CN113937242A - Hyperfine quantum dot film and preparation method of high-resolution QLED thereof - Google Patents
Hyperfine quantum dot film and preparation method of high-resolution QLED thereof Download PDFInfo
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- CN113937242A CN113937242A CN202110984773.8A CN202110984773A CN113937242A CN 113937242 A CN113937242 A CN 113937242A CN 202110984773 A CN202110984773 A CN 202110984773A CN 113937242 A CN113937242 A CN 113937242A
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- 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
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
- H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10K71/80—Manufacture or treatment specially adapted for the organic devices covered by this subclass using temporary substrates
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Abstract
The invention relates to a hyperfine quantum dot film and a preparation method of a high-resolution QLED thereof. Firstly, a template of a pixel bank structure is prepared by a photoetching method. In addition, the quantum dot thin film is formed on the PDMS stamp by a self-assembly method. And then contacting the PDMS stamp with a template with a pixel bank structure and heating. The viscosity of the PDMS stamp is weakened in the heating process at 80 ℃, so that the quantum dots at the contact part are taken away by the pixel bank template, and the residual quantum dots form an ultra-fine pixel pattern. And finally, attaching the PDMS stamp to the hole transport layer, and sequentially pressing and separating the PDMS stamp to transfer the ultra-fine pixilated quantum dot film to the hole transport layer. The composition technology adopted in the method enables the quantum dot film to have ultra-fine pixel points and the prepared pixel points are uniform. Finally, the pixel size of the QLED device can be reduced to a few micrometers or even below micrometers, so that a high-brightness ultrahigh-resolution display pixel unit can be obtained, and the QLED device can be applied to next generation display.
Description
Technical Field
The invention belongs to the technical field of high-resolution QLED preparation, and particularly relates to a hyperfine quantum dot film and a preparation method of a high-resolution QLED thereof.
Background
With the increasing amount of information displayed in modern society, there is a higher demand for new display technologies and products thereof. While new demands for next generation displays are mainly reflected in high resolution and high color gamut. Compared with novel display technologies such as Organic Light Emitting Diodes (OLED), micro-LEDs (micro-LEDs), laser display and the like, the quantum dot light emitting diodes (QLEDs) have wide prospects due to the inherent high color gamut and the possibility of realizing high resolution by a photoetching method and a transfer printing method.
However, previous quantum dot patterning techniques have limitations in achieving uniform pixel arrays with such ultra-high resolution and high fidelity levels. For example, previously reported photolithography techniques result in device performance degradation due to process-generated organic residues that hinder charge transport. In addition, imprinting of the structured stamp during contact printing can result in sagging and tilting of the elastomeric stamp structure, thereby exhibiting non-uniform pixel quality. This makes a patterning technique urgently needed to solve these critical problems.
Disclosure of Invention
The invention aims to provide a hyperfine quantum dot film and a preparation method of a high-resolution QLED (quantum dot light emitting diode) thereof, wherein the adopted composition technology enables the quantum dot film to have hyperfine pixel patterning and the prepared pixel points to be uniform, and finally the pixel size of a QLED device can be reduced to a few microns or even below micron, so that a high-brightness ultrahigh-resolution display pixel unit can be obtained and can be applied to next generation display.
In order to achieve the purpose, the technical scheme of the invention is as follows: a method for preparing a hyperfine quantum dot film comprises the steps of preparing a template with a pixel bank structure through a photoetching method, forming a quantum dot film on a PDMS stamp through a self-assembly method, contacting and heating the PDMS stamp with the template with the pixel bank structure, weakening viscosity of the PDMS stamp in a heating process at 80 ℃, leading quantum dots of a contacted part to be taken away by the template with the pixel bank structure, enabling the remaining quantum dots to form a hyperfine pixel pattern, attaching the PDMS stamp to a hole transmission layer, sequentially pressing and separating the PDMS stamp, and enabling the hyperfine quantum dot film to be transferred to the hole transmission layer.
