WO2016052835A1 - A plurality of host materials and an organic electroluminescent device comprising the same - Google Patents

A plurality of host materials and an organic electroluminescent device comprising the same Download PDF

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WO2016052835A1
WO2016052835A1 PCT/KR2015/006443 KR2015006443W WO2016052835A1 WO 2016052835 A1 WO2016052835 A1 WO 2016052835A1 KR 2015006443 W KR2015006443 W KR 2015006443W WO 2016052835 A1 WO2016052835 A1 WO 2016052835A1
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substituted
unsubstituted
compound
organic electroluminescent
alkyl
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PCT/KR2015/006443
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French (fr)
Inventor
Bitnari Kim
Nam-Kyun Kim
Hong-Yeop NA
Tae-Jin Lee
Jae-Hoon Shim
Kyung-Hoon Choi
Young-Jun Cho
Hee-Ryong Kang
Mi-Ja Lee
Hyun-Ju Kang
Hee-Choon Ahn
Ji-Song JUN
Young-Kwang Kim
Jin-Ri HONG
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Rohm And Haas Electronic Materials Korea Ltd.
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Priority claimed from KR1020150088863A external-priority patent/KR102432976B1/en
Application filed by Rohm And Haas Electronic Materials Korea Ltd. filed Critical Rohm And Haas Electronic Materials Korea Ltd.
Publication of WO2016052835A1 publication Critical patent/WO2016052835A1/en

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    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
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Definitions

  • the present disclosure relates to a plurality of host materials and an organic electroluminescent device comprising the same.
  • An electroluminescent (EL) device is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time.
  • An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • OLED organic electroluminescent device
  • electricity is applied to an organic light-emitting material which converts electric energy to light.
  • OLED has a structure comprising an anode, a cathode, and an organic layer disposed between the two electrodes.
  • the organic layer of OLED may comprise a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron buffering layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc.
  • a material for preparing the organic layer can be classified according to its function, as a hole injection material, a hole transport material, an electron blocking material, a light-emitting material, an electron buffering material, a hole blocking material, an electron transport material, an electron injection material, etc.
  • Holes and electrons are injected from an anode and a cathode, respectively, to the light-emitting layer by applying electricity to OLED; excitons having high energy are formed by recombinations between the holes and the electrons, which make organic light-emitting compounds be in an excited state, and the decay of the excited state results in a relaxation of the energy into a ground state, accompanied by light-emission.
  • the most important factor determining luminous efficiency in OLED is a light-emitting material.
  • the light-emitting material needs to have high quantum efficiency, high electron mobility, and high hole mobility.
  • the light-emitting layer formed by the light-emitting material needs to be uniform and stable. According to colors visualized by light-emission, the light-emitting material can be classified as a blue-, green-, or red-emitting material, and a yellow- or orange-emitting material can be additionally included therein. Furthermore, the light-emitting material can be classified according to its function, as a host material and a dopant material. Recently, the development of OLED providing high efficiency and long lifespan is urgent.
  • a host material which plays a role as a solvent in a solide state and transfers energy, should have high purity, and an appropriate molecular weight for being deposited under vacuum.
  • a host material should have high glass transition temperature and high thermal decomposition temperature to ensure thermal stability; high electrochemical stability to have long lifespan; ease of preparation for amorphous thin film; and good adhesion to materials of adjacent layers.
  • a host material should not move to an adjacent layer.
  • the light-emitting material can be prepared by combining a host with a dopant to improve color purity, luminous efficiency, and stability.
  • a device showing good EL performances comprises a light-emitting layer prepared by combining a host with a dopant.
  • the host material greatly influences the efficiency and lifespan of the EL device when using a host/dopant system, and thus its selection is important.
  • Korean Patent Appln. Laying-Open No. 10-2008-0080306 and WO 2013/112557 disclose an organic electroluminescent device using a biscarbazole derivative as a host material. However, they fail to specifically disclose an organic electroluminescent device using, along with the biscarbazole derivative, a compound in which one of benzene rings of the carbazole is fused with two other rings and the nitrogen atom of the carbazole is substituted with an aryl or heteroaryl group, as a host material.
  • the objective of the present disclosure is to provide an organic electroluminescent device having long lifespan while maintaining high luminous efficiency.
  • an organic electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and cathode, wherein the organic layer comprises one or more light-emitting layers; at least one layer of the one or more light-emitting layers comprises one or more dopant compounds and two or more host compounds; and a first host compound of the two or more host compounds is the compound represented by the following formula 1 and a second host compound is the compound represented by the following formula 2:
  • a 1 and A 2 each independently, represent a substituted or unsubstituted (C6-C30)aryl; provided that a substituent for A 1 and A 2 is not a nitrogen-containing heteroaryl;
  • L 1 represents a single bond or a substituted or unsubstituted (C6-C30)arylene
  • X 1 to X 16 each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C60)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or un
  • Ar 1 represents a substituted or unsubstituted 3- to 30-membered heteroaryl, or a substituted or unsubstituted (C6-C30)aryl;
  • L 2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 3- to 30-membered heteroarylene;
  • ring A represents ring B represents
  • Y represents O, S, C(R 4 )(R 5 ), or N(R 6 );
  • X represents O, S, C(R 7 )(R 8 ), or N(R 6 ); provided that both X and Y cannot simultaneously be N(R 6 );
  • R 1 to R 3 each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxy, a nitro, a hydroxy, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, -NR 9 R 10 or -SiR 11 R 12 R 13 ; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring;
  • R 4 to R 13 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR 14 R 15 , -SiR 16 R 17 R 18 , a cyano, a nitro, or a hydroxyl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring;
  • R 14 to R 18 have the same definition as R 4 to R 13 ;
  • a carbon atom(s) of the alicyclic or aromatic ring may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
  • heteroaryl(ene) and heterocycloalkyl each independently, contain at least one hetero atom selected from B, N, O, S, Si, and P;
  • a, b, and c each independently, represent an integer of 1 to 4; and where a, b, or c represents an integer of 2 or more, each of R 1 , R 2 , or R 3 may be the same or different.
  • an organic electroluminescent device having high efficiency and long lifespan is provided.
  • the organic electroluminescent device of the present disclosure can be used for the manufacture of a display system or a lighting system.
  • the organic electroluminescent device comprising the compound of formula 1 and the compound of formula 2 will be described in detail.
  • (C1-C30)alkyl indicates a linear or branched alkyl having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.
  • “(C2-C30) alkenyl” indicates a linear or branched alkenyl having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • (C2-C30)alkynyl indicates a linear or branched alkynyl having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.
  • “(C3-C30)cycloalkyl” indicates a mono- or polycyclic hydrocarbon having 3 to 30, preferably 3 to 20, and more preferably 3 to 7 carbon atoms and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • “3- to 7-membered heterocycloalkyl” indicates a cycloalkyl having 3 to 7, preferably 5 to 7 ring backbone atoms including at least one hetero atom selected from B, N, O, S, Si, and P, preferably O, S, and N, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc.
  • (C6-C30)aryl(ene) indicates a monocyclic or fused ring-based radical derived from an aromatic hydrocarbon and having 6 to 30, preferably 6 to 20, and more preferably 6 to 15 ring backbone carbon atoms, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.
  • “3- to 30-membered heteroaryl” indicates an aryl group having 3 to 30, preferably 5 to 20, and more preferably 5 to 18 ring backbone atoms including at least one, preferably 1 to 4, hetero atom selected from the group consisting of B, N, O, S, Si, and P; may be a monocyclic ring, or a fused ring condensed with at least one benzene ring; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl
  • the “nitrogen-containing heteroaryl” indicates a heteroaryl group containing at least one nitrogen as the hetero atom, and includes a monocyclic ring-type heteroaryl such as pyrrolyl, imidazolyl, pyrazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc.
  • halogen includes F, Cl, Br, and I.
  • substituted in the expression, “substituted or unsubstituted,” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e. a substituent.
  • the compound of formula 1 may be represented by any one of the following formulae 3, 4, 5, and 6.
  • a 1 , A 2 , L 1 , and X 1 to X 16 are as defined in formula 1.
  • a 1 and A 2 each independently, may represent preferably, a substituted or unsubstituted (C6-C18)aryl, and more preferably, a (C6-C18)aryl unsubstituted or substituted with a cyano, a halogen, a (C1-C6)alkyl, a (C6-C12)aryl or tri(C6-C12)arylsilyl.
  • a 1 and A 2 may be selected from the group consisting of a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted benzofluorenyl, a substituted or unsubstituted phenanthrenyl, a substituted or unsubstituted anthracenyl, a substituted or unsubstituted indenyl, a substituted or unsubstituted triphenylenyl, a substituted or unsubstituted pyrenyl, a substituted or unsubstituted tetracenyl, a substituted or unsubstituted perylenyl, a substituted or unsubstituted, a
  • the substituent of the substituted group such as the substituted phenyl may be a cyano, a halogen, a (C1-C6)alkyl, a (C6-C12)aryl, or a tri(C6-C12)arylsilyl.
