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CN111883675B - Hybrid type electroluminescent device, preparation method thereof and display device - Google Patents

Hybrid type electroluminescent device, preparation method thereof and display device Download PDF

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Publication number
CN111883675B
CN111883675B CN201910905359.6A CN201910905359A CN111883675B CN 111883675 B CN111883675 B CN 111883675B CN 201910905359 A CN201910905359 A CN 201910905359A CN 111883675 B CN111883675 B CN 111883675B
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layer
quantum dot
metal
electron injection
cathode
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CN111883675A (en
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李正吉
李哲
陈颖
余磊
庄锦勇
董婷
陈亚文
宋晶尧
向超宇
孙贤文
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Guangdong Juhua Printing Display Technology Co Ltd
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Guangdong Juhua Printing Display Technology Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

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  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to a hybrid electroluminescent device, a preparation method thereof and a display device. The hybrid electroluminescent device comprises a quantum dot light-emitting unit and an organic light-emitting unit; the quantum dot light-emitting unit comprises a first anode, a quantum dot light-emitting layer, a first electron injection layer and a first cathode which are arranged in a stacked mode; a first electron injection layer in direct contact with the first cathode, the first electron injection layer comprising a metal fluoride and a low work function metal; the organic light-emitting unit comprises a second anode, an organic light-emitting layer, a second electron injection layer and a second cathode which are arranged in a stacked mode, the second electron injection layer is directly contacted with the second cathode, and the second electron injection layer contains the metal fluoride and the low-work-function metal; wherein the metal fluoride is selected from at least one of alkali metal fluoride and alkaline earth metal fluoride, and the low work function metal is selected from at least one of metal elements having a work function of lower than 4 eV.

Description

Hybrid electroluminescent device, preparation method thereof and display device
Technical Field
The invention relates to the technical field of display, in particular to a hybrid electroluminescent device, a preparation method thereof and a display device.
Background
Because the Quantum Dot Lighting Emitting Diode (QD LED) has the advantages of high contrast, high color purity, wide color gamut (half-peak width of monochromatic light emission spectrum is less than 30 nm), high brightness, wide viewing angle and the like, the QD LED has great application potential in the next generation television display technology. However, since the lifetime of the blue quantum dots of the QD LED is very short, for example, the time for the blue quantum dots to decay to 95% of the initial brightness (LT 95) under the 1000nit brightness condition is often less than 10 hours, which is difficult to achieve the lifetime specified by the existing television product standards. Therefore, the biggest technical challenge for popularization and application of QD LED devices in the next generation television display technology is to develop a blue quantum dot material with longer lifetime, higher efficiency and better performance.
Since the light-emitting lifetime (LT 95 can reach 1400 hours) of the blue organic light-emitting material is much longer than that of the blue quantum dot light-emitting material, in order to improve the lifetime of the blue light-emitting material, it is a possible solution to design the light-emitting layer as a hybrid device containing the blue organic light-emitting layer, the red quantum dot light-emitting layer and the green quantum dot light-emitting layer. Fig. 1 is a schematic structural diagram of a current hybrid quantum dot (H-QLED) device, where the light-emitting layer includes a red quantum dot light-emitting layer, a green quantum dot light-emitting layer, and a blue organic material light-emitting layer, the organic electron transport layer (ETL 2) is shared by the red quantum dot light-emitting layer, the green quantum dot light-emitting layer, and the blue organic material light-emitting layer, and an inorganic electron transport layer (ETL 1) is disposed between the organic electron transport layer and the (red/green) quantum dot light-emitting layer. In order to provide a better viewing angle for the H-QLED device, by using a transparent oxide layer with low reflectivity as a cathode, as shown in fig. 2, the vacuum level of the H-QLED cathode is high (greater than-4.5 eV), a large electron injection barrier exists between the lowest unoccupied orbital level (-3 eV to-2 eV) of the organic material electron transport layer (ETL 2), which is not favorable for electron injection and transport, and the driving voltage of the H-QLED device is high. Therefore, although this hybrid structure can improve the emission lifetime of the blue pixel of the display device, the hybrid device has problems of high driving voltage (more than 12V) and high product power consumption.
Disclosure of Invention
In view of this, it is necessary to provide a hybrid type electroluminescent device having a low driving voltage in response to the problem of a high driving voltage of the hybrid device.
A hybrid electroluminescent device comprising a quantum dot light-emitting unit and an organic light-emitting unit;
the quantum dot light-emitting unit comprises a first anode, a quantum dot light-emitting layer, a first electron injection layer and a first cathode which are arranged in a stacked mode; the first electron injection layer is in direct contact with the cathode, the first electron injection layer comprising a metal fluoride and a low work function metal;
the organic light-emitting unit comprises a second anode, an organic light-emitting layer, a second electron injection layer and a second cathode which are arranged in a stacked mode, the second electron injection layer is in direct contact with the second cathode, the second electron injection layer comprises the metal fluoride and the low work function metal, and the second cathode is a transparent conductive oxide layer;
wherein the metal fluoride is at least one selected from the group consisting of alkali metal fluorides and alkaline earth metal fluorides, and the low work function metal is at least one selected from the group consisting of metal elements having a work function of less than 4 eV.
The mixed type electroluminescent device comprises a quantum dot luminescent unit and an organic luminescent unit, wherein the quantum dot luminescent unit and the organic luminescent unit adopt specific electron injection layers and are matched with a cathode, so that the injection barrier of electrons injected from the cathode to a quantum dot luminescent layer or an organic luminescent layer is reduced, the injection and transmission of electrons are facilitated, an organic electron transmission layer in the original mixed device can be omitted, and the driving voltage of the device is reduced; and because the potential barrier of electron injection is reduced, the injection and transmission efficiency of electrons is improved, and the luminous efficiency of the device can be improved.
In one embodiment, the metal fluoride is selected from at least one of sodium fluoride, lithium fluoride, potassium fluoride, magnesium fluoride, and calcium fluoride; the low work function metal is selected from at least one of magnesium, silver, barium and ytterbium.
In one embodiment, the first electron injection layer is a stacked structure including a metal fluoride layer formed of the metal fluoride and a metal layer formed of the low work function metal, the metal fluoride layer being in direct contact with the first cathode.
