The detailed implementation mode is ten: detailed description of the inventionthe bidentate phosphine-silver complex dual emission dye is used as a light emitting layer for the preparation of an electroluminescent device.
The method for preparing the electrophosphorescent device by using the multidentate phosphine-coordinated silver complex dual-emitting 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, setting evaporation rate at 0.1-0.3 nm s-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 silver complex dual-emission 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, silver, aluminum, calcium alloy, magnesium alloy, silver 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 silver complex dual-emitting dye is realized according to the following steps:
1mmol of polydentate phosphine, 1mmol of AgCl and 5ml of DCM are mixed, reacted at 40 ℃ for 1 hour, and then spin-dried to obtain DPPPPAgCl.
The resulting 1mmol of DPPPPPAgCl was dissolved in DCM and 10mmol of H was added under ice-water bath2O2And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.
Wherein the multidentate phosphine ligand to AgCl ratio is 1: 1.
The DPPPPAgCl and H2O2The ratio of the amounts of the components is 1: 2.
The volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.
The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment has the structural formula
The polydentate phosphine coordination silver complex dual-emitting dye obtained by the experiment is DPPPPOAgCl.
The nuclear magnetic resonance spectrometer is adopted to detect the multifunctional modified DPPPPPOAgCl prepared in the test, and the detection result is as follows:
1H NMR(TMS,CDCl3,400MHz):=8.018(t,J=7.6Hz,2H),7.742(t,J=7.6Hz,2H),7.667(s,2H),7.602(d,J=6.8Hz,1H),7.380-6.885(m,34H),6.808-6.733(m,2H),6.649(d,J=6.8Hz,2H),6.530-6.489ppm(m,1H);LDI-TOF:m/z(%):1002(100)[M+];elementalanalysis(%)for C56H46AgClOP4:C,67.11;H,4.63;
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPPOAgCl, and the phosphorescence spectrum is shown in figure 1. The thermogravimetric analysis spectrogram of the polydentate phosphine coordination silver complex dual-emission dye DPPPPOAgCl obtained by the experiment is shown in figure 2, and the graph shows that the cracking temperature of the polydentate phosphine coordination silver complex dual-emission dye DPPPPOAgCl is 425 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPPPPOAgCl as a luminescent 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 silver complex dual-emission dye on the hole transport layer to be mixed with a main material mCP to obtain the material 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 DPPPOAgCl (15nm)/TPBi (80nm)/LiF (10 nm)/Al.
The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgCl in the experiment is shown in figure 3, and the graph shows that the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgCl material has semiconductor characteristics and threshold value thereofThe voltage was 3.7V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPPOAgCl in the experiment is shown in FIG. 4, 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 silver complex dual-emitting dye DPPPPOAgCl in the experiment is shown in figure 5, and the graph shows that the luminance of the device is 2.5 cd.m-2When the current efficiency reaches the maximum value of 21.1 cd.A-1. The graph of the relationship between brightness and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgCl in the experiment is shown in FIG. 6, and the graph shows that the device has the brightness of 2 cd.m-2When the power efficiency reaches the maximum value of 16.2 lm.W-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgCl in the experiment is shown in figure 7, and the graph shows that the device has the brightness of 0.3 mA-cm-2Then, a maximum external quantum efficiency of 8% was obtained. The electroluminescence spectrum of the electroluminescence device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgCl in the experiment is shown in figure 8, and the electroluminescence peak of the device is at 603 nm. Fig. 25 is a graph of the 80K-300K temperature-variable lifetime of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in the first experiment, and it can be seen from the graph that the lifetime is sharply decreased with the increase of temperature, phosphorescence emission is performed at low temperature, and thermal excitation delayed fluorescence is exhibited with the increase of temperature, thereby embodying dual emission.
Experiment two: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:
1mmol of polydentate phosphine, 1mmol of AgBr and 5ml of DCM are mixed, reacted at 40 ℃ for 1 hour, and then dried in a spinning mode to obtain the DPPPPAgBr.
The resulting 1mmol of DPPPPPAgBr was dissolved in DCM and 10mmol of H was added under ice-water bath2O2And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.
Wherein the ratio of multidentate phosphine ligand to AgBr is 1: 1.
