CN112174875B - 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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- 150000001875 compounds Chemical class 0.000 title claims abstract description 102
- 230000005525 hole transport Effects 0.000 title abstract description 117
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 238000010791 quenching Methods 0.000 abstract description 6
- 230000000171 quenching effect Effects 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 105
- 239000002994 raw material Substances 0.000 description 62
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 239000002904 solvent Substances 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 24
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 238000002390 rotary evaporation Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 238000001514 detection method Methods 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 125000001246 bromo group Chemical group Br* 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical class OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- -1 trifluorovinyl group Chemical group 0.000 description 10
- 230000021615 conjugation Effects 0.000 description 9
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- 238000005481 NMR spectroscopy Methods 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 125000005619 boric acid group Chemical group 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
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- 239000000463 material Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
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- CCIVUDMVXNBUCY-UHFFFAOYSA-N 4-bromo-n-phenylaniline Chemical compound C1=CC(Br)=CC=C1NC1=CC=CC=C1 CCIVUDMVXNBUCY-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 6
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- 125000003566 oxetanyl group Chemical group 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical group C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 description 5
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- 238000010992 reflux Methods 0.000 description 5
- 125000005504 styryl group Chemical group 0.000 description 5
- QWMJEUJXWVZSAG-UHFFFAOYSA-N (4-ethenylphenyl)boronic acid Chemical group OB(O)C1=CC=C(C=C)C=C1 QWMJEUJXWVZSAG-UHFFFAOYSA-N 0.000 description 4
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- 229910052763 palladium Inorganic materials 0.000 description 4
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- 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
- 239000012296 anti-solvent Substances 0.000 description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- 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
- 230000000903 blocking effect Effects 0.000 description 2
- 125000005620 boronic acid group Chemical group 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
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 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
- 238000001291 vacuum drying Methods 0.000 description 2
- XZRMXDPWEPRYMF-UHFFFAOYSA-N (4-ethenylphenoxy)boronic acid Chemical group OB(O)OC1=CC=C(C=C)C=C1 XZRMXDPWEPRYMF-UHFFFAOYSA-N 0.000 description 1
- QOVUQHJLIWOBNB-UHFFFAOYSA-N C1=CC=CC=C1[P](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound C1=CC=CC=C1[P](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 QOVUQHJLIWOBNB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
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- 239000011259 mixed solution Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
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- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
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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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- 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
- H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
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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
- H10K85/649—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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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/90—Ring systems containing bridged rings containing more than four rings
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- Chemical & Material Sciences (AREA)
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
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- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
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 is as follows:wherein R is a non-conjugated group, R 1 、R 2 、R 3 R is R 4 Are each independently selected from an electron donating group, a crosslinkable group, and a hydrogen atom, and R 1 、R 2 、R 3 R is R 4 At least one of which is selected from electron donating groups. That is, the technical scheme of the invention can prevent exciton quenching of the luminous layer and ensure luminous efficiency of the luminous 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 realize hole transport, a hole transport layer is generally disposed between a light emitting layer and an anode of a light emitting device, and 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 energy level of the hole transporting layer, and thus, the high-energy exciton of the light emitting layer is transferred to the triplet energy level of the low-energy hole transporting layer, thereby causing quenching of the exciton of the light emitting layer, resulting in a decrease in light emitting efficiency of the light emitting layer.
Disclosure of Invention
The main object of the present invention is to provide a hole transport compound, which aims to prevent exciton quenching of a light emitting layer and ensure the light emitting efficiency of the light emitting layer.
In order to achieve the above object, the present invention provides a hole transport compound having a molecular structure of the following general formula:
wherein R is a non-conjugated group, R 1 、R 2 、R 3 R is R 4 Are each independently selected from an electron donating group, a crosslinkable group, and a hydrogen atom, and R 1 、R 2 、R 3 R is R 4 At least one of which is selected from electron donating groups.
Alternatively, in the molecular structure of the hole transport compound, R 1 、R 2 、R 3 R is R 4 At least one of which is selected from crosslinkable groups.
Alternatively, the crosslinkable group is selected from one of a trifluorovinyl group, a styryl group, an oxetanyl group, a siloxane group, and an unsaturated acid ester group.