The invention also provides a preparation method of the high-resolution QLED of the hyperfine quantum dot film, which comprises the steps of sequentially depositing a hole injection layer, a hole transport layer, the hyperfine quantum dot film, an electron transport layer and a metal cathode on the ITO layer of the transparent conductive substrate; wherein the content of the first and second substances,
the preparation process of the ultra-fine quantum dot film comprises the following steps: the method comprises the steps of preparing a template with a pixel bank structure through a photoetching method, forming a quantum dot film on a PDMS stamp through a self-assembly method, contacting and heating the PDMS stamp with the template with the pixel bank structure, weakening viscosity of the PDMS stamp in a heating process at 80 ℃, leading quantum dots of a contacted part to be taken away by the template with the pixel bank structure, forming ultra-fine pixel patterns by the remaining quantum dots, attaching the PDMS stamp to a hole transmission layer, and sequentially pressing and separating the PDMS stamp to transfer the ultra-fine quantum dot film to the hole transmission layer.
In an embodiment of the invention, the material of the hole injection layer is one of polymers PEDOT, PSS, molybdenum oxide, nickel oxide and cuprous thiocyanate.
In an embodiment of the invention, the material of the hole transport layer is one of polymers TFB, Poly TPD, PVK, or a mixture of at least two of them.
In an embodiment of the present invention, the material of the quantum dot is one of CdSe, InP, and halogen perovskite.
In an embodiment of the present invention, the material of the electron transport layer is ZnO nanoparticles, ZnO nanoparticles doped with metal cations, or a mixture of ZnO nanoparticles and a polymer.
In an embodiment of the invention, the material of the metal cathode is silver or aluminum.
In an embodiment of the present invention, the self-assembly method of the quantum dots is one of spin coating, inkjet printing, and LB film technology.
Compared with the prior art, the invention has the following beneficial effects:
(1) the composition technology adopted by the invention enables the quantum dot film to have ultra-fine pixel patterning and the prepared pixel points to be uniform. Finally, the pixel size of the QLED device can be reduced to a few micrometers or even below micrometers, so that a high-brightness ultrahigh-resolution display pixel unit can be obtained, and the QLED device can be applied to next generation display.
(2) The preparation process adopted by the invention is safe and pollution-free, does not generate byproducts, and has simple process and easy operation.
Drawings
Fig. 1 is a process flow diagram of a hyperfine patterning process of a quantum dot thin film according to a first embodiment and a second embodiment of the present invention;
fig. 2 is a schematic diagram of a hyperfine pattern of a quantum dot thin film according to a first embodiment and a second embodiment of the present invention;
FIG. 3 is a view of the optical microscope under the first embodiment of the present invention;
fig. 4 is a schematic structural diagram of a high-resolution QLED device according to a first embodiment and a second embodiment of the present invention.
Detailed Description
The technical scheme of the invention is specifically explained below with reference to the accompanying drawings.
The invention discloses a method for preparing a hyperfine quantum dot film and a high-resolution QLED thereof, which is characterized by comprising the following steps: and a hole injection layer, a hole transport layer, a hyperfine quantum dot film, an electron transport layer and a metal cathode are sequentially deposited on the ITO layer of the transparent conductive substrate.
The hyperfine quantum dot film is prepared by combining a photoetching method and a transfer printing method, and specifically comprises the following steps:
step 1: firstly, a layer of photoresist is spin-coated on a glass substrate, and then the photoresist is subjected to ultraviolet exposure under a patterned mask plate.
Step 2: after exposure, a patterned photoresist template is formed by development and then dried.
And step 3: the quantum dot film is formed on the PDMS stamp by a self-assembly method. And then contacting the PDMS stamp with the photoresist patterning template and heating at 80 ℃. The viscosity of PDMS is weakened in the heating process at 80 ℃, so that the quantum dots at the contacted part can be taken away by the photoresist, and the rest quantum dots form an ultra-fine pixel pattern.
