CN106749400B - Multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye, and synthesis method and application thereof - Google Patents
Multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye, and synthesis method and application thereof Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title abstract description 18
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 150
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 75
- 239000003446 ligand Substances 0.000 claims abstract description 50
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 239000000463 material Substances 0.000 claims description 115
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- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 25
- 229910015711 MoOx Inorganic materials 0.000 description 25
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- 238000001514 detection method Methods 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 12
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 12
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- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 8
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
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- 239000010949 copper Substances 0.000 description 6
- KIALCSMRIHRFPL-UHFFFAOYSA-N n-(2,5-diphenylpyrazol-3-yl)-4-nitrobenzamide Chemical compound C1=CC([N+](=O)[O-])=CC=C1C(=O)NC1=CC(C=2C=CC=CC=2)=NN1C1=CC=CC=C1 KIALCSMRIHRFPL-UHFFFAOYSA-N 0.000 description 5
- 150000001879 copper Chemical class 0.000 description 4
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- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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
- H10K85/30—Coordination compounds
- H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Biochemistry (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
A multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye, a synthetic method and application thereof relate to a multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye, a synthetic method and application thereof. The invention aims to solve the technical problem that the performance and stability of a device are poor due to a quenching effect caused by accumulation of excitons of phosphorescent and thermally excited delayed fluorescent dyes. The dye is formed by taking a multidentate phosphine ligand as a ligand and coordinating with CuX, and the synthesis method comprises the following steps: mixing 1mmol of polydentate phosphine ligand, 0.5-1 mmol of CuX and 5-10 ml of dichloromethane, reacting at 40-45 ℃ for 10-15 hours, spin-drying, and performing column chromatography purification by taking DCM (dichloromethane) and PE (petroleum ether) as eluent to obtain the product; in the invention, the multidentate coordination is utilized to increase the spin-orbit coupling of the ligand to the metal, and the charge transfer from the halogen to the ligand is regulated by the halogen, so that the phosphorescence emission of the copper complex is enhanced.
Description
Technical Field
The invention relates to a multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye, a synthetic method and application thereof.
Background
The research on organic light emitting materials and devices has attracted much attention and intensive research. Organic light-emitting diodes (OLEDs), which are referred to as third-generation flat panel display and lighting technologies, have outstanding advantages in energy saving and environmental protection, and currently, a commonly used method is to use phosphorescent dyes to construct electrophosphorescence, but heavy metals related to phosphorescent dyes are expensive and pollute the environment, and other materials are urgently needed to be used for replacement. Recently, it is called asThe third generation organic electroluminescent technology, the Thermally Activated Delayed Fluorescence (TADF) technology, has made a great progress in order to effectively utilize the Singlet (S, Singlet) generated during the electroluminescent process1) And Triplet (Triplet, T)1) Excitons, as the exciton distribution on electrogenesis obeys statistical probability, i.e. singlet and triplet excitons account for roughly 25% and 75%, respectively. Therefore, the external quantum efficiency of the fluorescent device based on Electroluminescence (EL) of the ITO glass substrate does not exceed 5%. However, all excitons may be concentrated to the radiating T by intersystem or reverse intersystem crossing1Or S1Excited state, thereby achieving 100% exciton utilization. Exciton utilization is the basis for achieving high performance OLEDs, with only one electroluminescent process being Fluorescent (FL), Phosphorescent (PH), and thermally-excited delayed fluorescence. Such single mode radiation will inevitably produce S for TADF and PH, respectively, even if the singlet or triplet radiative transition processes emit light1And T1Accumulation of excitons. Thus exacerbating exciton quenching and device efficiency degradation caused by Singlet-triplet annihilation and triplet-triplet annihilation (STA and TTA) effects. Since STA and TTA are proportional to exciton concentration. Quenching effects can thus be suppressed by reducing the transient exciton concentration, on the basis of which the emission is carried out via two channels, i.e.S in the course of electroluminescence1And T1All states can be in radiative transition, and the mode can realize more efficient and reasonable exciton distribution and improve the performance of the device. In view of T1The excitons in the initial state are in the majority, and the double-emitting electroluminescent dye must be cycled by reasonably controlled interstitial and anti-interstitial transitions to achieve S in the true sense1Exciton in state and T1Optimal distribution of the excitons in the states, and thus the balance and coordination of TADF and PH emission, remains a great challenge in how to construct a truly bi-radiative electroluminescent material.
As is known, most of copper complexes are exothermic to excite delayed fluorescence or phosphorescent, and few copper complexes have the characteristics of both thermal excitation delayed fluorescence and phosphorescence dual emission, mainly because the spin-orbit coupling between copper ions and ligands in the copper complexes is weak, so that effective phosphorescence emission is difficult to obtain, but at present, a dual-emission electroluminescent dye is not developed in the copper complexes, so that a very good platform is provided. The work not only embodies the convincing superiority of the dual-emission material in the aspect of exciton utilization rate, but also proves that a feasible way for modulating the emission ratio is feasible, and lays a foundation for the further development and application of the light-emitting material.
Disclosure of Invention
The invention provides a synthesis method and application of a multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye, aiming at solving the technical problem of poor device performance and stability caused by quenching effect caused by exciton accumulation of phosphorescent and thermally-excited delayed fluorescent dyes at present.
The polydentate phosphine-coordinated copper complex dual-emission electroluminescent dye is characterized by being formed by coordinating a polydentate phosphine ligand and CuX, and having a molecular structural formula as follows:
the multidentate phosphine ligand is DPA, PPADP, PPPADP or DPAP, wherein X is Cl, Br or I.
The synthesis method comprises the following steps:
mixing 1mmol of polydentate phosphine ligand, 0.5-1 mmol of CuX and 5-10 ml of dichloromethane, reacting at 40-45 ℃ for 10-15 hours, performing spin drying, and performing column chromatography purification by using Dichloromethane (DCM) and Petroleum Ether (PE) as eluent to obtain a polydentate phosphine coordinated copper complex;
the multidentate phosphine ligand is DPA, PPADP, PPPADP or DPAP, wherein X is Cl, Br or I.
The mass ratio of the multidentate phosphine ligand to CuX is (1-2): 1. The volume ratio of DCM (dichloromethane) to PE (petroleum ether) in the mixed solvent of DCM (dichloromethane) and PE is 1: 20.
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye is used as a guest material of a light-emitting layer for preparing an electroluminescent device. The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye has the characteristic of dual emission, can emit thermal excitation delayed fluorescence and phosphorescence, can simultaneously utilize singlet excitons and triplet excitons as singlet excitons and triplet excitons can be simultaneously transited, and realizes dynamic distribution of the excitons in the electroluminescent process, thereby realizing the maximum reduction of exciton accumulation, the improvement of device efficiency, the inhibition of device efficiency roll-off and the maximum utilization in the electroluminescent process. In the invention, the multidentate coordination is utilized to increase the spin-orbit coupling of the ligand to the metal, and the halogen is utilized to adjust the charge transfer from the halogen to the ligand, so that the phosphorescence emission of the copper complex is enhanced, and finally, the dual-emission performance of both thermally-excited delayed fluorescence and phosphorescence is obtained. Meanwhile, the conjugation degree of the ligand is increased by adding the benzene ring, so that the luminescent color of the copper complex is adjusted. The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye electroluminescent material prepared by the invention can realize an ultra-low voltage driven high-efficiency electroluminescent device, and the external quantum efficiency reaches the maximum value of 20.5%.
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye used for the electroluminescent guest material of the electroluminescent device has the following advantages:
1. can be used as a guest for a light-emitting layer of an electroluminescent device.
2. The performance of the electroluminescent device material is improved, and the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye guest material has good thermodynamic stability, the cracking temperature is 338-446 ℃, and the electroluminescent device has the characteristic of dual emission. The invention improves the luminous efficiency and brightness of the organic electroluminescent material, and is mainly applied to organic electroluminescent diode devices.
