WO2011016648A1 - Novel organic electroluminescent compounds and organic electroluminescent device using the same - Google Patents

Novel organic electroluminescent compounds and organic electroluminescent device using the same Download PDF

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WO2011016648A1
WO2011016648A1 PCT/KR2010/005017 KR2010005017W WO2011016648A1 WO 2011016648 A1 WO2011016648 A1 WO 2011016648A1 KR 2010005017 W KR2010005017 W KR 2010005017W WO 2011016648 A1 WO2011016648 A1 WO 2011016648A1
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substituent
alkyl
organic electroluminescent
aryl
compound
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French (fr)
Inventor
Chi Sik Kim
Young Jun Cho
Hyuck Joo Kwon
Bong Ok Kim
Sung Min Kim
Seung Soo Yoon
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DuPont Specialty Materials Korea Ltd
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Rohm and Haas Electronic Materials Korea Ltd
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Definitions

  • the present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device using the same.
  • the organic electroluminescent compound according to the present invention is represented by Chemical Formula 1:
  • the electroluminescent material In an organic EL device, the most important factor that determines its performance including luminescence efficiency and operation life is the electroluminescent material. Some requirements of the electroluminescent material include high electroluminescence quantum yield in solid state, high electron and hole mobility, resistance to decomposition during vacuum deposition, ability to form uniform film and stability.
  • the organic EL device commonly has a configuration of anode/hole injection layer (HIL)/hole transport layer (HTL)/emission material layer (EML)/electron transport layer (ETL)/electron injection layer (EIL)/cathode.
  • HIL hole injection layer
  • HTL hole transport layer
  • EML emission material layer
  • ETL electron transport layer
  • EIL electron injection layer
  • the electroluminescent materials may be divided into host materials and dopant materials.
  • an electroluminescent layer prepared by doping a dopant in a host is known to provide superior EL property.
  • development of an organic EL device having high efficiency and long operation life is becoming an imminent task.
  • development of materials which are much superior to existing electroluminescent materials is urgently needed.
  • tris(8-hydroxyquinoline)-aluminum(III) Alq
  • Alq tris(8-hydroxyquinoline)-aluminum(III)
  • a coumarin derivative, a quinacridone derivative, DPT, or the like are used as a dopant, with a doping concentration of several to tens %.
  • the existing electroluminescent materials exhibit an initial luminescence efficiency that allows commercialization, the efficiency degrades quickly with time. Due to the lifetime problem, they are difficult to be employed in high-performance, large-sized panels.
  • an object of the present invention is to provide an organic electroluminescent compound having luminescence efficiency and device operation life improved over existing materials and having superior backbone with appropriate color coordinates in order to solve the aforesaid problems.
  • Another object of the present invention is to provide an organic electroluminescent device employing the organic electroluminescent compound as an electroluminescent material.
  • the present invention provides an organic electroluminescent compound represented by Chemical Formula 1 and an organic electroluminescent device using the same.
  • the organic electroluminescent compound according to the present invention may be used to manufacture an OLED device having very superior operation life.
  • R 1 through R 14 independently represent hydrogen, deuterium, halogen, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), substituted or unsubstituted (C6-C30)aryl fused with one or more (C3-C30)cycloalkyl(s) with or without substituent(s), (C3-C30)heteroaryl with or without substituent(s), 5- to 7-membered heterocycloalkyl with or without substituent(s), 5- to 7-membered heterocycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), (C3-C30)cycloalkyl with or without substituent(s), (C3-C30)cycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), cyano, amino, (C1-C30)alkylamino with or without substituent(s), (C6
  • R 51 through R 58 and R 61 through R 63 are the same as defined in R 1 through R 14 ;
  • R 21 through R 28 independently represent (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or (C3-C30)heteroaryl with or without substituent(s),
  • R a , R b , R c , and R d independently represent (C1-C30)alkyl with or without substituent(s) or (C6-C30)aryl with or without substituent(s),
  • the Y represents S or O
  • R e and R f represent (C1-C30)alkyl with or without substituent(s), (C1-C30)alkoxy with or without substituent(s), (C6-C30)aryl with or without substituent(s) or (C6-C30)aryloxy with or without substituent(s); and
  • n an integer 1 or 2.
  • 'alkyl' 'alkoxy' and other substituents containing 'alkyl' moiety include both linear and branched species.
  • 'cycloalkyl' includes both adamantyl with or without substituent(s) and (C7-C30)bicycloalkyl with or without substituent(s).
  • 'aryl' means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen atom, and may include a 4- to 7-membered, particularly 5- or 6-membered, single ring or fused ring, including a plurality of aryls linked by single bond(s).
  • Specific examples include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc., but are not limited thereto.
  • the naphthyl includes 1-naphthyl and 2-naphthyl
  • the anthryl includes 1-anthryl, 2-anthryl and 9-anthryl
  • the fluorenyl includes 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl.
  • heteroaryl may be 5- or 6-membered monocyclic heteroaryl or polycyclic heteroaryl resulting from condensation with a benzene ring, and may be partially saturated.
  • the heteroaryl includes more than one heteroaryls linked by single bond(s).
  • the heteroaryl includes a divalent aryl group wherein the heteroatom(s) in the ring may be oxidized or quaternized to form, for example, an N-oxide or a quaternary salt.
  • monocyclic heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., polycyclic heteroaryl such as benzofuranyl, benzothiophenyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, is
  • the '(C1-C30)alkyl' groups described herein may include (C1-C20)alkyl or (C1-C10)alkyl and the '(C6-C30)aryl' groups include (C6-C20)aryl or (C6-C12)aryl.
  • the '(C3-C30)heteroaryl' groups include (C3-C20)heteroaryl or (C3-C12)heteroaryl and the '(C3-C30)cycloalkyl' groups include (C3-C20)cycloalkyl or (C3-C7)cycloalkyl.
  • the '(C2-C30)alkenyl or alkynyl' group include (C2-C20)alkenyl or alkynyl, (C2-C10)alkenyl or alkynyl.
  • R 31 through R 38 independently represent (C1-C30)alkyl, (C6-C30)aryl or (C3-C30)heteroaryl.
  • the R 1 through R 14 , R 21 through R 28 , R 51 through R 58 , and R 61 through R 63 are independently selected from hydrogen, deuterium, halogen, alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, ethylhexyl, heptyl, octyl, etc., aryl such as phenyl, naphthyl, fluorenyl, biphenyl, phenanthryl, terphenyl, pyrenyl, perylenyl, spirobifluorenyl, fluoranthenyl, chrysenyl, triphenylenyl, etc., aryl fused with one or more cycloalkyl such as 1,2-dihydroacenaphthyl, heteroaryl such as dibenzothiophenyl, dibenzofuryl, carbazolyl, pyridyl
  • heteroaryl such as dibenzothiophenyl, dibenzofuryl, carbazolyl, pyridyl, furyl, thienyl, quinolyl, triazinyl, pyrimidinyl, pyridazinyl, quinoxalinyl, phenanthrolinyl, etc., aryloxy such as biphenyloxy, etc., arylthio such as biphenylthio, etc., aralkyl such as biphenylmethyl, triphenylmethyl, etc., , or , but are not limited thereto, and may be further substituted as shown in Chemical Formula 1.
