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WO2018159970A1 - Organic electroluminescent device - Google Patents

Organic electroluminescent device Download PDF

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Publication number
WO2018159970A1
WO2018159970A1 PCT/KR2018/002357 KR2018002357W WO2018159970A1 WO 2018159970 A1 WO2018159970 A1 WO 2018159970A1 KR 2018002357 W KR2018002357 W KR 2018002357W WO 2018159970 A1 WO2018159970 A1 WO 2018159970A1
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WIPO (PCT)
Prior art keywords
substituted
unsubstituted
alkyl
aryl
membered
Prior art date
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PCT/KR2018/002357
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French (fr)
Inventor
Tae-Jin Lee
Jeong-Eun YANG
Dong-Hyung Lee
Sang-Hee Cho
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Rohm And Haas Electronic Materials Korea Ltd.
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Publication date
Priority claimed from KR1020180022906A external-priority patent/KR102690159B1/en
Application filed by Rohm And Haas Electronic Materials Korea Ltd. filed Critical Rohm And Haas Electronic Materials Korea Ltd.
Priority to US16/483,062 priority Critical patent/US11387417B2/en
Priority to CN201880011305.9A priority patent/CN110268542B/en
Priority to JP2019544041A priority patent/JP7109460B2/en
Publication of WO2018159970A1 publication Critical patent/WO2018159970A1/en

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Definitions

  • the present disclosure relates to an organic electroluminescent device comprising a light-emitting layer and a hole transport zone.
  • OLED organic electroluminescent device
  • TPD/Alq3 bilayer consisting of a light-emitting layer and a charge transport layer. Since then, the research on an OLED has been rapidly carried out, and it has been commercialized. At present, an OLED mainly uses phosphorescent materials having excellent luminous efficiency in panel implementation. Low driving voltage and high luminous efficiency are required for long lifespan and high resolution of display.
  • U.S. Patent No. 6,902,831 discloses an azulene derivative as an organic electroluminescent compound, but it does not specifically disclose an organic electroluminescent compound of a fused azulene derivative. In addition, the document does not specifically disclose that the performance of an OLED can be improved by combining a host compound containing a fused azulene derivative and a specific material contained in a hole transport zone.
  • the objective of the present disclosure is to provide an organic electroluminescent device having low driving voltage, high luminous efficiency and/or long lifespan properties by a combination of a light-emitting layer comprising a compound according to the present disclosure, and a hole transport zone comprising a compound having a specific HOMO (Highest Occupied Molecular Orbital) energy level.
  • a specific HOMO Highest Occupied Molecular Orbital
  • a light-emitting layer comprising a phosphorescent dopant is preferable to have a light-emitting material having excellent hole and electron current properties for low driving voltage, high efficiency, and long lifespan, and the material having the thermal stability for improvement of lifespan.
  • using a light-emitting material having a narrow energy band gap can contribute to improve driving voltage and luminous efficiency by minimizing the charge trap.
  • the azulene derivative comprised in the device of the present disclosure has a slow transition constant of the internal conversion of S 2 ⁇ S 1 , i.e. 7*10 -8 s, the transition constant of the internal conversion of S 1 ⁇ S 0 is fast, i.e.
  • the fluorescence quantum yield of S 2 ⁇ S 0 increases, and so the azulene derivative is one of the representative materials which violates Kasha's rule.
  • the levels of S 2 and S 1 of azulene are 3.565 eV and 1.771 eV, respectively, while the level difference of T 1 and S 0 is very small, i.e. the T 1 -S 0 transition is 1.711 eV.
  • the conventional hole transport zone has limitations in increasing the efficiency of the light-emitting layer comprising the fused azulene derivative compound.
  • a hole transport zone requires a compound having a high HOMO energy level in order to have a high hole mobility. If the HOMO energy level is high, the driving voltage decreases, but the efficiency of the light-emitting layer also decreases. On the contrary, if the HOMO energy level is low, the efficiency of the light-emitting layer increases, but the driving voltage also increases, and thus it is difficult to realize high luminous efficiency of the device.
  • the present inventors found that the above-mentioned problems can be solved by comprising a fused azulene derivative of the present disclosure in a light-emitting layer, and an arylamine derivative having a specific HOMO energy level of the present disclosure in a hole transport zone.
  • the present inventors found that the above objective can be achieved by an organic electroluminescent device comprising a first electrode, a second electrode facing the first electrode, a light-emitting layer between the first electrode and the second electrode, and a hole transport zone between the first electrode and the light-emitting layer, wherein the light-emitting layer comprises a compound represented by the following formula 1:
  • X 1 represents N-L-(Ar) a , S, or O,
  • L represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene,
  • Ar represents hydrogen, deuterium, a halogen, a cyano, 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 mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino,
  • Y 1 to Y 12 each independently, represent N or CR 1 ,
  • R 1 each independently, represents hydrogen, deuterium, a halogen, a cyano, 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 (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30
  • a represents an integer of 1 to 4, where if a is an integer of 2 or more, each of Ar may be the same or different;
  • the hole transport zone comprises an arylamine derivative
  • the HOMO energy level of the arylamine derivative satisfies the following equation 11:
  • an organic electroluminescent device having low driving voltage, high luminous efficiency and/or long lifespan properties can be provided. Also, it is possible to produce a display device or a lighting device by using the organic electroluminescent device of the present disclosure.
  • the organic electroluminescent device of the present disclosure comprises a first electrode, a second electrode facing the first electrode, a light-emitting layer between the first electrode and the second electrode, a hole transport zone between the first electrode and the light-emitting layer, and an electron transport zone between the light-emitting layer and the second electrode.
  • One of the first and second electrodes may be an anode, and the other may be a cathode.
  • the hole transport zone means a zone wherein holes are transported between the first electrode and the light-emitting layer.
  • the hole transport zone may comprise at least one of a hole injection layer, a hole transport layer, a hole auxiliary layer, a light-emitting auxiliary layer and an electron blocking layer.
  • the hole injection layer, the hole transport layer, the hole auxiliary layer, the light-emitting auxiliary layer and the electron blocking layer, respectively, may be a single layer, or a plurality of layers in which two or more layers are stacked.
  • the hole transport zone may comprise a first hole transport layer and a second hole transport layer, wherein the second hole transport layer may be at least one layer of a plurality of hole transport layers, and it may comprise at least one of a hole auxiliary layer, a light-emitting auxiliary layer and a electron blocking layer.
  • the hole transport zone may comprise a first hole transport layer and a second hole transport layer, wherein the first hole transport layer may be placed between the first electrode and the light-emitting layer, the second hole transport layer may be placed between the first hole transport layer and the light-emitting layer, and the second hole transport layer may serve as a hole transport layer, a light-emitting auxiliary layer, a hole auxiliary layer and/or an electron blocking layer.
  • the hole transport zone may comprise a p-doped hole injection layer, a hole transport layer, and a light-emitting auxiliary layer.
  • the p-doped hole injection layer means a hole injection layer doped with a p-dopant.
  • the p-dopant is a material capable of imparting p-type semiconductor properties.
  • the p-type semiconductor properties mean the properties of injecting or transporting holes at the HOMO energy level, i.e., the properties of materials having a high hole conductivity.
  • the hole transport layer may be placed between the anode (or the hole injection layer) and the light-emitting layer.
  • the hole transport layer may function to smoothly move the holes transferred from the anode to the light-emitting layer, and to block the electrons transferred from the cathode to remain in the light-emitting layer.
  • the light-emitting auxiliary layer may be placed between the anode and the light-emitting layer, or between the cathode and the light-emitting layer. When the light-emitting auxiliary layer is placed between the anode and the light-emitting layer, it can be used for promoting the hole injection and/or the hole transport, or for preventing the overflow of electrons.
  • the light-emitting auxiliary layer When the light-emitting auxiliary layer is placed between the cathode and the light-emitting layer, it can be used for promoting the electron injection and/or the electron transport, or for preventing the overflow of holes.
  • the hole auxiliary layer may be placed between the hole transport layer (or hole injection layer) and the light-emitting layer, and may be effective to promote or block the hole transport rate (or the hole injection rate), thereby enabling the charge balance to be controlled.
  • the electron blocking layer may be placed between the hole transport layer (or hole injection layer) and the light-emitting layer, and can confine the excitions within the light-emitting layer by blocking the overflow of electrons from the light-emitting layer to prevent a light-emitting leakage.
  • the further included hole transport layer may be used as a hole auxiliary layer or an electron blocking layer.
  • the light-emitting auxiliary layer, the hole auxiliary layer and/or the electron blocking layer may have an effect of improving the efficiency and/or the lifespan of the organic electroluminescent device.
  • the electron transport zone may comprise at least one of an electron buffer layer, a hole blocking layer, an electron transport layer and an electron injection layer, and preferably, at least one of an electron transport layer and an electron injection layer.
  • the electron buffer layer is a layer capable of improving the problem that light-emitting luminance deteriorates due to the change of current properties in the device when the device is exposed to a high temperature during a process of producing panels, and it can control the charge flow properties.
  • the light-emitting layer in which light is emitted, may be a single layer, or a plurality of layers in which two or more layers are stacked.
  • the doping concentration of the dopant compound with respect to the host compound of the light-emitting layer is preferably less than 20% by weight.
  • (C1-C30)alkyl is meant to be a linear or branched alkyl having 1 to 30 carbon atoms constituting the chain, in which the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert -butyl, etc.
  • (C3-C30)cycloalkyl is a mono- or polycyclic hydrocarbon having 3 to 30 ring backbone carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • (3- to 7-membered)heterocycloalkyl is a cycloalkyl having at least one heteroatom selected from the group consisting of B, N, O, S, Si, and P, preferably O, S, and N, and 3 to 7 ring backbone atoms, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc.
  • (C6-C30)aryl(ene) is a monocyclic or fused ring-type radical derived from an aromatic hydrocarbon having 6 to 30 ring backbone carbon atoms, in which the number of ring backbone carbon atoms is preferably 6 to 20, more preferably 6 to 15, may be partially saturated, 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 group having at least one, preferably 1 to 4 heteroatoms selected from the group consisting of B, N, O, S, Si, and P, and 3 to 30 ring backbone atoms, in which the number of ring backbone atoms is preferably 3 to 20, more preferably 5 to 15; 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,
  • substituted in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or functional group, i.e., a substituent.
