TWI613275B - Quantum dot composite material and manufacturing method and application thereof - Google Patents

Abstract

Quantum dot composite materials and methods for their manufacture and applications. Quantum dot composites include all-inorganic perovskite quantum dots and modification protection. The all-inorganic perovskite quantum dots have a chemical formula of CsPb(Cl _a Br _1-ab I _b ) ₃ , of which 0 a 1,0 b 1. The modification is protected on the surface of the all inorganic perovskite quantum dots.

Description

Quantum dot composite material and its manufacturing method and application

The invention relates to a quantum dot composite material and a manufacturing method and application thereof, and in particular to a quantum dot composite material with modified protection and a manufacturing method and application thereof.

Fluorescent powders and quantum dots are the most common luminescent materials at this stage. However, the current phosphor powder market has become saturated, and the half-height width of the spectroscopic spectrum of the phosphor powder is generally too wide, and it has been difficult to break through so far, which has led to limitations in the technology applied to the device. Therefore, people have become the research trend in the field of vector sub-points.

Nanomaterials have particles ranging from 1 to 100 nm and are classified according to size. Semiconductor nanocrystals (NCs) are also called quantum dots (QDs), and their particle size is classified into 0-dimensional nanomaterials. Nano materials are widely used in applications such as light-emitting diodes, solar cells, and biomarkers. Their unique optical, electrical, and magnetic properties make them an emerging industry.

Quantum dots have the characteristics of narrow half-height and wide, so the light-emitting characteristics applied to the light-emitting diode device can effectively solve the problem that the traditional fluorescent pink domain is not broad enough. Especially cause concern.

The disclosure relates to a quantum dot composite material and a method and application thereof.

a

1，0

b

1。 According to one aspect of the present disclosure, a quantum dot composite material is proposed. Quantum dot composites include all-inorganic perovskite quantum dots and are modified to protect the surface of all inorganic perovskite quantum dots. The all-inorganic perovskite quantum dots have a chemical formula of CsPb(Cl _a Br _1-ab I _b ) ₃ , of which 0

a

1,0

b

1.

a

1，0

b

1。 In accordance with another aspect of the present disclosure, a wavelength conversion film is provided that includes a quantum dot composite. Quantum dot composites include fully inorganic perovskite quantum dots with modified protection and are modified to protect the surface of the all inorganic perovskite quantum dots. The all-inorganic perovskite quantum dots have a chemical formula of CsPb(Cl _a Br _1-ab I _b ) ₃ , of which 0

a

1,0

b

1.

a

1，0

b

1，以及形成修飾性保護在該全無機鈣鈦礦量子點的表面上。 According to yet another aspect of the present disclosure, a method of producing a composite quantum dot, comprising the steps of: providing a full-inorganic perovskite of the quantum dot, wherein the quantum dot full-inorganic perovskite having the general chemical formula CsPb (Cl _a Br _1-ab I _b ) ₃ ,0

a

1,0

b

1, and the formation of a modification is protected on the surface of the all-inorganic perovskite quantum dot.

a

1，0

b

1。 According to still another aspect of the present disclosure, a light emitting device including a light emitting diode chip and a wavelength converting material is provided. The wavelength converting material is excited by the first light emitted by the light emitting diode to emit a second light different from the wavelength of the first light. The wavelength converting material includes a plurality of quantum dot composite materials. The quantum dot composites each comprise all inorganic perovskite quantum dots and are modified to protect the surface of the all inorganic perovskite quantum dots. The all-inorganic perovskite quantum dots have a chemical formula of CsPb(Cl _a Br _1-ab I _b ) ₃ , of which 0

a

1,0

b

1.

a

1，0

b

1。 In accordance with another aspect of the present disclosure, a quantum dot light emitting diode (QLED) is provided that includes a light emitting layer. The luminescent layer contains a quantum dot composite. Quantum dot composites include all-inorganic perovskite quantum dots and are modified to protect the surface of all inorganic perovskite quantum dots. The all-inorganic perovskite quantum dots have a chemical formula of CsPb(Cl _a Br _1-ab I _b ) ₃ , of which 0

a

1,0

b

1.

In order to better understand the above and other aspects of the present disclosure, the preferred embodiments are described below in detail with reference to the accompanying drawings.

11, 31, 41, 74‧‧‧ Quantum dot composites

13‧‧‧All inorganic perovskite quantum dots

15A‧‧‧Mesoporous particles

15B‧‧‧ polymer coating

15C, 15D‧‧‧Modified protection

102, 202, 302, 3102, 3202‧‧‧Light Emitter Wafer

302s‧‧‧Glossy

3102S1, 3102S2‧‧‧ surface

104, 204‧‧‧Base

106‧‧‧ epitaxial structure

108‧‧‧First type semiconductor layer

110‧‧‧ active layer

112‧‧‧Second type semiconductor layer

114, 214, 2048, 3214, 3214R, 3214G, 3214B, 3214W‧‧ First electrode

116, 216, 2050, 3216‧‧‧ second electrode

318, 418, 518, 618, 718, 818, 918, 1018, 1118, 1218, 1318, 1418, 1518, 1618, 1718, 2018, 2218, 2318 ‧ ‧ LED package structure

320, 2761‧‧‧ base

321‧‧‧ Gujing District

322‧‧‧ cup wall

323, 1523‧‧‧ accommodating space

324, 324A, 324B, 724, 3124, 3124R, 3124G, 3124B, 3124W‧‧‧ wavelength conversion layer

326‧‧‧Reflection wall

326s‧‧‧ top

428, 628‧‧‧ structural components

428a, 628a‧‧‧ accommodating area

530, 1830, 1830A, 1830B, 1830C, 1830D‧‧‧ optical layers

1737, 2837‧‧‧Transparent colloid

1134‧‧‧Interval space

1536‧‧‧Electrical parts

1822‧‧‧Light source

1838‧‧‧Side-light backlight module

1938‧‧‧Direct type backlight module

2538, 2638, 3038‧‧‧ illuminating devices

1820‧‧‧Frame

1840‧‧‧reflector

1842‧‧‧Light guide plate

1842a‧‧‧Glossy

1842b‧‧‧Glossy

1844‧‧‧reflector

1946‧‧‧Optical layer

2051‧‧‧Upright part

2053‧‧‧cross leg

2352‧‧‧ Conductive plate

2354‧‧‧ Conductive strip

1855, 2155, 2555‧‧‧ boards

2456, 2756, 2856, 2956‧‧‧ plug-in lighting unit

2157‧‧‧ pads

2658‧‧‧Light shell

2660‧‧‧heatsink

2762‧‧‧First substrate

2764‧‧‧second substrate

2766‧‧‧First electrode prong

2768‧‧‧Second electrode pins

2770‧‧‧First contact pad

2772‧‧‧Second contact pad

2774‧‧‧Insulation

3076‧‧‧shell

3078‧‧‧Transparent lampshade

3080‧‧‧Circuit board

3082‧‧‧ drive circuit

3184‧‧‧Lighting device

3577, 3677‧‧‧ wavelength conversion film

3579‧‧‧Transparent substrate

3687‧‧‧Transparent substrate

3689‧‧ ‧ thin layer of quantum dots

3763‧‧‧Lighting layer

3765‧‧‧ hole injection layer

3767‧‧‧electron injection layer

3769‧‧‧Anode

3775‧‧‧ cathode

S‧‧‧ spacer

FIG. 1A illustrates a method of fabricating a quantum dot composite according to an embodiment.

FIG. 1B illustrates the structure of a quantum dot composite according to an embodiment.

FIG. 2 illustrates the structure of a quantum dot composite according to an embodiment.

FIG. 3A illustrates the structure of a quantum dot composite according to an embodiment.

FIG. 3B illustrates the structure of a quantum dot composite according to an embodiment.

Figure 3C depicts a quantum dot composite material modified for ligand exchange according to an embodiment.

FIG. 3D illustrates a quantum dot composite material modified to protect microvesicles formed by microemulsification according to an embodiment.

FIG. 3E illustrates a quantum dot composite material modifiedly protected as a coating of a cerium-containing material according to an embodiment.

FIG. 3F illustrates a quantum dot composite material modifiedly protected as a coating of a cerium-containing material according to an embodiment.

Figure 4 illustrates the structure of a quantum dot composite according to an embodiment.

FIG. 5 illustrates a light emitting diode wafer according to an embodiment.

FIG. 6 illustrates a light emitting diode wafer according to an embodiment.

FIG. 7 illustrates a light emitting diode package structure according to an embodiment.

FIG. 8 illustrates a light emitting diode package structure according to an embodiment.

FIG. 9 illustrates a light emitting diode package structure according to an embodiment.

FIG. 10 illustrates a light emitting diode package structure according to an embodiment.

FIG. 11 illustrates a light emitting diode package structure according to an embodiment.

FIG. 12 illustrates a light emitting diode package structure according to an embodiment.

FIG. 13 illustrates a light emitting diode package structure according to an embodiment.

FIG. 14 illustrates a light emitting diode package structure according to an embodiment.

FIG. 15 illustrates a light emitting diode package structure according to an embodiment.

FIG. 16 illustrates a light emitting diode package structure according to an embodiment.

FIG. 17 illustrates a light emitting diode package structure according to an embodiment.

FIG. 18 illustrates a light emitting diode package structure according to an embodiment.

FIG. 19 illustrates a light emitting diode package structure according to an embodiment.

FIG. 20 illustrates a light emitting diode package structure according to an embodiment.

FIG. 21 illustrates a light emitting diode package structure according to an embodiment.

Figure 22 illustrates a display module in accordance with an embodiment.

Figure 23 illustrates a display module in accordance with an embodiment.

FIG. 24 is a perspective view of a light emitting diode package structure according to an embodiment.

Figure 25 is a perspective view of a light emitting diode package structure in accordance with an embodiment.

FIG. 26 is a perspective view of a light emitting diode package structure according to an embodiment.

27 to 30 illustrate a method of fabricating a light emitting device according to an embodiment.

FIG. 31 illustrates a plug-in type light emitting unit according to an embodiment.

Figure 32 illustrates a plug-in lighting unit in accordance with an embodiment.

Figure 33 illustrates a plug-in lighting unit in accordance with an embodiment.

Figure 34 illustrates a light emitting device in accordance with an embodiment.

Figure 35 illustrates a wavelength conversion film in accordance with an embodiment.

Figure 36 illustrates a wavelength conversion film in accordance with an embodiment.

Figure 37 is a perspective view of a quantum dot light emitting diode according to an embodiment.

38 is a perspective view of a portion of a pixel corresponding to a pixel device according to an embodiment.

Figure 39 is a cross-sectional view showing a portion of a pixel corresponding to a pixel device according to an embodiment.

Figure 40 is an X-ray diffraction pattern of an all-inorganic perovskite quantum dot according to an embodiment.

Figure 41 is a photoexcited fluorescence spectrum of an all inorganic perovskite quantum dot according to an embodiment.

Figure 42 shows the CIE map position of an all inorganic perovskite quantum dot according to an embodiment.

Figure 43 is an X-ray diffraction pattern of an all-inorganic perovskite quantum dot according to an embodiment. Spectrum.

Figure 44 is a photoexcited fluorescence spectrum of an all inorganic perovskite quantum dot according to an embodiment.

Figure 45 shows the CIE map position of an all inorganic perovskite quantum dot according to an embodiment.

Figure 46 is a photoexcited fluorescence spectrum of an all inorganic perovskite quantum dot according to an embodiment.

Figure 47 is a photoexcited fluorescence spectrum of the comparative inorganic non-modified perovskite quantum dots (PQDs) and the example quantum dot composites (MP-PQDs).

Figure 48 is a photo-excited fluorescence spectrum of a light-emitting diode package structure.

Figure 49 is a photo-excited fluorescence spectrum of the light-emitting diode package structure.

Figure 50 is a CIE map position of the LED package structure.

Figure 51 is a photo-excited fluorescence spectrum of inorganic perovskite quantum dots and quantum dot composites.

Figure 52 is the thermal stability test results of inorganic perovskite quantum dots and quantum dot composites.

Figure 53 shows the results of the thermal reproducibility test for quantum dot composites.

Figure 54 is a graph showing the light output power of the light-emitting diode package structure over time.

Figure 55 shows the comparison of the emission spectra of quantum dot composites with typical green phosphors.

Fig. 56 is a view showing a comparison of electroluminescence spectra of the white light emitting diode package structures of the embodiment and the comparative example.

Fig. 57 shows an NTSC comparison of the white light emitting diode package structure of the embodiment and the comparative example.

Figure 58 is a graph showing the results of thermal stability testing of the quantum dot composite of the examples and the inorganic perovskite quantum dots of the comparative examples by a thermal controller.

Figure 59A is a graph showing the results of a thermal cycle test of the quantum dot composite of the examples.

Figure 59B is a graph showing the results of a comparative inorganic perovskite quantum dot thermal cycle test.

Figure 60 is a temperature resistance test curve of the light-emitting diode package structure of the embodiment, wherein the quantum dot composite material comprises a modified protection of green all-inorganic perovskite quantum dots and polymer coating.

Figure 61 is a temperature resistance test curve of the light-emitting diode package structure of the embodiment, wherein the quantum dot composite material comprises green all-inorganic perovskite quantum dots, and the modification protection is a two-layer film structure, wherein the inner layer is a germanium-containing material package. The cover and the outer layer are polymer coating bodies.

Figure 62 is a temperature resistance test curve of the light-emitting diode package structure of the embodiment, wherein the quantum dot composite material comprises green all-inorganic perovskite quantum dots, and the modified protection system is mesoporous particles.

Fig. 63 is a temperature resistance test curve of the light emitting diode package structure of the comparative example.

Fig. 64 is a graph showing the results of photostability test of the quantum dot composite of the example and the comparative inorganic perovskite quantum dot.

Fig. 65 is a comparison of the wavelength conversion film emission spectrum (λ ex = 460 nm) and the chlorophyll a and leaf green b absorption spectra of the examples.

Figure 66A is a comparison of the luminescence spectrum of the comparative red luminescent powder with the chlorophyll a absorption spectrum.

Figure 66B is a comparison of the luminescence spectrum of the comparative red luminescent powder with the chlorophyll a absorption spectrum.

Figure 66C shows the luminescence spectrum and chlorophyll a absorption light of the comparative example red phosphor Comparison of the spectrum.

Embodiments of this disclosure present a quantum dot composite and its use. Quantum dot composites include all-inorganic perovskite quantum dots that exhibit a half-height and wide spectral spectroscopy and excellent solid color. In addition, all inorganic perovskite quantum dots have a modified protection on the surface, so the quantum dot composite has good stability.

It should be noted that the disclosure does not show all possible embodiments, and other embodiments not disclosed in the disclosure may also be applied. Furthermore, the dimensional ratios on the drawings are not drawn in proportion to the actual product. Therefore, the description and illustration are for illustrative purposes only and are not intended to be limiting. In addition, the description in the embodiments, such as the detailed structure, the process steps, the material application, and the like, are for illustrative purposes only and are not intended to limit the scope of the disclosure. The details of the steps and the details of the embodiments may be varied and modified in accordance with the needs of the actual application process without departing from the spirit and scope of the disclosure. The same/similar symbols are used to describe the same/similar elements.

In an embodiment, the quantum dot composite comprises all inorganic perovskite quantum dots and is modified to protect on the surface of the all inorganic perovskite quantum dots.

a

1，0

b

1。實施例之全無機鈣鈦礦量子點能受第一光線激發而發出不同於第一光線之波長的第二 光線，並具有具優異的量子效率，能展現出半高寬窄的放光光譜及優異的純色性，因此光線波長轉換效果佳，且應用在發光裝置能提升發光效果。在一實施例中，第一光線是由藍光發光二極體或紫外光發光二極體所發射出來。 The all-inorganic perovskite quantum dots have a chemical formula of CsPb(Cl _a Br _1-ab I _b ) ₃ , of which 0

a

1,0

b

1. The all-inorganic perovskite quantum dot of the embodiment can be excited by the first light to emit a second light having a wavelength different from that of the first light, and has excellent quantum efficiency, and can exhibit a half-height width and wide spectral spectrum and excellent The pure color, therefore, the light wavelength conversion effect is good, and the application in the light-emitting device can enhance the luminous effect. In one embodiment, the first light is emitted by a blue light emitting diode or an ultraviolet light emitting diode.

