CN115835676A - Electroluminescent device and preparation method thereof - Google Patents
Electroluminescent device and preparation method thereof Download PDFInfo
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- CN115835676A CN115835676A CN202111093849.4A CN202111093849A CN115835676A CN 115835676 A CN115835676 A CN 115835676A CN 202111093849 A CN202111093849 A CN 202111093849A CN 115835676 A CN115835676 A CN 115835676A
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Abstract
The application discloses an electroluminescent device, including positive pole, luminescent layer, electron transport layer and the negative pole of range upon range of setting, electroluminescent device still includes the wall, the wall sets up the luminescent layer with between the electron transport layer, and/or between electron transport layer and the negative pole, the material of wall is selected from Ag 2 At least one of S nanocrystals, niS nanocrystals, and Ni (OH) S nanocrystals. The spacer layer of the electroluminescent device is arranged between the light-emitting layer and the electron transport layer, so that the quenching effect of a dangling bond on the surface of the material of the electron transport layer on the light-emitting layer can be weakened; the spacing layer is arranged between the electron transport layer and the cathode, and can passivate the surface of the electron transport layer and reduce the number of oxygen vacancies, thereby weakening the oxidation of the cathode by the oxygen vacancies in the electron transport layer. In addition, the application also discloses a preparation method of the electroluminescent device.
Description
Technical Field
The application relates to the technical field of display, in particular to an electroluminescent device and a preparation method of the electroluminescent device.
Background
Currently, widely used electroluminescent devices are organic electroluminescent devices (OLEDs) and quantum dot electroluminescent devices (QLEDs). The conventional OLED and QLED device structure mainly includes an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode. Under the action of an electric field, holes generated by an anode of the electroluminescent device and electrons generated by a cathode move, are respectively injected into the hole transport layer and the electron transport layer and finally migrate to the light emitting layer, and when the holes and the electrons meet at the light emitting layer, energy excitons are generated, so that light emitting molecules are excited to finally generate visible light.
Commonly used electron transport layer materials are zinc oxide particles, magnesium zinc oxide particles, aluminum zinc oxide particles, and the like. The electron transport layer material has a small size and a large specific surface area, atoms on the particle surface can form a large number of dangling bonds, the dangling bonds can capture carriers (mainly electrons), so that the electron transport efficiency is reduced, the electron-hole transport is unbalanced, and a certain exciton quenching is generated on the light emitting layer material, especially quantum dots of the quantum dot light emitting layer, so that the optical performance of the electroluminescent device is influenced. In addition, the surface of the electron transport layer material particles has a large number of oxygen vacancies which can cause the adsorption of oxygen molecules, and oxidative groups such as hydroxyl groups which have strong oxidizability and can cause the oxidation of electrodes, thereby reducing the conductive capability and stability of the device, and easily causing the scintillation phenomenon because the contact between the electron transport layer and the cathode is poor.
Disclosure of Invention
In view of the above, the present application provides an electroluminescent device, which aims to solve the problem of unbalanced electron-hole transport caused by low electron transport efficiency of the conventional electroluminescent device.
The embodiment of the application is realized by that the electroluminescent device comprises an anode, a luminescent layer, an electron transport layer and a cathode which are arranged in a laminated manner, and the electroluminescent device also comprises a spacing layer, wherein the spacing layer is arranged between the luminescent layer and the electron transport layer and/or between the electron transport layer and the cathode, and the material of the spacing layer is selected from Ag 2 At least one of S nanocrystals, niS nanocrystals, and Ni (OH) S nanocrystals.
Optionally, in some embodiments of the present application, the material of the spacer layer includes Ag 2 S nanocrystals and NiS nanocrystals, said Ag 2 The molar ratio of the S nanocrystal to the NiS nanocrystal ranges from (4; and/or
The material of the spacing layer is Ag 2 S nanocrystal and NiS nanocrystal, and the Ag is 2 The molar ratio of the S nanocrystal to the NiS nanocrystal ranges from (4.
Optionally, in some embodiments of the present application, the material of the spacer layer includes Ag 2 S nanocrystals and Ni (OH) S nanocrystals, said Ag 2 The molar ratio of the S nanocrystals to the Ni (OH) S nanocrystals ranges from (4; and/or
The material of the spacing layer is Ag 2 S nanocrystals and Ni (OH) S nanocrystals, the Ag 2 The molar ratio of the S nanocrystals to the Ni (OH) S nanocrystals was in the range of (4.
Optionally, in some embodiments of the present application, the material of the spacer layer includes NiS nanocrystals and Ni (OH) S nanocrystals, and the molar ratio of the NiS nanocrystals to the Ni (OH) S nanocrystals is in a range of (6; and/or
The material of the spacing layer consists of NiS nanocrystals and Ni (OH) S nanocrystals, and the molar ratio of the NiS nanocrystals to the Ni (OH) S nanocrystals is in the range of (6.
Optionally, in some embodiments of the present application, the material of the spacer layer includes Ag 2 S nanocrystals, niS nanocrystals and Ni (OH) S nanocrystals, said Ag 2 The molar ratio of the S nanocrystal, the NiS nanocrystal, and the Ni (OH) S nanocrystal is in the range of (8; and/or
The material of the spacing layer is Ag 2 S nanocrystal, niS nanocrystal and Ni (OH) S nanocrystal, and the Ag is 2 The molar ratio of the S nanocrystal, the NiS nanocrystal, and the Ni (OH) S nanocrystal is in the range of (8.
Optionally, in some embodiments of the present application, the spacer layer is located between the light emitting layer and the electron transport layer, and the thickness of the spacer layer is 5 to 10nm.
Optionally, in some embodiments of the present application, the spacer layer is located between the electron transport layer and the cathode, and a thickness of the spacer layer is greater than 0 and equal to or less than 2nm.
Optionally, in some embodiments of the present application, the material of the electron transport layer is selected from ZnO, tiO 2 、BaTiO 3 Mixing, addingAt least one of aluminum zinc oxide, lithium-doped zinc oxide and magnesium-doped zinc oxide; and/or
The light-emitting layer is an organic light-emitting layer or a quantum dot light-emitting layer, the material of the organic light-emitting layer is selected from at least one of diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives or fluorene derivatives, blue light-emitting TBPe fluorescent materials, green light-emitting TTPA fluorescent materials, orange light-emitting TBRb fluorescent materials and red light-emitting DBP fluorescent materials, and the material of the quantum dot light-emitting layer is selected from at least one of II-VI compounds, III-V compounds and I-III-VI compounds; and/or
The cathode is made of at least one of Ag, al and Au.
Optionally, in some embodiments of the present application, the thickness of the electron transport layer is in a range of 30-55nm.
