CN113666929B - Carbazole fluorene spiro-compound and organic electroluminescent device - Google Patents

Carbazole fluorene spiro-compound and organic electroluminescent device Download PDF

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CN113666929B
CN113666929B CN202111049531.6A CN202111049531A CN113666929B CN 113666929 B CN113666929 B CN 113666929B CN 202111049531 A CN202111049531 A CN 202111049531A CN 113666929 B CN113666929 B CN 113666929B
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CN113666929A (en
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钱超
许军
朱东林
黄明辉
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Nanjing Topto Materials Co Ltd
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Abstract

The invention discloses a carbazole fluorene spiro-compound and an organic electroluminescent device, which take a spiro-fluorenyl-furan composite structure as a core, and the core has good thermal stability, chemical stability and hole transmission capability. According to the invention, the mode of coupling the ortho-position and meta-position of the phenyl group on the core structure with diarylamine is adopted, so that the steric hindrance and torque of the material can be improved, the solubility of the material molecule is further improved, the good solubility reduces the preparation cost and the environmental cost of the material, and the recovery and the reutilization of the material are facilitated. The material can be recycled, so that the production cost of the material is greatly reduced, and the use efficiency is improved. Meanwhile, the materials are all melting materials, the film forming property and the film forming uniformity of the materials can be improved due to the shape, the hole blocking condition in the evaporation process is effectively avoided, the stability of the device is improved, and the service life of the device is further prolonged.

Description

Carbazole fluorene spiro compound and organic electroluminescent device
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a carbazole fluorene spiro compound and an organic electroluminescent device.
Background
Organic Light-emitting Devices (OLEDs) have the advantages of being thin and Light, emitting Light actively, having a wide viewing angle, fast response, low energy consumption, excellent low-temperature and anti-seismic properties, and potentially flexible design. The OLED is an all-solid-state device, has no vacuum cavity and no liquid component, is not afraid of vibration, is convenient to use, has the characteristics of high resolution, wide visual angle, wide working temperature range and the like, and can be widely applied to the fields of weaponry and severe environment. In addition, the OLED can be used as a plane backlight source and an illumination light source in the display field. Therefore, the OLED has good development prospect.
OLEDs do not require a backlight system as in LCDs, which operate to selectively block certain areas of backlight to allow the image to appear, but they are self-illuminating, and their power consumption is particularly important for battery-powered devices, since OLEDs do not require a backlight system, and is therefore less than LCDs (most of the power consumed by LCDs is used in backlight systems).
The current research on the improvement of the performance of the organic electroluminescent device includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the organic electroluminescent device, not only the innovation of the structure and the manufacturing process of the organic electroluminescent device is required, but also the continuous research and innovation of the organic electro-photoelectric functional material are required, and the organic electroluminescent functional material with higher performance is created.
Disclosure of Invention
The invention aims to provide a carbazole fluorene spiro-compound and an organic electroluminescent device based on the prior art.
The technical scheme of the invention is as follows:
a carbazole fluorene-containing spiro-compound with a structure shown as a formula 1 is characterized in that,
Figure BDA0003252391020000011
wherein the content of the first and second substances,
R 1 or R 2 Each independently is H or a group of formula 2, and R 1 And R 2 When the reaction is not simultaneously H, the reaction solution is not H,
the group of formula 2 has the structure
Figure BDA0003252391020000021
/>
Ar 1 Or Ar 2 Each independently is a substituted or unsubstituted group as follows: c 6-30 Aromatic group, C 6-30 An aromatic derivative group; the substituent is selected from deuterium and C 1-10 Alkyl, deuterated C 1-10 Alkyl radical, C 3-10 Cycloalkyl, deuterated C 3-10 Cycloalkyl, C 6-20 Aromatic radicals or deuterated C 6-20 Aromatic radicalOne or more of the clusters.
In a preferred embodiment, R 1 Is H, R 2 Is a group of formula 2; or R 1 Is a group of formula 2, R 2 Is H.