  • X 1 to X 16 each independently, may represent preferably, hydrogen, a cyano, a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C20)aryl, a substituted or unsubstituted 5- to 20-membered heteroaryl, or a substituted or unsubstituted tri(C6-C12)arylsilyl.
  • X 1 to X 16 each independently, may represent more preferably, hydrogen; a cyano; a (C1-C10)alkyl; a (C6-C20)aryl unsubstituted or substituted with a cyano, a (C1-C10)alkyl, or a tri(C6-C12)arylsilyl; a 5- to 20-membered heteroaryl unsubstituted or substituted with a (C1-C10)alkyl, a (C6-C15)aryl, or a tri(C6-C12)arylsilyl; or a tri(C6-C12)arylsilyl unsubstituted or substituted with a (C1-C10)alkyl.
  • X 1 to X 16 may represent hydrogen; a cyano; a (C1-C6)alkyl; phenyl, biphenyl, terphenyl, or naphthyl, unsubstituted or substituted with a cyano, a (C1-C6)alkyl or triphenylsilyl; dibenzothiophenyl or dibenzofuranyl, unsubstituted or substituted with a (C1-C6)alkyl, phenyl, biphenyl, naphthyl, or triphenylsilyl; or triphenylsilyl unsubstituted or substituted with a (C1-C6)alkyl.
  • L 1 represents a single bond, or a substituted or unsubstituted (C6-C30)arylene.
  • L 1 may represent preferably, a single bond, or a substituted or unsubstituted (C6-C15)arylene.
  • L 1 may represent a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, or a substituted or unsubstituted biphenylene. More specifically, L 1 may represent a single bond, or any one of the following formulae 7 to 19.
  • Xi to Xp each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C60)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or un
  • Xi to Xp each independently, may represent preferably, hydrogen, a halogen, a cyano, a (C1-C10)alkyl, a (C3-C20)cycloalkyl, a (C6-C12)aryl, a (C1-C6)alkyldi(C6-C12)arylsilyl, or a tri(C6-C12)arylsilyl; and more preferably, hydrogen, a cyano, a (C1-C6)alkyl, or a tri(C6-C12)arylsilyl.
  • the compound of formula 2 may be represented by any one of the following formulae 20 to 23.
  • Ar 1 , L 2 , X, Y, R 1 to R 3 , a, b, and c are as defined in formula 2 above.
  • Ar 1 may represent preferably, a substituted or unsubstituted 5- to 20-membered heteroaryl, and more preferably, a substituted or unsubstituted nitrogen-containing 5- to 20-membered heteroaryl.
  • Ar 1 may be selected from the group consisting of a substituted or unsubstituted triazinyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted quinolyl, a substituted or unsubstituted isoquinolyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted naphthyridinyl, and a substituted or unsubstituted quinoxalinyl.
  • Ar 1 may be selected from the group consisting of a substituted or unsubstituted triazinyl, a substituted or unsubstituted quinazolinyl, or a substituted or unsubstituted quinoxalinyl.
  • the substituent for the substituted group of Ar 1 may be preferably, a (C6-C20)aryl or a 5- to 20-membered heteroaryl, and specifically, may be at least one selected from phenyl, naphthyl, biphenyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, and dibenzothiophenyl.
  • L 2 may represent preferably, a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted 5- to 20-membered heteroarylene; and more preferably, a single bond, or a substituted or unsubstituted (C6-C20)arylene.
  • L 2 may represent a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, or a substituted or unsubstituted naphthylene.
  • X and Y each independently, may be selected from O, S, and N(R 6 ); provided that both X and Y cannot simultaneously be N(R 6 ).
  • X and Y each independently, may be selected from O and S.
  • X and Y each independently, may be selected from O and S, and at least one of X and Y may be S.
  • R 6 may represent preferably, a substituted or unsubstituted (C6-C30)aryl, and specifically a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, or a substituted or unsubstituted biphenyl.
  • R 1 to R 3 each independently, may represent preferably, hydrogen, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C3-C20)cycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, -NR 9 R 10 or -SiR 11 R 12 R 13 , or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring.
  • R 9 to R 13 may represent preferably, a substituted or unsubstituted (C6-C30)aryl.
  • R 1 to R 3 may represent hydrogen.
  • the first host compound represented by formula 1 includes the following, but is not limited thereto.
  • the second host compound represented by formula 2 includes the following, but is not limited thereto:
  • the compound of formula 1 and the compound of formula 2 can be easily prepared by a synthetic method known to one skilled in the art.
  • the compound of formula 2 can be prepared as follows: After preparing a five (5) ring-condensed compound represented by the following formula A, the compound of formula A is subjected to bromination to obtain a compound represented by the following formula B; the compound of formula B is fused with an indene ring, an indole ring, a benzofuran ring, or a benzothiophene ring to obtain a mother nucleus structure; and *-L 2 -Ar 1 is then connected to the prepared mother nucleus structure, thereby the compound of formula 2 is obtained.
  • Y represents O, S, C(R 4 )(R 5 ), or N(R 6 ); and X represents O, S, C(R 7 )(R 8 ), or N(R 6 ).
  • X can be selected from O, S, N(R 6 ), and C(R 7 )(R 8 ).
  • the organic electroluminescent device of the present disclosure comprises an anode, a cathode, and an organic layer disposed between the anode and cathode, wherein the organic layer comprises one or more light-emitting layers; at least one layer of the one or more light-emitting layers comprises one or more dopant compounds and two or more host compounds; and a first host compound of the two or more host compounds is the compound represented by formula 1 and a second host compound is the compound represented by formula 2.
  • the light-emitting layer indicates a layer from which light is emitted. It is preferable that a doping amount of the dopant compound is less than 20 wt% based on the total amount of the host compound and the dopant compound.
  • the weight ratio in the light-emitting layer between the first host material and the second host material may be in the range of 1:99 to 99:1.
  • the organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an electron buffering layer, an interlayer, a hole blocking layer, and an electron blocking layer.
  • the dopant to be comprised in the organic electroluminescent device of the present disclosure is preferably at least one phosphorescent dopant.
  • the phosphorescent dopant material for the organic electroluminescent device of the present disclosure is not limited, but may be preferably selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) or platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) or platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
  • the phosphorescent dopant may be selected from the group consisting of compounds represented by the following formulae 101 to 103.
  • L is selected from the following structures:
  • R 100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
  • R 101 to R 109 and R 111 to R 123 each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a cyano, or a substituted or unsubstituted (C1-C30)alkoxy;
  • R 106 to R 109 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl;
  • R 120 to R 123 may be linked to an
  • R 124 to R 127 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • R 124 to R 127 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl;
  • R 201 to R 211 each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • R 208 to R 211 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl;
  • f and g each independently, represent an integer of 1 to 3; when f or g is an integer of 2 or more, each of R 100 may be the same or different; and n represents an integer of 1 to 3.
  • the phosphorescent dopant material includes the following:
  • the organic layer may further comprise at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the organic layer may further comprise at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4 th period, transition metals of the 5 th period, lanthanides and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound comprising the metal.
  • a surface layer may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer and a metal oxide layer.
  • a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer
  • a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer.
  • the chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.;
  • the metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and the metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a hole injection layer, a hole transport layer, an electron blocking layer, or a combination thereof may be disposed between the anode and the light-emitting layer.
  • the hole injection layer may be composed of two or more layers in order to lower an energy barrier for injecting holes from the anode to a hole transport layer or an electron blocking layer (or a voltage for injecting a hole). Each of the layers may comprise two or more compounds.
  • the hole transport layer or electron blocking layer may be composed of two or more layers.
  • An electron buffering layer, a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof may be disposed between the light-emitting layer and the cathode.
  • the electron buffering layer may be composed of two or more layers in order to control the electron injection and improve characteristics of interface between the light-emitting layer and the electron injection layer.
  • Each of the layers may comprise two or more compounds.
  • the hole blocking layer or electron transport layer may be composed of two or more layers, and each of the layers may comprise two or more compounds.
  • 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 may be placed on at least one surface of a pair of electrodes.
  • the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium.
  • the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium.
  • the oxidative dopant includes various Lewis acids and acceptor compounds
  • the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof.
  • a reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more light-emitting layers and emitting white light.
  • a material for preparing an organic electroluminescent device comprises the compound of formula 1 and the compound of formula 2.
  • the material may be specifically for preparing a light-emitting layer of the organic electroluminescent device, and more specifically for a host of a light-emitting layer of the organic electroluminescent device.
  • the material may be a composition or mixture.
  • the material may further comprise a conventional material which has been comprised for an organic electroluminescent material.
  • each layer of the organic electroluminescent device of the present disclosure dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as inkjet printing, nozzle printing, slot coating, spin coating, dip coating, and flow coating methods can be used.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as inkjet printing, nozzle printing, slot coating, spin coating, dip coating, and flow coating methods can be used.
  • wet film-forming methods such as inkjet printing, nozzle printing, slot coating, spin coating, dip coating, and flow coating methods.
  • a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
  • two or more host compounds for a light-emitting layer may be co-evaporated or mixture-evaporated.