The DPPPPAgBr and H2O2The amount ratio of (A) to (B) is 1: 2.
the volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.
The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment has the structural formula
The polydentate phosphine coordination silver complex dual-emitting dye obtained by the experiment is DPPPPOAgBr.
The nuclear magnetic resonance apparatus is adopted to detect the multifunctional modified DPPPPPOAgBr prepared in the test, and the detection result is as follows:
1H NMR(TMS,CDCl3,400MHz):=7.992(t,J=8Hz,2H),7.745(t,J=7.2Hz,2H),7.641(s,2H),7.589(d,J=6.4Hz,1H),7.373-7.147(m,21H),7.082-6.881(m,13H),6.808(s,1H),6.729-6.657(m,3H),6.557-6.517ppm(m,1H);LDI-TOF:m/z(%):1046(100)[M+];elemental analysis(%)for C56H46AgBrOP4:C,64.26;H,4.43;
the experiment obtains the ultraviolet fluorescence spectrum of the polydentate phosphine coordination silver complex dual-emission dye DPPPPOAgBr, and the phosphorescence spectrum is shown in figure 1. The thermogravimetric analysis spectrogram of the polydentate phosphine coordination silver complex dual-emission dye DPPPPOAgBr obtained in the experiment is shown in figure 2, and the graph shows that the cracking temperature of the polydentate phosphine coordination silver complex dual-emission dye DPPPPOAgBr is 433 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPPPPOAgBr as the luminescent 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 silver complex dual-emission dye on the hole transport layer to be mixed with a main material mCP to obtain the material 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 DPPPOAgBr (15nm)/TPBi (80nm)/LiF (10 nm)/Al.
The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgBr in the experiment is shown in figure 3, so that the graph shows that the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgBr 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 silver complex dual-emitting dye DPPPPOAgBr in the experiment is shown in figure 4, 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 silver complex dual-emitting dye DPPPPOAgBr in the experiment is shown in figure 5, and the graph shows that the luminance of the device is 2.5 cd.m-2When the current efficiency reaches the maximum value of 21cd & A-1. The graph of the relationship between brightness and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgBr in the experiment is shown in figure 6, and the graph shows that the device has the brightness of 5 cd.m-2When the power efficiency reaches the maximum value of 11 lm.W-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgBr in the experiment is shown in figure 7From this figure, it is found that the device has a luminance of 0.6mA cm-2Then, a maximum external quantum efficiency of 8.2% was obtained. The electroluminescence spectrum of the electroluminescence device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgBr in the experiment is shown in figure 8, and the electroluminescence peak of the device is shown at 605 nm. FIG. 26 is a graph of the 80K-300K temperature-variable lifetime of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment two, from which it can be seen that the lifetime is sharply reduced with the increase of temperature, phosphorescence emission is performed at low temperature, and thermal excitation delayed fluorescence is exhibited with the increase of temperature, thereby embodying dual emission.
Experiment three: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:
1mmol of polydentate phosphine, 1mmol of AgI and 5ml of DCM are mixed, reacted at 40 ℃ for 1 hour, and then spin-dried to obtain DPPPPAgI.
The resulting 1mmol of DPPPPPAgI was dissolved in DCM and 10mmol of H was added under ice-water bath2O2And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.
Wherein the multidentate phosphine ligand to AgI ratio is 1: 1.
The DPPPPAgI and the DPPPPAgI H2O2The amount ratio of (A) to (B) is 1: 2.
the volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.
The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment is DPPPPOAgI.
The nuclear magnetic resonance apparatus is adopted to detect the multifunctional modified DPPPPPOAgI prepared by the test, and the detection result is as follows:
1H NMR(TMS,CDCl3,400MHz):=7.928(t,J=7.6Hz,2H),7.736(t,J=8Hz,2H),7.604(d,J=8Hz,4H),7.443-7.238(m,15H),7.212-7.015(m,13H),6.969-6.824(m,6H),6.705(s,3H),6.565ppm(t,J=8Hz,1H);LDI-TOF:m/z(%):1093(100)[M+];elementalanalysis(%)for C56H46AgIOP4:C,61.50;H,4.24;
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPPOAgI, and the phosphorescence spectrum is shown in figure 1. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgI obtained in the experiment is shown in figure 2, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgI is 437 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPPPPOAgI as a luminescent 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 silver complex dual-emission dye on the hole transport layer to be mixed with a main material mCP to obtain the material 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 DPPPPOAgI (15nm)/TPBi (80nm)/LiF (10 nm)/Al.
