CN112239479B - Organic photoelectric material, preparation method and application thereof, and corresponding device - Google Patents
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- CN112239479B CN112239479B CN201910643914.2A CN201910643914A CN112239479B CN 112239479 B CN112239479 B CN 112239479B CN 201910643914 A CN201910643914 A CN 201910643914A CN 112239479 B CN112239479 B CN 112239479B
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
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- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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Abstract
The invention belongs to an organic electroluminescent device and discloses an organic photoelectric material, a preparation method and application thereof and a corresponding device, wherein the organic photoelectric material is p-PO15NCzDPA or m-PO15NCzDPA and has a chemical structural formula shown as the following formula. According to the invention, the p-PO15NCzDPA or m-PO15NCzDPA is used for constructing the light-emitting layer or the electron transport layer, especially for constructing the homojunction structure of the light-emitting layer and the electron transport layer, so that the structure and the preparation process of the device can be effectively simplified, and the problem of insufficient orthogonal solvent type in the device prepared by a solution method is solved. The material provided by the invention has good thermal stability, higher fluorescence quantum efficiency and higher electron carrier mobility.
Description
Technical Field
The invention belongs to the technical field of organic electroluminescent devices (such as diode display), and particularly relates to an organic photoelectric material, a preparation method, application thereof and a corresponding device.
Background
Since an article entitled "Organic electroluminescent diodes" was published in appl.phys.lett. journal by c.w.tang and s.a.vanslyke in 1987 (c.w.tang, s.a.vanslyke. Organic electroluminescent diodes, appl.phys.lett.,1987,51(12):913-915), studies on OLEDs formally step into the high-speed development of the track, the OLED technology has been shifted from simple basic research to the phase of energetically developing new display products over thirty years. White light OLEDs (woled) made of RGB tricolor dyes were reported in the Science journal by kido, m.kimura, k.nagai, multilayer white light-emitting organic electroluminescent device Science,1995,267(5202): 1332-1331334, university of mountain j.kido et al in 1995, which work has an important role in expanding the application field of OLED technology; in 2009, the K.Leo group reported in Nature a high efficiency WOLED with power efficiency up to 124lm/W, which combines the structure of a full phosphor-light multiple light emitting layer, a p-i-n electrical doping technique and a light extraction technique (S.Reineke, F.Lindner, G.Schwartz, et al.white organic light-emitting diodes with fluorescent tube efficacy. Nature,2009,459(14): 234-. WOLEDs play an important role both in achieving full color displays and in solid state lighting.
In order to meet the development requirements of low cost and high performance, the WOLED technology needs to be studied more deeply. At present, the WOLED has a technical bottleneck, most high-performance electroluminescent devices are prepared by adopting a vacuum evaporation technology at the present stage, and expensive vacuum equipment and a more complex process flow are not beneficial to reducing the cost of the OLED. In contrast, solution-process device fabrication techniques (e.g., spin-coating, ink-jet printing, etc.) are advantageous for fabricating large-size, low-cost OLED panels. In recent years, highly efficient devices based in part on Solution processes have been reported, for example, korean j.y.lee team reported green Thermally Activated Delayed Fluorescence (TADF) OLEDs (y.j.cho, k.s.yook, j.y.lee.high Efficiency in a Solution-Processed Thermally Activated Delayed Fluorescence Device Using a Delayed-Fluorescence emission Material with Improved solubility.adv.material., 2014,26(38):6642 6646) with External Quantum Efficiency (EQE) up to 18.3%; the Sushi health team at the university of southern China reported that the EQE of flexible yellow-green OLED prepared by Solution method reaches 17.5% (G.Xie, X.Li, D.Chen, et al. evaluation-and Solution-Process-Feasible high Efficiency thin threne-9,9 ', 10, 10' -tetroxide-Based thermal Activated Delayed emission with Reduced Efficiency Roll-Off.Adv.Mater.,2016,28(1): 181-187). However, the solution method for preparing WOLED is still an extremely weak link, and the reason for this is complex, and roughly comprises: 1. the structure of the white light device is more complex than that of a monochromatic light device, the number of organic functional layers and light emitting layers is often more to ensure the performance of the device, but the types of orthogonal solvents which can be selected and used in the solution method preparation process are insufficient, so that the multilayer structure which can be realized by the evaporation process is difficult to complete. 2. Blue light materials are still a bottleneck, and the light color quality of the white light device is limited if the light color cannot reach a deep blue region. Due to the stability of the blue light material, the efficiency of the device is seriously reduced under high brightness, and the service life of the device is short. 3. The spectral stability is greatly changed along with the voltage, the more the number of the luminescent dyes is, the greater the difficulty of regulating and controlling the spectrum is. 4. The difference of band gaps of different luminescent materials is large, the commonly adopted host-guest doping technology has high requirements on energy band matching, and particularly, the number of blue light host materials with excellent performance is small.
Disclosure of Invention
In view of the above defects or improvement requirements of the prior art, the present invention aims to provide an organic photoelectric material, a preparation method, applications thereof and a corresponding device, wherein a light emitting layer or an electron transport layer is constructed by using p-PO15NCzDPA or m-PO15NCzDPA, especially a light emitting layer-electron transport layer homojunction structure is constructed, so that the structure and the preparation process of the device can be effectively simplified, and the problem of insufficient orthogonal solvent type in the preparation of the device by a solution method is solved. The material provided by the invention has good thermal stability, higher fluorescence quantum efficiency and higher electron carrier mobility. Based on the invention, the solution method can be particularly realized to prepare the white light organic electroluminescent device with the homojunction structure of the luminescent layer and the electron transport layer, and the direct regulation and control of the luminescent spectrum can be realized by changing the mass percentages of yellow, red and green dyes in the luminescent layer. The efficiency roll-off of the device under high brightness is small, and the spectral stability is good.
To achieve the above object, according to one aspect of the present invention, there is provided an organic photoelectric material, specifically p-PO15NCzDPA or m-PO15NCzDPA, having a chemical structural formula shown by the following formula:
or
According to another aspect of the present invention, there is provided a method for preparing the above organic photoelectric material, wherein the synthetic route is as follows:
according to a further aspect of the present invention, the present invention provides the use of the above organic photoelectric material as a light emitting layer or an electron transport layer in an organic electroluminescent device.
As a further preference of the invention, the organic photoelectric material is applied as a light-emitting layer and an electron transport layer at the same time, and correspondingly forms a light-emitting layer-electron transport layer homojunction structure based on p-PO15NCzDPA or m-PO15 NCzDPA.
According to a further aspect of the present invention, there is provided a light emitting layer-electron transport layer homojunction structure, characterized in that the light emitting layer-electron transport layer homojunction structure is based on p-PO15NCzDPA or m-PO15NCzDPA, wherein the p-PO15NCzDPA or m-PO15NCzDPA has a chemical formula as shown in the following formula:
or
According to another aspect of the present invention, there is provided an organic electroluminescent device comprising, from bottom to top, an anode, an organic functional layer and a cathode, the organic functional layer comprising, from bottom to top, a hole transport layer, a light-emitting layer-electron transport layer and an electron injection layer, wherein the light-emitting layer-electron transport layer is in particular of a light-emitting layer-electron transport layer homojunction structure as claimed in claim 5.
