CN111244200A - Light emitting device, display device, method for manufacturing display device, and power generation device - Google Patents

Abstract

The present invention relates to the technical field of optoelectronic devices, and specifically provides a light-emitting device, a display device, a manufacturing method of the display device, and a power generation device. The light-emitting device includes a light source, a substrate, and a core functional unit, the core functional unit includes an anode, a core functional layer, and a cathode, and the core functional layer is disposed between the anode and the cathode; the core functional layer A first transmission layer is also included between the cathode and the core functional layer; the material of the core functional layer is mixed with nano-particles and semiconductor materials; and a light source is provided on the side of the substrate opposite to the core functional unit. The light-emitting device of the present invention can effectively adjust the light-emitting brightness, so as to obtain light-emitting effects with different brightness requirements. The display device based on the light-emitting device can realize the adjustment of the brightness of each pixel unit, thereby forming an effective display, which greatly expands the structure and application of the light-emitting display device.

Description

Light-emitting device, display device, and manufacturing method of display device, and power generation device

technical field

The invention belongs to the field of optoelectronic technology, and in particular relates to a light-emitting device, a display device, a manufacturing method of the display device, and a power generation device.

Background technique

As a luminescent material, colloidal quantum dots (QDs) have incomparable advantages over other luminescent materials, such as continuously adjustable luminescence wavelength, ultra-high internal quantum efficiency, excellent color purity, etc. Has huge application prospects. Due to the optical properties of the material, quantum dots are used in LCD panels to improve color gamut. At the same time, with the deepening of quantum dot electroluminescence (quantum dot light-emitting diode, QLED) research, more and more progress has been made in the industrialization process.

At present, the quantum dot display technology on the market mainly uses the principle of quantum dot photoluminescence. The quantum dot material is mounted on a blue backlight, and the blue light excites the quantum dots to emit red light and green light. The three primary colors of red, green and blue formed in this way can be Enlarging the range to improve the saturation of the liquid crystal display, but this technology is only an improvement of the performance of the liquid crystal display, and the control of the color and the color level is also controlled by the deflection of the liquid crystal. On the other hand, quantum dot electroluminescence technology (QLED), which is currently undergoing technical development, is similar to OLED technology and belongs to an active light-emitting type. When powered on, quantum dot pixels emit light, and switching and color levels are realized by controlling the current or voltage of the device. adjustment.

However, the structure of the current quantum dot display device is all film layer structure, and the layer structure is relatively simple except for the material, and it can only achieve photoluminescence and cannot realize the function of photoelectric power generation at the same time.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a light-emitting device, aiming to provide a device structure with adjustable light intensity.

Further, the present invention also provides a display device and a manufacturing method thereof, aiming at providing a richer structure for the photoluminescence display device and realizing the adjustment of the photoluminescence display.

Finally, the present invention also provides a power generation device.

The present invention is realized in this way:

A light-emitting device includes a light source, a substrate, and a core functional unit, wherein the core functional unit includes an anode, a core functional layer, and a cathode, and the core functional layer is arranged between the anode and the cathode; the core functional unit a first transport layer is also included between the layer and the cathode;

The material of the core functional layer is formed by mixing nanoparticles and semiconductor materials;

It also includes a light source disposed on the side of the substrate facing away from the core functional unit.

Correspondingly, a display device includes a plurality of repeatedly arranged pixel units; the pixel units include the above-mentioned light-emitting devices, the light-emitting devices share the same substrate, and the light sources are all located on the same substrate side.

Correspondingly, a method for manufacturing a display device includes at least the following steps:

provide a substrate;

A pixel definition layer and a first electrode are formed on a surface of the substrate, a plurality of pixel grooves are formed by the pixel definition layer, and the first electrode is arranged in the pixel groove;

forming a core functional layer on the first electrode in the pixel groove;

forming a second electrode on the core functional layer;

A light source is arranged on the side of the substrate facing away from the core functional layer;

Wherein, if the first electrode is an anode and the second electrode is a cathode, before forming the second electrode on the core functional layer, it further includes the step of forming a first transport layer on the core functional layer, the second electrode is formed on the first transport layer;

Or if the first electrode is a cathode and the second electrode is an anode, before forming the core functional layer on the first electrode in the pixel groove, it also includes forming a first transport layer on the first electrode step, the core functional layer is formed on the first transport layer.

And, a power generation device, comprising a substrate and a core functional unit provided on one side of the substrate, the core functional unit comprising an anode, a core functional layer, and a cathode, the core functional layer provided on the anode and the between the cathodes; a first transport layer is also included between the core functional layer and the cathode;

The material of the core functional layer is formed by mixing nanoparticles and semiconductor materials.

The beneficial effects of the present invention are as follows:

Compared with the prior art, the light-emitting device provided by the present invention is provided with electrodes at the upper and lower ends of the core functional layer. The light emitted by the light source can make the core functional layer generate excitons. The generated excitons are dissociated, the probability of excitons recombination luminescence is reduced, or even quenched without emitting light, thereby realizing the effective adjustment of the light intensity of the light-emitting device.

In the display device provided by the present invention, electrodes are arranged at the upper and lower ends of the core functional layer, and the core functional layer can generate excitons under the action of the light source, and after the cathode and anode electrodes are energized, the photogenerated excitons can be dissociated. The probability of exciton recombination emission is reduced, and even quenching does not emit light, so as to effectively adjust the intensity of the light. Through the structural design of the present invention, the brightness of each pixel can be adjusted, thereby forming an effective display, which greatly enriches the structure of the light-emitting display device.

The manufacturing method of the display device provided by the invention has the advantages of simple processing technology, high product qualification rate, suitable for large-scale production, adjustable luminous intensity of the obtained product, and broad market prospect.

In the power generation device provided by the present invention, under the irradiation of sunlight, the core functional layer of the core functional unit will be excited to generate excitons, and the excitons will dissociate at the interface between the nano-luminescent material and the semiconductor material, and the dissociated electrons and holes will dissociate. It can form a current loop to realize the power generation function.

