Quantum dot light-emitting diode device and manufacturing method therefor, and display apparatus

Abstract

The present disclosure provides a quantum dot light-emitting diode device and a manufacturing method therefor, and a display apparatus. The quantum dot light-emitting diode device comprises: a substrate, and a carrier layer, a free radical barrier layer, and a quantum dot layer which are sequentially stacked on the substrate; the carrier layer comprises a first cross-linked structure in which a first free radical is cross-linked to a carrier material; the quantum dot layer comprises a second cross-linked structure in which a second free radical is cross-linked to a first ligand of a quantum dot, wherein the quantum dot comprises a first quantum dot body and the first ligand linked to the surface of the first quantum dot body; and the free radical barrier layer comprises: a third cross-linked structure in which the first free radical is cross-linked to a free radical barrier material, and a fourth cross-linked structure in which the second free radical is cross-linked to the free radical barrier material.

Description

A quantum dot light-emitting diode device and its manufacturing method, and a display device Technical Field

[0001] The present disclosure relates to the field of display technology, and in particular to a quantum dot light emitting diode device, a manufacturing method thereof, and a display device. Background Art

[0002] With the continuous development and evolution of nanoscience and technology, the preparation of nanomaterials with specifically patterned structures has become an increasingly important research direction in modern nanoscience and technology. Quantum dots, a new type of nanomaterial, have attracted widespread attention from researchers due to their numerous advantages since their emergence. The successful preparation of specifically patterned quantum dot layers has not only expanded their applications but also sparked a new wave of research in the nanotechnology community. Quantum dot light-emitting diode displays (QLEDs) are a new display technology developed based on organic light-emitting displays (OLEDs). The difference between the two is that the light-emitting layer in QLEDs is a quantum dot layer. The principle behind QLEDs is that electrons and holes are injected into the quantum dot layer through an electron / hole transport layer, where they recombine to produce light. Compared to OLED displays, QLEDs offer advantages such as a narrow emission peak, high color saturation, and a wide color gamut.

[0003] Summary of the Invention

[0004] The present disclosure provides a quantum dot light-emitting diode device, a method for manufacturing the same, and a display device. The specific solutions are as follows:

[0005] The embodiment of the present disclosure provides a quantum dot light-emitting diode device, comprising: a substrate, and a carrier layer, a radical blocking layer, and a quantum dot layer sequentially stacked on the substrate; wherein:

[0006] The carrier layer includes a first cross-linked structure formed by cross-linking first free radicals and carrier materials;

[0007] The quantum dot layer includes a second cross-linked structure formed by cross-linking a second free radical and a first ligand of the quantum dot, wherein the quantum dot includes a first quantum dot body and the first ligand connected to the surface of the first quantum dot body;

[0008] The radical blocking layer includes a third cross-linked structure formed by cross-linking the first radicals and the radical blocking material, and a fourth cross-linked structure formed by cross-linking the second radicals and the radical blocking material.

[0009] Optionally, in a specific implementation, in the quantum dot light-emitting diode device provided in the embodiment of the present disclosure, the radical blocking material includes a second quantum dot body and a second ligand connected to the surface of the second quantum dot body, and the polarity of the second ligand is different from that of the first ligand; wherein,

[0010] The third cross-linked structure is formed by cross-linking the first free radical and the second ligand, and the fourth cross-linked structure is formed by cross-linking the second free radical and the second ligand.

[0011] Optionally, in a specific implementation, in the quantum dot light-emitting diode device provided in the embodiment of the present disclosure, the structure of the second ligand includes oleic acid or oleylamine.

[0012] Optionally, in a specific implementation, in the quantum dot light-emitting diode device provided in an embodiment of the present disclosure, the quantum dot layer includes: a first light-emitting portion emitting light at a first wavelength, a second light-emitting portion emitting light at a second wavelength, and a third light-emitting portion emitting light at a third wavelength; wherein the first light-emitting portion, the second light-emitting portion, and the third light-emitting portion are arranged in the same layer and spaced apart, and the first wavelength is greater than the second wavelength and greater than the third wavelength;

[0013] The radical blocking layer includes: a first blocking portion corresponding to the first light-emitting portion, a second blocking portion corresponding to the second light-emitting portion, and a third blocking portion corresponding to the third light-emitting portion; wherein,

[0014] The first barrier portion emits light at a wavelength less than or equal to the first wavelength, the second barrier portion emits light at a wavelength less than or equal to the second wavelength, and the third barrier portion emits light at a wavelength equal to the third wavelength.

[0015] Optionally, in a specific implementation, in the quantum dot light-emitting diode device provided in the embodiment of the present disclosure, the radical blocking material includes polyethyleneimine, polymethyl methacrylate or polystyrene.

[0016] Optionally, in a specific implementation, in the quantum dot light-emitting diode device provided in the embodiment of the present disclosure, the thickness of the free radical blocking layer is less than or equal to 10 nm.

[0017] Optionally, in a specific implementation, in the quantum dot light-emitting diode device provided in the embodiment of the present disclosure, the carrier layer is a carrier transport layer or a carrier injection layer.

[0018] Optionally, in a specific implementation, in the quantum dot light-emitting diode device provided in the embodiment of the present disclosure, the carrier transport layer is a hole transport layer or an electron transport layer.

[0019] Optionally, in a specific implementation, in the quantum dot light-emitting diode device provided in the embodiment of the present disclosure, the carrier transport layer is a hole transport layer, and the carrier material is a hole transport material; wherein,

[0020] The hole transport material includes TFB, and the structure of the first ligand includes

[0021] Optionally, in a specific implementation, in the quantum dot light-emitting diode device provided in the embodiment of the present disclosure, the first free radical includes a nitrogen carbene free radical, and the second free radical includes a benzophenone free radical.

[0022] Accordingly, the embodiment of the present disclosure further provides a quantum dot light-emitting diode device, comprising: a substrate, and a carrier layer and a quantum dot layer sequentially stacked on the substrate; the carrier layer has a first cross-linking structure inside, and the quantum dot layer has a second cross-linking structure inside; wherein,

[0023] The first cross-linked structure is cross-linked by the second free radical and the carrier material, and the structure of the carrier material includes a carbon-carbon double bond;

[0024] The second cross-linked structure is cross-linked by the second free radical and the first ligand of the quantum dot, wherein the quantum dot includes a first quantum dot body and the first ligand connected to the surface of the first quantum dot body, and the structure of the first ligand includes a carbon-carbon double bond.

[0025] Optionally, in a specific implementation, in the quantum dot light-emitting diode device provided in the embodiment of the present disclosure, the carrier layer is a carrier transport layer or a carrier injection layer.

[0026] Optionally, in a specific implementation, in the quantum dot light-emitting diode device provided in the embodiment of the present disclosure, the carrier transport layer is a hole transport layer or an electron transport layer.

[0027] Optionally, in a specific implementation, in the quantum dot light-emitting diode device provided in the embodiment of the present disclosure, the carrier transport layer is a hole transport layer, and the carrier material is a hole transport material; wherein,

[0028] The structure of the hole transport material includes

[0029] The structure of the first ligand includes

[0030] Optionally, in a specific implementation, in the quantum dot light-emitting diode device provided in the embodiment of the present disclosure, the second free radical includes a benzophenone free radical.

[0031] Correspondingly, an embodiment of the present disclosure further provides a display device, including a display panel, wherein the display panel includes the above-mentioned quantum dot light-emitting diode device provided by the embodiment of the present disclosure.

