TWI698515B - Nano composite fluorescent powder, its preparation method and luminescent device - Google Patents

Abstract

y<0.4，R選自Sn⁴⁺,Ti³⁺,V²⁺,Mn³⁺,Fe²⁺,Co³⁺,Ni³⁺,Nb⁵⁺,Mo⁵⁺,Tc⁵⁺,Ru⁴⁺,Rh⁴⁺,Pd⁴⁺,Sb⁵⁺,Ta⁵⁺,W⁵⁺,Re⁴⁺,Os⁴⁺,Ir⁴⁺,Pt⁴⁺中的一種或多種。該奈米複合螢光粉具有優異的分散性、發光效率高且封裝性好，其粒徑尺寸可適配於micro/min-LED等發光裝置上，在可見光或紫外光激發下可獲得紅外光，有望應用於微小型檢測裝置，虹膜/面部臉部檢測、醫療檢測或氣體檢測裝置等。 The present invention provides a nano-composite phosphor. The nano-composite phosphor includes a carrier and an infrared phosphor loaded on the carrier, wherein the carrier is an oxide, and the chemical composition of the infrared phosphor The general formula is ZnGa _2-xy O ₄ ：xCr ³⁺ ,yR, where x and y are mole fractions, and 0<x<0.4, 0

y<0.4, R is selected from Sn ⁴⁺ ,Ti ³⁺ ,V ²⁺ ,Mn ³⁺ ,Fe ²⁺ ,Co ³⁺ ,Ni ³⁺ ,Nb ⁵⁺ ,Mo ⁵⁺ ,Tc ⁵⁺ ,Ru ⁴⁺ One or more of, Rh ⁴⁺ , Pd ⁴⁺ , Sb ⁵⁺ , Ta ⁵⁺ , W ⁵⁺ , Re ⁴⁺ , Os ⁴⁺ , Ir ⁴⁺ , and Pt ⁴⁺ . The nano-composite phosphor has excellent dispersibility, high luminous efficiency and good encapsulation. Its particle size can be adapted to light-emitting devices such as micro/min-LED, and infrared light can be obtained under the excitation of visible light or ultraviolet light. , It is expected to be used in micro detection devices, iris/face detection, medical detection or gas detection devices, etc.

Description

Nano composite fluorescent powder and its preparation method and light emitting device

The invention belongs to the technical field of semiconductors, and specifically relates to a nanocomposite phosphor, a preparation method thereof, and a light emitting device.

With the continuous development of semiconductor technology, mirco-LED (miniature light-emitting diode) and mini-LED (sub-millimeter light-emitting diode) are driving another revolution in LED display technology. Micro-LED technology is to thin, miniaturize, and array the LED (light emitting diode) backlight, making the size of the LED unit less than 100 microns, which inherits the high efficiency, high brightness, high reliability and reliability of inorganic LEDs. It has the characteristics of fast response time, self-illumination without backlight, small size, light weight, and energy saving effect. Mini-LED refers to an LED with a grain size of about 100 microns to 200 microns. It adopts a local dimming design and has better color rendering. It can bring more fine HDR partitions to the LCD panel, and the thickness is also close to OLED , It can save power up to 80%, so it is demanded for backlight applications such as power saving, thinner, HDR, and special-shaped displays. It is suitable for applications such as mobile phones, TVs, car panels, and gaming laptops.

Compared with quantum dot LEDs (QLEDs), LEDs (pc-LEDs) that use phosphors as the light-emitting center have more stable performance. However, with the development of mirco-LED and mini-LED, the chip size continues to shrink, making pc-LED material size also face a bottleneck. Generally, the luminous flux will increase with the increase of the thickness of the phosphor layer or the concentration of the phosphor. However, most phosphors are micron-sized and uneven, and too thick a phosphor layer will also produce high The scattering effect and low dispersion problems.

Therefore, there is an urgent need for a new phosphor and a preparation method thereof to be applied to light-emitting devices such as mirco/mini-LED and to solve various problems existing in the prior art.

It should be noted that the information disclosed in the foregoing background section is only used to enhance the background understanding of the present invention, so it may include information that does not constitute the prior art known to those of ordinary skill in the art.