The all-inorganic perovskite quantum dots can be changed by the composition and/or size adjustment, and the luminescence color (second ray wavelength) can be changed by the band width (Band Gap), for example, from blue, green to red gamut. Flexible use.

The all inorganic perovskite quantum dots have a nanometer size. For example, the total inorganic perovskite quantum dots have a particle size ranging from 1 nm to 100 nm, such as from 1 nm to 20 nm.

a

1；或全無機鈣鈦礦量子點具有化學通式CsPb(Br_1-bI_b)₃，其中0

b

1。 For example, a fully inorganic perovskite quantum dot has the chemical formula CsPb(Cl _a Br _1-a ) ₃ , where 0

a

1; or an all-inorganic perovskite quantum dot having the chemical formula CsPb(Br _1-b I _b ) ₃ , wherein 0

b

1.

1時，全無機鈣鈦礦量子點為藍色量子點。及/或，粒徑範圍7nm至10nm的全無機鈣鈦礦量子點為藍色量子點。一實施例中，從藍色量子點激發出之(第二)光線的波峰位置為400nm至500nm，半高寬為10nm至30nm。 In embodiments, the all inorganic perovskite quantum dots can be blue quantum dots. For example, in the example of the chemical formula CsPb(Cl _a Br _1-a ) ₃ , when 0<a

At 1 o'clock, the all-inorganic perovskite quantum dots are blue quantum dots. And/or, the all inorganic perovskite quantum dots having a particle size ranging from 7 nm to 10 nm are blue quantum dots. In one embodiment, the (second) light excited from the blue quantum dots has a peak position of 400 nm to 500 nm and a full width at half maximum of 10 nm to 30 nm.

b

1時，全無機鈣鈦礦量子點為紅色量子點。及/或，粒徑範圍10nm 至14nm的全無機鈣鈦礦量子點為的紅色量子點。一實施例中，從紅色量子點激發出之(第二)光線的波峰位置為570nm至700nm，半高寬為20nm至60nm。 In embodiments, the fully inorganic perovskite quantum dots can be red quantum dots. For example, in the example of the chemical formula CsPb(Br _1-b I _b ) ₃ , when 0.5

b

At 1 o'clock, the all inorganic perovskite quantum dots are red quantum dots. And/or red quantum dots of all inorganic perovskite quantum dots having a particle size ranging from 10 nm to 14 nm. In one embodiment, the (second) light excited from the red quantum dots has a peak position of 570 nm to 700 nm and a full width at half maximum of 20 nm to 60 nm.

b<0.5時，全無機鈣鈦礦量子點為綠色量子點。及/或，粒徑範圍8nm至12nm的全無機鈣鈦礦量子點為的綠色量子點。一實施例中，綠色全無機鈣鈦礦量子點激發出之(第二)光線的波峰位置範圍為500~570nm，半高寬範圍為15nm~40nm。 In embodiments, the all inorganic perovskite quantum dots can be green quantum dots. For example, in the example having the chemical formula CsPb(Br _1-b I _b ) ₃ , when 0

When b < 0.5, the all inorganic perovskite quantum dots are green quantum dots. And/or green quantum dots of all inorganic perovskite quantum dots having a particle size ranging from 8 nm to 12 nm. In one embodiment, the (second) light excited by the green all-inorganic perovskite quantum dots has a peak position ranging from 500 to 570 nm and a full width at half maximum ranging from 15 nm to 40 nm.

The modified protection formed on the all-inorganic perovskite quantum dots provides protection for all inorganic perovskite quantum dots, avoiding the properties of all inorganic perovskite quantum dots being affected by other adjacent wavelength converting materials, for example, avoiding different compositions The ion exchange phenomenon between the all-inorganic perovskite quantum dots affects the desired composition and optical properties, including adverse effects such as changes in the position of the light, and the broadening of the FWHM. Modular protection also avoids the loss of properties of all inorganic perovskite quantum dots from external environments such as heat, light, moisture, and oxygen. Therefore, the modified protection of quantum dot composites can improve the environmental tolerance of inorganic perovskite quantum dots, and can protect the total inorganic perovskite quantum dots to maintain the desired composition and optical properties, improve stability and service life. It can also further enhance the reliability of device products using quantum dot composite materials.

In an embodiment, the cosmetic protection may include mesoporous particles, inorganic shell coatings, ligand exchanges, microcapsule coatings, polymer coatings, and cerium-containing materials. Body, oxide or nitride dielectric coating The combination or combination of the above provides physical or chemical modification protection properties to the all inorganic perovskite quantum dots.

In an embodiment, the surface of the mesoporous particles has a plurality of pores. The mesoporous particles may have a particle size of from 200 nm to 1000 nm. The pore size of the mesoporous particles is greater than or substantially equal to the particle size of the all inorganic perovskite quantum dots to accommodate the inclusion of all inorganic perovskite quantum dots in the pores. For example, the size of the pores may be from 1 nm to 100 nm, or from 2 nm to 20 nm. Due to the high specific surface area of mesoporous particles, it can strongly adsorb all-inorganic perovskite quantum dots, and the all-inorganic perovskite quantum dots can enter the pores by physical adsorption. In embodiments, the material of the mesoporous particles may comprise silica, which has high transparency and does not degrade the light extraction efficiency from the all-inorganic perovskite quantum dots.

The material of the inorganic shell coating may include a binary or ternary compound containing a Group II, Group III, Group V, Group VI element, such as CuInS2, PbS, PbSe, PbTe, PbSeS, PbSeTe, PbSTe or SnPbS, or A III-V or II-VI binary, ternary compound such as ZnS, ZnSe, ZnTe, CdS, CdTe, ZnCdS, InP, one of which may comprise a combination of two or more materials.

In an embodiment, the ligand exchange may be formed by subjecting the surface of the all-inorganic perovskite quantum dot to a ligand exchange treatment, for example, Tri-n-octyl phosphine oxide (TOPO), 9,10- 1,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide; DOPO, oleic acid, oligomer A sulfur-containing compound or a combination thereof provides a ligand. Polymers can also be polymerized with each other, or Polymerization reaction.

In one embodiment, the ligand exchange system is formed by subjecting the surface of the all-inorganic perovskite quantum dots to a sulfurization treatment. The vulcanization treatment includes, for example, a ligand exchange reaction of a wholly inorganic perovskite quantum dot with a sulfur-containing compound. For example, the sulfur-containing compound used in the sulfurization treatment may include a sulfur-containing quaternary ammonium salt.

In one embodiment, for example, the vulcanization treatment to form a ligand exchange can include providing a oleic acid mixed with an all-inorganic perovskite quantum dot and providing a sulfur treatment reagent having a sulfur-containing compound and oleic acid, Inorganic perovskite quantum dot mixing. In one embodiment, the sulfur treatment reagent is prepared by mixing an organic solution in which a halogen-containing quaternary ammonium salt is dissolved with an aqueous solution in which an alkali metal sulfide is dissolved to obtain a sulfur treatment reagent. For example, the halogen-containing quaternary ammonium salt used in the sulfurization treatment may have the formula R ₄ NX, wherein R is an alkyl group, an alkoxy group, a phenyl group, or an alkylphenyl group of one to twenty carbon chains. , X is chlorine, bromine or iodine. Alkylphenyl groups such as tolyl and p-xylylene. Halogen-containing quaternary ammonium salts such as dodecyldimethylammonium bromide, cetyltrimethylammonium chloride, tetrabutylammonium bromide. An alkali metal sulfide such as sodium sulfide or the like.

The sulfur-containing quaternary ammonium salt may, for example, include didodecyl dimethylammonium sulfide (SDDA), Hexadecyltrimethylammonium sulfide (SHTA), tetrabutylammonium sulfide ( Tetrabutylammonium sulfide, STBA), etc. Di-dodecyldimethylammonium sulfide (SDDA) can be obtained by reacting dodecyldimethylammonium bromide (cation) with a sulfide ion (anion). Cetyltrimethylammonium sulfide (SHTA) can be obtained by reacting cetyltrimethylammonium chloride with sulfur ions. Tetrabutylammonium sulfide (STBA) can be tetrabutyl The ammonium bromide is reacted with sulfur ions.

The microcapsule coating can coat all inorganic perovskite quantum dots or mesoporous particles. In addition, microvesicles can be used to form micelles to coat all inorganic perovskite quantum dots or mesoporous particles in a microcapsule coating.

The polymer coating can coat all inorganic perovskite quantum dots. In some embodiments, the polymer coating can coat mesoporous particles in which all inorganic perovskite quantum dots are buried in the pores. For example, the material of the polymer coating may include polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyethylene isophthalate (PEN), poly benzene. Ethylene (PS), polyvinylidene fluoride (PVDF), polyvinyl acetate (PVAC), polypropylene (PP), polyamine (PA), polycarboxylate (PC), polyimine (PI), Epoxy, silicone or a combination of the above. In one embodiment, the polymerization of the material may be carried out in a state in which the wholly inorganic perovskite quantum dots are mixed with one or more of the above materials, such that the polymer coating forms a coated inorganic nitrile quantum dot/ Mesoporous particles to form a quantum dot composite. The polymer coating body may be a polymer coating body.

The ruthenium-containing material coating may include SiOR, SiO ₂ , Si(OR) ₄ or Si(OMe) ₃ C ₃ H ₆ S, or ruthenium titanium oxide-based coating, or other silica material, or The combination. In some embodiments, the ruthenium containing material coating provides chemical modification protection to the all inorganic perovskite quantum dots.

The oxidized or nitrided dielectric coating may include a metal oxide or a metal nitride such as Al ₂ O ₃ , Si ₃ N ₃ , or the like, or a combination thereof.

1A to 4 illustrate quantum dot compounding according to an embodiment The structure of the material.

Referring to FIGS. 1A and 1B, the quantum dot composite 11 includes all-inorganic perovskite quantum dots 13 and is modified and protected on the surface of the all-inorganic perovskite quantum dots 13, in this case, the modified protective system mesoporous particles 15A. Wherein the wholly inorganic perovskite quantum dot 13 is buried in the pores of the mesoporous particles 15A.

Referring to FIG. 2, the difference between the quantum dot composite material 31 and the quantum dot composite material 11 shown in FIG. 1 is that the modification protection further includes the cladding body 15B covering the mesoporous particles 15A and buried in the mesopores. Fully inorganic perovskite quantum dots 13 in the pores of particle 15A. For example, the covering body 15B includes a polymer coating body (for example, a high molecular polymer), a cerium-containing material coating body (such as SiO ₂ or the like), an oxidized or nitrided dielectric coating body (such as Al ₂ O _{3 ).} , Si ₃ N _{3 ,} etc.), one of the microcapsule coatings or any combination of the above. Further, the material of the covering body 15B is light transmissive.

Referring to FIGS. 3A and 3B, the quantum dot composite 41 includes an all-inorganic perovskite quantum dot 13 and a modifying protection 15C formed on the surface of the all-inorganic perovskite quantum dot 13. The modifying protection 15C can be an inorganic shell coating. As shown, the all-inorganic perovskite quantum dots 13 are coated as a core-shell structure with a core-shell structure as a core and a surface of a core coated with an inorganic shell coating. The material of the inorganic shell coating may include a binary or ternary compound containing a Group II, Group III, Group V, Group VI element, such as CuInS2, PbS, PbSe, PbTe, PbSeS, PbSeTe, PbSTe or SnPbS, or A III-V or II-VI binary, ternary compound such as ZnS, ZnSe, ZnTe, CdS, CdTe, ZnCdS, InP, one of which may comprise a combination of two or more materials.

In one embodiment, the modifying protection 15C can include ligand exchange. As shown in Fig. 3C, the ligand on the surface of the all-inorganic perovskite quantum dot 13 is modified to carry out polymerization of a common leaving group at the end of the ligand (e.g., Br, I, etc.). The end of the ligand has an oligomer or a polymer structure.

In one embodiment, the cosmetic protection 15C may comprise a microcapsule coating which can coat the all-inorganic perovskite quantum dots 13 by microvesicles to form a surface having hydrophilic or hydrophobic properties, such as 3D illustration.

In one embodiment, the decorative protection 15C may comprise a single layer film (shell layer) formed by a coating of a cerium-containing material or a multilayer film structure, wherein the cerium-containing material coating body may include SiOR, SiO ₂ , Si (OR) ₄ or Si(OMe) ₃ C ₃ H ₆ S, or a ruthenium titanium oxide coating, or other silica material, or a combination thereof. As shown in Figure 3E, the fully inorganic perovskite quantum dots 13 are modified by a SiOR material. As shown in Figure 3F, the fully inorganic perovskite quantum dots 13 are coated with a SiO ₂ material.

Referring to FIG. 4, the difference between the quantum dot composite material 71 and the quantum dot composite material 41 shown in FIG. 3 is that the modification protection 15D is a two-layer (shell) multilayer film structure, which may include none. The shell layer coating body, the ligand exchange, the microcapsule coating body, the cerium-containing material coating body, or any combination thereof. In other embodiments, the cosmetic protection may be a (shell) structure of other more layers of film, such as a three layer film, a four layer film, or the like.

The quantum dot composite of the present disclosure is not limited to the structures as shown in Figs. 1 to 4, but may be suitably modulated according to the embodiment of the present disclosure.

In an embodiment, for example, a quantum dot composite can be formed as After the quantum dot composite material of the structure shown in FIG. 3A to 3F or FIG. 4 or other quantum dot composite material having more protective layers such as a three-layer film or a four-layer film, the mesoporous particles are buried. Formed in the pores. For example, after performing a ligand exchange reaction or a vulcanization treatment on the surface of the all-inorganic perovskite quantum dot, a total inorganic perovskite quantum dot having a ligand exchanged on the surface is buried in the pore of the mesoporous particle to form a quantum. Point composite.

In the embodiment, for example, the quantum dot composite material may use a quantum dot composite material having a structure as shown in FIG. 3A to 3F or FIG. 4 or other modifiers having more layers such as a three-layer film or a four-layer film. After the protected quantum dot composite is buried in the pores of the mesoporous particles, an additional coating is formed on the mesoporous particles (for example, a polymer coating, a coating containing a niobium material, or an oxidized or nitrided dielectric coating). Body) formed by coating. For example, the all-inorganic perovskite quantum dots having the surface-formed ligand exchange are first embedded in the pores of the mesoporous particles, and then the mesoporous particles are coated with the coating to form a quantum dot composite.

The quantum dot composite according to the embodiment can be applied to wavelength conversion elements, light-emitting devices, and photoelectric conversion devices in various fields, such as a light-emitting diode package, a quantum dot light-emitting diode (QLED), a plant illumination, a display, a solar cell, Bio Label, Biosensor, Image Sensor, etc. Since the quantum dot composite material according to the embodiment has excellent light-emitting characteristics and stable properties, it can be applied to various products to improve product performance stability and service life.

In an embodiment, the light emitting device comprises a light emitting diode chip and a wavelength converting material. The wavelength converting material includes the above quantum dot composite. Wavelength conversion material The (quantum dot composite) can be excited by the first light emitted by the light emitting diode chip to emit a second light different from the wavelength of the first light.

The modification protection of the at least one all-inorganic perovskite quantum dot CsPb (Cl _a Br _1-ab I _b ) ₃ can be selected as a stability and service life of the quantum dot composite lifting device.

The wavelength conversion material (or wavelength conversion layer) in the light-emitting device is not limited to use a single quantum dot composite material/all inorganic perovskite quantum dots, in other words, two or more types may be used (ie, two, three, four types). , or more) different types of modified quantum dot composites and/or all inorganic perovskite quantum dots of different properties. The nature of the all inorganic perovskite quantum dots can vary depending on the chemical formula and/or size of the material.

For example, the all-inorganic perovskite quantum dots include a first all-inorganic perovskite quantum dot of a different nature mixed with a second all-inorganic perovskite quantum dot. In other embodiments, the all-inorganic perovskite quantum dots further comprise a third, fourth, or more total inorganic having properties different from the first all-inorganic perovskite quantum dots and the second all-inorganic perovskite quantum dots. Perovskite quantum dot mixing.