  • R 1 through R 14 may be exemplified as following structures but are not limited thereto.
  • R 41 through R 48 independently represent (C1-C30)alkyl, (C6-C30)aryl or (C3-C30)heteroaryl.
  • the R 1 through R 14 are exemplified as the following structures, but are not limited thereto.
  • organic electroluminescent compound according to the present invention may be specifically exemplified as following compounds but is not limited thereto.
  • the organic electroluminescent compound according to the present invention may be prepared as shown in following Reaction Scheme 1.
  • R 1 through R 14 , X and Y are the same as defined in the Chemical Formula 1.
  • an organic electroluminescent device which comprises a first electrode; a second electrode; and one or more organic layer(s) interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more organic electroluminescent compound(s) represented by Chemical Formula 1.
  • the organic electroluminescent compound is used as a host material of the electroluminescent layer.
  • the organic layer may include the electroluminescent layer, and the electroluminescent layer may further include one or more dopants besides one or more organic electroluminescent compounds of Chemical Formula 1.
  • the dopant applied to the organic electroluminescent device of the present invention is not specifically limited.
  • the dopant applied to the organic electroluminescent device of the present invention is selected from following Chemical Formulas 2 and 3.
  • Ar 11 and Ar 12 independently represent (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), (C4-C30)heteroaryl with or without substituent(s), (C6-C30)arylamino with or without substituent(s), (C1-C30)alkylamino, 5- to 7-membered heterocycloalkyl with or without substituent(s), 5- to 7-membered heterocycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), (C3-C30)cycloalkyl with or without substituent(s) or (C3-C30)cycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), or Ar 11 and Ar 12 may be linked via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicylic ring or a mono
  • Ar 13 represents (C6-C30)aryl with or without substituent(s), (C4-C30)heteroaryl with or without substituent(s) or a substituent selected from the following structures, when c is 1:
  • Ar 13 represents (C6-C30)arylene with or without substituent(s), (C4-C30)heteroarylene with or without substituent(s) or a substituent selected from the following structures, when c is 2:
  • Ar 14 and Ar 15 independently represent (C6-C30)arylene with or without substituent(s) or (C4-C30)heteroarylene with or without substituent(s);
  • R 201 through R 203 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without substituent(s) or (C6-C30)aryl with or without substituent(s);
  • d represents an integer from 1 to 4.
  • e represents an integer 0 or 1.
  • the meaning of the electroluminescent layer may be a single layer as a layer where the light is emitted or may be a multiple layer where two or more layers are laminated.
  • the electroluminescent host of the present invention when host-dopant are used in mixture, it is confirmed that the luminous efficiency are remarkably improved by the electroluminescent host of the present invention. It may be configured at doping concentration of 0.5 to 10wt%.
  • the electroluminescent host of the present invention has superior conductivity with respect to the hole and electron and excellent stability in material, thereby showing a characteristic of remarkably increasing its life span as well as improving the luminous efficiency.
  • the dopant compound of Chemical Formula 3 may be exemplified as the compound described in KR Patent Application No. 10-2009-0023442, more preferably, be selected from the following structures. However, they are not limited thereto.
  • the organic layer may further include, in addition to the organic electroluminescent compound represented by Chemical Formula 1, one or more compound(s) selected from the group consisting of arylamine compounds and styrylarylamine compounds, at the same time.
  • the arylamine compounds or styrylarylamine compounds are exemplified in Korean Patent Application No. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.
  • the organic layer may further include, in addition to the organic electroluminescent compound represented by Chemical Formula 1, one or more metal(s) selected from the group consisting of organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements or complex compound(s).
  • the organic layer may include an electroluminescent layer and a charge generating layer.
  • the organic layer may include, in addition to the organic electroluminescent compound of Chemical Formula 1, one or more organic electroluminescent layer(s) emitting blue, green or red light at the same time in order to embody a white-emitting organic electroluminescent device.
  • the compound emitting blue, green or red light may be exemplified by the compounds described in Korean Patent Application No. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.
  • a layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on the inner surface of one or both electrode(s) among the pair of electrodes. More specifically, a metal chalcogenide (including oxide) layer of silicon or aluminum may be placed on the anode surface of the electroluminescent medium layer, and a metal halide layer or metal oxide layer may be placed on the cathode surface of the electroluminescent medium layer. Operation stability may be attained therefrom.
  • the chalcogenide may be, for example, SiO x (1 ⁇ x ⁇ 2), AlO x (1 ⁇ x ⁇ 1.5), SiON, SiAlON, etc.
  • the metal halide may be, for example, LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.
  • the metal oxide may be, for example, Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • the organic electroluminescent device it is also preferable to arrange on at least one surface of the pair of electrodes thus manufactured a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant.
  • a mixed region of an electron transport compound and a reductive dopant or a mixed region of a hole transport compound and an oxidative dopant.
  • the electron transport compound is reduced to an anion, injection and transport of electrons from the mixed region to an electroluminescent medium are facilitated.
  • the hole transport compound is oxidized to a cation, injection and transport of holes from the mixed region to an electroluminescent medium are facilitated.
  • Preferable oxidative dopants include various Lewis acids and acceptor compounds.
  • Preferable reductive dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof.
  • a white-emitting electroluminescent device having two or more electroluminescent layers may be manufactured by employing a reductive dopant layer as a charge generating layer.
  • the organic electroluminescent compound according to the present invention exhibits good luminous efficiency and excellent life property, it may be used to manufacture OLED devices having very superior operation life.
  • Compound 2-1 (30 g, 71.21 mmol), sulfuric acid (100 mL), and acetic acid (100 mL) were mixed and stirred under reflux at 120°C. 10 hours later, the mixture was cooled to room temperature and distilled water was added thereto. After filtering the produced solid under reduced pressure, recrystallization with methanol and EA yielded Compound 2-2 (4 g, 9.91 mmol, 13.95%).
  • Compound 2-6 was obtained by combining Compound 2-5 in Preparation Example 1 according to the same method as preparation of Compound 1-3.
  • Compound 28 (2.1 g, 2.95mmol, 53 %) was obtained by combining unrefined Compound 2-6 in Preparation Example 1 according to the same method as preparation of Compound 4 .
  • 1,4-dimethyl-2,5-dibromobenzene (10 g, 37.88 mmol), 2-(methoxycarbonyl)phenylboronic acid (17 g, 94.71 mmol), Pd(PPh 3 ) 4 (2.18 g, 1.89 mmol), 2M K 2 CO 3 aqueous solution (60 mL), toluene (200 mL), and ethanol (100 mL) were mixed and stirred under reflux. 6 hours later, the mixture was cooled to room temperature. After adding distilled water and extracting with EA, the remaining moisture was removed by using magnesium sulfate. Drying followed by column separation yielded Compound 3-1 (11 g, 29.37 mmol, 77.55 %).