The purpose of the present invention is to provide a nano-composite phosphor and a preparation method thereof. The nano-composite phosphor can be used in light-emitting devices such as mirco/mini-LED, micro/min-LD, etc., to solve the existing fluorescent Powder luminous efficiency is low, the size is limited, and the dispersion is poor.

y<0.4，R選自Sn⁴⁺,Ti³⁺,V²⁺,Mn³⁺,Fe²⁺,Co³⁺,Ni³⁺,Nb⁵⁺,Mo⁵⁺,Tc⁵⁺,Ru⁴⁺,Rh⁴⁺,Pd⁴⁺,Sb⁵⁺,Ta⁵⁺,W⁵⁺,Re⁴⁺,Os⁴⁺,Ir⁴⁺,Pt⁴⁺中的一種或多種。 In order to achieve the above object, the present invention adopts the following technical solutions: the present invention provides a nanocomposite phosphor, the nanocomposite phosphor comprising a carrier and an infrared phosphor supported on the carrier, wherein the carrier It is an oxide, and the general chemical formula of the infrared phosphor is ZnGa _2-xy O ₄ : xCr ³⁺ , yR, where x and y are mole fractions, and 0<x<0.4, 0

y<0.4, R is selected from Sn ⁴⁺ ,Ti ³⁺ ,V ²⁺ ,Mn ³⁺ ,Fe ²⁺ ,Co ³⁺ ,Ni ³⁺ ,Nb ⁵⁺ ,Mo ⁵⁺ ,Tc ⁵⁺ ,Ru ⁴⁺ One or more of, Rh ⁴⁺ , Pd ⁴⁺ , Sb ⁵⁺ , Ta ⁵⁺ , W ⁵⁺ , Re ⁴⁺ , Os ⁴⁺ , Ir ⁴⁺ , and Pt ⁴⁺ .

According to an embodiment of the present invention, the particle size of the nanocomposite phosphor is less than 200 nm.

According to an embodiment of the present invention, the luminescence wave of the nanocomposite phosphor The length is 600nm~2000nm, and the excitation wavelength of the nanocomposite phosphor is 250~600nm.

According to an embodiment of the present invention, the carrier has a mesoporous structure, and the oxide is selected from one or more of silicon dioxide, titanium dioxide, silicon oxide, titanium oxide, and zinc oxide.

The present invention also provides a method for preparing the above-mentioned nanocomposite phosphor, which includes: weighing the molar ratio of each element in ZnGa _2-xy O ₄ : xCr ³⁺ , yR containing Zn, Ga, Cr, Compounds of the R element are respectively dissolved to form a solution and then mixed to form a precursor solution; the carrier is placed in the precursor solution and mixed, and the mixed solution is heated and baked to form a powder; the powder is ground Afterwards, calcining for 6-20 hours to obtain the nanocomposite phosphor.

According to an embodiment of the present invention, the calcining treatment includes: heating the ground powder to 200°C~700°C at a rate of 2°C/min~5°C/min, and continue calcining for 1h~10h; Then increase the temperature to 500°C~1200°C at a rate of 2°C/min~5°C/min, and continue calcination for 1h~10h.

According to an embodiment of the present invention, the solid-to-liquid ratio mg:ml of the carrier to the precursor solution is 100:0.5-100:20; the molar concentration of the precursor solution is 0.1M-1.5M.

The present invention also provides a light-emitting device, comprising: an excitation light source and an encapsulation layer on the excitation light source, and the material of the encapsulation layer includes the above-mentioned nanocomposite phosphor and an encapsulation colloid.

According to an embodiment of the present invention, based on the total mass of the encapsulation layer, the mass fraction of the nanocomposite phosphor is 50%-100%.

According to an embodiment of the present invention, as the thickness of the encapsulation layer changes, the mass fraction of the nanocomposite phosphor changes gradually or continuously, and the average mass fraction of the nanocomposite phosphor is 50 %~100%.

According to an embodiment of the present invention, the excitation light source is a micro-LED chip, a micro-LD chip, or a sub-millimeter light-emitting diode chip (mini-LED). chip) or sub-millimeter laser diode chip (mini-LD chip), the chip is a horizontal chip, a vertical chip or a flip-chip chip.

