CN109791989A - Organnic electroluminescent device - Google Patents

Organnic electroluminescent device Download PDF

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CN109791989A
CN109791989A CN201780059142.7A CN201780059142A CN109791989A CN 109791989 A CN109791989 A CN 109791989A CN 201780059142 A CN201780059142 A CN 201780059142A CN 109791989 A CN109791989 A CN 109791989A
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unsubstituted
substituted
alkyl
aryl
yuan
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CN109791989B (en
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李泰珍
D-H·李
金宾瑞
吴洪世
金荣光
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Rohm and Haas Electronic Materials Korea Ltd
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Rohm and Haas Electronic Materials Korea Ltd
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Abstract

This disclosure relates to a kind of Organnic electroluminescent device.The Organnic electroluminescent device of the disclosure can provide low driving voltage and excellent luminous efficiency by the inclusion of the specific combination of host compound and hole mobile material.

Description

Organnic electroluminescent device
Technical field
This disclosure relates to a kind of Organnic electroluminescent device.
Background technique
El light emitting device (EL device) is a kind of self-emission display apparatus, the advantage is that it provides broader view Angle, bigger contrast and faster response time.First organic el device is to be developed by Eastman Kodak in 1987 , by using small aromatic diamine molecule and aluminum complex as material [" the applied physics flash report for forming luminescent layer (Appl.Phys.Lett.)》51,913,1987]。
Organic el device (OLED) converts electrical energy into light and applying electric energy to luminous organic material, and usually wraps Include anode, cathode and the dielectric layer formed between two electrodes.The dielectric layer of organic el device may include hole injection layer, sky Cave transport layer, electronic barrier layer, luminescent layer, electron buffer layer, hole blocking layer, electron transfer layer, electron injecting layer etc..For The material of dielectric layer is divided into hole-injecting material, hole mobile material, electron-blocking materials, luminescent material, electronics according to function Padded coaming, hole barrier materials, electron transport material, electron injection material etc..In organic el device, by applying voltage By the hole from anode and the electron injection from cathode into luminescent layer, and by hole and electronics in conjunction with generation Exciton with high-energy.When organic luminescent compounds return to ground state from excitation state, organic luminescent compounds pass through energy It is moved to excitation state, and light is issued by energy.
1987, Tang of Eastman Kodak etc. was bis- using the TPD/ALq3 being made of luminescent layer and charge transport layer Layer develops low molecule green emitting Organnic electroluminescent device.Hereafter, the exploitation of organic el device is affected rapidly, and The device has been commercialized at present.Current organic el device is mainly used for panel using the phosphor material with excellent luminous efficiency Manufacture.For the long-time service and high-resolution of display, low driving voltage and high efficiency are needed.If high-efficient, exist Service life reduces the problem of increasing with driving voltage.If driving voltage reduces, there are problems that low efficiency.In order to obtain low drive The fast hole transmission layer of hole mobility and the low luminescent layer of driving voltage can be used in dynamic voltage.However, this will lead to efficiency It reduces.
Korean Patent Publication No 2015-0066202 discloses a kind of Organnic electroluminescent device, and it uses in this way Compound, wherein diaryl amine etc. is bonded respectively with 5 member rings of benzo [b] fluorenes in hole transmission layer and phenyl ring.However, should Bibliography not specifically discloses the combination of the following two compound applied to Organnic electroluminescent device, in a compound In, diaryl amine is bonded on the 5th carbon location of the naphthalene nucleus of benzo [b] fluorenes, in another compound, nitrogenous heteroaryl With the nitrogen atom bonding of indolocarbazole.
Summary of the invention
Problem to be solved
The purpose of the disclosure is to provide tool by including the specific combination of compound in hole transport area and luminescent layer There is the Organnic electroluminescent device of low driving voltage and excellent luminous efficiency.
Solution to the problem
The inventors discovered that can improve what efficiency when reducing driving voltage reduced by following Organnic electroluminescent device Problem, the Organnic electroluminescent device include: first electrode；The second electrode opposite with first electrode；Setting is in the first electricity One or more luminescent layers between pole and second electrode；And one or more layers between first electrode and luminescent layer is set Hole transport area, wherein at least one layer in hole transport area includes the compound that is indicated by following formula 1, and luminescent layer is at least One layer of compound comprising being indicated by following formula 2:
Wherein
Ar1To Ar6Each independently represent substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6- C30) aryl, substituted or unsubstituted (5 to 30 yuan) heteroaryl or substituted or unsubstituted spiral shell [fluorenes-(C3-C30) cycloalkanes]；Or Ar1And Ar2、Ar3And Ar4And Ar5And Ar6It is interconnected to form monocycle or polycyclic, (3 to 30 yuan) alicyclic ring or aromatic ring or its group It closes, the hetero atom that carbon atom can be selected from nitrogen, oxygen and sulphur at least one is replaced；
L1Indicate that singly-bound, substituted or unsubstituted (C6-C30) arlydene or substituted or unsubstituted (5 to 30 yuan) Asias are miscellaneous Aryl；
L2Indicate singly-bound, substituted or unsubstituted (C1-C30) alkylidene, substituted or unsubstituted (C6-C30) arlydene Or substituted or unsubstituted (5 to 30 yuan) inferior heteroaryl, condition are that wherein n is 0, L2It is not present；
R1And R2Each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5 to 30 yuan) heteroaryl, substituted or unsubstituted (C3-C30) naphthenic base, take Generation or unsubstituted (3 to 7 yuan) Heterocyclylalkyl, substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl ,-NR11R12、- SiR13R14R15、-SR16、-OR17, cyano, nitro or hydroxyl；Or connect with adjacent substituent group with formed monocycle or it is polycyclic, (3 to 30 yuan) alicyclic ring or aromatic ring or combinations thereof, the hetero atom that carbon atom can be selected from nitrogen, oxygen and sulphur by least one are replaced；
R11To R17It each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substitution or does not take (C6-C30) aryl in generation, substituted or unsubstituted (5 to 30 yuan) heteroaryl, substituted or unsubstituted (3 to 7 yuan) Heterocyclylalkyl Or substituted or unsubstituted (C3-C30) naphthenic base；Or connect with adjacent substituent group with formed monocycle or it is polycyclic, (3 to 30 Member) alicyclic ring or aromatic ring or combinations thereof, carbon atom can be by least one hetero atom displacement selected from nitrogen, oxygen and sulphur；
M indicates 1 to 2 integer, and wherein m is 2, each NAr1Ar2It may be the same or different；
N indicates 0 to 2 integer, and wherein n is 2, each NAr3Ar4It may be the same or different；
A indicates 1 to 5 integer, and wherein a is the integer of two or more, each R1It may be the same or different；
B indicates 1 to 4 integer, and wherein b is the integer of two or more, each R2It may be the same or different；
Ma indicates substituted or unsubstituted nitrogenous (3 to 30 yuan) heteroaryl；
L3Indicate singly-bound, substituted or unsubstituted (C6-C30) arlydene or substituted or unsubstituted nitrogenous (3 to 30 yuan) Inferior heteroaryl；
Formula 2 and formula 2-a are in the position of the e and f of formula 2, f and g or g and h, and the position of the * in formula 2-a condensed is formed Ring；
R3To R5Each independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C1-C30) alkane Base (C6-C30) aryl, substituted or unsubstituted (C3-C30) naphthenic base, takes substituted or unsubstituted (3 to 30 yuan) heteroaryl Generation or unsubstituted three (C1-C30) alkyl tin groups, alkyl silane groups, substituted or unsubstituted two (C1-C30) alkyl (C6-C30) aryl-silane Base, two (C6-C30) aryl-silane base of substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted three (C6-C30) virtue Base silane base, substituted or unsubstituted single or two (C1-C30) alkyl aminos, substituted or unsubstituted single or two (C6-C30) virtue Base amino or substituted or unsubstituted (C1-C30) alkyl (C6-C30) arylamino；
R indicates hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl (C1- C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C1-C30) alkyl (C6-C30) aryl, take Generation or unsubstituted (3 to 30 yuan) heteroaryl, substituted or unsubstituted (C3-C30) naphthenic base, substituted or unsubstituted three (C1- C30) alkyl tin groups, alkyl silane groups, substituted or unsubstituted two (C1-C30) alkyl (C6-C30) aryl-silanes base, substituted or unsubstituted (C1-C30) (C6-C30) aryl-silane of alkyl two base, substituted or unsubstituted three (C6-C30) aryl-silanes base, replace or not Substituted list or two (C1-C30) alkyl aminos, substituted or unsubstituted single or two (C6-C30) arylaminos or substitution do not take (C1-C30) alkyl (C6-C30) arylamino in generation；
O and q each independently represents 1 to 4 integer, and p indicates 1 to 2 integer, and wherein o, p and q are two or more Integer, each of R3 to R5 may be the same or different；
Heteroaryl (inferior heteroaryl) is selected from the hetero atom of B, N, O, S, Si and P containing at least one；And
Heterocyclylalkyl contains at least one hetero atom for being selected from O, S and N.
