WO2011126225A1 - Novel compounds for organic electronic material and organic electroluminescent device using the same - Google Patents

Novel compounds for organic electronic material and organic electroluminescent device using the same Download PDF

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WO2011126225A1
WO2011126225A1 PCT/KR2011/001920 KR2011001920W WO2011126225A1 WO 2011126225 A1 WO2011126225 A1 WO 2011126225A1 KR 2011001920 W KR2011001920 W KR 2011001920W WO 2011126225 A1 WO2011126225 A1 WO 2011126225A1
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alkyl
organic
compound
heteroaryl
aryl
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PCT/KR2011/001920
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French (fr)
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Soo Yong Lee
Young Jun Cho
Hyuck Joo Kwon
Bong Ok Kim
Sung Min Kim
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Rohm And Haas Electronic Materials Korea Ltd.
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Publication of WO2011126225A1 publication Critical patent/WO2011126225A1/en

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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
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Definitions

  • the present invention relates to novel compounds for organic electronic materials and an organic electroluminescent device using the same. More particularly, the compounds for organic electronic materials are used as transport materials.
  • electroluminescent (EL) devices are advantageous in that they provide wide view angle, superior contrast and fast response rate as self-emissive display devices.
  • Eastman Kodak first developed an organic EL device using a low-molecular-weight aromatic diamine and aluminum complex as a substance for forming an electroluminescent layer [ Appl. Phys. Lett. 51, 913, 1987].
  • An organic EL device is a device wherein, when charge is applied to an organic film formed between an electron injection electrode (cathode) and a hole injection electrode (anode), an electron and a hole form a pair and then become extinct with emitting light.
  • a device can be formed on a transparent flexible substrate such as plastics. The device can be operated at a lower voltage (not more than 10 V) with relatively lower power consumption but excellent color purity, as compared to a plasma display panel or an inorganic EL display.
  • 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.
  • Organic electroluminescent materials are generally classified into high-molecular materials and low-molecular materials.
  • the low-molecular materials include metal complexes and thoroughly organic electroluminescent materials which do not contain metal, from the aspect of molecular structure.
  • Such electroluminescent materials include chelate complexes such as tris(8-quinolinolato)aluminum complexes, coumarin derivatives, tetraphenylbutadiene derivatives, bis(styrylarylene) derivatives and oxadiazole derivatives. From those materials, it is reported that light emission of visible region from blue to red can be obtained.
  • electroluminescent materials for red, green and blue
  • OLED organic light-emitting diode
  • the important issue is to develop red, green and blue electroluminescent materials with high efficiency and long life, in order to enhance the overall feature of the organic electroluminescent (EL) devices.
  • the EL materials are classified into host materials and dopant materials. It is generally known that a device structure having the most excellent EL properties can be fabricated with an EL layer prepared by doping a dopant to a host.
  • aluminum complexes such as tris(8-hydroxyquinoline)aluminum(III) (Alq) used before multi-layer thin film OLED, which was announced by Kodak in 1987, and beryllium complexes [T. Sato et.al. J. Mater. Chem. 10 (2000) 1151] such as bis(10-hydroxybenzo-[h]quinolinato)beryllium (Bebq) announced in Japan in the middle of 1990.
  • Alq tris(8-hydroxyquinoline)aluminum(III)
  • Bebq bis(10-hydroxybenzo-[h]quinolinato)beryllium
  • the noteworthy things of the conventional electron transport materials are that there are problems such as the slight improvement of only driving voltage differently from announcement, the significant deterioration of the device operation life, or the appearance of the side effect properties including deviation of the device operation life in each color and deterioration of thermal stability. It is the reality that the above-mentioned side effect properties have become a large obstacle in achieving the object such as increase of consumption power and brightness, which are hindrances in production of the large-sized OLED panel.
  • an object of the present invention is to provide novel compounds for organic electronic materials that weak points of the conventional electron transport materials are compensated, and that efficiency in electron transport, consumption power and device operation life are improved.
  • Another object of the present invention is to provide an organic electroluminescent device including the novel the compounds for organic electronic materials.
  • the compound for organic electronic materials according to the present invention as electron transport materials exhibits excellent electron transport efficiency, it may prevent crystallization during the production of devices. Further, since it provides good layer formation, it may improve electrical current properties of devices. Therefore, it may be used to manufacture OLED devices having reduced driving voltage and improved power efficiency:
  • X represents -C(R 1 )(R 2 )-, -Si(R 3 )(R 4 )-, -S- or -O-;
  • R 1 through R 4 independently represent (C1-C30)alkyl, (C6-C30)aryl or (C3-C30)heteroaryl, or R 1 and R 2 or R 3 and R 4 may be linked via (C3-C12)alkylene or (C3-C12)alkenylene with or without a fused ring to from a spiro ring or a fused ring;
  • Ar 1 through Ar 4 independently represent hydrogen, (C1-C30)alkyl, halogen, di(C1-C30)alkylboranyl, di(C6-C30)arylboranyl, cyano, (C3-C30)cycloalkyl, morpholino, thiomorpholino, piperidino, 5- to 7-membered heterocycloalkyl, (C7-C30)bicycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, carbazolyl, (C6-C30)ar(C1-C30)alkyl, (C6-C30)arylthio, mono- or di(C1-C30)alkylamino, mono- or di(C6-C30)arylamino, tri(
  • the alkyl, aryl or heteroaryl of R 1 through R 4 and the alkyl, cycloalkyl, heterocycloalkyl, bicycloalkyl, alkylboranyl, arylboranyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, heteroaryl, aralkyl, arylthio, alkylamino, arylamino, trialkylsilyl, dialkylarylsilyl or triarylsilyl of Ar 1 through Ar 4 may be further substituted by one or more substituent(s) selected from the group consisting of deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C7-C30)bicycloalkyl, (C2-C30)alkenyl, (C2-C30)
  • alkyl includes linear or branched saturated monovalent hydrocarbon radical containing only carbon atoms and hydrogen atoms, or a combination thereof.
  • alkoxy and alkylthio are respectively an -O-alkyl group and an -S-alkyl group, wherein alkyl is the same as defined above.
  • 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 aryl groups having single bond(s) therebetween.
  • 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.
  • the heteroaryl also includes heteroaryl groups having single bond(s) therebetween.
  • the alkyl moiety of "(C1-C30)alkyl, di(C1-C30)alkylboranyl, mono- or di(C1-C30)alkylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, (C6-C30)ar(C1-C30)alkyl, (C1-C30)alkoxy" or the like may have 1 to 20 carbon atoms, more specifically 1 to 10 carbon atoms.
  • the aryl moiety of "(C6-C30)aryl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, (C6-C30)ar(C1-C30)alkyl, (C6-C30)aryloxy, (C6-C30)arylthio” or the like may have 6 to 20 carbon atoms, more specifically 6 to 12 carbon atoms.
  • the heteroaryl of "(C3-C30)heteroaryl” may have 4 to 20 carbon atoms, more specifically 4 to 12 carbon atoms.
  • the cycloalkyl of "(C3-C30)cycloalkyl” may have 3 to 20 carbon atoms, more specifically 3 to 7 carbon atoms.
  • the alkenyl or alkynyl of "(C2-C30)alkenyl or alkynyl” may have 2 to 20 carbon atoms, more specifically 2 to 10 carbon atoms.
  • X represents -C(R 1 )(R 2 )-, -Si(R 3 )(R 4 )-, -S- or -O-;
  • R 1 through R 4 independently represent (C1-C30)alkyl or (C6-C30)aryl, or R 1 and R 2 or R 3 and R 4 may be linked via (C3-C12)alkylene or (C3-C12)alkenylene with or without a fused ring to form a spiro ring or a fused ring;
  • R 1 and R 2 may be linked via alkylene or alkenylene with or without a fused ring to form a spiro ring or a fused ring but are not limited thereto.