Correspondingly, the embodiment of the application also provides a preparation method of the electroluminescent device, which comprises the following steps:
providing a substrate, and forming a laminated anode and a light-emitting layer on the substrate;
forming an electron transport layer on the light emitting layer;
forming a cathode on the electron transport layer;
before forming the electron transport layer on the light emitting layer, the preparation method further includes: forming the spacer layer on the light-emitting layer; and/or
Before forming a cathode on the electron transport layer, the preparation method further includes: the spacer layer is formed on the electron transport layer.
Correspondingly, the embodiment of the application also provides a preparation method of the electroluminescent device, which comprises the following steps:
providing a substrate, and forming a cathode on the substrate;
forming an electron transport layer on the cathode;
forming a light-emitting layer and an anode stacked on the electron transport layer;
before forming the electron transport layer on the cathode, the preparation method further includes: forming the above spacer layer on the cathode; and/or
Before forming the stacked light emitting layer and anode on the electron transport layer, the preparation method further includes: the spacer layer is formed on the electron transport layer.
The electroluminescent device comprises a spacing layer arranged between the luminescent layer and the electron transport layer and/or between the electron transport layer and the cathode, and the material of the spacing layer is selected from Ag 2 At least one of S nanocrystals, niS nanocrystals, and Ni (OH) S nanocrystals. The spacing layer is arranged between the light emitting layer and the electron transport layer, so that the quenching effect of dangling bonds on the surface of the material of the electron transport layer on the light emitting layer can be weakened. The spacing layer is arranged between the electron transport layer and the cathode, and can passivate the surface of the electron transport layer and reduce the number of oxygen vacancies, thereby weakening the oxidation of the cathode by the oxygen vacancies in the electron transport layer. The spacing layer can also cover electron transmission material particles on the surface of the electron transmission layer, so that the surface smoothness of the electron transmission layer is improved, the contact between the electron transmission layer and the cathode is improved, the stability of the electroluminescent device is improved, and the possible flicker phenomenon of the electroluminescent device is reduced or even avoided.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic structural diagram of an electroluminescent device provided in an embodiment of the present application;
FIG. 2 is a schematic diagram of another electroluminescent device provided in an embodiment of the present application;
FIG. 3 is a schematic diagram of a structure of another electroluminescent device provided in the embodiments of the present application;
fig. 4 is a flowchart of a process for fabricating an electroluminescent device according to an embodiment of the present disclosure;
FIG. 5 is a flow chart illustrating the fabrication of another electroluminescent device provided in the examples of the present application;
FIG. 6 is an AFM surface topography of the surface of the second spacer layer away from the electron transport layer of example 1 of the present application;
FIG. 7 is an AFM surface topography of the surface of the electron transport layer of comparative example 1 of the present application away from the light emitting layer.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application. Furthermore, it should be understood that the detailed description and specific examples, while indicating exemplary embodiments of the invention, are given by way of illustration and explanation only, and are not intended to limit the scope of the invention. In the present application, unless indicated to the contrary, the use of the directional terms "upper" and "lower" generally refer to the upper and lower positions of the device in actual use or operation, and more particularly to the orientation of the figures of the drawings; . In addition, in the description of the present application, the term "including" means "including but not limited to".
Various embodiments of the invention may exist in a range of forms; it is to be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the stated range, such as 1, 2,3, 4,5, and 6, as applicable regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any number (fractional or integer) recited within the range so indicated.
The embodiment of the application provides an electroluminescence deviceThe optical device 100 includes an anode 10, a light-emitting layer 40, an electron transport layer 50, and a cathode 60, which are stacked. The electroluminescent device 100 further comprises a spacer layer arranged between the light-emitting layer 40 and the electron transport layer 50 and/or between the electron transport layer 50 and the cathode 60. The material of the spacing layer is selected from Ag 2 At least one of S nanocrystals, niS nanocrystals, and Ni (OH) S nanocrystals.
As an example, referring to fig. 1, an electroluminescent device 100 includes an anode 10, a hole injection layer 20, a hole transport layer 30, a light emitting layer 40, an electron transport layer 50, and a cathode 60, which are stacked. The electroluminescent device 100 further comprises a first spacer layer 70, the first spacer layer 70 being arranged between the light-emitting layer 40 and the electron-transporting layer 50.
As an example, referring to fig. 2, another electroluminescent device 100 is provided in the present embodiment, which includes an anode 10, a hole injection layer 20, a hole transport layer 30, a light emitting layer 40, an electron transport layer 50, and a cathode 60, which are stacked. The electroluminescent device 100 further comprises a second spacer layer 80, the second spacer layer 80 being arranged between the electron transport layer 50 and the cathode 60.
As an example, referring to fig. 3, an electroluminescent device 100 is provided in an embodiment of the present application, which includes an anode 10, a hole injection layer 20, a hole transport layer 30, a light emitting layer 40, an electron transport layer 50, and a cathode 60, which are stacked. The electroluminescent device 100 further comprises a first spacer layer 70 and a second spacer layer 80, the first spacer layer 70 being disposed between the light-emitting layer 40 and the electron transport layer 50, the second spacer layer 80 being disposed between the electron transport layer 50 and the cathode 60.
The materials of the first and second spacers 70 and 80 may be selected from, but not limited to, ag 2 At least one of S nanocrystals, niS nanocrystals, and Ni (OH) S (nickel sulfide with hydroxyl) nanocrystals. When the electroluminescent device 100 includes both the first spacer layer 70 and the second spacer layer 80, the materials of the first spacer layer 70 and the second spacer layer 80 may be the same or different.
The first spacer layer 70 or the second spacer layerThe material of the spacer 80 is selected from Ag 2 When the S nanocrystal and the NiS nanocrystal are two, the Ag is 2 The molar ratio of S nanocrystals to NiS nanocrystals ranges from (4 2 The molar ratio of S nanocrystals to NiS nanocrystals ranges from (4: 1.
the material of the first spacing layer 70 or the second spacing layer 80 is selected from Ag 2 When S nanocrystal and Ni (OH) S nanocrystal are two types, the Ag is 2 The molar ratio of the S nanocrystal to the Ni (OH) S nanocrystal is in the range of (4 2 The molar ratio of S nanocrystals to Ni (OH) S nanocrystals ranges from (4: 1.
when the material of the first spacer layer 70 or the second spacer layer 80 is selected from both NiS nanocrystals and Ni (OH) S nanocrystals, the molar ratio of the NiS nanocrystals to the Ni (OH) S nanocrystals is in the range of (6: 1.
the material of the first spacing layer 70 or the second spacing layer 80 is selected from Ag 2 When S nanocrystal, niS nanocrystal and Ni (OH) S nanocrystal are three, the Ag is 2 The molar ratio of the S nanocrystal, the NiS nanocrystal, and the Ni (OH) S nanocrystal is in the range of (8 2 The molar ratio of the S nanocrystal, niS nanocrystal, and Ni (OH) S nanocrystal is in the range of (8: 1:1.
the thickness of the first spacer layer 70 ranges from 5 to 10nm. The excessive thickness of the first spacer layer 70 may affect electron transport, so that the brightness and efficiency of the electroluminescent device 100 at the same voltage are lowered; if the thickness is too small, the light-emitting layer 40 cannot be protected, so that the electron transport layer material and the light-emitting layer material are mutually permeated, and the light-emitting layer material is optically quenched.