[0032] Accordingly, the embodiments of the present disclosure further provide a method for manufacturing a quantum dot light-emitting diode device, which is used to manufacture the above-mentioned quantum dot light-emitting diode device provided in the embodiments of the present disclosure. The manufacturing method includes:

[0033] Spin coating a carrier material thin film on the substrate; wherein the carrier material thin film contains a first photosensitive material;

[0034] Spin coating a free radical blocking material film on the carrier material film;

[0035] Spin coating a quantum dot film on the free radical blocking material film; the quantum dot film contains a second photosensitive material;

[0036] Using a mask to shield the quantum dot film, the mask having a light-shielding area and a light-transmitting area, the light-transmitting area corresponding to a target area on the quantum dot film where a quantum dot layer is to be formed, and the light-shielding area corresponding to a non-target area where the quantum dot film is to be removed;

[0037] The carrier material film, the free radical blocking material film, and the quantum dot film in the target area are simultaneously irradiated with light using a one-step exposure method; wherein, under illumination, the first photosensitive material in the carrier material film generates a first free radical that triggers a cross-linking reaction of the carrier material to form a first cross-linked structure; under illumination, the second photosensitive material in the quantum dot film generates a second free radical that triggers a polymerization reaction of the first ligand of the quantum dot to form a second cross-linked structure; the free radical blocking material in the free radical blocking material film cross-links with the first free radical that permeates the free radical blocking material film to form a third cross-linked structure; and the free radical blocking material in the free radical blocking material film cross-links with the second free radical that permeates the free radical blocking material film to form a fourth cross-linked structure.

[0038] removing the quantum dot film in the non-target area by using a first solvent;

[0039] A second solvent is used to remove the free radical blocking material film and the carrier material film in the non-target area to form a carrier layer, a free radical blocking layer and a quantum dot layer stacked in sequence in the target area.

[0040] Accordingly, the embodiments of the present disclosure further provide a method for manufacturing a quantum dot light-emitting diode device, which is used to manufacture the above-mentioned quantum dot light-emitting diode device provided in the embodiments of the present disclosure. The manufacturing method includes:

[0041] Spin coating a carrier material film on a substrate; wherein the carrier material film comprises a carrier material and a second photosensitive material, and the structure of the carrier material comprises a carbon-carbon double bond;

[0042] Spin-coating a quantum dot film on the carrier material film; wherein the quantum dot film comprises quantum dots and the second photosensitive material, the quantum dots comprise a first quantum dot body and the first ligand connected to the surface of the first quantum dot body, and the structure of the first ligand comprises a carbon-carbon double bond;

[0043] Using a mask to shield the quantum dot film, the mask having a light-shielding area and a light-transmitting area, the light-transmitting area corresponding to a target area on the quantum dot film where a quantum dot layer is to be formed, and the light-shielding area corresponding to a non-target area where the quantum dot film is to be removed;

[0044] The carrier material film and the quantum dot film in the target area are simultaneously irradiated with light using the one-step exposure method; wherein, under the irradiation, the second photosensitive material in the carrier material film generates a second free radical that triggers a cross-linking reaction of the carrier material to form a first cross-linked structure, and the second photosensitive material in the quantum dot film generates the second free radical that triggers a polymerization reaction of the first ligand of the quantum dot to form a second cross-linked structure;

[0045] removing the quantum dot film in the non-target area by using a first solvent;

[0046] A second solvent is used to remove the carrier material film in the non-target area to form a carrier layer and a quantum dot layer stacked in sequence in the target area. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] FIG1 is a schematic structural diagram of a quantum dot light-emitting diode device provided in the related art;

[0048] FIG2 is a schematic diagram of large-area peeling of a quantum dot pattern in a quantum dot light-emitting diode device provided in the related art;

[0049] FIG3 is a schematic structural diagram of a quantum dot light-emitting diode device provided in an embodiment of the present disclosure;

[0050] FIG4 is a schematic diagram of the structure of quantum dots in a quantum dot layer provided by an embodiment of the present disclosure;

[0051] FIG5 is a schematic structural diagram of another quantum dot light-emitting diode device provided in an embodiment of the present disclosure;

[0052] FIG6 is a schematic structural diagram of a free radical blocking material provided in an embodiment of the present disclosure;

[0053] FIG7 is a schematic flow chart of a method for manufacturing a quantum dot light-emitting diode device according to an embodiment of the present disclosure;

[0054] 8A-8G are schematic structural diagrams of the quantum dot light-emitting diode device shown in FIG5 after each step is performed;

[0055] FIG9 is a schematic structural diagram of another quantum dot light-emitting diode device provided in an embodiment of the present disclosure;

[0056] FIG10 is a schematic flow chart of a method for manufacturing another quantum dot light-emitting diode device according to an embodiment of the present disclosure;

[0057] 11A-11F are schematic structural diagrams of the quantum dot light-emitting diode device shown in FIG9 after each step is performed;

[0058] FIG12 is a schematic diagram showing the mechanism of the cross-linking reaction of the hole transport layer;

[0059] FIG13 is a schematic diagram showing that peeling of a quantum dot pattern in a quantum dot light-emitting diode device provided by an embodiment of the present disclosure is improved. DETAILED DESCRIPTION

[0060] In order to make the purpose, technical solutions and advantages of the embodiments of the present disclosure clearer, the technical solutions of the embodiments of the present disclosure will be clearly and completely described below in conjunction with the drawings of the embodiments of the present disclosure. Obviously, the described embodiments are part of the embodiments of the present disclosure, not all of the embodiments. And in the absence of conflict, the embodiments in the present disclosure and the features in the embodiments can be combined with each other. Based on the described embodiments of the present disclosure, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present disclosure.

[0061] Unless otherwise defined, the technical or scientific terms used in this disclosure shall have the usual meanings understood by persons of ordinary skill in the field to which this disclosure belongs. The words “include” or “comprise” and the like used in this disclosure mean that the elements or objects preceding the word include the elements or objects listed after the word and their equivalents, without excluding other elements or objects. The words “connect” or “connected” and the like are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. “Inside”, “outside”, “upper”, “lower”, etc. are only used to indicate relative positional relationships. When the absolute position of the object being described changes, the relative positional relationship may also change accordingly.

[0062] It should be noted that the sizes and shapes of the figures in the accompanying drawings do not reflect the actual scale and are only for the purpose of illustrating the present disclosure. The same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions.

[0063] Colloidal solutions of quantum dots can be patterned using methods such as printing, transfer, and photolithography. However, printing equipment is expensive and has limited resolution. In recent years, many researchers have conducted extensive research on photolithographic patterning. Direct photolithography, which uses cross-linked ligands to crosslink and solidify the quantum dot ligands under ultraviolet light, can produce higher-resolution QLED devices. However, this method can easily cause color mixing due to residual quantum dots when producing full-color devices, thereby reducing the color gamut of quantum dot electroluminescent devices.