In one embodiment, the second electron injection layer is a stacked structure including a metal fluoride layer formed of the metal fluoride and a metal layer formed of the low work function metal, the metal fluoride layer being in direct contact with the second cathode.
In one embodiment, the number of the metal layers is one or more;
when the number of the metal layers is one, the metal layers are formed by at least one low work function metal;
when the number of the metal layers is multiple, each of the multiple metal layers is formed by one kind of the low work function metal, or at least one of the multiple metal layers is formed by more than two kinds of the low work function metals.
In one embodiment, the metal fluoride layer is a sodium fluoride layer.
In one embodiment, the first cathode is a transparent conductive oxide layer.
In one embodiment, the second cathode is the transparent conductive oxide layer.
In one embodiment, the transparent conductive oxide layer is an IZO (indium zinc oxide) single layer, an ITO (indium tin oxide) single layer, or a multi-layer structure composed of an IZO layer and an ITO layer.
In one embodiment, the thickness of the first electron injection layer is 1nm to 20nm, and the thickness of the second electron injection layer is 1nm to 20nm.
In one embodiment, an electron transport layer is further disposed between the quantum dot light-emitting layer and the first electron injection layer, and the electron transport layer is a zinc oxide layer or an insulating material doped zinc oxide layer.
In one embodiment, an electron transport regulation layer is further arranged between the electron transport layer and the quantum dot light-emitting layer, and the electron transport regulation layer comprises an insulating material.
In one embodiment, the quantum dot luminescent material of the quantum dot luminescent layer is a quantum dot luminescent material containing a long-chain organic ligand, and a short-chain organic ligand is bound to the surface of the quantum dot luminescent layer close to the surface of the first anode.
In one embodiment, the quantum dot luminescent material is at least one selected from CdSe, inP, gaSe, znS and CdS quantum dots.
In one embodiment, the quantum dot light-emitting layer comprises a red quantum dot light-emitting layer and a green quantum dot light-emitting layer which are arranged in the same layer, and the organic light-emitting layer is a blue organic light-emitting layer.
Another object of the present invention is to provide a method for preparing a hybrid electroluminescent device, which comprises the steps of forming a quantum dot light-emitting unit and an organic light-emitting unit;
wherein the forming of the quantum dot light emitting unit comprises the steps of:
providing a first anode, and sequentially forming a quantum dot light-emitting layer, a first electron injection layer and a first cathode on the first anode; the first electron injection layer is in direct contact with the first cathode, the first electron injection layer comprising a metal fluoride and a low work function metal;
the forming of the organic light emitting unit includes the steps of:
providing a second anode, and sequentially forming an organic light-emitting layer, a second electron injection layer and a second cathode on the second anode; the second electron injection layer is in direct contact with the second cathode, the second electron injection layer comprising the metal fluoride and the low work function metal; wherein the metal fluoride is at least one selected from the group consisting of alkali metal fluorides and alkaline earth metal fluorides, and the low work function metal is at least one selected from the group consisting of metal elements having a work function of less than 4 eV.
Still another object of the present invention is to provide a display device comprising the hybrid type electroluminescent device or the hybrid type electroluminescent device prepared by the method.
Drawings
FIG. 1 is a schematic structural diagram of a conventional H-QLED device;
fig. 2 is a schematic diagram of an energy level structure of the H-QLED device shown in fig. 1;
fig. 3 is a schematic structural diagram of a hybrid electroluminescent device according to an embodiment of the present invention;
fig. 4 is a schematic diagram of the energy level structure of the hybrid electroluminescent device shown in fig. 3;
fig. 5 is a schematic structural diagram of a hybrid electroluminescent device according to another embodiment of the present invention.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present.
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.
As shown in fig. 3, the hybrid electroluminescent device 100 according to an embodiment of the present invention includes a quantum dot light emitting unit 110 and an organic light emitting unit 130.
The quantum dot light-emitting unit 110 includes a first anode 111, a quantum dot light-emitting layer 114, a first electron injection layer 117, and a first cathode 118, which are stacked, wherein the first electron injection layer 117 is in direct contact with the first cathode 118, the first electron injection layer 117 includes a metal fluoride selected from at least one of alkali metal fluoride and alkaline earth metal fluoride, and a low work function metal selected from at least one of metal elements having a function lower than 4 eV; the first cathode 118 is a transparent conductive oxide layer.
The organic light emitting unit 130 includes a second anode 131, an organic light emitting layer 134, a second electron injection layer 137, and a second cathode 138, which are stacked; wherein the second electron injection layer 137 is in direct contact with the second cathode 138; the second electron injecting layer 137 also includes a metal fluoride selected from at least one of alkali metal fluoride and alkaline earth metal fluoride, and a low work function metal selected from at least one of metal elements having a function lower than 4 eV; the second cathode 138 is a transparent conductive oxide layer.
The hybrid electroluminescent device 100 includes the quantum dot light emitting unit 110 and the organic light emitting unit 130, wherein an organic material electron transport layer is not required to be disposed between the quantum dot light emitting layer 114 of the quantum dot light emitting unit 110 and the first cathode 118, but a specific first electron injection layer 117 is adopted, and by matching the first electron injection layer 117 and the first cathode 118, as shown in fig. 4, ohmic contact is formed between the first electron injection layer 117 and the first cathode 118, so that an injection barrier for electrons injected from the first cathode 117 to the quantum dot light emitting layer 114 is reduced, electron injection is facilitated, an organic electron transport layer in an original hybrid device is omitted, and a driving voltage of the device is reduced; and because the potential barrier of electron injection is reduced, the injection and transmission efficiency of electrons is improved, so that the luminous efficiency of the device can be improved.
Because the electron current required by the quantum dot light-emitting material for efficient light emission is higher than that of the organic light-emitting material, the design of the first electron injection layer of the quantum dot light-emitting unit 110 and the second electron injection layer of the organic light-emitting unit 130 in the hybrid electroluminescent device needs to be selected according to the quantum dot light-emitting material and the organic light-emitting material, so that the efficiency of electron injection and transmission can meet the light-emitting requirements of the quantum dot light-emitting material and the organic light-emitting material at the same time, a balanced result is obtained, the quantum dot light-emitting unit and the organic light-emitting unit can be ensured to effectively emit light, and the final light-emitting efficiency is not lower than 40% of the optimized efficiency of single light emission.
