CN115692564A - Heterojunction nanomaterial, electron transport thin film, and display device - Google Patents
Heterojunction nanomaterial, electron transport thin film, and display device Download PDFInfo
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Abstract
The invention relates to a heterojunction nano material, an electron transport film and a display device. The heterojunction nano-material comprises: the heterojunction-type solar cell comprises a first metal selenide and a second metal selenide compounded on the first metal selenide, wherein the second metal selenide is silver-doped metal selenide, and a heterojunction is formed between the first metal selenide and the second metal selenide. The heterojunction nano material contains a first metal selenide and a second metal selenide compounded on the first metal selenide, the second metal selenide is silver-doped metal selenide, and a heterojunction is formed between the first metal selenide and the second metal selenide, so that free electron migration is facilitated, and the heterojunction nano material has higher conductivity; in addition, compared with a pure metal selenide nanometer material, the heterojunction nanometer material has a better light scattering effect.
Description
Technical Field
The invention relates to the technical field of display, in particular to a heterojunction nano material, an electron transmission film and a display device.
Background
With the rapid development of display technologies, display devices such as quantum dot light emitting diodes (QLEDs) have received much attention. The quantum dot light-emitting diode (QLED) using the semiconductor quantum dot material as the light-emitting layer has wide application prospects in the fields of flat panel display, solid state lighting and the like due to the good characteristics of high color purity, high light-emitting efficiency, adjustable light-emitting color, stable devices and the like.
For quantum dot light-emitting diodes, a common electron transport layer material is zinc oxide, and zinc oxide easily causes electric leakage of a device when used as an electron transport layer due to more defect states of zinc oxide, and zinc oxide has poor stability in the environment, so that a display device has a larger problem in stability.
Disclosure of Invention
Based on the heterojunction nano material, the electron transmission film and the display device, the heterojunction nano material is high in conductivity and has a good light scattering effect, and when the heterojunction nano material is used as an electron transmission layer of the display device, the light emitting performance and the stability of the display device can be effectively improved.
The technical scheme of the invention for solving the technical problems is as follows.
A heterojunction nanomaterial comprising:
the heterojunction solar cell comprises a first metal selenide and a second metal selenide compounded on the first metal selenide, wherein the second metal selenide is silver-doped metal selenide, and a heterojunction is formed between the first metal selenide and the second metal selenide.
In some of these embodiments, in the heterojunction nanomaterial, the first metal selenide is a nanorod and the second metal selenide is nanoparticulate and distributed on the surface of the first metal selenide.
In some embodiments, the first metal selenide is 20nm to 30nm in diameter and 30nm to 100nm in length.
In some embodiments, the second metal selenide has a particle size of 10nm to 20nm in the heterojunction nanomaterial.
In some embodiments, the first metal selenide is selected from SnSe, sb, and combinations thereof 2 Se 3 、In 4 Se 3 、ZnSe、MoSe 2 And WSe 2 At least one of (1).
In some embodiments, the second metal selenide is selected from AgSnSe, agSbSe, in the heterojunction nanomaterial 2 、AgIn 3 Se 3 、AgZnSe、AgMoSe 2 And AgWSe 2 At least one of (1).
In some embodiments, the mass ratio of the second metal selenide to the first metal selenide in the heterojunction nanomaterial is (0.2-0.5): 1.
The invention provides an electron transport film, and the components of the electron transport film comprise the heterojunction nano material.
The present invention provides a display device including:
the anode, the quantum dot light-emitting layer, the electron transmission layer and the cathode are sequentially stacked;
the components of the electron transport layer comprise the heterojunction nanometer material, or the electron transport layer is the electron transport film.
In some of the embodiments, the display device further includes:
a hole transport layer disposed between the anode and the light emitting layer; the component of the hole transport layer comprises a third metal selenide, and the third metal selenide is a P-type doped metal selenide.
In some embodiments, the P-type doping element is at least one selected from the group consisting of Sn, zn, and Mo.
In some of the embodiments, the metal selenide in the third metal selenide is selected from SnSe, sb 2 Se 3 、In 4 Se 3 、ZnSe、MoSe 2 And WSe 2 Wherein the P-type doping element is different from an element contained in the metal selenide in the third metal selenide.
In some embodiments, the P-type doped metal selenide in the display device has the formula (Sn) x Sb 1-x ) 2 Se 3 (ii) a Wherein x is more than 0 and less than 0.9.
In some of these embodiments, the anode is at least one of indium tin oxide, indium zinc oxide, and aluminum-doped zinc oxide.
In some embodiments, the material of the quantum dot light emitting layer is selected from at least one of CdS, znSe, and CdZnS.
In some of the embodiments, the cathode is made of a material selected from at least one of Ag, au, al, and Cu.
Compared with the prior art, the heterojunction nano material and the display device have the following beneficial effects:
the heterojunction nano material contains a first metal selenide and a second metal selenide compounded on the first metal selenide, wherein the second metal selenide is silver-doped metal selenide, and a heterojunction is formed between the first metal selenide and the second metal selenide, so that free electron migration is facilitated, and the heterojunction nano material has higher conductivity; in addition, compared with a pure metal selenide nanometer material, the heterojunction nanometer material has a better light scattering effect.
