Sky blue light source LED packaging device

Abstract

The invention provides a sky-green light source LED packaging device, and belongs to the technical field of luminescent materials. The azure light source LED packaging device comprises a light-emitting substrate, wherein the light-emitting substrate comprises fluorescent powder; the fluorescent powder comprises blue-green fluorescent powder and green fluorescent powder; the light-emitting peak wavelength of the blue-green fluorescent powder is 490-500 nm, the molecular formula of the blue-green fluorescent powder is (Ba1-x-ySrxEuy) Si2N2O2, and x is greater than or equal to 0.001 and less than or equal to 0.3; 0.001 < = y < = 0.1; the blue-green fluorescent powder is of an orthogonal structure and is crystallized in a space group Pcca. According to the invention, on the basis of realizing azure luminescence, the luminescence performance of the azure luminescence is improved, especially the luminescence intensity of the azure luminescence is improved, and the anti-aging performance of the azure light source LED packaging device is also improved.

Description

Technical Field

[0001] This application relates to the field of luminescent materials technology, and more specifically, to a sky-blue light source LED packaging device. Background Technology

[0002] With the rapid development of the automotive industry and intelligent technology, intelligent driving technology is maturing and beginning to be widely applied. Intelligent driving systems not only rely on advanced sensors, algorithms, and control systems, but also require efficient and accurate information exchange methods to communicate with the driver and other road users. As a key component of information exchange, the performance and reliability of intelligent driving indicator lights directly affect driving safety and the driving experience.

[0003] Currently, mainstream automakers such as Li Auto, XPeng, and Xiaomi have taken the lead in deploying the intelligent driving indicator light, commonly known as the "little blue light," in their mass-produced models. The installation locations cover areas such as the center of the front and rear lights, below the exterior rearview mirrors, and both sides of the rear of the vehicle. The XY color point range of this indicator light is (X=0.012-0.2-0.2-0.04, Y=0.494-0.4-0.32-0.32), and the light color is sky blue.

[0004] However, traditional sky-blue LED devices have poor luminous brightness and poor anti-aging performance, so it is necessary to provide a new type of sky-blue LED packaging device. Summary of the Invention

[0005] To address the aforementioned issues, this application provides a sky-blue LED packaging device. This sky-blue LED packaging device exhibits excellent luminous brightness, adjustable color point, and superior anti-aging properties.

[0006] In one aspect, this application provides a sky-blue light source LED packaging device.

[0007] The sky-blue LED packaging device of this application includes a light-emitting matrix, wherein the light-emitting matrix includes phosphor; the phosphor includes blue-green phosphor; the emission peak wavelength of the blue-green phosphor is 490nm~500nm, and its molecular formula is (Ba 1-x-y Sr x Eu y The blue-green phosphor has an orthorhombic structure and is crystallized in space group Pcca.

[0008] Based on the above scheme, this application can improve the luminescence performance of azure light emission, especially the luminescence intensity of azure light emission, while also improving the anti-aging performance of fluorescent materials. Furthermore, the color point is more flexible and adjustable compared to traditional azure schemes.

[0009] In some embodiments, the phosphor further includes a green phosphor, wherein the peak emission wavelength of the green phosphor is 500 nm to 530 nm.

[0010] Based on the above scheme, blue-green phosphors can be combined with green phosphors to improve the luminescence intensity of sky-blue emission while achieving sky-blue emission, and also improve the anti-aging performance of fluorescent materials and the flexibility of color point adjustment.

[0011] In some embodiments, the green phosphor comprises a molecular formula of M 3-a Al5O 12 :aCe 3+ (Ba,Sr) 2-b SiO4, Ca c Mg(SiO4) d At least one of Cl2; wherein M is at least one of Y, Lu, and Ga; and parameters a, b, c, and d satisfy the following conditions: 0.001≤a≤0.5; 0.001≤b≤0.5; 7.5≤c≤8.5; 3.5≤d≤4. Based on the above scheme, while meeting the color point requirements, the luminous brightness and anti-aging performance of the device can be further improved, and the landing point and slope can be flexibly adjusted in the target color area.

[0012] In some embodiments, based on the total mass of the phosphors, the blue-green phosphor accounts for 8% to 40% of the mass, and the green phosphor accounts for 60% to 92% of the mass. Based on the above scheme, the matching degree between the green phosphor and the blue-green phosphor can be further improved, thereby further enhancing the luminescence intensity and long-term aging resistance of the phosphors.

[0013] In some embodiments, the luminescent matrix further includes a fluorescent adhesive.

[0014] In some embodiments, the fluorescent adhesive comprises silicone.

