Orange fluorescent powder as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of nano composite luminescent materials and LED display and illumination luminescent devices, and particularly relates to orange fluorescent powder as well as a preparation method and application thereof, and the molecular formula of the orange fluorescent powder is KC20H24O6Cl4InxSb (1-x), wherein 0 lt; xlt; 1. The orange fluorescent powder can emit orange light, the quantum yield is up to 0.96, and the orange fluorescent powder can be used in the fields of illumination, display and the like and has a good application prospect.

Description

Technical Field

[0001] This invention belongs to the technical field of nanocomposite luminescent materials and LED display and lighting devices, specifically relating to an orange phosphor, its preparation method and application. Background Technology

[0002] With the rapid development of modern display and lighting technologies, the demand for high-performance light source materials is increasing daily. Among various light source materials, phosphors, as an important optical material, are widely used in LED lighting, display devices, fluorescent displays, optoelectronic devices, and other fields. Especially for white LED applications, orange phosphors have become a key research focus due to their excellent optical properties and stability. Orange phosphors can not only effectively improve the luminous efficiency of LEDs but also enhance the color rendering of light sources, meeting people's demands for higher-quality, energy-saving, and environmentally friendly lighting products.

[0003] Existing orange phosphors mostly utilize phosphorescent materials or phosphors doped with certain rare-earth metals, but their performance, manufacturing costs, and environmental friendliness still have room for improvement. For example, traditional orange phosphors require high-temperature and high-pressure conditions during manufacturing, and also pose certain environmental pollution problems. To improve the luminous efficiency of phosphors, reduce production costs, and ensure their environmental friendliness, developing novel, efficient, and tunable orange phosphors has become an urgent technical challenge.

[0004] This invention proposes a novel orange phosphor and its preparation method, employing a self-assembly reaction preparation technique that enables the preparation of orange phosphors with excellent luminescence properties under relatively mild conditions. The phosphor's crystal structure and molecular composition are precisely designed, exhibiting excellent stability and high luminescence efficiency, making it suitable for LED light source applications. Furthermore, the use of multiple self-assembly reaction methods allows for flexible adjustment of raw material ratios and reaction conditions according to actual needs, improving the controllability and reaction efficiency of the preparation process.

[0005] Therefore, the technical background of this invention not only responds to the urgent need for high-efficiency, low-cost, and environmentally friendly phosphor materials, but also provides a new preparation method for related industries, possessing significant application value and broad market prospects. Summary of the Invention

[0006] To overcome the shortcomings of existing technologies, this invention aims to provide a novel orange phosphor, its preparation method, and its applications. This material exhibits orange light emission and a quantum yield as high as 0.96, making it suitable for applications in lighting and displays, with promising prospects.

[0007] Objective 1 of this invention: To provide an orange fluorescent powder with the molecular formula KC 20 H 24 O6Cl4Inx Sb (1-x) ; where 0 < x < 1.

[0008] Preferably according to the present invention, x is 0.14, 0.32, 0.53 or 0.72.

[0009] Preferably according to the present invention, the orange orange phosphor has a unit cell parameter of the crystal structure as follows: α = 90°, β = 97.204(5), γ = 90, and the space group is P21 / n.

[0010] Objective two of the present invention: Provide a preparation method of the above orange phosphor. Preferably according to the present invention, the above orange phosphor can be prepared by the following scheme:

[0011] Scheme 1: Prepare by self-assembly reaction of antimony salt, indium salt, KCl and in solvent A;

[0012] Scheme 2: Prepare by self-assembly reaction of antimony oxide, indium salt, KCl, and hydrochloric acid in solvent A;

[0013] Scheme 3: Prepare by self-assembly reaction of antimony salt, indium oxide, KCl, and hydrochloric acid in solvent A;

[0014] Scheme 4: Prepare by self-assembly reaction of antimony oxide, indium oxide, KCl, and hydrochloric acid in solvent A.

[0015] Preferably according to the present invention, in Scheme 1 and 3, the antimony salt is SbCl3 and / or Sb(OAc)3.

[0016] Preferably according to the present invention, in Scheme 1 and 2, the indium salt is InCl3 and / or In(OAc)3.

[0017] Preferably according to the present invention, in Scheme 1, the molar ratio of the antimony salt, indium salt, KCl and is (1 - x):x:0.1 to 10:1, where 0 < x < 1, and the best ratio is 0.6:0.4:1:1.