According to the display device, the electron transmission layer of the display device contains the heterojunction nano material, so that the potential barrier of a carrier in the interface transmission process can be effectively reduced, the carrier mobility is increased, the light emitting performance of the device can be improved by utilizing the heterojunction effect and the better light scattering effect, and the light emitting performance such as external quantum efficiency is further improved; meanwhile, the stability of the display device can be improved, and the service life of the display device can be prolonged.
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 embodiments or the prior art descriptions 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 is a schematic structural diagram of a display device according to an embodiment.
Description of reference numerals:
11: an anode; 12: a quantum dot light emitting layer; 13: an electron transport layer; 14: a cathode; 15: a substrate; 16: a hole transport layer.
Detailed Description
The heterojunction nanomaterial, the electron transport thin film, and the display device of the present invention are further described in detail with reference to specific examples below. The present invention 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 invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention 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 invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
One embodiment of the present invention provides a heterojunction nano-material, comprising: the first metal selenide and the second metal selenide compounded on the first metal selenide are silver-doped metal selenides, and a heterojunction is formed between the first metal selenide and the second metal selenide.
It can be understood that silver in the second metal selenide is a doped metal; in other words, the metal element in the metal selenide in the second metal selenide is not silver.
The heterojunction nano material contains a first metal selenide and a second metal selenide compounded on the first metal selenide, the second metal selenide is silver-doped metal selenide, and a heterojunction is formed between the first metal selenide and the second metal selenide, so that free electron migration is facilitated, and the heterojunction nano material has high conductivity; in addition, compared with a pure metal selenide nanometer material, the heterojunction nanometer material has a better light scattering effect.
In some examples, the first metal selenide is a nanorod, and the second metal selenide is a nanoparticle and is distributed on a surface of the first metal selenide. Therefore, free electrons on the second metal selenide can be transferred to the surface of the first metal selenide, and the heterojunction nano material has higher conductivity. When the second metal selenide is in the form of nanoparticles and is distributed on the surface of the nanorod-shaped first metal selenide, the specific distribution manner of the second metal selenide is not particularly limited, and the second metal selenide only needs to be distributed on the surface of the first metal selenide, for example, the second metal selenide can be distributed on the surface of the first metal selenide at intervals.
In some examples, the first metal selenide is 20nm to 30nm in diameter and 1000nm to 2000nm in length; optionally, the first metal selenide is 20nm to 25nm in diameter and 1000nm to 1500nm in length; optionally, the first metal selenide is 20nm in diameter and 1000nm in length.
In some examples, the second metal selenide has a particle size of 10nm to 20nm in the heterojunction nanomaterial; optionally, the particle size of the second metal selenide is 10nm to 15nm; optionally, the second metal selenide has a particle size of 10nm.
In some of these examples, the first metal selenide in the heterojunction nanomaterial is selected from SnSe, sb 2 Se 3 、In 4 Se 3 、ZnSe、MoSe 2 And WSe 2 At least one of (1).
In some specific examples, the first metal selenide in the heterojunction nanomaterial is selected from Sb 2 Se 3 And ZnSe.
In some of these examples, the second metal selenide in the heterojunction nanomaterial is selected from AgSnSe, agSbSe 3 、AgIn 3 Se 3 、AgZnSe、AgMoSe 2 And AgWSe 2 At least one of (a).
It is understood that the kind of the metal selenide in the second metal selenide and the kind of the first metal selenide can be the same or different; optionally, the metal selenide in the second metal selenide is the same kind as the first metal selenide. For example, when the first metal selenide is SnSe, the second metal selenide is AgSnSe; when the first metal selenide is Sb 2 Se 3 When the second metal selenide is AgSbSe 3 (ii) a When the first metal selenide is In 4 Se 3 When the second metal selenide is AgIn 3 Se 3 (ii) a When the first metal selenide is ZnSe, the second metal selenide is AgZnSe; when the first metal selenide is MoSe 2 When the second metal selenide is AgMoSe 2 (ii) a When the first metal selenide is WSe 2 When the second metal selenide is AgWSe 2 。
In some specific examples, the first metal selenide is Sb in the heterojunction nanomaterial 2 Se 3 The second metal selenide is AgSbSe 3 . Therefore, the performance of the heterojunction nano material can be further improved.
In some examples, the mass ratio of the second metal selenide to the first metal selenide in the heterojunction nanomaterial is (0.2-0.5): 1; optionally, the mass ratio of the second metal selenide to the first metal selenide is (0.25-0.43): 1. By controlling the mass ratio of the second metal selenide to the first metal selenide, the control of the conductivity of the material and the control of the transmission of carriers are facilitated.
An embodiment of the present invention provides an application of the above heterojunction nano-material as an electron transport layer material, or in the preparation of an electron transport layer.
The invention provides an electron transport film, and the components of the electron transport film comprise the heterojunction nano material.
In some examples, the electron transport film is made of the heterojunction nano material.
Referring to fig. 1, an embodiment of the invention provides a display device 10, including: the anode 11, the quantum dot light-emitting layer 12, the electron transport layer 13 and the cathode 14 are sequentially stacked, and the electron transport layer 14 comprises the heterojunction nano-material or the electron transport film.