The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPPOAgI in the experiment is shown in figure 3, and therefore, the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPPOAgI material has semiconductor characteristics and the threshold voltage of the material is 3.5V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgI in the experiment is shown in figure 4, and the figure shows that the starting voltage of the device is 3.7V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgI in the experiment is shown in figure 5, and the graph shows that the luminance of the device is 2.5 cd.m-2When the current efficiency reaches the maximum value of 21cd & A-1. The graph of the relationship between brightness and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgI in the experiment is shown in FIG. 6, and the graph shows that the device has the brightness of 6 cd.m-2When the power efficiency reaches the maximum value of 16lm W-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgI in the experiment is shown in figure 7, and the graph shows that the device has the brightness of 0.6 mA-cm-2Then, a maximum external quantum efficiency of 8.1% was obtained. The electroluminescence spectrum of the electroluminescence device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPPPPOAgI in the experiment is shown in figure 8, and the electroluminescence peak of the device is at 602 nm. FIG. 27 is a graph of the 80K-300K temperature-variable lifetime of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment III, from which it can be seen that the lifetime is sharply reduced with the increase of temperature, phosphorescence emission is performed at low temperature, and thermal excitation delayed fluorescence is exhibited with the increase of temperature, thereby embodying dual emission.
Experiment four: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:
1mmol of polydentate phosphine, 1mmol of AgCl and 5ml of DCM were mixed, reacted at 40 ℃ for 10 hours, and then spin-dried to obtain DPNAPAAgCl.
The resulting 1mmol of DPNAPAAgCl was dissolved in DCM and 10mmol of H were added under ice-water bath2O2And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.
Wherein the multidentate phosphine ligand to AgI ratio is 1: 1.
The DPNAPAAgCl and H2O2The amount ratio of (A) to (B) is 1: 2.
the volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.
The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment has the structural formula
The polydentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment is DPNAPAOGCl.
The multifunctional modified DPNAPAOGCl prepared by the test is detected by mass spectrum, and the detection result is as follows:
m/z:575.09(100.0%),576.09(92.9%),575.59(73.5%),576.59(68.3%),576.08(32.0%),577.08(29.7%),576.09(26.6%),577.09(24.8%),576.59(23.5%),577.59(21.8%),578.09(7.7%),577.09(7.2%),577.59(5.7%),576.59(4.6%),577.59(2.0%),578.59(1.9%),576.59(1.8%),577.09(1.3%),577.09(1.1%),578.09(1.0%);LDI-TOF:m/z(%):1152(100)[M+],Elemental Analysis for C68H52AgClOP4:C,70.88;H,4.55;
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPAOGCl, and the phosphorescence spectrum is shown in figure 9. The thermogravimetric analysis spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPOAgCl obtained in the experiment is shown in fig. 10, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPOAgCl is 338 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAgCl 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 silver complex dual-emission dye on the hole transport layer to be mixed with a main material mCP to obtain the material 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 DPNAPAgCl (15nm)/TPBi (80nm)/LiF (10 nm)/Al.
The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAGCl in the experiment is shown in figure 11, so that the graph shows that the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAGCl material has semiconductor characteristics, and the threshold voltage of the material is 4V. The voltage-luminance relationship curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAgCl in the experiment is shown in FIG. 12, and the figure shows that the starting voltage of the device is 4V. FIG. 13 shows the luminance-current efficiency relationship curve of the electroluminescent device prepared from DPNAPAAGCl as a multidentate phosphine-coordinated silver complex dual-emitting dye, and it can be seen from the graph that the luminance of the device is 2.5 cd.m-2When the current efficiency reaches the maximum value of 11.7 cd.A-1. The graph of the relationship between luminance and power efficiency of the electroluminescent device prepared by using the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAGCl in the experiment is shown in FIG. 14, 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 relationship curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAGCl in the experiment is shown in figure 15, and the graph shows that the device has the brightness of 6 mA-cm-2Then, a maximum external quantum efficiency of 21% was obtained. The electroluminescence spectrum of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAgCl in the experiment is shown in FIG. 16, and the electroluminescent peak of the device is 611 nm. FIG. 28 is a graph of the 80K-300K temperature-variable lifetime of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment IV, from which it can be seen that the lifetime is sharply reduced with the increase of temperature, phosphorescence emission is performed at low temperature, and thermal excitation delayed fluorescence is exhibited with the increase of temperature, thereby embodying dual emission.
