CN114672314A - Core-shell structure quantum dot, preparation method thereof, quantum dot light-emitting film and diode - Google Patents
Core-shell structure quantum dot, preparation method thereof, quantum dot light-emitting film and diode Download PDFInfo
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Abstract
The invention discloses a quantum dot with a core-shell structure, a preparation method thereof, a quantum dot light-emitting film and a quantum dot light-emitting diode. The core-shell structure quantum dot comprises a core body of a first quantum dot and a shell layer coated on the core body, wherein the shell layer is made of a material comprising a second quantum dot, and the band gap of the second quantum dot is smaller than that of the first quantum dot. The quantum dot with the core-shell structure can enable electron-hole pairs to directly excite the second quantum dot in the shell layer to emit light, effectively improves the injection rate of current carriers, and is high in EQE and high in light emitting efficiency. And the shell thickness of the core-shell structure quantum dot can be controlled and adjusted, and the first quantum dot can be selected to control the emission wavelength of the core-shell structure quantum dot, so that the all-band core-shell structure quantum dot can be obtained. The quantum dot light-emitting film and the quantum dot light-emitting diode have high EQE and high light-emitting efficiency.
Description
Technical Field
The invention belongs to the technical field of photoelectricity, and particularly relates to a quantum dot with a core-shell structure and a preparation method thereof, a quantum dot light-emitting film and a quantum dot light-emitting diode.
Background
Quantum dots are semiconductor nanoparticles, and excitons are confined in three dimensions due to quantum size effects, so the quantum dots are also called zero-dimensional materials, and the characteristic of the quantum dots enables the properties of the quantum dots to be different from those of bulk materials and general molecules, so that the quantum dots become the focus of attention of researchers in various fields. The quantum dots have a continuously wider excitation spectrum and a narrow and symmetrical emission spectrum, so that the quantum dots with different sizes and colors can be excited by a light source with a single wavelength, and have the advantages of narrow emission spectrum, wide color gamut, good stability, low manufacturing cost and the like, which cannot be realized by the traditional fluorescent dye. Meanwhile, compared with the traditional fluorescent material, the fluorescent material has higher fluorescence quantum efficiency, stronger fluorescence intensity, high molar extinction coefficient and larger Stokes shift, so that the fluorescent material can be used as a substitute material in the fields of display and illumination. With the continuous development of electronic science and technology, the demand of people on healthy life is continuously improved, and especially, the wide application of electronic devices in daily life is required to be higher.
In the past two decades, the efficiency and life parameters of the three primary colors of red, green and blue QLED device are widely concerned by researchers at home and abroad, and with the development of quantum dot material synthesis, the photoelectric performance of the device of the II-VI family quantum dot material can be comparable to the level of an Organic Light Emitting Diode (OLED) in commercial application. According to the QLEDs electroluminescence mechanism, carriers are injected through a cathode electrode and an anode electrode, and reach the quantum dot light emitting layer from an electron and hole transport layer to emit light in a combined mode.
In the current QLED device, the most widely used light emitting layer is core/shell quantum dots, i.e. traditional i-type and ii-type quantum dots, by coating a wide band gap shell material on the outer layer of the quantum dot core, so the injection and transmission of charges need to overcome the high potential barrier of the shell layer, which leads to the decrease of charge injection efficiency, and the ignition voltage of QLEDs inevitably increases because the carrier transmission needs to overcome the large potential barrier of the shell layer to reach the light emitting core, which also leads to the poor performance of the device. In addition, the emission peak wavelength of the I-type quantum dot core-shell structure is controlled by a light-emitting core, and because electrons and holes are all limited in the core, the band gap structure of the I-type quantum dot core-shell structure is difficult to effectively realize the full-wave band, and the red shift phenomenon is gradually weakened along with the increase of the size of the quantum dot, so that the control of the emission peak wavelength is difficult to a certain extent.
In addition, the quantum yield of the prepared solid film is sharply reduced due to the limitation of the quantum dot structure. Although the surface defects of the luminescent core can be modified by increasing the thickness of the shell layer and the dot spacing of the quantum dots after film formation can be increased, the quantum yield of the quantum dot film can be improved, but the problem that the quantum yield is gradually reduced and even quenched along with the increase of the shell layer caused by the core/shell structure also occurs, so that the photoelectric property of the QLED device prepared by the method is poor.
Therefore, how to obtain the full-waveband quantum dots through the quantum dot structure design and improve the carrier injection barrier in the quantum dot light-emitting diode to improve the device performance become the problems to be solved urgently.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a quantum dot with a core-shell structure and a preparation method thereof, so as to solve the technical problems of unsatisfactory photoelectric properties and difficulty in controlling emission peak wavelength caused by high potential barrier of a shell layer of the quantum dot with the core-shell structure.
The invention also aims to provide a quantum dot light-emitting diode with a quantum dot light-emitting film, which aims to solve the technical problems that the photoelectric performance of the quantum dot light-emitting diode is not ideal due to the fact that the quantum dots with the core-shell structures have high carrier injection barrier and emission peak wavelength is difficult to control in the existing quantum dot light-emitting diode.
In order to achieve the above object, according to an aspect of the present invention, there is provided a quantum dot with a core-shell structure. The core-shell structure quantum dot comprises a core body of a first quantum dot and a shell layer coated on the core body, wherein the shell layer is made of a material comprising a second quantum dot, and the band gap of the second quantum dot is smaller than that of the first quantum dot.
In one aspect of the invention, a preparation method of the core-shell structure quantum dot is provided. The preparation method of the core-shell structure quantum dot comprises the following steps:
preparing first quantum dots and preparing a dispersion liquid containing the first quantum dots;
mixing the dispersion liquid of the first quantum dots and the precursor solution of the second quantum dots, and carrying out second quantum dot generation reaction treatment; wherein the second quantum dot has a smaller band gap than the first quantum dot.
In yet another aspect of the present invention, a quantum dot light emitting film is provided. The quantum dot luminescent film comprises core-shell structure quantum dots, wherein the core-shell structure quantum dots are the core-shell structure quantum dots or the core-shell structure quantum dots prepared by the preparation method.
