WO2022233116A1 - 一种单基质双发射荧光粉及其制备方法与应用 - Google Patents

一种单基质双发射荧光粉及其制备方法与应用 Download PDF

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WO2022233116A1
WO2022233116A1 PCT/CN2021/128249 CN2021128249W WO2022233116A1 WO 2022233116 A1 WO2022233116 A1 WO 2022233116A1 CN 2021128249 W CN2021128249 W CN 2021128249W WO 2022233116 A1 WO2022233116 A1 WO 2022233116A1
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emission
matrix
light
chloride
containing compound
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王静
甘伟江
楼孙棋
曹鲁豫
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Sun Yat Sen University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/74—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing arsenic, antimony or bismuth
    • C09K11/75—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing arsenic, antimony or bismuth containing antimony
    • C09K11/755—Halogenides
    • C09K11/756—Halogenides with alkali or alkaline earth metals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G7/00—Botany in general
    • A01G7/04—Electric or magnetic or acoustic treatment of plants for promoting growth
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V9/00—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters
    • F21V9/30—Elements containing photoluminescent material distinct from or spaced from the light source
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/14—Measures for saving energy, e.g. in green houses

Definitions

  • the present invention relates to the technical field of luminescent materials, and more particularly, to a single-matrix double-emitting phosphor and a preparation method and application thereof.
  • Light is the basic factor of plant growth and development. It can not only provide the energy required for photosynthesis of plants, but also regulate plant life activities, such as seed germination, seedling formation, flowering and fruiting and other processes. At the same time, greenhouse planting and environment-controlled indoor planting have attracted much attention as a method of environmental protection, energy saving and sustainable development. It can be seen that plant lighting technology is an indispensable part of modern agricultural construction, especially for the lack of land resources. For areas with light conditions and light conditions, plant light is particularly important. Studies have shown that photoreceptors of plants dominate many processes of metabolism and growth and development of plants, and the response spectral ranges are mainly concentrated in blue light at 400-500 nm, red light at 600-780 nm and deep red light.
  • the emission spectrum of traditional lighting sources does not match the spectrum required for plant growth, resulting in low utilization of light energy, wasting energy, and affecting the effective growth of plants.
  • the LED lighting source has the advantages of high luminous efficiency, low heat generation, small size, long life, and the emission spectrum can be adjusted by changing the phosphor composition to match the absorption spectrum required for plant growth. It has advantages in the field of plant lighting. obvious.
  • Lead-based halide perovskite materials have good optoelectronic properties and have been used to fabricate devices such as light-emitting diodes, solar cells, and photodetectors.
  • the toxicity and chemical instability of lead will pose a fatal threat to life and health and severely limit the service life and application prospects of equipment.
  • the use of non-toxic metal ions to replace lead ions in lead halide perovskites can effectively solve the problem of lead-based
  • lead-free perovskite phosphors have a narrow excitation spectrum range, and cannot achieve stable and adjustable light color, and cannot meet the matching requirements of the absorption spectrum required for plant growth.
  • CN109973842A discloses a preparation method of a long afterglow LED plant lamp light-emitting chip.
  • the specific steps of the preparation method are as follows: (1) Phosphor BaMgAl 10 O 17 :Eu 2+ , Sr 2 SiO 4 :Eu 2+ , CaAlSiN: Eu 2+ , SrAl 2 O 4 : Eu 2+ , Dy 3+ , CaAl 2 O 4 : Eu 2+ , Dy 3+ , ZnG a2 O 4 : Cr 3+ , Bi 3+ were dry-milled and mixed for 30 ⁇ Mixed powder A was obtained in 45min; wherein the phosphors BaMgAl 10 O 17 :Eu 2+ , Sr 2 SiO 4 :Eu 2+ , CaAlSiN:Eu 2+ , SrAl 2 O 4 :Eu 2+ ,Dy 3+ ,CaAl 2 O 4 : Eu 2+ , Dy 3+ and Z
  • the perovskite material of the long afterglow LED plant lamp light-emitting chip disclosed above is not a single-matrix fluorescent material, and it is mainly aimed at adjusting the illumination brightness of red and blue LED plant lamps to achieve automatic modulation of spectrum, and does not solve the problem of using single-matrix fluorescence.
  • the material can realize multi-color tunability, achieve stable wide-spectrum excitation, and meet the requirements of the absorption spectrum required by plants.
  • the technical problem to be solved by the present invention is to overcome the defects and deficiencies that the existing perovskite fluorescent materials cannot achieve stable wide-spectrum excitation and emission powder light, and cannot well fit the absorption spectrum required by plants, and provide a single-substrate dual
  • the emitting phosphor can realize light color by doping trivalent ions Bi 3+ and Sb 3+ in the single-host lead-free inorganic perovskite Cs 2 SnCl 6 and adjusting the content of trivalent ions Bi 3+ and Sb 3+ It is stable and adjustable, effectively absorbs near-ultraviolet light within 300 ⁇ 400nm, emits red and blue light at 400 ⁇ 525nm and 550 ⁇ 850nm, which matches the absorption spectrum required by plants. The powder light required.
  • Another object of the present invention is to provide a method for preparing a single-matrix double-emitting phosphor.
  • Another object of the present invention is to provide an application of a single-substrate dual-emitting phosphor in the preparation of plant lighting equipment.