The beneficial effects of the present invention are: the nanocomposite phosphor provided by the present invention uses an oxide carrier with a mesoporous structure to support the infrared phosphor, so that it has a nanometer size and has good dispersibility; the infrared phosphor The light powder uses Cr or its mixture (such as Sn or Ni) as the light emitting center, and the intensity of fluorescent light emission can be increased by adjusting the concentration of the light emitting center; in addition, traditional bulk phosphors are unevenly dispersed on microchips , The packaging effect is poor, and the phosphor of the present invention applied to micro/min-LED, micro/min-LD and other light-emitting devices still has good packaging density and light-emitting characteristics.

In short, the nanocomposite phosphor provided by the present invention has excellent dispersibility, high luminous efficiency and good encapsulation, and its particle size can be adapted to light-emitting devices such as micro/min-LED and micro/min-LD. Infrared light can be obtained under the excitation of visible light or ultraviolet light, which is expected to be applied to micro-small detection devices, iris/face detection, medical detection or gas detection devices, etc.

Figure 1 is a high-resolution electron microscope image of the mesoporous nanosilica of Example 1; Figure 2 is a Fourier transform infrared spectroscopy analysis of the mesoporous nanosilica of Example 1; Figure 3 is an implementation The X-ray diffraction spectrum of the nanocomposite phosphor of Example 1; Figure 4 is a high-resolution electron microscope image of the nanocomposite phosphor of Example 1; Figure 5 is the nanocomposite phosphor of Example 1 The photoluminescence spectra of the powder; Figure 6 is the photoluminescence relative intensity diagram of the nanocomposite phosphors of Examples 2 to 7; Figure 7 is the light of the nanocomposite phosphors of Examples 8 to 11 Graph of relative intensity of luminescence.

Figure 8 is a graph of the relative intensity of photoluminescence of the min-LED light-emitting device with different nano-composite phosphors in Example 13.

Typical embodiments embodying the features and advantages of the present disclosure will be described in detail in the following description. It should be understood that the present disclosure can have various changes in different embodiments, which do not depart from the scope of the present disclosure, and the descriptions and drawings therein are essentially for illustrative purposes, rather than limiting the present disclosure. .

The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges. These numerical ranges should be considered as specifically disclosed herein.

y<0.4，R選自Sn⁴⁺,Ti³⁺,V²⁺,Mn³⁺,Fe²⁺,Co³⁺,Ni³⁺,Nb⁵⁺,Mo⁵⁺,Tc⁵⁺,Ru⁴⁺,Rh⁴⁺,Pd⁴⁺,Sb⁵⁺,Ta⁵⁺,W⁵⁺,Re⁴⁺,Os⁴⁺,Ir⁴⁺,Pt⁴⁺中的一種或多種。 One aspect of the present invention is to provide a nano-composite phosphor. The nano-composite phosphor includes a carrier and an infrared phosphor supported on the carrier, wherein the carrier is an oxide, and the infrared phosphor The general chemical formula of light powder is ZnGa _2-xy O ₄ : xCr ³⁺ ,yR(ZGOCR), where x and y are mole fractions, and 0<x<0.4, 0

y<0.4, R is selected from Sn ⁴⁺ ,Ti ³⁺ ,V ²⁺ ,Mn ³⁺ ,Fe ²⁺ ,Co ³⁺ ,Ni ³⁺ ,Nb ⁵⁺ ,Mo ⁵⁺ ,Tc ⁵⁺ ,Ru ⁴⁺ One or more of, Rh ⁴⁺ , Pd ⁴⁺ , Sb ⁵⁺ , Ta ⁵⁺ , W ⁵⁺ , Re ⁴⁺ , Os ⁴⁺ , Ir ⁴⁺ , and Pt ⁴⁺ .

In some embodiments, the carrier in the nanocomposite phosphor has a mesoporous structure, and the oxide as the carrier is preferably silicon dioxide, titanium dioxide, silicon oxide, titanium oxide, zinc oxide, etc. For example, silicon oxide (MSNs) is the carrier. As the main crystal lattice, infrared phosphors with chromium (Cr) or its mixture (such as tin (Sn) or nickel (Ni)) as the emission center are loaded to make it have nano It has good dispersibility at the same time of rice size.

