CN112174875A - Hole transport compound, preparation method thereof and light emitting device - Google Patents
Hole transport compound, preparation method thereof and light emitting device Download PDFInfo
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- 230000005525 hole transport Effects 0.000 title claims abstract description 148
- 150000001875 compounds Chemical class 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 76
- 238000006243 chemical reaction Methods 0.000 claims description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 125000001246 bromo group Chemical group Br* 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000005619 boric acid group Chemical group 0.000 claims description 10
- -1 trifluorovinyl group Chemical group 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 125000004185 ester group Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 125000003566 oxetanyl group Chemical group 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 125000005504 styryl group Chemical group 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000010791 quenching Methods 0.000 abstract description 8
- 230000000171 quenching effect Effects 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 109
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 239000002904 solvent Substances 0.000 description 32
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- 238000002390 rotary evaporation Methods 0.000 description 17
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- 239000000047 product Substances 0.000 description 14
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 11
- 238000001514 detection method Methods 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
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- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical class OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 8
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- 239000003480 eluent Substances 0.000 description 7
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- CCIVUDMVXNBUCY-UHFFFAOYSA-N 4-bromo-n-phenylaniline Chemical compound C1=CC(Br)=CC=C1NC1=CC=CC=C1 CCIVUDMVXNBUCY-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- QWMJEUJXWVZSAG-UHFFFAOYSA-N (4-ethenylphenyl)boronic acid Chemical group OB(O)C1=CC=C(C=C)C=C1 QWMJEUJXWVZSAG-UHFFFAOYSA-N 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 4
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- 238000001291 vacuum drying Methods 0.000 description 4
- HNWFFTUWRIGBNM-UHFFFAOYSA-N 2-methyl-9,10-dinaphthalen-2-ylanthracene Chemical compound C1=CC=CC2=CC(C3=C4C=CC=CC4=C(C=4C=C5C=CC=CC5=CC=4)C4=CC=C(C=C43)C)=CC=C21 HNWFFTUWRIGBNM-UHFFFAOYSA-N 0.000 description 3
- RAPHUPWIHDYTKU-WXUKJITCSA-N 9-ethyl-3-[(e)-2-[4-[4-[(e)-2-(9-ethylcarbazol-3-yl)ethenyl]phenyl]phenyl]ethenyl]carbazole Chemical compound C1=CC=C2C3=CC(/C=C/C4=CC=C(C=C4)C4=CC=C(C=C4)/C=C/C=4C=C5C6=CC=CC=C6N(C5=CC=4)CC)=CC=C3N(CC)C2=C1 RAPHUPWIHDYTKU-WXUKJITCSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- WTEWXIOJLNVYBZ-UHFFFAOYSA-N n-[4-[4-(4-ethenyl-n-naphthalen-1-ylanilino)phenyl]phenyl]-n-(4-ethenylphenyl)naphthalen-1-amine Chemical compound C1=CC(C=C)=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC(C=C)=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 WTEWXIOJLNVYBZ-UHFFFAOYSA-N 0.000 description 3
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- HTGPRXPCTBXRBH-UHFFFAOYSA-N 1,3,5,7-tetrakis(4-iodophenyl)adamantane Chemical compound C1=CC(I)=CC=C1C1(CC(C2)(C3)C=4C=CC(I)=CC=4)CC2(C=2C=CC(I)=CC=2)CC3(C=2C=CC(I)=CC=2)C1 HTGPRXPCTBXRBH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 125000006617 triphenylamine group Chemical group 0.000 description 2
- KPRDJPMEFCHAKS-CPNJWEJPSA-N (5z)-5-benzylidene-7-methylindeno[1,2-b]pyridine Chemical compound C=1C(C)=CC=C(C2=NC=CC=C22)C=1\C2=C\C1=CC=CC=C1 KPRDJPMEFCHAKS-CPNJWEJPSA-N 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
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- 125000005620 boronic acid group Chemical group 0.000 description 1
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
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- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
- C07C211/55—Diphenylamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
- C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
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- C07C2603/90—Ring systems containing bridged rings containing more than four rings
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Abstract
The invention discloses a hole transport compound, a preparation method thereof and a light-emitting device, wherein the molecular structure of the hole transport compound has the following general formula:
wherein R is a non-conjugated group, R1、R2、R3And R4Each independently selected from an electron donating group, a crosslinkable group and a hydrogen atom, and R1、R2、R3And R4At least one of which is selected from electron donating groups. Namely, the technical scheme of the invention can prevent exciton quenching of the luminescent layer and ensure the luminescent efficiency of the luminescent layer.
Description
Technical Field
The invention relates to the technical field of hole transport materials, in particular to a hole transport compound, a preparation method thereof and a light-emitting device.
Background
In order to transport holes, a hole transport layer is usually disposed between a light emitting layer and an anode of the light emitting device, and the hole transport layer plays a key role in the light emitting device. However, in the blue device, the exciton energy of the light emitting layer of the blue device is high and higher than the triplet level of the hole transport layer, and thus, the high-energy exciton of the light emitting layer is transferred to the triplet level of the low-energy hole transport layer, thereby causing exciton quenching of the light emitting layer, resulting in a decrease in the light emitting efficiency of the light emitting layer.