[0018] Preferably according to the present invention, in Scheme 2, the molar ratio of the antimony oxide, indium salt, KCl, and hydrochloric acid is 0.5(1 - x):x:0.1 to 10:1, where 0 < x < 1, and the best ratio is 0.3:0.4:1:1.

[0019] Preferably according to the present invention, in Scheme 3, the antimony salt, indium oxide, KCl, The molar ratio of it to hydrochloric acid is (1 - x):0.5x:0.1 to 10:1, where 0 < x < 1, and the optimal ratio is 0.6:0.2:1:1.

[0020] According to the preference of the present invention, in Embodiment 4, the antimony oxide, indium oxide, KCl, and hydrochloric acid have a molar ratio of 0.5(1 - x):0.5x:0.1 to 10:1, where 0 < x < 1, and the optimal ratio is 0.3:0.2:1:1.

[0021] According to the preference of the present invention, in Embodiment 2, the amount of substance of the hydrochloric acid is 6 to 60 times that of the antimony oxide.

[0022] According to the preference of the present invention, in Embodiment 3, the amount of substance of the hydrochloric acid is 6 to 60 times that of the indium oxide.

[0023] According to the preference of the present invention, in Embodiment 4, the amount of substance of the hydrochloric acid is 6 to 60 times the total amount of the antimony oxide and the indium oxide.

[0024] According to the preference of the present invention, the solvent is selected from at least one of alcohols (such as methanol, ethanol, ethylene glycol, propanol), nitriles (such as acetonitrile), halogenated hydrocarbons (such as dichloromethane, chloroform, 1,2 - dichloroethane), ethers (such as diethyl ether, isopropyl ether), ketones (such as acetone), alkanes (such as n - hexane), sulfoxides (such as dimethyl sulfoxide) or amides (such as DMF, DMAc).

[0025] Object of the invention three: Provide a white phosphor combination, which comprises the above orange phosphor.

[0026] According to the preference of the present invention, the white phosphor combination is composed of a blue phosphor, a green phosphor and the above orange phosphor.

[0027] According to the preference of the present invention, the blue phosphor is commercial BaMgAl 10 O 17 :Eu.

[0028] According to the preference of the present invention, the green phosphor is commercial (Sr,Ba)2SiO4:Eu.

[0029] According to the preference of the present invention, by weight, the weight ratio of the blue phosphor: the green phosphor: the orange phosphor is 10:7:20.

[0030] Object of the invention four: Provide an application of the above orange phosphor in optoelectronic materials.

[0031] Object of the invention five: Provide an application of the above orange phosphor in LEDs, preferably in WLEDs. <000009

[0032] The technical features and beneficial effects of this invention are as follows:

[0033] 1. This invention provides an orange fluorescent powder with the molecular formula KC. 20 H 24 O6Cl4In x Sb (1-x The ratio of indium to antimony has a relatively small impact on the luminescence properties of phosphors, which gives the synthesis process greater tolerance and enhances the flexibility of the production process.

[0034] 2. This invention utilizes a self-assembly reaction technique to prepare orange phosphors in a solvent. This preparation method employs mild reaction conditions, can be completed at normal pressure and low temperature, reducing energy consumption and material loss during production, thereby effectively lowering production costs and enhancing market competitiveness.

[0035] 3. The orange phosphor of the present invention has excellent luminous efficiency and stability, and can effectively improve the brightness and color performance of LED light sources. Attached Figure Description

[0036] Figure 1 This is a stacked diagram of the single-crystal structure of the orange phosphor in Example 1.

[0037] Figure 2 This is the smallest asymmetric unit of the single-crystal structure of the orange phosphor in Example 1.

[0038] Figure 3 This is a schematic diagram showing the color of the orange phosphor obtained in Example 1 under sunlight and its luminescence under 365nm ultraviolet light.

[0039] Figure 4 The excitation curve (λ) of the orange phosphor obtained in Example 1. em =630nm) and emission curve (λ) ex =360nm).

[0040] Figure 5 The maximum emission peak (λ) of the orange phosphor obtained in Example 1 max The lifetime decay curve of (=630nm).

[0041] Figure 6 This invention relates to a white LED device based on the orange phosphor of the present invention and its electroluminescence spectrum.

