CN117693214A - Quantum dot light-emitting device, preparation method thereof and display device - Google Patents
Quantum dot light-emitting device, preparation method thereof and display device Download PDFInfo
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- CN117693214A CN117693214A CN202211372275.9A CN202211372275A CN117693214A CN 117693214 A CN117693214 A CN 117693214A CN 202211372275 A CN202211372275 A CN 202211372275A CN 117693214 A CN117693214 A CN 117693214A
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- quantum dot
- ligand
- dot light
- layer
- emitting device
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Abstract
The application relates to a manufacturing method of a quantum dot light emitting device, which comprises the following steps: providing a quantum dot light-emitting prefabricated layer, wherein the quantum dot light-emitting prefabricated layer is arranged on the surface of an anode, the quantum dot light-emitting prefabricated layer comprises a plurality of quantum dots, and at least part of the quantum dots are combined with a first ligand; contacting a solution containing a second ligand with at least the surface of the quantum dot light-emitting prefabricated layer, which is far away from the anode, wherein the contacted first ligand is replaced by the second ligand to form a quantum dot light-emitting layer; forming a cathode on one side of the quantum dot light-emitting layer far away from the anode; the first ligand is selected from P-type semiconductor organic matters, and the second ligand is selected from N-type semiconductor organic matters. The hole and electron injection capability of the quantum dot light-emitting device obtained by the method is improved, so that the light-emitting efficiency of the quantum dot is improved, and the light-emitting performance of the quantum dot light-emitting device is improved.
Description
Technical Field
The application relates to the technical field of display, in particular to a quantum dot light emitting device, a preparation method thereof and a display device.
Background
Quantum Dots (QDs) are a special material whose dimensions in three dimensions are limited to the order of nanometers, and this remarkable quantum confinement effect gives quantum dots a number of unique nanoproperties: the emission wavelength is continuously adjustable, the light-emitting wavelength is narrow, the absorption spectrum is wide, the light-emitting intensity is high, the fluorescence lifetime is long, the biocompatibility is good, and the like. The characteristics lead the quantum dots to have wide application prospect in the fields of flat panel display, solid state lighting, photovoltaic solar energy, biological markers and the like. Particularly in the aspect of flat panel display application, quantum dot light emitting diodes (QLEDs) based on quantum dot luminescence have demonstrated great application potential in the aspects of display image quality, device performance, manufacturing cost and the like by means of the characteristics of quantum dot nanomaterials and further optimization.
Specifically, the application of the quantum dots in the backlight source module shows that the quantum dots are adopted to replace the traditional fluorescent powder, the color gamut of the display screen can be improved from 72% NTSC to 110% NTSC, and the color gamut is greatly improved. Further, when the quantum dot gets rid of the backlight technology and the active matrix is utilized to form the quantum dot light emitting diode display device, compared with the traditional LCD adopting the backlight technology, the self-luminous quantum dot light emitting diode has more outstanding display effect, smaller power consumption and wider adaptable temperature range under the scenes of black representation, high brightness condition and the like, and can prepare the display screen with the color gamut as high as 130 percent NTSC.
However, the current quantum dot light emitting technology generally has the problem that the carrier transmission capability of the quantum dot light emitting layer in the device is low, and the problem greatly limits the light emitting efficiency of the quantum dot light emitting device.
Disclosure of Invention
Based on this, it is necessary to provide a quantum dot light emitting device, a method of manufacturing the same, and a display device, which can improve the carrier transport capability of the quantum dot light emitting layer, thereby contributing to an improvement in light emitting efficiency.
An embodiment of the present application provides a method for manufacturing a quantum dot light emitting device, including the following steps:
Providing a quantum dot light-emitting prefabricated layer, wherein the quantum dot light-emitting prefabricated layer is arranged on the surface of an anode, the quantum dot light-emitting prefabricated layer comprises a plurality of quantum dots, and at least part of the quantum dots are combined with a first ligand;
contacting a solution containing a second ligand with at least the surface of the quantum dot light-emitting prefabricated layer, which is far away from the anode, wherein the contacted first ligand is replaced by the second ligand to form a quantum dot light-emitting layer;
forming a cathode on one side of the quantum dot light-emitting layer away from the anode;
the first ligand is selected from P-type semiconductor organic matters, and the second ligand is selected from N-type semiconductor organic matters.
In one embodiment, the method for manufacturing the quantum dot light emitting prefabricated layer includes the following steps:
dispersing the quantum dots in an organic solvent to form a colloid solution;
adding the first ligand into the colloid solution, and heating for reaction to form a quantum dot solution combined with the first ligand;
and coating the quantum dot solution combined with the first ligand on the surface of the anode to form the quantum dot light-emitting prefabricated layer.
In one embodiment, the method for manufacturing the quantum dot light emitting prefabricated layer includes the following steps:
Dispersing the quantum dots in an organic solvent to form a colloid solution;
heating the colloid solution in an inert atmosphere, adding a third ligand, and then carrying out heat preservation reaction to form a quantum dot solution combined with the third ligand; the third ligand is selected from at least one of oleic acid and oleylamine;
adding the first ligand into the quantum dot solution combined with the third ligand, and heating for reaction to form the quantum dot solution combined with the first ligand;
and coating the quantum dot solution combined with the first ligand on the surface of the anode to form the quantum dot light-emitting prefabricated layer.
In one embodiment, the concentration of the quantum dots in the colloidal solution is 20 mg/mL-100 mg/mL; and/or
The feeding mole ratio of the quantum dots to the first ligand is 1:0.5-1:2; and/or
The feeding mole ratio of the quantum dots to the second ligand is 1:0.5-1:2; and/or
In the solution containing the second ligand, the concentration of the second ligand is 10 mg/mL-100 mg/mL; and/or
And contacting the solution containing the second ligand with at least the surface of the quantum dot light-emitting prefabricated layer at the side far away from the anode for 1-5 minutes.
The embodiment of the application also provides a quantum dot light emitting device, which comprises a cathode, an anode and a quantum dot light emitting layer arranged between the cathode and the anode, wherein the quantum dot light emitting layer comprises a plurality of quantum dots, at least part of the surfaces of the quantum dots are combined with a first ligand and a second ligand, the first ligand is selected from P-type semiconductor organic matters, and the second ligand is selected from N-type semiconductor organic matters.
In one embodiment, the first ligand is closer to the anode than the second ligand, and the second ligand is closer to the cathode than the first ligand.
In one embodiment, the first ligand comprises a-NH-containing ligand 2 and/or-COOH P-type semiconductor organics; and/or
The second ligand comprises an N-type semiconductor organic matter containing-SH.
In one embodiment, the first ligand comprises a-NH-containing ligand 2 At least one aromatic amine organic matter of (2) and aromatic amine organic matter containing-COOH; and/or
The second ligand comprises an N-heterocyclic organic matter containing-SH.
In one embodiment, the first ligand comprises at least one of 4,4',4 "-tricarboxylic acid triphenylamine, 4', 4" -triaminetrianiline, 4-aminotrianiline, and 4,4' -diaminotriphenylamine; and/or
The second ligand comprises at least one of 2-mercaptopyridine, 2-mercaptobenzimidazole, 2-mercaptomethyl benzimidazole, 5-methoxy-2-mercaptobenzimidazole, methylthioimidazole, 4-amino-2-mercaptopyrimidine, 4, 6-diamino-2-mercaptopyrimidine, 2-mercapto-4-amino-6-hydroxypyrimidine, 4-phenyl-2-mercapto-pyrimidine, 4, 5-dimethyl-2-mercaptopyrimidine, 2-mercapto-5-nitropyridine, 4-mercapto-2-methylpyridine, 4-amino-3-mercaptopyridine, 2-mercaptopyridine-3-ethylsulfone, and benzyl (3-mercapto- [4] pyridyl) carbamate.
In one embodiment, the thickness of the quantum dot light-emitting layer is 15 nm-35 nm; and/or
The molar ratio of the first ligand to the second ligand is 1:10-10:1.
In one embodiment, the quantum dot comprises at least one of a single structure quantum dot and a core-shell structure quantum dot, the material of the single structure quantum dot is selected from at least one of group II-VI compound, group IV-VI compound, group III-V compound and group I-III-VI compound, wherein the group II-VI compound is selected from at least one of CdS, cdSe, cdTe, znS, znSe, znTe, znO, hgS, hgSe, hgTe, cdSeS, cdSeTe, cdSTe, znSeS, znSeTe, znSTe, hgSeS, hgSeTe, hgSTe, cdZnS, cdZnSe, cdZnTe, cdHgS, cdHgSe, cdHgTe, hgZnS, hgZnSe, hgZnTe, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe and HgZnSTe, the group IV-VI compound is selected from at least one of SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe and SnPbSTe, the group III-V compound is selected from at least one of GaN, gaP, gaAs, gaSb, alN, alP, alAs, alSb, inN, inP, inAs, inSb, gaNP, gaNAs, gaNSb, gaPAs, gaPSb, alNP, alNAs, alNSb, alPAs, alPSb, inNP, inNAs, inNSb, inPAs, inPSb, gaAlNP, gaAlNAs, gaAlNSb, gaAlPAs, gaAlPSb, gaInNP, gaInNAs, gaInNSb, gaInPAs, gaInPSb, inAlNP, inAlNAs, inAlNSb, inAlPAs or InAlPSb, and the group I-III-VI compound is selected from CuInS 2 、CuInSe 2 AgInS 2 At least one of (a) and (b); and/or
The core of the quantum dot with the core-shell structure comprises any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure comprises CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS, znS and at least one of the quantum dots with the single structure; and/or
The anode and/or cathode materials include one or more of a metal, a carbon material, and a metal oxide, the metal including one or more of Al, ag, cu, mo, au, ba, ca, yb and Mg; the carbon material comprises one or more of graphite, carbon nanotubes, graphene and carbon fibers; the metal oxide comprises one or more of doped or undoped metal oxide, ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO, or a composite electrode comprising doped or undoped transparent metal oxide and metal sandwiched therebetween, and the composite electrode comprises AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, znS/Ag/ZnS, znS/Al/ZnS, tiO 2 /Ag/TiO 2 TiO 2 /Al/TiO 2 One or more of the following.