  • a co-evaporation indicates a process for two or more materials to be deposited as a mixture, by introducing each of the two or more materials into respective crucible cells, and applying electric current to the cells for each of the materials to be evaporated.
  • a mixture-evaporation indicates a process for two or more materials to be deposited as a mixture, by mixing the two or more materials in one crucible cell before the deposition, and applying electric current to the cell for the mixture to be evaporated.
  • the organic electroluminescent device of the present disclosure can be used for the manufacture of a display system or a lighting system.
  • OLED was produced using the light-emitting material of the present disclosure as follows.
  • a transparent electrode indium tin oxide (ITO) thin film (10 ⁇ /sq) on a glass substrate for an organic electroluminescent device (OLED) (Geomatec) was subjected to an ultrasonic washing with acetone, ethanol, and distilled water sequentially, and was then stored in isopropanol.
  • the ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • HI-1 was introduced into a cell of the vacuum vapor depositing apparatus, and then the pressure in the chamber of the apparatus was controlled to 10 -6 torr.
  • HI-1 a first hole injection layer having a thickness of 80 nm on the ITO substrate.
  • HI-2 was then introduced into another cell of the vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a second hole injection layer having a thickness of 5 nm on the first hole injection layer.
  • HT-1 was introduced into one cell of the vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer.
  • HT-2 or HT-3 was then introduced into another cell of the vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a second hole transport layer having a thickness of 60 nm on the first hole transport layer.
  • a host material a first host compound and a second host compound shown in Table 1 below were introduced into two cells of the vacuum vapor depositing apparatus, respectively.
  • a dopant compound shown in Table 1 was introduced into another cell.
  • the two host compounds were evaporated at the same rate of 1:1, while the dopant was evaporated at a different rate from the host compounds, so that the dopant was deposited in a doping amount of 3 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 40 nm on the hole transport layer.
  • ET-1 and EI-1 were introduced into two cells of the vacuum vapor depositing apparatus, respectively, and evaporated at the same rate of 1:1, thereby forming an electron transport layer having a thickness of 30 nm on the light-emitting layer.
  • an Al cathode having a thickness of 80 nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer.
  • OLED was produced in the same manner as in Device Examples 1-1 to 1-6, except that only a second host compound shown in Table 1 below was used as a host for a light-emitting layer.
  • OLED was produced in the same manner as in Device Examples 1-1 to 1-6, except that only a first host compound shown in Table 1 below was used as a host for a light-emitting layer.
  • the organic electroluminescent device using a plurality of host materials of the present disclosure can have longer lifespan than one using one host compound.

Abstract

The present disclosure relates to a plurality of host materials and an organic electroluminescent device comprising the same. By comprising a specific combination of host materials, the organic electroluminescent device of the present disclosure can show high luminous efficiency and long lifespan.

Description

A PLURALITY OF HOST MATERIALS AND AN ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present disclosure relates to a plurality of host materials and an organic electroluminescent device comprising the same.
An electroluminescent (EL) device is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time. An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
In an organic electroluminescent device (OLED), electricity is applied to an organic light-emitting material which converts electric energy to light. Generally, OLED has a structure comprising an anode, a cathode, and an organic layer disposed between the two electrodes. The organic layer of OLED may comprise a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron buffering layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. A material for preparing the organic layer can be classified according to its function, as a hole injection material, a hole transport material, an electron blocking material, a light-emitting material, an electron buffering material, a hole blocking material, an electron transport material, an electron injection material, etc. Holes and electrons are injected from an anode and a cathode, respectively, to the light-emitting layer by applying electricity to OLED; excitons having high energy are formed by recombinations between the holes and the electrons, which make organic light-emitting compounds be in an excited state, and the decay of the excited state results in a relaxation of the energy into a ground state, accompanied by light-emission.
The most important factor determining luminous efficiency in OLED is a light-emitting material. The light-emitting material needs to have high quantum efficiency, high electron mobility, and high hole mobility. Furthermore, the light-emitting layer formed by the light-emitting material needs to be uniform and stable. According to colors visualized by light-emission, the light-emitting material can be classified as a blue-, green-, or red-emitting material, and a yellow- or orange-emitting material can be additionally included therein. Furthermore, the light-emitting material can be classified according to its function, as a host material and a dopant material. Recently, the development of OLED providing high efficiency and long lifespan is urgent. In particular, considering EL requirements for a middle or large-sized OLED panel, materials showing better performances than conventional ones must be urgently developed. In order to achieve the development, a host material which plays a role as a solvent in a solide state and transfers energy, should have high purity, and an appropriate molecular weight for being deposited under vacuum. In addition, a host material should have high glass transition temperature and high thermal decomposition temperature to ensure thermal stability; high electrochemical stability to have long lifespan; ease of preparation for amorphous thin film; and good adhesion to materials of adjacent layers. Furthermore, a host material should not move to an adjacent layer.
The light-emitting material can be prepared by combining a host with a dopant to improve color purity, luminous efficiency, and stability. Generally, a device showing good EL performances comprises a light-emitting layer prepared by combining a host with a dopant. The host material greatly influences the efficiency and lifespan of the EL device when using a host/dopant system, and thus its selection is important.
Korean Patent Appln. Laying-Open No. 10-2008-0080306 and WO 2013/112557 disclose an organic electroluminescent device using a biscarbazole derivative as a host material. However, they fail to specifically disclose an organic electroluminescent device using, along with the biscarbazole derivative, a compound in which one of benzene rings of the carbazole is fused with two other rings and the nitrogen atom of the carbazole is substituted with an aryl or heteroaryl group, as a host material.
The objective of the present disclosure is to provide an organic electroluminescent device having long lifespan while maintaining high luminous efficiency.
The present inventors found that the above objective can be achieved by an organic electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and cathode, wherein the organic layer comprises one or more light-emitting layers; at least one layer of the one or more light-emitting layers comprises one or more dopant compounds and two or more host compounds; and a first host compound of the two or more host compounds is the compound represented by the following formula 1 and a second host compound is the compound represented by the following formula 2:
Figure PCTKR2015006443-appb-I000001
wherein A1 and A2, each independently, represent a substituted or unsubstituted (C6-C30)aryl; provided that a substituent for A1 and A2 is not a nitrogen-containing heteroaryl;
L1 represents a single bond or a substituted or unsubstituted (C6-C30)arylene;
X1 to X16, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C60)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, or a substituted or unsubstituted mono- or di-(C6-C30)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring;
Figure PCTKR2015006443-appb-I000002
wherein Ar1 represents a substituted or unsubstituted 3- to 30-membered heteroaryl, or a substituted or unsubstituted (C6-C30)aryl;
L2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 3- to 30-membered heteroarylene;
ring A represents
Figure PCTKR2015006443-appb-I000003
ring B represents
Figure PCTKR2015006443-appb-I000004
Y represents O, S, C(R4)(R5), or N(R6); X represents O, S, C(R7)(R8), or N(R6); provided that both X and Y cannot simultaneously be N(R6);
R1 to R3, each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxy, a nitro, a hydroxy, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, -NR9R10 or -SiR11R12R13; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring;
R4 to R13, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR14R15, -SiR16R17R18, a cyano, a nitro, or a hydroxyl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring;
R14 to R18 have the same definition as R4 to R13;
a carbon atom(s) of the alicyclic or aromatic ring may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
the heteroaryl(ene) and heterocycloalkyl, each independently, contain at least one hetero atom selected from B, N, O, S, Si, and P;
a, b, and c, each independently, represent an integer of 1 to 4; and where a, b, or c represents an integer of 2 or more, each of R1, R2, or R3 may be the same or different.
According to the present disclosure, an organic electroluminescent device having high efficiency and long lifespan is provided. In addition, the organic electroluminescent device of the present disclosure can be used for the manufacture of a display system or a lighting system.
Hereinafter, the present disclosure will be described in detail. However, the following description is intended to explain the present disclosure, and is not meant in any way to restrict the scope of the present disclosure.
The organic electroluminescent device comprising the compound of formula 1 and the compound of formula 2 will be described in detail.
Herein, “(C1-C30)alkyl” indicates a linear or branched alkyl having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. “(C2-C30) alkenyl” indicates a linear or branched alkenyl having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc. “(C2-C30)alkynyl” indicates a linear or branched alkynyl having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc. “(C3-C30)cycloalkyl” indicates a mono- or polycyclic hydrocarbon having 3 to 30, preferably 3 to 20, and more preferably 3 to 7 carbon atoms and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. “3- to 7-membered heterocycloalkyl” indicates a cycloalkyl having 3 to 7, preferably 5 to 7 ring backbone atoms including at least one hetero atom selected from B, N, O, S, Si, and P, preferably O, S, and N, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc. Furthermore, “(C6-C30)aryl(ene)” indicates a monocyclic or fused ring-based radical derived from an aromatic hydrocarbon and having 6 to 30, preferably 6 to 20, and more preferably 6 to 15 ring backbone carbon atoms, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc. “3- to 30-membered heteroaryl” indicates an aryl group having 3 to 30, preferably 5 to 20, and more preferably 5 to 18 ring backbone atoms including at least one, preferably 1 to 4, hetero atom selected from the group consisting of B, N, O, S, Si, and P; may be a monocyclic ring, or a fused ring condensed with at least one benzene ring; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl such as benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. The “nitrogen-containing heteroaryl” indicates a heteroaryl group containing at least one nitrogen as the hetero atom, and includes a monocyclic ring-type heteroaryl such as pyrrolyl, imidazolyl, pyrazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc. and a fused ring-type heteroaryl such as benzoimidazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl, etc. Furthermore, “halogen” includes F, Cl, Br, and I.
