TWI683449B - Quantum dot material, manufacturing method of the quantum dot material and display device of the quantum dot material - Google Patents

Abstract

The present invention discloses a quantum dot material comprising an optical core, an inorganic ligand layer which includes a least one SiO _xmaterial wrapped on the surface of the optical core, and a water-vapor barring layer wrapped on the surface of the inorganic ligand layer. The abovementioned water-vapor barring layer is formed by stacking a plurality of stacked structures including at least one metal oxide in an irregular arrangement. In addition, a manufacturing method and application of the quantum dot material are also disclosed by the present invention.

Description

Composite quantum dot material, preparation method and display device

The invention relates to a composite quantum dot material, a preparation method of the composite quantum dot material and a display device thereof, in particular to a composite quantum dot material and a preparation method of the composite quantum dot material which can improve the stability and luminous efficiency of the quantum dot and the composite quantum dot material Display device.

Since the quantum dots were made, they have attracted wide interest in the scientific and industrial circles due to their excellent photoelectric properties. Compared with traditional fluorescent materials, the luminous properties of quantum dots have more advantages such as narrower half-width, smaller particles, no scattering loss, and adjustable spectrum with size. They are widely considered to be in the fields of display, lighting, and bioluminescent marking. Has significant application prospects.

Each unit has invested a lot of time and labor costs in the research of quantum dot materials, so that the photoelectric performance of quantum dots has been continuously improved, and related application components have also appeared one after another.

Among them, the application of quantum dots as light-emitting materials in display devices is considered to be the first application field of quantum dots to achieve breakthroughs. However, as a superior light-emitting material, quantum dots still have many basic problems that have not yet been solved. Especially, the "quantum dot stability problem" has plagued many research units and has become one of the bottlenecks restricting the development of quantum dots. . Furthermore, the stability of quantum dots in other applications, such as solar cells, biomarkers, and environmental pollution treatment, is also a great challenge.

In view of the above deficiencies, the present invention aims to propose a composite quantum dot material that can improve the stability of quantum dots and luminous efficiency, a method for preparing the composite quantum dot material, and a display device thereof.

First, the present invention proposes a composite quantum dot material. The composite quantum dot material comprising: an optical core; a ligand of the inorganic layer, coated on the surface of the optical core, the inorganic alignment layer comprises at least a silicon oxide (SiO _x) material; and an aqueous oxygen barrier layer , Coated on the surface of the inorganic ligand layer. Wherein, the water-oxygen barrier layer is formed by stacking a plurality of laminated structures including at least one metal oxide in an irregular arrangement.

Furthermore, the present invention also provides a method for preparing a composite quantum dot material, including the following steps: (A) providing an optical core, and silanizing the optical core; (B) adding a surfactant and a non-polar Solvent in the optical core after silanization treatment; (C) Add a silicon-containing compound so that the surface of the optical core has at least silicon monoxide (SiO _x ) material; (D) Add an aqueous compound, the aqueous compound and the The silicon-containing compound undergoes hydrolysis and condensation reactions to form an inorganic ligand layer; (E) a zinc acetate hydrate and ethanol are mixed and added to the optical core coated with the inorganic ligand layer; and (F) The optical core coated with the inorganic ligand layer is immersed in an aqueous solution of sodium hydroxide (NaOH)-ethanol (Ethanol) to form a composite quantum dot material.

The present invention also proposes another method for preparing a composite quantum dot material, which includes the following steps: (G) providing an optical core and silanizing the optical core; (H) adding a surfactant and a non-polar solvent to The optical core after silanization treatment; (I) Add a silicon-containing compound so that the surface of the optical core has at least silicon monoxide (SiO _x ) material; (J) Add an aqueous compound, the aqueous compound and the silicon-containing The compound undergoes hydrolysis and condensation reactions to form an inorganic ligand layer; (K) Titanium isopropoxide (TTIP) or tetrabutyl titanate (TBOT) is added to the optical layer coated with the inorganic ligand layer Core; and (L) immersing the optical core coated with the inorganic ligand layer in a water-alcohol solution to form a composite quantum dot material.

The present invention also proposes another method for preparing a composite quantum dot material, which includes the following steps: (M) providing an optical core anchored on an inorganic oxide; (N) adding a non-polar solvent to at least one quantum dot grown in inorganic Oxide; (O) adding a silicon-containing compound to form an inorganic ligand layer on the surface of the optical core; (P) mixing a zinc acetate hydrate and ethanol and adding to the optical layer coated with the inorganic ligand layer Core; and (Q) immersing the optical core coated with the inorganic ligand layer in an aqueous solution of sodium hydroxide (NaOH)-ethanol (Ethanol) to form a composite quantum dot material.

The present invention also proposes another method for preparing a composite quantum dot material, which includes the following steps: (R) providing an optical core anchored on an inorganic oxide; (S) adding a non-polar solvent to at least one quantum dot grown in inorganic Oxide; (T) adding a silicon-containing compound to form an inorganic ligand layer on the surface of the optical core; (U) adding titanium isopropoxide (TTIP) or tetrabutyl titanate (TBOT) to the coating The optical core with the inorganic ligand layer; and (V) immersing the optical core with the inorganic ligand layer in a water-alcohol solution to form a composite quantum dot material.

Furthermore, the present invention further proposes a composite quantum dot display device, comprising: a backlight; at least one composite quantum dot material, which is provided on the backlight; and a liquid crystal display module, which is disposed on a material containing at least one composite quantum dot material On the backlight.

Wherein, the at least one composite quantum dot material includes: an optical core; an inorganic ligand layer coated on the surface of the optical core, the inorganic ligand layer including at least silicon oxide (SiO _x ) material; and a water The oxygen barrier layer is coated on the surface of the inorganic ligand layer. Wherein, the water-oxygen barrier layer is formed by stacking at least one metal oxide layered structure.

The present invention further proposes another composite quantum dot display device, including: a micro-luminescence source, which is an active micro LED die or a passive micro LED die; and at least one composite quantum dot material, which is placed on the micro-luminescence source. Wherein, the at least one composite quantum dot material includes: an optical core; an inorganic ligand layer coated on the surface of the optical core, the inorganic ligand layer including at least silicon oxide (SiO _x ) material; and a water The oxygen barrier layer is coated on the surface of the inorganic ligand layer. Wherein, the water-oxygen barrier layer is formed by stacking at least one metal oxide layered structure.

The above brief description of the present invention aims to provide a basic description of several aspects and technical features of the present invention. The brief description of the invention is not a detailed description of the invention, so its purpose is not to specifically list the key or important elements of the invention, nor to define the scope of the invention, but to present several concepts of the invention in a concise manner.

In order to understand the technical features and practical effects of the present invention, and to implement it in accordance with the contents of the specification, the preferred embodiments as shown in the drawings are further described in detail below:

Example: Composite quantum dot material

First, please refer to the first figure, which is a schematic diagram of a composite quantum dot material according to a preferred embodiment of the present invention. As shown in the first figure, the composite quantum dot material 142 of this preferred embodiment includes: an optical core 421, an inorganic ligand layer 1001, and a water-oxygen barrier layer 2001.

Wherein, the optical core 421 may be quantum dots made of semiconductor materials, for example: Group II-VI quantum dots (CdSe or CdS), Group III-V quantum dots ((Al, In, Ga)P, (Al, In, Ga) As or (Al, In, Ga) N), Group II-VI quantum dots with shell-core structure (CdSe/ZnS), Group III-V quantum dots with shell-core structure (InP/ZnS ), non-spherical II-VI quantum dots (ZnCdSeS) with alloy structure, a combination of any two of the above, or a combination of any two or more of the above.

The optical core 421 may also be a perovskite quantum dot having the chemical formula MAX ₃ , and the perovskite quantum dot mainly includes an organic-inorganic hybrid perovskite quantum dot, an all-inorganic perovskite quantum dot, or a combination thereof. Among them, the cation M is an organic ion of methylamine ion, ethylamine ion, formamidine ion or inorganic ion of cesium ion (Cs ⁺ ); metal ion A is divalent lead ion (Pb ²⁺ ), tin (Sn ²⁺⁾ ) or germanium ion (Ge ^2+); X is a halogen ion belonging to a cubic, or orthogonal tetragonal system chloride (Cl ^-), bromide ion (Br ^-) or an iodide ion (I ^-).