Optionally, the hole transport compound has a molecular structure as follows:
wherein R is 1 、R 2 、R 4 Are selected from electron donating groups.
Optionally, the hole transport compoundIn the molecular structure of the substance, R 1 、R 2 、R 3 R is R 4 And the molecular structure of R is selected from the electron donor groups 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 an alkaline substance, and bonding an electron donating group of the first raw material to a non-conjugated group of the second raw material in an atmosphere of inert gas to obtain a hole transporting compound.
Optionally, the preparation process of the first raw material comprises the following steps:
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 method is applied to preparing the hole transport layer, 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. In addition, the conjugation of the molecular structure of the hole transport compound is reduced by the introduction of the non-conjugated group, so that the problem of the reduction of the triplet energy level of the hole transport compound caused by conjugation is avoided, 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 the light emitting layer, and the exciton of the light emitting layer cannot be transferred to the hole transport layer prepared by the hole transport compound with the high-energy triplet energy level because the exciton cannot be transferred to the high-energy level.
Drawings
FIG. 1 is a diagram showing the reaction process of a first feedstock according to the present invention;
FIG. 2 is a diagram showing the reaction process of the hole transporting compound in example 1 of the present invention;
FIG. 3 is a diagram showing the reaction process of the hole transporting 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.
Reference numerals illustrate:
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In one embodiment of the present invention, the molecular structure of the hole transporting compound has the following formula:
wherein R is a non-conjugated group, R 1 、R 2 、R 3 R is R 4 Are each independently selected from an electron donating group, a crosslinkable group, and a hydrogen atom, and R 1 、R 2 、R 3 R is R 4 At least one of which is selected from electron donating groups.
According to the technical scheme, when the method is applied to preparing the hole transport layer, 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. In addition, the conjugation of the molecular structure of the hole transport compound is reduced by the introduction of the non-conjugated group, so that the problem of the reduction of the triplet energy level of the hole transport compound caused by conjugation is avoided, 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 the light emitting layer, and the exciton of the light emitting layer cannot be transferred to the hole transport layer prepared by the hole transport compound with the high-energy triplet energy level because the exciton cannot be transferred to the high-energy level.
It should be noted that, the unconjugated group in the embodiment of the present invention has a unconjugated bulky stereo structure, which reduces the conjugation of the hole-transporting compound molecule on the one hand; on the other hand, the molecules of the hole transport compound are spread, the distance between molecules of the hole transport compound is increased, pi-pi accumulation is not easy to occur between molecules of the hole transport compound, and thus, the hole transport is improvedThe triplet state energy level of the compound is higher than the exciton energy of the light-emitting layer, so that the light-emitting layer of the light-emitting layer cannot be transferred to the hole-transporting layer prepared by the hole-transporting compound with high-energy triplet state energy level, and 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, R 1 、 R 2 、R 3 R is R 4 At least two of the electron donating groups can enhance the transmission of holes, so that more holes can be transmitted to the light emitting layer, and the light emitting efficiency of the light emitting layer can be improved.
In one embodiment of the present invention, R in the molecular structure of the hole transporting compound 1 、R 2 、R 3 R is R 4 At 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-linking group, so that a net structure is formed, the penetration of solvent is effectively blocked, and when the organic light-emitting device is applied to the preparation of the hole transport layer, the solvent deposited on the surface of the hole transport layer cannot penetrate into the hole transport layer, the solvent resistance of the hole transport layer is endowed, the mutual dissolution between the hole transport layer and the adjacent layer is prevented, and the requirement of the light-emitting device on ink-jet printing is met. To supplement the explanation, 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 the embodiment of the present invention introduces a plurality of crosslinkable groups into the molecular structure of the hole transport compound, thereby forming a plurality of side chains through the plurality of crosslinkable groups, further improving the degree of crosslinking of the hole transport compound, thereby forming a more compact network structure, thereby 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 acid ester group. It should be noted that, the trifluoro vinyl group, the styryl group and the unsaturated acid ester group have unsaturated carbon-carbon double bonds, and under the high temperature condition, the adjacent molecules are crosslinked through the polymerization reaction between the unsaturated carbon-carbon double bonds, so as to form a network structure, and effectively prevent the permeation of external solvents. The oxetanyl and the siloxane are used as cross-linking agents, and the ring-opening reaction of the oxetanyl and the siloxane is carried out under the high-temperature condition so as to realize the cross-linking of the hole transport compound, thereby blocking the penetration of external solvents and improving the solvent resistance of the hole transport layer.