[0015] In some embodiments, the mass ratio of the silicone to the phosphor is 0.7 to 2.5:1. Based on the above scheme, it is beneficial to ensure that the silicone and the phosphor form a uniformly composed luminescent matrix, thus facilitating the guarantee of the overall device's luminescence quality.

[0016] In some embodiments, the azure light source LED packaging device further includes a bracket, two LED chips, and bonding wires; the bracket has a cavity structure and includes a positive electrode and a negative electrode; the two LED chips are disposed at the bottom of the cavity structure, and the two LED chips are respectively connected to the positive electrode and the negative electrode of the bracket through bonding wires; the light-emitting matrix fills the gap between the two LED chips and the cavity structure.

[0017] In some embodiments, the LED chip includes a blue light chip with a peak wavelength of 450nm to 455nm.

[0018] In some embodiments, the material of the bracket includes at least one of PCT and EMC.

[0019] In some embodiments, the welding wire is made of any one of gold wire, silver wire, gold-silver alloy wire, and copper wire.

[0020] In some embodiments, two LED chips are arranged in series or in parallel at the bottom of the cavity structure.

[0021] The embodiments of this application have at least the following beneficial effects: This application uses the molecular formula (Ba) 1-x-y Sr x Eu y Using Si2N2O2 blue-green phosphor as the phosphor, the sky-blue light source LED packaging device of this application not only achieves sky-blue light emission but also improves the luminous performance of sky-blue light emission, especially the luminous intensity of sky-blue light emission, while also improving the anti-aging performance of the fluorescent material.

[0022] This application uses the molecular formula (Ba 1-x-y Sr x Eu y The blue-green phosphor of Si2N2O2 is compounded with green phosphor to form phosphor, which enables the sky-blue light source LED packaging device of this application to not only achieve sky-blue light emission, but also to better improve the luminous intensity of sky-blue light emission, and to better improve the anti-aging performance of the fluorescent material and the flexibility of color point adjustment.

[0023] This application, by limiting the total mass of the phosphors, with blue-green phosphors accounting for 8% to 15% and green phosphors accounting for 85% to 92%, can further improve the matching degree between green and blue-green phosphors. In addition to achieving azure light emission, it can also achieve flexible and adjustable XY landing points in the target color region, and further improve the luminescence intensity and anti-long-term aging performance of the phosphors. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0025] Figure 1 This is a schematic diagram of the structure of this application.

[0026] Figure 1 In the middle, 1-light-emitting substrate, 2-LED bracket, 3-LED chip, 4-welding wire.

[0027] Figure 2 The image shows the refined XRD pattern of the blue-green phosphor in Example 1.

[0028] Figure 3 The image shows the emission spectrum of the azure light source LED package device in Example 1.

[0029] Figure 4 The image shows the emission spectrum of the azure light source LED package device in Example 2.

[0030] Figure 5 The image shows the emission spectrum of the LED packaged device in Comparative Example 1.

[0031] Figure 6 The image shows the emission spectrum of the LED packaged device in Comparative Example 2.

[0032] Figure 7 This is a schematic diagram showing the position of azure in the CIE XYZ chromaticity diagram. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0034] In the description of this application, the terms "upper," "lower," "right," etc., refer to the orientation or positional relationship shown in the accompanying drawings, and are used only for ease of description and simplification of operation. They do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this application. In addition, the terms "first" and "second" are used only for descriptive distinction and have no special meaning.

[0035] The technical solutions in this application will now be described clearly and in detail with reference to the accompanying drawings.

[0036] Blue-green fluorescent powder The blue-green phosphor of this application has an emission peak wavelength of 490nm~500nm, and its molecular formula is (Ba 1-x- y Sr x Eu y The green phosphor has a peak emission wavelength of 500 nm to 530 nm, wherein 0.001 ≤ x ≤ 0.3 and 0.001 ≤ y ≤ 0.1.

[0037] The blue-green phosphor of this application has (Ba 1-x-y Sr x Eu y The Si2N2O2 crystal structure is an orthorhombic structure and crystallizes with space group Pcca. It is understood that the term "space group Pcca" in this application refers to the orthorhombic non-point space group numbered 54 in International Tables Crystallography A.