Further, the full quantum dot inorganic perovskite having the general chemical formula ₃ CsPbCl blue full quantum dot inorganic perovskite, CsPbBr ₃ whole green quantum dot inorganic perovskite having the general chemical formula CsPb (I / Br) ₃ amber light all-inorganic perovskite quantum dots, red light all-inorganic perovskite quantum dots with the chemical formula CsPbI ₃ or a combination thereof. The composite quantum dot material 142 of the preferred embodiment can be excited by the first light to emit a second light with a wavelength different from the first light, and has excellent quantum efficiency and light wavelength conversion efficiency, and can exhibit a half-height width The light emission spectrum and excellent pure color make the light wavelength conversion effect good, and the application in the light-emitting device can improve its luminous efficiency.

The aforementioned quantum dots can be flexibly used by adjusting the composition and/or size and changing the emission color (second light wavelength) according to the difference in band width (Band Gap), for example, from blue, green to red color gamut; Among them, the quantum dots have a nanometer size. In the preferred embodiment, the particle size of the optical core 421 is between 1 nanometer (nm) and 30 nanometers (for example, 20 nanometers). However, the user can first determine the color of the optical fluorescence of the optical core 421, and then determine the appropriate size of the optical core 421 according to the selected semiconductor material. The present invention should not be limited to this.

Wherein, the inorganic alignment layer 1001 based on the coated surface of the optical core 421, and the inorganic alignment layer 1001 comprises at least a silicon oxide (SiO _x) material. In the preferred embodiment, the thickness of the silicon oxide (SiO _x ) material is between 1 nanometer (nm) and 1000 nanometers, such as 10 nanometers to 100 nanometers. The silicon oxide (SiO _x ) material may be silicon dioxide (SiO ₂ ) or silicon monoxide (SiO). It is worth noting that the high transmittance of silicon dioxide (SiO ₂ ) will not reduce the light extraction efficiency from at least one quantum dot, and can reduce the ligand loss (Ligand) of quantum dots and achieve the improvement of quantum efficiency. It also prevents photo-oxidation of quantum dots.

In addition, the preferred embodiment further coats a surface of the inorganic ligand layer 1001 with a water-oxygen barrier layer 2001, and the water-oxygen barrier layer 2001 is composed of a layered structure 201 including at least one metal oxide , Stacked in an irregular arrangement, can effectively reduce the effect of the inorganic ligand layer 1001 that may cause the poor performance of the quantum dot (optical core 421) nanostructure in the cured polymer material. Wherein, the at least one metal oxide is titanium oxide (TiO ₂ ), zinc oxide (ZnO), aluminum oxide (AlO _x ) or a combination thereof.

On the other hand, please refer to the second figure, which is a schematic diagram of a composite quantum dot material according to another preferred embodiment of the present invention. As shown in the second figure, the composite quantum dot material 142' according to another preferred embodiment includes a certain amount of precursor 431, an optical core 421, an inorganic ligand layer 1001, and a water-oxygen barrier layer 2001.

The difference between the composite quantum dot material 142 of this embodiment and the first figure is that the composite quantum dot material 142' of this embodiment further includes a certain amount of precursor 431, and the quantitative precursor 431 is an inorganic oxide, and in the possible In an embodiment, the inorganic oxide may be a nanosphere structure, and the material may be at least one inorganic oxide, such as silicon dioxide (SiO ₂ ), silicon monoxide (SiO), or a combination thereof. In addition, please refer to the tenth A (the scale of which is 15 nanometers), the tenth B (the scale of which is 20 nanometers), and the tenth C (the scale of which is 50 nanometers), which is another invention. Electron display of the composite quantum dot material of the preferred embodiment (containing quantitative precursors). As shown in Figures 10A, 10B, and 10C, first, the quantitative precursor 431 is subjected to an amination step; after completion, the optical core 421 can be anchored and grown on the quantitative precursor 431 The inorganic ligand layer 1001 is coated on the surface of the quantitative precursor 431 and the optical core 421. Finally, the water-oxygen barrier layer 2001 is coated on the surface of the core of the inorganic ligand layer 1001 to form the composite quantum dot material 142' of this embodiment.

Example: Preparation method of composite quantum dot material

Please refer to the third figure, which is a flow chart of the preparation method of the composite quantum dot material according to the first preferred embodiment of the present invention. As shown in the third figure, the composite quantum dot material of the present invention can be prepared by: (A) providing an optical core and silanizing the optical core; (B) adding a surfactant and a non-polar Solvent in the optical core after silanization treatment; (C) Add a silicon-containing compound so that the surface of the optical core has at least silicon monoxide (SiO _x ) material; (D) Add an aqueous compound, the aqueous compound and the The silicon-containing compound undergoes hydrolysis and condensation reactions to form an inorganic ligand layer; (E) a zinc acetate hydrate and ethanol are mixed and added to the optical core coated with the inorganic ligand layer; and (F) The optical core coated with the inorganic ligand layer is immersed in an aqueous solution of sodium hydroxide (NaOH)-ethanol (Ethanol) to form a composite quantum dot material.

In step (A) of this embodiment, the optical core may be a quantum dot made of semiconductor material, for example: group II-VI quantum dots (CdSe or CdS), group III-V quantum dots ((Al, In , Ga) P, (Al, In, Ga) As or (Al, In, Ga) N), Group II-VI quantum dots with shell-core structure (CdSe/ZnS), III- with shell-core structure Group V quantum dots (InP/ZnS), non-spherical II-VI quantum dots with alloy structure (ZnCdSeS), a combination of any two of the above, or a combination of any two or more of the above.

The optical core may also be a perovskite quantum dot with the chemical formula MAX ₃ , the perovskite quantum dot mainly includes an organic-inorganic hybrid perovskite quantum dot, an all-inorganic perovskite quantum dot, or a combination thereof. Among them, the cation M is an organic ion of methylamine ion, ethylamine ion, formamidine ion or inorganic ion of cesium ion (Cs ⁺ ); metal ion A is divalent lead ion (Pb ²⁺ ), tin (Sn ²⁺⁾ ) or germanium ion (Ge ^2+); X is a halogen ion belonging to a cubic, or orthogonal tetragonal system chloride (Cl ^-), bromide ion (Br ^-) or an iodide ion (I ^-). Further, the full quantum dot inorganic perovskite having the general chemical formula CsPbCl full blue quantum dots _3-inorganic perovskite having the general chemical formula CsPbBr whole green quantum dot _3-inorganic perovskite having the general chemical formula Amber light all-inorganic perovskite quantum dots of CsPb(I/Br) ₃ , red light all-inorganic perovskite quantum dots with the chemical formula CsPbI ₃ , or a combination thereof.

In step (B) of this embodiment, the surfactant is Triton X-100 (Triton X-100, C ₁₄ H ₂₂ O(C ₂ H ₄ O) _n ) or nonylphenol polyether-5 (Igepal CO-520); the non-polar solvent is Hexane, Cyclohexane, Benzene, Toluene, Chloroform or Ethyl acetate.

In step (C) of this embodiment, the silicon-containing compound is tetraethyl silicate (TEOS), tetramethyl silicate (TMOS), or 3-aminopropyltriethoxysilane (APTES). The silicon oxide (SiO _x ) material may be silicon dioxide (SiO ₂ ), silicon monoxide (SiO) or a combination thereof.

In step (D) of this embodiment, the aqueous compound is pure water (H ₂ O) or ammonia (NH ₄ OH) solution.