As the concentration of the emission center in the infrared phosphor increases, that is, for example, the concentration of doped Cr ³⁺ and Sn ⁴⁺ increases, the fluorescence emission intensity can be increased, but too high concentration will also affect the fluorescence emission intensity. In some embodiments, the concentration of Cr ³⁺ , that is, the number of moles of the added Cr ³⁺ partially substituted for Ga ³⁺ is 1%~5%, preferably 2%; the concentration of R ion is 1%~5 %.

In some embodiments, the particle size of the nanocomposite phosphor is less than 200 nm. The particle size makes it suitable for light-emitting devices such as micro-LED or min-LED. Among them, the mini-LED size is usually between 100-200μm; the micro-LED size is below 100μm.

In some embodiments, the emission wavelength of the nano-composite phosphor is 600 nm to 2000 nm, and the excitation wavelength of the nano-composite phosphor is 250 to 600 nm. The nanocomposite phosphor of the present invention can generate infrared light under the excitation of visible light or ultraviolet light emitted by micro-LED or min-LED, and can be applied to small electronic devices, such as remote control, car sensor, safety , Visual recognition, biomedical images, etc.

One aspect of the present invention also provides a method for preparing the above-mentioned nanocomposite phosphor, including:

y<0.4，R選自Sn⁴⁺,Ti³⁺,V²⁺,Mn³⁺,Fe²⁺,Co³⁺,Ni³⁺,Nb⁵⁺,Mo⁵⁺,Tc⁵⁺,Ru⁴⁺,Rh⁴⁺,Pd⁴⁺,Sb⁵⁺,Ta⁵⁺,W⁵⁺,Re⁴⁺,Os⁴⁺,Ir⁴⁺,Pt⁴⁺中的一種或多種。 S1: Weigh the compounds containing zinc (Zn), gallium (Ga), chromium (Cr) and R elements according to the general chemical formula ZnGa _2-xy O ₄ : xCr ³⁺ , yR in molar ratio of each element, and dissolve them separately After forming a solution, mix to form a precursor solution; where 0<x<0.4, 0

y<0.4, R is selected from Sn ⁴⁺ ,Ti ³⁺ ,V ²⁺ ,Mn ³⁺ ,Fe ²⁺ ,Co ³⁺ ,Ni ³⁺ ,Nb ⁵⁺ ,Mo ⁵⁺ ,Tc ⁵⁺ ,Ru ⁴⁺ One or more of, Rh ⁴⁺ , Pd ⁴⁺ , Sb ⁵⁺ , Ta ⁵⁺ , W ⁵⁺ , Re ⁴⁺ , Os ⁴⁺ , Ir ⁴⁺ , and Pt ⁴⁺ .

Specifically, in some embodiments, the Zn-containing compound is one or more of Zn-containing oxides, carbonates, nitrates, and halides; the Ga-containing compound is Ga-containing oxides, carbonic acid One or more of salt, nitrate, and halide; the compound containing Cr is one or more of oxide, carbonate, nitrate, and halide containing Cr; the compound containing R is one containing R One or more of oxides, carbonates, nitrates, and halides. After dissolving the above-mentioned compounds containing zinc (Zn), gallium (Ga), chromium (Cr), and R, respectively, the respective solutions are formed and then mixed uniformly to form a precursor solution.

S2: The carrier is placed in the precursor solution and mixed, and the mixed solution is heated and baked to form a powder; the carrier has a mesoporous structure, and the oxide of the carrier is preferably silicon dioxide, titanium dioxide, and oxide Silicon, titanium oxide, zinc oxide, etc.

Specifically, the carrier can be purchased commercially, or it can be made on-the-spot using methods commonly used in the art. Taking mesoporous nanosilica as the carrier as an example, a certain amount of mesoporous nanosilica is mixed in the prepared precursor solution, and the mixed solution is placed in a vacuum oven at 60℃~ Bake at 110°C for 1~24h, after all the solvents are evaporated, a powder will be formed.

S3: After grinding the powder, calcining for 6~20h to obtain the powder Rice composite phosphor.