In one embodiment of the present invention, the molecular structure of the hole transporting compound is as follows:
wherein R is 1 、R 2 、R 4 Are selected from electron donating groups. It should be noted that, in the embodiment of the present invention, the three electron donating groups are introduced on the non-conjugated groups, so that the hole transporting performance of the hole transporting layer prepared by the hole transporting compound is enhanced. Of course, a tri-crosslinkable group may be introduced to the tri-electron donating group, the crosslinkable group being selected from one of a trifluorovinyl group, a styryl group, an oxetanyl group, a siloxane group, and an unsaturated acid ester group. Thus, the hole transport performance of the hole transport layer is improved, and the solvent resistance of the hole transport layer is also improved, so that the condition is provided for the ink-jet printing of the light-emitting device.
In one embodiment of the present invention, R in the molecular structure of the hole transporting compound 1 、R 2 、R 3 R is R 4 And the molecular structure of R is selected from the electron donor groups as follows:
according to the embodiment of the invention, the four electron donating groups are introduced on the non-conjugated groups, so that the hole transporting performance of the hole transporting layer prepared by the hole transporting compound is further enhanced. Of course, four crosslinkable groups may be introduced to the four electron donating groups, the crosslinkable groups being selected from one of trifluoroethyl, styryl, oxetanyl, siloxane groups and unsaturated acid ester groups. Thus, the hole transport performance of the hole transport layer is improved, and the light emitting device is also providedInkjet printing provides conditions.
In one embodiment of the invention, the electron donating group is an electron donating group comprising a nitrogen atom and a carbon-carbon double bond. According to the embodiment of the invention, the nitrogen atoms and the carbon-carbon double bonds are simultaneously introduced into the electron donating groups, so that on one hand, the introduction of the nitrogen atoms ensures the hole transport performance of the prepared hole transport layer, and on the other hand, the introduction of the carbon-carbon double bonds enables molecules of the hole transport compound to be cross-linked, thereby forming a reticular structure, effectively blocking the permeation of solvents and ensuring the anti-solvent effect of the hole transport layer. And the electron donating group is selected from one of carbazole group, diphenylamine group and triphenylamine group, and the carbazole group, the diphenylamine group and the triphenylamine group have good hole transmission performance, so that the hole transmission is ensured.
In one embodiment of the invention, the electron donating group molecular structure is selected from one of the following structures:
in the embodiment of the invention, the nitrogen atom and the carbon-carbon double bond are introduced, and a plurality of benzene rings are also introduced, so that the electron donating group has high stability through the introduction of the benzene rings, thereby further ensuring the stable transmission of the holes of the hole transport compound, and realizing the stable transmission of the hole by the hole transport layer prepared by the hole transport compound.
In one embodiment of the present invention, the molecular structure of the hole transporting compound is selected from one of the following molecular structures:
in the embodiment of the invention, the introduction of the unconjugated group reduces the conjugation of the molecular structure of the hole transport compound, so that the problem of triplet energy level reduction 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 by the hole transport compound with high-energy triplet energy level, and the light-emitting efficiency of the light-emitting layer is ensured. In addition, the embodiment of the invention introduces nitrogen atoms and carbon-carbon double bonds simultaneously through the electron donating groups, so that the hole transport performance of the prepared hole transport layer is ensured, the molecules of the hole transport compound can be crosslinked, the permeation of a solvent is effectively blocked, and the anti-solvent effect of the hole transport layer is ensured.