[0064] In the related art, there is a method of patterning quantum dots with the assistance of a sacrificial layer (such as a hole transport layer). The method of patterning quantum dots with the assistance of a sacrificial layer can adopt a one-step exposure process, that is, after coating a layer of hole transport material and a layer of quantum dot material, the two film layers are exposed in one step. The hole transport material and the quantum dot material can each undergo a cross-linking reaction under ultraviolet light irradiation. In this way, in the unexposed area, the quantum dot material can be developed along with the hole transport material, so that it is not easy to form mixed colors. However, the solvents of the quantum dot material and the hole transport material need to be an orthogonal system. A problem faced here is that the cross-linking agents used for the hole transport layer material and the quantum dot material are different. Taking the use of a hole transport material as a sacrificial layer to make a quantum dot light-emitting diode device with an upright structure as an example, as shown in Figure 1, a hole injection layer 2 is first formed on a substrate 1, and then a hole transport material film layer 3 is spin-coated on the hole injection layer 2. The material of the hole transport material film layer 3 is, for example, TFB, and the hole transport material film layer 3 contains a diazide compound (for example, RN=N + =N -, R can be an alkyl group, a benzene ring, etc.), the ultraviolet absorption wavelength of the biazide compound is 254nm; then a quantum dot material film layer 4 is spin-coated on the hole transport material film layer 3, the ligand of the quantum dot is, for example, methacryloyloxyethyl succinate, and a benzophenone-based crosslinker is added to the quantum dot material film layer 4, and the ultraviolet absorption wavelength of the benzophenone-based crosslinker is 365nm. Using an ultraviolet high-pressure mercury lamp, the hole transport material film layer 3 and the quantum dot material film layer 4 in the target area are exposed in a single exposure (e.g., 20 seconds). Ideally, the diazide compound in the target area generates nitrogen carbene radicals under ultraviolet (UV) irradiation, initiating a cross-linking reaction of the hole transport material, and the benzophenone cross-linker in the target area generates benzophenone radicals under UV irradiation, initiating a polymerization reaction of the quantum dot ligands. Therefore, ideally, both the hole transport material film layer 3 and the quantum dot material film layer 4 form a stable cross-linked structure in the target area. The unexposed hole transport material film layer 3 and the quantum dot material film layer 4 are then developed away to pattern the quantum dot layer. However, when a one-step exposure process is used for the hole transport material film layer 3 and the quantum dot material film layer 4, large-scale peeling (peeling) of the quantum dot pattern in the target area may be observed after development, as shown in Figure 2. The inventors of this case have found that the reason for the large-area peeling of the quantum dot pattern is that during the one-step exposure, as shown in FIG1 , the diazide compound in the hole transport material film layer 3 generates nitrogen carbene radicals (the mechanism is: ), the benzophenone cross-linking agent in the quantum dot material film layer 4 generates benzophenone free radicals (the mechanism is: ), these two different free radicals Free radicals will quench each other at the interface between the two layers of materials, resulting in mutual dissipation of free radicals at the interface between the hole transport material film layer 3 and the quantum dot material film layer 4. No effective cross-linking reaction occurs at the interface, so the adhesion between the hole transport material film layer 3 and the quantum dot material film layer 4 is weakened, which ultimately makes it difficult for the quantum dot material film layer 4 to leave a pattern on the hole transport material film layer 3, and is washed away by the developer, causing the pixel pattern of the quantum dot layer to peel.

[0065] In view of this, the embodiment of the present disclosure provides a quantum dot light emitting diode device, as shown in FIG3 , comprising: a substrate 10, and a carrier layer 20, a radical blocking layer 30, and a quantum dot layer 40 sequentially stacked on the substrate 10; wherein,

[0066] The carrier layer 20 includes a first cross-linked structure formed by cross-linking first free radicals and carrier materials;

[0067] The quantum dot layer 40 includes a second cross-linked structure formed by cross-linking the second free radicals and the first ligands of the quantum dots. As shown in FIG4 , the quantum dots in the quantum dot layer 40 include a first quantum dot body QD1 and a first ligand X1 connected to the surface of the first quantum dot body QD1.

[0068] The radical blocking layer 30 includes a third cross-linked structure formed by cross-linking the first radical and the radical blocking material, and a fourth cross-linked structure formed by cross-linking the second radical and the radical blocking material.

[0069] The above-mentioned quantum dot light-emitting diode device provided by the embodiment of the present disclosure, by arranging a free radical blocking layer between the carrier layer and the quantum dot layer, so that when the carrier layer is used as a sacrificial layer to pattern the quantum dots, a layer of free radical blocking material film can be first coated on the carrier material film before coating the quantum dot film. In this way, when the carrier material film and the quantum dot film are exposed at one time using a one-step exposure method, a first free radical will be generated in the carrier material film, and a second free radical will be generated in the quantum dot film. The first free radical and the second free radical near the position of the free radical blocking material film will both penetrate into the free radical blocking material film and undergo a cross-linking reaction with the free radical blocking material. Therefore, due to the presence of the free radical blocking material film, the first free radical and the second free radical will not collide, thereby avoiding mutual quenching between the first free radical and the second free radical. In this way, the carrier material film, the free radical blocking material film and the quantum dot film can all achieve cross-linking reactions, so the adhesion between the quantum dot film and the free radical blocking material film and between the free radical blocking material film and the carrier material film is strong, so that the quantum dot film will not peel off the free radical blocking material film during development.

[0070] Currently, electroluminescent devices can be divided into upright and inverted structures. The difference between the upright and inverted structures lies in the different order in which the film layers are fabricated. Specifically, the upright structure has an anode, hole injection layer, hole transport layer, quantum dot layer, electron transport layer, and cathode formed in sequence on a substrate. The inverted structure has an electron transport layer, quantum dot layer, hole transport layer, hole injection layer, and anode formed in sequence on a substrate. The quantum dot light-emitting diode device in the embodiments of the present disclosure can have either an upright or inverted structure.

[0071] It should be noted that the principle of luminescence of electroluminescent devices is: the holes in the anode and the electrons in the cathode are transferred to the quantum dot layer to recombine and emit light. Due to the difference in energy level barriers between the anode and the light-emitting layer and between the cathode and the light-emitting layer, the transmission of electrons and holes is more difficult and the transmission rate and quantity are also very different. Therefore, in order to balance the concentration of electrons and holes, a hole injection layer and a hole transport layer are generally set between the quantum dot layer and the anode, and an electron transport layer is set between the quantum dot layer and the cathode. Of course, in the specific implementation, the required layers can be selected according to actual needs.

[0072] In specific implementation, in the above-mentioned quantum dot light-emitting diode device provided in the embodiment of the present disclosure, when the quantum dot light-emitting diode device provided in the embodiment of the present disclosure is an upright structure and only a hole injection layer is provided between the quantum dot layer and the anode, the carrier layer of the present disclosure can be a carrier injection layer, that is, the carrier layer is a hole injection layer.

[0073] In specific implementation, in the above-mentioned quantum dot light-emitting diode device provided in the embodiment of the present disclosure, when the quantum dot light-emitting diode device provided in the embodiment of the present disclosure is an upright structure and a hole transport layer is provided between the quantum dot layer and the anode, the carrier layer of the present disclosure can be a carrier transport layer, that is, the carrier transport layer is a hole transport layer; when the quantum dot light-emitting diode device provided in the embodiment of the present disclosure is an inverted structure and an electron transport layer is provided between the quantum dot layer and the cathode, the carrier layer of the present disclosure can be a carrier transport layer, that is, the carrier transport layer is an electron transport layer.

[0074] Taking the quantum dot light-emitting diode device shown in Figure 3 as an upright structure and the carrier layer 20 as a hole transport layer as an example, as shown in Figure 5, the quantum dot light-emitting diode device with an upright structure also includes: an anode 50 arranged between the substrate 10 and the carrier layer 20 (hole transport layer), a hole injection layer 60 arranged between the anode 50 and the carrier layer 20, an electron transport layer (not shown) arranged on the side of the quantum dot layer 40 away from the substrate 10, and a cathode (not shown) arranged on the side of the electron transport layer away from the substrate 10.

[0075] In a specific implementation, in the quantum dot light-emitting diode device provided in the embodiment of the present disclosure, as shown in FIG5 , since the carrier transport layer is a hole transport layer, the carrier material is a hole transport material; optionally, the hole transport material may include but is not limited to TFB (structural formula: ), the structure of the first ligand X1 of the quantum dot in the quantum dot layer 40 shown in FIG4 may include but is not limited to

[0076] In a specific implementation, in the quantum dot light-emitting diode device provided in the embodiment of the present disclosure, when the TFB material is spin-coated, the TFB material contains a diazide compound (e.g., RN=N+ =N - , R can be an alkyl group, a benzene ring, etc.), a diazide compound is a photosensitive material that produces nitrogen carbene radicals under ultraviolet light. The mechanism is: That is, the first free radical in the present disclosure can be a nitrogen carbene free radical Nitrogen carbene radicals can react with TFB materials to form a stable first cross-linked structure; when spin-coating quantum dot materials, the benzophenone cross-linking agent contained in the quantum dot materials has a structure of Benzophenone crosslinking agent is also a photosensitive material. It will produce benzophenone free radicals under ultraviolet light. The mechanism is as follows: That is, the second free radical in the present disclosure can be a benzophenone free radical Benzophenone radicals can react with the first ligand of the quantum dots in the quantum dot layer A polymerization reaction occurs to form a stable second cross-linked structure.