In yet another aspect of the present invention, a quantum dot light emitting diode is provided. The quantum dot light-emitting diode comprises an anode and a cathode which are oppositely arranged, and a quantum dot light-emitting layer arranged between the anode and the cathode; the quantum dot light-emitting layer contains the core-shell structure quantum dot or the core-shell structure quantum dot prepared by the preparation method or the quantum dot light-emitting film.
Compared with the prior art, the invention has the following technical effects:
the core-shell structure quantum dot adopts the second quantum dot with relatively narrow band gap as the shell material to coat the second quantum dot with relatively wide band gap as the core body. Therefore, the electron-hole pair can directly excite the quantum dot in the shell layer, namely the second quantum dot to emit light, carriers formed by electrons and holes can directly emit light in the shell layer in a combined mode, the situation that the carriers enter the core body quantum dot to emit light in a combined mode by overcoming the shell layer physical potential barrier as in the traditional core-shell quantum dot is avoided, and the injection rate of the carriers is effectively improved. Therefore, compared with the traditional core-shell quantum dot, the quantum dot with the core-shell structure has higher External Quantum Efficiency (EQE) and high luminous efficiency. And the shell thickness of the core-shell structure quantum dot can be controlled and adjusted, and the first quantum dot is controlled and selected to control the emission wavelength of the core-shell structure quantum dot, so that the all-band core-shell structure quantum dot can be obtained.
The preparation method of the core-shell structure quantum dot directly mixes the precursor solution of the second quantum dot with the first quantum dot dispersion liquid to grow the second quantum dot on the surface of the first quantum dot in situ and form a relatively narrow band gap shell layer. The core-shell structure quantum dot prepared by the preparation method has a firm structure, and has the advantages that the current carrier can be directly subjected to composite luminescence in the shell layer of the core-shell structure quantum dot, and the current carrier does not need to overcome the physical potential barrier of the shell layer and enter the core body to perform composite luminescence, so that the luminous efficiency of the core-shell structure quantum dot is effectively improved. And the generation of the first quantum dots and the thickness of a shell layer formed by the in-situ grown second quantum dots can be effectively controlled, so that the light-emitting wavelength of the core-shell structure quantum dots is adjusted, and the full-wave-band core-shell structure quantum dots can be obtained. In addition, the conditions of the preparation method of the core-shell structure quantum dot are easy to control, so that the prepared core-shell structure quantum dot has stable structure and performance, high efficiency and low cost.
The quantum dot light-emitting film and the quantum dot light-emitting diode have high EQE and high light-emitting efficiency because the quantum dot light-emitting film and the quantum dot light-emitting diode contain the quantum dot with the core-shell structure.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows an embodiment Cd of the present inventionxZn1-xA schematic structure diagram of the Se/CdSe core-shell structure quantum dots;
FIG. 2 is a schematic process flow diagram of a preparation method of a core-shell structure quantum dot according to an embodiment of the present invention;
fig. 3 is a schematic diagram of a structure of a quantum dot light emitting diode with a positive configuration according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of an inverse quantum dot light emitting diode structure according to an embodiment of the present invention;
FIG. 5 is TEM images of core-shell structured quantum dots provided in example 11 of the present invention and comparative example 11;
fig. 6 is TEM images of core-shell structured quantum dots provided in example 12 of the present invention and comparative example 12;
fig. 7 is TEM images of core-shell structured quantum dots provided in example 13 of the present invention and comparative example 13;
FIG. 8 is a graph of a QE test for the QED diodes provided in example 21 and comparative example 21 of the present invention;
FIG. 9 is a schematic diagram of the structures and band gap relationships of type I quantum dots, inverse type I quantum dots and type II quantum dots.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting, and that all other embodiments that can be made by one of ordinary skill in the art based on the embodiments described herein will fall within the scope of the invention without inventive faculty.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
The related names referred to in this specification explain:
type i quantum dots: is a shell structure, as shown in fig. 9(a), wherein the band gap range of the core quantum dot is within the band gap range of the shell quantum dot.
Inverse i-type quantum dots: is a shell structure, as shown in fig. 9(B), wherein the band gap range of the shell quantum dot is within the band gap range of the core quantum dot;
type II quantum dots: the quantum dots are of a shell layer structure, wherein the lower limit value of the band gap range of the shell layer quantum dots is larger than the lower limit value of the band gap range of the core body quantum dots and is smaller than the upper limit value of the band gap range of the core body quantum dots; and the upper limit value of the band gap range of the shell layer quantum dot is greater than the upper limit value of the band gap range of the core body quantum dot, as shown in fig. 9 (C);
or the upper limit value of the band gap range of the shell layer quantum dots is larger than the lower limit value of the band gap range of the core body quantum dots and smaller than the upper limit value of the band gap range of the core body quantum dots; and the lower limit of the band gap range of the shell quantum dot is smaller than the lower limit of the band gap range of the core quantum dot, as shown in fig. 9 (D).
In one aspect, the embodiment of the invention provides a core-shell structure quantum dot. The core-shell structure quantum dot is a core-shell composite structure, namely comprises a core body and a shell layer coated on the core body. Wherein the core body includes a first quantum dot as a crystal nucleus; the material of the shell layer comprises a second quantum dot, and the band gap of the second quantum dot is smaller than that of the first quantum dot, namely the band gap of the second quantum dot is narrower than that of the first quantum dot. Therefore, as the shell layer contains the second quantum dots with relatively narrow band gaps, the carriers formed by electrons and holes can directly excite the second quantum dots to emit light, namely the carriers can directly carry out compound light emission in the shell layer, and the shell layer physical barrier does not need to be overcome to enter the core body to excite the first quantum dots contained in the core body to emit light. Therefore, the quantum dot with the core-shell structure provided by the embodiment of the invention has the advantages that the injection rate of a carrier is increased, the EQE is high, and the luminous efficiency is improved.
In addition, the shell thickness of the core-shell structure quantum dot in the embodiment of the invention can be adjusted by controlling and adjusting the coating process conditions, and the first quantum dot is controlled and selected to control the emission wavelength of the core-shell structure quantum dot in the embodiment of the invention, so that the all-band core-shell structure quantum dot in the invention can be obtained.