Herein, “substituted” in the expression, “substituted or unsubstituted,” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e. a substituent. In the present disclosure, the substituents of the substituted alkyl, the substituted alkenyl, the substituted alkynyl, the substituted cycloalkyl, the substituted aryl(ene), the substituted heteroaryl(ene), the substituted arylalkyl, the substituted trialkylsilyl, the substituted triarylsilyl, the substituted dialkylarylsilyl, the substituted alkyldiarylsilyl, the substituted mono- or di-arylamino, the substituted mono- or polycyclic alicyclic or aromatic ring, the substituted cycloalkenyl, the substituted heterocycloalkyl, and the substituted nitrogen-containing heteroaryl, each independently, are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxy, a nitro, a hydroxy, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a 3- to 7-membered heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a 3- to 30-membered heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a cyano, a (C6-C30)aryl unsubstituted or substituted with a 3- to 30-membered heteroaryl or a tri(C6-C30)arylsilyl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, an amino, a mono- or di- (C1-C30)alkylamino, a mono- or di- (C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a (C1-C30)alkylcarbonyl, a (C1-C30)alkoxycarbonyl, a (C6-C30)arylcarbonyl, a di(C6-C30)arylboronyl, a di(C1-C30)alkylboronyl, a (C1-C30)alkyl(C6-C30)arylboronyl, a (C6-C30)aryl(C1-C30)alkyl, and a (C1-C30)alkyl(C6-C30)aryl.
According to one embodiment of the present disclosure, the compound of formula 1 may be represented by any one of the following formulae 3, 4, 5, and 6.
Figure PCTKR2015006443-appb-I000005
Figure PCTKR2015006443-appb-I000006
wherein A1, A2, L1, and X1 to X16 are as defined in formula 1.
A1 and A2, each independently, may represent preferably, a substituted or unsubstituted (C6-C18)aryl, and more preferably, a (C6-C18)aryl unsubstituted or substituted with a cyano, a halogen, a (C1-C6)alkyl, a (C6-C12)aryl or tri(C6-C12)arylsilyl. Specifically, A1 and A2, each independently, may be selected from the group consisting of a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted benzofluorenyl, a substituted or unsubstituted phenanthrenyl, a substituted or unsubstituted anthracenyl, a substituted or unsubstituted indenyl, a substituted or unsubstituted triphenylenyl, a substituted or unsubstituted pyrenyl, a substituted or unsubstituted tetracenyl, a substituted or unsubstituted perylenyl, a substituted or unsubstituted chrysenyl, a substituted or unsubstituted phenylnaphthyl, a substituted or unsubstituted naphthylphenyl, and a substituted or unsubstituted fluoranthenyl. The substituent of the substituted group such as the substituted phenyl may be a cyano, a halogen, a (C1-C6)alkyl, a (C6-C12)aryl, or a tri(C6-C12)arylsilyl.
X1 to X16, each independently, may represent preferably, hydrogen, a cyano, a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C20)aryl, a substituted or unsubstituted 5- to 20-membered heteroaryl, or a substituted or unsubstituted tri(C6-C12)arylsilyl. X1 to X16, each independently, may represent more preferably, hydrogen; a cyano; a (C1-C10)alkyl; a (C6-C20)aryl unsubstituted or substituted with a cyano, a (C1-C10)alkyl, or a tri(C6-C12)arylsilyl; a 5- to 20-membered heteroaryl unsubstituted or substituted with a (C1-C10)alkyl, a (C6-C15)aryl, or a tri(C6-C12)arylsilyl; or a tri(C6-C12)arylsilyl unsubstituted or substituted with a (C1-C10)alkyl. Specifically, X1 to X16, each independently, may represent hydrogen; a cyano; a (C1-C6)alkyl; phenyl, biphenyl, terphenyl, or naphthyl, unsubstituted or substituted with a cyano, a (C1-C6)alkyl or triphenylsilyl; dibenzothiophenyl or dibenzofuranyl, unsubstituted or substituted with a (C1-C6)alkyl, phenyl, biphenyl, naphthyl, or triphenylsilyl; or triphenylsilyl unsubstituted or substituted with a (C1-C6)alkyl.
L1 represents a single bond, or a substituted or unsubstituted (C6-C30)arylene. L1 may represent preferably, a single bond, or a substituted or unsubstituted (C6-C15)arylene. Specifically, L1 may represent a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, or a substituted or unsubstituted biphenylene. More specifically, L1 may represent a single bond, or any one of the following formulae 7 to 19.
Figure PCTKR2015006443-appb-I000007
Figure PCTKR2015006443-appb-I000008
Figure PCTKR2015006443-appb-I000009
Figure PCTKR2015006443-appb-I000010
Figure PCTKR2015006443-appb-I000011
wherein
Xi to Xp, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C60)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, or a substituted or unsubstituted mono- or di-(C6-C30)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one hetero atom selected from the group consisting of nitrogen, oxygen, and sulfur; and
Figure PCTKR2015006443-appb-I000012
represents a bonding site.
Xi to Xp, each independently, may represent preferably, hydrogen, a halogen, a cyano, a (C1-C10)alkyl, a (C3-C20)cycloalkyl, a (C6-C12)aryl, a (C1-C6)alkyldi(C6-C12)arylsilyl, or a tri(C6-C12)arylsilyl; and more preferably, hydrogen, a cyano, a (C1-C6)alkyl, or a tri(C6-C12)arylsilyl.
According to one embodiment of the present disclosure, the compound of formula 2 may be represented by any one of the following formulae 20 to 23.
Figure PCTKR2015006443-appb-I000013
Figure PCTKR2015006443-appb-I000014
wherein Ar1, L2, X, Y, R1 to R3, a, b, and c are as defined in formula 2 above.
Ar1 may represent preferably, a substituted or unsubstituted 5- to 20-membered heteroaryl, and more preferably, a substituted or unsubstituted nitrogen-containing 5- to 20-membered heteroaryl. Specifically, Ar1 may be selected from the group consisting of a substituted or unsubstituted triazinyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted quinolyl, a substituted or unsubstituted isoquinolyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted naphthyridinyl, and a substituted or unsubstituted quinoxalinyl. More specifically, Ar1 may be selected from the group consisting of a substituted or unsubstituted triazinyl, a substituted or unsubstituted quinazolinyl, or a substituted or unsubstituted quinoxalinyl. The substituent for the substituted group of Ar1 may be preferably, a (C6-C20)aryl or a 5- to 20-membered heteroaryl, and specifically, may be at least one selected from phenyl, naphthyl, biphenyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, and dibenzothiophenyl.
L2 may represent preferably, a single bond, a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted 5- to 20-membered heteroarylene; and more preferably, a single bond, or a substituted or unsubstituted (C6-C20)arylene. Specifically, L2 may represent a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, or a substituted or unsubstituted naphthylene.
Preferably, X and Y, each independently, may be selected from O, S, and N(R6); provided that both X and Y cannot simultaneously be N(R6). According to one embodiment of the present disclosure, X and Y, each independently, may be selected from O and S. According to another embodiment of the present disclosure, X and Y, each independently, may be selected from O and S, and at least one of X and Y may be S. R6 may represent preferably, a substituted or unsubstituted (C6-C30)aryl, and specifically a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, or a substituted or unsubstituted biphenyl.
R1 to R3, each independently, may represent preferably, hydrogen, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C3-C20)cycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, -NR9R10 or -SiR11R12R13, or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring. R9 to R13, may represent preferably, a substituted or unsubstituted (C6-C30)aryl. Specifically, R1 to R3 may represent hydrogen.
The first host compound represented by formula 1 includes the following, but is not limited thereto.