  • Compound 3-2 (9 g, 24.03 mmol) was mixed with acetic acid (100 mL) and H 3 PO 4 (100 mL) and the mixture was heated at 120°C. 10 hours later, the mixture was cooled to room temperature and distilled water was added thereto. Filtering the produced solid under reduced pressure and washing with NaOH aqueous solution and methanol yielded Compound 3-3 (6 g, 17.72 mmol, 73.76 %).
  • Compound 3-4 (6.3 g, 12.95 mmol, 73.1 %) was obtained by combining Compound 3-3 in Preparation Example 1 according to the same method as preparation of Compound 1-1.
  • Compound 3-5 (4.3 g, 9.18 mmol, 70.1 %) was obtained by combining Compound 3-4 in Preparation Example 1 according to the same method as preparation of Compound 1-2 .
  • Compound 3-6 was obtained by combining Compound 3-5 in Preparation Example 1 according to the same method as preparation of Compound 1-3.
  • Organic electroluminescent Compounds 1 to 35 were prepared according to Preparation Example 1 and Table 1 shows 1 H NMR and MS/FAB of the prepared organic electroluminescent compounds.
  • An OLED device was manufactured using the electroluminescent material according to the present invention.
  • a transparent electrode ITO thin film (15 ⁇ / ⁇ ) obtained from a glass for OLED (produced by Samsung Corning) was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and stored in isopropanol before use.
  • an ITO substrate was equipped in a substrate folder of a vacuum vapor deposition apparatus, and 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was placed in a cell of the vacuum vapor deposition apparatus, which was then ventilated up to 10 -6 torr of vacuum in the chamber. Then, electric current was applied to the cell to evaporate 2-TNATA, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
  • 2-TNATA 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine
  • NPB N,N' -bis(a-naphthyl)- N,N' -diphenyl-4,4'-diamine
  • an electroluminescent layer was formed thereon as follows.
  • Compound 4 was placed in a cell of a vacuum vapor deposition apparatus as host, and Compound E was placed in another cell as a dopant.
  • the two materials were evaporated at different rates such that an electroluminescent layer having a thickness of 30 nm was vapor-deposited on the hole transport layer at 2 to 5 wt% based on host.
  • Alq tris(8-hydroxyquinoline)-aluminum(III) having a following structure was vapor-deposited with a thickness of 20 nm as an electron transport layer. Then, after vapor-depositing lithium quinolate (Liq) of a following structure with a thickness of 1 to 2 nm as an electron injection layer, an Al cathode having a thickness of 150 nm was formed using another vacuum vapor deposition apparatus to manufacture an OLED.
  • Liq lithium quinolate
  • Each compound used in the OLED was purified by vacuum sublimation at 10 -6 torr.
  • An OLED device was manufactured in the same manner as Example 1 except that 9,10-di(naphthalen-3-yl)anthracene (DNA) was used on the electroluminescent layer as host material.
  • DNA 9,10-di(naphthalen-3-yl)anthracene
  • Luminous efficiency of the OLED devices including the organic electroluminescent compound according to the present invention manufactured in Example 1 and Comparative Example 1 and the conventional electroluminescent compound was measured at 5,000 cd/m 2 . The result is given in Table 2.

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Abstract

Provided are novel organic electroluminescent compounds and an organic electroluminescent device using the same. Since the organic electroluminescent compound disclosed herein exhibits good luminescent efficiency and excellent life property, it may be used to manufacture OLED devices having very superior operation life.

Description

NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME
The present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device using the same. The organic electroluminescent compound according to the present invention is represented by Chemical Formula 1:
[Chemical Formula 1]
Figure PCTKR2010005017-appb-I000001
In an organic EL device, the most important factor that determines its performance including luminescence efficiency and operation life is the electroluminescent material. Some requirements of the electroluminescent material include high electroluminescence quantum yield in solid state, high electron and hole mobility, resistance to decomposition during vacuum deposition, ability to form uniform film and stability.
In general, the organic EL device commonly has a configuration of anode/hole injection layer (HIL)/hole transport layer (HTL)/emission material layer (EML)/electron transport layer (ETL)/electron injection layer (EIL)/cathode. Organic electroluminescent devices emitting blue, green or red light may be created depending on how to form the emission material layer.
In functional aspect, the electroluminescent materials may be divided into host materials and dopant materials. In general, an electroluminescent layer prepared by doping a dopant in a host is known to provide superior EL property. Recently, development of an organic EL device having high efficiency and long operation life is becoming an imminent task. Especially, considering the level of EL performance required for medium-to-large sized OLED panels, development of materials which are much superior to existing electroluminescent materials is urgently needed.
For green fluorescent materials, tris(8-hydroxyquinoline)-aluminum(III) (Alq) is used as a host and a coumarin derivative, a quinacridone derivative, DPT, or the like are used as a dopant, with a doping concentration of several to tens %. Although the existing electroluminescent materials exhibit an initial luminescence efficiency that allows commercialization, the efficiency degrades quickly with time. Due to the lifetime problem, they are difficult to be employed in high-performance, large-sized panels.
Accordingly, development of host materials that can provide satisfactory operation life of OLED devices, better stability and excellent performance are required.
Accordingly, an object of the present invention is to provide an organic electroluminescent compound having luminescence efficiency and device operation life improved over existing materials and having superior backbone with appropriate color coordinates in order to solve the aforesaid problems. Another object of the present invention is to provide an organic electroluminescent device employing the organic electroluminescent compound as an electroluminescent material.
In one general aspect, the present invention provides an organic electroluminescent compound represented by Chemical Formula 1 and an organic electroluminescent device using the same. With superior luminescence efficiency and excellent life property, the organic electroluminescent compound according to the present invention may be used to manufacture an OLED device having very superior operation life.
[Chemical Formula 1]
Figure PCTKR2010005017-appb-I000002
wherein
R1 through R14 independently represent hydrogen, deuterium, halogen, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), substituted or unsubstituted (C6-C30)aryl fused with one or more (C3-C30)cycloalkyl(s) with or without substituent(s), (C3-C30)heteroaryl with or without substituent(s), 5- to 7-membered heterocycloalkyl with or without substituent(s), 5- to 7-membered heterocycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), (C3-C30)cycloalkyl with or without substituent(s), (C3-C30)cycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), cyano, amino, (C1-C30)alkylamino with or without substituent(s), (C6-C30)arylamino with or without substituent(s), NR21R22, BR23R24, PR25R26, P(=O)R27R28, RaRbRcSi-, RdY-, ReC(=O)-, RfC(=O)O-, (C6-C30)ar(C1-C30)alkyl with or without substituent(s), (C2-C30)alkenyl with or without substituent(s), (C2-C30)alkynyl with or without substituent(s), (C6-C30)aryloxycarbonyl with or without substituent(s), (C1-C30)alkoxycarbonyloxy with or without substituent(s), (C1-C30)alkylcarbonyloxy with or without substituent(s), (C6-C30)arylcarbonyloxy with or without substituent(s), (C6-C30)aryloxycarbonyloxy with or without substituent(s), carboxyl, nitro,
Figure PCTKR2010005017-appb-I000003
,
Figure PCTKR2010005017-appb-I000004
or hydroxyl, or each of them may be linked to an adjacent substituent via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fuse ring to form an alicylic ring or a mono- or polycyclic aromatic ring;
X, Y and W independently represent -(CR51R52)m-, -(R51)C=C(R52)-, -N(R53)-, -S-, -O-, -Si(R54)(R55)-, -P(R56)-, -P(=O)(R57)-, -C(=O)- or -B(R58)-;
R51 through R58 and R61 through R63 are the same as defined in R1 through R14;
the heterocycloalkyl or heteroaryl may contain one or more heteroatom(s) selected from B, N, O, S, P(=O), Si and P; and
the R21 through R28 independently represent (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or (C3-C30)heteroaryl with or without substituent(s),
the Ra, Rb, Rc, and Rd independently represent (C1-C30)alkyl with or without substituent(s) or (C6-C30)aryl with or without substituent(s),
the Y represents S or O,
the Re and Rf represent (C1-C30)alkyl with or without substituent(s), (C1-C30)alkoxy with or without substituent(s), (C6-C30)aryl with or without substituent(s) or (C6-C30)aryloxy with or without substituent(s); and
m represents an integer 1 or 2.