In one embodiment, the quantum dot light emitting device further includes at least one of an electron injection layer, an electron transport layer, a hole transport layer, and a hole injection layer.
In one embodiment, the material of the electron transport layer and/or the electron injection layer comprises an inorganic material and/or an organic material; the inorganic material is selected from one or more of doped or undoped zinc oxide, barium oxide, aluminum oxide, nickel oxide, titanium oxide, tin oxide, tantalum oxide, zirconium oxide, nickel oxide, titanium lithium oxide, zinc aluminum oxide, zinc manganese oxide, zinc tin oxide, zinc lithium oxide, indium tin oxide, cadmium sulfide, zinc sulfide, molybdenum sulfide, tungsten sulfide, copper sulfide, zinc stannate, indium phosphide, gallium phosphide, copper indium sulfide, copper gallium sulfide and barium titanate, and the doped element comprises one or more of aluminum, magnesium, lithium, manganese, yttrium, lanthanum, copper, nickel, zirconium, cerium and gadolinium; the organic material is selected from one or more of quinoxaline compounds, imidazole compounds, triazine compounds, fluorene compounds and hydroxyquinoline compounds; and/or
The material of the hole transport layer and/or the hole injection layer comprises TFB, cuPc, PVK, poly-TPD, DNTPD, TCATA, TCCA, CBP, TPD, NPB, NPD, PEDOT: PSS, TAPC, MCC, F 4 -TCNQ, HATCN, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylene Amines, polyanilines, transition metal oxides, transition metal sulfides, transition metal stannides, doped graphene, undoped graphene, and C 60 At least one of them.
An embodiment of the present application provides a display device, including a quantum dot light emitting device manufactured by a method for manufacturing a quantum dot light emitting device described in any one of the embodiments described above, or including a quantum dot light emitting device described in any one of the embodiments described above.
In the manufacturing method of the quantum dot luminescent device, at least part of quantum dots in the luminescent layer are combined with the first ligand and the second ligand, wherein the first ligand is selected from P-type semiconductor organic matters, and the hole mobility of the P-type semiconductor organic matters is higher, so that the capability of injecting holes into the luminescent layer is improved; the second ligand is selected from N-type semiconductor organic matters, the electron mobility of the N-type semiconductor organic matters is higher, the capability of injecting electrons into the light-emitting layer is improved, holes and electrons are combined to be more favorable for being simultaneously transmitted to the quantum dots, the carrier transmission capability is enhanced, the light-emitting efficiency of the quantum dots is improved, and the light-emitting performance of the quantum dot light-emitting device is further improved.
Drawings
Fig. 1 is a schematic diagram illustrating ligand exchange between a first ligand and a second ligand in a process of fabricating a quantum dot light emitting device according to an embodiment;
fig. 2 is a schematic structural diagram of a quantum dot light emitting device of embodiment 1;
reference numerals illustrate:
110: an anode; 120: quantum dot light emitting prefabricated layer; 121: a first ligand; 130: a quantum dot light emitting layer; 131: a second ligand; 200: a quantum dot light emitting device; 210: a substrate; 220: a hole injection layer; 230: a hole transport layer; 240: an electron transport layer; 250: and a cathode.
Detailed Description
In order that the invention may be understood, a more complete description of the invention will be rendered by reference to the embodiments that are illustrated in the appended drawings. This application may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the present application, the technical features described in an open manner include a closed technical scheme composed of the listed features, and also include an open technical scheme including the listed features.
An embodiment of the present application provides a method for manufacturing a quantum dot light emitting device, including the following steps S10 to S30.
Step S10: providing a quantum dot light-emitting prefabricated layer, wherein the quantum dot light-emitting prefabricated layer is arranged on the surface of an anode, the quantum dot light-emitting prefabricated layer comprises a plurality of quantum dots, and at least part of the quantum dots are combined with a first ligand.
Step S20: and (3) contacting the solution containing the second ligand with at least the surface of the quantum dot light-emitting prefabricated layer, which is far away from the anode, and replacing the contacted first ligand by the second ligand to form the quantum dot light-emitting layer.
Step S30: and forming a cathode on one side of the quantum dot light-emitting layer away from the anode.
Wherein the first ligand is selected from P-type semiconductor organic matters, and the second ligand is selected from N-type semiconductor organic matters.
The inventor finds that the main reason why the carrier transmission capability of the quantum dot luminescent layer is limited is that in the quantum dot generating process, in order to enable the quantum dot to stably grow according to the expected shape, the surface of the quantum dot is generally distributed with a certain amount of ligand consisting of oleic acid or oleylamine, wherein the oleic acid and the oleylamine are compounds consisting of long carbon chains, and the long carbon chains form a large potential barrier to prevent normal movement of carriers such as holes, electrons and the like, so that the carrier transmission capability is limited, and the luminescent efficiency of the quantum dot luminescent device is reduced. Therefore, the inventor provides the method, improves the traditional manufacturing process of the quantum dot luminescent layer, and in the quantum dot luminescent device manufactured by the method, the quantum dots in the luminescent layer are combined with the first ligand and the second ligand, wherein the first ligand is selected from the P-type semiconductor organic matters, and the hole mobility of the P-type semiconductor organic matters is higher, so that the capability of injecting holes into the luminescent layer is improved; the second ligand is selected from N-type semiconductor organic matters, the electron mobility of the N-type semiconductor organic matters is higher, the capability of injecting electrons into the light-emitting layer is improved, the first ligand and the second ligand can replace original oleic acid or oleylamine ligands, the hole and the electrons are more favorably transmitted to the quantum dot at the same time, the carrier transmission capability is enhanced, the light-emitting efficiency of the quantum dot is improved, and the light-emitting performance of the quantum dot light-emitting device is further improved.
As can be appreciated, P-type semiconductor organics refer to semiconductor organics that are predominantly hole conductive, with higher hole mobility; the N-type semiconductor organic matter is mainly electronic conduction semiconductor organic matter and has higher electronic mobility.
Further details of the steps from step S10 to step S30 are as follows:
step S10: providing a quantum dot light-emitting prefabricated layer, wherein the quantum dot light-emitting prefabricated layer is arranged on the surface of an anode, the quantum dot light-emitting prefabricated layer comprises a plurality of quantum dots, and at least part of the quantum dots are combined with a first ligand.
In one embodiment, the first ligand may include, but is not limited to, a ligand comprising-NH 2 and/or-COOH P-type semiconductor organics.
Further, the first ligand may include, but is not limited to, a-NH-containing ligand 2 At least one aromatic amine organic matter of (C) and (B) containing-COOH. The aromatic amine organic matter is a good P-type semiconductor organic matter and is favorable for hole transmission.
Further, the first ligand may include, but is not limited to, at least one of 4,4',4 "-tricarboxylic acid triphenylamine, 4', 4" -triaminetrianiline, 4-aminotrianiline, and 4,4' -diaminotriphenylamine.
In one embodiment, the method for manufacturing the quantum dot light emitting preform layer includes the following steps S10a to S10c.
Step S10a: and dispersing the quantum dots in an organic solvent to form a colloid solution.
Further, the concentration of the quantum dots in the colloidal solution is 20 mg/mL-100 mg/mL. In the concentration range, the quantum dots are not easy to agglomerate in the organic solvent, and a better dispersing effect can be obtained, so that the quantum dots and the ligand have a proper contact area in the subsequent ligand exchange reaction process. If the concentration of the quantum dots is too low, the dispersity of the quantum dots in the organic solvent is too high, the spacing between particles is too large, excessive grafting of the ligand is easy to cause, and finally the luminous performance of the quantum dot luminous layer is affected; if the concentration of quantum dots is too high, agglomerates are easily formed, and a good contact environment with the ligand cannot be formed. It is understood that the concentration of the quantum dot in the colloidal solution may be, for example, 20mg/mL, 30mg/mL, 40mg/mL, 50mg/mL, 60mg/mL, 70mg/mL, 80mg/mL, 90mg/mL, 100mg/mL, etc., without being limited thereto.
Further, the organic solvent is at least one selected from the group consisting of 1-Octadecene (ODE), 1-hexadecene, and 1-eicosene. The quantum dots have good dispersion performance in the organic solvent, are high-boiling-point olefins, are not easy to volatilize in the subsequent high-temperature reaction process, and can still be used as a good dispersion medium of the quantum dots.