Please refer to Figures 7A and 7B, which are electrographic images of the optical core coated with the inorganic ligand layer according to the preferred embodiment of the present invention (the scale of which is 20 nanometers), through step (A) of the above preparation method To (D), the production of the inorganic ligand layer 1001a covering the optical core 421a can be completed. First, as shown in Figure 7A, the scale size is 20 nanometers. It is obvious from the figure that the size of the optical core 421a of the composite quantum dot material is about 5 nanometers, and the thickness of the inorganic ligand layer 1001a is about 3 nanometers, and the inorganic ligand layer 1001a of the composite quantum dot material is covered with a single optical core 421a; further, as shown in the seventh figure B, the scale bar size is also 20 nanometers, which can be clearly seen from the figure The size of the optical core 421b of the composite quantum dot material is about 7nm, the thickness of the inorganic ligand layer 1001b is about 11.5nm, and the inorganic ligand layer 100b of the composite quantum dot material is also covered with a single optical core 421b . From this, it can be seen that the present invention can control the thickness of the inorganic ligand layer covering the optical core by adjusting the concentration of the solvent or compound in the above steps (A) to (D).

At the same time, refer to the eighth figure A, which is an electric display diagram in which the water and oxygen barrier layer of the composite quantum dot material of the preferred embodiment of the present invention is titanium oxide. The composite quantum dot material 142a made by the above preparation method includes: an optical core, an inorganic ligand layer coated on the surface of the optical core, and a water oxygen layer coated on the surface of the inorganic ligand layer A barrier layer, and the water-oxygen barrier layer is formed by stacking a layered structure containing at least one metal oxide in an irregular arrangement (refer to Figure 8A, the scale of which is 100 nm) . Among them, the optical core is a quantum dot made of the above semiconductor material or a perovskite quantum dot with the chemical formula MAX ₃ ; the inorganic ligand layer is silicon dioxide (SiO ₂ ), silicon monoxide (SiO) or A combination thereof; the at least one metal oxide is titanium oxide (TiO ₂ ). In addition, the eighth B and C diagrams are metallographic diagrams of the water-oxygen barrier layer of the composite quantum dot material of the preferred embodiment of the present invention being titanium oxide, wherein the fluorescent yellow part in the eighth B diagram is the composite quantum dot material In the material containing silicon (Si) (the scale size is 15 nm), the fluorescent green part in Figure 8C is the material containing titanium (Ti) in the composite quantum dot material (the scale size is 15 nm).

In addition, please refer to the fourth figure, which is a flow chart of the preparation method of the composite quantum dot material according to the second preferred embodiment of the present invention. As shown in the fourth figure, the composite quantum dot material of the present invention can also be prepared by: (G) providing an optical core and silanizing the optical core; (H) adding a surfactant and a non- polar solvent in the warp Silane of the optical core after the treatment; (the I) adding a silicon-containing compound, such that the optical core surface having at least one silicon oxide (SiO _x) material; (J) was added an aqueous compound, the aqueous compound The silicon-containing compound undergoes hydrolysis and condensation reactions to form an inorganic ligand layer; (K) Titanium isopropoxide (TTIP) or tetrabutyl titanate (TBOT) is added to the inorganic ligand layer The optical core; and (L) immersing the optical core coated with the inorganic ligand layer in a water-alcohol solution to form a composite quantum dot material.

In step (G) of this embodiment, the optical core may be a quantum dot made of a semiconductor material, for example: group II-VI quantum dots (CdSe or CdS), group III-V quantum dots ((Al, In , Ga) P, (Al, In, Ga) As or (Al, In, Ga) N), Group II-VI quantum dots with shell-core structure (CdSe/ZnS), III- with shell-core structure Group V quantum dots (InP/ZnS), non-spherical II-VI quantum dots with alloy structure (ZnCdSeS), a combination of any two of the above, or a combination of any two or more of the above.

The optical core may also be a perovskite quantum dot with the chemical formula MAX ₃ , the perovskite quantum dot mainly includes an organic-inorganic hybrid perovskite quantum dot, an all-inorganic perovskite quantum dot, or a combination thereof. Among them, the cation M is an organic ion of methylamine ion, ethylamine ion, formamidine ion or inorganic ion of cesium ion (Cs ⁺ ); metal ion A is divalent lead ion (Pb ²⁺ ), tin (Sn ²⁺⁾ ) or germanium ion (Ge ^2+); X is a halogen ion belonging to a cubic, or orthogonal tetragonal system chloride (Cl ^-), bromide ion (Br ^-) or an iodide ion (I ^-). Further, the full quantum dot inorganic perovskite having the general chemical formula CsPbCl full blue quantum dots _3-inorganic perovskite having the general chemical formula CsPbBr whole green quantum dot _3-inorganic perovskite having the general chemical formula Amber light all-inorganic perovskite quantum dots of CsPb(I/Br) ₃ , red light all-inorganic perovskite quantum dots with the chemical formula CsPbI ₃ , or a combination thereof.

In step (H) of this embodiment, the surfactant is Triton X-100 (Triton X-100, C ₁₄ H ₂₂ O(C ₂ H ₄ O) _n ) or nonylphenol polyether-5 (Igepal CO-520); the non-polar solvent is Hexane, Cyclohexane, Benzene, Toluene, Chloroform or Ethyl acetate.

In step (I) of this embodiment, the silicon-containing compound is tetraethyl silicate (TEOS), tetramethyl silicate (TMOS), or 3-aminopropyltriethoxysilane (APTES). The silicon oxide (SiO _x ) material may be silicon dioxide (SiO ₂ ), silicon monoxide (SiO) or a combination thereof.

In step (J) of this embodiment, the aqueous compound is pure water (H ₂ O) or ammonia (NH ₄ OH) solution.

Reference can also be made to the ninth graph A, which is an electrical display diagram of the water-oxygen barrier layer of the composite quantum dot material of the preferred embodiment of the present invention being zinc oxide (the scale of which is 100 nanometers). The composite quantum dot material 142b made by the above preparation method includes: an optical core, an inorganic ligand layer coated on the surface of the optical core, and a water oxygen layer coated on the surface of the inorganic ligand layer A barrier layer, and the water-oxygen barrier layer is formed of a layered structure containing at least one metal oxide, stacked in an irregular arrangement (refer to Figure 9A, the scale of which is 100 nm) . Among them, the optical core is a quantum dot made of the above semiconductor material or a perovskite quantum dot with the chemical formula MAX ₃ ; the inorganic ligand layer is silicon dioxide (SiO ₂ ), silicon monoxide (SiO) or A combination thereof; the at least one metal oxide is zinc oxide (ZnO). In addition, figures 9B and 9C are metallographic diagrams of the water-oxygen barrier layer of the composite quantum dot material of the preferred embodiment of the present invention being zinc oxide, wherein the fluorescent blue part in figure 9B is the composite quantum dot The material contains silicon (Si) (the scale of which is 250 nanometers). The fluorescent yellow part in Figure 9C is the material containing zinc (Zn) in the composite quantum dot material (the scale of which is 250 nanometers). .

Finally, the preparation method of composite quantum dot materials containing quantitative precursors is as follows. First, please refer to the fifth figure, which is a flowchart of a method for preparing a composite quantum dot material (containing a quantitative precursor) according to a third preferred embodiment of the present invention. As shown in the fifth figure, the steps of the preparation method include: (a) providing an optical core anchored on an inorganic oxide, and in a possible implementation form, the inorganic oxide may be a nanosphere structure; (B) adding a non-polar solvent to at least one quantum dot grown on the inorganic oxide; (c) adding a silicon-containing compound so that the optical core surface has at least silicon oxide (SiO _x ) material; and (d) formed on the outer coated with at least a silicon oxide (SiO _x) composite material of a quantum dot material.

Among them, the surfactant is Triton X-100 (Triton X-100, C ₁₄ H ₂₂ O (C ₂ H ₄ O) _n ) or nonylphenol polyether-5 (Igepal CO-520). Wherein, the silicon-containing compound is tetraethyl silicate (TEOS), tetramethyl silicate (TMOS) or 3-aminopropyltriethoxysilane (APTES).