As a further preference of the present invention, the thickness of the light-emitting layer is preferably 10nm to 30 nm; the thickness of the electron transport layer is 20nm to 60 nm;
a hole injection layer is further arranged between the hole transport layer and the anode, and the hole injection layer and the hole transport layer are specifically: PSS film as hole injection layer and Poly-TPD film as hole transport layer, their thickness satisfies preferably 10nm to 50 nm; or (II) a PEDOT solution prepared by a solution method, wherein a PSS film is used as a hole injection layer and a poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (TFB) film is used as a hole transport layer, and the thicknesses of the film and the TFB film preferably both satisfy 10nm to 50 nm; or (III) a PEDOT: PSS film prepared by a solution method and having a thickness of preferably 10nm to 30nm is used as a hole injection layer, and a composite film consisting of dipyrazino [2,3-F:2',3' -H ] quinoxaline 2,3,6,7,10, 11-Hexacyano (HATCN) and 4,4' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (NPB) having a thickness of preferably 30nm to 80nm is used as a hole transport layer; or, the hole transport layer is in direct contact with the anode, and the hole transport layer is specifically: (IV) a composite film prepared by a solution method, preferably having a thickness of 30nm to 80nm, of dipyrazino [2,3-F:2',3' -H ] quinoxaline 2,3,6,7,10, 11-Hexanenitrile (HATCN) and 1, 1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC) is used as a hole transport layer;
the electron injection layer is LiF or Cs prepared by a vacuum evaporation method2CO3Or LiQ or Libpps, the thickness of the electron injection layer is 0.5nm to 5 nm;
the anode is a composite oxide metal film, preferably an Indium Tin Oxide (ITO) film of 50nm to 150 nm; the cathode is a metal cathode or a composite metal cathode prepared by a vacuum thermal evaporation method, wherein the metal cathode is preferably a metal Al cathode with the thickness of 80nm to 150 nm; the composite metal cathode is preferably a Mg/Al composite metal cathode or a Yb/Al composite metal cathode or a Sm/Al composite metal cathode, and in the composite metal cathodes, the Al metal layers are all 50nm to 90nm in thickness, and the other metal layer is all 1nm to 3nm in thickness.
As a further preferable aspect of the present invention, the organic functional layer further includes an exciton blocking layer disposed between the hole transport layer and the light emitting layer-electron transport layer;
preferably, when the hole injection layer and the transmission layer are PEDOT: PSS and Poly-TPD films prepared by a solution method or PEDOT: PSS and Poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (TFB) films prepared by a solution method, the exciton blocking layer is a PVK film with the thickness of 5nm to 20 nm;
when the hole injection layer and the transmission layer are a PEDOT/PSS film prepared by a solution method and a composite film composed of a dipyrazino [2, 3-F/2 ',3' -H ] quinoxaline 2,3,6,7,10, 11-Hexanenitrile (HATCN) and 4,4 '-bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (NPB), or when the hole transmission layer is a composite film composed of a dipyrazino [2, 3-F/2', 3'-H ] quinoxaline 2,3,6,7,10, 11-Hexanenitrile (HATCN) and 1, 1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC) prepared by a solution method, the exciton blocking layer is 4,4' -tris (carbazol-9-yl) triphenylamine (TCTA) or 1 with the exciton blocking layer of 3nm to 20nm, 3-bis-9-carbazolylbenzene (mCP).
As a further preferred embodiment of the present invention, the organic electroluminescent device is a white organic electroluminescent device, and the luminescent layer-electron transport layer is further doped with a yellow luminescent dye, or co-doped with a yellow luminescent dye and a green luminescent dye, or co-doped with a red luminescent dye and a green luminescent dye, or co-doped with a yellow luminescent dye, a red luminescent dye and a green luminescent dye; wherein the doping concentration of the yellow light-emitting dye or the red light-emitting dye is 0.05 wt% to 2.0 wt%, and the doping concentration of the green light-emitting dye is 5.0 wt% to 20.0 wt%;
the yellow light-emitting dye has a light-emitting wavelength of 570-620 nm, the red light-emitting dye has a light-emitting wavelength of 620-680 nm, and the green light-emitting dye has a light-emitting wavelength of 490-570 nm.
According to a final aspect of the present invention, the present invention provides a method for preparing the above organic electroluminescent device, which is characterized in that the method is based on a solution method for preparing an organic functional layer, specifically, a hole injection layer and a hole transport layer are formed on a transparent substrate with an anode by spin coating through a solution method, or a single hole transport layer is formed on a transparent substrate with an anode by spin coating through a solution method; then, spin-coating an organic solution dissolving p-PO15NCzDPA or m-PO15NCzDPA to form a light-emitting layer-electron transport layer, and finally preparing an electron injection layer and a cathode by vacuum evaporation to obtain an organic electroluminescent device;
preferably, after the hole transport layer is formed and before the light emitting layer-electron transport layer starts to be formed, the method further comprises the step of forming a PVK thin film by spin coating with a PVK organic solution.
Compared with the prior art, the technical scheme of the invention adopts the multifunctional organic photoelectric material p-PO15NCzDPA or m-PO15NCzDPA to prepare the luminescent layer-electron transport layer homojunction structure, the p-PO15NCzDPA or m-PO15NCzDPA is taken as the luminescent material of the blue light luminescent unit in the luminescent layer and is taken as the main body material in the yellow light luminescent unit, the red light luminescent unit and the green light luminescent unit, and the electron transport layer is also constructed by the p-PO15NCzDPA or m-PO15 NCzDPA. Based on the invention, a solution method can be adopted to prepare the homojunction structure of the light-emitting layer and the electron transport layer. The homojunction structure provided by the invention simplifies the device structure to a great extent and solves the problem of insufficient types of orthogonal solvents in the common solution process. In addition, the defect that interface potential barrier is increased due to the fact that different light-colored dyes adopt different light-emitting main bodies in the prior art is overcome, so that the starting voltage and the driving voltage are reduced, and the overall performance of the device is improved.
The p-PO15NCzDPA and m-PO15NCzDPA materials are obtained for the first time, and have the characteristics of high fluorescence quantum efficiency, high electron carrier transmission capability and good material solubility. The fluorescence quantum yield of the material is more than 90%, and high-efficiency blue light emission can be realized. The mobility of the material can reach 2.7 multiplied by 10 according to the flight time method-3cm2Vs to 5.3X 10-3cm2Vs, ensures the high-efficiency electron transport capability of the material when used as an electron transport layer, and is beneficial to obtainingHigher device efficiency. The thermal decomposition temperature of the compound is high, and the glass transition temperature (T) can reach more than 450 ℃ by TAG measurementg) Higher, exemplified by DSC results of m-PO15NCzDPA, TgThe temperature reaches 145 ℃, and the good thermodynamic property ensures that a device using the material has higher stability. The compound has high self blue light fluorescence luminous efficiency and proper triplet state energy level, is used as a main material, and can ensure efficient composite luminescence of excitons in a luminescent layer after yellow, red and green light luminescent dyes are doped, so that the device has high luminous efficiency and small efficiency roll-off. Can be widely applied to the field of electroluminescence.