For example, the first fully inorganic perovskite quantum dot and the second fully inorganic perovskite quantum dot can have different particle sizes. In other embodiments, the all-inorganic perovskite quantum dots further comprise a third, fourth, or more of a particle size different from the first all-inorganic perovskite quantum dot and the second all-inorganic perovskite quantum dot. Inorganic perovskite quantum dots.

a

1， 0

b

1。其中，第一全無機鈣鈦礦量子點與第二全無機鈣鈦礦量子點具有不同的a。及/或，第一全無機鈣鈦礦量子點與第二全無機鈣鈦礦量子點具有不同的b。此概念亦可延伸至具有第三、第四、或更多種之全無機鈣鈦礦量子點的例子中。 In some embodiments, the first all-inorganic perovskite quantum dot and the second all-inorganic perovskite quantum dot each have a chemical formula of CsPb(Cl _a Br _1-ab I _b ) ₃ ,0

a

1, 0

b

1. Wherein, the first all-inorganic perovskite quantum dot has a different a from the second all-inorganic perovskite quantum dot. And/or, the first all-inorganic perovskite quantum dot has a different b than the second all-inorganic perovskite quantum dot. This concept can also be extended to examples having third, fourth, or more all-inorganic perovskite quantum dots.

b

1的紅色量子點、具有化學通式CsPb(Br_1-bI_b)₃且0

b<0.5的綠色量子點及具有化學通式CsPb(Cl_aBr_1-a)₃且0<a

1的藍色量子點所組成的群組。或者，第一全無機鈣鈦礦量子點與第二全無機鈣鈦礦量子點可選自粒徑範圍為10nm至14nm的紅色全無機鈣鈦礦量子點、粒徑範圍為8nm至12nm的綠色全無機鈣鈦礦量子點及粒徑範圍為7nm至10nm的藍色全無機鈣鈦礦量子點所組成的群組。 For example, the first all-inorganic perovskite quantum dot and the second all-inorganic perovskite quantum dot may be selected from the group consisting of the chemical formula CsPb(Br _1-b I _b ) ₃ and 0.5

b

a red quantum dot of 1 having a chemical formula of CsPb(Br _1-b I _b ) ₃ and 0

Green quantum dots with b<0.5 and having the chemical formula CsPb(Cl _a Br _1-a ) ₃ and 0<a

A group of 1 blue quantum dots. Alternatively, the first all-inorganic perovskite quantum dot and the second all-inorganic perovskite quantum dot may be selected from red all-inorganic perovskite quantum dots having a particle size ranging from 10 nm to 14 nm, and having a particle size ranging from 8 nm to 12 nm. A group consisting of all inorganic perovskite quantum dots and blue all-inorganic perovskite quantum dots having a particle size ranging from 7 nm to 10 nm.

The wavelength converting material (or wavelength converting layer) may further comprise other fluorescent materials, including inorganic fluorescent materials and/or organic fluorescent materials, for use with fully inorganic perovskite quantum dots. Here, the inorganic fluorescent material/organic fluorescent material may refer to other kinds of fluorescent quantum dots and/or non-quantum dot structures different from the all-inorganic perovskite quantum dot CsPb (Cl _a Br _1-ab I _b ) ₃ described. Fluorescent material.

For example, inorganic fluorescent materials such as aluminate fluorescent powder (such as LuYAG, GaYAG, YAG, etc.), phthalic acid fluorescent powder, sulfide fluorescent powder, nitride fluorescent powder, fluoride fluorescent powder, etc. . The organic fluorescent material comprises a group consisting of a single molecule structure, a multi-molecular structure, an oligomer (Oligomer), and a polymer, the compound having a perylene group, having a benzimidazole group. a compound of a group, a compound having a Naphthalene group, a compound having an anthracene group, a compound having a phenanthrene group, a compound having a fluorene group, a compound having a 9-fluorenone group, a compound having a carbazole group, having a glutarimide a compound of a group, a compound having a 1,3-diphenylbenzene group, a compound having a benzopyrene group, a compound having a pyrene group, a compound having a pyridine group, a compound having a thiophene group, having 2,3-dihydro a compound of the -1H-benzo[de]isoquinoline-1,3-dione group, a compound having a benzimidazole group, and a combination thereof. For example, a yellow fluorescent material such as YAG:Ce, and/or an inorganic yellow fluorescent powder of an oxynitride, a cerium salt, a nitride component, and/or an organic yellow fluorescent powder. The red fluorescent powder includes, for example, a fluorinated phosphor A ₂ [MF ₆ ]: Mn ⁴⁺ , wherein A is a group selected from the group consisting of Li, Na, K, Rb, Cs, NH ₄ , and combinations thereof. M is a group selected from the group consisting of Ge, Si, Sn, Ti, Zr, and combinations thereof. Alternatively, the red phosphor may include (Sr, Ca)S: Eu, (Ca, Sr) ₂ Si ₅ N ₈ :Eu, CaAlSiN ₃ :Eu, (Sr,Ba) ₃ SiO ₅ :Eu.

b<0.5及/或粒徑範圍8nm至12nm之綠色量子點(例如CsPbBr₃)的量子點複合材料與紅色螢光粉K₂SiF₆：Mn⁴⁺之混合。 In one embodiment, for example, the illuminating device uses a blue light emitting diode wafer, and the wavelength converting material is used to contain a chemical formula of CsPb(Br _1-b I _b ) ₃

A mixture of a quantum dot composite of b < 0.5 and/or a green quantum dot (eg, CsPbBr ₃ ) having a particle size ranging from 8 nm to 12 nm and a red phosphor K ₂ SiF ₆ :Mn ⁴⁺ .

Quantum dot composite materials can be applied to various light-emitting devices such as lighting fixtures or light-emitting modules (front light modules, backlight modules) for display screens of mobile phones, television screens, etc., panel pixels or sub-pictures of displays have advantages . Again, when using The more inorganic inorganic perovskite quantum dots of different compositions, that is, the more inorganic perovskite quantum dots using different kinds of illuminating waves, the wider the emission spectrum of the illuminating device, and even the full spectrum requirement. . Therefore, the use of the quantum dot composite material containing the all-inorganic perovskite quantum dots can improve the color gamut of the display device, and can also effectively improve the color purity and color authenticity of the display device, and can also greatly enhance the NTSC.

For example, the light emitting device can be applied to a light emitting diode package structure. Taking a white light emitting diode package structure as an example, the wavelength conversion material contains green all-inorganic perovskite quantum dots and red all-inorganic perovskite quantum dots excited by blue light-emitting diodes, or the wavelength converting material contains red all-inorganic calcium-titanium. The mineral quantum dots and the yellow fluorescent powder are excited by the blue light emitting diode, or the wavelength converting material contains the green all inorganic perovskite quantum dots and the red fluorescent powder excited by the blue light emitting diode, or the wavelength converting material contains the red all inorganic Perovskite quantum dots, green all-inorganic perovskite quantum dots, and blue all-inorganic perovskite quantum dots are excited by ultraviolet light-emitting diodes.

FIG. 5 illustrates a light emitting diode wafer 102 in accordance with an embodiment. The light emitting diode wafer 102 includes a substrate 104, an epitaxial structure 106, a first electrode 114 and a second electrode 116. The epitaxial structure 106 includes a first type semiconductor layer 108, an active layer 110, and a second type semiconductor layer 112 that are sequentially stacked from the substrate 104. The first electrode 114 and the second electrode 116 are connected to the first type semiconductor layer 108 and the second type semiconductor layer 112, respectively. Substrate 104 may comprise an insulating material (eg, a sapphire material) or a semiconductor material. The first type semiconductor layer 108 and the second type semiconductor layer 112 have opposite conductivity types. For example, the first type semiconductor layer 108 has an N type semiconductor layer, and the second type semiconductor layer 112 has a P type semiconductor layer, wherein the first electrode 114 is an N electrode, The second electrode 116 is a P electrode. For example, the first type semiconductor layer 108 has a P type semiconductor layer, and the second type semiconductor layer 112 has an N type semiconductor layer, wherein the first electrode 114 is a P electrode and the second electrode 116 is an N electrode. The mounting type of the light-emitting diode wafer 102 may be any of a face-up mounter or a flip chip mounter. In the flip-chip mounting process, the LED array 102 is inverted such that the first electrode 114 and the second electrode 116 face the substrate, such as a circuit board, and the contact pads are electrically connected through the solder.

FIG. 6 illustrates a light emitting diode chip 202 according to another embodiment, which is a vertical light emitting diode chip. The light emitting diode chip 202 includes a substrate 204 and an epitaxial structure 106. The epitaxial structure 106 includes a first type semiconductor layer 108, an active layer 110, and a second type semiconductor layer 112 that are sequentially stacked from the substrate 204. The first electrode 214 and the second electrode 216 are respectively connected to the substrate 204 and the second type semiconductor layer 112. The material of the substrate 204 is selected from the group consisting of metals, alloys, conductors, semiconductors, and combinations thereof. The substrate 204 may include a semiconductor material of the same conductivity type as the first type semiconductor layer 108, or a conductive material such as metal or the like that may form an ohmic contact with the first type semiconductor layer 108. For example, the first type semiconductor layer 108 has an N type semiconductor layer, and the second type semiconductor layer 112 has a P type semiconductor layer, wherein the first electrode 214 is an N electrode and the second electrode 216 is a P electrode. For example, the first type semiconductor layer 108 has a P type semiconductor layer, and the second type semiconductor layer 112 has an N type semiconductor layer, wherein the first electrode 214 is a P electrode and the second electrode 216 is an N electrode.

In an embodiment, the P-type semiconductor layer may be a P-type GaN material, and the N-type semiconductor layer may be an N-type GaN material. In an embodiment, the P-type semi-conductive The bulk layer may be a P-type AlGaN material, and the N-type semiconductor layer may be an N-type AlGaN material. The active layer 110 is a multiple quantum well structure.

In one embodiment, the first light emitted by the LED chips 102, 202 has a wavelength of 220 nm to 480 nm. In one embodiment, the LED chips 102, 202 can be ultraviolet light emitting diode chips, and emit a first light having a wavelength of 200 nm to 400 nm. In one embodiment, the LED chips 102, 202 can be blue LED chips, and the first light is emitted at a wavelength of 430 nm to 480 nm.

In an embodiment, the wavelength converting material of the light emitting device can be included in the wavelength converting layer and/or doped in the light transmissive substrate. In some embodiments, the wavelength converting material can be coated on the light emitting face of the light emitting diode wafer. The following illuminating devices are exemplified by some devices using wavelength converting materials.

FIG. 7 illustrates a light emitting diode package structure 318 according to an embodiment. The LED package structure 318 includes a light emitting diode chip 302, a susceptor 320, a wavelength conversion layer 324, and a reflective wall 326. The pedestal 320 has a solid crystal region 321 and a cup wall 322 surrounding the die bonding region 321 and defines an accommodating space 323. The LED chip 302 is disposed in the accommodating space 323 and can be fixed on the die bonding region 321 of the susceptor 320 through an adhesive. The wavelength conversion layer 324 is located on the light exiting side of the LED substrate 302. In more detail, the wavelength conversion layer 324 is located above the accommodating space 323 corresponding to the light emitting surface 302s of the LED array 302, and is located at the cup wall 322. On the top. The reflective wall 326 can be disposed on the outer sidewall of the wavelength conversion layer 324 and positioned on the top surface of the cup wall 322. The reflective wall 326 is formed of a material having light reflective properties and low light leakage, such as reflective glass, quartz, light reflective patches, polymeric plastics, or other suitable materials. The polymer plastic may be polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polystyrene (PS), polyethylene (PP), nylon. One of materials (polyamide, PA), polycarbonate (PC), epoxy, and silicone, or a combination of two or more materials. The light reflecting power of the reflective wall 326 can be varied by adding other filler particles. The filler particles can have composite materials of different particle sizes or different materials. The material of the filler particles may be, for example, titanium oxide (TiO ₂ ), cerium oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), boron nitride (BN), zinc oxide (ZnO), or the like. This concept can be applied to other embodiments, and the description will not be repeated later. In this example, the gap between the LED chip 302 and the wavelength conversion layer 324 is separated by an air gap in the accommodating space 323 defined by the cup wall 322. In other words, the space 323 is accommodated. Other materials in contact with the LED substrate 302 are not filled.

In an embodiment, the wavelength conversion layer 324 includes one or more wavelength converting materials. Therefore, the luminescent properties of the LED package structure 318 can be adjusted through the wavelength conversion layer 324. In some embodiments, the wavelength conversion layer 324 also includes a light transmissive substrate into which the wavelength converting material is doped. The wavelength conversion layer 324 includes, for example, at least one of the above-described quantum dot composite materials doped in a light transmissive substrate. In an embodiment, the light transmissive substrate comprises a transparent colloid, and the transparent colloid material may be polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polystyrene (polyvinyl methacrylate). Polystyrene, PS), Polypropylene (PP), Polyamide (PA), Polycarbonate (polycarbonate, PC), polyimide (PI), polydimethylsiloxane (PDMS), epoxy (epoxy) and silicone (silicone) or one or more of two or more materials The combination. In an embodiment, the light transmissive substrate comprises a glass material or a ceramic material, and the quantum dot composite material is mixed with a glass material or a ceramic material to form a glass quantum dot film or a ceramic quantum dot film.

In some embodiments, the wavelength conversion layer 324 and the LED array 302 (in this case, the accommodating space 323) are spaced apart from each other, which may prevent the wavelength conversion layer 324 from being thermally stable due to being too close to the LED substrate 302. The chemical and chemical stability can improve the lifetime of the wavelength conversion layer 324 and improve the reliability of the LED package structure product. This concept will not be repeated.

In other alternative embodiments, the air gap defined in the accommodating space 323 of the cup wall 322 may also be filled in a transparent encapsulant (not shown), and the transparent encapsulant may be polymethyl methacrylate. , PMMA), polyethylene terephthalate (PET), polystyrene (PS), polyethylene (polypropylene, PP), nylon (polyamide, PA), polycarbonate (polycarbonate, PC) One of materials such as polyimide (PI), polydimethylsiloxane (PDMS), epoxy, and silicone or a combination of two or more materials. In some embodiments, the transparent encapsulant can be doped with one or more wavelength converting materials. In other alternative embodiments, one or more wavelength converting materials may be coated on the light emitting face of the light emitting diode chip 302. Therefore, in addition to the wavelength conversion layer 324, the light-emitting properties of the light-emitting diode package structure are more transparent to the package (transparent) containing the wavelength conversion material. The colloid and/or the coating containing the wavelength converting material on the surface of the LED substrate 302 is adjusted. The type of wavelength conversion material of the wavelength conversion layer 324, the encapsulant and/or the coating may be appropriately adjusted depending on the actual needs of the product. This concept can be applied to other embodiments, and the description will not be repeated later.

FIG. 8 illustrates a light emitting diode package structure 418 according to an embodiment, which is different from the light emitting diode package structure 318 of FIG. The light emitting diode package structure 418 further includes a structural element 428 for supporting, encapsulating, or protecting the wavelength conversion layer 324. As shown, the structural component 428 has a receiving region 428a for receiving the wavelength converting layer 324 such that the upper and lower surfaces of the wavelength converting layer 324 are covered by the structural component 428. The structural component 428 is located on the top surface of the cup wall 322, thereby supporting the wavelength conversion layer 324 above the accommodating space 323 corresponding to the light emitting surface 302s of the LED array 302. The structural component 428 is preferably formed of a transparent material or a light transmissive material to avoid blocking light exiting the wavelength conversion layer 324. Structural element 428 can also have encapsulating material properties. For example, structural component 428 can comprise a material of quartz, glass, polymeric plastic. Alternatively, structural element 428 can be used to protect wavelength conversion layer 324 from foreign materials such as moisture or oxygen that can adversely affect its properties. In an embodiment, the structural element 428 may be a barrier film and/or a tantalum titanium oxide disposed on the surface of the wavelength conversion layer 324 to block foreign matter such as moisture or oxygen. The niobium titanium oxide may be a glass material such as SiTiO4, which has light transmittance and oxidation resistance, and may be coated or film-coated on the surface of the wavelength conversion layer 324. The material of the barrier film may include an inorganic material such as a metal oxide (such as SiO ₂ , Al ₂ O _{3 ,} etc.) or a metal nitride (such as Si ₃ N _{3 ,} etc.), and may be a multilayer barrier film for coating or filming. The mode is disposed on the surface of the wavelength conversion layer 324. This concept can be applied to other embodiments, and the description will not be repeated later. The reflective wall 326 can be disposed around the outer sidewall of the structural member 428 and on the top surface of the cup wall 322.

