WO2015099484A1 - Organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

Organic electroluminescent compounds and organic electroluminescent device comprising the same Download PDF

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WO2015099484A1
WO2015099484A1 PCT/KR2014/012891 KR2014012891W WO2015099484A1 WO 2015099484 A1 WO2015099484 A1 WO 2015099484A1 KR 2014012891 W KR2014012891 W KR 2014012891W WO 2015099484 A1 WO2015099484 A1 WO 2015099484A1
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substituted
unsubstituted
aryl
alkyl
membered
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Ji-Song JUN
Doo-Hyeon Moon
Hee-Choon Ahn
Kyung-Joo Lee
Tae-Jin Lee
Chi-Sik Kim
Young-Jun Cho
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DuPont Specialty Materials Korea Ltd
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Rohm and Haas Electronic Materials Korea Ltd
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Definitions

  • the present invention relates to organic electroluminescent compounds and organic electroluminescent device comprising the same.
  • An electroluminescent 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 for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • the most important factor determining luminous efficiency in an organic EL device is the light-emitting material.
  • fluorescent materials have been widely used as a light-emitting material.
  • phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, development of phosphorescent light-emitting materials are widely being researched.
  • Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp) 2 ), tris(2-phenylpyridine)iridium (Ir(ppy) 3 ) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red, green and blue materials, respectively.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • BCP bathocuproine
  • BAlq aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate)
  • an organic EL device has a structure of a multilayer comprising a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer.
  • the selection of a compound comprised in the hole transport layer is known as a method for improving the characteristics of a device such as hole transport efficiency to the light-emitting layer, luminous efficiency, lifespan, etc.
  • CuPc copper phthalocyanine
  • NPB 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl
  • TPD N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine
  • MTDATA 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine
  • an organic EL device using these materials is problematic in quantum efficiency and operational lifespan. It is because, when an organic EL device is driven under high current, thermal stress occurs between an anode and the hole injection layer.
  • Korean Patent Appln. Laying-Open No. 10-2012-025984 discloses a compound in which the 9-position of a fluorene is bonded to dibenzothiophene or dibenzofuran, as a hole injection material or a hole transport material.
  • the above reference does not disclose a compound in which the 9-position of a fluorene is bonded to dibenzothiophene, dibenzofuran, or fluorene, and carbazole.
  • the objective of the present invention is to provide i) an organic electroluminescent compound having high luminous efficiency, and ii) an organic electroluminescent device comprising the compound having long operational lifespan and improved power and current efficiencies.
  • Ar 1 represents a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; or may be linked to an adjacent substituent(s) to form a (C3-C30), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
  • L 1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene;
  • X represents -O-, -S-, or -C(R 7 )(R 8 )-;
  • R 1 to R 6 each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, 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)heter
  • R 7 to R 18 each independently, represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted, (C3-C30), mono- or polycyclic, alicyclic or aromatic ring;
  • a, b, c, and f each independently, represent an integer of 0 to 4; where a, b, c, or f represents an integer of 2 or more, each of R 1 , R 2 , R 3 , or R 6 may be the same or different;
  • d and e each independently, represent an integer of 0 to 3; where d or e represents an integer of 2 or more, each of R 4 or R 5 may be the same or different; and
  • heterocycloalkyl and the heteroaryl(ene), each independently, contain at least one hetero atom selected from B, N, O, S, P( O), Si, and P.
  • organic electroluminescent compound according to the present invention By using the organic electroluminescent compound according to the present invention, it is possible to manufacture an organic electroluminescent device having excellent current and luminous efficiencies.
  • the present invention relates to an organic electroluminescent compound of formula 1, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the material.
  • the organic electroluminescent compound represented by the above formula 1 will be described in detail.
  • alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; “alkenyl” includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.; “alkynyl” includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.; “cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; “(3- to 7- membered)heterocycloalkyl” is a cycloalkyl having 3 to 7 ring backbone atoms including at least one
  • 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.
  • Ar 1 preferably represents a substituted or unsubstituted (C1-C20)alkyl, or a substituted or unsubstituted (C6-C21)aryl; more preferably represents a substituted or unsubstituted (C6-C18)aryl; and even more preferably represents a (C6-C18)aryl unsubstituted or substituted with a (C6-C18)aryl.
  • Ar 1 may represent phenyl, naphthyl, phenanthrenyl, or biphenyl, each may be substituted with phenyl or naphthyl; and more specifically, phenyl, naphthyl-substituted phenyl, naphthyl, phenyl-substituted naphthyl, phenanthrenyl, or biphenyl.
  • L 1 preferably represents a single bond, a substituted or unsubstituted (C6-C21)arylene, or a substituted or unsubstituted (3- to 21-membered)heteroarylene. Specifically, L 1 may represent a single bond.
  • X preferably represents -O-, -S-, or -C(R 7 )(R 8 )-, wherein R 7 and R 8 , each independently, may represent a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered)heteroaryl; and more preferably, X represents -O-, -S-, or -C(R 7 )(R 8 )-, wherein R 7 and R 8 , each independently, may represent an unsubstituted (C1-C10)alkyl, or an unsubstituted (C6-C18)aryl.
  • X may represent -O-, -S-, -C(CH 3 )(CH 3 )-, or -C(C 6 H 5 )(C 6 H 5 )-.
  • R 1 to R 6 each independently, preferably represent hydrogen, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C21)aryl, a substituted or unsubstituted (5- to 21-membered)heteroaryl, or a di(C6-C21)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted, (C5-C21), mono- or polycyclic aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur.
  • R 4 and R 5 each independently, represent a substituted or unsubstituted (C1-C10)alkyl
  • R 1 , R 2 , R 3 , and R 6 each independently, represent an unsubstituted (C6-C18)aryl, or a (6- to 18-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl; or may be linked to an adjacent substituent(s) to form a (C6-C18), mono- or polycyclic aromatic ring unsubstituted or substituted with a (C6-C12)aryl, whose carbon atom may be replaced with one (1) nitrogen.
  • R 1 , R 2 , R 3 , and R 6 each independently, may represent phenyl, or phenyl-substituted carbazole; or may be linked to an adjacent substituent(s) to form a phenyl- or naphthyl-substituted indole ring.
  • a, b, c, d, e, and f each independently, preferably represent an integer of 0 to 2; more preferably, a, b, c, and f, each independently, represent an integer of 0 to 2, and e and d, each independently, represent an integer of 0 or 1; and even more preferably, a, b, c, and f, each independently, represent an integer of 0 or 1, and e and d, each independently, represent 0.
  • a, b, d, e, and f may represent 0, and c may represent an integer of 0 or 1.
