CN109912592B - Compound containing pyridoindole and application of compound in organic electroluminescent device - Google Patents
Compound containing pyridoindole and application of compound in organic electroluminescent device Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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Abstract
The invention discloses a pyridoindole-containing compound and application thereof in an organic electroluminescent device, wherein the compound consists of pyridoindole groups, has deep HOMO energy level and hole mobility, and is suitable for being used as a hole transport material or an electron blocking material; in addition, the compound has the characteristics of strong group rigidity, difficult intermolecular crystallization and aggregation and good film forming property. After the organic electroluminescent functional layer material is applied to an OLED device, the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a pyridoindole-containing compound and application thereof in an organic electroluminescent device.
Background
The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect. The OLED light-emitting device is of a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and the various different functional materials are mutually overlapped together according to the application to form the OLED light-emitting device. When voltage is applied to two end electrodes of the OLED light-emitting device as a current device, positive and negative charges in the organic layer functional material film layer are acted through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, namely OLED electroluminescence is generated.
At present, the OLED display technology has been applied in the fields of smart phones, tablet computers, and the like, and will further expand to large-size application fields such as televisions, but compared with actual product application requirements, the light emitting efficiency, the service life, and other performances of the OLED device need to be further improved. The research on the improvement of the performance of the OLED light emitting 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 OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the OLED photoelectric functional material are needed to create the functional material of the OLED with higher performance. The photoelectric functional materials of the OLED applied to the OLED device can be divided into two broad categories from the application, i.e., charge injection transport materials and light emitting materials, and further, the charge injection transport materials can be further divided into electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials, and the light emitting materials can be further divided into main light emitting materials and doping materials. In order to fabricate a high-performance OLED light-emitting device, various organic functional materials are required to have good photoelectric properties, for example, as a charge transport material, good carrier mobility, high glass transition temperature, etc. are required, and as a host material of a light-emitting layer, a material having good bipolar property, appropriate HOMO/LUMO energy level, etc. is required.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, and the OLED device structure applied in industry comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transport material, a light emitting material, an electron transport material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional materials have stronger selectivity, and the performance of the same materials in the devices with different structures can also be completely different. Therefore, aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, a more suitable OLED functional material or material combination with high performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual demand of the current OLED display illumination industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and the development of organic functional materials with higher performance is very important as a material enterprise.
Disclosure of Invention
In view of the above problems in the prior art, the present application provides a pyridoindole-containing compound and its application in an organic electroluminescent device. The compound has higher glass transition temperature and molecular thermal stability, proper HOMO and LUMO energy levels and high hole mobility, and can effectively improve the luminous efficiency of the device and prolong the service life of the OLED device after being applied to the manufacture of the OLED device.
The technical scheme of the invention is as follows: a pyridoindole-containing compound has a structure shown in a general formula (1):
wherein X represents a single bond; i is equal to 0 or 1;
a represents a single bond, an oxygen atom, C1-10One of linear chain or branched alkyl substituted alkylidene, aryl substituted alkylidene, alkyl substituted imino or aryl substituted imino;
X1、X2、X3、X4、X5、X6、X7、X8independently represent C-H or N atoms, and the number of N atoms is 0, 1 or 2;
m, n, p, q are equal to 0 or 1; and m + n + p + q is more than or equal to 1;
e is optionally substituted with one or more R1A substituted pyridoindole group;
R1is represented by substituted or unsubstituted C6To C30Aryl and substituted or unsubstituted C5To C30One of heteroarylSeed growing; the heteroatom is nitrogen, oxygen or sulfur.
On the basis of the scheme, the invention can also be improved as follows.
Preferably, the compound containing pyridoindole, E can be represented by the general formula (2);
wherein Ar is1Is represented by a single bond, substituted or unsubstituted C6-30Arylene, substituted or unsubstituted C5-30One of heteroarylene groups; the heteroatom is nitrogen, oxygen or sulfur;
Ar2is represented by substituted or unsubstituted C6-30Aryl, substituted or unsubstituted C5-30One of heteroaryl; the heteroatom is nitrogen, oxygen or sulfur;
z represents C-H or N atom, and at least one Z represents N atom.
Preferably, the compound containing pyridoindole in the general formula (1)
Expressed as:
any one of the above.
Preferably, the pyridoindole-containing compound has a structure represented by the general formula (2):
in (1)One kind of the medicine.
