CN110734388B - Hole injection compound and application thereof - Google Patents

Hole injection compound and application thereof Download PDF

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CN110734388B
CN110734388B CN201810798471.XA CN201810798471A CN110734388B CN 110734388 B CN110734388 B CN 110734388B CN 201810798471 A CN201810798471 A CN 201810798471A CN 110734388 B CN110734388 B CN 110734388B
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hole injection
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黄雪明
鄢亮亮
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EverDisplay Optronics Shanghai Co Ltd
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Abstract

The invention provides a hole injection compound and application thereof, wherein an organic light-emitting element doped with the compound in a hole transport layer has low starting voltage and can effectively improve the service life of the device. The problems that the existing hole transport material is not stable in the device preparation process or the driving heat resistance is not stable enough, the service life is shortened and the like are solved.

Description

Hole injection compound and application thereof
Technical Field
The invention belongs to the field of photoelectric materials, and relates to a hole injection compound and application thereof.
Background
It is known from the prior art that organic materials can be doped to influence their conductivity properties. The doping material can be used in an organic light-emitting device by proper matching doping so as to reduce the starting voltage and improve the service life of the device.
Compounds commonly used for doping generally have a lower LUMO energy level or a higher HOMO energy level. The compounds with lower LUMO energy level can be used as P-type doping materials, and generally have good strong electron acceptor properties, such as tetrafluorotetracyanoquinodimethane (TCNQF 4) used in hole transport layer materials (US 2005/0255334A 1) and Tetracyanoquinodimethane (TCNQ) (M.Pfeiffer, A.Beyer, T.Fritz, K.Leo, appl.Phys.Lett.,73 (22), 3202-3204 (1998)). However, the aforementioned compounds commonly used for research have problems of being not very stable in the device fabrication process or insufficient in stability to drive heat resistance, decreasing lifetime, and the like.
The present invention has been made to solve the above problems, and an object of the present invention is to provide an electron-accepting material suitable for an organic light-emitting device.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a hole injection compound and an application thereof, and an organic light emitting element doped with the compound in a hole transport layer has a low turn-on voltage and can effectively improve the device lifetime.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a hole injection compound, which has a structure shown in a formula I:
Figure BDA0001736524110000021
wherein, X 1 -X 6 Are each independently CX 7 Any one of B or N, X 7 Any group satisfying its chemical environment, R 1 、R 2 And R 3 Are O, S, = N (CN) and = CR respectively and independently 4 R 5 Or any one of substituted or unsubstituted quinones, R 4 And R 5 Each independently is any group that satisfies its chemical environment, and n is an integer from 0 to 5.
As a preferred embodiment of the present invention, X is 7 Is any one of cyano, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkynyl, acyl, aldehyde, carboxyl, ester group, mercapto, sulfinyl, sulfonyl, phosphino, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl or substituted or unsubstituted quinonyl.
As a preferable embodiment of the present invention, X is 7 Cyano, halogen, C1-C12 alkyl, C2-C12 alkynyl, C2-C12 acyl, aldehyde group, carboxyl, C1-C12 ester group, sulfhydryl, C1-C12 sulfinyl, C1-C12 sulfonyl, C1-C12 phosphino, phenyl, 5-6 membered heteroaryl, quinonyl, and the same or different R by 1 or more than 1 6 Substituted phenyl, substituted by 1 or more R which may be the same or different 6 In substituted 5-to 6-membered heteroaryl or by 1 or more R, which may be the same or different 6 Any one of substituted quinonyl groups.
As a preferable embodiment of the present invention, R is 4 And R 5 Each independently is any one of substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, cyano, halogen, substituted or unsubstituted alkynyl, acyl, aldehyde group, carboxyl, ester group, sulfhydryl, sulfinyl, sulfonyl or phosphino.
As a preferable embodiment of the present invention, R is 4 And R 5 Each independently is phenyl, 5-to 6-membered heteroaryl, cyano, halogen, C2-C12 alkynyl, C2-C12 acyl,aldehyde group, carboxyl group, ester group of C1-C12, sulfhydryl group, sulfinyl group of C1-C12, sulfonyl group of C1-C12, phosphino group of C1-C12, R with 1 or more than 1 same or different 6 Substituted phenyl or substituted by 1 or more R, the same or different 6 Any one of substituted 5-to 6-membered heteroaryl.
As a preferred embodiment of the present invention, R is 6 Is any one or the combination of at least two of halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, cyano, nitro, amino, C1-C6 alkylamino, hydroxyl, hydroxymethyl, carboxyl, sulfydryl, sulfonyl, phenyl or 5-to 6-membered heteroaryl.
In a preferred embodiment of the present invention, the halogen is any one of fluorine, chlorine, bromine, and iodine.
In a preferred embodiment of the present invention, the 5-to 6-membered heteroaryl group is any one of pyrazolyl, furyl, thiazolyl, oxazolyl, isoxazolyl, imidazolyl, triazolyl, thienyl, thiadiazolyl, pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl.