In an embodiment, the first quantum dot is CdxZn1-xSe; wherein CdxZn1-x1 > x.gtoreq.0 in Se, preferably 1 > x.gtoreq.0 in SeX is more than or equal to 0.7 and more than or equal to 0.3. These types of first quantum dots have relatively wide bandgaps, and quantum dot cores of different wavelength ranges can also be formed through selection of the first quantum dots. When the first quantum dot is CdxZn1-xIn the case of Se, the quantum dot core with the wavelength range of 420-650nm can be obtained by adjusting the proportion of cadmium in the core, namely the value of x.
In another embodiment, the second quantum dot is CdSe. The quantum dots have relatively narrow band gaps, for example, the band gap of the first quantum dot is narrow, so that electron-hole pairs can emit light compositely without overcoming a shell physical barrier and entering the core quantum dot as in the case of the traditional core-shell structure quantum dot, but the second quantum dot in the shell can be directly excited to emit light, the injection rate of carriers is effectively improved, and the EQE and the light emitting efficiency of the core-shell structure quantum dot in the embodiment of the invention are improved.
Therefore, in a specific embodiment, the first quantum dot is CdxZn1-xWhen Se is added, the second quantum dots are CdSe, and the core-shell structure quantum dots are in the core-shell structure shown in figure 1 and are formed by CdxZn1-xSe quantum dots are used as a core body, CdSe quantum dots are used as a coating layer to coat CdxZn1-xA Se quantum dot core.
The quantum dots CdSe with shell layers have band gaps relative to the quantum dot crystal nucleus CdxZn1-xThe Se is narrow, so that the injection rate of carriers is effectively improved, and the EQE and the luminous efficiency of the quantum dot with the core-shell structure in the embodiment of the invention are improved. And quantum dot crystal nucleus CdxZn1-xThe fluorescence quantum efficiency of Se is 30-50%, and Cd can be obtained by coating and passivating the outer layer of CdSexZn1-xThe fluorescence quantum efficiency of Se/CdSe is more than 75 percent; for the fluorescence quantum efficiency of quantum dots, the growth quality of the core and the shell has an influence on the quantum dots, and the quantum dot core CdxZn1-xThe lattice matching degree of Se and shell quantum dots CdSe is good, crystal face defects can not be generated on a core-shell interface of the quantum dots, namely crystal face defects can not be generated due to lattice dislocation, and the exciton quenching problem caused by defect states is effectively reducedAnd better fluorescence quantum efficiency can be kept. In addition, the wide band gap homogeneous alloy Cd is selectedxZn1- xSe is taken as the crystal nucleus of the quantum dot, the value of x can be adjusted and the control of the nucleation process can be realized by adjusting the proportion of cadmium in the crystal nucleus, and the crystal nucleus Cd of the quantum dot can be realizedxZn1-xThe wavelength of Se can be adjusted, and particularly, a quantum dot crystal nucleus with the wavelength range of 420-650nm can be obtained; a CdSe shell layer with a narrower band gap relative to the core grows on the outer layer of the core, the wavelength of an emission peak is regulated and controlled through the thickness of the CdSe shell layer, the full-band quantum dot with the core-shell structure can be obtained, the half peak width of the quantum dot with the core-shell structure is narrow, namely the first quantum dot CdxZn1-xThe target wavelength of the quantum dots with the core-shell structure in the embodiment of the invention can be realized through the combined action of Se and the second quantum dots CdSe on the synergistic regulation effect of the wavelength.
Further, the inventor finds that the quantum dots with the core-shell structure have certain dangling bonds and defect states on the surface of the luminescent shell layer, so that the fluorescence quantum yield of the quantum dots with the core-shell structure has a certain relation with the thickness of the CdSe shell layer, namely the emission wavelength, and the variation range is 50-85%. And the quantum dots with the core-shell structure can be obtained by regulating and controlling the component proportion of elements contained in the first quantum dots in the core body and the thickness of the shell layer, so that the quantum dots with different particle diameters can be obtained, and the quantum dots with the core-shell structure with different light-emitting wavelengths can be obtained. Therefore, in one embodiment, the particle size of the core body of the core-shell structure quantum dot is preferably controlled to be 3-12nm, and the particle size of the core-shell structure quantum dot is 5-18nm through adjustment of the thickness of the shell layer.
Therefore, the core-shell structure quantum dots in the embodiments are inverse i-type and core-shell structure quantum dots, which have small physical barriers, and the electrons and holes injected to the surface of the core-shell structure quantum dots are subjected to small interface barriers, and the electrons and holes are directly injected to the second quantum dot of the shell layer without crossing a wide-band gap shell layer to perform radiative recombination luminescence, so that the core-shell structure quantum dots EQE and the luminescence efficiency are high, and as determined, the EQE of the core-shell structure quantum dots in the embodiments of the present invention is 10 to 20%, and the luminescence efficiency is high.
Correspondingly, the embodiment of the invention provides a preparation method of the quantum dot with the core-shell structure. The process flow of the preparation method of the core-shell structure quantum dot is shown in fig. 2, and the preparation method comprises the following steps:
s01: preparing first quantum dots and preparing a dispersion liquid containing the first quantum dots;
s02: and mixing the dispersion liquid of the first quantum dots and the precursor solution of the second quantum dots, and carrying out second quantum dot generation reaction treatment.
Wherein the first quantum dot in step S01 is the core-shell first quantum dot described in the core-shell structure quantum dot, and thus, the method for preparing the first quantum dot may be prepared according to the existing method for preparing the corresponding first quantum dot. In one embodiment, a mixed solution for preparing the first quantum dots is directly used as a dispersion of the first quantum dots. In addition, the particle size of the first quantum dot may be controllably adjusted by the steps of the method for preparing the first quantum dot and the related process conditions, such that the particle size of the first quantum dot is preferably 3 to 12 nm.