Disclosure of Invention
The invention mainly aims to provide a hole transport compound, aiming at preventing exciton quenching of a luminescent layer and ensuring the luminescent efficiency of the luminescent layer.
In order to achieve the above object, the present invention provides a hole transport compound, the molecular structure of which has the following general formula:
wherein R is a non-conjugated group, R1、R2、R3And R4Each independently selected from an electron donating group, a crosslinkable group and a hydrogen atom, and R1、R2、R3And R4At least one of which is selected from electron donating groups.
Alternatively, in the molecular structure of the hole transport compound, R1、R2、R3And R4At least one of which is selected from crosslinkable groups.
Optionally, the crosslinkable group is selected from one of a trifluorovinyl group, a styryl group, an oxetanyl group, a siloxane group, and an unsaturated ester group.
Alternatively, the molecular structure of the hole transport compound is as follows:
in the formula, R1、R2、R4Are selected from electron donating groups.
Alternatively, in the molecular structure of the hole transport compound, R1、R2、R3And R4Are all selected from the electron donating groups, and the molecular structure of R is as follows:
optionally, the electron donating group is an electron donating group containing a nitrogen atom and a carbon-carbon double bond.
Optionally, the molecular structure of the electron donating group is selected from one of the following structures:
the invention also provides a preparation method of the hole transport compound, which comprises the following steps:
providing a first raw material, a second raw material, an organic solvent and an alkaline substance; the first raw material is a first compound with an electron-donating group, and the second raw material is a second compound with a non-conjugated group;
mixing a first raw material, a second raw material, an organic solvent and a basic substance, and bonding an electron-donating group of the first raw material to a non-conjugated group of the second raw material in an inert gas atmosphere to obtain the hole-transporting compound.
Optionally, the preparation process of the first raw material comprises:
mixing a bromine substituent, a boric acid substituent, a palladium catalyst and an alkaline compound, adding a reaction solvent under an inert atmosphere, and controlling the reaction temperature and the reaction time to enable the bromine substituent and the boric acid substituent to react to obtain a first raw material.
The invention also provides a light-emitting device, which comprises an anode, a light-emitting layer, a hole transport layer and a cathode, wherein the light-emitting layer is clamped between the anode and the cathode, the hole transport layer is arranged between the light-emitting layer and the anode, and the hole transport layer comprises the hole transport compound; and/or the hole transport layer comprises the hole transport compound prepared by the preparation method.
According to the technical scheme, when the hole transport layer is prepared, the molecular structure of the hole transport compound comprises a non-conjugated group and an electron-donating group, and the electron-donating group is bonded to the non-conjugated group, so that the requirement of the hole transport layer on hole transport is met. And the introduction of the non-conjugated group reduces the conjugation of the molecular structure of the hole transport compound, thereby avoiding the problem of reduction of the triplet state energy level of the hole transport compound caused by conjugation, improving the triplet state energy level of the hole transport compound, enabling the triplet state energy level of the hole transport compound to be higher than the exciton energy of the light emitting layer, and because excitons cannot be transferred to the high-energy level, the excitons of the light emitting layer cannot be transferred to the hole transport layer prepared from the hole transport compound with the high-energy triplet state energy level, namely the technical scheme of the invention can prevent quenching of the excitons of the light emitting layer and ensure the light emitting efficiency of the light emitting layer.
Drawings
FIG. 1 is a diagram of a reaction process of a first feedstock according to the present invention;
FIG. 2 is a reaction scheme of a hole transport compound in example 1 of the present invention;
FIG. 3 is a reaction scheme of a hole transport compound in example 2 of the present invention;
fig. 4 is a schematic structural view of a light-emitting device according to embodiment 3 of the present invention.
The reference numbers illustrate:
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. 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.
In one embodiment of the present invention, the molecular structure of the hole transport compound has the following general formula:
wherein R is a non-conjugated group, R1、R2、R3And R4Each independently selected from an electron donating group, a crosslinkable group and a hydrogen atom, and R1、R2、R3And R4At least one of which is selected from electron donating groups.
According to the technical scheme, when the hole transport layer is prepared, the molecular structure of the hole transport compound comprises a non-conjugated group and an electron-donating group, and the electron-donating group is bonded to the non-conjugated group, so that the requirement of the hole transport layer on hole transport is met. And the introduction of the non-conjugated group reduces the conjugation of the molecular structure of the hole transport compound, thereby avoiding the problem of reduction of the triplet state energy level of the hole transport compound caused by conjugation, improving the triplet state energy level of the hole transport compound, enabling the triplet state energy level of the hole transport compound to be higher than the exciton energy of the light emitting layer, and because excitons cannot be transferred to the high-energy level, the excitons of the light emitting layer cannot be transferred to the hole transport layer prepared from the hole transport compound with the high-energy triplet state energy level, namely the technical scheme of the invention can prevent quenching of the excitons of the light emitting layer and ensure the light emitting efficiency of the light emitting layer.
