CN108735904B - QLED capable of improving light-emitting efficiency and preparation method thereof - Google Patents
QLED capable of improving light-emitting efficiency and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 11
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- 238000005054 agglomeration Methods 0.000 claims description 9
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- 239000000243 solution Substances 0.000 claims description 9
- 238000004528 spin coating Methods 0.000 claims description 9
- 230000005525 hole transport Effects 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 229910003087 TiOx Inorganic materials 0.000 claims description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
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- 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
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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Abstract
The invention discloses a QLED (quantum dot light emitting diode) capable of improving light emitting efficiency and a preparation method thereof. According to the invention, the nanoparticle layer with the mutually agglomerated nanoparticles is introduced to the top of the QLED, and the nanoparticle layer has a non-planar structure, so that the optical extraction rate of the QLED can be improved by utilizing the nanoparticle layer, and the luminous efficiency of the QLED is effectively improved. Meanwhile, the structure of the invention does not influence the electrical performance of the device of the QLED and meets the industrialized requirement.
Description
Technical Field
The invention relates to the field of display, in particular to a QLED capable of improving light extraction efficiency and a preparation method thereof.
Background
Compared with organic fluorescent luminophors, quantum dot-based QLEDs have the advantages of high color purity, long service life, easiness in dispersion and the like, can be prepared by a printing process, and are generally considered to be powerful competitors of next-generation display technologies.
In the prior art, the QLED is a planar thin film structure, and optical reflection occurs at the interface of the thin films due to the difference in refractive index of each thin film. Light emitted from the quantum dots may be confined to the QLED. Theoretical calculations suggest that only about 20% of the light will be emitted from the QLED and the remaining 80% of the light will be confined to different parts of the QLED, which results in lower light extraction efficiency of the existing QLED.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, an object of the present invention is to provide a QLED capable of improving light extraction efficiency and a manufacturing method thereof, and to solve the problem of low light extraction efficiency of the conventional QLED.
The technical scheme of the invention is as follows:
the QLED capable of improving the light-emitting efficiency sequentially comprises a substrate, a bottom electrode, a quantum dot light-emitting layer, a nanoparticle layer and a top electrode, wherein nanoparticles are agglomerated with each other, and the nanoparticle layer is of a non-planar structure.
The QLED capable of improving the light extraction efficiency is characterized in that the agglomeration degree of the nanoparticle layer is as follows: less than 1 μm in plan and less than 100nm in the longitudinal direction.
The QLED capable of improving the light extraction efficiency is characterized in that the nanoparticle layer is of an amorphous non-planar structure.
The QLED capable of improving the light extraction efficiency is characterized in that the thickness of the nanoparticle layer is 10-100 nm.
The QLED capable of improving the light extraction efficiency is characterized in that the material of the nanoparticle layer is TiOxOr ZnO.
The QLED capable of improving the light extraction efficiency is characterized in that the size of the nanoparticles in the nanoparticle layer is less than 30 nm.
The QLED capable of improving the light emitting efficiency is characterized in that an electron transmission layer is further arranged between the quantum dot light emitting layer and the nanoparticle layer of the QLED.
The QLED capable of improving the light emitting efficiency is characterized in that a hole transport layer and a hole injection layer are further arranged between the bottom electrode of the QLED and the quantum dot light emitting layer.
The preparation method of the QLED capable of improving the light extraction efficiency comprises the following steps:
A. manufacturing a bottom electrode on a substrate;
B. depositing a quantum dot light-emitting layer on the bottom electrode;
C. preparing a nanoparticle layer with nanoparticles agglomerated with each other on the quantum dot light-emitting layer by a solution method, wherein the nanoparticle layer is of a non-planar structure;
D. and manufacturing a top electrode on the surface of the nano particle layer.
In the preparation method, in the step C, the nanoparticle layer is prepared by a spin coating method.
Has the advantages that: according to the invention, the nanoparticle layer with the mutually agglomerated nanoparticles is introduced to the top of the QLED, and the nanoparticle layer has a non-planar structure, so that the optical extraction rate of the QLED can be improved by utilizing the nanoparticle layer, and the luminous efficiency of the QLED is effectively improved. Meanwhile, the structure of the invention does not influence the electrical performance of the device of the QLED and meets the industrialized requirement.