[0077] In specific implementation, in order to prevent the interface between the hole transport layer and the quantum dot layer The present invention provides a free radical blocking layer between the quantum dot layer and the hole transport layer, which requires the selection of a suitable free radical blocking material so that can cross-link with free radical blocking materials to avoid Collision occurs. Optionally, the free radical blocking material provided by the present disclosure may adopt quantum dot material, and the solvent requirement for this quantum dot material is that it needs to be orthogonal to the solvent of the hole transport layer and the quantum dot layer, and does not affect the electroluminescent properties of the quantum dot layer. As shown in Figure 6, the free radical blocking material may include a second quantum dot body QD2 and a second ligand X2 connected to the surface of the second quantum dot body QD2, the polarity of the second ligand X2 is different from the polarity of the first ligand X1 (for example, the polarity of the second ligand X2 is less than the polarity of the first ligand X1), so that the solvent of the free radical blocking material is orthogonal to the solvent of the carrier material and the solvent of the quantum dot, so that the previous film layer will not be affected when the latter film layer is spin-coated. In addition, by selecting a suitable second ligand X2 material, the third cross-linking structure in the free radical blocking layer 30 is formed by the first free radical. The first free radical is cross-linked with the second ligand X2, that is, the first free radical penetrates from the edge of the carrier layer 20 into the free radical blocking layer 30 and reacts with the second ligand X2; and the fourth cross-linked structure in the free radical blocking layer 30 is formed by the second free radical. The second free radicals are cross-linked with the second ligand X2, that is, the second free radicals penetrate from the edge of the quantum dot layer 40 into the free radical blocking layer 30 and react with the second ligand X2. In addition, the free radical blocking material can also enhance the luminescence of the quantum dot layer 40.

[0078] In specific implementation, it is necessary to ensure that the second ligand of the free radical blocking material has a different polarity from the first ligand of the quantum dot layer, and also to ensure that the first free radical and the second free radical can undergo a cross-linking reaction with the second ligand. Optionally, as shown in FIG6 , the structure of the second ligand X2 may include but is not limited to oleic acid or oleylamine, so that the free radical blocking material can be dispersed in octane; since the TFB material of the hole transport layer can be dispersed in a chlorobenzene system, the quantum dot material of the quantum dot layer 40 (ligand is ) can be dispersed in propylene glycol methyl ether acetate (PGMEA). Octane, chlorobenzene and PGMEA are orthogonal solvents, so that the free radical blocking material has no effect on the hole transport layer and the quantum dot layer. Specifically, oleic acid or oleylamine both have CH single bonds and can react with the first free radical. and the second free radical A C-H insertion reaction occurs. Therefore, when fabricating a quantum dot light-emitting diode device with an upright structure, the present disclosure prevents collisions between the first and second free radicals due to the presence of the free radical blocking material film, thereby avoiding mutual quenching between the first and second free radicals. Thus, the carrier material film, the free radical blocking material film, and the quantum dot film can all undergo cross-linking reactions. Consequently, strong adhesion is achieved between the quantum dot film and the free radical blocking material film, as well as between the free radical blocking material film and the carrier material film. This prevents the quantum dot film from peeling off the free radical blocking material film during development.

[0079] It should be noted that the hole transport material in the embodiment of the present disclosure is not limited to TFB, and the photosensitive material added to the hole transport material is not limited to diazide compounds; the first ligand of the quantum dot layer in the embodiment of the present disclosure is not limited to The photosensitive material added to the quantum dot layer is not limited to dibenzophenone crosslinkers; as long as the free radicals generated by the photosensitive material in the hole transport material and the free radicals generated by the photosensitive material in the quantum dot material are different when the hole transport layer is used as a sacrificial layer to pattern the quantum dot layer, a free radical blocking layer can be set between the quantum dot layer and the hole transport layer. It is necessary to ensure that the solvent of the free radical blocking material is orthogonal to the solvent of the carrier material and the solvent of the quantum dots, and to ensure that the free radicals generated by the photosensitive material in the hole transport material and the free radicals generated by the photosensitive material in the quantum dot material can both undergo cross-linking reactions with the free radical blocking material, and all fall within the scope of protection of the present disclosure.

[0080] In specific implementation, in order to achieve full-color display, the quantum dot layer generally includes patterned quantum dots of different colors. In the above-mentioned quantum dot light-emitting diode device provided in the embodiment of the present disclosure, as shown in Figure 5, the quantum dot layer 40 includes: a first light-emitting portion 401 with a light-emitting wavelength of a first wavelength, a second light-emitting portion (not shown) with a light-emitting wavelength of a second wavelength, and a third light-emitting portion (not shown) with a light-emitting wavelength of a third wavelength; wherein the first light-emitting portion 401, the second light-emitting portion and the third light-emitting portion are in the same layer and are arranged at intervals, and the first wavelength>the second wavelength>the third wavelength; in this way, the use of quantum dots with three light-emitting wavelengths can achieve full-color display of the quantum dot light-emitting diode device.

[0081] Optionally, the embodiment of the present disclosure takes the first wavelength as red light wavelength, the second wavelength as green light wavelength, and the third wavelength as blue light wavelength as an example, that is, the quantum dot layer includes a first light-emitting portion with red light-emitting colors, a second light-emitting portion with green light-emitting colors, and a third light-emitting portion with blue light-emitting colors respectively.

[0082] In a specific implementation, in the above-mentioned quantum dot light-emitting diode device provided in the embodiment of the present disclosure, as shown in Figure 5, the free radical blocking layer 30 may include: a first blocking portion 301 arranged corresponding to the first light-emitting portion 401, a second blocking portion (not shown) arranged corresponding to the second light-emitting portion, and a third blocking portion (not shown) arranged corresponding to the third light-emitting portion; since the free radical blocking layer material is a quantum dot material, in order to prevent the luminous color of each blocking layer from being mixed with the luminous color of the corresponding quantum dot layer, the luminous color of each blocking layer is preferably consistent with the luminous color of the corresponding quantum dot layer, so the luminous wavelength of the first blocking portion 301 is equal to the first wavelength, that is, the luminous color of the first blocking portion 301 is red; the luminous wavelength of the second blocking portion is equal to the second wavelength, that is, the luminous color of the second blocking portion is green, and the luminous wavelength of the third blocking portion is equal to the third wavelength, that is, the luminous color of the third blocking portion is blue.

[0083] In practice, because different colored quantum dots require different driving voltages for light emission, blue quantum dots generally have a higher turn-on voltage, around 5V, while red and green quantum dots have relatively lower turn-on voltages, generally around 2.5V. Furthermore, blue quantum dots have a lower luminance, so a blue first barrier can be placed below the red first light-emitting portion, and a blue second barrier can be placed below the green second light-emitting portion. This prevents the lower blue first and second barrier portions from emitting light when the red first and green second light-emitting portions are illuminated, thus preventing cross-coloring. Therefore, the emission wavelength of the first barrier portion 301 can be less than or equal to the first wavelength, the emission wavelength of the second barrier portion can be less than or equal to the second wavelength, and the emission wavelength of the third barrier portion can be the third wavelength.