Figure PCTKR2015006443-appb-I000015
Figure PCTKR2015006443-appb-I000016
Figure PCTKR2015006443-appb-I000017
Figure PCTKR2015006443-appb-I000018
Figure PCTKR2015006443-appb-I000019
Figure PCTKR2015006443-appb-I000020
Figure PCTKR2015006443-appb-I000021
Figure PCTKR2015006443-appb-I000022
Figure PCTKR2015006443-appb-I000023
Figure PCTKR2015006443-appb-I000024
Figure PCTKR2015006443-appb-I000025
Figure PCTKR2015006443-appb-I000026
Figure PCTKR2015006443-appb-I000027
Figure PCTKR2015006443-appb-I000028
Figure PCTKR2015006443-appb-I000029
Figure PCTKR2015006443-appb-I000030
Figure PCTKR2015006443-appb-I000031
Figure PCTKR2015006443-appb-I000032
Figure PCTKR2015006443-appb-I000033
Figure PCTKR2015006443-appb-I000034
Figure PCTKR2015006443-appb-I000035
Figure PCTKR2015006443-appb-I000036
Figure PCTKR2015006443-appb-I000037
Figure PCTKR2015006443-appb-I000038
Figure PCTKR2015006443-appb-I000039
Figure PCTKR2015006443-appb-I000040
Figure PCTKR2015006443-appb-I000041
Figure PCTKR2015006443-appb-I000042
Figure PCTKR2015006443-appb-I000043
Figure PCTKR2015006443-appb-I000044
Figure PCTKR2015006443-appb-I000045
Figure PCTKR2015006443-appb-I000046
Figure PCTKR2015006443-appb-I000047
Figure PCTKR2015006443-appb-I000048
Figure PCTKR2015006443-appb-I000049
Figure PCTKR2015006443-appb-I000050
Figure PCTKR2015006443-appb-I000051
Figure PCTKR2015006443-appb-I000052
Figure PCTKR2015006443-appb-I000053
Figure PCTKR2015006443-appb-I000054
Figure PCTKR2015006443-appb-I000055
Figure PCTKR2015006443-appb-I000056
Figure PCTKR2015006443-appb-I000057
Figure PCTKR2015006443-appb-I000058
Figure PCTKR2015006443-appb-I000059
Figure PCTKR2015006443-appb-I000060
Figure PCTKR2015006443-appb-I000061
Figure PCTKR2015006443-appb-I000062
Figure PCTKR2015006443-appb-I000063
Figure PCTKR2015006443-appb-I000064
Figure PCTKR2015006443-appb-I000065
Figure PCTKR2015006443-appb-I000066
Figure PCTKR2015006443-appb-I000067
The second host compound represented by formula 2 includes the following, but is not limited thereto:
Figure PCTKR2015006443-appb-I000068
Figure PCTKR2015006443-appb-I000069
Figure PCTKR2015006443-appb-I000070
Figure PCTKR2015006443-appb-I000071
Figure PCTKR2015006443-appb-I000072
Figure PCTKR2015006443-appb-I000073
Figure PCTKR2015006443-appb-I000074
Figure PCTKR2015006443-appb-I000075
Figure PCTKR2015006443-appb-I000076
Figure PCTKR2015006443-appb-I000077
Figure PCTKR2015006443-appb-I000078
Figure PCTKR2015006443-appb-I000079
Figure PCTKR2015006443-appb-I000080
Figure PCTKR2015006443-appb-I000081
Figure PCTKR2015006443-appb-I000082
Figure PCTKR2015006443-appb-I000083
Figure PCTKR2015006443-appb-I000084
Figure PCTKR2015006443-appb-I000085
Figure PCTKR2015006443-appb-I000086
Figure PCTKR2015006443-appb-I000087
The compound of formula 1 and the compound of formula 2 can be easily prepared by a synthetic method known to one skilled in the art. For example, the compound of formula 2 can be prepared as follows: After preparing a five (5) ring-condensed compound represented by the following formula A, the compound of formula A is subjected to bromination to obtain a compound represented by the following formula B; the compound of formula B is fused with an indene ring, an indole ring, a benzofuran ring, or a benzothiophene ring to obtain a mother nucleus structure; and *-L2-Ar1 is then connected to the prepared mother nucleus structure, thereby the compound of formula 2 is obtained.
Figure PCTKR2015006443-appb-I000088
In formulae A and B, Y represents O, S, C(R4)(R5), or N(R6); and X represents O, S, C(R7)(R8), or N(R6).
The method for preparing the mother nucleus of the compound of formula 2 described above can be illustrated in the following reaction schemes 1 to 4.
Figure PCTKR2015006443-appb-I000089
Figure PCTKR2015006443-appb-I000090
Figure PCTKR2015006443-appb-I000091
Figure PCTKR2015006443-appb-I000092
In reaction schemes 1 to 4 above, X can be selected from O, S, N(R6), and C(R7)(R8).
The organic electroluminescent device of the present disclosure comprises an anode, a cathode, and an organic layer disposed between the anode and cathode, wherein the organic layer comprises one or more light-emitting layers; at least one layer of the one or more light-emitting layers comprises one or more dopant compounds and two or more host compounds; and a first host compound of the two or more host compounds is the compound represented by formula 1 and a second host compound is the compound represented by formula 2.
The light-emitting layer indicates a layer from which light is emitted. It is preferable that a doping amount of the dopant compound is less than 20 wt% based on the total amount of the host compound and the dopant compound. In the organic electroluminescent device of the present disclosure, the weight ratio in the light-emitting layer between the first host material and the second host material may be in the range of 1:99 to 99:1.
The organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an electron buffering layer, an interlayer, a hole blocking layer, and an electron blocking layer.
The dopant to be comprised in the organic electroluminescent device of the present disclosure is preferably at least one phosphorescent dopant. The phosphorescent dopant material for the organic electroluminescent device of the present disclosure is not limited, but may be preferably selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) or platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) or platinum (Pt), and even more preferably ortho-metallated iridium complex compounds. Preferably, the phosphorescent dopant may be selected from the group consisting of compounds represented by the following formulae 101 to 103.
Figure PCTKR2015006443-appb-I000093
Figure PCTKR2015006443-appb-I000094
wherein L is selected from the following structures:
Figure PCTKR2015006443-appb-I000095
R100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
R101 to R109 and R111 to R123, each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a cyano, or a substituted or unsubstituted (C1-C30)alkoxy; R106 to R109 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl; R120 to R123 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a quinoline unsubstituted or substituted with an alkyl or aryl;
R124 to R127, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; R124 to R127 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl;
R201 to R211, each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl; R208 to R211 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a fluorene unsubstituted or substituted with an alkyl, a dibenzothiophene unsubstituted or substituted with an alkyl, or a dibenzofuran unsubstituted or substituted with an alkyl;
f and g, each independently, represent an integer of 1 to 3; when f or g is an integer of 2 or more, each of R100 may be the same or different; and n represents an integer of 1 to 3.
Specifically, the phosphorescent dopant material includes the following:
Figure PCTKR2015006443-appb-I000096
Figure PCTKR2015006443-appb-I000097
Figure PCTKR2015006443-appb-I000098
Figure PCTKR2015006443-appb-I000099
Figure PCTKR2015006443-appb-I000100
Figure PCTKR2015006443-appb-I000102
Figure PCTKR2015006443-appb-I000103
Figure PCTKR2015006443-appb-I000104
Figure PCTKR2015006443-appb-I000105
Figure PCTKR2015006443-appb-I000106
Figure PCTKR2015006443-appb-I000107
Figure PCTKR2015006443-appb-I000108
Figure PCTKR2015006443-appb-I000109
Figure PCTKR2015006443-appb-I000110
Figure PCTKR2015006443-appb-I000111
Figure PCTKR2015006443-appb-I000112
Figure PCTKR2015006443-appb-I000113
Figure PCTKR2015006443-appb-I000114
Figure PCTKR2015006443-appb-I000115
Figure PCTKR2015006443-appb-I000116
Figure PCTKR2015006443-appb-I000117
Figure PCTKR2015006443-appb-I000118
Figure PCTKR2015006443-appb-I000119
Figure PCTKR2015006443-appb-I000120
Figure PCTKR2015006443-appb-I000121
Figure PCTKR2015006443-appb-I000122
In the organic electroluminescent device of the present disclosure, the organic layer may further comprise at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device of the present disclosure, the organic layer may further comprise at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4th period, transition metals of the 5th period, lanthanides and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound comprising the metal.
In the organic electroluminescent device of the present disclosure, preferably, at least one layer (hereinafter, "a surface layer”) may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer and a metal oxide layer. Specifically, a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer. Such a surface layer provides operation stability for the organic electroluminescent device. Preferably, the chalcogenide includes SiOX (1≤X≤2), AlOX (1≤X≤1.5), SiON, SiAlON, etc.; the metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and the metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
A hole injection layer, a hole transport layer, an electron blocking layer, or a combination thereof may be disposed between the anode and the light-emitting layer. The hole injection layer may be composed of two or more layers in order to lower an energy barrier for injecting holes from the anode to a hole transport layer or an electron blocking layer (or a voltage for injecting a hole). Each of the layers may comprise two or more compounds. The hole transport layer or electron blocking layer may be composed of two or more layers.
An electron buffering layer, a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof may be disposed between the light-emitting layer and the cathode. The electron buffering layer may be composed of two or more layers in order to control the electron injection and improve characteristics of interface between the light-emitting layer and the electron injection layer. Each of the layers may comprise two or more compounds. The hole blocking layer or electron transport layer may be composed of two or more layers, and each of the layers may comprise two or more compounds.
In the organic electroluminescent device of the present disclosure, 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 may be placed on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium. Furthermore, the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium. Preferably, the oxidative dopant includes various Lewis acids and acceptor compounds, and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. A reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more light-emitting layers and emitting white light.