The p-PO15NCzDPA or the m-PO15NCzDPA can be applied to a White Organic Light Emitting Diode (WOLED). The organic photoelectric material forming the homojunction structure has the blue light emission with the light-emitting peak wavelength of 440nm to 448nm, and preferably, the thickness of a light-emitting layer in the homojunction is 10nm to 30 nm. The spectrum regulation of the white light device can be realized by co-doping yellow, red and green light luminescent dyes into p-PO15NCzDPA or m-PO15NCzDPA, and the pre-doping concentration can be adjusted. Preferably, the doping concentration of the yellow and red dyes is 0.05 wt% to 2.0 wt%, and the doping concentration of the green dye is 5.0 wt% to 20.0 wt%. Preferably, the yellow light-emitting dye has an emission wavelength of 570nm to 620nm, the red light-emitting dye has an emission wavelength of 620nm to 680nm, and the green light-emitting dye has an emission wavelength of 490nm to 570 nm. The invention can prepare the white light organic electroluminescent device with a light-emitting layer-electron transport layer homojunction structure by using a solution method. The scheme provided by the invention can solve the problem that the spectrum of the white light device with the multi-luminescent-layer structure is unstable along with the voltage change in the prior art, and the luminescent-layer structure design method provided by the invention can ensure that the exciton recombination zone is uniformly distributed in the luminescent layer, the exciton recombination zone is basically not changed along with the change of the driving voltage, the spectrum is hardly changed, and the luminescent light color is relatively stable. And the regulation of the white color temperature from cold white light to warm white light can be easily realized through the regulation of the mass percentage of the concentration of the pre-doped dye. Compared with the prior art that for ultralow doping concentration (lower than 0.1 wt%), extremely high difficulty and poor repeatability are achieved in the process of preparing a vacuum evaporation device, the technical scheme provided by the invention has the advantages that the process difficulty is greatly reduced, the doping concentration can be finely controlled, and the repeatability of the device is good.
The novel organic photoelectric material and the corresponding device provided by the invention can effectively solve the related problems in the prior art. Firstly, p-PO15NCzDPA or m-PO15NCzDPA can be directly used for constructing a luminescent layer to realize blue light emission, and the light color can reach (0.15 +/-0.01, 0.07 +/-0.01) and belongs to the deep blue light color. And as a pure fluorescent material, the material has advantages over phosphorescent materials in terms of stability and device lifetime. Secondly, the electron carrier mobility of p-PO15NCzDPA and m-PO15NCzDPA materials is higher and reaches 10-3cm2the/Vs is in magnitude, so that the preparation method can be used for preparing a homojunction structure of a light emitting layer and an electron transport layer, and the preparation process of the device is simplified. Particularly, for a device manufactured by a solution method, a solvent is generally required to be added for each layer of functional layer structure, and the subsequently added solvent is required to be immiscible with all layers manufactured previously, so that even if only one layer is added, the process difficulty is greatly increased. The homojunction structure provided by the invention, namely the p-PO15NCzDPA (or m-PO15NCzDPA) used for forming the light-emitting layer and the electron transport layer, can effectively reduce the requirement on the solvent type. Thirdly, the organic photoelectric material provided by the invention has a proper energy level, the HOMO and LUMO energy level difference is about 3.0eV, the organic photoelectric material can be used as a main body of yellow, red and green dyes, the precise regulation and control can be realized by a pre-doping method, and the quality of a white light device can be improved.
The invention also particularly optimizes other structures of the organic electroluminescent device such as specific materials of a hole injection-transmission layer, an electron injection layer and the like by matching with the homojunction structure of the luminescent layer and the electron transmission layer, preferably uses PEDOT, PSS film, Poly-TPD film, TFB film, HATCN/NPB composite film or HATCN/TAPC composite film, PVK film and the like as the hole injection layer and the hole transmission layer, preferably uses LiF or Cs2CO3Or LiQ or Libpps is used as an electron injection layer, so that energy band matching of materials of each functional layer in the device can be realized, and good working efficiency of the whole device is ensured.
The invention also regulates and controls the position of the composite area of the luminescent layer by further optimizing the proportion of the luminescent layer and the electronic transmission function layer, and can realize the regulation of the light color and the color temperature by controlling the doping concentration proportion of yellow light, red light and green light luminescent dyes in the luminescent layer, the working principle is that the incomplete energy transfer from a blue light material to other light color luminescent dyes is reasonably utilized, the emission of light with different colors is ensured to be realized at the same time, the regulation effect on the light color and the color temperature of white light is completed, and the proportion of the thickness of the luminescent layer to the thickness of the electronic transmission layer can be preferably 1.: 1 to 1: and 6, the doping concentration and the doping type of the luminescent dye are preferably controlled, so that efficient, stable and balanced white light emission can be further realized. The p-PO15NCzDPA or m-PO15NCzDPA material has high electron mobility, high self-luminous efficiency and good solubility, so that the material can be applied to the preparation of devices by a solution method. The invention utilizes the homojunction structure of the luminescent layer and the electron transport layer, thus after the front-end hole injection and the preparation of the hole transport layer and the exciton blocking layer are completed, the regulation and control of the position of the composite region of the luminescent layer can be easily realized only by the method of pre-doping the luminescent dyes, and the ratio of the thickness of the electron transport layer to the thickness of the luminescent layer is controlled to be 1: 1.5 to 6: 1, finally realizing a high-performance white light device.
In summary, the present invention provides organic optoelectronic materials and their use in OLEDs, especially WOLEDs; the material provided by the invention can realize blue light emission, and has good thermal stability, higher fluorescence quantum efficiency and higher electron carrier mobility. Based on the material, a light emitting layer-electron transmission layer homojunction structure is prepared by a solution method, white light emission is realized by combining a method of pre-doping yellow, red and green dyes into a light emitting layer, and the spectrum of the WOLED can be regulated and controlled by adjusting the mass percentage of the doped dyes. The device structure and the preparation process are simple, and the use of orthogonal solvent types is reduced. And due to the excellent performance of the material and the integral optimization of the device, the efficiency roll-off of the device under high brightness is small, and the spectral stability is good. Provides a new choice for improving the commercial utilization value of WOLED.
Drawings
Fig. 1 is a structural diagram of an electroluminescent device according to embodiment 1 of the present invention.
Fig. 2 is a structural diagram of an electroluminescent device of embodiment 2 provided by the present invention.
Fig. 3 is a structural diagram of an electroluminescent device according to embodiment 3 of the present invention.
FIG. 4 is a Current Density (Current Density) -Voltage (Voltage) -Luminance curve (luminence) of example 2 of the present invention.
Fig. 5 is a Current Efficiency (CE) -Luminance (luminence) -Power Efficiency (PE) curve of example 2 of the present invention.
FIG. 6 shows the variation of Electroluminescence (EL) -Wavelength (wavelet) with luminance in example 2 of the present invention.
Fig. 7 is a general structural diagram of an electroluminescent device provided by the present invention.
Fig. 8 is a test curve of carrier mobility for the material provided by the present invention.
FIG. 9 is a thermal stability test glass transition temperature curve for a material provided by the present invention.
The numerical values in fig. 1 to 3, 7 represent the energy levels (in eV), the work functions thereof for ITO and Al, and the HOMO level (lower) and the LUMO level (upper) for organic materials. High T in FIGS. 1, 2 and 71This indicates that the exciton-blocking layer has a high triplet energy level and can confine excitons more favorably in the light-emitting layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The organic photoelectric functional material for preparing the homojunction structure of the light-emitting layer and the electron transport layer has one of the structures and synthetic routes shown in the following figures:
the preparation method of the compounds can be specifically as follows:
1, 5-azacarbazole (2.0g,11.8mmol), p-bromoiodobenzene (3.33g,11.8mmol), cuprous iodide (0.05g,0.25mmol), K were added to a 100ml single-necked flask2CO3(3.45g,25mmol) and 18-crown-6 (6.6mg,0.25mmol) were dissolved in 5ml of DMPU solution. In N2Under the protection of (3), heating to 180 ℃ and reacting for 48 hours. After the reaction is terminated, cooling to room temperature, extracting, spin-drying, and performing dichloromethane: methanol 15:1 column chromatography gave 2.5g of product (1), yield: 66 percent.