The thickness of the second spacer layer 80 is greater than 0 and equal to or less than 2nm. The excessively large thickness of the spacer layer 70 may greatly increase the injection work function of electrons, which may make it difficult to transport carriers, and thus, the external quantum efficiency of the electroluminescent device 100 may be greatly reduced.
The thickness of the electron transport layer 50 ranges from 30 to 55nm. Too low a thickness of the electron transport layer 50 results in too fast electron injection efficiency and thus electron-hole mobility imbalance; too large a thickness results in too slow an electron injection efficiency and an imbalance in electron-hole mobility. The imbalance of electron-hole mobility causes recombination of electrons and holes in the functional layers other than the light emitting layer, which results in a decrease in brightness of the electroluminescent device 100, and charges are easily accumulated at the interface of the adjacent functional layers, which results in unstable lifetime of the electroluminescent device 100.
The material of the electron transport layer 50 may be selected from, but not limited to, znO, tiO 2 、BaTiO 3 At least one of aluminum-doped zinc oxide (AZO), lithium-doped zinc oxide (LZO) and magnesium-doped zinc oxide (MZO).
The first spacer layer 70 disposed between the light-emitting layer 40 and the electron transport layer 50 can reduce the quenching effect of dangling bonds on the surface of the material of the electron transport layer on the light-emitting layer. The second spacer 80 is disposed between the electron transport layer 50 and the cathode 60 and can passivate the surface of the electron transport layer 50, reducing the number of oxygen vacancies, and thereby reducing the oxidation of the cathode 60 by oxygen vacancies in the electron transport layer 50. The second spacer 80 may also cover the electron transport material particles on the surface of the electron transport layer 50, thereby improving the surface flatness of the electron transport layer 50, improving the contact between the electron transport layer 50 and the cathode 60, improving the stability of the electroluminescent device 100, and reducing or even avoiding the possible flicker phenomenon of the electroluminescent device 100.
The material of the anode 10 is a material known in the art for an anode of an electroluminescent device, and for example, may be selected from, but not limited to, a doped metal oxide electrode, a composite electrode, and the like. The metal oxide electrode may be selected from, but not limited to, at least one of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), and aluminum-doped magnesium oxide (AMO). The composite electrode is a composite electrode formed by sandwiching metal between doped or undoped transparent metal oxides, such as AZO/Ag/AZO, AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO 2 /Ag/TiO 2 、TiO 2 /Al/TiO 2 ZnS/Ag/ZnS, znS/Al/ZnS and the like.
The material of the hole injection layer 20 is a material known in the art for a hole injection layer, and may be selected from, for example, but not limited to, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN), poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS), and s-MoO doped therewith 3 (PEDOT: PSS: s-MoO) 3 ) At least one of (1).
The material of the hole transport layer 30 is a material known in the art for hole transport layers, and may be selected from, for example, but not limited to, poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine](PTAA), 2', 7' -tetrakis [ N, N-di (4-methoxyphenyl) amino]-9,9 '-spirobifluorene (spiro-omeTAD), 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline](TAPC), N ' -bis (1-naphthyl) -N, N ' -diphenyl-1, 1' -diphenyl-4, 4' -diamine (NPB), 4' -bis (N-carbazole) -1,1' -biphenyl (CBP), poly [ (9, 9-dioctylfluorenyl-2, 7-diyl) -co- (4, 4' - (N- (p-butylphenyl)) diphenylamine)](TFB), poly (9-vinylcarbazole) (PVK), polytriphenylamine (Poly-TPD), PEODT: PSS, moO 3 、WO 3 、NiO、CuO、V 2 O 5 And CuS.
The light emitting layer 40 may be an organic light emitting layer or a quantum dot light emitting layer. When the electroluminescent device 100 is a quantum dot electroluminescent device, the light-emitting layer 40 is a quantum dot light-emitting layer. When the electroluminescent device 100 is an organic electroluminescent device, the light-emitting layer 40 is an organic light-emitting layer.
The material of the organic light emitting layer is a material known in the art for an organic light emitting layer of an electroluminescent device, and for example, may be selected from at least one of diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives or fluorene derivatives, TBPe fluorescent materials emitting blue light, TTPA fluorescent materials emitting green light, TBRb fluorescent materials emitting orange light, and DBP fluorescent materials emitting red light.
The material of the quantum dot light-emitting layer is a quantum dot material known in the art for a quantum dot light-emitting layer of an electroluminescent device, and for example, may be selected from but not limited to at least one of single-structure quantum dots and core-shell structure quantum dots. For example, the quantum dots may be selected from, but not limited to, at least one of group II-VI compounds, group III-V compounds, and group I-III-VI compounds. By way of example, the group II-VI compound may be selected from, but not limited to, at least one of CdSe, cdS, cdTe, znSe, znS, cdTe, znTe, znSeTe, znTeS, cdSeS, cdSeTe, cdTeS, cdZnSeTe, cdZnSTe, and CdSe @ ZnS; the III-V compound may be selected from, but not limited to, at least one of InP, inAs, gaP, gaAs, gaSb, alN, alP, inAsP, inNP, inNSb, gaAlNP, and InAlNP; the group I-III-VI compound may be selected from, but is not limited to, at least one of CuInS2, cuInSe2, and AgInS 2.
The material of the cathode 60 is a material known in the art for a cathode of an electroluminescent device, and for example, may be selected from, but not limited to, at least one of silver (Ag), aluminum (Al), and gold (Au).
It can be understood that, in addition to the above functional layers, the electroluminescent device 100 may further include some functional layers that are conventionally used in electroluminescent devices and contribute to improving the performance of electroluminescent devices, such as an electron blocking layer, a hole blocking layer, an electron injection layer, an interface modification layer, and the like.
It is understood that the materials of the layers of the electroluminescent device 100 may be adjusted according to the light emitting requirements of the electroluminescent device 100.
The electroluminescent device 100 further comprises a substrate. The material of the substrate is a material known in the art for electroluminescent device substrates such as glass and the like.
It is understood that the electroluminescent device 100 may be a front-facing electroluminescent device or an inverted electroluminescent device. When the electroluminescent device 100 is an upright electroluminescent device, the substrate is bonded to the anode 10 on the side away from the light-emitting layer 40. When the electroluminescent device 100 is an inverted electroluminescent device, the substrate is bonded to the cathode 60 on the side away from the electron transport layer 50.
Referring to fig. 4, an embodiment of the present application further provides a method for manufacturing a front-mounted electroluminescent device, including the following steps:
step S11: providing a substrate on which an anode 10 and a light-emitting layer 40 are sequentially formed;
step S12: forming an electron transport layer 50 on the light emitting layer 40;
step S13: a cathode 60 is formed on the electron transport layer 50.