It is to be noted that the non-conjugated groups of the examples of the present invention have a non-conjugated skeletonThe volume space structure, the non-conjugated volume space structure reduces the conjugation of the hole transport compound molecule; on the other hand, the hole transport compound molecules are spread, the space between the molecules of the hole transport compound is increased, and pi-pi accumulation is not easy to occur between the molecules of the hole transport compound, so that the triplet state energy level of the hole transport compound is improved, the triplet state energy level of the hole transport compound is higher than the exciton energy of the light emitting layer, and the light emitting layer of the light emitting layer cannot be transferred to the hole transport layer prepared from the hole transport compound with the triplet state energy level of high energy, so that exciton quenching of the light emitting layer is avoided. In addition, in order to ensure efficient transport of holes, the electron-donating group is an electron-donating group containing a nitrogen atom. Preferably, R1、 R2、R3And R4At least two of the electron donating groups are selected from electron donating groups, so that the hole transmission is enhanced, more holes are transmitted to the light-emitting layer, and the light-emitting efficiency of the light-emitting layer is improved.
In one embodiment of the present invention, in the molecular structure of the hole transport compound, R1、R2、R3And R4At least one of which is selected from crosslinkable groups. According to the embodiment of the invention, the cross-linking between molecules of the hole transport compound is realized by introducing the cross-linkable group, so that a net structure is formed, the permeation of a solvent is effectively blocked, and when the method is applied to the preparation of the hole transport layer, the solvent deposited on the surface of the hole transport layer cannot permeate into the hole transport layer, so that the solvent resistance of the hole transport layer is endowed, the mutual solubility between the hole transport layer and an adjacent layer is prevented, and the requirement on the ink-jet printing of a light-emitting device is met. In addition, in order to further improve the solvent resistance of the prepared hole transport layer, it is preferable that the molecular structure of the hole transport compound includes at least two crosslinkable groups, and in the embodiment of the present invention, a plurality of crosslinkable groups are introduced into the molecular structure of the hole transport compound, so that a plurality of side chains are formed through the plurality of crosslinkable groups, and the crosslinking degree of the hole transport compound is further improved, thereby forming a more compact network structure, and thus improving the solvent resistance of the hole transport compound.
In one embodiment of the present invention, the crosslinkable group is selected from one of a trifluorovinyl group, a styryl group, an oxetanyl group, a siloxane group, and an unsaturated ester group. It should be noted that the trifluorovinyl group, the styryl group and the unsaturated ester group have unsaturated carbon-carbon double bonds, and adjacent molecules are crosslinked through a polymerization reaction between the unsaturated carbon-carbon double bonds under a high temperature condition, so that a network structure is formed, and permeation of an external solvent is effectively blocked. Under the condition of high temperature, the ring-opening reaction of the oxetanyl and the siloxane group realizes the crosslinking of the hole transport compound, thereby blocking the permeation of an external solvent and improving the solvent resistance of the hole transport layer.
In one embodiment of the present invention, the molecular structure of the hole transport compound is as follows:
In one embodiment of the present invention, in the molecular structure of the hole transport compound, R1、R2、R3And R4Are all selected from the electron donating groups, and the molecular structure of R is as follows:
In one embodiment of the invention, the electron donating group is an electron donating group containing a nitrogen atom and a carbon-carbon double bond. According to the embodiment of the invention, the electron-donating group is introduced into the nitrogen atom and the carbon-carbon double bond at the same time, so that on one hand, the introduction of the nitrogen atom ensures the hole transmission performance of the prepared hole transmission layer, and on the other hand, the introduction of the carbon-carbon double bond enables the molecules of the hole transmission compound to be crosslinkable, thereby forming a net structure, effectively blocking the permeation of a solvent and ensuring the anti-solvent effect of the hole transmission layer. And the electron-donating group is selected from one of a carbazole group, a diphenylamine group and a triphenylamine group, and the carbazole group, the diphenylamine group and the triphenylamine group have good hole transmission performance, so that hole transmission is ensured.
In one embodiment of the present invention, the electron donating group molecular structure is selected from one of the following structures:
it should be noted that in the embodiment of the present invention, a plurality of benzene rings are introduced while introducing a nitrogen atom and a carbon-carbon double bond, and by introducing the plurality of benzene rings, an electron-donating group has high stability, so that stable transmission of a hole transport compound is further ensured, and stable transmission of a hole by a hole transport layer prepared from the hole transport compound is achieved.
In one embodiment of the present invention, the molecular structure of the hole transport compound is selected from one of the following molecular structures:
in the embodiment of the invention, the introduction of the non-conjugated group reduces the conjugation of the molecular structure of the hole transport compound, so that the problem of reduction of the triplet state energy level of the hole transport compound caused by conjugation is avoided, excitons of the light emitting layer are prevented from being transferred to the hole transport layer prepared from the hole transport compound with the high-energy triplet state energy level, and the light emitting efficiency of the light emitting layer is ensured. In addition, the embodiment of the invention simultaneously introduces nitrogen atoms and carbon-carbon double bonds through electron-donating groups, thereby ensuring the hole transport performance of the prepared hole transport layer, realizing the cross-linking among molecules of the hole transport compound, effectively blocking the penetration of a solvent and ensuring the solvent resistance effect of the hole transport layer.