And 4, step 4: and finally, attaching the PDMS stamp to the hole transport layer, and sequentially pressing and separating the PDMS stamp to transfer the ultra-fine quantum dot film to the hole transport layer.
And 5: and annealing the ultra-fine quantum dot film transferred to the hole transport layer at 80 ℃.
The following are specific embodiments of the present invention.
Example one
A process flow diagram of a hyperfine quantum dot film and a preparation method of a high-resolution QLED thereof, as shown in fig. 1. The method specifically comprises the following steps:
(1) preparing a photoresist bank template: a layer of photoresist is statically spun on a glass substrate, wherein the spinning speed is 3000rpm, and the spinning time is 45 s. The photoresist under each pixel hole was then uv exposed using a patterned mask plate (diameter of individual pixel hole is 1 μm) and then washed away by development. The remaining photoresist formed a bank-shaped template with a diameter of 500 nm.
(2) And (3) generation of a super-fine quantum dot film: and self-assembling the red CdSe quantum dots on the PDMS stamp by utilizing the LB film technology. And then contacting the PDMS stamp with the photoresist bank template and heating at 80 ℃. The viscosity of PDMS is weakened in the heating process at 80 ℃, so that the quantum dots at the contacted part can be taken away by the photoresist, and the rest quantum dots form an ultra-fine pixel pattern. And finally, attaching the PDMS stamp to the hole transport layer, sequentially pressing and separating the PDMS stamp to transfer the ultra-fine quantum dot film onto the hole transport layer, and annealing at 80 ℃, wherein fig. 2 is a schematic diagram of the ultra-fine composition of the quantum dot film. As shown in fig. 3, a 500nm diameter pixel composed of quantum dots can be seen by observation under an optical microscope.
(3) As shown in fig. 4, the nano QLED device structure sequentially includes an ITO layer, a hole injection layer, a hole transport layer, a super-fine quantum dot film, an electron transport layer, and a metal cathode. The hole injection layer uses PEDOT PSS solution, the hole transport layer uses TFB solution, spin coating is carried out by a spin coater to form a film, the rotating speed is 3000rpm, and the time is 45 s. The patterned quantum dot film is transferred to the hole transport layer, and then the electron transport layer is formed by spin coating a ZnO nanoparticle solution doped with organic polymer PVP at 2000rpm for 45 s. And depositing 100nm Ag electrode on the metal cathode by a vacuum coating machine.
Example two
(1) Preparing a photoresist bank template: a layer of photoresist is statically spun on a glass substrate, wherein the spinning speed is 3000rpm, and the spinning time is 45 s. The photoresist under each pixel hole was then uv exposed using a patterned mask plate (diameter of individual pixel hole is 1 μm) and then washed away by development. The remaining photoresist formed a bank-shaped template with a diameter of 500 nm.
(2) And (3) generation of a super-fine quantum dot film: and (3) self-assembling the red InP quantum dots on the PDMS stamp by using a spin coating film forming method. And then contacting the PDMS stamp with the photoresist bank template and heating at 80 ℃. The viscosity of PDMS is weakened in the heating process at 80 ℃, so that the quantum dots at the contacted part can be taken away by the photoresist, and the rest quantum dots form an ultra-fine pixel pattern. And finally, attaching the PDMS stamp to the hole transport layer, sequentially pressing and separating the PDMS stamp to transfer the ultra-fine quantum dot film to the hole transport layer, and annealing at 80 ℃. Fig. 2 is a schematic diagram of a hyperfine patterning of a quantum dot thin film.