  • R 3 and R 4 may be linked via alkylene or alkenylene with or without a fused ring to form a spiro ring or a fused ring but are not limited thereto.
  • Ar 1 through Ar 4 are independently selected from the group consisting of (C3-C30)cycloalkyl, morpholino, thiomorpholino, (C7-C30)bicycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C6-C30)aryloxy, (C3-C30)heteroaryl, carbazolyl, (C6-C30)arylthio, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl or tri(C6-C30)arylsilyl.
  • alkyl or aryl of R 1 through R 4 and the cycloalkyl, bicycloalkyl, alkenyl, alkynyl, aryl, aryloxy, heteroaryl, arylthio, trialkylsilyl, dialkylarylsilyl or triarylsilyl of Ar 1 through Ar 4 may be further substituted by one or more substituent(s) selected from the group consisting of deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C7-C30)bicycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl
  • the compounds for organic electronic materials according to the present invention may be exemplified by the compounds having following structures but are not limited thereto.
  • the compounds for organic electronic materials according to the present invention may be prepared as shown in following Scheme 1.
  • X and Ar 1 through Ar 4 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 compounds for organic electronic material(s) represented by Chemical Formula 1.
  • the compounds for organic electronic materials are used as a material of the electron transport layer.
  • the OLED consumption power is remarkably reduced due to the decrease of driving voltage and superior luminous efficiency is acquired.
  • the organic layer comprises one or more layer(s) including the compound for organic electric material represented by Chemical Formula 1 and one or more electroluminescent layer(s) including a fluorescent host and a fluorescent dopant or a phosphorescent host and a phosphorescent dopant.
  • the fluorescent host, fluorescent dopant, phosphorescent host or the phosphorescent dopant applied to the organic electroluminescent device of the present invention is not specifically limited.
  • the organic layer may further include, in addition to the compound for organic electric material 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 compounds for organic electronic materials 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 compound for organic electric material 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 (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 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. 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.
  • the compound for organic electronic materials according to the present invention as electron transport materials exhibits excellent electron transport efficiency, it may prevent crystallization during the production of devices. Further, since it provides good layer formation, it may improve electrical current properties of devices. Therefore, it may be used to manufacture OLED devices having reduced driving voltage, improved power efficiency and the same or higher luminous efficiency.
  • the present invention is further described with respect to the compounds for organic electronic materials according to the present invention, processes for preparing the same, and luminescence properties of devices employing the same.
  • the following examples are provided for illustrative purposes only and they are not intended to limit the scope of the present invention.
  • Compound A-1 (16g, 0.082mol) was dissolved in acetic acid (400mL). Fuming nitric acid (172mL, 4.1mol) and sulfuric acid (43mL) were added using dropping funnel at 0°C and stirred for 24 hours. After filtering a produced solid under reduced pressure, the mixture was washed with acetic acid and distilled water. After distilling an obtained organic layer under reduced pressure and removing a solvent, Compound B-1 (16g, 81.5%) was obtained via purification by column chromatography.
  • Organic electroluminescent Compounds 1 to 66 were prepared according to Preparation Examples 1 to 3. Table 1 shows 1 H NMR and MS/FAB of the prepared organic electroluminescent compounds.
  • An OLED device was manufactured using the compound for organic electronic materials 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
  • N , N '-bis( ⁇ -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.
  • an electroluminescent layer was formed thereon as follows. After respectively adding tris(8-hydroxyquinoline)-aluminum(III) (Alq3), which is an electroluminescent host as a luminous material in a cell of a vacuum vapor deposition apparatus and coumarin 545T as an electroluminescent dopant in another cell. The two cells were evaporated at different rates such that an electroluminescent layer having a thickness of 30 nm was vapor-deposited on the hole transport layer.
  • the doping concentration may be 2 to 5 mol% on the basis of Alq3.
  • the compound for organic electronic materials e.g. Compound 2
  • the compound for organic electronic materials e.g. Compound 2
  • Liq lithium quinolate
  • 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 device as an electroluminescent material was purified by vacuum sublimation at 10 -6 torr.
  • the driving voltage and the luminous efficiencies of the OLED comprising the compound for organic electronic materials according to the present invention or the conventional electron transport materials in the Examples 1-5 and Comparative Example 1 were measured at 1,000 cd/m 2 , respectively, and the results are shown in Table 2.
  • 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
  • N , N '-bis( ⁇ -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.
  • a compound according to the present invention (e.g.: Compound 7) purified by vacuum sublimation at 10 -6 torr was placed in a cell of a vacuum vapor deposition apparatus as a host, and an electroluminescent dopant (e.g.: Compound (piq) 2 Ir(acac)) was placed in another cell.
  • 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 through doping at 4 to 10 wt%.
  • An OLED device was manufactured in the same manner as Example 8 except the hole blocking layer.
  • An OLED device was manufactured in the same manner as Example 6 except that 4,4'-bis(carbazol-9-yl)biphenyl (CBP) instead of the compounds of the present invention as a host material at one cell of the vacuum vapor deposition apparatus.
  • CBP 4,4'-bis(carbazol-9-yl)biphenyl
  • the organic electroluminescent compounds according to the present invention have excellent luminous properties compared with the conventional material.
  • the organic electroluminescent compounds according to the present invention have excellent luminous properties compared with the conventional material. They have superior current properties compared with the device of Comparative Example 2 as the conventional material. They showed reduction of 0.2 V or more in a driving voltage and show high power efficiency of 1.1 times or more compared with the device of Comparative Example 2.
  • the compound for organic electronic materials according to the present invention as electron transport materials exhibits excellent electron transport efficiency, it may prevent crystallization during the production of devices. Further, since it provides good layer formation, it may improve electrical current properties of devices. Therefore, it may be used to manufacture OLED devices having reduced driving voltage, improved power efficiency and the same or higher luminous efficiency.

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Abstract

Provided are novel compounds for organic electronic material and an organic electroluminescent device using the same. Since the compound for organic electric material exhibits excellent electron transport efficiency, it may prevent crystallization during the production of devices. Further, since it provides good layer formation, it may improve electrical current property of devices. Therefore, it may be used to manufacture OLED devices having reduced driving voltage and improved power efficiency.

Description

NOVEL COMPOUNDS FOR ORGANIC ELECTRONIC MATERIAL AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME
The present invention relates to novel compounds for organic electronic materials and an organic electroluminescent device using the same. More particularly, the compounds for organic electronic materials are used as transport materials.
Among display devices, electroluminescent (EL) devices are advantageous in that they provide wide view angle, superior contrast and fast response rate as self-emissive display devices. In 1987, Eastman Kodak first developed an organic EL device using a low-molecular-weight aromatic diamine and aluminum complex as a substance for forming an electroluminescent layer [Appl. Phys. Lett. 51, 913, 1987].
An organic EL device is a device wherein, when charge is applied to an organic film formed between an electron injection electrode (cathode) and a hole injection electrode (anode), an electron and a hole form a pair and then become extinct with emitting light. A device can be formed on a transparent flexible substrate such as plastics. The device can be operated at a lower voltage (not more than 10 V) with relatively lower power consumption but excellent color purity, as compared to a plasma display panel or an inorganic EL display.
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.
Organic electroluminescent materials are generally classified into high-molecular materials and low-molecular materials. The low-molecular materials include metal complexes and thoroughly organic electroluminescent materials which do not contain metal, from the aspect of molecular structure. Such electroluminescent materials include chelate complexes such as tris(8-quinolinolato)aluminum complexes, coumarin derivatives, tetraphenylbutadiene derivatives, bis(styrylarylene) derivatives and oxadiazole derivatives. From those materials, it is reported that light emission of visible region from blue to red can be obtained.