Description of drawings

In order to illustrate the technical solutions in the embodiments of the present invention more clearly, the following briefly introduces the accompanying drawings used in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained from these drawings without any creative effort.

1 is a schematic structural diagram of a light-emitting device provided by the present invention;

2 is a schematic top view of a display device provided by the present invention;

3 is a schematic cross-sectional view of the display device shown in FIG. 2 provided by the present invention along line A-A;

4 is another schematic cross-sectional view of the display device shown in FIG. 2 provided by the present invention along line A-A;

5 is a schematic cross-sectional view of the display device including the second transmission layer provided by the present invention along the line A-A in FIG. 2;

6 is a schematic cross-sectional view of the display device including the first transmission layer provided by the present invention along the line A-A in FIG. 2;

7 is a schematic cross-sectional view of the display device provided by the present invention including a first transmission layer and a second transmission layer along the line A-A in FIG. 2;

8 is a schematic cross-sectional view of the display device with a second auxiliary function layer added on the basis of FIG. 7 according to the present invention along the line A-A in FIG. 2;

9 is a schematic cross-sectional view of the display device with a first auxiliary function layer added on the basis of FIG. 7 according to the present invention along the line A-A in FIG. 2;

10 is a schematic cross-sectional view of the display device along the line A-A in FIG. 2 with a first auxiliary function layer and a second auxiliary function layer added simultaneously on the basis of the present invention;

11 is a schematic diagram of a substrate of a display device provided by the present invention;

12 is a schematic top view of the display device provided by the present invention forming an anode on a substrate;

13 is a schematic cross-sectional view of the semi-finished product of the display device provided in FIG. 12 of the present invention along line B-B;

14 is a schematic top view of the semi-finished product of the display device provided in FIG. 12 of the present invention forming a pixel defining layer on the surface of the anode and the exposed substrate;

15 is a schematic cross-sectional view of the semi-finished product of the display device provided in FIG. 14 of the present invention along line C-C;

16 is a schematic top view of the semi-finished product of the display device provided in FIG. 14 of the present invention forming a core functional layer in a pixel groove formed by a pixel defining layer;

17 is a schematic cross-sectional view of the semi-finished product of the display device provided in FIG. 16 of the present invention along the D-D line;

18 is a schematic top view of the semi-finished product of the display device provided in FIG. 16 of the present invention forming a cathode on the core functional layer;

19 is a schematic cross-sectional view of the semi-finished product of the display device provided in FIG. 18 of the present invention along the line E-E;

20 is a schematic top view of the semi-finished product of the display device provided in FIG. 18 of the present invention forming a light source on the other surface of the substrate;

21 is a schematic cross-sectional view of the display device provided in FIG. 20 of the present invention along line F-F;

22 is a schematic structural diagram of a power generation device provided by the present invention;

11-substrate; 12-anode; 13-pixel defining layer; 14-pixel groove; 15-core functional layer; 16-cathode; 17-light source; 18-second transmission layer; 19-first transmission layer; 20-the second auxiliary function layer; 21-the first auxiliary function layer;

In addition, it should be noted that, since the device of the present invention can be large or small, the figures shown in the accompanying drawings are only partial schematic diagrams, and are not complete device views.

Detailed ways

In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the present invention will be further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.

Explanation of terms: In the present invention, nano-luminescent materials and nanoparticles have the same meaning.

Referring to FIG. 1, one aspect of the present invention provides a light-emitting device, comprising a light source 17, a substrate 11, and a core functional unit including an anode 12, a core functional layer 15 and a cathode 16, the substrate 11 is disposed on the light source 17 and the Between the core functional units, in the core functional unit, the core functional layer 15 is arranged between the anode 12 and the cathode 16, the material of the core functional layer 15 is mixed with nanoparticles and semiconductor materials, and the core functional layer 15 and the cathode 16 A first transport layer 19 is also included therebetween.

Specifically, in the light-emitting device of the present invention, the materials of the substrate 11 , the anode 12 , and the cathode 16 are all transparent materials, so as to facilitate light extraction.

Preferably, the nanoparticles are quantum dots or nanorods or nanosheets;

The semiconductor material is at least one of an inorganic semiconductor material, an organic semiconductor material, and an organic-inorganic hybrid perovskite type semiconductor material.

Further preferably, the materials of the nanoparticles are II-VI group nanocrystals, II-V group nanocrystals, III-VI group nanocrystals, III-V group nanocrystals, IV-VI group nanocrystals, I-III- At least one of group VI nanocrystals, group II-IV-VI nanocrystals, and group IV nanocrystals.

Preferably, the material of the first transport layer 19 is selected from at least one of ZnO, TiO ₂ , SnO ₂ , Ta ₂ O ₃ , AlZnO, ZnSnO, InSnO, Ca, Ba, CsF, LiF, Cs ₂ CO ₃ .

Preferably, the above-mentioned light-emitting device further includes a second transport layer (not shown in FIG. 1 ), and the second transport layer is disposed between the anode 12 and the core functional layer 15 .

Preferably, the material of the second transmission layer is selected from poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), polyvinylcarbazole, poly(N, N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1, 4-phenylenediamine), 4,4',4"-tris(carbazol-9-yl)triphenylamine, 4,4'-bis(9-carbazole)biphenyl, N,N'-diphenyl -N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-(1-naphthalene base)-1,1'-biphenyl-4,4'-diamine, at least one of NiO _x , MoS ₂ , MoSe ₂ , WS ₂ , and WSe ₂ .

The above-mentioned light-emitting device may further include a first auxiliary function layer (not shown in FIG. 1 ), and the auxiliary function layer is disposed between the first transport layer 19 and the cathode 16 . The material of the first auxiliary functional layer is selected from tris(8-hydroxyquinoline)aluminum, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene, 2,9 -At least one of dimethyl-4,7-biphenyl-1,10-phenanthroline and 4,7-diphenyl-1,10-phenanthroline.