In the display device 10, the electron transport layer 14 includes the heterojunction nanomaterial with a specific composition, and the heterojunction nanomaterial includes the first metal selenide and the second metal selenide having a heterojunction effect, which is beneficial to transfer free electrons on the second metal selenide to the surface of the first metal selenide, so that the heterojunction nanomaterial has high electrical conductivity. Therefore, the display device can effectively reduce the potential barrier of the carrier in the interface transmission process, increase the carrier mobility, and improve the light emitting performance of the device by utilizing the heterojunction effect and the better light scattering effect, thereby improving the light emitting performance such as external quantum efficiency; meanwhile, the thermal stability of the display device can be improved, so that the service life of the display device is prolonged.
In some of the examples, in the display device 10, the thickness of the electron transport layer 13 is 20nm to 100nm; optionally, the thickness of the electron transport layer 13 is 30nm to 100nm; optionally, the thickness of the electron transport layer 13 is 50nm.
It is understood that in some of these examples, display device 10 also includes substrate 15. Further, an anode 11, a light-emitting layer 12, an electron transport layer 13, and a cathode 14 are sequentially stacked on a substrate 15.
Further, the substrate 15 may be a rigid material (e.g., glass) or a flexible material (e.g., polyimide).
In some examples, the display device 10 further includes a hole transport layer 16, the hole transport layer 16 is disposed between the anode 11 and the light-emitting layer 13, and a composition of the hole transport layer 16 includes a third metal selenide, and the third metal selenide is a P-type doped metal selenide.
In some examples thereof, the P-type doping element is selected from at least one of Sn, zn, and Mo elements in the display device 10.
In some examples of the display device 10, the metal selenide in the third metal selenide is selected from SnSe, sb 2 Se 3 、In 4 Se 3 、ZnSe、MoSe 2 And WSe 2 Wherein the P-type doping element is different from an element contained in the metal selenide in the third metal selenide.
It can be understood that when the metal selenide in the third metal selenide is SnSe, the P-type doping element can be selected from Zn element or Mo element; in this case, the third metal selenide has the general formula Zn x Sn 1-x Se or Mo x Sn 1-x Se; when the metal selenide in the third metal selenide is Sb 2 Se 3 When the P-type doping element is selected from Sn element, zn element or Mo element, the third metal selenide is (Sn) x Sb 1-x ) 2 Se 3 、(Zn x Sb 1-x ) 2 Se 3 Or (Mo) x Sb 1-x ) 2 Se 3 (ii) a When the metal selenide In the third metal selenide is In 4 Se 3 When the P-type doping element is selected from Sn, zn or Mo, the third metal selenide is (Sn) x In 1-x ) 4 Se 3 、(Zn x In 1-x ) 4 Se 3 Or (Mo) x In 1-x ) 4 Se 3 (ii) a When the metal selenide in the third metal selenide is ZnSe, the P-type doping element is selected from Sn element or Mo element, and the third metal selenide is Sn x Zn 1-x Se or Mo x Zn 1-x Se; when the metal selenide in the third metal selenide is MoSe 2 When the P-type doping element is selected from Sn element or Zn element, the third metal selenide is Sn x Mo 1-x Se 2 Or Zn x Mo 1-x Se 2 (ii) a When the metal selenide in the third metal selenide is WSe 2 When the P-type doping element is selected from Sn, zn or Mo, the third metal selenide is Sn x W 1-x Se 2 、Zn x W 1-x Se 2 Or Mo x W 1-x Se 2 (ii) a Wherein x is greater than 0,1-x is greater than 0. Conventional hole transport layer materials are typically TFB (poly [ (9, 9-di-N-octylfluorenyl-2, 7-diyl) -alt- (4, 4' - (N- (4-N-butyl) phenyl) -diphenylamine)]) However, TFB is a hole transport layer, and has a high barrier for injecting quantum dot light emitting (QD) layer, and is difficult to inject, so that holes are easily blocked at the interface between hole transport and light emitting layer, resulting in degradation of TFB layer, and further affecting the stability of the device. The specific type of P-type elements are doped in the metal selenide, so that the conductivity of the P-type selenide is effectively improved; the p-type selenide is used as a hole transport layer of the quantum dot light-emitting diode, so that the potential barrier of a current carrier in the interface transport process is effectively reduced, the transport of a hole is promoted, and the hole and the electron can be combined more quickly.
In some preferred examples, the metal selenide in the third metal selenide is Sb in the display device 10 2 Se 3 。
Sb 2 Se 3 Has a small defect binding energy and a small defect pair loadingThe current capture capability is low, and the non-radiative recombination of holes and electrons in the transmission layer is reduced.
It is also understood that the metal selenide in the third metal selenide is Sb 2 Se 3 When the P-type doping element is selected from at least one of Sn, zn and Mo.
The valence electrons of Sn, zn and Mo are lower than those of Sb, and the material is favorable for forming hole conducting property.
It can be understood that the third metal selenide (P-type doped metal selenide) has the general formula (Sn) x Sb 1-x ) 2 Se 3 、(Zn x Sb 1-x ) 2 Se 3 Or (Mo) x Sb 1-x ) 2 Se 3 (ii) a Wherein x is more than 0 and less than 0.9. It is further understood that x can be 0.1, 0.3, 0.5, 0.7, 0.9, etc. Alternatively, 0.1 < x < 0.5; optionally, x =0.5.
The carrier mobility of the hole transport layer can be adjusted by different doping ratios.