Step S10b: and adding the first ligand into the colloid solution, and heating to react to form the quantum dot solution combined with the first ligand.
Further, the conditions of the heating reaction are: the temperature is 100-250 ℃ and the time is 0.5-1 hour. Within this range of conditions, it is advantageous to allow the quantum dot to sufficiently bind to and coordinate with the first ligand, and if the reaction temperature is too low or the reaction time is too short, the ligand coordination reaction is insufficient, and if the reaction is too high or the reaction time is too long, degradation or other side reactions of the ligand on the surface of the quantum dot may occur.
Further, the feeding mole ratio of the quantum dots to the first ligand is 1:0.5-1:2. The feeding molar ratio is in the range, and the modification effect of the first ligand on the surface of the quantum dot is best. When the feeding amount of the first ligand is lower than the range, the surface modification effect of the first ligand on the quantum dots is reduced, and agglomeration easily occurs among the quantum dots, so that the luminous performance of the quantum dot device is reduced. When the feeding amount of the first ligand is higher than the range, the adsorption and desorption reactions between the first ligand and the quantum dots are too fast, dynamic balance between adsorption and desorption is damaged, uneven distribution of the first ligand on the surface of the quantum dots is easily caused, excessive feeding amount of the first ligand can cause excessive first ligand distributed on the surface of the quantum dots, the formed first ligand layer is too thick, light must be transmitted through the ligand layer in the light emitting process of the quantum dots, and the ligand can absorb part of light energy, so that when the ligand layer is too thick, loss of the light energy is increased, and the light emitting efficiency of the quantum dots is reduced. It is understood that the molar ratio of the quantum dot to the first ligand may be, for example, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, etc., without being limited thereto. Preferably, the feeding molar ratio of the quantum dots to the first ligand is 1:0.8-1:1.2. More preferably, the molar ratio of the quantum dot to the first ligand is 1:1, and the binding capacity of the first ligand on the surface of the quantum dot tends to be saturated.
It will be appreciated that after the heating reaction is completed and the temperature of the reaction solution is reduced to room temperature, the single solution or mixed solution of ethyl acetate, ethanol and acetone can be used for precipitation and washing step by step for multiple times, and then the washed product is redispersed in a proper organic solvent to form the final quantum dot solution containing the first ligand. Among them, suitable organic solvents are, for example, but not limited to, non-polar solvents such as toluene, xylene, cyclohexane, n-hexane, n-octane, n-decane, chloroform, ODE, etc.
Step S10c: and coating the quantum dot solution combined with the first ligand on the surface of the anode to form a quantum dot light-emitting prefabricated layer.
It is understood that the thickness of the anode is conventional, e.g., the thickness of the anode may be, but is not limited to, 15nm to 100nm.
Specifically, the coating method may adopt a conventional solution processing method, such as inkjet printing, spin coating, drop coating, soaking, coating, evaporation and the like, and the thickness of the quantum dot light emitting prefabricated layer may be controlled by adjusting the concentration of the quantum dot solution, the coating speed, the coating time and the like.
In one embodiment, the method for fabricating the quantum dot light emitting prefabricated layer includes the following steps S10a 'to S10d':
Step S10a': and dispersing the quantum dots in an organic solvent to form a colloid solution. The specific details of this step are substantially the same as those of step S10a, and will not be described here again.
Step S10b': heating the colloid solution in an inert atmosphere, adding a third ligand, and then carrying out heat preservation reaction to form a quantum dot solution combined with the third ligand; the third ligand is selected from at least one of oleic acid and oleylamine.
The quantum dots can be grown according to the expected shape through the step S10b', and the final shape is more suitable for manufacturing the quantum dot light emitting device.
Further, the volume ratio of the colloidal solution to the third ligand is 90:1-120:1. Within this range, the third ligand may be well dispersed in the colloidal solution, and be in sufficient contact with the quantum dot and attached to the surface of the quantum dot in a proper ratio. If the dosage of the third ligand is too small, the quantum dots in the precursor colloidal solution formed by the quantum dots and the third ligand cannot be fully wrapped; if the amount of the third ligand is too large, the amount of the first ligand needs to be greatly increased to replace the third ligand when the first ligand is introduced later, which is unfavorable for the balance of the forward ligand exchange.
Further, the step S10b' is performed under an inert atmosphere, so that the reaction of the oxygen-containing gas and the colloidal solution containing the quantum dots under the high temperature condition can be avoided to generate byproducts. It will be appreciated that an inert atmosphere may be provided by passing an inert gas such as argon, nitrogen or the like.
Further, in step S10b ', the colloidal solution formed in step S10a' is heated, so that the colloidal solution is in a good solution state, and the coordination reaction can be smoothly performed after the third ligand is introduced. Further, the temperature is heated to 150-250 ℃.
Further, the conditions of the incubation reaction are: the temperature is 150-250 ℃, and the reaction time is 0.5-1 hour. Under the high temperature state, the third ligand can be uniformly distributed on the surface of the quantum dot, so that the third ligand is combined with the quantum dot to form a coordination bond.
The third ligand is modified on the surface of the quantum dot in the step S10b', so that other impurities on the surface of the quantum dot can be removed, wherein the impurities can be organic matters containing groups or atoms such as-OH, N, P, -CO and the like, for example, trace H adsorbed on the surface 2 O、O 2 Etc., to grow the quantum dots into a desired shape and to be able to provide a favorable environment for the next ligand exchange with the first ligand.
Step S10c': and adding the first ligand into the quantum dot solution combined with the third ligand, and heating to react to form the quantum dot solution combined with the first ligand. The specific technical details of step S10c' are substantially the same as those of step S10b, and are not described herein.
Step S10d': and coating the quantum dot solution combined with the first ligand on the surface of the anode to form a quantum dot light-emitting prefabricated layer. The specific details of this step are substantially the same as those of step S10a, and will not be described here again.
Step S20: and (3) contacting the solution containing the second ligand with at least the surface of the quantum dot light-emitting prefabricated layer, which is far away from the anode, and replacing the contacted first ligand by the second ligand to form the quantum dot light-emitting layer.
In one embodiment, the second ligand may include, but is not limited to, an N-type semiconductor organic compound including-SH. The N-heterocyclic organic compound is a good N-type semiconductor organic compound and is beneficial to electron transmission.
Further, the second ligand may include, but is not limited to, N-heterocyclic organics including-SH.
Further, the second ligand may include, but is not limited to, at least one of 2-mercaptopyridine, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, 5-methoxy-2-mercaptobenzimidazole, methylthioimidazole, 4-amino-2-mercaptopyrimidine, 4, 6-diamino-2-mercaptopyrimidine, 2-mercapto-4-amino-6-hydroxypyrimidine, 4-phenyl-2-mercapto-pyrimidine, 4, 5-dimethyl-2-mercaptopyrimidine, 2-mercapto-5-nitropyridine, 4-mercapto-2-methylpyridine, 4-amino-3-mercaptopyridine, 2-mercaptopyridine-3-ethylsulfone, and benzyl (3-mercapto- [4] pyridyl) carbamate.
Referring to fig. 1, fig. 1 shows a schematic diagram of a second ligand replacing a first ligand for ligand exchange in a quantum dot light emitting device manufacturing process. As shown in a of fig. 1, the quantum dot light emitting pre-fabricated layer 120 formed through step S10, the quantum dot light emitting pre-fabricated layer 120 includes a plurality of quantum dots, and at least some of the quantum dots are bound with a first ligand 121 composed of a P-type semiconductor organic substance. As shown in b of fig. 1, after step S20, the solution containing the second ligand is at least contacted with the surface of the quantum dot light emitting prefabricated layer on the side far away from the anode, and the second ligand replaces the contacted first ligand, so that ligand exchange is realized. It will be appreciated that the side of the quantum dot light emitting prefabricated layer 120 closer to the anode 110 has been cured to form a film and is adhered to the anode 110, and even if the semi-finished light emitting device including the anode and the quantum dot light emitting prefabricated layer is completely immersed in the solution, the distributed first ligands 121 on the side of the quantum dot light emitting prefabricated layer 120 closer to the anode 110 will not be immersed in the solution including the second ligands 131 in step S30, so that the portion of the first ligands 121 will not be in contact with the solution including the second ligands 131, and further, the portion of the first ligands 121 will not be in ligand exchange with the second ligands 131. The side of the quantum dot light emitting prefabricated layer 120 further away from the anode 110 is not attached to the cathode or other film layer, and is in an exposed state, so that the solution containing the second ligand is at least contacted with the surface of the quantum dot light emitting prefabricated layer far away from the anode, and the first ligand 121 distributed in the quantum dot light emitting prefabricated layer 120 relatively far away from the anode 110 is contacted with the solution containing the second ligand 131, so that ligand replacement occurs, and the part of the first ligand 121 is replaced by the second ligand 131.
It can be understood that the quantum dot light-emitting layer 130 formed in step S20 has the first ligand 121 on the side (hole side) closer to the anode 110, and the ligand is selected from P-type semiconductor organic matters, which is beneficial to improving the hole injection capability; the quantum dot light emitting layer 130 has a second ligand 131 on a side (closer to the electron side and the cathode side) opposite to the anode 110, and the ligand is selected from N-type semiconductor organic matters, which is beneficial to improving the electron injection capability.