  • the above substituents may be at least one selected from the group consisting of a methyl, a tert -butyl, a phenyl unsubstituted or substituted with a pyridinyl(s), a naphthyl, a biphenyl, a dimethylfluorenyl, a phenylfluorenyl, a diphenylfluorenyl, a phenanthrenyl, a triphenylenyl, a pyridinyl, a triazinyl substituted with a phenyl(s) and/or a naphthyl(s), an indolyl substituted with a diphenyl(s), a benzoimidazolyl substituted with a phenyl(s), a quinolyl, a quinazolinyl substituted with a phenyl(s), a carbazolyl, a dibenzofuranyl,
  • X 1 represents N-L-(Ar) a , S, or O.
  • L represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene; preferably, a single bond, a substituted or unsubstituted (C6-C25)arylene, or a substituted or unsubstituted (5- to 25-membered)heteroarylene; and more preferably, a single bond, an unsubstituted (C6-C18)arylene, or an unsubstituted (5- to 18-membered)heteroarylene, wherein the heteroarylene may comprise at least one of nitrogen, oxygen, and/or sulfur.
  • L may represent a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted pyridylene, a substituted or unsubstituted pyrimidinylene, a substituted or unsubstituted triazinylene, a substituted or unsubstituted quinazolinylene, a substituted or unsubstituted quinoxalinylene, a substituted or unsubstituted naphthyridinylene, a substituted or unsubstituted benzoquinazolinylene, a substituted or unsubstituted benzothienopyrimidinylene, a substituted or unsubstituted acenaphthopyrimidinylene, a substituted or unsubstituted
  • Ar represents hydrogen, deuterium, a halogen, a cyano, 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 mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; preferably, hydrogen, a substituted or unsubstituted (C6-C25)aryl, a substituted or unsubstituted (5- to 30-membered)heteroaryl, or a substituted or unsubstituted di(C6-C25)aryla
  • Ar may represent a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted benzoquinazolinyl, a substituted or unsubstituted quinoxalinyl, a substituted or unsubstituted benzoquinoxalinyl, a substituted or unsubstituted quinolyl, a substituted or unsubstituted benzoquinolyl, a substituted or unsubstituted iso
  • a represents an integer of 1 to 4, preferably, 1 or 2, where if a is an integer of 2 or more, each of Ar may be the same or different.
  • Y 1 to Y 12 each independently, represent N or CR 1 . According to one embodiment of the present disclosure, all of Y 1 to Y 12 may represent CR 1 , and according to another embodiment of the present disclosure, at least one of Y 1 to Y 12 may represent N. Where there are a plurality of R 1 ’s, each of R 1 may be the same or different.
  • R 1 each independently, represents hydrogen, deuterium, a halogen, a cyano, 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 (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30
  • R 1 may each independently represent hydrogen, a substituted or unsubstituted methyl, a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted quinoxalinyl, a substituted or unsubstituted phenylbiphenylamino, etc.
  • At least one adjacent pair of Y 1 to Y 12 in formula 1 are CR 1 , and the adjacent two R 1 ’s of CR 1 are fused together to each independently form a ring represented by any one of the following formulas 2 to 6, but is not limited thereto.
  • the formed ring may be a substituted or unsubstituted benzene ring, a naphthalene ring, a furan ring, a thiophene ring, a substituted or unsubstituted pyrrole ring, a pyridine ring, a benzofuran ring, a benzothiophene ring, a substituted or unsubstituted indole ring, a dibenzofuran ring, a dibenzothiophene ring, a substituted or unsubstituted carbazole ring, a phenanthrene ring, etc., including the ring of formulas 2 to 6.
  • A represents N or CR 2 . According to one embodiment of the present disclosure, A may all represent CR 2 , and according to another embodiment of the present disclosure, at least one of A may represent N. Where there are a plurality of R 2 ’s, each of R 2 may be the same or different.
  • R 2 each independently, represents hydrogen, deuterium, a halogen, a cyano, 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 (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30
  • R 3 represents hydrogen, deuterium, a halogen, a cyano, 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 (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)ary
  • the OLED according to the present disclosure comprises a hole transport zone between the first electrode and the light-emitting layer, wherein the hole transport zone comprises an arylamine derivative, and the HOMO energy level of the arylamine derivative satisfies the following equation 11.
  • the HOMO energy level of the arylamine derivative satisfies the following equation 12.
  • the OLED according to the present disclosure comprises a first hole transport layer between the first electrode and the light-emitting layer, and a second hole transport layer between the first hole transport layer and the light-emitting layer, wherein the second hole transport layer comprises an arylamine derivative containing a fluorene or a fused flourene, and the HOMO energy level of the arylamine derivative satisfies the equation 11.
  • the second hole transport layer may be a single layer or a plurality of layers, and the second hole transport layer may serve as a hole transport layer, a light-emitting auxiliary layer, a hole auxiliary layer and/or an electron blocking layer.
  • the hole transport zone includes a compound having a HOMO energy level of less than -5.0, e.g., -5.1 or less, it has a value lower than the HOMO energy level of the compound represented by the formula 1 comprised in the light-emitting layer.
  • the injection of holes is hindered, and the driving voltage is increased. That is, even if the luminous efficiency of the device increases, since the driving voltage increases as the luminous efficiency increases, there is no gain in terms of power efficiency (lm/W), and rather low power efficiency can be exhibited.
  • the hole transport zone comprises a compound having a HOMO energy level exceeding -4.65
  • the energy barrier between the layer containing it, e.g., the second hole transport layer, and the light-emitting layer becomes too large, and the injection of holes is hindered.
  • the difference between the upper limit value and the lower limit value of the HOMO energy level of the compound comprised in the hole transport zone may be more appropriate about 0.3 eV or less.
  • the arylamine derivative comprised in the hole transport zone, preferably the second hole transport layer, for example, at least one of the light-emitting auxiliary layer and the hole auxiliary layer may comprise a compound represented by the following formula 11.
  • L a to L c each independently, represent a single bond, a substituted or unsubstituted (C6-C30)arylene, a substituted or unsubstituted (3- to 30-membered)heteroarylene, or a substituted or unsubstituted (C3-C30)cycloalkylene; preferably, a single bond, a substituted or unsubstituted (C6-C25)arylene, a substituted or unsubstituted (5- to 25-membered)heteroarylene, or a substituted or unsubstituted (C3-C25)cycloalkylene; more preferably, a single bond, a (C6-C18)arylene unsubstituted or substituted with a di(C6-C18)arylamino(s), an unsubstituted (5- to 18-membered)heteroarylene, or an unsubstituted (C3-C18
  • L a to L c each independently, may represent a single bond, a phenylene unsubstituted or substituted with a diphenylamino(s), or an unsubstituted biphenylene.
  • Ar 1 to Ar 3 each independently, represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl, with the proviso that at least one of Ar 1 to Ar 3 is selected from the following formulas.
  • * represents a bonding site with L a , L b , or L c .
  • X each independently, represents O, S, NR 8 , or CR 9 R 10
  • Z and V each independently, represent O or S.
  • B ring represents a substituted or unsubstituted C10 aryl; preferably, an unsubstituted C10 aryl. According to one embodiment of the present disclosure, B ring may represent a naphthalene ring.
  • L d represents a single bond, or a substituted or unsubstituted (C6-C30)arylene.
  • R 11 to R 35 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 (5- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR 36 R 37 , -SiR 38 R 39 R 40 , -SR 41 , -OR 42 , a cyano, a nitro, or a hydroxyl, or may be linked to an adjacent substituent(s) to form a substituted or unsubstitute
  • R 11 to R 35 may represent hydrogen; R 11 , R 12 , R 14 to R 17 , R 22 to R 28 , and R 30 to R 35 , each independently, may be fused with the other adjacent R 11 , R 12 , R 14 to R 17 , R 22 to R 28 , and R 30 to R 35 to form a substituted or unsubstituted benzene ring.
  • R 13 and R 17 each independently, may represent a biphenyl; R 17 may represent a phenyl substituted with a diphenylamino; two adjacent R 16 ’s may be fused with each other to form an unsubstituted benzene ring; R 18 and R 19 , each independently, may represent a methyl, a phenyl, or a triphenylenyl, and may be the same or different from each other; R 21 and R 22 , each independently, may represent a methyl; R 28 and R 29 , each independently, may represent a methyl or a phenyl, and may be the same or different from each other; and R 18 and R 19 , or R 20 and R 21 may be linked to each other to form a spiro structure, e.g., spiro[fluorene-fluorene] or spiro[fluorene-benzofluorene].
  • a spiro structure e.g., spir
  • R 8 to R 10 and R 36 to R 42 each independently, represent hydrogen, deuterium, a cyano, 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 (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C
  • a 1 to A 12 each independently, represent N or CR 43 .
  • each R 43 may be the same or different from each other.
  • R 43 each independently, represents hydrogen, deuterium, a halogen, a cyano, 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 (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted or unsubstituted
  • b, c, e, g, h, j, k, m, n, o, q, r, and s each independently, represent an integer of 1 to 4; d, f, p, and t, each independently, represent an integer of 1 to 3; i represents an integer of 1 to 6; l represents 1 or 2; where each of b to t is an integer of 2 or more, each of R 11 , R 12 , R 14 to R 17 , R 22 to R 28 , and R 30 to R 35 may be the same or different.
  • the heteroaryl(ene) or the heterocycloalkyl contains at least one heteroatom selected from B, N, O, S, Si, and P, and preferably, at least one heteroatom selected from N, O, and S.
  • the compound represented by formula 1 may be specifically exemplified by the following compounds, but is not limited thereto.
  • the arylamine derivative satisfying the equation 11 may be specifically exemplified by the following compounds, but is not limited thereto.
  • the compound of formula 1 according to the present disclosure may be produced by a synthetic method known to one skilled in the art.
  • the compound of formula 1 may be produced by referring to the following reaction schemes, but are not limited thereto.
  • the compound represented by formula 11 may be produced by a synthetic method known to one skilled in the art, and for example, by using or modifying the synthetic methods disclosed in Korean Patent Application Laid-Open Nos. 2014-0104895 A, 2015-0012488 A, 2015-0066202 A, and Korean Patent No. 1476231 B.