Invention effect
According to the disclosure, can provide a kind of with the organic electroluminescent of low driving voltage and excellent luminous efficiency dress It sets, and it can be used and manufactures display device or lighting device.
Specific embodiment
Hereinafter, the disclosure will be described in detail.It is intended to explain the disclosure however, being described below, and It is not intended to be limiting in any manner the scope of the present disclosure.
Term " organic electroluminescent compounds " in the disclosure refers to the change that can be used in Organnic electroluminescent device Object is closed, and is can be contained in any layer for constituting Organnic electroluminescent device as needed.
Term " electroluminescent organic material " in the disclosure refers to the material that can be used in Organnic electroluminescent device, And it may include at least one compound.When necessary, electroluminescent organic material, which can be contained in, constitutes organic electroluminescence hair In any layer of electro-optical device.For example, electroluminescent organic material can be auxiliary for hole-injecting material, hole mobile material, hole Help material, shine auxiliary material, electron-blocking materials, luminescent material, electronics padded coaming, hole barrier materials, electron-transport Material or electron injection material.
Hereinafter, the Organnic electroluminescent device of the disclosure will be described in detail.
Herein, " (C1-C30) alkyl (alkylidene) " refers to the linear chain or branched chain that chain is constituted with 1 to 30 carbon atom Alkyl, wherein carbon atom number is preferably 1 to 10, and more preferably 1 to 6, and including methyl, ethyl, n-propyl, isopropyl, just Butyl, isobutyl group, tert-butyl etc.." (C2-C30) alkenyl " refers to the linear chain or branched chain alkene that chain is constituted with 2 to 30 carbon atoms Base, wherein carbon atom number is preferably 2 to 20, and more preferably 2 to 10, and including vinyl, 1- acrylic, 2- acrylic, 1- Cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 2- methyl butyl- 2- base etc.." (C2-C30) alkynyl " is that have 2 to 30 carbon atom structures The linear chain or branched chain alkynyl of chaining, wherein carbon atom number is preferably 2 to 20, and more preferably 2 to 10, and including acetenyl, 1- Amyl- 2- alkynyl of propinyl, 2-propynyl, 1- butynyl, 2- butynyl, 3- butynyl, 1- methyl etc.." (C3-C30) naphthenic base " It is monocycle or polycyclic hydrocarbon with 3 to 30 ring skeleton carbon atoms, wherein carbon atom number is preferably 3 to 20, and more preferably 3 to 7, And including cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl etc.." (3 to 7 yuan) Heterocyclylalkyl " is that have at least one hetero atom With the naphthenic base of 3-7 ring skeleton atom, the hetero atom is selected from the group being made of B, N, O, S, Si and P, preferably O, S and N, And including tetrahydrofuran, pyrrolidines, tiacyclopentane, oxinane etc.." (C6-C30) aryl (arlydene) " is to be derived from The monocycle or condensed ring type group of aromatic hydrocarbons with 6 to 30 ring skeleton carbon atoms, wherein ring skeleton carbon atom number be preferably 6 to 20, more preferably 6, it can be fractional saturation, and including phenyl, xenyl, terphenyl, naphthalene, binaphthyl, phenyl Naphthalene, naphthylphenyl, fluorenyl, phenylfluorenyl, benzo fluorenyl, dibenzo fluorenyl, phenanthryl, phenyl phenanthryl, anthryl, indenyl, Sanya Phenyl, pyrenyl, aphthacene base (tetracenyl), base (perylenyl), Qu Ji (chrysenyl), thick four benzene base (naphthacenyl), fluoranthene base (fluoranthenyl) etc.." (5 to 30 yuan) heteroaryl (inferior heteroaryl) " is that have at least 1 A, preferably 1 to 4 is selected from by the hetero atom of B, N, O, S, Si and P group formed and the aryl of 5 to 30 ring skeleton atoms, Middle ring skeletal atom number is preferably 5 to 20, and more preferably 5 to 15；It is monocycle or the fused rings condensed at least one phenyl ring； It can fractional saturation；It can be the group for connecting at least one heteroaryl or aryl with heteroaryl by singly-bound and being formed； And including the ring-like heteroaryl of monocycle, including furyl, thienyl, pyrrole radicals, imidazole radicals, pyrazolyl, thiazolyl, thiadiazoles Base, isothiazolyl, isoxazolyl, oxazolyl, oxadiazoles base, triazine radical, tetrazine base, triazolyl, tetrazole radical, furyl, pyridine Base, pyrazinyl, pyrimidine radicals, pyridazinyl etc. and condensed ring type heteroaryl, including benzofuranyl, benzothienyl, different benzo furan It mutters base, dibenzofuran group, dibenzothiophene, benzo naphtho- thiophenyl, benzimidazolyl, benzothiazolyl, benzisothia Oxazolyl, benzo isoxazolyl, benzoxazolyl, isoindolyl, indyl, indazolyl, diazosulfide, quinolyl, isoquinolin Base, cinnoline base, quinazolyl, quinoxalinyl, carbazyl, phenoxazine base, phenanthridinyl, benzodioxole base etc..It is " nitrogenous (5 to 30 yuan) heteroaryl (inferior heteroaryl) " is that have at least one hetero atom N, and preferably 1 to 4 heteroatomic and 5 to 30 The aryl of a ring skeleton atom, wherein ring skeleton atomicity is preferably 5 to 20, and more preferably 5 to 15；It is monocycle or at least The condensed fused rings of one phenyl ring；It can fractional saturation；It can be by singly-bound by least one heteroaryl or aryl with it is miscellaneous The group of aryl connection and formation；And including the ring-like heteroaryl of monocycle, including pyrrole radicals, imidazole radicals, pyrazolyl, triazine radical, Tetrazine base, triazolyl, tetrazole radical, pyridyl group, pyrazinyl, pyrimidine radicals, pyridazinyl etc., and condense ring-like heteroaryl, including benzene And imidazole radicals, isoindolyl, indyl, indazolyl, diazosulfide base, quinolyl, isoquinolyl, quinolyl, quinazolyl, Quinoxalinyl, carbazyl, phenanthridinyl etc.." halogen " includes F, Cl, Br and I.
Herein, " substituted " in " substituted or unsubstituted " statement refers to that the hydrogen atom in some functional group is another A atom or functional group's (i.e. substituent group) displacement.In Ar1To Ar6、L1To L3、R1To R5、R11To R17, substituted alkane in R and Ma Base (alkylidene), the aryl (arlydene) replaced, the heteroaryl (inferior heteroaryl) replaced, nitrogenous heteroaryl (the sub- heteroaryl replaced Base), replace naphthenic base, substituted Heterocyclylalkyl, substituted trialkylsilanyl, substituted di alkylaryl silylation, take The alkyl diaryl silylation in generation, substituted triaryl silane base, substituted list or dialkyl amido, substituted list or diaryl Amino, substituted alkyl aryl amino, substituted aryl alkyl, substituted alkylaryl and substituted spiral shell [fluorenes-(C3-C30) ring The substituent group of alkane is each independently selected from least one of the group being made up of: deuterium, halogen, cyano, carboxyl, nitre Base, hydroxyl, (C1-C30) alkyl, halogenated (C1-C30) alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C1-C30) alcoxyl Base, (C1-C30) alkylthio group, (C3-C30) naphthenic base, (C3-C30) cycloalkenyl, (3 to 7 yuan) Heterocyclylalkyl, (C6-C30) fragrant oxygen Base, (C6-C30) arylthio, it is unsubstituted or replaced by (C6-C30) aryl (5 to 30 yuan) heteroaryl, it is unsubstituted or by (5 to 30 yuan) heteroaryl replace (C6-C30) aryl, three (C1-C30) alkyl tin groups, alkyl silane groups, three (C6-C30) aryl-silane bases, two (C1-C30) alkyl (C6-C30) aryl-silane base, two (C6-C30) aryl-silane base of (C1-C30) alkyl, amino, Dan Huo bis- (C1-C30) alkyl amino, unsubstituted or by (C1-C30) alkyl-substituted single or two (C6-C30) fragrant aminos, (C1-C30) alkane Base (C6-C30) arylamino, (C1-C30) alkyl-carbonyl, (C1-C30) alkoxy carbonyl, (C6-C30) aryl carbonyl, two (C6-C30) arylboranyl, two (C1-C30) boron alkyl alkyl, (C1-C30) alkyl (C6-C30) arylboranyl, (C6- C30) aryl (C1-C30) alkyl and (C1-C30) alkyl (C6-C30) aryl；It is preferably chosen from the group being made up of: (C1-C6) alkyl, unsubstituted or (C6-C18) aryl, the Yi Jiwei that are replaced by cyano, (C1-C6) alkyl or (C6-C12) aryl (5 to the 20 yuan) heteroaryl for replacing or being replaced by (C6-C12) aryl.