The above light-emitting device may further include a second auxiliary function layer (not marked in FIG. 1 ), the second auxiliary function layer being disposed between the anode 12 and the second transport layer.

Preferably, the material of the second auxiliary functional layer is selected from at least one of polyethylenedioxythiophene-poly(styrene sulfonate), MoO _x , WO _x , CrO _x , CuO, and CuS.

In the light-emitting device provided by the present invention, under the action of the light source 17, the material of the core functional layer 15 is excited by light to generate excitons, and after the anode 12 and the cathode 16 are energized, the photo-generated excitons will dissociate, and the excitons will be dissociated. The probability of recombination emission is reduced, or even quenched, so that no light can be seen from the cathode 16. Therefore, the intensity of the light emitted by the core functional layer 15 can be controlled by adjusting the voltage of the anode 12 and the cathode 16. When no voltage is applied to the electrodes, the dissociation of excitons is the least, and the light generated by the light-emitting device is the strongest. After the voltage is applied, some excitons dissociate, and the pixel unit emits less light. The higher the voltage, the weaker the pixel unit emits light. , not even glowing at all. Through the structure of the present invention, a light-emitting device whose light intensity can be effectively adjusted is obtained.

In another aspect, the present invention also provides a display device. Referring to Figures 2, 3 or 2, 4, the device includes the following parts:

(1) Substrate 11: The substrate 11 has a first surface and a second surface opposite to the first surface.

(2) A number of anodes 12: A number of anodes 12 are laid on the first surface of the substrate 11, and adjacent anodes 12 have intervals between them.

(3) Pixel defining layer 13: The pixel defining layer 13 is stacked in the gap formed by the anodes 12 spaced apart from each other, and the pixel defining layer 13 is enclosed around the anode 12 to form a plurality of pixel grooves 14 (refer to FIG. 14) , the bottom of each pixel groove 14 thus obtained corresponds to an anode 12 .

(4) Core functional layer 15 : the core functional layer 15 is stacked in the pixel groove 14 , that is, stacked on the anode 12 .

(5) The first transport layer 19 : the first transport layer 19 is arranged between the core functional layer 15 and the cathode 16 .

(6) Cathode 16 : The cathode 16 is stacked on the core functional layer 15 .

(7) Light source 17: The light source 17 is arranged at the position of the second surface of the substrate 11, which can be directly attached to the second surface or have a certain gap with the second surface, and is mainly used to provide the core functional layer 15 with light source, so that the core functional layer 15 is excited to generate excitons.

In addition, in the device capable of emitting light or generating electricity of the present invention, as shown in FIG. 3 , the pixel defining layer 13 may partially extend to the surface of the anode 12 ; or as shown in FIG. 4 , the pixel defining layer 13 may be directly stacked on the substrate 11 . A plurality of pixel grooves 14 (refer to FIG. 14 ) are enclosed by the pixel defining layer 13 on the first surface (ie, the bottom of the gap formed by the anodes 12 spaced apart from each other).

In a specific embodiment, the positions of the anode 12 and the cathode 16 can be interchanged, thereby forming a positive device or an inverted device.

In the device structure of the present invention, the core functional layer 15 is pixelized, and the core functional layer 15 is divided, so that the structure formed by each pixel slot 14 and the anode 12, the core functional layer 15 and the cathode 16 is a sub-pixel unit. Several sub-pixel units constitute a pixel unit. When electrodes are added to the two opposite surfaces of the core functional layer 15, under the action of the light source 17, the material of the core functional layer 15 placed in each pixel slot 14 is excited by light to generate excitons, while the anode 12 and the cathode 16 After electrification, the photo-generated excitons will dissociate, the probability of excitons recombination emission is reduced, and even quenched, so that no light can be seen from the cathode 16 end, so the voltage of the anode 12 and the cathode 16 can be adjusted to achieve the desired effect. Control the intensity of light emitted by the core functional layer 15 . When no voltage is applied to the electrodes, the excitons dissociate the least, the light generated by the display device is the strongest, and the luminous display effect is the best. After the voltage is applied, some excitons dissociate, and the pixel unit emits less light, and the higher the voltage , the weaker the pixel unit emits light, or even does not emit light at all. Through the structure of the present invention, the brightness of each pixel unit can be adjusted, thereby forming an effective display device, which can effectively control the effect of light emission.

In other words, the display device provided by the present invention includes a plurality of pixel units arranged repeatedly, and each of the pixel units includes the above-mentioned light-emitting devices, when the substrates 11 of all the light-emitting devices are the same substrate (integrated When all the light sources 17 are located on the same side of the substrate 11 and the pixel units are located on the side of the substrate 11 facing away from the light sources 17, the display device structure of the present invention can be obtained.

Specifically, the substrate 11 can be a rigid substrate or a flexible substrate, and different substrate materials are used according to the requirements of different occasions.

Preferably, the rigid substrate is glass, which has good light transmittance, and the light generated by the light source 17 can pass through the substrate 11 to effectively illuminate the core functional layer 15 . Of course, the rigid substrate can also be other transparent rigid materials other than glass.

Preferably, the flexible substrate includes but is not limited to polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polystyrene (PS) ), polyethersulfone (PES), polycarbonate (PC), polyarylate (PAT), polyarylate (PAR), polyimide (PI), polyvinyl chloride (PVC), polyethylene ( PE), polyvinylpyrrolidone (PVP), one or more of textile fibers.

The light source 17 of the present invention is used to emit light to the core functional layer 15, so that the excited core functional layer 15 emits light. The core functional layer 15 may share one or more light sources 17, or each core functional layer 15 may be provided with a corresponding light source 17, so The light source 17 may be a light-emitting backplane, an LED light source or an OLED light-emitting device.

In the anode 12 of the present invention, a transparent electrode is used as the anode 12 to ensure that the light emitted by the light source 17 can pass through. The specific material used can be any one of thin-layer metal, carbon material, and metal oxide. These materials have good light-transmitting properties and ensure high-quality incident light. Of course, the material of the anode 12 can also be other transparent materials other than the listed materials.