In addition, refer to the sixth figure again, which is a flow chart of a method for preparing a composite quantum dot material (containing a quantitative precursor) according to a fourth preferred embodiment of the invention. As shown in the sixth figure, the steps of the preparation method include: (a') providing at least a certain amount of precursor, and subjecting the at least certain amount of precursor to amination treatment, the at least certain amount of precursor is an inorganic oxide, And the inorganic oxide has a nanosphere structure; (b') provides at least one optical core; (c') adds a surfactant or a non-polar solvent so that the at least one optical core is formed on the at least a certain amount of precursor an upper surface thereof; (d ') a silicon-containing compound is added so that the optical surface of the core having at least one silicon oxide (SiO _x) material; and (e') formed in the outer coated with at least a silicon oxide (SiO _x) Material-composite quantum dot material.

Among them, the amination treatment is a chemical unit process in which amine groups are introduced into organic compound molecules. Amination can not only introduce one amine group into the organic compound, but also replace two or three amine groups. The chemical treatment methods are mainly divided into two types: reduction, reduction of compounds containing nitro; and ammonolysis, direct reaction with organic halides and ammonia, and replacement of halogen atoms with amine groups. Among them, the surfactant is Triton X-100 (Triton X-100, C ₁₄ H ₂₂ O (C ₂ H ₄ O) _n ) or nonylphenol polyether-5 (Igepal CO-520). Wherein, the silicon-containing compound is tetraethyl silicate (TEOS), tetramethyl silicate (TMOS) or 3-aminopropyltriethoxysilane (APTES).

For the composite quantum dot materials containing quantitative precursors prepared according to the above method, please refer to the aforementioned tenth A, ten B and ten C electrical display diagrams.

Embodiment: display device of composite quantum dot material

The composite quantum dot material of the present invention can be applied to various light-emitting devices such as lighting fixtures, light-emitting modules (front light modules, backlight modules) for display devices such as mobile phone screens and TV screens, or panel paintings for display devices Prime or sub-pixel. Furthermore, when using more kinds of composite quantum dot materials with different compositions, that is, using more kinds of quantum dots with different luminous waves, the wider the emission spectrum of the light source, the full spectrum can be even achieved. Therefore, the use of the composite quantum dot material of the present invention can improve the color gamut of the display device, and can also effectively improve the color purity and color authenticity of the display device.

First, please refer to the eleventh figure, which is a schematic diagram of a composite quantum dot light emitting diode (QD-LED) package structure according to the first embodiment of the present invention. As shown in FIG. 11, the composite quantum dot light-emitting diode 100a adopts a chip package and includes a substrate 120, a metal electrode 122, a light-emitting diode chip 130, a wavelength conversion film 140, and a barrier layer 150 (barrier layer), and on both sides of the metal electrode 122, the light-emitting diode chip 130, the wavelength conversion film 140 and the barrier layer 150, a silicon-containing material (such as silicone resin) )'S protective layer 160 is used to block the penetration of moisture and oxygen. Wherein, the barrier layer 150 (barrier layer) is preferably selected from glass and silicone; among which glass is the best choice. The periphery of the overall composite quantum dot light-emitting diode 100a can be further coated with a metal oxide layer 151 by an atomic layer deposition system (ALD). The composition of the metal oxide layer 151 may be atomic-grade alumina material.

The relative position of the composite quantum dot light emitting diode 100a is to place the substrate 120 at the bottom. The metal electrode 122 is disposed above the substrate 120. The light emitting diode chip 130 is disposed above the metal electrode 122 and electrically connected to the metal electrode 122. The wavelength conversion film 140 and the barrier layer 150 are both disposed on the light emitting diode chip 130, and the barrier layer 150 covers the wavelength conversion film 140 to prevent the wavelength conversion film 140 from being subjected to light emission. The heat energy generated when the polar body wafer 130 emits light affects the efficiency of wavelength conversion, and even destroys the wavelength conversion film 140. The material of the barrier layer 150 is polymethyl methacrylate (PMMA), optical glass, epoxy plastic ester, silicone resin (Silicone resin), or the like.

The wavelength conversion film 140 is a wavelength conversion film 140 having the aforementioned composite quantum dot materials 142, 142' (please also refer to the first figure or the second figure). The wavelength conversion film 140 may also have the aforementioned composite quantum The dot materials 142, 142' are mixed with a transparent colloid material (not shown) to form a composite wavelength conversion film 140. The transparent colloid material may be polymathic methacrylate (PMMA), ethylene terephthalic acid Ester (polyethylene terephthalate, PET), polystyrene (PS), polyethylene (polypropylene, PP), nylon (polyamide, PA), polycarbonate (polycarbonate, PC), epoxy (epoxy), silicone Silicone resin, silicone, or a combination thereof.

The composite wavelength conversion film 140 may further include other fluorescent materials (not shown), such as inorganic fluorescent materials or organic fluorescent materials mixed with the foregoing quantum dot materials 142, 142', and inorganic fluorescent materials such as aluminum Salt phosphor powder (such as LuYAG, GaYAG, YAG, etc.), silicate phosphor powder, sulfide phosphor powder, nitride phosphor powder, fluoride phosphor powder, fluorosilicic acid containing tetravalent manganese ion Potassium (KSF), etc. Organic fluorescent materials include single molecular structure, multi-molecular structure, oligomer (Oligomer) and polymer (Polymer). The fluorescent material is composed of a main crystal, a co-activator (sensitizer) and an activator. The fluorescent material may be yellow, blue, green, orange, red, or a combination thereof, such as yellow-orange and red-yellow nitride phosphors. The material of the fluorescent material is selected from organic phosphors and fluorescents Pigments, inorganic phosphors, radioactive elements or combinations thereof.

In this embodiment, the manufacturing method of the wavelength conversion film 140 is as follows: First, step (A) is performed to disperse the composite quantum dot material through a polar or non-polar solvent. Next, step (B) is performed, the dispersion liquid containing the composite quantum dot material and the transparent glue material are uniformly mixed, and placed in an oven to form a composite quantum dot glue material. Furthermore, step (C) is performed to apply the composite quantum dot glue material on the transparent substrate by a doctor blade coating method, or infiltrate the composite quantum dot glue material into the gap between the two transparent substrates by the infiltration method. Finally, step (D) is performed to perform UV curing or thermal curing molding of the glue material to complete the fabrication of the wavelength conversion film 140.

In this embodiment, another manufacturing method of the wavelength conversion film 140 is as follows: First, step (a) is performed to stack a plurality of nanospheres into a periodic or non-periodic stack structure. Next, step (b) is performed, a skeleton colloid is infiltrated into the gap of the stacked structure, and the skeleton colloid is mixed with the aforementioned composite quantum dot material. Furthermore, step (c) is performed to cure the skeleton colloid and remove the plurality of nanospheres in the stacked structure with a deballing agent. Finally, step (d) is performed to complete the wavelength conversion film 140. The wavelength conversion film 140 includes a periodic or aperiodic nano-spherical hole structure.

After step (d) is performed, if there is a demand for increasing the light intensity for a spectrum of more wavelengths, step (e) can be further performed, in which the nano-spherical hole structure in the wavelength conversion film 140 penetrates into the aforementioned compound Quantum dot material.

The manufacturing method of the wavelength conversion film can also be carried out through the following methods: first, step (f) is performed, and a plurality of the aforementioned composite quantum dot materials are stacked in a periodic or non-periodic one. Next, step (g) is performed, and a skeleton colloid penetrates into the gaps of the stacked structure. Furthermore, step (h) is performed to cure the skeleton colloid. Finally, step (i) is performed, and the wavelength conversion film 140 is completed, and the wavelength conversion film includes periodic or aperiodic complex quantum dot materials.

In another embodiment, the manufacturing method of the composite wavelength conversion film 140 is as follows: First, step (a1) is performed to stack a plurality of nanospheres into a periodic or non-periodic stack structure. Next, step (b1) is performed, a skeleton colloid is infiltrated into the gap of the stacked structure, and the skeleton colloid is mixed with the aforementioned composite quantum dot material, and the aforementioned fluorescent material, transparent colloid material or a combination thereof. Furthermore, step (c1) is performed to cure the skeleton colloid, and remove the plurality of nanospheres in the stacked structure with a deballing agent. Finally, step (d1) is performed to complete the composite wavelength conversion film 140. The composite wavelength conversion film 140 includes a periodic or aperiodic nano-spherical hole structure.