FIG. 9 illustrates a light emitting diode package structure 518 according to an embodiment, which differs from the light emitting diode package structure 418 of FIG. 8 in that the light emitting diode package structure 518 further includes an optical layer 530 disposed on the reflective wall. 326 and structural element 428. The optical layer 530 can be used to adjust the light exit path of the light. For example, the optical layer 530 may be a transparent colloid containing diffusing particles, and the transparent colloid may be polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polystyrene. (polystyrene, PS), polyethylene (polypropylene, PP), nylon (polyamide, PA), polycarbonate (polycarbonate, PC), polyimide (PI), polydimethylsiloxane (polydimethylsiloxane, One of materials such as PDMS), epoxy, and silicone or a combination of two or more materials. The diffusion particles may include TiO ₂ , SiO ₂ , Al ₂ O ₃ , BN, ZnO, etc., and the diffusion particles may have the same or different particle diameters. This concept can also be applied to other embodiments, and the description will not be repeated. For example, the light emitting diode package structure 318 of FIG. 7 , the light emitting diode package structure 618 of FIG. 10 , the light emitting diode package structure 1018 of FIG. 14 , and the like may be applied to the wavelength conversion layer 324 . An optical layer 530 is disposed to adjust the light exiting path of the light.

FIG. 10 illustrates a light emitting diode package structure 618 according to an embodiment, which is described below with respect to the light emitting diode package structure 318 of FIG. hair The photodiode package structure 618 further includes a structural component 628 having a receiving region 628a for receiving and supporting the wavelength conversion layer 324 across the LED substrate 302 and disposed on the cup wall 322. The structural component 628 located on the lower surface of the wavelength conversion layer 324 is preferably formed of a transparent material or a light transmissive material to avoid blocking the light output of the wavelength conversion layer 324, such as quartz, glass, polymer, or other suitable material. This concept can be applied to other embodiments, and the description will not be repeated later.

FIG. 11 illustrates a light emitting diode package structure 718 according to an embodiment, which is different from the light emitting diode package structure 318 of FIG. The light emitting diode package structure 718 omits the wavelength conversion layer 324 and the reflective wall 326 shown in FIG. 7 , and includes the wavelength conversion layer 724 filled in the accommodating space 323 . The wavelength conversion layer 724 can include a transparent colloid and a wavelength converting material. A transparent colloid can be used as the encapsulant, and the wavelength converting material can be doped in the transparent colloid. The wavelength conversion layer 724 can cover the LED array 302 or can be further overlying the pedestal 320. The transparent colloid of the wavelength conversion layer 724 may be polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polystyrene (PS), or polyethylene (polypropylene). PP), nylon (polyamide, PA), polycarbonate (polycarbonate, PC), polyimide (PI), polydimethylsiloxane (PDMS), epoxy (epoxy) and silicone One of the materials such as (silicone) or a combination of two or more materials.

FIG. 12 illustrates a light emitting diode package structure 818 according to an embodiment, which differs from the light emitting diode package structure 718 of FIG. 11 in that the light emitting diode package structure 818 further includes a structural element 628 that spans the wavelength. The conversion layer 724 is disposed on the cup wall 322 to protect the wavelength conversion material of the wavelength conversion layer 724 from damage by foreign matter such as moisture or oxygen. In an embodiment, the structural element 628 may be a barrier film and/or a niobium titanium oxide disposed on the surface of the wavelength conversion layer 724 to block foreign matter such as moisture or oxygen. The niobium titanium oxide may be a glass material such as SiTiO4, which has light transmittance and oxidation resistance, and may be coated or film-coated on the surface of the wavelength conversion layer 724. The material of the barrier film may include an inorganic material such as a metal oxide (such as SiO ₂ , Al ₂ O _{3 ,} etc.) or a metal nitride (such as Si ₃ N _{3 ,} etc.), and may be a multilayer barrier film for coating or filming. The mode is disposed on the surface of the wavelength conversion layer 724.

FIG. 13 illustrates a light emitting diode package structure 918 including a pedestal 320, a light emitting diode chip 302, a wavelength conversion layer 324, and a reflective wall 326, in accordance with an embodiment. The light emitting diode chip 302 is disposed on the die bonding region of the susceptor 320. The wavelength conversion layer 324 is disposed on the light-emitting surface of the light-emitting diode wafer 302. The reflective wall 326 is disposed on the sidewall of the wavelength conversion layer 324. The LED chip 302 can be electrically connected to the pedestal 320 through a wire that passes through an opening (not shown) of the wavelength conversion layer 324.

FIG. 14 illustrates a light emitting diode package structure 1018 according to an embodiment, which is different from the light emitting diode package structure 918 of FIG. The LED package 1018 further includes an optical layer 530 disposed on the wavelength conversion layer 324 and the reflective wall 326. The LED chip 302 can be electrically connected to the pedestal 320 through a wire that passes through the opening of the wavelength conversion layer 324 and the optical layer 530 (not shown). hit The wire can be pulled out of the upper or side surface of the optical layer 530.

FIG. 15 illustrates a light emitting diode package structure 1118 including a light emitting diode chip 302, a wavelength conversion layer 324, and a reflective wall 326, in accordance with an embodiment. The reflective wall 326 surrounds the sidewall of the LED chip 302 and forms a spacer space 1134 having a higher height than the LED array 302. The wavelength conversion layer 324 is disposed on the top surface 326s of the reflective wall 326, and is separated from the LED substrate 302 by the spacing space 1134. This can avoid affecting the wavelength conversion layer 324 due to being too close to the LED substrate 302. The thermal stability and chemical stability can improve the lifetime of the wavelength conversion layer 324 and improve the reliability of the LED package structure. This concept will not be repeated.

FIG. 16 illustrates a light emitting diode package structure 1218 according to an embodiment, which differs from the light emitting diode package structure 1118 of FIG. 15 in that a wavelength conversion layer 324 is disposed on an inner sidewall of the reflective wall 326.

FIG. 17 illustrates a light emitting diode package structure 1318 according to an embodiment, which is different from the light emitting diode package structure 1118 of FIG. 15 as follows. The light emitting diode package structure 1318 further includes a structural element 428, wherein the wavelength conversion layer 324 is disposed in the receiving region 428a defined by the structural element 428. Structural element 428 can be used to support, encapsulate, or protect wavelength conversion layer 324. The structural elements 428 overlying the wavelength conversion layer 324 are disposed on the top surface 326s of the reflective wall 326, while the light emitting diode wafer 302 is spaced apart by a spacing space 1134. The structural component 428 is preferably formed of a transparent material or a light transmissive material to avoid blocking the light output of the wavelength conversion layer 324, and may also have packaging material properties. For example, the structural component 428 may include materials of quartz, glass, and polymer plastic. . Alternatively, structural element 428 can be used to protect wavelength conversion layer 324 from foreign materials such as moisture or oxygen that can adversely affect its properties. In an embodiment, the structural element 428 may be a barrier film and/or a tantalum titanium oxide disposed on the surface of the wavelength conversion layer 324 to block foreign matter such as moisture or oxygen. The niobium titanium oxide may be a glass material such as SiTiO4, which has light transmittance and oxidation resistance, and may be coated or film-coated on the surface of the wavelength conversion layer 324. The material of the barrier film may include an inorganic material such as a metal oxide (such as SiO ₂ , Al ₂ O _{3 ,} etc.) or a metal nitride (such as Si ₃ N _{3 ,} etc.), and may be a multilayer barrier film for coating or filming. The mode is disposed on the surface of the wavelength conversion layer 324.

In one embodiment, the spacing space 1134 can be an empty space that is not filled with other materials. In another embodiment, the spacing space 1134 is preferably formed of a transparent material or a light transmissive material to avoid blocking light from the wavelength conversion layer 324, such as quartz, glass, polymer, or other suitable materials.

b

1；及/或，紅色全無機鈣鈦礦量子點的粒徑範圍為10nm至14nm。紅色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃上可形成有修飾性保護，亦即波長轉換層324/波長轉換層724係包含紅色量子點複合材料。 In an embodiment, the light emitting diode package structure 318, 418, 518, 618, 718, 818, 918, 1018, 1118, 1218 or 1318 emits white light. The light emitting diode chip 302 can be a blue light emitting diode wafer. The wavelength conversion layer 324 / wavelength conversion layer 724 comprises yellow phosphor powder YAG: Ce and red all inorganic perovskite quantum dots CsPb (Br _1-b I _b ) ₃ , of which 0.5

b

1; and/or, the red all inorganic perovskite quantum dots have a particle size ranging from 10 nm to 14 nm. The red all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ can be modified to protect, that is, the wavelength conversion layer 324 / wavelength conversion layer 724 comprises a red quantum dot composite.

b<0.5，紅色全無機鈣鈦礦量子點的b參數範圍0.5

b

1；及/或，綠色全無機鈣鈦礦量子點的粒徑範圍為8nm至12nm，紅色全無機鈣鈦礦量子點的粒徑範圍為10nm至14nm。實施例中，綠色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃與紅色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃其中至少一者係包含在量子點複合材料中，亦即其表面係形成有修飾性保護。 In an embodiment, the light emitting diode package structure 318, 418, 518, 618, 718, 818, 918, 1018, 1118, 1218 or 1318 emits white light. The light emitting diode chip 302 can be a blue light emitting diode wafer. The wavelength conversion layer 324 / wavelength conversion layer 724 comprises a green all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ and a red all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ , wherein green The b-parameter range of the all-inorganic perovskite quantum dots is 0.

b<0.5, b parameter range of red all inorganic perovskite quantum dots 0.5

b

1; and/or, the green all-inorganic perovskite quantum dots have a particle size ranging from 8 nm to 12 nm, and the red all-inorganic perovskite quantum dots have a particle size ranging from 10 nm to 14 nm. In an embodiment, at least one of the green all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ and the red all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ is included in the quantum dot In the composite material, that is, the surface thereof is formed with a modification protection.

1，綠色全無機鈣鈦礦量子點的b參數範圍是0

b<0.5，紅色全無機鈣鈦礦量子點的b參數範圍0.5

b

1；及/或，藍色全無機鈣鈦礦量子點的粒徑範圍為7nm至10nm，綠色全無機鈣鈦礦量子點的粒徑範圍為8nm至12nm，紅色全無機鈣鈦礦量子點的粒徑範圍為10nm至14nm。實施例中，藍色全無機鈣鈦礦量子點CsPb(Cl_aBr_1-a)₃、綠色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃及紅色 全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃其中至少一者係包含在量子點複合材料中，亦即其表面係形成有修飾性保護。 In an embodiment, the light emitting diode package structure 318, 418, 518, 618, 718, 818, 918, 1018, 1118, 1218 or 1318 emits white light, and the light emitting diode chip 302 may be an ultraviolet light emitting diode chip. The wavelength conversion layer 324 / wavelength conversion layer 724 comprises a blue all-inorganic perovskite quantum dot CsPb (Cl _a Br _1-a ) ₃ , a green all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ , red The all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ , wherein the a parameter range of the blue all-inorganic perovskite quantum dot is 0<a

1, the b parameter range of the green all-inorganic perovskite quantum dot is 0

b<0.5, b parameter range of red all inorganic perovskite quantum dots 0.5

b

1; and/or, the blue all-inorganic perovskite quantum dots have a particle size ranging from 7 nm to 10 nm, and the green all-inorganic perovskite quantum dots have a particle size ranging from 8 nm to 12 nm, and the red all-inorganic perovskite quantum dots The particle size ranges from 10 nm to 14 nm. In the examples, the blue all-inorganic perovskite quantum dot CsPb(Cl _a Br _1-a ) ₃ , the green all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ and the red all-inorganic perovskite quantum At least one of the points CsPb(Br _1-b I _b ) ₃ is contained in the quantum dot composite, that is, the surface system is formed with a modification protection.

b<0.5，紅色全無機鈣鈦礦量子點的b參數範圍0.5

b

1；及/或，綠色全無機鈣鈦礦量子點為粒徑範圍8nm至12nm，紅色全無機鈣鈦礦量子點的粒徑範圍為10nm至14nm，但本揭露並不限於此。實施例中，綠色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃及紅色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃其中至少一者係包含在量子點複合材料中，亦即其表面係形成有修飾性保護。發光二極體晶片302可以覆晶的方式藉由其第一電極302a與第二電極302b電性連接在基座或電路板(未顯示)。 FIG. 18 illustrates a light emitting diode package structure 1418 including a light emitting diode chip 302, a reflective wall 326, and a wavelength conversion layer 324, in accordance with an embodiment. The reflective wall 326 is disposed on a side surface of the light emitting diode wafer 302. The wavelength conversion layer 324 is disposed on the upper surface (light-emitting surface) of the light-emitting diode wafer 302. The wavelength conversion layer 324 may include a first wavelength conversion layer 324A and a second wavelength conversion layer 324B of different properties. In one embodiment, for example, the first wavelength conversion layer 324A contains a red all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ , and the peak position of the light-emitting wavelength is between 570 nm and 700 nm, and the second wavelength The conversion layer 324B contains a green all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ , and the peak position of the light-emitting wavelength is between 500 nm and 570 nm, wherein the b-parameter range of the green all-inorganic perovskite quantum dot is 0.

b<0.5, b parameter range of red all inorganic perovskite quantum dots 0.5

b

1; and/or, the green all-inorganic perovskite quantum dots have a particle size ranging from 8 nm to 12 nm, and the red all-inorganic perovskite quantum dots have a particle diameter ranging from 10 nm to 14 nm, but the disclosure is not limited thereto. In an embodiment, at least one of the green all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ and the red all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ is included in the quantum dot In the composite material, that is, the surface thereof is formed with a modification protection. The LED chip 302 can be electrically connected to the susceptor or the circuit board (not shown) by the first electrode 302a and the second electrode 302b.

FIG. 19 illustrates a light emitting diode package structure 1518 including a pedestal 320, a light emitting diode chip 302, and a wavelength conversion layer 724 according to an embodiment. With reflective wall 326. The reflective wall 326 is disposed on the pedestal 320 and defines an accommodating space 1523. The LED chip 302 is disposed in the accommodating space 1523 and electrically connected to the conductive member 1536 on the susceptor 320 in a flip chip manner. The wavelength conversion layer 724 is filled in the accommodating space 1523 and is in contact with the luminescent diode chip 302.

FIG. 20 illustrates a light emitting diode package structure 1618 according to an embodiment, which differs from the light emitting diode package structure 1518 of FIG. 19 in that the light emitting diode package structure 1618 further includes a structural element 628 configured for wavelength conversion. The layer 724 and the reflective wall 326 are used to encapsulate and protect the wavelength conversion layer 724 to prevent the wavelength conversion layer 724 from being damaged by external substances such as moisture or oxygen. In an embodiment, the structural element 628 may be a barrier film and/or a niobium titanium oxide disposed on the surface of the wavelength conversion layer 724 to block foreign matter such as moisture or oxygen. The niobium titanium oxide may be a glass material such as SiTiO4, which has light transmittance and oxidation resistance, and may be coated or film-coated on the surface of the wavelength conversion layer 724 and the reflection wall 326. The material of the barrier film may include an inorganic material such as a metal oxide (such as SiO ₂ , Al ₂ O _{3 ,} etc.) or a metal nitride (such as Si ₃ N _{3 ,} etc.), and may be a multilayer barrier film for coating or filming. The manner is disposed on the surface of the wavelength conversion layer 724 and the reflective wall 326.

b

1；及/或，紅色全無機鈣鈦礦量子點的粒徑範圍為10nm至14nm。實施例中，紅色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃係包含在量子點複合材料中，亦即其表面係形成有 修飾性保護。 In an embodiment, the LED package structures 1518, 1618 emit white light. The light emitting diode chip 302 can be a blue light emitting diode wafer. The wavelength conversion layer 724 comprises a red all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ and a yellow phosphor YAG:Ce, wherein 0.5

b

1; and/or, the red all inorganic perovskite quantum dots have a particle size ranging from 10 nm to 14 nm. In the examples, the red all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ is included in the quantum dot composite, that is, the surface system is formed with a modification protection.

b<0.5，紅色全無機鈣鈦礦量子點的b參數範圍0.5

b

1；及/或，綠色全無機鈣鈦礦量子點的粒徑範圍為8nm至12nm，紅色全無機鈣鈦礦量子點的粒徑範圍為10nm至14nm。實施例中，綠色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃及紅色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃其中至少一者係包含在量子點複合材料中，亦即其表面係形成有修飾性保護。 In an embodiment, the LED package structures 1518, 1618 emit white light. The light emitting diode chip 302 can be a blue light emitting diode wafer. The wavelength conversion layer 724 comprises a green all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ and a red all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ , wherein the green all-inorganic perovskite The b parameter range of a quantum dot is 0.

b<0.5, b parameter range of red all inorganic perovskite quantum dots 0.5

b

1; and/or, the green all-inorganic perovskite quantum dots have a particle size ranging from 8 nm to 12 nm, and the red all-inorganic perovskite quantum dots have a particle size ranging from 10 nm to 14 nm. In an embodiment, at least one of the green all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ and the red all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ is included in the quantum dot In the composite material, that is, the surface thereof is formed with a modification protection.