In the step S02, the step of mixing the precursor solution of the second quantum dot with the dispersion of the first quantum dot and performing the reaction process of generating the second quantum dot is to directly grow the second quantum dot in situ on the surface of the first quantum dot and form a shell layer covering the first quantum dot, where the covered first quantum dot is a core body. Wherein the second quantum dot has a smaller band gap than the first quantum dot. Therefore, as described above, the prepared core-shell structure quantum dot is the quantum dot with the inverse I-type core-shell structure, and the carrier can directly excite the second quantum dot in the shell layer to emit light, so that the injection rate of the carrier is effectively improved, the EQE is improved, and the light emitting efficiency is higher. And the shell thickness of the core-shell structure quantum dot can be controlled and adjusted, and the first quantum dot is controlled and selected to control the emission wavelength of the core-shell structure quantum dot, so that the all-band core-shell structure quantum dot can be obtained.
In an embodiment, in the step S02, the method for mixing the dispersion of the first quantum dots and the precursor solution of the second quantum dots includes the following steps:
and gradually adding the precursor solution of the second quantum dot into the dispersion liquid of the first quantum dot to perform mixing treatment, heating to the reaction treatment temperature for generating the second quantum dot, and performing the reaction treatment in the step S02.
In a preferred embodiment, the temperature of the dispersion of the first quantum dots is first raised to the temperature of the second quantum dot formation reaction treatment, the precursor solution of the second quantum dots is gradually added to the dispersion of the first quantum dots to perform the mixing treatment, and then the temperature is raised to the reaction treatment temperature of the second quantum dot formation to perform the reaction treatment in step S02.
The formation of the second quantum dots is controlled by the feeding mode of the precursor solution of the second quantum dots, so that the generated second quantum dots can effectively grow on the surfaces of the first quantum dots in situ, can be uniformly distributed, and can better coat the first quantum dots, thereby forming the core-shell structure quantum dots with stable structure and stable photoelectric performance.
In another embodiment, the mixing process is performed on the dispersion of the first quantum dots and the precursor solution of the second quantum dots according to a ratio of a thickness of a shell layer formed by the generated second quantum dots to 2 to 6 nm. And the mixing treatment between the dispersion liquid of the first quantum dots and the precursor solution of the second quantum dots is controlled by the proportion of 2-6nm of the thickness of the shell layer formed on the surface of the particles containing the first quantum dots in situ in the dispersion liquid. In this way, the shell thickness of the core-shell structure quantum dot is controlled by controlling the feeding amount of the precursor solution of the second quantum dot, so that the adjustment and control of the light-emitting wavelength of the core-shell structure quantum dot are realized.
As in the specific embodiment, when the first quantum dot is CdxZn1-xAnd when Se is generated, the precursor solution of the second quantum dot is a salt solution for forming CdSe. By front of said second quantum dotControlling a driving body so as to control the type of quantum dots in a shell layer, thereby generating CdxZn1-xAnd the Se/CdSed core-shell structure quantum dots.
In addition, the reaction treatment temperature in step S02 can be flexibly determined according to the temperature for generating the second quantum dots, and if the precursor solution of the second quantum dots is the precursor solution of CdSed, the reaction treatment temperature is preferably 220-.
Therefore, the preparation method of the core-shell structure quantum dot directly mixes the precursor solution of the second quantum dot with the first quantum dot dispersion liquid to grow the second quantum dot on the surface of the first quantum dot in situ and form a relatively narrow band gap shell layer. Therefore, the generated core-shell structure quantum dot has a firm structure, can generate full-waveband core-shell structure quantum dots and high carrier injection rate as described above, and has high EQE and high luminous efficiency. In addition, the conditions of the preparation method of the core-shell structure quantum dot are easy to control, so that the prepared core-shell structure quantum dot has stable structure and performance, high efficiency and low cost.
On the other hand, the embodiment of the invention also provides a quantum dot light-emitting film. The quantum dot light-emitting film comprises core-shell structure quantum dots, wherein the core-shell structure quantum dots are core-shell structure quantum dots or core-shell structure quantum dots prepared by the preparation method according to the embodiment of the invention. Therefore, the quantum dot luminescent film provided by the embodiment of the invention comprises the core-shell structure quantum dots, so that the quantum yield of the quantum dot luminescent film is high, the luminescence EQE is high, and the luminescence efficiency is high.
In addition, the thickness of the quantum dot light-emitting film can be flexibly controlled and regulated according to the requirements of specific applications, and the film forming method can also be flexibly selected according to the specific applications.
In another aspect, an embodiment of the present invention further provides a quantum dot light emitting diode, where the quantum dot light emitting diode includes an anode and a cathode that are oppositely disposed, and a quantum dot light emitting functional layer that is combined between the anode and the cathode in a stacked manner, and the quantum dot light emitting functional layer includes a quantum dot light emitting layer. The quantum dot light-emitting layer contains the quantum dot with the core-shell structure or the quantum dot light-emitting film. In this way, the quantum dot light-emitting layer in the quantum dot light-emitting diode according to the embodiment of the invention contains the quantum dot with the core-shell structure or includes the quantum dot light-emitting film. Therefore, the quantum yield in the quantum dot light-emitting layer is high, and after carriers injected by the anode and the cathode are transmitted into the quantum dot light-emitting layer, the carriers can be directly subjected to composite light-emitting in the shell layer of the core-shell structure quantum dot, so that the EQE of the quantum dot light-emitting diode is improved, and the light-emitting efficiency is high.
In some embodiments, quantum dot light emitting diodes of embodiments of the present invention may be of positive and inverse type.
In one embodiment, the positive type quantum dot light emitting diode has a structure as shown in fig. 3, and includes a stacked structure of an anode 1 and a cathode 5 which are oppositely disposed, wherein the anode 1 may be stacked and bonded on a substrate 01, and a quantum dot light emitting function layer is stacked and bonded between the anode 1 and the cathode 5. The quantum dot light-emitting functional layer comprises a quantum dot light-emitting layer 3. Further, a hole function layer such as a hole injection layer (not shown in fig. 3), a hole transport layer 3, and an electron blocking layer (not shown in fig. 3) may be further disposed between the quantum dot light emitting layer 3 and the anode 1; an electron-functional layer such as an electron transport layer 4, an electron injection layer (not shown in fig. 3), and a hole blocking layer (not shown in fig. 3) may be further disposed between the cathode 5 and the quantum dot light emitting layer 3.
