CN110571343A - light emitting diode device, preparation method thereof and display substrate - Google Patents
light emitting diode device, preparation method thereof and display substrate Download PDFInfo
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- CN110571343A CN110571343A CN201910864795.3A CN201910864795A CN110571343A CN 110571343 A CN110571343 A CN 110571343A CN 201910864795 A CN201910864795 A CN 201910864795A CN 110571343 A CN110571343 A CN 110571343A
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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]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
- H10K50/166—Electron transporting layers comprising a multilayered structure
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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Abstract
The invention provides a light-emitting diode device, a preparation method thereof and a display substrate, belongs to the technical field of display, and can at least partially solve the problems of low brightness and low efficiency of the existing light-emitting diode device caused by high electron mobility relative to hole mobility. A light emitting diode device of the present invention includes: a light emitting layer; a first electrode and a second electrode respectively positioned at two sides of the luminescent layer; the electron transport layer is positioned between the luminous layer and the second electrode, two sides of the electron transport layer are respectively connected with the luminous layer and the second electrode, and the electron transport layer comprises a nano-particle material; wherein, in any two sub-electron transport layers, the electron transport layer has at least two sub-electron transport layers, and the particle diameter of the nano-particle material of the sub-electron transport layer close to the luminescent layer is smaller than that of the nano-particle material of the sub-electron transport layer far away from the luminescent layer.
Description
Technical Field
the invention belongs to the technical field of display, and particularly relates to a light-emitting diode device, a preparation method thereof and a display substrate.
Background
Quantum Dot Light Emitting Diodes (QLEDs) devices have the advantages of high color gamut, self-luminescence, low start voltage, and fast response speed, and thus have attracted wide attention in the display field. The substrate working principle of the quantum dot light-emitting diode device is as follows: electrons and holes are injected into two sides of the quantum dot light-emitting layer respectively, and the electrons and the holes are compounded in the quantum dot light-emitting layer to form photons, and finally, the photons emit light.
in a prior art quantum dot light emitting diode device, holes are generally transported to a quantum dot light emitting layer by a hole injection transport layer, and electrons are generally transported to the quantum dot light emitting layer by an electron transport layer. However, since the mobility of electrons is different from that of holes, the specific mobility of electrons is greater than that of holes, so that excessive electrons are accumulated in the quantum dot light-emitting layer, and the problems of low brightness and efficiency of the quantum dot light-emitting diode device are caused.
Disclosure of Invention
The invention at least partially solves the problems of low brightness and low efficiency of the existing light-emitting diode device caused by high electron mobility relative to hole mobility, and provides a light-emitting diode device with high brightness and high efficiency.
the technical scheme adopted for solving the technical problem of the invention is a light-emitting diode device, which comprises:
A light emitting layer;
The first electrode and the second electrode are respectively positioned at two sides of the luminous layer;
The electron transport layer is positioned between the light emitting layer and the second electrode, two sides of the electron transport layer are respectively connected with the light emitting layer and the second electrode, and the electron transport layer comprises a nano-particle material;
The electron transport layer is provided with at least two sub-electron transport layers, and in any two sub-electron transport layers, the particle size of the nanoparticle material of the sub-electron transport layer close to the light-emitting layer is smaller than that of the nanoparticle material of the sub-electron transport layer far away from the light-emitting layer.
it is further preferred that the electron transport layer has three sub electron transport layers.
It is further preferred that the nanoparticle material in the electron transport layer is an oxide or a sulfide.
It is further preferred that the nanoparticle material in the electron transport layer is zinc oxide.
It is further preferred that the nanoparticle material in the electron transport layer has a particle size of 3 to 15 nm.
It is further preferred that each of the sub electron transport layers has a thickness of 6 to 30 nm.
further preferably, the light-emitting layer is a quantum dot light-emitting layer.
Further preferably, the light emitting diode device further includes: a hole injection layer and a hole transport layer between the light emitting layer and the first electrode.