Three electroluminescent materials (for red, green and blue) are employed to realize a full-colored organic light-emitting diode (OLED) display. The important issue is to develop red, green and blue electroluminescent materials with high efficiency and long life, in order to enhance the overall feature of the organic electroluminescent (EL) devices. From the aspect of function, the EL materials are classified into host materials and dopant materials. It is generally known that a device structure having the most excellent EL properties can be fabricated with an EL layer prepared by doping a dopant to a host. Recently, development of organic EL devices with high efficiency and long life comes to the fore as an urgent subject, and particularly urgent is development of a material with far better EL properties as compared to conventional EL materials as considering EL properties required for a medium to large sized OLED panel.
Also, as representative examples of the conventional electron transport materials, there are aluminum complexes such as tris(8-hydroxyquinoline)aluminum(III) (Alq) used before multi-layer thin film OLED, which was announced by Kodak in 1987, and beryllium complexes [T. Sato et.al. J. Mater. Chem. 10 (2000) 1151] such as bis(10-hydroxybenzo-[h]quinolinato)beryllium (Bebq) announced in Japan in the middle of 1990. However, in case of those materials, their limitation came to the fore as the OLED had been commercialized since 2002. Since a lot of electron transport materials having high performance have been researched and presented since then, they stand close to be commercialized.
Figure PCTKR2011001920-appb-I000001
Meanwhile, as nonmetal complex series, electron transport materials having a good property announced until now include spiro-PBD[N. Johansson et.al. Adv. Mater. 10 (1998) 1136], PyPySPyPy[M. Uchida et.al. Chem. Mater. 13 (2001) 2680] and TPBI[Y.-T. Tao et.al. Appl. Phys. Lett. 77 (2000) 1575] by Kodak. However, there is much to be desired in the view of electroluminescent properties and operation life.
Figure PCTKR2011001920-appb-I000002
The noteworthy things of the conventional electron transport materials are that there are problems such as the slight improvement of only driving voltage differently from announcement, the significant deterioration of the device operation life, or the appearance of the side effect properties including deviation of the device operation life in each color and deterioration of thermal stability. It is the reality that the above-mentioned side effect properties have become a large obstacle in achieving the object such as increase of consumption power and brightness, which are hindrances in production of the large-sized OLED panel.
Accordingly, an object of the present invention is to provide novel compounds for organic electronic materials that weak points of the conventional electron transport materials are compensated, and that efficiency in electron transport, consumption power and device operation life are improved. Another object of the present invention is to provide an organic electroluminescent device including the novel the compounds for organic electronic materials.
Provided are compounds for organic electronic materials represented by following Chemical Formula 1 and an organic electroluminescent device using the same. The compound for organic electronic materials according to the present invention as electron transport materials exhibits excellent electron transport efficiency, it may prevent crystallization during the production of devices. Further, since it provides good layer formation, it may improve electrical current properties of devices. Therefore, it may be used to manufacture OLED devices having reduced driving voltage and improved power efficiency:
[Chemical Formula 1]
Figure PCTKR2011001920-appb-I000003
wherein
X represents -C(R1)(R2)-, -Si(R3)(R4)-, -S- or -O-;
R1 through R4 independently represent (C1-C30)alkyl, (C6-C30)aryl or (C3-C30)heteroaryl, or R1 and R2 or R3 and R4 may be linked via (C3-C12)alkylene or (C3-C12)alkenylene with or without a fused ring to from a spiro ring or a fused ring;
Ar1 through Ar4 independently represent hydrogen, (C1-C30)alkyl, halogen, di(C1-C30)alkylboranyl, di(C6-C30)arylboranyl, cyano, (C3-C30)cycloalkyl, morpholino, thiomorpholino, piperidino, 5- to 7-membered heterocycloalkyl, (C7-C30)bicycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, carbazolyl, (C6-C30)ar(C1-C30)alkyl, (C6-C30)arylthio, mono- or di(C1-C30)alkylamino, mono- or di(C6-C30)arylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, nitro or hydroxyl;
the alkyl, aryl or heteroaryl of R1 through R4 and the alkyl, cycloalkyl, heterocycloalkyl, bicycloalkyl, alkylboranyl, arylboranyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, heteroaryl, aralkyl, arylthio, alkylamino, arylamino, trialkylsilyl, dialkylarylsilyl or triarylsilyl of Ar1 through Ar4 may be further substituted by one or more substituent(s) selected from the group consisting of deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C7-C30)bicycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, (C3-C30)heteroaryl substituted by (C1-C30)alkyl, (C3-C30)heteroaryl substituted by (C6-C30)aryl, (C6-C30)ar(C1-C30)alkyl, (C6-C30)arylthio, mono- or di(C1-C30)alkylamino, mono- or di(C6-C30)arylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, nitro and hydroxyl; and
the heterocycloalkyl or heteroaryl may contain one or more heteroatom(s) selected from B, N, O, S, P(=O), Si and P.
In the present invention, "alkyl" includes linear or branched saturated monovalent hydrocarbon radical containing only carbon atoms and hydrogen atoms, or a combination thereof. Also, "alkoxy" and "alkylthio" are respectively an -O-alkyl group and an -S-alkyl group, wherein alkyl is the same as defined above.
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 aryl groups having single bond(s) therebetween. 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. The heteroaryl also includes heteroaryl groups having single bond(s) therebetween.
In the present invention, the alkyl moiety of "(C1-C30)alkyl, di(C1-C30)alkylboranyl, mono- or di(C1-C30)alkylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, (C6-C30)ar(C1-C30)alkyl, (C1-C30)alkoxy" or the like may have 1 to 20 carbon atoms, more specifically 1 to 10 carbon atoms. The aryl moiety of "(C6-C30)aryl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, (C6-C30)ar(C1-C30)alkyl, (C6-C30)aryloxy, (C6-C30)arylthio" or the like may have 6 to 20 carbon atoms, more specifically 6 to 12 carbon atoms. The heteroaryl of "(C3-C30)heteroaryl" may have 4 to 20 carbon atoms, more specifically 4 to 12 carbon atoms. The cycloalkyl of "(C3-C30)cycloalkyl" may have 3 to 20 carbon atoms, more specifically 3 to 7 carbon atoms. The alkenyl or alkynyl of "(C2-C30)alkenyl or alkynyl" may have 2 to 20 carbon atoms, more specifically 2 to 10 carbon atoms.
In Chemical Formula 1, X represents -C(R1)(R2)-, -Si(R3)(R4)-, -S- or -O-;
R1 through R4 independently represent (C1-C30)alkyl or (C6-C30)aryl, or R1 and R2 or R3 and R4 may be linked via (C3-C12)alkylene or (C3-C12)alkenylene with or without a fused ring to form a spiro ring or a fused ring;
That is, R1 and R2 may be linked via alkylene or alkenylene with or without a fused ring to form a spiro ring or a fused ring but are not limited thereto.
Figure PCTKR2011001920-appb-I000004
Also, the R3 and R4 may be linked via alkylene or alkenylene with or without a fused ring to form a spiro ring or a fused ring but are not limited thereto.
Figure PCTKR2011001920-appb-I000005
Ar1 through Ar4 are independently selected from the group consisting of (C3-C30)cycloalkyl, morpholino, thiomorpholino, (C7-C30)bicycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C6-C30)aryloxy, (C3-C30)heteroaryl, carbazolyl, (C6-C30)arylthio, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl or tri(C6-C30)arylsilyl.