When the material of the anode 12 is a thin-layer metal, preferably, the thin-layer metal includes one or more of Al, Ag, Cu, Mo, and Au.

When the material of the anode 12 is a carbon material, preferably, the carbon material includes one or more of graphite, carbon nanotube, graphene, and carbon fiber.

When the material of the anode 12 is a metal oxide, it can be an undoped metal oxide or a doped metal oxide. Such as preferably include one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO.

In addition, the anode 12 may also be a composite electrode comprising thin layers of metal sandwiched between doped or undoped transparent metal oxides. When it is a composite electrode, the composite electrode includes AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO ₂ / One or more of Ag/TiO ₂ , TiO ₂ /Al/TiO ₂ , ZnS/Ag/ZnS, ZnS/Al/ZnS, TiO ₂ /Ag/TiO ₂ , TiO ₂ /Al/TiO ₂ .

The material of the core functional layer 15 of the present invention is a nano-luminescent material, or a mixture of a nano-luminescent material and an insulating material. In the present invention, the nano-luminescent material is also collectively referred to as nanoparticles.

The above-mentioned nano-luminescent material is at least one of quantum dots, nanorods or nanosheets.

Preferably, the nano-luminescent material is group II-VI nanocrystals, group II-V nanocrystals, group III-VI nanocrystals, group III-V nanocrystals, group IV-VI nanocrystals, group I-III-VI At least one of nanocrystals, group II-IV-VI nanocrystals, and group IV nanocrystals.

The above-mentioned several nanocrystals can be binary nanocrystals, ternary nanocrystals, quaternary nanocrystals, or a mixture of binary nanocrystals and ternary nanocrystals, binary nanocrystals and ternary nanocrystals, quaternary nanocrystals. A mixture of crystals, a mixture of ternary nanocrystals and quaternary nanocrystals.

More preferably, the crystal structure of the nanocrystal includes a single-core structure or a core-shell structure.

Among them, mononuclear structures such as II-VI group nanocrystals, II-V group nanocrystals, III-VI group nanocrystals, III-V group nanocrystals, IV-VI group nanocrystals, I-III-VI group nanocrystals, Mononuclear structure formed by II-IV-VI group nanocrystals and IV group nanocrystals.

The cases of the core-shell structure include: group II-VI nanocrystals, group II-V nanocrystals, group III-VI nanocrystals, group III-V nanocrystals, group IV-VI nanocrystals, group I-III-VI At least one of nanocrystals, group II-IV-VI nanocrystals, group IV nanocrystals forms a nucleus, and group II-VI nanocrystals, group II-V nanocrystals, group III-VI nanocrystals, group III-V nanocrystals At least one of nanocrystals, IV-VI group nanocrystals, I-III-VI group nanocrystals, II-IV-VI group nanocrystals, and IV group nanocrystals form a shell structure, such as can be made of II-VI group Nanocrystals form the nucleus and II-V nanocrystals, III-VI nanocrystals, III-V nanocrystals, IV-VI nanocrystals, I-III-VI nanocrystals, II-IV-VI nanocrystals , at least one of the group IV nanocrystals forms a core-shell structure of a shell;

II-V nanocrystals form the nucleus while II-VI nanocrystals, III-VI nanocrystals, III-V nanocrystals, IV-VI nanocrystals, I-III-VI nanocrystals, II-IV- At least one of group VI nanocrystals and group IV nanocrystals forms a core-shell structure of a shell;

Group III-VI nanocrystals form the nucleus while group II-VI nanocrystals, group II-V nanocrystals, group III-V nanocrystals, group IV-VI nanocrystals, group I-III-VI nanocrystals, II-IV- At least one of group VI nanocrystals and group IV nanocrystals forms a core-shell structure of a shell;

Group III-V nanocrystals form the nucleus while group II-VI nanocrystals, group II-V nanocrystals, group III-VI nanocrystals, group IV-VI nanocrystals, group I-III-VI nanocrystals, II-IV- At least one of group VI nanocrystals and group IV nanocrystals forms a core-shell structure of a shell;

Group IV-VI nanocrystals form the nucleus while group II-VI nanocrystals, group II-V nanocrystals, group III-VI nanocrystals, group III-V nanocrystals, group I-III-VI nanocrystals, II-IV- At least one of group VI nanocrystals and group IV nanocrystals forms a core-shell structure of a shell;

Group I-III-VI nanocrystals form the nucleus and II-VI nanocrystals, II-V nanocrystals, III-VI nanocrystals, III-V nanocrystals, IV-VI nanocrystals, II-IV- At least one of group VI nanocrystals and group IV nanocrystals forms a core-shell structure of a shell;

II-IV-VI nanocrystals form the nucleus and II-VI nanocrystals, II-V nanocrystals, III-VI nanocrystals, III-V nanocrystals, IV-VI nanocrystals, I-III- At least one of group VI nanocrystals and group IV nanocrystals forms a core-shell structure of a shell;

Group IV nanocrystals form the nucleus while group II-VI nanocrystals, group II-V nanocrystals, group III-VI nanocrystals, group III-V nanocrystals, group IV-VI nanocrystals, group I-III-VI nanocrystals , a core-shell structure in which at least one of II-IV-VI nanocrystals forms a shell; and the like.

Specifically, the quantum dots may be at least one of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe, GaP, GaAs, InP, and InAs. Of course, the quantum dots of the present invention are not limited to the listed ones, and other quantum dots that can achieve luminescence effects also belong to the scope of the present invention.