  • the organic electroluminescent device of the present disclosure may comprise a p-doped hole injection layer.
  • the p-doped hole injection layer is doped with a p-dopant, and the p-dopant may preferably be distributed substantially uniformly in the p-doped layer, which may be achieved by co-deposition of a p-dopant and a hole injection material.
  • the p-dopant may be contained in an amount of 0.01 to 50 wt%, preferably 0.1 to 20 wt%, more preferably 1 to 10 wt%, based on the hole injection material.
  • the p-dopant according to one embodiment of the present disclosure may include at least one of the following compounds P-1 to P-7.
  • T 1 to T 38 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C50)alkyl fluoride, a cyano, a substituted or unsubstituted (C1-C50)alkoxy, a substituted or unsubstituted (C1-C50)alkyl, a substituted or unsubstituted (C6-C50)aryl, or substituted or unsubstituted (3-30 membered)heteroaryl.
  • U 1 and U 2 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C50)alkyl fluoride, a cyano, a substituted or unsubstituted (C1-C50)alkoxy, a substituted or unsubstituted (C1-C50)alkyl, a substituted or unsubstituted (C6-C50)aryl, or substituted or unsubstituted (3-30 membered)heteroaryl.
  • U 3 to U 8 each independently, represent a substituted or unsubstituted (C1-C50)alkylene fluoride, a substituted or unsubstituted (C1-C50)alkylene, a substituted or unsubstituted (C6-C50)arylene, or substituted or unsubstituted (3-30 membered)heteroarylene.
  • the p-dopant may be specifically exemplified by the following compounds, but is not limited thereto.
  • the dopant comprised in the light-emitting layer of the organic electroluminescent device of the present disclosure may be at least one phosphorescent or fluorescent dopont, and is preferably at least one phosphorescent dopant.
  • the phosphorescent dopant material applied to the organic electroluminescent device of the present disclosure is not particulary limited, but may be preferably selected from the metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
  • the dopant comprised in the light-emitting layer of the organic electroluminescent device of the present disclosure may comprise the compound represented by the following formula 101, but is not limited thereto.
  • L is selected from the following structures 1 and 2:
  • R 100 to R 103 , and R 104 to R 107 each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen and/or deuterium, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a cyano, a substituted or unsubstituted (3- to 30-membered)heteroaryl, or a substituted or unsubstituted (C1-C30)alkoxy; or R 100 to R 103 may be linked to adjacent R 100 to R 103 , to form a substituted or unsubstituted fused ring, e.g., a substituted or unsubstituted, quinoline, benzofuropyridine, benzothienopyridine, indenopyridine, benzofuro
  • R 201 to R 211 each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen and/or deuterium, a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl; or may be linked to adjacent R 201 to R 211 to form a substituted or unsubstituted fused ring; and
  • n an integer of 1 to 3.
  • dopant compound is as follows, but are not limited thereto.
  • a display system e.g., a display system for smart phones, tablets, notebooks, PCs, TVs, or cars; or a lighting system, e.g., an outdoor or indoor lighting system, can be produced.
  • the organic electroluminescent device of the present disclosure is intended to explain one embodiment of the present disclosure, and is not meant in any way to restrict the scope of the disclosure.
  • the present disclosure may be embodied in other forms.
  • the present disclosure may be embodied in other forms.
  • the HOMO energy levels of the present disclosure were measured by using a density functional theory (DFT) in a Gaussian 03 program of Gaussian, Inc. Specifically, the HOMO and LUMO energy levels in the Device Examples and Comparative Examples of the present disclosure were extracted from the structure with the lowest energy by comparing the calculated energies of isomers after structurally optimizing all possible isomer structures at the level of B3LYP/6-31g*.
  • DFT density functional theory
  • the efficiency of the OLED device can be improved by comprising the compound of formula 1 in the light-emitting layer and the arylamine derivative having a specific HOMO energy level in the hole transport zone.
  • the following examples merely explain the properties of the OLED device according to the present disclosure for a detailed understanding thereof, but the present disclosure is not limited by the following examples.
  • OLED devices according to the present disclosure were produced.
  • a transparent electrode indium tin oxide (ITO) thin film (10 ⁇ /sq) on a glass substrate for an OLED device (GEOMATEC CO., LTD., Japan) was subjected to an ultrasonic washing with acetone and isopropyl alcohol, sequentially, and then was stored in isopropyl alcohol.
  • the ITO substrate was then mounted on a substrate holder of a vacuum vapor deposition apparatus.
  • Compound HI-1 was introduced into a cell of the vacuum vapor deposition apparatus, and then the pressure in the chamber of the apparatus was controlled to 10 -6 torr.
  • compound HI-2 was introduced into another cell of the vacuum vapor deposition apparatus and was evaporated by applying an electric current to the cell, thereby forming a second hole injection layer having a thickness of 5 nm on the first hole injection layer.
  • Compound HT-2-46 was then introduced into a cell of the vacuum vapor deposition apparatus and was evaporated by applying an electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer.
  • the compound of the second hole transport layer shown in Table 1 was then introduced into another cell of the vacuum vapor deposition apparatus and was evaporated by applying an electric current to the cell, thereby forming a second hole transport layer (auxiliary layer) having a thickness of 60 nm on the first hole transport layer.
  • a light-emitting layer was formed thereon as follows:
  • the host material shown in Table 1 was introduced into one cell of the vacuum vapor depositing apparatus as a host, and compound D-39 was introduced into another cell as a dopant.
  • the two materials were evaporated and the dopant was deposited in a doping amount of 2 wt% based on the amount of the host and dopant to form a light-emitting layer having a thickness of 40 nm on the hole transport layer.
  • Compound ET-1 and compound EI-1 were then introduced into the other two cells and evaporated at a rate of 1:1 to form an electron transport layer having a thickness of 35 nm on the light-emitting layer.
  • an Al cathode having a thickness of 80 nm was deposited on the electron injection layer by another vacuum vapor deposition apparatus.
  • an OLED device was produced.
  • OLED devices were produced in the same manner as in Device Example 1, except that the compound shown in the following Table 1 was used in the second hole transport layer, and the compound CBP was used in the host.
  • An OLED device was produced in the same manner as in Device Example 1, except that the compound shown in the following Table 1 was used in the second hole transport layer.
  • OLED devices were produced in the same manner as in Device Example 1, except that compound HT-1 and compound HI-2 were deposited at a ratio of 1:0.03 instead of the first and second hole injection layers to form a hole injection layer having a thickness of 5 nm, and compound HT-1 was then evaporated to form a first hole transport layer having a thickness of 100 nm, and the compound shown in Table 1 was used in the second hole transport layer.
  • the driving voltage, the luminous efficiency, and the CIE color coordinates at luminance of 1,000 nits, and the lifespan (measured as the percentage to which the luminance decreased from 100% after 16.6 hours at a constant current and at a luminance of 5,000 nits) of the OLED devices produced in Device Examples 1 to 33 and Comparative Examples 1 to 20 are provided in Table 1 below.
  • the HOMO energy levels of the compounds comprised in the second hole transport layer of Device Examples 1 to 33 and Comparative Examples 1 to 20 are shown in Table 2 below.
  • Device Examples 1 to 33 exhibit lower driving voltage, higher luminous efficiency and/or longer lifespan than the Comparative Examples, by comprising the fused azulene derivative compound of the present disclosure in the light-emitting layer and the compound having the specific HOMO energy level of the present disclosure between the first hole transport layer and the light-emitting layer.

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Abstract

The present disclosure relates to an organic electroluminescent device comprising a light-emitting layer and a hole transport zone. By comprising a specific combination of a light-emitting layer and a hole transport zone, it is possible to provide an organic electroluminescent device having low driving voltage, high luminous efficiency and/or long lifespan properties.

Description

ORGANIC ELECTROLUMINESCENT DEVICE
The present disclosure relates to an organic electroluminescent device comprising a light-emitting layer and a hole transport zone.
In 1987, Tang et al. of Eastman Kodak first developed a small molecule green organic electroluminescent device (OLED) of TPD/Alq3 bilayer consisting of a light-emitting layer and a charge transport layer. Since then, the research on an OLED has been rapidly carried out, and it has been commercialized. At present, an OLED mainly uses phosphorescent materials having excellent luminous efficiency in panel implementation. Low driving voltage and high luminous efficiency are required for long lifespan and high resolution of display.
U.S. Patent No. 6,902,831 discloses an azulene derivative as an organic electroluminescent compound, but it does not specifically disclose an organic electroluminescent compound of a fused azulene derivative. In addition, the document does not specifically disclose that the performance of an OLED can be improved by combining a host compound containing a fused azulene derivative and a specific material contained in a hole transport zone.
The objective of the present disclosure is to provide an organic electroluminescent device having low driving voltage, high luminous efficiency and/or long lifespan properties by a combination of a light-emitting layer comprising a compound according to the present disclosure, and a hole transport zone comprising a compound having a specific HOMO (Highest Occupied Molecular Orbital) energy level.
A light-emitting layer comprising a phosphorescent dopant is preferable to have a light-emitting material having excellent hole and electron current properties for low driving voltage, high efficiency, and long lifespan, and the material having the thermal stability for improvement of lifespan. In addition, for efficient energy transport from the host to the dopant of the light-emitting layer, using a light-emitting material having a narrow energy band gap can contribute to improve driving voltage and luminous efficiency by minimizing the charge trap. While the azulene derivative comprised in the device of the present disclosure has a slow transition constant of the internal conversion of S2→S1, i.e. 7*10-8 s, the transition constant of the internal conversion of S1→S0 is fast, i.e. 7*10-12 s. Thus, the fluorescence quantum yield of S2→S0 increases, and so the azulene derivative is one of the representative materials which violates Kasha's rule. According to a non-patent document of [Phys. Chem. Chem. Phys. 2015, 17, 23573, J. Phys. Chem. A, Vol. 103, No. 15, 1999 2529], the levels of S2 and S1 of azulene are 3.565 eV and 1.771 eV, respectively, while the level difference of T1 and S0 is very small, i.e. the T1-S0 transition is 1.711 eV. In addition, the intersystem crossing transition of S2→Tn transition is improved according to the conditions of the substitution material and the solvent polarity. Accordingly, there was report that due to the increase of the transition to the triplet, there may be an advantage in improvement of the phosphorous luminous properties. These azulene derivatives show a small energy gap of S1→T1, and have a relatively high HOMO characteristic compared to carbazole- or benzocarbazole-type compounds, thereby providing a narrow energy band gap.