In one embodiment, the molar ratio of quantum dots to second ligands is 1:0.5-1:2. The feeding molar ratio is in the range, and the second ligand has the best effect of modifying the surface of the quantum dot. The reason for this is the same as the reason for defining the range of the molar ratio of the quantum dot to the second ligand, and is not described in detail herein. Preferably, the feeding molar ratio of the quantum dots to the second ligand is 1:0.8-1:1.2. More preferably, the molar ratio of quantum dots to second ligand is 1:1.
In one embodiment, the concentration of the second ligand in the solution containing the second ligand is from 10mg/mL to 100mg/mL. The concentration of the second ligand may be, for example, but not limited to, 10mg/mL, 20mg/mL, 30mg/mL, 40mg/mL, 50mg/mL, 60mg/mL, 70mg/mL, 80mg/mL, 90mg/mL, 100mg/mL, and the like.
In one embodiment, the solvent in the solution containing the second ligand includes at least one of methanol, ethanol, propanol, isopropanol, butanol, benzyl alcohol, and phenethyl alcohol.
It will be appreciated that step S20a of preparing a solution containing the second ligand may also be included.
Step S20a: the second ligand is dispersed in its corresponding solvent.
In one embodiment, the solution containing the second ligand is contacted with at least the surface of the quantum dot light emitting pre-layer on the side remote from the anode for a period of time ranging from 1 minute to 5 minutes. The contact time is within the range, so that the quantum dots on the side, relatively far away from the anode, of the quantum dot light-emitting prefabricated layer can be sufficiently contacted with the second ligand, and the first ligand and the second ligand are subjected to ligand exchange, and the second ligand replaces the first ligand. If the time is too short, the ligand exchange is incomplete, and if the time is too long, other functional layers of the semi-finished light-emitting device, which are manufactured first, may be adversely affected. It is understood that the time of contact may be, for example, 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, or the like, without being limited thereto.
In one embodiment, the method may further include annealing during formation of the quantum dot light emitting prefabricated layer or formation of the quantum dot light emitting layer. Further, the annealing temperature is 80-150 ℃. The annealing temperature is within the temperature range, so that the solvent can be completely volatilized, and the film layer cannot be damaged due to the over-high temperature.
It will be appreciated that whether ligand exchange can occur or not is determined by the nature of the compound groups, and that the constituent elements of the quantum dots include metals, particularly transition metals such as zinc and cadmium, which have empty orbitals that are prone to coordination reactions, and atoms or ions of these transition metals, due to the fact that the d-orbitals and s and p-orbitals of the valence shell are empty orbitals, are very prone to form coordination bonds with molecules containing lone pairs of electrons. Further, molecules having a lone pair of electrons, herein containing-SH, -COOH, -NH 2 Compounds of (2) with respect to-SH, -COOH, -NH 2 Comparison of coordination ability of the compounds: SH not only has lone pair electrons which can form coordination bonds with empty orbitals of metal, but also can enter into empty orbitals of SH to form feedback coordination bonds, so that after the three, the coordination ability of SH is strongest, COOH has two pairs of lone pair electrons which can form coordination bonds with metal, the coordination ability is inferior, and NH 2 Only one lone pair of electrons can form a coordination bond with the metal, with the least coordination ability. It will be appreciated that a ligand containing a strongly coordinating group may be substituted for a ligand containing a weakly coordinating group, and ligand interaction may occur, whereby a second ligand herein may displace the first ligand, and if a third ligand is also present on the side remote from the anode, the second ligand may likewise displace it.
Further, when the same coordination group is contained, the longer the carbon chain of the ligand is, the more steric hindrance is, the more coordination stability is not facilitated, when the quantum dot is heated, the dynamic balance of desorption and adsorption exists between the ligand and the quantum dot, even if the coordination group is the same, the probability that the ligand with smaller steric hindrance and larger concentration collides with the quantum dot to be adsorbed is larger,in the dynamic equilibrium that is reformed, ligands with short carbon chains and small steric hindrance can be substituted for ligands with long carbon chains and large steric hindrance. Thus, further, when a third ligand is included, if the third ligand includes oleic acid, the first ligand should include P-type semiconductor organic containing-COOH; if the third ligand comprises oleylamine, the first ligand may comprise a compound containing-NH 2 At least one of the P-type semiconductor organic compound of (c) and the P-type semiconductor organic compound containing-COOH, so that the third ligand can smoothly undergo ligand exchange with the first ligand. Furthermore, after the oleic acid or the oleylamine with the long carbon chain is replaced by the first ligand, the surface of the quantum dot is not influenced by the long carbon chain any more, so that the luminous performance of the quantum dot can be effectively improved.
It is understood that the first ligand and the quantum dot can be successfully coordinated through the step S10c', which is not only to replace part or all of the third ligand by the coordination competitive advantage with the third ligand, but also to realize the coordination bonding through the space gap with smaller steric hindrance.
In one embodiment, the quantum dot light emitting layer has a thickness of 15nm to 35nm. It is understood that the thickness of the quantum dot light emitting layer may be, for example, but not limited to, 15nm, 20nm, 25nm, 30nm, 35nm, and the like.
Step S30: and forming a cathode on one side of the quantum dot light-emitting layer away from the anode.
It will be appreciated that the cathode may be formed in a manner conventional in the art, such as evaporation or the like.
It will be appreciated that the thickness of the cathode is conventional, for example the thickness of the cathode may be, but is not limited to, 15nm to 100nm.
It can be appreciated that the quantum dot device obtained by the method for manufacturing the quantum dot light emitting device has a positive structure.
In one embodiment, the quantum dot comprises at least one of a single-structure quantum dot and a core-shell structure quantum dot, wherein the material of the single-structure quantum dot is selected from at least one of II-VI compound, IV-VI compound, III-V compound and I-III-VI compound, and the II-VI compound is selected from CdS, cdSe, cdTe, znS, znSe, znTe, znO, hgSAt least one of HgSe, hgTe, cdSeS, cdSeTe, cdSTe, znSeS, znSeTe, znSTe, hgSeS, hgSeTe, hgSTe, cdZnS, cdZnSe, cdZnTe, cdHgS, cdHgSe, cdHgTe, hgZnS, hgZnSe, hgZnTe, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe and HgZnSTe, at least one of SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe and SnPbSTe, at least one of GaN, gaP, gaAs, gaSb, alN, alP, alAs, alSb, inN, inP, inAs, inSb, gaNP, gaNAs, gaNSb, gaPAs, gaPSb, alNP, alNAs, alNSb, alPAs, alPSb, inNP, inNAs, inNSb, inPAs, inPSb, gaAlNP, gaAlNAs, gaAlNSb, gaAlPAs, gaAlPSb, gaInNP, gaInNAs, gaInNSb, gaInPAs, gaInPSb, inAlNP, inAlNAs, inAlNSb, inAlPAs or InAlPSb, and at least one of CuInS 2 、CuInSe 2 AgInS 2 At least one of them.
In one embodiment, the core of the quantum dot of the core-shell structure comprises any one of the quantum dots of the single structure, and the shell material of the quantum dot of the core-shell structure comprises CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS, znS and at least one of the quantum dots of the single structure.
In one embodiment, the material of the anode and/or cathode comprises one or more of a metal, a carbon material, and a metal oxide, the metal comprising one or more of Al, ag, cu, mo, au, ba, ca, yb and Mg; the carbon material comprises one or more of graphite, carbon nano tube, graphene and carbon fiber; the metal oxide comprises one or more of doped or undoped metal oxide, ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO, or composite electrode comprising doped or undoped transparent metal oxide and metal sandwiched therebetween, and the composite electrode comprises AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, znS/Ag/ZnS, znS/Al/ZnS, tiO 2 /Ag/TiO 2 TiO 2 /Al/TiO 2 One or more of the following.
In one embodiment, the method further comprises the step of forming at least one of an electron injection layer, an electron transport layer, a hole transport layer, and a hole injection layer.
Further, an electron injection layer, an electron transport layer, a hole transport layer, or a hole injection layer may be formed using a conventional solution processing method. Further, the thickness of the hole injection layer may be, for example, 10nm to 50nm. Further, the thickness of the hole transport layer may be, for example, 10nm to 50nm. Further, the thickness of the electron injection layer may be, for example, 10nm to 70nm. Further, the thickness of the electron transport layer may be, for example, 10nm to 70nm.
In one embodiment, the material of the electron transport layer and/or the electron injection layer comprises an inorganic material and/or an organic material; the inorganic material is selected from one or more of doped or undoped zinc oxide, barium oxide, aluminum oxide, nickel oxide, titanium oxide, tin oxide, tantalum oxide, zirconium oxide, nickel oxide, titanium lithium oxide, zinc aluminum oxide, zinc manganese oxide, zinc tin oxide, zinc lithium oxide, indium tin oxide, cadmium sulfide, zinc sulfide, molybdenum sulfide, tungsten sulfide, copper sulfide, zinc stannate, indium phosphide, gallium phosphide, copper indium sulfide, copper gallium sulfide and barium titanate, and the doped element comprises one or more of aluminum, magnesium, lithium, manganese, yttrium, lanthanum, copper, nickel, zirconium, cerium and gadolinium; the organic material is selected from one or more of quinoxaline compound, imidazole compound, triazine compound, fluorene compound and hydroxyquinoline compound.