(3) As shown in fig. 4, the nano QLED device structure layer sequentially includes an ITO layer, a hole injection layer, a hole transport layer, a patterned quantum dot film, an electron transport layer, and a metal cathode. The hole injection layer is made of cuprous thiocyanate, the hole transport layer is made of Poly TPD, and the hole transport layer is formed by spin coating through a spin coater at the rotating speed of 3000rpm for 45 s. The patterned quantum dot film is transferred to the hole transport layer, and then the electron transport layer is formed by spin coating ZnMgO nanoparticle solution at 3000rpm for 45 s. And depositing a 100nm Al electrode on the metal cathode by a vacuum coating machine.
In conclusion, the invention has low manufacturing cost and simple preparation process, not only has high preparation speed, but also can be carried out in the atmospheric environment of normal temperature and normal pressure without special requirements for the preparation environment.
The above are preferred embodiments of the present invention, and all changes made according to the technical scheme of the present invention that produce functional effects do not exceed the scope of the technical scheme of the present invention belong to the protection scope of the present invention.
Claims (8)
1. A method for preparing a hyperfine quantum dot film is characterized in that a template with a pixel bank structure is prepared through a photoetching method, a quantum dot film is formed on a PDMS stamp through a self-assembly method, the PDMS stamp is contacted with the template with the pixel bank structure and is heated, the viscosity of the PDMS stamp is weakened in the heating process at 80 ℃, so that quantum dots of the contacted part are taken away by the template with the pixel bank structure, the rest quantum dots form hyperfine pixel patterns, the PDMS stamp is attached to a hole transmission layer, and the PDMS stamp is pressed and separated in sequence, so that the hyperfine quantum dot film is transferred to the hole transmission layer.
2. A method for preparing a high-resolution QLED (quantum light emitting diode) with a hyperfine quantum dot film is characterized in that a hole injection layer, a hole transport layer, the hyperfine quantum dot film, an electron transport layer and a metal cathode are sequentially deposited on an ITO (indium tin oxide) layer of a transparent conductive substrate; wherein the content of the first and second substances,
the preparation process of the ultra-fine quantum dot film comprises the following steps: the method comprises the steps of preparing a template with a pixel bank structure through a photoetching method, forming a quantum dot film on a PDMS stamp through a self-assembly method, contacting and heating the PDMS stamp with the template with the pixel bank structure, weakening viscosity of the PDMS stamp in a heating process at 80 ℃, leading quantum dots of a contacted part to be taken away by the template with the pixel bank structure, forming ultra-fine pixel patterns by the remaining quantum dots, attaching the PDMS stamp to a hole transmission layer, and sequentially pressing and separating the PDMS stamp to transfer the ultra-fine quantum dot film to the hole transmission layer.
3. The method for preparing the QLED with high resolution of the hyperfine quantum dot film according to claim 2, wherein the hole injection layer is made of one of polymers PEDOT, PSS, molybdenum oxide, nickel oxide and cuprous thiocyanate.
4. The method for preparing a high-resolution QLED with ultra-fine quantum dot film according to claim 2, wherein the material of the hole transport layer is one or a mixture of at least two of polymers TFB, Poly TPD and PVK.
5. The method for preparing a high-resolution QLED with ultra-fine quantum dot thin film according to claim 2, wherein the material of the quantum dot is one of CdSe, InP and halogen perovskite.
6. The method for preparing the high-resolution QLED with the hyperfine quantum dot film as claimed in claim 2, wherein the material of the electron transport layer is ZnO nanoparticles, ZnO nanoparticles doped with metal cations or a mixture of ZnO nanoparticles and polymer.
7. The method for preparing a high-resolution QLED with ultra-fine quantum dot thin film according to claim 2, wherein the metal cathode is made of silver or aluminum.
8. The method for preparing a high-resolution QLED with a hyperfine quantum dot thin film according to claim 2, wherein the self-assembly method of the quantum dot is one of spin coating, inkjet printing and LB film technology.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115172638A (en) * | 2022-07-05 | 2022-10-11 | 福州大学 | Method for preparing micro-nano QLED (quantum dot light emitting diode) by transfer printing patterned self-assembly insulating material |
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