The technical scheme adopted for solving the technical problem of the invention is a preparation method of a light-emitting diode device, wherein the light-emitting diode device is the light-emitting diode device, and the method comprises the following steps:
And forming the first electrode, the light-emitting layer, the electron transport layer, and the second electrode on the substrate.
Further preferably, the step of forming an electron transport layer includes: sequentially forming a plurality of sub electron transport material layers on a substrate, wherein the nano-particle materials in the plurality of sub electron transport material layers are the same; and simultaneously carrying out a patterning process on the plurality of sub-electron transport material layers to form a plurality of sub-electron transport layers.
The technical scheme adopted for solving the technical problem of the invention is a display substrate which comprises the light emitting diode device.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
Fig. 1 is a schematic structural diagram of a light emitting diode device according to an embodiment of the present invention;
Fig. 2 is a schematic flow chart of a method for manufacturing a light emitting diode device according to an embodiment of the invention;
Wherein the reference numerals are: 1 a light emitting layer; 2 a first electrode; 3 a second electrode; 4 an electron transport layer; 41 a first sub electron transport layer; 42 a second sub electron transport layer; 43 a third sub electron transport layer; 5 a hole injection layer; 6 hole transport layer.
Detailed Description
in order to make the technical solutions of the present invention better understood, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
In the present invention, the two structures "in the same layer" means that they are formed of the same material layer and thus are in the same layer in a stacked relationship, but do not represent that they are equidistant from the substrate nor that they are completely identical in structure with other layers between the substrate.
in the present invention, the "patterning process" refers to a step of forming a structure having a specific pattern, which may be a photolithography process including one or more steps of forming a material layer, coating a photoresist, exposing, developing, etching, stripping a photoresist, and the like; of course, the "patterning process" may also be an imprinting process, an inkjet printing process, or other processes.
example 1:
As shown in fig. 1 and 2, the present embodiment provides a light emitting diode device including:
A light-emitting layer 1;
a first electrode 2 and a second electrode 3 respectively positioned at both sides of the light emitting layer 1;
the electron transport layer 4 is positioned between the luminescent layer 1 and the second electrode 3, two sides of the electron transport layer 4 are respectively connected with the luminescent layer 1 and the second electrode 3, and the electron transport layer 4 comprises a nano-particle material;
the electron transport layer 4 has at least two sub-electron transport layers, and of any two sub-electron transport layers, the particle size of the nanoparticle material of the sub-electron transport layer close to the light emitting layer 1 is smaller than the particle size of the nanoparticle material of the sub-electron transport layer far from the light emitting layer 1.
The light emitting diode device includes a first electrode 2, a light emitting layer 1, an electron transport layer 4, and a second electrode 3. Specifically, the first electrode 2 may be an anode, and the second electrode 3 may be a cathode. The particle diameters of the nanoparticle materials of different sub electron transport layers in the electron transport layer 4 are different, and the particle diameters of the nanoparticle materials of different sub electron transport layers increase in order along the direction in which the light emitting layer 1 is directed to the second electrode 3. Each of the sub electron transport layers may be formed of only the nanoparticle material or may be formed of a substrate containing the nanoparticle material.
In fig. 1, the positions of the upper and lower edges of each layer in the light emitting diode device respectively represent the LUMO level and HOMO level of the corresponding layer, and do not represent the actual structural misalignment of each layer.
it should be noted that the braz equation is a formula representing the relationship between the nanoparticles of the material and the energy band, and the formula is specifically as follows:
Wherein E (r) represents the nanoparticle absorption band gap, q represents the unit charge, m represents the effective mass,r represents the nanoparticle radius, h represents the Planck constant, ε represents the dielectric constant, EryIndicating the effective rydberg energy.
as can be seen from the bras formula, the smaller the particle size of the nanoparticle material in the electron transport layer 4, the larger the energy band (e.g., LUMO, which represents the Lowest Orbital of the Unoccupied electron level, or HOMO, which represents the Highest Orbital of the Unoccupied electron level) of the electron transport layer 4, the smaller the velocity at which the electron propagates.