The above-mentioned sub-pixel unit includes a red sub-pixel unit (ie, a red light-emitting device), a green sub-pixel unit (ie, a green light-emitting device), and a blue sub-pixel unit (ie, a blue light-emitting device). For example, when quantum dots are used as the material of the core functional layer 15, in three consecutive or adjacent pixel slots 14, there should be red light-emitting quantum dots (RED QDs), green light-emitting quantum dots (GREEN QDs), Blue light quantum dots (BLUE QDs) are composed of sub-pixel units where the quantum dots of these three colors are located to form a pixel unit, which finally emits white light. For example, in the schematic diagram of the partial structure shown in FIG. 3 or FIG. 4, in order from left to right, the material of the core functional layer 15 of the first pixel slot is red light quantum dots, and the material of the core functional layer 15 of the middle pixel slot is green light quantum dots , and the material of the core functional layer 15 of the pixel slot on the right is blue light quantum dots. Of course, the arrangement of quantum dots of other structures is also feasible. For example, the center connection of three adjacent pixel slots forms a triangle, then the three pixel slots are respectively red light quantum dots, green light quantum dots, and blue light quantum dots. The arrangement form of the quantum dots of the present invention is not limited to the aforementioned structure, and can also be other arrangement forms that can realize light extraction.

When the material of the core functional layer 15 is a mixture of nano-luminescent materials and insulating materials, the mass percentage of the nano-luminescent materials is 1% to 50%. Therefore, the quenching caused by energy transfer between quantum dots is reduced, and the luminous efficiency of the material is improved. At the same time, the interface between the nanoluminescent material and the insulating material can serve as the center of exciton dissociation, and the exciton dissociates under the action of the electric field. At this time, the preferred insulating material of the insulating material is an inorganic insulating material and/or an organic polymer insulating material.

Further preferably, the inorganic insulating material such as SiO ₂ , Al ₂ O ₃ , etc.; and/or the organic polymer insulating material such as methyl methacrylate, lauryl methacrylate, epoxy acrylate, epoxy resin , modified epoxy resin, etc.

In addition, the material of the core functional layer 15 can also be a mixture of nano-luminescent materials and semiconductor materials. When the material of the core functional layer 15 is a mixture of nano-luminescent material and semiconductor material, the mass percentage of the nano-luminescent material is 1% to 50%, and the photo-generated excitons in the nano-luminescent material will be transferred under the electric field At the interface between the nano-luminescent material and the semiconductor material, the generated excitons will be annihilated at the interface (quenching due to dissociation of electrons and holes), or the energy will be transferred to the semiconductor material and finally annihilated. In the power generation device, the generated excitons will dissociate at the interface between the nano-luminescent material and the semiconductor material. Due to the high intensity of sunlight, the dissociated electrons and holes can form a current loop to generate electricity. That is, when the structure including the substrate 11, the anode 12, the core functional layer 15, and the cathode 16, and the material of the core functional layer 15 is a mixture of nanoparticles and semiconductor materials, it can be used as a power generation device under the irradiation of sunlight, A schematic diagram of the specific structure of the power generation device can be shown in FIG. 22 .

The semiconductor materials involved include, but are not limited to, at least one of inorganic semiconductor materials, organic semiconductor materials, and organic-inorganic hybrid perovskite semiconductor materials.

Preferably, the inorganic semiconductor material includes but is not limited to ZnO, NiO _x , MoO _x , WO _x , CrO _x , CuO, MoS ₂ , MoSe ₂ , WS ₂ , WSe ₂ , CuS, graphene, C ₆₀ , etc., or It is a doped or undoped inorganic perovskite semiconductor.

Further preferably, the general structural formula of the inorganic perovskite semiconductor material is AMX ₃ , wherein A is a Cs ⁺ ion, and M is a divalent metal cation, including but not limited to Pb ²⁺ , Sn ²⁺ , Cu ²⁺ , Ni ²⁺ , Cd ²⁺ , Cr ²⁺ , Mn ²⁺ , Co ²⁺ , Fe ²⁺ , Ge ²⁺ , Yb ²⁺ , Eu ²⁺ , X is a halogen anion, including but not limited to Cl ^- , Br ^- , I ^- .

Preferably, the organic semiconductor material includes but is not limited to (9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), polyvinylcarbazole, poly(N,N'bis (4-butylphenyl)-N,N'-bis(phenyl)benzidine), poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-benzene) diamine), 4,4',4"-tris(carbazol-9-yl)triphenylamine, 4,4'-bis(9-carbazole)biphenyl, N,N'-diphenyl-N, N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-(1-naphthyl)- 1,1'-biphenyl-4,4'-diamine, etc.

Further preferably, the general structural formula of the organic-inorganic hybrid perovskite semiconductor material is BNY ₃ , wherein B is an organic amine cation, including but not limited to CH ₃ (CH ₂ ) _n-2 NH ₃ ⁺ (n ≥ 2) or NH ₃ (CH ₂ ) _n NH ₃ ²⁺ (n≥ 2), when n=2, the inorganic metal halide octahedron NY ₆ ^4- is connected by a common top, and the metal cation N is located in the halogen octahedron In the body center of the hexahedron, the organic amine cation B fills the voids between the octahedrons to form an infinitely extended three-dimensional structure; when n>2, the inorganic metal halide octahedrons NY ₆ ^4- connected in a co-top manner are in two The dimensional direction extends to form a layered structure, and the organic amine cation bilayer (protonated monoamine) or organic amine cationic monolayer (protonated bisamine) is inserted between the layers, and the organic layer and the inorganic layer overlap each other to form a stable two-dimensional Layered structure; N is a divalent metal cation, including but not limited to Pb ²⁺ , Sn ²⁺ , Cu ²⁺ , Ni ²⁺ , Cd ²⁺ , Cr ²⁺ , Mn ²⁺ , Co ²⁺ , Fe ²⁺ , Ge ²⁺ , Yb ²⁺ , Eu ²⁺ ; Y is a halogen anion, including but not limited to Cl ^- , Br ^- , I ^- .

The material of the core functional layer 15 is a mixture of nano-luminescent materials and semiconductor materials, and the structure includes a transmission layer (such as the second transmission layer 18 and/or the first transmission layer 19), and when there is no light source 17, in the case of sunlight , can generate photoelectricity, that is, the structure of the present invention can be used as a solar cell. In the present invention, a transparent electrode should be used as the cathode 16 to ensure the light extraction effect. The specific material used can be any one of thin-layer metal, carbon material, and metal oxide. These materials have good light-transmitting properties and ensure high-quality light-transmitting effects. When used as a photoelectric device, they can also The total amount of sunlight entering the core functional layer 15 is guaranteed. Of course, the material of the cathode 16 may also be other transparent materials other than the listed materials.