1，綠色全無機鈣鈦礦量子點的b參數範圍是0

b<0.5，紅色全無機鈣鈦礦量子點的b參數範圍0.5

b

1；及/或，藍色全無機鈣鈦礦量子點的粒徑範圍為7nm至10nm，綠色全無機鈣鈦礦量子點的粒徑範圍為8nm至12nm，紅色全無機鈣鈦礦量子點的粒徑範圍為10nm至14nm。實施例中，藍色全無機鈣鈦礦量子點CsPb(Cl_aBr_1-a)₃、綠色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃及紅色 全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃其中至少一者係包含在量子點複合材料中，亦即其表面係形成有修飾性保護。 In an embodiment, the LED package structures 1518, 1618 emit white light, and the LED chip 302 can be an ultraviolet light emitting diode chip. The wavelength conversion layer 724 comprises a blue all-inorganic perovskite quantum dot CsPb (Cl _a Br _1-a ) ₃ , a green all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ , and a red all-inorganic perovskite The quantum dot CsPb(Br _1-b I _b ) ₃ , wherein the a parameter range of the blue all-inorganic perovskite quantum dot is 0<a

1, the b parameter range of the green all-inorganic perovskite quantum dot is 0

b<0.5, b parameter range of red all inorganic perovskite quantum dots 0.5

b

1; and/or, the blue all-inorganic perovskite quantum dots have a particle size ranging from 7 nm to 10 nm, and the green all-inorganic perovskite quantum dots have a particle size ranging from 8 nm to 12 nm, and the red all-inorganic perovskite quantum dots The particle size ranges from 10 nm to 14 nm. In the examples, the blue all-inorganic perovskite quantum dot CsPb(Cl _a Br _1-a ) ₃ , the green all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ and the red all-inorganic perovskite quantum At least one of the points CsPb(Br _1-b I _b ) ₃ is contained in the quantum dot composite, that is, the surface system is formed with a modification protection.

b<0.5，紅色全無機鈣鈦礦量子點的b參數範圍0.5

b

1；及/或，綠色全無機鈣鈦礦量子點為粒徑範圍8nm至12nm，紅色全無機鈣鈦礦量子點的粒徑範圍為10nm至14nm，但本揭露並不限於此。實施例中，綠色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃及紅色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃其中至少一者係包含在量子點複合材料中，亦即其表面係形成有修飾性保護。透明膠體1737可用作封裝膠體，覆蓋波長轉換層324與基座320。 FIG. 21 illustrates a light emitting diode package structure 1718 including a pedestal 320, a light emitting diode chip 302, a wavelength conversion layer 324, and a transparent colloid 1737, in accordance with an embodiment. The LED chip 302 is electrically connected to the susceptor 320 in a flip chip manner. The wavelength conversion layer 324 is disposed on the upper surface and the side surface of the light emitting diode wafer 302 and may extend onto the upper surface of the susceptor 320. In one embodiment, for example, the first wavelength conversion layer 324A contains a red all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ , and the peak position of the light-emitting wavelength is between 570 nm and 700 nm, and the second wavelength The conversion layer 324B contains a green all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ , and the peak position of the light-emitting wavelength is between 500 nm and 570 nm, wherein the b-parameter range of the green all-inorganic perovskite quantum dot is 0.

b<0.5, b parameter range of red all inorganic perovskite quantum dots 0.5

b

1; and/or, the green all-inorganic perovskite quantum dots have a particle size ranging from 8 nm to 12 nm, and the red all-inorganic perovskite quantum dots have a particle diameter ranging from 10 nm to 14 nm, but the disclosure is not limited thereto. In an embodiment, at least one of the green all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ and the red all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ is included in the quantum dot In the composite material, that is, the surface thereof is formed with a modification protection. The transparent colloid 1737 can be used as an encapsulant covering the wavelength conversion layer 324 and the pedestal 320.

FIG. 22 illustrates an application of the edge-lit backlight module 1838 according to an embodiment. The edge-lit backlight module 1838 includes a frame 1820, a light source 1822, and a light guide plate 1842. Light source 1822 includes a circuit board 1855 located on frame 1820 and as The plurality of LED package structures 1318 are shown on the circuit board 1855. The light-emitting diode package 1318 has a light-emitting direction that is one of the light-emitting surfaces 1842a of the light guide plate 1842. The frame 1820 has a reflective sheet 1840. The light emitted from the LED package structure 1318 can be concentrated on the light guide plate 1842. The light is then emitted through the light-emitting surface 1842b of the light guide plate 1842 to the upper optical layer 1830 (or display panel). Optical layer 1830 can include, for example, optical layers 1830A, 1830B, 1830C, 1830D. For example, optical layers 1830A and 1830D can be diffusion sheets, and optical layers 1830B, 1830C can be brightness enhancing sheets. A reflective sheet 1844 can be disposed beneath the light guide plate 1842 to further direct light up to the optical layers 1830A, 1830B, 1830C, 1830D (or display panel, not shown). The edge-lit backlight module of the embodiment is not limited to the use of the light-emitting diode package structure 1318 as described in FIG. 17, and other light-emitting diode package structures disclosed herein may be used.

FIG. 23 illustrates a direct-lit backlight module 1938 that includes a secondary optics 1946 disposed on the LED package structure 1318, in accordance with an embodiment. The light exiting direction of the light emitting diode package structure 1318 is toward the optical layer 1830. The reflective sheet 1840 can facilitate the concentrated emission of light from the LED package structure 1318 to the optical layer 1830 (or display panel). The direct type backlight module of the embodiment is not limited to the use of the light emitting diode package structure 1318 as described in FIG. 17, and other light emitting diode package structures disclosed herein may be used.

24 and 25 are respectively a perspective view and a perspective view of a light emitting diode package structure 2018 according to an embodiment. The LED package structure 2018 includes a first electrode 2048 and a second electrode 2050 for electrically connecting to the outside, such as It is connected to the pad 2157 of the circuit board 2155. As shown, the first electrode 2048 and the second electrode 2050 have an L shape, the upright portion 2051 is attached to the bottom of the base 320 and the base 320 is exposed, and the leg portion 2053 connecting the upright portion 2051 is embedded in the cup wall. The cup wall 322 is exposed in 322. The positive and negative electrodes of the LED chip 302 can be electrically connected to the first electrode 2048 and the upright portion 2051 of the second electrode 2050. The wavelength conversion layer 724 is filled in the accommodating space 323 defined by the susceptor 320 and the cup wall 322.

FIG. 26 is a perspective view of a light emitting diode package structure 2218 according to an embodiment, which is different from the light emitting diode package structure 2018 shown in FIGS. 24 and 25 by an L-shaped first electrode 2048 and The second electrode 2050 has an upright portion 2051 extending beyond the base 320 and the cup wall 322, and the leg portion 2053 is connected to the upright portion 2051 and extends in a direction away from the cup wall 322 to electrically connect the circuit board 2155. Pad 2157.

In some embodiments, the LED package structure 2018 of FIG. 24 and FIG. 25 and the LED package structure 2218 of FIG. 26 have a base 320 and a cup wall 322 which are made of a transparent material, so that the light is emitted. The light emitted by the polar body chip 302 can be directly emitted from the light emitting surface (not blocked by the opaque material or reflected by the reflective material) to emit the LED package structures 2018, 2218, for example, the light can be directed upward in the direction perpendicular to the pedestal 320. The lower two sides are shot, and the wide angle (for example, greater than 180 degrees) is emitted.

27 to 30 illustrate a method of fabricating a light emitting device according to an embodiment.

Referring to FIG. 27, the conductive plate 2352 is patterned to be on the conductive plate. 2352 forms a plurality of conductive strips 2354 that are separated from each other. The conductive plate 2352 can be patterned in a etched manner. Then, the light emitting diode package structure 2318 is disposed on the conductive plate 2352, wherein the first electrode and the second electrode (not shown) of the light emitting diode package structure 2318 correspond to the conductive strip 2354, so that the light emitting diode package structure 2318 The conductive plate 2352 is electrically connected. In one embodiment, a reflow process can be performed to bond the first electrode and the second electrode to different conductive strips 2354. Then, the conductive plate 2352 is subjected to a cutting step to obtain a plug-in type light-emitting unit 2456 as shown in Fig. 28. In one embodiment, the cutting can be performed in a punch manner.

Referring to FIG. 29, the plug-in type light-emitting unit 2456 is then inserted on the circuit board 2555 to obtain a light-emitting device 2538 having a light-emitting strip type. The plug-in type light emitting unit 2456 can be electrically connected to the circuit board 2555 by the conductive strips 2354 as the first electrodes and the second electrodes. In one embodiment, the circuit board 2555 has a drive circuit that can be used to provide the power required for the plug-in illumination unit 2456 to function.

Referring to FIG. 30, a light-emitting device 2538 having a light-emitting strip type is disposed on the heat sink 2660, and a lamp housing 2658 is disposed to cover the light-emitting device 2538 to obtain a light-emitting device 2638 having a lamp structure.

In an embodiment, the LED package structure 2318 can apply, for example, the LED package structures 318, 418, 518, 618, 718, 818, 918, 1018, 1118, 1218, as described in FIGS. 7-21. 1318, 1418, 1518, 1618, 1718. In some embodiments, the LED package structure 2318 applies the LED package structures 318, 418, 518, 618, 718, and 818 of FIGS. 7 to 12, wherein the pedestal 320 and the cup wall 322 are transparent. Light-emitting diode crystal The light emitted by the sheet 302 can be directly emitted from the light emitting surface (not blocked by the opaque material or reflected by the reflective material) to emit the LED package structure 318, 418, 518, 618, 718, 818, 2318, for example, the light can be vertical It is emitted in the direction of the pedestal 320 to the upper and lower sides, and is emitted at a wide angle (for example, greater than 180 degrees).

b

1。及/或，紅色全無機鈣鈦礦量子點的粒徑範圍為10nm至14nm。實施例中，紅色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃係包含在量子點複合材料中，亦即其表面係形成有修飾性保護。 In some embodiments, the LED package 2318/plug-in lighting unit 2456 emits white light. The light emitting diode chip 302 can be a blue light emitting diode wafer, and the wavelength converting material comprises red all inorganic perovskite quantum dots CsPb(Br _1-b I _b ) ₃ and yellow fluorescent powder YAG:Ce, wherein 0.5

b

1. And/or, the red all inorganic perovskite quantum dots have a particle size ranging from 10 nm to 14 nm. In the examples, the red all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ is included in the quantum dot composite, that is, the surface system is formed with a modification protection.

b<0.5，紅色全無機鈣鈦礦量子點的b參數範圍0.5

b

1。及/或，綠色全無機鈣鈦礦量子點的粒徑範圍為8nm至12nm，紅色全無機鈣鈦礦量子點的粒徑範圍為10nm至14nm。實施例中，綠色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃及紅色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃其中至少一者係包含在量子點複合材料中，亦即其表面係形成有修飾性保護。 In an embodiment, the light emitting diode package structure 2318/plug-in light emitting unit 2456 emits white light. The light-emitting diode chip 302 can be a blue light-emitting diode wafer, and the wavelength conversion material comprises a green all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ and a red all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ , wherein the b parameter range of the green all-inorganic perovskite quantum dot is 0

b<0.5, b parameter range of red all inorganic perovskite quantum dots 0.5

b

1. And/or, the green all-inorganic perovskite quantum dots have a particle size ranging from 8 nm to 12 nm, and the red all-inorganic perovskite quantum dots have a particle size ranging from 10 nm to 14 nm. In an embodiment, at least one of the green all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ and the red all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ is included in the quantum dot In the composite material, that is, the surface thereof is formed with a modification protection.

1、綠色全無機鈣鈦礦量子點的b參數範圍是0

b<0.5，紅色全無機鈣鈦礦量子點的b參數範圍0.5

b

1。及/或，藍色全無機鈣鈦礦量子點的粒徑範圍為7nm至10nm，綠色全無機鈣鈦礦量子點的粒徑範圍為8nm至12nm，紅色全無機鈣鈦礦量子點的粒徑範圍為10nm至14nm。實施例中，藍色全無機鈣鈦礦量子點CsPb(Cl_aBr_1-a)₃、綠色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃及紅色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃其中至少一者係包含在量子點複合材料中，亦即其表面係形成有修飾性保護。 In an embodiment, the light emitting diode package structure 2318/plug-in light emitting unit 2456 emits white light. The light emitting diode chip 302 can be an ultraviolet light emitting diode chip, and the wavelength converting material comprises a blue all-inorganic perovskite quantum dot CsPb (Cl _a Br _1-a ) ₃ , and a green all-inorganic perovskite quantum dot CsPb ( Br _1-b I _b ) ₃ , red all inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ . The a parameter range of the blue all-inorganic perovskite quantum dot is 0<a

1. The b parameter range of the green all-inorganic perovskite quantum dot is 0.

b<0.5, b parameter range of red all inorganic perovskite quantum dots 0.5

b

1. And/or, the blue all-inorganic perovskite quantum dots have a particle size ranging from 7 nm to 10 nm, and the green all-inorganic perovskite quantum dots have a particle size ranging from 8 nm to 12 nm, and the particle size of the red all-inorganic perovskite quantum dots The range is from 10 nm to 14 nm. In the examples, the blue all-inorganic perovskite quantum dot CsPb(Cl _a Br _1-a ) ₃ , the green all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ and the red all-inorganic perovskite quantum At least one of the points CsPb(Br _1-b I _b ) ₃ is contained in the quantum dot composite, that is, the surface system is formed with a modification protection.

FIG. 31 illustrates a plug-in lighting unit 2756 in accordance with an embodiment. The plug-in type light emitting unit 2756 includes a light emitting diode chip 302, a base 2761, a first electrode pin 2766, and a second electrode pin 2768. The susceptor 2761 includes a first substrate 2762, a second substrate 2764, and an insulating layer 2774. The insulating layer 2774 is disposed between the first substrate 2762 and the second substrate 2764 to electrically isolate the first substrate 2762 and the second substrate 2764. The LED chip 302 is disposed on a die attach region in the susceptor 2761 serving as a die plate, wherein the LED chip 302 is disposed across the insulating layer 2774 and is flip-chip disposed on the first substrate 2762 and On the second substrate 2764, the positive and negative electrodes of the LED substrate 302 are electrically connected to the first contact pad 2770 and the second contact pad 2772 on the first substrate 2762 and the second substrate 2764, thereby electrically connecting First electrode pins 2766 and second electrode pins 2768 extending from the first substrate 2762 and the second substrate 2764, respectively. The LED chip 302 can be electrically connected to the first contact pad 2770 and the second contact pad 2772 by solder (not shown).

Figure 32 illustrates a plug-in lighting unit 2856 in accordance with another embodiment. The plug-in lighting unit 2856 includes a transparent colloid 2837 and a plug-in lighting unit 2756 as described in FIG. The transparent colloid 2837 covers the entire LED chip 302 and the pedestal 2761 and covers a portion of the first electrode pin 2766 and the second electrode pin 2768.

FIG. 33 illustrates a plug-in type light-emitting unit 2956 according to still another embodiment, which differs from the plug-in type light-emitting unit 2856 shown in FIG. 32 in that a transparent colloid 2837 covers the entire LED chip 302, and A portion of the surface of the pedestal 2761 on the same side as the illuminating diode chip 302 is covered, and the first electrode pin 2766 and the second electrode pin 2768 are not covered.