Drawings
FIG. 1 is a ultraviolet fluorescence spectrum of a multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye in a first experiment, a second experiment and a third experiment, a fluorescence spectrum and a phosphorescence spectrum dissolved in a dichloromethane solvent are respectively shown in ■ ● A, which respectively shows the ultraviolet spectra of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye in the first experiment, the second experiment and the third experiment, and □ A delta respectively shows the fluorescence spectra of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye dissolved in the dichloromethane solvent in the first experiment, the second experiment and the third experiment; FIG. 2 is a thermogravimetric analysis chart showing the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dyes in experiment one, experiment two and experiment three, ■. tanglesolidup-solidup-a-solidup respectively shows the thermogravimetric analysis chart of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dyes in experiment one, experiment two and experiment three; FIG. 3 is a chart showing UV fluorescence spectra, fluorescence spectra and phosphorescence spectra of multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes dissolved in dichloromethane solvent in experiment four, experiment five and experiment six, ■ ● A represents the UV spectra of multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment four, experiment five and experiment six, respectively, □ A represents the fluorescence spectra of multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes dissolved in dichloromethane solvent in experiment four, experiment five and experiment six, respectively, and Zhi represents the phosphorescence spectra of multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment four, experiment five and experiment six, respectively; FIG. 4 is a thermogravimetric analysis chart showing multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment four, experiment five and experiment six, wherein ■. tanglesolidup-solidup-a-solidup respectively shows the thermogravimetric analysis chart of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment four, experiment five and experiment six; FIG. 5 is a graph showing ultraviolet fluorescence spectra, fluorescence spectra and phosphorescence spectra of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye dissolved in a methylene chloride solvent in experiment seven, experiment eight and experiment nine, ■ ● A indicates the ultraviolet spectra of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye dissolved in the methylene chloride solvent in experiment seven, experiment eight and experiment nine, respectively, □ A indicates the fluorescence spectra of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye dissolved in the methylene chloride solvent in experiment seven, experiment eight and experiment nine, respectively, and Z indicates the phosphorescence spectra of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment seven, experiment eight and experiment nine; FIG. 6 is a thermogravimetric analysis chart showing multidentate phosphine-coordinated copper complex dual-emission electroluminescent dyes in experiment seven, experiment eight and experiment nine, and ■. tanglesolidup-solidup respectively shows the thermogravimetric analysis chart of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dyes in experiment seven, experiment eight and experiment nine; FIG. 7 is a chart showing UV fluorescence spectra of multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes, fluorescence spectra and phosphorescence spectra dissolved in dichloromethane solvent in experiment ten, experiment eleven and experiment twelve, ■ ● A.The.The.The.The.The.The.The.The.The.The.The.The.The.The.No. □ A.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.The.; FIG. 8 is a thermogravimetric analysis chart showing multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment ten, experiment eleven and experiment twelve, wherein ■. tanglesolidup-solidup respectively shows the thermogravimetric analysis chart of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment ten, experiment eleven and experiment twelve; FIG. 9 is a voltage-current density relationship curve of the electroluminescent device of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment one, experiment two and experiment three, ■ ● A-solidup respectively represents the voltage-current density relationship curve of the electroluminescent device of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment one, experiment two and experiment three; FIG. 10 is a voltage-luminance relationship curve of an electroluminescent device of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment one, experiment two, experiment three, ■ ● A-solidup respectively representing the voltage-luminance relationship curve of an electroluminescent device of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment one, experiment two, experiment three; FIG. 11 is a luminance-current efficiency relationship curve of an electroluminescent device of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment one, experiment two, experiment three, ■ ● A-solidup respectively representing the luminance-current efficiency relationship curve of an electroluminescent device of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment one, experiment two, experiment three; FIG. 12 is a luminance-power efficiency relationship curve of the electroluminescent device of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment one, experiment two, experiment three, ■ ● A-solidup respectively representing the luminance-power efficiency relationship curve of the electroluminescent device of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment one, experiment two, experiment three; FIG. 13 is the current density-external quantum efficiency curve efficiencies of the electroluminescent devices of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment one, experiment two and experiment three, ■ ● A-solidup respectively represents the current density-external quantum efficiency curve efficiencies of the electroluminescent devices of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment one, experiment two and experiment three; FIG. 14 is an electroluminescence spectrum of an electroluminescence device of multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment one, experiment two and experiment three, ■ ● A-solidup respectively indicates the electroluminescence spectrum of the electroluminescence device of multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment one, experiment two and experiment three; FIG. 15 is a graph showing the voltage-current density relationship among electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment four, experiment five and experiment six, wherein ■ ● A represents the voltage-current density relationship among electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment four, experiment five and experiment six, respectively; FIG. 16 is a graph showing the voltage-luminance relationship between the electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment four, experiment five and experiment six, wherein ■ ● A-solidup respectively indicates the voltage-luminance relationship between the electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment four, experiment five and experiment six; FIG. 17 is a graph showing the relationship between luminance and current efficiency of electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment four, experiment five and experiment six, wherein ■ ● A-solidup represents the relationship between luminance and current efficiency of electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment four, experiment five and experiment six, respectively; FIG. 18 is a graph showing the relationship between luminance and power efficiency of electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment four, experiment five and experiment six, wherein ■ ● A-solidup represents the relationship between luminance and power efficiency of electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment four, experiment five and experiment six, respectively; FIG. 19 is the current density-external quantum efficiency curve efficiencies of electroluminescent devices of multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment four, experiment five and experiment six, wherein ■ ● A-solidup represents the current density-external quantum efficiency curve efficiencies of electroluminescent devices of multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment four, experiment five and experiment six, respectively; FIG. 20 is an electroluminescence spectrum of an electroluminescence device of multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment four, experiment five and experiment six, ■ ● A-solidup respectively indicates the electroluminescence spectra of the electroluminescence device of multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment four, experiment five and experiment six; FIG. 21 is a graph showing the voltage-current density relationship among electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment seven, experiment eight and experiment nine, wherein ■ ● A is a tangle-solidup respectively showing the voltage-current density relationship among electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment seven, experiment eight and experiment nine; FIG. 22 is a graph showing the voltage-luminance relationship between the electroluminescent devices using the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment seven, experiment eight or experiment nine, wherein ■ ● A-solidup respectively indicates the voltage-luminance relationship between the electroluminescent devices using the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment seven, experiment eight or experiment nine; FIG. 23 is a graph showing the relationship between luminance and current efficiency of an electroluminescent device using a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment seven, experiment eight or experiment nine, wherein ■ ● A represents the relationship between luminance and current efficiency of an electroluminescent device using a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment seven, experiment eight or experiment nine, respectively; FIG. 24 is a graph showing the relationship between luminance and power efficiency of electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment seven, experiment eight and experiment nine, wherein ■ ● A-solidup represents the relationship between luminance and power efficiency of electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment seven, experiment eight and experiment nine, respectively; FIG. 25 is the current density-external quantum efficiency curve efficiencies of electroluminescent devices with multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in the seventh, eighth and ninth experiments, ■ ● A-solidup respectively representing the current density-external quantum efficiency curve efficiencies of electroluminescent devices with multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in the seventh, eighth and ninth experiments; FIG. 26 is an electroluminescence spectrum of an electroluminescence device of multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment seven, experiment eight and experiment nine, ■ ● A-solidup respectively indicates the electroluminescence spectra of the electroluminescence device of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment seven, experiment eight and experiment nine; FIG. 27 is a graph showing the voltage-current density relationship among electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment ten, experiment eleven and experiment twelve, wherein ■ ● A-solidup indicates the voltage-current density relationship among electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment ten, experiment eleven and experiment twelve, respectively; FIG. 28 is a graph showing the voltage-luminance relationship among electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment ten, experiment eleven and experiment twelve, wherein ■ ● A-solidup indicates the voltage-luminance relationship among electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment ten, experiment eleven and experiment twelve, respectively; fig. 29 is a luminance-current efficiency relationship curve of the electroluminescent device of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment ten, experiment eleven, and experiment twelve, wherein ■ ● a-solidup represents the luminance-current efficiency relationship curve of the electroluminescent device of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment ten, experiment eleven, and experiment twelve, respectively; FIG. 30 is a graph showing the relationship between luminance and power efficiency of electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment ten, experiment eleven, and experiment twelve, wherein ■ ● A-solidup indicates the relationship between luminance and power efficiency of electroluminescent devices using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment ten, experiment eleven, and experiment twelve, respectively; fig. 31 is the current density-external quantum efficiency curve efficiencies of the electroluminescent devices of multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment ten, experiment eleven and experiment twelve, wherein ■ ● a-solidup represents the current density-external quantum efficiency curve efficiencies of the electroluminescent devices of multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment ten, experiment eleven and experiment twelve, respectively; FIG. 32 is an electroluminescence spectrum of an electroluminescence device using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment ten, experiment eleven and experiment twelve, wherein ■ ● A-solidup indicates the electroluminescence spectra of the electroluminescence device using multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dyes in experiment ten, experiment eleven and experiment twelve, respectively; FIG. 33 is a plot of the temperature swing lifetime of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment one; FIG. 34 is a temperature swing lifetime spectrum of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment two; FIG. 35 is a temperature swing lifetime spectrum of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment three; FIG. 36 is a temperature swing lifetime spectrum of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment IV; FIG. 37 is a temperature swing lifetime spectrum of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment five; FIG. 38 is a graph showing the temperature-variable lifetime of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment six; FIG. 39 is a temperature-variable lifetime spectrum of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment seven; FIG. 40 is a graph showing the temperature-variable lifetime of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment VIII; FIG. 41 is a temperature swing lifetime spectrum of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment nine; FIG. 42 is a graph of temperature swing lifetime of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment ten; FIG. 43 is a temperature swing lifetime spectrum of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experimental eleven; FIG. 44 is a temperature swing lifetime spectrum of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experimental twelve.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye is formed by coordinating a multidentate phosphine ligand and CuX, and has a molecular structural formula as follows:
The second embodiment is as follows: the synthesis method of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye comprises the following steps:
mixing 1mmol of polydentate phosphine ligand, 0.5-1 mmol of CuX and 5-10 ml of dichloromethane, reacting at 40-45 ℃ for 10-15 hours, spin-drying, and performing column chromatography purification by taking DCM and PE as eluent to obtain a polydentate phosphine coordination copper complex;
the multidentate phosphine ligand is DPA, PPADP, PPPADP or DPAP, wherein X is Cl, Br or I.