In the present invention, 'alkyl' 'alkoxy' and other substituents containing 'alkyl' moiety include both linear and branched species. In the present invention, 'cycloalkyl' includes both adamantyl with or without substituent(s) and (C7-C30)bicycloalkyl with or without substituent(s).
In the present invention, 'aryl' means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen atom, and may include a 4- to 7-membered, particularly 5- or 6-membered, single ring or fused ring, including a plurality of aryls linked by single bond(s). Specific examples include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc., but are not limited thereto. The naphthyl includes 1-naphthyl and 2-naphthyl, the anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, and the fluorenyl includes 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl. In the present invention, 'heteroaryl' means an aryl group containing 1 to 4 heteroatom(s) selected from B, N, O, S, P(=O), Si and P as aromatic ring backbone atom(s), other remaining aromatic ring backbone atoms being carbon. It may be 5- or 6-membered monocyclic heteroaryl or polycyclic heteroaryl resulting from condensation with a benzene ring, and may be partially saturated. Further, the heteroaryl includes more than one heteroaryls linked by single bond(s). The heteroaryl includes a divalent aryl group wherein the heteroatom(s) in the ring may be oxidized or quaternized to form, for example, an N-oxide or a quaternary salt. Specific examples include monocyclic heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., polycyclic heteroaryl such as benzofuranyl, benzothiophenyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl, benzodioxolyl, etc., an N-oxide thereof (e.g., pyridyl N-oxide, quinolyl N-oxide, etc.), a quaternary salt thereof, etc., but are not limited thereto.
The '(C1-C30)alkyl' groups described herein may include (C1-C20)alkyl or (C1-C10)alkyl and the '(C6-C30)aryl' groups include (C6-C20)aryl or (C6-C12)aryl. The '(C3-C30)heteroaryl' groups include (C3-C20)heteroaryl or (C3-C12)heteroaryl and the '(C3-C30)cycloalkyl' groups include (C3-C20)cycloalkyl or (C3-C7)cycloalkyl. The '(C2-C30)alkenyl or alkynyl' group include (C2-C20)alkenyl or alkynyl, (C2-C10)alkenyl or alkynyl.
In 'with or without substituent(s)', the substituent is further substituted by one or more substituent(s) selected from the group consisting of deuterium, halogen, (C1-C30)alkyl with or without halogen substituent(s), (C6-C30)aryl, (C3-C30)heteroaryl with or without (C6-C30)aryl substituent(s), 5- to 7-membered heterocycloalkyl containing one or more selected from B, N, O, S, P(=O), Si and P, 5- to 7-membered heterocycloalkyl fused with one or more aromatic ring(s), (C3-C30)cycloalkyl, (C3-C30)cycloalkyl fused with one or more aromatic ring(s), tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, (C2-C30)alkenyl, (C2-C30)alkynyl, cyano, carbazolyl, NR31R32, BR33R34, PR35R36, P(=O)R37R38, (C6-C30)ar(C1-C30)alkyl, (C1-C30)alkyl(C6-C30)aryl, (C1-C30)alkyloxy, (C1-C30)alkylthio, (C6-C30)aryloxy, (C6-C30)arylthio, (C1-C30)alkoxycarbonyl, (C1-C30)alkylcarbonyl, (C6-C30)arylcarbonyl, (C6-C30)aryloxycarbonyl, (C1-C30)alkoxycarbonyloxy, (C1-C30)alkylcarbonyloxy, (C6-C30)arylcarbonyloxy, (C6-C30)aryloxycarbonyloxy, carboxyl, nitro and hydroxyl, or is linked to an adjacent substituent to form a ring, and
the R31 through R38 independently represent (C1-C30)alkyl, (C6-C30)aryl or (C3-C30)heteroaryl.
The R1 through R14, R21 through R28, R51 through R58, and R61 through R63 are independently selected from hydrogen, deuterium, halogen, alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, ethylhexyl, heptyl, octyl, etc., aryl such as phenyl, naphthyl, fluorenyl, biphenyl, phenanthryl, terphenyl, pyrenyl, perylenyl, spirobifluorenyl, fluoranthenyl, chrysenyl, triphenylenyl, etc., aryl fused with one or more cycloalkyl such as 1,2-dihydroacenaphthyl, heteroaryl such as dibenzothiophenyl, dibenzofuryl, carbazolyl, pyridyl, furyl, thienyl, quinolyl, triazinyl, pyrimidinyl, pyridazinyl, quinoxalinyl, phenanthrolinyl, etc., heterocycloalkyl fused with one or more aromatic ring such as benzopyrrolidino, benzopiperidino, dibenzomorpholino, dibenzoazepino, etc., amino substituted by aryl such as phenyl, naphthyl, fluorenyl, biphenyl, phenanthryl, terphenyl, pyrenyl, perylenyl, spirobifluorenyl, fluoranthenyl, chrysenyl, triphenylenyl, etc. or heteroaryl such as dibenzothiophenyl, dibenzofuryl, carbazolyl, pyridyl, furyl, thienyl, quinolyl, triazinyl, pyrimidinyl, pyridazinyl, quinoxalinyl, phenanthrolinyl, etc., aryloxy such as biphenyloxy, etc., arylthio such as biphenylthio, etc., aralkyl such as biphenylmethyl, triphenylmethyl, etc.,
Figure PCTKR2010005017-appb-I000005
, or
Figure PCTKR2010005017-appb-I000006
, but are not limited thereto, and may be further substituted as shown in Chemical Formula 1.
More specifically, the R1 through R14 may be exemplified as following structures but are not limited thereto.