In another preferred embodiment, ar 1 Or Ar 2 Each independently is a substituted or unsubstituted group as follows: phenyl, biphenyl, dibenzofuranyl or 9, 9-dimethylfluorenyl, the substituents being chosen from deuterium, C 1-10 Alkyl, deuterated C 1-10 Alkyl radical, C 3-10 Cycloalkyl, deuterated C 3-10 Cycloalkyl, C 6-20 Aromatic radicals or deuterated C 6-20 One or more of aromatic groups.
In another preferred embodiment, ar 1 Or Ar 2 Each independently is a substituted or unsubstituted group as follows: phenyl, biphenyl, dibenzofuranyl, or 9, 9-dimethylfluorenyl, the substituents being selected from one or more of deuterium, methyl, deuterated methyl, ethyl, deuterated ethyl, propyl, deuterated propyl, tert-butyl, deuterated tert-butyl, phenyl, deuterated phenyl, cyclopentyl, deuterated cyclopentyl, cyclohexyl, deuterated cyclohexyl, or adamantyl.
In a preferred embodiment, ar 1 Or Ar 2 The substitution in (a) is selected from one or more of deuterium, methyl, deuterated methyl, tert-butyl, phenyl and adamantyl.
Further, the spiro compound is any one of the following compounds:
Figure BDA0003252391020000022
/>
Figure BDA0003252391020000031
/>
Figure BDA0003252391020000041
/>
Figure BDA0003252391020000051
/>
Figure BDA0003252391020000061
/>
Figure BDA0003252391020000071
/>
Figure BDA0003252391020000081
/>
Figure BDA0003252391020000091
Figure BDA0003252391020000101
the carbazole fluorene spiro compound with the structure shown in formula 1 can be synthesized through the following reaction route:
Figure BDA0003252391020000102
in the reaction route of the above formula,
Figure BDA0003252391020000103
is denoted by R 1 Or R 2 One of them is Cl and the other is hydrogen; />
Figure BDA0003252391020000104
Is denoted by R 1 Or R 2 Any one of which is-NAr 1 (Ar 2 ) And the other is hydrogen.
The invention also comprises an organic electroluminescent device which comprises a first electrode, a second electrode and an organic layer formed between the first electrode and the second electrode, wherein the organic layer contains the compound.
Further, the organic layer comprises a hole injection layer, a first hole transport layer, a second hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer; at least one of the hole injection layer, the first hole transport layer, the second hole transport layer, the light-emitting layer, the hole blocking layer, the electron transport layer, and the electron injection layer contains the above compound.
Further, the first hole transporting layer and the second hole transporting layer contain the above-described compound.
The invention relates to an electronic display device containing the organic electroluminescent device.
The invention relates to an OLED lighting device containing the organic electroluminescent device.
Unless otherwise indicated, the following terms used in the specification and claims have the meanings discussed below:
"alkyl" means a saturated aliphatic group of 1 to 20 carbon atoms, including straight and branched chain groups (a numerical range referred to herein, e.g., "1 to 20", means that the group, in this case alkyl, may contain 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 20 carbon atoms). More preferably, the alkyl group is a medium size alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, pentyl, and the like. Preferably, alkyl is lower alkyl having 1 to 6 or 1 to 4 carbon atoms, such as methyl, ethyl, propyl, 2-propyl, n-butyl, isobutyl or tert-butyl, and the like. Alkyl groups may be substituted or unsubstituted. When substituted alkyl, the substituent is preferably one or more, more preferably 1 to 3, most preferably 1 or 2 substituents.
"cycloalkyl" means a monocyclic or fused ring all carbon (a "fused" ring meaning that each ring in the system shares an adjacent pair of carbon atoms with other rings in the system) group in which one or more rings do not have a fully attached pi-electron system, examples of cycloalkyl (without limitation) being cyclopropane, cyclopropenyl, cyclobutane, cyclopentanyl, cyclopentenyl, cyclohexane, cyclohexenyl, bridged ring, cyclohexadienyl, cycloheptanyl and cycloheptatrienyl. Cycloalkyl groups may be substituted and unsubstituted. When substituted, the substituents are preferably one or more groups each selected from the group consisting of: alkyl, hydroxy, alkoxy, cyano, halogen.