Also, the alkyl or aryl of R1 through R4 and the cycloalkyl, bicycloalkyl, alkenyl, alkynyl, aryl, aryloxy, heteroaryl, arylthio, trialkylsilyl, dialkylarylsilyl or triarylsilyl of Ar1 through Ar4 may be further substituted by one or more substituent(s) selected from the group consisting of deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C7-C30)bicycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, (C3-C30)heteroaryl substituted by (C1-C30)alkyl, (C3-C30)heteroaryl substituted by (C6-C30)aryl, (C6-C30)ar(C1-C30)alkyl, (C6-C30)arylthio, mono- or di(C1-C30)alkylamino, mono- or di(C6-C30)arylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, nitro and hydroxyl.
The compounds for organic electronic materials according to the present invention may be exemplified by the compounds having following structures but are not limited thereto.
Figure PCTKR2011001920-appb-I000006
Figure PCTKR2011001920-appb-I000007
Figure PCTKR2011001920-appb-I000008
Figure PCTKR2011001920-appb-I000009
Figure PCTKR2011001920-appb-I000010
Figure PCTKR2011001920-appb-I000011
Figure PCTKR2011001920-appb-I000012
Figure PCTKR2011001920-appb-I000013
Figure PCTKR2011001920-appb-I000014
Figure PCTKR2011001920-appb-I000015
Figure PCTKR2011001920-appb-I000016
Figure PCTKR2011001920-appb-I000017
Figure PCTKR2011001920-appb-I000018
Figure PCTKR2011001920-appb-I000019
Figure PCTKR2011001920-appb-I000020
Figure PCTKR2011001920-appb-I000021
Figure PCTKR2011001920-appb-I000022
Figure PCTKR2011001920-appb-I000023
Figure PCTKR2011001920-appb-I000024
Figure PCTKR2011001920-appb-I000025
Figure PCTKR2011001920-appb-I000026
Figure PCTKR2011001920-appb-I000027
The compounds for organic electronic materials according to the present invention may be prepared as shown in following Scheme 1.
[Scheme 1]
Figure PCTKR2011001920-appb-I000028
wherein
X and Ar1 through Ar4 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 compounds for organic electronic material(s) represented by Chemical Formula 1. The compounds for organic electronic materials are used as a material of the electron transport layer.
When the compounds for organic electronic materials represented by the Chemical Formula 1 according to the present invention are used in the electron transport layer, the OLED consumption power is remarkably reduced due to the decrease of driving voltage and superior luminous efficiency is acquired.
Also, the organic layer comprises one or more layer(s) including the compound for organic electric material represented by Chemical Formula 1 and one or more electroluminescent layer(s) including a fluorescent host and a fluorescent dopant or a phosphorescent host and a phosphorescent dopant. The fluorescent host, fluorescent dopant, phosphorescent host or the phosphorescent dopant applied to the organic electroluminescent device of the present invention is not specifically limited.
In the organic electronic device of the present invention, the organic layer may further include, in addition to the compound for organic electric material 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 compounds for organic electronic materials 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 compound for organic electric material 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.
The compound for organic electronic materials according to the present invention as electron transport materials exhibits excellent electron transport efficiency, it may prevent crystallization during the production of devices. Further, since it provides good layer formation, it may improve electrical current properties of devices. Therefore, it may be used to manufacture OLED devices having reduced driving voltage, improved power efficiency and the same or higher luminous efficiency.
The present invention is further described with respect to the compounds for organic electronic materials 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 2
Figure PCTKR2011001920-appb-I000029
Preparation of Compound A
After 2,7-dibromofluorene (10 g, 0.037 mol) was added to THF (200mL) under nitrogen atmosphere and cooled to -78℃, n-BuLi (2.5M in Hexane) (1.2 equivalent) was slowly added thereto. 2 hours later, 1M HCl was added and the mixture was stirred for 30 minutes and washed with EA and distilled water three times. After removing a solvent by a rotary-type evaporator in residual liquid obtained by filtering an produced organic layer by a silica gel filter, Compound A (7 g, 97 %) was obtained as a while solid.
Preparation of Compound B
Compound A (10 g, 0.05 mol) was dissolved in acetic acid (100mL). After fuming nitric acid (equivalent weight: 50) and sulfuric acid (30 mL) were added to the mixture at 0℃, the mixture was slowly heated to the room temperature and stirred for 30 minutes. A produced solid was filtered under reduced pressure and washed with acetic acid twice. After distilling an obtained organic layer under reduced pressure and removing a solvent, Compound B (4.2 g, 30 %) was obtained as a pure yellow solid via purification by column chromatography.
Preparation of Compound C
After hydrochloric acid (30 mL), ethanol (12 mL), SnCl2 (4 g) and Compound B (4.2 g, 0.014 mol) were stirred under reflux for 4 hours at nitrogen atmosphere, a produced solid was filtered and the mixture was washed with hydrochloric acid. After acetic acid (20 mL) and anhydrous acetic acid (20 mL) were mixed, the produced white solid (3 g) was slowly added at 0℃. 20 minutes later, the mixture was slowly heated to room temperature and stirred for 24 hours. Upon completion of the reaction, distilled water was slowly added to the mixture and a solvent was removed by a rotary-type evaporator. After extracting with dichloro methane, the reaction mixture was washed with distilled water three times. After distilling an obtained organic layer under reduced pressure and removing a solvent, Compound C (3.5 g, 75 %) was obtained as a pure white solid via purification by column chromatography.
Preparation of Compound D
After acetic acid (10 mL) and fuming nitric acid (10 mL) were mixed at -10℃, Compound C (3.5 g, 0.0145 mol) was slowly added at the same temperature. 10 minutes later, a reactant was added to cold distilled water and filtered under reduced pressure. Compound D (3.4 g, 59 %) was obtained as a pure yellow solid by purifying an obtained organic material by column chromatography.
Preparation of Compound E
Sulfuric acid (24 mL) and distilled water (20 mL) were slowly added to Compound D (3.4 g, 0.009 mol) in order. Subsequently, a reactant was stirred under reflux for 2 hours at 90℃. Upon completion of the reaction, the reactant was added to cold distilled water and filtered under reduced pressure. Compound E (2 g, 70 %) was obtained as a pure yellow solid by purifying an obtained organic material by column chromatography.
Preparation of Compound F
After bromobenzene (1.1 g), Pd(OAc)2 (0.04 g) and Cs2CO3 (4.1 g) were added to Compound E (2 g, 0.006 mol), toluene (25 mL) and P(t-Bu)3 (0.4 mL) were added to the mixture under nitrogen atmosphere. The mixture was stirred under reflux for 12 hours at 80℃. Upon completion of the reaction, the mixture was extracted with EA and distilled water and a solvent was removed by a rotary-type evaporator. Compound F (2 g, 71 %) was obtained as a yellow solid by purifying an obtained organic material by column chromatography.
Preparation of Compound G
After ethanol (20 mL) was added to Compound F (2 g, 0.0043 mol) and the mixture was stirred for 10 minutes, Pd/C (0.3 g) was stirred under reflux for 4 hours at 90℃ at hydrogen (5 psi) atmosphere. Upon completion of the reaction, a reactant was filtered under reduced pressure. Compound G (1.8 g, 74 %) was obtained as a yellow solid by purifying an obtained organic material by column chromatography.
Preparation of Compound 2
After 2-naphthoic acid (1.4 g) and acetic acid (50 mL) were added to Compound G (1.3 g, 0.003 mol), the mixture was stirred under reflux for 12 hours. Upon completion of the reaction, the mixture was extracted with EA and distilled water and a solvent was removed by a rotary-type evaporator. Compound 2 (1.2 g, 55 %) was obtained as an ivory solid by purifying an obtained organic material by column chromatography.