In another embodiment, the structure of the quantum dot light emitting diode with the inversion structure is as shown in fig. 4, and comprises a laminated structure of an anode 1 and a cathode 5 which are oppositely arranged, wherein the cathode 5 can be laminated and combined on a substrate 01, and a quantum dot light emitting function layer is laminated and combined between the anode 1 and the cathode 5. The quantum dot light-emitting functional layer comprises a quantum dot light-emitting layer 3. Further, a hole function layer such as a hole injection layer (not shown in fig. 4), a hole transport layer 3, and an electron blocking layer (not shown in fig. 4) may be further disposed between the quantum dot light emitting layer 3 and the anode 1; an electron-functional layer such as an electron transport layer 4, an electron injection layer (not shown in fig. 4), and a hole blocking layer (not shown in fig. 4) may be further disposed between the cathode 5 and the quantum dot light emitting layer 3.
In further embodiments, substrate 01 comprises a rigid, flexible substrate, or the like;
the anode 1 includes: one or more of indium tin oxide, fluorine-doped tin oxide, indium zinc oxide, graphene and carbon nanotubes; in order to form a high-quality electron transport material thin film, the anode 1 needs to be subjected to a pretreatment process. Such as can be processed according to the following basic processing steps: cleaning a substrate 01 containing the anode 1 with a cleaning agent to primarily remove stains on the surface, then sequentially and respectively ultrasonically cleaning in deionized water, acetone, absolute ethyl alcohol and deionized water for 20min to remove impurities on the surface, and finally blowing the substrate with high-purity nitrogen to obtain the anode 1.
The hole injection layer includes PEODT: PSS (poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid)), WoO3、MoO3、NiO、V2O5CuO, HATCN (2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene), CuS, molybdenum sulfide, tungsten sulfide, and the like.
The hole transport layer 2 may be a small molecule organic substance or a high molecule conductive polymer, and includes: TFB (Poly [ (9, 9-di-N-octylfluorenyl-2, 7-diyl) -alt- (4,4' - (N- (4-N-butyl) phenyl) -diphenylamine)]) PVK (polyvinylcarbazole), TCTA (4,4 '-tris (carbazol-9-yl) triphenylamine), TAPC (4,4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline)]) Poly-TBP, Poly-TPD, NPB (N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine), CBP (4,4' -bis (9-carbazole) biphenyl), peot: PSS, MoO3、WoO3、NiO、CuO、V2O5CuS, etc.; the hole transport layer 2 can be arranged on the anode 2 or the cathode 5 on a spin coater, and a prepared solution of the hole transport material is used for spin coating to form a film; the film thickness is controlled by adjusting the concentration of the solution, the spin-coating speed and the spin-coating time, and then a thermal annealing process is performed at an appropriate temperature.
The quantum dot light-emitting layer 3 comprises the core-shell structure quantum dot or the quantum dot light-emitting film structure, and according to the actual requirement of the quantum dot light-emitting diode, the quantum dot light-emitting layer 3 can comprise any one of a red light quantum dot light-emitting layer, a green light quantum dot light-emitting layer and a blue light quantum dot light-emitting layer, through the selection of the light-emitting wavelength of the core-shell structure quantum dot. The thickness of the quantum dot light emitting layer 3 may be conventional, for example, 20 to 60 nm. The quantum dot light emitting layer 3 may be prepared as follows: and (3) spin-coating the prepared quantum dot light emitting layer 3 slurry with a certain concentration on a substrate spin coater coated with the hole transport layer to form a film, controlling the thickness of the light emitting layer to be about 20-60 nm by adjusting the concentration of the solution, the spin-coating speed and the spin-coating time, and drying at a proper temperature.
The electron transport layer 4 comprises ZnO, TiO2、SnO、Ta2O3、AlZnO、ZnSnO、InSnO、Alq3、Ca、Ba、CsF、LiF、CsCO3、ZnMgO、ZnMgLiO、ZnInO、ZrO、Alq3One or more of TAZ, TPBI, PBD, BCP, Bphen, the thickness may be, but is not more than in recent years, 20-60 nm. The electron transport layer 4 is an electron transport material thin film, which can be formed by a spin coating process, including but not limited to drop coating, spin coating, soaking, coating, printing, vapor deposition, and the like. For example, a prepared precursor solution with a certain concentration is spin-coated to form a film, the thickness of the electron transport layer 4 is controlled to be about 20-60 nm by adjusting the concentration of the solution, the spin-coating speed (preferably, the rotation speed is 2000-6000 rpm) and the spin-coating time, and then the film is annealed at a temperature of 200 ℃ -250 ℃ (for example, 200 ℃) to form a film. The step can be annealing in air or in nitrogen atmosphere, and the annealing atmosphere is selected according to actual needs.
The cathode 5 includes: al, Ag, Au, Ca, Ba, Cu, Mo, or an alloy thereof. In an embodiment, the metal layer may be formed by evaporation, for example, a layer of metal silver or aluminum with a thickness of 100nm may be, but not limited to, thermally evaporated through a mask in an evaporation chamber to serve as the cathode 5, or a nano Ag wire or a Cu wire is used, which has a smaller resistance so that carriers can be smoothly injected.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art and obviously show the advanced performance of the quantum dot with the core-shell structure and the preparation method thereof according to the embodiment of the present invention, the above technical solution is illustrated by a plurality of embodiments below.
1. Core-shell structure quantum dot and preparation method embodiment thereof
Example 11
The embodiment provides a quantum dot with a core-shell structure and a preparation method thereof. The core-shell structure quantum dot is Cd0.6Zn0.4Se/CdSe quantum dots, wherein Cd0.6Zn0.4Se/CdSe is nuclear quantum dots, CdSe is shell quantum dots, and the average particle size is 11 nm.