In an embodiment, the plug-in lighting unit 2856 or 2956 may include a wavelength converting material doped in the transparent colloid 2837, or a wavelength converting layer containing a wavelength converting material disposed on the surface of the LED wafer 302. In an embodiment, the transparent colloid 2837 can be any translucent polymer glue, such as PMMA, PET, PEN, PS, PP, PA, PC, PI, PDMS, Epoxy, silicone or other suitable materials, or Combination of the above. The transparent colloid 2837 can be doped with other substances according to actual needs to adjust the light properties. For example, diffusion particles can be doped to change the light path. The diffusion particles may include TiO ₂ , SiO ₂ , Al ₂ O ₃ , BN, ZnO, etc., and may have the same or different particle diameters.

Figure 34 illustrates a light emitting device 3038 in accordance with an embodiment. The bulb type illumination device 3038 includes a plug-in type illumination unit 2956, a housing 3076, a transparent cover 3078, and a circuit board 3080 as shown in FIG. The plug-in type light-emitting unit 2956 is inserted into the circuit board 3080 and electrically connected to the circuit board 3080, thereby being electrically connected to the driving circuit 3082 of the circuit board 3080. The plug-in lighting unit 2956, along with the circuit board 3080, is disposed in an accommodation space defined by the associated housing 3076 and the transparent shade 3078.

The transparent colloid disclosed in the disclosure may be any translucent polymer glue, for example, PMMA, PET, PEN, PS, PP, PA, PC, PI, PDMS, Epoxy, silicone or other suitable materials, or Combination of the above.

The transparent colloid can be doped with other substances according to actual needs to adjust the light properties. For example, diffusion particles can be doped to change the light path. The diffusion particles may include TiO ₂ , SiO ₂ , Al ₂ O ₃ , BN, ZnO, etc., and may have the same or different particle diameters.

The illuminating device of the embodiment is not limited to the above examples, and may also include other types of illuminating diode package structures, illuminating modules applied to display devices such as backlight modules or front light modules, or lighting devices. The lamp, bulb, or other type of structure.

A single light-emitting diode package structure unit is not limited to the use of a single light-emitting diode wafer, and two or more light-emitting diode chips of the same or different light-emitting colors/wavelengths may be used.

b

1。及/或，紅色全無機鈣鈦礦量子點的粒徑範圍為10nm至14nm。實施例中，紅色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃係包含在量子點複合材料中，亦即其表面係形成有修飾性保護。 In an embodiment, the LED package structures 2018, 2218 and the plug-in lighting units 2856, 2956 emit white light. The light emitting diode chip 302 can be a blue light emitting diode wafer, and the wavelength converting material comprises red all inorganic perovskite quantum dots CsPb(Br _1-b I _b ) ₃ and yellow fluorescent powder YAG:Ce, wherein 0.5

b

1. And/or, the red all inorganic perovskite quantum dots have a particle size ranging from 10 nm to 14 nm. In the examples, the red all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ is included in the quantum dot composite, that is, the surface system is formed with a modification protection.

b<0.5，紅色全無機鈣鈦礦量子點的b參數範圍0.5

b

1。及/或，綠色全無機鈣鈦礦量子點的粒徑範圍為8nm至12nm，紅色全無機鈣鈦礦量子點的粒徑範圍為10nm至14nm。實施例中，綠色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃及紅色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃其中至少一者係包含在量子點複合材料中，亦即其表面係形成有修飾性保護。 In an embodiment, the LED package structures 2018, 2218 and the plug-in lighting units 2856, 2956 emit white light. The light-emitting diode chip 302 can be a blue light-emitting diode wafer, and the wavelength conversion material comprises a green all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ and a red all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ , wherein the b parameter range of the green all-inorganic perovskite quantum dot is 0

b<0.5, b parameter range of red all inorganic perovskite quantum dots 0.5

b

1. And/or, the green all-inorganic perovskite quantum dots have a particle size ranging from 8 nm to 12 nm, and the red all-inorganic perovskite quantum dots have a particle size ranging from 10 nm to 14 nm. In an embodiment, at least one of the green all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ and the red all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ is included in the quantum dot In the composite material, that is, the surface thereof is formed with a modification protection.

1、綠色全無機鈣鈦礦量子點的b參 數範圍是0

b<0.5，紅色全無機鈣鈦礦量子點的b參數範圍0.5

b

1。及/或，藍色全無機鈣鈦礦量子點的粒徑範圍為7nm至10nm，綠色全無機鈣鈦礦量子點的粒徑範圍為8nm至12nm，紅色全無機鈣鈦礦量子點的粒徑範圍為10nm至14nm。實施例中，藍色全無機鈣鈦礦量子點CsPb(Cl_aBr_1-a)₃、綠色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃及紅色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃其中至少一者係包含在量子點複合材料中，亦即其表面係形成有修飾性保護。 In an embodiment, the LED package structures 2018, 2218 and the plug-in lighting units 2856, 2956 emit white light. The light emitting diode chip 302 can be an ultraviolet light emitting diode chip, and the wavelength converting material comprises a blue all-inorganic perovskite quantum dot CsPb (Cl _a Br _1-a ) ₃ , and a green all-inorganic perovskite quantum dot CsPb ( Br _1-b I _b ) ₃ , red all inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ . The a parameter range of the blue all-inorganic perovskite quantum dot is 0<a

1. The b parameter range of the green all-inorganic perovskite quantum dot is 0.

b<0.5, b parameter range of red all inorganic perovskite quantum dots 0.5

b

1. And/or, the blue all-inorganic perovskite quantum dots have a particle size ranging from 7 nm to 10 nm, and the green all-inorganic perovskite quantum dots have a particle size ranging from 8 nm to 12 nm, and the particle size of the red all-inorganic perovskite quantum dots The range is from 10 nm to 14 nm. In the examples, the blue all-inorganic perovskite quantum dot CsPb(Cl _a Br _1-a ) ₃ , the green all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ and the red all-inorganic perovskite quantum At least one of the points CsPb(Br _1-b I _b ) ₃ is contained in the quantum dot composite, that is, the surface system is formed with a modification protection.

The quantum dot composite of the examples can also be applied to a wavelength conversion film.

Figure 35 illustrates a wavelength conversion film 3577 comprising quantum dot composites (e.g., quantum dot composites 11, 31, 41, 71, shown in Figures 1 through 4, or other types), in accordance with an embodiment. The quantum dot composite) is combined with a transparent substrate 3579 in which the quantum dot composite is mixed in a transparent substrate 3579. The material of the transparent substrate 3579 may be polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polystyrene (PS), polyethylene (polypropylene, PP). , nylon (polyamide, PA), polycarbonate (polycarbonate, PC), polyimide (PI), polydimethylsiloxane (PDMS), epoxy (epoxy) and silicone (silicone) Or one of the materials or a combination of two or more materials. In an embodiment, the transparent substrate 3579 may comprise a glass material or a ceramic material, and the quantum dot composite material is mixed with a glass material or a ceramic material to form a glass quantum dot film or a ceramic quantum dot film. The transparent substrate 3579 can be flexible Or inflexible material.

Figure 36 illustrates a wavelength conversion film 3677 comprising a quantum dot composite (e.g., quantum dot composites 11, 31, 41, 71, shown in Figures 1 through 4, or other types) according to another embodiment. The quantum dot composite) and the transparent substrate 3687. The quantum dot composite can be formed on the transparent substrate 3687, for example, in a coating manner to form a thin layer of quantum dots 3689. The wavelength conversion film 3677 can be a flexible substrate or a non-flexible substrate. The material of the transparent substrate 3687 may be polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polystyrene (PS), polyethylene (polypropylene, PP). , nylon (polyamide, PA), polycarbonate (polycarbonate, PC), polyimide (PI), polydimethylsiloxane (PDMS), epoxy (epoxy) and silicone (silicone) Or one of the materials or a combination of two or more materials. In an embodiment, the transparent substrate 3687 comprises a glass material or a ceramic material.

b

1及/或粒徑範圍為10nm至14nm，放出之紅光的波長範圍在620nm至680nm。量子點複合材料具有修飾性保護在全無機 鈣鈦礦量子點上，能提高全無機鈣鈦礦量子點對太陽光的耐受性，增加產品之穩定性及使用壽命。 In the embodiment, the wavelength conversion films 3577 and 3677 as shown in FIG. 35 and FIG. 36 can be designed to convert wavelength light in the sunlight which is not beneficial to plant growth into a plant for absorption after absorbing sunlight. Light rays that can benefit from growth are emitted. For example, chlorophyll can absorb red light of 600-700 nm, and red light can promote plant growth, flowering and prolong flowering. For example, a quantum dot composite of a wavelength conversion film is a red all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ , of which 0.5

b

1 and/or particle size ranges from 10 nm to 14 nm, and the emitted red light has a wavelength in the range of 620 nm to 680 nm. Quantum dot composites have modified protection on all inorganic perovskite quantum dots, which can improve the tolerance of all inorganic perovskite quantum dots to sunlight and increase the stability and service life of the products.

In embodiments, wavelength converting materials including quantum dot composites can also be applied to the microsizer technology. Hereinafter, the quantum dot light-emitting diode and the pixel structure according to the embodiment will be described as an example.

b

1，及/或粒徑範圍為10nm至14nm，且紅色全無機鈣鈦礦量子點表面具有修飾性保護；綠色量子點複合材料包括綠色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)₃，0

b<0.5，及/或粒徑範圍為8nm至12nm，且綠色全無機鈣鈦礦量子點表面具有修飾性保護；藍色量子點複合材料包括藍色全無機鈣鈦礦量子點CsPb(Cl_aBr_1-a)₃，其中0<a

1及/或粒徑範圍為7nm至10nm，且藍色全無機鈣鈦礦量子點表面具有修飾性保護。 Figure 37 is a perspective view of a quantum dot light emitting diode (QLED) according to an embodiment. The quantum dot light emitting diode comprises a light emitting layer 3763, and the light emitting layer 3763 comprises an all-inorganic perovskite quantum dot composite material, such as a red all-inorganic perovskite quantum dot composite material, a green all-inorganic perovskite quantum dot composite material, and a blue color. All inorganic perovskite quantum dot composites or combinations thereof. The light emitting layer 3763 may be disposed between the hole injection layer 3765 and the electron injection layer 3767. An anode 3769, such as a light transmissive anode, can be disposed on the hole injection layer 3765. The cathode 3775 can be disposed on the electron injection layer 3767. Among them, the red quantum dot composite material includes a red all-inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ , 0.5

b

1, and / or particle size range of 10nm to 14nm, and the red all inorganic perovskite quantum dot surface has a modified protection; green quantum dot composite material includes green all inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ ,0

b<0.5, and/or particle size range from 8 nm to 12 nm, and the green all-inorganic perovskite quantum dot surface has modified protection; the blue quantum dot composite material includes blue all-inorganic perovskite quantum dot CsPb (Cl _a Br _1-a ) ₃ , where 0<a

1 and/or particle size ranges from 7 nm to 10 nm, and the blue all-inorganic perovskite quantum dot surface has modified protection.

In an embodiment, the wavelength converting material including the quantum dot composite material can also be applied to a size-reduced light-emitting device, such as a miniature light-emitting diode. (Micro LED) is smaller than the size of a general light-emitting diode.

For example, please refer to FIG. 38 and FIG. 39 simultaneously, respectively, which are a perspective view and a cross-sectional view of a light emitting device according to an embodiment. In an embodiment, the light-emitting device 3184 can be a miniaturized light-emitting diode device, including a light-emitting diode chip 3102, a plurality of wavelength conversion layers 3124, and a plurality of spacer layers S. The light-emitting diode wafer 3102 includes surfaces 3102S1 and 3102S2 on opposite sides of each other, wherein the surface 3102S1 is a light-emitting surface of the light-emitting diode wafer 3102. These wavelength conversion layers 3124 are located on the light-emitting side of the light-emitting diode wafer 3102. More specifically, these wavelength conversion layers 3124 are spaced apart from one surface 3102S1 of the light-emitting diode wafer 3102. These spacer layers S are located on the surface 3102S1 of the light-emitting diode wafer 3102 and are disposed between the wavelength conversion layers 3124 at intervals.

In one embodiment, the LED chip 3102 is a vertical LED chip, including a first electrode 3214 and a second electrode 3216, which are respectively disposed on the surface 3102S1 and the surface 3102S2. The light-emitting side of the light-emitting diode wafer 3102 is located on the same side as the first electrode 3214.

In one embodiment, the wavelength conversion layer 3124 includes at least a wavelength conversion layer 3124R, 3124G, 3124B that can be excited by the LED chip 3102 to separate red, green, and blue light, respectively. The configuration can be applied to the display as a pixel configuration, wherein the different wavelength conversion layers 3124 can be divided into different sub-pixels, that is, the wavelength conversion layer 3124R corresponding to the red sub-pixel, and the wavelength conversion corresponding to the green sub-pixel. Layer 3124G and wavelength conversion layer 3124B corresponding to blue sub-pixels.

In an embodiment, the wavelength conversion layer 3124 further includes a corresponding white sub-picture. The wavelength conversion layer 3124W of the element is also disposed on the surface 3102S1 of the light-emitting diode wafer 3102 via the spacer layer S and the wavelength conversion layers 3124R, 3124G, and 3124B.

The pixels include at least a red sub-pixel, a green sub-pixel, and a blue sub-pixel, and the white sub-pixel can also be configured according to the design. The pixels or sub-pixels can be arranged in an array.

In the embodiment, the material of the spacer layer S may include an absorbing or reflecting light material, which can prevent the light corresponding to the sub-pixels of different colors from affecting each other to improve the display effect of the display. The light absorbing material may include, for example, black glue or the like. The light-reflecting substance may include, for example, white glue or the like.

In addition, the first electrode 3214 may include first electrodes 3214R, 3214G, 3214B, and 3214W corresponding to the red sub-pixel, the green sub-pixel, the blue sub-pixel, and the white sub-pixel, respectively. The second electrode 3216 may be a common electrode of a red sub-pixel, a green sub-pixel, a blue sub-pixel, and a white sub-pixel. In other embodiments, the first electrode 3214 may be configured to correspond to a sub-pixel of different colors. Separate electrodes. Through the separately controlled electrodes, the sub-pixels of different colors can be addressed and individually driven to illuminate.

In an embodiment, for example, the LED chip 3102 can be an ultraviolet light emitting diode chip, and the first light is emitted at a wavelength of 200 nm to 400 nm. Or the light emitting diode chip 3102 can be a blue light emitting diode chip, and emit a first light having a wavelength of 430 nm to 480 nm.

b

1，及/或粒徑範圍為10nm至14nm，且紅色全無機鈣鈦礦量子點的表面具有修飾性保護。對應綠色次畫素的波長轉換層3124G的波長轉換材料可包括綠色量子點複合材料，其包括綠色全無機鈣鈦礦量子點CsPb(Br_1-bI_b)3，0

b<0.5，及/或粒徑範圍為8nm至12nm，且綠色全無機鈣鈦礦量子點的表面具有修飾性保護。對應藍色次畫素的波長轉換層3124B的波長轉換材料可包括藍色量子點複合材料，其包括藍色全無機鈣鈦礦量子點CsPb(Cl_aBr_1-a)₃，其中0<a

1及/或粒徑範圍為7nm至10nm，且藍色全無機鈣鈦礦量子點的表面具有修飾性保護，及/或藍色螢光粉。波長轉換材料可摻雜在透光基材中。 In an embodiment, the wavelength converting material corresponding to the red sub-pixel wavelength converting layer 3124R may comprise a red quantum dot composite comprising red all inorganic perovskite quantum dots CsPb (Br _1-b I _{b) 3} , 0.5

b

1, and / or particle size ranging from 10 nm to 14 nm, and the surface of the red all-inorganic perovskite quantum dot has a modification protection. The wavelength converting material corresponding to the wavelength conversion layer 3124G of the green sub-pixel may include a green quantum dot composite including a green all-inorganic perovskite quantum dot CsPb (Br _1-b I _{b) 3} ,0

b < 0.5, and / or particle size ranging from 8 nm to 12 nm, and the surface of the green all-inorganic perovskite quantum dot has a cosmetic protection. The wavelength converting material corresponding to the blue sub-pixel wavelength converting layer 3124B may comprise a blue quantum dot composite comprising a blue all-inorganic perovskite quantum dot CsPb(Cl _a Br _1-a ) ₃ , where 0<a

1 and/or particle size ranges from 7 nm to 10 nm, and the surface of the blue all-inorganic perovskite quantum dots has a modifying protection, and/or a blue phosphor. The wavelength converting material can be doped in the light transmissive substrate.