  • Ar 1 represents a substituted or unsubstituted (C1-C20)alkyl, or a substituted or unsubstituted (C6-C21)aryl
  • L 1 represents a single bond, a substituted or unsubstituted (C6-C21)arylene, or a substituted or unsubstituted (3- to 21-membered)heteroarylene
  • X represents -O-, -S-, or -C(R 7 )(R 8 )-, wherein R 7 and R 8 , each independently, represent a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered)heteroaryl
  • R 1 to R 6 each independently, represent hydrogen, a substituted or unsubstituted (C1-C20)alkyl, or a
  • Ar 1 represents a substituted or unsubstituted (C6-C18)aryl
  • L 1 represents a single bond
  • X represents -O-, -S-, or -C(R 7 )(R 8 )-, wherein R 7 and R 8 , each independently, represent a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered)heteroaryl
  • R 1 to R 6 each independently, represent an unsubstituted (C6-C18)aryl, or a (6- to 18-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl; or may be linked to an adjacent substituent(s) to form a (C6-C18), mono- or polycyclic aromatic
  • the compound of formula 1 can be represented by the following formula 2:
  • Ar 1 , L 1 , X, R 1 to R 6 , a, b, d, e, and f are as defined in formula 1.
  • Ar 2 represents a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; or may be linked to an adjacent substituent(s) to form a (C3-C30), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur.
  • Ar 2 preferably represents a substituted or unsubstituted (C1-C20)alkyl, or a substituted or unsubstituted (C6-C21)aryl; more preferably represents a (C6-C18)aryl unsubstituted or substituted with a (C1-C10)alkyl; and even more preferably represents an unsubstituted (C6-C12)aryl.
  • Ar 2 may represent phenyl or naphthyl.
  • R 21 and R 22 each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, 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-member
  • R 21 and R 22 each independently, preferably represent hydrogen, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered)heteroaryl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted, (C5-C21), mono- or polycyclic, aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; and more preferably represent a (C1-C10)alkyl unsubstituted or substituted with a (C6-C12)aryl, an unsubstituted (C6-C18)aryl, or a (6- to 18-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl; or may be linked to an
  • g represents an integer of 0 to 4; c and h, each independently, represent an integer of 0 to 3; where c, g, or h represents an integer of 2 or more, each of R 3 , R 21 , or R 22 may be the same or different.
  • g represents an integer of 0 to 2
  • c and h each independently, represent 0 or 1.
  • c, g, and h may represent 0.
  • the compound of formula 1 can be represented by the following formula 3:
  • L 1 , X, Ar 1 , R 1 , R 2 , R 4 to R 6 , a, b, d, e, and f are as defined in formula 1; A .
  • Ar 3 represents a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; or may be linked to an adjacent substituent(s) to form a (C3-C30), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur.
  • Ar 3 preferably represents a substituted or unsubstituted (C1-C20)alkyl, or a substituted or unsubstituted (C6-C21)aryl; more preferably represents a (C6-C18)aryl unsubstituted or substituted with a (C1-C10)alkyl; and even more preferably represents an unsubstituted (C6-C12)aryl.
  • Ar 3 may represent phenyl or naphthyl.
  • R 23 represents hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, 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
  • R 23 preferably represents hydrogen, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered)heteroaryl; and more preferably represent a (C1-C10)alkyl unsubstituted or substituted with a (C6-C12)aryl, an unsubstituted (C6-C18)aryl, or a (6- to 18-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl.
  • i represents an integer of 0 to 2; and c represents 0 or 1.
  • i represents 0 or 1
  • c represents 0.
  • the specific compounds of the present invention include the following compounds, but are not limited thereto:
  • the organic electroluminescent compound of the present invention preferably has a molecular weight of 1000 or less, more preferably 950 or less, more preferably 925 or less, and even more preferably 900 or less.
  • a molecular weight 1000 or less, more preferably 950 or less, more preferably 925 or less, and even more preferably 900 or less.
  • the organic electroluminescent compound of the present invention preferably has a glass transition temperature of 90°C or more, and more preferably 110°C or more. By having the glass transition temperature as above, the compound can have excellent thermal stability.
  • organic electroluminescent compounds of the present invention can be prepared by a synthetic method known to a person skilled in the art. For example, they can be prepared according to the following reaction schemes.
  • R 1 to R 6 , X, Ar 1 , L 1 , and a to f are as defined in formula 1 above.
  • R 1 to R 6 , R 21 , R 22 , X, Ar 1 , Ar 2 , L 1 , and a to h are as defined in formula 2 above, and Hal represents a halogen.
  • A, B, C, R 1 , R 2 , R 4 to R 6 , X, Ar 1 , L 1 , a, b, and d to f are as defined in formula 3 above.
  • the present invention provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
  • the above material can be comprised of the organic electroluminescent compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescent materials.
  • the organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes.
  • the organic layer may comprise at least one organic electroluminescent compound of formula 1.
  • the organic layer comprises a light-emitting layer, and may further comprise at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
  • the organic electroluminescent compound according to the present invention can be comprised in at least one of the light-emitting layer and the hole transport layer. Where used in the hole transport layer, the organic electroluminescent compound of the present invention can be comprised as a hole transport material. Where used in the light-emitting layer, the organic electroluminescent compound of the present invention can be comprised as a host material.
  • the organic electroluminescent device comprising the organic electroluminescent compound of the present invention can further comprise one or more compounds other than the organic electroluminescent compound according to the present invention as host materials, and can further comprise one or more dopants.
  • the organic electroluminescent compound according to the present invention is comprised as a host material (first host material)
  • the other compound may be comprised as a second host material.
  • the weight ratio of the first host material to the second host material is in the range of 1:99 to 99:1.
  • the host material other than the organic electroluminescent compound according to the present invention can be from any of the known fluorescent or phosphorescent hosts, preferably phosphorescent hosts in terms of luminous efficiency.
  • the phosphorescent host selected from the group consisting of the compounds of formulae 11 to 13 below is preferable in terms of luminous efficiency.
  • R 31 to R 34 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted of unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, or -SiR 35 R 36 R 37 ;
  • R 35 to R 37 each independently represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • L 4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene;
  • M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl;
  • Y 1 and Y 2 each independently represent -O-, -S-, -N(R 41 )-, or -C(R 42 )(R 43 )-, provided that Y 1 and Y 2 do not simultaneously exist;
  • R 41 to R 43 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl, and R 42 and R 43 may be the same or different;
  • n and n each independently represent an integer of 1 to 3;
  • j, k, p, and q each independently represent an integer of 0 to 4.
  • each of (Cz-L 4 ), each of (Cz), each of R 31 , each of R 32 , each of R 33 , or each of R 34 may be the same or different.
  • preferable examples of the host material are as follows:
  • the dopant comprised in the organic electroluminescent device according to the present invention is preferably at least one phosphorescent dopant.