The invention also provides a preparation method of the hole transport compound, which comprises the following steps: providing a first raw material, a second raw material, an organic solvent and an alkaline substance; the first raw material is a first compound with an electron-donating group, and the second raw material is a second compound with a non-conjugated group; mixing a first raw material, a second raw material, an organic solvent and a basic substance, and bonding an electron-donating group of the first raw material to a non-conjugated group of the second raw material in an inert gas atmosphere to obtain the hole-transporting compound. When the non-conjugated group is applied to preparing a hole transport layer, the introduction of the non-conjugated group reduces the conjugation of the molecular structure of the hole transport compound, so that the problem of reduction of the triplet energy level of the hole transport compound caused by conjugation is solved, the triplet energy level of the hole transport compound is improved, the triplet energy level of the hole transport compound is higher than the exciton energy of a light emitting layer, and thus excitons of the light emitting layer cannot be transferred to the hole transport layer prepared from the hole transport compound with the high-energy triplet energy level, namely the technical scheme of the invention can prevent exciton quenching of the light emitting layer and ensure the light emitting efficiency of the light emitting layer.
Specifically, the preparation method of the hole transport compound comprises the following steps: first, 2mmol of the second raw material, 18mmol of the first raw material and 80mmol of Cs were sequentially added to a 250mL two-necked flask2CO3Adding 150ml of DMF solvent into the two-mouth bottle under the nitrogen atmosphere, and stirring for 30 minutes at room temperature to fully dissolve the solid in the two-mouth bottle; then heating the two bottles, carrying out reflux reaction at 155 ℃ for 12 hours, and cooling the two bottles to room temperature after the reaction is finished to obtain a product solution; finally, the product solution was poured into water, extracted 3 times with dichloromethane, over anhydrous MgSO4Drying, filtering, removing the solvent by rotary evaporation, separating and purifying by using a silica gel chromatographic column by using n-hexane/dichloromethane as an eluent, removing the solvent by rotary evaporation, and drying in vacuum for 12h to obtain the hole transport compound. Of course, the second raw material may be selected from one of 2,6, 14-tribromotriptycene and 1,3,5, 7-tetrakis (4-iodophenyl) adamantane, which is not limited thereto, and the above is within the scope of the embodiments of the present invention.
In an embodiment of the present invention, the preparation process of the first raw material comprises: mixing a bromine substituent, a boric acid substituent, a palladium catalyst and an alkaline compound, adding a reaction solvent under an inert atmosphere, and controlling the reaction temperature and the reaction time to enable the bromine substituent and the boric acid substituent to react to obtain a first raw material. Of course, the bromine substituent is selected from one of a bromine substituent and 4-bromophenylaniline and the boronic acid substituent is selected from 4-vinylbenzeneboronic acid and 4- [1,2,2 (trifluorovinyl) oxy]The inert atmosphere of one of the phenylboronic acids may be a nitrogen atmosphere, and may be an atmosphere of other inert gases. In order to ensure the adequate progress of the SUZUKI coupling reaction, it is preferable that the reaction temperature is 100 ℃ and the reaction time is 24 hours. The reaction solvent is a mixed solvent of toluene/ethanol/water (V/V ═ 8:1:1), the palladium catalyst is tetrakistriphenylphosphine palladium, and the basic substance is potassium carbonate or sodium carbonate. It should be noted that, in the following description,in order to improve the purity of the prepared first raw material, the invention can extract for multiple times to further effectively remove impurities, and the organic layer liquid after dichloromethane extraction adopts anhydrous MgSO4Drying, filtering, removing solvent by rotary evaporation, adding the obtained product into a silica gel chromatographic column for separation and purification, wherein the eluent for the separation and purification of the silica gel chromatographic column adopts a mixed solution of n-hexane/dichloromethane, and the collected extracting solution is subjected to rotary evaporation to obtain the first raw material.
Specifically, in an embodiment of the present invention, the preparing step of the first raw material includes: first, 4mmol of a bromine-substituted compound, 4.5mmol of a boric acid-substituted compound, and 0.2mmol of tetrakistriphenylphosphine palladium Pd (PPh) were sequentially added to a 250mL two-necked flask3)48mmol of potassium carbonate K2CO3Adding stirring magnetons, vacuumizing and changing nitrogen for three times, and enabling the two-mouth bottle to be in a nitrogen atmosphere; then, adding 120ml of a mixed solvent of tetrahydrofuran THF/water (V/V ═ 2:1), and carrying out reflux reaction at 100 ℃ for 24 hours; then, the reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation, dichloromethane was added to extract the reaction solution for 3 times, and the organic layer was extracted with anhydrous MgSO4Drying, filtering, and removing the solvent by rotary evaporation; and finally, separating and purifying by using a silica gel chromatographic column, and removing the solvent by rotary evaporation by using n-hexane/dichloromethane as an eluent to obtain the first raw material.
When the bromine substituent is 3-bromocarbazole and the boric acid substituent is 4-vinylphenylboronic acid, the product obtained by the reaction of 3-bromocarbazole and 4-vinylphenylboronic acid is a first raw material M1, the reaction process of the first raw material M1 is shown in figure 1, the yield of the first raw material M1 is 72%, and HPLC-MS and 1HNMR are used for identifying the first raw material M1 to obtain the molecular formula C of the first raw material M120H15N, detection value [ M +1 ]]+270.32, theoretical molecular weight 269.12. The NMR result of the first raw material M1 was 1HNMR (500MHz, CDCl3), (TMS, ppm):10.1(s,1H), 8.12(d,1H), 7.87(d,1H), 7.77(s,1H), 7.63-7.69(M,2H), 7.50-7.52(M,5H), 7.29(M,1H), 6.72(M,1H), 5.76(d,1H), 5.25(d,1H), whereby the structural formula of the first raw material M1 was determined.