After performing step (d1), if there is a need to increase the light intensity for a spectrum of more wavelengths, step (e1) can be performed, and the nanospherical hole structure in the composite wavelength conversion film 140 penetrates into the aforementioned Composite quantum dot material.

In the above two embodiments, the plurality of nanospheres can be selected from silicon dioxide (SiO ₂ ), polystyrene (Polystyrene, PS), polydimethylsiloxane (Polydimethylsiloxane), polymethylmethacrylate (Polymethylmethacrylate) ) Nanospheres with diameters ranging from 10 nanometers to 1000 nanometers.

The liquid skeleton colloid may be a light-curing glue or a heat-curing glue mixed with fluorescent materials, or a pure light-curing glue or a heat-curing glue. Furthermore, the material of the photocurable adhesive includes acrylate monomers, acrylate oligomer monomers, or a combination thereof. In this embodiment, it is implemented using an acrylate monomer. The main reason is that acrylates have excellent weather resistance, transparency, color retention and mechanical strength, and acrylate monomers can be selected from tripropylene glycol diacrylate (TPGDA) and neopentyl glycol diacrylate ( Neopropylene glycol diacrylate (NPGDA), Propoxylated neopropylene glycol diacrylate (PO-NPGDA), Trimethyloipropane triacrylate (TMPTA), ethoxylated trihydroxy Ethoxylated trimethyloipropane triacrylate (EO-TMPTA), Propoxylated trimethyloipropane triacrylate (PO-TMPTA), Propoxylated glyceryl triacrylate , GPTA), di-(trimethylolpropane) tetraacrylate (Di-trimethyloipropane tetraacrylate, di-TMPTA), ethoxylated pentaerythritol tetraacrylate (EO-PETA), dipentaerythritol hexaacrylate (Dipentaerythritol hexaacrylate, DPHA) or a combination thereof.

The method of curing the skeleton colloid is based on the type of skeleton colloid and different methods are used. If the skeleton colloid is a photo-curable adhesive containing a photo-hardening agent, external environmental factors such as ultraviolet rays will be used for curing; otherwise, if it is a thermo-curable adhesive, it will be cured by means such as oven heating.

When the material of the plurality of nanospheres is silicon compound, the deballing agent is hydrofluoric acid (HF). The plurality of nanospheres in the stacked structure can be removed without corroding the skeleton colloid. When a plurality of nanospheres are high-molecular polymers, the organic solvent is used to achieve the goal.

In this embodiment, the process steps of the light emitting diode wafer 130 can be divided into upstream, midstream, and downstream. The upstream includes forming substrates (such as sapphire substrates, ceramic substrates, metal substrates, etc.), single crystal rods (such as GaN, GaAs, GaP, etc.), single wafer, structural design, epitaxial wafer, midstream includes metal evaporation, photoetching, heat treatment, cutting, downstream package includes flip-chip, surface mount device (SMD) and Chip package (CSP).

In this embodiment, the wavelength conversion film 140 of the composite quantum dot light-emitting diode 100 a and the composite quantum dot materials 142 and 142 ′ included in the composite wavelength conversion film 140 can be emitted by the light-emitting diode chip 130 The first light is excited and emits a second light with a wavelength different from that of the first light, and has excellent quantum efficiency, can exhibit a half-height wide and narrow light emission spectrum and excellent pure color, so the light wavelength conversion effect is good, And applied to the backlight can improve the luminous effect. The light-emitting diode chip 130 emitting the first light is emitted from the blue light-emitting diode chip or the ultraviolet light-emitting diode chip.

Please refer to the twelfth figure, which is a schematic diagram of a composite quantum dot light emitting diode (QD-LED) package structure according to a second embodiment of the present invention. As shown in FIG. 12, a light-emitting diode chip 130 is provided on the plastic electrode wafer carrier 180 (connected through metal wires 190) of the composite quantum dot light-emitting diode 100 b. The protective layer 160 is surrounded to form a cup-shaped structure to block the penetration of moisture and oxygen; and a transparent colloidal material 170 is filled therein. The transparent colloid material 170 may be polymathic methacrylate (PMMA), polyethylene terephthalate (PET), polystyrene (PS), and polypropylene (PP) , Nylon (polyamide, PA), polycarbonate (polycarbonate, PC), epoxy (epoxy), silicone resin (silicone resin), silicone (silicone) or a combination thereof. In the embodiment of FIG. 12, the transparent colloidal material 170 is made of silicone resin; the protective layer 160 and the transparent colloidal material 170 are provided with a wavelength conversion film 140 or a compound sandwiched by a barrier layer 150 Wavelength conversion film 140. The periphery of the overall composite quantum dot light-emitting diode 100a can be further coated with a metal oxide layer 151 by an atomic layer deposition system (ALD). The composition of the metal oxide layer 151 may be atomic-grade alumina material.

Please refer to FIG. 13, which is a schematic diagram of a composite quantum dot light emitting diode (QD-LED) package structure according to a third embodiment of the present invention. As shown in FIG. 13, the plastic electrode wafer carrier 180 of the composite quantum dot light-emitting diode 100c is provided with a light-emitting diode wafer 130 (connected through a metal wire 190). And pass through the protective layer 160 to form a cup-shaped structure to block the penetration of moisture and oxygen; and filled with a transparent colloidal material 170 mixed with composite quantum dot materials 142, 142'. The transparent colloid material 170 may be polymathic methacrylate (PMMA), polyethylene terephthalate (PET), polystyrene (PS), or polyethylene (polypropylene, PP), nylon (polyamide, PA), polycarbonate (polycarbonate, PC), epoxy (epoxy), silicone resin (silicone resin), silicone (silicone) or a combination thereof. The periphery of the overall composite quantum dot light-emitting diode 100a can be further coated with a metal oxide layer 151 by an atomic layer deposition system (ALD). The composition of the metal oxide layer 151 may be atomic-grade alumina material.

Please refer to FIG. 14, which is a schematic diagram of a composite quantum dot liquid crystal display device according to an embodiment of the invention. As shown in FIG. 14, the composite quantum dot liquid crystal display device 52 includes a side light type backlight module 32 and a liquid crystal display module 42. The side light type backlight module 32 includes a frame 380, a backlight 100 and a light guide plate 320. In this embodiment, the backlight 100 is any composite quantum dot light emitting diode (QD-LED) 100a, 100b, or 100c in the eleventh to thirteenth figures, and the light exit direction of the backlight 100 is the surface light guide plate 320 In terms of light incidence, and the backlight module 32 further has at least one reflective sheet 322 to concentrate the light emitted from the backlight 100 to the light guide plate 320, and then the light is emitted to the upper liquid crystal display module 42 through the light exit surface of the light guide plate 320 .

Please refer to FIG. 15A, which is a schematic diagram of a composite quantum dot liquid crystal display device according to another embodiment of the present invention. As shown in FIG. 15A, the composite quantum dot liquid crystal display device 54 includes a backlight module 34 and a liquid crystal display module 42 all the way down. The direct backlight module 34 includes a frame 380 and a backlight 100. In this embodiment, the backlight 100 is any composite quantum dot light-emitting diode 100a, 100b, or 100c in the eleventh to thirteenth figures, or a blue light-emitting diode (LED), and the light exit direction of the backlight 100 To face the liquid crystal display module 42, the frame 380 further has at least one reflective sheet 322 to concentrate the light emitted from the backlight 100 to the liquid crystal display module 42, and the light is then emitted by the liquid crystal display module 42.

The liquid crystal display module 42 includes a glass substrate 420 disposed above the edge-lit backlight module 32 or directly below the backlight module 34, and a thin film transistor layer 424 disposed between the glass substrate 420 and the side The optical backlight module 32 or the direct backlight module 34 is between the backlight module 34, and a liquid crystal molecular layer 422 is disposed between the glass substrate 420 and the thin film transistor layer 424.