Experiment five: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:
1mmol of polydentate phosphine, 1mmol of AgBr and 5ml of DCM are mixed and reacted at 40 ℃ for 10 hours, and then the mixture is dried in a rotary manner to obtain DPNAPAAgBr.
The resulting 1mmol of DPNAAgBr was dissolved in DCM and 10mmol of H were added under ice-water bath2O2And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.
Wherein the multidentate phosphine ligand to AgI ratio is 1: 1.
The DPNAAgBr and H2O2The amount ratio of (A) to (B) is 1: 2.
the volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.
The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment has the structural formula
The polydentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment is DPNAPAOGBr.
The multifunctional modified DPNAPAOGBr prepared in the test is detected by mass spectrum, and the detection result is as follows:
m/z:597.06(100.0%),598.06(97.3%),598.06(92.9%),599.06(90.4%),597.56(73.5%),598.56(71.5%),598.56(68.3%),599.56(66.5%),598.06(26.6%),599.06(24.8%),599.06(24.3%),600.06(23.9%),598.57(6.3%),599.56(6.2%),599.57(5.9%),600.56(5.7%),599.06(1.6%),599.07(1.1%),600.07(1.0%);LDI-TOF:m/z(%):1192(100)[M+],Elemental Analysis for C68H52AgBrOP4:C,68.24;H,4.38;
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPAAgBr, and the phosphorescence spectrum is shown in figure 9. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPAOGBr obtained in the experiment is shown in figure 10, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPAOGBr is 424 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAgBr 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 silver complex dual-emission dye on the hole transport layer to be mixed with a main material mCP to obtain the material 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 DPNAPAgBr (15nm)/TPBi (80nm)/LiF (10 nm)/Al.
The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAGBr in the experiment is shown in figure 11, so that the graph shows that the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAGBr material has semiconductor characteristics, and the threshold voltage of the material is 3.9V. The voltage-brightness relationship curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAgBr in the experiment is shown in figure 12, 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 silver complex double-emitting dye DPNAPAAgBr in the experiment is shown in FIG. 13, and the graph shows that the device has the luminance of 2.5 cd.m-2When the current efficiency reaches the maximum value of 9 cd. A-1. The graph of the relationship between luminance and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAgBr in the experiment is shown in FIG. 14, and the graph shows that the device has the luminance of 2.1 cd.m-2When the power efficiency reaches the maximum value of 47.7 lm.W-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAgBr in the experiment is shown in figure 15, and the graph shows that the device has the brightness of 6 mA-cm-2Then, a maximum external quantum efficiency of 20.2% was obtained. The electroluminescence spectrum of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAgBr in the experiment is shown in FIG. 16, and the electroluminescent peak of the device is at 612 nm. FIG. 29 shows the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment fiveThe 80K-300K temperature-variable lifetime spectrum of the material shows that the lifetime is sharply reduced along with the temperature rise, phosphorescence emission is realized at low temperature, and thermal excitation delayed fluorescence is realized along with the temperature rise, so that double emission is realized.
Experiment six: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:
1mmol of polydentate phosphine, 1mmol of AgI and 5ml of DCM are mixed and reacted at 40 ℃ for 10 hours, followed by spin-drying and spin-drying to obtain DPNAPAAgI.
The resulting 1mmol of DPNAPAAgI was dissolved in DCM and 10mmol of H were added under ice-water bath2O2And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.
Wherein the multidentate phosphine ligand to AgI ratio is 1: 1.
The DPNAAgI and H2O2The amount ratio of (A) to (B) is 1: 2.
the volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.