[0042] Figure 7 This is a CIE coordinate diagram of a white LED device based on the orange phosphor of this invention. Detailed Implementation

[0043] To make the invention's objectives, technical solutions, and effects clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments; however, this does not limit the invention to the embodiments described. Experimental methods in the following embodiments that do not specify specific conditions are performed according to conventional methods and conditions, or according to the product manual.

[0044] The reagents and solvents involved in this invention are all commercially available.

[0045] Example 1: Method for synthesizing orange phosphor in this invention

[0046] Weigh out SbCl3 (0.6 equivalents), InCl3 (0.4 equivalents), KCl (1 equivalent), and dibenzo-18-crown ether-6 (1 equivalent), add methanol, and sonicate for 5–10 min until completely dissolved. Volatilize at room temperature for 2–5 days, precipitating colorless blocky crystals. Under 365 nm UV excitation, this substance emits orange light. Filter, wash with a small amount of anhydrous methanol, and dry to obtain the product, yield 81.6%.

[0047] Example 2: Method for synthesizing orange phosphor in this invention

[0048] Weigh out Sb₂O₃ (0.3 equivalents), InCl₃ (0.4 equivalents), KCl (1 equivalent), and dibenzo-18-crown ether-6 (1 equivalent), add methanol, and then add 2 equivalents of hydrochloric acid (37% HCl, ~12.0 mol / L) dropwise. Sonicate for 5–10 min until completely dissolved. Allow to evaporate at room temperature for 2–5 days, precipitating colorless blocky crystals. This substance emits orange light when excited by a 365 nm UV lamp. Filter, wash with a small amount of anhydrous methanol, and dry to obtain the product, with a yield of 79.1%.

[0049] Example 3: Method for synthesizing orange phosphor in this invention

[0050] Weigh out SbCl3 (0.6 equivalents), In2O3 (0.2 equivalents), KCl (1 equivalent), and dibenzo-18-crown ether-6 (1 equivalent), add methanol, and add 1.5 equivalents of hydrochloric acid (37% HCl, ~12.0 mol / L) dropwise. Sonicate for 5–10 min until completely dissolved. Volatilize at room temperature for 2–5 days, precipitating colorless blocky crystals. This substance emits orange light when excited by a 365 nm UV lamp. Filter, wash with a small amount of anhydrous methanol, and dry to obtain the product, yield 77.6%.

[0051] Example 4: Method for synthesizing orange phosphor in this invention

[0052] Weigh out Sb₂O₃ (0.3 equivalents), In₂O₃ (0.2 equivalents), KCl (1 equivalent), and dibenzo-18-crown-6 (1 equivalent), add methanol, and then add 3.5 equivalents of hydrochloric acid (37% HCl, ~12.0 mol / L) dropwise. Sonicate for 5–10 min until completely dissolved. Allow to evaporate at room temperature for 2–5 days, precipitating colorless blocky crystals. This substance emits orange light when excited by a 365 nm UV lamp. Filter, wash with a small amount of anhydrous methanol, and dry to obtain the product, with a yield of 79.8%.

[0053] Example 5: Method for synthesizing orange phosphor in this invention

[0054] Weigh out SbCl3 (0.6 equivalents), InCl3 (0.4 equivalents), KCl (1 equivalent), and dibenzo-18-crown ether-6 (1 equivalent), add methanol, and sonicate for 5–10 min until completely dissolved. Use ethyl acetate as the antisolvent for vapor diffusion; after 5–7 days, colorless blocky crystals precipitate. Filter, wash with a small amount of anhydrous methanol, and dry to obtain the product, yield 70.5%.

[0055] Example 6: Method for synthesizing orange phosphor in this invention

[0056] Weigh out Sb₂O₃ (0.3 equivalents), InCl₃ (0.4 equivalents), KCl (1 equivalent), and dibenzo-18-crown-6 (1 equivalent), add methanol, and then add 2 equivalents of hydrochloric acid (37% HCl, ~12.0 mol / L) dropwise. Sonicate for 5–10 min until completely dissolved. Use ethyl acetate as the antisolvent for vapor diffusion; after 5–7 days, colorless blocky crystals precipitate. Filter, wash with a small amount of anhydrous methanol, and dry to obtain the product, yield 78.3%.