  • the dopant materials applied to the organic electroluminescent device according to the present invention are not limited, but may be preferably selected from metallated complex compounds of iridium, osmium, copper and platinum, more preferably selected from ortho-metallated complex compounds of iridium, osmium, copper and platinum, and even more preferably ortho-metallated iridium complex compounds.
  • the phosphorescent dopants may be preferably selected from 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(s); a cyano; a substituted or unsubstituted (C1-C30)alkoxy; a substituted or unsubstituted (C6-C30)aryl; or a substituted or unsubstituted (C3-C30)cycloalkyl; R 106 to R 109 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g.
  • R 120 to R 123 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g. quinoline unsubstituted or substituted with a halogen, alkyl, or aryl;
  • 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; and R 124 to R 127 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g. fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl;
  • R 201 to R 211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl, and R 208 to R 211 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g. fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl;
  • r and s each independently represent an integer of 1 to 3; where r or s is an integer of 2 or more, each of R 100 may be the same or different; and
  • t represents an integer of 1 to 3.
  • the phosphorescent dopant materials include the following:
  • compositions for preparing an organic electroluminescent device comprises the compound according to the present invention as a host material or a hole transport material.
  • the organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes.
  • the organic layer comprises a light-emitting layer, and the light-emitting layer may comprise the composition for preparing the organic electroluminescent device according to the present invention.
  • the organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compound represented by formula 1, 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 d-transition elements of the Periodic Table, or at least one complex compound comprising said metal.
  • the organic layer may further comprise a light-emitting layer and a charge generating layer.
  • the organic electroluminescent device according to the present invention may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound according to the present invention. Also, if needed, a yellow or orange light-emitting layer can be comprised in the device.
  • a surface layer is preferably 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.
  • said chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.; said metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and said metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a mixed region of an electron transport compound and an reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant is preferably 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; 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 electroluminescent layers and emitting white light.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, and flow coating methods can be used.
  • 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.
  • An OLED device was produced using the organic electroluminescent compound according to the present invention.
  • a transparent electrode indium tin oxide (ITO) thin film (10 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) device (Geomatec, Japan) was subjected to an ultrasonic washing with acetone and isopropan alcohol, sequentially, and then was stored in isopropan alcohol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • N 1 ,N 1' -([1,1'-biphenyl]-4,4'-diyl)bis(N 1 -(naphthalen-1-yl)-N 4 ,N 4 -diphenylbenzen-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
  • compound C-58 was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, 9-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9'-phenyl-9H,9'H-3,3'-bicarbazole was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-1 was introduced into another cell as a dopant.
  • the two materials were evaporated at different rates and were deposited in a doping amount of 15 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, 2-(4-(9,10-di(naphthalene-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was introduced into one cell and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rate and were deposited in a doping amount of 50 wt% each to form an electron transport layer having a thickness of 30 nm on the light-emitting layer.
  • an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer.
  • All the materials used for producing the OLED device were purified by vacuum sublimation at 10 -6 torr prior to use.
  • the produced OLED device showed a green emission having a luminance of 1000 cd/m 2 and a current density of 2.0 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound C-43 to form a hole transport layer in a thickness of 20 nm; and introducing 9-(4-([1,1'-biphenyl]-4-yl)quinazolin-2-yl)-9'-phenyl-9H,9'H-3,3'-bicarbazole into one cell of the vacuum vapor depositing apparatus as a host, introducing compound D-87 into another cell as a dopant, and evaporating the two materials at different rates and depositing them 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 30 nm on the hole transport layer.
  • the produced OLED device showed a red emission having a luminance of 2100 cd/m 2 and a current density of 14.4 mA/cm 2 .
  • Comparative Example 1 Production of an OLED device comprising a
  • An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound R-1 as above to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a green emission having a luminance of 2200 cd/m 2 and a current density of 27.5 mA/cm 2 .
  • Comparative Example 2 Production of an OLED device comprising a
  • An OLED device was produced in the same manner as in Device Example 2, except for evaporating compound R-1 as above to form a hole transport layer in a thickness of 20 nm.
  • the produced OLED device showed a red emission having a luminance of 100 cd/m 2 and a current density of 2.0 mA/cm 2 .
  • an organic electroluminescent device using the organic electroluminescent compound according to the present invention has excellent luminous and lifespan characteristics.

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Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. By using the organic electroluminescent compound according to the present invention, an organic electroluminescent device can have a long lifespan and an improvement in current and power efficiencies.

Description

ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present invention relates to organic electroluminescent compounds and organic electroluminescent device comprising the same.
An electroluminescent device (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 for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
The most important factor determining luminous efficiency in an organic EL device is the light-emitting material. Until now, fluorescent materials have been widely used as a light-emitting material. However, in view of electroluminescent mechanisms, since phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, development of phosphorescent light-emitting materials are widely being researched. Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C3’)iridium(acetylacetonate) ((acac)Ir(btp)2), tris(2-phenylpyridine)iridium (Ir(ppy)3) and bis(4,6-difluorophenylpyridinato-N,C2)picolinate iridium (Firpic) as red, green and blue materials, respectively.
At present, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known phosphorescent host materials. Recently, Pioneer (Japan) et al. developed a high performance organic EL device using bathocuproine (BCP) and aluminum(III)bis(2-methyl-8-quinolinate)(4-phenylphenolate) (BAlq) etc. as host materials, which were known as hole blocking layer materials.
Though these materials provide good light-emitting characteristics, they have the following disadvantages: (1) Due to their low glass transition temperature and poor thermal stability, their degradation may occur during a high-temperature deposition process in a vacuum, and the lifespan of the device decreases. (2) The power efficiency of an organic EL device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage. Although an organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) than one comprising fluorescent materials, a significantly high driving voltage is necessary. Thus, there is no merit in terms of power efficiency (lm/W). (3) Further, the operational lifespan of an organic EL device is short and luminous efficiency is still required to be improved.
Meanwhile, in order to enhance its efficiency and stability, an organic EL device has a structure of a multilayer comprising a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. The selection of a compound comprised in the hole transport layer is known as a method for improving the characteristics of a device such as hole transport efficiency to the light-emitting layer, luminous efficiency, lifespan, etc.
In this regard, copper phthalocyanine (CuPc), 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (MTDATA), etc. were used as a hole injection and transport material. However, an organic EL device using these materials is problematic in quantum efficiency and operational lifespan. It is because, when an organic EL device is driven under high current, thermal stress occurs between an anode and the hole injection layer. Thermal stress significantly reduces the operational lifespan of the device. Further, since the organic material used in the hole injection layer has very high hole mobility, the hole-electron charge balance may be broken and quantum yield (cd/A) may decrease. Therefore, a hole transport and injection layer for improving durability of an organic EL device still needs to be developed.