Preferably, a pyridoindole-containing compound, Ar1Is one of a single bond, phenylene, naphthylene, biphenylene, anthracenylene, furylene, carbazolyl, naphthyridinylene, quinolylene, thienylene, pyridylene, peryleneene, 9-dimethylfluorenyl, phenanthrylene, dibenzofuranylene and dibenzothiophenylene;
ar is2Is represented by one of phenyl, naphthyl, biphenyl, anthryl, furyl, carbazolyl, naphthyridine, quinolyl, thienyl, pyridyl, perylene, 9-dimethylfluorenyl, phenanthryl, dibenzofuryl and dibenzothienyl.
Preferably, the compound containing pyridoindole has a specific structural formula:
The invention also provides a preparation method of the compound containing pyridoindole, and the preparation method relates to a reaction equation:
the specific reaction process is as follows:
dissolving raw material A and intermediate M in mixed solution of toluene and ethanol, removing oxygen, and adding Pd (PPh)3)4And K2CO3Reacting for 10-24 hours at 95-110 ℃ in an inert atmosphere, cooling and filtering after the raw materials are completely reacted, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain a target compound;
wherein the dosage of the toluene and the ethanol is 30-50 mL of toluene and 5-10 mL of ethanol used per gram of the raw material A, the molar ratio of the intermediate M to the raw material A is 1-3: 1, and Pd (PPh)3)4The molar ratio of the raw material A to the raw material A is 0.006-0.03: 1, and K2CO3The molar ratio of the raw material A to the raw material A is 1.5-4.5: 1.
The invention also provides an organic electroluminescent device which comprises at least one functional layer containing the pyridoindole-containing compound.
Preferably, the organic electroluminescent device comprises a hole transport layer/electron blocking layer, and the hole transport layer/electron blocking layer contains the pyridoindole-containing compound.
Preferably, an organic electroluminescent device comprises a light-emitting layer containing the pyridoindole-containing compound.
The invention also provides a lighting or display element comprising the organic electroluminescent device.
The beneficial technical effects of the invention are as follows:
the compound has asymmetric molecules, avoids intermolecular aggregation, has the characteristics of strong group rigidity, difficult intermolecular crystallization and aggregation, good film forming property and high glass transition temperature and thermal stability, and can keep the stability of a film layer formed by the material when the compound is applied to an OLED device and prolong the service life of the OLED device.
The compound structure of the invention ensures that the distribution of electrons and holes in the luminescent layer is more balanced, and under the proper HOMO energy level, the hole injection/transmission performance is improved; under a proper LUMO energy level, the organic electroluminescent material plays a role in blocking electrons, and improves the recombination efficiency of excitons in the luminescent layer; when the pyridoindole is used as a light-emitting functional layer material of an OLED light-emitting device, the pyridoindole is matched with the branched chain in the range of the pyridoindole compound can effectively improve the exciton utilization rate and the high fluorescence radiation efficiency, reduce the efficiency roll-off under high current density, reduce the voltage of the device, improve the current efficiency of the device and prolong the service life of the device.
The compound has good application effect in OLED luminescent devices and good industrialization prospect.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in the present invention;
wherein, 1 is a transparent substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is a hole transmission or electron blocking layer, 5 is a luminescent layer, 6 is an electron transmission or hole blocking layer, 7 is an electron injection layer, and 8 is a cathode reflection electrode layer;
fig. 2 is a graph of current efficiency versus temperature.
Detailed Description
Example 1: synthesis of intermediate M:
(1) dissolving raw material B and raw material C in mixed solution of toluene and ethanol, removing oxygen, and adding Pd (PPh)3)4And K2CO3Reacting for 10-24 hours at 95-110 ℃ in an inert atmosphere, continuously monitoring the reaction process by TLC (thin layer chromatography) in the reaction process, cooling and filtering after the raw materials are completely reacted, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain an intermediate S;
wherein the dosage of the toluene and the ethanol is 30-50 mL of toluene and 5-10 mL of ethanol used per gram of the raw material C, the molar ratio of the raw material B to the raw material C is (1-1.5): 1, and Pd (PPh)3)4The molar ratio of the raw material C to the raw material C is (0.006-0.02): 1, K2CO3The molar ratio of the raw material C to the raw material C is (1.5-2): 1.