"aromatic group" means a monocyclic or fused ring group of 6 to 30 ring atoms having a conjugated pi-electron system. The ring atoms thereof may all be C atoms, e.g. C 6-30 An aromatic group; carbazolyl, oxyfluorenyl, dibenzothienyl, phenyl, naphthyl, tetrahydronaphthyl, indanyl, anthracenyl, fluorenyl, 9-dimethylfluorenyl, and the like. The aromatic hydrocarbon group may be substituted or unsubstituted. When substituted, the substituents are preferably one or more, more preferably one, two or three, and even more preferably one or two, and include: alkyl, aryl, hydroxy, alkoxy, cyano, halogen.
The term "a" in a group refers to the site of attachment of the group to another group or parent ring. When there are multiple attachment sites in a group to other groups or parent rings, it is meant that multiple attachment sites of the group are possible, if not explicitly mentioned.
The room temperature of the invention is 25 +/-5 ℃.
The invention has the beneficial effects that:
the invention designs a compound used as an organic electroluminescent material, which has the following characteristics:
firstly, the compound in the invention takes a spiro-fluorenyl-carbazole composite structure as a core, the core has good thermal stability, chemical stability and hole transmission capability, and the organic electroluminescent material prepared by using the compound also has good thermal stability and chemical stability, the stability and the service life of the device are improved by the characteristics, and meanwhile, the light-emitting efficiency of the device can be further improved by the good hole transmission performance.
Secondly, the organic electroluminescent material designed by the invention has the structure that the ortho-position and the meta-position of the phenyl on the core are coupled with diarylamine. The connection mode has large torque, so that the triplet state energy level of material molecules is improved, the excitons can be effectively limited in the luminescent layer by the high triplet state energy level, the energy is prevented from being reversely transferred from the luminescent layer to the second hole transport layer, the efficiency of the device is further improved, and the service life of the device is further prolonged.
Thirdly, the core invention point of the compound designed by the invention is that the ortho-position and the meta-position of the phenyl on the core structure are coupled with diarylamine. The connection mode can improve the steric hindrance and the torque of the material, further improve the solubility of material molecules, reduce the preparation cost and the environmental cost of the material due to good solubility, and is beneficial to recycling and reusing of the material. The material can be recycled, the production cost of the material is greatly reduced, and the use efficiency is improved. Meanwhile, the materials are all melting materials (the materials are in liquid state during evaporation), the film forming property and the film forming uniformity of the materials can be improved due to the shape, the hole blocking condition in the evaporation process is effectively avoided, the stability of the device is improved, and the service life of the device is further prolonged.
The organic electroluminescent device prepared by using the compound designed by the invention has better luminous efficiency and service life.
Drawings
FIG. 1 is a schematic view of the structure of an organic electroluminescent device according to the present invention;
the reference numbers in the figures represent respectively: 1-anode, 2-hole injection layer, 3-first hole transport layer, 4-second hole transport layer, 5-luminescent layer, 6-hole barrier layer, 7-electron transport layer, 8-electron injection layer and 9-cathode.
FIG. 2 is an HPLC chart of Compound 1 prepared in example 1 of the present invention.
FIG. 3 is a DSC chart of Compound 1 prepared in example 1 of the present invention, and it can be seen from FIG. 3 that the Tg value of Compound 1 is 166.33 ℃.
Fig. 4 is a TGA spectrum of compound 1 prepared in example 1 of the present invention, and it can be seen from fig. 4 that the thermal weight loss temperature Td value is 445.14 ℃.
FIG. 5 is a graph showing the life of organic electroluminescent devices in application example 1 and comparative example 1 of the present invention; as can be seen from fig. 5, the T97% lifetimes of the organic electroluminescent devices prepared in application example 1 and comparative example 1 of the present invention were 607h and 453h, respectively.