Figure PCTKR2010005017-appb-I000007
Figure PCTKR2010005017-appb-I000008
Figure PCTKR2010005017-appb-I000009
Figure PCTKR2010005017-appb-I000010
Figure PCTKR2010005017-appb-I000011
Figure PCTKR2010005017-appb-I000012
wherein
R71 through R132 independently represent hydrogen, deuterium, halogen, (C1-C30)alkyl, (C6-C30)aryl, (C6-C30)aryl fused with one or more (C3-C30)cycloalkyl(s), (C3-C30)heteroaryl, 5- to 7-memebered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more aromatic ring(s), (C3-C30)cycloalkyl, (C3-C30)cycloalkyl fused with one or more aromatic ring(s), cyano, amino, (C1-C30)alkylamino, (C6-C30)arylamino, NR41R42, BR43R44, PR45R46, P(=O)R47R48, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, (C6-C30)ar(C1-C30)alkyl, (C1-C30)alkyloxy, (C1-C30)alkylthio, (C6-C30)aryloxy, (C6-C30)arylthio, (C1-C30)alkoxycarbonyl, (C1-C30)alkylcarbonyl, (C6-C30)arylcarbonyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryloxycarbonyl, (C1-C30)alkoxycarbonyloxy, (C1-C30)alkylcarbonyloxy, (C6-C30)arylcarbonyloxy, (C6-C30)aryloxycarbonyloxy, carboxyl, nitro or hydroxyl, or each of them may be linked to an adjacent substituent via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicylic ring or a mono- or polycyclic aromatic ring, and
the R41 through R48 independently represent (C1-C30)alkyl, (C6-C30)aryl or (C3-C30)heteroaryl.
The R1 through R14 are exemplified as the following structures, but are not limited thereto.
Figure PCTKR2010005017-appb-I000013
Figure PCTKR2010005017-appb-I000014
Figure PCTKR2010005017-appb-I000015
The organic electroluminescent compound according to the present invention may be specifically exemplified as following compounds but is not limited thereto.
Figure PCTKR2010005017-appb-I000016
Figure PCTKR2010005017-appb-I000017
Figure PCTKR2010005017-appb-I000018
Figure PCTKR2010005017-appb-I000019
Figure PCTKR2010005017-appb-I000020
Figure PCTKR2010005017-appb-I000021
Figure PCTKR2010005017-appb-I000022
Figure PCTKR2010005017-appb-I000023
Figure PCTKR2010005017-appb-I000024
The organic electroluminescent compound according to the present invention may be prepared as shown in following Reaction Scheme 1.
[Reaction Scheme 1]
Figure PCTKR2010005017-appb-I000025
Figure PCTKR2010005017-appb-I000026
wherein
R1 through R14, X and Y are the same as defined in the Chemical Formula 1.
Provided is an organic electroluminescent device, which comprises a first electrode; a second electrode; and one or more organic layer(s) interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more organic electroluminescent compound(s) represented by Chemical Formula 1. The organic electroluminescent compound is used as a host material of the electroluminescent layer.
In addition, the organic layer may include the electroluminescent layer, and the electroluminescent layer may further include one or more dopants besides one or more organic electroluminescent compounds of Chemical Formula 1. The dopant applied to the organic electroluminescent device of the present invention is not specifically limited.
Preferably, the dopant applied to the organic electroluminescent device of the present invention is selected from following Chemical Formulas 2 and 3.
[Chemical Formula 2]
Figure PCTKR2010005017-appb-I000027
[Chemical Formula 3]
Figure PCTKR2010005017-appb-I000028
wherein
Ar11 and Ar12 independently represent (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), (C4-C30)heteroaryl with or without substituent(s), (C6-C30)arylamino with or without substituent(s), (C1-C30)alkylamino, 5- to 7-membered heterocycloalkyl with or without substituent(s), 5- to 7-membered heterocycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), (C3-C30)cycloalkyl with or without substituent(s) or (C3-C30)cycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), or Ar11 and Ar12 may be linked via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicylic ring or a mono- or polycyclic aromatic ring;
Ar13 represents (C6-C30)aryl with or without substituent(s), (C4-C30)heteroaryl with or without substituent(s) or a substituent selected from the following structures, when c is 1:
Figure PCTKR2010005017-appb-I000029
Ar13 represents (C6-C30)arylene with or without substituent(s), (C4-C30)heteroarylene with or without substituent(s) or a substituent selected from the following structures, when c is 2:
Figure PCTKR2010005017-appb-I000030
Ar14 and Ar15 independently represent (C6-C30)arylene with or without substituent(s) or (C4-C30)heteroarylene with or without substituent(s);
R201 through R203 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without substituent(s) or (C6-C30)aryl with or without substituent(s);
d represents an integer from 1 to 4; and
e represents an integer 0 or 1.
The meaning of the electroluminescent layer may be a single layer as a layer where the light is emitted or may be a multiple layer where two or more layers are laminated. In the configuration of the present invention, when host-dopant are used in mixture, it is confirmed that the luminous efficiency are remarkably improved by the electroluminescent host of the present invention. It may be configured at doping concentration of 0.5 to 10wt%. Compared to other host materials, the electroluminescent host of the present invention has superior conductivity with respect to the hole and electron and excellent stability in material, thereby showing a characteristic of remarkably increasing its life span as well as improving the luminous efficiency.
The dopant compound of Chemical Formula 3 may be exemplified as the compound described in KR Patent Application No. 10-2009-0023442, more preferably, be selected from the following structures. However, they are not limited thereto.
Figure PCTKR2010005017-appb-I000031
Figure PCTKR2010005017-appb-I000032
Figure PCTKR2010005017-appb-I000033
Figure PCTKR2010005017-appb-I000034
Figure PCTKR2010005017-appb-I000035
Figure PCTKR2010005017-appb-I000036
Figure PCTKR2010005017-appb-I000037
In the organic electronic device of the present invention, the organic layer may further include, in addition to the organic electroluminescent compound represented by Chemical Formula 1, one or more compound(s) selected from the group consisting of arylamine compounds and styrylarylamine compounds, at the same time. The arylamine compounds or styrylarylamine compounds are exemplified in Korean Patent Application No. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.
Further, in the organic electroluminescent device of the present invention, the organic layer may further include, in addition to the organic electroluminescent compound represented by Chemical Formula 1, one or more metal(s) selected from the group consisting of organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements or complex compound(s). The organic layer may include an electroluminescent layer and a charge generating layer.
Further, the organic layer may include, in addition to the organic electroluminescent compound of Chemical Formula 1, one or more organic electroluminescent layer(s) emitting blue, green or red light at the same time in order to embody a white-emitting organic electroluminescent device. The compound emitting blue, green or red light may be exemplified by the compounds described in Korean Patent Application No. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.
In the organic electroluminescent device of the present invention, a layer (hereinafter referred to as 'surface layer') selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on the inner surface of one or both electrode(s) among the pair of electrodes. More specifically, a metal chalcogenide (including oxide) layer of silicon or aluminum may be placed on the anode surface of the electroluminescent medium layer, and a metal halide layer or metal oxide layer may be placed on the cathode surface of the electroluminescent medium layer. Operation stability may be attained therefrom.