The third concrete implementation mode: the present embodiment is different from the second embodiment in that the substance ratio of the multidentate phosphine ligand to CuX is (1 to 2): 1. The rest is the same as the second embodiment.
The fourth concrete implementation mode: the present embodiment is different from the second embodiment in that the substance ratio of the multidentate phosphine ligand to CuX is 1: 1. The rest is the same as the second embodiment.
The fifth concrete implementation mode: the difference between the second embodiment and the second embodiment is that the volume ratio of the DCM to the PE in the mixed solvent of DCM and PE is 1: 20. The rest is the same as the second embodiment.
The sixth specific implementation mode: the present embodiment is different from the second embodiment in that the reaction is carried out at 42 ℃ for 12 hours. The rest is the same as the second embodiment.
The seventh embodiment: this embodiment is different from the second embodiment in that the reaction is carried out at 43 ℃ for 13 hours. The rest is the same as the second embodiment.
The specific implementation mode is eight: this embodiment is different from the second embodiment in that the reaction is carried out at 44 ℃ for 14 hours. The rest is the same as the second embodiment.
The specific implementation method nine: this embodiment is different from the second embodiment in that the reaction is carried out at 45 ℃ for 15 hours. The rest is the same as the second embodiment.
The detailed implementation mode is ten: the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye is used as a guest material of a light-emitting layer to prepare an electroluminescent device.
The method for preparing the electrophosphorescent device by using the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye as a light-emitting layer in the embodiment is as follows:
firstly, putting the glass or plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument with the vacuum degree of 1 multiplied by 10-6mbar, evaporation rate set to 0.1-0.3 nm-1Evaporating an anode conducting layer which is made of Indium Tin Oxide (ITO) and has the thickness of 1-100 nm on a glass or plastic substrate;
secondly, evaporating a hole injection layer material MoOx on the anode conducting layer to obtain a hole injection layer with the thickness of 2-10 nm;
thirdly, evaporating a hole transport layer material TAPC on the hole injection layer to obtain a hole transport layer with the thickness of 20-40 nm;
fourthly, evaporating and plating a bidentate phosphine coordination copper complex dual-emission electroluminescent dye on the hole transport layer to be mixed with a main material mCP to obtain a mixture with the thickness of 5-15 nm;
fifthly, evaporating and plating an electron transport layer material TPBi on the light-emitting layer, wherein the thickness of the electron transport layer material TPBi is 10-80 nm;
sixthly, evaporating and plating an electron injection layer material LiF on the electron transport layer, wherein the thickness of the electron injection layer is 1-10 nm;
and seventhly, evaporating a cathode conducting layer which is made of metal and has the thickness of 1-100 nm on the electron injection layer to obtain the electroluminescent device.
And seventhly, the metal is calcium, magnesium, copper, aluminum, calcium alloy, magnesium alloy, copper alloy or aluminum alloy.
The following experiments are adopted to verify the effect of the invention:
experiment one: the synthesis method of the experimental multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye is realized according to the following steps:
mixing 1mmol of polydentate phosphine ligand, 1mmol of CuCl and 5ml of DCM, reacting at 40 ℃ for 10-15 hours, spin-drying, and purifying by taking DCM and PE as eluent column chromatography to obtain a polydentate phosphine coordination copper complex;
wherein the multidentate phosphine ligand to CuCl ratio is 1: 1.
The volume ratio of the DCM to the PE in the mixed solvent of the DCM and the PE is 1: 20.
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment is DPACuCl.
The mass spectrum is adopted to detect the multifunctional modified DPACuCl prepared by the test, and the detection result is as follows:
m/z:1288.13(100.0％),1290.13(89.1％),1289.13(82.2％),1291.13(73.3％),1290.13(63.9％),1292.13(57.0％),1291.13(52.5％),1293.13(46.8％),1290.14(33.3％),1292.14(29.7％),1292.13(21.3％),1292.13(19.9％),1294.13(19.0％),1293.13(16.3％),1294.12(12.7％),1295.13(10.4％),1292.12(10.2％),1294.12(9.1％),1291.14(8.9％),1293.13(8.4％),1293.14(7.9％),1295.13(7.5％),1294.13(6.6％),1293.14(5.2％),1295.14(4.6％),1296.13(4.2％),1294.13(3.4％),1296.13(3.0％),1296.12(2.0％),1295.14(1.8％),1297.12(1.7％),1292.14(1.4％),1294.14(1.3％),1294.14(1.1％),1297.13(1.0％),1296.14(1.0％)。Elemental Analysis(％)for:C76H56Cu2Cl2P4:C,70.70；H,4.37。
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPACuCl, and the phosphorescence spectrum is shown in figure 1. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuCl obtained by the experiment is shown in figure 2, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuCl is 407 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuCl as a light-emitting layer comprises the following steps:
firstly, putting the plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument with the vacuum degree of 1 multiplied by 10-6mbar, evaporation rate set at 0.1nm s-1An anode conducting layer with the thickness of 10nm is formed on a glass or plastic substrate by vapor deposition of Indium Tin Oxide (ITO);
secondly, evaporating a hole injection layer material MoOx on the anode conducting layer to obtain a 10 nm-thick hole injection layer;
thirdly, evaporating a hole transport layer material TAPC on the hole injection layer to obtain a hole transport layer with the thickness of 40 nm;
fourthly, evaporating and plating a bidentate phosphine coordination copper complex dual-emission electroluminescent dye on the hole transport layer to be mixed with a main material mCP to obtain a mixture with the thickness of 15 nm;
fifthly, evaporating and plating an electron transport layer material TPBi on the light-emitting layer, wherein the thickness of the electron transport layer material TPBi is 80 nm;
sixthly, evaporating and plating an electron injection layer material LiF on the electron transport layer, wherein the thickness of the electron injection layer is 10 nm;
and seventhly, evaporating a cathode conducting layer which is made of metal and has the thickness of 10nm on the electron injection layer to obtain the electrophosphorescent device. And seventhly, the metal is aluminum. The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP DPACuCl (15nm)/TPBi (80nm)/LiF (10 nm)/Al. The experiment shows that the electricity of the electroluminescent device prepared by the multidentate phosphine coordinated copper complex dual-emitting electroluminescent dye DPACuClThe voltage-current density relationship curve is shown in fig. 9, and it can be known from the graph that the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuCl material has semiconductor characteristics, and the threshold voltage of the material is 4V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuCl in the experiment is shown in FIG. 10, and the figure shows that the starting voltage of the device is 4V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared from the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuCl in the experiment is shown in FIG. 11, and the graph shows that the device has the luminance of 2.4 cd.m-2When the current efficiency reaches the maximum value of 11.8 cd.A-1. The graph of the relationship between luminance and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuCl in the experiment is shown in FIG. 12, and the graph shows that the device has the luminance of 2.1 cd.m-2When the power efficiency reaches the maximum value of 6lm W-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuCl in the experiment is shown in figure 13, and the graph shows that the device has the brightness of 6 mA-cm-2Then, a maximum external quantum efficiency of 14.3% was obtained. The electroluminescence spectrum of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuCl in the experiment is shown in FIG. 14, and the electroluminescence peak of the device is shown at 605 nm. From fig. 33, it can be seen that: the lifetime is sharply decreased with increasing temperature, phosphorescent emission at low temperature, and thermal excitation delayed fluorescence property is exhibited with increasing temperature, thereby exhibiting dual emission.
Experiment two: the synthesis method of the experimental multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye is realized according to the following steps:
mixing 1mmol of polydentate phosphine ligand, 1mmol of CuBr and 5ml of DCM, reacting at 40-45 ℃ for 10-15 hours, spin-drying, and performing column chromatography purification by taking DCM and PE as eluent to obtain a polydentate phosphine coordination copper complex;
wherein the multidentate phosphine ligand to CuBr ratio is 1: 1.
The volume ratio of the DCM to the PE in the mixed solvent of the DCM and the PE is 1: 20.
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment is DPACuBr.