According to another aspect of the present disclosure, a material for preparing an organic electroluminescent device is provided. The material comprises the compound of formula 1 and the compound of formula 2. The material may be specifically for preparing a light-emitting layer of the organic electroluminescent device, and more specifically for a host of a light-emitting layer of the organic electroluminescent device. The material may be a composition or mixture. The material may further comprise a conventional material which has been comprised for an organic electroluminescent material.
In order to form each layer of the organic electroluminescent device of the present disclosure, dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as inkjet printing, nozzle printing, slot coating, spin coating, dip coating, and flow coating methods can be used. Where a layer is formed with the first host compound and the second host compound of the present disclosure, they may be co-evaporated or mixture-evaporated.
When using a wet film-forming method, a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
In the organic electroluminescent device of the present disclosure, two or more host compounds for a light-emitting layer may be co-evaporated or mixture-evaporated. Herein, a co-evaporation indicates a process for two or more materials to be deposited as a mixture, by introducing each of the two or more materials into respective crucible cells, and applying electric current to the cells for each of the materials to be evaporated. Herein, a mixture-evaporation indicates a process for two or more materials to be deposited as a mixture, by mixing the two or more materials in one crucible cell before the deposition, and applying electric current to the cell for the mixture to be evaporated.
The organic electroluminescent device of the present disclosure can be used for the manufacture of a display system or a lighting system.
Hereinafter, the preparation method of the host compound, and the luminescent properties of the device comprising the compound will be explained in detail with reference to the following examples.
Example 1: Preparation of compounds C-1 and C-7
Figure PCTKR2015006443-appb-I000123
Figure PCTKR2015006443-appb-I000124
Preparation of compound 1-1
After introducing compound 4-bromodibenzothiophene (50g, 189.98mmol), 2-methylthiophenylboronic acid (31.9g, 189.89mmol), tetrakis(triphenylphosphine)palladium (11g, 9.499mmol), sodium carbonate (60g, 569.94mmol), toluene (900mL), ethanol (280mL) and distilled water (280mL) into a reaction vessel, the mixture was stirred at 120°C for 3 hours. After completion of the reaction, the mixture was washed with distilled water and extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate, and the solvent was removed therefrom by a rotary evaporator. The products were purified by column chromatography to obtain compound 1-1 (58g, 99%).
Preparation of compound 1-2
After dissolving compound 1-1 (58g, 189.98mmol) in tetrahydrofuran (THF) (500mL) and acetic acid (580mL), hydrogen peroxide (35%) (23mL) was slowly added dropwise thereto. The obtained mixture was stirred at room temperature for 10 hours. After completion of the reaction, the mixture was concentrated to remove the solvent, and extracted with dichloromethane and purified water. The remaining moisture was removed from the obtained organic layer with magnesium sulfate, and then the organic layer was dried, concentrated, and directly used for the next reaction.
Preparation of compound 1-3
After dissolving compound 1-2 (58g) in trifluoromethane sulfonic acid (300mL), the mixture was stirred at room temperature for 2 days, and then added dropwise to a solution of pyridine (600mL)/purified water (1.5mL). The mixture was warmed and was under reflux at 120°C for 4 hours. After completion of the reaction, the mixture was extracted with dichloromethane. The obtained organic layer was subjected to column chromatography to obtain compound 1-3 (15.4g, 28%).
Preparation of compound 1-4
After dissolving compound 1-3 (15.4g, 53.03mmol) in chloroform (550mL), the mixture was cooled to 0°C. Bromine (2.7mL, 53.03mmol) was slowly added dropwise to the mixture. After completion of the addition, the mixture was warmed slowly to room temperature, and stirred for 8 hours. After completion of the reaction, bromine was removed from the mixture by using aqueous sodium thiosulfate solution. The product was filtered to obtain compound 1-4 (12.8g, 65.4%).
Preparation of compound 1-5
After introducing compound 1-4 (12.8g, 34.66mmol), chloroaniline (4.7mL, 45.06mmol), palladium acetate (0.31g, 45.06mmol), t-butylphosphine (50%) (1.4mL, 2.77mmol) and sodium t-butoxide (8.3g, 86.65mmol) into toluene (170mL), the mixture was stirred under reflux for 1 day. After completion of the reaction, the mixture was cooled to room temperature, and extracted with distilled water and ethyl acetate. The obtained organic layer was distilled under reduced pressure, and purified by column chromatography to obtain compound 1-5 (13.7g, 77%).
Preparation of compound 1-6
After introducing compound 1-5 (13.7g, 32.94mmol), palladium acetate (0.4g, 1.646mmol), tricyclohexylphosphonium tetrafluoroborate (C18H34P.BF4) (1.21g, 3.29mmol), cesium carbonate (32.1g, 98.82mmol) and dimethylacetamide (DMA) (250mL) into a reaction vessel, the mixture was stirred at 180°C for 7 hours. After completion of the reaction, the mixture was extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate, distilled under reduced pressure, and purified by column chromatography to obtain compound 1-6 (5.6g, 45%).
Preparation of compound C-1
After dissolving compound 1-6 (5g, 13.17mmol), compound 1-7 (4.6g, 15.81mmol), palladium acetate (1.2g, 5.27mmol), 50% t-butylphosphine (5mL, 10.54mmol) and cesium carbonate (13g, 39.5mmol) in toluene (65mL), the mixture was under reflux at 130°C for 3 hours. After completion of the reaction, the mixture was extracted with dichloromethane/purified water. The obtained organic layer was subjected to column chromatography to obtain compound C-1 (4.4g, 57%).
UV: 319 nm, PL: 525 nm, Melting point: 261°C, MS/EIMS Found 584; Calculated 583
Preparation of compound C-7
After dissolving compound 1-6 (1.6g, 4.21mmol), and compound 1-8 (1.7g, 6.32mmol) in dimethylformamide (DMF) (30mL), NaH (0.5g, 12.63 mmol, 60% in mineral oil) was added to the mixture. The mixture was stirred at room temperature for 12 hours, and methanol and distilled water were added thereto. The obtained solid was filtered under reduced pressure, and subjected to column chromatography to obtain compound C-7 (1.4g, 54%).
UV: 342 nm, PL: 528 nm, Melting point: 360°C, MS/EIMS Found 611; Calculated 610
Example 2: Preparation of compounds C-13 and C-19
Figure PCTKR2015006443-appb-I000125
Figure PCTKR2015006443-appb-I000126
Preparation of compound 2-1
After introducing compound 4-bromodibenzofuran (50g, 202.35mmol), 2- methylthiophenylboronic acid (34g, 202.35mmol), tetrakis(triphenylphosphine)palladium (11.7g, 10.117mmol), sodium carbonate (64g, 607.06mmol), toluene (1,000mL), ethanol (300mL), and distilled water (300mL) into a reaction vessel, the mixture was stirred at 120°C for 3 hours. After completion of the reaction, the mixture was washed with distilled water, and extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed therefrom by a rotary evaporator. The products were purified by column chromatography to obtain compound 2-1 (58g, 99%).
Preparation of compound 2-2
After dissolving compound 2-1 (58g, 202.35mmol) in THF (580mL) and acetic acid (580mL), hydrogen peroxide (35%) (26mL) was slowly added dropwise thereto. The mixture was stirred at room temperature for 10 hours. After completion of the reaction, the mixture was concentrated to remove the solvent, and then extracted with dichloromethane and purified water. The remaining moisture was removed from the obtained organic layer with magnesium sulfate, concentrated, and directly used for the next reaction.
Preparation of compound 2-3
While stirring a solution of pyridine (600mL)/purified water (1.5mL), compound 2-2 was added dropwise thereto. The mixture was then warmed and was under reflux at 120°C for 4 hours. After completion of the reaction, the mixture was extracted with dichloromethane, and the obtained organic layer was subjected to column chromatography to obtain compound 2-3 (48.6g, 93%).
Preparation of compound 2-4
After dissolving compound 2-3 (43.6g, 158.9mmol) in chloroform (800mL), the mixture was cooled to 0°C. Bromine (8.55mL, 166.87mmol) was slowly added dropwise to the mixture. After the addition, the mixture was slowly warmed to room temperature and stirred for 8 hours. After completion of the reaction, bromine was removed from the mixture by using aqueous sodium thiosulfate solution. The product was filtered to obtain compound 2-4 (44g, 70%).
Preparation of compound 2-5
After introducing compound 2-4 (20g, 56.62mmol), chloroaniline (7.7mL, 73.61mmol), palladium acetate (0.5g, 2.26mmol), t-butylphosphine (50%) (2.2mL, 4.53mmol) and sodium t-butoxide (13.6g, 141.55mmol) into toluene (280mL), the mixture was stirred under reflux for 1 day. After completion of the reaction, the mixture was cooled to room temperature, and extracted with distilled water and ethyl acetate. The obtained organic layer was distilled under reduced pressure and purified by column chromatography to obtain compound 2-5 (11g, 48.6%).
Preparation of compound 2-6
After introducing compound 2-5 (11g, 27.5mmol), palladium acetate (0.3g, 1.37mmol), C18H34P.BF4 (1g, 2.75mmol), cesium carbonate (26g, 82.5mmol) and DMA (135mL) into a reaction vessel, the mixture was stirred at 180°C for 7 hours. After completion of the reaction, the mixture was extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate, distilled under reduced pressure, and purified by column chromatography to obtain compound 2-6 (4g, 40%).