Further, in some of the examples, in the display device 10, the metal selenide in the third metal selenide is Sb 2 Se 3 When the P-type doping element is Sn. Sn is adopted for doping, sn replaces Sb to form a P-type semiconductor, and the Sn doping can also form a small interface barrier with an ITO electrode, so that the stability of the hole transport layer is higher. In other words, the third metal selenide (P-type doped metal selenide) has a general formula of (Sn) x Sb 1-x ) 2 Se 3 (0＜x＜0.9)。
In some of these examples, hole transport layer 16 has a thickness of 20nm to 100nm in display device 10; optionally, the thickness of the hole transport layer 16 is 20nm to 50nm; optionally, the hole transport layer 16 is 25nm thick.
It is understood that the anode 11, the light-emitting layer 12 and the cathode 14 may be made of materials commonly used in the art, and the present invention is not limited thereto.
In some of the examples, the material of the anode in the display device 10 is selected from at least one of indium tin oxide, indium zinc oxide, and aluminum-doped zinc oxide; optionally, the material of the anode is indium tin oxide.
In some of these examples, the anode further includes a metal reflective layer in the display device 10.
In some specific examples, the anode 11 is formed of Ag/ITO or ITO/Ag/ITO in the display device 10.
In some of these examples, the light emitting layer in display device 10 is a quantum dot light emitting layer 12, in which case display device 10 is a quantum dot light emitting diode. It is understood that the light emitting layer in the display device 10 may be a blue light emitting layer, a red light emitting layer, or a green light emitting layer. It is understood that the kind of the light emitting layer is not limited thereto, and in some examples, the light emitting layer may also be an organic light emitting layer.
In some of these examples, the material of the quantum dot light emitting layer 12 in the display device 10 is a core-shell quantum dot or a graded shell based quantum dot material.
In some of the examples, in display device 10, the material of quantum dot light emitting layer 12 is selected from at least one of CdS, znSe, and CdZnS; optionally, the material of the quantum dot light emitting layer 12 is selected from CdS/ZnSe or CdZnS/ZnSe.
In some of the examples, the material of the cathode is selected from at least one of Ag, au, al, and Cu in the display device 10.
In some of the examples, the thickness of the light emitting layer in the display device 10 is 20nm to 30nm.
An embodiment of the present invention provides a method for manufacturing the display device 10, including steps S100 to S600.
Step S100: an anode 11 is formed on a substrate 16. Step S200: a hole transport layer 16 is formed on the anode 11.
In some examples, in step S200, a material of the hole transport layer 16 is used to prepare a target material for magnetron sputtering, and the hole transport layer 16 is formed on the anode 11 by magnetron sputtering.
In some examples, in step S200, the magnetron sputtering conditions are: the power is 60W-80W, the speed is 1 nm/min-5 nm/min, the pressure is 0.6 Pa-1.2 Pa, and the time is 10 min-30 min.
In some examples, in step S200, the magnetron sputtering is performed under argon gas, and the flow rate of argon gas is 5sccm to 20sccm.
In some specific examples, in step S200, the magnetron sputtering conditions are: the power is 12W, the speed is 2nm/min, the pressure is 1Pa, the flow rate of argon is 10sccm, and the sputtering time is 15min.
Step S300: a light-emitting layer is formed on the hole transport layer 16.
Step S400: an electron transport layer 13 is formed on the light emitting layer, wherein the preparation of the electron transport layer 13 includes steps S410 to S450.
Step S410: mixing a selenium source and a first organic solvent, and keeping the temperature at 100-500 ℃ for 2-8 h to obtain a first precursor solution.
In some examples, in step S410, the selenium source is selected from at least one of selenium dioxide, amine selenide, and hydrogen selenide; optionally, the selenium source is selenium oxide.
In some examples, in step S410, the first organic solvent is selected from at least one of Octadecene (ODE), oleic acid, and oleylamine; optionally, the first organic solvent is selected from at least one of octadecene and oleic acid; optionally, the first organic solvent is octadecene.
In some examples, in step S410, the temperature is maintained at 100-300 ℃ for 3-6 h.
In some specific examples, in step S410, the temperature is maintained at 200 ℃ for 5h.
Step S420: mixing metal salt, surfactant and second organic solvent, and keeping the temperature at 100-500 ℃ for 0.1-1 h to obtain second precursor solution.
In some examples, the incubation is performed in step S420 under a nitrogen atmosphere.
In some examples, in step S420, the metal salt is selected from at least one of tin acetate, antimony acetate, indium acetate, zinc acetate, molybdenum acetate, and tungsten acetate;
in some examples, in step S420, the surfactant is selected from at least one of cetyl acrylamide (HDA) and Oleic Acid (OA); alternatively, the surfactant is selected from both cetyl acrylamide (HDA) and Oleic Acid (OA).
In some examples, in step S420, the second organic solvent is selected from at least one of Octadecene (ODE), oleic acid, and oleylamine; optionally, the second organic solvent is selected from at least one of octadecene and oleic acid; optionally, the second organic solvent is octadecene.
It is understood that the first organic solvent and the second organic solvent may be the same or different, and optionally, the first organic solvent and the second organic solvent are the same.
In some examples, in step S420, the temperature is maintained at 100-300 ℃ for 0.5-1 h.
In some specific examples, in step S420, the temperature is maintained at 220 ℃ for 1h.
Step S430: mixing a certain volume of the first precursor solution and the second precursor solution, and reacting at 200-300 ℃. It is understood that the volume of the first precursor liquid is based on the mass ratio of the second metal selenide to the first metal selenide.
Step S440: the silver salt and the remaining first precursor solution are added to the reaction solution of step S430 to continue the reaction.