Korean Patent Appln. Laying-Open No. 10-2012-025984 discloses a compound in which the 9-position of a fluorene is bonded to dibenzothiophene or dibenzofuran, as a hole injection material or a hole transport material. However, the above reference does not disclose a compound in which the 9-position of a fluorene is bonded to dibenzothiophene, dibenzofuran, or fluorene, and carbazole.
The objective of the present invention is to provide i) an organic electroluminescent compound having high luminous efficiency, and ii) an organic electroluminescent device comprising the compound having long operational lifespan and improved power and current efficiencies.
The present inventors found that the above objective can be achieved by an organic electroluminescent compound represented by the following formula 1:
Figure PCTKR2014012891-appb-I000001
wherein
Ar1 represents a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; or may be linked to an adjacent substituent(s) to form a (C3-C30), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene;
X represents -O-, -S-, or -C(R7)(R8)-;
R1 to R6, each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, 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, -SiR11R12R13, -SR14, -OR15, -COR16, or -B(OR17)(OR18); 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 nitrogen, oxygen, and sulfur;
R7 to R18, each independently, represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted, (C3-C30), mono- or polycyclic, alicyclic or aromatic ring;
a, b, c, and f, each independently, represent an integer of 0 to 4; where a, b, c, or f represents an integer of 2 or more, each of R1, R2, R3, or R6 may be the same or different;
d and e, each independently, represent an integer of 0 to 3; where d or e represents an integer of 2 or more, each of R4 or R5 may be the same or different; and
the heterocycloalkyl and the heteroaryl(ene), each independently, contain at least one hetero atom selected from B, N, O, S, P(=O), Si, and P.
By using the organic electroluminescent compound according to the present invention, it is possible to manufacture an organic electroluminescent device having excellent current and luminous efficiencies.
Hereinafter, the present invention will be described in detail. However, the following description is intended to explain the invention, and is not meant in any way to restrict the scope of the invention.
The present invention relates to an organic electroluminescent compound of formula 1, an organic electroluminescent material comprising the compound, and an organic electroluminescent device comprising the material.
The organic electroluminescent compound represented by the above formula 1 will be described in detail.
Herein, “alkyl” includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; “alkenyl” includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.; “alkynyl” includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.; “cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; “(3- to 7- membered)heterocycloalkyl” is a cycloalkyl having 3 to 7 ring backbone atoms including at least one heteroatom selected from B, N, O, S, P(=O), Si, and P, preferably O, S, and N, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc.; “aryl(ene)” is a monocyclic or fused ring derived from an aromatic hydrocarbon, and includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.; “(3- to 30-membered)heteroaryl(ene)” is an aryl having 3 to 30 ring backbone atoms including at least one, preferably 1 to 4 heteroatom selected from the group consisting of B, N, O, S, P(=O), Si, and P; is 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 including furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, bipyridyl, pyrazinyl, pyrimidyl, pyridazinyl, etc., and a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, naphthofuranyl, naphthothiophenyl, benzonaphthofuranyl, benzonaphthothiophenyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indolinyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, indolocarbazolyl, etc. Further, “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. The substituents of the substituted (C1-C30)alkyl, the substituted (C2-C30)alkenyl, the substituted (C2-C30)alkynyl, the substituted (C1-C30)alkoxy, the substituted (C3-C30)cycloalkyl, the substituted (C3-C30)cycloalkenyl, the substituted (3- to 7- membered)heterocycloalkyl, the substituted (C6-C30)aryl(ene), the substituted (3- to 30- membered)heteroaryl(ene), and the substituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring in Ar1, L1, and R1 to R18 each independently are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C6-C30)aryl unsubstituted or substituted with a (3- to 30-membered)heteroaryl, 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, and preferably each independently are at least one selected from the group consisting of a (C1-C30)alkyl and a (C6-C21)aryl.
In formula 1 above, Ar1 preferably represents a substituted or unsubstituted (C1-C20)alkyl, or a substituted or unsubstituted (C6-C21)aryl; more preferably represents a substituted or unsubstituted (C6-C18)aryl; and even more preferably represents a (C6-C18)aryl unsubstituted or substituted with a (C6-C18)aryl. Specifically, Ar1 may represent phenyl, naphthyl, phenanthrenyl, or biphenyl, each may be substituted with phenyl or naphthyl; and more specifically, phenyl, naphthyl-substituted phenyl, naphthyl, phenyl-substituted naphthyl, phenanthrenyl, or biphenyl.
L1 preferably represents a single bond, a substituted or unsubstituted (C6-C21)arylene, or a substituted or unsubstituted (3- to 21-membered)heteroarylene. Specifically, L1 may represent a single bond.
X preferably represents -O-, -S-, or -C(R7)(R8)-, wherein R7 and R8, each independently, may represent a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered)heteroaryl; and more preferably, X represents -O-, -S-, or -C(R7)(R8)-, wherein R7 and R8, each independently, may represent an unsubstituted (C1-C10)alkyl, or an unsubstituted (C6-C18)aryl. Specifically, X may represent -O-, -S-, -C(CH3)(CH3)-, or -C(C6H5)(C6H5)-.
R1 to R6, each independently, preferably represent hydrogen, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C21)aryl, a substituted or unsubstituted (5- to 21-membered)heteroaryl, or a di(C6-C21)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted, (C5-C21), mono- or polycyclic aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur. More preferably, R4 and R5, each independently, represent a substituted or unsubstituted (C1-C10)alkyl; and R1, R2, R3, and R6, each independently, represent an unsubstituted (C6-C18)aryl, or a (6- to 18-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl; or may be linked to an adjacent substituent(s) to form a (C6-C18), mono- or polycyclic aromatic ring unsubstituted or substituted with a (C6-C12)aryl, whose carbon atom may be replaced with one (1) nitrogen. Specifically, R1, R2, R3, and R6, each independently, may represent phenyl, or phenyl-substituted carbazole; or may be linked to an adjacent substituent(s) to form a phenyl- or naphthyl-substituted indole ring.
a, b, c, d, e, and f, each independently, preferably represent an integer of 0 to 2; more preferably, a, b, c, and f, each independently, represent an integer of 0 to 2, and e and d, each independently, represent an integer of 0 or 1; and even more preferably, a, b, c, and f, each independently, represent an integer of 0 or 1, and e and d, each independently, represent 0. Specifically, a, b, d, e, and f may represent 0, and c may represent an integer of 0 or 1.
According to one embodiment of the present invention, in formula 1 above, Ar1 represents a substituted or unsubstituted (C1-C20)alkyl, or a substituted or unsubstituted (C6-C21)aryl; L1 represents a single bond, a substituted or unsubstituted (C6-C21)arylene, or a substituted or unsubstituted (3- to 21-membered)heteroarylene; X represents -O-, -S-, or -C(R7)(R8)-, wherein R7 and R8, each independently, represent a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered)heteroaryl; R1 to R6, each independently, represent hydrogen, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C21)aryl, a substituted or unsubstituted (5- to 21-membered)heteroaryl, or a di(C6-C21)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted, (C5-C21), mono- or polycyclic aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; a, b, c, d, e, and f, each independently, represent an integer of 0 to 2; where a, b, c, d, e, or f represents 2, each of R1, R2, R3, R4, R5, or R6 may be the same or different; and the heteroaryl(ene) contains at least one hetero atom selected from N, O, and S.