In one embodiment, the metal fluoride is selected from at least one of sodium fluoride, lithium fluoride, potassium fluoride, magnesium fluoride, and calcium fluoride; the low work function metal is selected from at least one of magnesium, silver, barium and ytterbium.
In one embodiment, the first electron injection layer 117 is a stacked structure including a metal fluoride layer (not shown) formed of the metal fluoride and at least one metal layer (not shown) formed of the low work function metal, which are stacked, and directly contact the first cathode 118.
In one embodiment, the second electron injection layer 137 is also a stacked structure including a metal fluoride layer (not shown) formed of the metal fluoride and at least one metal layer (not shown) formed of the low work function metal, which are stacked, and directly contact the second cathode 138. In one embodiment, the number of metal layers is one; the metal layer is formed from at least one of the low work function metals described above.
In one embodiment, the number of metal layers is multiple, and each of the multiple metal layers is formed of a low work function metal.
In one embodiment, the number of metal layers is multiple, and at least one of the multiple metal layers is formed by more than two low work function metals.
It is to be understood that the metal layer may be a single-layer metal layer formed of one kind of low work function metal, a single-layer alloy metal layer formed of an alloy containing two or more kinds of low work function metals, or a stacked metal structure in which a single-layer metal layer and/or a single-layer alloy metal layer are sequentially stacked. For example, the first and second electron injection layers 117 and 137 may have a two-layer stack structure composed of a metal fluoride layer and a single metal layer, such as NaF (sodium fluoride)/Mg-Ag alloy (magnesium silver alloy), naF/Ag, and NaF/Mg, or a multi-layer stack structure composed of a metal fluoride layer and a multi-metal layer, such as NaF/Mg-Ag alloy/Ag, naF/barium (Ba)/Mg-Ag alloy/Ag, naF/Ba/Mg, naF/ytterbium (Yb)/Mg-Ag alloy/Ag, naF/Yb/Mg-Ag alloy, naF/Yb/Ag, and NaF/Yb/Mg, respectively.
In the present embodiment, the metal fluoride layer is a sodium fluoride layer.
Further, the metal layer is Ag, yb, ba, mg or Mg-Ag alloy.
Therefore, the sodium fluoride layer is matched with the low-work-function metal single layer or the laminated structure to be used as the first electron injection layer 117 and the second electron injection layer 137, so that the electron transmission performance of the quantum dot light-emitting layer can be improved, and the electron transmission performance of the blue organic light-emitting layer cannot be influenced, and the electron injection and transmission performance of the red and green quantum dot light-emitting layers and the blue organic light-emitting layer can be balanced.
Meanwhile, because oxides such as IZT and ITO are used as materials of the transparent cathode, a sputtering process is usually required for thin film deposition, and a functional layer (such as an electron transport layer) in a device is damaged due to the existence of a large number of high-energy particles in the sputtering process. The low work function metal in the first electron injection layer 117 and the second electron injection layer 137 may reduce the metal element in the alkali metal fluoride or the alkaline earth metal fluoride to form a part of the alkali metal or the alkaline earth metal simple substance, and simultaneously form a part of the low work function metal fluoride, so as to maintain the electron injection effect of the alkali metal or the alkaline earth metal; compared with chlorides and bromides of corresponding metal elements, the fluoride of the alkali metal fluoride or the alkaline earth metal fluoride has stronger ionic bond, free halogen anions are not easy to release, the diffusion of the free halogen anions to the anode direction is avoided, the device can be protected from being damaged as little as possible in the sputtering manufacturing process of the cathode, and the service life of the device is prolonged.
In one embodiment, the first electron injection layer 117 has a thickness of 1nm to 20nm, and the second electron injection layer 137 has a thickness of 1nm to 20nm.
In one embodiment, the transparent conductive oxide layer is an IZO single layer, an ITO single layer, or a multi-layer structure composed of an IZO layer and an ITO layer.
The transparent conductive oxide layer is used as a cathode, and the light transmittance of the transparent conductive oxide layer is not lower than 40%. Specifically, the transparent conductive oxide layer is an IZO layer, an IZO/ITO/IZO layer or an ITO/IZO/ITO layer.
In this embodiment, an electron transport layer 116 (ETL) is further disposed between the quantum dot light emitting layer and the first electron injection layer 117, and the electron transport layer 116 is a zinc oxide layer or an insulating material doped zinc oxide layer. Preferably, the insulating material is PMMA (polymethylmethacrylate).
Further, when the electron transport layer 116 is an insulating material doped zinc oxide layer, the doping concentration of the insulating material is 0.5wt% to 10wt%.
Further, the thickness of the electron transport layer 116 is 15nm to 50nm. In this embodiment, with continued reference to fig. 3, an electron transport adjusting layer 115 is further disposed between the electron transport layer 116 and the quantum dot light emitting layer 114, and the electron transport adjusting layer 115 includes an insulating material.
Further, the insulating material is polymethyl methacrylate.
Therefore, the adjustment of the electron transmission rate is realized by adding the electron transmission adjusting layer 115, the electron transmission rate can be adjusted by changing the thickness of the electron transmission layer 115, the electron current of the quantum dot light emitting layer 114 is effectively adjusted, the current carriers in the quantum dot light emitting layer 114 realize the electrical balance, and the device performance is further improved.
Further, the thickness of the electron transit adjusting layer 115 is 10nm to 60nm.
In the present embodiment, the quantum dot light emitting layer 114 includes a red quantum dot layer 1141 and a green quantum dot layer 1143 disposed in the same layer, and the organic light emitting layer 134 is a blue organic light emitting layer. In one embodiment, the organic light emitting layer 134 includes a host material, which may be a TADF (thermally activated delayed fluorescence) material or an exciplex-based organic material.
Specifically, the organic light emitting layer 134 is made of a blue OLED light emitting layer ink, and preferably has a thickness of 10nm to 150nm.
In an embodiment, the red quantum dot light-emitting layer 1141 and the green quantum dot layer 1143 respectively include red and green quantum dot materials, or a mixed layer of an organic material and a quantum dot material, or a mixed layer including multiple quantum dot materials.