[0084] Alternatively, as shown in FIG5 , taking the red first light-emitting portion 401 as an example, the first barrier portion 301 also uses a red quantum dot material, and the second ligand of the quantum dot material of the first barrier portion 301 is oleic acid or oleylamine, so the quantum dot material of the first barrier portion 301 can be dispersed in an octane system; since the TFB material of the hole transport layer can be dispersed in a chlorobenzene system, the quantum dot material of the first light-emitting portion 401 (ligand is ) is dispersed in propylene glycol methyl ether acetate (PGMEA). Octane, chlorobenzene and PGMEA are orthogonal solvents. Therefore, when the patterned first light-emitting portion is made by a one-step exposure method, the first free radicals generated in the hole transport layer and the second free radicals generated within the quantum dot layer Both can undergo C-H insertion reaction with oleic acid or oleylamine in the free radical blocking material. Therefore, selecting quantum dot materials with oleic acid or oleylamine as ligands as free radical blocking materials can not only prevent peeling of the quantum dot layer, but also not affect the electroluminescent properties of the quantum dot layer, and can also enhance the luminescence of the quantum dot layer.

[0085] Optionally, the first quantum dot body and the second quantum dot body provided in the embodiment of the present disclosure may include but are not limited to quantum dot bodies such as CdS, CdSe, ZnSe, InP, PbS, CsPbCl3, CsPbBr3, CsPhI3, CdS / ZnS, CdSe / ZnSe, CdSe / ZnS, ZnSe, InP / ZnS, PbS / ZnS, CsPbCl3 / ZnS, CsPbBr3 / ZnS, and CsPhI3 / ZnS. Quantum dots of different colors may have different particle sizes, for example.

[0086] In a specific implementation, in the above-mentioned quantum dot light-emitting diode device provided in the embodiment of the present disclosure, as shown in FIG5 , the radical blocking material of the radical blocking layer 30 may also include, but is not limited to, polyethyleneimine (PEIE), polymethyl methacrylate (PMMA) or polystyrene (PS). Taking PEIE as an example of the radical blocking material, PEIE has good solubility in alcohols and is orthogonal to the solvents of the hole transport layer and the quantum dot layer. PEIE will not affect the photochemical reactions within the hole transport layer and the quantum dot layer, and under one-step exposure, the first free radical generated in the hole transport layer and the second free radical generated in the quantum dot layer can both penetrate into the PEIE at the interface and react with the CH bond inside it, thereby preventing the first free radical and the second free radical from colliding and quenching, and avoiding peeling of the quantum dot layer. In addition, PEIE can also serve as an electron blocking layer to reduce the damage to the device caused by excessive electron injection into the electron transport layer and the hole transport layer. Therefore, while PEIE serves as a radical blocking layer, it can also serve as an electron blocking layer, which has a good beneficial effect on improving device efficiency and improving device life.

[0087] In specific implementations, in the quantum dot light-emitting diode device provided in the embodiments of the present disclosure, as shown in Figures 3 and 5, the thickness of the radical blocking layer 30 cannot be too thick. If the thickness is too thick, the first and second radicals will have limited penetration into the radical blocking layer 30, preventing the radical blocking layer 30 from fully cross-linking. During subsequent development, the quantum dot layer is prone to peeling due to insufficient cross-linking within the radical blocking layer 30. Therefore, the thickness of the radical blocking layer 30 is critical. In the embodiments of the present disclosure, the thickness of the radical blocking layer 30 is set to be less than or equal to 10 nm, which is most suitable within the range of 0-10 nm. Furthermore, the optimal film thickness can be optimized through experimental procedures to achieve the patterning effect of the quantum dots.

[0088] It should be noted that Figures 3 and 5 of the embodiments of the present disclosure are illustrated using a device with an upright structure as an example. When an inverted structure is adopted, the carrier layer can be an electron transport layer. By selecting suitable electron transport materials and photosensitive materials added to the electron transport layer, the first ligand of the quantum dot layer, and the photosensitive materials and free radical blocking materials added to the quantum dot layer, the free radicals generated by the electron transport layer and the quantum dot layer under one-step exposure can undergo a cross-linking reaction with the free radical blocking material, which are all protected by the embodiments of the present disclosure.

[0089] The present disclosure does not limit the light emitting type of the quantum dot light emitting diode device, such as being not limited to bottom-emitting light or top-emitting light.

[0090] Specifically, the substrate provided by the embodiment of the present disclosure may include a base substrate, a driving circuit located on the base substrate, and a passivation layer, a planarization layer, and other structures located above the driving circuit.

[0091] Optionally, the substrate may be a flexible substrate or a rigid substrate. The flexible substrate may be, for example, a PI substrate, and the rigid substrate may be, for example, a glass substrate.

[0092] In specific implementation, the quantum dot light-emitting diode device provided in the embodiment of the present disclosure also includes other functional film layers well known to those skilled in the art, which will not be described in detail here.

[0093] Based on the same inventive concept, the present disclosure also provides a method for manufacturing a quantum dot light-emitting diode device, which is used to manufacture the quantum dot light-emitting diode device shown in FIG. 5 . As shown in FIG. 7 , the manufacturing method includes:

[0094] S701, spin-coating a carrier material thin film on a substrate; wherein the carrier material thin film contains a first photosensitive material;

[0095] Specifically, taking the production of the red first light-emitting portion 401 in Figure 5 as an example; as shown in Figure 8A, an anode 50 is formed on the substrate 10, a hole injection layer 60 is formed on the anode 50, and a layer of carrier material film 20' (i.e., a hole transport material film, the material can be TFB) is spin-coated on the hole injection layer 60; wherein, the carrier material film 20' contains a first photosensitive material, and the first photosensitive material can be a diazide compound.

[0096] S702, spin coating a free radical blocking material film on the carrier material film;

[0097] Specifically, as shown in FIG8B , a free radical blocking material film 30' is spin-coated on the carrier material film 20'. The free radical blocking material can be a red quantum dot material, a blue quantum dot material, or a polymer material such as PEIE. In this embodiment, the free radical blocking material is a red quantum dot material (whose ligand is oleylamine or oleic acid). Specifically, the free radical blocking material film 30' has a thickness of 0-10 nm and a concentration of 5 mg / mL.

[0098] S703, spin coating a quantum dot film on the free radical blocking material film; the quantum dot film contains a second photosensitive material;

[0099] Specifically, as shown in FIG8C , a red quantum dot film 40 'is spin-coated on the radical blocking material film 30 '; the quantum dot film 40 'has a second photosensitive material, which can be a benzophenone cross-linking agent; the first ligand of the quantum dots in the quantum dot film 40 'can be Optionally, the concentrations of the quantum dot film 40 ′ and the benzophenone-based cross-linking agent may be 25 mg / mL and 0.75 mg / mL, respectively.

[0100] S704, using a mask to block the quantum dot film, the mask having a light-shielding area and a light-transmitting area, the light-transmitting area corresponding to a target area on the quantum dot film where a quantum dot layer is to be formed, and the light-shielding area corresponding to a non-target area where the quantum dot film is to be removed;

[0101] Specifically, as shown in FIG8D , a mask 100 is used to block the quantum dot film 40 ′. The mask 100 has a light-shielding area 101 and a light-transmitting area 102. The light-transmitting area 102 corresponds to the target area for forming the quantum dot layer 40 on the quantum dot film 40 ′, and the light-shielding area 101 corresponds to the non-target area for removing the quantum dot film 40 ′.