Detailed Description
Embodiments of the various aspects are further illustrated and described below. It should be understood that the description herein is not intended to limit the claims to the particular aspects described. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the disclosure as defined by the appended claims.
As used herein, in "substituted" or "unsubstituted," the term "substituted" means that at least one hydrogen in the group is re-coordinated to a hydrocarbyl group, a hydrocarbon derivative group, a halogen, or a cyano (-CN). The term "unsubstituted" means that at least one hydrogen in the group does not re-coordinate with the hydrocarbyl, hydrocarbon derivative group, halogen, or cyano (-CN). Examples of the hydrocarbon group or hydrocarbon derivative group may include, but are not limited to, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C5 to C20 heteroaryl group, a C1 to C20 alkylamino group, a C6 to C20 arylamino group, a C6 to C20 heteroarylamino group, a C6 to C20 arylheteroarylamino group, and the like.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
Figure BDA0003252391020000131
the synthesis of compound 1 is as follows:
Figure BDA0003252391020000132
adding SM1 (50g, 0.155mol) and super-dry THF (500 ml) into a 2L three-mouth bottle, stirring and cooling to below-60 ℃, dropwise adding n-butyl lithium (65.2ml, 1.05eq), controlling the internal temperature to be not more than-60 ℃ in the dropwise adding process, keeping the temperature and stirring for 45-60 min after the dropwise adding is finished, respectively dropwise adding a THF (500 ml) solution of SM2 (40.2g, 1eq), transferring to the room temperature and stirring overnight after the dropwise adding is finished. The reaction was stopped, quenched by addition of 1000ml of saturated aqueous ammonium chloride, the layers were separated by stirring, the aqueous phase was extracted with more DCM (1000 ml), the organic phases were combined and concentrated under reduced pressure to give a brown oil ZJ1, ESI-MS (M/z) (M +): theoretical 502.40, found 502.31; ZJ1 was used directly in the next reaction.
Adding ZJ1 (78g, 0.155mol) and DCM (800 ml) into a 2L single-neck bottle, stirring and cooling to below 0 ℃, quickly dropwise adding methanesulfonic acid (89.5g, 6 eq) after dropwise adding, moving to room temperature and stirring, and monitoring by HPLC (high performance liquid chromatography) that TM-ZJ1 is less than or equal to 0.5%. The reaction was stopped, the reaction was quenched with 800ml ethanol, concentrated at low temperature under reduced pressure to remove most of the DCM, filtered, the filter cake was washed with DCM (500 ml), 800ml ethanol was added, concentrated at low temperature to remove most of the DCM, filtered, the filter cake was rinsed with ethanol (250ml × 2), and dried by forced air at 85 ℃ to give 53.4g of a pale grey solid ZJ2, ESI-MS (M/z) (M +): theoretical value 484.39, found value 484.44; elemental analysis results (molecular formula C31H18 BrN): theoretical value C,76.87; h,3.75; br,16.50; n,2.89; found C,76.80; h,3.72; br,16.55; and N,2.94.
Under the protection of nitrogen, 24.22g (0.05 mol) of ZJ2, 8.2g (0.0525 mol) of o-chlorobenzeneboronic acid are added into a reaction bottle, 300ml of toluene, 75ml of ethanol, 20.7g (0.15 mol) of potassium carbonate, 75ml of water and 0.5775g of palladium tetrakistriphenylphosphine are added, then the reaction solution is heated and refluxed overnight, and HPLC sampling is carried out to detect the completion of the reaction. The reaction solution was added with water, separated, the organic phase was passed through silica gel, concentrated to dryness, and added with ethanol to boil to give 20.6g of product 1-a, ESI-MS (M/z) (M +): theoretical 516.03, found 515.84; elemental analysis (molecular formula C37H22 ClN): theoretical value C,86.12; h,4.30; cl,6.87; n,2.71; found C,86.10; h,4.36; cl,6.89; and N,2.65. The product yield was about 80%.