However, the conventional hole transport zone has limitations in increasing the efficiency of the light-emitting layer comprising the fused azulene derivative compound. A hole transport zone requires a compound having a high HOMO energy level in order to have a high hole mobility. If the HOMO energy level is high, the driving voltage decreases, but the efficiency of the light-emitting layer also decreases. On the contrary, if the HOMO energy level is low, the efficiency of the light-emitting layer increases, but the driving voltage also increases, and thus it is difficult to realize high luminous efficiency of the device.
The present inventors found that the above-mentioned problems can be solved by comprising a fused azulene derivative of the present disclosure in a light-emitting layer, and an arylamine derivative having a specific HOMO energy level of the present disclosure in a hole transport zone. Specifically, the present inventors found that the above objective can be achieved by an organic electroluminescent device comprising a first electrode, a second electrode facing the first electrode, a light-emitting layer between the first electrode and the second electrode, and a hole transport zone between the first electrode and the light-emitting layer, wherein the light-emitting layer comprises a compound represented by the following formula 1:
Figure PCTKR2018002357-appb-I000001
wherein,
X1 represents N-L-(Ar)a, S, or O,
L represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene,
Ar represents hydrogen, deuterium, a halogen, a cyano, 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 mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino,
Y1 to Y12, each independently, represent N or CR1,
R1, each independently, represents hydrogen, deuterium, a halogen, a cyano, 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 (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted ring, and
a represents an integer of 1 to 4, where if a is an integer of 2 or more, each of Ar may be the same or different; and
the hole transport zone comprises an arylamine derivative, and the HOMO energy level of the arylamine derivative satisfies the following equation 11:
-5.0 eV ≤ HOMO ≤ -4.65 eV --- (11).
According to the present disclosure, an organic electroluminescent device having low driving voltage, high luminous efficiency and/or long lifespan properties can be provided. Also, it is possible to produce a display device or a lighting device by using the organic electroluminescent device of the present disclosure.
Hereinafter, the present disclosure will be described in detail. However, the following description is intended to explain the disclosure, and is not meant in any way to restrict the scope of the present disclosure.
The organic electroluminescent device of the present disclosure comprises a first electrode, a second electrode facing the first electrode, a light-emitting layer between the first electrode and the second electrode, a hole transport zone between the first electrode and the light-emitting layer, and an electron transport zone between the light-emitting layer and the second electrode. One of the first and second electrodes may be an anode, and the other may be a cathode.
The hole transport zone means a zone wherein holes are transported between the first electrode and the light-emitting layer. For example, the hole transport zone may comprise at least one of a hole injection layer, a hole transport layer, a hole auxiliary layer, a light-emitting auxiliary layer and an electron blocking layer. The hole injection layer, the hole transport layer, the hole auxiliary layer, the light-emitting auxiliary layer and the electron blocking layer, respectively, may be a single layer, or a plurality of layers in which two or more layers are stacked. According to one embodiment of the present disclosure, the hole transport zone may comprise a first hole transport layer and a second hole transport layer, wherein the second hole transport layer may be at least one layer of a plurality of hole transport layers, and it may comprise at least one of a hole auxiliary layer, a light-emitting auxiliary layer and a electron blocking layer. According to another embodiment of the present disclosure, the hole transport zone may comprise a first hole transport layer and a second hole transport layer, wherein the first hole transport layer may be placed between the first electrode and the light-emitting layer, the second hole transport layer may be placed between the first hole transport layer and the light-emitting layer, and the second hole transport layer may serve as a hole transport layer, a light-emitting auxiliary layer, a hole auxiliary layer and/or an electron blocking layer.
According to another embodiment of the present disclosure, the hole transport zone may comprise a p-doped hole injection layer, a hole transport layer, and a light-emitting auxiliary layer. Herein, the p-doped hole injection layer means a hole injection layer doped with a p-dopant. The p-dopant is a material capable of imparting p-type semiconductor properties. The p-type semiconductor properties mean the properties of injecting or transporting holes at the HOMO energy level, i.e., the properties of materials having a high hole conductivity.
The hole transport layer may be placed between the anode (or the hole injection layer) and the light-emitting layer. The hole transport layer may function to smoothly move the holes transferred from the anode to the light-emitting layer, and to block the electrons transferred from the cathode to remain in the light-emitting layer. The light-emitting auxiliary layer may be placed between the anode and the light-emitting layer, or between the cathode and the light-emitting layer. When the light-emitting auxiliary layer is placed between the anode and the light-emitting layer, it can be used for promoting the hole injection and/or the hole transport, or for preventing the overflow of electrons. When the light-emitting auxiliary layer is placed between the cathode and the light-emitting layer, it can be used for promoting the electron injection and/or the electron transport, or for preventing the overflow of holes. Also, the hole auxiliary layer may be placed between the hole transport layer (or hole injection layer) and the light-emitting layer, and may be effective to promote or block the hole transport rate (or the hole injection rate), thereby enabling the charge balance to be controlled. Further, the electron blocking layer may be placed between the hole transport layer (or hole injection layer) and the light-emitting layer, and can confine the excitions within the light-emitting layer by blocking the overflow of electrons from the light-emitting layer to prevent a light-emitting leakage. When an organic electroluminescent device includes two or more hole transport layers, the further included hole transport layer may be used as a hole auxiliary layer or an electron blocking layer. The light-emitting auxiliary layer, the hole auxiliary layer and/or the electron blocking layer may have an effect of improving the efficiency and/or the lifespan of the organic electroluminescent device.
The electron transport zone may comprise at least one of an electron buffer layer, a hole blocking layer, an electron transport layer and an electron injection layer, and preferably, at least one of an electron transport layer and an electron injection layer. The electron buffer layer is a layer capable of improving the problem that light-emitting luminance deteriorates due to the change of current properties in the device when the device is exposed to a high temperature during a process of producing panels, and it can control the charge flow properties.
The light-emitting layer, in which light is emitted, may be a single layer, or a plurality of layers in which two or more layers are stacked. The doping concentration of the dopant compound with respect to the host compound of the light-emitting layer is preferably less than 20% by weight.
Herein, "(C1-C30)alkyl" is meant to be a linear or branched alkyl having 1 to 30 carbon atoms constituting the chain, in which the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. "(C3-C30)cycloalkyl" is a mono- or polycyclic hydrocarbon having 3 to 30 ring backbone carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. "(3- to 7-membered)heterocycloalkyl" is a cycloalkyl having at least one heteroatom selected from the group consisting of B, N, O, S, Si, and P, preferably O, S, and N, and 3 to 7 ring backbone atoms, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc. "(C6-C30)aryl(ene)" is a monocyclic or fused ring-type radical derived from an aromatic hydrocarbon having 6 to 30 ring backbone carbon atoms, in which the number of ring backbone carbon atoms is preferably 6 to 20, more preferably 6 to 15, may be partially saturated, 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 group having at least one, preferably 1 to 4 heteroatoms selected from the group consisting of B, N, O, S, Si, and P, and 3 to 30 ring backbone atoms, in which the number of ring backbone atoms is preferably 3 to 20, more preferably 5 to 15; 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, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthothiophenyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. "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 functional group, i.e., a substituent. The substituents of the substituted alkyl, the substituted aryl(ene), the substituted heteroaryl(ene), the substituted cycloalkyl, the substituted heterocycloalkyl, the substituted alkoxy, the substituted arylalkyl, the substituted trialkylsilyl, the substituted dialkylarylsilyl, the substituted alkyldiarylsilyl, the substituted triarylsilyl, the substituted mono- or di- alkylamino, the substituted mono- or di- arylamino, the substituted alkylarylamino, and the substituted ring in L, Ar, R1, La to Ld, Ar1 to Ar3, and R8 to R43 in the formulas of the present disclosure, 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 (5- to 50-membered)heteroaryl unsubstituted or substituted with a (C1-C30)alkyl(s) and/or a (C6-C30)aryl(s), a (C6-C30)aryl unsubstituted or substituted with a (3- to 50-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; preferably, at least one selected from the group consisting of a (C1-C20)alkyl, a (C6-C25)aryl unsubstituted or substituted with a (C1-C20)alkyl(s) and/or a (3- to 30-membered)heteroaryl(s); a (5- to 40-membered)heteroaryl unsubstituted or substituted with a (C1-C20)alkyl(s) and/or a (C6-C25)aryl(s); and a di(C6-C20)arylamino. For example, the above substituents may be at least one selected from the group consisting of a methyl, a tert-butyl, a phenyl unsubstituted or substituted with a pyridinyl(s), a naphthyl, a biphenyl, a dimethylfluorenyl, a phenylfluorenyl, a diphenylfluorenyl, a phenanthrenyl, a triphenylenyl, a pyridinyl, a triazinyl substituted with a phenyl(s) and/or a naphthyl(s), an indolyl substituted with a diphenyl(s), a benzoimidazolyl substituted with a phenyl(s), a quinolyl, a quinazolinyl substituted with a phenyl(s), a carbazolyl, a dibenzofuranyl, a dibenzothiophenyl, a benzocarbazolyl unsubstituted or substituted with a phenyl(s), a dibenzocarbazolyl, a benzophenanthrothiophenyl, a diphenylamino, a dimethylfluorenylphenylamino, or a substituted or unsubstituted (16- to 33-membered)heteroaryl containing at least one of nitrogen, oxygen and sulfur.
In formula 1, X1 represents N-L-(Ar)a, S, or O.
In formula 1, L represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene; preferably, a single bond, a substituted or unsubstituted (C6-C25)arylene, or a substituted or unsubstituted (5- to 25-membered)heteroarylene; and more preferably, a single bond, an unsubstituted (C6-C18)arylene, or an unsubstituted (5- to 18-membered)heteroarylene, wherein the heteroarylene may comprise at least one of nitrogen, oxygen, and/or sulfur.