According to one embodiment of the Organnic electroluminescent device of the disclosure, formula 1 can be indicated by following formula 3 or formula 4:
Wherein
Ar1To Ar6、L1、L2、R1、R2, a, b, m and n be as defined in formula 1.
According to one embodiment of the Organnic electroluminescent device of the disclosure, formula 2 can be by any of following formula 5 into formula 10 A expression:
Wherein Ma, L3、R3To R5, R, o, p and q be as defined in formula 2.
In above-mentioned formula 1, Ar1To Ar6Each independently represent substituted or unsubstituted (C1-C30) alkyl, substitution or not (C6-C30) aryl, substituted or unsubstituted (5 to 30 yuan) heteroaryl or the substituted or unsubstituted spiral shell [fluorenes-(C3- replaced C30) cycloalkane]；Or Ar1And Ar2、Ar3And Ar4And Ar5And Ar6Can be interconnected to form monocycle or it is polycyclic, (3 to 30 Member) alicyclic ring or aromatic ring or combinations thereof, carbon atom can be by least one hetero atom displacement selected from nitrogen, oxygen and sulphur.
Preferably, Ar1To Ar4Each independently represent substituted or unsubstituted (C6-C25) aryl, substituted or unsubstituted (5 to 15 yuan) heteroaryl or substituted or unsubstituted spiral shell [fluorenes-(C5-C8) cycloalkane], it is highly preferred that Ar1To Ar4It is respectively independent Ground indicates (C6-C25) aryl that is unsubstituted or being replaced by (C1-C6) alkyl or (C6-C20) aryl；It is unsubstituted or by (C1-C6) (5 to 15 yuan) heteroaryl that alkyl or (C6-C12) aryl replace；Unsubstituted spiral shell [fluorenes-pentamethylene]；Or unsubstituted spiral shell [fluorenes-hexamethylene].Specifically, Ar1To Ar4Can each independently represent phenyl, xenyl, terphenyl, by methyl substituted fluorenes Base, the fluorenyl being substituted by phenyl, by methyl substituted benzo fluorenyl, naphthylphenyl, by phenyl that fluorenes replaces, be substituted by phenyl Pyridyl group, dibenzofuran group, dibenzothiophene, by methyl substituted bisbenzothiazole base, the dibenzo being substituted by phenyl Thiazolyl, spiral shell [fluorenes-pentamethylene], spiral shell [fluorenes-hexamethylene] etc..
Preferably, Ar5And Ar6Each independently represent substituted or unsubstituted (C1-C6) alkyl or substituted or unsubstituted (C6-C12) aryl；Or it can be interconnected to form monocycle or polycyclic, (5 to 15 yuan) alicyclic ring or aromatic ring or combinations thereof, it is more excellent Selection of land, Ar5And Ar6Each independently represent unsubstituted (C1-C6) alkyl or unsubstituted (C6-C12) aryl；Or it can be with It is interconnected so as to form monocycle (5 to 15 yuan) alicyclic ring.Specifically, Ar5And Ar6Methyl, phenyl etc. can be each independently represented, or Person can be interconnected so as to form spiro cyclopentane.
In formula 1, L1Indicate singly-bound, substituted or unsubstituted (C6-C30) arlydene or substituted or unsubstituted (5 to 30 Member) inferior heteroaryl, preferably expression singly-bound, substituted or unsubstituted (C6-C20) arlydene or substituted or unsubstituted (5 to 15 Member) inferior heteroaryl, more preferably expression singly-bound, unsubstituted (C6-C20) arlydene or unsubstituted (5 to 15 yuan) inferior heteroaryl. Specifically, L1It can indicate singly-bound, phenylene, naphthylene, biphenylene, naphthylene phenylene, pyridine phenylene, sub- pyridine Base, phenylene sub-pyridyl group, sub- bipyridyl, dibenzo furylidene, dibenzo Asia thienyl etc..
In formula 1, L2Indicate singly-bound, substituted or unsubstituted (C1-C30) alkylidene, substituted or unsubstituted (C6- C30) arlydene or substituted or unsubstituted (5 to 30 yuan) inferior heteroaryl, condition are the L when n is 02It is not present.L2It is preferred that indicating Singly-bound or substituted or unsubstituted (C6-C12) arlydene more preferably indicate singly-bound or unsubstituted (C6-C12) arlydene.Tool For body, L2It can indicate singly-bound, phenylene etc..
In formula 1, R1And R2Each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substitution Or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5 to 30 yuan) heteroaryl, substituted or unsubstituted (C3-C30) ring Alkyl, substituted or unsubstituted (3 to 7 yuan) Heterocyclylalkyl, substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl ,- NR11R12、-SiR13R14R15、-SR16、-OR17, cyano, nitro or hydroxyl；Or it connect with adjacent substituent group to form monocycle Or polycyclic, (3 to 30 yuan) alicyclic ring or aromatic ring or combinations thereof, carbon atom can be selected from the hetero atom of nitrogen, oxygen and sulphur by least one Displacement, preferably each independently represents hydrogen or substituted or unsubstituted (C6-C20) aryl, more preferably each independently indicates hydrogen Or unsubstituted (C6-C20) aryl.Specifically, R1And R2Hydrogen, biphenyl etc. can be each independently represented.
Herein, R11To R17It each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, take Generation or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5 to 30 yuan) heteroaryl, substituted or unsubstituted (3 to 7 yuan) Heterocyclylalkyl or substituted or unsubstituted (C3-C30) naphthenic base；Or it is connect with adjacent substituent group to form monocycle or more Ring, (3 to 30 yuan) alicyclic ring or aromatic ring or combinations thereof, the hetero atom that carbon atom can be selected from nitrogen, oxygen and sulphur by least one are replaced.
In formula 2, Ma indicates substituted or unsubstituted nitrogenous (3 to 30 yuan) heteroaryl, preferably indicates substituted or unsubstituted Nitrogenous (5 to 15 yuan) heteroaryl.Nitrogenous heteroaryl can be chosen at least one of free group consisting of substitution: (C1- C6) alkyl；(C6-C18 aryl that is unsubstituted or being replaced by cyano, (C1-C6) alkyl or (C6-C12) aryl；And it is unsubstituted Or (5 to 20 yuan) heteroaryl replaced by (C6-C12) aryl.Specifically, Ma can indicate substituted or unsubstituted pyridyl group, Substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted triazine radical, substituted or unsubstituted quinazolyl or substitution do not take The quinoxalinyl in generation.In addition, Ma can indicate unsubstituted or by phenyl, naphthalene, xenyl, terphenyl, binaphthyl, naphthalene Pyridyl group, the pyrimidine radicals, triazine that phenyl, phenyl napthyl, dimethyl fluorenyl, cyano-phenyl, phenylpyridyl or carbazyl replace Base, quinazolyl or quinoxalinyl.
In formula 2, L3Indicate singly-bound, substituted or unsubstituted (C6-C30) arlydene or substituted or unsubstituted nitrogenous (3 To 30 yuan) inferior heteroaryl, preferably expression singly-bound, substituted or unsubstituted (C6-C15) arlydene or substituted or unsubstituted nitrogenous It is (5 to 15 yuan) inferior heteroaryl, more preferably expression singly-bound, unsubstituted or by (C1-C6) alkyl-substituted (C6-C15) arlydene or not Nitrogenous (5 to the 15 yuan) inferior heteroaryl replaced.Specifically, L3It can indicate singly-bound, phenylene, naphthylene, dimethyl fluorenylidene Or sub-pyridyl group.
In formula 2, R3To R5Each independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substitution or not (C6-C30) aryl (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C1- replaced C30) alkyl (C6-C30) aryl, substituted or unsubstituted (3 to 30 yuan) heteroaryl, substituted or unsubstituted (C3-C30) cycloalkanes Base, substituted or unsubstituted three (C1-C30) alkyl tin groups, alkyl silane groups, substituted or unsubstituted two (C1-C30) alkyl (C6-C30) virtue Base silane base, two (C6-C30) aryl-silane base of substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted three (C6- C30) aryl-silane base, substituted or unsubstituted single or two (C1-C30) alkyl aminos, substituted or unsubstituted single or two (C6- C30) arylamino or substituted or unsubstituted (C1-C30) alkyl (C6-C30) arylamino；It is preferred that each independently representing hydrogen Or substituted or unsubstituted (C6-C12) aryl, more preferably each independently indicate hydrogen or unsubstituted (C6-C12) aryl.Tool Body, R3To R5Hydrogen or phenyl can be each independently represented.