Meanwhile, since the particle diameter of the nanoparticle material of the sub electron transport layer close to the light emitting layer 1 is smaller than that of the nanoparticle material of the sub electron transport layer far from the light emitting layer 1, the energy band of the sub electron transport layer close to the light emitting layer 1 is higher than that of the sub electron transport layer far from the light emitting layer 1, that is, when electrons are transported from the cathode to the electron transport layer 4, the electron velocity gradually decreases as approaching to the light emitting layer 1, so that the electron mobility of the light emitting diode device can be reduced.
however, if the particle sizes of the nanoparticle materials of two adjacent sub-electron transport layers are too different, the energy band difference between the two layers is larger, and it is difficult for electrons to be transported from one sub-electron transport layer to the other sub-electron transport layer, which may affect the normal migration of electrons. Therefore, on the premise of ensuring that the propagation rate of electrons is continuously reduced, the electron propagation is smoother as the number of the electron transport layers is larger, and the electron mobility can be more accurately controlled.
In the light emitting diode device of this embodiment, by providing at least two sub-electron transport layers made of nanoparticle materials with different particle diameters, it is possible to gradually reduce the electron rate, i.e., reduce the electron mobility, on the premise of ensuring normal electron transport, so that the electron mobility is close to or equal to the hole mobility, and further improve the brightness, efficiency, and other properties of the light emitting diode device.
In addition, in the prior art, in order to reduce the electron mobility, an insulating electron blocking layer is disposed between the light emitting layer 1 and the electron transport layer 4 to reduce the electron mobility. However, if the thickness of the blocking layer is too large, it may affect that electrons cannot be transported into the light emitting layer 1, and if the thickness of the blocking layer is too small, it does not play a role in reducing the electron mobility. Therefore, the method for reducing the electron mobility in the prior art has a complex manufacturing process, and the best effect of reducing the electron mobility is difficult to achieve. In the light emitting diode device of this embodiment, the size of the doped particles in the electron transport layer 4 is changed without additionally adding a barrier layer, so as to reduce the electron mobility.
Preferably, the electron transport layer 4 has three sub electron transport layers.
Wherein, that is, the electron transport layer 4 has three sub-electron transport layers, that is, a first sub-electron transport layer 41, a second sub-electron transport layer 42, and a third sub-electron transport layer 43 in the direction of the light emitting layer 1 pointing to the second electrode 3, respectively, and the particle size of the nanoparticle material of the first sub-electron transport layer 41 is smaller than that of the nanoparticle material of the second sub-electron transport layer 42, and the particle size of the nanoparticle material of the second sub-electron transport layer 42 is smaller than that of the nanoparticle material of the third sub-electron transport layer 43 (e.g., 3 ≦ a < b < c ≦ 15nm, a represents the particle size of the nanoparticle material of the first sub-electron transport layer 41, b represents the particle size of the nanoparticle material of the second sub-electron transport layer 42, and c represents the particle size of the nanoparticle material of the third sub-electron transport layer 43), so that the electron transport rate gradually decreases during the electron transport from the third sub-electron transport layer 43 to the first sub-electron transport layer 41 via the second sub-electron transport layer 42 Is small.
The electron transport layer 4 is set to three sub-electron transport layers, so that electron mobility can be reduced, the luminous efficiency of the light emitting diode device is guaranteed, the manufacturing process of the light emitting diode device is simple, and manufacturing cost is saved.
Note that the first sub electron transport layer 41 (i.e., closest to the light emitting layer 1) has both the Electron Transport (ETL) and electron blocking (HBL) functions. The third electron transport layer 43, i.e., farthest from the light emitting layer 1, has both Electron Transport (ETL) and Electron Injection (EIL) functions.