In one embodiment, the material of the hole transport layer and/or the hole injection layer comprises TFB, cuPc, PVK, poly-TPD, DNTPD, TCATA, TCCA, CBP, TPD, NPB, NPD, PEDOT: PSS, TAPC, MCC, F 4 -TCNQ, HATCN, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, polyaniline, transition metal oxides, transition metal sulfides, transition metal stannides, doped graphene, undoped graphene and C 60 At least one of them.
The application further provides a quantum dot luminescent device, which comprises a cathode, an anode and a quantum dot luminescent layer arranged between the cathode and the anode, wherein the quantum dot luminescent layer comprises a plurality of quantum dots, at least part of the surfaces of the quantum dots are combined with a first ligand and a second ligand, the first ligand is selected from P-type semiconductor organic matters, and the second ligand is selected from N-type semiconductor organic matters.
At least part of quantum dots in the light-emitting layer of the quantum dot light-emitting device are combined with the first ligand and the second ligand, wherein the first ligand is selected from P-type semiconductor organic matters, and the hole mobility of the P-type semiconductor organic matters is higher, so that the capability of injecting holes into the light-emitting layer is improved; the second ligand is selected from N-type semiconductor organic matters, the electron mobility of the N-type semiconductor organic matters is higher, the capability of injecting electrons into the light-emitting layer is improved, holes and electrons are combined to be more favorable for being simultaneously transmitted to the quantum dots, the carrier transmission capability is enhanced, the light-emitting efficiency of the quantum dots is improved, and the light-emitting performance of the quantum dot light-emitting device is further improved.
In one embodiment, the first ligand is closer to the anode than the second ligand, and the second ligand is closer to the cathode than the first ligand. The first ligand is selected from P-type semiconductor organic matters with higher hole mobility, which is beneficial to improving the transmission capacity of hole carriers, so that the first ligand is closer to the anode, the effect of the first ligand can be effectively exerted, and the holes of the anode are easy to inject into the light-emitting layer; similarly, the second ligand is selected from N-type semiconductor organic matters with higher electron mobility, which is favorable for improving the transmission capability of electron carriers, so that the second ligand is closer to the cathode, the effect of the second ligand can be effectively exerted, electrons of the cathode are easily injected into the light-emitting layer, and the first ligand and the second ligand are matched and acted with each other, so that the quantum dot light-emitting device has better light-emitting efficiency.
In one embodiment, the first ligand may include, but is not limited to, a ligand comprising-NH 2 and/or-COOH-containing P-type semiconductor organics. Further, the first ligand may include, but is not limited to, a-NH-containing ligand 2 At least one aromatic amine organic matter of (C) and (B) containing-COOH. Still further, the first ligand may include, but is not limited to, triphenylamine 4,4 '-tricarboxylic acid, 4' At least one of triamino triphenylamine, 4-aminotrianiline and 4,4' -diaminotriphenylamine.
In one embodiment, the second ligand may include, but is not limited to, an N-type semiconductor organic compound including-SH. Further, the second ligand may include, but is not limited to, N-heterocyclic organics including-SH. Still further, the second ligand may include, but is not limited to, at least one of 2-mercaptopyridine, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, 5-methoxy-2-mercaptobenzimidazole, methylthioimidazole, 4-amino-2-mercaptopyrimidine, 4, 6-diamino-2-mercaptopyrimidine, 2-mercapto-4-amino-6-hydroxypyrimidine, 4-phenyl-2-mercapto-pyrimidine, 4, 5-dimethyl-2-mercaptopyrimidine, 2-mercapto-5-nitropyridine, 4-mercapto-2-methylpyridine, 4-amino-3-mercaptopyridine, 2-mercaptopyridine-3-ethylsulfone, and benzyl (3-mercapto- [4] pyridyl) carbamate.
In one embodiment, the quantum dot light emitting layer has a thickness of 15nm to 35nm.
In one embodiment, the molar ratio of the first ligand to the second ligand is from 1:10 to 10:1.
In one embodiment, the quantum dot comprises at least one of a single-structure quantum dot and a core-shell structure quantum dot, the material of the single-structure quantum dot is selected from at least one of II-VI compound, IV-VI compound, III-V compound and I-III-VI compound, wherein the II-VI compound is selected from at least one of CdS, cdSe, cdTe, znS, znSe, znTe, znO, hgS, hgSe, hgTe, cdSeS, cdSeTe, cdSTe, znSeS, znSeTe, znSTe, hgSeS, hgSeTe, hgSTe, cdZnS, cdZnSe, cdZnTe, cdHgS, cdHgSe, cdHgTe, hgZnS, hgZnSe, hgZnTe, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe and HgZnSTe, the IV-VI compound is selected from at least one of SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe and SnPbSTe, and the III-V compound is selected from GaN, gaP, gaAs, gaSb, alN, alP, alAs, alSb, inN, inP, inAs, inSb, gaNP, gaNAs, gaNSb, gaPAs, gaPSb, alNP, alNAs, alNSb, alP At least one of As, alPSb, inNP, inNAs, inNSb, inPAs, inPSb, gaAlNP, gaAlNAs, gaAlNSb, gaAlPAs, gaAlPSb, gaInNP, gaInNAs, gaInNSb, gaInPAs, gaInPSb, inAlNP, inAlNAs, inAlNSb, inAlPAs or InAlPSb, the I-III-VI compound is selected from CuInS 2 、CuInSe 2 AgInS 2 At least one of them.
In one embodiment, the core of the quantum dot of the core-shell structure comprises any one of the quantum dots of the single structure, and the shell material of the quantum dot of the core-shell structure comprises CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS, znS and at least one of the quantum dots of the single structure.
In one embodiment, the material of the anode and/or cathode comprises one or more of a metal, a carbon material, and a metal oxide, the metal comprising one or more of Al, ag, cu, mo, au, ba, ca, yb and Mg; the carbon material comprises one or more of graphite, carbon nano tube, graphene and carbon fiber; the metal oxide comprises one or more of doped or undoped metal oxide, ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO, or composite electrode comprising doped or undoped transparent metal oxide and metal sandwiched therebetween, and the composite electrode comprises AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, znS/Ag/ZnS, znS/Al/ZnS, tiO 2 /Ag/TiO 2 TiO 2 /Al/TiO 2 One or more of the following.
In one embodiment, the quantum dot light emitting device further includes at least one of an electron injection layer, an electron transport layer, a hole transport layer, and a hole injection layer.
In one embodiment, the material of the electron transport layer and/or the electron injection layer comprises an inorganic material and/or an organic material; the inorganic material is selected from one or more of doped or undoped zinc oxide, barium oxide, aluminum oxide, nickel oxide, titanium oxide, tin oxide, tantalum oxide, zirconium oxide, nickel oxide, titanium lithium oxide, zinc aluminum oxide, zinc manganese oxide, zinc tin oxide, zinc lithium oxide, indium tin oxide, cadmium sulfide, zinc sulfide, molybdenum sulfide, tungsten sulfide, copper sulfide, zinc stannate, indium phosphide, gallium phosphide, copper indium sulfide, copper gallium sulfide and barium titanate, and the doped element comprises one or more of aluminum, magnesium, lithium, manganese, yttrium, lanthanum, copper, nickel, zirconium, cerium and gadolinium; the organic material is selected from one or more of quinoxaline compound, imidazole compound, triazine compound, fluorene compound and hydroxyquinoline compound.
In one embodiment, the material of the hole transport layer and/or the hole injection layer comprises TFB, cuPc, PVK, poly-TPD, DNTPD, TCATA, TCCA, CBP, TPD, NPB, NPD, PEDOT: PSS, TAPC, MCC, F 4 -TCNQ, HATCN, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, polyaniline, transition metal oxides, transition metal sulfides, transition metal stannides, doped graphene, undoped graphene and C 60 At least one of them.
An embodiment of the present application further provides a display apparatus, including a quantum dot light emitting device manufactured by the method for manufacturing a quantum dot light emitting device in any one of the above embodiments, or including a quantum dot light emitting device in any one of the above embodiments. It will be appreciated that the display device may be, but is not limited to, a display screen of a cell phone, tablet, computer, television or the like.
The following are specific examples.
Example 1
S11: preparation of Quantum dot solution bound with first ligand
S111: a proper amount of quantum dot CdS/ZnS is dispersed in 20mL of 1-octadecene to form a quantum dot colloid solution with the concentration of 20 mg/mL. Then heating the quantum dot colloid solution to 100 ℃ in argon atmosphere, and then according to the volume ratio of the quantum dot colloid solution to the oleylamine of 90:1, injecting oleylamine according to a proportion, and carrying out heat preservation reaction for 30min to form a quantum dot solution containing the oleylamine ligand.
S112: adding the 4,4 '-triphenyltricarboxylic acid triphenylamine into the quantum dot solution containing the oily amine ligand prepared in the step S10a1 according to the molar ratio of the quantum dot to the 4,4' -triphenyltricarboxylic acid triphenylamine of 1:1, and continuously stirring and reacting for 30min at 100 ℃. After the reaction is finished, after the reaction solution is cooled to room temperature, the reaction solution is precipitated and washed in two steps by using a mixed solvent of ethyl acetate and ethanol and a mixed solvent of acetone and ethanol, and then the precipitate is redispersed in toluene to form a quantum dot solution combined with a first ligand.