Further, in order to improve the electrical balance of the carriers in the quantum dot light emitting layer 114, a plurality of quantum dot materials with different carrier transport characteristics may be selected for matching and mixing, such as mixing the electron dominant quantum dot and the hole dominant quantum dot.
Further, the quantum dot material is selected from at least one of CdSe, inP, gaSe, znS and CdS quantum dot materials.
Further, the thickness of the quantum dot light emitting layer 114 is 10nm to 100nm.
In one embodiment, the quantum dot light emitting material of the quantum dot light emitting layer 114 is a quantum dot material containing long-chain organic ligands, and the quantum dots of the quantum dot light emitting layer 114 near the surface of the first anode 118 are bonded with short-chain organic ligands.
At present, the quantum dots used in the preparation of display devices mostly use oil-soluble organic ligands with long chains in the synthesis process, which is beneficial to the stability of the quantum dots in a synthesis system. However, the long-chain oil-soluble organic ligand adversely affects the subsequent applications of the quantum dot, for example, in a QLED, the long-chain ligand has insulation property and hinders the carrier transport performance. Therefore, when the quantum dot material containing the long-chain organic matter material is formed into a film, the long-chain organic matter ligand introduced in the quantum dot synthesis process is replaced by the short-chain organic matter ligand by adopting the short-chain organic matter ligand for in-situ ligand replacement. Thus, the ligand combined with the surface of the quantum dot at the interface between the quantum dot light emitting layer 114 and the Hole Transport Layer (HTL) is a short-chain organic ligand, so that the diffusion distance for transferring charges to the core of the quantum dot can be shortened, the transmission of carriers is facilitated, the performance of the device is improved, the light emitting efficiency is improved, and the service life is prolonged.
Further, the short-chain organic ligand is selected from pyridine.
The short-chain organic matter ligand is selected to be easy to replace with the long-chain organic matter ligand of the quantum dot, so that the in-situ replacement of the ligand is easy to realize, and the diffusion distance of charge transfer to the quantum dot core can be greatly shortened. In an embodiment, the quantum dot light emitting unit 110 of the hybrid electroluminescent device 100 further includes a first hole transport layer 113 disposed between the first anode 111 and the quantum dot light emitting layer 114.
In one embodiment, the organic light emitting unit 130 also includes a second hole transport layer 133 disposed between the second anode 131 and the organic light emitting layer 134. Further, the materials of the first hole transport layer 113 and the second hole transport layer 133 are respectively selected from one of PVK (Poly (9-vinylcarbazole)), poly-TPD (polytriphenylamine), TFB (Poly [ (N, N ' - (4-N-butylphenyl) -N, N ' -diphenyl-1, 4-phenylenediamine) -ALT- (9, 9-di-N-octylfluorenyl-2, 7-diyl) ]), NPB (N, N-diphenyl-N, N-di (naphthyl-1) -4, 4-biphenyldiamine), TPD (polybisthienylpyrrolopyrroledione-thiophene), CBP (4, 4' -di (9-carbazole) biphenyl), TCTA (4, 4',4 ″ -tris (carbazol-9-yl) triphenylamine), mCP (9, 9' - (1, 3-phenyl) di-9H-carbazole).
In this way, by using the cross-linked organic material as the material of the first and/or second hole transport layer, adverse effects of a solvent on the HTL during the production of the organic light emitting layer or the quantum dot light emitting layer can be avoided, and stability between the HTL and the organic light emitting layer or the quantum dot light emitting layer can be improved.
In the present embodiment, the thickness of the first hole transport layer 113 and the second hole transport layer is preferably 10nm to 50nm.
Further, the first hole transporting layer 113 and the second hole transporting layer 133 are made of the same material and have the same thickness.
In an embodiment, the quantum dot light emitting layer 110 further includes a first Hole Injection Layer (HIL) 112 disposed between the first anode 111 and the first hole transport layer 113, and/or a first light extraction layer (CPL) 119 disposed over the first cathode 118.
In one embodiment, the organic light emitting unit 130 further includes a second hole injection layer 132 disposed between the second anode 131 and the second hole transport layer 133, and/or a second light extraction layer 139 disposed over the second cathode 138.
Further, the materials of the first and second hole injection layers 112 and 132, respectively, may be polythiophene derivatives, such as PEDOT: PSS (a mixture of poly (3, 4-ethylenedioxythiophene) and polystyrene sulfonic acid).
Further, the thickness of the first hole injection layer 112 and the second hole injection layer 132 is 10nm to 70nm.
Further, each of the first light extraction layer 119 and the second light extraction layer 139 should have a suitable light refractive index n and high transparency, preferably, the light refractive index is 1.9 to 2.1.
Specifically, the material of the first light extraction layer 119 and the second light extraction layer 139 may be an aromatic amine (such as NPB) or a derivative of an aromatic amine.
Further, the thickness of the first light extraction layer 119 and the second light extraction layer 139 ranges from 10nm to 200nm.
In an embodiment, the first anode 111 and the second anode 131 may be a transparent electrode or a reflective electrode such as ITO, ITO/Ag/ITO, or the like.
Further, the thickness of the first anode 111 and the second anode 131 is 10nm to 2000nm.
A hybrid electroluminescent device 200 according to another embodiment of the present invention, as shown in fig. 5, includes a red quantum dot light-emitting unit, a green quantum dot light-emitting unit, and a blue organic light-emitting unit.
The red quantum dot light-emitting unit, the green quantum dot light-emitting unit and the blue organic light-emitting unit respectively comprise anodes arranged in a stacked mode, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a light-emitting layer, an Electron Injection Layer (EIL), a cathode and a light extraction layer (CPL), the light-emitting layer of the red quantum dot light-emitting unit is a red quantum dot light-emitting layer, the light-emitting layer of the green quantum dot light-emitting unit is a green quantum dot light-emitting layer, the light-emitting layer of the blue organic light-emitting unit is a blue organic light-emitting layer, and the red quantum dot light-emitting unit and the green quantum dot light-emitting unit respectively comprise a hole transport layer arranged between the hole injection layer and the quantum dot light-emitting layer. In other embodiments, other structural functional layers may also be included in each light-emitting unit.