The preparation method of the positive electroluminescent device further comprises the following steps: forming a first spacer layer 70 on the light emitting layer 40; and/or forming a second spacer layer 80 on the electron transport layer 50.
It is understood that, when the front electroluminescent device further includes the hole injection layer 20 and the hole transport layer 30, the step S11 is: a substrate is provided, and an anode 10, a hole injection layer 20, a hole transport layer 30, and a light-emitting layer 40 are sequentially formed on the substrate.
Referring to fig. 5, an embodiment of the present application further provides a method for manufacturing an inverted electroluminescent device, including the following steps:
step S21: providing a substrate on which a cathode 60 is formed;
step S22: forming an electron transport layer 50 on the cathode 60;
step S23: forming a light emitting layer 40 on the electron transport layer 50;
step S24: an anode 10 is formed on the light emitting layer 40.
The preparation method of the inverted electroluminescent device further comprises the following steps: forming a second spacer 80 on the cathode 60; and/or forming a first spacer layer 70 on the electron transport layer 50.
It is understood that when the inverted electroluminescent device further includes the hole injection layer 20 and the hole transport layer 30, the step S24 is: a hole transport layer 30, a hole injection layer 20, and an anode 10 are sequentially formed on the light-emitting layer 40.
In the above two preparation methods:
the method for forming the anode 10, the light-emitting layer 40, the electron transport layer 50, the cathode 60, the first spacer layer 70 and the second spacer layer 80 can be performed by a conventional technique in the art, and can be a chemical method or a physical method, for example. The chemical method can be chemical vapor deposition, continuous ion layer adsorption and reaction, anodic oxidation, electrolytic deposition, coprecipitation, etc. The physical method can be a physical coating method or a solution processing method, and the physical coating method can be a thermal evaporation coating method CVD, an electron beam evaporation coating method, a magnetron sputtering method, a multi-arc ion coating method, a physical vapor deposition method PVD, an atomic layer deposition method, a pulse laser deposition method and the like; the solution processing method may be spin coating, printing, ink jet printing, blade coating, printing, dip-coating, dipping, spray coating, roll coating, casting, slit coating, stripe coating, or the like.
Preferably, the electroluminescent device 100 is fabricated in an inert gas atmosphere.
In one embodiment, the method for forming the first spacer layer 70 is: mixing Ag 2 At least one of the S nanocrystal, the NiS nanocrystal, and the Ni (OH) S (nickel oxysulfide) nanocrystal is dispersed in an organic solvent to obtain a dispersion, and then the dispersion is disposed on the light emitting layer 40 or the electron transport layer 50.
The method of forming the second spacer layer 80 is: mixing Ag with water 2 At least one of S nanocrystals, niS nanocrystals, and Ni (OH) S (nickel-rich hydroxysulfide) nanocrystals is dispersed in an organic solvent to obtain a dispersion, and then the dispersion is disposed on the electron transport layer 50 or on the cathode 60.
The organic solvent is methanol, ethanol and other organic solvents which are conventionally used for dispersing the nanocrystalline.
It can be understood that, when the electroluminescent device 100 further includes other functional layers such as an electron blocking layer, a hole blocking layer, an electron injection layer, and/or an interface modification layer, the method for manufacturing the quantum dot light emitting diode 100 further includes a step of forming each functional layer.
The present application will be specifically described below with reference to specific examples, which are only some examples of the present application and are not intended to limit the present application.
Example 1
Providing a glass substrate, and depositing ITO on the substrate to obtain an anode 10 with the thickness of 20 nm;
spin-coating PEDOT (PSS: s-MoO) on the ITO anode 10 3 Annealing the material at 150 ℃ for 20mins to obtain a hole injection layer 20 with the thickness of 15 nm;
spin-coating a PVK material on the hole injection layer 20 in a nitrogen atmosphere, and then annealing at 130 ℃ for 30mins to obtain a hole transport layer 30 with the thickness of 25 nm;
a CdSe @ ZnS quantum dot material is spin-coated on the hole transport layer 30 to obtain a light emitting layer 40 with the thickness of 30 nm;
spin coating Ag on the light emitting layer 40 2 S, carrying out nano-crystalline ethanol dispersion, and then annealing at 120 ℃ for 10mins to obtain a first spacing layer 70 with the thickness of 8 nm;
spin-coating MZO material on the first spacing layer 70, and then annealing at 90 ℃ for 20mins to obtain an electron transmission layer 50 with the thickness of 40 nm;
spin coating Ag on the electron transport layer 50 2 S, annealing the nano-crystalline ethanol dispersion liquid at 150 ℃ for 20S, and then annealing at 80 ℃ for 20mins to obtain a second interlayer 80 with the thickness of 1 nm;
performing vapor plating of Ag on the second spacer 80 to obtain a cathode 60 with a thickness of 120 nm;
and packaging to obtain the electroluminescent device 100.
Example 2
Providing a glass substrate, and depositing an ITO anode 10 with the thickness of 20nm on the substrate;
spin-coating PEDOT (PSS: s-MoO) on the ITO anode 10 3 Annealing the material at 150 ℃ for 20mins to obtain a hole injection layer 20 with the thickness of 15 nm;
spin-coating a PVK material on the hole injection layer 20 in a nitrogen atmosphere, and then annealing at 130 ℃ for 3mins to obtain a hole transport layer 30 with the thickness of 25 nm;
a CdSe @ ZnS quantum dot material is spin-coated on the hole transport layer 30 to obtain a light emitting layer 40 with the thickness of 30 nm;
spin-coating an NiS nanocrystalline ethanol dispersion liquid on the quantum dot light-emitting layer 40, and then annealing at 120 ℃ for 10mins to obtain a first spacing layer 70 with the thickness of 8 nm;
spin-coating MZO material on the first spacing layer 70, and then annealing at 90 ℃ for 20mins to obtain an electron transmission layer 50 with the thickness of 40 nm;
spin-coating NiS nanocrystalline ethanol dispersion on the electron transport layer 50, then annealing at 150 ℃ for 20s, and then annealing at 80 ℃ for 20mins to obtain a second interlayer 80;
performing vapor plating of Ag on the second spacer 80 to obtain a cathode 60 with a thickness of 120 nm;
and packaging to obtain the electroluminescent device 100.