[0038] It should be noted that blue-green phosphor (Ba) can be used. 1-x-y Sr x Eu y Si2N2O2 can be understood as: using oxynitrogen silicate (BaSi2N2O2) as a matrix, and introducing Sr into its structure through simultaneous doping. 2+ and Eu 2+ , making Sr 2+ and Eu 2+ All dopants are injected into the Ba sites to partially replace Ba. 2+ Among them, Eu 2+ The doping is to introduce luminescent centers into the oxynitrosilicate matrix, the luminescent centers Eu 2+ Ions are situated within a specific crystal field provided by the oxygen-nitrogen silicate matrix, thus achieving narrow-band blue-green emission; Sr 2+ Co-doping with Sr is beneficial for improving the structural rigidity of phosphor crystals because Sr 2+ The ionic radius is smaller than that of the substituted Ba. 2+ The ionic radius, Sr doping will cause lattice shrinkage in the oxynitrosilicate matrix, thereby increasing crystal rigidity and thus improving the luminescence stability of the phosphor. Here, x can be understood as the Sr... 2+ At the molar doping concentration of the Ba site, y can be understood as Eu 2+ Regarding the molar doping concentration at the Ba site, this application controls x within the range of 0.001 ≤ x ≤ 0.3 and y within the range of 0.001 ≤ y ≤ 0.1, thereby reducing the Sr doping concentration. 2+ and Eu 2+ It can better achieve BaSix N y O z1 The crystal structure was regulated and optimized, which enabled the blue-green phosphor to achieve azure emission while improving the luminescence performance of azure emission, especially the luminescence intensity of azure emission, and also improved the anti-aging performance of the fluorescent material.

[0039] In some embodiments, 0.001 ≤ x ≤ 0.1; 0.001 ≤ y ≤ 0.03. Based on the above scheme, the Sr introduced by doping is... 2+ and Eu 2+ It can better achieve BaSi x N y O z1 By regulating and optimizing the crystal structure, the luminous efficiency, color purity, and long-term aging performance of blue-green phosphors in sky blue emission can be better improved.

[0040] Preparation method of blue-green phosphor This application does not limit the specific preparation method of the blue-green phosphor, as long as the blue-green phosphor of this application can be obtained. For example, in some embodiments, a solid-state sintering method can be used for preparation.

[0041] In some embodiments, the preparation method of the blue-green phosphor of this application includes the following steps: S1, Preparation of reaction raw materials: According to the elemental composition of the inorganic substances in the blue-green phosphor, provide the corresponding reaction raw materials of Ba, Sr, Eu, Si, N and O.

[0042] It should be noted that this application does not limit the specific form in which the Ba reaction raw materials are added, as long as no other impurities are introduced and the corresponding mass of Ba element is provided. For example, in some embodiments, the Ba reaction raw materials include Ba oxides and / or carbonates.

[0043] For example, in some embodiments, the reaction feedstock for Ba is selected from barium carbonate (BaCO3).

[0044] This application does not limit the specific form in which Sr reaction raw materials are added, as long as no other impurities are introduced and the appropriate mass of Sr element is provided. For example, in some embodiments, the Sr reaction raw materials include Sr oxides and / or carbonates.

[0045] For example, in some embodiments, the reaction feedstock for Sr includes strontium carbonate (SrCO3).

[0046] This application does not limit the specific form in which Si reaction raw materials are added, as long as no other impurities are introduced and the appropriate mass of Si element is provided. For example, in some embodiments, the Si reaction raw materials include Si oxides and / or nitrides.

[0047] For example, in some embodiments, the reactants for Si include silicon nitride.

[0048] This application does not limit the specific form in which Eu reactants are added, as long as no other impurities are introduced and the appropriate mass of Eu element is provided. For example, in some embodiments, the Eu reactants include Eu oxides and / or nitrides.

[0049] For example, in some embodiments, the reactants for Eu include europium oxide.

[0050] In this application, O is provided by oxides of other elements, and N is provided by nitrides of other elements.

[0051] S2, Preparation of the mixture: Mix each reactant with the flux evenly to obtain the mixture.

[0052] This application does not limit the specific flux used, as long as it can achieve the effects described herein. For example, in some embodiments, the flux used in this application includes at least one of metal halides, NH4Cl, NH4F, H3BO3, and alkaline earth metal halides. Based on the above scheme, the added flux reduces the temperature of subsequent heat treatment, promotes grain growth and phase purification, and improves luminescence performance and batch stability. For example, the flux can form a liquid phase environment when melted at high temperature, reducing the mass transfer resistance between reactant particles, shortening the ion diffusion path, and facilitating the contact and reaction of various reactants, such as promoting the combination reaction of Ba, Si, N, and O elements.

[0053] In some embodiments, the flux content is 1.5% to 3% by mass, based on the total mass of the mixture. Based on the above scheme, while achieving the aforementioned effects, it is possible to avoid abnormal grain growth or lattice distortion caused by excessive flux, which could negatively reduce luminescence performance.

[0054] This application does not limit the specific mixing method, as long as it can ensure that the reactants and flux are mixed evenly. For example, in some embodiments, a ball mill can be used for mixing, which is beneficial to further improve the mixing uniformity of the materials and promotes the formation of the target crystal structure in the subsequent solid-state sintering process.