When the material of the cathode 16 is a thin-layer metal, preferably, the thin-layer metal includes one or more of Al, Ag, Cu, Mo, and Au.

When the material of the cathode 16 is a carbon material, preferably, the carbon material includes one or more of graphite, carbon nanotube, graphene, and carbon fiber.

When the material of the cathode 16 is a metal oxide, it can be an undoped metal oxide or a doped metal oxide. Such as preferably include one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO.

In addition, the cathode 16 may also be a composite electrode comprising a thin layer of metal sandwiched between doped or undoped transparent metal oxides. When it is a composite electrode, the composite electrode includes AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO ₂ / One or more of Ag/TiO ₂ , TiO ₂ /Al/TiO ₂ , ZnS/Ag/ZnS, ZnS/Al/ZnS, TiO ₂ /Ag/TiO ₂ , TiO ₂ /Al/TiO ₂ .

Preferably, the light source 17 is any one of a blue light source and an ultraviolet light source, and of course it can also be a light source of other colors.

Please refer to FIG. 5 , the structure shown in the figure is a display device including a substrate 11 , an anode 12 , a pixel defining layer 13 , a second transmission layer 18 , a core functional layer 15 , a cathode 16 and a light source 17 , and the display device has a light-emitting effect , can be used as a light-emitting display device, the second transmission layer 18 is stacked between the anode 12 and the core functional layer 15 .

Referring to FIG. 6, the structure shown in the figure is a display device including a substrate 11, an anode 12, a pixel defining layer 13, a core functional layer 15, a first transmission layer 19, a cathode 16 and a light source 17, and the device has a light-emitting effect, As a light-emitting display device, the first transmission layer 19 is stacked between the core functional layer 15 and the cathode 16 .

Referring to FIG. 7 , the structure shown in the figure is a display device including a substrate 11 , an anode 12 , a second transmission layer 18 , a pixel definition layer 13 , a core functional layer 15 , a first transmission layer 19 , a cathode 16 and a light source 17 , The display device has a light-emitting effect and can be used as a light-emitting display device. The second transport layer 18 is stacked between the anode 12 and the core functional layer 15 , and the first transport layer 19 is stacked between the core functional layer 15 and the cathode 16 .

In the structure of the display device shown in FIGS. 5 to 7 , the second transport layer 18 has the function of transporting holes; the first transport layer 19 has the function of transporting electrons.

Preferably, in any of the above structures of the display device including the second transmission layer 18, the second transmission layer 18 is selected from poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl) ) diphenylamine), polyvinylcarbazole, poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), poly(9,9-dioctylfluorene) -Co-bis-N,N-phenyl-1,4-phenylenediamine), 4,4',4"-tris(carbazol-9-yl)triphenylamine, 4,4'-bis(9- carbazole) biphenyl, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N' -at least one of diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine. As another embodiment, the second transmission layer 18 may also include, but is not limited to, at least one of NiO _x , MoS ₂ , MoSe ₂ , WS ₂ , and WSe _2. Preferably, the thickness of the second transmission layer 18 is 5˜200 nm.

Preferably, in any of the above structures of the display device including the first transport layer 19, the first transport layer 19 is selected from ZnO, TiO ₂ , SnO ₂ , Ta ₂ O ₃ , AlZnO, ZnSnO, InSnO, Ca, Ba , CsF, LiF, Cs ₂ CO ₃ and other inorganic materials one or more. Preferably, the thickness of the first transmission layer 19 is 5˜200 nm.

Please refer to FIG. 8 , which shows a structure including a substrate 11 , an anode 12 , a pixel defining layer 13 , a second auxiliary functional layer 20 , a second transmission layer 18 , a core functional layer 15 , a first transmission layer 19 , and a cathode 16 And the display device of the light source 17 , the second auxiliary function layer 20 is stacked between the second transmission layer 18 and the anode 12 .

Please refer to FIG. 9 , which shows a structure including a substrate 11 , an anode 12 , a pixel definition layer 13 , a second transmission layer 18 , a core functional layer 15 , a first transmission layer 19 , a first auxiliary functional layer 21 , and a cathode 16 And the display device of the light source 17 , the first auxiliary function layer 21 is stacked between the cathode 16 and the first transmission layer 19 .

Please refer to FIG. 10, which shows a structure including a substrate 11, an anode 12, a second auxiliary functional layer 20, a second transfer layer 18, a pixel definition layer 13, a core functional layer 15, a first transfer layer 19, a first A display device with auxiliary function layer 21 , cathode 16 and light source 17 , the second auxiliary function layer 20 is stacked between the second transmission layer 18 and the anode 12 , and the first auxiliary function layer 21 is stacked on the cathode 16 and the first transport layer 19 .

In the structure of the display device shown in FIGS. 8 to 10 , the second auxiliary functional layer 20 has the function of promoting hole transport; the first auxiliary functional layer 21 has the function of promoting electron transport.

In any of the above-mentioned structures of the display device including the second auxiliary function layer 20, the second auxiliary function layer 20 is selected from polyethylene dioxythiophene-poly(styrene sulfonate), MoO _x , WO _x , One or more of CrO _x , CuO, CuS, etc. Preferably, the thickness of the second auxiliary function layer 20 is 1˜50 nm.

In any of the above structures of the display device including the first auxiliary function layer 21, the first auxiliary function layer 21 is selected from the group consisting of tris(8-hydroxyquinoline)aluminum, 1,3,5-tris(1-phenyl) -1H-benzimidazol-2-yl)benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline One or more of materials such as linoline. Preferably, the thickness of the first auxiliary function layer 21 is 1˜50 nm.