[0102] S705, using a one-step exposure method to simultaneously irradiate the carrier material film, the free radical blocking material film, and the quantum dot film in the target area; wherein, under irradiation, the first photosensitive material in the carrier material film generates a first free radical that triggers a cross-linking reaction of the carrier material to form a first cross-linked structure; under irradiation, the second photosensitive material in the quantum dot film generates a second free radical that triggers a polymerization reaction of the first ligand of the quantum dot to form a second cross-linked structure; the free radical blocking material in the free radical blocking material film cross-links with the first free radical that penetrates into the free radical blocking material film to form a third cross-linked structure; and the free radical blocking material in the free radical blocking material film cross-links with the second free radical that penetrates into the free radical blocking material film to form a fourth cross-linked structure;

[0103] Specifically, as shown in FIG8E , a one-step exposure method is used to simultaneously irradiate the carrier material film 20 ′, the radical blocking material film 30 ′ and the quantum dot film 40 ′ in the target area with light (e.g., ultraviolet light, as indicated by the arrows); wherein the first photosensitive material (RN=N + =N - ) generates the first free radical under light (UV) The TFB is triggered to undergo a cross-linking reaction to form a first cross-linking structure, and the second photosensitive material (benzophenone cross-linking agent) in the quantum dot film 40' generates a second free radical under light (UV). The first ligand to trigger quantum dots The polymerization reaction occurs to form a second cross-linked structure, and the free radical blocking material (the first ligand is oleylamine or oleic acid) in the free radical blocking material film 30' and the first free radical that penetrates into the free radical blocking material film 30' A cross-linking reaction occurs to form a third cross-linking structure, and the free radical blocking material in the free radical blocking material film 30' reacts with the second free radical that penetrates into the free radical blocking material film 30'. A cross-linking reaction occurs to form a fourth cross-linking structure.

[0104] S706, removing the quantum dot film in non-target areas using a first solvent;

[0105] Specifically, as shown in FIG8F , a first solvent (eg, PGMEA) is used to remove the quantum dot film 40 ′ in non-target areas.

[0106] S707, using a second solvent to remove the free radical blocking material film and the carrier material film in the non-target area, so as to form a carrier layer, a free radical blocking layer and a quantum dot layer stacked in sequence in the target area;

[0107] Specifically, as shown in FIG8G , a second solvent (such as toluene) is used to remove the radical blocking material film 30 ′ and the carrier material film 20 ′ in the non-target area to form a carrier layer 20, a radical blocking layer 30 and a quantum dot layer 40 (i.e., the first light-emitting portion 401) stacked in sequence in the target area.

[0108] Then, repeat step S701 to spin-coat a carrier material film 20 ′ on the hole injection layer 60 to step S707 to fabricate a green second light-emitting portion and a blue third light-emitting portion, thereby fabricating full-color quantum dots.

[0109] Thereafter, an electron transport layer is formed on the quantum dot layer 40 , and a cathode is formed on the electron transport layer.

[0110] After the preparation of the above-mentioned film layers is completed, packaging is performed to complete the production of the quantum dot light-emitting diode device with an upright structure in the embodiment of the present disclosure.

[0111] It should be noted that the embodiments of the present disclosure mainly use the light-emitting device with an upright structure as an example to explain in detail the method for manufacturing a quantum dot light-emitting diode device. Of course, the embodiments of the present disclosure are also applicable to the manufacture of quantum dot light-emitting diode devices in an upright structure.

[0112] In the structure shown in FIG5 , in order to prevent the collision and mutual quenching of different free radicals in the hole transport layer and the quantum dot layer, a free radical blocking layer is added between the hole transport layer and the quantum dot layer, but this will increase the production cost accordingly. It is particularly important to solve the problem of free radical quenching without changing the original structure of the quantum dot light-emitting diode device. This requires that the hole transport layer and the quantum dot layer use the same photosensitive material (cross-linking agent). The material of the hole transport layer in FIG5 is TFB (structural formula is ), TFB molecules contain benzene rings and carbon-hydrogen bonds. In order to reduce the residue of the hole transport layer as a sacrificial layer, the hole transport layer needs to be photopatterned. Contains carbon-oxygen bonds, carbonyl groups, carbon-carbon double bonds and carbon-hydrogen bonds. In this embodiment, a benzophenone-type cross-linking agent is used as a photosensitive material in the quantum dot layer 40 to realize the patterning of quantum dots. In addition, the benzophenone-type cross-linking agent has little damage to the efficiency of the quantum dot device and is a very gentle cross-linking agent. However, the mechanism of cross-linking quantum dots by benzophenone-type cross-linking agents is that benzophenone free radicals initiate the polymerization reaction of the carbon-carbon double bond on the first ligand. The efficiency of the carbon-hydrogen insertion reaction of benzophenone free radicals is very low. Previously, attempts were made to replace the photosensitive material of the hole transport layer with a benzophenone-type cross-linking agent, but even if the exposure dose is large (>10000mJ / cm 2 ), the hole transport layer still cannot achieve patterning. When the photosensitive material of the quantum dot layer is replaced with a diazide compound, although quantum dot patterning can be achieved, the device efficiency is significantly damaged, essentially reducing it by more than half. Therefore, in order to ensure that the photosensitive materials of the quantum dot layer and the hole transport layer are the same and to minimize damage to the quantum dot device, the present disclosure improves the material of the hole transport layer.

[0113] Therefore, based on the same inventive concept, the embodiment of the present disclosure further provides a quantum dot light-emitting diode device, as shown in FIG9 , comprising: a substrate 10, and a carrier layer 20 and a quantum dot layer 40 sequentially stacked on the substrate 10; the carrier layer 20 has a first cross-linked structure inside, and the quantum dot layer 40 has a second cross-linked structure inside; wherein,

[0114] The first cross-linked structure is cross-linked by the second free radical and the carrier material, and the structure of the carrier material includes a carbon-carbon double bond;

[0115] The second cross-linked structure is cross-linked by the second free radical and the first ligand of the quantum dot, where as shown in Figure 4, the quantum dots in the quantum dot layer 40 include a first quantum dot body QD1 and a first ligand X1 connected to the surface of the first quantum dot body QD1, and the structure of the first ligand X1 includes a carbon-carbon double bond.

[0116] The quantum dot light-emitting diode device shown in FIG9 provided by the embodiment of the present disclosure adopts a carrier material containing a carbon-carbon double bond and a quantum dot material containing a ligand carbon-carbon double bond, so that the carrier layer and the quantum dot layer can use the same photosensitive material (cross-linker). Therefore, when a patterned quantum dot layer is produced by a one-step exposure method, since the free radicals generated by the carrier layer and the quantum dot layer are the same, free radical quenching will not occur at the interface between the two, and there is no need to add a free radical blocking layer between the two. Therefore, the problem of peeling of the quantum dot layer can be avoided while saving production costs.

[0117] In a specific implementation, the quantum dot light-emitting diode device shown in FIG9 can have an upright structure or an inverted structure, and the carrier layer can be a carrier transport layer or a carrier injection layer. The carrier transport layer can be a hole transport layer or an electron transport layer. For details, please refer to the relevant description of the quantum dot light-emitting diode device described above and will not be repeated here.

[0118] In a specific implementation, in the quantum dot light-emitting diode device provided in the embodiment of the present disclosure, as shown in FIG9 , the quantum dot light-emitting diode device is in an upright structure, and the carrier transport layer 20 is a hole transport layer as an example, that is, the carrier material is a hole transport material; wherein,

[0119] The structure of the hole transport material may include but is not limited to

[0120] The structure of the first ligand X1 includes but is not limited to

[0121] Specifically, the relevant description about the quantum dot layer in this embodiment can refer to the description of the aforementioned quantum dot light emitting diode device, which will not be repeated here.

[0122] Specifically, since benzophenone radicals can initiate free radical polymerization of carbon-carbon double bonds, the present disclosure uses hole transport materials containing carbon-carbon double bonds, so that the photoinitiated polymerization reaction of benzophenone radicals can be achieved, thereby realizing the patterning of the hole transport layer. Therefore, in the above-mentioned quantum dot light-emitting diode device provided by the embodiment of the present disclosure, the second radical may include but is not limited to benzophenone radicals. In this way, when making the quantum dot light-emitting diode device shown in Figure 9, when coating the hole transport material film on the substrate, a benzophenone-type crosslinking agent is added to the hole transport material; when coating the quantum dot film on the hole transport material film, a benzophenone-type crosslinking agent is added to the quantum dot material; then, a one-step exposure method can be used to achieve patterning of the quantum dots, and peeling of the quantum dot layer will not occur.