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 an alkaline substance, and bonding an electron donating group of the first raw material to a non-conjugated group of the second raw material in an atmosphere of inert gas to obtain a hole transporting compound. When the method is applied to preparing the hole transport layer, the introduction of the unconjugated group reduces the conjugation of the molecular structure of the hole transport compound, so that the problem of the reduction of the triplet energy level of the hole transport compound caused by conjugation is avoided, the triplet energy level of the hole transport compound is improved, and the triplet energy level of the hole transport compound is higher than the exciton energy of the light-emitting layer, so that the exciton of the light-emitting layer cannot be transferred to the hole transport layer prepared by the hole transport compound with the triplet energy level of high energy, namely the technical scheme of the invention can prevent the 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: firstly, 2mmol of the second raw material, 18mmol of the first raw material and 80mmol of Cs are sequentially added into a 250mL two-necked flask 2 CO 3 150ml of DMF solvent is added into the two-mouth bottle under the nitrogen atmosphere, and the mixture is stirred for 30 minutes at room temperature so as to fully dissolve the solid in the two-mouth bottle; then, heating the two bottles, carrying out reflux reaction for 12 hours at 155 ℃, 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, and passed over anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying by using a silica gel chromatographic column by taking normal hexane/dichloromethane as an eluent, removing the solvent by rotary evaporation, and drying in vacuum for 12 hours 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-tetra (4-iodophenyl) adamantane, and the invention is not limited thereto, and all the above are within the scope of the embodiments of the invention.
In one embodiment of the present invention, the preparation process of the first raw material includes: 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 boric acid substituent is selected from 4-vinylphenylboric acid and 4- [1,2 (trifluorovinyl) oxy group]The inert atmosphere may be one of the phenylboronic acids, and may be another inert gas atmosphere. In order to ensure sufficient progress of the SUZUKI coupling reaction, the reaction temperature is preferably 100℃and the reaction time is preferably 24 hours. In addition, the reaction solvent is a mixed solvent of toluene/ethanol/water (V/V/V=8:1:1), the palladium catalyst is tetraphenylpalladium phosphate, and the alkaline substance is potassium carbonate or sodium carbonate. In order to improve the purity of the prepared first raw material, the method can extract for multiple times, further effectively remove impurities, and the organic layer liquid after dichloromethane extraction adopts anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, adding the obtained product into a silica gel chromatographic column for separation and purification, adopting a mixed solution of n-hexane and dichloromethane as an eluent for separation and purification of the silica gel chromatographic column, and rotary evaporating the collected extract to obtain the first raw material.
Specifically, in one embodiment of the present invention, the preparation steps of the first raw material include: first, 4mmol of a bromine substituent, 4.5mmol of a boric acid substituent, and 0.2mmol of tetraphenylpalladium Pd (PPh) were sequentially introduced into a two-necked flask of 250mL 3 ) 4 8mmol of potassium carbonate K 2 CO 3 Adding a stirring magnet, and performing vacuumizing and nitrogen exchange operation for three times repeatedly to ensure that the two-mouth bottles are in nitrogen atmosphere; then, 120ml of a tetrahydrofuran THF/water (V/v=2:1) mixed solvent was added and the mixture was refluxed at 100 ℃ for 24 hours; then, the reaction mixture was cooled to room temperature, the solvent was removed by rotary evaporation, methylene chloride was added to extract 3 times, and the organic layer was dried over anhydrous MgSO 4 Drying, filtering and rotary steaming to remove the solvent; and finally, separating and purifying by adopting a silica gel chromatographic column, and removing the solvent by rotary evaporation by taking normal hexane/dichloromethane as an eluent to obtain a 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 FIG. 1, the yield of the first raw material M1 is 72%, and the first raw material M1 is identified by utilizing HPLC-MS and 1HNMR to obtain the molecular formula C of the first raw material M1 20 H 15 N, detection value [ M+1 ]] + 270.32 and a theoretical molecular weight of 269.12. The structural formula of the first raw material M1 was determined by nuclear magnetic resonance results 1HNMR (500 MHz, CDCl 3), delta (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) of the first raw material M1.