The preparation method of the core-shell structure quantum dot comprises the following steps:
s11: weighing 5mmol of selenium simple substance and 5ml of TOP, and mixing to prepare 1M Se/TOP anion precursor solution; weighing 5mmol of cadmium oxide, 5ml of oleic acid and 20ml of octadecene, removing water and oxygen in vacuum or inert atmosphere, and heating to 250 ℃ to obtain clear 0.2M Cd (OA)2A solution; weighing 0.5mmol of cadmium oxide, 5mmol of zinc acetate, 6mL of oleic acid and 20mL of ODE, mixing, heating to 100 ℃, removing water and oxygen in vacuum or inert atmosphere, and keeping the temperature for a period of time until a uniform mixed precursor solution is formed; heating the solution to 300 ℃, then quickly injecting 1ml of Se/TOP into the solution for reaction for 30min to obtain the alloy quantum dot crystal nucleus Cd0.6Zn0.4Se；
S12: to the above Cd0.6Zn0.4The Se nucleus solution is slowly added with 2ml Se/TOP solution and 10ml Cd (OA) required for growth shell2In Cd0.6Zn0.4Growing a CdSe shell layer on the Se outer layer; keeping the temperature for reaction for 30min, cooling to room temperature, taking n-heptane as a solvent and ethanol as a non-solvent, precipitating and purifying the quantum dots for three times to obtain Cd0.6Zn0.4Se/CdSe quantum dots.
Example 12
The embodiment provides a quantum dot with a core-shell structure and a preparation method thereof. The core-shell structure quantum dot is Cd0.3Zn0.7Se/CdSe quantum dots, wherein Cd0.3Zn0.7Se is the quantum dots of the nuclear body,CdSe is shell quantum dots, and the average particle size is 10 nm.
The preparation method of the core-shell structure quantum dot comprises the following steps:
s11: weighing 5mmol of selenium simple substance and 5ml of TOP, and mixing to prepare 1M Se/TOP anion precursor solution; weighing 5mmol of cadmium oxide, 5ml of oleic acid and 20ml of octadecene, removing water and oxygen in vacuum or inert atmosphere, and heating to 250 ℃ to obtain clear 0.2M Cd (OA)2A solution; weighing 0.3mmol of cadmium oxide, 5mmol of zinc acetate, 6mL of oleic acid and 20mL of ODE, mixing, heating to 100 ℃, removing water and oxygen in vacuum or inert atmosphere, and keeping the temperature for a period of time until a uniform mixed precursor solution is formed; heating the solution to 310 ℃, then quickly injecting 1ml of Se/TOP into the solution for reaction for 30min to obtain the alloy quantum dot crystal nucleus Cd0.3Zn0.7Se；
S12: to the above Cd0.3Zn0.7The Se nucleus solution is slowly added with 1ml Se/TOP solution and 5ml Cd (OA) required for growth shell2In Cd0.3Zn0.7Growing a CdSe shell layer on the Se outer layer; keeping the temperature for reaction for 30min, cooling to room temperature, taking n-heptane as a solvent and ethanol as a non-solvent, precipitating and purifying the quantum dots for three times to obtain Cd0.3Zn0.7Se/CdSe quantum dots.
Example 13
The embodiment provides a core-shell structure quantum dot and a preparation method thereof. The core-shell structure quantum dot is Cd0.15Zn0.85Se/CdSe quantum dots, wherein Cd0.15Zn0.85Se is a nuclear body quantum dot, CdSe is a shell layer quantum dot, and the average grain diameter is 8 nm.
The preparation method of the core-shell structure quantum dot comprises the following steps:
s11: weighing 5mmol of selenium simple substance and 5ml of TOP, and mixing to prepare 1M Se/TOP anion precursor solution; weighing 5mmol of cadmium oxide, 5ml of oleic acid and 20ml of octadecene, removing water and oxygen in vacuum or inert atmosphere, and heating to 250 ℃ to obtain clear 0.2M Cd (OA)2A solution; weighing 0.15mmol of cadmium oxide, 5mmol of zinc acetate, 6mL of oleic acid and 20mL of ODE, mixing, heating to 100 ℃, removing water and oxygen in vacuum or inert atmosphere, and keeping the temperature for a period of time until the mixture is uniformMixed precursor solution of (a); heating the solution to 310 ℃, then quickly injecting 1ml of Se/TOP into the solution for reaction for 30min to obtain the alloy quantum dot crystal nucleus Cd0.15Zn0.85Se；
S12: to the above Cd0.15Zn0.851ml of Se/TOP solution required for the growth of the shell and 5ml of Cd (OA) are slowly added to the Se nucleus solution2In Cd0.15Zn0.85Growing a CdSe shell layer on the Se outer layer; keeping the temperature for reaction for 30min, cooling to room temperature, taking n-heptane as a solvent and ethanol as a non-solvent, precipitating and purifying the quantum dots for three times to obtain Cd0.15Zn0.85Se/CdSe quantum dots.
Comparative example 11
The comparative example provides a core-shell structure quantum dot and a preparation method thereof. The core-shell structure quantum dot is Cd0.6Zn0.4Se/ZnS quantum dots, wherein Cd0.6Zn0.4Se is a nuclear body quantum dot, ZnS is a shell layer quantum dot, and the average grain diameter is 8 nm.
The preparation method of the core-shell structure quantum dot comprises the following steps:
s11: weighing 5mmol of selenium simple substance and 5ml of TOP, and mixing to prepare 1M Se/TOP anion precursor solution; weighing 5mmol of cadmium oxide, 5ml of oleic acid and 20ml of octadecene, removing water and oxygen in vacuum or inert atmosphere, and heating to 250 ℃ to obtain clear 0.2M Cd (OA)2A solution; weighing 0.5mmol of cadmium oxide, 5mmol of zinc acetate, 6mL of oleic acid and 20mL of ODE, mixing, heating to 100 ℃, removing water and oxygen in vacuum or inert atmosphere, and keeping the temperature for a period of time until a uniform mixed precursor solution is formed; heating the solution to 300 ℃, then quickly injecting 1ml of Se/TOP into the solution for reaction for 30min to obtain the alloy quantum dot crystal nucleus Cd0.6Zn0.4Se；
S12: to the above Cd0.6Zn0.42ml of S/TOP solution required for growth shell is slowly added into the Se crystal nucleus solution, and then Cd is added0.6Zn0.4Growing a ZnS shell layer on the Se outer layer; keeping the temperature for reaction for 30min, cooling to room temperature, taking n-heptane as a solvent and ethanol as a non-solvent, precipitating and purifying the quantum dots for three times to obtain Cd0.6Zn0.4Se/ZnS quantum dots.