Drawings
Fig. 1 is a schematic structural diagram of a QLED according to a preferred embodiment of the present invention capable of improving light extraction efficiency.
Fig. 2 is a schematic structural diagram of a QLED embodiment capable of improving light extraction efficiency according to the present invention.
Fig. 3 is a flowchart illustrating a method for manufacturing a QLED with improved light extraction efficiency according to a preferred embodiment of the present invention.
FIG. 4 is a schematic diagram illustrating the variation of the spin speed with time during spin coating according to an embodiment of the present invention.
Fig. 5 is an SEM cross-sectional view of nanoparticle agglomeration in a QLED prepared according to a first embodiment of the present invention.
Fig. 6 is a schematic diagram of the variation of the emission intensity of the QLED with wavelength according to the first embodiment of the present invention.
FIG. 7 is a schematic diagram illustrating the variation of the spin speed with time during spin coating according to a second embodiment of the present invention.
FIG. 8 is a schematic view showing the variation of the spin speed with time during spin coating in the third embodiment of the present invention.
Detailed Description
The invention provides a QLED capable of improving light extraction efficiency and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a QLED capable of improving light extraction efficiency according to a preferred embodiment of the present invention, and as shown in the figure, the QLED sequentially includes a substrate 11, a bottom electrode 12, a quantum dot light emitting layer 13, a nanoparticle layer 14 in which nanoparticles are agglomerated with each other, and a top electrode 15, where the nanoparticle layer 14 is a non-planar structure.
The invention adds the non-planar structure on the top electrode interface of the QLED to improve the optical extraction rate of the QLED, thereby effectively improving the luminous efficiency of the QLED. The non-planar structure formed by the nanoparticle layer 14 can ensure that the manufacturing process is simple and is beneficial to large-scale application, and the added non-planar structure does not influence the original device electrical performance of the QLED.
The nanoparticle layer 14 introduced in the present invention needs to be capable of mutually agglomerating nanoparticles, and preferably, the agglomeration degree of the nanoparticle layer 14 is: less than 1 μm in plan and less than 100nm in the longitudinal direction. That is, in the nanoparticle layer 14, the nanoparticles are agglomerated into an agglomerate having a size of less than 1 μm in a plane and a thickness of less than 100nm in a longitudinal direction. Under the conditions, the light emitting efficiency can be further improved, and the original electrical performance of the QLED is ensured. For the agglomeration of the nanoparticles, it is possible to control the agglomeration by solution processing, for example, controlling the rotation speed and time, etc. Wherein the agglomerated nanoparticles may be uniformly distributed on the quantum dot light emitting layer 13.
Preferably, the nanoparticle layer 14 is an amorphous, non-planar structure. Namely, the mutual agglomeration of the nanoparticles in the nanoparticle layer 14 is irregular and disordered, and the adjacent nanoparticles can be agglomerated at will, so that the distribution uniformity of the nanoparticles can be improved, and the light extraction efficiency is improved.
The nanoparticle layer 14 may be not only a single layer but also a multilayer structure. If a multilayer structure is adopted, the optical extraction rate can be improved, and therefore the light extraction efficiency is improved. The thickness of the nanoparticle layer 14 is preferably 10 to 100nm, for example, 50 nm.
Further, the material of the nanoparticle layer 14 is TiOxOr ZnO, or a derivative thereof, or an ETL material having an electron transport function. Alternatively, the material of the nanoparticle layer may be a doped material, for example, Mg doped ZnO (i.e., in Zn)O doped with Mg, the same applies below), Al doped ZnO, La doped ZnO, Y doped ZnO, Mg doped TiO, Al doped TiO, La doped TiO, or Y doped TiO. The doping concentration is preferably less than 10% by mass.
Further, the nanoparticle size in the nanoparticle layer 14 is less than 30 nm. For example if the nanoparticles are spherical, their diameter is less than 30nm, if irregularly shaped, their maximum length is less than 30 nm.