When the bromine substituent is 3-bromocarbazole and the boric acid substituent is 4- [1,2,2 (trifluorovinyl) oxy]Phenylboronic acids3-bromocarbazole and 4- [1,2, 2- (trifluorovinyl) oxy group]The obtained product of phenylboronic acid is first raw material M2, the reaction process of first raw material M2 is shown in figure 1, the yield of first raw material M2 is 69%, HPLC-MS and 1HNMR are used for identifying the first raw material M2, and the molecular formula C of the first raw material M2 is obtained20H12F3NO, detection value [ M +1]+340.13, theoretical molecular weight 339.09. Nuclear magnetic resonance result of first raw material M2 1HNMR (500MHz, CDCl3), (TMS, ppm):1HNMR (500MHz, CDCl3), (TMS, ppm): 10.0(s,1H), 8.11(d,1H), 7.85(d,1H), 7.74(s,1H), 7.61-7.66(M,2H), 7.49-6.81(M,5H), 7.29(M,1H), thereby determining the structural formula of the first raw material M2.
When the bromine substituent is 4-bromophenylaniline, the boric acid substituent is 4-vinylphenylboronic acid, the product obtained by reacting 4-bromophenylaniline with 4-vinylphenylboronic acid is taken as a first raw material M3, the reaction process of the first raw material M3 is shown in figure 3, the yield of the first raw material M3 is 88%, and HPLC-MS and 1HNMR are used for identifying the first raw material M3 to obtain the molecular formula C of the first raw material M320H17N, detection value [ M +1 ]]+272.22, theoretical molecular weight 271.14. The NMR result of the first raw material M3 was 1HNMR (500MHz, CDCl3), (TMS, ppm):7.51-7.54(M,6H), 7.28(M,2H), 7.20(t,2H), 6.81(M, 1H), 6.69(d,2H), 6.72(M,1H), 5.76(d,1H), 5.25(d,1H), 4.0(s,1H), whereby the structural formula of the first raw material M3 was determined.
When the bromine substituent is 4-bromophenylaniline, the boric acid substituent is 4- [1,2,2 (trifluorovinyl) oxy]Phenylboronic acid, 4-bromophenylaniline and 4- [1,2, 2- (trifluorovinyl) oxy group]The obtained product of phenylboronic acid is first raw material M4, the reaction process of the first raw material M4 is shown in figure 1, the yield of the first raw material M4 is 83%, and HPLC-MS and 1HNMR are used for identifying the first raw material M4, so that the molecular formula C of the first raw material M4 is obtained20H14F3NO, detection value [ M +1]+342.16, theoretical molecular weight 341.10. Nuclear magnetic resonance results of the first raw material M4 1HNMR (500MHz, CDCl3), (TMS, ppm):1HNMR (500MHz, CDCl3), (TMS, ppm):7.49 to 7.52(M,6H), 7.26(M,2H), 7.19(t,2H), 6.80(M,1H), 6.67(d,2H), 3.9(s,1H), whereby the structural formula of the first raw material M4 was determined.
The invention also provides a light-emitting device, which comprises an anode, a light-emitting layer, a hole transport layer and a cathode, wherein the light-emitting layer is clamped between the anode and the cathode, the hole transport layer is arranged between the light-emitting layer and the anode, and the hole transport layer comprises a hole transport compound; and/or the hole transport layer comprises a hole transport compound prepared by the preparation method. The triplet energy level of the hole transport compound is higher than the exciton energy of the luminescent layer, so that excitons of the luminescent layer cannot be transferred to the hole transport layer prepared from the hole transport compound with the triplet energy level of high energy, thereby avoiding the transfer of the excitons of the luminescent layer to the hole transport layer, avoiding the quenching of the excitons of the luminescent layer and ensuring the luminous efficiency of the luminescent device.
The invention also provides a preparation method of the light-emitting device, which comprises the following steps: and depositing the hole transport compound or the hole transport compound prepared by the preparation method between the light-emitting layer and the anode to obtain the hole transport layer. Of course, in order to ensure sufficient crosslinking of the hole transport compound deposited between the light-emitting layer and the anode, after the step of "depositing the hole transport compound between the light-emitting layer and the anode", the hole transport compound is heated to cure and crosslink the hole transport compound, thereby improving the solvent resistance of the prepared hole transport layer. Preferably, the heating temperature is 230 ℃ and the heating time is 30min, however, the heating temperature and the heating time may also be adjusted according to the thickness of the prepared hole transport layer, and the embodiment of the present invention is not limited thereto, and the above is all prepared within the protection scope of the embodiment of the present invention.
The technical solution of the present invention is further described below with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the scope of the invention.