The mass spectrum is adopted to detect the multifunctional modified DPACuBr prepared by the test, and the detection result is as follows:
m/z:1378.03(100.0％),1380.03(89.1％),1379.03(79.0％),1381.03(70.4％),1376.03(51.4％),1380.03(48.6％),1378.03(45.8％),1382.02(43.4％),1377.03(42.2％),1381.03(40.0％),1383.03(35.6％),1380.03(26.4％),1382.03(23.6％),1379.03(20.8％),1382.02(19.9％),1379.03(16.8％),1378.04(16.4％),1383.03(15.7％),1380.03(14.6％),1382.03(14.5％),1384.03(14.5％),1380.03(10.2％),1384.02(9.7％),1381.04(8.7％),1385.02(7.9％),1383.04(7.7％),1380.03(6.9％),1382.03(6.1％),1384.03(5.3％),1381.03(4.6％),1379.04(4.6％),1381.04(4.1％),1381.03(3.8％),1383.04(3.5％),1382.03(3.4％),1379.03(3.2％),1385.03(3.1％),1381.03(2.9％),1386.03(2.9％),1382.04(1.7％),1385.03(1.7％),1382.03(1.7％),1384.04(1.6％),1384.03(1.4％)。Elemental Analysis(％)for:C76H56Cu2Br2P4:C,66.14；H,4.09。
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPACuBr, and the phosphorescence spectrum is shown in figure 1.
The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPACuBr obtained in the experiment is shown in figure 2, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPACuBr is 403 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPACuBr as the light-emitting layer comprises the following steps:
first, will be throughPutting the plastic substrate cleaned by deionized water into a vacuum evaporation instrument with the vacuum degree of 1 multiplied by 10-6mbar, evaporation rate set at 0.1nm s-1An anode conducting layer with the thickness of 10nm is formed on a glass or plastic substrate by vapor deposition of Indium Tin Oxide (ITO);
secondly, evaporating a hole injection layer material MoOx on the anode conducting layer to obtain a 10 nm-thick hole injection layer;
thirdly, evaporating a hole transport layer material TAPC on the hole injection layer to obtain a hole transport layer with the thickness of 40 nm;
fourthly, evaporating and plating a bidentate phosphine coordination copper complex dual-emission electroluminescent dye on the hole transport layer to be mixed with a main material mCP to obtain a mixture with the thickness of 15 nm;
fifthly, evaporating and plating an electron transport layer material TPBi on the light-emitting layer, wherein the thickness of the electron transport layer material TPBi is 80 nm;
sixthly, evaporating and plating an electron injection layer material LiF on the electron transport layer, wherein the thickness of the electron injection layer is 10 nm;
and seventhly, evaporating a cathode conducting layer which is made of metal and has the thickness of 10nm on the electron injection layer to obtain the electrophosphorescent device. And seventhly, the metal is aluminum. The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP DPACuBr (15nm)/TPBi (80nm)/LiF (10 nm)/Al. The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuBr in the experiment is shown in fig. 9, and therefore, the graph shows that the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuBr material has semiconductor characteristics, and the threshold voltage of the material is 3.8V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuBr in the experiment is shown in figure 10, and the figure shows that the starting voltage of the device is 4V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuBr in the experiment is shown in FIG. 11, and the graph shows that the luminance of the device is 2.6 cd.m-2When the current efficiency reaches the maximum value of 13cd & A-1. The experiment shows that the brightness of an electroluminescent device prepared by the multidentate phosphine coordinated copper complex dual-emission electroluminescent dye DPACuBrThe degree-power efficiency curve is shown in FIG. 12, which shows that the luminance of the device is 2.1 cd.m-2When the power efficiency reaches the maximum value of 6.8 lm.W-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPACuBr in the experiment is shown in figure 13, and the graph shows that the device has the brightness of 6 mA-cm-2Then, a maximum external quantum efficiency of 12.8% was obtained. The electroluminescence spectrum of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuBr in the experiment is shown in FIG. 14, and the electroluminescence peak of the device is at 608 nm. As can be seen from fig. 34: the lifetime is sharply decreased with increasing temperature, phosphorescent emission at low temperature, and thermal excitation delayed fluorescence property is exhibited with increasing temperature, thereby exhibiting dual emission.
Experiment three: the synthesis method of the experimental multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye is realized according to the following steps:
mixing 1mmol of polydentate phosphine ligand, 1mmol of CuI and 5ml of DCM, reacting at 40-45 ℃ for 10-15 hours, spin-drying, and performing column chromatography purification by taking DCM and PE as eluent to obtain a polydentate phosphine coordination copper complex;
wherein the multidentate phosphine ligand to CuI ratio is 1: 1.
The volume ratio of the DCM to the PE in the mixed solvent of the DCM and the PE is 1: 20.
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment is DPACuI.
The mass spectrum is adopted to detect the multifunctional modified DPACuI prepared by the test, and the detection result is as follows:
m/z:1472.00(100.0％),1473.00(82.2％),1475.00(73.3％),1474.00(44.6％),1474.00(44.6％),1474.01(33.3％),1476.00(19.9％),1477.00(16.3％),1476.01(14.9％),1476.01(14.9％),1475.01(8.9％),1477.01(7.6％),1478.00(6.6％),1479.01(1.8％),1476.01(1.8％)
Elemental Analysis(％)for:C76H56Cu2I2P4:C,61.93；H,3.83。
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPACuI, and the phosphorescence spectrum is shown in figure 1. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPACuI obtained by the experiment is shown in figure 2, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPACuI is 383 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuI as a light-emitting layer comprises the following steps:
firstly, putting the plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument with the vacuum degree of 1 multiplied by 10-6mbar, evaporation rate set at 0.1nm s-1An anode conducting layer with the thickness of 10nm is formed on a glass or plastic substrate by vapor deposition of Indium Tin Oxide (ITO);
secondly, evaporating a hole injection layer material MoOx on the anode conducting layer to obtain a 10 nm-thick hole injection layer;
thirdly, evaporating a hole transport layer material TAPC on the hole injection layer to obtain a hole transport layer with the thickness of 40 nm;
fourthly, evaporating and plating a bidentate phosphine coordination copper complex dual-emission electroluminescent dye on the hole transport layer to be mixed with a main material mCP to obtain a mixture with the thickness of 15 nm;
fifthly, evaporating and plating an electron transport layer material TPBi on the light-emitting layer, wherein the thickness of the electron transport layer material TPBi is 80 nm;
sixthly, evaporating and plating an electron injection layer material LiF on the electron transport layer, wherein the thickness of the electron injection layer is 10 nm;
and seventhly, evaporating a cathode conducting layer which is made of metal and has the thickness of 10nm on the electron injection layer to obtain the electrophosphorescent device. And seventhly, the metal is aluminum. The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP DPACuI (15nm)/TPBi (80nm)/LiF (10 nm)/Al. This experiment uses multiple teethThe voltage-current density relation curve of the electroluminescent device prepared from the phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuI is shown in FIG. 9, and therefore, the graph shows that the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuI material has semiconductor characteristics, and the threshold voltage of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuI material is 3.9V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuI in the experiment is shown in FIG. 10, and the figure shows that the starting voltage of the device is 3.8V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuI in the experiment is shown in FIG. 11, and the graph shows that the device has the luminance of 2.4 cd.m-2When the current efficiency reaches the maximum value of 17.7 cd.A-1. The graph of the relationship between luminance and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuI in the experiment is shown in FIG. 12, and the graph shows that the device has the luminance of 2.1 cd.m-2When the power efficiency reaches the maximum value of 7.7 lm.W-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuI in the experiment is shown in figure 13, and the graph shows that the device has the brightness of 6 mA-cm-2Then, the maximum external quantum efficiency of 13.2% was obtained. The electroluminescence spectrum of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPACuI in the experiment is shown in FIG. 14, and the electroluminescent peak of the device is at 610 nm. As can be seen from fig. 35: the lifetime is sharply decreased with increasing temperature, phosphorescent emission at low temperature, and thermal excitation delayed fluorescence property is exhibited with increasing temperature, thereby exhibiting dual emission.
Experiment four: the synthesis method of the experimental multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye is realized according to the following steps:
mixing 1mmol of polydentate phosphine ligand, 1mmol of CuCl and 5ml of DCM, reacting at 40 ℃ for 10-15 hours, spin-drying, and purifying by taking DCM and PE as eluent column chromatography to obtain a polydentate phosphine coordination copper complex;
wherein the multidentate phosphine ligand to CuCl ratio is 1: 1.
The volume ratio of the DCM to the PE in the mixed solvent of the DCM and the PE is 1: 20.
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment is PPADCUCl.
The mass spectrum is adopted to detect the multifunctional modified PPADCuCl prepared by the test, and the detection result is as follows:
m/z:478.09(100.0％),478.59(64.9％),479.09(44.6％),479.09(32.0％),479.59(28.9％),479.59(20.7％),479.09(20.7％),480.08(14.2％),480.59(9.2％),480.09(9.2％),480.09(6.6％),479.59(3.5％),481.09(2.9％),480.59(1.9％),480.59(1.1％)。Elemental Analysis(％)for:C60H45ClCuP3:C,75.23；H,4.74。
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye PPADCuCl, and the phosphorescence spectrum is shown in figure 3. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUCl obtained by the experiment is shown in figure 4, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUCl is 338 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUCl as a light-emitting layer comprises the following steps:
firstly, putting the plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument with the vacuum degree of 1 multiplied by 10-6mbar, evaporation rate set at 0.1nm s-1An anode conducting layer with the thickness of 10nm is formed on a glass or plastic substrate by vapor deposition of Indium Tin Oxide (ITO);
secondly, evaporating a hole injection layer material MoOx on the anode conducting layer to obtain a 10 nm-thick hole injection layer;
thirdly, evaporating a hole transport layer material TAPC on the hole injection layer to obtain a hole transport layer with the thickness of 40 nm;
fourthly, evaporating and plating a bidentate phosphine coordination copper complex dual-emission electroluminescent dye on the hole transport layer to be mixed with a main material mCP to obtain a mixture with the thickness of 15 nm;
fifthly, evaporating and plating an electron transport layer material TPBi on the light-emitting layer, wherein the thickness of the electron transport layer material TPBi is 80 nm;
sixthly, evaporating and plating an electron injection layer material LiF on the electron transport layer, wherein the thickness of the electron injection layer is 10 nm;
and seventhly, evaporating a cathode conducting layer which is made of metal and has the thickness of 10nm on the electron injection layer to obtain the electrophosphorescent device. And seventhly, the metal is aluminum. The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP PPADCuCl (15nm)/TPBi (80nm)/LiF (10 nm)/Al.