[0123] Based on the same inventive concept, the present disclosure also provides a method for manufacturing a quantum dot light-emitting diode device, which is used to manufacture the quantum dot light-emitting diode device shown in FIG9 . As shown in FIG10 , the manufacturing method includes:

[0124] S1001, spin-coating a carrier material thin film on a substrate; wherein the carrier material thin film comprises a carrier material and a second photosensitive material, and the structure of the carrier material includes a carbon-carbon double bond;

[0125] Specifically, take the production of the red first light-emitting portion 401 in FIG9 as an example; as shown in FIG11A, an anode 50 is formed on a substrate 10, a hole injection layer 60 is formed on the anode 50, and a layer of carrier material film 20' (i.e., a hole transport material film, the material can be ); wherein the carrier material film 20' further comprises a second photosensitive material, and the second photosensitive material can be a benzophenone crosslinking agent. Optionally, the concentration of the carrier material film can be 1 mg / mL-8 mg / mL.

[0126] S1002, spin-coating a quantum dot film on the carrier material film; wherein the quantum dot film comprises quantum dots and a second photosensitive material, the quantum dots comprising a first quantum dot body and a first ligand connected to a surface of the first quantum dot body, the structure of the first ligand comprising a carbon-carbon double bond;

[0127] Specifically, as shown in FIG11B , a red quantum dot film 40 'is spin-coated on the carrier material film 20 '; the quantum dot film 40 'has a second photosensitive material, which can be a benzophenone cross-linking agent; the first ligand of the quantum dots in the quantum dot film 40 'can be Optionally, the concentration of the quantum dot film 40 ′ may be 0.75 mg / mL-25 mg / mL.

[0128] S1003, using a mask to block the quantum dot film, the mask having a light-shielding area and a light-transmitting area, the light-transmitting area corresponding to a target area on the quantum dot film where a quantum dot layer is to be formed, and the light-shielding area corresponding to a non-target area where the quantum dot film is to be removed;

[0129] Specifically, as shown in FIG11C , a mask 100 is used to block the quantum dot film 40 ′. The mask 100 has a light-shielding area 101 and a light-transmitting area 102. The light-transmitting area 102 corresponds to the target area for forming the quantum dot layer 40 on the quantum dot film 40 ′, and the light-shielding area 101 corresponds to the non-target area for removing the quantum dot film 40 ′.

[0130] S1004, using a one-step exposure method to simultaneously illuminate the carrier material film and the quantum dot film in the target area; wherein, under illumination, the second photosensitive material in the carrier material film generates a second free radical that triggers a cross-linking reaction of the carrier material to form a first cross-linked structure; and the second photosensitive material in the quantum dot film generates a second free radical that triggers a polymerization reaction of the first ligand of the quantum dot to form a second cross-linked structure.

[0131] Specifically, as shown in FIG11D , a one-step exposure method is used to simultaneously irradiate the carrier material film 20 'and the quantum dot film 40 'in the target area with light (e.g., ultraviolet light, as indicated by the arrow); wherein the second photosensitive material (benzophenone crosslinking agent) in the carrier material film 20 'generates a second free radical under the light (UV) Trigger The carbon-carbon double bonds of the cross-linked structure undergo a cross-linking reaction to form a first cross-linked structure. The mechanism of the cross-linking reaction is shown in FIG12 , wherein the structure of the benzophenone cross-linking agent is It represents the structure formed by the hydrogen abstraction reaction of the benzophenone free radical generated by the benzophenone crosslinking agent. The specific structure is The second photosensitive material (benzophenone crosslinking agent) in the quantum dot film 40' generates a second free radical under light (UV) The first ligand to trigger quantum dots A polymerization reaction occurs to form a second cross-linked structure.

[0132] S1005, removing the quantum dot film in non-target areas using a first solvent;

[0133] Specifically, as shown in FIG. 11E , a first solvent (eg, PGMEA) is used to remove the quantum dot film 40 ′ in non-target areas.

[0134] S1006, using a second solvent to remove the carrier material film in the non-target area, so as to form a carrier layer and a quantum dot layer stacked in sequence in the target area;

[0135] Specifically, as shown in FIG11F , a second solvent (eg, toluene) is used to remove the carrier material film 20 ′ in the non-target area to form a carrier layer 20 and a quantum dot layer 40 (ie, the first light-emitting portion 401 ) stacked in sequence in the target area.

[0136] Then, repeat the above step S1001 to spin-coat a carrier material film 20 ′ on the hole injection layer 60 to step S1006 to realize the production of the green second light-emitting portion and the blue third light-emitting portion, thereby realizing the production of full-color quantum dots.

[0137] Thereafter, an electron transport layer is formed on the quantum dot layer 40 , and a cathode is formed on the electron transport layer.

[0138] After the preparation of the above-mentioned film layers is completed, packaging is performed to complete the production of the quantum dot light-emitting diode device with an upright structure in the embodiment of the present disclosure.

[0139] It should be noted that the embodiments of the present disclosure mainly use the light-emitting device with an upright structure as an example to explain in detail the method for manufacturing a quantum dot light-emitting diode device. Of course, the embodiments of the present disclosure are also applicable to the manufacture of quantum dot light-emitting diode devices in an upright structure.

[0140] The inventors of this case used the quantum dot light-emitting diode device fabrication method provided by the embodiments of the present disclosure to fabricate a quantum dot light-emitting diode device. Fluorescence microscopy revealed a significant improvement in the peeling of the quantum dot pixel pattern, as shown in Figure 13. However, peeling still occurred in a small portion of the quantum dot pixel pattern. Therefore, it was necessary to further adjust the crosslinker concentration of the hole transport layer and the exposure time to ensure sufficient photocrosslinking reaction in the hole transport layer, thereby further reducing the occurrence of peeling.

[0141] Based on the same inventive concept, the embodiments of the present disclosure further provide a display device, including a display panel, which includes the above-mentioned quantum dot light-emitting diode device provided in the embodiments of the present disclosure. The principle of solving the problem of the display device is similar to that of the aforementioned quantum dot light-emitting diode device, so the implementation of the display device can refer to the implementation of the aforementioned quantum dot light-emitting diode device, and the repeated parts will not be repeated here. The display device can be any product or component with a display function, such as a mobile phone, a tablet computer, a television, a monitor, a laptop computer, a digital photo frame, a navigator, etc. The other essential components of the display device should be understood by ordinary technicians in this field, and will not be repeated here, nor should they be used as a limitation to the present invention.

[0142] The embodiments of the present disclosure provide a quantum dot light-emitting diode device, a manufacturing method thereof, and a display device. A free radical blocking layer is provided between a carrier layer and a quantum dot layer. Thus, when the carrier layer is used as a sacrificial layer to pattern quantum dots, a layer of free radical blocking material film can be coated on the carrier material film before the quantum dot film is coated. Thus, when the carrier material film and the quantum dot film are exposed at one time using a one-step exposure method, a first free radical will be generated in the carrier material film, and a second free radical will be generated in the quantum dot film. The first free radical and the second free radical near the free radical blocking material film will both penetrate into the free radical blocking material film and undergo a cross-linking reaction with the free radical blocking material. Therefore, due to the presence of the free radical blocking material film, the first free radical and the second free radical will not collide, thereby avoiding mutual quenching between the first free radical and the second free radical. In this way, the carrier material film, the free radical blocking material film and the quantum dot film can all achieve cross-linking reactions, so the adhesion between the quantum dot film and the free radical blocking material film and between the free radical blocking material film and the carrier material film is strong, so that the quantum dot film will not peel off the free radical blocking material film during development.