According to one embodiment of the present disclosure, L may represent a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted pyridylene, a substituted or unsubstituted pyrimidinylene, a substituted or unsubstituted triazinylene, a substituted or unsubstituted quinazolinylene, a substituted or unsubstituted quinoxalinylene, a substituted or unsubstituted naphthyridinylene, a substituted or unsubstituted benzoquinazolinylene, a substituted or unsubstituted benzothienopyrimidinylene, a substituted or unsubstituted acenaphthopyrimidinylene, a substituted or unsubstituted (13- to 16- membered)heteroarylene containing at least one of nitrogen, oxygen, and sulfur.
In formula 1, Ar represents hydrogen, deuterium, a halogen, a cyano, 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 mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; preferably, hydrogen, a substituted or unsubstituted (C6-C25)aryl, a substituted or unsubstituted (5- to 30-membered)heteroaryl, or a substituted or unsubstituted di(C6-C25)arylamino; and more preferably, hydrogen, a substituted or unsubstituted (C6-C18)aryl, a substituted or unsubstituted (5- to 25-membered)heteroaryl, or a substituted or unsubstituted di(C6-C18)arylamino.
According to one embodiment of the present disclosure, Ar may represent a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted benzoquinazolinyl, a substituted or unsubstituted quinoxalinyl, a substituted or unsubstituted benzoquinoxalinyl, a substituted or unsubstituted quinolyl, a substituted or unsubstituted benzoquinolyl, a substituted or unsubstituted isoquinolyl, a substituted or unsubstituted benzoisoquinolyl, a substituted or unsubstituted triazolyl, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted carbazolyl, a substituted or unsubstituted dibenzothiophenyl, a substituted or unsubstituted benzothiophenyl, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted benzofuranyl, a substituted or unsubstituted naphthyridinyl, a substituted or unsubstituted benzothienopyrimidinyl, a substituted or unsubstituted benzothienoquinolinyl, a substituted or unsubstituted benzofuroquinolinyl, a substituted or unsubstituted triaindenyl, a substituted or unsubstituted phenanthroimidazolyl, a substituted or unsubstituted (9- to 25- membered)heteroaryl containing at least one of nitrogen, oxygen, and sulfur, a substituted or unsubstituted diphenylamino, a substituted or unsubstituted phenylbiphenylamino, or a substituted or unsubstituted fluorenylphenylamino.
In formula 1, a represents an integer of 1 to 4, preferably, 1 or 2, where if a is an integer of 2 or more, each of Ar may be the same or different.
In formula 1, Y1 to Y12, each independently, represent N or CR1. According to one embodiment of the present disclosure, all of Y1 to Y12 may represent CR1, and according to another embodiment of the present disclosure, at least one of Y1 to Y12 may represent N. Where there are a plurality of R1’s, each of R1 may be the same or different.
R1, each independently, represents hydrogen, deuterium, a halogen, a cyano, 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 (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted ring; preferably, hydrogen, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C25)aryl, a substituted or unsubstituted (5- to 25-membered)heteroaryl, or a substituted or unsubstituted di(C6-C25)arylamino; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic, (C3-C25) aromatic ring, whose carbon atom(s) may be replaced with at least one heteroatom selected from nitrogen, oxygen, and sulfur; and more preferably, hydrogen, a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C6-C18)aryl, a substituted or unsubstituted (5- to 18-membered)heteroaryl, or a substituted or unsubstituted di(C6-C18)arylamino; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic, (C5-C18) aromatic ring, whose carbon atom(s) may be replaced with at least one heteroatom selected from nitrogen, oxygen, and sulfur.
According to one embodiment of the present disclosure, R1 may each independently represent hydrogen, a substituted or unsubstituted methyl, a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted quinoxalinyl, a substituted or unsubstituted phenylbiphenylamino, etc.
According to one embodiment of the present disclosure, at least one adjacent pair of Y1 to Y12 in formula 1 are CR1, and the adjacent two R1’s of CR1 are fused together to each independently form a ring represented by any one of the following formulas 2 to 6, but is not limited thereto. For example, the formed ring may be a substituted or unsubstituted benzene ring, a naphthalene ring, a furan ring, a thiophene ring, a substituted or unsubstituted pyrrole ring, a pyridine ring, a benzofuran ring, a benzothiophene ring, a substituted or unsubstituted indole ring, a dibenzofuran ring, a dibenzothiophene ring, a substituted or unsubstituted carbazole ring, a phenanthrene ring, etc., including the ring of formulas 2 to 6.
Figure PCTKR2018002357-appb-I000002
Figure PCTKR2018002357-appb-I000003
In formulas 2 to 6,
Figure PCTKR2018002357-appb-I000004
represents a bonding site of between C and R1 in the adjacent CR1 of formula 1.
In formulas 4 and 6, A represents N or CR2. According to one embodiment of the present disclosure, A may all represent CR2, and according to another embodiment of the present disclosure, at least one of A may represent N. Where there are a plurality of R2’s, each of R2 may be the same or different.
R2, each independently, represents hydrogen, deuterium, a halogen, a cyano, 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 (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; preferably, a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl; and more preferably a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl.
In formula 5, R3 represents hydrogen, deuterium, a halogen, a cyano, 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 (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; preferably, a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl; and more preferably an unsubstituted (C6-C18)aryl, or an unsubstituted (5- to 18-membered)heteroaryl. For example, R3 may represent a phenyl.
The OLED according to the present disclosure comprises a hole transport zone between the first electrode and the light-emitting layer, wherein the hole transport zone comprises an arylamine derivative, and the HOMO energy level of the arylamine derivative satisfies the following equation 11.
-5.0 eV ≤ HOMO ≤ -4.65 eV --- (11)
According to one embodiment of the present disclosure, the HOMO energy level of the arylamine derivative satisfies the following equation 12.
-5.0 eV ≤ HOMO ≤ -4.70 eV --- (12)
According to one embodiment of the present disclosure, the OLED according to the present disclosure comprises a first hole transport layer between the first electrode and the light-emitting layer, and a second hole transport layer between the first hole transport layer and the light-emitting layer, wherein the second hole transport layer comprises an arylamine derivative containing a fluorene or a fused flourene, and the HOMO energy level of the arylamine derivative satisfies the equation 11. Herein, the second hole transport layer may be a single layer or a plurality of layers, and the second hole transport layer may serve as a hole transport layer, a light-emitting auxiliary layer, a hole auxiliary layer and/or an electron blocking layer.
When the hole transport zone includes a compound having a HOMO energy level of less than -5.0, e.g., -5.1 or less, it has a value lower than the HOMO energy level of the compound represented by the formula 1 comprised in the light-emitting layer. As a result, the injection of holes is hindered, and the driving voltage is increased. That is, even if the luminous efficiency of the device increases, since the driving voltage increases as the luminous efficiency increases, there is no gain in terms of power efficiency (lm/W), and rather low power efficiency can be exhibited. Meanwhile, if the hole transport zone comprises a compound having a HOMO energy level exceeding -4.65, the energy barrier between the layer containing it, e.g., the second hole transport layer, and the light-emitting layer becomes too large, and the injection of holes is hindered. As a result, the luminous efficiency can be reduced. Further, according to one embodiment of the present disclosure, the difference between the upper limit value and the lower limit value of the HOMO energy level of the compound comprised in the hole transport zone may be more appropriate about 0.3 eV or less.
According to one embodiment of the present disclosure, the arylamine derivative comprised in the hole transport zone, preferably the second hole transport layer, for example, at least one of the light-emitting auxiliary layer and the hole auxiliary layer may comprise a compound represented by the following formula 11.
Figure PCTKR2018002357-appb-I000005
In formula 11, La to Lc, each independently, represent a single bond, a substituted or unsubstituted (C6-C30)arylene, a substituted or unsubstituted (3- to 30-membered)heteroarylene, or a substituted or unsubstituted (C3-C30)cycloalkylene; preferably, a single bond, a substituted or unsubstituted (C6-C25)arylene, a substituted or unsubstituted (5- to 25-membered)heteroarylene, or a substituted or unsubstituted (C3-C25)cycloalkylene; more preferably, a single bond, a (C6-C18)arylene unsubstituted or substituted with a di(C6-C18)arylamino(s), an unsubstituted (5- to 18-membered)heteroarylene, or an unsubstituted (C3-C18)cycloalkylene. According to one embodiment of the present disclosure, La to Lc, each independently, may represent a single bond, a phenylene unsubstituted or substituted with a diphenylamino(s), or an unsubstituted biphenylene.
In formula 11, Ar1 to Ar3, each independently, represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl, with the proviso that at least one of Ar1 to Ar3 is selected from the following formulas.
Figure PCTKR2018002357-appb-I000006
Figure PCTKR2018002357-appb-I000007
Figure PCTKR2018002357-appb-I000008
Figure PCTKR2018002357-appb-I000009
In the above formulas, * represents a bonding site with La, Lb, or Lc.
In the above formulas, X, each independently, represents O, S, NR8, or CR9R10, and Z and V, each independently, represent O or S.
In the above formulas, B ring represents a substituted or unsubstituted C10 aryl; preferably, an unsubstituted C10 aryl. According to one embodiment of the present disclosure, B ring may represent a naphthalene ring.
In the above formulas, Ld represents a single bond, or a substituted or unsubstituted (C6-C30)arylene.
In the above formulas, R11 to R35, 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 (5- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR36R37, -SiR38R39R40, -SR41, -OR42, a cyano, a nitro, or a hydroxyl, or may be linked to an adjacent substituent(s) to form a substituted or unsubstituted ring, wherein the ring comprises a spiro structure; preferably, hydrogen, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C6-C25)aryl, a substituted or unsubstituted (5- to 25-membered)heteroaryl, or -NR36R37, or may be linked to an adjacent substituent to form a substituted or unsubstituted ring, wherein the ring may comprise a spiro structure; and more preferably, hydrogen, an unsubstituted (C1-C10)alkyl, a (C6-C18)aryl unsubstituted or substituted with a di(C6-C18)arylamino(s), or -NR36R37, or may be linked to an adjacent substituent to form an unsubstituted ring, wherein the ring may comprise a spiro structure. According to one embodiment of the present disclosure, R11 to R35 may represent hydrogen; R11, R12, R14 to R17, R22 to R28, and R30 to R35, each independently, may be fused with the other adjacent R11, R12, R14 to R17, R22 to R28, and R30 to R35 to form a substituted or unsubstituted benzene ring. For example, R13 and R17, each independently, may represent a biphenyl; R17 may represent a phenyl substituted with a diphenylamino; two adjacent R16’s may be fused with each other to form an unsubstituted benzene ring; R18 and R19, each independently, may represent a methyl, a phenyl, or a triphenylenyl, and may be the same or different from each other; R21 and R22, each independently, may represent a methyl; R28 and R29, each independently, may represent a methyl or a phenyl, and may be the same or different from each other; and R18 and R19, or R20 and R21 may be linked to each other to form a spiro structure, e.g., spiro[fluorene-fluorene] or spiro[fluorene-benzofluorene].