According to another embodiment of the present invention, in formula 1 above, Ar1 represents a substituted or unsubstituted (C6-C18)aryl; L1 represents a single bond; X represents -O-, -S-, or -C(R7)(R8)-, wherein R7 and R8, each independently, represent a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered)heteroaryl; R1 to R6, each independently, represent an unsubstituted (C6-C18)aryl, or a (6- to 18-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl; or may be linked to an adjacent substituent(s) to form a (C6-C18), mono- or polycyclic aromatic ring unsubstituted or substituted with a (C6-C12)aryl, whose carbon atom may be replaced with one (1) nitrogen; a, b, c, and f, each independently, represent an integer of 0 to 2; e and d, each independently, represent an integer of 0 or 1; where a, b, c, or f represents 2, each of R1, R2, R3, or R6 may be the same or different; and the heteroaryl contains one or two hetero atom(s) selected from N, O, and S.
According to another embodiment of the present invention, the compound of formula 1 can be represented by the following formula 2:
Figure PCTKR2014012891-appb-I000002
wherein Ar1, L1, X, R1 to R6, a, b, d, e, and f are as defined in formula 1.
In formula 2 above, Ar2 represents a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; or may be linked to an adjacent substituent(s) to form a (C3-C30), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur. Ar2 preferably represents a substituted or unsubstituted (C1-C20)alkyl, or a substituted or unsubstituted (C6-C21)aryl; more preferably represents a (C6-C18)aryl unsubstituted or substituted with a (C1-C10)alkyl; and even more preferably represents an unsubstituted (C6-C12)aryl. Specifically, Ar2 may represent phenyl or naphthyl.
In formula 2 above, R21 and R22, each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, 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, -SiR11R12R13, -SR14, -OR15, -COR16, or -B(OR17)(OR18); 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 nitrogen, oxygen, and sulfur; and R9 to R18, each independently, represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl. R21 and R22, each independently, preferably represent hydrogen, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered)heteroaryl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted, (C5-C21), mono- or polycyclic, aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; and more preferably represent a (C1-C10)alkyl unsubstituted or substituted with a (C6-C12)aryl, an unsubstituted (C6-C18)aryl, or a (6- to 18-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl; or may be linked to an adjacent substituent(s) to form a (C6-C18), mono- or polycyclic, aromatic ring unsubstituted or substituted with a (C6-C12)aryl whose carbon atom(s) may be replaced with one (1) nitrogen.
In formula 2 above, g represents an integer of 0 to 4; c and h, each independently, represent an integer of 0 to 3; where c, g, or h represents an integer of 2 or more, each of R3, R21, or R22 may be the same or different. Preferably, g represents an integer of 0 to 2, and c and h, each independently, represent 0 or 1. Specifically, c, g, and h may represent 0.
According to another embodiment of the present invention, the compound of formula 1 can be represented by the following formula 3:
Figure PCTKR2014012891-appb-I000003
wherein L1, X, Ar1, R1, R2, R4 to R6, a, b, d, e, and f are as defined in formula 1; A
Figure PCTKR2014012891-appb-I000004
.
In formula 3 above, Ar3 represents a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; or may be linked to an adjacent substituent(s) to form a (C3-C30), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur. Ar3 preferably represents a substituted or unsubstituted (C1-C20)alkyl, or a substituted or unsubstituted (C6-C21)aryl; more preferably represents a (C6-C18)aryl unsubstituted or substituted with a (C1-C10)alkyl; and even more preferably represents an unsubstituted (C6-C12)aryl. Specifically, Ar3 may represent phenyl or naphthyl.
In formula 3 above, R23 represents hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, 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, -SiR11R12R13, -SR14, -OR15, -COR16, or -B(OR17)(OR18); and R9 to R18, each independently, represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl. R23 preferably represents hydrogen, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered)heteroaryl; and more preferably represent a (C1-C10)alkyl unsubstituted or substituted with a (C6-C12)aryl, an unsubstituted (C6-C18)aryl, or a (6- to 18-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl.
In formula 3 above, i represents an integer of 0 to 4; c represents an integer of 0 to 2; where c or i represents an integer of 2 or more, each of R3 or R23 may be the same or different. Preferably, i represents an integer of 0 to 2, and c represents 0 or 1. Specifically, i represents 0 or 1, and c represents 0.
The specific compounds of the present invention include the following compounds, but are not limited thereto:
Figure PCTKR2014012891-appb-I000005
Figure PCTKR2014012891-appb-I000006
Figure PCTKR2014012891-appb-I000007
Figure PCTKR2014012891-appb-I000008
Figure PCTKR2014012891-appb-I000009
Figure PCTKR2014012891-appb-I000010
Figure PCTKR2014012891-appb-I000011
Figure PCTKR2014012891-appb-I000012
Figure PCTKR2014012891-appb-I000013
Figure PCTKR2014012891-appb-I000014
Figure PCTKR2014012891-appb-I000015
Figure PCTKR2014012891-appb-I000016
Figure PCTKR2014012891-appb-I000017
Figure PCTKR2014012891-appb-I000018
The organic electroluminescent compound of the present invention preferably has a molecular weight of 1000 or less, more preferably 950 or less, more preferably 925 or less, and even more preferably 900 or less. By having the molecular weight as above, thermal decomposition of the compound during deposition by sublimation can be decreased or removed.
In addition, the organic electroluminescent compound of the present invention preferably has a glass transition temperature of 90°C or more, and more preferably 110°C or more. By having the glass transition temperature as above, the compound can have excellent thermal stability.
The organic electroluminescent compounds of the present invention can be prepared by a synthetic method known to a person skilled in the art. For example, they can be prepared according to the following reaction schemes.
[Reaction Scheme 1]
Figure PCTKR2014012891-appb-I000019
wherein R1 to R6, X, Ar1, L1, and a to f are as defined in formula 1 above.
[Reaction Scheme 2]
Figure PCTKR2014012891-appb-I000020
wherein R1 to R6, R21, R22, X, Ar1, Ar2, L1, and a to h are as defined in formula 2 above, and Hal represents a halogen.
[Reaction Scheme 3]
Figure PCTKR2014012891-appb-I000021
wherein A, B, C, R1, R2, R4 to R6, X, Ar1, L1, a, b, and d to f are as defined in formula 3 above.
The present invention provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
The above material can be comprised of the organic electroluminescent compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescent materials.