  • Another object of the present invention is to provide a plant lighting LED.
  • a single-matrix double-emission phosphor the chemical formula of the single-matrix double-emission phosphor is:
  • x and y are the molar percentages of doping ions Bi 3+ and Sb 3+ , respectively, relative to the host ions Sn 4+ .
  • the fluorescent powder material of the invention is a single-matrix dual-emission fluorescent powder, and the single-matrix dual-emission fluorescent material only needs a single matrix to emit blue and red two kinds of light, which solves the possible reabsorption caused by the combination of two or more fluorescent materials.
  • the different aging rates of various fluorescent materials cause unstable light color, and the proportion of various fluorescent powders is complicated.
  • the host material of the single-host double-emitting fluorescent material is lead-free all-inorganic perovskite Cs 2 SnCl 6 , and the light-emitting centers are respectively trivalent ions Bi 3+ and Sb 3+ .
  • the trivalent ion Bi 3+ emits blue light in the matrix, with an emission peak at 400-525 nm, and Sb 3+ produces red light with an emission peak at 550-850 nm, which is in line with the absorption spectrum required by plants.
  • the two light colors are mixed to obtain pink light that meets the needs of plant lighting.
  • the single-host dual-emitting fluorescent material of the present invention can obtain a dual-emitting fluorescent powder with adjustable light color by changing the doping ratio of trivalent ions Bi 3+ and Sb 3+ and selecting different ratios within a certain range.
  • the doping ratio of Bi 3+ and Sb 3+ By adjusting the doping ratio of Bi 3+ and Sb 3+ , the ratio of blue light and red light can be effectively adjusted, and the pink light required for plant growth can be obtained.
  • different plant species and different growth cycles in the plant growth process require different light colors, so an adjustable light source with a suitable blue-red ratio is required to meet different needs.
  • the phosphor material of the present invention can pass Bi 3+ , Sb The adjustment of the doping ratio of 3+ can realize the adjustment of different light sources.
  • the dual emission fluorescent material of the present invention Due to the doping of Bi 3+ and Sb 3+ ions, the dual emission fluorescent material of the present invention has a very wide excitation spectrum, has effective absorption in the range of 300-400 nm, and can effectively absorb the near-ultraviolet emitted by the ultraviolet LED chip.
  • the light emits blue and red light at 400-525nm and 550-850nm, and can be adjusted to obtain the required light source.
  • Reabsorption is when the emission spectrum of one phosphor overlaps the excitation spectrum of another phosphor, resulting in a decrease in the former's luminescence.
  • the excitation spectrum of the blue-red light of the single-host dual-emission fluorescent material of the present invention is both at 300-400 nm, and the excitation and emission spectra of the two do not overlap, which can avoid reabsorption.
  • the luminescence center is in the same matrix, the luminescence of the material has a similar aging rate, which reduces the problem of unstable composite light color caused by different aging rates of different phosphor materials.
  • the single-matrix double-emitting fluorescent material of the present invention avoids the re-absorption effect of the composite of various fluorescent powders, and reduces the instability of the composite light color caused by the different aging rates of the various fluorescent powders, and the complex adjustment of the ratio of different fluorescent powders, etc. question. Avoiding re-absorption in applications can make more efficient use of the excitation energy of LEDs.
  • the stability of light color means that the ratio of luminous peaks remains unchanged, which better maintains the stability of the energy of light absorbed by plants. Scale preparation.
  • the content of fixed Sb ions is 0.15, and the content of Bi ions is changed between 0.005 and 0.09, and the relative intensity of the red and blue emission peaks of the sample will change accordingly, so that the light color can be adjusted, and the light from red to blue can be obtained. , to meet the requirements of plant LED lighting for different light colors at different stages of plant growth.
  • the content of fixed Bi ions is 0.09, and the content of Sb ions is changed between 0.05 and 0.25, and the relative intensities of the red and blue emission peaks of the sample will change accordingly, and the light from blue to red can be adjusted to achieve adjustable light color. , to meet the requirements of plant LED lighting for different light colors at different stages of plant growth
  • the present invention also specifically protects a method for preparing the above-mentioned single-substrate dual-emitting phosphor, comprising the following steps:
  • the preparation process of the pink fluorescent material in the present invention is simple, easy to implement, low in cost, low in toxicity, and has broad prospects for large-scale industrial application.
  • the Cs-containing compound is Cs oxide, Cs carbonate, Cs hydroxide, Cs nitrate or Cs chloride;
  • the Sn-containing compound is Sn oxide, Sn carbonate, Sn hydroxide, Sn nitrate or Sn chloride;
  • the Bi-containing compound is Bi oxide, Bi carbonate, Bi hydroxide, Bi nitrate or Bi chloride;
  • the Sb-containing compound is an oxide of Sb, a carbonate of Sb, a hydroxide of Sb, a nitrate of Sb, or a chloride of Sb.
  • Chloride can provide both cations and anions required for the reaction, which is better for the preparation of pure phases. Therefore, further preferably, the Cs-containing compound is Cs chloride; the Sn-containing compound is Sn chloride; the Bi-containing compound is Bi chloride; the Sb-containing compound is Sb chloride matter.
  • the cooling is cooling to room temperature at a rate of 10-30°C/1h.
  • the control of the cooling rate can better achieve the high luminous efficiency of the material.