Herein, R8 to R10 and R36 to R42, each independently, represent hydrogen, deuterium, a cyano, 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 (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino, or may be linked to an adjacent substituent to form a substituted or unsubstituted ring; preferably, hydrogen, a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl; more preferably, a (C6-C18)aryl unsubstituted or substituted with a (C1-C10)alkyl. According to one embodiment of the present disclosure, R36 and R37, each independently, may represent a phenyl, a naphthylphenyl, a biphenyl, or a dimethylfluorenyl.
In the above formulas, A1 to A12, each independently, represent N or CR43. When R43 is plural, each R43 may be the same or different from each other. R43, each independently, represents hydrogen, deuterium, a halogen, a cyano, 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 (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino, or may be linked to an adjacent substituent to form a substituted or unsubstituted ring; preferably, hydrogen, deuterium, a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 25-membered)heteroaryl, or two or more adjacent R43’s may be linked to each other to form a substituted or unsubstituted ring; more preferably, hydrogen, deuterium, an unsubstituted (C6-C18)aryl, or unsubstituted (5- to 18-membered)heteroaryl, or two or more adjacent R43’s may be linked to each other to form an unsubstituted ring. According to one embodiment of the present disclosure, R43, each independently, may represent hydrogen, or an unsubstituted pyridine, or two adjacent R43’s may be linked to each other to form a benzene ring.
In the above formulas, b, c, e, g, h, j, k, m, n, o, q, r, and s, each independently, represent an integer of 1 to 4; d, f, p, and t, each independently, represent an integer of 1 to 3; i represents an integer of 1 to 6; l represents 1 or 2; where each of b to t is an integer of 2 or more, each of R11, R12, R14 to R17, R22 to R28, and R30 to R35 may be the same or different.
The heteroaryl(ene) or the heterocycloalkyl contains at least one heteroatom selected from B, N, O, S, Si, and P, and preferably, at least one heteroatom selected from N, O, and S.
The compound represented by formula 1 may be specifically exemplified by the following compounds, but is not limited thereto.
Figure PCTKR2018002357-appb-I000010
Figure PCTKR2018002357-appb-I000011
Figure PCTKR2018002357-appb-I000012
Figure PCTKR2018002357-appb-I000013
Figure PCTKR2018002357-appb-I000014
Figure PCTKR2018002357-appb-I000015
Figure PCTKR2018002357-appb-I000016
Figure PCTKR2018002357-appb-I000017
Figure PCTKR2018002357-appb-I000018
Figure PCTKR2018002357-appb-I000019
Figure PCTKR2018002357-appb-I000020
Figure PCTKR2018002357-appb-I000021
Figure PCTKR2018002357-appb-I000022
Figure PCTKR2018002357-appb-I000023
Figure PCTKR2018002357-appb-I000024
Figure PCTKR2018002357-appb-I000025
Figure PCTKR2018002357-appb-I000026
Figure PCTKR2018002357-appb-I000027
Figure PCTKR2018002357-appb-I000028
Figure PCTKR2018002357-appb-I000029
Figure PCTKR2018002357-appb-I000030
Figure PCTKR2018002357-appb-I000031
Figure PCTKR2018002357-appb-I000032
Figure PCTKR2018002357-appb-I000033
Figure PCTKR2018002357-appb-I000034
Figure PCTKR2018002357-appb-I000035
Figure PCTKR2018002357-appb-I000036
Figure PCTKR2018002357-appb-I000037
Figure PCTKR2018002357-appb-I000038
Figure PCTKR2018002357-appb-I000039
Figure PCTKR2018002357-appb-I000040
Figure PCTKR2018002357-appb-I000041
Figure PCTKR2018002357-appb-I000042
Figure PCTKR2018002357-appb-I000043
Figure PCTKR2018002357-appb-I000044
Figure PCTKR2018002357-appb-I000045
Figure PCTKR2018002357-appb-I000046
Figure PCTKR2018002357-appb-I000047
Figure PCTKR2018002357-appb-I000048
Figure PCTKR2018002357-appb-I000049
Figure PCTKR2018002357-appb-I000050
Figure PCTKR2018002357-appb-I000051
Figure PCTKR2018002357-appb-I000052
Figure PCTKR2018002357-appb-I000053
Figure PCTKR2018002357-appb-I000054
Figure PCTKR2018002357-appb-I000055
Figure PCTKR2018002357-appb-I000056
Figure PCTKR2018002357-appb-I000057
Figure PCTKR2018002357-appb-I000058
Figure PCTKR2018002357-appb-I000059
Figure PCTKR2018002357-appb-I000060
Figure PCTKR2018002357-appb-I000061
Figure PCTKR2018002357-appb-I000062
Figure PCTKR2018002357-appb-I000063
Figure PCTKR2018002357-appb-I000064
Figure PCTKR2018002357-appb-I000065
Figure PCTKR2018002357-appb-I000066
Figure PCTKR2018002357-appb-I000067
Figure PCTKR2018002357-appb-I000068
Figure PCTKR2018002357-appb-I000069
Figure PCTKR2018002357-appb-I000070
Figure PCTKR2018002357-appb-I000071
Figure PCTKR2018002357-appb-I000072
Figure PCTKR2018002357-appb-I000073
Figure PCTKR2018002357-appb-I000074
Figure PCTKR2018002357-appb-I000075
Figure PCTKR2018002357-appb-I000076
Figure PCTKR2018002357-appb-I000077
Figure PCTKR2018002357-appb-I000078
Figure PCTKR2018002357-appb-I000079
Figure PCTKR2018002357-appb-I000080
Figure PCTKR2018002357-appb-I000081
Figure PCTKR2018002357-appb-I000082
Figure PCTKR2018002357-appb-I000083
The arylamine derivative satisfying the equation 11 may be specifically exemplified by the following compounds, but is not limited thereto.
Figure PCTKR2018002357-appb-I000084
Figure PCTKR2018002357-appb-I000085
Figure PCTKR2018002357-appb-I000086
Figure PCTKR2018002357-appb-I000087
Figure PCTKR2018002357-appb-I000088
Figure PCTKR2018002357-appb-I000089
Figure PCTKR2018002357-appb-I000090
Figure PCTKR2018002357-appb-I000091
Figure PCTKR2018002357-appb-I000092
Figure PCTKR2018002357-appb-I000093
Figure PCTKR2018002357-appb-I000094
Figure PCTKR2018002357-appb-I000095
Figure PCTKR2018002357-appb-I000096
Figure PCTKR2018002357-appb-I000097
Figure PCTKR2018002357-appb-I000098
Figure PCTKR2018002357-appb-I000099
Figure PCTKR2018002357-appb-I000100
Figure PCTKR2018002357-appb-I000101
Figure PCTKR2018002357-appb-I000102
Figure PCTKR2018002357-appb-I000103
Figure PCTKR2018002357-appb-I000104
Figure PCTKR2018002357-appb-I000105
Figure PCTKR2018002357-appb-I000106
Figure PCTKR2018002357-appb-I000107
Figure PCTKR2018002357-appb-I000108
Figure PCTKR2018002357-appb-I000109
Figure PCTKR2018002357-appb-I000110
Figure PCTKR2018002357-appb-I000111
Figure PCTKR2018002357-appb-I000112
The compound of formula 1 according to the present disclosure may be produced by a synthetic method known to one skilled in the art. For example, the compound of formula 1 may be produced by referring to the following reaction schemes, but are not limited thereto.
[Reaction Scheme 1]
Figure PCTKR2018002357-appb-I000113
Figure PCTKR2018002357-appb-I000114
Figure PCTKR2018002357-appb-I000115
Figure PCTKR2018002357-appb-I000116
[Reaction Scheme 2]
Figure PCTKR2018002357-appb-I000117
Figure PCTKR2018002357-appb-I000118
Figure PCTKR2018002357-appb-I000119
[Reaction Scheme 3]
Figure PCTKR2018002357-appb-I000120
Figure PCTKR2018002357-appb-I000121
Figure PCTKR2018002357-appb-I000122
In reaction schemes 1 to 3, L, Ar, Y1 to Y12, and a are as defined in formula 1.
The compound represented by formula 11 may be produced by a synthetic method known to one skilled in the art, and for example, by using or modifying the synthetic methods disclosed in Korean Patent Application Laid-Open Nos. 2014-0104895 A, 2015-0012488 A, 2015-0066202 A, and Korean Patent No. 1476231 B.
The organic electroluminescent device of the present disclosure may comprise a p-doped hole injection layer. The p-doped hole injection layer is doped with a p-dopant, and the p-dopant may preferably be distributed substantially uniformly in the p-doped layer, which may be achieved by co-deposition of a p-dopant and a hole injection material. Also, the p-dopant may be contained in an amount of 0.01 to 50 wt%, preferably 0.1 to 20 wt%, more preferably 1 to 10 wt%, based on the hole injection material.
The p-dopant according to one embodiment of the present disclosure may include at least one of the following compounds P-1 to P-7.
Figure PCTKR2018002357-appb-I000123
Figure PCTKR2018002357-appb-I000124
In the above formulas, T1 to T38, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C50)alkyl fluoride, a cyano, a substituted or unsubstituted (C1-C50)alkoxy, a substituted or unsubstituted (C1-C50)alkyl, a substituted or unsubstituted (C6-C50)aryl, or substituted or unsubstituted (3-30 membered)heteroaryl. In the above formulas, =Z1 to =Z11, each independently, may be represented by any one of the following formulas.