(2) Weighing 0.01mol of an intermediate S under the protection of nitrogen, dissolving the intermediate S in 150mL of tetrahydrofuran, cooling to-78 ℃, adding 1.6mol/L n-butyllithium tetrahydrofuran solution into a reaction system, reacting at-78 ℃ for 3h, adding triisopropyl borate, reacting for 2h, raising the temperature of the reaction system to 0 ℃, adding 10mL of 2mol/L hydrochloric acid solution, stirring for 3h, completely reacting, adding diethyl ether for extraction, adding anhydrous magnesium sulfate into an extract, drying, performing rotary evaporation, and recrystallizing by using an ethanol solvent to obtain an intermediate M;
wherein the molar ratio of the intermediate S to the n-butyllithium is 1: 1-1.5; the molar ratio of the intermediate S to the triisopropyl borate is 1: 1-1.5.
Synthesis example of intermediate M-1:
(1) 0.01mol of the raw material C-1 and 0.012mol of the raw material B-1 were dissolved in toluene and ethyl150mL of alcohol (V)Toluene：VEthanol5: 1) adding 0.0002mol of Pd (PPh) into the mixed solution after deoxygenation3)4And 0.02mol of K2CO3Reacting at 110 ℃ for 24 hours under an inert atmosphere, continuously monitoring the reaction process by TLC in the reaction process, cooling and filtering after the raw materials are completely reacted, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain an intermediate S-1; elemental analysis Structure (molecular formula C)23H15BrN2): theoretical value C, 69.19; h, 3.79; br, 20.01; n, 7.02; test values are: c, 69.23; h, 3.82; br, 20.06; n, 7.04; ESI-MS (M/z) (M +): theoretical value is 398.04, found 398.15.
(2) Weighing 0.01mol of an intermediate S-1, dissolving the intermediate S-1 in 150mL of tetrahydrofuran under the protection of nitrogen, cooling to-78 ℃, adding 8mL of 1.6mol/L tetrahydrofuran solution of n-butyllithium into a reaction system, reacting for 3h at-78 ℃, adding 0.013mol of triisopropyl borate, reacting for 2h, raising the temperature of the reaction system to 0 ℃, adding 10mL of 2mol/L hydrochloric acid solution, stirring for 3h, completely reacting, adding diethyl ether for extraction, adding anhydrous magnesium sulfate into an extract liquid, drying, carrying out rotary evaporation, and recrystallizing by using an ethanol solvent to obtain an intermediate M-1; elemental analysis Structure (molecular formula C)23H17BN2O2): theoretical value C, 75.85; h, 4.70; b, 2.97; n, 7.69; o, 8.79; test values are: c, 75.87; h, 4.73; b, 2.98; n, 7.73; and O, 8.82. ESI-MS (M/z) (M)+): theoretical value is 364.14, found 364.25.
The intermediate M is prepared by a synthesis method of the intermediate M-1, and the specific structure is shown in Table 1.
TABLE 1
Example 2: synthesis of Compound 2:
in a 250mL three-necked flask, 0.01mol of the raw material A-1 and 0.012mol of the raw material B-1 were dissolved in 150mL (V) of toluene and ethanolToluene：VEthanol5: 1) adding 0.0002mol of Pd (PPh) into the mixed solution after deoxygenation3)4And 0.02mol of K2CO3Reacting at 110 ℃ for 24 hours under an inert atmosphere, continuously monitoring the reaction process by TLC in the reaction process, cooling and filtering after the raw materials are completely reacted, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain a target product; elemental analysis Structure (molecular formula C)42H28N2): theoretical value C, 89.97; h, 5.03; n, 5.00; test values: c, 89.98; h, 5.07; n, 5.01; ESI-MS (M/z) (M +): theoretical value is 560.23, found 560.27.
Example 3: synthesis of compound 15:
in a 250mL three-necked flask, 0.01mol of the raw material A-2 and 0.012mol of the raw material B-3 were dissolved in 150mL (V) of toluene and ethanolToluene：VEthanol5: 1) adding 0.0002mol of Pd (PPh) into the mixed solution after deoxygenation3)4And 0.02mol of K2CO3Reacting at 110 ℃ for 24 hours under an inert atmosphere, continuously monitoring the reaction process by TLC in the reaction process, cooling and filtering after the raw materials are completely reacted, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain a target product; elemental analysis Structure (molecular formula C)42H28N2): theoretical value C, 89.97; h, 5.03; n, 5.00; test values are: c, 89.98; h, 5.08; n, 5.07; ESI-MS (M/z) (M +): theoretical value is 560.23, found 560.28.