Example 3
Providing a glass substrate, and depositing an ITO anode 10 with the thickness of 20nm on the substrate;
spin-coating PEDOT (PSS: s-MoO) on the ITO anode 10 3 Annealing the material at 150 ℃ for 20mins to obtain a hole injection layer 20 with the thickness of 15 nm;
spin-coating a PVK material on the hole injection layer 20 in a nitrogen atmosphere, and then annealing at 130 ℃ for 30mins to obtain a hole transport layer 30 with the thickness of 25 nm;
a CdSe @ ZnS quantum dot material is spin-coated on the hole transport layer 30 to obtain a light emitting layer 40 with the thickness of 30 nm;
spin-coating a Ni (OH) S nanocrystalline ethanol dispersion liquid on the light-emitting layer 40, and then annealing at 120 ℃ for 10mins to obtain a first spacing layer 70 with the thickness of 8 nm;
spin-coating MZO material on the first spacing layer 70, and then annealing at 90 ℃ for 20mins to obtain an electron transmission layer 50 with the thickness of 40 nm;
spin-coating Ni (OH) S nanocrystalline ethanol dispersion on the electron transport layer 50, then annealing at 150 ℃ for 20S, and then annealing at 80 ℃ for 20mins to obtain a second interlayer 80 with the thickness of 1 nm;
performing vapor plating of Ag on the second spacer 80 to obtain a cathode 60 with a thickness of 120 nm;
and packaging to obtain the electroluminescent device 100.
Example 4
Providing a glass substrate, and depositing an ITO anode 10 with the thickness of 20nm on the substrate;
spin-coating PEDOT (PSS: s-MoO) on the ITO anode 10 3 Annealing the material at 150 ℃ for 20mins to obtain a hole injection layer 20 with the thickness of 15 nm;
spin-coating a PVK material on the hole injection layer 20 in a nitrogen atmosphere, and then annealing at 130 ℃ for 30mins to obtain a hole transport layer 30 with the thickness of 25 nm;
a CdSe @ ZnS quantum dot material is spin-coated on the hole transport layer 30 to obtain a light emitting layer 40 with the thickness of 30 nm;
spin coating Ag on the light emitting layer 40 2 The S nanocrystal and NiS nanocrystal ethanol dispersion liquid is annealed at 120 ℃ for 10mins to obtain a first spacing layer 70 with the thickness of 8nm, wherein the Ag is 2 The molar ratio of the S nanocrystal to the NiS nanocrystal is 3:1;
spin-coating MZO material on the first spacing layer 70, and then annealing at 90 ℃ for 20mins to obtain an electron transmission layer 50 with the thickness of 40 nm;
spin coating Ag on the electron transport layer 50 2 The S nanocrystal and the NiS nanocrystal ethanol dispersion are annealed for 20S at 150 ℃ and then for 20mins at 80 ℃ to obtain a second interlayer 80 with the thickness of 1nm, wherein the Ag is 2 The molar ratio of the S nanocrystal to the NiS nanocrystal is 3:1;
performing vapor plating of Ag on the second spacer 80 to obtain a cathode 60 with a thickness of 120 nm;
and packaging to obtain the electroluminescent device 100.
Example 5
Providing a glass substrate, and depositing an ITO anode 10 with the thickness of 20nm on the substrate;
spin-coating PEDOT (PSS: s-MoO) on the ITO anode 10 3 Annealing the material at 150 ℃ for 20mins to obtain a hole injection layer 20 with the thickness of 15 nm;
spin-coating a PVK material on the hole injection layer 20 in a nitrogen atmosphere, and then annealing at 130 ℃ for 30mins to obtain a hole transport layer 30 with the thickness of 25 nm;
a CdSe @ ZnS quantum dot material is spin-coated on the hole transport layer 30 to obtain a light emitting layer 40 with the thickness of 30 nm;
spin coating Ag on the light emitting layer 40 2 The S nanocrystal and NiS nanocrystal ethanol dispersion liquid is annealed at 120 ℃ for 10mins to obtain a first spacing layer 70 with the thickness of 8nm, wherein the Ag is 2 The molar ratio of the S nanocrystal to the NiS nanocrystal is 1:1;
spin-coating MZO material on the first spacing layer 70, and then annealing at 90 ℃ for 20mins to obtain an electron transmission layer 50 with the thickness of 40 nm;
spin coating Ag on the electron transport layer 50 2 Annealing S nanocrystal and NiS nanocrystal at 150 deg.C for 20S, and annealing at 80 deg.C for 20mins to obtain a second spacer 80 with a thickness of 1nm, wherein Ag is in the form of a thin film 2 The molar ratio of the S nanocrystal to the NiS nanocrystal is 1:1;
performing vapor plating of Ag on the second spacer 80 to obtain a cathode 60 with a thickness of 120 nm;
and packaging to obtain the electroluminescent device 100.
Example 6
Providing a glass substrate, and depositing an ITO anode 10 with the thickness of 20nm on the substrate;
spin-coating PEDOT (PSS: s-MoO) on the ITO anode 10 3 Annealing the material at 150 ℃ for 20mins to obtain a hole injection layer 20 with the thickness of 15 nm;
spin-coating a PVK material on the hole injection layer 20 in a nitrogen atmosphere, and then annealing at 130 ℃ for 30mins to obtain a hole transport layer 30 with the thickness of 25 nm;
a CdSe @ ZnS quantum dot material is spin-coated on the hole transport layer 30 to obtain a light emitting layer 40 with the thickness of 30 nm;
spin coating Ag on the light emitting layer 40 2 The S nanocrystal and Ni (OH) S nanocrystal ethanol dispersion are annealed for 10mins at 120 ℃ to obtain a first spacer layer 70 with the thickness of 8nm, wherein Ag is 2 The molar ratio of the S nanocrystal to the Ni (OH) S nanocrystal is 3:1;
spin-coating MZO material on the first spacing layer 70, and then annealing at 90 ℃ for 20mins to obtain an electron transmission layer 50 with the thickness of 40 nm;
spin coating Ag on the electron transport layer 50 2 Dispersing S nanocrystal and Ni (OH) S nanocrystal in ethanol, annealing at 150 deg.C for 20S, and annealingAnnealing at 80 deg.C for 20mins to obtain a second spacer layer 80 with a thickness of 1nm, wherein Ag is 2 The molar ratio of the S nanocrystal to the Ni (OH) S nanocrystal is 3:1;
evaporating Ag on the second spacer 80 to obtain a cathode 60 with a thickness of 120 nm;
and packaging to obtain the electroluminescent device 100.
Example 7
Providing a glass substrate, and depositing an ITO anode 10 with the thickness of 20nm on the substrate;
spin-coating PEDOT (PSS: s-MoO) on the ITO anode 10 3 Annealing the material at 150 ℃ for 20mins to obtain a hole injection layer 20 with the thickness of 15 nm;
spin-coating a PVK material on the hole injection layer 20 in a nitrogen atmosphere, and then annealing at 130 ℃ for 30mins to obtain a hole transport layer 30 with the thickness of 25 nm;
a CdSe @ ZnS quantum dot material is spin-coated on the hole transport layer 30 to obtain a light emitting layer 40 with the thickness of 30 nm;
spin coating Ag on the light emitting layer 40 2 The S nanocrystal and Ni (OH) S nanocrystal ethanol dispersion are annealed for 10mins at 120 ℃ to obtain a first spacer layer 70 with the thickness of 8nm, wherein Ag is 2 The molar ratio of the S nanocrystal to the Ni (OH) S nanocrystal is 1:1;
spin-coating MZO material on the first spacing layer 70, and then annealing at 90 ℃ for 20mins to obtain an electron transmission layer 50 with the thickness of 40 nm;
spin coating Ag on the electron transport layer 50 2 The ethanol dispersion of S nanocrystal and Ni (OH) S nanocrystal is annealed for 20S at 150 ℃ and then for 20mins at 80 ℃ to obtain a second interlayer 80 with the thickness of 1nm, wherein Ag is 2 The molar ratio of the S nanocrystal to the Ni (OH) S nanocrystal is 1:1;
performing vapor plating of Ag on the second spacer 80 to obtain a cathode 60 with a thickness of 120 nm;
and packaging to obtain the electroluminescent device 100.