[0055] S3, first sintering: The mixture is heated at a temperature T1 under an inert gas atmosphere to form a first powder cake; wherein T1 ≥ 1300°C.

[0056] This application considers that the optimal crystallization temperature of BaSi2N2O2 is close to 1300℃. Therefore, under an inert gas atmosphere, a reaction temperature of ≥1300℃ is used to avoid potential oxidation side reactions between the reactant BaCO3 and air (oxygen), and to suppress the decomposition of silicon nitride Si3N4. This reduces the formation of impurity phases such as BaSiN2 and SiO2, achieving the directional formation of a pure-phase BaSi2N2O2 lattice and providing stable lattice sites for activating ions. Simultaneously, it avoids abnormal growth in the subsequent high-temperature stage caused by insufficient grain development at low temperatures. Furthermore, a temperature of ≥1300℃ is beneficial for eliminating pores and residual gases, reducing defects such as pores and cracks inside the first powder cake, and improving powder density.

[0057] For example, the sintering temperature T1 for the first sintering is 1300℃~1450℃.

[0058] This application does not limit the specific sintering time of the first sintering, which can be adjusted according to the specific temperature T1 used. For example, in some embodiments, the sintering time of the first sintering is 3 hours to 16 hours.

[0059] S4, Crushing: Crushing the first powder cake to obtain fluorescent powder.

[0060] Based on the above scheme, this application first pulverizes the first powder cake obtained by the first sintering and then performs a second sintering, which is beneficial for element A and element RE to be better doped into the target basic lattice during subsequent heating, so as to form the blue-green phosphor with orthorhombic structure and crystallized in space group Pcca.

[0061] In some embodiments, the first powder cake is pulverized to a size that allows it to pass through a 100-mesh sieve. Based on the above approach, it is more beneficial for subsequent Eu... 3+ The reduction and in Ba 2+ Precise replacement of lattice sites.

[0062] S5, Second sintering: Under a nitrogen-hydrogen mixed atmosphere, the phosphor is sintered at temperature T2 to form a second powder cake; wherein 1200℃≤T2 <T1。

[0063] Based on the above scheme, it is beneficial to Eu 2+ It can evenly occupy Ba 2+ The lattice sites are precisely located to avoid ion occupancy disorder caused by oxidation, which can better improve the luminescence intensity of blue-green phosphors.

[0064] For example, 1200℃≤T2≤(T1-50℃).

[0065] This application does not limit the specific sintering time of the second sintering; it can be adjusted according to the specific temperature T2 used. For example, in some embodiments, the sintering time of the second sintering is 2 hours to 10 hours.

[0066] In some embodiments, the hydrogen content in the nitrogen-hydrogen mixed atmosphere is ≥2% to better achieve Eu 3+ Restore to Eu 2+ In some embodiments, the hydrogen content in the nitrogen-hydrogen mixture atmosphere is 2% to 10%.

[0067] S6, Post-processing: Crush the second powder cake to obtain the blue-green fluorescent powder.

[0068] In some embodiments, the second powder cake is pulverized to the point where it can pass through a 300-mesh sieve.

[0069] In some embodiments, the post-processing of S6 further includes impurity removal, drying, and grading after pulverization. Based on the above scheme, it is possible to better remove impurities from the second powder cake.

[0070] In some embodiments, impurity removal is performed by acid washing to remove water-soluble and acid-soluble impurities.

[0071] This application does not limit the specific type of acid, as long as it can achieve the effect of this application. For example, in some embodiments, nitric acid is used as the acid for impurity removal, so as to achieve impurity removal without introducing other elements.

[0072] This application does not limit the specific acid concentration, as long as it achieves the desired effect. For example, in some embodiments, a nitric acid solution with a mass concentration of 3% to 7% is used for impurity removal. Based on the above method, impurity removal can be achieved without damaging the crystal structure of the target blue-green phosphor.

[0073] Luminescent matrix The luminescent matrix of this application includes any kind of phosphor, and the phosphor includes any of the blue-green phosphors mentioned above.

[0074] In some embodiments, the phosphor further includes a green phosphor, wherein the emission peak wavelength of the green phosphor is 500 nm to 530 nm. Based on the above scheme, the blue-green phosphor and the green phosphor can be combined to better improve the luminescence intensity of the sky-blue emission while achieving sky-blue emission, and to better improve the anti-aging performance of the fluorescent material and the flexibility of color point adjustment.

[0075] In some embodiments, the green phosphor comprises a molecular formula of M3-a Al5O 12 :aCe 3+ (Ba,Sr) 2-b SiO4, Ca c Mg(SiO4) d At least one of Cl2; wherein M is at least one of Y, Lu, and Ga; and parameters a, b, c, and d satisfy the following conditions: 0.001≤a≤0.5; 0.001≤b≤0.5; 7.5≤c≤8.5; 3.5≤d≤4.5. Based on the above scheme, the green phosphor of this application can be better matched with blue-green phosphor, realizing flexible adjustment of the phosphor's emission color within the specified sky-blue color region, which is beneficial to meeting different fluorescence requirements.