It can be understood that the blue organic light emitting layer, the green quantum dot light emitting layer and the red quantum dot light emitting layer respectively form a blue organic light emitting unit, a green quantum dot light emitting unit and a red quantum dot light emitting unit with an anode, a hole injection layer, a hole transport layer, an electron injection layer, a cathode and the like which are positioned at two sides of the light emitting layer. The structural layers having the same function may be disposed in the same layer, or may be disposed in different layers, for example: in the specific embodiment, the red and green quantum dot light-emitting units and the hole injection layer with the hole injection function in the organic light-emitting unit are arranged in the same layer; the electron injection layer with the electron injection function is arranged on a different layer, an electron transmission layer is further arranged between the electron injection layer of the red and green quantum dot light-emitting units and the quantum dot light-emitting layer, and the electron injection layer of the organic light-emitting unit is directly arranged on the blue organic light-emitting layer. The structure layers with the same function in each light-emitting unit can be formed by the same process of the same material, or the layers in each light-emitting unit can be formed by the same or different processes, the thickness of the structure layers with the same function in each light-emitting unit can be the same or different, and the light-emitting requirement of each light-emitting unit only needs to be met; such as: in the hybrid electroluminescent device 100, a first electron injection layer 117 may be formed on the quantum dot light emitting layer 114, and a second electron injection layer 137 may be formed on the organic light emitting layer 134, respectively; the electron injection layer shared by the quantum dot light emitting layer 114 and the organic light emitting layer 134 may be formed at once by a solution method.
Another embodiment of the present invention provides a method for manufacturing a hybrid electroluminescent device, including the steps of forming a quantum dot light-emitting unit and an organic light-emitting unit.
The method for forming the quantum dot light-emitting unit comprises the following steps:
providing a first anode, and sequentially forming a quantum dot light-emitting layer, a first electron injection layer and a first cathode on the first anode; a first electron injection layer in direct contact with the first cathode, the first electron injection layer comprising a metal fluoride and a low work function metal;
the forming of the organic light emitting unit includes the steps of:
providing a second anode, and sequentially forming an organic light-emitting layer, a second electron injection layer and a second cathode on the second anode; a second electron injection layer in direct contact with the second cathode, the second electron injection layer also comprising the metal fluoride and the low work function metal;
wherein the metal fluoride is selected from at least one of alkali metal fluoride and alkaline earth metal fluoride, and the low work function metal is selected from at least one of metal elements having a work function of lower than 4 eV.
It can be understood that the structural layers having the same function in the quantum dot light-emitting unit and the quantum dot light-emitting unit may be formed simultaneously by the same process and the same material, or may be formed separately.
Specifically, a hole injection layer, a hole transport layer, a buffer layer, a light emitting layer (including a red quantum dot light emitting layer, a green quantum dot light emitting layer, and a blue organic material light emitting layer), and an electron transport layer (prepared on the red quantum dot light emitting layer and the green quantum dot light emitting layer) may be sequentially prepared on a substrate already including an anode by a solution method, wherein the solution method refers to methods such as inkjet printing, spin coating, slit extrusion coating, nozzle printing, gravure printing, and the like. And then preparing the electron injection layer, the cathode and the light extraction layer in sequence by adopting a vacuum-free evaporation method or a sputtering method.
It should be noted here in particular that the solvents of the individual layers should have orthogonality, i.e. that the ink used for the later produced layer of the adjacent layers should not damage the previously produced functional layer. Common solvent choices are: the solvent of TFB is chlorobenzene, toluene, xylene, etc.; solvents for QDs include n-hexane, n-octane, n-decane, etc.
The buffer layer is a short-chain organic matter ligand solution of the quantum dot, after liquid phase ligand replacement occurs at the interface of the quantum dot light-emitting layer material close to the hole transport layer, a quantum dot light-emitting layer film with the short-chain organic matter ligand combined on the surface of the quantum dot is obtained, and the rest ligand solution which is not replaced is volatilized, so that a solid film is not formed.
Another embodiment of the present invention provides a display device comprising the hybrid type electroluminescent device described above.
The following are specific examples
Example 1 a top-emitting hybrid electroluminescent (H-QLED) device was prepared on a substrate already containing a reflective anode:
(1) Printing a Hole Injection Layer (HIL) ink (PEDOT: PSS) on the reflecting anode in the pixel pit in an ink-jet printing mode, and forming a HIL layer with the thickness of 50nm through vacuum drying and baking treatment;
(2) Printing Hole Transport Layer (HTL) ink (TFB) on the HIL layer in the pixel pits in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an HTL layer with the thickness of 30nm;
(3) Respectively printing red and green quantum dot light-emitting layer inks and a blue organic material light-emitting layer ink on the HTL layer in the pixel pit in an ink-jet printing mode, and performing vacuum drying and baking treatment to form a mixed light-emitting layer (EML layer) with the thickness of 60nm;
(4) Depositing ZnO on the quantum dot light-emitting layers (the red quantum dot light-emitting layer and the green quantum dot light-emitting layer) in an ink-jet printing mode to form an Electron Transport Layer (ETL), wherein the thickness of the ETL is 20nm;
(5) Sequentially depositing NaF with the thickness of 3nm and Ag with the thickness of 2nm on the ETL layer and the organic material light-emitting layer in a vacuum evaporation mode to form a double-layer Electron Injection Layer (EIL);
(6) And depositing a transparent conductive oxide film IZO on the EIL as a cathode in a sputtering mode, wherein the thickness of the transparent conductive oxide film IZO is 70nm, and obtaining the H-QLED device.
Example 2 a top-emitting hybrid electroluminescent (H-QLED) device was prepared on a substrate already containing a reflective anode:
(1) Printing a Hole Injection Layer (HIL) ink (PEDOT: PSS) on the reflecting anode in the pixel pit in an ink-jet printing mode, and forming a HIL layer with the thickness of 50nm through vacuum drying and baking treatment;
(2) Printing Hole Transport Layer (HTL) ink (TFB) on the HIL layer in the pixel pits in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an HTL layer with the thickness of 30nm;
(3) Respectively printing red and green quantum dot light-emitting layer inks and a blue organic material light-emitting layer ink on the HTL layer in the pixel pit in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an EML layer with the thickness of 60nm;
(4) And (3) depositing PMMA on the quantum dot light-emitting layer in an ink-jet printing mode to form an electronic transmission adjusting layer with the thickness of 5nm.