Example 8
Providing a glass substrate, and depositing an ITO anode 10 with the thickness of 20nm on the substrate;
at the placeThe ITO anode 10 is spin-coated with PEDOT, PSS, s-MoO 3 Annealing the material at 150 ℃ for 20mins to obtain a hole injection layer 20 with the thickness of 15 nm;
spin-coating a PVK material on the hole injection layer 20 in a nitrogen atmosphere, and then annealing at 130 ℃ for 30mins to obtain a hole transport layer 30 with the thickness of 25 nm;
a CdSe @ ZnS quantum dot material is spin-coated on the hole transport layer 30 to obtain a light emitting layer 40 with the thickness of 30 nm;
and spin-coating NiS nanocrystals and an ethanol dispersion solution of Ni (OH) S nanocrystals on the light-emitting layer 40, and then annealing at 120 ℃ for 10mins to obtain a first spacer layer 70 with a thickness of 8nm, wherein the molar ratio of the NiS nanocrystals to the Ni (OH) S nanocrystals is 1:1;
spin-coating MZO material on the first spacing layer 70, and then annealing at 90 ℃ for 20mins to obtain an electron transmission layer 50 with the thickness of 40 nm;
and spin-coating an ethanol dispersion solution of NiS nanocrystals and Ni (OH) S nanocrystals on the electron transport layer 50, then annealing at 150 ℃ for 20S, and then annealing at 80 ℃ for 20mins to obtain a second spacer layer 80 with the thickness of 1nm, wherein the molar ratio of the NiS nanocrystals to the Ni (OH) S nanocrystals is 1:1;
evaporating Ag on the second spacer 80 to obtain a cathode 60 with a thickness of 120 nm;
and packaging to obtain the electroluminescent device 100.
Example 9
Providing a glass substrate, and depositing an ITO anode 10 with the thickness of 20nm on the substrate;
spin-coating PEDOT (PSS: s-MoO) on the ITO anode 10 3 Annealing the material at 150 ℃ for 20mins to obtain a hole injection layer 20 with the thickness of 15 nm;
spin-coating a PVK material on the hole injection layer 20 in a nitrogen atmosphere, and then annealing at 130 ℃ for 30mins to obtain a hole transport layer 30 with the thickness of 25 nm;
a CdSe @ ZnS quantum dot material is spin-coated on the hole transport layer 30 to obtain a light emitting layer 40 with the thickness of 30 nm;
and spin-coating NiS nanocrystals and an ethanol dispersion solution of Ni (OH) S nanocrystals on the light-emitting layer 40, and then annealing at 120 ℃ for 10mins to obtain a first spacer layer 70 with a thickness of 8nm, wherein the molar ratio of the NiS nanocrystals to the Ni (OH) S nanocrystals is 6:1;
spin-coating MZO material on the first spacing layer 70, and then annealing at 90 ℃ for 20mins to obtain an electron transmission layer 50 with the thickness of 40 nm;
and spin-coating NiS nanocrystalline and Ni (OH) S nanocrystalline ethanol dispersion liquid on the electron transport layer 50, then annealing at 150 ℃ for 20S, and then annealing at 80 ℃ for 20mins to obtain a second interlayer 80 with the thickness of 1nm, wherein the molar ratio of the NiS nanocrystalline to the Ni (OH) S nanocrystalline is 6:1;
performing vapor plating of Ag on the second spacer 80 to obtain a cathode 60 with a thickness of 120 nm;
and packaging to obtain the electroluminescent device 100.
Example 10
Providing a glass substrate, and depositing an ITO anode 10 with the thickness of 20nm on the substrate;
spin-coating PEDOT (PSS: s-MoO) on the ITO anode 10 3 Annealing the material at 150 ℃ for 20mins to obtain a hole injection layer 20 with the thickness of 15 nm;
spin-coating a PVK material on the hole injection layer 20 in a nitrogen atmosphere, and then annealing at 130 ℃ for 30mins to obtain a hole transport layer 30 with the thickness of 25 nm;
a CdSe @ ZnS quantum dot material is spin-coated on the hole transport layer 30 to obtain a light emitting layer 40 with the thickness of 30 nm;
spin coating Ag on the light emitting layer 40 2 The ethanol dispersion of S nanocrystal, niS nanocrystal and Ni (OH) S nanocrystal is annealed at 120 ℃ for 10mins to obtain a first spacer layer 70 with the thickness of 8nm, wherein Ag is 2 The molar ratio of the S nanocrystal to the NiS nanocrystal to the Ni (OH) S nanocrystal is 6:1:1;
spin-coating MZO material on the first spacing layer 70, and then annealing at 90 ℃ for 20mins to obtain an electron transmission layer 50 with the thickness of 40 nm;
spin coating Ag on the electron transport layer 50 2 The ethanol dispersion of the S nanocrystal, the NiS nanocrystal and the Ni (OH) S nanocrystal is annealed for 20S at 150 ℃ and then for 20mins at 80 ℃ to obtain a second interlayer 80 with the thickness of 1nm, wherein,Ag 2 the molar ratio of the S nanocrystal to the NiS nanocrystal to the Ni (OH) S nanocrystal is 6:1:1;
performing vapor plating of Ag on the second spacer 80 to obtain a cathode 60 with a thickness of 120 nm;
and packaging to obtain the electroluminescent device 100.