S12: preparation of a solution containing the second ligand
Dispersing 2-mercaptobenzimidazole in an ethanol solution, wherein the concentration of a second ligand is 10mg/ml, and the feeding mole ratio of the quantum dots to the second ligand is 1:1.
s13: fabrication of Quantum dot light emitting devices
Fig. 2 shows a schematic structural diagram of a quantum dot light emitting device 200 fabricated and formed in step S10c of example 1, and the fabrication steps are as follows:
s131: spin-coating PEDOT PSS on a substrate 210 containing an anode 110, wherein the anode 110 is made of ITO, the thickness of the anode 110 is 50nm, the spin-coating revolution is 2000 rpm, the spin-coating time is 40s, and annealing is performed at 150 ℃ for 15min, so that a hole injection layer 220 with the thickness of 25nm is formed;
s132: spin-coating a TFB chlorobenzene solution with a concentration of 10mg/ml on the hole injection layer 220 formed in the step S10c1, spin-coating for 40S at 3000 rpm, and annealing at 150 ℃ for 30min to form a hole transport layer 230 with a thickness of 25 nm;
s133: spin-coating the quantum dot solution with the concentration of the first ligand combined prepared in the step S10a on the hole transport layer 230 formed in the step S10c2, spin-coating the quantum dot solution at a rotation speed of 3000 rpm for 40S, and annealing the quantum dot solution at 100 ℃ for 5min to form a quantum dot light-emitting prefabricated layer with a thickness of 15 nm;
s134: soaking the semi-finished product of the device manufactured in the steps S10c 1-S133 in the solution containing the second ligand prepared in the step S10b, reacting for 1min, and annealing at 80 ℃ for 5min to form a quantum dot luminescent layer 130 with the thickness of 15 nm;
S135: spin-coating a ZnO ethanol solution with the concentration of 30mg/ml on the quantum dot luminescent layer 130 formed in the step S10c4, spin-coating the ZnO ethanol solution for 3000 r/min, annealing the ZnO ethanol solution for 40S at 80 ℃ for 30min, and forming an electron transport layer 240 with the thickness of 50 nm;
s136: on the electron transport layer 240 formed in step S10c5, a high vacuum (10 -7 Torr) conditionsA 150nm silver layer was evaporated as cathode 250.
Example 2
S21: preparation of Quantum dot solution bound with first ligand
S211: a proper amount of quantum dot ZnSe is dispersed in 20mL of 1-hexadecene to form a quantum dot colloid solution with the concentration of 30 mg/mL. Then heating the quantum dot colloid solution to 200 ℃ in argon atmosphere, and then according to the volume ratio of the quantum dot colloid solution to the oleylamine of 120:1, injecting oleylamine according to a proportion, and carrying out heat preservation reaction for 30min to form a quantum dot solution containing the oleylamine ligand.
S212: adding 4,4 '-triaminetrianiline into the quantum dot solution of the oil-containing amine ligand prepared in the step S211 according to the mol ratio of the quantum dot to the 4,4' -triaminetrianiline of 1:1.5, and continuously stirring at 200 ℃ for reacting for 1h. After the reaction is finished, after the reaction solution is cooled to room temperature, the reaction solution is precipitated and washed in two steps by using a mixed solvent of ethyl acetate and ethanol and a mixed solvent of acetone and ethanol, and then the precipitate is redispersed in n-octane to form a quantum dot solution combined with a first ligand.
S22: preparation of a solution containing the second ligand
Dispersing 2-mercaptobenzimidazole in an ethanol solution, wherein the concentration of a second ligand is 10mg/ml, and the feeding mole ratio of the quantum dots to the second ligand is 1:1.
s23: fabrication of Quantum dot light emitting devices
S231: spin-coating PEDOT PSS on a substrate 210 containing an anode 220, wherein the anode 220 is made of ITO, the thickness of the anode 220 is 50nm, the spin-coating revolution is 2000 rpm, the spin-coating time is 40s, and annealing is performed at 150 ℃ for 15min to form a hole injection layer with the thickness of 25 nm;
s232: spin-coating TFB chlorobenzene solution with the concentration of 10mg/ml on the hole injection layer formed in the step S231, spin-coating for 40S at the rotation speed of 3000 r/min, and annealing for 30min at the temperature of 150 ℃ to form a hole transport layer with the thickness of 25 nm;
s233: spin-coating the quantum dot solution with the concentration of the first ligand combined prepared in the step S21 on the hole transport layer formed in the step S232, spin-coating for 2000 revolutions per minute, spin-coating for 40S, and annealing at 100 ℃ for 5min to form a quantum dot light-emitting prefabricated layer with the thickness of 25 nm;
s234: soaking the semi-finished product of the device manufactured in the steps S231-S233 in the solution containing the second ligand prepared in the step S22, reacting for 1min, and then annealing for 5min at 80 ℃ to form a quantum dot luminescent layer with the thickness of 25 nm;
S235: spin-coating a ZnO ethanol solution with the concentration of 30mg/ml on the quantum dot luminescent layer formed in the step S234, spin-coating the ZnO ethanol solution at the rotation speed of 3000 r/min, spin-coating time of 40S, and annealing at 80 ℃ for 30min to form an electron transport layer with the thickness of 50 nm;
s236: on the electron transport layer formed in step S235, a high vacuum (10 -7 Torr) was used as a cathode by vapor deposition of a 150nm silver layer.
Example 3
S31: preparation of Quantum dot solution bound with first ligand
S311: and dispersing a proper amount of quantum dot CdSe/ZnSe/ZnS in 20mL of 1-eicosene to form a quantum dot colloid solution with the concentration of 50 mg/mL. Then heating the quantum dot colloid solution to 250 ℃ in argon atmosphere, and then according to the volume ratio of the quantum dot colloid solution to the oleylamine of 110:1, injecting oleylamine according to a proportion, and carrying out heat preservation reaction for 30min to form a quantum dot solution containing the oleylamine ligand.
S312: adding 4-aminotrianiline into the quantum dot solution containing the oil amine ligand prepared in the step S311 according to the mol ratio of the quantum dot to the 4-aminotrianiline of 1:2, and continuously stirring at 250 ℃ for reaction for 1h. After the reaction is finished, after the reaction solution is cooled to room temperature, the reaction solution is precipitated and washed in two steps by using a mixed solvent of ethyl acetate and ethanol and a mixed solvent of acetone and ethanol, and then the precipitate is redispersed in n-hexane to form a quantum dot solution combined with a first ligand.
S32: preparation of a solution containing the second ligand
Dispersing 2-mercaptobenzimidazole in an ethanol solution, wherein the concentration of a second ligand is 10mg/ml, and the feeding mole ratio of the quantum dots to the second ligand is 1:1.
s33: fabrication of Quantum dot light emitting devices
S331: spin-coating PEDOT PSS on a substrate 210 containing an anode 220, wherein the anode 220 is made of ITO, the thickness of the anode 220 is 50nm, the spin-coating revolution is 2000 rpm, the spin-coating time is 40s, and annealing is performed at 150 ℃ for 15min to form a hole injection layer with the thickness of 25 nm;
s332: spin-coating TFB chlorobenzene solution with the concentration of 10mg/ml on the hole injection layer formed in the step S331, spin-coating for 40S at the rotation speed of 3000 r/min, and annealing for 30min at the temperature of 150 ℃ to form a hole transport layer with the thickness of 25 nm;
s333: spin-coating the quantum dot solution with the concentration of the first ligand combined prepared in the step S31 on the hole transport layer formed in the step S332, spin-coating the quantum dot solution at 1500 rpm for 40S, and annealing the quantum dot solution at 100 ℃ for 5min to form a quantum dot light-emitting prefabricated layer with the thickness of 35 nm;
s334: soaking the semi-finished product of the device manufactured in the steps S331-S333 in the solution containing the second ligand prepared in the step S32 for 1min, and then annealing at 80 ℃ for 5min to form a quantum dot luminescent layer with the thickness of 35 nm;
S335: spin-coating a ZnO ethanol solution with the concentration of 30mg/ml on the quantum dot luminescent layer formed in the step S334, spin-coating the ZnO ethanol solution at the rotation speed of 3000 r/min, spin-coating time of 40S, and annealing at 80 ℃ for 30min to form an electron transport layer with the thickness of 50 nm;
s336: on the electron transport layer formed in step S335, a high vacuum (10 -7 Torr) was used as a cathode by vapor deposition of a 150nm silver layer.
Comparative example 1
CS11: preparation of Quantum dot solution bound with first ligand
CS111: a proper amount of quantum dot CdS/ZnS is dispersed in 20mL of 1-octadecene to form a quantum dot colloid solution with the concentration of 20 mg/mL. Then heating the quantum dot colloid solution to 100 ℃ in argon atmosphere, and then according to the volume ratio of the quantum dot colloid solution to the oleylamine of 90:1, injecting oleylamine according to the proportion, and reacting for 30min at a constant temperature. After the reaction is finished, after the reaction solution is cooled to room temperature, the reaction solution is precipitated and washed in two steps by using a mixed solvent of ethyl acetate and ethanol and a mixed solvent of acetone and ethanol, and then the precipitate is redispersed in n-octane to form a quantum dot solution containing an oleylamine ligand.