1-a (20g, 38.76mmol), 1-b (14.0g, 1eq), sodium tert-butoxide (7.95g, 2eq), tri-tert-butylphosphine (3.4ml, 0.04eq) and toluene (200 ml) are added into a 2L reaction kettle, palladium tris-dibenzylidene acetone (0.76g, 0.02eq) is added under the protection of N2, the temperature is increased to 100 ℃, the reaction is stirred after the addition is finished, and the ZJ2 is monitored by HPLC to be basically completely reacted. Stopping reaction, adding 100ml of water and 1500ml of ethanol, stirring, cooling, crystallizing to room temperature, performing suction filtration, leaching a filter cake by using 100ml of ethanol, adding 600ml of toluene into the filter cake, heating, refluxing and dissolving to be clear, passing through silica gel and activated carbon while the filter cake is hot, evaporating 300ml of toluene from the filtrate under normal pressure, adding 300ml of ethanol, stirring, cooling, crystallizing overnight, performing suction filtration, recrystallizing the filter cake by using toluene (300 ml) + ethanol-toluene (300 ml) for four times, performing suction filtration, and performing forced air drying on the filter cake at 85 ℃ to obtain a final target product, namely a white solid compound 1 (18.6 g,22.06mmol, the yield is 56.9%), ESI-MS (M/z) (M +): theoretical 841.05, found 840.68; elemental analysis (molecular formula C64H44N 2): theoretical value C,91.40; h,5.27; n,3.33; found C,91.29; h,5.29; and N,3.42.
Example 2:
Figure BDA0003252391020000151
the synthesis method of the compound 3 is as follows:
Figure BDA0003252391020000152
the preparation was substantially the same as in example 1 except that compound 1-b was replaced with compound 2-b to give the final target compound 3 in 53.5% yield, ESI-MS (M/z) (M +): theoretical 841.05, found 840.83; elemental analysis (molecular formula C64H44N 2): theoretical value C,91.40; h,5.27; n,3.33; found C,91.33; h,5.32; and N,3.35.
Example 3:
Figure BDA0003252391020000153
the synthesis of compound 23 is as follows:
Figure BDA0003252391020000161
the preparation method was substantially the same as in example 1 except that the compound 1-a was replaced with the compound 3-a to give the final objective compound, compound 23, in a yield of 60.8%, ESI-MS (M/z) (M +): theoretical 841.05, found 840.52; elemental analysis (molecular formula C64H44N 2): theoretical value C,91.40; h,5.27; n,3.33; found C,91.38; h,5.22; and N,3.40.
Example 4:
Figure BDA0003252391020000162
the synthesis of compound 25 is as follows:
Figure BDA0003252391020000163
the preparation was carried out in substantially the same manner as in example 1 except that the compound 1-a was replaced with the compound 4-a and the compound 1-b was replaced with the compound 4-b to obtain the final objective compound 25 in a yield of 57.4%, ESI-MS (M/z) (M +): theoretical 841.05, found 840.71; elemental analysis (molecular formula C64H44N 2): theoretical value C,91.40; h,5.27; n,3.33; found C,91.44; h,5.26; and N,3.30.
Example 5:
Figure BDA0003252391020000171
the synthesis of compound 47 is as follows:
Figure BDA0003252391020000172
the preparation was substantially the same as in example 1 except that compound 1-b was replaced with compound 5-b to give the final objective compound 47 in 62.8% yield, ESI-MS (M/z) (M +): theoretical 800.98, found 800.63, elemental analysis result (molecular formula C61H40N 2): theoretical value C,91.47; h,5.03; n,3.50; found C,91.38; h,5.08; n,3.54.
Example 6:
Figure BDA0003252391020000173
the synthesis of compound 53 is as follows:
Figure BDA0003252391020000181
the preparation was carried out in substantially the same manner as in example 1 except that the compound 1-b was replaced with the compound 6-b to give the final objective compound 53 in a yield of 64.3%, ESI-MS (M/z) (M +): theoretical 800.98, found 800.44, elemental analysis result (molecular formula C61H40N 2): theoretical value C,91.47; h,5.03; n,3.50; found C,91.52; h,5.00; and N,3.48.