In formula 2, R indicates hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) Aryl (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C1-C30) alkyl (C6- C30) aryl, substituted or unsubstituted (3 to 30 yuan) heteroaryl, substituted or unsubstituted (C3-C30) naphthenic base, substitution or not Three (C1-C30) alkyl tin groups, alkyl silane groups of substitution, take substituted or unsubstituted two (C1-C30) alkyl (C6-C30) aryl-silanes base Generation or two (C6-C30) aryl-silane base of unsubstituted (C1-C30) alkyl, substituted or unsubstituted three (C6-C30) aryl-silane Base, substituted or unsubstituted single or two (C1-C30) alkyl aminos, substituted or unsubstituted single or two (C6-C30) arylaminos Or substituted or unsubstituted (C1-C30) alkyl (C6-C30) arylamino, preferably indicate substituted or unsubstituted (C6-C15) virtue Base or substituted or unsubstituted nitrogenous (5 to 15 yuan) heteroaryl, more preferably indicate unsubstituted or alkyl-substituted by (C1-C6) (C6-C15) aryl or unsubstituted nitrogenous (5 to 15 yuan) heteroaryl.Specifically, R can indicate phenyl, naphthalene, dimethyl fluorenyl Or pyridyl group.
It include following compound by the compound that formula 1 indicates, but not limited to this:
It include following compound by the compound that formula 2 indicates, but not limited to this:
The compound of the formula 1 and 2 of the disclosure can be prepared by synthetic method well known by persons skilled in the art.For example, The compound of formula 1 can be prepared according to following formulas.
[reaction equation 1]
Wherein Ar1To Ar6、L1、L2、R1、R2, a, b, m and n be as defined in formula 1.
Organnic electroluminescent device according to one embodiment of the disclosure may include first electrode；It is opposite with first electrode Second electrode；One or more luminescent layers between the first electrode and the second electrode are set；And it is arranged in first electrode One or more layers hole transport area between luminescent layer, wherein at least one layer in hole transport area includes the change indicated by formula 1 Object is closed, and at least one layer of luminescent layer includes the compound indicated by formula 2.
According to one embodiment of the disclosure, the compound of formula 1 and formula 2 be can be contained in same layer, or can be with Respectively it is comprised in the different layers of Organnic electroluminescent device.The compound of formula 1 can be contained in hole transport area, and And the compound of formula 2 can be contained in luminescent layer, more specifically, the compound of formula 1 can be contained in hole transmission layer In, and the compound of formula 2 can be for example comprised in luminescent layer as main compound, but not limited to this.
Other than luminescent layer and hole transport area, selected from the auxiliary layer, electron transfer layer, electron buffer layer, electronics of shining At least one layer in implanted layer, middle layer and hole blocking layer can be included between first electrode and second electrode.
The hole transport area of the disclosure can be made of at least one layer in group consisting of: hole transmission layer, Hole injection layer, electronic barrier layer and hole auxiliary layer, and every layer can be made of one or more layers.
According to one embodiment of the disclosure, hole transport area includes hole transmission layer.In addition, hole transport area can wrap Hole transmission layer is included, and further includes one or more layers in hole injection layer, electronic barrier layer and hole auxiliary layer.
Herein, hole auxiliary layer or the auxiliary that shines are placed between hole transmission layer and luminescent layer, and can be used for The transmission rate in hole is controlled.Hole auxiliary layer or luminous auxiliary layer, which can provide, improves Organnic electroluminescent device The effect of efficiency and service life.
Luminous auxiliary can be placed between anode and luminescent layer, or be placed between cathode and luminescent layer.When will send out When light auxiliary is placed between anode and luminescent layer, it can be used for promoting hole injection and/or hole transport, or for preventing electricity Son overflows.When luminous auxiliary to be placed between cathode and luminescent layer, it can be used for that electron injection and/or electronics is promoted to pass It is defeated, or for preventing hole from overflowing.Furthermore, it is possible to which hole auxiliary is placed on hole transmission layer (or hole injection layer) and is shone Between layer, and it can be effectively facilitated or stop hole transport rate (or hole injection rate), so as to flat to charge Weighing apparatus is controlled.Furthermore, it is possible to electronic blocking is placed between hole transmission layer (or hole injection layer) and luminescent layer, and The leakage that shines can be prevented by stopping the electronics spilling come light emitting layer that exciton is limited in luminescent layer.Work as organic electroluminescence When light emitting device includes two or more hole transmission layers, also included hole transmission layer may be used as hole auxiliary layer or Electronic barrier layer.Hole auxiliary layer and electronic barrier layer can have the efficiency for improving Organnic electroluminescent device and/or service life Effect.
According to one embodiment of the disclosure, hole transmission layer can be made of single layer, and include the disclosure by formula 1 The hole mobile material of the compound of expression can be contained in wherein.
According to another embodiment of the present disclosure, hole transport area may include hole transmission layer, and hole transmission layer It can be made of the multilayer of two or more layers.Hole mobile material comprising the compound indicated by the formula 1 of the disclosure can be with It is comprised in at least one layer of multilayer.In the hole transmission layer or other layers comprising 1 compound of formula, it may include for normal Advise any compound of hole mobile material.For example, may include the compound of following formula 11.
Wherein
L11Indicate that singly-bound, substituted or unsubstituted (C6-C30) arlydene or substituted or unsubstituted (5 to 30 yuan) Asias are miscellaneous Aryl；
Ar11And Ar12Each independently represent substituted or unsubstituted (C6-C30) aryl or it is substituted or unsubstituted (5 to 30 yuan) heteroaryl or Ar11And L11Nitrogenous (5 to 30 yuan) heteroaryl can be formed with the nitrogen being bonded；
R21To R23Each independently represent hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, substituted or unsubstituted (C1-C30) it alkyl, substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted (C2-C30) alkynyl, substitution or does not take (C1-C30) alkoxy in generation, substituted or unsubstituted (C3-C30) naphthenic base, substituted or unsubstituted (C3-C30) cycloalkenyl, Substituted or unsubstituted (3 to 7 yuan) Heterocyclylalkyl, substituted or unsubstituted (C6-C30) aryl, it is substituted or unsubstituted (5 to 30 yuan) heteroaryl ,-NR31R32、-SiR33R34R35、-SR36、-OR37、-COR38Or-B (OR39)(OR40), or with adjacent substitution Base connects to form monocycle or polycyclic, (3 to 30 yuan) alicyclic ring or aromatic ring, or combinations thereof, carbon atom can be substituted at least one choosing It is replaced from the hetero atom of nitrogen, oxygen and sulphur；
R31To R40Each independently represent hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, substituted or unsubstituted (C1-C30) it alkyl, substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted (C2-C30) alkynyl, substitution or does not take (C1-C30) alkoxy in generation, substituted or unsubstituted (C3-C30) naphthenic base, substituted or unsubstituted (C3-C30) cycloalkenyl, Substituted or unsubstituted (3 to 7 yuan) Heterocyclylalkyl, substituted or unsubstituted (C6-C30) aryl or it is substituted or unsubstituted (5 to 30 yuan) heteroaryl, connect with adjacent substituent group to be formed monocycle or it is polycyclic, (3 to 30 yuan) alicyclic or aromatic ring or its group It closes, the hetero atom that carbon atom can be selected from nitrogen, oxygen and sulphur by least one is replaced；
X indicates 1 to 4 integer, and wherein x is the integer of two or more, each R21It may be the same or different；
Y indicates integer of 1 to 3, and wherein y is the integer of two or more, each R22It may be the same or different；
Heteroaryl (inferior heteroaryl) is selected from the hetero atom of B, N, O, S, Si and P containing at least one；And
Heterocyclylalkyl contains at least one hetero atom for being selected from O, S and N.
The compound of the formula 2 of the disclosure can be comprised in luminescent layer.It, can be by the formula of the disclosure when being used for luminescent layer 2 organic electroluminescent compounds are included therein as material of main part.Preferably, luminescent layer also may include one or more Dopant.If desired, the compound of the formula 2 of the disclosure may be used as total material of main part.That is, in addition luminescent layer can wrap Containing the compound in addition to the organic electroluminescent compounds of the formula 2 of the disclosure (the first material of main part) as the second main body material Material.Herein, the weight ratio of the first material of main part and the second material of main part is in the range of 1:99 to 99:1.