Figure PCTKR2018002357-appb-I000125
Figure PCTKR2018002357-appb-I000126
In the above formulas, U1 and U2, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C50)alkyl fluoride, a cyano, a substituted or unsubstituted (C1-C50)alkoxy, a substituted or unsubstituted (C1-C50)alkyl, a substituted or unsubstituted (C6-C50)aryl, or substituted or unsubstituted (3-30 membered)heteroaryl. U3 to U8, each independently, represent a substituted or unsubstituted (C1-C50)alkylene fluoride, a substituted or unsubstituted (C1-C50)alkylene, a substituted or unsubstituted (C6-C50)arylene, or substituted or unsubstituted (3-30 membered)heteroarylene.
The p-dopant may be specifically exemplified by the following compounds, but is not limited thereto.
Figure PCTKR2018002357-appb-I000127
Figure PCTKR2018002357-appb-I000128
Figure PCTKR2018002357-appb-I000129
The dopant comprised in the light-emitting layer of the organic electroluminescent device of the present disclosure may be at least one phosphorescent or fluorescent dopont, and is preferably at least one phosphorescent dopant. The phosphorescent dopant material applied to the organic electroluminescent device of the present disclosure is not particulary limited, but may be preferably selected from the metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
The dopant comprised in the light-emitting layer of the organic electroluminescent device of the present disclosure may comprise the compound represented by the following formula 101, but is not limited thereto.
Figure PCTKR2018002357-appb-I000130
In formula 101, L is selected from the following structures 1 and 2:
Figure PCTKR2018002357-appb-I000131
wherein, R100 to R103, and R104 to R107, each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen and/or deuterium, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a cyano, a substituted or unsubstituted (3- to 30-membered)heteroaryl, or a substituted or unsubstituted (C1-C30)alkoxy; or R100 to R103 may be linked to adjacent R100 to R103, to form a substituted or unsubstituted fused ring, e.g., a substituted or unsubstituted, quinoline, benzofuropyridine, benzothienopyridine, indenopyridine, benzofuroquinoline, benzothienoquinoline, or indenoquinoline ring; and R104 to R107 may be linked to adjacent R104 to R107 to form a substituted or unsubstituted fused ring, e.g., a substituted or unsubstituted, naphthyl, fluorene, dibenzothiophene, dibenzofuran, indenopyridine, benzofuropyridine, or benzothienopyridine ring;
R201 to R211, each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen and/or deuterium, a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl; or may be linked to adjacent R201 to R211 to form a substituted or unsubstituted fused ring; and
n represents an integer of 1 to 3.
The specific examples of the dopant compound are as follows, but are not limited thereto.
Figure PCTKR2018002357-appb-I000132
Figure PCTKR2018002357-appb-I000133
Figure PCTKR2018002357-appb-I000134
Figure PCTKR2018002357-appb-I000135
Figure PCTKR2018002357-appb-I000136
Figure PCTKR2018002357-appb-I000137
Figure PCTKR2018002357-appb-I000138
Figure PCTKR2018002357-appb-I000139
Figure PCTKR2018002357-appb-I000140
Figure PCTKR2018002357-appb-I000141
Figure PCTKR2018002357-appb-I000142
Figure PCTKR2018002357-appb-I000143
Figure PCTKR2018002357-appb-I000144
Figure PCTKR2018002357-appb-I000145
Figure PCTKR2018002357-appb-I000146
Figure PCTKR2018002357-appb-I000147
Figure PCTKR2018002357-appb-I000148
Figure PCTKR2018002357-appb-I000149
Figure PCTKR2018002357-appb-I000150
Figure PCTKR2018002357-appb-I000151
Figure PCTKR2018002357-appb-I000152
Figure PCTKR2018002357-appb-I000153
By using the organic electroluminescent device of the present disclosure, a display system, e.g., a display system for smart phones, tablets, notebooks, PCs, TVs, or cars; or a lighting system, e.g., an outdoor or indoor lighting system, can be produced.
The organic electroluminescent device of the present disclosure is intended to explain one embodiment of the present disclosure, and is not meant in any way to restrict the scope of the disclosure. The present disclosure may be embodied in other forms. The present disclosure may be embodied in other forms.
The HOMO energy levels of the present disclosure were measured by using a density functional theory (DFT) in a Gaussian 03 program of Gaussian, Inc. Specifically, the HOMO and LUMO energy levels in the Device Examples and Comparative Examples of the present disclosure were extracted from the structure with the lowest energy by comparing the calculated energies of isomers after structurally optimizing all possible isomer structures at the level of B3LYP/6-31g*.
Hereinafter, it will be explained whether the efficiency of the OLED device can be improved by comprising the compound of formula 1 in the light-emitting layer and the arylamine derivative having a specific HOMO energy level in the hole transport zone. However, the following examples merely explain the properties of the OLED device according to the present disclosure for a detailed understanding thereof, but the present disclosure is not limited by the following examples.
Device Examples 1 to 27: Producing an OLED device according to the
present disclosure
OLED devices according to the present disclosure were produced. A transparent electrode indium tin oxide (ITO) thin film (10 Ω/sq) on a glass substrate for an OLED device (GEOMATEC CO., LTD., Japan) was subjected to an ultrasonic washing with acetone and isopropyl alcohol, sequentially, and then was stored in isopropyl alcohol. The ITO substrate was then mounted on a substrate holder of a vacuum vapor deposition apparatus. Compound HI-1 was introduced into a cell of the vacuum vapor deposition 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 the above-introduced material, thereby forming a first hole injection layer having a thickness of 90 nm on the ITO substrate. Next, compound HI-2 was introduced into another cell of the vacuum vapor deposition apparatus and was evaporated by applying an electric current to the cell, thereby forming a second hole injection layer having a thickness of 5 nm on the first hole injection layer. Compound HT-2-46 was then introduced into a cell of the vacuum vapor deposition apparatus and was evaporated by applying an electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer. The compound of the second hole transport layer shown in Table 1 was then introduced into another cell of the vacuum vapor deposition apparatus and was evaporated by applying an electric current to the cell, thereby forming a second hole transport layer (auxiliary layer) having a thickness of 60 nm on the first hole transport layer. After forming the hole injection layer and the hole transport layer, a light-emitting layer was formed thereon as follows: The host material shown in Table 1 was introduced into one cell of the vacuum vapor depositing apparatus as a host, and compound D-39 was introduced into another cell as a dopant. The two materials were evaporated and the dopant was deposited in a doping amount of 2 wt% based on the amount of the host and dopant to form a light-emitting layer having a thickness of 40 nm on the hole transport layer. Compound ET-1 and compound EI-1 were then introduced into the other two cells and evaporated at a rate of 1:1 to form an electron transport layer having a thickness of 35 nm on the light-emitting layer. After depositing compound 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 deposited on the electron injection layer by another vacuum vapor deposition apparatus. Thus, an OLED device was produced.
Comparative Examples 1 to 19: Producing an OLED device not according to
the present disclosure
OLED devices were produced in the same manner as in Device Example 1, except that the compound shown in the following Table 1 was used in the second hole transport layer, and the compound CBP was used in the host.
Comparative Example 20: Producing an OLED device not according to the
present disclosure
An OLED device was produced in the same manner as in Device Example 1, except that the compound shown in the following Table 1 was used in the second hole transport layer.
The compounds used in Device Examples 1 to 27 and Comparative Examples 1 to 20 are as follows.
Figure PCTKR2018002357-appb-I000154
Figure PCTKR2018002357-appb-I000155
Device Examples 28 to 33: Producing an OLED device according to the
present disclosure
OLED devices were produced in the same manner as in Device Example 1, except that compound HT-1 and compound HI-2 were deposited at a ratio of 1:0.03 instead of the first and second hole injection layers to form a hole injection layer having a thickness of 5 nm, and compound HT-1 was then evaporated to form a first hole transport layer having a thickness of 100 nm, and the compound shown in Table 1 was used in the second hole transport layer.
The driving voltage, the luminous efficiency, and the CIE color coordinates at luminance of 1,000 nits, and the lifespan (measured as the percentage to which the luminance decreased from 100% after 16.6 hours at a constant current and at a luminance of 5,000 nits) of the OLED devices produced in Device Examples 1 to 33 and Comparative Examples 1 to 20 are provided in Table 1 below.
Figure PCTKR2018002357-appb-I000156
Figure PCTKR2018002357-appb-I000157
Figure PCTKR2018002357-appb-I000158
Figure PCTKR2018002357-appb-I000159
Figure PCTKR2018002357-appb-I000160
Figure PCTKR2018002357-appb-I000161
Figure PCTKR2018002357-appb-I000162
Figure PCTKR2018002357-appb-I000163
Figure PCTKR2018002357-appb-I000164
The HOMO energy levels of the compounds comprised in the second hole transport layer of Device Examples 1 to 33 and Comparative Examples 1 to 20 are shown in Table 2 below.
Figure PCTKR2018002357-appb-I000165
Figure PCTKR2018002357-appb-I000166
Figure PCTKR2018002357-appb-I000167
Figure PCTKR2018002357-appb-I000168
From Table 1 above, it can be confirmed that Device Examples 1 to 33 exhibit lower driving voltage, higher luminous efficiency and/or longer lifespan than the Comparative Examples, by comprising the fused azulene derivative compound of the present disclosure in the light-emitting layer and the compound having the specific HOMO energy level of the present disclosure between the first hole transport layer and the light-emitting layer.

Claims (10)

  1. An organic electroluminescent device comprising a first electrode, a second electrode facing the first electrode, a light-emitting layer between the first electrode and the second electrode, and a hole transport zone between the first electrode and the light-emitting layer, wherein the light-emitting layer comprises a compound represented by the following formula 1:
    Figure PCTKR2018002357-appb-I000169
    wherein,
    X1 represents N-L-(Ar)a, S, or O,
    L represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene,
    Ar represents hydrogen, deuterium, a halogen, a cyano, 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 mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino,
    Y1 to Y12, each independently, represent N or CR1,
    R1, each independently, represents hydrogen, deuterium, a halogen, a cyano, 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 (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted ring, and
    a represents an integer of 1 to 4, where if a is an integer of 2 or more, each of Ar may be the same or different; and
    the hole transport zone comprises an arylamine derivative, and the HOMO energy level of the arylamine derivative satisfies the following equation 11:
    -5.0 eV ≤ HOMO ≤ -4.65 eV --- (11).