It can be understood that step S430 generates a first metal selenide nanorod through reaction, and step S440 generates second metal selenide particles on the surface of the first metal selenide nanorod.
Step S500: a cathode 14 is formed on the electron transport layer 13.
Step S600: an encapsulation layer (not shown) is formed on the cathode 14 to encapsulate the light emitting layer.
According to the display device, a selenide semiconductor material is used as a transmission layer material of the display device, specifically, a heterojunction nano material of a first metal selenide and a second metal selenide (silver-doped metal selenide) is used as an electron transmission layer of the display device, and a specific third metal selenide (P-type doped metal selenide) is used as a hole transmission layer of the display device, so that a carrier transmission interface barrier is effectively reduced, and the carrier mobility is increased; the thermal matching of the interfaces of the functional layers is good, the thermal stability of the display device is effectively improved, and the service life of the display device is prolonged.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Hereinafter, the heterojunction nanomaterial, the electron transport film, and the display device according to the present invention are exemplified, and it is understood that the heterojunction nanomaterial, the electron transport film, and the display device of the present invention are not limited to the following examples.
Example 1
The specific structure of the quantum dot light-emitting diode is as follows: substrate/anode [ (Ag, 150 nm)/ITO, 15 nm)]Hole transport layer (Sn) 0.1 Sb 0.9 ) 2 Se 3 25 nm)/luminescent layer (CdS/ZnSe, 20 nm)/electron transport layer (AgSbSe) 2 /Sb 2 Se 3 30 nm)/cathode (silver, 20 nm)/encapsulation layer.
(1) Providing an Ag (150 nm)/ITO (15 nm) electrode, namely an anode, and forming the anode on a substrate;
(2) Preparation of hole transport layer
60g of (Sn) 0.1 Sb 0.9 ) 2 Se 3 (wherein 3g of Sn, 27.4g of Sb and 29.6g of Se) is prepared into a target material for magnetron sputtering, a hole transport layer is formed on an Ag (150 nm)/ITO (15 nm) electrode by adopting a magnetron sputtering method, the radio-frequency sputtering power is 72W, the sputtering rate is 2nm/min, the sputtering pressure is 1Pa, the Ar gas flow is 10sccm, the sputtering is carried out for 15min, and the film thickness is 25nm.
(3) Preparation of Quantum dot light emitting layer
CdS/ZnSe nano-particles with the particle size of about 12nm are dissolved in a chloroform solvent, the concentration is 10mg/ml, 9 drops of CdS/ZnSe nano-particles are printed on a hole transport layer, and the CdS/ZnSe nano-particles are dried; the film thickness was about 20nm.
(4) Preparation of an Electron transport layer (AgSbSe) 2 /Sb 2 Se 3 Materials):
adding 24mmol of SeO 2 And 30mL of organic solvent Octadecene (ODE), stirring and heating to 200 ℃, keeping the temperature for 5h 2 Completely dissolving to obtain 0.8mol/L Se-ODE precursor solution;
1.2mmol of Sb (CH) 3 COO) 3 Adding 8mmol of hexadecyl acrylamide (HDA), 15mL of ODE and 6mL of Oleic Acid (OA) into a flask, stirring and heating to 220 ℃ under the nitrogen atmosphere, and preserving heat for 1h to obtain an antimony precursor solution;
2mL of Se-ODE precursor solution was added to the antimony precursor solutionReacting at 240 deg.C for 2min, adding 0.4mmol CH 3 COOAg, stirring for 3min, adding 6mL Se-ODE precursor solution, and reacting for 10min to obtain AgSbSe 2 And Sb 2 Se 3 AgSbSe with mass ratio of 0.25 2 /Sb 2 Se 3 A heterojunction nanorod; sb 2 Se 3 Has a diameter of 20nm and a length of 1000nm, agSbSe 2 The particle diameter of (2) is 10nm;
AgSbSe 2 /Sb 2 Se 3 The heterojunction nanorod is prepared into 20mg/mL ink, 10 drops of the ink are printed on the quantum dot light emitting layer film, and the ink is dried to be about 30nm in thickness, namely the electron transport layer film.
(5) The cathodes were stacked.
(6) And (6) packaging.
Example 2
The specific structure of the quantum dot light-emitting diode is as follows: substrate/anode [ (Ag, 150 nm)/ITO, 15 nm)]Hole transport layer (Sn) 0.5 Sb 0.5 ) 2 Se 3 25 nm)/luminescent layer (CdS/ZnSe, 20 nm)/electron transport layer (AgSbSe) 2 /Sb 2 Se 3 30 nm)/cathode (silver, 20 nm)/encapsulation layer.
Substantially the same as in example 1, except that the hole transport layer prepared in step (2) is different, that is, the hole transport layer is different; the step (2) is specifically as follows:
(2) Preparation of hole transport layer
60g of (Sn) 0.5 Sb 0.5 ) 2 Se 3 (wherein 14.9g of Sn, 15.3g of Sb and 29.8g of Se) is prepared into a target material for magnetron sputtering, a hole transport layer is formed on an Ag (150 nm)/ITO (15 nm) substrate electrode by adopting a magnetron sputtering method, the radio frequency sputtering power is 70W, the sputtering rate is 2nm/min, the sputtering pressure is 1Pa, the Ar gas flow is 10sccm, the sputtering is carried out for 15min, and the film thickness is 25nm.