  • the single-substrate dual-emitting fluorescent powder of the invention has wide-spectrum excitation, can effectively absorb and emit powder light in the near-ultraviolet light spectrum that fits the absorption band of plants, and at the same time realizes light color adjustment, and can be widely used in fluorescent powder light color adjustment.
  • the invention particularly specifically protects the application of the above-mentioned single-substrate dual-emitting phosphor in the preparation of plant lighting equipment.
  • the ultraviolet LED chip of the plant lighting device in the application has an emission wavelength of 300 nm to 400 nm, more preferably 365 nm.
  • the present invention also specifically protects a plant lighting LED, which is prepared by encapsulating the single-substrate dual-emitting phosphor powder and an ultraviolet LED diode chip.
  • the dual-emission fluorescent material of the present invention is doped with trivalent ions Bi 3+ and Sb 3+ , and the emission peaks are located at 400-525 nm (Bi 3+ ) and 550-850 nm (Sb 3+ ), respectively, which are similar to those of plants.
  • the required absorption spectrum is matched, and the content of trivalent ions Bi 3+ and Sb 3+ can be adjusted to achieve stable and adjustable light color, and obtain the pink light required for plant growth.
  • the dual emission fluorescent material of the present invention has a very wide excitation spectrum, can effectively absorb in the range of 300-400 nm, and can effectively absorb the near-ultraviolet light emitted by the ultraviolet LED chip.
  • the dual emission fluorescent material of the present invention is a single matrix material, which can effectively avoid reabsorption, unstable light color caused by different aging rates, and The complex ratio adjustment and other problems can make the light color stable and not produce large color drift.
  • the preparation process of the pink fluorescent material of the present invention is simple, easy to realize, low in cost and low in toxicity, and can be applied in large-scale industrialization.
  • FIG. 1 is the XRD patterns of the single-matrix double-emitting phosphors of Examples 1-4.
  • FIG. 2 is the XRD patterns of the single-matrix double-emitting phosphors of Examples 5-8.
  • 3 is an emission spectrum diagram of the single-matrix double-emitting phosphors of Examples 1-4.
  • FIG. 5 is an emission spectrum diagram of the single-matrix dual-emitting phosphor of Example 3.
  • FIG. 6 is an excitation spectrum diagram of monitoring different emission wavelength positions of the single-matrix dual-emitting phosphor of Example 3.
  • FIG. 6 is an excitation spectrum diagram of monitoring different emission wavelength positions of the single-matrix dual-emitting phosphor of Example 3.
  • the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.
  • a single-matrix double-emission phosphor the chemical formula of the single-matrix double-emission phosphor is: Cs 2 Sn 0.845 Bi 0.005 Sb 0.15 Cl 6 .
  • the preparation method is as follows:
  • a single-matrix double-emission phosphor the chemical formula of the single-matrix double-emission phosphor is: Cs 2 Sn 0.843 Bi 0.007 Sb 0.15 Cl 6 .
  • the preparation method is as follows:
  • a single-matrix double-emission phosphor the chemical formula of the single-matrix double-emission phosphor is: Cs 2 Sn 0.845 Bi 0.01 Sb 0.15 Cl 6 .
  • the preparation method is as follows:
  • a single-matrix double-emission phosphor the chemical formula of the single-matrix double-emission phosphor is: Cs 2 Sn 0.845 Bi 0.048 Sb 0.15 Cl 6 .
  • the preparation method is as follows:
  • a single-matrix double-emission phosphor the chemical formula of the single-matrix double-emission phosphor is: Cs 2 Sn 0.86 Bi 0.09 Sb 0.05 Cl 6 .
  • the preparation method is as follows:
  • a single-matrix double-emission phosphor the chemical formula of the single-matrix double-emission phosphor is: Cs 2 Sn 0.81 Bi 0.09 Sb 0.1 Cl 6 .
  • the preparation method is as follows:
  • a single-matrix double-emission phosphor the chemical formula of the single-matrix double-emission phosphor is: Cs 2 Sn 0.81 Bi 0.09 Sb 0.15 Cl 6 .
  • the preparation method is as follows:
  • a single-matrix double-emission phosphor the chemical formula of the single-matrix double-emission phosphor is: Cs 2 Sn 0.845 Bi 0.09 Sb 0.25 Cl 6 .
  • the preparation method is as follows:
  • Fig. 1 is the XRD patterns of Examples 1-4.
  • the XRD patterns of the phosphors prepared in Examples 1-4 are basically consistent with the standard card (ICSD#9023), which further confirms the purity of the phosphors prepared in Examples 1-4 of the present application. high.
  • Fig. 2 is the XRD patterns of Examples 5-8.
  • the XRD patterns of the phosphors prepared in Examples 5-8 are basically consistent with the standard card (ICSD#9023), which further confirms the purity of the phosphors prepared in Examples 5-8 of the present application. high.
  • Fig. 3 and Fig. 4 show that a series of double-emitting phosphor samples with different ion concentrations (the ions are Bi 3+ and Sb 3+ ) obtained according to the preparation method of the present invention (the chemical composition expression is: Cs 2 Sn 1-xy Bi x Sb y Cl 6 , where x and y are the molar percentages of doping ions Bi 3+ , Sb 3+ , relative to host ions Sn 4+ , respectively, the value range: 0.005 ⁇ x ⁇ 0.09, 0.05 ⁇ y ⁇ 0.25) have similar spectral properties.