[Preparation Example 2] Preparation of Compound 49
Figure PCTKR2011001920-appb-I000030
Preparation of Compound H
Dibenzo[b,d]thiophen (9.2g, 0.05 mol), hydrogen peroxide (21.6 mL) and methanol (300 mL) were mixed and stirred for 5 minutes at room temperature. Subsequently, ZrCl4 (46.5 g) was added and stirred for 3 minutes at room temperature. After extraction with CHCl3 and distilled water, Compound H was obtained (97 % yield) via column separation.
Preparation of Compound I
Compound H (8.5g, 0.042 mol), H2SO4 (36.7 mL), AcOH (36.7 mL) and HNO3 (40 mL) were added and stirred at room temperature for 2 hours. Upon completion of the reaction, distilled water was added to produce a solid. Compound I was obtained at a yield of 89 % by filtering the solid.
Preparation of Compound J
Compound I (9.2 g, 0.03 mol), HCl (60 mL), SnCl2 (47 mL) and AcOH (100 mL) were added and stirred for 12 hours. Upon completion of the reaction, the reaction mixture was washed with MeOH after filtration using HCl to obtain Compound J at a yield of 74 %.
Preparation of Compound K
Compound J (11g, 0.05 mol), CuBr2 (22.8 g), t-BuNO2 (9.2 mL) and Acetonitrile (255 mL) were added and stirred under reflux for 12 hours. Upon completion of the reaction, the reaction mixture was extracted with EA and distilled water to obtain Compound K at a yield of 70 % via column chromatography.
Preparation of Compound L
Compound K (9.7 g, 0.03 mol), LiAlH4 (1.3 g) and THF (174 mL) were added and stirred under reflux for 3 hours. Upon completion of the reaction, the reaction mixture was extracted with EA and distilled water to obtain Compound L at a yield of 47 % via column chromatography.
Preparation of Compound 49
Compound 49 was obtained at a yield of 42 % through the processes of C-1 to G-1 using Compound L as an intermediate in the same manner as that of Example 1.
[Preparation Example 3] Preparation of Compound 8
Figure PCTKR2011001920-appb-I000031
Preparation of Compound A-1
After 2,7-dibromofluorene (30g 0.109mol) was added to THF (500 mL) under nitrogen atmosphere, the mixture was cooled to -78℃ and n-BuLi (2.5M in Hexane) (52.7 mL, 0.131mol) was slowly added thereto. 1 hour later, water was added to the mixture and the reaction was completed. The mixture was extracted with EA and filtered by a silica gel filter. After removing obtained residual liquid by a rotary-type evaporator, Compound A-1 (16g, 75.6%) was obtained as a white solid.
Preparation of Compound B-1
Compound A-1 (16g, 0.082mol) was dissolved in acetic acid (400mL). Fuming nitric acid (172mL, 4.1mol) and sulfuric acid (43mL) were added using dropping funnel at 0℃ and stirred for 24 hours. After filtering a produced solid under reduced pressure, the mixture was washed with acetic acid and distilled water. After distilling an obtained organic layer under reduced pressure and removing a solvent, Compound B-1 (16g, 81.5%) was obtained via purification by column chromatography.
Preparation of Compound C-1
A solid produced after stirring Compound B-1 (19g, 0.067mol), SnCl2 (120g, 0.536mol), HCl (152mL), and ethanol (80mL) under reflux for 4 hours at nitrogen atmosphere was filtered. After acetic acid (250 mL) and anhydrous acetic acid (100 mL) were mixed, the obtained solid was slowly added and stirred under reflux for 24 hours at room temperature. Upon completion of the reaction, C-1 (10g, 48.4%) was obtained as a white solid via filtration.
Preparation of Compound D-1
After Compound C-1 (10g, 0.0324mol) was dissolved in acetic acid at -10℃, fuming nitric acid (75 mL) was slowly added at the same temperature. 10 minutes later, a reactant was added to cold distilled water and filtered to obtain a solid. After washing the obtained solid with distilled water and hexane, D-1 (5g, 38.7%) was obtained as a yellow solid via drying.
Preparation of Compound E-1
After sulfuric acid (30 mL) and distilled water (8 mL) were slowly added to Compound D-1 (5g, 0.0126mol) in order, a reactant was stirred under reflux for 2 hours at 150℃. Upon completion of the reaction, the reactant was added to cold distilled water and filtered under reduced pressure. Compound E-1 (3.5g, 88.4%) was obtained as a blood red solid by purifying an obtained organic material by column chromatography.
Preparation of Compound H
After Compound E-1 (0.4 g, 0.078 mol) was dissolved in ethanol (10 mL), the mixture was added to Pd/C (70mg) and stirred under reflux for 4 hours at 90℃. Upon completion of the reaction, a reactant was filtered and hydrochloric acid was added thereto. After removing a solvent, Compound H (0.43g, 91%) was obtained via recrystallization (Ethanol: THF = 1:1).
Preparation of Compound I-3
Compound I-1 (13g), Compound I-2 (4g), K2CO3 (4g), and Cu powder (0.15g) were added and stirred for 6 hours at 220℃. After removing overused Compound I-1 via distillation, Compound I-3 (6g, 80%) was obtained as a white solid via recrystallization with methanol.
Preparation of Compound I-4
After Compound I-3 (1g) was dissolved in ethanol, excess KOH solution (10M in H2O) was added thereto and stirred. Upon completion of the reaction, the mixture was extracted with hydrochloric acid to obtain Compound I-4 (0.5g, 70%) as white solid via filtration.
Preparation of Compound J
Compound H (0.5 mmol) and Compound I-4 (1 mmol) were added to glacial acetic acid and stirred for 2 hours. After filtering a produced solid, Compound J (1g, 33.5%) was obtained via purification by column chromatography.
Preparation of Compound 8
Compound J (1g, 1.32 mmol), iodobenzene (5.3 mmol), CuI (0.07 mmol), 18-crown-6 (0.1 mmol) and 1,2-dichlorobenzene (50 mL) were added and stirred under reflux at 180℃. Upon completion of the reaction, the mixture was extracted with EA and Compound 8 (1g, 83%) was obtained as a pure solid via purification by column chromatography.
Organic electroluminescent Compounds 1 to 66 were prepared according to Preparation Examples 1 to 3. Table 1 shows 1H NMR and MS/FAB of the prepared organic electroluminescent compounds.