Example 4: synthesis of compound 38:
compound 38 was prepared as in example 2, except that intermediate M-1 was used in place of starting material B-1. Elemental analysis Structure (molecular formula C)48H32N2): theoretical value C, 90.54; h, 5.07; n, 4.40; test values are: c, 90.57; h, 5.11; n, 4.43. ESI-MS (M/z) (M)+): theoretical value is 636.26, found 636.27.
Example 5: synthesis of compound 42:
compound 42 was prepared as in example 2, except that starting material A-1 was replaced with starting material A-2 and starting material B-1 was replaced with intermediate M-2. Elemental analysis Structure (molecular formula C)52H34N2): theoretical value C, 90.93; h, 4.99; n, 4.08; test values are: c, 90.97; h, 5.05; and N, 4.12. ESI-MS (M/z) (M)+): theoretical value is 686.27, found 686.31.
Example 6: synthesis of compound 58:
compound 58 was prepared as in example 2, except that starting material A-1 was replaced with starting material A-3. Elemental analysis Structure (molecular formula C)42H28N2): theoretical value C, 89.97; h, 5.03; n, 5.00; test values are: c, 90.01; h, 5.06; and N, 5.03. ESI-MS (M/z) (M)+): theoretical value is 560.23, found 560.27.
Example 7: synthesis of compound 64:
compound 64 was prepared in the same manner as in example 2, except that the starting material A-1 was replaced with the starting material A-4 and the starting material B-4 was replaced withRaw material B-1. Elemental analysis Structure (molecular formula C)42H28N2): theoretical value C, 89.97; h, 5.03; n, 5.00; test values are: c, 90.03; h, 5.07; and N, 5.02. ESI-MS (M/z) (M)+): theoretical value is 560.23, found 560.29.
Example 8: synthesis of compound 70:
Example 9: synthesis of compound 98:
compound 98 was prepared as in example 2, except that starting material A-1 was replaced with starting material A-4 and starting material B-1 was replaced with intermediate M-2. Elemental analysis Structure (molecular formula C)54H34N2): theoretical value C, 90.93; h, 4.99; n, 4.08; test values are: c, 90.97; h, 5.03; and N, 4.13. ESI-MS (M/z) (M)+): theoretical value is 686.27, found 686.31.
Example 10: synthesis of compound 102:
in a 250mL three-necked flask, 0.01mol of the raw material A-5 and 0.012mol of the raw material B-1 were dissolved in 150mL (V) of toluene and ethanolToluene：VEthanol5: 1) adding 0.0002mol of Pd (PPh) into the mixed solution after deoxygenation3)4And 0.02molK2CO3Reacting at 110 ℃ for 24 hours under an inert atmosphere, continuously monitoring the reaction process by TLC in the reaction process, cooling and filtering after the raw materials are completely reacted, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain a target product; elemental analysis Structure (molecular formula C)42H26N2): theoretical value C, 90.29; h, 4.69; n, 5.01; test values are: c, 92.31; h, 4.74; and N, 5.08. ESI-MS (M/z) (M)+): theoretical value is 558.21, found 558.27.
Example 11: synthesis of compound 134:
compound 134 can be prepared as in example 10, except that starting material A-6 is used instead of starting material A-5, and intermediate M-1 is used instead of starting material B-1. Elemental analysis Structure (molecular formula C)48H30N2): theoretical value C, 90.82; h, 4.76; n, 4.41; test values are: c, 90.85; h, 4.79; n, 4.44. ESI-MS (M/z) (M)+): theoretical value is 634.24, found 634.27.
Example 12: synthesis of compound 140:
compound 140 was prepared as in example 10, except that intermediate M-3 was used in place of starting material B-1. Elemental analysis Structure (molecular formula C)51H31N3): theoretical value C, 89.32; h, 4.56; n, 6.13; test values are: c, 89.34; h, 4.59; and N, 6.17. ESI-MS (M/z) (M)+): theoretical value is 685.25, found 685.31.
Example 13: synthesis of compound 143:
preparation method of compound 143The procedure was conducted in the same manner as in example 10 except that the starting material A-5 was replaced with the starting material A-7. Elemental analysis Structure (molecular formula C)45H32N2): theoretical value C, 89.97; h, 5.37; n, 4.66; test values are: c, 90.02; h, 5.41; and N, 4.69. ESI-MS (M/z) (M)+): theoretical value is 600.26, found 600.32.