The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment is DPNAPAOGI.
The multifunctional modified DPNAPOAgI prepared in the test is detected by mass spectrometry, and the detection result is as follows:
m/z:621.05(100.0%),622.05(92.9%),621.56(73.5%),622.56(68.3%),622.06(26.6%),623.06(24.8%),623.56(5.7%),622.56(4.6%),622.56(1.8%),623.06(1.1%),624.06(1.0%);LDI-TOF:m/z(%):1243(100)[M+],Elemental Analysisfor C68H52AgIOP4:C,65.66;H,4.21
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPAOGI, and the phosphorescence spectrum is shown in figure 9. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPAOAgI obtained in the experiment is shown in figure 10, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPAOAgI is 446 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAgI 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 silver complex dual-emission dye on the hole transport layer to be mixed with a main material mCP to obtain the material 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 DPNAPAgI (15nm)/TPBi (80nm)/LiF (10 nm)/Al.
The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAOGI in the experiment is shown in figure 11, so that the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAOGI material has semiconductor characteristics, and the threshold voltage of the material is 3.8V. The experiment is carried out by preparing multidentate phosphine coordination silver complex dual-emitting dye DPNAPAOGIThe voltage-luminance relationship curve of the electroluminescent device is shown in fig. 12, and the starting voltage of the device is 3.8V. FIG. 13 shows the luminance-current efficiency relationship curve of the electroluminescent device prepared from DPNAPAOGI, which is a multidentate phosphine-coordinated silver complex dual-emitting dye, and it can be seen from the graph that the luminance of the device is 2.5 cd.m-2When the current efficiency reaches the maximum value of 13.4 cd.A-1. The graph of the relationship between luminance and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAOGI in the experiment is shown in FIG. 14, and the graph shows that the device has the luminance of 2.1 cd.m-2When the power efficiency reaches the maximum value of 70.7 lm.W-1. The current density-external quantum efficiency relationship curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAOGI in the experiment is shown in figure 15, and the graph shows that the device has the brightness of 6 mA-cm-2Then, a maximum external quantum efficiency of 19.2% was obtained. The electroluminescence spectrum of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAOGI in the experiment is shown in FIG. 16, and the electroluminescent peak of the device is 621 nm. FIG. 30 is a graph of the 80K-300K temperature-variable lifetime of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment six, and it can be seen from the graph that the lifetime is sharply reduced with the increase of temperature, phosphorescence emission is performed at low temperature, and thermal excitation delayed fluorescence is exhibited with the increase of temperature, thereby embodying dual emission.
Experiment seven: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:
1mmol of polydentate phosphine, 1mmol of AgCl and 5ml of DCM are mixed and reacted at 40 ℃ for 10 hours, and then the reaction product is dried in a spinning mode to obtain DPAPAgCl.
The resulting 1mmol of DPAPAgCl was dissolved in DCM and 10mmol of H were added under ice-water bath2O2And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.
Wherein the multidentate phosphine ligand to AgI ratio is 1: 1.
The DPAPAgCl and H2O2The ratio of the amounts of the components is 1: 2.
The volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.
The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment is DPAPOAgCl.
The mass spectrum is adopted to detect the multifunctional modified DPAPOAgCl prepared by the test, and the detection result is as follows:
m/z:650.11(100.0%),651.11(92.9%),650.61(86.5%),651.61(80.4%),651.11(37.0%),652.11(34.3%),651.11(32.0%),652.11(29.7%),651.61(27.7%),652.61(25.7%),652.11(11.8%),653.11(11.0%),652.61(9.7%),651.61(7.1%),651.61(3.3%),653.61(2.7%),652.61(2.3%),653.12(1.5%),652.12(1.2%),652.61(1.1%;LDI-TOF:m/z(%):1302(100)[M+],Elemental Analysis for C80H58AgClOP4:C,73.77;H,4.49;
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgCl, and the phosphorescence spectrum is shown in figure 17. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated silver complex dual-emission dye DPAPOAgCl obtained in the experiment is shown in fig. 18, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated silver complex dual-emission dye DPAPOAgCl is 389 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPAPOAgCl as a luminescent 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 silver complex dual-emission dye on the hole transport layer to be mixed with a main material mCP to obtain the material 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 DPAPOAgCl (15nm)/TPBi (80nm)/LiF (10 nm)/Al.