Table 1
Comp. 1H NMR(CDCl3, 200 MHz) MS/FAB
found calculated
1 δ = 1.72(6H, s), 7.41~7.51(12H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 8.28(4H, m) 578.70 578.25
2 δ = 1.72(6H, s), 7.45~7.5(6H, m), 7.56(2H, s), 7.58~7.59(8H, m), 7.84(2H, s), 7.92(2H, m), 8(4H, m), 8.49(2H, m), 9.09(2H, m) 678.82 678.28
3 δ = 1.72(6H, s), 7.56(2H, s), 7.84(2H, s) 598.83 598.37
4 δ = 1.72(6H, s), 7.25(4H, m), 7.41~7.52(16H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 7.85(4H, m) 730.90 730.31
5 δ = 1.72(6H, s), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.82(4H, m), 7.84(2H, s), 7.88~7.93(6H, m), 8.12(4H, m), 8.93(4H, m) 778.94 778.31
6 δ = 1.72(6H, s), 2.53(12H, s), 7.12(2H, m), 7.34(2H, s), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.77(2H, m), 7.84(2H, s), 8.07(2H, m), 8.32(2H, m) 839.00 838.35
7 δ = 1.72(6H, s), 7.25~7.33(4H, m), 7.41~7.51(13H, m), 7.56(2H, s), 7.58~7.63(7H, m), 7.84(2H, s), 7.94~7.98(4H, m), 8.12(1H, m), 8.28(4H, m), 8.55(1H, m) 909.09 908.36
8 δ = 1.72(6H, s), 7.25~7.33(6H, m), 7.45~7.5(8H, m), 7.56(2H, s), 7.58~7.68(10H, m), 7.79(4H, m), 7.84(2H, s), 7.94(2H, m), 8.12(2H, m), 8.55(2H, m) 909.09 908.36
9 δ = 1.35(18H, s), 1.72(6H, s), 7.38(4H, m), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 8.56(4H, m) 690.92 690.37
10 δ = 1.72(6H, s), 3.83(6H, s), 7.05(4H, m), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 7.97(4H, m) 638.76 638.27
11 δ = 1.72(6H, s), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.69~7.73(4H, m), 7.84(2H, s), 7.88(2H, m), 8.56(2H, m) 628.72 628.24
12 δ = 1.72(6H, s), 7.44~7.5(8H, m), 7.56(2H, s), 7.58(6H, m), 7.84(2H, s), 8.28(2H, m), 8.64(2H, m) 714.70 714.22
13 δ = 1.72(6H, s), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.77(2H, m), 7.84(2H, s), 8.22(2H, m), 8.36(2H, m), 8.65(2H, m) 668.70 668.22
14 δ = 0.25(18H, s), 1.72(6H, s), 7.45~7.5(10H, m), 7.56(2H, s), 7.58(4H, m), 7.77(4H, m), 7.84(2H, s), (H, ) 723.07 722.33
15 δ = 1.72(6H, s), 7.37(12H, m), 7.45~7.55(28H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 7.89(4H, m) 1095.48 1094.42
16 δ = 1.72(18H, s), 7.28(2H, m), 7.38(2H, m), 7.45~7.55(8H, m), 7.56(2H, s), 7.58~7.63(6H, m), 7.77(2H, m), 7.84(2H, s), 7.87~7.93(4H, m) 811.02 810.37
17 δ = 1.72(6H, s), 7.25~7.33(3H, m), 7.45~7.5(13H, m), 7.56(2H, s), 7.58~7.63(9H, m), 7.69(1H, m), 7.77(2H, m), 7.84(2H, s), 7.87(1H, m), 7.94~8(2H, m), 8.12(1H, m), 8.18(1H, m), 8.55(1H, m) 909.09 908.36
18 δ = 1.72(6H, s), 7.32~7.38(4H, m), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.66~7.72(6H, m), 7.81(2H, m), 7.84(2H, s), 7.89(2H, m) 758.86 758.27
19 δ = 1.72(6H, s), 7.45~7.52(10H, m), 7.56(2H, s), 7.58(4H, m), 7.8(2H, m), 7.84(2H, s), 7.86(2H, m), 7.98~8(4H, m), 8.45(2H, m) 790.99 790.22
20 δ = 0.66(12H, s), 1.72(6H, s), 7.33(2H, m), 7.45~7.52(8H, m), 7.56(2H, s), 7.58~7.61(8H, m), 7.8(2H, m), 7.84(2H, s), 7.85~7.89(4H, m) 843.17 842.33
21 δ = 1.72(6H, s), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.67(4H, m), 7.8(4H, m), 7.84(2H, s), 8.7(2H, s) 682.77 682.26
22 δ = 1.72(6H, s), 7.14(2H, m), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.7(2H, m), 7.84(2H, s), 7.97(2H, m), 8.12(2H, m), 8.53(2H, m), 9.26~9.3(4H, m) 734.85 734.29
23 δ = 1.72(6H, s), 7.41(4H, m), 7.51(8H, m), 7.56(2H, s), 7.68(4H, m), 7.79(4H, m), 7.84(2H, s), 8.05(4H, m), 8.28(4H, m) 866.96 866.31
24 δ = 1.72(6H, s), 7.41~7.51(18H, m), 7.56(2H, s), 7.58(4H, m), 7.68(4H, m), 7.79(4H, m), 7.84(2H, s), 8.28(8H, m) 1017.19 1016.41
25 δ = 1.72(6H, s), 7.41~7.51(12H, m), 7.56(2H, s), 7.58(4H, m), 7.73~7.79(8H, m), 7.84(2H, s) 742.95 742.22
26 δ = 1.72(6H, s), 7.07(4H, m), 7.41~7.51(12H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 8.1(4H, m) 710.82 710.27
27 δ = 1.72(6H, s), 7.33~7.45(12H, m), 7.48(4H, s), 7.5(4H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s) 836.74 838.11
28 δ = 1.72(6H, s), 7.41~7.51(12H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 8.03(4H, m) 746.90 746.20
29 δ = 1.72(6H, s), 7.41~7.51(12H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 8.05(4H, m) 714.77 714.25
30 δ = 1.72(6H, s), 7.45~7.52(12H, m), 7.56(2H, s), 7.58(4H, m), 7.83(4H, m), 7.84(2H, s) 840.69 842.09
31 δ = 0.14(12H, s), 1.72(6H, s), 7.04(4H, s), 7.33~7.5(16H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s) 795.13 794.33
32 δ = 0.14(12H, s), 1.72(6H, s), 7.04(2H, s), 7.14~7.17(4H, m), 7.43~7.5(8H, m), 7.56(2H, s), 7.58(4H, m), 7.65(2H, s), 7.7(2H, m), 7.84(2H, s), 8.53(2H, m), 9.19(2H, m), 9.3(2H, m) 951.27 950.37
33 δ = 1.72(6H, s), 7.14(4H, m), 7.41(2H, m), 7.51(4H, m), 7.56(2H, s), 7.7(4H, m), 7.84(2H, s), 8.15(4H, m), 8.28(4H, m), 8.53(4H, m), 9.3(4H, m) 889.02 888.34
34 δ = 1.72(6H, s), 7.4~7.41(4H, m), 7.51(4H, m), 7.56(2H, s), 7.84(2H, s), 7.9(2H, m), 8.01(2H, m), 8.28(4H, m), 8.41(2H, m) 580.68 580.24
35 δ = 1.72(6H, s), 7.36~7.4(4H, m), 7.56(2H, s), 7.84(2H, s), 7.85~7.9(4H, m), 8.01(2H, m), 8.38~8.41(4H, m), 8.59(2H, m) 582.66 582.23
36 δ = 1.72(6H, s), 7.45~7.5(6H, m), 7.56(2H, s), 7.57~7.58(6H, m), 7.67~7.8(12H, m), 7.84(2H, s), 8.24(2H, m), 8.7(2H, s) 834.97 834.32
37 δ = 1.72(6H, s), 7.41~7.5(8H, m), 7.56(2H, s), 7.58~7.6(6H, m), 7.78(2H, m), 7.84(2H, s), 7.98(2H, m), 8.06(2H, m), 8.44(2H, m) 680.80 680.27
38 δ = 1.72(6H, s), 2.61(6H, s), 7.06(2H, s), 7.45~7.5(6H, m), 7.56(2H, s), 7.58~7.59(6H, m), 7.75(2H, m), 7.84(2H, s), 7.95(2H, m), 8.16(2H, m) 708.85 708.30
39 δ = 1.72(6H, s), 7.42~7.5(12H, m), 7.56(2H, s), 7.58~7.63(6H, m), 7.84(2H, s), 7.92(2H, m), 8.51(2H, m) 680.80 680.27
40 δ = 1.72(6H, s), 2.36(6H, s), 6.83(2H, m), 7.31(2H, m), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 7.85(8H, m) 771.00 770.25
41 δ = 1.72(6H, s), 2.3(6H, s), 6.08(2H, m), 6.95(2H, m), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 7.85(8H, m) 738.87 738.30
42 δ = 1.71(6H, m), 1.72(6H, s), 6.9(2H, m), 7.44~7.45(6H, m), 7.48(2H, s), 7.5(4H, m), 7.56(2H, s), 7.58(4H, m), 7.74(4H, m), 7.84(2H, s) 864.79 866.14
43 δ = 1.72(6H, s), 2.64(6H, s), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 7.85(8H, m) 774.96 774.23