[0057] Example 7: Method for synthesizing orange phosphor in this invention

[0058] Weigh out SbCl3 (0.6 equivalents), In2O3 (0.2 equivalents), KCl (1 equivalent), and dibenzo-18-crown-6 (1 equivalent), add methanol, and add 1.5 equivalents of hydrochloric acid (37% HCl, ~12.0 mol / L) dropwise. Sonicate for 5–10 min until completely dissolved. Use ethyl acetate as the antisolvent for vapor diffusion; colorless blocky crystals precipitate after 5–7 days. Filter, wash with a small amount of anhydrous methanol, and dry to obtain the product, yield 68.5%.

[0059] Example 8: Method for synthesizing orange phosphor in this invention

[0060] Weigh out Sb₂O₃ (0.3 equivalents), In₂O₃ (0.2 equivalents), KCl (1 equivalent), and dibenzo-18-crown-6 (1 equivalent), add methanol, and then add 3.5 equivalents of hydrochloric acid (37% HCl, ~12.0 mol / L) dropwise. Sonicate for 5–10 min until completely dissolved. Use ethyl acetate as the antisolvent for vapor diffusion; colorless blocky crystals precipitate after 5–7 days. Filter, wash with a small amount of anhydrous methanol, and dry to obtain the product, yield 65.5%.

[0061] Application Example 1: Structural Characterization of the Orange Phosphor in this Invention

[0062] The single crystals obtained in Examples 1-4 above were characterized by X-ray single-crystal diffraction. A Bruker D8 Venture diffractometer was used, with Mo-Kα radiation. The test temperature was 273K; data acquisition and processing were performed using Bruker APEX4 software. The results showed that the crystal parameters and single-crystal structures of the crystals obtained in Examples 1-8 were consistent, the only difference being that Sb and In exhibited disordered occupancy, with the specific proportions affected by the feed ratio. ICP-OES was used to characterize the Sb and In content and molecular formula of the orange phosphors obtained under different Sb:In feed ratios (molar ratios) (Table 1). Taking the single crystal obtained in Example 1 as an example, the cell parameters were... α(°)=90; β(°)=97.204(5); γ(°)=90. The crystal belongs to the monoclinic system, space group P21 / n, and other key crystallographic parameters are shown in Table 2. The single-crystal packing diagram of the orange phosphor is shown in Table 2. Figure 1 See the smallest asymmetric unit. Figure 2 Detailed bond length information is shown in Table 3, and detailed bond angle information is shown in Table 4.

[0063] Table 1

[0064]

[0065] Table 2

[0066]

[0067] Table 3

[0068]

[0069]

[0070] Table 4

[0071]

[0072] Application Example 1: Photophysical Characterization of the Orange Phosphor in this Invention

[0073] The orange phosphors obtained in the above examples were subjected to photophysical characterization. Their luminescence properties were measured in a solid state at room temperature using an Edinburgh FLS920 fluorescence spectrometer. The results showed that the orange phosphors prepared under different conditions exhibited consistent luminescence properties, as detailed in Table 1. Taking the single crystal obtained in Example 1 as an example, this material can emit orange-red light under ultraviolet excitation (…). Figure 3 The emission color coordinates are (0.58, 0.41) (Table 1). Its excitation and emission spectra are as follows: Figure 4 As shown, the maximum emission peak is located at 630 nm, and the maximum emission lifetime is 8.0 μs. Figure 5 This material exhibits phosphorescence emission. Its light emission quantum yield is 0.96, indicating a high efficiency in light conversion.

[0074] Application Example 2: Preparation and Characterization of White LEDs Based on the Orange Phosphor of the Present Invention

[0075] The orange phosphor produced in Example 1 was used in combination with commercial blue phosphor BaMgAl. 10 O 17 White LEDs (WLEDs) were prepared by adjusting the mass ratio of Eu, commercial green phosphor (Sr, Ba)2SiO4:Eu, and other components. The optimal mass ratio was determined to be: blue phosphor: green phosphor: orange phosphor = 10:7:20, which resulted in uniform white light output. The specific preparation steps were: 1) Weigh the three phosphors at a mass ratio of 10:7:20 and mix thoroughly until no obvious particle stratification occurred; 2) Thoroughly mix the phosphor mixture with AB glue; 3) Fill the mixture into 365nm UV LED beads using an acupuncture needle and dry at 100℃ for shaping. Device performance test results: After lighting, it exhibited bright and pure white light, and the electroluminescence spectrum was as follows. Figure 6 As shown, the color coordinates are (0.31, 0.35) (see...) Figure 7 The color temperature is 6469K, and the color rendering index is 94.7. Test data confirms that this WLED has high luminous efficiency and stable luminous performance, meeting the core technical requirements for white light lighting.