Example 11
Providing a glass substrate, and depositing an ITO anode 10 with the thickness of 20nm on the substrate;
spin-coating PEDOT (PSS: s-MoO) on the ITO anode 10 3 Annealing the material at 150 ℃ for 20mins to obtain a hole injection layer 20 with the thickness of 15 nm;
spin-coating a PVK material on the hole injection layer 20 in a nitrogen atmosphere, and then annealing at 130 ℃ for 30mins to obtain a hole transport layer 30 with the thickness of 25 nm;
a CdSe @ ZnS quantum dot material is spin-coated on the hole transport layer 30 to obtain a light emitting layer 40 with the thickness of 30 nm;
spin coating Ag on the light emitting layer 40 2 The S nanocrystal, the NiS nanocrystal and the Ni (OH) S nanocrystal ethanol dispersion are annealed for 10mins at 120 ℃ to obtain a first spacing layer 70 with the thickness of 8nm, wherein the Ag is 2 The molar ratio of the S nanocrystal to the NiS nanocrystal to the Ni (OH) S nanocrystal is 1:1:1;
spin-coating MZO material on the first spacing layer 70, and then annealing at 90 ℃ for 20mins to obtain an electron transmission layer 50 with the thickness of 40 nm;
spin coating Ag on the electron transport layer 50 2 The ethanol dispersion of S nanocrystal, niS nanocrystal and Ni (OH) S nanocrystal is annealed for 20S at 150 ℃ and then for 20mins at 80 ℃ to obtain a second interlayer 80 with the thickness of 1nm, wherein Ag is 2 The molar ratio of the S nanocrystal to the NiS nanocrystal to the Ni (OH) S nanocrystal is 1:1:1;
performing vapor plating of Ag on the second spacer 80 to obtain a cathode 60 with a thickness of 120 nm;
and packaging to obtain the electroluminescent device 100.
Example 12
Providing a glass substrate, and depositing an ITO anode 10 with the thickness of 20nm on the substrate;
spin-coating PEDOT (PSS: s-MoO) on the ITO anode 10 3 Annealing the material at 150 ℃ for 20mins to obtain a hole injection layer 20 with the thickness of 15 nm;
spin-coating a PVK material on the hole injection layer 20 in a nitrogen atmosphere, and then annealing at 130 ℃ for 30mins to obtain a hole transport layer 30 with the thickness of 25 nm;
a CdSe @ ZnS quantum dot material is spin-coated on the hole transport layer 30 to obtain a light emitting layer 40 with the thickness of 30 nm;
spin coating Ag on the light emitting layer 40 2 S, carrying out nano-crystalline ethanol dispersion, and then annealing at 120 ℃ for 10mins to obtain a first spacing layer 70 with the thickness of 8 nm;
coating MZO material on the first spacing layer 70 in a spin mode, and then annealing at 90 ℃ for 20mins to obtain an electron transmission layer 50 with the thickness of 40 nm;
evaporating Ag on the electron transport layer 50 to obtain a cathode 60 with the thickness of 120 nm;
and packaging to obtain the electroluminescent device 100.
Example 13
Providing a glass substrate, and depositing an ITO anode 10 with the thickness of 20nm on the substrate;
spin-coating PEDOT (PSS: s-MoO) on the ITO anode 10 3 Annealing the material at 150 ℃ for 20mins to obtain a hole injection layer 20 with the thickness of 15 nm;
spin-coating a PVK material on the hole injection layer 20 in a nitrogen atmosphere, and then annealing at 130 ℃ for 30mins to obtain a hole transport layer 30 with the thickness of 25 nm;
a CdSe @ ZnS quantum dot material is spin-coated on the hole transport layer 30 to obtain a light emitting layer 40 with the thickness of 30 nm;
spin-coating MZO material on the luminous layer 40, and then annealing at 90 ℃ for 20mins to obtain an electron transmission layer 50 with the thickness of 40 nm;
spin-coating NiS nanocrystalline ethanol dispersion liquid on the electron transport layer 50, then annealing at 150 ℃ for 20s, and then annealing at 80 ℃ for 20mins to obtain a second spacer layer 80 with the thickness of 1 nm;
performing vapor plating of Ag on the second spacer 80 to obtain a cathode 60 with a thickness of 120 nm;
and packaging to obtain the electroluminescent device 100.
Comparative example 1
Providing a glass substrate, and depositing an ITO anode with the thickness of 20nm on the substrate;
spin-coating PEDOT, PSS, s-MoO on the ITO anode 3 Annealing the material at 150 ℃ for 20mins to obtain a hole injection layer 20 with the thickness of 15 nm;
spin-coating a PVK material on the hole injection layer in a nitrogen atmosphere, and then annealing at 130 ℃ for 30mins to obtain a hole transport layer 30 with the thickness of 25 nm;
spin-coating CdSe @ ZnS quantum dot material on the hole transport layer to obtain a light-emitting layer with the thickness of 30 nm;
spin-coating MZO material on the luminescent layer, and then annealing at 90 ℃ for 20mins to obtain an electron transport layer 50 with the thickness of 40 nm;
evaporating Ag on the electron transport layer to obtain a cathode 60 with the thickness of 120 nm;
and packaging to obtain the electroluminescent device.
Comparative example 2
Providing a glass substrate, and depositing an ITO anode with the thickness of 20nm on the substrate;
spin-coating PEDOT, PSS, s-MoO on the ITO anode 3 Annealing the material at 150 ℃ for 20mins to obtain a hole injection layer 20 with the thickness of 15 nm;
spin-coating a PVK material on the hole injection layer in a nitrogen atmosphere, and then annealing at 130 ℃ for 30mins to obtain a hole transport layer 30 with the thickness of 25 nm;
spin-coating CdSe @ ZnS quantum dot material on the hole transport layer to obtain a light-emitting layer with the thickness of 30 nm;
spin coating Mg on the light emitting layer: ag 2 S, annealing the material at 90 ℃ for 20mins to obtain an electron transport layer with the thickness of 40 nm;
evaporating Ag on the electron transport layer to obtain a cathode 60 with the thickness of 120 nm;
and packaging to obtain the electroluminescent device.
AFM surface topography tests were performed on the surface of the second spacer layer 80 of example 1 away from the electron transport layer 50 and the surface of the electron transport layer of comparative example 1 away from the light-emitting layer, and the AFM surface topography maps of the surface of the second spacer layer 80 of example 1 away from the electron transport layer 50 and the surface of the electron transport layer of comparative example 1 away from the light-emitting layer are respectively referred to fig. 6 and fig. 7.
As can be seen from fig. 6 and 7, the flatness of the surface of the second spacer layer 80 away from the electron transport layer 50 in example 1 in fig. 6 is significantly higher than that of the surface of the electron transport layer away from the light emitting layer in comparative example 1 in fig. 7.
The electron transport layers of the electroluminescent devices of example 1 and comparative example 1 were subjected to XPS test to measure the amount of oxygen vacancies (or oxygen defects) contained in the electron transport layers, and the results of the measurement are shown in the following table:
table one:
as can be seen from table 1, the electroluminescent device 100 of example 1 including the first spacer layer 70 and the second spacer layer 80 has significantly better oxidation resistance than the electroluminescent device of comparative example 1 not including the first spacer layer 70 and the second spacer layer 80 of the present application, which is helpful to improve the stability of the electroluminescent device 100.