An electron transmission layer is also arranged between the quantum dot light-emitting layer 13 and the nanoparticle layer 14 of the QLED. And a hole transport layer and a hole injection layer are also arranged between the bottom electrode 12 of the QLED and the quantum dot light-emitting layer 13. For example, as shown in fig. 2, it is a schematic structural diagram of a specific embodiment of a QLED capable of improving light extraction efficiency, and it sequentially includes, from bottom to top: the organic electroluminescent device comprises a substrate 21, a bottom electrode 22, a hole injection layer 23, a hole transport layer 24, a quantum dot light emitting layer 25, an electron transport layer 26, a nanoparticle layer 27 and a top electrode 28.
The thickness of the quantum dot light emitting layer is preferably 10-100 nm. The bottom electrode may be patterned ITO or TCO, etc. The top electrode is an aluminum electrode or a silver electrode, and the thickness of the top electrode is preferably 30-800 nm. The hole injection layer is made of PEDOT (PSS) and MoO3、VO2Or WO3At least one of (1). The thickness of the hole injection layer is preferably 10 to 150 nm. The hole transport layer is made of TFB, poly-TPD, PVK, NiO and MoO3NPB and CBP. The thickness of the hole transport layer is preferably 10 to 150 nm. The material of the electron transport layer is preferably LiF, CsF or Cs2CO3、ZnO、Alq3At least one of (1).
The invention also provides a preparation method of the QLED capable of improving the light extraction efficiency, as shown in fig. 3, which comprises the following steps:
s1, manufacturing a bottom electrode on the substrate;
s2, depositing a quantum dot light-emitting layer on the bottom electrode;
s3, preparing a nanoparticle layer with nanoparticles agglomerated with each other on the quantum dot light-emitting layer by a solution method, wherein the nanoparticle layer is of a non-planar structure;
and S4, manufacturing a top electrode on the surface of the nano particle layer.
Further, in step S3, the nanoparticle layer is formed by a spin coating method. The nanoparticles were uniformly spread by spin coating. In addition, in the rotation process, the nano particles form agglomeration with certain distribution and size, so that the flatness of the surface is damaged, and the light extraction efficiency is increased.
Example one
In this embodiment, the material of the nanoparticle layer is ETL-1, and ETL-1 is specifically ZnO, and the corresponding relationship between the rotation speed and time during spin coating is shown in fig. 4. After a substrate, a bottom electrode, a hole injection layer, a hole transport layer and a quantum dot light emitting layer are prepared in sequence, ETL-1 solution is added into the A point in a low-speed rotation mode, and the A point is uniformly spread on a substrate. The solution begins to volatilize along with the increase of time and the increase of the rotating speed, and a solvent (alcohols, such as methanol, ethanol, propanol and the like) is added in the 40 th second, and the solvent drives the quantum dot particles to be arranged and changed under the action of the solvent and high-speed rotation, so that the nano particles form agglomeration with certain distribution and size, the surface flatness is damaged, and the light extraction efficiency is increased. The surface of the ETL-1 material was agglomerated and the surface after metal evaporation was shown in FIG. 5. The surface is distributed with bulges with different sizes, the flatness of the metal electrode is damaged, and as shown in fig. 6, the luminous intensity of the QLED is improved by 10 percent after being processed compared with that of the QLED without being processed.
Example two
After the material of ETL-1 is spin-coated, another layer of nano particle material ETL-2 is spin-coated, wherein the material of ETL-2 is Y-doped ZnO, and the doping proportion is 2.5% (namely, the mass ratio of Y in the material of ETL-2 is 2.5%). The correspondence between the rotation speed and the time when ETL-2 was spin-coated is shown in FIG. 7. At point A, a slow spin is applied to the ETL-2 solution to spread it evenly over the substrate. The solution begins to volatilize along with the increase of time and the increase of the rotating speed, and at the 20 th second, the solvent (alcohols, such as methanol, ethanol, propanol and the like) of the ETL-1 is added, and due to the action of the solvent, partial penetration occurs on the materials of the ETL-1 layer and the ETL-2 layer under the high-speed rotation, so that the roughness of the film is increased, the flatness of the surface is damaged, and the light extraction efficiency is increased.