Example 3
The specific structure of the quantum dot light-emitting diode is as follows: substrate/anode [ (Ag, 150 nm)/ITO, 15 nm)]Hole transport layer (Sn) 0.3 Sb 0.7 ) 2 Se 3 25 nm)/luminescent layer (CdS/ZnSe, 20 nm)/electron transport layer (AgSbSe) 2 /Sb 2 Se 3 30 nm)/cathode (silver, 20 nm)/encapsulation layer.
Substantially the same as in example 1, except that the hole transport layer prepared in step (2) is different, that is, the hole transport layer is different; the step (2) is specifically as follows:
(2) Preparation of hole transport layer
60g of (Sn) 0.3 Sb 0.7 ) 2 Se 3 (wherein 8.9g of Sn, 21.4g of Sb and 29.7g of Se) is prepared into a target material for magnetron sputtering, a hole transport layer is formed on an Ag (150 nm)/ITO (15 nm) substrate electrode by adopting a magnetron sputtering method, the radio frequency sputtering power is 70W, the sputtering rate is 2nm/min, the sputtering pressure is 1Pa, the Ar gas flow is 10sccm, the sputtering is carried out for 15min, and the film thickness is 25nm.
Example 4
The specific structure of the quantum dot light-emitting diode is as follows: substrate/anode [ (Ag, 150 nm)/ITO, 15 nm)]Hole transport layer (Sn) 0.1 Sb 0.9 ) 2 Se 3 25 nm)/luminescent layer (CdS/ZnSe, 20 nm)/electron transport layer (ZnSe/AgZnSe, 30 nm)/cathode (silver, 20 nm)/encapsulation layer.
Substantially the same as in example 1, except that the electron transport layer material prepared in step (4) was different, that is, the electron transport layer was different; the step (4) is specifically as follows:
(4) Preparation of the Electron transport layer (ZnSe/AgZnSe Material) 24mmol of SeO were added 2 And 30mL of organic solvent Octadecene (ODE), stirring and heating to 200 ℃, keeping the temperature for 5h 2 Completely dissolving to obtain 0.8mol/L Se-ODE precursor solution;
2mmol of Zn (CH) 3 COO), 8mmol of hexadecyl acrylamide (HDA), 15mL of ODE and 6mL of Oleic Acid (OA) are added into a flask, stirred and heated to 220 ℃ under the nitrogen atmosphere, and the temperature is kept for 1h to obtain zinc precursor solution;
adding 2mL of Se-ODE precursor solution into zinc precursor solution, reacting for 2min at 240 ℃, and adding 0.4mmol of CH 3 COOAg, stirring for 3min, adding 6mL of Se-ODE precursor solution, and reacting for 10min to obtain a ZnSe/AgZnSe heterojunction nanorod with the mass ratio of ZnSe/AgZnSe being 0.43;
preparing the ZnSe/AgZnSe heterojunction nanorod into 20mg/mL ink, printing 10 drops of the ink on the quantum dot light emitting layer film, and drying to obtain the electron transmission layer film with the thickness of about 30nm.
Example 5
The specific structure of the quantum dot light-emitting diode is as follows: substrate/anode [ (Ag, 150 nm)/ITO, 15 nm)]Hole transport layer (Sn) 0.1 Sb 0.9 ) 2 Se 3 25 nm)/luminescent layer (CdS/ZnSe, 20 nm)/electron transport layer (AgSbSe) 2 /Sb 2 Se 3 30 nm)/cathode (silver, 20 nm)/encapsulation layer.
(1) Providing an Ag (150 nm)/ITO (15 nm) electrode, namely an anode, and forming the anode on a substrate;
(2) Preparation of hole transport layer
60g of (Sn) 0.1 Sb 0.9 ) 2 Se 3 (wherein 3g of Sn, 27.4g of Sb and 29.6g of Se) is prepared into a target material for magnetron sputtering, a hole transport layer is formed on an Ag (150 nm)/ITO (15 nm) electrode by adopting a magnetron sputtering method, the radio-frequency sputtering power is 70W, the sputtering rate is 2nm/min, the sputtering pressure is 1Pa, the Ar gas flow is 10sccm, the sputtering is carried out for 15min, and the film thickness is 25nm.
(3) Preparation of Quantum dot light emitting layer
Dissolving CdS/ZnSe nano-particles with the particle size of about 12nm in a chloroform solvent at the concentration of 10mg/ml, printing 9 drops on the hole transport layer, and drying; the film thickness was about 20nm.
(4) Preparation of an Electron transport layer (AgSbSe) 2 /Sb 2 Se 3 Materials):
adding 24mmol of SeO 2 And 30mL of organic solvent Octadecene (ODE), stirring and heating to 200 ℃, keeping the temperature for 5h 2 Completely dissolving to obtain 0.8mol/L Se-ODE precursor solution;
1.2mmol of Sb (CH) 3 COO) 3 Adding 8mmol of hexadecyl acrylamide (HDA), 15mL of ODE and 6mL of Oleic Acid (OA) into a flask, stirring and heating to 220 ℃ under the nitrogen atmosphere, and preserving heat for 1h to obtain an antimony precursor solution;
1.84mL of Se-ODE precursor solution is added into the antimony precursor solution to react for 2min at 240 ℃, and 0.4mmol of CH is added 3 COOAg, stirring for 3min, adding 6mL of Se-ODE precursor solution, and reacting for 10min to obtain AgSbSe 2 And Sb 2 Se 3 AgSbSe with mass ratio of about 0.4 2 /Sb 2 Se 3 A heterojunction nanorod;
AgSbSe 2 /Sb 2 Se 3 The heterojunction nanorod is prepared into 20mg/mL ink, 10 drops of the ink are printed on the quantum dot light-emitting layer film, and the ink is dried to be about 30nm in thickness, namely the electron transport layer film.