In another embodiment, in the example where the LED chip 3102 is a blue LED chip, the wavelength conversion layer 3124B corresponding to the blue sub-pixel can be a transparent substrate directly from the LED. Wafer 3102 provides blue light corresponding to the blue sub-pixels. The wavelength conversion layer 3124W corresponding to the white sub-pixel may include a yellow phosphor, such as YAG:Ce, which may be excited by a portion of the first light (blue light, wavelength 430 nm to 480 nm) emitted by the LED chip 3102. Light, yellow light mixed with the remaining blue light to emit white light.

In the embodiment, the miniature light-emitting diodes as shown in FIGS. 38 and 39 can be applied to a micro LED display. Compared with the general light-emitting diode technology, the miniature light-emitting diode has a small size and the pixel pitch is reduced from millimeter to micrometer, so that a high-density and small-sized light-emitting light can be formed on one integrated circuit wafer. Polar body array, and color is easier to debug accurately, there are Longer illuminating life and higher brightness, as well as better material stability, long life, no image imprinting and so on. The advantages of this technology can still utilize the characteristics of high efficiency, high brightness, high reliability and fast response time of the light-emitting diode, and the characteristics of self-illumination without backlight, more energy-saving, simple mechanism, small size, thin shape, etc. . In addition, the miniature light-emitting diode technology achieves high resolution.

In order to make the disclosure more obvious and easy to understand, the following specific embodiments are described in detail below:

[Preparation of all inorganic perovskite quantum dots]

First, the synthesis of Cs precursor: 0.814g of Cs ₂ CO ₃ , 40mL of octadecene (ODE) and 2.5mL of oleic acid (OA) into a 100mL three-necked flask, under vacuum and temperature 120 After removing water for one hour in an environment of ° C, it was heated to 150 ° C under a nitrogen system until Cs ₂ CO _{3 was} completely reacted with oleic acid to obtain a Cs precursor (Cs-Oleate precursor).

Then, 5 mL of ODE and 0.188 mmol of PbX ₂ (X=Cl, Br, or I, which determines the halogen component of the total inorganic perovskite quantum dot) are added to a 25 mL three-necked flask under vacuum at a temperature of 120 ° C. After one hour of water removal, 0.5 mL of oleylamine and 0.5 mL of OA were injected into a three-necked flask under a nitrogen system. After the solution was clarified, the temperature was raised to 140-200 ° C (heating temperature can be adjusted to full inorganic The particle size of the perovskite quantum dot), then 0.4 mL of the Cs-Oleate precursor was quickly injected into the three-necked flask and waited for 5 seconds. After cooling the reaction system in an ice water bath, the whole inorganic perovskite quantum was purified by centrifugation. Point CsPb(Cl _a Br _1-ab I _b ) ₃ .

[Red/Green Fully Inorganic Perovskite Quantum Dots CsPb(Br _1-b I _b ) ₃ ]

Figure 40 is an X-ray diffraction pattern of an all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ . In Fig. 40, from the bottom to the top are all inorganic perovskite quantum dots CsPbI ₃ , CsPb (Br _0.2 I _0.8 ) ₃ , CsPb (Br _0.3 I _0.7 ) ₃ , CsPb (Br _0.4 I _0.6 ) ₃ , CsPb ( Br _0.5 I _0.5 ) ₃ , CsPb (Br _0.6 I _0.4 ) ₃ , CsPb (Br _0.8 I _0.2 ) ₃ , CsPbBr ₃ , XRD patterns at nucleation temperatures of 180 ° C, the above different ratios of Br and I calcium and titanium The XRD peak of all synthesized inorganic-inorganic perovskite quantum dots CsPb(Br _1-b I _b ) ₃ can be found by comparing the XRD pattern of the mineral quantum dots with the known cubic phase CsPbI ₃ and CsPbBr ₃ standard spectra. The positions are consistent with the cubic phase standard map, indicating that the synthesized all-inorganic perovskite quantum dots CsPb (Br _1-b I _b ) ₃ are cubic phases.

Figure 41 is a normalized photoexcited fluorescence (PL) spectrum of an all inorganic perovskite quantum dot CsPb (Br _1-b I _b ) ₃ using 460 nm excitation light. The peak position (strongest light release position) and the full width at half maximum (FWHM) of the data are shown in Table 1. Figure 42 shows the CIE map position of the all inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ .

From Fig. 41, Fig. 42 and Table 1, it is found that the total inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ increases with the content of I element and the content of Br decreases, that is, the b value increases from 0.4 to 1. The luminescence peak produces a red shift phenomenon, that is, gradually shifts from 557 nm to 687 nm. This phenomenon can be explained by the quantum confinement effect. That is, since the I ion particle size is larger than the Br ion particle size, when the content of the I element in the all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ increases, the material size will become large and cause the emission spectrum. A red shift occurs.

The all-inorganic perovskite quantum dots in the all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ , b=0.5-1 are red quantum dots. Among them, the red strong inorganic perovskite quantum dot CsPb (Br _0.4 I _0.6 ) _{3 has} the strongest light-emitting position of 625 nm, which is in line with the red light-emitting band commonly used in the market. The half-height of the light wave is 35nm, which is narrower than the current common commercial red fluorescent powder, that is, it has better solid color. When applied to the light-emitting device, it can improve the light-emitting efficiency of the product, or when it is combined with other kinds of firefly. When the light substance is mixed to obtain a light-emitting device, the color rendering property of the product can be increased.

In the all-inorganic perovskite quantum dot CsPb(Br _1-b I _b ) ₃ , the all-inorganic perovskite quantum dot with b = 0.4 (CsPb(Br _0.6 I _0.4 ) ₃ ) is a green quantum dot with the strongest light emission. The position is 557nm, which is in line with the green emission band commonly used in the market. The half-height of the light wave is 27nm, which is narrower than the current common commercial green fluorescent powder, that is, it has better solid color, which can improve the light-emitting efficiency of the product when applied to the light-emitting device, or when it is combined with other kinds of firefly. When the light substance is mixed to obtain a light-emitting device, the color rendering property of the product can be increased.

[All inorganic perovskite quantum dots CsPb(Cl _a Br _1-a ) ₃ ]

Figure 43 is an X-ray diffraction pattern of the all inorganic perovskite quantum dot CsPb (Cl _a Br _1-a ) ₃ 3 . a = 0, 0.5, 1. Compared with the known cubic phase CsPBr3 and CsPbCl ₃ standard spectra, the XRD peak positions of all synthetic all-inorganic perovskite quantum dots CsPb(Cl _a Br _1-a ) ₃ can be found to be in the cube phase standard. The map is consistent, indicating that the synthetic all-inorganic perovskite quantum dot CsPb (Cl _a Br _1-a ) ₃ conforms to the cubic phase. The nucleation temperature of the all inorganic perovskite quantum dot CsPb (Cl _a Br _1-a ) ₃ was 180 °C.

Figure 44 is a normalized photoexcited fluorescence spectrum of the all-inorganic perovskite quantum dot CsPb (Cl _a Br _1-a ) ₃ (a = 0, 0.5, 1). The excitation light has a wavelength of 380 nm. The peak position (strongest light release position) and the full width at half maximum (FWHM) of the displayed data are shown in Table 2. Figure 45 shows the CIE map position of the all inorganic perovskite quantum dot CsPb(Cl _a Br _1-a ) ₃ .

From Fig. 44, Fig. 45 and Table 2, it is found that the total inorganic perovskite quantum dot CsPb(Cl _a Br _1-a ) ₃ increases with the content of Cl and the content of Br increases, that is, the value of a increases from 1 to 1. 0, the luminescence peak produces a red shift phenomenon, that is, gradually shifts from 406 nm to 514 nm. This phenomenon can be explained by the quantum confinement effect. That is, since the Cl ion particle size is smaller than the Br ion particle size, when the Cl element content in the all-inorganic perovskite quantum dot CsPb(Cl _a Br _1-a ) ₃ is decreased, the material size will become large and the emission spectrum is caused. A red shift occurs. In the all-inorganic perovskite quantum dot CsPb(Cl _a Br _1-a ) ₃ , a = 0 (CsPbBr ₃ , that is, the chemical formula CsPb (Br _1-b I _b ) ₃ b = 1) of all inorganic calcium titanium The ore quantum dots are green quantum dots, and the all-inorganic perovskite quantum dots of a=0.5, 1 (CsPb(Cl _0.5 Br _0.5 ) ₃ , CsPbCl ₃ ) are blue quantum dots.

Figure 46 is a normalized photoexcited fluorescence spectrum of the 41st and 44th images, showing the total inorganic perovskite quantum dot CsPb (Cl _a Br _1-ab I _b ) ₃ with Cl, Br, The luminescent properties of the I element content change. The light covers the red, green, and blue ranges, and each light wave has a half width and a narrow width. Therefore, various desired luminescence peak positions can be obtained by adjusting the composition of the all-inorganic perovskite quantum dots, and the materials can exhibit excellent photoelectric properties when applied to a light-emitting device.

[Quantum dot composites - mesoporous particles as a modification protection]

The quantum dot composite is prepared by dissolving the synthesized all-inorganic perovskite quantum dots (particle size distribution about 10 nm, crystal plane spacing about 5.78 Å) in a non-polar solvent hexane (10 mg/ml), and then Cerium oxide mesoporous particles (pore size about 12-14nm) are added to the total inorganic perovskite quantum dot solution to the total inorganic perovskite quantum After mixing at a ratio of about 1:10 to the cerium oxide mesoporous particles, the mixture was stirred for about one hour. After centrifugation at 3000 rpm for 10 minutes, a powder of the quantum dot composite material was obtained.

The comparison of the photoexcited fluorescence spectra of the all-inorganic perovskite quantum dots (PQDs) without modification of the comparative example of Fig. 47 with the quantum dot composites of the examples (MP-PQDs) shows that the quantum dot composites are all After the inorganic perovskite quantum dots enter the pores of the mesoporous particles, the all-inorganic perovskite quantum dots in the same pores will slightly agglomerate, causing the spectrum to be red-shifted by about 10 nm, but the difference in the half-height of the peaks is not Big.

Figures 48 and 49 are photoexcited fluorescence spectra of different examples of light emitting diode packages. The light-emitting diode package structure is obtained by mixing an all-inorganic perovskite quantum dot or a quantum dot composite material with a transparent encapsulant (silicone/germanium resin), and then dispensing on a blue light-emitting diode wafer (light-emitting wavelength: 450 nm). Curing is formed.

In the results of the comparative example of Fig. 48, the curve G-PQDs indicates the use of a green all-inorganic perovskite quantum dot CsPbBr ₃ , and the R-PQDs indicates the use of a red all-inorganic perovskite quantum dot CsPb (Br _0.4 I _0.6 ) ₃ , G -PQDs+R-PQDs means mixing green all-inorganic perovskite quantum dots CsPbBr ₃ and red all-inorganic perovskite quantum dots CsPb(Br _0.4 I _0.6 ) ₃ , wherein no modification is formed above the all-inorganic perovskite quantum dots Sexual protection. Figure 48 shows that the G-PQDs+R-PQDs curve peak position shifts G-PQDs and R-PQDs curves, and the full width at half maximum of the waveform is broadened. This result is presumed to be green and red all-inorganic perovskite quantum dots. This is caused by the phenomenon of ion exchange between them, and this unstable nature is not suitable for application to products.

In Fig. 49, R-PQDs indicates the use of red all-inorganic perovskite quantum dots CsPb (Br _0.4 I _0.6 ) ₃ (comparative example), and the curve MP G-PQDs indicates the use of cerium oxide mesoporous particles for modification protection and green Quantum dot composite composed of inorganic perovskite quantum dots CsPbBr ₃ (Example), curve MP G-PQDs+R-PQDs indicates the use of the above-mentioned quantum dot composites including green all-inorganic perovskite quantum dots and red Inorganic perovskite quantum dots (Examples). Comparing the curve of Fig. 49, it can be found that the use of the modified quantum dot composite can avoid the mutual dissolution of ion exchange between all inorganic perovskite quantum dots of different compositions, and thus can exhibit all-inorganic perovskite quantum. The respective desired light-emitting characteristics, that is, a narrow half-height width and a strong luminous intensity.

Figure 50 is a CIE diagram of a light-emitting diode package structure, showing that a blue light-emitting diode (blue chip) excites a quantum dot composite material composed of green all-inorganic perovskite quantum dots and mesoporous particles (MP G- PQDs) and color coordinates of red all-inorganic perovskite quantum dots (R-PQDs). When the quantum dot composite material containing the modification protection according to the embodiment is applied to the display, the NTSC is 104%, which is superior to the NTSC (86%) of the display using the general fluorescent powder.

[Quantum point composites - using ligand exchange, mesoporous particles, polymer coatings as a modification protection]

The all inorganic perovskite quantum dot CsPbBr ₃ discussed herein can be prepared as described in [Preparing all inorganic perovskite quantum dots].

The quantum dot composite (expressed as CsPbBr ₃ /SDDA) is formed by surface sulfur treatment of the all-inorganic perovskite quantum dot CsPbBr ₃ . The sulfur treatment reagent (SDDA) used for the sulfur treatment is prepared by first dissolving didodecyldimethylammonium bromide (DDAB) in organic toluene, and dissolving sodium sulfide in water to form an aqueous solution of sodium sulfide. The sulfur solution is obtained by uniformly mixing the organic solution with the aqueous solution. In the process of mixing the two solutions, the sulfur ions (anions) in the aqueous solution are combined with the dodecyldimethylammonium bromide (cation), and the sulfur ions will be transferred from the aqueous phase to the organic toluene phase. The surface sulfur treatment method is to take 1.5mL of total inorganic perovskite quantum dot CsPbBr ₃ (10mg/mL) solution and 10μL of oleic acid (OA) for 10 minutes, then add 1.5mL sulfur treatment reagent SDDA, centrifuge and disperse at 9000rpm. After being used in n-hexane, a solution of CsPbBr ₃ /SDDA is obtained, which is dried to obtain a quantum dot composite CsPbBr ₃ /SDDA.

The quantum dot composite (expressed as MP-CsPbBr ₃ /SDDA) is a solution of the quantum dot composite CsPbBr ₃ /SDDA in a non-polar solvent hexane (10 mg/ml), followed by the addition of cerium oxide mesoporous particles to the mixed solution. After mixing the total inorganic perovskite quantum dots with the cerium oxide mesoporous particles at a ratio of about 1:10, the mixture was stirred for about one hour. After centrifugation at 4000 rpm for 30 minutes, a powder of the quantum dot composite MP-CsPbBr ₃ /SDDA was obtained.

The quantum dot composite (expressed as MP-CsPbBr ₃ /SDDA@PMMA) was mixed with 20 mg of quantum dot composite MP-CsPbBr ₃ /SDDA, 3 mL of methyl methacrylate and 10 mg of BASF catalyst for 10 minutes, and then the mixture was placed in a mold. It was prepared by placing it in an oven at 50 ° C for 10 minutes.

Figure 51 shows the photoexcited fluorescence spectra of all inorganic perovskite quantum dots and quantum dot composites. The green all-inorganic perovskite quantum dot CsPbBr ₃ (Comparative Example) has a light-emitting position of 515 nm and a full width at half maximum of about 21 nm. After surface sulfur treatment (CsPbBr ₃ /SDDA curve, examples), the light-emitting position was 515 nm, and the full width at half maximum was about 21 nm. After further physical adsorption with cerium oxide mesoporous particles (MP-CsPbBr ₃ /SDDA curve, examples), due to the phenomenon of aggregation of all inorganic perovskite quantum dots, the luminescence position exhibited red shift to 524 nm, half height The width is 22nm. After further forming a methyl methacrylate polymer coating coated with cerium oxide mesoporous particles (MP-CsPbBr ₃ /SDDA@PMMA curve, examples), the light-emitting position was 523 nm, and the full width at half maximum was 22 nm.

Figure 52 shows the thermal stability test results of the all-inorganic perovskite quantum dots and quantum dot composites, in which the quantum dot composite MP-CsPbBr ₃ /SDDA@PMMA has a light intensity of 70% at 100 ° C, which is higher than other The material has better thermal stability.