[0076] In some embodiments, based on the total mass of the phosphors, the blue-green phosphor accounts for 8% to 15% of the mass, and the green phosphor accounts for 85% to 92% of the mass. Based on the above scheme, the matching degree between the green phosphor and the blue-green phosphor can be further improved, thereby further enhancing the luminescence intensity and long-term aging resistance of the phosphors.

[0077] In some embodiments, the luminescent matrix further includes a fluorescent adhesive. This allows for the formation of a luminescent matrix with a uniform component distribution through the fluorescent adhesive and phosphor.

[0078] In some embodiments, this application does not limit the specific type of fluorescent adhesive, as long as it can achieve the effect of this application. For example, in some embodiments, the fluorescent adhesive includes, but is not limited to, silicone.

[0079] This application does not limit the specific type of silicone rubber, as long as it can achieve the effect of this application. For example, in some embodiments, the silicone rubber used includes at least one of vinyl silicone resin and polyurethane resin. The polyurethane resin has a molecular weight of 2000-10000 for its polyurethane groups, and the mass of the polyurethane resin is 35%-45% of the mass of the vinyl silicone resin.

[0080] This application does not limit the specific amount of fluorescent adhesive added, as long as the desired effect is achieved. For example, in some embodiments, the mass ratio of the fluorescent adhesive to the phosphor is 0.7~2.5:1. Based on the above scheme, it is beneficial to form a uniformly composed luminescent matrix between the silicone and the phosphor, which helps to ensure the overall luminescence quality of the device.

[0081] support The stent of this application has a cavity structure, and the stent includes a positive electrode and a negative electrode.

[0082] This application does not limit the specific material of the support; it can be selected according to actual needs. For example, in some embodiments, the material of the support includes at least one of PCT and EMC.

[0083] LED chips This application does not limit the specific type of LED chip; any type can be selected according to actual needs. For example, in some embodiments, the LED chip of this application includes a blue light chip with a peak wavelength of 450nm~455nm.

[0084] In some embodiments, two LED chips are included, which are disposed at the bottom of the cavity structure and are respectively connected to the positive and negative terminals of the bracket via bonding wires.

[0085] Welding line The bonding wires in this application are used to bond the positive or negative terminals of LED chips and brackets.

[0086] This application does not limit the specific type of welding wire, as long as it can achieve the effect of this application. For example, in some embodiments, the material of the welding wire includes any one of gold wire, silver wire, gold-silver alloy wire, and copper wire.

[0087] Sky blue LED packaging device The sky-blue light source LED packaging device of this application includes any of the above-mentioned light-emitting substrates, any of the above-mentioned brackets, two of the above-mentioned LED chips, and any of the above-mentioned bonding wires.

[0088] The bracket has a cavity structure and includes a positive electrode and a negative electrode; two LED chips are disposed at the bottom of the cavity structure and are respectively connected to the positive electrode and the negative electrode of the bracket via bonding wires; the light-emitting matrix fills the gap between the two LED chips and the cavity structure.

[0089] In some embodiments, the LED chip includes a blue light chip with a peak wavelength of 450nm to 455nm.

[0090] In some embodiments, two LED chips are arranged in series or in parallel at the bottom of the cavity structure.

[0091] For example, the azure light source LED packaging device of this application includes an LED bracket, two LED chips, bonding wires, and a light-emitting matrix. The LED bracket has a cavity structure, and a positive and a negative electrode are disposed on the LED bracket. Two LED chips are disposed at the bottom of the cavity structure, and a filling gap is formed between the two LED chips and the cavity structure, with the light-emitting matrix filling the filling gap; the two LED chips are respectively connected to the positive and negative electrodes of the LED bracket via bonding wires. The light-emitting matrix includes phosphor; the phosphor includes blue-green phosphor and green phosphor; the blue-green phosphor has an emission peak wavelength of 490nm~500nm, and its molecular formula is (Ba... 1-x-y Sr x Eu y The green phosphor contains Si₂N₂O₂, wherein 0.001≤x≤0.3 and 0.001≤y≤0.1, and the peak emission wavelength of the green phosphor is 500nm~530nm. Based on the above scheme, compared with traditional azure light source LED packaging devices, the azure light source LED packaging device of this application improves the luminous performance of azure light emission, especially the luminous intensity of azure light emission, while also improving the anti-aging performance of the fluorescent material.

[0092] Test methods (a) Photoelectric integrating sphere test: The test was conducted using the Yuanfang HAAS-2000 photoelectric integrating sphere equipment.