Specifically, in some embodiments, the powder is ground and then placed in a boat-shaped crucible for calcination. The calcination includes: heating the ground powder at a temperature of 2°C/min~5°C/min. The temperature is increased to 200°C~700°C at a rate of ℃/min, and the calcination is continued for 1h~10h; then the temperature is increased to 500°C~1200°C at a rate of 2°C/min~5°C/min, and the calcination is continued for 1h~10h.

Calcining in this way can make the precursor solution uniformly form a stable crystal phase in the mesopores.

In some embodiments, the solid-to-liquid ratio mg:ml of the carrier to the precursor solution is 100:0.5-100:20; the molar concentration of the precursor solution is preferably 0.1M-1.5M. Wherein, the molar concentration of the precursor solution refers to the number of millimoles of the total solute contained in 1 ml of the precursor solution. As the molar concentration of the precursor solution increases, the content of the infrared phosphor finally loaded on the carrier increases, and the fluorescence intensity can be relatively increased. However, the molar concentration of the precursor solution should not be too high, and is preferably in the aforementioned range.

Another aspect of the present invention is to provide a light-emitting device, comprising: an excitation light source and an encapsulation layer on the excitation light source, and the material of the encapsulation layer includes the aforementioned nanocomposite phosphor and an encapsulation colloid.

Specifically, in some embodiments, the excitation light source includes, but is not limited to, a micro-LED chip, a micro-LD chip, and a sub-millimeter light-emitting diode chip. (mini-LED chip) or sub-millimeter laser diode chip (mini-LD chip), the chip is a horizontal chip, a vertical chip or a flip-chip chip. The encapsulation colloid is a commonly used colloid, which is commercially available, and is preferably a silicone-based silicone rubber.

In the manufacturing process, firstly, the excitation light source is die-bonded and bonded on a substrate; a certain amount of nano-composite phosphor and silica gel are mixed separately; then the mixture is packaged on the chip and baked to form the luminescence Device.

In some embodiments, based on the total mass of the encapsulation layer, the mass fraction of the nanocomposite phosphor is 50%-100%. That is, the mass of the nanocomposite phosphor accounts for 50%-100% of the total mass of the encapsulation layer.

In some embodiments, as the thickness of the encapsulation layer changes, the mass fraction of the nanocomposite phosphor changes gradually or continuously, and the average mass fraction of the nanocomposite phosphor is 50%~ 100%. That is, the concentration (mass fraction) of the nano-phosphor powder may be higher or lower as the distance to the excitation light source wafer is closer, and the concentration may change gradually or continuously.

The higher the quality of the phosphor, the thinner and denser the phosphor layer formed, which is conducive to the heat dissipation of the chip, reduces the occurrence of colloidal cracks, and improves the light efficiency of the LED chip; the lower the quality of the phosphor, The phosphor layer formed will be more transparent, which is conducive to obtaining a larger distance between adjacent light-emitting wafers in the later process, reducing the precision requirements for cutting and separating the light-emitting wafer covered with phosphor or phosphor colloid, thereby improving the reliability and reliability of the device. Uniformity. Therefore, by making the phosphor in the encapsulation layer have a gradient concentration, for example, the phosphor concentration of the part close to the chip is higher, and the phosphor concentration of the part far away from the chip is lower, so that the light efficiency can be improved on the one hand, and the other This is conducive to the later process.

The following is illustrated by specific embodiments:

Example 1

(1) Preparation of mesoporous nanosilica (MSNs)

Dissolve 5.728 g of Hexadecyl trimethyl ammonium bromide (CTAB) in 280 mL of deionized water and 80 mL of absolute ethanol, then add 0.5 mL of aqueous ammonia (NH ₄ OH) in an oil bath at 60°C Mix well for 30 minutes. When the CTAB is dissolved, add 14.6 mL of Tetraethyl orthosilicate (TEOS) slowly, and mix it evenly for 2 hours in an oil bath at 60°C.