Example 7:
Figure BDA0003252391020000182
the synthesis of compound 65 was as follows:
Figure BDA0003252391020000183
the preparation method was substantially the same as in example 1 except that compound 1-a was replaced with compound 7-a and compound 1-b was replaced with compound 7-b to give the final target compound 65 in a yield of 61.2%, ESI-MS (M/z) (M +): theoretical 800.98, found 800.82, elemental analysis result (molecular formula C61H40N 2): theoretical value C,91.47; h,5.03; n,3.50; found C,91.50; h,5.00; and N,3.50.
Example 8:
Figure BDA0003252391020000191
the synthesis of compound 71 was as follows:
Figure BDA0003252391020000192
the preparation was carried out in substantially the same manner as in example 1 except that the compound 1-b was replaced with the compound 8-b to obtain the final objective compound 71 in a yield of 60.1%, ESI-MS (M/z) (M +): theoretical 855.07, found 854.89, elemental analysis result (molecular formula C65H46N 2): theoretical value C,91.30; h,5.42; n,3.28; found C,91.34; h,5.36; and N,3.30.
Example 9:
Figure BDA0003252391020000201
the synthesis of compound 99 was as follows:
Figure BDA0003252391020000202
the preparation method was substantially the same as in example 1 except that the compound 1-b was replaced with the compound 9-b to give the final objective compound 99 in a yield of 57.5%, ESI-MS (M/z) (M +): theoretical 899.17, found 898.88, elemental analysis result (molecular formula C68H54N 2): theoretical value C,90.83; h,6.05; n,3.12; found C,90.88; h,6.10; and N,3.02.
Example 10:
Figure BDA0003252391020000203
the synthesis of compound 100 is as follows:
Figure BDA0003252391020000211
the preparation method was substantially the same as in example 1, except that the compound 1-a was replaced with the compound 10-a, and the compound 1-b was replaced with the compound 10-b, to obtain the final objective compound 100 in a yield of 58.9%, ESI-MS (M/z) (M +): theoretical 899.17, found 898.88, elemental analysis result (molecular formula C68H54N 2): theoretical value C,90.83; h,6.05; n,3.12; found C,90.75; h,6.15; and N,3.10.
And (3) testing the material properties:
compounds 1, 3, 23, 25, 47, 53, 65, 71, 99, 100 of the present invention were tested for a temperature Td of thermal weight loss and a melting point Tm, and the test results are shown in table 1 below.
Note: the thermogravimetric analysis was carried out on a TGA N-1000 thermogravimetric analyzer at a temperature Td of 5% weight loss in a nitrogen atmosphere, the nitrogen flow rate was 10mL/min, the melting point Tg (glass transition temperature) was measured by differential scanning calorimetry (DSC, new Zedoku DSC N-650), and the temperature rise rate was 10 ℃/min.
Table 1:
Figure BDA0003252391020000212
Figure BDA0003252391020000221
/>
from the data, the compound synthesized by the invention has excellent thermal stability, which indicates that the compounds according to the structural general formula of the invention have excellent thermal stability and can meet the use requirements of organic electroluminescent materials.
Testing the performance of the device:
application example 1:
adopting ITO as the anode substrate material of the reflecting layer, and sequentially using water, acetone and N 2 Carrying out surface treatment on the glass substrate by plasma;
depositing 10nm of HT-1 doped with 5% HAT-CN above the ITO anode substrate to form a Hole Injection Layer (HIL);
evaporating HT-1 with the thickness of 100nm above the Hole Injection Layer (HIL) to form a first Hole Transport Layer (HTL);
vacuum evaporating the compound 1 designed by the invention above the first Hole Transport Layer (HTL) to form a second hole transport layer (GPL) with the thickness of 30 nm;
GH and G1 are used as green light main body materials and are subjected to co-evaporation according to the mass ratio of 5;
evaporating HB-1 on the light-emitting layer to obtain a Hole Blocking Layer (HBL) with the thickness of 20 nm;
co-evaporating ET-1 and LiQ on a Hole Blocking Layer (HBL) according to the proportion of 5 to obtain an Electron Transport Layer (ETL) with the thickness of 30 nm;
mixing magnesium (Mg) and silver (Ag) according to a ratio of 9;
thereafter, silver (Ag) was evaporated over the electron injection layer to form a cathode having a thickness of 100nm, DNTPD having a thickness of 50nm was deposited on the above-mentioned cathode sealing layer, and further, the surface of the cathode was sealed with a UV hardening adhesive and a sealing film (seal cap) containing a moisture scavenger to protect the organic electroluminescent device from oxygen or moisture in the atmosphere, thereby preparing an organic electroluminescent device.
