example 1, except that the aryl amine derivative represented by Formula 1-14 (HT-3) , obtained in Preparation Example 3, was used as the hole transport material, instead of the aryl amine derivative represented by Formula 1-5 (HT-I) , obtained in Preparation Example 1.
[Example 4] Manufacture of OELD by Use of Aryl Amine Derivative Obtained in Preparation Example 4 (HT-4)
An OELD was manufactured in the same manner as in Example 1, except that the aryl amine derivative represented by Formula 1-17 (HT-4), obtained in Preparation Example 4, was used as the hole transport material, instead of the aryl amine derivative represented by Formula 1-5 (HT-I) , obtained in Preparation Example 1. [Comparative Example 1] Manufacture of OELD by Use of NPB
An OELD was manufactured in the same manner as in Example 1, except that NPB was used as the hole transport material, instead of the aryl amine derivative represented by Formula 1-5 (HT-I), obtained in Preparation Example 1. [Experimental Example 1]
For each of the OELDs manufactured in Examples 1 to 4 and Comparative example 1, luminous efficiency was measured at a current density of lOmA/cm2, the results of which are shown below in Table 5.
Example 1 had a luminance of 608cd/m2 and thus exhibited a luminous efficiency of 6.1cd/A at a current density of lOmA/cm2 and a voltage of 5.2V, Example 2 had a luminance of 618cd/m2 and thus exhibited a luminous efficiency of 6.5cd/A at a current density of lOmA/cm2 and a voltage of 5.3V, Example 3 had a luminance of 602cd/m2 and thus exhibited a luminous efficiency of 6.1cd/A at a current density of lOmA/cm2 and a voltage of 5.5V, and Example 4 had a luminance of 609cd/m2 and thus exhibited a luminous efficiency of β.Ocd/A at a current density of lOmA/cm2 and a voltage of 5.7V. Also, Comparative Example 1 had a luminance of 560cd/m2 and thus exhibited a luminous efficiency of 5. βcd/A at a current density of lOmA/cm2 and a voltage of 5.7V.
Table 5
Figure imgf000032_0001
Consequently, first of all, the inventive materials have an effect of reducing a driving voltage as compared to existing NPB because material stability ensured by their increased glass transition temperature (T9) contributes to device stability, and additionally can also improve luminous efficiency.
Although the above preparation examples and examples of the present invention have described only the preparation and test results of the aryl amine derivatives represented by Formulas 1- 5, 1-1, 1-14, and 1-17, it is apparent to those skilled in the art that not only aryl amine derivatives of the present invention other than those described in the above preparation examples and examples can be easily prepared, but also OELDs comprising them may be manufactured based on the above description and common knowledge in the art.

Claims

CLAIMS1. An aryl amine derivative represented by the followingFormula 1 :
[Formula 1]
Figure imgf000034_0001
wherein, Ar1 to Ar4, X1, and X2 are each independently a C5-C30 aromatic ring group that is an aromatic ring group substituted or unsubstituted by at least one kind selected from the group consisting of a Ci-C30 alkyl group, a C2-C30 alkenyl group, a C2-C30 alkynyl group, a C5-C3O aryl group, a C5-C3O heteroaryl group, a C5-C3O aryloxy group, a Ci-C30 alkyloxy group, a C5-C30 arylamino group, a C5-C30 diarylamino group, a C6-C30 arylalkyl group, a C3-C30 cycloalkyl group, a C3-C30 heterocycloalkyl group, and a halogen atom; R1 to R11 are each independently selected from the group consisting of a hydrogen atom, a Ci-C30 alkyl group, a C2-C30 alkenyl group, a C2-C30 alkynyl group, a C5-C30 aryl group, a C5-C30 heteroaryl group, a C5-C30 aryloxy group, a Ci-C30 alkyloxy group, a C5-C30 arylamino group, a C5-C30 diarylamino group, a C6~C30 arylalkyl group, a C3-C30 cycloalkyl group, a C3-C30 heterocycloalkyl group, and a halogen atom; and n and m are each independently an integer of 0 to 2.
2. The aryl amine derivative as claimed in claim 1, wherein the aromatic ring group is selected from the group consisting of benzene, biphenyl, terphenyl, naphthalene, anthracene, triphenylamine, phenanthrene, pyrene, fluorene, and xanthene .
3. The aryl amine derivative as claimed in claim 1, wherein the Cx-C30 alkyl group, the C2-C30 alkenyl group, the C2-C30 alkynyl group, the C5-C30 aryl group, the C5-C30 heteroaryl group, the C5-C30 aryloxy group, the Ci-C30 alkyloxy group, the C5-C30 arylamino group, the C5-C30 diarylamino group, the C6-C30 arylalkyl group, the C3-C30 cycloalkyl group, and the C3-C30 heterocycloalkyl group in Ar1 to Ar4, X1, X2, and R1 to R11 are each independently further substituted or unsubstituted by at least one kind of substituent selected from the group consisting of halogen, an amino group, a nitrile group, a nitro group, a Ci~C4o alkyl group, a C2-C40 alkenyl group, a Ci-C40 alkoxy group, a C3-C40 cycloalkyl group, a C2-C40 heterocycloalkyl group, a C5-C40 aryl group, and a C4-C40 heteroaryl group.
4. The aryl amine derivative as claimed in claim 1, which is selected from the group consisting of compounds represented by the following Formulas:
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001

Figure imgf000038_0001
5. An organic electroluminescent device comprising:
(i) an anode;
(ii) a cathode; and
(iii) one or more organic layers between the anode and the cathode, at least one of the one or more organic layers comprising the aryl amine derivative represented by Formula 1, as claimed in any one of claims 1 to 4.
6. The organic electroluminescent device as claimed in claim 5, wherein the organic layer comprising the aryl amine derivative represented by Formula 1 comprises a hole transport layer.
PCT/KR2008/007608 2007-12-24 2008-12-23 Aryl amine derivative and organic electroluminescence device using the same Ceased WO2009082157A2 (en)

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