The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgCl in the experiment is shown in figure 19, so that the graph shows that the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgCl material has semiconductor characteristics, and the threshold voltage of the material is 3.2V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgCl in the experiment is shown in figure 20, and the figure shows that the starting voltage of the device is 3.4V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgCl in the experiment is shown in figure 21, and the graph shows that the luminance of the device is 2.5 cd.m-2When the current efficiency reaches the maximum value of 11.6 cd.A-1. The graph of the relationship between brightness and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgCl in the experiment is shown in FIG. 22, and the graph shows that the device has the brightness of 2.1 cd.m-2When the power efficiency reaches the maximum value of 5.7 lm.W-1. The experiment shows that the current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine coordination silver complex dual-emitting dye DPAPOAgClThe line is shown in FIG. 23, from which it is clear that the device has a luminance of 6mA cm-2Then, a maximum external quantum efficiency of 8.2% was obtained. The electroluminescence spectrum of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgCl in the experiment is shown in figure 24, and the electroluminescent peak of the device is known to be at 607 nm. FIG. 31 is a graph of the 80K-300K temperature-variable lifetime of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment seven, and it can be seen from the graph that the lifetime is sharply reduced with the increase of temperature, phosphorescence emission is performed at low temperature, and thermal excitation delayed fluorescence is displayed with the increase of temperature, so that dual emission is reflected.
Experiment eight: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:
1mmol of polydentate phosphine, 1mmol of AgBr and 5ml of DCM are mixed and reacted at 40 ℃ for 10 hours, and then the mixture is dried in a spinning mode to obtain DPAPAgBr.
The resulting 1mmol of DPAPAgBr was dissolved in DCM and 10mmol of H were added under ice-water bath2O2And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.
Wherein the multidentate phosphine ligand to AgI ratio is 1: 1.
The DPAPAgBr and H2O2The amount ratio of (A) to (B) is 1: 2.
the volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.
Performing column chromatography purification by taking DCM and PE as eluent to obtain a multidentate phosphine coordination silver complex;
wherein the ratio of multidentate phosphine ligand to AgBr 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 silver complex dual-emitting dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment is DPAPOAgBr.
The mass spectrum is adopted to detect the multifunctional modified DPAPOAgBr prepared by the test, and the detection result is as follows:
m/z:672.08(100.0%),673.08(97.3%),673.08(92.9%),674.08(90.4%),672.59(86.5%),673.58(84.2%),673.59(80.4%),674.58(78.2%),674.09(36.0%),675.09(33.4%),674.09(26.2%),673.09(24.2%),673.09(12.8%),674.59(9.3%),674.09(8.1%),675.59(6.2%),674.59(5.9%),673.59(5.8%),674.59(4.2%),675.59(3.2%),673.59(2.5%),673.59(2.1%),675.09(1.8%),674.09(1.5%),675.09(1.1%),676.09(1.0%);LDI-TOF:m/z(%):1347(100)[M+],Elemental Analysis forC80H58AgBrOP4:C,71.33;H,4.34;
the experiment obtains the ultraviolet fluorescence spectrum of the polydentate phosphine coordination silver complex dual-emission dye DPAPOAgBr, and the phosphorescence spectrum is shown in figure 17. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated silver complex dual-emission dye DPAPOAgBr obtained in the experiment is shown in fig. 18, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated silver complex dual-emission dye DPAPOAgBr is 396 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPAPOAgBr as the luminescent 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 silver complex dual-emission dye on the hole transport layer to be mixed with a main material mCP to obtain the material 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 DPAPOAgBr (15nm)/TPBi (80nm)/LiF (10 nm)/Al.