In the present invention, the C1-C12 alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 3-hexyl, n-heptyl, 2-heptyl, n-octyl, 2-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, and the like, but is not limited thereto. The C1-C6 alkyl groups have similar meanings. At least one hydrogen atom on the C1-C6 halogenated alkyl, namely the C1-C6 alkyl is replaced by a halogen atom, and the halogen can be any one of fluorine, chlorine, bromine or iodine. The C1-C6 alkoxy group may be methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, etc., but is not limited thereto. The C1-C6 halogenated alkoxy can be that at least one of other hydrogen atoms except the hydrogen on the alpha carbon on the C1-C6 alkoxy is replaced by halogen atom, and the halogen can be any one of fluorine, chlorine, bromine or iodine.
In the present invention, the C3-C8 cycloalkyl group may be, but is not limited to, cyclopropyl, 2-methylcyclopropyl, 2,3-dimethylcyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, cyclohexyl, 4-methylcyclohexyl, or 4-ethylcyclohexyl. The C3-C8 halogenated cycloalkyl is characterized in that at least one hydrogen atom on the C3-C8 cycloalkyl is replaced by a halogen atom, and the halogen can be any one of fluorine, chlorine, bromine or iodine.
In the present invention, the alkynyl group having 2 to 12 carbon atoms is-C.ident.CR 7 In which R is 7 May be a hydrogen atom or a C1-C10 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 3-hexyl, n-heptyl, 2-heptyl, n-octyl, 2-octyl, n-nonyl or n-decyl group, etc., but is not limited thereto.
In the invention, the acyl of C2-C12 is-COR 8 In which R is 8 There may be C1-C11 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 3-hexyl, n-heptyl, 2-heptyl, n-octyl, 2-octyl, n-nonyl, n-decyl or n-undecyl groups, etc., but not limited to the above groups.
In the present invention, the C1-C12 ester group is-OCOR 9 In which R is 9 There may be C1-C11 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 3-hexyl, n-heptyl, 2-heptyl, n-octyl, 2-octyl, n-nonyl, n-decyl or n-undecyl groups, etc., but not limited to the above groups.
In the present invention, the C1-C12 sulfinyl group is-SOR 10 In which R is 10 It may be a C1-C12 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 3-hexyl, n-heptyl, 2-heptyl, n-octyl, 2-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, but not limited theretoThe above groups are limited.
In the invention, the C1-C12 sulfonyl is-OSOR 11 The structure of (1), the R 11 There may be C1 to C12 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 3-hexyl, n-heptyl, 2-heptyl, n-octyl, 2-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl groups, but not limited to these groups.
In the present invention, the C1-C12 phosphino group is-PR 12 R 13 The structure of (1), the R 12 And R 13 Each of which is independently a hydrogen atom or a C1-C12 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, a 3-hexyl group, an n-heptyl group, a 2-heptyl group, an n-octyl group, a 2-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group or an n-dodecyl group, but not limited thereto.
The hole-injecting compound provided by the present invention is preferably:
Figure BDA0001736524110000051
Figure BDA0001736524110000061
or->
Figure BDA0001736524110000062
Any one of them.
The second object of the present invention is to provide a hole transport material doped with the hole injection compound provided by the present invention.
The invention also aims to provide an organic electroluminescent device, and a hole transport layer of the organic electroluminescent device is prepared from the hole transport material provided by the invention.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention provides a hole injection compound and application thereof, and an organic light-emitting element doped with the compound in a hole transport layer has low starting voltage and can effectively improve the service life of the device. If the doping amount is the same as that of F4-TCNQ, and other structures in the OLED are the same, the OLED has higher efficiency (not lower than 80 Cd/A), lower voltage (not higher than 3.6V) and longer service life (not lower than 195 h).
Detailed Description
For the purpose of facilitating an understanding of the present invention, the following examples are set forth herein. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The invention provides a preparation method of a hole injection compound, which comprises the following steps:
dissolving a compound shown as a formula II and a compound shown as a formula III in a solvent, adding a catalyst, heating to reflux reaction, cooling and crystallizing the solution after the reaction, and purifying and drying the obtained solid after solid-liquid separation to obtain a reaction intermediate; and dissolving the reaction intermediate in a solvent, adding an oxidant and an alkali solution, carrying out water outlet and solid-liquid separation on a reaction system after the reaction is finished, washing and purifying to obtain the hole injection compound.
Figure BDA0001736524110000071
For ease of illustration, Y in the compound of formula II 1 -Y 6 And with X in the compounds of the formula I 1 -X 6 Corresponding when X 1 -X 6 In which at least one group is CX 7 Or BX 8 When is corresponding to Y 1 -Y 6 Group of = CHX 7 Or = BHX 8 When X is present 1 -X 6 In which at least one group is N, corresponding to Y 1 -Y 6 is-NH 2 When Y is 1 And Y 2 、Y 3 And Y 4 Or Y 5 And Y 6 When both are amino, then Y 1 To carbon atoms and Y 2 To carbon atom, Y 3 To carbon atoms and Y 4 To carbon atoms or Y 5 To carbon atoms and Y 6 The carbon atoms connected are connected by double bonds. When Y is 1 And Y 2 、Y 3 And Y 4 Or Y 5 And Y 6 Wherein both groups are CX 7 Or BX 8 When then Z 1 And Z 2 All are halogen; when Y is 1 And Y 2 、Y 3 And Y 4 Or Y 5 And Y 6 When both radicals are amino, Z 1 And Z 2 Are all-SCH 3 (ii) a When Y is 1 And Y 2 、Y 3 And Y 4 Or Y 5 And Y 6 One of the two groups being amino and the other being CX 7 Or BX 8 When Z is 1 And Z 2 One of which is halogen and the other is-SCH 3 . In the compound shown in the formula III, R can be R 1 、R 2 Or R 3 However, in order to improve the selectivity and yield of the reaction, R is preferred in the present invention 1 、R 2 And R 3 Are the same group.