Example 1
As shown in the reaction scheme of compound a1 in the hole transport compound shown in fig. 2, the preparation method of compound a 1: firstly, 2mmol of 2,6, 14-tribromotriptycene, 18mmol of a first raw material M1 and 80mmol of CsCO are sequentially added into a 250mL two-mouth bottle3Adding DMF solvent into a two-mouth bottle under the nitrogen atmosphere150ml, stirred at room temperature for 30 minutes to fully dissolve the solids in the two-necked flask; then heating the two bottles, carrying out reflux reaction at 155 ℃ for 12 hours, and cooling the two bottles to room temperature after the reaction is finished to obtain a product solution; finally, the product solution was poured into water, extracted 3 times with dichloromethane, over anhydrous MgSO4Drying, filtering, removing solvent by rotary evaporation, separating and purifying by silica gel chromatographic column with n-hexane/dichloromethane as eluent, removing solvent by rotary evaporation to obtain product, vacuum drying for 12h to obtain compound A1, and calculating to obtain the yield of 43%. Identification of compound A1 by HPLC-MS and 1HNMR gave compound A1 of formula C80H53N3Detection value [ M +1 ]]+1056.50, theoretical molecular weight 1055.42. The NMR detection result of the compound A1 was 1HNMR (500MHz, CDCl3), (TMS, ppm):8.55(d,3H), 7.89-7.94(m,9H), 7.77(d,3H), 7.53-7.59(m,12H), 7.16-7.45 (d,15H), 6.72(m,3H), 5.76(d,3H), 5.19-5.25(m,5H), thereby confirming the structural formula of the compound A1.
Referring to the reaction scheme shown in fig. 1 for preparing the first raw material M1, the preparation process of the first raw material M1 includes: 4mmol of 3-bromocarbazole, 4.5mmol of 4-3-bromocarbazole and 0.2mmol of tetratriphenylphosphine palladium Pd (PPh) are sequentially added into a 250mL two-mouth bottle3)4And 8mmol of potassium carbonate K2CO3Adding stirring magnetons into the two-mouth bottle, vacuumizing and changing nitrogen for three times until the two-mouth bottle is in the nitrogen atmosphere; then adding 120ml of Tetrahydrofuran (THF)/water mixed solvent with the volume ratio of 2:1, and carrying out reflux reaction at 100 ℃ for 24 h; cooling the two-mouth bottle to room temperature after the reaction is finished, removing the solvent in the two-mouth bottle by rotary evaporation, extracting for 3 times by adopting dichloromethane, and passing an organic layer through anhydrous MgSO4Drying, filtering, removing solvent by rotary evaporation, separating and purifying by silica gel chromatographic column with n-hexane/dichloromethane as eluent, removing solvent by rotary evaporation, and vacuum drying for 12h to obtain the first raw material M1, wherein the yield is 72% by calculation. Identification of the first starting material M1 by HPLC-MS and 1HNMR gave the first starting material M1 of the formula C20H15N, detection value [ M +1 ]]+270.32, theoretical molecular weight 269.12. Of the first feedstock M1The result of nuclear magnetic resonance examination was 1HNMR (500MHz, CDCl3), (TMS, ppm):10.1(s,1H), 8.12(d,1H), 7.87(d,1H), 7.77(s,1H), 7.63-7.69(M,2H), 7.50-7.52(M,5H), 7.29(M,1H), 6.72(M,1H), 5.76(d,1H), 5.25(d,1H), whereby the structural formula of the first raw material M1 was determined.
Example 2
As shown in the preparation schematic diagram of compound A8 in the hole transport compound shown in fig. 3, the preparation method of compound A8: first, 2mmol of 1,3,5, 7-tetrakis (4-iodophenyl) adamantane, 18mmol of the first raw material M4, and 80mmol of CsCO were sequentially added to a 250mL two-necked flask3Adding 150ml of DMF solvent into the two-mouth bottle under the nitrogen atmosphere, and stirring for 30 minutes at room temperature to fully dissolve the solid in the two-mouth bottle; then heating the two bottles, carrying out reflux reaction at 155 ℃ for 12 hours, and cooling the two bottles to room temperature after the reaction is finished to obtain a product solution; finally, the product solution was poured into water, extracted 3 times with dichloromethane, over anhydrous MgSO4Drying, filtering, removing solvent by rotary evaporation, separating and purifying by silica gel chromatographic column with n-hexane/dichloromethane as eluent, removing solvent by rotary evaporation to obtain product, vacuum drying for 12h to obtain compound A8, and calculating to obtain the yield of 51%. Identification of compound A8 by HPLC-MS and 1HNMR gave compound A8 of formula C114H80F12N4O4Detection value [ M +1 ]]+ 1797.81, theoretical molecular weight 1796.60. The NMR test result of the compound A8 was 1HNMR (500MHz, CDCl3), (TMS, ppm):7.55-7.57(m,16H), 7.37(d,8H), 7.24(m,8H), 7.00-7.10(m,28H), 6.81(d,8H), 2.02(d,6H), 1.71(d,6H), whereby the structural formula of the compound A8 was determined.