The voltage-current density relation curve of the electroluminescent device prepared from the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPADCuCl in the experiment is shown in figure 15, so that the graph shows that the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPADCuCl material has semiconductor characteristics, and the threshold voltage of the material is 3.9V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPADCuCl in the experiment is shown in figure 16, and the figure shows that the starting voltage of the device is 4V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared from the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPADCUCl in the experiment is shown in FIG. 17, and the graph shows that the device has the luminance of 2.4 cd.m-2When the current efficiency reaches the maximum value of 11.5 cd.A-1. The graph of the relationship between luminance and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPADCUCl in the experiment is shown in FIG. 18, and the graph shows that the device has the luminance of 2.1 cd.m-2When the power efficiency reaches the maximum value of 60lm W-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPADCUCl in the experiment is shown in figure 19, and the graph shows that the device has the brightness of 6 mA-cm-2Then obtain the maximum external quantum effectThe ratio was 22.1%. The electroluminescence spectrum of an electroluminescence device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescence dye PPADCuCl in the experiment is shown in figure 20, and the electroluminescence peak of the device is at 610 nm. As can be seen from fig. 36: the lifetime is sharply decreased with increasing temperature, phosphorescent emission at low temperature, and thermal excitation delayed fluorescence property is exhibited with increasing temperature, thereby exhibiting dual emission.
Experiment five: the synthesis method of the experimental multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye is realized according to the following steps:
mixing 1mmol of polydentate phosphine ligand, 1mmol of CuBr and 5ml of DCM, reacting at 40-45 ℃ for 10-15 hours, spin-drying, and performing column chromatography purification by taking DCM and PE as eluent to obtain a polydentate phosphine coordination copper complex;
wherein the multidentate phosphine ligand to CuBr ratio is 1: 1.
The volume ratio of the DCM to the PE in the mixed solvent of the DCM and the PE is 1: 20.
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment is PPADCUBr.
The mass spectrum is adopted to detect the multifunctional modified PPADCUBr prepared by the test, and the detection result is as follows:
m/z:500.06(100.0％),501.06(97.3％),500.56(64.9％),501.56(63.1％),501.06(44.6％),502.06(43.4％),501.56(28.9％),502.56(28.1％),502.06(20.1％),501.06(15.6％),502.06(9.2％),503.06(9.0％),501.06(5.1％),502.57(3.9％),501.57(2.7％),503.56(1.9％),501.57(1.7％),502.57(1.2％)。Elemental Analysis(％)for C60H45BrCuP3:C,71.89；H,4.53。
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye PPADCuBr, and the phosphorescence spectrum is shown in figure 3. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUBr obtained by the experiment is shown in figure 4, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUBr is 424 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUBr as a light-emitting layer comprises the following steps:
firstly, putting the plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument with the vacuum degree of 1 multiplied by 10-6mbar, evaporation rate set at 0.1nm s-1An anode conducting layer with the thickness of 10nm is formed on a glass or plastic substrate by vapor deposition of Indium Tin Oxide (ITO);
secondly, evaporating a hole injection layer material MoOx on the anode conducting layer to obtain a 10 nm-thick hole injection layer;
thirdly, evaporating a hole transport layer material TAPC on the hole injection layer to obtain a hole transport layer with the thickness of 40 nm;
fourthly, evaporating and plating a bidentate phosphine coordination copper complex dual-emission electroluminescent dye on the hole transport layer to be mixed with a main material mCP to obtain a mixture with the thickness of 15 nm;
fifthly, evaporating and plating an electron transport layer material TPBi on the light-emitting layer, wherein the thickness of the electron transport layer material TPBi is 80 nm;
sixthly, evaporating and plating an electron injection layer material LiF on the electron transport layer, wherein the thickness of the electron injection layer is 10 nm;
and seventhly, evaporating a cathode conducting layer which is made of metal and has the thickness of 10nm on the electron injection layer to obtain the electrophosphorescent device. And seventhly, the metal is aluminum. The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP: PPDPCuBr (15nm)/TPBi (80nm)/LiF (10 nm)/Al. The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUBr in the experiment is shown in figure 15, so that the graph shows that the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUBr material has semiconductor characteristics, and the threshold voltage of the material is 3.8V. The voltage-brightness relationship curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUBr in the experiment is shown in FIG. 16As shown, the turn-on voltage of the device is 3.9V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPADCuBr in the experiment is shown in FIG. 17, and the graph shows that the device has the luminance of 2.6 cd.m-2When the current efficiency reaches the maximum value of 7.8 cd.A-1. The graph of the relationship between brightness and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUBr in the experiment is shown in FIG. 18, and the graph shows that the device has the brightness of 2.1 cd.m-2When the power efficiency reaches the maximum value of 40lm W-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUBr in the experiment is shown in figure 19, and the graph shows that the device has the brightness of 6 mA-cm-2Then, a maximum external quantum efficiency of 20.5% was obtained. The electroluminescence spectrum of an electroluminescence device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescence dye PPABCUBr in the experiment is shown in figure 20, and the electroluminescence peak of the device is at 610 nm. As can be seen from fig. 37: the lifetime is sharply decreased with increasing temperature, phosphorescent emission at low temperature, and thermal excitation delayed fluorescence property is exhibited with increasing temperature, thereby exhibiting dual emission.
Experiment six: the synthesis method of the experimental multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye is realized according to the following steps:
mixing 1mmol of polydentate phosphine ligand, 1mmol of CuI and 5ml of DCM, reacting at 40-45 ℃ for 10-15 hours, spin-drying, and performing column chromatography purification by taking DCM and PE as eluent to obtain a polydentate phosphine coordination copper complex;
wherein the multidentate phosphine ligand to CuI ratio is 1: 1.
The volume ratio of the DCM to the PE in the mixed solvent of the DCM and the PE is 1: 20.
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment is PPADCUI.
The mass spectrum is adopted to detect the multifunctional modified PPDPCuI prepared by the test, and the detection result is as follows:
m/z:524.05(100.0％),524.56(64.9％),525.05(44.6％),525.56(28.9％),525.06(20.7％),526.06(9.2％),525.56(3.5％),526.56(1.9％)。Elemental Analysis(％)for C60H45CuIP3:C,68.67；H,4.32。
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye PPABCUI, and the phosphorescence spectrum is shown in figure 3. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUI obtained by the experiment is shown in figure 4, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUI is 446 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUI as a light-emitting layer comprises the following steps:
firstly, putting the plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument with the vacuum degree of 1 multiplied by 10-6mbar, evaporation rate set at 0.1nm s-1An anode conducting layer with the thickness of 10nm is formed on a glass or plastic substrate by vapor deposition of Indium Tin Oxide (ITO);
secondly, evaporating a hole injection layer material MoOx on the anode conducting layer to obtain a 10 nm-thick hole injection layer;
thirdly, evaporating a hole transport layer material TAPC on the hole injection layer to obtain a hole transport layer with the thickness of 40 nm;
fourthly, evaporating and plating a bidentate phosphine coordination copper complex dual-emission electroluminescent dye on the hole transport layer to be mixed with a main material mCP to obtain a mixture with the thickness of 15 nm;
fifthly, evaporating and plating an electron transport layer material TPBi on the light-emitting layer, wherein the thickness of the electron transport layer material TPBi is 80 nm;
sixthly, evaporating and plating an electron injection layer material LiF on the electron transport layer, wherein the thickness of the electron injection layer is 10 nm;
seven is atAnd evaporating a cathode conducting layer on the electron injection layer, wherein the evaporating material is metal and the thickness of the cathode conducting layer is 10nm, so that the electrophosphorescent device is obtained. And seventhly, the metal is aluminum. The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP PPABCuI (15nm)/TPBi (80nm)/LiF (10 nm)/Al. The voltage-current density relation curve of the electroluminescent device prepared from the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUI in the experiment is shown in FIG. 15, and therefore, the graph shows that the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUI material has semiconductor characteristics, and the threshold voltage of the material is 3.7V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUI in the experiment is shown in FIG. 16, and the figure shows that the starting voltage of the device is 3.8V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared from the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCuI in the experiment is shown in FIG. 17, and the graph shows that the device has the luminance of 2.4 cd.m-2When the current efficiency reaches the maximum value of 13.2 cd.A-1. The graph of the relationship between luminance and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCuI in the experiment is shown in FIG. 18, and the graph shows that the device has the luminance of 2.1 cd.m-2When the power efficiency reaches the maximum value of 77.7 lm.W-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUI in the experiment is shown in figure 19, and the graph shows that the device has the brightness of 6 mA-cm-2Then, a maximum external quantum efficiency of 20.1% was obtained. The electroluminescence spectrum of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPABCUI in the experiment is shown in FIG. 20, and the electroluminescence peak of the device is at 610 nm. As can be seen from fig. 38: the lifetime is sharply decreased with increasing temperature, phosphorescent emission at low temperature, and thermal excitation delayed fluorescence property is exhibited with increasing temperature, thereby exhibiting dual emission.