[0093] (II) Aging test: The Dongguan Weihuang WHTH-800 LED aging analysis instrument was used. The test conditions were: 85℃, 85% relative humidity, 3V test voltage, and 350mA test current. The initial brightness of the LED device and the luminous brightness of the LED device after 1000 hours of operation were tested. The luminous flux Φ (unit: lm) was used as the indicator for evaluating brightness.

[0094] The following specific embodiments and comparative examples are provided to better illustrate this application. Unless otherwise specified, the raw materials used in the following embodiments are all from common commercially available products, and the devices or equipment used are all purchased from conventional commercial sales channels.

[0095] Example 1 Please see Figure 1 This embodiment provides a sky-blue light source LED packaging device, which is manufactured through the following steps: Step 1, blue-green phosphor Ba 0.934 Sr 0.05 Eu 0.016 Preparation of Si2N2O2: 1.1 Preparation of reaction raw materials: According to Ba 0.934 Sr 0.05 Eu 0.016 The stoichiometric ratio of Si2N2O2 is as follows: 184.71g of barium carbonate (purity ≥99.9%), and the corresponding masses of strontium carbonate (purity ≥99.9%), silicon dioxide (purity greater than 99.9%), silicon nitride (purity ≥99.9%), europium oxide (purity of 5N), and 2.65g of fluxing ammonium fluoride.

[0096] 1.2 Preparation of the mixture: The above-mentioned reactants and fluxes are loaded into a mixing tank and mixed evenly to obtain a mixture.

[0097] 1.3, First sintering: The above mixture was placed into a molybdenum crucible and covered, then placed in a carbon tube furnace and sintered at 1380°C for 12 hours in high-purity nitrogen (purity ≥99.99%) to obtain the first powder cake.

[0098] 1.4, Crushing: The first powder cake obtained in 1.3 above is crushed and passed through a 100-mesh sieve to obtain fluorescent powder.

[0099] 1.5, Second sintering: The phosphor obtained in 1.4 above was placed into a molybdenum crucible and covered. It was then placed in a carbon tube furnace and sintered at 1280°C for 6 hours in a high-purity hydrogen-nitrogen mixture (hydrogen volume content 2%) to obtain the second powder cake.

[0100] 1.6 Post-processing: The second powder cake obtained in 1.5 above was pulverized by a jaw crusher and a roller crusher, passed through a 300-mesh sieve, and then washed in a 5% nitric acid solution for 30 minutes. After filtration and drying, the blue-green fluorescent powder Ba was obtained. 0.934 Sr 0.05 Eu 0.016 Si2N2O2.

[0101] This application uses a Bruker D8 X-ray diffractometer to perform X-ray diffraction tests on the blue-green phosphor obtained in this embodiment, and uses the GSAS-II project software package to refine and solve the X-ray diffraction test results. The refined XRD pattern of the blue-green phosphor in Example 1 is shown below. Figure 2 As shown. It should be noted that, generally, when Rwp satisfies Rwp < 15%, the refinement result is considered to have converged, meaning that the calculated crystal structure matches the measurement data.

[0102] Depend on Figure 2As can be seen from the refined XRD pattern of the blue-green phosphor in Example 1, the refined result Rwp is 10.449%, and the refined result converges, indicating that the measured data of the blue-green phosphor obtained in Example 1 matches the calculated crystal structure. This proves that the blue-green phosphor obtained in Example 1 is indeed the orthorhombic non-point space group Pcca, numbered 54 in International Crystallographic Table A, and its molecular formula is Ba. 0.934 Sr 0.05 Eu 0.016 Si2N2O2.

[0103] Step 2, Preparation of phosphor: The blue-green phosphor Ba obtained above 0.934 Sr 0.05 Eu 0.016 Si2N2O2 and green phosphor Lu 3-a Al5O 12 :aCe 3 + The phosphor was obtained by mixing the two powders at a mass ratio of 10% to 90%.

[0104] Step 3, Preparation of luminescent matrix 1: Using silicone as a fluorescent adhesive, the silicone and the phosphor obtained in step 2 were mixed at a mass ratio of 1:1 to obtain luminescent matrix 1.

[0105] Step 4, Assembly of LED packaged devices: 4.1, as follows Figure 1 The PCT material bracket with a cavity structure shown is used as LED bracket 2, and positive and negative electrodes are welded onto LED bracket 2 for later use.

[0106] 4.2 Using a Sanan blue light chip with a peak wavelength of 450nm~455nm and a size of 22 mil×35 mil as LED chip 3, two LED chips 3 are set in series at the bottom of the cavity structure of LED bracket 2, and gold wire 4 is used to solder the two LED chips 3 to the positive and negative electrodes of LED bracket 2 respectively.