In the preparation method provided by the invention, the selection of specific conditions such as specific solvent, reaction time, catalyst and post-treatment method (such as solid-liquid separation, crystallization, washing, drying, purification and the like) is a conventional technical means in the field, and therefore, the detailed description is omitted.
Example 1
A method for preparing a hole injection compound HI1 comprises the following steps:
as shown in the following chemical reaction formula, the compounds 1 and 2 generate an intermediate compound 3 under the action of a catalyst, because of C (CN) 2 For electron deficient groups, compound 3 is deprotonated and oxidized to give HI1.
Figure BDA0001736524110000081
The specific synthesis steps are as follows:
a250 mL single neck flask was charged with 4.0g of compound 1,8.1g of Compound 2, 40mL of a mixed solution of trifluorotoluene and 80mL of ethanol, stirred for 20min to be sufficiently mixed and dissolved, and then 0.32g of (C) was added 6 F 13 CH 2 CH 2 ) 3 SnH, refluxing and reacting for 24h at 78 ℃, stopping heating, cooling the device in ice-added water to crystallize, filtering the obtained solid, recrystallizing the solid by using ethanol, drying the solid in a vacuum drying oven at the constant temperature of 35 ℃ for 6h, adding the dried substance into a 50ml single-neck flask, and adding 2.3g K 3 [Fe(CN) 6 ]1.2g of saturated aqueous KOH solution, 20ml of CHCl 3 Stirring the solution at normal temperature for 6h, adding anhydrous sodium sulfate into the device after the reaction is finished, filtering after the water is completely removed, and adding a small amount of CHCl 3 Washing, then concentrating the filtrate and using CHCl 3 Recrystallisation three times and final sublimation afforded a tan solid (43% yield).
Characterization data:
tm (DSC) 306 ℃, and purity is 99.9%; 13 C NMR(100MHz,CDCl 3 )δ(ppm):149.0,140.9,128.9,116.1,107.6,96.5,73.6。
example 2
This example provides a method for preparing a hole injection compound HI 2:
as shown in the following chemical reaction formula, compounds 4 and 5 can generate compound 6 under the condition of heating reflux in ethanol, and the target compound HI2 can be obtained after deprotonation and oxidation of compound 6.
Figure BDA0001736524110000091
Figure BDA0001736524110000101
Adding 2.8g of compound 4,9.1g of compound 5 and 120mL of ethanol solution into a 250mL single-neck flask, stirring for 20min to fully mix and dissolve, refluxing at 78 ℃ for 24h, stopping heating, cooling the device in ice-added water to crystallize the compoundThen filtering the obtained solid, recrystallizing the solid by using ethanol, then placing the solid in a vacuum drying oven for drying for 6 hours at the constant temperature of 35 ℃, adding the dried substance into a 50ml single-neck flask, and then adding 2.3g K 3 [Fe(CN) 6 ]1.2g of saturated aqueous KOH solution, 20ml of CHCl 3 Stirring the solution at normal temperature for 6h, adding anhydrous sodium sulfate into the device after the reaction is finished, filtering after the water is completely removed, and adding a small amount of CHCl 3 Washing, then concentrating the filtrate and using CHCl 3 Recrystallisation three times and final sublimation gave a tan solid (72% yield).
Characterization data:
tm (DSC) is 300 ℃, and the purity is 99.9 percent; 13 C NMR(100MHz,CDCl 3 )δ(ppm):163.4,140.0,118.2,71.3。
example 3
This example provides a method for preparing a hole injection compound HI 3:
as shown in the following chemical reaction scheme, the specific reaction conditions in the preparation method were the same as HI2, and the product was a tan solid (yield 52%).
Figure BDA0001736524110000111
Characterization data:
tm (DSC) of 336 ℃ and purity of 99.9 percent; 13 C NMR(100MHz,CDCl 3 )δ(ppm):187.0,175.2,163.0,144.5,138.7,131.0,126.7,117.2,100.0。
example 4
This example provides a method for preparing a hole injecting compound HI 4:
as shown in the following chemical reaction scheme, the specific reaction conditions in the preparation method were the same as HI2, and the product was a tan solid (yield 47%).
Figure BDA0001736524110000121
Characterization data:
Tm(DSC) 347 ℃ and the purity is 99.9 percent; 13 C NMR(100MHz,CDCl 3 )δ(ppm):163.0,155.9,145.6,138.5,133.2,117.2,107.7,100.1。
application examples and comparative examples:
the invention provides an OLED device which sequentially comprises an anode (ITO, 80 nm)/a hole injection layer/a hole transport layer (NPB, 100 nm)/a light emitting layer (TCTA: ir (ppy) 3 (8%), 20 nm)/electron transport layer (BPhen (40%): liQ (60%), 30 nm)/cathode (Mg/Ag, 20 nm); the materials for the hole injection layer and the hole transport layer were selected as shown in table 1:
TABLE 1
Serial number Hole injection layer (10 nm)
Application example 1 NPB:HI1(4％)
Application example 2 NPB:HI2(4％)
Application example 3 NPB:HI3(4％)
Application example 4 NPB:HI4(4％)
Comparative example NPB:F4-TCNQ(4％)
In the application examples and comparative examples, the corresponding structural formulas for the abbreviations of the materials are as follows:
Figure BDA0001736524110000131
the device performance test tests the luminous efficiency of the OLED period provided by the application example, and the test method comprises the following steps: device performance (LE, V) data were measured at 1000nits brightness and lifetime (LT 95) data at a current density of 40mA/cm 2 Calculated under the condition.
The performance test results are shown in table 2:
TABLE 2
Item Color LE(Cd/A) V(V) LT95(hr)
Application example 1 green 87 3.1 228
Application example 2 green 81 3.4 196
Application example 3 green 89 3.6 210
Application example 4 green 96 3.2 326
Comparative example green 30 4.5 33
As can be seen from the properties of table 2, the materials of the present invention are highly suitable for use as hole injection materials in OLED devices and have very good hole injection properties. Compared with the comparative example, the materials selected for the device examples had higher efficiency (not less than 80 Cd/A), lower voltage (not more than 3.6V), and longer life (not less than 195 h).
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (4)