[0143] Obviously, those skilled in the art may make various changes and modifications to the present disclosure without departing from the spirit and scope of the present disclosure. Thus, if these modifications and variations of the present disclosure fall within the scope of the claims of the present disclosure and their equivalents, the present disclosure is intended to include these modifications and variations.

Claims

1. A quantum dot light emitting diode device, wherein: include: A substrate, and a carrier layer, a free radical blocking layer and a quantum dot layer sequentially stacked on the substrate; wherein, The carrier layer includes a first cross-linked structure formed by cross-linking first free radicals and carrier materials; The quantum dot layer includes a second cross-linked structure formed by cross-linking a second free radical and a first ligand of the quantum dot, wherein the quantum dot includes a first quantum dot body and the first ligand connected to the surface of the first quantum dot body; The radical blocking layer includes a third cross-linked structure formed by cross-linking the first radicals and the radical blocking material, and a fourth cross-linked structure formed by cross-linking the second radicals and the radical blocking material.

2. The quantum dot light-emitting diode device according to claim 1, wherein: The free radical blocking material includes a second quantum dot body and a second ligand connected to the surface of the second quantum dot body, wherein the polarity of the second ligand is different from that of the first ligand; wherein, The third cross-linked structure is formed by cross-linking the first free radical and the second ligand, and the fourth cross-linked structure is formed by cross-linking the second free radical and the second ligand.

3. The quantum dot light emitting diode device according to claim 2, wherein: The structure of the second ligand includes oleic acid or oleylamine.

4. The quantum dot light emitting diode device according to claim 2, wherein: The quantum dot layer includes: a first light-emitting portion emitting light at a first wavelength, a second light-emitting portion emitting light at a second wavelength, and a third light-emitting portion emitting light at a third wavelength; wherein the first light-emitting portion, the second light-emitting portion, and the third light-emitting portion are arranged in the same layer and spaced apart, and the first wavelength is greater than the second wavelength and greater than the third wavelength; The radical blocking layer includes: a first blocking portion corresponding to the first light-emitting portion, a second blocking portion corresponding to the second light-emitting portion, and a third blocking portion corresponding to the third light-emitting portion; wherein, The first barrier portion emits light at a wavelength less than or equal to the first wavelength, the second barrier portion emits light at a wavelength less than or equal to the second wavelength, and the third barrier portion emits light at a wavelength equal to the third wavelength.

5. The quantum dot light emitting diode device according to claim 1, wherein: The radical blocking material includes polyethyleneimine, polymethyl methacrylate or polystyrene.

6. The quantum dot light-emitting diode device according to any one of claims 1 to 5, wherein: The thickness of the free radical blocking layer is less than or equal to 10 nm.

7. The quantum dot light-emitting diode device according to any one of claims 1 to 6, wherein: The carrier layer is a carrier transport layer or a carrier injection layer.

8. The quantum dot light-emitting diode device according to claim 7, wherein: The carrier transport layer is a hole transport layer or an electron transport layer.

9. The quantum dot light emitting diode device according to claim 8, wherein: The carrier transport layer is a hole transport layer, and the carrier material is a hole transport material; wherein, The hole transport material includes TFB, and the structure of the first ligand includes 10. The quantum dot light-emitting diode device according to any one of claims 1 to 9, wherein: The first free radical includes a nitrogen carbene free radical, and the second free radical includes a benzophenone free radical.

11. A quantum dot light emitting diode device, wherein: include: A substrate, and a carrier layer and a quantum dot layer sequentially stacked on the substrate; The carrier layer has a first cross-linking structure inside, and the quantum dot layer has a second cross-linking structure inside; wherein, The first cross-linked structure is cross-linked by the second free radical and the carrier material, and the structure of the carrier material includes a carbon-carbon double bond; The second cross-linked structure is cross-linked by the second free radical and the first ligand of the quantum dot, wherein the quantum dot includes a first quantum dot body and the first ligand connected to the surface of the first quantum dot body, and the structure of the first ligand includes a carbon-carbon double bond.

12. The quantum dot light emitting diode device according to claim 11, wherein: The carrier layer is a carrier transport layer or a carrier injection layer.

13. The quantum dot light emitting diode device according to claim 12, wherein: The carrier transport layer is a hole transport layer or an electron transport layer.

14. The quantum dot light emitting diode device according to claim 13, wherein: The carrier transport layer is a hole transport layer, and the carrier material is a hole transport material; wherein, The structure of the hole transport material includes The structure of the first ligand includes 15. The quantum dot light-emitting diode device according to any one of claims 11 to 14, wherein: The second free radical includes a benzophenone free radical.

16. A display device, wherein: Comprising a display panel, the display panel comprises the quantum dot light emitting diode device according to any one of claims 1 to 15.

17. A method for manufacturing a quantum dot light-emitting diode device, for manufacturing the quantum dot light-emitting diode device according to any one of claims 1 to 10, wherein: The production method comprises: Spin coating a carrier material thin film on the substrate; wherein the carrier material thin film contains a first photosensitive material; Spin coating a free radical blocking material film on the carrier material film; Spin coating a quantum dot film on the free radical blocking material film; the quantum dot film contains a second photosensitive material; Using a mask to shield the quantum dot film, the mask having a light-shielding area and a light-transmitting area, the light-transmitting area corresponding to a target area on the quantum dot film where a quantum dot layer is to be formed, and the light-shielding area corresponding to a non-target area where the quantum dot film is to be removed; The carrier material film, the free radical blocking material film, and the quantum dot film in the target area are simultaneously irradiated with light using a one-step exposure method; wherein, under illumination, the first photosensitive material in the carrier material film generates a first free radical that triggers a cross-linking reaction of the carrier material to form a first cross-linked structure; under illumination, the second photosensitive material in the quantum dot film generates a second free radical that triggers a polymerization reaction of the first ligand of the quantum dot to form a second cross-linked structure; the free radical blocking material in the free radical blocking material film cross-links with the first free radical that permeates the free radical blocking material film to form a third cross-linked structure; and the free radical blocking material in the free radical blocking material film cross-links with the second free radical that permeates the free radical blocking material film to form a fourth cross-linked structure. removing the quantum dot film in the non-target area by using a first solvent; A second solvent is used to remove the free radical blocking material film and the carrier material film in the non-target area to form a carrier layer, a free radical blocking layer and a quantum dot layer stacked in sequence in the target area.

18. A method for manufacturing a quantum dot light-emitting diode device, for manufacturing the quantum dot light-emitting diode device according to any one of claims 11 to 15, wherein: The production method comprises: Spin coating a carrier material film on a substrate; wherein the carrier material film comprises a carrier material and a second photosensitive material, and the structure of the carrier material comprises a carbon-carbon double bond; Spin-coating a quantum dot film on the carrier material film; wherein the quantum dot film comprises quantum dots and the second photosensitive material, the quantum dots comprise a first quantum dot body and the first ligand connected to the surface of the first quantum dot body, and the structure of the first ligand comprises a carbon-carbon double bond; Using a mask to shield the quantum dot film, the mask having a light-shielding area and a light-transmitting area, the light-transmitting area corresponding to a target area on the quantum dot film where a quantum dot layer is to be formed, and the light-shielding area corresponding to a non-target area where the quantum dot film is to be removed; The carrier material film and the quantum dot film in the target area are simultaneously irradiated with light using a one-step exposure method; wherein, under the irradiation, the second photosensitive material in the carrier material film generates a second free radical that triggers a cross-linking reaction of the carrier material to form a first cross-linked structure, and the second photosensitive material in the quantum dot film generates the second free radical that triggers a polymerization reaction of the first ligand of the quantum dot to form a second cross-linked structure; removing the quantum dot film in the non-target area by using a first solvent; A second solvent is used to remove the carrier material film in the non-target area to form a carrier layer and a quantum dot layer stacked in sequence in the target area.

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