Preparation of compound C-13
After dissolving compound 2-6 (3.5g, 9.63mmol), compound 1-7 (2.78g, 11.55mmol), palladium acetate (0.86g, 3.85mmol), 50% t-butylphosphine (3.7mL, 7.704mmol) and cesium carbonate (9.4g, 28.8mmol) in toluene (100mL), the mixture was under reflux at 130°C for 3 hours. After completion of the reaction, the mixture was extracted with dichloromethane/purified water. The obtained organic layer was subjected to column chromatography to obtain compound C-13 (2.5g, 46%).
UV: 296 nm, PL: 535 nm, Melting point: 290°C, MS/EIMS Found 568; Calculated 567
Preparation of compound C-19
After dissolving compound 2-6 (3g, 8.2mmol) and compound 1-8 (2.65g, 9.9mmol) in dimethylformamide (DMF) (40mL), NaH (1g, 24.76mmol, 60% in mineral oil) was added thereto. The mixture was stirred at room temperature for 12 hours, and methanol and distilled water were added thereto. The obtained solid was filtered under reduced pressure, and subjected to column chromatography to obtain compound C-19 (3.1g, 63%).
UV: 342 nm, PL: 532 nm, Melting point: 353°C, MS/EIMS Found 595; Calculated 594
Example 3: Preparation of compound C-20
Figure PCTKR2015006443-appb-I000127
Preparation of compound 1-1
After introducing benzo[b][1]benzocyano[2,3-g]benzofuran (30g, 109mmol) and chloroform (540mL) into a flask, the mixture was cooled to 0°C. Bromine (5.8mL, 114mmol) was slowly added dropwise to the mixture. The mixture was then stirred for 3 hours. After completion of the reaction, the mixture was extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate, and distilled under reduced pressure. The resultant was subjected to column chromatography to obtain compound 1-1 (23g, yield: 60%).
Preparation of compound 1-2
After introducing compound 1-1 (18g, 52.1 mmol), 2-chloroaniline (8.2mL, 78.1 mmol), palladium acetate (1.1g, 5.21 mmol), tri-tert-butylphosphine (5mL (50%), 10.4 mmol), sodium tert-butoxide (15 g, 156 mmol) and toluene (260 mL) into a flask, the mixture was stirred under reflux for 4 hours. After completion of the reaction, the mixture was extracted with methylene chloride (MC), dried with magnesium sulfate, and distilled under reduced pressure. The resultant was subjected to column chromatography to obtain compound 1-2 (18g, yield: 90%).
Preparation of compound 1-3
After introducing compound 1-2 (18g, 47.0 mmol), palladium acetate (1.0g, 4.70 mmol), tricyclohexylphosphonium tetrafluoroborate (3.4g, 9.40 mmol), cesium carbonate (46 g, 141 mmol) and dimethylacetamide (240 mL) into a flask, the mixture was stirred under reflux for 4 hours. After completion of the reaction, the mixture was extracted with methylene chloride (MC), dried with magnesium sulfate, and distilled under reduced pressure. The resultant was subjected to column chromatography to obtain compound 1-3 (6.7g, yield: 40%).
Preparation of compound C-20
After dissolving compound 1-3 (3 g, 8.25 mmol) and compound B (3.4g, 10.7 mmol) in dimethylformamide (DMF) (40 mL) of a flask, NaH (1g, 24.76mmol, 60% in mineral oil) was added to the mixture. The mixture was then stirred at room temperature for 12 hours, and methanol and distilled water were added thereto. The obtained solid was filtered under reduced pressure and subjected to column chromatography to obtain compound C-20 (3.6g, yield: 67%).
Figure PCTKR2015006443-appb-I000128
Example 4: Preparation of compound C-22
Figure PCTKR2015006443-appb-I000129
Preparation of compound 1-1
After introducing benzo[b][1]benzocyano[2,3-g]benzofuran (30g, 109 mmol) and chloroform (540mL) into a flask, the mixture was cooled to 0°C. Bromine (5.8mL, 114 mmol) was slowly added dropwise to the mixture. The mixture was then stirred for 3 hours. After completion of the reaction, the mixture was extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate and distilled under reduced pressure. The resultant was subjected to column chromatography to obtain compound 1-1 (23g, yield: 60%).
Preparation of compound 1-2
After introducing compound 1-1 (18g, 52.1 mmol), 2-chloroaniline (8.2mL, 78.1 mmol), palladium acetate (1.1g, 5.21 mmol), tri-tert-butylphosphine (5mL (50%), 10.4 mmol), sodium tert-butoxide (15g, 156 mmol) and toluene (260mL) into a flask, the mixture was stirred under reflux for 4 hours. After completion of the reaction, the mixture was extracted with methylene chloride (MC), dried with magnesium sulfate, and distilled under reduced pressure. The product was subjected to column chromatography to obtain compound 1-2 (18g, yield: 90%).
Preparation of compound 1-3
After introducing compound 1-2 (18g, 47.0 mmol), palladium acetate (1.0g, 4.70 mmol), tricyclohexylphosphonium tetrafluoroborate (3.4g, 9.40 mmol), cesium carbonate (46g, 141 mmol) and dimethylacetamide (240mL) into a flask, the mixture was stirred under reflux for 4 hours. After completion of the reaction, the mixture was extracted with methylene chloride(MC), dried with magnesium sulfate, and then distilled under reduced pressure. The resultant was subjected to column chromatography to obtain compound 1-3 (6.7g, yield: 40%).
Preparation of compound C-22
After introducing compound 1-3 (6.7g, 18.4 mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (7.8g, 20.2 mmol), tris(dibenzylindeneacetone) dipalladium (0.8g, 0.92 mmol), tri-tert-butylphosphine ((0.9mL) (50%), 1.84 mmol), sodium tert-butoxide (4.4g, 46.1 mmol), and toluene (100mL) into a flask, the mixture was stirred under reflux for 3 hours. After completion of the reaction, the mixture was extracted with methylene chloride (MC), dried with magnesium sulfate, and distilled under reduced pressure. The resultant was subjected to column chromatography to obtain compound C-22 (8.3g, yield: 67%).
Figure PCTKR2015006443-appb-I000130
[Device Examples 1-1 to 1-6] OLED produced by a co-evaporation of a
first host compound and a second host compound of the present disclosure
OLED was produced using the light-emitting material of the present disclosure as follows. A transparent electrode indium tin oxide (ITO) thin film (10 Ω/sq) on a glass substrate for an organic electroluminescent device (OLED) (Geomatec) was subjected to an ultrasonic washing with acetone, ethanol, and distilled water sequentially, and was then stored in isopropanol. The ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus. HI-1 was introduced into a cell of the vacuum vapor depositing apparatus, and then the pressure in the chamber of the apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate HI-1, thereby forming a first hole injection layer having a thickness of 80 nm on the ITO substrate. HI-2 was then introduced into another cell of the vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a second hole injection layer having a thickness of 5 nm on the first hole injection layer. HT-1 was introduced into one cell of the vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer. HT-2 or HT-3 was then introduced into another cell of the vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a second hole transport layer having a thickness of 60 nm on the first hole transport layer. As a host material, a first host compound and a second host compound shown in Table 1 below were introduced into two cells of the vacuum vapor depositing apparatus, respectively. A dopant compound shown in Table 1 was introduced into another cell. The two host compounds were evaporated at the same rate of 1:1, while the dopant was evaporated at a different rate from the host compounds, so that the dopant was deposited in a doping amount of 3 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 40 nm on the hole transport layer. ET-1 and EI-1 were introduced into two cells of the vacuum vapor depositing apparatus, respectively, and evaporated at the same rate of 1:1, thereby forming an electron transport layer having a thickness of 30 nm on the light-emitting layer. After depositing EI-1 as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 80 nm was then deposited by another vacuum vapor deposition apparatus on the electron injection layer.
Figure PCTKR2015006443-appb-I000131
[Comparative Examples 1-1 to 1-4] OLED using a second host compound as
a sole host
OLED was produced in the same manner as in Device Examples 1-1 to 1-6, except that only a second host compound shown in Table 1 below was used as a host for a light-emitting layer.
[Comparative Examples 2-1 to 2-2] OLED using a first host compound as a
sole host
OLED was produced in the same manner as in Device Examples 1-1 to 1-6, except that only a first host compound shown in Table 1 below was used as a host for a light-emitting layer.
The characteristics of the organic electroluminescent devices produced in device examples 1-1 to 1-6, comparative examples 1-1 to 1-4, and comparative examples 2-1 to 2-2 are shown in Table 1 below.
Figure PCTKR2015006443-appb-I000132
Figure PCTKR2015006443-appb-I000133
The organic electroluminescent device using a plurality of host materials of the present disclosure can have longer lifespan than one using one host compound.