Figure 53 shows the results of the thermal reproducibility test of quantum dot composites. The quantum dot composite MP-CsPbBr ₃ /SDDA@PMMA can recover its light intensity to 95% after returning from high temperature to room temperature. .

[Light Emitting Diode Package Structure]

Figure 54 is a light output power (LOP) curve of a light-emitting diode package structure using different wave-converting materials. The wave-converting materials used were respectively commercial YAG phosphor powder (Commercial YAG) used as a reference, and all-inorganic perovskite quantum dots (QD W/O protection) on which the comparative examples were not modified, and implemented. Total inorganic perovskite in quantum dot composites The modification protection at the sub-point is composed of a polymer coating (QD W/polymer encapsulation protection), and the modification protection on the all-inorganic perovskite quantum dot in the quantum dot composite of the embodiment is a two-layer film structure. The layer is a coating of the cerium-containing material and the outer layer is a polymer coating (QD W/Si base & polymer encapsulation protection). From the results shown in Fig. 54, it was found that the light-emitting diode package structure uses the quantum dot composite material according to the embodiment as compared with the all-inorganic perovskite quantum dot (Comparative Example) which is not modifiedly protected thereon. The subsequent reduction in light output power is small and exhibits better product reliability.

[White light emitting diode package structure]

The white light emitting diode package structure is a green fluorescent material (green all-inorganic perovskite quantum dot CsPbBr ₃ / green fluorescent powder β-SiAlON: Eu ²⁺ ) and red fluorescent material (K ₂ SiF ₆ : Mn ^{4). +} ) Adding silicone (Dow Corning OE6631; A glue: B glue = 1:2), stirring and mixing evenly, then putting it into a vacuum defoaming machine for defoaming to obtain a fluorescent slurry, and then adding the fluorescent slurry to the solution. The blue light-emitting diode wafer was formed by curing in an oven (150 ° C for 2 hours).

Figure 55 shows a quantum dot composite (MP-CsPbBr ₃ /SDDA@PMMA) containing green all-inorganic perovskite quantum dots CsPbBr ₃ used in a white light emitting diode package structure and a general β-SiAlON:Eu ²⁺ green Comparison of the emission spectrum of phosphor powder. The quantum dot composite MP-CsPbBr ₃ /SDDA@PMMA of the examples has a narrow full width at half maximum of about 23 nm and a peak position at 523 nm.

Figure 56 shows a white light emitting diode package structure of the embodiment (top view, using MP-CsPbBr ₃ /SDDA@PMMA) and a general (comparative example) white light emitting diode package structure (below figure, using β-SiAlON) :Eu ²⁺ ) comparison of electroluminescence spectra. In the white light emitting diode package structure of the embodiment, the half-width of the light wave in the green light range is narrow.

Fig. 57 is a view showing the white light emitting diode package structure (indicated by MP-CsPbBr ₃ /SDDA@PMMA) of the embodiment and the white light emitting diode package structure of the general (comparative example) (indicated by β-SiAlON:Eu ²⁺ ) NTSC comparison. The white light emitting diode package structure of the embodiment has a wider color gamut NTSC.

[heat stability test]

Figure 58 is a graph showing the thermal stability of a quantum dot composite (MP-CsPbBr ₃ ) of the example and a comparative example of an all inorganic perovskite quantum dot (CsPbBr ₃ ) by a thermal controller at a temperature ranging from 25 ° C to 100 ° C. Compared with the all-inorganic perovskite quantum dot CsPbBr ₃ (the curve is represented by CsPbBr ₃ ) without modification protection in the comparative example, the quantum dot composite of the example (the cerium dioxide mesoporous particle modified protection is embedded with all-inorganic calcium and titanium) The mineral quantum dot CsPbBr ₃ , the curve is expressed by MP-CsPbBr ₃ ), the relative intensity decreases with increasing temperature, indicating better thermal stability.

Fig. 59A and Fig. 59B are the results of the thermal cycle test of the quantum dot composite (MP-CsPbBr ₃ ) of the example and the comparative inorganic nitride quantum dot (CsPbBr ₃ ), respectively. After the temperature reduction of the quantum dot composite of the embodiment to room temperature by thermal cycling, the relative light emission intensity is almost the same as before the temperature rise, and comparing the 59A and 59B, it can be found that the quantum dot composite of the embodiment is compared. The example has better thermal stability.

The 60th, 61st, and 62th graphs are the temperature resistance test curves of the light-emitting diode package structure of the embodiment, and the quantum dot composite material used for the wavelength conversion material is a modified modification of the green all-inorganic perovskite quantum dots with different types. They are respectively polymer-coated (Green-QD W/polymer encapsulation protection), two-layer membrane structure in which the inner layer is a coating of cerium-containing material and the outer layer is a polymer coating (Green-QD W/Si base & polymer encapsulation). Protection), and mesoporous particles (Green-QD W/mesoporous). Fig. 63 is a temperature resistance test curve of a comparative example of a light-emitting diode package structure in which green all-inorganic perovskite quantum dots (Green-QD W/O protection) which are not modified with modification are used. Among them, the normalized graph obtained by using the maximum output power before heating is 100%. The values of the curves are shown in Table 3. From the results of the 60th, 61st, 62th, 63th and 3rd tables, it can be found that the quantum dot composites with modified modification on the all inorganic perovskite quantum dots have better temperature resistance properties than the comparative examples. .

[Light Stability Test]

Figure 64 is a graph showing the photostability test results of the quantum dot composite (MP-CsPbBr ₃ ) of the example and the comparative inorganic nitride quantum dot (CsPbBr ₃ ). The test was carried out by irradiating UV (wavelength 365 nm, power 6 W) light to an example quantum dot composite MP-CsPbBr ₃ dispersed in hexane, and a comparative total inorganic perovskite quantum dot CsPbBr ₃ . After 96 hours of illumination, the relative emission intensity of the comparative inorganic nitride quantum dot CsPbBr ₃ decreased to 40% compared to that before illumination. The relative light-emitting intensity of the quantum dot composite MP-CsPbBr ₃ of the example was reduced to 80% compared with that before the illuminating, and the light stability was better than that of the comparative example.

[wavelength conversion film]

Figure 65 is a comparison of the wavelength conversion film luminescence spectrum (λ ex = 460 nm) and the chlorophyll a and chlorophyll b absorption spectra of the examples. The quantum dot composite of the wavelength conversion film is composed of red all-inorganic perovskite quantum dots and cerium oxide mesoporous particles modified. In comparison with the chlorophyll a absorption spectra of the comparative examples of the 66A to 66C, the general red fluorescent powders CaAlSiN ₃ :Eu ²⁺ , K ₂ SiF ₆ :Mn ⁴⁺ , CaS are used, respectively. Eu ²⁺ . From the results of Figs. 65 to 66C, it is understood that the red light wavelength range emitted by using the red all-inorganic perovskite quantum dots according to the examples is more in line with the absorption matching of the red portion of chlorophyll a.

According to the above embodiment, including modified protection in the all inorganic perovskite Quantum dot composites on quantum dots have excellent light-emitting properties and stable properties, so they can be used in a variety of device products to improve performance stability and service life.

In conclusion, the present invention has been disclosed in the above preferred embodiments, and is not intended to limit the present invention. A person skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.

11‧‧‧Quantum point composites

13‧‧‧All inorganic perovskite quantum dots

15A‧‧‧Mesoporous particles

Claims (33)

A quantum dot composite material comprising: an all-inorganic perovskite quantum dot having a chemical formula of CsPb(Cl _a Br _1-ab I _b ) ₃ , wherein a 1,0 b 1, wherein the all-inorganic perovskite quantum dot comprises a chemical formula of CsPb(Br _1-b I _b ) ₃ and 0.5 b a red all-inorganic perovskite quantum dot of 1 having a chemical formula of CsPb(Br _1-b I _b ) ₃ and 0 a green all-inorganic perovskite quantum dot with b<0.5, or having the chemical formula CsPb(Cl _a Br _1-a ) ₃ and 0<a a blue all-inorganic perovskite quantum dot; and a modification protection comprising a mesoporous particle having a plurality of pores on the outer surface, the all-inorganic perovskite quantum dot being buried in the pores. The quantum dot composite material according to claim 1, wherein the modified protection further comprises an inorganic shell coating, a ligand exchange, a microcapsule coating, a polymer coating, and a bismuth-containing material package. a coated, oxidized or nitrided dielectric coating or a combination thereof as described above on the surface of the wholly inorganic perovskite quantum dot, and/or the inorganic shell coating, the microcapsule coating, the polymerization The inclusion body, the ruthenium-containing material coating, the oxidized or nitrided dielectric coating, or a combination thereof, coats the mesoporous particles. The quantum dot composite material according to claim 2, wherein the cerium-containing material coating body comprises a cerium-titanium oxide-based coating body. The quantum dot composite according to claim 1, wherein the modification protection further comprises the ligand exchange, the surface of the all-inorganic perovskite quantum dot having the ligand exchanged and buried in the mesoporous particle Among these pores. The quantum dot composite of claim 4, wherein the ligand exchange is formed by sulfur treatment of the surface of the all inorganic perovskite quantum dots. The quantum dot composite material according to claim 4, wherein the modification protection further comprises the polymer coating body, the cerium-containing material coating body or the oxidized or nitrided dielectric coating body, and the package thereof The mesoporous particles are covered. The quantum dot composite material according to claim 1, wherein the mesoporous particles have a particle size of from 200 nm to 1000 nm, and the pores of the mesoporous particles have a size of from 1 nm to 100 nm. The quantum dot composite of claim 7, wherein the pore has a size of from 2 nm to 20 nm. The quantum dot composite material according to claim 2, wherein: the material of the mesoporous particles comprises cerium oxide; and the material of the inorganic shell coating comprises a group II, III, V or VI. a binary or ternary compound of a group element; the cerium-containing material coating comprises SiOR, SiO ₂ , Si(OR) ₄ or Si(OMe) ₃ C ₃ H ₆ S; the ligand exchange comprises tri-n-octyl oxidation Tri-n-octyl phosphine oxide (TOPO), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene 10- Oxide; DOPO), oleic acid, oligomer, or sulfur-containing compound provides a ligand; the material of the polymer coating includes polymethyl methacrylate (PMMA), poly-p-phenylene Ethylene glycolate (PET), polyethylene isophthalate (PEN), polystyrene (PS), polyvinylidene fluoride (PVDF), polyvinyl acetate (PVAC), polypropylene (PP), Polyamine (PA), polycarboxylate (PC), polyimine (PI), epoxy or silicone; the oxidized or nitrided dielectric coating comprises a metal oxide or Metal nitride. The quantum dot composite according to claim 9, wherein the sulfur-containing compound comprises a sulfur-containing quaternary ammonium salt. The quantum dot composite according to claim 1, wherein the total inorganic perovskite quantum dot has a particle diameter ranging from 1 nm to 100 nm. The quantum dot composite material according to claim 1, wherein the red all-inorganic perovskite quantum dots have a particle diameter ranging from 10 nm to 14 nm, and the green all-inorganic perovskite quantum dots have a particle diameter ranging from 8 nm to At 12 nm, the blue all inorganic perovskite quantum dots have a particle size ranging from 7 nm to 10 nm. The quantum dot composite material according to any one of claims 1 to 12, which is applied to a light emitting diode package, a quantum dot light emitting diode (QLED), a plant illumination, a display, a solar cell, and a bioluminescence. Bio Label, image sensor. A method for fabricating a quantum dot composite material, comprising: providing an all-inorganic perovskite quantum dot, wherein the all-inorganic perovskite quantum dot has a chemical formula of CsPb(Cl _a Br _1-ab I _b ) ₃ ,0 a 1,0 b And forming a modification on the surface of the all-inorganic perovskite quantum dot, the method comprising: subjecting a surface of the all-inorganic perovskite quantum dot to a vulcanization treatment, wherein the vulcanization treatment comprises the all-inorganic calcium-titanium The mineral quantum dot is subjected to a ligand exchange reaction with a sulfur-containing compound, the sulfur-containing compound comprising a sulfur-containing quaternary ammonium salt; and the vulcanized and treated total inorganic perovskite quantum dot is buried in the pore of the mesoporous particle; And coating the mesoporous particles with a polymer coating. The method for producing a quantum dot composite according to claim 14, wherein the vulcanization treatment comprises: providing an oleic acid mixed with the all-inorganic perovskite quantum dot; and providing a sulfur treatment with the sulfur-containing compound The reagent is mixed with the oleic acid, the all-inorganic perovskite quantum dot, wherein the sulfur treatment reagent is prepared by mixing an organic solution in which a halogen-containing quaternary ammonium salt is dissolved with an aqueous solution in which an alkali metal sulfide is dissolved. The sulfur treatment reagent is obtained. The method for producing a quantum dot composite according to claim 15, wherein the halogen-containing quaternary ammonium salt has the formula R ₄ NX, and R is an alkyl group of one to twenty carbon chains, an alkoxy group. , phenyl, or alkylphenyl, X is chlorine, bromine or iodine. A light emitting device comprising: a light emitting diode wafer; and a wavelength converting material excited by the first light emitted by the light emitting diode to emit a second light different from the wavelength of the first light, the wavelength conversion The material includes a quantum dot composite as described in any one of claims 1 to 12. The illuminating device of claim 17, wherein the wavelength converting material further comprises an inorganic fluorescent material or an organic fluorescent material different from the quantum dot composite. The illuminating device of claim 17, wherein the all-inorganic perovskite quantum dot of the quantum dot composite comprises the green all-inorganic perovskite quantum dot. The illuminating device of claim 19, wherein the all-inorganic perovskite quantum dot comprises a green all-inorganic perovskite quantum dot having a chemical formula of CsPbBr ₃ , the wavelength converting material further comprising K ₂ SiF ₆ : Mn ⁴⁺ , the light emitting diode chip includes a blue light emitting diode wafer. The illuminating device of claim 17, comprising a wavelength conversion layer disposed on a light exiting side of the light emitting diode chip, wherein the wavelength converting layer comprises the wavelength converting material. The light-emitting device of claim 21, comprising: a plurality of the wavelength conversion layers disposed at intervals on the light-emitting side of the light-emitting diode wafer; and a plurality of spacer layers disposed in the wavelength conversion layers The spacer layers include light absorbing materials or light reflecting materials. The light-emitting device of claim 22, which is a miniature light-emitting diode. The illuminating device of claim 22, wherein the illuminating diode chip has a first electrode and a second electrode on opposite sides, and the light emitting side of the illuminating diode chip is One electrode is on the same side. The illuminating device according to claim 22, which is applied to the display device The display device includes a plurality of pixels, each of which includes at least one red sub-pixel, a green sub-pixel, and a blue sub-pixel, the red sub-pixel, the green sub-pixel, and the blue sub-pixel Each of the wavelength conversion layers includes one of the pixels, and the wavelength conversion layers corresponding to the red sub-pixel, the green sub-pixel, and the blue sub-pixel are separated by the intervals The layers are disposed apart from each other on the light exiting side of the light emitting diode chip. The illuminating device of claim 25, wherein the pixels further comprise a white sub-pixel, the other one of the wavelength conversion layers, and the red layer is separated by the spacer layer The pixel, the green sub-pixel, and the blue sub-pixel. The light-emitting device of claim 21, wherein the wavelength conversion layer and the light-emitting diode wafer are in contact with each other or are separated from each other. The light-emitting device of claim 21, wherein the wavelength conversion layer further comprises a transparent colloid, and the wavelength conversion material is doped in the transparent colloid. The illuminating device of claim 21, comprising a plurality of stacked wavelength conversion layers each having a different illuminating wavelength band. The illuminating device of claim 21, further comprising a transparent colloid encapsulating the wavelength conversion layer and the illuminating diode chip. The illuminating device of claim 21, further comprising a structural component, wherein the structural component has an accommodating area for accommodating the wavelength conversion layer to enable the wavelength The upper and lower surfaces of the conversion layer are covered by the structural component to support, encapsulate, and protect the wavelength conversion layer; the structural component is on the lower surface of the wavelength conversion layer, and has an accommodating area for accommodating and supporting The wavelength conversion layer; and the structural element is on an upper surface of the wavelength conversion layer for protecting the wavelength conversion layer. The illuminating device of claim 17, further comprising a susceptor having a solid crystal region therein, wherein the illuminating diode wafer is on the die bonding region. The illuminating device of claim 17, further comprising a reflective wall outside the wavelength conversion layer.