Place the mixed solution in a centrifuge tube for centrifugation and wash it with anhydrous methanol three times, then put it in a vacuum oven together with the centrifuge tube, and hold the temperature at 110°C for 3 hours to form a white dry substance. Grind the obtained white dried material and place it in a boat-shaped crucible. At a temperature rising rate of 5°C per minute, the temperature is raised to 550°C, and the temperature is maintained for five hours and then cooled in the furnace to form mesoporous nanosilica. Then they were analyzed by high-resolution transmission electron microscope (High-resolution transmission electron microscope-) and Fourier-transform infrared spectrum (FTIR) (as shown in Figure 1 and Figure 2, respectively). According to HRTEM analysis, the appearance of secondary mesoporous nanosilica is polygonal particles with a particle size of about 64nm. FTIR analysis of the major functional groups known as ^{Si-O-Si (1100cm -1} ), Si-OH (1600cm -1), Si-H (2400cm -1) and OH (3500cm ^-1).

(2) Preparation of precursor solution

Place 4.5861 g of Ga ₂ O ₃ in a 60 mL aqueous solution containing 40 mL of nitric acid, and dissolve the solid in an oil bath at 95° C. to obtain a 0.25 M gallium nitrate solution. Then take 1mL of 0.25M Gallium(III)nitrate solution and mix it with 23.4mg of Zinc acetate, 1mg of Chromium nitrate and 0.48mg of Stannous chloride , Form a precursor solution.

(3) Preparation of nano-composite phosphor

The precursor solution prepared in step (2) was mixed with 100 mg of MSNs prepared in step (1), and then placed in a vacuum oven and baked at 110° C. for 3 hours to form a powder. Grind the powder It is placed in a ship-shaped crucible, and the temperature rises to 600°C at a heating rate of 5°C per minute, and the temperature is maintained for 2 hours; then at a heating rate of 2°C per minute to 1000°C, the temperature is maintained for 4 hours and then the furnace is cooled to obtain the Rice composite phosphor (ZGOCS@MSNs).

Through the analysis of XRD spectrum (as shown in Figure 3), ZGOCS@MSNs is a single-phase solid solution with a cubic spinel structure; it is analyzed by a high-resolution electron microscope (as shown in Figure 4), It can be known that the particle size of ZGOCS@MSNs is 57nm, and it can be observed that the spherical particles with a darker color in the center of the particles are ZGOCS. And observed by the photoluminescence spectra (PL) (as shown in Figure 5), the excitation range of the ZGOCS@MSNs is 250nm-600nm, and the excitation peak is 406nm ( ⁴ A ₂ → ⁴ T ₁ ) and 550nm ( ⁴ A ₂ → ⁴ T ₂ ); the luminous range is 650nm-750nm, the luminous peak is 705nm ( ² E→ ⁴ A ₂ ), and the half-maximum width (FWHM) is 50nm. Compared with 460nm blue light, with 406nm ultraviolet light source as excitation, ZGOCS@MSNs has higher luminous intensity.

Examples 2~7

The nanocomposite phosphor was prepared according to the method of Example 1, except that the molar fractions of Cr ³⁺ and Sn ⁴⁺ co-doped were changed, as shown in Table 1:

Observe the luminescence properties of the nanocomposite phosphors prepared in the above different examples through PL spectroscopy, and convert the integral area of the luminescent region into a relative intensity distribution diagram (as shown in Figure 6), and it can be seen that it has 2% Cr ^{3 +} and 2% Sn ⁴⁺ nanocomposite phosphor has the highest fluorescence intensity.

Examples 8~11

Prepare nanocomposite phosphors according to the method of Example 4 (the molar concentration of the precursor solution is 0.125M), except that the molar concentration of the precursor solution is increased respectively, as shown in Table 2:

Observe the luminescence properties of the nanocomposite phosphors prepared in the above different embodiments through PL spectroscopy, and convert the integral area of the luminescence area into a relative intensity distribution diagram (as shown in Figure 7), which shows that the molar concentration is increased Four times the nano-composite phosphor has the highest fluorescence intensity.

Example 12

Choose 9*5mil size, 473nm GaN-containing Mini-LED chip with a luminous band of 473nm, a particle size of 57nm, and a luminous peak of 705nm ZGOCS@MSNs as the phosphor. The encapsulant is made of silicone, ZGOCS@MSNs The mass ratio of phosphor to silicone-based silicone is 1:1.