CS112: adding the 4,4 '-triphenyltricarboxylic acid triphenylamine into the quantum dot solution containing the oily amine ligand prepared in the step CS111 according to the molar ratio of the quantum dot to the 4,4' -triphenyltricarboxylic acid triphenylamine of 1:1, and continuously stirring at 100 ℃ for reaction for 30min. After the reaction is finished, after the reaction solution is cooled to room temperature, the reaction solution is precipitated and washed in two steps by using a mixed solvent of ethyl acetate and ethanol and a mixed solvent of acetone and ethanol, and then the precipitate is redispersed in toluene to form a quantum dot solution combined with a first ligand.
CS12: fabrication of Quantum dot light emitting devices
CS121: spin-coating PEDOT PSS on a substrate 210 containing an anode 220, wherein the anode 220 is made of ITO, the thickness of the anode 220 is 50nm, the spin-coating revolution is 2000 rpm, the spin-coating time is 40s, and annealing is performed at 150 ℃ for 15min to form a hole injection layer with the thickness of 25 nm;
CS122: spin-coating TFB chlorobenzene solution with the concentration of 10mg/ml on the hole injection layer formed in the step CS121, spin-coating for 40s at 3000 rpm, and annealing at 150 ℃ for 30min to form a hole transport layer with the thickness of 25 nm;
CS123: spin-coating the quantum dot solution with the concentration of the first ligand combined prepared in the step CS11 on the hole transport layer formed in the step CS122, spin-coating for 40s at 3000 rpm, and annealing at 100 ℃ for 5min to form a quantum dot luminescent layer with the thickness of 15 nm;
CS124: spin-coating a ZnO ethanol solution with the concentration of 30mg/ml on the quantum dot luminescent layer formed in the step CS123, spin-coating the ZnO ethanol solution at the rotation speed of 3000 r/min, spin-coating the ZnO ethanol solution for 40s, and annealing the ZnO ethanol solution at the temperature of 80 ℃ for 30min to form an electron transport layer with the thickness of 50 nm;
CS125: on the electron transport layer formed in step CS124, a high vacuum (10 -7 Torr) was used as a cathode by vapor deposition of a 150nm silver layer.
Comparative example 2
CS21: preparation of Quantum dot solution containing only Oleamine ligands, free of first ligands consisting of P-type semiconductor organics
CS211: a proper amount of quantum dot CdS/ZnS is dispersed in 20mL of 1-octadecene to form a quantum dot colloid solution with the concentration of 20 mg/mL. Then heating the quantum dot colloid solution to 100 ℃ in argon atmosphere, and then according to the volume ratio of the quantum dot colloid solution to the oleylamine of 90:1, injecting oleylamine according to the proportion, and reacting for 30min at a constant temperature. After the reaction is finished, after the reaction solution is cooled to room temperature, the reaction solution is precipitated and washed in two steps by using a mixed solvent of ethyl acetate and ethanol and a mixed solvent of acetone and ethanol, and then the precipitate is redispersed in n-octane to form a quantum dot solution containing an oleylamine ligand.
CS22: preparation of a solution containing the second ligand
Dispersing 2-mercaptobenzimidazole in an ethanol solution, wherein the concentration of a second ligand is 10mg/ml, and the feeding mole ratio of the quantum dots to the second ligand is 1:1.
CS23: fabrication of Quantum dot light emitting devices
CS231: spin-coating PEDOT PSS on a substrate 210 containing an anode 220, wherein the anode 220 is made of ITO, the thickness of the anode 220 is 50nm, the spin-coating revolution is 2000 rpm, the spin-coating time is 40s, and annealing is performed at 150 ℃ for 15min to form a hole injection layer with the thickness of 25 nm;
CS232: spin-coating TFB chlorobenzene solution with the concentration of 10mg/ml on the hole injection layer formed in the step CS231, spin-coating for 40s at the rotation speed of 3000 r/min, and annealing for 30min at the temperature of 150 ℃ to form a hole transport layer with the thickness of 25 nm;
CS233: spin-coating the quantum dot solution containing only the oleylamine ligand, which is prepared in the step CS21, on the hole transport layer formed in the step CS232 for 2000 revolutions per minute for 40 seconds, and annealing at 100 ℃ for 5 minutes to form a quantum dot luminescent layer with the thickness of 15 nm;
CS234: soaking the semi-finished product of the device manufactured in the steps CS 231-CS 233 in the solution containing the second ligand prepared in the step CS22 for 1min, and then annealing at 80 ℃ for 5min to form a quantum dot luminescent layer with the thickness of 15 nm;
CS235: spin-coating a ZnO ethanol solution with the concentration of 30mg/ml on the quantum dot luminescent layer formed in the step CS234, spin-coating the ZnO ethanol solution at the rotation speed of 3000 r/min, spin-coating time of 40s, and annealing at 80 ℃ for 30min to form an electron transport layer with the thickness of 50 nm;
CS236: on the electron transport layer formed in step CS235, a high vacuum (10 -7 Torr) was used as a cathode by vapor deposition of a 150nm silver layer.
Comparative example 3
CS31: preparation of Quantum dot solution containing only Oleamine ligands, free of first ligands consisting of P-type semiconductor organics
CS311: a proper amount of quantum dot CdS/ZnS is dispersed in 20mL of 1-octadecene to form a quantum dot colloid solution with the concentration of 20 mg/mL. Then heating the quantum dot colloid solution to 100 ℃ in argon atmosphere, and then according to the volume ratio of the quantum dot colloid solution to the oleylamine of 90:1, injecting oleylamine according to the proportion, and reacting for 30min at a constant temperature. After the reaction is finished, after the reaction solution is cooled to room temperature, the reaction solution is precipitated and washed in two steps by using a mixed solvent of ethyl acetate and ethanol and a mixed solvent of acetone and ethanol, and then the precipitate is redispersed in n-octane to form a quantum dot solution containing an oleylamine ligand.
CS32: fabrication of Quantum dot light emitting devices
CS321: spin-coating PEDOT PSS on a substrate 210 containing an anode 220, wherein the anode 220 is made of ITO, the thickness of the anode 220 is 50nm, the spin-coating revolution is 2000 rpm, the spin-coating time is 40s, and annealing is performed at 150 ℃ for 15min to form a hole injection layer with the thickness of 25 nm;
CS322: spin-coating TFB chlorobenzene solution with the concentration of 10mg/ml on the hole injection layer formed in the step CS321, spin-coating for 40s at 3000 rpm, and annealing at 150 ℃ for 30min to form a hole transport layer with the thickness of 25 nm;
CS323: spin-coating the quantum dot solution containing only the oleylamine ligand, which is prepared in the step CS31, on the hole transport layer formed in the step CS322 for 1500 revolutions per minute for 40 seconds, and annealing at 100 ℃ for 5 minutes to form a quantum dot luminescent layer with the thickness of 15 nm;
CS324: spin-coating a ZnO ethanol solution with the concentration of 30mg/ml on the quantum dot luminescent layer formed in the step CS323, spin-coating the ZnO ethanol solution at the rotation speed of 3000 r/min, spin-coating time of 40s, and annealing at 80 ℃ for 30min to form an electron transport layer with the thickness of 50 nm;
CS325: on the electron transport layer formed in step CS324, a high vacuum (10 -7 Torr) was used as a cathode by vapor deposition of a 150nm silver layer.
The quantum dot light emitting devices fabricated in examples 1 to 3 and comparative examples 1 to 3 were measured for external quantum efficiency by an EQE optical test instrument to evaluate the light emitting efficiency of the devices, and the test results are shown in table 1 below.
TABLE 1 external quantum efficiency of Quantum dot light emitting devices
| Numbering device | External Quantum Efficiency (EQE)/(%) |
| Example 1 | 20.5 |
| Example 2 | 19.8 |
| Example 3 | 20.2 |
| Comparative example 1 | 15.3 |
| Comparative example 2 | 16.2 |
| Comparative example 3 | 11.7 |
As can be seen from table 1, in example 1 to example 3, compared with comparative example 1 to comparative example 3, at least some of the quantum dots in the quantum dot light emitting layers of example 1 to example 3 were bound with the first ligand and the second ligand, and since the first ligand of example 1 to example 3 is selected from P-type semiconductor organic matters having higher hole mobility, it is advantageous to improve the ability to transfer hole carriers to the quantum dot light emitting layer, and the second ligand is selected from N-type semiconductor organic matters having higher electron mobility, it is advantageous to improve the ability to transfer electron carriers to the quantum dot light emitting layer, and therefore, both the ability of holes and electrons in example 1 to example 3 to migrate to the quantum dot light emitting layer is stronger than that in comparative example 1 to comparative example 3, and the light emitting efficiency of the quantum dot light emitting devices fabricated in example 1 to example 3 is significantly superior to that in comparative example 1 to comparative example 3.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples represent only a few embodiments of the present application, which are described in more detail and are not thereby to be construed as limiting the scope of the invention. It should be noted that it would be obvious to those skilled in the art that various modifications and improvements could be made without departing from the inventive concept of the present application, which would be within the scope of the present application. Accordingly, the scope of protection of the present application is to be determined by the claims appended hereto.