  2. The organic electroluminescent device according to claim 1, wherein the substituents of the substituted alkyl, the substituted aryl(ene), the substituted heteroaryl(ene), the substituted cycloalkyl, the substituted alkoxy, the substituted trialkylsilyl, the substituted dialkylarylsilyl, the substituted alkyldiarylsilyl, the substituted triarylsilyl, the substituted mono- or di- alkylamino, the substituted mono- or di- arylamino, the substituted alkylarylamino, and the substituted ring in L, Ar, and R1, 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 (5- to 50-membered)heteroaryl unsubstituted or substituted with a (C1-C30)alkyl(s) or a (C6-C30)aryl(s); a (C6-C30)aryl unsubstituted or substituted with a (3- to 50-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 device according to claim 1, wherein at least one adjacent pair of Y1 to Y12 in formula 1 are CR1, and the adjacent two R1’s of CR1 are fused together to each independently form a ring represented by any one of the following formulas 2 to 6:
    Figure PCTKR2018002357-appb-I000170
    Figure PCTKR2018002357-appb-I000171
    wherein,
    A represents N or CR2;
    R2 and R3, each independently, represent hydrogen, deuterium, a halogen, a cyano, 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 (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; and
    Figure PCTKR2018002357-appb-I000172
    represents a bonding site of between C and R1 in the adjacent CR1.
  4. The organic electroluminescent device according to claim 1, wherein the arylamine derivative comprises a compound represented by the following formula 11:
    Figure PCTKR2018002357-appb-I000173
    wherein,
    La to Lc, each independently, represent a single bond, a substituted or unsubstituted (C6-C30)arylene, a substituted or unsubstituted (3- to 30-membered)heteroarylene, or a substituted or unsubstituted (C3-C30)cycloalkylene,
    Ar1 to Ar3, each independently, represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl, with the proviso that at least one of Ar1 to Ar3 is selected from the following formulas:
    Figure PCTKR2018002357-appb-I000174
    Figure PCTKR2018002357-appb-I000175
    Figure PCTKR2018002357-appb-I000176
    Figure PCTKR2018002357-appb-I000177
    wherein,
    X, each independently, represents O, S, NR8, or CR9R10,
    B ring represents a substituted or unsubstituted C10 aryl,
    Z and V, each independently, represent O or S,
    A1 to A12, each independently, represent N or CR43,
    Ld represents a single bond, or a substituted or unsubstituted (C6-C30)arylene,
    R11 to R35, 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 (5- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkyl, -NR36R37, -SiR38R39R40, -SR41, -OR42, a cyano, a nitro, or a hydroxyl, or may be linked to an adjacent substituent to form a substituted or unsubstituted ring, wherein the ring comprises a spiro structure,
    R8 to R10 and R36 to R43, each independently, represent hydrogen, deuterium, a cyano, 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 (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino, or may be linked to an adjacent substituent to form a substituted or unsubstituted ring, and
    b, c, e, g, h, j, k, m, n, o, q, r, and s, each independently, represent an integer of 1 to 4; d, f, p, and t, each independently, represent an integer of 1 to 3; i represents an integer of 1 to 6; l represents 1 or 2; where each of b to t is an integer of 2 or more, each of R11, R12, R14 to R17, R22 to R28, and R30 to R35 may be the same or different.
  5. The organic electroluminescent device according to claim 4, wherein the substituents of the substituted alkyl, the substituted aryl(ene), the substituted heteroaryl(ene), the substituted cycloalkyl, the substituted heterocycloalkyl, the substituted arylalkyl, and the substituted ring in La to Ld, Ar1 to Ar3, and R8 to R43, 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 (5- to 50-membered)heteroaryl unsubstituted or substituted with a (C1-C30)alkyl(s) or a (C6-C30)aryl(s); a (C6-C30)aryl unsubstituted or substituted with a (3- to 50-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.
  6. The organic electroluminescent device according to claim 1, wherein the HOMO energy level of the arylamine derivative satisfies the following equation 12:
    -5.0 eV ≤ HOMO ≤ -4.70 eV ----(12).
  7. The organic electroluminescent device according to claim 1, comprising a first hole transport layer between the first electrode and the light-emitting layer, and a second hole transport layer between the first hole transport layer and the light-emitting layer, wherein the second hole transport layer comprises an arylamine derivative containing a fluorene or a fused flourene, and the HOMO energy level of the arylamine derivative satisfies the equation 11.
  8. The organic electroluminescent device according to claim 1, wherein the compound represented by formula 1 is at least one selected from the following compounds:
    Figure PCTKR2018002357-appb-I000178
    Figure PCTKR2018002357-appb-I000179
    Figure PCTKR2018002357-appb-I000180
    Figure PCTKR2018002357-appb-I000181
    Figure PCTKR2018002357-appb-I000182
    Figure PCTKR2018002357-appb-I000183
    Figure PCTKR2018002357-appb-I000184
    Figure PCTKR2018002357-appb-I000185
    Figure PCTKR2018002357-appb-I000186
    Figure PCTKR2018002357-appb-I000187
    Figure PCTKR2018002357-appb-I000188
    Figure PCTKR2018002357-appb-I000189
    Figure PCTKR2018002357-appb-I000190
    Figure PCTKR2018002357-appb-I000191
    Figure PCTKR2018002357-appb-I000192
    Figure PCTKR2018002357-appb-I000193
    Figure PCTKR2018002357-appb-I000194
    Figure PCTKR2018002357-appb-I000195
    Figure PCTKR2018002357-appb-I000196
    Figure PCTKR2018002357-appb-I000197
    Figure PCTKR2018002357-appb-I000198
    Figure PCTKR2018002357-appb-I000199
    Figure PCTKR2018002357-appb-I000200
    Figure PCTKR2018002357-appb-I000201
    Figure PCTKR2018002357-appb-I000202
    Figure PCTKR2018002357-appb-I000203
    Figure PCTKR2018002357-appb-I000204
    Figure PCTKR2018002357-appb-I000205
    Figure PCTKR2018002357-appb-I000206
    Figure PCTKR2018002357-appb-I000207
    Figure PCTKR2018002357-appb-I000208
    Figure PCTKR2018002357-appb-I000209
    Figure PCTKR2018002357-appb-I000210
    Figure PCTKR2018002357-appb-I000211
    Figure PCTKR2018002357-appb-I000212
    Figure PCTKR2018002357-appb-I000213
    Figure PCTKR2018002357-appb-I000214
    Figure PCTKR2018002357-appb-I000215
    Figure PCTKR2018002357-appb-I000216
    Figure PCTKR2018002357-appb-I000217
    Figure PCTKR2018002357-appb-I000218
    Figure PCTKR2018002357-appb-I000219
    Figure PCTKR2018002357-appb-I000220
    Figure PCTKR2018002357-appb-I000221
    Figure PCTKR2018002357-appb-I000222
    Figure PCTKR2018002357-appb-I000223
    Figure PCTKR2018002357-appb-I000224
    Figure PCTKR2018002357-appb-I000225
    Figure PCTKR2018002357-appb-I000226
    Figure PCTKR2018002357-appb-I000227
    Figure PCTKR2018002357-appb-I000228
    Figure PCTKR2018002357-appb-I000229
    Figure PCTKR2018002357-appb-I000230
    Figure PCTKR2018002357-appb-I000231
    Figure PCTKR2018002357-appb-I000232
    Figure PCTKR2018002357-appb-I000233
    Figure PCTKR2018002357-appb-I000234
    Figure PCTKR2018002357-appb-I000235
    Figure PCTKR2018002357-appb-I000236
    Figure PCTKR2018002357-appb-I000237
    Figure PCTKR2018002357-appb-I000238
    Figure PCTKR2018002357-appb-I000239
    Figure PCTKR2018002357-appb-I000240
    Figure PCTKR2018002357-appb-I000241
    Figure PCTKR2018002357-appb-I000242
    Figure PCTKR2018002357-appb-I000243
    Figure PCTKR2018002357-appb-I000244
    Figure PCTKR2018002357-appb-I000245
    Figure PCTKR2018002357-appb-I000246
    Figure PCTKR2018002357-appb-I000247
    Figure PCTKR2018002357-appb-I000248
    Figure PCTKR2018002357-appb-I000249
    Figure PCTKR2018002357-appb-I000250
    Figure PCTKR2018002357-appb-I000251
  9. The organic electroluminescent device according to claim 1, wherein the arylamine derivative is at least one selected from the following compounds:
    Figure PCTKR2018002357-appb-I000252
    Figure PCTKR2018002357-appb-I000253
    Figure PCTKR2018002357-appb-I000254
    Figure PCTKR2018002357-appb-I000255
    Figure PCTKR2018002357-appb-I000256
    Figure PCTKR2018002357-appb-I000257
    Figure PCTKR2018002357-appb-I000258
    Figure PCTKR2018002357-appb-I000259
    Figure PCTKR2018002357-appb-I000260
    Figure PCTKR2018002357-appb-I000261
    Figure PCTKR2018002357-appb-I000262
    Figure PCTKR2018002357-appb-I000263
    Figure PCTKR2018002357-appb-I000264
    Figure PCTKR2018002357-appb-I000265
    Figure PCTKR2018002357-appb-I000266
    Figure PCTKR2018002357-appb-I000267
    Figure PCTKR2018002357-appb-I000268
    Figure PCTKR2018002357-appb-I000269
    Figure PCTKR2018002357-appb-I000270
    Figure PCTKR2018002357-appb-I000271
    Figure PCTKR2018002357-appb-I000272
    Figure PCTKR2018002357-appb-I000273
    Figure PCTKR2018002357-appb-I000274
    Figure PCTKR2018002357-appb-I000275
    Figure PCTKR2018002357-appb-I000276
    Figure PCTKR2018002357-appb-I000277
    Figure PCTKR2018002357-appb-I000278
    Figure PCTKR2018002357-appb-I000279
    Figure PCTKR2018002357-appb-I000280
  10. The organic electroluminescent device according to claim 1, wherein the hole transport zone comprises a p-doped hole injection layer, a hole transport layer, and a light-emitting auxiliary layer.
PCT/KR2018/002357 2017-02-28 2018-02-27 Organic electroluminescent device WO2018159970A1 (en)

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