In addition, please refer to FIG. 15B, which is a schematic diagram of a composite quantum dot liquid crystal display device according to still another embodiment of the present invention. As shown in FIG. 15B, the composite quantum dot liquid crystal display device 54 includes a backlight module 34, a liquid crystal display module 42, a wavelength conversion layer 140 or a composite wavelength conversion layer 140, and a direct type backlight mode. Group 34 includes frame 380 and backlight 100. In this embodiment, the backlight source 100 may also be any composite quantum dot light emitting diode (QD-LED) 100a, 100b, or 100c in Figures 11 to 13, or a blue light emitting diode (LED), The light exit direction of the backlight source 100 faces the liquid crystal display module 42, and the frame 380 further has at least one reflective sheet 322 to concentrate the light emitted by the backlight source 100, and then to the wavelength conversion layer 140 or the composite wavelength conversion layer 140. The liquid crystal display module 42 emits light from the liquid crystal display module 42 again. The difference between this embodiment and FIG. 15a is that in the direct backlight module 34, the aforementioned wavelength conversion layer 140 or the composite wavelength conversion layer 140 can also be placed on the backlight 100 (refer to FIGS. 11 and 12) .

The liquid crystal display module 42 includes a glass substrate 420 disposed above the edge-lit backlight module 32 or directly below the backlight module 34, and a thin film transistor layer 424 disposed between the glass substrate 420 and the side The optical backlight module 32 or the direct backlight module 34 is between the backlight module 34, and a liquid crystal molecular layer 422 is disposed between the glass substrate 420 and the thin film transistor layer 424.

In addition, please refer to FIG. 16, which is a schematic diagram of a composite quantum dot micro LED display device according to the first embodiment of the present invention. As shown in FIG. 16, the composite quantum dot micro LED display device 200a includes a micro light source 240 which is an active type light emitting diode die or a passive type light emitting diode The polar body grains and at least one composite quantum dot material 142 are coated on the surface of the micro-luminescence source. Wherein, the at least one composite quantum dot material 142 includes an optical core; an inorganic ligand layer is coated on the surface of the optical core (refer to the first figure), and the inorganic ligand layer includes at least silicon oxide (SiO _x ) Material; and a water-oxygen barrier layer, coated on the surface of the inorganic ligand layer. Wherein, the water-oxygen barrier layer is formed by stacking at least one metal oxide layered structure.

The optical core may be quantum dots made of semiconductor materials, for example: Group II-VI quantum dots (CdSe or CdS), Group III-V quantum dots ((Al, In, Ga) P, (Al, In , Ga) As or (Al, In, Ga) N), group II-VI quantum dots with shell-core structure (CdSe/ZnS), group III-V quantum dots with shell-core structure (InP/ZnS) , Non-spherical II-VI quantum dots (ZnCdSeS) with alloy structure, a combination of any two of the above, or a combination of any two or more of the above.

The optical core may also be a perovskite quantum dot with the chemical formula MAX ₃ , the perovskite quantum dot mainly includes an organic-inorganic hybrid perovskite quantum dot, an all-inorganic perovskite quantum dot, or a combination thereof. Among them, the cation M is an organic ion of methylamine ion, ethylamine ion, formamidine ion or inorganic ion of cesium ion (Cs ⁺ ); metal ion A is divalent lead ion (Pb ²⁺ ), tin (Sn ²⁺⁾ ) or germanium ion (Ge ^2+); X is a halogen ion belonging to a cubic, or orthogonal tetragonal system chloride (Cl ^-), bromide ion (Br ^-) or an iodide ion (I ^-).

The silicon oxide (SiO _x ) material may be silicon dioxide (SiO ₂ ) or silicon monoxide (SiO). The at least one metal oxide is titanium oxide (TiO ₂ ), zinc oxide (ZnO), aluminum oxide (AlO _x ), or a combination thereof.

In this embodiment, the micro light emitting source 220 includes a light emitting diode chip 220 and a plurality of spacer layers 260, and the at least one composite quantum dot material 142 is disposed on the light emitting side of the light emitting diode chip 220. More specifically, The at least one composite quantum dot material 142 is coated on the light emitting side surface of the light emitting diode chip 220 at intervals, and the plurality of spacer layers 260 are spaced between the light emitting diode chip 220 and the at least one composite quantum dot material 142 between. Wherein, the light-emitting diode chip 220 is a vertical type light-emitting diode chip, which includes a first electrode 222, a second electrode 224, and sequentially disposed between the first electrode 222 and the second electrode 224 The P-type semiconductor layer, the light-emitting layer 226, and the N-type semiconductor layer, and the light-emitting diode wafer 220 has the light output measured on the same side as the first electrode 222.

In this embodiment, at least one composite quantum dot material 142 is coated on the surface of the microluminescence source by atomizing spraying. The method of atomizing spraying is to mix at least one composite quantum dot material 142 with a glue material (such as silicone glue) ) After uniformly spraying on the surface of the micro-luminescence source 240, the color required for a single light-emitting diode wafer 220 is automatically aligned and sprayed on the light-emitting diode wafer 220 using an atomizing spraying machine , And then to achieve a full-color micro LED display device (Micro LED).

Please refer to Figure 17, which is a schematic diagram of a quantum dot micro LED display device according to a second embodiment of the present invention. As shown in FIG. 17, the composite quantum dot micro LED display device 220b includes a micro light source 240 which is an active light emitting diode die or a passive light emitting diode The polar body grains and at least one composite quantum dot material 142 are coated on the surface of the micro-luminescence source 240. Wherein the at least one composite material includes a quantum dot optical core; a ligand of the inorganic layer, coated on the surface of the optical core, the inorganic alignment layer comprises at least a silicon oxide (SiO _x) material; and a water oxygen The barrier layer is coated on the surface of the inorganic ligand layer. Wherein, the water-oxygen barrier layer is formed by stacking a laminated structure containing at least one metal oxide (refer to the first figure).

The difference between this embodiment and the composite quantum dot micro LED display device 200a of FIG. 16 is that a photoresist layer 144 is further provided between the micro light source 240 and the at least one composite quantum dot material 142 , Such as photoresist mask (PRM), barrier layer (barrier layer) or a combination thereof. Wherein, the material of the photoresist layer 144 is polymethyl methacrylate (PMMA), or other photoresist materials such as positive photoresist phenol-formaldehyde resin (phenol-formaldehyde resin) or epoxy resin (epoxy resin), negative type Photoresist polyisoprene rubber and inverted photoresist; etc. In addition, the photoresist layer 144 may also be the wavelength conversion film 140 or the composite wavelength described in the ninth and tenth drawings Conversion film 140.

In this embodiment, a photoresist layer 144 is formed between the micro-luminescence source 240 and the at least one composite quantum dot material 142 by atomizing spraying and yellow light lithography process, and transmits two wavelength conversions of green light and red light The spraying process to achieve a full-color Micro LED display device.

Please refer to Figure 18, which is a schematic diagram of a composite quantum dot micro LED display device according to a third embodiment of the present invention. As shown in FIG. 18, the composite quantum dot micro LED display device 200c includes a micro light source 240 which is an active light emitting diode die or a passive light emitting diode The polar body grains and at least one composite quantum dot material 142 are coated on the surface of the micro-luminescence source 240. Wherein the at least one composite material includes a quantum dot optical core; a ligand of the inorganic layer, coated on the surface of the optical core, the inorganic alignment layer comprises at least a silicon oxide (SiO _x) material; and a water oxygen The barrier layer is coated on the surface of the inorganic ligand layer. Wherein, the water-oxygen barrier layer is formed by stacking at least one metal oxide layered structure.

The difference between this embodiment and the composite quantum dot micro-LED display device 200b of FIG. 17 is that the at least one composite quantum dot material 142 can further form a composite photoresist layer 146 with a photoresist material . Wherein the photoresist material is polymethyl methacrylate (PMMA), or other photoresist materials such as positive type photoresist phenol-formaldehyde resin (phenol-formaldehyde resin) or epoxy resin (epoxy resin), negative type photoresist polymer Isoprene rubber (polyisoprene rubber) and inversion type photoresist; etc. In addition, the composite photoresist layer 146 may also be the wavelength conversion film 140 or the composite wavelength conversion film 140 described in the ninth and tenth figures of the drawings .