Second material of main part can be any of phosphorescence host.For luminous efficiency, it is preferably chosen from by following formula The main body of 12 groups formed to the compound of formula 17.
H-(Cz-L4)c-M-----------(12)
H-(Cz)d-L4-M-----------(13)
Wherein
Cz is indicated with flowering structure:
A expression-O- or-S-；And
R41To R44It each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substitution or does not take (C6-C30) aryl, substituted or unsubstituted (5 to 30 yuan) heteroaryl or the-SiR in generation45R46R47；Wherein R45To R47Respectively solely On the spot indicate substituted or unsubstituted (C1-C30) alkyl or substituted or unsubstituted (C6-C30) aryl；L4It indicates singly-bound, take Generation or unsubstituted (C6-C30) arlydene or substituted or unsubstituted (5 to 30 yuan) inferior heteroaryl；M indicates substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted (5 to 30 yuan) heteroaryl；Y1And Y2Each independently represent-O- ,-S- ,-N (R51)-or-C (R52)(R53)-, condition is Y1And Y2It does not exist simultaneously；R51To R53It each independently represents substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted (5 to 30 yuan) heteroaryl；R52With R53It may be the same or different；C and d each independently represent integer of 1 to 3；J, k, r and s each independently represent 0 to 4 integer； I indicates 0 to 3 integer；If c, d, i, j, k, r or s indicate the integer of two or more, each (Cz-L4), each (Cz), every A R41, each R42, each R43Or each R44It may be the same or different；
Wherein
Y3To Y5Each independently represent CR54Or N；
R54Indicate hydrogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or substitution Or unsubstituted (5 to 30 yuan) heteroaryl；
B1And B2Each independently represent hydrogen, substituted or unsubstituted (C6-C30) aryl or it is substituted or unsubstituted (5 to 30 yuan) heteroaryl；
B3Indicate substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted (5 to 30 yuan) heteroaryl；And
L5Indicate that singly-bound, substituted or unsubstituted (C6-C30) arlydene or substituted or unsubstituted (5 to 30 yuan) Asias are miscellaneous Aryl.
Specifically, the preferred embodiment of the second material of main part is as follows, but not limited to this.
[wherein TPS indicates tri-phenyl-silane base]
It include that dopant in the Organnic electroluminescent device according to the disclosure is preferably at least a kind of phosphorescent dopants. Phosphorescent dopant material applied to the Organnic electroluminescent device according to the disclosure is not particularly limited, but is preferably selected from iridium (Ir), the metallization complex of osmium (Os), copper (Cu) and platinum (Pt) is more preferably selected from iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt) ortho position metal complex, the even more preferably iridium complex compound of ortho position metal.
It include that dopant in the Organnic electroluminescent device of the disclosure can be selected from by following formula 101 to 104 table of formula Group composed by the compound shown, but not limited to this.
Wherein L' is selected from flowering structure:
R100、R134And R135Each independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl or substitution or not (C3-C30) naphthenic base replaced；
R101To R109And R111To R123Each independently represent hydrogen, deuterium, halogen, unsubstituted or replaced by deuterium or halogen (C1-C30) it alkyl, substituted or unsubstituted (C3-C30) naphthenic base, substituted or unsubstituted (C6-C30) aryl, cyano or takes Generation or unsubstituted (C1-C30) alkoxy；R106To R109Adjacent substituents can be interconnected so as to form it is substituted or unsubstituted Fused rings, for example, it is unsubstituted or by alkyl-substituted fluorenes, it is unsubstituted or by alkyl-substituted dibenzothiophenes or it is unsubstituted or by Alkyl-substituted dibenzofurans；R120To R123Adjacent substituents can be interconnected to form it is substituted or unsubstituted condensed Ring, such as quinoline that is unsubstituted or being replaced by least one of alkyl, aryl, aralkyl and alkaryl；
R124To R133And R136To R139Each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl Or substituted or unsubstituted (C6-C30) aryl；R124To R127Adjacent substituents can be interconnected so as to form it is substituted or unsubstituted Fused rings, such as it is unsubstituted or by alkyl-substituted fluorenes, it is unsubstituted or by alkyl-substituted dibenzothiophenes or it is unsubstituted or By alkyl-substituted dibenzofurans；
X indicates CR61R62, O or S；
R61And R62Each independently represent substituted or unsubstituted (C1-C10) alkyl or substituted or unsubstituted (C6- C30) aryl；
R201To R211Each independently represent hydrogen, deuterium, halogen, unsubstituted or (C1-C30) alkane for being replaced by deuterium or halogen Base, substituted or unsubstituted (C3-C30) naphthenic base or (C6-C30) aryl that is unsubstituted or being replaced by alkyl or deuterium；R208 To R211Adjacent substituents can be interconnected so as to form substituted or unsubstituted fused rings, for example, unsubstituted or replaced by alkyl Fluorenes, unsubstituted or by alkyl-substituted dibenzothiophenes or unsubstituted or by alkyl-substituted dibenzofurans；
T and u each independently represent integer of 1 to 3；Wherein t or u is the integer of two or more, each R100Can it is identical or It is different；And
W indicates integer of 1 to 3.
The specific example of dopant compound is as follows, but not limited to this.
The Organnic electroluminescent device of the disclosure also may include at least one selected from by compound and base based on arylamine The compound of the group composed by the compound of styryl arylamine.
In addition, dielectric layer also may include selected from by the periodic table of elements in the Organnic electroluminescent device of the disclosure 1st race's metal, group II metal, the 4th row transition metals, the 5th row transition metals, lanthanide series and d- transition elements have At least one of group metal or at least one complex comprising the metal composed by machine metal.
In the Organnic electroluminescent device of the disclosure, it is preferable that can will be selected from chalcogenide layer, metal halide It is placed on one or two inner surface of electrode at least one layer (hereinafter, " superficial layer ") of metal oxide layer.Specifically, excellent The chalkogenide (including oxide) of silicon or aluminium is placed on the anode surface of electroluminescent medium layer by choosing, and preferably by metal Halide layer or metal oxide are placed on the cathode surface of electrode light-emitting dielectric layer.This superficial layer can be sent out for organic electroluminescence Electro-optical device provides operational stability.Preferably, chalkogenide includes SiOX(1≤X≤2)、AlOX(1≤X≤1.5)、SiON、 SiAlON etc.；The metal halide includes LiF, MgF2、CaF2, rare earth metal fluoride etc.；The metal oxide includes Cs2O、Li2O, MgO, SrO, BaO, CaO etc..
First electrode can be anode.It may include hole transport area between anode and luminescent layer, and hole transport Area may include hole transmission layer.Other than hole transmission layer, hole injection layer, electronic barrier layer or its group can also be used It closes.Multilayer can be used for hole injection layer, with reduce from anode to hole transmission layer or the hole of electronic barrier layer inject gesture It builds (or hole injecting voltage).Every layer can be used simultaneously two kinds of compounds.Electronic barrier layer can also be formed by multilayer.
Second electrode can be cathode.Between luminescent layer and cathode, it can be used selected from electron buffer layer, hole resistance Barrier, electron transfer layer or layer of electron injecting layer or combinations thereof.Multilayer can be used for electron buffer layer, to be injected into electronics Row controls and enhances the interfacial characteristics between luminescent layer and electron injecting layer.Two kinds of compounds can be used simultaneously in each layer. Hole blocking layer or electron transfer layer can also be formed by multilayer, and every layer may include two or more compounds.
Preferably, in the Organnic electroluminescent device of the disclosure, electron transport compound and reproducibility can be adulterated The Mixed Zone of the Mixed Zone of agent or hole transport compound and oxidisability dopant is placed at least one surface of electrode pair On.In this case, electron transport compound is reduced into anion, therefore is easier from Mixed Zone to inject electronics simultaneously It is transmitted to luminescence medium.In addition, hole transport compound is oxidized to cation, therefore it is easier to infuse hole from Mixed Zone Enter or be transmitted to luminescence medium.Preferably, oxidisability dopant includes various lewis acids and acceptor compound；Reproducibility doping Agent includes alkali metal, alkali metal compound, alkaline-earth metal, rare earth metal and its mixture.Reproducibility dopant layer may be used as Charge generation layer, to prepare the organic el device that there are two or more luminescent layers and emit white light.
In order to formed constitute the disclosure organic el device each layer, can using vacuum deposition, sputtering, plasma, from The wet types such as dry types film build method or ink jet printing, nozzle print, slot coated, spin coating, dip-coating, flow coating processes such as son plating Film build method.