[0107] 4.3 Fill the gap between the two LED chips 3 and the cavity structure with the light-emitting matrix 1 obtained in step 3 to obtain a sky-blue light source LED package device.

[0108] Example 2 The difference from Example 1 is as follows: Example 2: The green phosphor in Example 1 was replaced with an equal mass of Ca. c Mg(SiO4) d Cl2.

[0109] Example 3 The difference from Example 1 is as follows: No green fluorescent powder was added in Example 3.

[0110] Comparative Example 1 The difference from Example 1 is as follows: In Comparative Example 1, no phosphor was added, and the phosphor from Example 1 was replaced with an equal mass of fluorescent gel.

[0111] Comparative Example 2 The difference from Example 1 is as follows: In Comparative Example 2, Sr was not doped.

[0112] This application used an integrating sphere testing device to test the fluorescence performance of the LED packaging devices of Example 1, Example 2, Comparative Example 1, and Comparative Example 2, respectively, and the test results are summarized as follows: Figures 3 to 6 , and as shown in Table 1.

[0113] in, Figure 3 The emission spectrum of the azure light source LED packaged device in Example 1 shows that the strongest emission peak of Example 1 is located near 490nm, which belongs to the blue-blue-green light band. Combined with the XY landing point, it indicates that Example 1 can achieve azure light emission.

[0114] Figure 4 The emission spectrum of the azure light source LED packaged device in Example 2 shows that the main peak of Example 2 is still located near 490nm, indicating that it belongs to the same light-emitting system as Example 1. However, the position of the shoulder peak and the full width at half maximum (FWHM) are different from those of Example 1. Combined with the XY landing point, this indicates that this application can achieve azure light emission by using the composition of green phosphor, and can also achieve flexible and adjustable XY landing point in the target color region.

[0115] Figure 5 The following is the emission spectrum of the LED packaged device in Comparative Example 1. It can be seen that Comparative Example 1 is a sky blue LED chip with a long wavelength of 490nm.

[0116] Figure 6 The emission spectrum of the LED packaged device in Comparative Example 2 shows that the main peak of Comparative Example 2 is located around 490nm. There are significant differences in spectral shape and full width at half maximum (FWHM) compared to the example. It can be seen that the emission is obtained by excitation of a single blue powder. Combined with the XY landing point, it can be seen that it can achieve sky blue emission. However, due to the excitation of a single powder, the slope of the color point is a fixed value and the landing point cannot be adjusted.

[0117] Table 1 shows the test results of the light and color parameters of the LED packaging devices of Examples 1, 2, Comparative Examples 1 and 2.

[0118] Table 1

[0119] In Table 1, “\” indicates that it does not exist, “x” represents the color coordinate x, “y” represents the color coordinate y, and “Φ0” represents the luminous flux corresponding to the initial brightness. “Brightness ratio 1” refers to the brightness ratio of each embodiment or comparative example relative to comparative example 1.

[0120] It should be noted that, Figure 7 This is a schematic diagram of the area where the color coordinates of azure are located in the CIE XYZ chromaticity diagram. Azure luminescence can be achieved when the color point coordinates (color coordinates x and y) of each embodiment are within the color frame required by the standard.

[0121] Combination Figure 7 As shown in Table 1, although Comparative Example 2 showed an improvement in luminescence intensity compared to Comparative Example 1, its color purity decreased significantly. In contrast, the color point coordinates of Examples 1 to 3 of this application are all in the CIE XYZ chromaticity diagram for azure, and their luminescence intensity is significantly improved compared to Comparative Example 1. This indicates that when the blue-green phosphor satisfies the emission peak wavelength of 490nm~500nm and the molecular formula is (Ba... 1-x-y Sr x Eu y When Si2N2O2, 0.001≤x≤0.3; 0.001≤y≤0.1, and the green phosphor satisfies the emission peak wavelength of 500nm~530nm, it can achieve sky blue emission and also flexibly adjust the XY landing point in the target color region, and further improve the emission intensity of sky blue emission.

[0122] This application further conducted aging tests on the sky-blue light source LED packaging devices of the above-mentioned Embodiments 1 and 2, as well as Comparative Examples 1 and 2. The performance of the sky-blue light source LED packaging devices after aging was tested, and the parameter changes after aging relative to before aging are recorded as shown in Table 2.

[0123] Table 2

[0124] In Table 2, △x refers to the difference in color coordinate x after aging compared to before aging, △y refers to the difference in color coordinate y after aging compared to before aging, and △Φ(lm) refers to the percentage value of brightness after aging divided by brightness before aging, i.e. brightness retention rate.