The electroluminescent devices 100 of examples 1 to 13 and the electroluminescent devices of comparative examples 1 to 2 were subjected to a luminance and external quantum efficiency performance test using JVL test equipment. The monitoring of the electrical performance data is respectively carried out on the 1 st day, the 10 th day and the 30 th day after the preparation of the device is finished, and the test results are shown in the following table II:
table two:
as can be seen from Table 2:
comparative example 1 compared to example 1, the electron transport layer did not have Ag 2 The spacing and the cladding of the S spacer layer, at the initial stage of the device preparation completion, even though the EQE of the electroluminescent device is substantially identical to the efficiency of the electroluminescent device 100 of example 1, the brightness of comparative example 1 is relatively low; at day 10, the electroluminescent device of comparative example 1 has a significantly higher positive aging effect than the electroluminescent device 100 of example 1 due to oxygen adsorption, and the EQE is accelerated rapidly, indicating that the cathode is oxidized to a higher degree, whereas at day 30, the electroluminescent device of comparative example 1 enters a significantly negative aging (i.e., the performance is significantly degraded) stage, and the lifetime stability is poor.
Example 12 in contrast to example 1, no Ag was disposed between the electron transport layer and the cathode 2 The S spacer layer, the luminance and EQE of the electroluminescent device 100 of example 12 were not significantly impaired, but the stability of the electroluminescent device 100 was significantly deteriorated due to the oxidation of the cathode after the placement, and the performance was more significantly deteriorated after the long-term placement.
Example 13 compared to example 2, in the case of EQE approximately equivalent to that of example 2, the brightness is lower when no NiS spacer layer is disposed between the electron transport layer and the light emitting layer, and a large amount of charges are accumulated at the interface between the light emitting layer and the hole transport layer, so that the stability of the electroluminescent device 100 is reduced and aging phenomenon is more significant. Although the EQE of the electroluminescent device 100 of example 13 increased significantly at day 10, it had dropped to a level close to (somewhat reduced from) the initial level at day 30, and continued placement would enter a severe negative-aging lifetime decay state.
The electroluminescent device and the method for manufacturing the same provided by the embodiments of the present application are described in detail above, and the principles and embodiments of the present application are explained herein by applying specific examples, and the description of the embodiments above is only used to help understanding the method and the core concept of the present application; meanwhile, for those skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
Claims (10)
1. An electroluminescent device comprises an anode, a luminescent layer, an electron transport layer and a cathode which are arranged in a laminated manner, and is characterized in that: the electroluminescent device also comprises a spacing layer, the spacing layer is arranged between the luminescent layer and the electron transport layer and/or between the electron transport layer and the cathode, and the material of the spacing layer is selected from Ag 2 At least one of S nanocrystals, niS nanocrystals, and Ni (OH) S nanocrystals.
2. An electroluminescent device as claimed in claim 1, characterized in that: the material of the spacing layer comprises Ag 2 S nanocrystals and NiS nanocrystals, said Ag 2 The molar ratio of the S nanocrystal to the NiS nanocrystal ranges from (4; and/or
The material of the spacing layer is Ag 2 S nanocrystal and NiS nanocrystal, and Ag 2 The molar ratio of the S nanocrystal to the NiS nanocrystal ranges from (4.
3. An electroluminescent device as claimed in claim 1, characterized in that: the material of the spacing layer comprises Ag 2 S nanocrystals and Ni (OH) S nanocrystals, said Ag 2 The molar ratio of the S nanocrystals to the Ni (OH) S nanocrystals ranges from (4; and/or
The material of the spacing layer is Ag 2 S nanocrystals and Ni (OH) S nanocrystals, the Ag 2 The molar ratio of the S nanocrystals to the Ni (OH) S nanocrystals was in the range of (4.
4. An electroluminescent device as claimed in claim 1, characterized in that: the material of the spacing layer comprises NiS nanocrystals and Ni (OH) S nanocrystals, wherein the molar ratio of the NiS nanocrystals to the Ni (OH) S nanocrystals is in the range of (6; and/or
The material of the spacing layer consists of NiS nanocrystals and Ni (OH) S nanocrystals, and the molar ratio of the NiS nanocrystals to the Ni (OH) S nanocrystals is in the range of (6.
5. An electroluminescent device as claimed in claim 1, characterized in that: the material of the spacing layer comprises Ag 2 S nanocrystals, niS nanocrystals and Ni (OH) S nanocrystals, said Ag 2 The molar ratio of the S nanocrystal, the NiS nanocrystal, and the Ni (OH) S nanocrystal is in the range of (8; and/or
The material of the spacing layer is Ag 2 S nanocrystal, niS nanocrystal and Ni (OH) S nanocrystal, and the Ag is 2 The molar ratio of the S nanocrystal, the NiS nanocrystal, and the Ni (OH) S nanocrystal is in the range of (8.
6. An electroluminescent device as claimed in claim 1, characterized in that: the spacing layer is positioned between the light-emitting layer and the electron transport layer, and the thickness of the spacing layer is 5-10nm; and/or the presence of a gas in the gas,
the spacing layer is positioned between the electron transport layer and the cathode, and the thickness of the spacing layer is greater than 0 and less than or equal to 2nm.
7. An electroluminescent device as claimed in claim 1, characterized in that: the material of the electron transport layer is selected from ZnO and TiO 2 、BaTiO 3 At least one of aluminum-doped zinc oxide, lithium-doped zinc oxide and magnesium-doped zinc oxide; and/or
The light-emitting layer is an organic light-emitting layer or a quantum dot light-emitting layer, the material of the organic light-emitting layer is at least one selected from diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives or fluorene derivatives, blue light-emitting TBPe fluorescent materials, green light-emitting TTPA fluorescent materials, orange light-emitting TBRb fluorescent materials and red light-emitting DBP fluorescent materials, and the material of the quantum dot light-emitting layer is at least one selected from II-VI compounds, III-V compounds and I-III-VI compounds; and/or
The cathode is made of at least one of Ag, al and Au.
8. An electroluminescent device as claimed in claim 1, characterized in that: the thickness of the electron transport layer is in the range of 30-55nm.
9. A preparation method of an electroluminescent device is characterized by comprising the following steps:
providing a substrate, and forming a laminated anode and a light-emitting layer on the substrate;
forming an electron transport layer on the light emitting layer;
forming a cathode on the electron transport layer;
before forming the electron transport layer on the light emitting layer, the preparation method further includes: forming a spacer layer according to any one of claims 1 to 8 on the light emitting layer; and/or
Before forming a cathode on the electron transport layer, the preparation method further includes: forming the spacer layer of any one of claims 1-8 on the electron transport layer.
10. A preparation method of an electroluminescent device is characterized by comprising the following steps:
providing a substrate, and forming a cathode on the substrate;
forming an electron transport layer on the cathode;
forming a light-emitting layer and an anode stacked on the electron transport layer;
before forming the electron transport layer on the cathode, the preparation method further includes: forming a spacer layer according to any one of claims 1 to 8 on the cathode; and/or
Before forming the laminated light emitting layer and anode on the electron transport layer, the preparation method further includes: forming the spacer layer of any one of claims 1-8 on the electron transport layer.
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