Experiment seven: the synthesis method of the experimental multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye is realized according to the following steps:
mixing 1mmol of polydentate phosphine ligand, 1mmol of CuCl and 5ml of DCM, reacting at 40 ℃ for 10-15 hours, spin-drying, and purifying by taking DCM and PE as eluent column chromatography to obtain a polydentate phosphine coordination copper complex;
wherein the multidentate phosphine ligand to CuCl ratio is 1: 1.
The volume ratio of the DCM to the PE in the mixed solvent of the DCM and the PE is 1: 20.
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment is PPPADPCuCl.
The mass spectrum is adopted to detect the multifunctional modified PPPADPCuCl prepared by the test, and the detection result is as follows:
m/z:461.09(100.0％),461.60(61.6％),462.09(44.6％),462.09(32.0％),462.60(27.5％),462.59(19.7％),462.10(18.7％),463.09(14.2％),463.59(8.8％),463.10(8.3％),463.10(6.0％),462.60(2.9％),464.10(2.7％),463.60(1.7％)。Elemental Analysis(％)for C57H47CuClP3:C,74.10；H,5.13。
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye PPPADPCuCl, and the phosphorescence spectrum is shown in figure 5. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuCl obtained by the experiment is shown in figure 6, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuCl is 425 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated copper complex double-emitting electroluminescent dye PPPADPCuCl as the light-emitting layer comprises the following steps:
firstly, putting the plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument with the vacuum degree of 1 multiplied by 10-6mbar, evaporation rate set at 0.1nm s-1The evaporation material on the glass or plastic substrate is oxidationIndium Tin (ITO), an anode conductive layer having a thickness of 10 nm;
secondly, evaporating a hole injection layer material MoOx on the anode conducting layer to obtain a 10 nm-thick hole injection layer;
thirdly, evaporating a hole transport layer material TAPC on the hole injection layer to obtain a hole transport layer with the thickness of 40 nm;
fourthly, evaporating and plating a bidentate phosphine coordination copper complex dual-emission electroluminescent dye on the hole transport layer to be mixed with a main material mCP to obtain a mixture with the thickness of 15 nm;
fifthly, evaporating and plating an electron transport layer material TPBi on the light-emitting layer, wherein the thickness of the electron transport layer material TPBi is 80 nm;
sixthly, evaporating and plating an electron injection layer material LiF on the electron transport layer, wherein the thickness of the electron injection layer is 10 nm;
and seventhly, evaporating a cathode conducting layer which is made of metal and has the thickness of 10nm on the electron injection layer to obtain the electrophosphorescent device. And seventhly, the metal is aluminum. The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP PPADCuCl (15nm)/TPBi (80nm)/LiF (10 nm)/Al. The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuCl in the experiment is shown in figure 21, and the graph shows that the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuCl material has semiconductor characteristics and the threshold voltage is 4V. The voltage-brightness relationship curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPAPPDPCuCl in the experiment is shown in FIG. 22, and the figure shows that the starting voltage of the device is 4V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuCl in the experiment is shown in FIG. 23, and the graph shows that the luminance of the device is 2.4 cd.m-2When the current efficiency reaches the maximum value of 11.5 cd.A-1. The graph of the relationship between luminance and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuCl in the experiment is shown in FIG. 24, and the graph shows that the luminance of the device is 2.1 cd.m-2When the power efficiency reaches the maximum value of 62lm W-1. The true bookFIG. 25 shows the current density-external quantum efficiency relationship curve of an electroluminescent device prepared from the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuCl, and the graph shows that the device has the brightness of 6mA cm-2Then, the maximum external quantum efficiency of 13.1% was obtained. The electroluminescence spectrum of an electroluminescence device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescence dye PPPADPCuCl in the experiment is shown in figure 26, and the electroluminescence peak of the device is known to be 620 nm. As can be seen from fig. 39: the lifetime is sharply decreased with increasing temperature, phosphorescent emission at low temperature, and thermal excitation delayed fluorescence property is exhibited with increasing temperature, thereby exhibiting dual emission.
Experiment eight: the synthesis method of the experimental multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye is realized according to the following steps:
mixing 1mmol of polydentate phosphine ligand, 1mmol of CuBr and 5ml of DCM, reacting at 40-45 ℃ for 10-15 hours, spin-drying, and performing column chromatography purification by taking DCM and PE as eluent to obtain a polydentate phosphine coordination copper complex;
wherein the multidentate phosphine ligand to CuBr ratio is 1: 1.
The volume ratio of the DCM to the PE in the mixed solvent of the DCM and the PE is 1: 20.
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment is PPPADPCuBr.
The mass spectrum is adopted to detect the multifunctional modified PPPADPCuBr prepared by the test, and the detection result is as follows:
m/z:483.07(100.0％),484.07(97.3％),483.57(61.6％),484.57(60.0％),484.07(44.6％),485.07(43.4％),484.57(27.5％),485.57(26.7％),485.07(18.2％),484.07(13.6％),485.07(8.3％),486.07(8.1％),484.07(5.1％),484.57(3.7％),485.57(3.3％),486.57(1.6％)
Elemental Analysis(％)for C57H47CuBrP3:C,70.70；H,4.89。
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye PPPADPCuBr, and the phosphorescence spectrum is shown in figure 5. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuBr obtained by the experiment is shown in fig. 6, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuBr is 433 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated copper complex double-emitting electroluminescent dye PPPADPCuBr as the light-emitting layer comprises the following steps:
firstly, putting the plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument with the vacuum degree of 1 multiplied by 10-6mbar, evaporation rate set at 0.1nm s-1An anode conducting layer with the thickness of 10nm is formed on a glass or plastic substrate by vapor deposition of Indium Tin Oxide (ITO);
secondly, evaporating a hole injection layer material MoOx on the anode conducting layer to obtain a 10 nm-thick hole injection layer;
thirdly, evaporating a hole transport layer material TAPC on the hole injection layer to obtain a hole transport layer with the thickness of 40 nm;
fourthly, evaporating and plating a bidentate phosphine coordination copper complex dual-emission electroluminescent dye on the hole transport layer to be mixed with a main material mCP to obtain a mixture with the thickness of 15 nm;
fifthly, evaporating and plating an electron transport layer material TPBi on the light-emitting layer, wherein the thickness of the electron transport layer material TPBi is 80 nm;
sixthly, evaporating and plating an electron injection layer material LiF on the electron transport layer, wherein the thickness of the electron injection layer is 10 nm;
and seventhly, evaporating a cathode conducting layer which is made of metal and has the thickness of 10nm on the electron injection layer to obtain the electrophosphorescent device. And seventhly, the metal is aluminum. The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP PPADCuBr (15nm)/TPBi (80nm)/LiF (10 nm)/Al. The voltage-current density relationship curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuBr in the experiment is shown in figure 21, and the graph shows thatThe multidentate phosphine-coordinated copper complex double-emitting electroluminescent dye PPPADPCuBr material has the semiconductor characteristic, and the threshold voltage of the material is 6V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuBr in the experiment is shown in figure 22, and the figure shows that the starting voltage of the device is 3.9V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuBr in the experiment is shown in FIG. 23, and the graph shows that the luminance of the device is 2.6 cd.m-2When the current efficiency reaches the maximum value of 11.8 cd.A-1. The graph of the relationship between brightness and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuBr in the experiment is shown in FIG. 24, and the graph shows that the device has the brightness of 2.1 cd.m-2When the power efficiency reaches the maximum value of 65lm W-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye PPPADPCuBr in the experiment is shown in figure 25, and the graph shows that the device has the brightness of 6mA cm-2Then, a maximum external quantum efficiency of 14.5% was obtained. The electroluminescence spectrum of an electroluminescence device prepared by the multidentate phosphine-coordinated copper complex dual-emission electroluminescence dye PPPADPCuBr in the experiment is shown in figure 26, and the electroluminescence peak of the device is known to be 620nm from the figure. As can be seen from fig. 40: the lifetime is sharply decreased with increasing temperature, phosphorescent emission at low temperature, and thermal excitation delayed fluorescence property is exhibited with increasing temperature, thereby exhibiting dual emission.