Referring to the reaction scheme shown in fig. 1 for preparing the first raw material M4, the preparation process of the first raw material M4 includes: 4mmol of 4-bromophenylaniline and 4.5mmol of 4- [1,2, 2- (trifluorovinyl) oxy group were placed in a 250mL two-necked flask]Phenylboronic acid, 0.2mmol of palladium tetrakistriphenylphosphine Pd (PPh)3)4And 8mmol of potassium carbonate K2CO3Adding stirring magnetons into the two-mouth bottle, vacuumizing and changing nitrogen for three times until the two-mouth bottle is in the nitrogen atmosphere; then adding tetrahydrofuran with the volume ratio of 2:1120ml of mixed solvent of pyran (THF)/water is refluxed and reacted for 24 hours at 100 ℃; cooling the two-mouth bottle to room temperature after the reaction is finished, removing the solvent in the two-mouth bottle by rotary evaporation, extracting for 3 times by adopting dichloromethane, and passing an organic layer through anhydrous MgSO4Drying, filtering, removing solvent by rotary evaporation, separating and purifying by silica gel chromatographic column with n-hexane/dichloromethane as eluent, removing solvent by rotary evaporation, and vacuum drying for 12h to obtain the first raw material M4, wherein the yield is 83% by calculation. Identification of the first starting material M4 by HPLC-MS and 1HNMR gave the first starting material M4 of the formula C20H14F3NO, detection value [ M +1]+342.16, theoretical molecular weight 341.10. The NMR detection result of the first raw material M4 was 1HNMR (500MHz, CDCl3), (TMS, ppm):7.49-7.52(M,6H), 7.26(M,2H), 7.19(t,2H), 6.80(M,1H), 6.67(d,2H), 3.9(s,1H), thereby confirming the structural formula of the first raw material M4.
Example 3
Referring to fig. 3, an embodiment of the invention provides a light-emitting device 100, which includes an anode 20, a hole injection layer 30, a hole transport layer 40, a light-emitting layer 50, an electron transport layer 60, an electron injection layer 70, and a cathode 80, which are sequentially stacked, wherein a surface of the anode 20 facing away from the hole injection layer 30 is disposed on a glass substrate 10, and the hole transport layer 40 includes the compound a1 of example 1.
A method of making a light emitting device 100, comprising the steps of:
step one, cleaning an ITO substrate according to the following sequence: carrying out ultrasonic treatment on a 5% tetramethylammonium hydroxide solution for 15min, carrying out ultrasonic treatment on pure water for 15min, carrying out ultrasonic treatment on isopropanol for 15min, and drying in an oven for 1 h; the ITO substrate comprises a glass substrate and an anode deposited on the glass substrate;
transferring the ITO substrate to UV-ZONE equipment for surface treatment for 15min, and immediately transferring the ITO substrate to a glove box after the surface treatment;
sequentially preparing a hole injection layer and a hole transport layer on the ITO substrate, and heating and curing the hole transport layer at 230 ℃ for 30 min; preparing a luminescent layer, an electron transport layer, an electron injection layer and a cathode in sequence by using a vapor deposition film forming mode;
and step four, carrying out UV curing packaging, and baking for 60min at 80 ℃ to obtain the light-emitting device.
Referring to fig. 4, a light emitting device of ITO/HIL/HTL/EML/ETL/EIL/cathode is taken as a standard example, and a specific structure of the light emitting device of the embodiment of the present invention is as follows: ITO/HI001(40nm)/H1(15nm)/MADN 5% BCzVBi (40nm)/LG201 LiQ (8:2,20 nm)/Yb (1nm)/Al (120nm), wherein ITO is used as an anode, HI001 is used as a hole injection layer, H1 is used as a hole transport layer, MADN 5 wt% BCzVBi is used as a light emitting layer, LG201 LiQ is used as a hole transport layer, Yb is used as an electron injection layer, and Al is used as a cathode, and the exemplary device is named as an H1 device.
Referring to the method of this example, a hole transport layer was prepared using compound a2 to compound A8 to obtain a light emitting device exemplified in fig. 4, which is referred to as "H2 device", "H3 device", … … ", and" H8 device ", respectively.
Comparative example 1
Comparative example 1 a hole transport layer was prepared with VNPB, wherein the molecular structure of VNPB is as follows:
the device shown in fig. 4, designated as "R1 device", was prepared by the method described in example 3 and was constructed as follows: ITO/HI001(40nm)/VNPB (15nm)/MADN:5 wt% BCzVBi (40nm)/LG201: LiQ (8:2,20 nm)/Yb (1nm)/Al (120 nm).