The organic electroluminescent device comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes. The organic layer may comprise at least one organic electroluminescent compound of formula 1.
One of the first and second electrodes can be an anode, and the other can be a cathode. The organic layer comprises a light-emitting layer, and may further comprise at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
The organic electroluminescent compound according to the present invention can be comprised in at least one of the light-emitting layer and the hole transport layer. Where used in the hole transport layer, the organic electroluminescent compound of the present invention can be comprised as a hole transport material. Where used in the light-emitting layer, the organic electroluminescent compound of the present invention can be comprised as a host material.
The organic electroluminescent device comprising the organic electroluminescent compound of the present invention can further comprise one or more compounds other than the organic electroluminescent compound according to the present invention as host materials, and can further comprise one or more dopants.
Where the organic electroluminescent compound according to the present invention is comprised as a host material (first host material), the other compound may be comprised as a second host material. Herein, the weight ratio of the first host material to the second host material is in the range of 1:99 to 99:1.
The host material other than the organic electroluminescent compound according to the present invention can be from any of the known fluorescent or phosphorescent hosts, preferably phosphorescent hosts in terms of luminous efficiency. Specifically, the phosphorescent host selected from the group consisting of the compounds of formulae 11 to 13 below is preferable in terms of luminous efficiency.
Figure PCTKR2014012891-appb-I000022
Figure PCTKR2014012891-appb-I000023
Figure PCTKR2014012891-appb-I000024
wherein Cz represents the following structure;
Figure PCTKR2014012891-appb-I000025
R31 to R34 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted of unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, or -SiR35R36R37;
R35 to R37 each independently represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
L4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene;
M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl;
Y1 and Y2 each independently represent -O-, -S-, -N(R41)-, or -C(R42)(R43)-, provided that Y1 and Y2 do not simultaneously exist;
R41 to R43 each independently represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl, and R42 and R43 may be the same or different;
m and n each independently represent an integer of 1 to 3;
j, k, p, and q each independently represent an integer of 0 to 4; and
where m, n, j, k, p or q is an integer of 2 or more, each of (Cz-L4), each of (Cz), each of R31, each of R32, each of R33, or each of R34 may be the same or different.
Specifically, preferable examples of the host material are as follows:
Figure PCTKR2014012891-appb-I000026
Figure PCTKR2014012891-appb-I000027
Figure PCTKR2014012891-appb-I000028
Figure PCTKR2014012891-appb-I000029
Figure PCTKR2014012891-appb-I000030
Figure PCTKR2014012891-appb-I000031
Figure PCTKR2014012891-appb-I000032
Figure PCTKR2014012891-appb-I000033
Figure PCTKR2014012891-appb-I000034
Figure PCTKR2014012891-appb-I000035
Figure PCTKR2014012891-appb-I000036
Figure PCTKR2014012891-appb-I000037
Figure PCTKR2014012891-appb-I000038
Figure PCTKR2014012891-appb-I000039
Figure PCTKR2014012891-appb-I000040
Figure PCTKR2014012891-appb-I000041
Figure PCTKR2014012891-appb-I000042
Figure PCTKR2014012891-appb-I000043
[wherein TPS represents triphenylsilyl]
The dopant comprised in the organic electroluminescent device according to the present invention is preferably at least one phosphorescent dopant. The dopant materials applied to the organic electroluminescent device according to the present invention are not limited, but may be preferably selected from metallated complex compounds of iridium, osmium, copper and platinum, more preferably selected from ortho-metallated complex compounds of iridium, osmium, copper and platinum, and even more preferably ortho-metallated iridium complex compounds.
The phosphorescent dopants may be preferably selected from compounds represented by the following formulae 101 to 103.
Figure PCTKR2014012891-appb-I000044
Figure PCTKR2014012891-appb-I000045
Figure PCTKR2014012891-appb-I000046
wherein L is selected from the following structures:
Figure PCTKR2014012891-appb-I000047
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(s); a cyano; a substituted or unsubstituted (C1-C30)alkoxy; a substituted or unsubstituted (C6-C30)aryl; or a substituted or unsubstituted (C3-C30)cycloalkyl; R106 to R109 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g. fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl; and R120 to R123 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g. quinoline unsubstituted or substituted with a halogen, 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; and R124 to R127 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g. fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl;
R201 to R211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl, and R208 to R211 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, e.g. fluorene unsubstituted or substituted with alkyl, dibenzothiophene unsubstituted or substituted with alkyl, or dibenzofuran unsubstituted or substituted with alkyl;
r and s each independently represent an integer of 1 to 3; where r or s is an integer of 2 or more, each of R100 may be the same or different; and
t represents an integer of 1 to 3.
Specifically, the phosphorescent dopant materials include the following:
Figure PCTKR2014012891-appb-I000048
Figure PCTKR2014012891-appb-I000049
Figure PCTKR2014012891-appb-I000050
Figure PCTKR2014012891-appb-I000051
Figure PCTKR2014012891-appb-I000052
Figure PCTKR2014012891-appb-I000053
Figure PCTKR2014012891-appb-I000054
Figure PCTKR2014012891-appb-I000055
Figure PCTKR2014012891-appb-I000056
Figure PCTKR2014012891-appb-I000057
Figure PCTKR2014012891-appb-I000058
Figure PCTKR2014012891-appb-I000059
Figure PCTKR2014012891-appb-I000060
Figure PCTKR2014012891-appb-I000061
Figure PCTKR2014012891-appb-I000062
Figure PCTKR2014012891-appb-I000063
Figure PCTKR2014012891-appb-I000064
Figure PCTKR2014012891-appb-I000065
Figure PCTKR2014012891-appb-I000066
Figure PCTKR2014012891-appb-I000067
Figure PCTKR2014012891-appb-I000068
Figure PCTKR2014012891-appb-I000069
Figure PCTKR2014012891-appb-I000070
Figure PCTKR2014012891-appb-I000071
Figure PCTKR2014012891-appb-I000072
Figure PCTKR2014012891-appb-I000073
In another embodiment of the present invention, a composition for preparing an organic electroluminescent device is provided. The composition comprises the compound according to the present invention as a host material or a hole transport material.
In addition, the organic electroluminescent device according to the present invention comprises a first electrode; a second electrode; and at least one organic layer between the first and second electrodes. The organic layer comprises a light-emitting layer, and the light-emitting layer may comprise the composition for preparing the organic electroluminescent device according to the present invention.
The organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compound represented by formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device according to the present invention, 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 d-transition elements of the Periodic Table, or at least one complex compound comprising said metal. The organic layer may further comprise a light-emitting layer and a charge generating layer.
In addition, the organic electroluminescent device according to the present invention may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound or a green electroluminescent compound known in the field, besides the compound according to the present invention. Also, if needed, a yellow or orange light-emitting layer can be comprised in the device.