Example 14: synthesis of compound 155:
compound 155 was prepared as in example 10, except that starting material A-5 was replaced with starting material A-8. Elemental analysis Structure (molecular formula C)45H32N2): theoretical value C, 89.97; h, 5.37; n, 4.66; test values are: c, 90.01; h, 5.43; and N, 4.69. ESI-MS (M/z) (M)+): theoretical value is 600.26, found 600.33.
Example 15: synthesis of compound 182:
compound 182 is prepared as in example 10, except that starting material A-5 is replaced with starting material A-8 and starting material B-1 is replaced with intermediate M-4. Elemental analysis Structure (molecular formula C)51H36N2): theoretical value C, 90.50; h, 5.36; n, 4.14; test values are: c, 90.54; h, 5.38; and N, 4.17. ESI-MS (M/z) (M)+): theoretical value is 676.29, found 676.32.
Example 16: synthesis of compound 197:
compound 197 is prepared by the same method as in example 2, except that the starting material A-1 is replaced with the starting material A-9. Elemental analysis Structure (molecular formula C)42H28N2O): theoretical value C, 87.47; h, 4.89; and N,4.86; o, 2.77; test values are: c, 87.55; h, 4.93; n, 4.88; o, 2.81. ESI-MS (M/z) (M)+): theoretical value is 576.22, found 576.31.
Example 17: synthesis of compound 199:
compound 199 was prepared as in example 2, except that starting material A-10 was used in place of starting material A-1. Elemental analysis Structure (molecular formula C)42H28N2O): theoretical value C, 87.47; h, 4.89; n, 4.86; o, 2.77; test values are: c, 87.54; h, 4.93; n, 4.88; o, 2.79. ESI-MS (M/z) (M)+): theoretical value is 576.22, found 576.28.
Example 18: synthesis of compound 201:
compound 201 was prepared as in example 2, except that starting material A-11 was used in place of starting material A-1. Elemental analysis Structure (molecular formula C)45H34N2): theoretical value C, 89.67; h, 5.69; n, 4.65; test values are: c, 89.69; h, 5.71; and N, 4.68. ESI-MS (M/z) (M)+): theoretical value is 602.27, found 602.29.
Example 19: synthesis of compound 215:
compound 215 was prepared as in example 10, except that starting material A-12 was used in place of starting material A-5. Elemental analysis Structure (molecular formula C)41H25N3): theoretical value C, 87.99; h, 4.50; n, 7.51; test values are: c, 88.05; h, 4.53; n, 7.54. ESI-MS (M/z) (M)+): theoretical value is 559.20, found 559.26.
Example 20: synthesis of compound 223:
compound 223 was prepared as in example 10, except that starting material A-5 was replaced with starting material A-13 and starting material B-1 was replaced with intermediate M-2. Elemental analysis Structure (molecular formula C)51H31N3): theoretical value C, 89.32; h, 4.56; n, 6.13; test values are: c, 89.34; h, 4.62; and N, 6.15. ESI-MS (M/z) (M)+): theoretical value is 685.25, found 685.31.
Example 21: synthesis of compound 234:
compound 234 was prepared as in example 10, except that starting material A-5 was replaced with starting material A-14. Elemental analysis Structure (molecular formula C)40H24N4): theoretical value C, 85.69; h, 4.31; n, 9.99; test values are: c, 85.73; h, 4.33; and N, 10.03. ESI-MS (M/z) (M)+): theoretical value is 560.20, found 560.04.
Example 22: synthesis of compound 243:
compound 243 is prepared as in example 10, except that starting material A-5 is replaced with starting material A-14 and starting material B-1 is replaced with intermediate M-5. Elemental analysis Structure (molecular formula C)52H32N4): theoretical value C, 87.62; h, 4.52; n, 7.86; test values are: c, 87.65; h, 4.55; and N, 7.89. ESI-MS (M/z) (M)+): theoretical value is 712.26, found 712.31.
The organic compound is used in a light-emitting device, has high Tg (glass transition temperature) temperature and triplet state energy level (T1), and suitable HOMO and LUMO energy levels, and can be used as a hole blocking/electron transporting material and a light-emitting layer material. The thermal performance, T1 energy level and HOMO energy level of the compound of the present invention and the existing material were measured, respectively, and the results are shown in table 2.