When the bromo substituent is 3-bromocarbazole, the boronic acid substituent is 4- [1,2 (trifluoroethenyl) oxy]Phenylboronic acid, 3-bromocarbazole and 4- [1,2 (trifluoroethenyl) oxy]The phenylboronic acid is obtained as a first raw material M2, the reaction process of the first raw material M2 is shown in FIG. 1, the yield of the first raw material M2 is 69%, and the first raw material M2 is identified by HPLC-MS and 1HNMR to obtain the molecular formula C of the first raw material M2 20 H 12 F 3 NO, detection value [ M+1 ]] + 340.13 and a theoretical molecular weight of 339.09. Nuclear magnetic resonance results of first feedstock M2 1HNMR (500 MHz, CDCl 3), δ (TMS, ppm): 1HNMR (500 MHz, CDCl 3), delta (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 from 4-bromophenylaniline and 4-vinylphenylboronic acid is a first raw material M3, the reaction process of the first raw material M3 is shown in FIG. 3, the yield of the first raw material M3 is 88%, and the first raw material M3 is identified by HPLC-MS and 1HNMR to obtain the molecular formula C of the first raw material M3 20 H 17 N, detection value [ M+1 ]] + 272.22 and a theoretical molecular weight of 271.14. Nuclear magnetic resonance results of the first raw material M3 1HNMR (500 MHz, CDCl 3), delta (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), thereby determining the structural formula of the first raw material M3.
When the bromo substituent is 4-bromophenylaniline, the boronic acid substituent is 4- [1,2 (trifluoroethenyl) oxy]Phenylboronic acid, 4-bromophenylaniline and 4- [1,2 (trifluoroethenyl) oxy]The phenylboronic acid is obtained as a first raw material M4, the reaction process of the first raw material M4 is shown in FIG. 1, the yield of the first raw material M4 is 83%, and the first raw material M4 is identified by HPLC-MS and 1HNMR to obtain the molecular formula C of the first raw material M4 20 H 14 F 3 NO, detection value [ M+1 ]] + 342.16 and a theoretical molecular weight of 341.10. Nuclear magnetic resonance results of the first raw material M4 1HNMR (500 MHz, CDCl 3), δ (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 determining the structural formula of the first raw material M4.
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. Because the triplet energy level of the hole transport compound is higher than the exciton energy of the light emitting layer, the exciton of the light emitting layer cannot be transferred to the hole transport layer prepared by the hole transport compound with high-energy triplet energy level, so that the transfer of the exciton of the light emitting layer to the hole transport layer is avoided, the quenching of the exciton of the light emitting layer is avoided, and the light emitting efficiency of the light emitting device is ensured.
The invention also provides a preparation method of the light-emitting device, which comprises the following steps: and depositing a 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-transporting compound deposited between the light-emitting layer and the anode, after the step of "the hole-transporting compound is deposited between the light-emitting layer and the anode", the hole-transporting compound is heated to cure and crosslink the hole-transporting compound, improving the anti-solvent effect of the prepared hole-transporting layer. Preferably, the heating temperature is 230 ℃, and the heating time is 30min, however, the heating temperature and the heating time can also be adjusted according to the thickness of the prepared hole transport layer, and the embodiment of the invention is not limited thereto, and the embodiment of the invention is prepared within the protection scope of the embodiment of the invention.
The technical scheme of the invention is further described below with reference to specific embodiments. It should be understood that the detailed description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
As shown in the reaction scheme of the compound A1 in the hole transport compound shown in fig. 2, the preparation method of the compound A1: firstly, 2mmol of 2,6, 14-tribromotriptycene, 18mmol of first raw material M1 and 80mmol of CsCO are sequentially added into a 250mL two-port bottle 3 150ml of DMF solvent is added into the two-mouth bottle under the nitrogen atmosphere, and the mixture is stirred for 30 minutes at room temperature so as to fully dissolve the solid in the two-mouth bottle; then, heating the two bottles, carrying out reflux reaction for 12 hours at 155 ℃, 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, and passed over anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying with silica gel chromatographic column by using n-hexane/dichloromethane as eluent,the solvent was removed by rotary evaporation to give the product which was dried in vacuo for 12h to give compound A1, and the yield was calculated to be 43%. Identification of Compound A1 by HPLC-MS and 1HNMR gives Compound A1 of formula C 80 H 53 N 3 Detection value [ M+1 ]] + 1056.50 and a theoretical molecular weight of 1055.42. The structural formula of the compound A1 is determined by nuclear magnetic resonance detection results 1HNMR (500 MHz, CDCl 3), delta (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) of the compound A1.