[0076] Comparative Example 1

[0077] Based on Example 1, the In(III) doped system was removed, and a doping-free strategy was adopted to prepare the target product: SbCl3 (1 equivalent), KCl (1 equivalent), and dibenzo-18-crown ether-6 (1 equivalent) were accurately weighed and dissolved in anhydrous methanol. The solution was then ultrasonically treated for 5–10 min until a homogeneous and clear solution was formed. Vapor diffusion treatment was performed using diethyl ether as the antisolvent. After standing for 2–5 days, colorless crystals precipitated in the system, named substance A. Single-crystal X-ray diffraction experiments confirmed that the structure of substance A differed from that of the orange phosphor in this invention, indicating that the introduction of In(III) significantly altered the coordination environment and crystal packing mode of the antimony-based complex. The obtained crystals were separated by filtration, washed with a small amount of anhydrous methanol, and dried to obtain the final product, with a separation yield of 10.2%. The maximum emission peak wavelength of substance A was 635 nm, and the fluorescence quantum yield was approximately 0.1. In contrast, the quantum yield of the orange phosphor in this invention reached approximately 0.96, with a luminous efficiency nearly ten times higher than that of substance A.

[0078] Therefore, the doping of In(III) in this patent can not only change the composition and crystal structure of antimony-based phosphors, but also significantly improve their luminescence efficiency.

Claims

1. An orange fluorescent powder, characterized in that, The molecular formula is KC 20 H 24 O6Cl4In x Sb (1-x) , where 0 < x < 1; the crystal structure parameters of this orange phosphor are: α = 90°, β = 97.204(5)°, γ = 90°, and the space group is P21 / n.

2. A method for preparing an orange phosphor, characterized in that, It can be prepared by the following method: Option 1: Add antimony salt, indium salt, KCl and It is prepared by self-assembly reaction in a solvent; Option 2: Add antimony oxide, indium salt, KCl, It is prepared by self-assembly reaction of hydrochloric acid in a solvent; Option 3: Add antimony salt, indium oxide, KCl, It is prepared by self-assembly reaction of hydrochloric acid in a solvent; Option 4: Add antimony oxide, indium oxide, KCl, It is prepared by self-assembly reaction of hydrochloric acid in a solvent.

3. The method for preparing orange phosphor as described in claim 2, characterized in that, In schemes 1 and 3, the antimony salt is SbCl3 and / or Sb(OAc)3; In schemes 1 and 2, the indium salt is InCl3 and / or In(OAc)3.

4. The method for preparing orange phosphor as described in claim 2, characterized in that, In Scheme 1, the antimony salt, indium salt, KCl, and The molar ratio of the substances is (1-x):x:0.1~10:1, where 0 <x<1。 5. The method for preparing orange phosphor as described in claim 2, characterized in that, In Scheme 2, the antimony oxide, indium salt, KCl and The molar ratio is 0.5(1-x):x:0.1~10:1, where 0 <x<1。 6. The method for preparing orange phosphor as described in claim 2, characterized in that, In Scheme 3, the antimony salt, indium oxide, KCl, and The molar ratio of the substances is (1-x):0.5x:0.1 to 10:1, where 0 <x<1。 7. The method for preparing orange phosphor as described in claim 2, characterized in that, In Scheme 4, the antimony oxide, indium oxide, KCl and The molar ratio is 0.5(1-x):0.5x:0.1 to 10:1, where 0 <x<1。 8. The method for preparing orange phosphor as described in claims 2-7, characterized in that, One or more of the following conditions must be met: (1) The solvent is selected from at least one of methanol, ethanol, ethylene glycol, propanol, acetonitrile, dichloromethane, chloroform, 1,2-dichloroethane, diethyl ether, isopropyl ether, acetone, n-hexane, dimethyl sulfoxide, N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMAc); (2) In Scheme 2, the amount of hydrochloric acid is 6 to 60 times that of antimony oxide; (3) In Scheme 3, the amount of hydrochloric acid is 6 to 60 times that of indium oxide; (4) In Scheme 4, the amount of hydrochloric acid is 6 to 60 times the total amount of antimony oxide and indium oxide.

9. A phosphor composition, characterized in that, It contains the orange phosphor as described in claim 1.

10. The use of an orange phosphor as described in claim 1 or a phosphor composition as described in claim 9 in optoelectronic materials.

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