In this embodiment, a full-color micro LED display device is achieved by a spin coating process and a yellow light lithography process. Since the composite quantum dot material 142 of the present invention can be miscible with a non-polar solution, Through the methyl methacrylate (PMMA) electron photoresist, the solubility characteristics of toluene can be adjusted with different solubility. This method can prepare a composite photoresist layer 146 of composite quantum dot material mixed with methyl methacrylate (PMMA). To improve adhesion. Then, the composite photoresist layer 146 is covered on the micro-luminescence source 240 by spin coating, and the addressed quantum dot material deposition is formed in conjunction with the yellow light lithography.

Experimental results

Finally, the composite quantum dot material of the present invention is encapsulated in a light emitting diode element (as shown in Figures 11 to 13), and subjected to heat resistance, water and oxygen resistance experiments. First, please refer to Figure 19, which is a temperature test chart of the composite quantum dot material of the preferred embodiment of the present invention. As shown in Figure 19, during the heating process (solid line in the figure), the light emitting diode element encapsulated with the composite quantum dot material of the present invention and the conventional light emitting diode element will have both luminous intensity It decreases with increasing temperature. On the other hand, during the cooling process (the dotted line in the figure), the temperature of the conventional light-emitting diode element is reduced from about 150 degrees Celsius to 20 degrees, and its luminous intensity can only be restored to 20% of the original intensity. However, under the condition that the temperature of the light-emitting diode element encapsulated with the composite quantum dot material of the present invention is also reduced from about 150 degrees Celsius to 20 degrees Celsius, the luminous intensity can be restored to 80% of the original intensity. From this, it can be seen that the composite quantum dots of the present invention will not be destroyed even in a high-temperature environment, and the luminous intensity of the light-emitting element can be effectively maintained.

Furthermore, please refer to the twentieth and twenty-first figures, which are the water-blocking oxygen test charts of the composite quantum dot material according to the preferred embodiment of the present invention. As shown in the twentieth figure, experiments were conducted on conventional light-emitting diode elements, light-emitting diode elements encapsulated with the inorganic ligand layer of the present invention and optical cores, and composite quantum dot materials encapsulated with the present invention (including (The optical core of the quantum dot, the inorganic ligand layer of silicon oxide, and the water-oxygen barrier layer of titanium oxide) are used for firing. The firing environment is 60 degrees Celsius, and High temperature and high humidity environment with a relative humidity of 90%. It can be clearly seen from the figure that the conventional light-emitting diode element has a luminous intensity maintenance rate of only 10% of the original intensity around the 50th hour of the experiment; and the inorganic ligand layer package of the present invention The light-emitting diode element covered with the optical core maintains the luminous intensity maintenance rate at about 100% of the original intensity at the first 100 hours of the experiment; amazingly, the luminous diode encapsulated with the composite quantum dot material of the present invention Even after 100 hours of experiment in this high-temperature and high-humidity environment, the polar body's luminous intensity maintenance rate is still 95% of the original intensity, which has the effect of blocking water, oxygen and high temperature.

The twenty-first figure is also directed to the conventional light-emitting diode element, the light-emitting diode element encapsulated with the inorganic ligand layer of the present invention covering the optical core, and the composite quantum dot material encapsulated with the present invention (including the material as quantum The optical core of the dot, the inorganic ligand layer made of silicon oxide and the water-oxygen barrier layer made of titanium oxide) are burned, and the burning environment is changed to 25 degrees Celsius, and the relative General environment with 50% humidity. It can be clearly seen from the figure that the conventional light-emitting diode element is about 1000 hours after the experiment, and its luminous intensity maintenance rate is only 25% of the original intensity; and the inorganic ligand of the present invention is installed The light-emitting diode element with the optical core covered by the layer maintains the luminous intensity maintenance rate at the first 1000 hours of the experiment at 50% of the original intensity; it is also amazing that the composite quantum dot material of the present invention is encapsulated Even after 1000 hours of experiment in this high-temperature and high-humidity environment, the luminous intensity of the LED device remains 95% of the original intensity.

Finally, please refer to Figure 22, which is a comparison diagram of the color gamut of the composite quantum dot display device according to the preferred embodiment of the present invention. The present invention further applies the aforementioned light emitting diode element encapsulated with the composite quantum dot material of the present invention to a liquid crystal display device (refer to Figures 14 and 15A and 15B), as shown in Figure 22 It is shown that the spectrum of the composite quantum dot (liquid crystal) display device of the present invention is further subjected to Rec. 2020 color gamut calculation, and it is known that the color gamut range of the composite quantum dot (liquid crystal) display device of the present invention is about 90% (NTSC> 130%) (solid triangle area in the twentieth figure), compared with the Rec. 2020 color gamut range of the conventional wide color gamut display device is about 70% (NTSC> 90%) (dotted triangle area in the twentieth figure) From this, it can be seen that the Rec. 2020 color gamut of the quantum dot display device of the present invention is improved by nearly 1.3 times.

However, the above are only preferred embodiments of the present invention, and the scope of implementation of the present invention cannot be limited by this, that is, simple changes and modifications made according to the patent application scope and description of the present invention are still within the present invention. Covered.

142, 142a, 142b, 142’‧‧‧ composite quantum dot materials 421, 421a, 421b ‧‧‧ optical core 431‧‧‧ Quantitative precursors 1001, 1001a, 1001b ‧‧‧ inorganic ligand layer 2001‧‧‧Water Oxygen Barrier 201‧‧‧Layered structure 52, 54‧‧‧ quantum dot liquid crystal display device 42‧‧‧LCD display module 420‧‧‧Glass substrate 422‧‧‧Liquid crystal molecular layer 424‧‧‧thin film transistor layer 32‧‧‧sidelight backlight module 34‧‧‧Direct type backlight module 320‧‧‧Light guide plate 322‧‧‧Reflective film 380‧‧‧frame 100‧‧‧Backlight 100a, 100b, 100c ‧‧‧ quantum dot light emitting diode 120‧‧‧ substrate 122‧‧‧Metal electrode 130‧‧‧ LED chip 140‧‧‧ wavelength conversion film 144‧‧‧Photoresist layer 146‧‧‧composite photoresist layer 150‧‧‧ barrier 151‧‧‧Metal oxide layer 160‧‧‧Protective layer 170‧‧‧ Transparent colloidal material 180‧‧‧Plastic electrode chip carrier 190‧‧‧Metal wire 200a, 200b, 200c ‧‧‧ quantum dot micro-luminescence diode display device 220‧‧‧ LED chip 222‧‧‧First electrode 224‧‧‧Second electrode 226‧‧‧luminous layer 240‧‧‧Microluminescence source 260‧‧‧Spacer A-F‧‧‧Step G-L‧‧‧Step

The first figure is a schematic diagram of a composite quantum dot material according to a preferred embodiment of the present invention.

The second figure is a schematic diagram of a composite quantum dot material according to another preferred embodiment of the present invention.

The third figure is a flow chart of the preparation method of the composite quantum dot material according to the first preferred embodiment of the present invention.

The fourth figure is a flow chart of the preparation method of the composite quantum dot material according to the second preferred embodiment of the present invention.

The fifth figure is a flow chart of the preparation method of the composite quantum dot material according to the third preferred embodiment of the present invention.

The sixth figure is a flow chart of the preparation method of the composite quantum dot material according to the fourth preferred embodiment of the present invention.

FIG. 7A is an electrical display diagram of an inorganic ligand layer covering an optical core according to a preferred embodiment of the present invention.

FIG. 7B is an electrical display diagram of an inorganic ligand layer covering an optical core according to a preferred embodiment of the present invention.

The eighth figure A is an electro-display image of the composite quantum dot material in which the water-oxygen barrier layer is titanium oxide.

Figure 8B is a metallographic diagram of a composite quantum dot material in which the water-oxygen barrier layer is titanium oxide.