Preferably, the nanoparticle material in the electron transport layer 4 is an oxide or a sulfide.
wherein the nano-particle material of the oxide may be titanium oxide (TiO)2) Indium oxide (ln)2O3) Tin oxide (SnO)2) Magnesium oxide (MgO), tungsten trioxide (WO)3) Tricobalt tetraoxide (CO)3O4) Nickel oxide (NiO), molybdenum trioxide (MoO)3) Etc.; the nano-particle material of sulfide can be cadmium sulfide (CdS), zinc sulfide (ZnS), molybdenum sulfide (MoS)2) Carbonyl sulfide (CoS), and the like.
It should be noted that the nanoparticle material in the electron transport layer 4 is not limited to the above type, and may be formed of another suitable material, such as molybdenum selenide (MoSe).
Preferably, the nanoparticle material in the electron transport layer 4 is zinc oxide (ZnO).
specifically, the particle size of the nanoparticle material in the electron transport layer 4 is 3 to 15 nm. And each of the sub electron transport layers has a thickness of 6 to 30 nm.
Preferably, the light emitting layer 1 is a quantum dot light emitting layer.
In other words, the Light Emitting diode device of the present embodiment is a Quantum Dot Light Emitting diode (QLED).
If the light emitting layer 1 is a quantum dot light emitting layer, the electron mobility of the light emitting diode device is reduced and the light emitting effect is better.
The size of the particles in the quantum dot light emitting layer and the size of the nanoparticles in the electron transport layer 4 do not have any relationship, and the emission color of the quantum dot light emitting diode device can be adjusted by adjusting the size of the particles in the quantum dot light emitting layer.
Preferably, the light emitting diode device further includes: a hole injection layer 5 and a hole transport layer 6 between the light emitting layer 1 and the first electrode 2.
Wherein the hole transport layer 6 is closer to the light emitting layer 1 than the hole injection layer 5.
Example 2:
as shown in fig. 1 and fig. 2, this embodiment provides a method for manufacturing a light emitting diode device, where the light emitting diode device is the light emitting diode device in embodiment 1, and the method includes:
A step of forming the first electrode 2, the light-emitting layer 1, the electron transporting layer 4, and the second electrode 3 on the substrate.
Preferably, the step of forming the electron transport layer 4 includes:
Sequentially forming a plurality of sub electron transport material layers on the substrate, wherein the nano-particle materials in the plurality of sub electron transport material layers are the same;
And simultaneously carrying out patterning process on the plurality of sub electron transport material layers to form a plurality of sub electron transport layers.
preferably, if the sub electron transport material layer is formed of a substrate containing a nanoparticle material, it may be that the nanoparticle material and the substrate in the plurality of sub electron transport material layers are the same, but the particle diameters of the nanoparticle materials in different sub electron transport material layers are different.
Because the materials of the plurality of sub-electron transmission material layers are the same, the plurality of sub-electron transmission material layers can be etched simultaneously by using the same etching liquid, so that the plurality of sub-electron transmission layers are formed simultaneously, the preparation process of the light-emitting diode device is simplified, the production efficiency is improved, and the manufacturing cost is reduced.
It should be noted that, in the step of forming the electron transport layer 4, a sub electron transport material layer may be formed first, and a patterning process is performed on the sub electron transport material layer to form a sub electron transport material layer; and then another sub-electron transport material layer is formed, and a patterning process is performed on the sub-electron transport material layer to form another sub-electron transport material layer and the like.
Specifically, the method for manufacturing the light emitting diode device is as follows:
s11, the first electrode 2 is formed on the substrate.
Wherein the substrate may be formed of glass, flexible Polyethylene terephthalate (PET) material, or other suitable material. The first electrode 2 may be made of transparent Indium Tin Oxide (ITO), fluorine-doped SnO2 transparent conductive glass (FTO), or a conductive polymer, or may be an opaque metal electrode such as aluminum or silver.
S12, depositing a hole injection layer 5 and a hole transport layer 6 on the first electrode 2 in this order.