The chalcogenide may be, for example, SiOx(1 ≤ x ≤2), AlOx (1 ≤ x ≤ 1.5), SiON, SiAlON, etc. The metal halide may be, for example, LiF, MgF2, CaF2, a rare earth metal fluoride, etc. The metal oxide may be, for example, Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In the organic electroluminescent device according to the present invention, it is also preferable to arrange on at least one surface of the pair of electrodes thus manufactured a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant. In that case, since the electron transport compound is reduced to an anion, injection and transport of electrons from the mixed region to an electroluminescent medium are facilitated. In addition, since the hole transport compound is oxidized to a cation, injection and transport of holes from the mixed region to an electroluminescent medium are facilitated. Preferable oxidative dopants include various Lewis acids and acceptor compounds. Preferable reductive dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof.
Further, a white-emitting electroluminescent device having two or more electroluminescent layers may be manufactured by employing a reductive dopant layer as a charge generating layer.
Since the organic electroluminescent compound according to the present invention exhibits good luminous efficiency and excellent life property, it may be used to manufacture OLED devices having very superior operation life.
The present invention is further described with respect to organic electroluminescent compounds according to the present invention, processes for preparing the same, and luminescence properties of devices employing the same. However, the following examples are provided for illustrative purposes only and they are not intended to limit the scope of the present invention.
[Preparation Example 1] Preparation of Compound 4
Figure PCTKR2010005017-appb-I000038
Preparation of Compound 1-1
After 6,6,12,12-tetraethyl-6,12-dihydroindeno[1,2-b]fluorene (10 g, 27.28 mmol) and AlCl3 (7.27 g) were added into methylenechloride(MC) (500 mL) and phthalic anhydride (6.06 g, 40.92 mmol) was added thereto, the mixture was stirred under reflux at 40 ℃ for 12 hours. After slowly adding distilled water and adding hydrochloric acid thereto, the product was extracted with MC and the remaining moisture was removed by using magnesium sulfate. Drying followed by column separation yielded Compound 1-1 (12 g, 23.31 mmol, 85.47 %).
Preparation of Compound 1-2
After Compound 1-1 (12 g, 23.31 mmol) and acetic acid (60 mL) were added into sulfuric acid (60 mL), the mixture was stirred under reflux at 120 ℃ for 8 hours. After cooling to room temperature, adding distilled water and neutralizing with NaOH aqueous solution, the product was extracted with MC and the remaining moisture was removed by using magnesium sulfate. Drying followed by column separation yielded Compound 1-2 (3.5 g, 7.04 mmol, 30.23 %).
Preparation of Compound 1-3
After 2-bromonaphthalene (3.94 g, 19.02 mmol) was dissolved in THF (100 mL), and n-buLi (7.8 mL, 19.73 mmol, 2.5M in hexane) was slowly added at -78℃. 1 hour later, Compound 1-2 (3.5 g, 7.04 mmol) was added. The mixture was slowly heated and stirred under reflux at room temperature for 12 hours. After adding distilled water and extracting with ethyl acetate (EA), the remaining moisture was removed by using magnesium sulfate. Drying yielded Compound 1-3 (7 g) in a mixture state.
Preparation of Compound 4
Compound 1-3 (7 g, mixture), potassium iodide (KI) (4.4 g, 26.56 mmol), NaH2PO3H2O (5.6 g, 53.12 mmol), and acetic acid (60 mL) were mixed and stirred under reflux. 12 hours later, the mixture was cooled to room temperature. After adding distilled water, filtering the produced solid under reduced pressure, and washing the solid wiht NaOH aqueous solution, Compound 4 (3.2 g, 4.45 mmol) was obtained via column separation.
[Preparation Example 2] Preparation of Compound 28
Figure PCTKR2010005017-appb-I000039
Figure PCTKR2010005017-appb-I000040
Preparation of Compound 2-1
After 2-Bromo-9,9-dimethylfluorene (20 g, 73.21 mmol), AlCl3 (19.5 g, 146.4 mmol), and MC (500 mL) were mixed, Compound A was added thereto and stirred under reflux at 40 ℃. 12 hours later, distilled water and 1M HCl aqueous solution were added. After extracting with MC, distillation under reduced pressure followed by column separation yielded Compound 2-1 (30 g, 71.21 mmol, 97.21 %).
Preparation of Compound 2-2
Compound 2-1 (30 g, 71.21 mmol), sulfuric acid (100 mL), and acetic acid (100 mL) were mixed and stirred under reflux at 120℃. 10 hours later, the mixture was cooled to room temperature and distilled water was added thereto. After filtering the produced solid under reduced pressure, recrystallization with methanol and EA yielded Compound 2-2 (4 g, 9.91 mmol, 13.95%).
Preparation of Compound 2-3
Compound 2-2 (4.2 g, 10.37 mmol), 2-nitrophenylboronic acid (2 g, 12.49 mmol), Pd(PPh3)4 (0.59 g, 0.51 mmol), 3M K2CO3 aqueous solution (10 mL), toluene (70 mL), and ethanol (30 mL) were mixed and stirred under reflux. 12 hours later, the mixture was cooled to room temperature. After adding distilled water and extracting with EA, the remaining moisture was removed by using magnesium sulfate. Drying followed by column separation yielded Compound 2-3 (3.7 g, 8.30 mmol, 80.05%).
Preparation of Compound 2-4
Compound 2-3 (3.7 g, 8.30 mmol) was mixed with triethylphosphite (50 mL) and mixture was stirred under reflux. 10 hours later, the mixture was cooled to room temperature. Distillation followed by column separation yielded Compound 2-4 (2.5 g, 6.04 mmol, 72.84 %).
Preparation of Compound 2-5
Compound 2-4 (2.5 g, 6.04 mmol), iodobenzene (2.46 g, 12.09 mmol), CuI (1.72 g, 9.06 mmol), K2CO3 (2.50 g, 18.13 mmol), and 1.2-dichlorobenzene (50 mL) were mixed and heated at 190 ℃. 24 hours later, the mixture was cooled to room temperature and organic solvent was distilled under reduced pressure. After adding distilled water and extracting with EA, distillation under reduced pressure followed by column separation yielded Compound 2-5 (2.7g, 5.51mmol, 91.31%).
Preparation of Compound 2-6
Compound 2-6 was obtained by combining Compound 2-5 in Preparation Example 1 according to the same method as preparation of Compound 1-3.
Preparation of Compound 28
Compound 28 (2.1 g, 2.95mmol, 53 %) was obtained by combining unrefined Compound 2-6 in Preparation Example 1 according to the same method as preparation of Compound 4.
[Preparation Example 3] Preparation of Compound 30
Figure PCTKR2010005017-appb-I000041
Figure PCTKR2010005017-appb-I000042
Preparation of Compound 3-1
1,4-dimethyl-2,5-dibromobenzene (10 g, 37.88 mmol), 2-(methoxycarbonyl)phenylboronic acid (17 g, 94.71 mmol), Pd(PPh3)4 (2.18 g, 1.89 mmol), 2M K2CO3 aqueous solution (60 mL), toluene (200 mL), and ethanol (100 mL) were mixed and stirred under reflux. 6 hours later, the mixture was cooled to room temperature. After adding distilled water and extracting with EA, the remaining moisture was removed by using magnesium sulfate. Drying followed by column separation yielded Compound 3-1 (11 g, 29.37 mmol, 77.55 %).