In a 250ml single-neck flask were charged compound (1) (1.5g,4.6mmol), 9-anthraceneboronic acid (1.1g, 5.1mmol), and 25ml of a 2M aqueous solution of potassium carbonate dissolved in a solvent of 25ml of ethanol and 50ml of toluene. In N2Under the protection of (2), Pd (PPh3)4(0.1g, 0.1mmol) was added. The temperature was slowly raised to 110 ℃ and the mixture was reacted under reflux for 24 h. And cooling, separating liquid, rotatably steaming an organic layer, and carrying out column chromatography to obtain the product. The product obtained (2.1g,5.0mmol), NBS (0.9g,5.5mmol) was then dissolved in chloroform (50 ml). Under the protection of N2, the temperature is raised to 70 ℃ and the reaction is carried out for 6 h. After the reaction is terminated, cooling to room temperature, extracting, spin-drying, and performing dichloromethane: methanol 20:1 column chromatography gave 2.1g of product (3), yield: 84 percent. MS (APCI) M/z calcd for C30H18BrN3:499.07, Found [ M + H ]]+:500.08.
In a 250ml single-neck flask, compound (3) (2.00g,4.00mmol), diphenyl (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) phosphine oxide (1.62g, 4.00mmol), 2M aqueous potassium carbonate solution 20ml was dissolved in a solvent of 20ml ethanol, 40ml toluene. In N2Under the protection of (2), Pd (PPh3)4(0.09g, 0.08mmol) was added. The temperature was slowly raised to 110 ℃ and the mixture was reacted under reflux for 24 h. After cooling, liquid separation is carried out, an organic layer is steamed in a rotating mode, column chromatography is carried out, and the product p-PO15NCzDPA2.0g is obtained, wherein the yield is 72%. MS (APCI) M/z calcd for C48H32N3OP:697.23, Found [ M + H ]]+:698.24.
This gave p-PO15 NCzDPA.
1, 5-azacarbazole (1.0g,5.9mmol), m-bromoiodobenzene (1.67g,5.9mmol), cuprous iodide (0.02g,0.12mmol), K were added to a 100ml single-necked flask2CO3(1.72g,12mmol) and 18-crown-6 (3.3mg,0.12mmol) were dissolved in 3ml of DMPU solution. Under the protection of N2, the temperature is raised to 180 ℃ and the reaction is carried out for 48 h. After the reaction is terminated, cooling to room temperature, extracting, spin-drying, and performing dichloromethane: methanol 15:1 column chromatography gave 1.2g of product (2), yield: 60 percent.
In a 250ml single-neck flask were charged compound (2) (3g,9.2mmol), 9-anthraceneboronic acid (2.2g, 10.2mmol), and 25ml of a 2M aqueous solution of potassium carbonate dissolved in 25ml of ethanol, 50ml of toluene solvent. In N2Under the protection of (2), Pd (PPh3)4(0.2g, 0.2mmol) was added. The temperature was slowly raised to 110 ℃ and the mixture was reacted under reflux for 24 h. And cooling, separating liquid, rotatably steaming an organic layer, and carrying out column chromatography to obtain the product. The product obtained (4.2g,10mmol), NBS (1.8g,11mmol) was then dissolved in chloroform (50 ml). In N2Under the protection of (3), heating to 70 ℃ and reacting for 6 hours. After the reaction is terminated, cooling to room temperature, extracting, spin-drying, and performing dichloromethane: methanol 20:1 column chromatography gave 4.2g of product (4), yield: 82 percent. MS (APCI) M/z calcd for C30H18BrN3:499.07, Found [ M + H ]]+:500.08.
In a 250ml single-neck flask, compound (4) (4.00g,8.00mmol), diphenyl (3- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) phosphine oxide (3.24g, 8.00mmol), 20ml of a 2M aqueous potassium carbonate solution was dissolved in a solvent of 20ml ethanol, 40ml toluene. In N2Under the protection of (2), Pd (PPh3)4(0.18g, 0.16mmol) was added. The temperature was slowly raised to 110 ℃ and the mixture was reacted under reflux for 24 h. After cooling, liquid separation, rotary evaporation of an organic layer and column chromatography are carried out, and the product m-PO15NCzDPA is obtained, wherein the yield is 75%. MS (APCI) M/z calcd for C48H32N3OP:697.23, Found [ M + H ]]+:698.24.
This gave m-PO15 NCzDPA.
The homogeneous junction luminescent layer-electron transport layer structure prepared by a solution-soluble method based on the organic photoelectric material can be applied to a white light electroluminescent device with adjustable light color. The device generally comprises an anode and a cathode, and the device also sequentially comprises a hole injection layer and a hole transport layer (except for sequentially forming a hole injection layer and a hole transport layer respectively, when the material of the hole transport layer is changed, the hole injection layer can be omitted, namely, a single hole transport layer can be formed on a transparent substrate with the anode by a solution spin coating method, namely, the hole injection layer has an optional structure and is not required), an exciton blocking layer (optional and is not required; the efficiency of the device can be improved by the exciton blocking layer such as a PVK layer), an organic light emitting layer-electron transport layer homojunction structure and an electron injection layer from the anode to the cathode. That is, the organic functional layer sandwiched between the anode and the cathode of the device sequentially comprises a hole injection layer, a hole transport layer, an exciton blocking layer, a light emitting layer-electron transport layer and an electron injection layer from the anode to the cathode.
The carrier transport capacity of the material is tested by a time of flight (TOF) method, and fig. 8 shows a carrier mobility test curve of the material provided by the invention, so that the conclusion can be drawn that the novel organic photoelectric material has high electron carrier transport capacity and the mobility reaches 10-3cm2The order of magnitude of/V s, completely meets the requirement of preparing a high-performance electron transport layer structure. The thermodynamic stability of the material provided by the invention is tested, and fig. 9 is a glass transition temperature test curve of the novel organic photoelectric material provided by the invention, so that the conclusion can be drawn that the thermodynamic stability of the material is good.
The following are specific examples:
example 1
150nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing 30nm PEDOT: PSS on ITO glass by a spin coating method, and annealing for 10 minutes at 120 ℃. Preparing an exciton blocking layer by a PVK chlorobenzene solution spin coating method, wherein the exciton blocking layer is 20nm, and annealing is carried out for 30 minutes at 170 ℃. The m-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 60nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein the luminescent layer is 30nm, the doped yellow dye is 0.05 wt% of TBRb, and the doped green dye is 15 wt% of C545T. The evaporation method is used for preparing a 1.5nm LiQ electron injection layer and a 100nm Al metal cathode.
Evaluating the performance of the device: aluminum was used as the cathode of the device, the positive pole of direct current was applied to ITO (indium tin oxide), and the negative pole was applied to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a lighting voltage of 3.2V, the maximum current efficiency of 24.0cd/A, 17.1lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.35,0.33) are obtained. The brightness reaches 1000cd/m2The current efficiency roll-off was 7.3% and the power efficiency roll-off was 14.8%. The color rendering index CRI value was 75. The spectral stability is good with increasing voltage.
Example 2
150nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing 30nm PEDOT: PSS on ITO glass by a spin coating method, and annealing for 10 minutes at 120 ℃. Preparing an exciton blocking layer by a PVK chlorobenzene solution spin coating method, wherein the exciton blocking layer is 15nm, and annealing is carried out for 30 minutes at 170 ℃. The m-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 60nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein, the luminescent layer is 30nm and is doped with 1.0 wt% of yellow dye TBRb to prepare the white light device with yellow-blue complementary color. The evaporation method is used for preparing a 1.5nm LiQ electron injection layer and a 100nm Al metal cathode.
Evaluating the performance of the device: aluminum was used as the cathode of the device, the positive pole of direct current was applied to ITO (indium tin oxide), and the negative pole was applied to the metal layer. Current-voltage characteristics were measured using a computer-controlled Catherine 2400(Keithley2400) digital source meter using a spectral scan (Spect)rascan PR655) luminance meter to evaluate the luminescence properties. The device has the performance of a starting voltage of 3.2V, the maximum current efficiency of 20.4cd/A and 15.1lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.38 ) are used. The brightness reaches 1000cd/m2The current efficiency roll-off was 5.9% and the power efficiency roll-off was 27.0%. The color rendering index CRI value was 58. The spectral stability is good with increasing voltage.