Comparative example 12
The comparative example provides a core-shell structure quantum dot and a preparation method thereof. The core-shell structure quantum dot is Cd0.3Zn0.7Se/ZnS quantum dots, wherein Cd0.3Zn0.7Se is a nuclear body quantum dot, ZnS is a shell layer quantum dot, and the average grain diameter is 6 nm.
The preparation method of the core-shell structure quantum dot comprises the following steps:
prepared according to the preparation method of comparative example 11, and is different from comparative example 11 in that: when synthesizing crystal nucleus, 0.2mmol of cadmium oxide, 5mmol of zinc acetate, 6mL of oleic acid and 20mL of ODE are weighed and mixed to prepare the generated Cd0.3Zn0.7Se/ZnS quantum dots.
Comparative example 13
The comparative example provides a core-shell structure quantum dot and a preparation method thereof. The core-shell structure quantum dot is Cd0.15Zn0.85Se/ZnS quantum dots, wherein Cd0.15Zn0.85Se is a nuclear body quantum dot, ZnS is a shell layer quantum dot, and the average grain diameter is 5 nm.
The preparation method of the core-shell structure quantum dot comprises the following steps:
prepared according to the preparation method of comparative example 11, and is different from comparative example 11 in that: when synthesizing crystal nucleus, 0.2mmol of cadmium oxide, 5mmol of zinc acetate, 6mL of oleic acid and 20mL of ODE are weighed and mixed to prepare the generated Cd0.15Zn0.85Se/ZnS quantum dots.
2. Quantum dot light emitting film and quantum dot light emitting diode embodiments
Example 21
The embodiment provides a quantum dot light-emitting film and a quantum dot light-emitting diode. The structure of the quantum dot light-emitting diode embodiment is as shown in figure 3, and the positive quantum dot light-emitting diode embodiment comprises an ITO substrate/PEDOT, a PSS hole injection layer/TFB hole transport layer/blue core-shell Cd0.6Zn0.4Se/CdSe quantum dot light-emitting layer/ZnO electron transport layer/Ag anode. Wherein "/" represents the connection relationship of the laminated and combined layer structure, and the core-shell Cd0.6Zn0.4Se/CdSe Quantum dots to example 11Cd (2)0.6Zn0.4Se/CdSe core quantum dots.
The quantum dot light-emitting diode is prepared into each layer structure according to the following method:
s21, substrate cleaning: rubbing and washing the ITO substrate glass with isopropanol and acetone, washing with a detergent if necessary, then sequentially ultrasonically washing with acetone, deionized water and absolute ethyl alcohol for 15min, then rapidly drying by using a nitrogen gun, and finally treating for 10min under air plasma;
s22, PEDOT, PSS injection layer: and (3) spin-coating PEDOT (PSS) on the ITO substrate at the rotating speed of 4000rpm for 40 s. Annealing at 150 ℃ for 15min in the air after the spin coating is finished, and then transferring the mixture into a glove box filled with nitrogen;
s23, a hole transport layer: spin-coating a 10mg/mLTFB chlorobenzene solution on glass/ITO/PEDOT PSS at a rotating speed of 2000rpm for 35s, and annealing for 30min at 140-160 ℃ in a glove box after the spin-coating is finished;
s24, quantum dot layer: spin-coating quantum dots dissolved in n-octane solution on the hole transport layer at 2000rpm for 50 s; the concentration of the blue quantum dots is between 15 and 30mg/mL, and annealing is carried out for 10min at 100 ℃;
s25, an electronic transmission layer: spin-coating ZnO ethanol solution on the quantum dot layer at 2000rpm for 30s at ZnO concentration of 25mg/mL, and annealing at 80 deg.C for 15min in a glove box;
s26, putting the sample subjected to spin coating into a vacuum cavity, and evaporating a top layer electrode Ag, wherein the thickness of the electrode is 100 nm;
and S27, packaging by using curing glue after evaporation is finished, and isolating water and oxygen.
Example 22
The embodiment provides a quantum dot light-emitting film and a quantum dot light-emitting diode embodiment. The structure of the quantum dot light emitting diode is the same as that of the quantum dot light emitting layer in example 21 except that the structure is different. Wherein the quantum dot in the quantum dot light-emitting layer is Cd provided in embodiment 120.3Zn0.7Se/CdSe quantum dots.
Example 23
The embodiment provides a quantum dot light-emitting film and a quantum dot light-emitting diode embodiment. The structure of the quantum dot light emitting diode is the same as that of the quantum dot light emitting layer in example 21 except that the structure is different. Wherein the quantum dot in the quantum dot light-emitting layer is Cd provided in embodiment 130.15Zn0.85Se/CdSe quantum dots.
Comparative example 21
The embodiment provides a quantum dot light-emitting film and a quantum dot light-emitting diode embodiment. The structure of the quantum dot light emitting diode is the same as that of the quantum dot light emitting layer in example 21 except that the structure is different. Wherein the quantum dots in the quantum dot light-emitting layer are Cd provided by comparative example 110.6Zn0.4Se/ZnS quantum dots.
Comparative example 22
The embodiment provides a quantum dot light-emitting film and a quantum dot light-emitting diode embodiment. The structure of the quantum dot light emitting diode is the same as that of the quantum dot light emitting layer in example 21 except that the structure is different. Wherein the quantum dots in the quantum dot light-emitting layer are Cd provided by comparative example 120.3Zn0.7Se/ZnS quantum dots.