1. A hole injection compound having the structure of formula I:
Figure FDA0003893034260000011
wherein X 1 -X 6 Are each independently CX 7 Or any one of N, the X 7 Is cyano, R 1 、R 2 And R 3 Are each independently = CR 4 R 5 Or quinone, n is 1;
said R is 4 And R 5 Each independently is cyano or substituted by 1 or more R which may be the same or different 6 Substituted phenyl; the R is 6 Is any one of halogen, cyano, C1-C6 alkyl or C1-C6 haloalkyl.
2. The compound of claim 1, wherein the halogen is any one of fluorine, chlorine, bromine, or iodine.
3. A hole transport material, characterized in that the hole transport material is doped with the compound of claim 1 or 2.
4. An organic electroluminescent device, wherein a hole transport layer of the organic electroluminescent device is prepared from the hole transport material according to claim 3.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160041675A (en) * 2014-10-08 2016-04-18 주식회사 두산 Organic compound and organic electroluminescent device using the same
US20170047525A1 (en) * 2015-08-11 2017-02-16 The United States Government As Represented By The Secretary Of The Arm Y Benzotriimidazole materials

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160041675A (en) * 2014-10-08 2016-04-18 주식회사 두산 Organic compound and organic electroluminescent device using the same
US20170047525A1 (en) * 2015-08-11 2017-02-16 The United States Government As Represented By The Secretary Of The Arm Y Benzotriimidazole materials

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