Experiment nine: the synthesis method of the experimental multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye is realized according to the following steps:
mixing 1mmol of polydentate phosphine ligand, 1mmol of CuI and 5ml of DCM, reacting at 40-45 ℃ for 10-15 hours, spin-drying, and performing column chromatography purification by taking DCM and PE as eluent to obtain a polydentate phosphine coordination copper complex;
wherein the multidentate phosphine ligand to CuI ratio is 1: 1.
The volume ratio of the DCM to the PE in the mixed solvent of the DCM and the PE is 1: 20.
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment is PPPADPCuI.
The multifunctional modified PPPACuI prepared by the test is detected by adopting mass spectrum, and the detection result is as follows:
m/z:507.06(100.0％),507.56(61.6％),508.06(44.6％),508.56(27.5％),508.07(18.7％),509.06(8.3％),508.57(2.9％),509.57(1.7％)。Elemental Analysis(％)for C57H47CuIP3:C,67.43；H,4.67；Cu,6.26；I,12.50；P,9.15。
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye PPPADPCuI, and the phosphorescence spectrum is shown in figure 5. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuI obtained by the experiment is shown in figure 6, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuI is 437 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated copper complex double-emitting electroluminescent dye PPPADPCuI as the light-emitting layer comprises the following steps:
firstly, putting the plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument with the vacuum degree of 1 multiplied by 10-6mbar, evaporation rate set at 0.1nm s-1An anode conducting layer with the thickness of 10nm is formed on a glass or plastic substrate by vapor deposition of Indium Tin Oxide (ITO);
secondly, evaporating a hole injection layer material MoOx on the anode conducting layer to obtain a 10 nm-thick hole injection layer;
thirdly, evaporating a hole transport layer material TAPC on the hole injection layer to obtain a hole transport layer with the thickness of 40 nm;
fourthly, evaporating and plating a bidentate phosphine coordination copper complex dual-emission electroluminescent dye on the hole transport layer to be mixed with a main material mCP to obtain a mixture with the thickness of 15 nm;
fifthly, evaporating and plating an electron transport layer material TPBi on the light-emitting layer, wherein the thickness of the electron transport layer material TPBi is 80 nm;
sixthly, evaporating and plating an electron injection layer material LiF on the electron transport layer, wherein the thickness of the electron injection layer is 10 nm;
and seventhly, evaporating a cathode conducting layer which is made of metal and has the thickness of 10nm on the electron injection layer to obtain the electrophosphorescent device. And seventhly, the metal is aluminum. The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP PPPADPCuI (15nm)/TPBi (80nm)/LiF (10 nm)/Al. The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuI is shown in figure 21, and the graph shows that the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuI material has semiconductor characteristics and the threshold voltage is 6V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuI in the experiment is shown in FIG. 22, and the figure shows that the starting voltage of the device is 3.8V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuI in the experiment is shown in FIG. 23, and the graph shows that the luminance of the device is 2.4 cd.m-2When the current efficiency reaches the maximum value of 18cd & A-1. The graph of the relationship between luminance and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuI in the experiment is shown in FIG. 24, and the graph shows that the luminance of the device is 2.1 cd.m-2When the power efficiency reaches the maximum value of 70.7 lm.W-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye PPPADPCuI in the experiment is shown in figure 25, and the graph shows that the device has the brightness of 6mA cm-2Then, a maximum external quantum efficiency of 14.2% was obtained. The electroluminescence spectrum of the electroluminescence device prepared by the multidentate phosphine coordination copper complex dual-emitting electroluminescence dye PPPADPCuI in the experiment is shown in FIG. 26, and the electroluminescence peak of the device is 621nm, which is shown in FIG. 41: with temperatureThe lifetime is sharply reduced at an increased temperature, and phosphorescence emission is performed at a low temperature, and thermal excitation delayed fluorescence properties are exhibited as the temperature is increased, thereby embodying dual emission.
Experiment ten: the synthesis method of the experimental multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye is realized according to the following steps:
mixing 1mmol of polydentate phosphine ligand, 1mmol of CuCl and 5ml of DCM, reacting at 40 ℃ for 10-15 hours, spin-drying, and purifying by taking DCM and PE as eluent column chromatography to obtain a polydentate phosphine coordination copper complex;
wherein the multidentate phosphine ligand to CuCl ratio is 1: 1.
The volume ratio of the DCM to the PE in the mixed solvent of the DCM and the PE is 1: 20.
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment is DPAPCuCl.
The mass spectrum is adopted to detect the multifunctional modified DPAPCuCl prepared by the test, and the detection result is as follows:
m/z:620.12(100.0％),620.63(86.5％),621.12(44.6％),621.62(38.6％),621.13(37.0％),621.12(32.0％),621.62(27.7％),622.13(16.5％),622.12(14.2％),622.62(12.3％),622.13(11.8％),621.63(10.4％),623.13(5.3％),622.63(4.6％),622.63(3.1％),622.13(1.8％),623.63(1.4％)。Elemental Analysis(％)for C80H58CuClP4:C,77.35；H,4.71。
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPAPCuCl, and the phosphorescence spectrum is shown in figure 7. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPAPCuCl obtained by the experiment is shown in figure 8, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPAPCuCl is 421 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuCl as a light-emitting layer comprises the following steps:
firstly, putting the plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument with the vacuum degree of 1 multiplied by 10-6mbar, evaporation rate set at 0.1nm s-1An anode conducting layer with the thickness of 10nm is formed on a glass or plastic substrate by vapor deposition of Indium Tin Oxide (ITO);
secondly, evaporating a hole injection layer material MoOx on the anode conducting layer to obtain a 10 nm-thick hole injection layer;
thirdly, evaporating a hole transport layer material TAPC on the hole injection layer to obtain a hole transport layer with the thickness of 40 nm;
fourthly, evaporating and plating a bidentate phosphine coordination copper complex dual-emission electroluminescent dye on the hole transport layer to be mixed with a main material mCP to obtain a mixture with the thickness of 15 nm;
fifthly, evaporating and plating an electron transport layer material TPBi on the light-emitting layer, wherein the thickness of the electron transport layer material TPBi is 80 nm;
sixthly, evaporating and plating an electron injection layer material LiF on the electron transport layer, wherein the thickness of the electron injection layer is 10 nm;
and seventhly, evaporating a cathode conducting layer which is made of metal and has the thickness of 10nm on the electron injection layer to obtain the electrophosphorescent device. And seventhly, the metal is aluminum. The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP DPAPCuCl (15nm)/TPBi (80nm)/LiF (10 nm)/Al. The voltage-current density relation curve of the electroluminescent device prepared from the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuCl in the experiment is shown in fig. 27, and therefore, the graph shows that the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuCl material has semiconductor characteristics, and the threshold voltage of the material is 3.9V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuCl in the experiment is shown in figure 28, and the figure shows that the starting voltage of the device is 4V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuCl in the experiment is shown in FIG. 29, and the graph shows that the device has the luminance of 2.4 cd.m-2When the current efficiency reaches the maximum value of 16.7 cd.A-1. The graph 30 of the relationship between the brightness and the power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuCl is shown in the experiment, and the graph shows that the device has the brightness of 2.1 cd.m-2When the power efficiency reaches the maximum value of 10lm W-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuCl in the experiment is shown in figure 31, and the graph shows that the device has the brightness of 6 mA-cm-2Then, the maximum external quantum efficiency of 15.3% was obtained. The electroluminescence spectrum of the electroluminescence device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescence dye DPAPCuCl in the experiment is shown in figure 32, and the electroluminescence peak of the device is 621 nm. As can be seen from fig. 42: the lifetime is sharply decreased with increasing temperature, phosphorescent emission at low temperature, and thermal excitation delayed fluorescence property is exhibited with increasing temperature, thereby exhibiting dual emission.
Experiment eleven: the synthesis method of the experimental multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye is realized according to the following steps:
mixing 1mmol of polydentate phosphine ligand, 1mmol of CuBr and 5ml of DCM, reacting at 40-45 ℃ for 10-15 hours, spin-drying, and performing column chromatography purification by taking DCM and PE as eluent to obtain a polydentate phosphine coordination copper complex;
wherein the multidentate phosphine ligand to CuBr ratio is 1: 1.
The volume ratio of the DCM to the PE in the mixed solvent of the DCM and the PE is 1: 20.
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment is DPAPCuBr.