  • Figure 3 shows the emission spectra of the luminescent materials of Examples 1 to 4. It can be seen from Figure 3 that the doping amount of antimony (Sb 3+ ) ions in the sample is fixed, and the doping amount of bismuth (Bi 3+ ) ions in the sample is changed , the relative intensity of the red and blue emission peaks of the sample will change accordingly, so that the light color can be adjusted.
  • Sb 3+ antimony
  • Bi 3+ bismuth
  • Fig. 4 shows the emission spectra of the luminescent materials of Examples 5-8. It can be seen from Fig. 4 that the doping amount of bismuth (Bi 3+ ) ions in the samples is fixed, and the doping amount of antimony (Sb 3+ ) ions in the samples is changed , the relative intensity of the red and blue emission peaks of the sample will change accordingly, so that the light color can be adjusted.
  • Figure 5 is the emission spectrum diagram of the luminescent material of Example 3. It can be seen from Figure 5 that the pink fluorescent material has relatively excellent emission in both blue and red light bands under the excitation of 365 nm light, and the emission peaks are respectively located at: 400-525 nm (Bi 3+ ), 550-850 nm (Sb 3+ ), can emit pink light emission matching the absorption spectrum required for plant growth after combining. Chlorophyll A and B are hormones required for plant growth. Figure 5 shows that the emission spectrum of the material matches the absorption of chlorophyll A and B, which is suitable for plant lighting needs.
  • Example 6 is the excitation spectrum of the luminescent material of Example 3 monitored at different emission wavelength positions.
  • the excitation spectrum exhibits broadband absorption from 300 nm to 400 nm, indicating that the material can meet the excitation requirements of near-ultraviolet LED chips.

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Abstract

本发明公开了一种单基质双发射荧光粉及其制备方法与应用，属于发光材料技术领域。单基质双发射荧光粉的化学式为：Cs 2Sn 1-x-yBi xSb yCl 6，0.005≤x≤0.09，0.05≤y≤0.25，具有非常宽的激发光谱，在300～400nm内范围均可有效吸收，可有效的吸收紫外LED芯片所发出的近紫外光，掺杂了三价离子Bi 3+，Sb 3+，发射光谱分别位于400～525nm(Bi 3+)，550～850nm(Sb 3+)，均与植物所需的吸收光谱契合，调节三价离子Bi 3+，Sb 3+的含量即可实现光色稳定可调，得到植物生长所需的粉光，且为单基质材料，与多色荧光粉复合制备植物照明LED相比，可以有效的避免重吸收，光色不稳定，老化速率不同，以及不同荧光粉的配比调节复杂等问题，制备工艺方法简单，易于实现，且成本低，毒性小，可大规模工业化应用。