44 δ = 1.72(6H, s), 2.62(6H, s), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 7.85(8H, m) 742.83 742.28
45 δ = 1.72(6H, s), 2(6H, s), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s), 7.85~7.89(8H, m) 868.75 870.12
46 δ = 1.72(6H, s), 7.22(4H, m), 7.45~7.5(12H, m), 7.56(2H, s), 7.58~7.59(10H, m), 7.84(2H, s), 7.85(8H, m), 8.56(2H, m) 963.14 962.38
47 δ = 0.66(6H, s), 7.41~7.51(12H, m), 7.58(4H, m), 8.02(2H, s), 8.04(2H, s), 8.28(4H, m) 594.78 594.22
48 δ = 1.3(4H, m), 1.45(4H, m), 7.45~7.5(6H, m), 7.58~7.59(8H, m), 7.92(2H, m), 8(4H, m), 8.02(2H, s), 8.04(2H, s), 8.49(2H, m), 9.09(2H, m) 720.93 720.27
49 δ = 7.45~7.5(6H, m), 7.58~7.59(8H, m), 7.78(2H, s), 7.86(2H, s), 7.92(2H, m), 8(4H, m), 8.49(2H, m), 9.09(2H, m) 668.81 668.20
50 δ = 7.41(2H, m), 7.42(2H, s), 7.45(2H, m), 7.49(2H, s), 7.5~7.51(8H, m), 7.58(4H, m), 8.28(4H, m) 552.62 552.20
51 δ = 1.72(12H, s), 7.28(2H, m), 7.38(2H, m), 7.42(2H, s), 7.45(2H, m), 7.49(2H, s), 7.5~7.63(12H, m), 7.77(2H, m), 7.87~7.93(4H, m) 784.94 784.32
52 δ = 1.72(6H, s), 7.41(2H, m), 7.51~7.53(8H, m), 7.56(2H, s), 7.68(4H, m), 7.79(4H, m), 7.84(2H, s), 8.01(2H, m), 8.18(2H, m), 8.28(4H, m) 845.04 844.24
53 δ = 1.72(18H, s), 7.28(2H, m), 7.38(2H, m), 7.53~7.55(6H, m), 7.56(2H, s), 7.63~7.68(6H, m), 7.77~7.79(6H, m), 7.84(2H, s), 7.87~7.93(4H, m), 8.01(2H, m), 8.18(2H, m) 1077.36 1076.37
54 δ = 1.72(6H, s), 7.36~7.41(4H, m), 7.51~7.53(8H, m), 7.56(2H, s), 7.83(2H, m), 7.84(2H, s), 7.87~7.92(4H, m), 8~8.01(4H, m), 8.18(2H, m), 8.28(4H, m), 8.34(2H, m) 945.16 944.28
55 δ = 1.72(6H, s), 7.41(4H, m), 7.51~7.52(12H, m), 7.56(2H, s), 7.84(2H, s), 7.88(2H, m), 7.96(2H, m), 8.28(4H, m), 8.58(2H, m) 732.87 732.30
56 δ = 1.48(12H, m), 1.72(6H, s), 1.73(8H, m), 2.72(2H, m), 7.41(2H, m), 7.51~7.52(8H, m), 7.56(2H, s), 7.68(4H, m), 7.79(4H, m), 7.84(2H, s) 742.99 742.40
57 δ = 1.72(6H, s), 3.65(8H, m), 3.74(8H, m), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s) 596.72 596.29
58 δ = 1.72(6H, s), 5.6(2H, m), 6.9(2H, m), 7.33(2H, m), 7.4~7.41(6H, m), 7.51(4H, m), 7.56(2H, s), 7.6(4H, m), 7.84(2H, s), 8.28(4H, m) 630.78 630.28
59 δ = 1.72(6H, s), 7.41~7.43(8H, m), 7.51~7.55(8H, m), 7.56(2H, s), 7.84(2H, s), 8.28(4H, m) 626.75 626.25
60 δ = 1.72(6H, s), 6.95~7.01(6H, m), 7.28(4H, m), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s) 610.70 610.24
61 δ = 1.72(6H, s), 7.23~7.29(6H, m), 7.39(4H, m), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s) 642.83 642.19
62 δ = -0.33(18H, s), 1.72(6H, ), 7.45(2H, m), 7.5(4H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s) 570.87 570.26
63 δ = 0.66(12H, s), 1.72(6H, s), 7.18(4H, m), 7.27(4H, m), 7.45~7.5(8H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s) 695.01 694.29
64 δ = 1.72(6H, s), 7.37(12H, m), 7.45~7.55(24H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s) 943.29 942.36
65 δ = 1.72(6H, s), 5.35(2H, s), 6.91(2H, m), 7.04(2H, m), 7.34(2H, m), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.84(4H, s) 610.70 610.24
66 δ = 1.4~1.43(18H, m), 1.69(4H, m), 1.72(6H, s), 1.81(2H, m), 2.71(2H, m), 7.45~7.5(6H, m), 7.56(2H, s), 7.58(4H, m), 7.84(2H, s) 642.87 642.37
[Example 1-5] Manufacture of OLED device using the compound for organic electronic materials according to the present invention
An OLED device was manufactured using the compound for organic electronic materials 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(α-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.
Figure PCTKR2011001920-appb-I000032
After forming the hole injection layer and the hole transport layer, an electroluminescent layer was formed thereon as follows. After respectively adding tris(8-hydroxyquinoline)-aluminum(III) (Alq3), which is an electroluminescent host as a luminous material in a cell of a vacuum vapor deposition apparatus and coumarin 545T as an electroluminescent dopant in another cell. The two cells were evaporated at different rates such that an electroluminescent layer having a thickness of 30 nm was vapor-deposited on the hole transport layer. The doping concentration may be 2 to 5 mol% on the basis of Alq3.
Figure PCTKR2011001920-appb-I000033
Subsequently, the compound for organic electronic materials (e.g. Compound 2) was vapor-deposited with a thickness of 20 nm as an electron transport layer on the electroluminescent layer. Then, after vapor-depositing lithium quinolate (Liq) 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.
Figure PCTKR2011001920-appb-I000034
Each compound used in the OLED device as an electroluminescent material was purified by vacuum sublimation at 10-6 torr.
[Comparative Example 1] Electroluminescent properties of OLED device using conventional electron transport materials
After forming the hole injection layer, the hole transport layer and the electroluminescent layer in the same manner as that of Example 1, tris(8-hydroxyquinoline)-aluminum(III) (Alq3) 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.
The driving voltage and the luminous efficiencies of the OLED comprising the compound for organic electronic materials according to the present invention or the conventional electron transport materials in the Examples 1-5 and Comparative Example 1 were measured at 1,000 cd/m2, respectively, and the results are shown in Table 2.
Table 2
No Electron transport materials Driving voltage (V)@1,000cd/m2 Luminous efficiency(cd/A)@1,000cd/m2
Example 1 Compound 2 5.0 12.2
Example 2 Compound 19 4.9 12.5
Example 3 Compound 26 4.6 13.1
Example 4 Compound 52 4.5 13.3
Example 5 Compound 54 5.1 11.8
Comparative Example 1 Alq3 6 11.6
As shown in Table 2, when Compound 52 was used as electron transport materials (Example 4), the highest power efficiency appeared. In particular, the power efficiency of Compound 52 (Example 4) showed improvement of about 15 % compared with the case that conventional Alq3 was used as the electron transport layer (Comparative Example 1). The driving voltage of Compound 16 (Example 3) showed reduction of about 1.4 V compared with the conventional organic electroluminescent device (Comparative Example 1).