Bonding the Mini-LED chip to a substrate, mixing the phosphor and silicone-based silicone, and then encapsulating the mixture on the Mini-LED chip and baking it to form a phosphor containing ZGOCS@MSNs Pink Mini-LED lighting device.

Example 13

The method of Example 12 was used to prepare a Mini-LED light-emitting device. The PL spectrum (as shown in Figure 8) was used to observe the luminescence performance of the light-emitting devices prepared with the nanocomposite phosphors of Example 4 and Example 10. It can be further seen that when ZGOCS@MSNs phosphors are used After the light-emitting device, as the molar concentration of the precursor solution increases, the fluorescence intensity increases and the luminous efficiency becomes higher.

Those skilled in the art should note that the described embodiments of the present invention are only exemplary, and various other substitutions, changes and improvements can be made within the scope of the present invention. Therefore, the present invention is not limited to the above-mentioned embodiments, but is only limited by the scope of patent application.

Claims (11)

A nano-composite phosphor comprising a carrier and an infrared phosphor supported on the carrier, wherein the carrier is an oxide, and the general chemical formula of the infrared phosphor is ZnGa _2-xy O ₄ : xCr ³⁺ , yR, where x and y are both molar fractions, and 0<x<0.4, 0

y<0.4, R is selected from Sn ⁴⁺ ,Ti ³⁺ ,V ²⁺ ,Mn ³⁺ ,Fe ²⁺ ,Co ³⁺ ,Ni ³⁺ ,Nb ⁵⁺ ,Mo ⁵⁺ ,Tc ⁵⁺ ,Ru ⁴⁺ One or more of, Rh ⁴⁺ , Pd ⁴⁺ , Sb ⁵⁺ , Ta ⁵⁺ , W ⁵⁺ , Re ⁴⁺ , Os ⁴⁺ , Ir ⁴⁺ , and Pt ⁴⁺ . The nano-composite phosphor according to claim 1, wherein the particle size of the nano-composite phosphor is less than 200 nm. The nanocomposite phosphor according to claim 1, wherein the emission wavelength of the nanocomposite phosphor is 600 nm to 2000 nm, and the excitation wavelength of the nanocomposite phosphor is 250 to 600 nm. The nanocomposite phosphor according to claim 1, wherein the carrier has a mesoporous structure, and the oxide is selected from one or more of silicon dioxide, titanium dioxide, silicon oxide, titanium oxide, and zinc oxide. A method for preparing nanocomposite phosphors according to any one of claims 1 to 4, comprising: mol ratio scale of each element in yR according to the general chemical formula ZnGa _2-xy O ₄ : xCr ³⁺ Take compounds containing Zn, Ga, Cr, and R elements, respectively dissolve them to form a solution and mix to form a precursor solution; place the carrier in the precursor solution and mix, and the mixed solution is heated and baked to form a powder ; After the powder is ground, calcined for 6-20h to obtain the nanocomposite phosphor. The preparation method according to claim 5, wherein the calcining treatment includes: heating the ground powder to 200°C to 700°C at a rate of 2°C/min to 5°C/min, and holding Continue calcining for 1h~10h; then increase the temperature to 500℃~1200℃ at a rate of 2℃/min~5℃/min, and continue calcining for 1h~10h. The preparation method according to claim 5, wherein the solid-to-liquid ratio mg:ml of the carrier to the precursor solution is 100:0.5-100:20; the molar concentration of the precursor solution is 0.1M-1.5M. A light emitting device includes an excitation light source and an encapsulation layer on the excitation light source, wherein the material of the encapsulation layer includes the nanocomposite phosphor according to any one of claims 1 to 4 and an encapsulation colloid. The light emitting device according to claim 8, wherein, based on the total mass of the encapsulation layer, the mass fraction of the nanocomposite phosphor is 50%-100%. The light-emitting device according to claim 9, wherein as the thickness of the encapsulation layer changes, the mass fraction of the nanocomposite phosphor changes gradually or continuously, and the average mass fraction of the nanocomposite phosphor It is 50%~100%. The light-emitting device according to claim 8, wherein the excitation light source is a miniature light-emitting diode chip, a miniature laser diode chip, a sub-millimeter light-emitting diode chip or a sub-millimeter laser diode chip, and the chip is Horizontal chip, vertical chip or flip chip.

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