Of course, when the present invention includes the substrate 11, the core functional unit, and the material of the core functional layer 15 in the core functional unit is a mixture of nano-luminescent materials and semiconductor materials, or includes the substrate 11 and the second transport layer 18, the first When at least one of the transmission layer 19, the second auxiliary function layer 20, and the first auxiliary function layer 21 has a structure and the material of the core function layer 15 is a mixture of nano-luminescent materials and semiconductor materials, the above-mentioned display device formed can also be used as a power generator. The device, such as a solar cell, can generate electricity when sunlight is irradiated on the side of the substrate 11 or the side of the core functional unit.

At this time, the working principle is: sunlight is absorbed after irradiating the core functional layer 15, and the nano-luminescent material is excited to generate excitons. Due to the high intensity of sunlight, the rate and number of excitons are large. By controlling the electric field between the two electrodes , dissociate electrons and holes, and form a current loop, so as to achieve the effect of power generation.

Correspondingly, the present invention further provides a manufacturing method of any of the above-mentioned display devices.

Referring to FIGS. 11-21 , in one embodiment, the manufacturing method of the display device includes the following steps:

a). Provide a substrate 11, specifically as shown in FIG. 11, the substrate 11 has a first surface and a second surface facing away from the first surface;

b). A pixel defining layer 13 and a first electrode are formed on the first surface of the substrate 11 , and a plurality of pixel grooves 14 are formed by the pixel defining layer 13 , and the first electrodes are arranged in the pixel grooves 14 middle;

c). Forming the core functional layer 15 on the first electrode in the pixel groove 14;

d). Forming a second electrode on the core functional layer 15;

e). A light source 17 is provided on the side of the substrate 11 facing away from the core functional layer 15 , so that when the light source 17 emits light, the emitted light can be directed to the substrate 11 , and the light source 17 can be connected to the substrate 11 In direct contact with the second surface of the light source 17, of course, the light source 17 can also have a certain distance from the substrate 11.

Wherein, if the first electrode is the anode 12 and the second electrode is the cathode 16, before forming the second electrode on the core functional layer 15, it also includes forming a first transmission on the core functional layer 15 The step of layer 19, the second electrode is formed on the first transmission layer 19;

Or if the first electrode is the cathode 16 and the second electrode is the anode 12, before forming the core functional layer 15 on the first electrode in the pixel groove 14, it also includes forming on the first electrode In the step of the first transmission layer 19 , the core functional layer 15 is formed on the first transmission layer 19 . If the above-mentioned display device further includes any one of the second transmission layer 18 , the second auxiliary function layer 20 , and the first auxiliary function layer 21 , corresponding steps may be added to steps a) to e). If the second transport layer 18 is included, the second transport layer 18 is first formed on the anode 12, and then the core functional layer 15 is formed on the second transport layer 18, and the rest of the layer structures are handled in the same way. Expand further.

The order of forming the anode 12 and the pixel defining layer 13 can be interchanged. For example, the pixel defining layer 13 can be formed on the first surface of the substrate 11 first, and a plurality of pixel grooves 14 are formed by the pixel defining layer 13, and then the pixel defining layer 13 can be formed on the pixel defining layer 13. The anode 12 is formed in the tank 14 .

The above-mentioned core functional layer 15 can print the luminescent material into the designated pixel groove 14 by the method of inkjet printing, and obtain the pixelated core functional layer 15 after drying. The core functional layer 15 can also be prepared by chemical or physical methods, and then the pixelated nano-core functional layer 15 can be formed by photolithography. The chemical method includes but is not limited to one or more of chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodization method, electrolytic deposition method and co-precipitation method; physical method includes but not limited to physical coating method or solution The physical coating method includes but is not limited to one of thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion coating method, physical vapor deposition method, atomic layer deposition method, pulsed laser deposition method. One or more; solution methods include but are not limited to spin coating, printing, blade coating, dip-pulling, dipping, spraying, roll coating, casting, slot coating, strip coating Buffa.

In the manufacturing method of the light-emitting display device of the present invention, the involved substrate 11 , anode 12 , pixel defining layer 13 , core functional layer 15 , cathode 16 , second transmission layer 18 , first transmission layer 19 , second auxiliary function layer 20 . The materials used for the first auxiliary function layer 21 are all the same as the materials of the display device described above. In order to save space, they will not be repeated here.

In order to better illustrate the technical solutions of the present invention, the following description is made with reference to specific embodiments.

Example 1

As shown in FIG. 6, a display device includes a light source 17, a substrate 11, an anode 12, a pixel defining layer 13, a core functional layer 15, a first transmission layer 19, and a cathode 16; wherein, the substrate 11 is a transparent glass plate , the material of the anode 12 is ITO; the material of the pixel defining layer 13 is silicon dioxide, the material of the first transmission layer 19 is graphene, the material of the core functional layer 15 is a mixture of CdSe/ZnS quantum dots and ZnO, the material of the cathode 16 is The material is AZO.

The manufacturing method of the display device is as follows:

S1. Provide a substrate 11, the substrate 11 has an opposite first surface and a second surface, on the first surface of the substrate 11 a number of anodes 12 are prepared side by side and spaced apart from each other, on the edge of the anode 12 and by A pixel defining layer 13 is prepared on the exposed first surface of the substrate 11 at intervals, and a pixel groove is formed by surrounding the pixel defining layer 13, and the bottom plane of the formed pixel groove is the exposed anode 12 .

S2. Using the inkjet printing method, the CdSe/ZnS quantum dots and ZnO are mixed and printed into the surface of the anode 12 at the bottom of the pixel tank, and dried by vacuum heating to form the core functional layer 15;

S3. A graphene layer is formed by coating on the core functional layer 15, and the first transport layer 19 is formed from the graphene layer.

S4. The cathode 16 is prepared on the first transfer layer 19 by sputtering, and the cathode 16 covers the top of the pixel defining layer 13 .

S5. Disposing a light source on the second surface of the above-formed display device substrate.

The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.