[0125] According to the test results in Table 2, when the blue-green phosphor meets the emission peak wavelength requirement of 490nm~500nm, the molecular formula is (Ba 1-x-y Sr x Eu yWhen Si2N2O2, 0.001≤x≤0.3; 0.001≤y≤0.1, and the green phosphor satisfies the emission peak wavelength of 500nm~530nm, it can achieve sky blue emission and synergistically improve the luminous intensity and anti-aging performance of sky blue light source LED packaging devices.

[0126] Examples 4 to 6 The difference from Example 1 is as follows: The mass content of green phosphor in the phosphor was adjusted accordingly according to the values ​​listed in Table 1. The photoelectric integrating sphere testing technique was used to test the photometric parameters of the azure LED packaged devices in each embodiment and comparative example, and the results are summarized in Table 3.

[0127] In Example 4, the mass content of green phosphor was 8%; in Example 5, the mass content of green phosphor was 20%; and in Example 6, the mass content of green phosphor was 40%.

[0128] Table 3

[0129] In Table 3, "brightness ratio 2" refers to the brightness ratio of each embodiment relative to embodiment 1.

[0130] According to the test results in Table 3, when the blue-green phosphor and green phosphor of this application meet the following conditions: based on the total mass of the phosphor, the mass ratio of the blue-green phosphor is A, where A satisfies 8%≤A≤40%, and the mass ratio of the green phosphor is B, where B satisfies 60%≤B≤92%, the matching degree between the green phosphor and the blue-green phosphor can be further improved, thereby further improving the luminous intensity and anti-long-term aging performance of the sky-blue light source LED packaging device.

[0131] Obviously, the above embodiments of this application are merely examples for clear illustration and are not intended to limit the implementation of this application. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the scope of protection claimed by this application.

Claims

1. A sky-blue LED packaging device, characterized in that, Includes a luminescent matrix, wherein the luminescent matrix includes phosphor; The phosphor includes blue-green phosphor; The blue-green phosphor has a peak emission wavelength of 490nm~500nm, and its molecular formula is (Ba 1-x-y Sr x Eu y The blue-green phosphor has an orthorhombic structure and is crystallized in space group Pcca.

2. The sky-blue LED packaging device according to claim 1, characterized in that, 0.001≤x≤0.1; 0.001≤y≤0.

03.

3. The sky-blue LED packaging device according to claim 1, characterized in that, The phosphor also includes a green phosphor, wherein the peak emission wavelength of the green phosphor is 500nm~530nm.

4. The sky-blue LED packaging device according to claim 3, characterized in that, The green phosphor comprises molecules with the molecular formula M 3-a Al5O 12 :aCe 3+ (Ba,Sr) 2-b SiO4, Ca c Mg(SiO4) d At least one of Cl2; Wherein, M is at least one of Y, Lu, and Ga; And the parameters a, b, c, d satisfy the following conditions: 0.001≤a≤0.5; 0.001≤b≤0.5; 7.5≤c≤8.5; 3.5≤d≤4.

5.

5. The sky-blue LED packaging device according to claim 3, characterized in that, Based on the total mass of the phosphors, the mass percentage of the blue-green phosphors is A, where A satisfies 8% ≤ A ≤ 40%, and the mass percentage of the green phosphors is B, where B satisfies 60% ≤ B ≤ 92%.

6. The sky-blue LED packaging device according to claim 1, characterized in that, The luminescent matrix also includes fluorescent adhesive.

7. The sky-blue light source LED packaging device according to claim 6, characterized in that, The fluorescent adhesive includes silicone rubber.

8. The sky-blue light source LED packaging device according to claim 6, characterized in that, The mass ratio of the fluorescent adhesive to the fluorescent powder is 0.7~2.5:

1.

9. The sky-blue LED packaging device according to claim 1, characterized in that, It also includes an LED bracket, two LED chips, and bonding wires; The LED bracket has a cavity structure and includes a positive electrode and a negative electrode; Two LED chips are disposed at the bottom of the cavity structure, and the two LED chips are respectively connected to the positive and negative terminals of the LED bracket via bonding wires; The light-emitting matrix fills the gap between the two LED chips and the cavity structure.

10. The sky-blue light source LED packaging device according to claim 9, characterized in that, The LED chip includes a blue light chip with a peak wavelength of 450nm~455nm.

11. The sky-blue light source LED packaging device according to claim 9, characterized in that, The material of the LED bracket includes at least one of PCT and EMC.

12. The sky-blue LED packaging device according to claim 9, characterized in that, The welding wire can be made of any one of the following materials: gold wire, silver wire, gold-silver alloy wire, or copper wire.

13. The sky-blue light source LED packaging device according to claim 9, characterized in that, The two LED chips are arranged in series or in parallel at the bottom of the cavity structure.

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