Example 3
150nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing 30nm PEDOT: PSS on ITO glass by a spin coating method, and annealing for 10 minutes at 120 ℃. The light-emitting layer and the electron transport layer are prepared by a chloroform solution spin coating method of m-PO15NCzDPA, the thickness of the light-emitting layer and the electron transport layer is 70nm, and annealing is carried out for 10 minutes at 100 ℃. Wherein, the luminescent layer is 20nm, and is doped with 1.0 wt% of yellow dye TBRb to prepare the white light device with complementary yellow-blue color. The evaporation method is used for preparing a 1.5nm LiQ electron injection layer and a 100nm Al metal cathode.
Evaluating the performance of the device: aluminum was used as the cathode of the device, the positive pole of direct current was applied to ITO (indium tin oxide), and the negative pole was applied to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a starting voltage of 3.0V, the maximum current efficiency of 16.1cd/A and 14.4lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.36,0.38) are used. The brightness reaches 1000cd/m2The current efficiency roll-off was 8.9% and the power efficiency roll-off was 14.2%. The color rendering index CRI value was 56. The spectral stability is good with increasing voltage.
Example 4
150nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing 30nm PEDOT: PSS on ITO glass by a spin coating method, and annealing for 10 minutes at 120 ℃. The PVK chlorobenzene solution spin coating method is used for preparing the exciton blocking layer with the thickness of 5nm, and annealing is carried out for 30 minutes at 170 ℃. The m-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 65nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein, the luminescent layer is 25nm, is doped with 0.05 wt% of red dye DCJTB and is doped with 15 wt% of green dye C545T. The evaporation method is used for preparing a LiF electron injection layer with the thickness of 0.5nm and an Mg/Al composite metal cathode with the thickness of 1nm/90 nm.
Evaluating the performance of the device: the magnesium/aluminum metal is used as the cathode of the device, the positive pole of direct current is added to ITO (indium tin oxide), and the negative pole is added to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a lighting voltage of 3.3V, the maximum current efficiency of 18.2cd/A, 10.4lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.38,0.43) are obtained. The brightness reaches 1000cd/m2The current efficiency roll-off was 1.3% and the power efficiency roll-off was 0.8%. The color rendering index CRI value was 71. The spectral stability is good with increasing voltage.
Example 5
150nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing 30nm PEDOT: PSS on ITO glass by a spin coating method, and annealing for 10 minutes at 120 ℃. Preparing an exciton blocking layer by a PVK chlorobenzene solution spin coating method, wherein the exciton blocking layer is 20nm, and annealing is carried out for 30 minutes at 170 ℃. The m-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 60nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein the luminescent layer is 20nm and is doped with yellow-red dye 2.0 wt% PO-01-0.05 wt% Ir (MDQ)2(acac), doped green dye 20 wt% C545T. Preparation of 1.0nm Li by evaporation methodA bpss electron injection layer and a 150nm Al metal cathode.
Evaluating the performance of the device: aluminum was used as the cathode of the device, the positive pole of direct current was applied to ITO (indium tin oxide), and the negative pole was applied to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a starting voltage of 3.0V, the maximum current efficiency of 28.5cd/A and 20.1lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.39,0.45) are given. The brightness reaches 1000cd/m2The current efficiency roll-off was 2.0% and the power efficiency roll-off was 5.1%. Color rendering index CRI value of 81. The spectral stability is good with increasing voltage.
Example 6
150nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing 30nm PEDOT: PSS on ITO glass by a spin coating method, and annealing for 10 minutes at 120 ℃. Preparing an exciton blocking layer by a PVK chlorobenzene solution spin coating method, wherein the exciton blocking layer is 20nm, and annealing is carried out for 30 minutes at 170 ℃. The p-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 70nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein the luminescent layer is 30nm, the doped yellow dye is 0.08 wt% of TBRb, and the doped green dye is 15 wt% of C545T. The evaporation method is used for preparing a 1.5nm LiQ electron injection layer and a 100nm Al metal cathode.
Evaluating the performance of the device: aluminum was used as the cathode of the device, the positive pole of direct current was applied to ITO (indium tin oxide), and the negative pole was applied to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a lighting voltage of 3.2V, the maximum current efficiency of 20.0cd/A, 15.1lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.35,0.36) are used. The brightness reaches 1000cd/m2The current efficiency roll-off is 9.3 percentThe power efficiency roll-off was 18.0%. Color rendering index CRI value is 74. The spectral stability is good with increasing voltage.
Example 7
150nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing 30nm PEDOT: PSS on ITO glass by a spin coating method, and annealing for 10 minutes at 120 ℃. The PVK chlorobenzene solution spin coating method is used for preparing the exciton blocking layer with the thickness of 5nm, and annealing is carried out for 30 minutes at 170 ℃. The p-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 70nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein, the luminescent layer is 30nm and is doped with 1.0 wt% of yellow dye TBRb to prepare the white light device with complementary yellow-blue color. The evaporation method is used for preparing a 1.5nm LiQ electron injection layer and a 100nm Al metal cathode.
Evaluating the performance of the device: aluminum was used as the cathode of the device, the positive pole of direct current was applied to ITO (indium tin oxide), and the negative pole was applied to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a lighting voltage of 3.2V, the maximum current efficiency of 18.4cd/A, 16.1lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.39,0.42) are obtained. The brightness reaches 1000cd/m2The current efficiency roll-off was 7.9% and the power efficiency roll-off was 21.0%. Color rendering index CRI value of 55. The spectral stability is good with increasing voltage.
Example 8
150nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing 30nm ITO glass by a spin coating methodPEDOT: PSS, annealed at 120 ℃ for 10 min. Preparing an exciton blocking layer by a PVK chlorobenzene solution spin coating method, wherein the exciton blocking layer is 15nm, and annealing is carried out for 30 minutes at 170 ℃. The m-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 60nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein, the luminescent layer is 20nm, is doped with 1.0wt percent of yellow-red light dye PO-01 and is doped with 20wt percent of green light dye Ir (ppy)3. The evaporation method is used for preparing a LiF electron injection layer with the thickness of 1.0nm and an Al metal cathode with the thickness of 120 nm.
Evaluating the performance of the device: aluminum was used as the cathode of the device, the positive pole of direct current was applied to ITO (indium tin oxide), and the negative pole was applied to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a starting voltage of 3.4V, the maximum current efficiency of 33.4cd/A, 26.5lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.36,0.48) are used. The brightness reaches 1000cd/m2The current efficiency roll-off was 1.7% and the power efficiency roll-off was 13.6%. Color rendering index CRI value of 69. The spectral stability is good with increasing voltage.
Example 9
150nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing 30nm PEDOT: PSS on ITO glass by a spin coating method, and annealing for 10 minutes at 120 ℃. The PVK chlorobenzene solution spin coating method is used for preparing the exciton blocking layer with the thickness of 5nm, and annealing is carried out for 30 minutes at 170 ℃. The m-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 60nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein, the luminescent layer is 20nm, and is doped with yellow dye 2.0 wt% TBRb to prepare the white light device with complementary yellow-blue color. The evaporation method is used for preparing a 1.0nm LiF electron injection layer and a 1nm/80nm Sm/Al composite metal cathode.