When using wet type film build method, formed by the way that the material for constituting each layer to be dissolved or dispersed in suitable solvent Film, described solvent such as ethyl alcohol, chloroform, tetrahydrofuran, dioxanes etc..Solvent is not particularly limited, and the material for constituting each layer exists Be in the solvent it is soluble or dispersible, this will not cause any problem in forming layer.
By using the Organnic electroluminescent device of the disclosure, can manufacture for example for smart phone, tablet computer, pen Remember the display device of this computer, PC, TV or vehicle, or the lighting device of such as indoor or outdoors lighting device.
Hereinafter, by the preparation method of the host compound to the disclosure, the physical property of compound and include this The luminosity of the device of disclosed material of main part and hole mobile material is explained in detail.
Synthesize example 1: the preparation of compound C-4
The preparation of compound 1-1
100g indone (757mmol), 111.6g phthaladehyde (832mmol), the ethyl alcohol of 20% sodium ethoxide of 10.3g is molten Liquid (151mmol) and 1300mL ethyl alcohol are added in reaction vessel.After mixture is flowed back 2 hours, mixture is cooled to room temperature And it is stirred overnight.Reaction solution is cooled to 0 DEG C, the solid being separated by filtration is washed with cold methanol and hexane, obtains 95g chemical combination Object 1-1 (yield: 55%).
The preparation of compound 1-2
33.3g iodine (144mmol), 44g hypophosphorous acid (660mmol, 50% aqueous solution) and 2000mL acetic acid are added and reacted In container, and mixture is stirred 30 minutes at 80 DEG C.95g compound 1-1 (413mmol) is slowly added dropwise thereto, and will Mixture is stirred overnight under reflux.Reaction solution is cooled to room temperature, the solid being separated by filtration is washed with cold methanol and hexane It washs, obtains 73g compound 1-2 (yield: 82%).
The preparation of compound 1-3
By 30g compound 1-2 (139mmol), 39g potassium hydroxide (694mmol), 2.3g potassium iodide (14mmol), 1.58g Benzyltriethylammoinium chloride (7mmol), 70mL distilled water and 700mL dimethyl sulfoxide are added in reaction vessel, and by mixture It is stirred at room temperature 30 minutes.49g methyl iodide (347mmol) is added thereto and is stirred at room temperature overnight mixture.With Ethyl acetate diluting reaction solution is simultaneously washed with distilled water.Then with the organic layer of the dry extraction of magnesium sulfate.Use Rotary Evaporators Solvent is removed, products therefrom is purified with column chromatography, obtains 34g compound 1-3 (yield: 68%).
The preparation of compound 1-4
3g compound 1-3 (12mmol) is dissolved in 50mL methylene chloride in the reaction vessel.By 1.3g bromine (16mmol) is dissolved in 10mL methylene chloride and is added in reaction solution.Then mixture is stirred at room temperature 2 hours. With methylene chloride diluting reaction solution and it is washed with distilled water.Then with the organic layer of the dry extraction of magnesium sulfate.Use rotary evaporation Device removes solvent, and the solid being separated by filtration is washed with cold methanol, obtains 1.8g compound 1-4 (yield: 45%).
Compound 1-4 can also be obtained as follows:
By 1.3g compound 1-3 (5mmol), 10mL dimethylformamide and 1.23g N-bromosuccinimide (7mmol) is added in reaction vessel, and mixture is stirred at room temperature overnight.With ethyl acetate diluting reaction solution and with steam Distilled water washing.Then with the organic layer of the dry extraction of magnesium sulfate.Solvent is removed with rotary evaporator, the solid being separated by filtration is used Cold methanol washing, obtains 620mg compound 1-4 (yield: 36%).
The preparation of compound C-4
By the bis- -9,9- dimethyl -9H- fluorenes -2- base amine (31mmol) of 10g compound 1-4 (31mmol), 13.7g, 1.46g Tris(dibenzylideneacetone) dipalladium (0) (2mmol), 2.2mL tri-tert-butylphosphine (6mmol, 50% toluene solution), the 5.9g tert-butyl alcohol Sodium (62mmol) and 223mL toluene are added in reaction vessel, and mixture is flowed back 4 hours.Reaction solution is cooled to room temperature. Solvent is removed with Rotary Evaporators, products therefrom is purified with column chromatography, obtains 10.5g compound C-4 (yield: 52%).Chemical combination The property of object C-4 is shown in Table 1.
Synthesize example 2: the preparation of compound C-5
By 40g compound 1-4 (124mmol), 44.7g N-1,1'- biphenyl -4- base -9,9- dimethyl -9H- fluorenes -2- amine (124mmol), 3.4g tris(dibenzylideneacetone) dipalladium (0) (4mmol), (7mmol, 50% toluene are molten for 3mL tri-tert-butylphosphine Liquid), 17.8g sodium tert-butoxide (186mmol) and 600mL toluene reaction vessel is added, mixture is flowed back 3 hours.It will react molten Liquid is cooled to room temperature.Solvent is removed with Rotary Evaporators, products therefrom is purified with column chromatography, is obtained 37.8g compound C-5 and (is produced Rate: 51%).The property of compound C-5 is shown in Table 1.
Synthesize example 3: the preparation of compound C-7
By 10g compound 1-4 (31mmol), 16.5g N-1,1'- biphenyl -4- base -9,9- diphenyl -9H- fluorenes -2- amine (34mmol), 1.4g tris(dibenzylideneacetone) dipalladium (0) (2mmol), (3mmol, 50% toluene are molten for 1.2mL tri-tert-butylphosphine Liquid), 5.9g sodium tert-butoxide (62mmol) and 600mL toluene reaction vessel is added, mixture is flowed back 3 hours.By reaction solution It is cooled to room temperature.Remove solvent with Rotary Evaporators, products therefrom purified with column chromatography, obtain 11g compound C-7 (yield: 49%).The property of compound C-7 is shown in Table 1.
Synthesize example 4: the preparation of compound C-73
The preparation of compound 2-1
By bromo- 11,11- dimethyl -11H- benzo [b] fluorenes (31mmol) of 10g 2-, 10mL dimethylformamide and 7.2g N-bromosuccinimide (40mmol) is added in reaction vessel, and mixture is stirred at room temperature overnight.With acetic acid second Ester diluting reaction solution is simultaneously washed with distilled water.Then with the organic layer of the dry extraction of magnesium sulfate.It is removed with rotary evaporator molten Agent, the solid being separated by filtration, is washed with cold methanol, obtains 10.5mg compound 2-1 (yield: 84%).
The preparation of compound C-73
By 10g compound 2-1 (25mmol), 15.6g N-1,1'- biphenyl -4- base -9,9- diphenyl -9H- fluorenes -2- amine (55mmol), 2.3g tris(dibenzylideneacetone) dipalladium (0) (2.5mmol), (5mmol, 50% toluene are molten for 2mL tri-tert-butylphosphine Liquid), 9.6g sodium tert-butoxide (99mmol) and 240mL toluene reaction vessel is added, mixture is flowed back 3 hours.By reaction solution It is cooled to room temperature.Remove solvent with Rotary Evaporators, products therefrom purified with column chromatography, obtain 9.6g compound C-73 (yield: 47%).The property of compound C-73 is shown in Table 1.
Synthesize example 5: the preparation of compound C-25
By 4g compound 1-4 (12mmol), 7.9g N- ([1,1'- biphenyl] -4- base) -9,9- dimethyl-N-(4'- (4, 4,5,5- tetramethyl -1,3,2- dioxaborolan alkane -2- base)-[1,1'- biphenyl] -4- base) -9H- fluorenes -2- amine (12mmol), 0.72g tetrakis triphenylphosphine palladium (0.6mmol), 3.4g potassium carbonate (24mmol), 30mL toluene and 15mL ethyl alcohol add Enter in reaction vessel, 15mL distilled water is added thereto, and mixture is stirred 18 hours at 80 DEG C.After the reaction was completed, it uses Rotary evaporator removes ethyl alcohol and toluene, organic layer methylene chloride and distilled water extraction.Then with the dry organic layer of magnesium sulfate. Solvent is removed with Rotary Evaporators, products therefrom is purified with column chromatography, obtains 3.1g compound C-25 (yield: 33%).Chemical combination The property of object C-25 is shown in Table 1.
Synthesize example 6: the preparation of compound C-102
The preparation of compound 3-1
By 15g N- (9,9- dimethyl -9H- fluorenes -2- base) -11,11- dimethyl-N-(4- (naphthalene -2- base) phenyl) -11H- Benzo [b] fluorenes -2- amine (23mmol), 120mL dimethylformamide and 5.3g N-bromosuccinimide (30mmol) are added anti- It answers in container, and mixture is stirred at room temperature overnight.With ethyl acetate diluting reaction solution and it is washed with distilled water.Then With the organic layer of the dry extraction of magnesium sulfate.Solvent is removed with Rotary Evaporators, products therefrom is purified with column chromatography, obtains 15gization Close object 3-1 (yield: 89%).