In Table 2 showing the properties obtained when the compounds developed in the present invention were used as the electron transport layer, it is known that the compounds developed in the present invention are superior to the conventional materials in the view of performance.
[Examples 6 - 8] 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(α-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.
A compound according to the present invention (e.g.: Compound 7) purified by vacuum sublimation at 10-6 torr was placed in a cell of a vacuum vapor deposition apparatus as a host, and an electroluminescent dopant (e.g.: Compound (piq)2Ir(acac)) was placed in another cell. 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 through doping at 4 to 10 wt%.
Figure PCTKR2011001920-appb-I000035
Subsequently, bis(2-methyl-8-quinolinato)(p-phenylphenolato)aluminum(III) (BAlq) having a following structure was vapor-deposited with a thickness of 5 nm as a hole blocking layer on the electroluminescent layer. Tris(8-hydroxyquinoline)-aluminum(III) (Alq3) 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.
Figure PCTKR2011001920-appb-I000036
[Examples 9-10] Manufacture of OLED device using organic electroluminescent compounds according to the present invention
An OLED device was manufactured in the same manner as Example 8 except the hole blocking layer.
[Comparative Example 2] Electroluminescent properties of OLED device using conventional electroluminescent material
An OLED device was manufactured in the same manner as Example 6 except that 4,4'-bis(carbazol-9-yl)biphenyl (CBP) instead of the compounds of the present invention as a host material at one cell of the vacuum vapor deposition apparatus.
The driving voltage and the luminous efficiencies of the OLED comprising the organic electroluminescent compound according to the present invention (Examples 6 to 8 and Examples 9 to 10) or conventional EL compounds (Comparative Example 2) were measured at 1,000 cd/m2, respectively, and the results are shown in Table 3.
As shown in Table 3, the organic electroluminescent compounds according to the present invention have excellent luminous properties compared with the conventional material.
Table 3
Host material Luminous material Hole blocking layer @1,000cd/m2 color
Driving voltage (V) Luminous efficiency(cd/A)
Example 6 Compound 7 (piq)2Ir(acac) BAlq 7.1 7.2 red
Example 7 Compound 8 (piq)2Ir(acac) BAlq 6.8 7.3 red
Example 8 Compound 15 (piq)2Ir(acac) BAlq 6.9 7.4 red
Example 9 Compound 33 (piq)2Ir(acac) - 6.7 7.7 red
Example 10 Compound 34 (piq)2Ir(acac) - 7.0 7.6 red
Comparative Example 2 CBP (piq)2Ir(acac) BAlq 7.3 6.8 red
As shown in Table 3, the organic electroluminescent compounds according to the present invention have excellent luminous properties compared with the conventional material. They have superior current properties compared with the device of Comparative Example 2 as the conventional material. They showed reduction of 0.2 V or more in a driving voltage and show high power efficiency of 1.1 times or more compared with the device of Comparative Example 2.
The compound for organic electronic materials according to the present invention as electron transport materials exhibits excellent electron transport efficiency, it may prevent crystallization during the production of devices. Further, since it provides good layer formation, it may improve electrical current properties of devices. Therefore, it may be used to manufacture OLED devices having reduced driving voltage, improved power efficiency and the same or higher luminous efficiency.

Claims (9)

  1. A compound for organic electronic material represented by Chemical Formula 1:
    [Chemical Formula 1]
    Figure PCTKR2011001920-appb-I000037
    wherein
    X represents -C(R1)(R2)-, -Si(R3)(R4)-, -S- or -O-;
    R1 through R4 independently represent (C1-C30)alkyl, (C6-C30)aryl or (C3-C30)heteroaryl, or R1 and R2 or R3 and R4 may be linked via (C3-C12)alkylene or (C3-C12)alkenylene with or without a fused ring to from a spiro ring or a fused ring;
    Ar1 through Ar4 independently represent hydrogen, (C1-C30)alkyl, halogen, di(C1-C30)alkylboranyl, di(C6-C30)arylboranyl, cyano, (C3-C30)cycloalkyl, morpholino, thiomorpholino, piperidino, 5- to 7-membered heterocycloalkyl, (C7-C30)bicycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, carbazolyl, (C6-C30)ar(C1-C30)alkyl, (C6-C30)arylthio, mono- or di(C1-C30)alkylamino, mono- or di(C6-C30)arylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, nitro or hydroxyl;
    the alkyl, aryl or heteroaryl of R1 through R4 and the alkyl, cycloalkyl, heterocycloalkyl, bicycloalkyl, alkylboranyl, arylboranyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, heteroaryl, aralkyl, arylthio, alkylamino, arylamino, trialkylsilyl, dialkylarylsilyl or triarylsilyl of Ar1 through Ar4 may be further substituted by one or more substituent(s) selected from the group consisting of deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C7-C30)bicycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, (C3-C30)heteroaryl substituted by (C1-C30)alkyl, (C3-C30)heteroaryl substituted by (C6-C30)aryl, (C6-C30)ar(C1-C30)alkyl, (C6-C30)arylthio, mono- or di(C1-C30)alkylamino, mono- or di(C6-C30)arylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, nitro and hydroxyl; and
    the heterocycloalkyl or heteroaryl may contain one or more heteroatom(s) selected from B, N, O, S, P(=O), Si and P.
  2. The compound for organic electric material according to claim 1, wherein X represents -C(R1)(R2)-, -Si(R3)(R4)-, -S-, -O- or a divalent group selected from the following structures;
    Figure PCTKR2011001920-appb-I000038
    R1 through R4 independently represent (C1-C30)alkyl or (C6-C30)aryl;
    Ar1 through Ar4 independently represent (C3-C30)cycloalkyl, morpholino, thiomorpholino, (C7-C30)bicycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C6-C30)aryloxy, (C3-C30)heteroaryl, carbazolyl, (C6-C30)arylthio, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl or tri(C6-C30)arylsilyl; and
    the alkyl or aryl of R1 through R4 and the cycloalkyl, bicycloalkyl, alkenyl, alkynyl, aryl, aryloxy, heteroaryl, arylthio, trialkylsilyl, dialkylarylsilyl or triarylsilyl of Ar1 through Ar4 may be further substituted by one or more substituent(s) selected from the group consisting of deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C7-C30)bicycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, (C3-C30)heteroaryl substituted by (C1-C30)alkyl, (C3-C30)heteroaryl substituted by (C6-C30)aryl, (C6-C30)ar(C1-C30)alkyl, (C6-C30)arylthio, mono- or di(C1-C30)alkylamino, mono- or di(C6-C30)arylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, nitro and hydroxyl.
  3. An organic electroluminescent device comprising the compound for organic electric material according to any one of claims 1 to 2 as an electron transport material.
  4. The organic electroluminescent device according to claim 3, 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 layer(s) including the compound for organic electric material represented by Chemical Formula 1 and one or more electroluminescent layer(s) including a fluorescent host and a fluorescent dopant or a phosphorescent host and a phosphorescent dopant.
  5. The organic electroluminescent device according to claim 4, wherein the organic layer further comprises one or more amine compound(s) selected from the group consisting of arylamine compounds and styrylarylamine compounds.
  6. The organic electroluminescent device according to claim 4, wherein the organic layer further comprises 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).
  7. The organic electroluminescent device according to claim 4, wherein the organic layer comprises an electroluminescent layer and a charge generating layer.
  8. The organic electroluminescent device according to claim 4, which is a white light-emitting organic electroluminescent device wherein the organic layer comprises one or more organic electroluminescent layer(s) emitting blue, red or green light at the same time.
  9. The organic electroluminescent device according to claim 4, wherein a mixed region of a reductive dopant and an organic substance, or a mixed region of an oxidative dopant and an organic substance is placed on the inner surface of one or both electrode(s) among the pair of electrodes.
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