Evaluating the performance of the device: Sm/Al was used as the cathode of the device, the positive electrode of direct current was applied to ITO (indium tin oxide) and the negative electrode was applied to the metal layer.The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of 2.9V of lighting voltage, 19.5cd/A and 19.1lm/W of maximum current efficiency and 100cd/m of brightness2The CIE color coordinates of (0.39,0.38) are obtained. The brightness reaches 1000cd/m2The current efficiency roll-off was 2.3% and the power efficiency roll-off was 3.1%. The color rendering index CRI value is 54. The spectral stability is good with increasing voltage.
Example 10
150nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing 30nm PEDOT: PSS on ITO glass by a spin coating method, and annealing for 10 minutes at 120 ℃. Preparing an exciton blocking layer by a PVK chlorobenzene solution spin coating method, wherein the exciton blocking layer is 20nm, and annealing is carried out for 30 minutes at 170 ℃. The m-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 60nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein, the luminescent layer is doped with yellow dye 2.0 wt% TBRb at 20nm to prepare the white light device with complementary yellow-blue color. Preparation of 0.5nm Cs by evaporation method2CO3An electron injection layer and an 80nm Al metal cathode.
Evaluating the performance of the device: aluminum was used as the cathode of the device, the positive pole of direct current was applied to ITO (indium tin oxide), and the negative pole was applied to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a lighting voltage of 3.2V, the maximum current efficiency of 17.5cd/A, 14.3lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.37,0.40) are used. The brightness reaches 1000cd/m2The current efficiency roll-off was 3.3% and the power efficiency roll-off was 5.4%. Color rendering index CRI value of 55. The spectral stability is good with increasing voltage.
Example 11
50nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing 30nm PEDOT: PSS on ITO glass by a spin coating method, and annealing for 10 minutes at 120 ℃. Preparing an exciton blocking layer by a PVK chlorobenzene solution spin coating method, wherein the exciton blocking layer is 20nm, and annealing is carried out for 30 minutes at 170 ℃. The m-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 60nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein the luminescent layer is 30nm, the doped yellow dye is 0.05 wt% of TBRb, and the doped green dye is 15 wt% of C545T. And preparing a 5nm LiQ electron injection layer and a 100nm Al metal cathode by an evaporation method.
Evaluating the performance of the device: aluminum was used as the cathode of the device, the positive pole of direct current was applied to ITO (indium tin oxide), and the negative pole was applied to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a lighting voltage of 3.6V, the maximum current efficiency of 17.0cd/A, 14.5lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.37,0.40) are used. The brightness reaches 1000cd/m2The current efficiency roll-off was 17.3% and the power efficiency roll-off was 24.8%. Color rendering index CRI value of 55. The spectral stability is good with increasing voltage.
Example 12
100nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing 10nm PEDOT: PSS on ITO glass by a spin coating method, and annealing for 10 minutes at 120 ℃. Preparing a cavity transport layer with the thickness of 50nm by a spin coating method of a Poly-TPD chlorobenzene solution, and annealing for 30 minutes at 120 ℃. The m-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 60nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein the luminescent layer is 30nm, the doped yellow dye is 0.5 wt% of TBRb, and the doped green dye is 20 wt% of C545T. The evaporation method is used for preparing a 0.5nm LiQ electron injection layer and a 1nm/90nm Yb/Al composite metal cathode.
Evaluating the performance of the device: Yb/Al is used as the cathode of the device, the positive pole of direct current is added to ITO (indium tin oxide), and the negative pole is added to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a lighting voltage of 3.0V, the maximum current efficiency of 26.0cd/A and 20.1lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.34,0.32) are used. The brightness reaches 1000cd/m2The current efficiency roll-off was 5.3% and the power efficiency roll-off was 10.8%. The color rendering index CRI value was 77. The spectral stability is good with increasing voltage.
Example 13
150nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing an 80nm NPB-HATCN composite hole transport layer on ITO glass by a spin coating method, and annealing for 10 minutes at 100 ℃. Preparing an exciton blocking layer by a mCP chlorobenzene solution spin coating method, wherein the exciton blocking layer is 20nm, and annealing is carried out for 10 minutes at 70 ℃. The m-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 60nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein the luminescent layer is 30nm, the doped yellow dye is 1.5 wt% of TBRb, and the doped green dye is 20 wt% of C545T. The evaporation method is used for preparing a 1nm LiF electron injection layer and a 1nm/90nm Sm/Al composite metal cathode.
Evaluating the performance of the device: Sm/Al was used as the cathode of the device, the positive electrode of direct current was applied to ITO (indium tin oxide) and the negative electrode was applied to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. Watch of devicesThe current is at a starting voltage of 3.2V, the maximum current efficiency is 22.0cd/A, 17.1lm/W, and the luminance is at 100cd/m2The CIE color coordinates of (0.36,0.42) are used. The brightness reaches 1000cd/m2The current efficiency roll-off was 15.3% and the power efficiency roll-off was 17.8%. Color rendering index CRI value is 60. The spectral stability is good with increasing voltage.
Example 14
150nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing an 80nm TAPC-HATCN composite hole injection and hole transport layer on ITO glass by a spin coating method, and annealing for 10 minutes at 100 ℃. Preparing an exciton blocking layer by a TcTa chlorobenzene solution spin coating method, wherein the exciton blocking layer is 3nm, and annealing is carried out for 10 minutes at 150 ℃. The m-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 60nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein the luminescent layer is 30nm, the doped yellow dye is 1.5 wt% of TBRb, and the doped green dye is 20 wt% of C545T. The evaporation method is used for preparing a LiF electron injection layer with the thickness of 0.5nm and an Mg/Al composite metal cathode with the thickness of 3nm/50 nm.
Evaluating the performance of the device: the magnesium/aluminum composite electrode is used as the cathode of the device, the anode of direct current is added to ITO (indium tin oxide), and the cathode is added to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a lighting voltage of 3.2V, the maximum current efficiency of 25.0cd/A and 24.1lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.34,0.37) are obtained. The brightness reaches 1000cd/m2The current efficiency roll-off was 12.3% and the power efficiency roll-off was 15.5%. Color rendering index CRI value was 63. The spectral stability is good with increasing voltage.
Example 15
150nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing a 30nm TAPC-HATCN composite hole transport layer on ITO glass by a spin coating method, and annealing for 10 minutes at 100 ℃. Preparing an exciton blocking layer by a TcTa chlorobenzene solution spin coating method, wherein the exciton blocking layer is 20nm, and annealing is carried out for 10 minutes at 150 ℃. The p-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 60nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein, the luminescent layer is 20nm, is doped with 0.5 wt% of yellow dye DCJTB, and is doped with 5 wt% of green dye C545T. The evaporation method is used for preparing a LiF electron injection layer with the thickness of 0.5nm and an Mg/Al composite metal cathode with the thickness of 3nm/90 nm.
Evaluating the performance of the device: the magnesium/aluminum composite electrode is used as the cathode of the device, the anode of direct current is added to ITO (indium tin oxide), and the cathode is added to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has a starting voltage of 3.4V, a maximum current efficiency of 21.0cd/A, 19.1lm/W, and a brightness of 100cd/m2The CIE color coordinates of (0.35,0.33) are obtained. The brightness reaches 1000cd/m2The current efficiency roll-off was 15.3% and the power efficiency roll-off was 17.5%. The color rendering index CRI value was 71. The spectral stability is good with increasing voltage.