Description

一种单基质双发射荧光粉及其制备方法与应用 技术领域
本发明涉及发光材料技术领域，更具体地，涉及一种单基质双发射荧光粉及其制备方法与应用。
背景技术
光是植物生长发育的基本因素，它不仅可以提供植物的光合作用所需的能量，而且还可以调控植物生命活动，如种子萌发、幼苗形成、开花结果等过程。同时，温室种植和环境可控的室内种植作为一种环保节能且可持续发展的方法备受关注，由此可见，植物光照技术是现代农业建设中必不可少的一部分，特别是对缺少土地资源和光照条件的地区而言，植物光照尤为重要。研究表明，植物的光感受器支配着植物许多新陈代谢和生长发育过程，响应的光谱范围主要集中400～500nm的蓝光、600～780nm的红光和深红光。但是传统的照明光源，如白炽灯，高压钠灯等的发射光谱与植物生长所需要的光谱匹配度不高，从而造成光能的利用率不高，浪费能源，同时也会影响植物的有效生长，而LED照明光源，具有光效高、发热低、体积小、长寿命、可通过改变其中的荧光粉成分来调节其发射光谱来实现与植物生长所需吸收光谱匹配等优点，在植物光照领域优势明显。
铅基卤化钙钛矿材料具有良好的光电性质，已被用于制备发光二极管、太阳能电池和光电探测器等设备。但是铅的毒性和化学不稳定性将对生命健康造成致命威胁并且严重限制设备的使用寿命和应用前景，使用无毒的金属离子来代替卤化铅钙钛矿中的铅离子可以有效的解决铅基钙钛矿的毒性和稳定性问题，但是目前，无铅钙钛矿荧光粉的激发光谱范围较窄，且无法实现光色稳定可调，不能满足植物生长所需吸收光谱的匹配要求。CN109973842A公开了一种长余辉型LED植物灯发光芯片的制备方法，制备方法的具体步骤如下：(1)将荧光粉BaMgAl 10O 17:Eu 2+、Sr 2SiO 4:Eu 2+、CaAlSiN:Eu 2+、SrAl 2O 4:Eu 2+,Dy 3+、CaAl 2O 4:Eu 2+,Dy 3+、ZnG a2O 4:Cr 3+,Bi 3+进行干磨混匀处理30～45min得到混合粉体A；其中荧光粉BaMgAl 10O 17:Eu 2+、Sr 2SiO 4:Eu 2+、CaAlSiN:Eu 2+、SrAl 2O 4:Eu 2+,Dy 3+、CaAl 2O 4:Eu 2+,Dy 3+和ZnG a2O 4:Cr 3+,Bi 3+的质量比为(3～50):(3～50):(3～50):(1～10): (1～10):(1～10)；(2)将荧光粉Sr 3SiO 5:Eu 2+、CaAlSiN:Eu 2+、ZnGa 2O 4：Cr 3+,Bi 3+、Sr 2SiO 4:Eu 2+、SrAl 2O 4:Eu 2+,Dy 3+进行干磨混匀处理30～45min得到混合粉体B；其中荧光粉Sr 3SiO 5:Eu 2+、ZnGa 2O 4:Cr 3+,Bi 3+、Sr 2SiO 4:Eu 2+、SrAl 2O 4:Eu 2+,Dy 3+的质量比为(1～50):(1～10):(1～50):(1～5)；(3)采用环氧树脂将步骤(1)的混合粉体A封装在紫外LED芯片上或将步骤(2)的混合粉体B封装在蓝光LED芯片上，凝固即得长余辉型LED植物灯发光芯片。上述公开的长余辉型LED植物灯发光芯片的钙钛矿材料并非单基质荧光材料，且其主要针对的是红蓝LED植物灯照明亮度的调节，实现自动调制光谱，并未解决通过单基质荧光材料即可实现多色可调，达到稳定宽光谱激发，满足植物所需吸收光谱要求的问题。
发明内容
本发明要解决的技术问题是克服现有的钙钛矿荧光材料不能实现稳定的宽光谱激发发射粉光，不能很好地契合植物所需的吸收光谱的缺陷和不足，提供一种单基质双发射荧光粉，通过在单基质无铅无机钙钛矿Cs 2SnCl 6中掺杂三价离子Bi 3+，Sb 3+，调节三价离子Bi 3+，Sb 3+的含量即可实现光色稳定可调，在300～400nm内有效吸收近紫外光，在400～525nm和550～850nm发射红蓝光，与植物所需的吸收光谱契合，将两种光色进行混合，即可得到符合植物照明需求的粉光。
本发明的另一目的是提供一种单基质双发射荧光粉的制备方法。
本发明的再一目的在于提供一种单基质双发射荧光粉在制备植物照明设备中的应用。
本发明的再一目的在于提供一种植物照明LED。
本发明上述目的通过以下技术方案实现：
一种单基质双发射荧光粉，所述单基质双发射荧光粉的化学式为：
Cs 2Sn 1-x-yBi xSb yCl 6，0.005≤x≤0.09，0.05≤y≤0.25。
其中需要说明的是：式中x，y分别为掺杂离子Bi 3+，Sb 3+，相对基质离子Sn 4+占的摩尔百分含量。
其中需要说明的是：
本发明的荧光粉材料为单基质双发射荧光粉，单基质双发射荧光材料只需单一基质即可有蓝红两种发光，解决了两种或多种的荧光材料复合可能造成的重吸收，多种荧光材料自身老化速率不同造成的光色不稳定，多种荧光粉比例调配复 杂等问题。
上述单基质双发射荧光材料的基质材料为无铅全无机钙钛矿Cs 2SnCl 6，发光中心分别为三价离子Bi 3+，Sb 3+。在近紫外激发下，三价离子Bi 3+在该基质中发蓝光，发射峰位于400～525nm，Sb 3+产生红光，发射峰位于550～850nm，与植物所需的吸收光谱契合，将两种光色进行混合，即可得到符合植物照明需求的粉光。