Claims (10)

  1. An organic electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and cathode, wherein the organic layer comprises one or more light-emitting layers; at least one layer of the one or more light-emitting layers comprises one or more dopant compounds and two or more host compounds; and a first host compound of the two or more host compounds is the compound represented by the following formula 1 and a second host compound is the compound represented by the following formula 2:
    Figure PCTKR2015006443-appb-I000134
    wherein A1 and A2, each independently, represent a substituted or unsubstituted (C6-C30)aryl; provided that a substituent for A1 and A2 is not a nitrogen-containing heteroaryl;
    L1 represents a single bond or a substituted or unsubstituted (C6-C30)arylene;
    X1 to X16, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C2-C30)alkenyl, a substituted or unsubstituted (C2-C30)alkynyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C60)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, or a substituted or unsubstituted mono- or di-(C6-C30)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring;
    Figure PCTKR2015006443-appb-I000135
    wherein Ar1 represents a substituted or unsubstituted 3- to 30-membered heteroaryl, or a substituted or unsubstituted (C6-C30)aryl;
    L2 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted 3- to 30-membered heteroarylene;
    ring A represents
    Figure PCTKR2015006443-appb-I000136
    ring B represents
    Figure PCTKR2015006443-appb-I000137
    Y represents O, S, C(R4)(R5), or N(R6); X represents O, S, C(R7)(R8), or N(R6); provided that both X and Y cannot simultaneously be N(R6);
    R1 to R3, each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxy, a nitro, a hydroxy, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, -NR9R10 or -SiR11R12R13; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring;
    R4 to R13, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted 5- to 7-membered heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR14R15, -SiR16R17R18, a cyano, a nitro, or a hydroxyl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring;
    R14 to R18 have the same definition as R4 to R13;
    a carbon atom(s) of the alicyclic or aromatic ring may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
    the heteroaryl(ene) and heterocycloalkyl, each independently, contain at least one hetero atom selected from B, N, O, S, Si, and P;
    a, b, and c, each independently, represent an integer of 1 to 4; and where a, b, or c represents an integer of 2 or more, each of R1, R2, or R3 may be the same or different.
  2. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is represented by any one of the following formulae 3, 4, 5, and 6.
    Figure PCTKR2015006443-appb-I000138
    Figure PCTKR2015006443-appb-I000139
    wherein A1, A2, L1, and X1 to X16 are as defined in claim 1.
  3. The organic electroluminescent compound according to claim 1, wherein A1 and A2, each independently, are selected from the group consisting of a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted benzofluorenyl, a substituted or unsubstituted phenanthrenyl, a substituted or unsubstituted anthracenyl, a substituted or unsubstituted indenyl, a substituted or unsubstituted triphenylenyl, a substituted or unsubstituted pyrenyl, a substituted or unsubstituted tetracenyl, a substituted or unsubstituted perylenyl, a substituted or unsubstituted chrysenyl, a substituted or unsubstituted phenylnaphthyl, a substituted or unsubstituted naphthylphenyl, and a substituted or unsubstituted fluoranthenyl.
  4. The organic electroluminescent compound according to claim 1, wherein L1 represents a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, or a substituted or unsubstituted biphenylene.
  5. The organic electroluminescent compound according to claim 1, wherein the compound of formula 2 is represented by any one of the following formulae 20 to 23.
    Figure PCTKR2015006443-appb-I000140
    Figure PCTKR2015006443-appb-I000141
    wherein Ar1, L2, X, Y, R1 to R3, a, b, and c are as defined in claim 1.
  6. The organic electroluminescent compound according to claim 1, wherein Ar1 is selected from the group consisting of a substituted or unsubstituted triazinyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted quinolyl, a substituted or unsubstituted isoquinolyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted naphthyridinyl, and a substituted or unsubstituted quinoxalinyl.
  7. The organic electroluminescent compound according to claim 1, wherein L2 represents a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, or a substituted or unsubstituted naphthylene.
  8. The organic electroluminescent compound according to claim 1, wherein X and Y, each independently, are selected from O, S, and N(R6), and provided that both X and Y cannot simultaneously be N(R6).
  9. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is selected from the group consisting of:
    Figure PCTKR2015006443-appb-I000142
    Figure PCTKR2015006443-appb-I000143
    Figure PCTKR2015006443-appb-I000144
    Figure PCTKR2015006443-appb-I000145
    Figure PCTKR2015006443-appb-I000146
    Figure PCTKR2015006443-appb-I000147
    Figure PCTKR2015006443-appb-I000148
    Figure PCTKR2015006443-appb-I000149
    Figure PCTKR2015006443-appb-I000150
    Figure PCTKR2015006443-appb-I000151
    Figure PCTKR2015006443-appb-I000152
    Figure PCTKR2015006443-appb-I000153
    Figure PCTKR2015006443-appb-I000154
    Figure PCTKR2015006443-appb-I000155
    Figure PCTKR2015006443-appb-I000156
    Figure PCTKR2015006443-appb-I000157
    Figure PCTKR2015006443-appb-I000158
    Figure PCTKR2015006443-appb-I000159
    Figure PCTKR2015006443-appb-I000160
    Figure PCTKR2015006443-appb-I000161
    Figure PCTKR2015006443-appb-I000162
    Figure PCTKR2015006443-appb-I000163
    Figure PCTKR2015006443-appb-I000164
    Figure PCTKR2015006443-appb-I000165
    Figure PCTKR2015006443-appb-I000166
    Figure PCTKR2015006443-appb-I000167
    Figure PCTKR2015006443-appb-I000168
    Figure PCTKR2015006443-appb-I000169
    Figure PCTKR2015006443-appb-I000170
    Figure PCTKR2015006443-appb-I000171
    Figure PCTKR2015006443-appb-I000172
    Figure PCTKR2015006443-appb-I000173
    Figure PCTKR2015006443-appb-I000174
    Figure PCTKR2015006443-appb-I000175
    Figure PCTKR2015006443-appb-I000176
    Figure PCTKR2015006443-appb-I000177
    Figure PCTKR2015006443-appb-I000178
    Figure PCTKR2015006443-appb-I000179
    Figure PCTKR2015006443-appb-I000180
    Figure PCTKR2015006443-appb-I000181
    Figure PCTKR2015006443-appb-I000182
    Figure PCTKR2015006443-appb-I000184
    Figure PCTKR2015006443-appb-I000185
    Figure PCTKR2015006443-appb-I000186
    Figure PCTKR2015006443-appb-I000187
    Figure PCTKR2015006443-appb-I000188
    Figure PCTKR2015006443-appb-I000189
    Figure PCTKR2015006443-appb-I000190
    Figure PCTKR2015006443-appb-I000191
    Figure PCTKR2015006443-appb-I000192
    Figure PCTKR2015006443-appb-I000193
    Figure PCTKR2015006443-appb-I000194
  10. The organic electroluminescent compound according to claim 1, wherein the compound of formula 2 is selected from the group consisting of:
    Figure PCTKR2015006443-appb-I000195
    Figure PCTKR2015006443-appb-I000196
    Figure PCTKR2015006443-appb-I000197
    Figure PCTKR2015006443-appb-I000198
    Figure PCTKR2015006443-appb-I000199
    Figure PCTKR2015006443-appb-I000200
    Figure PCTKR2015006443-appb-I000201
    Figure PCTKR2015006443-appb-I000202
    Figure PCTKR2015006443-appb-I000203
    Figure PCTKR2015006443-appb-I000205
    Figure PCTKR2015006443-appb-I000206
    Figure PCTKR2015006443-appb-I000207
    Figure PCTKR2015006443-appb-I000208
    Figure PCTKR2015006443-appb-I000209
    Figure PCTKR2015006443-appb-I000210
    Figure PCTKR2015006443-appb-I000211
    Figure PCTKR2015006443-appb-I000212
    Figure PCTKR2015006443-appb-I000213
    Figure PCTKR2015006443-appb-I000214
PCT/KR2015/006443 2014-09-29 2015-06-24 A plurality of host materials and an organic electroluminescent device comprising the same WO2016052835A1 (en)

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WO2013112557A1 (en) * 2012-01-26 2013-08-01 Universal Display Corporation Phosphorescent organic light emitting devices having a hole transporting cohost material in the emissive region
KR20140000611A (en) * 2012-06-22 2014-01-03 (주)피엔에이치테크 Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same
KR20140039622A (en) * 2012-09-24 2014-04-02 주식회사 두산 New compounds and organic electro luminescence device using the same
KR101478990B1 (en) * 2013-12-27 2015-01-06 롬엔드하스전자재료코리아유한회사 Novel organic electroluminescent compounds and organic electroluminescent device comprising the same
WO2015099507A1 (en) * 2013-12-27 2015-07-02 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compound, and multi-component host material and organic electroluminescent device comprising the same

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WO2013112557A1 (en) * 2012-01-26 2013-08-01 Universal Display Corporation Phosphorescent organic light emitting devices having a hole transporting cohost material in the emissive region
KR20140000611A (en) * 2012-06-22 2014-01-03 (주)피엔에이치테크 Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same
KR20140039622A (en) * 2012-09-24 2014-04-02 주식회사 두산 New compounds and organic electro luminescence device using the same
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