Claims (22)

1. A light emitting device includes a light source, a substrate, a core function unit; the core function unit comprises an anode, a core function layer and a cathode, wherein the core function layer is arranged between the anode and the cathode; a first transmission layer is also arranged between the core functional layer and the cathode;

the material of the core functional layer is formed by mixing nano particles and semiconductor materials;

the light source is arranged on one side of the substrate opposite to the core function unit.

2. A light emitting device according to claim 1, further comprising a first auxiliary functional layer disposed between the cathode and the first transport layer.

3. A light emitting device according to claim 1, further comprising a second transport layer between the anode and the core functional layer.

4. A light emitting device according to claim 3, further comprising a second auxiliary functional layer between the anode and the second transport layer.

5. The light-emitting device according to claim 1, wherein the nanoparticle is a quantum dot or a nanorod or a nanosheet;

the semiconductor material is at least one of an inorganic semiconductor material, an organic semiconductor material and an organic-inorganic hybrid perovskite type semiconductor material.

6. The light-emitting device according to claim 1, wherein the substrate is a transparent substrate; the anode and the cathode are both transparent electrodes.

7. The light emitting device of claim 1, wherein the material of the first transport layer is selected from ZnO, TiO₂、SnO₂、Ta₂O₃、AlZnO、ZnSnO、InSnO、Ca、Ba、CsF、LiF、Cs₂CO₃At least one of (1).

8. The light-emitting device according to claim 2, wherein a material of the first auxiliary functional layer is at least one selected from the group consisting of aluminum tris (8-hydroxyquinoline), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene, 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline, and 4, 7-diphenyl-1, 10-phenanthroline.

9. A light emitting device according to claim 3, wherein the material of the second transport layer is selected from poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N ' bis (4-butylphenyl) -N, N ' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4', 4 ″ -tris (carbazol-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1 ' -biphenyl-4, 4' -diamine, poly (t-butyl-phenyl) diphenylamine), poly (t-butyl-phenyl) -N, N ' -bis (carbazol-9-yl) triphenylamine, poly (t-butyl-phenyl) -1,1 ' -biphenyl-4, 4' -diamine, n, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, NiO_x、MoS₂、MoSe₂、WS₂、WSe₂At least one of (1). .

10. A light-emitting device as claimed in claim 4, characterized in that the material of the second auxiliary functional layer is selected from the group consisting of polyethylenedioxythiophene-poly (styrenesulfonate), MoO_x、WO_x、CrO_xAt least one of CuO and CuS.

11. A display device includes a plurality of pixel units arranged repeatedly; the pixel cell comprises the light emitting device of any one of claims 1-10, the light emitting devices sharing the same substrate, the light sources all being located on the same side of the substrate.

12. The display device of claim 11, wherein the pixel cells include a red sub-pixel cell, a green sub-pixel cell, and a blue sub-pixel cell; the red sub-pixel unit is a red light emitting device, the green sub-pixel unit is a green light emitting device, and the blue sub-pixel unit is a blue light emitting device.

13. The display device of claim 11, further comprising a pixel definition layer disposed on the substrate, the pixel definition layer being located between adjacent ones of the core functional units.

14. A method of manufacturing a display device, comprising the steps of:

providing a substrate;

forming a pixel defining layer and a first electrode on one surface of the substrate, wherein the pixel defining layer is enclosed into a plurality of pixel grooves, and the first electrode is arranged in the pixel grooves;

forming a core function layer on the first electrode in the pixel groove;

forming a second electrode on the core functional layer;

arranging a light source on one side of the substrate, which is opposite to the core functional layer;

if the first electrode is an anode and the second electrode is a cathode, before forming the second electrode on the core functional layer, a step of forming a first transmission layer on the core functional layer is further included, and the second electrode is formed on the first transmission layer;

or if the first electrode is a cathode and the second electrode is an anode, before forming a core functional layer on the first electrode in the pixel groove, the method further comprises a step of forming a first transmission layer on the first electrode, wherein the core functional layer is formed on the first transmission layer.

15. The method of manufacturing a display device according to claim 14, further comprising forming a first auxiliary functional layer between the cathode and the first transfer layer.

16. The method for manufacturing a display device according to claim 14, wherein a material of the core functional layer is a mixture of nanoparticles and a semiconductor material;

the nano particles are quantum dots, nano rods or nano sheets;

the semiconductor material is at least one of an inorganic semiconductor material, an organic semiconductor material and an organic-inorganic hybrid perovskite type semiconductor material.

17. The method for manufacturing a display device according to claim 14, wherein materials forming the substrate, the cathode, and the anode are all transparent materials.

18. The method of manufacturing a display device according to claim 14, wherein a material of the first transport layer is selected from ZnO, TiO₂、SnO₂、Ta₂O₃、AlZnO、ZnSnO、InSnO、Ca、Ba、CsF、LiF、Cs₂CO₃At least one of (1).

19. The method for manufacturing a display device according to claim 15, wherein a material of the first auxiliary functional layer is at least one selected from the group consisting of tris (8-hydroxyquinoline) aluminum, 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene, 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline, and 4, 7-diphenyl-1, 10-phenanthroline.

20. A power generation device is characterized by comprising a substrate and a core function unit arranged on one side of the substrate, wherein the core function unit comprises an anode, a core function layer and a cathode, and the core function layer is arranged between the anode and the cathode; a first transmission layer is also arranged between the core functional layer and the cathode;

the material of the core functional layer is formed by mixing nano particles and semiconductor materials.

21. The power generation apparatus of claim 20, wherein the nanoparticles are quantum dots or nanorods or nanoplatelets;

the semiconductor material is at least one of an inorganic semiconductor material, an organic semiconductor material and an organic-inorganic hybrid perovskite type semiconductor material.

22. The power generation device of claim 20, wherein the material of the first transport layer is selected from ZnO, TiO₂、SnO₂、Ta₂O₃、AlZnO、ZnSnO、InSnO、Ca、Ba、CsF、LiF、Cs₂CO₃At least one of (1).

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