且本发明的单基质双发射荧光材料可以通过改变三价离子Bi 3+，Sb 3+的掺杂比例，在一定的范围内选择不同的比例，可得到光色可调的双发射荧光粉，通过Bi 3+，Sb 3+的掺杂比例的调控可以有效调节蓝光和红光的比例，可以得到植物生长所需的粉光。且植物种类不同以及植物生长过程中的不同生长周期所需要的光色不同，所以需要合适的蓝红配比的可调光源来达到不同需求，本发明的荧光粉材料可以通过Bi 3+，Sb 3+的掺杂比例的调控来实现不同光源的调节。
由于掺杂了Bi 3+，Sb 3+离子，本发明的双发射荧光材料具有非常宽的激发光谱，在300～400nm内范围均有有效吸收，可有效的吸收紫外LED芯片所发出的近紫外光，在400～525nm和550～850nm发出蓝光和红光，调节得到所需光源。
重吸收是指一种荧光粉的发射光谱与另一种荧光粉的激发光谱重叠，导致前者的发光降低。本发明的单基质双发射荧光材料的蓝红光的激发光谱均在300～400nm处，两者激发和发射光谱无重叠，可避免重吸收。且由于发光中心在同一基质中，使得材料的发光具有相似的老化速率，减少了不同荧光粉材料自身老化速率不同导致的复合光色不稳定问题。
本发明的单基质双发射荧光材料避免了多种荧光粉复合的重吸收效应，且减少了由于多种荧光粉老化速率不同导致的复合光色不稳定，以及不同荧光粉的配比调节复杂等问题。在应用中避免重吸收可以更高效的利用LED的激发能量，光色稳定说明发光峰比例保持不变，更好的维持植物吸收的光的能量的稳定，光色配比调节简单更适宜工业大规模制备。
优选地，所述单基质双发射荧光粉的化学式为：Cs 2Sn 1-x-yBi xSb yCl 6，0.005≤x≤0.09，y＝0.15。
固定Sb离子的含量为0.15，将Bi离子的含量在0.005～0.09之间改变，样品的红蓝发射峰相对强度会随之变化，从而实现光色可调，调节得到从红色到蓝色的光，满足植物LED照明在植物生长不同阶段对不同光色的要求。
优选地，所述单基质双发射荧光粉的化学式为：Cs 2Sn 1-x-yBi xSb yCl 6，x＝0.09，y＝0.05～0.25。
固定Bi离子的含量为0.09，将Sb离子的含量在0.05～0.25之间改变，样品的红蓝发射峰相对强度会随之变化，调节得到从蓝色到红色的光，从而实现光色可调，满足植物LED照明的在植物生长不同阶段对不同光色的要求
本发明同时还具体保护一种上述单基质双发射荧光粉的制备方法，包括如下步骤：
将含Cs的化合物、含Sn的化合物、含Bi的化合物和含Sb的化合物混合，加入盐酸水热反应完全，冷却，清洗，干燥反应产物得到单基质双发射荧光粉，其中，水热反应温度为80-220℃。通过对水热反应温度的控制可以制备出纯相产品，提高产品纯度。
本发明中的粉色荧光材料的制备工艺方法简单，易于实现，且成本低，毒性小，可大规模工业化应用的前景广阔。
优选地，所述含Cs的化合物为Cs的氧化物、Cs的碳酸盐、Cs的氢氧化物、Cs的硝酸盐或Cs的氯化物；
含Sn的化合物为Sn的氧化物、Sn的碳酸盐、Sn的氢氧化物、Sn的硝酸盐或Sn的氯化物；
含Bi的化合物为Bi的氧化物、Bi的碳酸盐、Bi的氢氧化物、Bi的硝酸盐或Bi的氯化物；
含Sb的化合物为Sb的氧化物、Sb的碳酸盐、Sb的氢氧化物、Sb的硝酸盐或Sb的氯化物。
氯化物既能提供反应所需阳离子，也能提供阴离子，更好的制备纯相。因此进一步优选地，所述含Cs的化合物为Cs的氯化物；所述含Sn的化合物为Sn的氯化物；所述含Bi的化合物为Bi氯化物；所述含Sb的化合物为Sb的氯化物。
优选地，所述冷却为以10～30℃/1h的速度冷却至室温。冷却速率的控制可以更好实现材料的高发光效率。
本发明的单基质双发射荧光粉具有宽光谱激发，可以在近紫外光光谱有效吸收并发射出契合植物吸收波段的粉光，同时实现光色可调，可以广泛应用于荧光粉光色调节，本发明尤其具体保护上述单基质双发射荧光粉在制备植物照明设备中的应用。
优选地，所述应用中植物照明设备的紫外LED芯片发射波长为300nm～400nm，进一步优选为365nm。
本发明还具体保护一种植物照明LED，所述LED由所述单基质双发射荧光粉与紫外光LED二极管芯片封装制备得到。
与现有技术相比，本发明的有益效果是：
(1)本发明的双发射荧光材料掺杂了三价离子Bi 3+，Sb 3+，发射峰分别位于400～525nm(Bi 3+)，550～850nm(Sb 3+)，均与植物所需的吸收光谱契合，调节三价离子Bi 3+，Sb 3+的含量即可实现光色稳定可调，得到植物生长所需的粉光。
(2)本发明的双发射荧光材料具有非常宽的激发光谱，在300～400nm内范围均可有效吸收，可有效的吸收紫外LED芯片所发出的近紫外光。
(3)本发明的双发射荧光材料为单基质材料，与多色荧光粉复合制备植物照明LED相比，可以有效的避免重吸收，老化速率不同导致的光色不稳定，以及不同荧光粉的配比调节复杂等问题，可以让光色稳定，不产生大的色漂移。
(4)本发明的粉色荧光材料的制备工艺方法简单，易于实现，且成本低，毒性小，可大规模工业化应用。
附图说明
图1为实施例1～4的单基质双发射荧光粉的XRD图谱。
图2为实施例5～8的单基质双发射荧光粉XRD图谱。
图3为实施例1～4的单基质双发射荧光粉的发射光谱图。