Claims (14)
1. The manufacturing method of the quantum dot light-emitting device is characterized by comprising the following steps of:
providing a quantum dot light-emitting prefabricated layer, wherein the quantum dot light-emitting prefabricated layer is arranged on the surface of an anode, the quantum dot light-emitting prefabricated layer comprises a plurality of quantum dots, and at least part of the quantum dots are combined with a first ligand;
contacting a solution containing a second ligand with at least the surface of the quantum dot light-emitting prefabricated layer, which is far away from the anode, wherein the contacted first ligand is replaced by the second ligand to form a quantum dot light-emitting layer;
forming a cathode on one side of the quantum dot light-emitting layer away from the anode;
the first ligand is selected from P-type semiconductor organic matters, and the second ligand is selected from N-type semiconductor organic matters.
2. The method for manufacturing a quantum dot light emitting device according to claim 1, wherein the method for manufacturing a quantum dot light emitting prefabricated layer comprises the steps of:
dispersing the quantum dots in an organic solvent to form a colloid solution;
adding the first ligand into the colloid solution, and heating for reaction to form a quantum dot solution combined with the first ligand;
and coating the quantum dot solution combined with the first ligand on the surface of the anode to form the quantum dot light-emitting prefabricated layer.
3. The method for manufacturing a quantum dot light emitting device according to claim 1, wherein the method for manufacturing a quantum dot light emitting prefabricated layer comprises the steps of:
dispersing the quantum dots in an organic solvent to form a colloid solution;
heating the colloid solution in an inert atmosphere, adding a third ligand, and then carrying out heat preservation reaction to form a quantum dot solution combined with the third ligand; the third ligand is selected from at least one of oleic acid and oleylamine;
adding the first ligand into the quantum dot solution combined with the third ligand, and heating for reaction to form the quantum dot solution combined with the first ligand;
and coating the quantum dot solution combined with the first ligand on the surface of the anode to form the quantum dot light-emitting prefabricated layer.
4. The method for manufacturing a quantum dot light-emitting device according to any one of claims 2 to 3, wherein the concentration of the quantum dot in the colloidal solution is 20mg/mL to 100mg/mL; and/or
The feeding mole ratio of the quantum dots to the first ligand is 1:0.5-1:2; and/or
The feeding mole ratio of the quantum dots to the second ligand is 1:0.5-1:2; and/or
In the solution containing the second ligand, the concentration of the second ligand is 10 mg/mL-100 mg/mL; and/or
And contacting the solution containing the second ligand with at least the surface of the quantum dot light-emitting prefabricated layer at the side far away from the anode for 1-5 minutes.
5. The quantum dot light-emitting device is characterized by comprising a cathode, an anode and a quantum dot light-emitting layer arranged between the cathode and the anode, wherein the quantum dot light-emitting layer comprises a plurality of quantum dots, at least part of the surfaces of the quantum dots are combined with a first ligand and a second ligand, the first ligand is selected from P-type semiconductor organic matters, and the second ligand is selected from N-type semiconductor organic matters.
6. The quantum dot light emitting device of claim 5, wherein the first ligand is closer to the anode than the second ligand, and wherein the second ligand is closer to the cathode than the first ligand.
7. The quantum dot light emitting device of any one of claims 5-6, wherein the first ligand comprises a-NH-containing ligand 2 and/or-COOH P-type semiconductor organics; and/or
The second ligand comprises an N-type semiconductor organic matter containing-SH.
8. The quantum dot light emitting device of any one of claims 5-6, wherein the first ligand comprises a-NH-containing ligand 2 At least one aromatic amine organic matter of (2) and aromatic amine organic matter containing-COOH; and/or
The second ligand comprises an N-heterocyclic organic matter containing-SH.
9. The quantum dot light emitting device of any one of claims 5-6, wherein the first ligand comprises at least one of 4,4',4 "-tricarboxylic acid triphenylamine, 4',4" -triaminetrianiline, 4-aminotrianiline, and 4,4' -diaminotriphenylamine; and/or
The second ligand comprises at least one of 2-mercaptopyridine, 2-mercaptobenzimidazole, 2-mercaptomethyl benzimidazole, 5-methoxy-2-mercaptobenzimidazole, methylthioimidazole, 4-amino-2-mercaptopyrimidine, 4, 6-diamino-2-mercaptopyrimidine, 2-mercapto-4-amino-6-hydroxypyrimidine, 4-phenyl-2-mercapto-pyrimidine, 4, 5-dimethyl-2-mercaptopyrimidine, 2-mercapto-5-nitropyridine, 4-mercapto-2-methylpyridine, 4-amino-3-mercaptopyridine, 2-mercaptopyridine-3-ethylsulfone, and benzyl (3-mercapto- [4] pyridyl) carbamate.
10. The quantum dot light emitting device of any one of claims 5-6, wherein the quantum dot light emitting layer has a thickness of 15nm to 35nm; and/or
The molar ratio of the first ligand to the second ligand is 1:10-10:1.
11. The quantum dot light emitting device of any one of claims 5-6, wherein the quantum dot comprises at least one of a single structure quantum dot and a core-shell structure quantum dot, the single structure quantum dot material is selected from at least one of group II-VI compounds, group IV-VI compounds, group III-V compounds, and group I-III-VI compounds, wherein the group II-VI compounds are selected from at least one of CdS, cdSe, cdTe, znS, znSe, znTe, znO, hgS, hgSe, hgTe, cdSeS, cdSeTe, cdSTe, znSeS, znSeTe, znSTe, hgSeS, hgSeTe, hgSTe, cdZnS, cdZnSe, cdZnTe, cdHgS, cdHgSe, cdHgTe, hgZnS, hgZnSe, hgZnTe, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe and HgZnSTe, the group IV-VI compounds are selected from at least one of SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe and SnPbSTe, and the group III-V compounds are selected from GaN, gaP, gaAs, gaSb, alN, alP, alAs, alSb, inN, inP, inAs, inSb, gaNP, gaNAs, gaNSb, gaPAs, gaPSb, alNP, alNAs, alNSb, alPAs, al PSb, inNP, inNAs, inNSb, inPAs, inPSb, gaAlNP, gaAlNAs, gaAlNSb, gaAlPAs, gaAlPSb, gaInNP, gaInNAs, gaInNSb, gaInPAs, gaInPSb, inAlNP, inAlNAs, inAlNSb, inAlPAs or InAlPSb, the group I-III-VI compound being selected from CuInS 2 、CuInSe 2 AgInS 2 At least one of (a) and (b); and/or
The core of the quantum dot with the core-shell structure comprises any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure comprises CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS, znS and at least one of the quantum dots with the single structure; and/or
The anode and/or cathode materials include one or more of a metal, a carbon material, and a metal oxide, the metal including one or more of Al, ag, cu, mo, au, ba, ca, yb and Mg; the carbon material comprises one or more of graphite, carbon nanotubes, graphene and carbon fibers; the metal oxide comprises one or more of doped or undoped metal oxide, ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO, or a composite electrode comprising doped or undoped transparent metal oxide and metal sandwiched therebetween, and the composite electrode comprises AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, znS/Ag/ZnS, znS/Al/ZnS, tiO 2 /Ag/TiO 2 TiO 2 /Al/TiO 2 One or more of the following.
12. The quantum dot light emitting device of any one of claims 5-6, further comprising at least one of an electron injection layer, an electron transport layer, a hole transport layer, and a hole injection layer.
13. The quantum dot light emitting device of claim 12, wherein the material of the electron transport layer and/or the electron injection layer comprises an inorganic material and/or an organic material; the inorganic material is selected from one or more of doped or undoped zinc oxide, barium oxide, aluminum oxide, nickel oxide, titanium oxide, tin oxide, tantalum oxide, zirconium oxide, nickel oxide, titanium lithium oxide, zinc aluminum oxide, zinc manganese oxide, zinc tin oxide, zinc lithium oxide, indium tin oxide, cadmium sulfide, zinc sulfide, molybdenum sulfide, tungsten sulfide, copper sulfide, zinc stannate, indium phosphide, gallium phosphide, copper indium sulfide, copper gallium sulfide and barium titanate, and the doped element comprises one or more of aluminum, magnesium, lithium, manganese, yttrium, lanthanum, copper, nickel, zirconium, cerium and gadolinium; the organic material is selected from one or more of quinoxaline compounds, imidazole compounds, triazine compounds, fluorene compounds and hydroxyquinoline compounds; and/or
The material of the hole transport layer and/or the hole injection layer comprises TFB, cuPc, PVK, poly-TPD, DNTPD, TCATA, TCCA, CBP, TPD, NPB, NPD, PEDOT: PSS, TAPC, MCC, F 4 -TCNQ, HATCN, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, polyaniline, transition metal oxides, transition metal sulfides, transition metal stannides, doped graphene, undoped graphene and C 60 At least one of them.
14. A display device comprising the quantum dot light-emitting device manufactured by the manufacturing method of the quantum dot light-emitting device according to any one of claims 1 to 4 or comprising the quantum dot light-emitting device according to any one of claims 5 to 13.
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