Example 16
100nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing 10nm PEDOT: PSS on ITO glass by a spin coating method, and annealing for 10 minutes at 120 ℃. The TFB chlorobenzene solution spin coating method is used for preparing a hole transport layer with the thickness of 50nm, and annealing is carried out for 30 minutes at the temperature of 120 ℃. The p-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 60nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein the luminescent layer is 30nm, the doped yellow dye is 0.5 wt% of TBRb, and the doped green dye is 20 wt% of C545T. The evaporation method is used for preparing a 0.5nm LiQ electron injection layer and a 1nm/90nm Yb/Al composite metal cathode.
Evaluating the performance of the device: Yb/Al is used as the cathode of the device, the positive pole of direct current is added to ITO (indium tin oxide), and the negative pole is added to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a lighting voltage of 3.0V, the maximum current efficiency of 26.0cd/A and 20.1lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.34,0.32) are used. The brightness reaches 1000cd/m2The current efficiency roll-off was 5.3% and the power efficiency roll-off was 10.8%. The color rendering index CRI value was 77. The spectral stability is good with increasing voltage.
Example 17
100nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing 50nm PEDOT: PSS on ITO glass by a spin coating method, and annealing for 10 minutes at 120 ℃. The TFB chlorobenzene solution spin coating method is used for preparing a hole transport layer with the thickness of 10nm, and annealing is carried out for 30 minutes at the temperature of 120 ℃. The p-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 70nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein the luminescent layer is 25nm, the doped yellow dye is 0.5 wt% of TBRb, and the doped green dye is 20 wt% of C545T. The evaporation method is used for preparing a 1.5nm LiQ electron injection layer and a 100nm Al metal cathode.
Evaluating the performance of the device: aluminum was used as the cathode of the device, the positive pole of direct current was applied to ITO (indium tin oxide), and the negative pole was applied to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a lighting voltage of 3.3V, the maximum current efficiency of 20.2cd/A, 17.1lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.38,0.40) are used. The brightness reaches 1000cd/m2The current efficiency roll-off was 8.3% and the power efficiency roll-off was 11.8%. The color rendering index CRI value was 73. The spectral stability is good with increasing voltage.
Example 18
150nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing 50nm PEDOT: PSS on ITO glass by a spin coating method, and annealing for 10 minutes at 120 ℃. Preparing a hole transport layer by a spin coating method of a Poly-TPD chlorobenzene solution at 10nm, and annealing for 30 minutes at 120 ℃. The m-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 60nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein the luminescent layer is 20nm, the doped yellow dye is 2.0 wt% of TBRb, and the doped green dye is 20 wt% of C545T. The evaporation method is used for preparing a LiF electron injection layer with the thickness of 0.5nm and an Al metal cathode with the thickness of 100 nm.
Evaluating the performance of the device: aluminum was used as the cathode of the device, the positive pole of direct current was applied to ITO (indium tin oxide), and the negative pole was applied to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a lighting voltage of 3.3V, the maximum current efficiency of 20.2cd/A, 17.1lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.38,0.40) are used. The brightness reaches 1000cd/m2The current efficiency roll-off was 8.3% and the power efficiency roll-off was 11.8%. The color rendering index CRI value was 73. The spectral stability is good with increasing voltage.
Example 19
100nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 deg.C), placing ITO (indium tin oxide) glass into a plasma reactor for 5 minutes oxygen plasma treatment, then adopting spin coating process to prepare organic layers in sequence, and finally conveyingAnd (4) preparing an electron injection layer and a cathode in a vacuum chamber. Firstly, preparing 50nm PEDOT: PSS on ITO glass by a spin coating method, and annealing for 10 minutes at 120 ℃. Preparing an exciton blocking layer by a spin coating method of a Poly-TPD chlorobenzene solution at 20nm, and annealing for 30 minutes at 170 ℃. The m-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 50nm, and the annealing is carried out for 10 minutes at 100 ℃. Wherein the luminescent layer is 15nm, is doped with 1.0 wt% of yellow-red light dye PO-01 and doped with 20 wt% of green light dye Ir (ppy)3. The evaporation method is used for preparing a LiF electron injection layer with the thickness of 1.0nm and an Al metal cathode with the thickness of 100 nm.
Evaluating the performance of the device: aluminum was used as the cathode of the device, the positive pole of direct current was applied to ITO (indium tin oxide), and the negative pole was applied to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a starting voltage of 3.6V, the maximum current efficiency of 32.5cd/A and 24.5lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.38,0.48) are used. The brightness reaches 1000cd/m2The current efficiency roll-off was 5.7% and the power efficiency roll-off was 11.6%. Color rendering index CRI value is 68. The spectral stability is good with increasing voltage.
Example 20
100nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing 30nm PEDOT: PSS on ITO glass by a spin coating method, and annealing for 10 minutes at 120 ℃. Preparing an exciton blocking layer by a PVK chlorobenzene solution spin coating method at 10nm, and annealing at 170 ℃ for 30 minutes. The p-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 60nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein, the luminescent layer is 30nm, is doped with yellow-red light dye 2.0 wt% PO-01 and doped with green light dye 20 wt% Ir (ppy)3. The evaporation method is used for preparing a 1.0nm Libpps electron injection layer and a 90nm Al metal cathode.
Device propertyThe evaluation of: aluminum was used as the cathode of the device, the positive pole of direct current was applied to ITO (indium tin oxide), and the negative pole was applied to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a lighting voltage of 3.2V, the maximum current efficiency of 38.5cd/A, 27.5lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.36,0.47) are obtained. The brightness reaches 1000cd/m2The current efficiency roll-off was 7.7% and the power efficiency roll-off was 13.6%. The color rendering index CRI value was 66. The spectral stability is good with increasing voltage.
Example 21
150nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing an 80nm NPB-HATCN composite hole transport layer on ITO glass by a spin coating method, and annealing for 10 minutes at 100 ℃. The m-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 70nm, and the luminescent layer and the electron transport layer are annealed for 10 minutes at 100 ℃. Wherein the luminescent layer is 10nm, the doped yellow dye is 1.5 wt% of TBRb, and the doped green dye is 20 wt% of C545T. The electron transport layer was 60 nm. The evaporation method is used for preparing a LiF electron injection layer with the thickness of 1nm and an Al metal cathode with the thickness of 100 nm.
Evaluating the performance of the device: al was used as the cathode of the device, the positive electrode of direct current was applied to ITO (indium tin oxide), and the negative electrode was applied to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a starting voltage of 3.3V, the maximum current efficiency of 19.0cd/A, 18.3lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.37,0.43) are obtained. The brightness reaches 1000cd/m2The current efficiency roll-off was 7.3% and the power efficiency roll-off was 15.8%. Color rendering index CRI value is 60. The spectral stability is good with increasing voltage.
Example 22
150nm ITO (indium tin oxide) glass was cleaned successively in a detergent and deionized water for 30 minutes by ultrasonic cleaning. Then vacuum drying for 2 hours (105 ℃), then putting ITO (indium tin oxide) glass into a plasma reactor for oxygen plasma treatment for 5 minutes, then adopting a spin coating process to prepare organic layers in sequence, and finally conveying the organic layers into a vacuum chamber to prepare an electron injection layer and a cathode. Firstly, preparing an 80nm NPB-HATCN composite hole transport layer on ITO glass by a spin coating method, and annealing for 10 minutes at 100 ℃. The p-PO15NCzDPA methanol solution is prepared into a luminescent layer and an electron transport layer by a spin coating method at 50nm, and the annealing is carried out for 10 minutes at 100 ℃. Wherein the luminescent layer is 30nm, the doped yellow dye is 1.5 wt% of TBRb, and the doped green dye is 20 wt% of C545T. The electron transport layer was 20 nm. The evaporation method is used for preparing a LiF electron injection layer with the thickness of 0.5nm and an Al metal cathode with the thickness of 90 nm.