The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgBr in the experiment is shown in figure 19, so that the graph shows that the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgBr material has semiconductor characteristics, and the threshold voltage of the material is 3.2V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgBr in the experiment is shown in figure 20, and the figure shows that the starting voltage of the device is 3.5V. The graph of the relationship between brightness and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgBr in the experiment is shown in figure 21, and the graph shows that the device has the brightness of 2.5 cd.m-2When the current efficiency reaches the maximum value of 12.3 cd.A-1. The graph of the relationship between brightness and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgBr in the experiment is shown in figure 22, and the graph shows that the device has the brightness of 2.1 cd.m-2When the power efficiency reaches the maximum value of 6.7 lm.W-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgBr in the experiment is shown in figure 23, and the graph shows that the device has the brightness of 6 mA-cm-2Then, a maximum external quantum efficiency of 8% was obtained. The electroluminescence spectrum of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPAPOAgBr in the experiment is shown in figure 24, and the electroluminescent peak of the device is at 602 nm. FIG. 32 is a graph showing the multidentate phosphine-coordinated copper complex dual emission electroluminescence in experiment eightThe graph shows that the service life of the luminescent dye is sharply reduced along with the temperature rise, the luminescent dye is phosphorescent emission at low temperature, and the luminescent dye shows thermal excitation delay fluorescence property along with the temperature rise, so that dual emission is realized.
Experiment nine: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:
1mmol of polydentate phosphine, 1mmol of AgI and 5ml of DCM are mixed and reacted at 40 ℃ for 10 hours, and then the mixture is dried in a spinning mode to obtain DPAPAgI.
The resulting 1mmol of DPAPAgI was dissolved in DCM and 10mmol of H were added under ice-water bath2O2And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.
Wherein the multidentate phosphine ligand to AgI ratio is 1: 1.
The DPAPAgI and H2O2The amount ratio of (A) to (B) is 1: 2.
the volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.
Performing column chromatography purification by taking DCM and PE as eluent to obtain a multidentate phosphine coordination silver complex;
wherein the multidentate phosphine ligand to AgI 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 silver complex dual-emitting dye obtained by the experiment has the structural formula
The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment is DPAPOAgI.
The mass spectrum is adopted to detect the multifunctional modified DPAPOAgI prepared by the test, and the detection result is as follows:
m/z:696.08(100.0%),697.08(92.9%),696.58(86.5%),697.58(80.4%),697.08(37.0%),698.08(34.3%),698.58(8.3%),697.58(7.1%),697.58(3.3%),699.08(1.5%),698.58(1.4%),698.08(1.2%);LDI-TOF:m/z(%):1347(100)[M+],Elemental Analysis for C80H58AgIOP4:C,68.93;H,4.19;
the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgI, and the phosphorescence spectrum is shown in figure 17. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated silver complex dual-emission dye DPAPOAgI obtained in the experiment is shown in fig. 18, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated silver complex dual-emission dye DPAPOAgI is 419 ℃.
The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPAPOAgI 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 silver complex dual-emission dye on the hole transport layer to be mixed with a main material mCP to obtain the material 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 DPAPOAgI (15nm)/TPBi (80nm)/LiF (10 nm)/Al.
The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgBr in the experiment is shown in figure 19, so that the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgI material has semiconductor characteristics, and the threshold voltage of the material is 3.2V. In this experiment, the multidentate phosphine was coordinated, and it can be seen from FIG. 20 that the turn-on voltage of the device was 3.5V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgI in the experiment is shown in FIG. 21, and the graph shows that the luminance of the device is 2.5 cd.m-2When the current efficiency reaches the maximum value of 12.7 cd.A-1. The graph of the relationship between brightness and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgI in the experiment is shown in FIG. 22, and the graph shows that the device has the brightness of 2.1 cd.m-2When the power efficiency reaches the maximum value of 6.7 lm.W-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgI in the experiment is shown in figure 23, and the graph shows that the device has the brightness of 6 mA-cm-2Then, a maximum external quantum efficiency of 8.2% was obtained. The electroluminescence spectrum of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPAPOAgI in the experiment is shown in figure 24, and the electroluminescent peak of the device is at 608 nm. FIG. 33 is a graph of the 80K-300K temperature-variable lifetime of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment nine, from which it can be seen that the lifetime is sharply reduced with the increase of temperature, phosphorescence emission is performed at low temperature, and thermal excitation delayed fluorescence is exhibited with the increase of temperature, thereby embodying dual emission.