Referring to the reaction scheme shown in fig. 1, a first raw material M1 is prepared, and the preparation process of the first raw material M1 includes: into a 250mL two-necked flask, 4mmol of 3-bromocarbazole, 4.5mmol of 4-3-bromocarbazole and 0.2mmol of tetraphenylpalladium Pd (PPh) were successively introduced 3 ) 4 8mmol of potassium carbonate K 2 CO 3 Adding stirring magnetic seeds into the two-mouth bottles, and vacuumizing and replacing nitrogen for three times until the two-mouth bottles are in nitrogen atmosphere; 120ml of Tetrahydrofuran (THF)/water mixed solvent with the volume ratio of 2:1 is added, and reflux reaction is carried out for 24 hours at 100 ℃; after the reaction was completed, the two-necked flask was cooled to room temperature, the solvent was removed from the flask by rotary evaporation, extraction was performed 3 times with methylene chloride, and the organic layer was subjected to anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying by using n-hexane/dichloromethane as eluent, and vacuum drying for 12h after removing solvent by rotary evaporation to obtain a first raw material M1, wherein the yield is calculated to be 72%. Identifying the first material M1 by HPLC-MS and 1HNMR to obtain the molecular formula C of the first material M1 20 H 15 N, detection value [ M+1 ]] + 270.32 and a theoretical molecular weight of 269.12. The first material M1 was subjected to nuclear magnetic resonance detection at 1HNMR (500 MHz, CDCl 3), delta (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), thereby determining the structural formula of the first material M1.
Example 2
Preparation schematic of Compound A8 in the hole transporting Compound as shown in FIG. 3, compound A8The preparation method comprises the following steps: first, 2mmol of 1,3,5, 7-tetrakis (4-iodophenyl) adamantane, 18mmol of the first starting material M4 and 80mmol of CsCO were sequentially introduced into a 250mL two-necked flask 3 150ml of DMF solvent is added into the two-mouth bottle under the nitrogen atmosphere, and the mixture is stirred for 30 minutes at room temperature so as to fully dissolve the solid in the two-mouth bottle; then, heating the two bottles, carrying out reflux reaction for 12 hours at 155 ℃, 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, and passed over anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying by using a silica gel chromatographic column by taking normal hexane/dichloromethane as an eluent, and performing rotary evaporation to remove the solvent to obtain a product, and drying the product in vacuum for 12 hours to obtain the compound A8, wherein the yield is calculated to be 51%. Identification of Compound A8 by HPLC-MS and 1HNMR gives Compound A8 of formula C 114 H 80 F 12 N 4 O 4 Detection value [ M+1 ]]+ 1797.81 and a theoretical molecular weight of 1796.60. The structural formula of the compound A8 is determined according to the nuclear magnetic resonance detection result 1HNMR (500 MHz, CDCl 3), delta (TMS, ppm) of the compound A8, 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) and 1.71 (d, 6H).
Referring to the reaction scheme shown in fig. 1, a first raw material M4 is prepared, and the preparation process of the first raw material M4 includes: into a 250mL two-necked flask, 4mmol of 4-bromophenylaniline and 4.5mmol of 4- [1,2 (trifluorovinyl) oxy were successively introduced]Phenylboronic acid, 0.2mmol of palladium tetraphenyl phosphorus Pd (PPh) 3 ) 4 8mmol of potassium carbonate K 2 CO 3 Adding stirring magnetic seeds into the two-mouth bottles, and vacuumizing and replacing nitrogen for three times until the two-mouth bottles are in nitrogen atmosphere; 120ml of Tetrahydrofuran (THF)/water mixed solvent with the volume ratio of 2:1 is added, and reflux reaction is carried out for 24 hours at 100 ℃; after the reaction was completed, the two-necked flask was cooled to room temperature, the solvent was removed from the flask by rotary evaporation, extraction was performed 3 times with methylene chloride, and the organic layer was subjected to anhydrous MgSO 4 Drying, filtering, removing solvent by rotary evaporation, separating and purifying with silica gel chromatographic column using n-hexane/dichloromethane as eluent, removing solvent by rotary evaporation, vacuum drying for 12 hr to obtain first material M4, and meteringThe yield thereof was found to be 83%. Identifying the first material M4 by HPLC-MS and 1HNMR to obtain the molecular formula C of the first material M4 20 H 14 F 3 NO, detection value [ M+1 ]] + 342.16 and a theoretical molecular weight of 341.10. The nuclear magnetic resonance detection result 1HNMR (500 MHz, CDCl 3), delta (TMS, ppm) of the first raw material M4 is 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 determining the structural formula of the first raw material M4.