(5) Depositing ZnO on the electron transport adjusting layer in an ink-jet printing mode to form an Electron Transport Layer (ETL) with the thickness of 20nm;
(6) Sequentially depositing NaF with the thickness of 3nm and Ag with the thickness of 2nm on the ETL layer and the organic material light-emitting layer in a vacuum evaporation mode to form a double-layer Electron Injection Layer (EIL);
(7) And depositing a transparent conductive oxide film IZO on the EIL in a sputtering mode to be used as a cathode, wherein the thickness is 70nm, and obtaining the H-QLED device.
Example 3 a top-emitting hybrid electroluminescent (H-QLED) device was prepared on a substrate already containing a reflective anode:
(1) Printing a Hole Injection Layer (HIL) ink (PEDOT: PSS) on a reflecting anode in a pixel pit in an ink-jet printing mode, and forming a HIL layer with the thickness of 50nm through vacuum drying and baking treatment;
(2) Printing Hole Transport Layer (HTL) ink (TFB) on the HIL layer in the pixel pits in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an HTL layer with the thickness of 30nm;
(3) Respectively printing red and green quantum dot light-emitting layer inks and a blue organic material light-emitting layer ink on the HTL layer in the pixel pit in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an EML layer with the thickness of 60nm;
(4) Depositing ZnO on the quantum dot light-emitting layer in an ink-jet printing mode to form an Electron Transport Layer (ETL), wherein the thickness of the ETL is 20nm;
(5) Sequentially depositing NaF with the thickness of 3nm, mg-Ag alloy with the thickness of 2nm and Ag with the thickness of 2nm on the ETL layer and the organic material light-emitting layer in a vacuum evaporation mode to form a three-layer Electron Injection Layer (EIL);
(6) And depositing a transparent conductive oxide film IZO on the EIL as a cathode in a sputtering mode, wherein the thickness of the transparent conductive oxide film IZO is 70nm, and obtaining the H-QLED device.
Example 4 a top-emitting hybrid electroluminescent (H-QLED) device was prepared on a substrate already containing a reflective anode:
(1) Printing a Hole Injection Layer (HIL) ink (PEDOT: PSS) on the reflecting anode in the pixel pit in an ink-jet printing mode, and forming a HIL layer with the thickness of 50nm through vacuum drying and baking treatment;
(2) Printing Hole Transport Layer (HTL) ink (TFB) on the HIL layer in the pixel pits in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an HTL layer with the thickness of 30nm;
(3) Respectively printing red and green quantum dot light-emitting layer ink and blue organic material light-emitting layer ink on the HTL layer in the pixel pit in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an EML layer with the thickness of 60nm;
(4) Depositing ZnO on the quantum dot light-emitting layer in an ink-jet printing mode to form an Electron Transport Layer (ETL), wherein the thickness is 20nm;
(5) Sequentially depositing CaF with the thickness of 3nm, yb with the thickness of 2nm and Mg-Ag alloy with the thickness of 2nm on the ETL layer and the organic material light-emitting layer in a vacuum evaporation mode to form a three-layer Electron Injection Layer (EIL);
(6) And depositing a transparent conductive oxide film IZO on the EIL as a cathode in a sputtering mode, wherein the thickness of the transparent conductive oxide film IZO is 70nm, and obtaining the H-QLED device.
Example 5 a top-emitting hybrid electroluminescent (H-QLED) device was prepared on a substrate already containing a reflective anode:
(1) Printing a Hole Injection Layer (HIL) ink (PEDOT: PSS) on the reflecting anode in the pixel pit in an ink-jet printing mode, and forming a HIL layer with the thickness of 50nm through vacuum drying and baking treatment;
(2) Printing Hole Transport Layer (HTL) ink (TFB) on the HIL layer in the pixel pits in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an HTL layer with the thickness of 30nm;
(3) Respectively printing red and green quantum dot light-emitting layer inks and a blue organic material light-emitting layer ink on the HTL layer in the pixel pit in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an EML layer with the thickness of 60nm;
(4) Depositing ZnO on the quantum dot light-emitting layer in an ink-jet printing mode to form an Electron Transport Layer (ETL), wherein the thickness is 20nm;
(5) Sequentially depositing NaF with the thickness of 3nm, ba with the thickness of 2nm, mg-Ag alloy with the thickness of 2nm and Ag with the thickness of 2nm on the ETL layer and the organic material light-emitting layer in a vacuum evaporation mode to form a four-layer Electron Injection Layer (EIL);
(6) And depositing a transparent conductive oxide film IZO on the EIL as a cathode in a sputtering mode, wherein the thickness of the transparent conductive oxide film IZO is 70nm, and obtaining the H-QLED device.
Example 6 a top-emitting hybrid electroluminescent (H-QLED) device was prepared on a substrate already containing a reflective anode:
(1) Printing a Hole Injection Layer (HIL) ink (PEDOT: PSS) on a reflecting anode in a pixel pit in an ink-jet printing mode, and forming a HIL layer with the thickness of 50nm through vacuum drying and baking treatment;
(2) Printing Hole Transport Layer (HTL) ink (TFB) on the HIL layer in the pixel pits in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an HTL layer with the thickness of 30nm;
(3) Respectively printing red and green quantum dot light-emitting layer ink and blue organic material light-emitting layer ink on the HTL layer in the pixel pit in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an EML layer with the thickness of 60nm;
(4) Depositing ZnO on the quantum dot light-emitting layer in an ink-jet printing mode to form an Electron Transport Layer (ETL), wherein the thickness of the ETL is 20nm;
(5) Sequentially depositing NaF with the thickness of 3nm, mg-Ag alloy with the thickness of 2nm and Ag with the thickness of 2nm on the ETL layer and the organic material light-emitting layer in a vacuum evaporation mode to form a three-layer Electron Injection Layer (EIL);
(6) And depositing a transparent conductive oxide film IZO/ITO/IZO on the EIL in a sputtering mode to be used as a cathode, wherein the thickness is 70nm, and obtaining the H-QLED device.