The hole injection layer 5 may be formed of an organic injection material, such as PEDOT: PSS (composed of 3, 4-ethylenedioxythiophene polymer and polystyrene sulfonate), etc., may also be formed of an inorganic oxide, such as molybdenum oxide (MoOx). The hole transport layer 6 may be formed of an organic material such as Polyvinylcarbazole (PVK), N-diphenyl-N, N-disubstituted phenylbenzidine derivative (TPD), etc., or an inorganic oxide such as nickel oxide (NiOx), vanadium oxide (VOx), etc.
S13, depositing the light-emitting layer 1 on the hole transport layer 6.
Wherein, the luminescent layer 1 is a quantum dot luminescent layer. The quantum dot light emitting layer is formed of an indium phosphide (InP) material or other suitable material.
And S14, sequentially forming a plurality of sub electron transport material layers on the substrate, wherein the materials of the plurality of sub electron transport material layers are the same.
Preferably, three sub electron transport material layers are sequentially formed on the substrate.
And S15, simultaneously carrying out a patterning process on the plurality of sub electron transport material layers to form a plurality of sub electron transport layers.
Wherein, the plurality of electron transport material layers are simultaneously exposed, developed, etched, etc. to form a plurality of electron transport layers.
S16, the second electrode 3 is formed on the electron transport layer farthest from the light emitting layer 1.
the second electrode 3 may be a transparent electrode such as ITO, thin aluminum, silver, or the like, or an opaque electrode such as a metal electrode of aluminum, silver, or the like.
Example 3:
The present embodiment provides a display substrate including the light emitting diode device.
Specifically, the display device formed by the display substrate can be any product or component with a display function, such as a light emitting diode display panel, electronic paper, a mobile phone, a tablet computer, a television, a display, a notebook computer, a digital photo frame, a navigator and the like.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
While embodiments in accordance with the invention have been described above, these embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments described. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention and various embodiments with various modifications as are suited to the particular use contemplated. The invention is limited only by the claims and their full scope and equivalents.
Claims (11)
1. A light emitting diode device, comprising:
A light emitting layer;
the first electrode and the second electrode are respectively positioned at two sides of the luminous layer;
The electron transport layer is positioned between the light emitting layer and the second electrode, two sides of the electron transport layer are respectively connected with the light emitting layer and the second electrode, and the electron transport layer comprises a nano-particle material;
The electron transport layer is provided with at least two sub-electron transport layers, and in any two sub-electron transport layers, the particle size of the nanoparticle material of the sub-electron transport layer close to the light-emitting layer is smaller than that of the nanoparticle material of the sub-electron transport layer far away from the light-emitting layer.
2. The light-emitting diode device according to claim 1, wherein the electron transport layer has three sub electron transport layers.
3. The light-emitting diode device according to claim 1, wherein the nanoparticle material in the electron transport layer is an oxide or a sulfide.
4. the light-emitting diode device according to claim 3, wherein the nanoparticle material in the electron transport layer is zinc oxide.
5. The light-emitting diode device according to claim 1, wherein the nanoparticle material in the electron transport layer has a particle size of 3 to 15 nm.
6. The light-emitting diode device according to claim 1, wherein each of the sub electron transport layers has a thickness of 6 to 30 nm.
7. The light-emitting diode device according to claim 1, wherein the light-emitting layer is a quantum dot light-emitting layer.
8. The light-emitting diode device according to claim 1, further comprising:
A hole injection layer and a hole transport layer between the light emitting layer and the first electrode.
9. A method for manufacturing a light emitting diode device, wherein the light emitting diode device is the light emitting diode device according to any one of claims 1 to 8, the method comprising:
And forming the first electrode, the light-emitting layer, the electron transport layer, and the second electrode on the substrate.
10. The method for manufacturing a light-emitting diode device according to claim 9, wherein the step of forming an electron transport layer comprises:
Sequentially forming a plurality of sub electron transport material layers on a substrate, wherein the nano-particle materials in the plurality of sub electron transport material layers are the same;
and simultaneously carrying out a patterning process on the plurality of sub-electron transport material layers to form a plurality of sub-electron transport layers.
11. A display substrate comprising the light-emitting diode device according to any one of claims 1 to 8.
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