The preparation of compound C-102
By 10g compound 3-1 (14mmol), 2.7g diphenylamines (16mmol), 0.63g tris(dibenzylideneacetone) dipalladium (0) (0.68mmol), 0.5mL tri-tert-butylphosphine (1.4mmol, 50% toluene solution), 2.6g sodium tert-butoxide (28mmol) and 260mL toluene is added in reaction vessel, flows back 3 hours at 80 DEG C.Reaction solution is cooled to room temperature.It is removed with Rotary Evaporators Solvent is removed, products therefrom is purified with column chromatography, obtains 3.1g compound C-102 (yield: 28%).The property of compound C-102 It is shown in Table 1.
Synthesize example 7: the preparation of compound C-103
The preparation of compound 4-1
By 26g 2- ([1,1'- xenyl] -4- base) -11,11- dimethyl -11H- benzo [b] fluorenes (66mmol), 330mL Dimethylformamide, 200mL methylene chloride and 15.2g N-bromosuccinimide (85mmol) are added in reaction vessel, will mix Object is closed to be stirred at room temperature overnight.With ethyl acetate diluting reaction solution and it is washed with distilled water.Then extracted with magnesium sulfate is dry The organic layer taken.Remove solvent with Rotary Evaporators, products therefrom purified with column chromatography, obtain 26g compound 4-1 (yield: 83%).
The preparation of compound C-103
By 13g compound 4-1 (27mmol), 9.9g N-1,1'- biphenyl -4- base -9,9- dimethyl -9H- fluorenes -2- amine (27mmol), 1.25g tris(dibenzylideneacetone) dipalladium (0) (1.4mmol), 1.1mL tri-tert-butylphosphine (2.7mmol, 50% first Benzole soln), 5.3g sodium tert-butoxide (54mmol) and 136mL toluene be added in reaction vessel, next time at 80 DEG C by reaction mixture Stream 3 hours.Reaction solution is cooled to room temperature.Solvent is removed with Rotary Evaporators, products therefrom is purified with column chromatography, obtained 4.5g compound C-103 (yield: 22%).The property of compound C-103 is shown in Table 1.
Synthesize example 8: the preparation of compound C-99
By 10g compound 1-4 (31mmol), 14.0g N- (9,9- dimethyl -9H- fluorenes -2- base) -11,11'- dimethyl - 11H- benzo [b] fluorenes -2- amine (31mmol), 1.42g tris(dibenzylideneacetone) dipalladium (0) (1.60mmol), the tertiary fourth of 1.6mL tri- Base phosphine (3.1mmol, 50% toluene solution), 5.9g sodium tert-butoxide (62mmol) and 155mL toluene are added in reaction vessel, and will Mixture flows back 16 hours at 80 DEG C.Reaction solution is cooled to room temperature.Solvent is removed with Rotary Evaporators, products therefrom is used Column chromatography purifying, obtains 9.1g compound C-99 (yield: 42%).The property of compound C-99 is shown in Table 1.
Synthesize example 9: the preparation of compound C-98
By 8g compound 1-4 (25mmol), 11.9g N- ([1,1':4', 1 "-tert-butyl] -4- base) -9,9- dimethyl - 9H- fluorenes -2- amine (27mmol), 1.13g tris(dibenzylideneacetone) dipalladium (0) (1.35mmol), 1.0mL tri-tert-butylphosphine (2.7mmol, 50% toluene solution), 4.8g sodium tert-butoxide (50mmol) and 125mL toluene are added in reaction vessel, by mixture It flows back 3 hours at 80 DEG C.Reaction solution is cooled to room temperature.Solvent is removed with rotary evaporator, obtained product is to use column Chromatography purifying, obtains 5.7g compound C-98 (yield: 34%).The characteristic of compound C-98 is shown in table 1.
Synthesize example 10: the preparation of compound C-10
By 7.4g compound 1-4 (23mmol), 9.4g 9,9- dimethyl-N-(4- (naphthalene -2- base) phenyl) -9H- fluorenes -2- Amine (23mmol), 1.05g tris(dibenzylideneacetone) dipalladium (0) (1.15mmol), 1.2mL tri-tert-butylphosphine (2.3mmol, 50% toluene solution), 4.4g sodium tert-butoxide (46mmol) and 200mL toluene be added in reaction vessel, by reaction mixture 80 It flows back 3 hours at DEG C.Reaction solution is cooled to room temperature.Solvent is removed with Rotary Evaporators, products therefrom is purified with column chromatography, Obtain 3.7g compound C-10 (yield: 25%).The property of compound C-10 is shown in Table 1.
[table 1]
In addition, the compound of the formula 2 of the disclosure is known compound, and synthetic method known in the art can be passed through Preparation.
Device example 1: the combined OLED device of the preparation hole mobile material comprising the disclosure and host compound
The combined OLED device of the preparation hole mobile material comprising the disclosure and host compound.It is being used for organic hair In the glass substrate of optical diode (OLED) device (Japanese Geomatec) transparent electrode tin indium oxide (ITO) film (10 Ω/ Sq ultrasonic cleaning successively) is carried out with acetone and isopropanol, is then stored in isopropanol.Next, ITO substrate is mounted on On the substrate support of vacuum phase deposition equipment.Compound HI-1 is added in the unit of the vacuum phase deposition equipment, so The pressure in the room of the equipment is controlled 10 afterwards-6Support.Hereafter, the material of above-mentioned addition is evaporated to unit application electric current, To form the first hole injection layer with a thickness of 90nm on ITO substrate.Then the vacuum gas is added in compound HI-2 In another unit of phase depositing device, and make its evaporation by applying electric current to unit, thus on the first hole injection layer Form the second hole injection layer with a thickness of 5nm.Compound HT-1 is added to another list of the vacuum phase deposition equipment In member, and make its evaporation by applying electric current to unit, to be formed on the second hole injection layer with a thickness of the first of 10nm Hole transmission layer.Second hole mobile material of the following table 2 is added in another unit of the vacuum phase deposition equipment, and Make its evaporation by applying electric current to unit, to form the second hole transport with a thickness of 60nm on the first hole transmission layer Layer.After forming hole injection layer and hole transmission layer, then following depositing light emitting layer.Compound H-17 is added as follows true As the layer main body that shines in one unit of vapor depos equipment, and compound D-71 is added in another unit.Two kinds Material is evaporated with different rate, and by based on main body and dopant total amount, the doping (amount of dopant) of 2wt% is deposited, To form the luminescent layer with a thickness of 40nm on the second hole transmission layer.Then compound ET-1 and compound EI-1 is added another It in outer two units, is evaporated, and is deposited to form the electron transfer layer with a thickness of 35nm on the light-emitting layer with the ratio of 1:1.It connects Get off, after deposited compound EI-1 is as the electron injecting layer with a thickness of 2nm on the electron transport layer, passes through another vacuum gas The Al cathode that phase depositing device deposition thickness on electron injecting layer is 80nm.It is prepared for OLED device as a result,.
Device example 2-6: the combined OLED device of the preparation hole mobile material comprising the disclosure and host compound
In addition to use compound shown in table 2 as the second hole mobile material other than, with identical with device example 1 Mode manufacture OLED device.
The assessment result of each device in device example 1 to 6 is shown in Table 2.OLED dress is provided in following table 2 Set driving voltage, luminous efficiency and the CIE chromaticity coordinates in the case where brightness is 1,000 nits.
Comparative example 1 to 3: manufacture does not include the hole mobile material of the disclosure and the combined OLED device of host compound
In addition to use compound shown in table 2 as the second hole mobile material other than, with identical with device example 1 Mode manufacture OLED device.
The assessment result of each device in comparative example 1 to 3 is shown in the following table 2.
[table 2]
Device example 7 to 14: the combined OLED dress of hole mobile material of the preparation comprising the disclosure and host compound It sets
In addition to using compound shown in table 3 as the second hole mobile material, and use compound H-12 as master Except body, OLED device is manufactured in a manner of identical with device example 1.
The brightness of the OLED device of device example 7 to 14 is provided in following table 3 as the driving electricity under 1,000 nits Pressure, luminous efficiency and CIE chromaticity coordinates.
Comparative example 4 and 5: preparation does not include the hole mobile material of the disclosure and the combined OLED device of host compound
In addition to using compound shown in table 3 as the second hole mobile material, and use compound H-12 as master Except body, OLED device is manufactured in a manner of identical with device example 1.
Provided in following table 3 driving voltage in the case where brightness is 1,000 nits of the OLED device of comparative example 4 and 5, Luminous efficiency and CIE chromaticity coordinates.