Preparation of Compound 3-2
Compound 3-1 (11 g, 29.37 mmol) was dissolved in THF (400 mL) and methylmagnesium bromide (48.96 mL, 146.88 mmol, 3.0M in diehtyl ether) was slowly added thereto. The mixture was stirred under reflux at 60℃ for 12 hours and cooled to room temperature. After slowly adding distilled water and extracting with EA, the remaining moisture was removed by using magnesium sulfate. Drying followed by column separation yielded Compound 3-2 (9 g, 24.03 mmol, 81.82 %).
Preparation of Compound 3-3
Compound 3-2 (9 g, 24.03 mmol) was mixed with acetic acid (100 mL) and H3PO4 (100 mL) and the mixture was heated at 120℃. 10 hours later, the mixture was cooled to room temperature and distilled water was added thereto. Filtering the produced solid under reduced pressure and washing with NaOH aqueous solution and methanol yielded Compound 3-3 (6 g, 17.72 mmol, 73.76 %).
Preparation of Compound 3-4
Compound 3-4 (6.3 g, 12.95 mmol, 73.1 %) was obtained by combining Compound 3-3 in Preparation Example 1 according to the same method as preparation of Compound 1-1.
Preparation of Compound 3-5
Compound 3-5 (4.3 g, 9.18 mmol, 70.1 %) was obtained by combining Compound 3-4 in Preparation Example 1 according to the same method as preparation of Compound 1-2.
Preparation of Compound 3-6
Compound 3-6 was obtained by combining Compound 3-5 in Preparation Example 1 according to the same method as preparation of Compound 1-3.
Preparation of Compound 30
Compound 30 (2.3 g, 3.33 mmol, 37 %) was obtained by combining Compound 3-6 in Preparation Example 1 according to the same method as preparation of Compound 4.
Organic electroluminescent Compounds 1 to 35 were prepared according to Preparation Example 1 and Table 1 shows 1H NMR and MS/FAB of the prepared organic electroluminescent compounds.
[Table 1]
Figure PCTKR2010005017-appb-I000043
Figure PCTKR2010005017-appb-I000044
Figure PCTKR2010005017-appb-I000045
[Example 1] Manufacture of OLED device using the organic electroluminescent compound according to the present invention
An OLED device was manufactured using the electroluminescent material according to the present invention.
First, a transparent electrode ITO thin film (15 Ω/□) obtained from a glass for OLED (produced by Samsung Corning) was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and stored in isopropanol before use.
Then, an ITO substrate was equipped in a substrate folder of a vacuum vapor deposition apparatus, and 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was placed in a cell of the vacuum vapor deposition apparatus, which was then ventilated up to 10-6 torr of vacuum in the chamber. Then, electric current was applied to the cell to evaporate 2-TNATA, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
Then, N,N'-bis(a-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB) was placed in another cell of the vacuum vapor deposition apparatus, and electric current was applied to the cell to evaporate NPB, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer.
After forming the hole injection layer and the hole transport layer, an electroluminescent layer was formed thereon as follows. Compound 4 was placed in a cell of a vacuum vapor deposition apparatus as host, and Compound E was placed in another cell as a dopant. The two materials were evaporated at different rates such that an electroluminescent layer having a thickness of 30 nm was vapor-deposited on the hole transport layer at 2 to 5 wt% based on host.
Figure PCTKR2010005017-appb-I000046
<Compound 4>
Figure PCTKR2010005017-appb-I000047
<Compound E>
Subsequently, tris(8-hydroxyquinoline)-aluminum(III) (Alq) having a following structure was vapor-deposited with a thickness of 20 nm as an electron transport layer. Then, after vapor-depositing lithium quinolate (Liq) of a following structure with a thickness of 1 to 2 nm as an electron injection layer, an Al cathode having a thickness of 150 nm was formed using another vacuum vapor deposition apparatus to manufacture an OLED.
Each compound used in the OLED was purified by vacuum sublimation at 10-6torr.
[Comparative Example 1] Manufacture of OLED device using conventional electroluminescent material
An OLED device was manufactured in the same manner as Example 1 except that 9,10-di(naphthalen-3-yl)anthracene (DNA) was used on the electroluminescent layer as host material.
Luminous efficiency of the OLED devices including the organic electroluminescent compound according to the present invention manufactured in Example 1 and Comparative Example 1 and the conventional electroluminescent compound was measured at 5,000 cd/m2. The result is given in Table 2.
[Table 2]
Figure PCTKR2010005017-appb-I000048
As shown in Table 2, the result that the material of the present invention is applied to the green-light emitting device shows that driving voltage is lowered and luminous efficiency is improved while maintaining color purity the same as or higher than that of Comparative Example 1.

Claims (10)

  1. An organic electroluminescent compound represented by Chemical Formula 1:
    Figure PCTKR2010005017-appb-I000049
    (1)
    wherein
    R1 through R14 independently represent hydrogen, deuterium, halogen, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), substituted or unsubstituted (C6-C30)aryl fused with one or more (C3-C30)cycloalkyl(s) with or without substituent(s), (C3-C30)heteroaryl with or without substituent(s), 5- to 7-membered heterocycloalkyl with or without substituent(s), 5- to 7-membered heterocycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), (C3-C30)cycloalkyl with or without substituent(s), (C3-C30)cycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), cyano, amino, (C1-C30)alkylamino with or without substituent(s), (C6-C30)arylamino with or without substituent(s), NR21R22, BR23R24, PR25R26, P(=O)R27R28, RaRbRcSi-, RdY-, ReC(=O)-, RfC(=O)O-, (C6-C30)ar(C1-C30)alkyl with or without substituent(s), (C2-C30)alkenyl with or without substituent(s), (C2-C30)alkynyl with or without substituent(s), (C6-C30)aryloxycarbonyl with or without substituent(s), (C1-C30)alkoxycarbonyloxy with or without substituent(s), (C1-C30)alkylcarbonyloxy with or without substituent(s), (C6-C30)arylcarbonyloxy with or without substituent(s), (C6-C30)aryloxycarbonyloxy with or without substituent(s), carboxyl, nitro,
    Figure PCTKR2010005017-appb-I000050
    ,
    Figure PCTKR2010005017-appb-I000051
    or hydroxyl, or each of them may be linked to an adjacent substituent via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fuse ring to form an alicylic ring or a mono- or polycyclic aromatic ring;
    X, Y and W independently represent -(CR51R52)m-, -(R51)C=C(R52)-, -N(R53)-, -S-, -O-, -Si(R54)(R55)-, -P(R56)-, -P(=O)(R57)-, -C(=O)- or -B(R58)-;
    R51 through R58 and R61 through R63 are the same as defined in R1 through R14;
    the heterocycloalkyl or heteroaryl may contain one or more heteroatom(s) selected from B, N, O, S, P(=O), Si and P; and
    the R21 through R28 independently represent (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or (C3-C30)heteroaryl with or without substituent(s),
    the Ra, Rb, Rc, and Rd independently represent (C1-C30)alkyl with or without substituent(s) or (C6-C30)aryl with or without substituent(s),
    the Y represents S or O,
    the Re and Rf represent (C1-C30)alkyl with or without substituent(s), (C1-C30)alkoxy with or without substituent(s), (C6-C30)aryl with or without substituent(s) or (C6-C30)aryloxy with or without substituent(s); and
    m represents an integer 1 or 2.