According to the present invention, at least one layer (hereinafter, "a surface layer”) is preferably 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, said chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; said metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and said metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In the organic electroluminescent device according to the present invention, a mixed region of an electron transport compound and an reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant is preferably 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. Further, 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 electroluminescent layers and emitting white light.
In order to form each layer of the organic electroluminescent device according to the present invention, dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as spin coating, dip coating, and flow coating methods can be used.
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.
Hereinafter, the organic electroluminescent compound, the preparation method of the compound, and the luminescent properties of the device will be explained in detail with reference to the following examples.
Example 1: Preparation of compound C-43
Preparation of compound 1-1
Figure PCTKR2014012891-appb-I000074
After dissolving 3-bromo-N-phenylcarbazole 9.3 g (28.70 mmol) and 9-(dibenzo[b,d]furan-4-yl)-9H-fluoren-9-ol 10 g (28.70 mmol) in dichloromethane 150mL in a reaction container, Eaton’s reagent 0.6 mL (0.9 M, 0.57 mmol) was slowly added dropwise to the mixture. After stirring the mixture for 30 minutes at room temperature, the reaction was completed with sodium hydrogen carbonate, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 1-1 (17 g, 90%).
Preparation of compound C-43
Figure PCTKR2014012891-appb-I000075
After introducing compound 1-1 10 g (15.32 mmol), N-phenylcarbazol-3-boronic acid 4.8 g (16.86 mmol), tetrakis(triphenylphosphine)palladium 0.5 g (0.46 mmol), sodium carbonate 4.1 g (38.30 mmol), toluene 76 mL, and ethanol 19 mL in a reaction container, distilled water 19 mL was added to the mixture, and the mixture was stirred at 120°C for 4 hours. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound C-43 (2.7 g, 22%).
UV=364 nm, PL=409 nm, melting point (MP)=236°C
molecular weight (MW)=814.97, glass transition temperature (Tg)=195°C
Example 2: Preparation of compound C-58
Figure PCTKR2014012891-appb-I000076
Preparation of compound 2-1
After introducing 2-bromocarbazole 100 g (0.406 mol), iodobenzene 166 g (0.813 mol), copper iodide 38.7 g (0.203 mol), ethylenediamine 27 mL (0.406 mol), cesium carbonate 265 g (0.813 mol), and toluene 1.3 L in a reaction container, the mixture was stirred under reflux for 3 hours. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 2-1 (116 g, 90%).
Preparation of compound 2-2
After introducing compound 2-1 116 g (0.362 mol), 2-chloroaniline 56 mL (0.542 mol), palladium(II)acetate 3.4 g (0.015 mol), tri-t-butyl phosphine 15 mL (50%, 0.030 mol), sodium tert-butoxide 87 g (0.905 mol), and toluene 1 L in a reaction container, the mixture was stirred under reflux for 5 hours. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 2-2 (75 g, 56%).
Preparation of compound 2-3
After introducing compound 2-2 75 g (203.33 mmol), palladium(II)acetate 2.3 g (10.17 mmol), tricyclohexylphosphine tetrafluoroborate 7.5 g (20.33 mmol), cesium carbonate 199 g (609.99 mmol), and N,N-dimethylacetamide 1 L in a reaction container, the mixture was stirred for 5 hours at 190°C. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 2-3 (30 g, 44%).
Preparation of compound 2-4
After introducing compound 2-3 10 g (30.08 mmol), iodobenzene 5 mL (45.12 mmol), copper iodide 2.8 g (15.04 mmol), diaminocyclohexane 7.2 mL (60.16 mmol), cesium carbonate 19.6 g (60.16 mmol), and xylene 150 mL in a reaction container, the mixture was stirred under reflux for 4 hours. After the reaction, the mixture was washed with distilled water, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 2-4 (11 g, 89%).
Preparation of compound C-58
After dissolving compound 2-4 8 g (19.58 mmol), 9-(dibenzo[b,d]furan-4-yl)-9H-fluoren-9-ol 4.2 g (12.03 mmol) in dichloromethane 60mL in a reaction container, Eaton’s reagent 0.3 mL (0.9 M, 0.24 mmol) was slowly added dropwise to the mixture. After stirring the mixture for 30 minutes at room temperature, the reaction was completed with sodium hydrogen carbonate, and an organic layer was extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound C-58 (2.7 g, 30%).
UV=344 nm, PL=393 nm, MP=305°C, MW=738.87, Tg=208°C
Device Example 1: Production of an OLED device comprising the organic
electroluminescent compound according to the present invention
An OLED device was produced using the organic electroluminescent compound according to the present invention. A transparent electrode indium tin oxide (ITO) thin film (10 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) device (Geomatec, Japan) was subjected to an ultrasonic washing with acetone and isopropan alcohol, sequentially, and then was stored in isopropan alcohol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus. N1,N1'-([1,1'-biphenyl]-4,4'-diyl)bis(N1-(naphthalen-1-yl)-N4,N4-diphenylbenzen-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the above introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. Then, compound C-58 was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, 9-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9'-phenyl-9H,9'H-3,3'-bicarbazole was introduced into one cell of the vacuum vapor depositing apparatus, as a host material, and compound D-1 was introduced into another cell as a dopant. The two materials were evaporated at different rates and were deposited in a doping amount of 15 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, 2-(4-(9,10-di(naphthalene-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was introduced into one cell and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rate and were deposited in a doping amount of 50 wt% each to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. Then, after depositing lithium quinolate as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the materials used for producing the OLED device were purified by vacuum sublimation at 10-6 torr prior to use.
The produced OLED device showed a green emission having a luminance of 1000 cd/m2 and a current density of 2.0 mA/cm2.
Device Example 2: Production of an OLED device comprising the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound C-43 to form a hole transport layer in a thickness of 20 nm; and introducing 9-(4-([1,1'-biphenyl]-4-yl)quinazolin-2-yl)-9'-phenyl-9H,9'H-3,3'-bicarbazole into one cell of the vacuum vapor depositing apparatus as a host, introducing compound D-87 into another cell as a dopant, and evaporating the two materials at different rates and depositing them 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 30 nm on the hole transport layer.
The produced OLED device showed a red emission having a luminance of 2100 cd/m2 and a current density of 14.4 mA/cm2.
Comparative Example 1: Production of an OLED device comprising a
conventional organic electroluminescent compound
Figure PCTKR2014012891-appb-I000077
An OLED device was produced in the same manner as in Device Example 1, except for evaporating compound R-1 as above to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a green emission having a luminance of 2200 cd/m2 and a current density of 27.5 mA/cm2.
Comparative Example 2: Production of an OLED device comprising a
conventional organic electroluminescent compound
An OLED device was produced in the same manner as in Device Example 2, except for evaporating compound R-1 as above to form a hole transport layer in a thickness of 20 nm.