[table 3]
Shown in table 2 and 3 as above, the device of device example 1 to 14 has preferably driving electricity compared to the device of comparative example Pressure and light-emitting efficiency characteristics.When device example 1 to 14 and comparative example are compared, it should be understood that higher light-emitting efficiency characteristics It is low HOMO (highest occupied molecular orbital) energy level due to the hole mobile material of the disclosure and obtains, and lower driving Voltage is the quick cavity transmission ability due to fluorenes and obtains (but without being bound by theory).The result shows that luminous efficiency improves When driving voltage increase the problem of overcome.
In view of the main feature of hole transmission layer (HTL), i.e. cavity transmission ability, low driving voltage is usually required quickly Hole transport.Therefore, it is necessary to high HOMO energy levels.Under high HOMO energy level, driving voltage is reduced, but is difficult to obtain high efficiency.Separately Outside, for luminescent layer, efficiency is reduced under low driving voltage, therefore is not readily available high efficiency.By using the disclosure Hole transmission layer and luminescent layer combination, relatively low driving voltage and high efficiency can be obtained.
It should be understood that this is because 5 (b) benzfluorenes have HOMO energy level relatively more lower than 2 (b) benzfluorenes, therefore offer Higher efficiency (but without being bound by theory).If HOMO energy level reduces, driving voltage increases.However, fluorenes counteracts increase Driving voltage, and low driving voltage may finally be provided.

Claims (10)

1. a kind of Organnic electroluminescent device comprising:
First electrode；
The second electrode opposite with the first electrode；
One or more luminescent layers between the first electrode and the second electrode are set；And
One or more layers hole transport area between the first electrode and the luminescent layer is set, wherein
At least one layer in the hole transport area includes the compound indicated by following formula 1, and
At least one layer of the luminescent layer includes the compound indicated by following formula 2:
Wherein
Ar1To Ar6Each independently represent substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) virtue Base, substituted or unsubstituted (5 to 30 yuan) heteroaryl or substituted or unsubstituted spiral shell [fluorenes-(C3-C30) cycloalkanes]；Or Ar1With Ar2、Ar3And Ar4And Ar5And Ar6It is interconnected to form monocycle or polycyclic, (3 to 30 yuan) alicyclic ring or aromatic ring or combinations thereof, The hetero atom that carbon atom can be selected from nitrogen, oxygen and sulphur at least one is replaced；
L1Indicate singly-bound, substituted or unsubstituted (C6-C30) arlydene or substituted or unsubstituted (5 to 30 yuan) inferior heteroaryl；
L2Indicate singly-bound, substituted or unsubstituted (C1-C30) alkylidene, substituted or unsubstituted (C6-C30) arlydene or substitution Or unsubstituted (5 to 30 yuan) inferior heteroaryl, condition are that wherein n is 0, L2It is not present；
R1And R2Each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5 to 30 yuan) heteroaryl, substituted or unsubstituted (C3-C30) naphthenic base, substitution Or unsubstituted (3 to 7 yuan) Heterocyclylalkyl, substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl ,-NR11R12、- SiR13R14R15、-SR16、-OR17, cyano, nitro or hydroxyl；Or connect with adjacent substituent group with formed monocycle or it is polycyclic, (3 to 30 yuan) alicyclic ring or aromatic ring or combinations thereof, the hetero atom that carbon atom can be selected from nitrogen, oxygen and sulphur by least one are replaced；
R11To R17Each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) it aryl, substituted or unsubstituted (5 to 30 yuan) heteroaryl, substituted or unsubstituted (3 to 7 yuan) Heterocyclylalkyl or takes Generation or unsubstituted (C3-C30) naphthenic base；Or it is connect with adjacent substituent group to form monocycle or polycyclic, (3 to 30 yuan) rouge Ring or aromatic ring or combinations thereof, the hetero atom that carbon atom can be selected from nitrogen, oxygen and sulphur by least one are replaced；
M indicates 1 to 2 integer, and wherein m is 2, each NAr1Ar2It can be identical or different；
N indicates 0 to 2 integer, and wherein n is 2, each NAr3Ar4It can be identical or different；
A indicates 1 to 5 integer, and wherein a is the integer of two or more, each R1It can be identical or different；
B indicates 1 to 4 integer, and wherein b is the integer of two or more, each R2It can be identical or different；
Ma indicates substituted or unsubstituted nitrogenous (3 to 30 yuan) heteroaryl；
L3Indicate singly-bound, substituted or unsubstituted (C6-C30) arlydene or substituted or unsubstituted nitrogenous (3 to 30 yuan) sub- heteroaryls Base；
Formula 2 and formula 2-a are condensed in the position of the * of the position and formula 2-a of the e and f of formula 2, f and g or g and h forms ring；
R3To R5Each independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6- C30) aryl (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C1-C30) alkyl (C6-C30) aryl, substituted or unsubstituted (3 to 30 yuan) heteroaryl, substituted or unsubstituted (C3-C30) naphthenic base, substitution Or unsubstituted three (C1-C30) alkyl tin groups, alkyl silane groups, substituted or unsubstituted two (C1-C30) alkyl (C6-C30) aryl-silane Base, two (C6-C30) aryl-silane base of substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted three (C6-C30) virtue Base silane base, substituted or unsubstituted single or two (C1-C30) alkyl aminos, substituted or unsubstituted single or two (C6-C30) virtue Base amino or substituted or unsubstituted (C1-C30) alkyl (C6-C30) arylamino；
R indicates hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl (C1-C30) Alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C1-C30) alkyl (C6-C30) aryl, substitution or Unsubstituted (3 to 30 yuan) heteroaryl, substituted or unsubstituted (C3-C30) naphthenic base, substituted or unsubstituted three (C1-C30) Alkyl tin groups, alkyl silane groups, substituted or unsubstituted two (C1-C30) alkyl (C6-C30) aryl-silanes base, substituted or unsubstituted (C1- C30) (C6-C30) aryl-silane of alkyl two base, substituted or unsubstituted three (C6-C30) aryl-silanes base, substituted or unsubstituted List or two (C1-C30) alkyl aminos, substituted or unsubstituted single or two (C6-C30) arylaminos or substituted or unsubstituted (C1-C30) alkyl (C6-C30) arylamino；
O and q each independently represents 1 to 4 integer, and p indicates 1 to 2 integer, and wherein o, p and q are the whole of two or more Number, R3To R5Each of can be identical or different；
The heteroaryl (inferior heteroaryl) is selected from the hetero atom of B, N, O, S, Si and P containing at least one；And
The Heterocyclylalkyl contains at least one hetero atom for being selected from O, S and N.
2. Organnic electroluminescent device according to claim 1, wherein formula 1 is indicated by following formula 3 or formula 4:
Wherein
Ar1To Ar6、L1、L2、R1、R2, a, b, m and n it is as defined in claim 1.
3. Organnic electroluminescent device according to claim 1, wherein in formula 1, Ar1To Ar4It each independently represents and takes Generation or unsubstituted (C6-C25) aryl, substituted or unsubstituted (5 to 15 yuan) heteroaryl or substituted or unsubstituted spiral shell [fluorenes-(C5-C8) cycloalkanes]].
4. Organnic electroluminescent device according to claim 1, wherein in formula 1, Ar5And Ar6It each independently represents and takes Generation or unsubstituted (C1-C6) alkyl or substituted or unsubstituted (C6-C12) aryl；Or be interconnected so as to form monocycle or Polycyclic, (5 to 15 yuan) alicyclic ring or aromatic ring or combinations thereof.
5. Organnic electroluminescent device according to claim 1, wherein formula 2 is indicated by any of following formula 5 to formula 10:
Wherein Ma, L3、R3To R5, R, o, p and q it is as defined in claim 1.
6. Organnic electroluminescent device according to claim 1, wherein in formula 2, Ma indicates substituted or unsubstituted pyrrole Piperidinyl, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted triazine radical, substituted or unsubstituted quinazolyl or substitution or Unsubstituted quinoxalinyl.
7. Organnic electroluminescent device according to claim 1, wherein in formula 2, R indicates substituted or unsubstituted (C6- C15) aryl or substituted or unsubstituted nitrogenous (5 to 15 yuan) heteroaryl.
8. Organnic electroluminescent device according to claim 1, wherein the compound indicated by formula 1 is selected from by following The group of composition:
9. Organnic electroluminescent device according to claim 1, wherein the compound indicated by formula 2 is selected from by following The group of composition:
10. Organnic electroluminescent device according to claim 1, wherein the hole transport area includes hole transmission layer, It and further include at least one layer of hole injection layer, electronic barrier layer and hole auxiliary layer.
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