  2. The organic electroluminescent compound according to claim 1, wherein in 'with or without substituent(s)', the substituent of R1 through R14, R21 through R28, R51 through R58, and R61 through R63 is further substituted by one or more substituent(s) selected from a group consisting of deuterium, halogen, (C1-C30)alkyl with or without halogen substituent(s), (C6-C30)aryl, (C3-C30)heteroaryl with or without (C6-C30)aryl substituent(s), 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more aromatic ring(s), (C3-C30)cycloalkyl, (C3-C30)cycloalkyl fused with one or more aromatic ring(s), tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, (C2-C30)alkenyl, (C2-C30)alkynyl, cyano, carbazolyl, NR31R32, BR33R34, PR35R36, P(=O)R37R38, (C6-C30)ar(C1-C30)alkyl, (C1-C30)alkyl(C6-C30)aryl, (C1-C30)alkyloxy, (C1-C30)alkylthio, (C6-C30)aryloxy, (C6-C30)arylthio, (C1-C30)alkoxycarbonyl, (C1-C30)alkylcarbonyl, (C6-C30)arylcarbonyl, (C6-C30)aryloxycarbonyl, (C1-C30)alkoxycarbonyloxy, (C1-C30)alkylcarbonyloxy, (C6-C30)arylcarbonyloxy, (C6-C30)aryloxycarbonyloxy, carboxyl, nitro and hydroxyl, or is linked to an adjacent substituent to form a ring, and
    the R31 through R38 independently represent (C1-C30)alkyl, (C6-C30)aryl or (C3-C30)heteroaryl.
  3. The organic electroluminescent compound according to claim 1, wherein R1 through R14 are selected from the following structures:
    Figure PCTKR2010005017-appb-I000052
    Figure PCTKR2010005017-appb-I000053
    Figure PCTKR2010005017-appb-I000054
    Figure PCTKR2010005017-appb-I000055
    Figure PCTKR2010005017-appb-I000056
    Figure PCTKR2010005017-appb-I000057
    wherein
    R71 through R132 independently represent hydrogen, deuterium, halogen, (C1-C30)alkyl, (C6-C30)aryl, (C6-C30)aryl fused with one or more (C3-C30)cycloalkyl(s), (C3-C30)heteroaryl, 5- to 7-memebered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more aromatic ring(s), (C3-C30)cycloalkyl, (C3-C30)cycloalkyl fused with one or more aromatic ring(s), cyano, amino, (C1-C30)alkylamino, (C6-C30)arylamino, NR41R42, BR43R44, PR45R46, P(=O)R47R48, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, (C6-C30)ar(C1-C30)alkyl, (C1-C30)alkyloxy, (C1-C30)alkylthio, (C6-C30)aryloxy, (C6-C30)arylthio, (C1-C30)alkoxycarbonyl, (C1-C30)alkylcarbonyl, (C6-C30)arylcarbonyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryloxycarbonyl, (C1-C30)alkoxycarbonyloxy, (C1-C30)alkylcarbonyloxy, (C6-C30)arylcarbonyloxy, (C6-C30)aryloxycarbonyloxy, carboxyl, nitro or hydroxyl, or each of them may be linked to an adjacent substituent via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicylic ring or a mono- or polycyclic aromatic ring, and
    the R41 through R48 independently represent (C1-C30)alkyl, (C6-C30)aryl or (C3-C30)heteroaryl.
  4. The organic electroluminescent compound according to claim 3, wherein R1 through R14 are selected from the following structures:
    Figure PCTKR2010005017-appb-I000058
    Figure PCTKR2010005017-appb-I000059
    Figure PCTKR2010005017-appb-I000060
  5. The organic electroluminescent compound according to claim 1, which is selected from the following structures:
    Figure PCTKR2010005017-appb-I000061
    Figure PCTKR2010005017-appb-I000062
    Figure PCTKR2010005017-appb-I000063
    Figure PCTKR2010005017-appb-I000064
    Figure PCTKR2010005017-appb-I000065
    Figure PCTKR2010005017-appb-I000066
    Figure PCTKR2010005017-appb-I000067
    Figure PCTKR2010005017-appb-I000068
    Figure PCTKR2010005017-appb-I000069
  6. An organic electroluminescent device comprising the organic electroluminescent compound according to any of claims 1 to 5.
  7. The organic electroluminescent device according to claim 6, which comprises a first electrode; a second electrode; and one or more organic layer(s) interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more organic electroluminescent compound(s) according to any of claims 1 to 5 and one or more dopant(s) represented by Chemical Formula 2 or 3:
    Figure PCTKR2010005017-appb-I000070
    (2)
    Figure PCTKR2010005017-appb-I000071
    (3)
    wherein
    Ar11 and Ar12 independently represent (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), (C4-C30)heteroaryl with or without substituent(s), (C6-C30)arylamino with or without substituent(s), (C1-C30)alkylamino, 5- to 7-membered heterocycloalkyl with or without substituent(s), 5- to 7-membered heterocycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), (C3-C30)cycloalkyl with or without substituent(s) or (C3-C30)cycloalkyl fused with one or more aromatic ring(s) with or without substituent(s), or Ar11 and Ar12 may be linked via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicylic ring or a mono- or polycyclic aromatic ring;
    Ar13 represents (C6-C30)aryl with or without substituent(s), (C4-C30)heteroaryl with or without substituent(s) or a substituent selected from the following structures, when c is 1:
    Figure PCTKR2010005017-appb-I000072
    Ar13 represents (C6-C30)arylene with or without substituent(s), (C4-C30)heteroarylene with or without substituent(s) or a substituent selected from the following structures, when c is 2:
    Figure PCTKR2010005017-appb-I000073
    Ar14 and Ar15 independently represent (C6-C30)arylene with or without substituent(s) or (C4-C30)heteroarylene with or without substituent(s);
    R201 through R203 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without substituent(s) or (C6-C30)aryl with or without substituent(s);
    d represents an integer from 1 to 4; and
    e represents an integer 0 or 1.
  8. The organic electroluminescent device according to claim 7, wherein the organic layer further comprises one or more amine compound(s) selected from a group consisting of arylamine compounds and styrylarylamine compounds, or one or more metal(s) selected from a group consisting of organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements or complex compound(s).
  9. The organic electroluminescent device according to claim 7, wherein the organic layer comprises an electroluminescent layer and a charge generating layer.
  10. The organic electroluminescent device according to claim 7, which is a white light-emitting organic electroluminescent device wherein the organic layer comprises one or more organic compound layer(s) emitting red, green or blue light at the same time.
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