The produced OLED device showed a red emission having a luminance of 100 cd/m2 and a current density of 2.0 mA/cm2.
It is verified that the luminous characteristics of the organic electroluminescent compound according to the present invention is superior to the conventional materials. In addition, an organic electroluminescent device using the organic electroluminescent compound according to the present invention has excellent luminous and lifespan characteristics.

Claims (8)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2014012891-appb-I000078
    wherein
    Ar1 represents a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; or may be linked to an adjacent substituent(s) to form a (C3-C30), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
    L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene;
    X represents -O-, -S-, or -C(R7)(R8)-;
    R1 to R6, each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, 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, -SiR11R12R13, -SR14, -OR15, -COR16, or -B(OR17)(OR18); 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 nitrogen, oxygen, and sulfur;
    R7 to R18, each independently, represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted, (C3-C30), mono- or polycyclic, alicyclic or aromatic ring;
    a, b, c, and f, each independently, represent an integer of 0 to 4; where a, b, c, or f represents an integer of 2 or more, each of R1, R2, R3, or R6 may be the same or different;
    d and e, each independently, represent an integer of 0 to 3; where d or e represents an integer of 2 or more, each of R4 or R5 may be the same or different; and
    the heterocycloalkyl and the heteroaryl(ene), each independently, contain at least one hetero atom selected from B, N, O, S, P(=O), Si, and P.
  2. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted (C1-C30)alkyl, the substituted (C2-C30)alkenyl, the substituted (C2-C30)alkynyl, the substituted (C1-C30)alkoxy, the substituted (C3-C30)cycloalkyl, the substituted (C3-C30)cycloalkenyl, the substituted (3- to 7-membered)heterocycloalkyl, the substituted (C6-C30)aryl(ene), the substituted (3- to 30-membered)heteroaryl(ene), and the substituted (C3-C30), mono- or polycyclic, alicyclic or aromatic ring in Ar1, L1, and R1 to R18, each independently, are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C6-C30)aryl unsubstituted or substituted with a (3- to 30-membered)heteroaryl, 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.
  3. The organic electroluminescent compound according to claim 1, wherein
    Ar1 represents a substituted or unsubstituted (C1-C20)alkyl, or a substituted or unsubstituted (C6-C21)aryl;
    L1 represents a single bond, a substituted or unsubstituted (C6-C21)arylene, or a substituted or unsubstituted (3- to 21-membered)heteroarylene;
    X represents -O-, -S-, or -C(R7)(R8)-, wherein R7 and R8, each independently, represent a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered)heteroaryl;
    R1 to R6, each independently, represent hydrogen, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C21)aryl, a substituted or unsubstituted (5- to 21-membered)heteroaryl, or a di(C6-C21)arylamino; or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted, (C5-C21), mono- or polycyclic aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
    a, b, c, d, e, and f, each independently, represent an integer of 0 to 2; where a, b, c, d, e, or f represents 2, each of R1, R2, R3, R4, R5, or R6 may be the same or different; and
    the heteroaryl(ene) contains at least one hetero atom selected from N, O, and S.
  4. The organic electroluminescent compound according to claim 1, wherein
    Ar1 represents a substituted or unsubstituted (C6-C18)aryl;
    L1 represents a single bond;
    X represents -O-, -S-, or -C(R7)(R8)-, wherein R7 and R8, each independently, represent a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered)heteroaryl;
    R1 to R6, each independently, represent an unsubstituted (C6-C18)aryl, or a (6- to 18-membered)heteroaryl unsubstituted or substituted with a (C6-C12)aryl; or may be linked to an adjacent substituent(s) to form a (C6-C18), mono- or polycyclic aromatic ring unsubstituted or substituted with a (C6-C12)aryl, whose carbon atom may be replaced with one (1) nitrogen;
    a, b, c, and f, each independently, represent an integer of 0 to 2; e and d, each independently, represent an integer of 0 or 1; where a, b, c, or f represents 2, each of R1, R2, R3, or R6 may be the same or different; and
    the heteroaryl contains one or two hetero atom(s) selected from N, O, and S.
  5. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is represented by the following formula 2:
    Figure PCTKR2014012891-appb-I000079
    wherein
    Ar1, L1, X, R1 to R6, a, b, d, e, and f are as defined in claim 1;
    Ar2 represents a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; or may be linked to an adjacent substituent(s) to form a (C3-C30), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
    R21 and R22, each independently, represent hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, 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, -SiR11R12R13, -SR14, -OR15, -COR16, or -B(OR17)(OR18); 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 nitrogen, oxygen, and sulfur;
    R9 to R18, each independently, represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
    g represents an integer of 0 to 4; c and h, each independently, represent an integer of 0 to 3; where c, g, or h represents an integer of 2 or more, each of R3, R21, or R22 may be the same or different; and
    the heterocycloalkyl and the heteroaryl(ene), each independently, contain at least one hetero atom selected from N, O, and S.
  6. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is represented by the following formula 3:
    Figure PCTKR2014012891-appb-I000080
    wherein
    L1, X, Ar1, R1, R2, R4 to R6, a, b, d, e, and f are as defined in claim 1; A
    Figure PCTKR2014012891-appb-I000081
    ;
    Ar3 represents a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; or may be linked to an adjacent substituent(s) to form a (C3-C30), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
    R23 represents hydrogen, deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, 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 (C1-C30)alkoxy, 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, -SiR11R12R13, -SR14, -OR15, -COR16, or -B(OR17)(OR18);
    R9 to R18, each independently, represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
    i represents an integer of 0 to 4; c represents an integer of 0 to 2; where c or i represents an integer of 2 or more, each of R3 or R23 may be the same or different; and
    the heterocycloalkyl and the heteroaryl(ene), each independently, represent at least one hetero atom selected from N, O, and S.
  7. The organic electroluminescent compound according to claim 1, wherein the compound is selected from the group consisting of:
    Figure PCTKR2014012891-appb-I000082
    Figure PCTKR2014012891-appb-I000083
    Figure PCTKR2014012891-appb-I000084
    Figure PCTKR2014012891-appb-I000085
    Figure PCTKR2014012891-appb-I000086
    Figure PCTKR2014012891-appb-I000087
    Figure PCTKR2014012891-appb-I000088
    Figure PCTKR2014012891-appb-I000089
    Figure PCTKR2014012891-appb-I000090
    Figure PCTKR2014012891-appb-I000091
    Figure PCTKR2014012891-appb-I000092
    Figure PCTKR2014012891-appb-I000093
    Figure PCTKR2014012891-appb-I000094
    Figure PCTKR2014012891-appb-I000095
  8. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
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CN111848414B (en) * 2020-07-30 2021-05-18 长春海谱润斯科技股份有限公司 Arylamine compound and organic electroluminescent device comprising same

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