(5) Cathodes were stacked.
(6) And (6) packaging.
Comparative example 1
Adopting traditional hole transport layer and electron transport layer materials; the specific structure is Ag (140 nm)/ITO (15 nm)/TFB (25 nm)/RQD (20 nm)/ZnO (30 nm)/Ag (20 nm).
Comparative example 2
The specific structure of the quantum dot light-emitting diode is as follows: substrate/anode [ (Ag, 150 nm)/ITO, 15 nm)]Hole transport layer (Sn) 0.1 Sb 0.9 ) 2 Se 3 25 nm)/luminescent layer (CdS/ZnSe, 20 nm)/electron transport layer (TiSbSe/Sb) 2 Se 3 30 nm)/cathode (silver, 20 nm)/encapsulation layer.
(1) Providing an Ag (150 nm)/ITO (15 nm) electrode, namely an anode, and forming the anode on a substrate;
(2) Preparation of hole transport layer
60g of (Sn) 0.1 Sb 0.9 ) 2 Se 3 (wherein 3g of Sn, 27.4g of Sb and 29.6g of Se) is prepared into a target material for magnetron sputtering, a hole transport layer is formed on an Ag (150 nm)/ITO (15 nm) electrode by adopting a magnetron sputtering method, the radio-frequency sputtering power is 70W, the sputtering rate is 2nm/min, the sputtering pressure is 1Pa, the Ar gas flow is 10sccm, the sputtering is carried out for 15min, and the film thickness is 25nm.
(3) Preparation of Quantum dot light emitting layer
CdS/ZnSe nano-particles with the particle size of about 12nm are dissolved in a chloroform solvent, the concentration is 10mg/ml, 9 drops of CdS/ZnSe nano-particles are printed on a hole transport layer, and the CdS/ZnSe nano-particles are dried; the film thickness was about 20nm.
(4) Preparation of the Electron transport layer
Preparation of TiSbSe/Sb 2 Se 3 Materials:
adding 24mmol of SeO 2 And 30mL of organic solvent Octadecene (ODE), stirring and heating to 200 ℃, keeping the temperature for 5h 2 Completely dissolved to obtainTo 0.8mol/L of the first precursor solution;
2mmol of Ti (CH) 3 COO), 8mmol of hexadecyl acrylamide (HDA), 15mL of ODE and 6mL of Oleic Acid (OA) are added into a flask, stirred and heated to 250 ℃ under the nitrogen atmosphere, and the temperature is kept for 1h to obtain a second precursor solution;
adding 2mL of first precursor solution into the second precursor solution, reacting for 2min at 250 ℃, adding 0.4mmol, stirring for 3min, adding 6mL of first precursor solution, and reacting for 10min to obtain TiSbSe 2 And Sb 2 Se 3 TiSbSe with mass ratio of about 0.46 2 /Sb 2 Se 3 A heterojunction nanorod;
mixing TiSbSe 2 /Sb 2 Se 3 The heterojunction nanorod is prepared into 20mg/mL ink, 10 drops of the ink are printed on the quantum dot light emitting layer film, and the ink is dried to be about 30nm in thickness, namely the electron transport layer film.
Comparative example 3
The specific structure of the quantum dot light-emitting diode is as follows: substrate/anode [ (Ag, 150 nm)/ITO, 15 nm)]Hole transport layer (Sn) 0.1 Sb 0.9 ) 2 S 3 25 nm)/luminescent layer (CdS/ZnSe, 20 nm)/electron transport layer (AgSbSe) 2 /Sb 2 Se 3 30 nm)/cathode (silver, 20 nm)/encapsulation layer.
(1) Providing an Ag (150 nm)/ITO (15 nm) electrode, namely an anode, and forming the anode on a substrate;
(2) Preparation of hole transport layer
60g of (Sn) 0.1 Sb 0.9 ) 2 S 3 (wherein 4.2g of Sn, 38.8g of Sb and 17g of S) is prepared into a target material for magnetron sputtering, a hole transport layer is formed on an Ag (150 nm)/ITO (15 nm) substrate electrode by adopting a magnetron sputtering method, the radio-frequency sputtering power is 70W, the sputtering rate is 2nm/min, the sputtering pressure is 1Pa, the Ar gas flow is 10sccm, the sputtering is carried out for 15min, and the film thickness is 25nm.
(3) Preparation of Quantum dot light emitting layer
Dissolving CdS/ZnSe nano-particles with the particle size of about 12nm in a chloroform solvent at the concentration of 10mg/ml, printing 9 drops on the hole transport layer, and drying; the film thickness was about 20nm.