Evaluating the performance of the device: al was used as the cathode of the device, the positive electrode of direct current was applied to ITO (indium tin oxide), and the negative electrode was applied to the metal layer. The current-voltage characteristics were measured using a computer-controlled cathelin 2400(Keithley2400) digital source meter, and the luminescence properties were evaluated using a spectral scanning (Spectrascan PR655) luminance meter. The device has the performance of a starting voltage of 3.1V, the maximum current efficiency of 18.4cd/A, 14.3lm/W and the brightness of 100cd/m2The CIE color coordinates of (0.35,0.42) are obtained. The brightness reaches 1000cd/m2The current efficiency roll-off was 11.3% and the power efficiency roll-off was 16.5%. Color rendering index CRI value is 62. The spectral stability is good with increasing voltage.
As the starting materials used in the above examples, commercially available products other than p-PO15NCzDPA and m-PO15NCzDPA were used as they were. The composite oxide metal film is Indium Tin Oxide (ITO) with the thickness of 50nm to 150nm, and the composite oxide metal film can be prepared on a substrate by adopting a magnetron sputtering method (of course, a commercial ITO glass product can also be directly adopted). Other parts in the preparation method which are not described in detail can refer to the related prior art; for example, the organic solution used in the present invention for preparing the organic electroluminescent device may employ a conventional orthogonal solvent.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (12)
1. An organic photoelectric material, which is p-PO15NCzDPA or m-PO15NCzDPA and has a chemical structural formula shown as the following formula:
2. a preparation method for preparing the organic photoelectric material of claim 1, wherein the synthetic route is as follows:
3. use of the organic photoelectric material according to claim 1 as a light-emitting layer or an electron transport layer in an organic electroluminescent device.
4. The use of the organic photovoltaic material according to claim 1, wherein the organic photovoltaic material is used as both a light-emitting layer and an electron transport layer, and a light-emitting layer-electron transport layer homojunction structure based on p-PO15NCzDPA or m-PO15NCzDPA is formed.
5. A light emitting layer-electron transport layer homojunction structure, wherein the light emitting layer-electron transport layer homojunction structure is based on p-PO15NCzDPA or m-PO15NCzDPA, wherein the p-PO15NCzDPA or m-PO15NCzDPA has a chemical formula as shown in the following formula:
6. an organic electroluminescent device comprising an anode, an organic functional layer and a cathode from bottom to top, wherein the organic functional layer comprises a hole transport layer, a light emitting layer-electron transport layer and an electron injection layer from bottom to top, and the light emitting layer-electron transport layer is the light emitting layer-electron transport layer homojunction structure according to claim 5.
7. The organic electroluminescent device according to claim 6, wherein the thickness of the light emitting layer is 10nm to 30 nm; the thickness of the electron transport layer is 20nm to 60 nm;
a hole injection layer is further arranged between the hole transport layer and the anode, and the hole injection layer and the hole transport layer are: PSS film as hole injection layer and Poly-TPD film as hole transport layer, their thickness satisfies 10nm to 50 nm; or (II) a PEDOT (poly (ethylene-CO-butylene-CO-diphenyl) amine) film prepared by a solution method is used as a hole injection layer and a poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) film is used as a hole transport layer, and the thicknesses of the PEDOT and the poly (ethylene-CO-butylene-CO-N- (4-butylphenyl) diphenylamine) film meet the range of 10nm to 50 nm; or (III) a PEDOT/PSS film prepared by a solution method and having a thickness of 10nm to 30nm is used as a hole injection layer, and a composite film consisting of dipyrazino [2,3-F:2',3' -H ] quinoxaline 2,3,6,7,10, 11-Hexacyano (HATCN) and 4,4' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (NPB) having a thickness of 30nm to 80nm is used as a hole transport layer; or, the hole transport layer is in direct contact with the anode, and the hole transport layer is: (IV) a composite film prepared by a solution method, wherein the composite film is composed of dipyrazino [2,3-F:2',3' -H ] quinoxaline 2,3,6,7,10, 11-Hexacyano (HATCN) and 1, 1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC), and the thickness of the composite film is 30nm to 80 nm;
the electron injection layer is LiF or Cs prepared by a vacuum evaporation method2CO3Or LiQ or Libpps, the thickness of the electron injection layer is 0.5nm to 5 nm;
the anode is a composite oxide metal film which is an Indium Tin Oxide (ITO) film with the thickness of 50nm to 150 nm; the cathode is a metal cathode or a composite metal cathode prepared by a vacuum thermal evaporation method, wherein the metal cathode is a metal Al cathode with the thickness of 80-150 nm; the composite metal cathode is a Mg/Al composite metal cathode or a Yb/Al composite metal cathode or a Sm/Al composite metal cathode, and in the composite metal cathodes, the thickness of the Al metal layer is 50nm to 90nm, and the thickness of the other metal layer is 1nm to 3 nm.
8. The organic electroluminescent device of claim 6, wherein the organic functional layer further comprises an exciton blocking layer disposed between the hole transport layer and the emissive layer-electron transport layer.
9. The organic electroluminescent device according to claim 8, wherein the exciton blocking layer is a PVK film of 5nm to 20nm when the hole injection layer and the transport layer are PEDOT, PSS and Poly-TPD films prepared by a solution method, or PEDOT, PSS and Poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) films prepared by a solution method;
when the hole injection layer and the transmission layer are a PEDOT/PSS film prepared by a solution method and a composite film composed of a dipyrazino [2, 3-F/2 ',3' -H ] quinoxaline 2,3,6,7,10, 11-Hexanenitrile (HATCN) and 4,4 '-bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (NPB), or when the hole transmission layer is a composite film composed of a dipyrazino [2, 3-F/2', 3'-H ] quinoxaline 2,3,6,7,10, 11-Hexanenitrile (HATCN) and 1, 1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC) prepared by a solution method, the exciton blocking layer is 4,4' -tris (carbazol-9-yl) triphenylamine (TCTA) or 1 with the exciton blocking layer of 3nm to 20nm, 3-bis-9-carbazolylbenzene (mCP).
10. The organic electroluminescent device according to claim 6, wherein the organic electroluminescent device is a white organic electroluminescent device, and the luminescent layer-electron transport layer is further doped with a yellow luminescent dye, or co-doped with a yellow luminescent dye and a green luminescent dye, or co-doped with a red luminescent dye and a green luminescent dye, or co-doped with a yellow luminescent dye, a red luminescent dye and a green luminescent dye; wherein the doping concentration of the yellow light-emitting dye or the red light-emitting dye is 0.05 wt% to 2.0 wt%, and the doping concentration of the green light-emitting dye is 5.0 wt% to 20.0 wt%;
the yellow light-emitting dye has a light-emitting wavelength of 570-620 nm, the red light-emitting dye has a light-emitting wavelength of 620-680 nm, and the green light-emitting dye has a light-emitting wavelength of 490-570 nm.
11. A method for preparing the organic electroluminescent device according to any one of claims 6 to 10, wherein the method for preparing the organic functional layer is based on a solution method, wherein the hole injection layer and the hole transport layer are formed on the transparent substrate having the anode by spin coating through a solution method, or the hole transport layer is formed on the transparent substrate having the anode by spin coating through a solution method; and then, spin-coating by using an organic solution for dissolving p-PO15NCzDPA or m-PO15NCzDPA to form a light-emitting layer-electron transport layer, and finally, preparing by using vacuum evaporation to form an electron injection layer and a cathode, thereby preparing the organic electroluminescent device.
12. The method of manufacturing an organic electroluminescent device according to claim 11, further comprising spin-coating a PVK thin film using a PVK organic solution after the hole transport layer is formed and before the formation of the light emitting layer-electron transport layer is started.
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