Example 7 a top-emitting hybrid electroluminescent (H-QLED) device was prepared on a substrate already containing a reflective anode:
(1) Printing a Hole Injection Layer (HIL) ink (PEDOT: PSS) on the reflecting anode in the pixel pit in an ink-jet printing mode, and forming a HIL layer with the thickness of 50nm through vacuum drying and baking treatment;
(2) Printing Hole Transport Layer (HTL) ink (TFB) on the HIL layer in the pixel pits in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an HTL layer with the thickness of 30nm;
(3) Printing short-chain organic matter ligands on an HTL layer in a pixel pit where a quantum dot light-emitting layer is to be deposited to form a solution buffer layer, then printing quantum dot light-emitting layer ink on the buffer layer in an ink-jet printing mode, performing liquid phase ligand replacement on the short-chain organic matter ligands and long-chain organic matter ligands on the surfaces of quantum dots in the quantum dot light-emitting layer ink, and performing vacuum drying and baking treatment to form a quantum dot light-emitting layer with the thickness of 60nm; printing blue organic material luminescent layer ink on an HTL layer in a pixel pit of an organic material luminescent layer, and performing vacuum drying and baking treatment to form an organic material luminescent layer with the thickness of 60nm to finish the preparation of an emitting layer (ETL);
(4) Depositing ZnO on the quantum dot light-emitting layer in an ink-jet printing mode to form an Electron Transport Layer (ETL), wherein the thickness of the ETL is 20nm;
(5) Sequentially depositing NaF with the thickness of 3nm and Ag with the thickness of 2nm on the ETL layer and the organic material light-emitting layer in a vacuum evaporation mode to form a double-layer Electron Injection Layer (EIL);
(6) And depositing a transparent conductive oxide film IZO on the EIL as a cathode in a sputtering mode, wherein the thickness of the transparent conductive oxide film IZO is 70nm, and obtaining the H-QLED device.
Comparative example 1 a top-emitting electroluminescent (H-QLED) device was prepared on a substrate already containing a reflective anode:
(1) Printing a Hole Injection Layer (HIL) ink (PEDOT: PSS) on a reflecting anode in a pixel pit in an ink-jet printing mode, and forming a HIL layer with the thickness of 50nm through vacuum drying and baking treatment;
(2) Printing Hole Transport Layer (HTL) ink (TFB) on the HIL layer in the pixel pits in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an HTL layer with the thickness of 30nm;
(3) Respectively printing red and green quantum dot light-emitting layer ink and blue organic material light-emitting layer ink on the HTL layer in the pixel pit in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an EML layer with the thickness of 60nm;
(4) Depositing ZnO on the quantum dot light-emitting layer in an ink-jet printing mode to form an electron transport layer (ETL 1), wherein the thickness is 20nm;
(5) Depositing an organic electron transport layer material on the ETL layer and the organic material light-emitting layer in an ink-jet printing mode to form an electron transport layer (ETL 2);
(6) And depositing a transparent conductive oxide film IZO on the ETL2 in a sputtering mode to be used as a cathode, wherein the thickness is 70nm, and obtaining the H-QLED device.
Comparative example 2 a top-emitting electroluminescent (H-QLED) device was prepared on a substrate already containing a reflective anode:
(1) Printing a Hole Injection Layer (HIL) ink (PEDOT: PSS) on the reflecting anode in the pixel pit in an ink-jet printing mode, and forming a HIL layer with the thickness of 50nm through vacuum drying and baking treatment;
(2) Printing Hole Transport Layer (HTL) ink (TFB) on the HIL layer in the pixel pits in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an HTL layer with the thickness of 30nm;
(3) Respectively printing red and green quantum dot light-emitting layer inks and a blue organic material light-emitting layer ink on the HTL layer in the pixel pit in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an EML layer with the thickness of 60nm;
(4) Depositing ZnO on the quantum dot light-emitting layer in an ink-jet printing mode to form an Electron Transport Layer (ETL), wherein the thickness of the ETL is 20nm;
(5) Sequentially depositing 2nm Mg-Ag alloy and 2nm Ag on the ETL layer in a vacuum evaporation mode to form a double-layer EIL layer;
(6) And depositing a transparent conductive oxide film IZO on the ETL in a sputtering mode to be used as a cathode, wherein the thickness is 70nm, and obtaining the H-QLED device.
Comparative example 3 a top-emitting electroluminescent (H-QLED) device was prepared on a substrate already containing a reflective anode:
(1) Printing a Hole Injection Layer (HIL) ink (PEDOT: PSS) on the reflecting anode in the pixel pit in an ink-jet printing mode, and forming a HIL layer with the thickness of 50nm through vacuum drying and baking treatment;
(2) Printing Hole Transport Layer (HTL) ink (TFB) on the HIL layer in the pixel pits in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an HTL layer with the thickness of 30nm;
(3) Respectively printing red and green quantum dot light-emitting layer inks and a blue organic material light-emitting layer ink on the HTL layer in the pixel pit in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an EML layer with the thickness of 60nm;
(4) Depositing ZnO on the quantum dot light-emitting layer in an ink-jet printing mode to form an Electron Transport Layer (ETL), wherein the thickness of the ETL is 20nm;
(5) Depositing NaF with the thickness of 2nm on the ETL layer in a vacuum evaporation mode to form an EIL layer;
(6) And depositing a transparent conductive oxide film IZO on the ETL in a sputtering mode to be used as a cathode, wherein the thickness is 70nm, and obtaining the H-QLED device.
Comparative example 4 a top-emitting electroluminescent (H-QLED) device was prepared on a substrate already containing a reflective anode:
(1) Printing a Hole Injection Layer (HIL) ink (PEDOT: PSS) on a reflecting anode in a pixel pit in an ink-jet printing mode, and forming a HIL layer with the thickness of 50nm through vacuum drying and baking treatment;
(2) Printing Hole Transport Layer (HTL) ink (TFB) on the HIL layer in the pixel pits in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an HTL layer with the thickness of 30nm;
(3) Respectively printing red and green quantum dot light-emitting layer ink and blue organic material light-emitting layer ink on the HTL layer in the pixel pit in an ink-jet printing mode, and performing vacuum drying and baking treatment to form an EML layer with the thickness of 60nm;
(4) Depositing ZnO on the quantum dot light-emitting layer in an ink-jet printing mode to form an Electron Transport Layer (ETL), wherein the thickness of the ETL is 20nm;
(5) Sequentially depositing 2nm of NaCl, 2nm of Mg-Ag alloy and 2nm of Ag on the ETL layer in a vacuum evaporation mode to form a double-layer EIL layer;
(6) And depositing a transparent conductive oxide film IZO on the ETL in a sputtering mode to be used as a cathode, wherein the thickness is 70nm, and obtaining the H-QLED device.