Figure BDA0003252391020000231
Application examples 2 to 10
Organic electroluminescent devices according to application examples 2 to 10 were produced by using compounds 3, 23, 25, 47, 53, 65, 71, 99 and 100 according to examples 2 to 17 of the present invention as the second hole transporting material, respectively, and the other portions were the same as application example 1.
Comparative examples 1 to 4:
the difference from application example 1 is that compounds 1 and 2 in KR1020180098121A, GP-1 and GP-2 and KR1020170116984A were used as the second hole transporting material in place of compound 1 in the present application, respectively, and the rest was the same as application example 1.
The characteristics of the organic electroluminescent element produced in the above application example and the organic electroluminescent element produced in the comparative example were that the current density was 10mA/cm 2 The results of measurements under the conditions of (1) are shown in Table 2.
Table 2:
Figure BDA0003252391020000241
as can be seen from the above Table 2, when the compound of the present invention is applied to an organic electroluminescent device, the luminous efficiency is greatly improved under the same current density, the start voltage of the device is reduced, the power consumption of the device is relatively reduced, and the service life of the device is correspondingly improved.
The organic electroluminescent devices prepared in the comparative examples 1 to 4 and the application examples 1 to 10 were subjected to a light emission life test to obtain data of light emission life T97% (time for which the light emission luminance was reduced to 97% of the initial luminance), and the test apparatus was a TEO light emitting device life test system. The results are shown in Table 3:
table 3:
Figure BDA0003252391020000251
as can be seen from Table 3, the compound of the present invention has a greatly improved service life and a broad application prospect when applied to an organic electroluminescent device under the same current density.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.

Claims (7)

1. A carbazole fluorene-containing spiro-compound with a structure shown as a formula 1 is characterized in that,
Figure FDA0003969573700000011
wherein the content of the first and second substances,
R 1 is a group of the formula 2,R 2 is H, the group of formula 2 has the structure
Figure FDA0003969573700000012
Ar 1 Is 9, 9-dimethylfluorenyl, ar 2 Is 9, 9-dimethylfluorenyl or substituted or unsubstituted biphenyl, the substituents being selected from one or more of deuterium, methyl, deuterated methyl or adamantyl.
2. The spiro compound according to claim 1 which is any one of the following compounds:
Figure FDA0003969573700000013
/>
Figure FDA0003969573700000021
/>
Figure FDA0003969573700000031
/>
Figure FDA0003969573700000041
/>
Figure FDA0003969573700000051
/>
Figure FDA0003969573700000061
3. an organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode, wherein the organic layer contains the compound according to any one of claims 1 to 2.
4. The organic electroluminescent device according to claim 3, wherein the organic layer comprises a hole injection layer, a first hole transport layer, a second hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer; at least one of the hole injection layer, the first hole transport layer, the second hole transport layer, the light-emitting layer, the hole blocking layer, the electron transport layer, and the electron injection layer contains the compound according to any one of claims 1 to 2.
5. The organic electroluminescent device according to claim 4, wherein the first hole transport layer and the second hole transport layer contain the compound according to any one of claims 1 to 2.
6. An electronic display device comprising the organic electroluminescent element according to claim 3.
7. An OLED lighting device characterized by comprising the organic electroluminescent device according to claim 3.
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