(4) Preparation of an Electron transport layer (AgSbSe) 2 /Sb 2 Se 3 Materials):
adding 24mmol of SeO 2 And 30mL of organic solvent Octadecene (ODE), stirring and heating to 200 ℃, keeping the temperature for 5h 2 Completely dissolving to obtain 0.8mol/L Se-ODE precursor solution;
1.2mmol of Sb (CH) 3 COO) 3 Adding 8mmol of hexadecyl acrylamide (HDA), 15mL of ODE and 6mL of Oleic Acid (OA) into a flask, stirring and heating to 220 ℃ in a nitrogen atmosphere, and preserving heat for 1h to obtain an antimony precursor solution;
adding 2mL of Se-ODE precursor solution into the antimony precursor solution, reacting for 2min at 240 ℃, and adding 0.4mmol of CH 3 COOAg, stirring for 3min, adding 6mL of Se-ODE precursor solution, and reacting for 10min to obtain AgSbSe 2 And Sb 2 Se 3 AgSbSe with mass ratio of 0.25 2 /Sb 2 Se 3 A heterojunction nanorod;
AgSbSe 2 /Sb 2 Se 3 The heterojunction nanorod is prepared into 20mg/mL ink, 10 drops of the ink are printed on the quantum dot light emitting layer film, and the ink is dried to be about 30nm in thickness, namely the electron transport layer film.
(5) Cathodes were stacked.
(6) And (6) packaging.
Materials of the hole transport layer and the electron transport layer of examples 1 to 5 and comparative examples 1 to 3 are shown in table 1.
TABLE 1
The conductivity of the electron transport layer thin films prepared in examples and comparative examples and the EQE, luminance and lt95@1000nit of the display devices prepared in examples and comparative examples were respectively tested using a test method commonly used in the art, and the test criteria were:
and (4) EQE: the external quantum efficiency of the device is expressed, the proportion of the device exciton converted into photon emission is shown, and the higher the proportion is, the higher the device efficiency is;
brightness: adopting the brightness number of a brightness meter under the condition of fixed voltage, wherein the brightness of the device is compared under the condition of fixed 3V voltage;
LT95@1000nit: the time required for the device to decay to 950nit brightness at 1000nit brightness is indicated, and the service life of the device is represented.
The results are shown in Table 2.
TABLE 2
As can be seen from table 2, for the hole transport layer, the doping of a specific element in the metal selenide can promote the carrier transport of the device and improve the device efficiency, and the higher the doping ratio of the P-type doping element is in a certain range, the better the carrier transport is, and the higher the device efficiency is; in the electron transport layer, the higher the mass ratio of the second metal selenide to the first metal selenide is, the better the conductivity of the material is, and the synergistic effect of the two promotes the stability of the device.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present patent shall be subject to the content of the appended claims, and the description and drawings can be used to explain the content of the claims.
Claims (11)
1. A heterojunction nanomaterial, comprising:
the heterojunction solar cell comprises a first metal selenide and a second metal selenide compounded on the first metal selenide, wherein the second metal selenide is silver-doped metal selenide, and a heterojunction is formed between the first metal selenide and the second metal selenide.
2. The heterojunction nanomaterial of claim 1, wherein the first metal selenide is a nanorod and the second metal selenide is nanoparticulate and distributed on the surface of the first metal selenide.
3. The heterojunction nanomaterial of claim 2, wherein the first metal selenide is 20nm to 30nm in diameter and 1000nm to 2000nm in length; and/or
The particle size of the second metal selenide is 10 nm-20 nm.
4. A heterojunction nanomaterial as claimed in any of claims 1 to 3, wherein said first metal selenide is selected from SnSe, sb 2 Se 3 、In 4 Se 3 、ZnSe、MoSe 2 And WSe 2 At least one of (a); and/or
The second metal selenide is selected from AgSnSe and AgSbSe 2 、AgIn 3 Se 3 、AgZnSe、AgMoSe 2 And AgWSe 2 At least one of (1).
5. A heterojunction nanomaterial as claimed in any of claims 1 to 3, wherein the mass ratio of the second metal selenide to the first metal selenide is (0.2 to 0.5): 1.
6. An electron transport film, wherein the composition of the electron transport film comprises the heterojunction nanomaterial of any of claims 1 to 6.
7. A display device, comprising:
the anode, the quantum dot light-emitting layer, the electron transport layer and the cathode are sequentially stacked;
wherein the electron transport layer comprises the heterojunction nano-material as described in any one of claims 1 to 5 in the composition, or the electron transport layer is the electron transport film as described in claim 6.
8. The display device according to claim 7, further comprising:
the hole transport layer is arranged between the anode and the light-emitting layer, and the components of the hole transport layer comprise a third metal selenide, wherein the third metal selenide is a P-type doped metal selenide.
9. The display device according to claim 8, wherein the P-type doped element is at least one selected from a Sn element, a Zn element, and a Mo element; and/or
The metal selenide in the third metal selenide is selected from SnSe and Sb 2 Se 3 、In 4 Se 3 、ZnSe、MoSe 2 And WSe 2 Wherein the P-type doping element is different from an element contained in the metal selenide in the third metal selenide.
10. The display device of claim 8, wherein the P-type doped metal selenide has a formula of (Sn) x Sb 1-x ) 2 Se 3 (ii) a Wherein x is more than 0 and less than 0.9.
11. The display device according to claim 7, wherein a material of the anode is selected from at least one of indium tin oxide, indium zinc oxide, and aluminum-doped zinc oxide; and/or
The material of the quantum dot light-emitting layer is selected from at least one of CdS, znSe and CdZnS; and/or
The cathode is made of at least one of Ag, au, al and Cu.
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