The mass spectrum is adopted to detect the multifunctional modified DPAPCuBr prepared by the test, and the detection result is as follows:
m/z:642.10(100.0％),643.10(97.3％),642.60(85.4％),643.60(84.2％),643.10(44.6％),644.10(43.4％),643.60(38.6％),644.60(37.5％),644.10(35.1％),643.10(30.0％),645.10(15.6％),644.10(13.4％),643.60(10.3％),644.60(9.0％),643.10(6.9％),644.60(4.6％),645.60(4.5％),644.10(3.1％),644.11(2.2％),645.10(2.1％),642.60(1.1％),644.60(1.1％)
Elemental Analysis(％)for C80H58CuBrP4:C,74.68；H,4.54；Br,6.21；Cu,4.94；P,9.63。
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPAPCuBr, and the phosphorescence spectrum is shown in figure 7. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuBr obtained in the experiment is shown in FIG. 8, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuBr is 419 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPAPCuBr as the light-emitting layer comprises the following steps:
firstly, putting the plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument with the vacuum degree of 1 multiplied by 10-6mbar, evaporation rate set at 0.1nm s-1An anode conducting layer with the thickness of 10nm is formed on a glass or plastic substrate by vapor deposition of Indium Tin Oxide (ITO);
secondly, evaporating a hole injection layer material MoOx on the anode conducting layer to obtain a 10 nm-thick hole injection layer;
thirdly, evaporating a hole transport layer material TAPC on the hole injection layer to obtain a hole transport layer with the thickness of 40 nm;
fourthly, evaporating and plating a bidentate phosphine coordination copper complex dual-emission electroluminescent dye on the hole transport layer to be mixed with a main material mCP to obtain a mixture with the thickness of 15 nm;
fifthly, evaporating and plating an electron transport layer material TPBi on the light-emitting layer, wherein the thickness of the electron transport layer material TPBi is 80 nm;
sixthly, evaporating and plating an electron injection layer material LiF on the electron transport layer, wherein the thickness of the electron injection layer is 10 nm;
and seventhly, evaporating a cathode conducting layer which is made of metal and has the thickness of 10nm on the electron injection layer to obtain the electrophosphorescent device. And seventhly, the metal is aluminum. The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP DPAPCuBr (15nm)/TPBi (80nm)/LiF (10 nm)/Al. The voltage-current density relation curve of the electroluminescent device prepared from the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuBr in the experiment is shown in fig. 27, and the graph shows that the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuBr material has semiconductor characteristics and the threshold voltage of the material is 3.8V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuBr in the experiment is shown in figure 28, and the figure shows that the starting voltage of the device is 3.9V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuBr in the experiment is shown in FIG. 29, and the graph shows that the luminance of the device is 2.6 cd.m-2When the current efficiency reaches the maximum value of 16.1 cd.A-1. The graph of the relationship between brightness and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuBr in the experiment is shown in FIG. 30, and the graph shows that the device has the brightness of 2.1 cd.m-2When the power efficiency reaches the maximum value of 12.6 lm.W-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuBr in the experiment is shown in figure 31, and the graph shows that the device has the brightness of 6 mA-cm-2Then, a maximum external quantum efficiency of 15.4% was obtained. The electroluminescence spectrum of the electroluminescence device prepared by the multidentate phosphine-coordinated copper complex dual-emission electroluminescence dye DPAPCuBr in the experiment is shown in figure 32, and the electroluminescence peak of the device is 621 nm. As can be seen from fig. 43: the lifetime is sharply decreased with increasing temperature, phosphorescent emission at low temperature, and thermal excitation delayed fluorescence property is exhibited with increasing temperature, thereby exhibiting dual emission.
Experiment twelve: the synthesis method of the experimental multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye is realized according to the following steps:
mixing 1mmol of polydentate phosphine ligand, 1mmol of CuI and 5ml of DCM, reacting at 40-45 ℃ for 10-15 hours, spin-drying, and performing column chromatography purification by taking DCM and PE as eluent to obtain a polydentate phosphine coordination copper complex;
wherein the multidentate phosphine ligand to CuI ratio is 1: 1.
The volume ratio of the DCM to the PE in the mixed solvent of the DCM and the PE is 1: 20.
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye obtained by the experiment is DPAPCuI.
The mass spectrum is adopted to detect the multifunctional modified DPAPCuI prepared by the test, and the detection result is as follows:
m/z:666.09(100.0％),666.59(86.5％),667.09(44.6％),667.59(38.6％),667.10(37.0％),668.09(16.5％),667.60(10.4％),668.60(4.6％),668.10(1.8％)
Elemental Analysis(％)for C80H58CuIP4:C,72.05；H,4.38。
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPAPCuI, and the phosphorescence spectrum is shown in figure 7. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPAPCuI obtained by the experiment is shown in figure 8, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye DPAP is 423 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuI as a light-emitting layer comprises the following steps:
firstly, putting the plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument with the vacuum degree of 1 multiplied by 10-6mbar, evaporation rate set at 0.1nm s-1An anode conducting layer with the thickness of 10nm is formed on a glass or plastic substrate by vapor deposition of Indium Tin Oxide (ITO);
secondly, evaporating a hole injection layer material MoOx on the anode conducting layer to obtain a 10 nm-thick hole injection layer;
thirdly, evaporating a hole transport layer material TAPC on the hole injection layer to obtain a hole transport layer with the thickness of 40 nm;
fourthly, evaporating and plating a bidentate phosphine coordination copper complex dual-emission electroluminescent dye on the hole transport layer to be mixed with a main material mCP to obtain a mixture with the thickness of 15 nm;
fifthly, evaporating and plating an electron transport layer material TPBi on the light-emitting layer, wherein the thickness of the electron transport layer material TPBi is 80 nm;
sixthly, evaporating and plating an electron injection layer material LiF on the electron transport layer, wherein the thickness of the electron injection layer is 10 nm;
and seventhly, evaporating a cathode conducting layer which is made of metal and has the thickness of 10nm on the electron injection layer to obtain the electrophosphorescent device. And seventhly, the metal is aluminum. The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP DPAPCuI (15nm)/TPBi (80nm)/LiF (10 nm)/Al. The voltage-current density relation curve of the electroluminescent device prepared from the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuI in the experiment is shown in fig. 27, and the graph shows that the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuI material has semiconductor characteristics and the threshold voltage of the material is 3.9V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuI in the experiment is shown in figure 28, and the figure shows that the starting voltage of the device is 3.9V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuI in the experiment is shown in FIG. 29, and the graph shows that the device has the luminance of 2.4 cd.m-2When the current efficiency reaches the maximum value of 15.7 cd.A-1. The graph of the relationship between luminance and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye DPAPCuI in the experiment is shown in FIG. 30, and the graph shows that the device has the luminance of 2.1 cd.m-2When the power efficiency reaches the maximum value of 10lm W-1. The experiment uses multidentate phosphine coordinated copper complex dual-emission electroluminescent dyeThe current density-external quantum efficiency curve of the electroluminescent device prepared by DPAPCuI is shown in FIG. 31, from which it can be seen that the device has a brightness of 6mA cm-2Then, a maximum external quantum efficiency of 15% is obtained. The electroluminescence spectrum of the electroluminescence device prepared by the multidentate phosphine-coordinated copper complex dual-emitting electroluminescence dye DPAPCuI in the experiment is shown in figure 32, and the electroluminescence peak of the device is 621 nm. As can be seen from fig. 44: the lifetime is sharply decreased with increasing temperature, phosphorescent emission at low temperature, and thermal excitation delayed fluorescence property is exhibited with increasing temperature, thereby exhibiting dual emission.
Claims (9)
1. The application of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye is characterized in that the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye is used as a guest material of a light-emitting layer for preparing an electroluminescent device; the polydentate phosphine-coordinated copper complex dual-emission electroluminescent dye is formed by coordinating a polydentate phosphine ligand and CuX, and the molecular structural formula is as follows:
the polydentate phosphine ligand is PPADP, wherein X is Cl, Br or I.
2. The use of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye as claimed in claim 1, wherein the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye is synthesized by the following method:
mixing 1mmol of polydentate phosphine ligand, 0.5-1 mmol of CuX and 5-10 mL of dichloromethane, reacting at 40-45 ℃ for 10-15 hours, spin-drying, and performing column chromatography purification by using dichloromethane and petroleum ether as eluent to obtain a polydentate phosphine coordination copper complex;
the polydentate phosphine ligand is PPADP, wherein X is Cl, Br or I.
3. The use of the multidentate phosphine-coordinated copper complex dual-emitter electroluminescent dye according to claim 2, wherein the mass ratio of the multidentate phosphine ligand to CuX is (1-2): 1.
4. Use of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye according to claim 2, wherein the substance ratio of multidentate phosphine ligand to CuX is 1: 1.
5. Use of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye according to claim 2, characterized in that the reaction is carried out at 41 ℃ for 11 hours.
6. Use of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye according to claim 2, characterized in that the reaction is carried out at 42 ℃ for 12 hours.
7. Use of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye according to claim 2, characterized in that the reaction is carried out at 43 ℃ for 13 hours.
8. Use of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye according to claim 2, characterized in that the reaction is carried out at 44 ℃ for 14 hours.
9. Use of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye according to claim 2, characterized in that the reaction is carried out at 45 ℃ for 15 hours.
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| Balanced Dual Emissions from Tridentate Phosphine-Coordinate Copper(I) Complexes toward Highly Efficient Yellow OLEDs;Zhang, Jing et al.;《 Advanced Materials》;20161231;第5975-5979页 * |
| Photophysical Properties of Highly Luminescent Copper(I) Halide Complexes Chelated with 1,2-Bis(diphenylphosphino)benzene;Akira Tsuboyama et al.;《Inorganic Chemistry》;20070227;第1992-2001页 * |
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