图4为实施例5～8的单基质双发射荧光粉的发射光谱图。
图5为实施例3的单基质双发射荧光粉的发射光谱图。
图6为实施例3的单基质双发射荧光粉的监测不同发射波长位置的激发光谱图。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明，但实施例并不对本发明做任何形式的限定。除非另有说明，本发明实施例采用的原料试剂为常规购买的原料试剂。
实施例1
一种单基质双发射荧光粉，所述单基质双发射荧光粉的化学式为：Cs 2Sn 0.845Bi 0.005Sb 0.15Cl 6。
制备方法如下：
分别称取2mmol氯化铯(CsCl)、1mmol氯化亚锡(SnCl 2)、0.005mmol氯化铋(BiCl 3)和0.176mmol氯化锑(SbCl 3)，以上原料纯度均在99.9％以上。将称取的上述原料倒入10ml水热釜，随后加入3ml盐酸(36-38％)。将水热釜放入马弗炉中于180℃保温12小时，然后以5℃/h的速度降至室温。待降至室温后，取出水热釜中的固体物并用乙醇冲洗3次。将冲洗干净的固体物质放入烘箱内于80℃烘烤8小时至完全干燥。
实施例2
一种单基质双发射荧光粉，所述单基质双发射荧光粉的化学式为：Cs 2Sn 0.843Bi 0.007Sb 0.15Cl 6。
制备方法如下：
分别称取2mmol氯化铯(CsCl)、1mmol氯化亚锡(SnCl 2)、0.007mmol氯化铋(BiCl 3)和0.176mmol氯化锑(SbCl 3)，以上原料纯度均在99.9％以上。将称取的上述原料倒入10ml水热釜，随后加入3ml盐酸(36-38％)。将水热釜放入马弗炉中于180℃保温12小时，然后以5℃/h的速度降至室温。待降至室温后，取出水热釜中的固体物并用乙醇冲洗3次。将冲洗干净的固体物质放入烘箱内于80℃烘烤8小时至完全干燥。
实施例3
一种单基质双发射荧光粉，所述单基质双发射荧光粉的化学式为：Cs 2Sn 0.845Bi 0.01Sb 0.15Cl 6。
制备方法如下：
分别称取2mmol氯化铯(CsCl)、1mmol氯化亚锡(SnCl 2)、0.01mmol氯化铋(BiCl 3)和0.176mmol氯化锑(SbCl 3)，以上原料纯度均在99.9％以上。将称取的上述原料倒入10ml水热釜，随后加入3ml盐酸(36-38％)。将水热釜放入马弗炉中于180℃保温12小时，然后以5℃/h的速度降至室温。待降至室温后，取出水热釜中的固体物并用乙醇冲洗3次。将冲洗干净的固体物质放入烘箱内于80℃烘烤8小时至完全干燥。
实施例4
一种单基质双发射荧光粉，所述单基质双发射荧光粉的化学式为：Cs 2Sn 0.845Bi 0.048Sb 0.15Cl 6。
制备方法如下：
分别称取2mmol氯化铯(CsCl)、1mmol氯化亚锡(SnCl 2)、0.05mmol氯化铋(BiCl 3)和0.176mmol氯化锑(SbCl 3)，以上原料纯度均在99.9％以上。将称取的上述原料倒入10ml水热釜，随后加入3ml盐酸(36-38％)。将水热釜放入马弗炉中于180℃保温12小时，然后以5℃/h的速度降至室温。待降至室温后，取出水热釜中的固体物并用乙醇冲洗3次。将冲洗干净的固体物质放入烘箱内于80℃烘烤8小时至完全干燥。
实施例5
一种单基质双发射荧光粉，所述单基质双发射荧光粉的化学式为：Cs 2Sn 0.86Bi 0.09Sb 0.05Cl 6。
制备方法如下：
分别称取2mmol氯化铯(CsCl)、1mmol氯化亚锡(SnCl 2)、0.1mmol氯化铋(BiCl 3)和0.053mmol氯化锑(SbCl 3)，以上原料纯度均在99.9％以上。将称取的上述原料倒入10ml水热釜，随后加入3ml盐酸(36-38％)。将水热釜放入马弗炉中于180℃保温12小时，然后以5℃/h的速度降至室温。待降至室温后，取出水热釜中的固体物并用乙醇冲洗3次。将冲洗干净的固体物质放入烘箱内于80℃烘烤8小时至完全干燥。
实施例6
一种单基质双发射荧光粉，所述单基质双发射荧光粉的化学式为：Cs 2Sn 0.81Bi 0.09Sb 0.1Cl 6。
制备方法如下：
分别称取2mmol氯化铯(CsCl)、1mmol氯化亚锡(SnCl 2)、0.1mmol氯化铋(BiCl 3)和0.111mmol氯化锑(SbCl 3)，以上原料纯度均在99.9％以上。将称取的上述原料倒入10ml水热釜，随后加入3ml盐酸(36-38％)。将水热釜放入马弗炉中于180℃保温12小时，然后以5℃/h的速度降至室温。待降至室温后，取出水热釜中的固体物并用乙醇冲洗3次。将冲洗干净的固体物质放入烘箱内于80℃烘烤8小时至完全干燥。
实施例7
一种单基质双发射荧光粉，所述单基质双发射荧光粉的化学式为：Cs 2Sn 0.81Bi 0.09Sb 0.15Cl 6。
制备方法如下：
分别称取2mmol氯化铯(CsCl)、1mmol氯化亚锡(SnCl 2)、0.1mmol氯化铋(BiCl 3)和0.176mmol氯化锑(SbCl 3)，以上原料纯度均在99.9％以上。将称取的上述原料倒入10ml水热釜，随后加入3ml盐酸(36-38％)。将水热釜放入马弗炉中于180℃保温12小时，然后以5℃/h的速度降至室温。待降至室温后，取出水热釜中的固体物并用乙醇冲洗3次。将冲洗干净的固体物质放入烘箱内于80℃烘烤8小时至完全干燥。