Figure 8C is a metallographic diagram of a composite quantum dot material in which the water-oxygen barrier layer is titanium oxide.

FIG. 9A is an electrographic display diagram of the water-oxygen barrier layer of the composite quantum dot material of the preferred embodiment of the present invention being zinc oxide.

Figure 9B is a metallographic diagram of the composite quantum dot material in which the water-oxygen barrier layer is zinc oxide.

Figure 9C is a metallographic diagram of the composite quantum dot material in which the water-oxygen barrier layer is zinc oxide.

Figure 10A is an electrical display diagram of a composite quantum dot material according to another preferred embodiment of the present invention.

Figure 10B is an electrical display diagram of a composite quantum dot material according to another preferred embodiment of the present invention.

Figure 10C is an electrical display diagram of a composite quantum dot material according to another preferred embodiment of the present invention.

FIG. 11 is a schematic diagram of a composite quantum dot light emitting diode (QD-LED) package structure according to the first embodiment of the present invention.

FIG. 12 is a schematic diagram of a composite quantum dot light emitting diode (QD-LED) package structure according to a second embodiment of the present invention.

FIG. 13 is a schematic diagram of a composite quantum dot light emitting diode (QD-LED) package structure according to a third embodiment of the present invention.

FIG. 14 is a schematic diagram of a composite quantum dot liquid crystal display device according to an embodiment of the invention.

FIG. 15A is a schematic diagram of a composite quantum dot liquid crystal display device according to another embodiment of the invention.

Fig. 15B is a schematic diagram of a composite quantum dot liquid crystal display device according to still another embodiment of the present invention.

FIG. 16 is a schematic diagram of a composite quantum dot micro LED display device according to the first embodiment of the present invention.

FIG. 17 is a schematic diagram of a composite quantum dot micro LED display device according to a second embodiment of the present invention.

Figure 18 is a schematic diagram of a composite quantum dot micro LED display device according to a third embodiment of the present invention.

Figure 19 is a temperature test chart of a composite quantum dot material according to a preferred embodiment of the present invention.

Figure 20 is a water-blocking oxygen test chart of a composite quantum dot material according to a preferred embodiment of the present invention.

Figure 21 is a water-blocking oxygen test chart of a composite quantum dot material according to a preferred embodiment of the present invention.

Figure 22 is a comparison diagram of the color gamut of a composite quantum dot display device according to a preferred embodiment of the present invention.

142‧‧‧compound quantum dot material

201‧‧‧Layered structure

421‧‧‧Optical core

1001‧‧‧Inorganic ligand layer

2001‧‧‧Water Oxygen Barrier

Claims (19)

A composite quantum dot material, comprising: a certain amount of precursor, which is at least one inorganic oxide; an optical core, formed on the surface of the quantitative precursor; an inorganic ligand layer, coated on the surface of the optical core, The inorganic ligand layer includes at least silicon oxide (SiO _x ) material; and a water-oxygen barrier layer, covering the surface of the inorganic ligand layer; wherein, the water-oxygen barrier layer includes at least one The stacked structure of metal oxides is stacked. The composite quantum dot material according to claim 1, wherein the optical core is a perovskite quantum dot having the chemical formula MAX ₃ , and the M is a cation, the A is a metal ion, and the X is a halogen ion. The composite quantum dot material according to claim 2, wherein the perovskite quantum dot is an organic-inorganic hybrid perovskite quantum dot or an all-inorganic perovskite quantum dot. The composite quantum dot material according to claim 1, wherein the at least silicon monoxide (SiO _x ) material is silicon dioxide (SiO ₂ ), silicon monoxide (SiO), or a combination thereof. The composite quantum dot material according to claim 1, wherein the at least one metal oxide is titanium oxide (TiO ₂ ), zinc oxide (ZnO), aluminum oxide (AlO _x ), or a combination thereof. The composite quantum dot material according to claim 1, wherein the at least one inorganic oxide is silicon dioxide (SiO ₂ ), silicon monoxide (SiO), or a combination thereof. A method for preparing a composite quantum dot material, comprising: (A) providing at least one optical core, and performing silanization treatment on the at least one optical core; (B) adding a surfactant and a non-polar solvent to the silanization treatment after the at least one optical core; (C) a silicon-containing compound is added, such that the at least one optical surface of the core having at least one silicon oxide (SiO _x) material; (D) adding an aqueous compound, the compound with the silicon-containing aqueous The compound undergoes hydrolysis and condensation reactions to form an inorganic ligand layer; and (E) adding titanium isopropoxide (TTIP) or tetrabutyl titanate (TBOT), or mixing a zinc acetate hydrate and ethanol to The at least one optical core coated with the inorganic ligand layer. The method for preparing a composite quantum dot material according to claim 7, wherein in this step (A), a certain amount of precursor can also be provided to link with the at least one optical core. The method for preparing a composite quantum dot material according to claim 7, wherein the surfactant is Triton X-100 (Triton X-100, C ₁₄ H ₂₂ O(C ₂ H ₄ O) _n ) or nonyl Phenol-5 (Igepal CO-520). The method for preparing a composite quantum dot material according to claim 7, wherein the silicon-containing compound is tetraethyl silicate (TEOS), tetramethyl silicate (TMOS) or 3-aminopropyltriethoxy Silane (APTES). The method for preparing a composite quantum dot material according to claim 7, wherein in this step (E), titanium isopropoxide (TTIP) or tetrabutyl titanate (TBOT) is added, then a Step (F1) will cover the inorganic ligand layer The optical core is immersed in an aqueous solution of sodium hydroxide (NaOH)-ethanol (Ethanol) to form a composite quantum dot material. The method for preparing a composite quantum dot material as described in claim 7, wherein in this step (E) the zinc acetate hydrate and ethanol are mixed, then a step (F2) can also be performed to coat the inorganic ligand The optical core of the layer is immersed in a water-alcohol solution to form a composite quantum dot material. A composite quantum dot material, comprising: an optical core; an inorganic ligand layer coated on the surface of the optical core, the inorganic ligand layer comprising at least silicon oxide (SiO _x ) material; and a water-oxygen barrier A layer covering the surface of the inorganic ligand layer; wherein the water-oxygen barrier layer is formed by stacking a layered structure including at least one metal oxide. The composite quantum dot material according to claim 13, wherein the optical core is a perovskite quantum dot having the chemical formula MAX ₃ , and the M is a cation, the A is a metal ion, and the X is a halogen ion. The composite quantum dot material according to claim 14, wherein the perovskite quantum dot is an organic-inorganic hybrid perovskite quantum dot or an all-inorganic perovskite quantum dot. The composite quantum dot material according to claim 13, wherein the at least silicon monoxide (SiO _x ) material is silicon dioxide (SiO ₂ ), silicon monoxide (SiO), or a combination thereof. The composite quantum dot material according to claim 13, wherein the at least one metal oxide is titanium oxide (TiO ₂ ), zinc oxide (ZnO), aluminum oxide (AlO _x ), or a combination thereof. A composite quantum dot display device, comprising: a backlight; at least one composite quantum dot material, which is arranged on the backlight; and a liquid crystal display module, which is arranged on the at least one composite quantum dot material; wherein, the at least one compound The quantum dot material includes: an optical core; an inorganic ligand layer coated on the surface of the optical core, the inorganic ligand layer including at least silicon oxide (SiO _x ) material; and a water-oxygen barrier layer, including Covering the surface of the inorganic ligand layer; wherein the water-oxygen barrier layer is formed by stacking at least one metal oxide layered structure. A composite quantum dot display device, comprising: a micro-luminescence source, which is an active micro LED die or a passive micro LED die; and at least one composite quantum dot material coated on the micro-luminescence source; wherein, the at least one compound The quantum dot material includes: an optical core; an inorganic ligand layer coated on the surface of the optical core, the inorganic ligand layer including at least silicon oxide (SiO _x ) material; and a water-oxygen barrier layer, including Covering the surface of the inorganic ligand layer; wherein the water-oxygen barrier layer is formed by stacking at least one metal oxide layered structure.

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