Performance detection
The devices of examples 1 to 7 and comparative examples 1 to 4 were placed at the same current density (10 mA/cm) 2 ) Testing the relative brightness of the device under the condition (1), and normalizing the brightness of the comparative example 1 to obtain a corresponding brightness value; and the drive voltage of the device was measured. Through performance measurement, the driving voltage of the devices of examples 1 to 7 of the present application is reduced, compared with comparative examples 1 to 4, and the relative brightness of the devices is obviously improved and the service life of the devices is prolonged from the comparative example higher than 12V to 8V.
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, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (14)

1. A hybrid electroluminescent device comprises a quantum dot light-emitting unit and an organic light-emitting unit;
the quantum dot light-emitting unit comprises a first anode, a quantum dot light-emitting layer, a first electron injection layer and a first cathode which are arranged in a stacked mode, wherein the first electron injection layer is in direct contact with the first cathode, and the first electron injection layer comprises metal fluoride and low-work-function metal;
the organic light-emitting unit comprises a second anode, an organic light-emitting layer, a second electron injection layer and a second cathode which are arranged in a stacked mode, the second electron injection layer is in direct contact with the second cathode, and the second electron injection layer comprises the metal fluoride and the low-work-function metal;
wherein the metal fluoride is selected from at least one of alkali metal fluoride and alkaline earth metal fluoride, and the low work function metal is selected from at least one of metal elements having a function of less than 4 eV;
an electron transmission layer is further arranged between the quantum dot light-emitting layer and the first electron injection layer, the electron transmission layer is a zinc oxide layer or an insulating material doped zinc oxide layer, an electron transmission adjusting layer is further arranged between the electron transmission layer and the quantum dot light-emitting layer, and the electron transmission adjusting layer comprises an insulating material.
2. The hybrid electroluminescent device as claimed in claim 1, wherein the metal fluoride is selected from at least one of sodium fluoride, lithium fluoride, potassium fluoride, magnesium fluoride and calcium fluoride; the low work function metal is selected from at least one of magnesium, silver, barium and ytterbium.
3. The hybrid electroluminescent device as claimed in claim 1, wherein the first electron injection layer is a stacked structure including a metal fluoride layer formed of the metal fluoride and a metal layer formed of the low work function metal, the metal fluoride layer being in direct contact with the first cathode; and/or the presence of a gas in the gas,
the second electron injection layer is a laminated structure including a metal fluoride layer formed of the metal fluoride and a metal layer formed of the low work function metal, the metal fluoride layer being in direct contact with the second cathode.
4. A hybrid electroluminescent device according to claim 3, wherein the number of metal layers is one or more;
when the number of the metal layers is one, the metal layers are formed by at least one low work function metal;
when the number of the metal layers is multiple, each of the multiple metal layers is formed of one kind of the low work function metal, or at least one of the multiple metal layers is formed of two or more kinds of the low work function metals.
5. A hybrid electroluminescent device according to claim 3, characterized in that the metal fluoride layer is a sodium fluoride layer.
6. The hybrid electroluminescent device as claimed in claim 1, wherein the first electron injection layer has a thickness of 1nm to 20nm, and the second electron injection layer has a thickness of 1nm to 20nm.
7. The hybrid electroluminescent device of claim 1, wherein the first cathode is a transparent conductive oxide layer, the second cathode is the transparent conductive oxide layer, and the transparent conductive oxide layer is an IZO single layer, an ITO single layer, or a multilayer structure consisting of an IZO layer and an ITO layer.
8. The hybrid electroluminescent device as claimed in claim 1, wherein the electron transport layer has a thickness of 15nm to 50nm, and the electron transport adjusting layer has a thickness of 10nm to 60nm.
9. The hybrid electroluminescent device of claim 8, wherein the insulating material is polymethylmethacrylate; and/or the presence of a gas in the gas,
when the electron transport layer is an insulating material doped zinc oxide layer, the doping concentration of the insulating material is 0.5wt% -10 wt%.
10. The hybrid electroluminescent device according to any one of claims 1 to 9, wherein the quantum dot luminescent material of the quantum dot luminescent layer is a quantum dot luminescent material containing a long-chain organic ligand, and the quantum dot of the quantum dot luminescent layer near the surface of the first anode is bonded with a short-chain organic ligand.
11. The hybrid electroluminescent device as claimed in claim 10, wherein the quantum dot luminescent material is at least one selected from CdSe, inP, gaSe, znS and CdS quantum dots.
12. The hybrid electroluminescent device as claimed in claim 10, wherein the organic light emitting layer is a blue organic light emitting layer, and the quantum dot light emitting layer comprises a red quantum dot light emitting layer and a green quantum dot light emitting layer disposed in the same layer.
13. A preparation method of a hybrid electroluminescent device is characterized by comprising the steps of forming a quantum dot light-emitting unit and an organic light-emitting unit;
wherein the forming of the quantum dot light emitting unit comprises the steps of:
providing a first anode, and sequentially forming a quantum dot light-emitting layer, an electron transmission adjusting layer, an electron transmission layer, a first electron injection layer and a first cathode on the first anode; the first electron injection layer is in direct contact with the first cathode, the first electron injection layer comprises metal fluoride and low work function metal, the electron transport layer is a zinc oxide layer or an insulating material doped zinc oxide layer, and the electron transport adjusting layer comprises an insulating material;
the forming of the organic light emitting unit includes the steps of:
providing a second anode, and sequentially forming an organic light-emitting layer, a second electron injection layer and a second cathode on the second anode; the second electron injection layer is in direct contact with the second cathode, and the second electron injection layer comprises the metal fluoride and the low work function metal;
wherein the metal fluoride is at least one selected from the group consisting of alkali metal fluorides and alkaline earth metal fluorides, and the low work function metal is at least one selected from the group consisting of metal elements having a work function of less than 4 eV.
14. A display device comprising the hybrid electroluminescent device according to any one of claims 1 to 12 or the hybrid electroluminescent device produced by the production method according to claim 13.
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