Comparative example 23
The embodiment provides a quantum dot light-emitting film and a quantum dot light-emitting diode embodiment. The structure of the quantum dot light emitting diode is the same as that of the quantum dot light emitting layer in example 21 except that the structure is different. Wherein the quantum dots in the quantum dot light-emitting layer are Cd provided in comparative example 130.15Zn0.85Se/ZnS quantum dots.
3. Nuclear shell structure quantum dot and quantum dot light-emitting diode related photoelectric performance test
3.1 the core-shell structure quantum dots provided in the above examples 11 to 13 and comparative examples 11 to 13 were respectively subjected to TEM analysis, wherein TEM photographs of the core-shell structure quantum dots provided in examples 11 and 11 are shown in fig. 5, TEM photographs of the core-shell structure quantum dots provided in examples 12 and 12 are shown in fig. 6, and TEM photographs of the core-shell structure quantum dots provided in examples 13 and 13 are shown in fig. 7. As can be seen from fig. 5 to 7, the particle size range of the core-shell structure quantum dots synthesized in the embodiment of the present invention is 8 to 11nm, and the particle size of the corresponding comparative core-shell structure quantum dots is smaller than 8nm, meanwhile, the core-shell structure quantum dots in the embodiment of the present invention are all in a regular spherical shape, and the problem of irregular shape of the quantum dots does not occur due to the increase of the particle size. Therefore, compared with the traditional core-shell structure quantum dot, the core-shell structure quantum dot provided by the embodiment of the invention has the advantages of relatively larger particle size, uniform particle size and good spherical appearance.
3.2 the quantum dots of the core-shell structure provided in the above examples 11 to 13 and comparative examples 11 to 13, and the quantum dot light emitting diodes provided in the examples 21 to 23 and comparative examples 21 to 23 were respectively subjected to the related performance tests in the following table 1, and the test results are shown in the following table 1, wherein the EQE test curve of the quantum dot light emitting diodes provided in the examples 21 and comparative examples 21 is shown in fig. 8.
The service life test of the quantum dot light-emitting diode adopts a 128-channel service life test system customized by Guangzhou New View company. The system is constructed by driving a QLED by a constant voltage and constant current source and testing the change of voltage or current; a photodiode detector and test system to test the variation of brightness (photocurrent) of the QLED; the luminance meter test calibrates the luminance (photocurrent) of the QLED.
TABLE 1
| PL/FWHM(nm) | QY(％) | D(nm) | EQE(％) | |
| Example 1 | 624/20 | 85 | 11 | 15.5 |
| Example 2 | 532/23 | 82 | 10 | 18 |
| Example 3 | 472/22 | 75 | 8 | 12 |
| Comparative example 1 | 618/24 | 72 | 8 | 7 |
| Comparative example 2 | 535/28 | 70 | 6 | 6 |
| Comparative example 3 | 467/26 | 65 | 5 | 3 |
As can be seen from table 1, the EQE of the quantum dot with the core-shell structure according to the embodiment of the present invention is significantly improved compared with the EQE of the quantum dot with the traditional core-shell structure, and the light emitting efficiency is high. And the shell layer thickness of the quantum dot with the core-shell structure in the embodiment of the invention can be controlled and adjusted, and the element of the quantum dot with the core body can be controlled and selected to control and adjust the emission wavelength of the quantum dot with the core-shell structure in the embodiment of the invention, so that the quantum dot with the core-shell structure in a full waveband can be obtained.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A core-shell structure quantum dot comprises a core body of a first quantum dot and a shell layer coated on the core body, and is characterized in that: the material of the shell layer comprises second quantum dots, and the band gaps of the second quantum dots are smaller than those of the first quantum dots.
2. The core-shell quantum dot of claim 1, wherein: the first quantum dot is CdxZn1-xSe; wherein, x is more than 1 and is more than or equal to 0; the second quantum dot is CdSe.
3. The core-shell quantum dot of claim 2, wherein: the fluorescence quantum efficiency of the core-shell structure quantum dot is more than 75%; and/or
X is more than or equal to 0.7 and more than or equal to 0.3.
4. The core-shell structure quantum dot according to any of claims 1 to 3, characterized in that: the particle size of the core body is 3-12 nm; and/or
The particle size of the core-shell structure quantum dot is 5-18 nm.
5. A preparation method of a core-shell structure quantum dot is characterized by comprising the following steps:
preparing first quantum dots and preparing a dispersion liquid containing the first quantum dots;
mixing the dispersion liquid of the first quantum dots and the precursor solution of the second quantum dots, and carrying out second quantum dot generation reaction treatment; wherein the second quantum dot has a smaller band gap than the first quantum dot.
6. The method of claim 5, wherein: the method for mixing the dispersion liquid of the first quantum dots and the precursor solution of the second quantum dots comprises the following steps:
and gradually adding the precursor solution into the dispersion liquid of the first quantum dots for mixing treatment, and then heating to the temperature for the second quantum dot generation reaction treatment.
7. The method of claim 5 or 6, wherein: the dispersion liquid of the first quantum dots and the precursor solution of the second quantum dots are mixed according to the proportion that the thickness of a shell layer formed by the generated second quantum dots is 2-6 nm.
8. The method of claim 5 or 6, wherein: the first quantum dot is CdxZn1-xSe, and the precursor solution of the second quantum dot is a CdSe-generating salt solution.
9. A quantum dot luminescent film is characterized in that the quantum dot luminescent film comprises quantum dots, wherein the quantum dots are the core-shell structure quantum dots according to any one of claims 1 to 4 or the core-shell structure quantum dots prepared by the preparation method according to any one of claims 5 to 8.
10. The quantum dot light-emitting diode is characterized by comprising an anode and a cathode which are oppositely arranged, and a quantum dot light-emitting functional layer which is combined between the anode and the cathode in a laminating way, wherein the quantum dot light-emitting functional layer comprises a quantum dot light-emitting layer; the quantum dot light-emitting layer comprises the core-shell structure quantum dot as claimed in any one of claims 1 to 4 or the core-shell structure quantum dot prepared by the preparation method as claimed in any one of claims 5 to 8 or the quantum dot light-emitting film as claimed in claim 9.
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