EXAMPLE III
ETL-3 is a mixture of two nano materials N and M (the mass ratio of N to M can be from 1:99 to 99: 1), the solubility of solvent L to N is far higher than that to M, wherein M is ZnO, N is TiOxAnd L is benzene (such as toluene) or alcohol (such as methanol, ethanol, propanol, etc.). The correspondence between the rotation speed and time in the ETL-3 spin coating is shown in FIG. 8. At point A, the ETL-3 solution was added with slow rotation to spread evenly over the substrate. The solution began to evaporate with increasing time and increasing rotation speed, and at 80 th second, L solvent was added in a 100 μ L dose, 10 second intervals, 3 consecutive times. Due to the action of the solvent, N materials on the surface of the film are partially dissolved under the action of high-speed rotation, so that the roughness of the film is increased, the flatness of the surface is damaged, and the light extraction efficiency is increased.
In the embodiment, the QLED structure is improved, and experiments prove that the light emitting efficiency of the QLED can be improved by 5% -30%.
In summary, the nanoparticle layer with the mutually agglomerated nanoparticles is introduced to the top of the QLED, and the nanoparticle layer has a non-planar structure, so that the optical extraction rate of the QLED can be improved by using the nanoparticle layer, and the light-emitting efficiency of the QLED can be effectively improved. Meanwhile, the structure of the invention does not influence the electrical performance of the device of the QLED and meets the industrialized requirement.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (9)
1. A QLED capable of improving light-emitting efficiency is characterized by sequentially comprising a substrate, a bottom electrode, a quantum dot light-emitting layer, a nanoparticle layer and a top electrode, wherein nanoparticles are agglomerated with each other, and the nanoparticle layer is of a non-planar structure;
the agglomeration degree of the nanoparticle layer is as follows: less than 1 μm in plan and less than 100nm in the longitudinal direction.
2. A QLED capable of improving light extraction efficiency as recited in claim 1, wherein the nanoparticle layer has an amorphous non-planar structure.
3. The QLED of claim 1, wherein the thickness of the nanoparticle layer is 10-100 nm.
4. The QLED of claim 1, wherein the material of the nanoparticle layer is TiOxOr ZnO.
5. The QLED of claim 1, wherein the nanoparticle layer has a nanoparticle size of less than 30 nm.
6. The QLED of claim 1, wherein an electron transport layer is disposed between the quantum dot light emitting layer and the nanoparticle layer.
7. The QLED of claim 6, wherein a hole transport layer and a hole injection layer are disposed between the bottom electrode and the quantum dot light emitting layer.
8. The method according to claim 1, wherein the method for manufacturing a QLED with improved light extraction efficiency comprises the steps of:
A. manufacturing a bottom electrode on a substrate;
B. depositing a quantum dot light-emitting layer on the bottom electrode;
C. preparing a nanoparticle layer with nanoparticles agglomerated with each other on the quantum dot light-emitting layer by a solution method, wherein the nanoparticle layer is of a non-planar structure;
D. and manufacturing a top electrode on the surface of the nano particle layer.
9. The production method according to claim 8, wherein in the step C, the nanoparticle layer is produced by a spin coating method.
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| CN201710261921.7A CN108735904B (en) | 2017-04-20 | 2017-04-20 | QLED capable of improving light-emitting efficiency and preparation method thereof |
| PCT/CN2018/078767 WO2018192324A1 (en) | 2017-04-20 | 2018-03-13 | Quantum dot light-emitting diode capable of improving light extraction efficiency and preparation method therefor |
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| CN110048009B (en) * | 2019-04-29 | 2021-05-14 | 京东方科技集团股份有限公司 | QLED device, preparation method thereof and display panel |
| CN112331780B (en) * | 2019-12-02 | 2022-07-08 | 广东聚华印刷显示技术有限公司 | Quantum dot light-emitting device and preparation method thereof |
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