Example 3
Referring to fig. 3, an embodiment of the present 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 a compound A1 of the above embodiment 1.
A method of manufacturing a light emitting device 100, comprising the steps of:
step one, cleaning an ITO substrate according to the following sequence: 5% tetramethylammonium hydroxide solution is subjected to ultrasonic treatment for 15min, pure water is subjected to ultrasonic treatment for 15min, isopropanol is subjected to ultrasonic treatment for 15min, and the drying is performed for 1h; the ITO substrate comprises a glass substrate and an anode deposited on the glass substrate;
transferring the ITO substrate to UV-Ozone equipment for surface treatment for 15min, and immediately transferring the ITO substrate to a glove box after the 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 30min; sequentially preparing a light-emitting layer, an electron transport layer, an electron injection layer and a cathode by utilizing a vapor deposition film-forming mode;
and step four, carrying out UV curing encapsulation, and baking at 80 ℃ for 60min to obtain the light-emitting device.
Referring to fig. 4, an ITO/HIL/HTL/EML/ETL/EIL/cathode light emitting device is shown as a standard example, and the specific structure of the light emitting device according to the embodiment of the present invention is as follows: ITO/HI001 (40 nm)/H1 (15 nm)/MADN: 5% BCzVBi (40 nm)/LG 201: liQ (8:2, 20 nm)/Yb (1 nm)/Al (120 nm), 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% by weight 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, al is used as a cathode, and the example device is denoted as an "H1 device".
Referring to the method of this example, the hole transport layer was prepared using the compounds A2 to A8 to obtain the light emitting device illustrated in fig. 4, which was respectively designated as "H2 device", "H3 device", … …, "H8 device".
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 shown in example 3, and had the structure: ITO/HI001 (40 nm)/VNPB (15 nm)/MADN 5wt% BCzVBi (40 nm)/LG 201:LiQ (8:2, 20 nm)/Yb (1 nm)/Al (120 nm).
Referring to the conventional method, triplet energy levels and maximum external quantum efficiencies of hole transport layers of H1 to H8 devices and R1 devices were tested, and the results are shown in the following table:
| test device | Triplet 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 of the above tables, the triplet energy level and the maximum external quantum efficiency of the hole transport layer prepared in the examples of the present invention are significantly higher than those of the hole transport layer prepared in the comparative examples. Overall, the triplet energy level and external quantum efficiency of the H1 device to the H4 device are higher than those of the H5 device to the H8 device, because the hole transport compound for preparing the hole transport layer of the H5 device to the H8 device is connected with more benzene rings, so that the electron donating property of the obtained hole transport compound is stronger, the triplet energy level and external quantum efficiency of the H5 device to the H8 device are reduced by the enhancement of the electron donating property, and accordingly, the introduction of the electron withdrawing group is beneficial to the improvement of the triplet energy level and external quantum efficiency of the device. In addition, H1 devices have the highest triplet energy level due to their hole transporting compounds containing carbazole groups. The embodiment of the invention improves the external quantum efficiency of the light-emitting device by improving the triplet state energy level of the hole transport layer, thereby ensuring the light-emitting efficiency of the light-emitting device, and has potential application prospects in the fields of electroluminescence, photovoltaic cells, sensors and the like.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the content of the present invention or direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (2)
1. A hole transporting compound characterized in that the molecular structure of the hole transporting compound is selected from one of the following molecular structures:
2. 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 claim 1.
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| 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 |
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| 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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| Tetrasubstituted adamantane derivatives with arylamine groups: Solution-processable hole-transporting and host materials with high triplet energy and good thermal stability for organic light-emitting devices;Yu Gu et al.;《Organic Electronics》;20151231;第25卷;第193-199页 * |
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