实施例8
一种单基质双发射荧光粉，所述单基质双发射荧光粉的化学式为：Cs 2Sn 0.845Bi 0.09Sb 0.25Cl 6。
制备方法如下：
分别称取2mmol氯化铯(CsCl)、1mmol氯化亚锡(SnCl 2)、0.1mmol氯化铋(BiCl 3)和0.333mmol氯化锑(SbCl 3)，以上原料纯度均在99.9％以上。将称取的上述原料倒入10ml水热釜，随后加入3ml盐酸(36-38％)。将水热釜放入马弗炉中于180℃保温12小时，然后以5℃/h的速度降至室温。待降至室温后，取出水热釜中的固体物并用乙醇冲洗3次。将冲洗干净的固体物质放入烘箱内于80℃烘烤8小时至完全干燥。
结果检测
图1为实例1～4的XRD图谱，实施例1～4制备的荧光粉的XRD谱图与标准卡片(ICSD#9023)基本一致，进一步证实了本申请实施例1～4制备的荧光粉纯度高。图2为实例5～8的XRD图谱，实施例5～8制备的荧光粉的XRD谱图与标准卡片(ICSD#9023)基本一致，进一步证实了本申请实施例5～8制备的荧光粉纯度高。
针对测试上述实例1～8所制备的系列材料的光谱性质等测试。
图3和图4的结果显示，按照本发明所述的制备方法获得的一系列具有不同离子浓度(离子分别为Bi 3+和Sb 3+)的双发射荧光粉样品(化学组成表达式为：Cs 2Sn 1-x-yBi xSb yCl 6，式中x，y分别为掺杂离子Bi 3+，Sb 3+，相对基质离子Sn 4+占的摩尔百分含量，取值范围：0.005≤x≤0.09，0.05≤y≤0.25)具有相似的光谱性质。
图3为实例1～4的发光材料的发射光谱，从图3可以看出，固定样品中锑(Sb 3+)离子的掺杂量，改变样品中铋(Bi 3+)离子的掺杂量，样品的红蓝发射峰相对强度会随之变化，从而实现光色可调。
图4为实例5～8的发光材料的发射光谱，从图4可以看出，固定样品中铋(Bi 3+)离子的掺杂量，改变样品中锑(Sb 3+)离子的掺杂量，样品的红蓝发射峰相对强度会随之变化，从而实现光色可调。
图5为实例3的发光材料的发射光谱图，由图5看出，本粉色荧光材料在365nm光激发下，在蓝和红光波段均具有较为优异的发射，发射峰分别位于：400～525nm(Bi 3+)，550～850nm(Sb 3+)，结合之后可发出与植物生长所需吸收光谱匹配的粉光发射。叶绿素A，B是植物生长所需要的激素，图5可以说明材料的发射光谱与叶绿素A，B的吸收匹配，适用于植物照明需求。
图6为实例3的发光材料的监测不同发射波长位置的激发光谱图，激发光谱呈现从300nm～400nm的宽带吸收，表明该材料能满足近紫外LED芯片的激发要求。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种单基质双发射荧光粉，其特征在于，所述单基质双发射荧光粉的化学式为：Cs 2Sn 1-x-yBi xSb yCl 6，0.005≤x≤0.09，0.05≤y≤0.25。
  2. 如权利要求1所述单基质双发射荧光粉，其特征在于，所述单基质双发射荧光粉的化学式为：Cs 2Sn 1-x-yBi xSb yCl 6，0.005≤x≤0.09，y＝0.15。
  3. 如权利要求1所述单基质双发射荧光粉，其特征在于，所述单基质双发射荧光粉的化学式为：Cs 2Sn 1-x-yBi xSb yCl 6，x＝0.09，y＝0.15。
  4. 一种权利要求1～3任意一项所述单基质双发射荧光粉的制备方法，其特征在于，包括如下步骤：
    将含Cs的化合物、含Sn的化合物、含Bi的化合物和含Sb的化合物混合，加入盐酸水热反应完全，冷却，清洗，干燥反应产物得到单基质双发射荧光粉，其中，水热反应温度为80-220℃。
  5. 如权利要求4所述单基质双发射荧光粉的制备方法，其特征在于，所述含Cs的化合物为Cs的氧化物、Cs的碳酸盐、Cs的氢氧化物、Cs的硝酸盐或Cs的氯化物；
    含Sn的化合物为Sn的氧化物、Sn的碳酸盐、Sn的氢氧化物、Sn的硝酸盐或Sn的氯化物；
    含Bi的化合物为Bi的氧化物、Bi的碳酸盐、Bi的氢氧化物、Bi的硝酸盐或Bi的氯化物；
    含Sb的化合物为Sb的氧化物、Sb的碳酸盐、Sb的氢氧化物、Sb的硝酸盐或Sb的氯化物。
  6. 如权利要求5所述单基质双发射荧光粉的制备方法，其特征在于，所述含Cs的化合物为Cs的氯化物；所述含Sn的化合物为Sn的氯化物；所述含Bi的化合物为Bi氯化物；所述含Sb的化合物为Sb的氯化物。
  7. 如权利要求5所述单基质双发射荧光粉的制备方法，其特征在于，所述冷却为以10～30℃/1h的速度冷却至室温。
  8. 一种权利要求1～3任意一项所述单基质双发射荧光粉在制备植物照明设备中的应用。
  9. 如权利要求8所述应用，其特征在于，所述应用中植物照明设备的紫外 LED芯片发射波长为300nm～400nm。
  10. 一种植物照明LED，其特征在于，所述LED由权利要求1～3任意一项所述单基质双发射荧光粉与紫外光LED二极管芯片封装制备得到。
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