TABLE 2
Note: the triplet energy level T1 was measured by Hitachi F4600 fluorescence spectrometer under the conditions of 2X 10-5A toluene solution of (4); the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 differential scanning calorimeter of Germany Titan company), the heating rate is 10 ℃/min; the thermogravimetric temperature Td is a temperature at which 1% of the weight loss is observed in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan, and the nitrogen flow rate is 20 mL/min; the highest occupied molecular orbital HOMO energy level was tested by the ionization energy testing system (IPS3) in an atmospheric environment.
As can be seen from the data in the table above, compared with the CBP and TPBi materials applied at present, the organic compound of the invention has high glass transition temperature, can improve the phase stability of the material film, and further improves the service life of the device; the material has high triplet state energy level, and can block energy loss of a light-emitting layer, so that the light-emitting efficiency of the device is improved. Meanwhile, the material and the application material have similar HOMO energy levels. Therefore, the organic material containing pyridoindole can effectively improve the luminous efficiency and prolong the service life of the device after being applied to different functional layers of an OLED device.
The application effect of the synthesized OLED material in the device is explained in detail through device examples 1-21 and device comparative example 1. Compared with the device embodiment 1, the device embodiments 2 to 21 and the device comparative example 1 have the same manufacturing process, adopt the same substrate material and electrode material, and keep the film thickness of the electrode material consistent, except that the device embodiments 2 to 13 change the material of the light emitting layer in the device; device examples 14-21 were prepared by changing the hole blocking/electron transporting layer materials of the devices, and the performance test results of the devices obtained in each example are shown in table 3.
Device example 1:
as shown in fig. 1, an electroluminescent device is prepared by the steps of: a) cleaning the ITO anode layer 2 on the transparent substrate layer 1, respectively ultrasonically cleaning the ITO anode layer 2 for 15 minutes by using deionized water, acetone and ethanol, and then treating the ITO anode layer 2 in a plasma cleaner for 2 minutes; b) evaporating a hole injection layer material HAT-CN on the ITO anode layer 2 in a vacuum evaporation mode, wherein the thickness of the hole injection layer material HAT-CN is 10nm, and the hole injection layer material HAT-CN is used as a hole injection layer 3; c) evaporating a hole transport material NPB (N-propyl bromide) on the hole injection layer 3 in a vacuum evaporation mode, wherein the thickness of the hole transport material NPB is 80nm, and the hole transport layer/electron blocking layer 4 is formed; d) a luminescent layer 5 is evaporated on the hole transport/electron barrier layer 4, the host material is the compound 2 and the compound GH of the invention, the doping material is Ir (ppy)3Compound 2, GH and Ir (ppy)3The mass ratio of the three is 50:50:10, and the thickness is 40 nm; e) an electron transport material TPBI is evaporated on the light-emitting layer 5 in a vacuum evaporation mode, the thickness of the TPBI is 35nm, and the organic material of the TPBI layer is used as a hole blocking/electron transport layer 6; f) vacuum evaporating an electron injection layer LiF with the thickness of 1nm on the hole blocking/electron transport layer 6, wherein the layer is an electron injection layer 7; g) vacuum evaporating cathode Al (100nm) on the electron injection layer 7, which is a cathode reflection electrode layer 8; after the electroluminescent device was fabricated according to the above procedure, the driving voltage and current efficiency of the device were measured, and the results are shown in table 3. The molecular mechanism formula of the related material is as follows:
device example 2: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: Compound 15, GH and Ir (ppy)3A mixed composition of 50:50:10 by weight ratio)/hole blocking/electron transporting layer 6 (thickness: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 3: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: Compound 38, GH and Ir (ppy)3A mixed composition of 50:50:10 by weight ratio)/hole blocking/electron transporting layer 6 (thickness: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 4: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: Compound 42 and Ir (ppy)3Mixed and doped in a weight ratio of 90: 10)/hole blocking/electron transport layer 6 (thickness: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 5: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: Compound 58, GH and Ir (ppy)3A mixed composition of 50:50:10 by weight ratio)/hole blocking/electron transporting layer 6 (thickness: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 6: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: Compound 64, GH and Ir (ppy)3A mixed composition of 50:50:10 by weight ratio)/hole blocking/electron transporting layer 6 (thickness: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 7: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: NPB)/hole injection layer: compound 70 and Ir (ppy)3Mixed and doped in a weight ratio of 90: 10)/hole blocking/electron transport layer 6 (thickness: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 8: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: Compound 98, GH and Ir (ppy)3A mixed composition of 50:50:10 by weight ratio)/hole blocking/electron transporting layer 6 (thickness: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 9: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: Compound 102 and Ir (ppy)3Mixed and doped in a weight ratio of 90: 10)/hole blocking/electron transport layer 6 (thickness: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 10: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: Compound 134, GH and Ir (ppy)3A mixed composition of 50:50:10 by weight ratio)/hole blocking/electron transporting layer 6 (thickness: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 11: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: Compound 197, GH and Ir (ppy)3A mixed composition of 50:50:10 by weight ratio)/hole blocking/electron transporting layer 6 (thickness: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 12: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/hairpinOptical layer 5 (thickness: 40nm, material: Compound 199, GH and Ir (ppy)3A mixed composition of 50:50:10 by weight ratio)/hole blocking/electron transporting layer 6 (thickness: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 13: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: Compound 201, GH and Ir (ppy)3A mixed composition of 50:50:10 by weight ratio)/hole blocking/electron transporting layer 6 (thickness: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 14: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3Mixed at a weight ratio of 90: 10)/hole blocking/electron transport layer 6 (thickness: 35nm, material: compound 140)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 15: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy))3Mixed and doped in a weight ratio of 90: 10)/hole blocking/electron transport layer 6 (thickness: 35nm, material: compound 143)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 16: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3Mixed and doped in a weight ratio of 90: 10)/hole blocking/electron transport layer 6 (thickness: 35nm, material: compound 155)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 17: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness:80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3Mixed and doped in a weight ratio of 90: 10)/hole blocking/electron transport layer 6 (thickness: 35nm, material: compound 182)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 18: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3Mixed and doped in a weight ratio of 90: 10)/hole blocking/electron transport layer 6 (thickness: 35nm, material: compound 215)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 19: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3Mixed and doped in a weight ratio of 90: 10)/hole blocking/electron transport layer 6 (thickness: 35nm, material: compound 223)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 20: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3Mixed and doped in a weight ratio of 90: 10)/hole blocking/electron transport layer 6 (thickness: 35nm, material: compound 234)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 21: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3Mixed and doped in a weight ratio of 90: 10)/hole blocking/electron transport layer 6 (thickness: 35nm, material: compound 243)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device comparative example 1: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: HAT-CN)Degree: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy)3Mixed and doped in a weight ratio of 90: 10)/hole blocking/electron transport layer 6 (thickness: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm). The inspection data of the obtained electroluminescent device are shown in Table 3.
TABLE 3
From the results in table 3, it can be seen that the organic compound of the present invention can be applied to the fabrication of OLED light emitting devices, and compared with the comparative examples, the organic compound has a better improvement in efficiency and lifetime than the known OLED materials, and in particular, the service life of the device is greatly improved.
Further, the efficiency of the OLED device prepared by the material is stable when the OLED device works at low temperature, the efficiency test is carried out on the device examples 2, 9 and 17 and the device comparative example 1 at the temperature of-10-80 ℃, and the obtained results are shown in the table 4 and the figure 2.
TABLE 4
As can be seen from the data in table 4 and fig. 2, device examples 2, 9 and 17 are device structures in which the material of the present invention and the known material are combined, and compared with device comparative example 1, the efficiency is high at low temperature, and the efficiency is smoothly increased in the temperature increasing process.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. A pyridoindole-containing compound, characterized in that the specific structural formula of the compound is:
2. an organic electroluminescent element comprising at least one functional layer containing the pyridoindole-containing compound according to claim 1.
3. The organic electroluminescent device according to claim 2, comprising a light-emitting layer, wherein the light-emitting layer contains the pyridoindole-containing compound according to claim 1.
4. A lighting or display element comprising the organic electroluminescent device according to any one of claims 2 to 3.
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| PCT/CN2018/120716 WO2019114769A1 (en) | 2017-12-13 | 2018-12-12 | Compound containing pyridoindole and use thereof in organic electroluminescence device |
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| CN112574045B (en) * | 2020-12-08 | 2022-04-01 | 武汉华星光电半导体显示技术有限公司 | Hole transport material, preparation method thereof and electroluminescent device |
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