The triplet energy levels and maximum external quantum efficiencies of the hole transport layers of the H1-H8 and R1 devices were tested according to conventional methods, and the results are shown in the following table:
| test device | Triplet state energy level | Maximum external quantum efficiency (%) |
| R1 device | 2.30 | 1.24 |
| H1 device | 3.02 | 4.40 |
| H2 device | 2.97 | 3.73 |
| H3 device | 2.86 | 3.42 |
| H4 device | 2.99 | 3.81 |
| H5 device | 2.81 | 3.31 |
| H6 device | 2.93 | 3.64 |
| H7 device | 2.87 | 3.55 |
| H8 device | 3.01 | 4.15 |
As can be seen from the comparison in the above table, compared with the comparative example, the triplet energy level and the maximum external quantum efficiency of the hole transport layer prepared in the example of the present invention are significantly higher than those of the hole transport layer prepared in the comparative example. On the whole, compared with H5-H8 devices, the triplet level and external quantum efficiency of H1-H4 devices are higher, because more benzene rings are connected with the hole transport compounds for preparing the hole transport layers of the H5-H8 devices, the electron donating property of the obtained hole transport compounds is stronger, the enhancement of the electron donating property reduces the triplet level and external quantum efficiency of the H5-H8 devices, and correspondingly, the introduction of the electron-withdrawing group is beneficial to improving the triplet level and external quantum efficiency of the devices. In addition, the H1 device has the highest triplet energy level due to the carbazole group contained in its hole transporting compound. The embodiment of the invention improves the external quantum efficiency of the luminescent device by improving the triplet state energy level of the hole transport layer, thereby ensuring the luminescent efficiency of the luminescent device, and the luminescent device has potential application prospect in the fields of electroluminescence, photovoltaic cells, sensors and the like.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. A hole transport compound having a molecular structure according to the following formula:
wherein R is a non-conjugated group, R1、R2、R3And R4Each independently selected from electron donating groupsA crosslinkable group and a hydrogen atom, and R1、R2、R3And R4At least one of which is selected from electron donating groups.
2. The hole transport compound of claim 1, wherein the hole transport compound has a molecular structure in which R is1、R2、R3And R4At least one of which is selected from crosslinkable groups.
3. The hole transport compound of claim 2, wherein the crosslinkable group is selected from one of a trifluorovinyl group, a styryl group, an oxetanyl group, a siloxane group, and an unsaturated ester group.
4. The hole transport compound of claim 1, having the following molecular structure:
in the formula, R1、R2、R4Are selected from electron donating groups.
5. The hole transport compound of claim 1, wherein the hole transport compound has a molecular structure in which R is1、R2、R3And R4Are all selected from the electron donating groups, and the molecular structure of R is as follows:
6. the hole transport compound of claim 1, wherein the electron donating group is an electron donating group comprising a nitrogen atom and a carbon-carbon double bond.
7. The hole transport compound of claim 6, wherein the molecular structure of the electron donating group is selected from one of the following structures:
8. a method for preparing a hole transport compound, comprising the steps of:
providing a first raw material, a second raw material, an organic solvent and an alkaline substance; the first raw material is a first compound with an electron-donating group, and the second raw material is a second compound with a non-conjugated group;
mixing a first raw material, a second raw material, an organic solvent and a basic substance, and bonding an electron-donating group of the first raw material to a non-conjugated group of the second raw material in an inert gas atmosphere to obtain the hole-transporting compound.
9. The method for producing a hole transport compound according to claim 8, wherein the first raw material is produced by a process comprising:
mixing a bromine substituent, a boric acid substituent, a palladium catalyst and an alkaline compound, adding a reaction solvent under an inert atmosphere, and controlling the reaction temperature and the reaction time to enable the bromine substituent and the boric acid substituent to react to obtain a first raw material.
10. A light-emitting device comprising an anode, a light-emitting layer, a hole-transporting layer, and a cathode, wherein the light-emitting layer is sandwiched between the anode and the cathode, the hole-transporting layer is provided between the light-emitting layer and the anode, and the hole-transporting layer comprises the hole-transporting compound according to any one of claims 1 to 7;
and/or the hole transport layer includes the hole transport compound produced by the production method according to claim 8 or 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| US20090105488A1 (en) * | 2007-10-22 | 2009-04-23 | Chien-Hong Cheng | Triptycene derivatives and their application |
| CN102282695A (en) * | 2009-01-19 | 2011-12-14 | 新日铁化学株式会社 | Organic electroluminescent element |
| KR20160035448A (en) * | 2014-09-23 | 2016-03-31 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
| KR20160116219A (en) * | 2015-03-27 | 2016-10-07 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
| KR20180022043A (en) * | 2016-08-23 | 2018-03-06 | 덕산네오룩스 주식회사 | Compound for organic electric element, organic electric element comprising the same and electronic device thereof |
| KR20180092783A (en) * | 2017-02-10 | 2018-08-20 | 주식회사 엘지화학 | Compound and organic light emitting device comprising the same |
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| US20090105488A1 (en) * | 2007-10-22 | 2009-04-23 | Chien-Hong Cheng | Triptycene derivatives and their application |
| CN102282695A (en) * | 2009-01-19 | 2011-12-14 | 新日铁化学株式会社 | Organic electroluminescent element |
| KR20160035448A (en) * | 2014-09-23 | 2016-03-31 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
| KR20160116219A (en) * | 2015-03-27 | 2016-10-07 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
| KR20180022043A (en) * | 2016-08-23 | 2018-03-06 | 덕산네오룩스 주식회사 | Compound for organic electric element, organic electric element comprising the same and electronic device thereof |
| KR20180092783A (en) * | 2017-02-10 | 2018-08-20 | 주식회사 엘지화학 | Compound and organic light emitting device comprising the same |
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| ANURAG KRISHNA ET AL.: "Novel hole transporting materials based on triptycene core for high efficiency mesoscopic perovskite solar cells", 《CHEMICAL SCIENCE》 * |
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