CN116694323B - Leadless double perovskite yellow light fluorescent powder and preparation method and application thereof - Google Patents
Leadless double perovskite yellow light fluorescent powder and preparation method and application thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 230000005284 excitation Effects 0.000 abstract description 17
- 238000000695 excitation spectrum Methods 0.000 abstract description 13
- 238000000295 emission spectrum Methods 0.000 abstract description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 26
- 239000011521 glass Substances 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000011780 sodium chloride Substances 0.000 description 13
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 229910021617 Indium monochloride Inorganic materials 0.000 description 6
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 6
- UKCIUOYPDVLQFW-UHFFFAOYSA-K indium(3+);trichloride;tetrahydrate Chemical compound O.O.O.O.Cl[In](Cl)Cl UKCIUOYPDVLQFW-UHFFFAOYSA-K 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
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- 239000011734 sodium Substances 0.000 description 5
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 238000001514 detection method Methods 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
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- 241000196324 Embryophyta Species 0.000 description 1
- 241001085205 Prenanthella exigua Species 0.000 description 1
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- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
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- 231100000053 low toxicity Toxicity 0.000 description 1
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- 230000009103 reabsorption Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
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- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- 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
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Abstract
The invention discloses lead-free double perovskite yellow light fluorescent powder and a preparation method and application thereof, and belongs to the technical field of luminescent materials. The chemical formula of the leadless double perovskite yellow light fluorescent powder is Cs 2NaIn1‑ xTexCl6, wherein x is the mole percentage content of doped ion Te 4+ relative to matrix ion In 3+, and the value range is as follows: 0.00< x <1.00. The matrix material of the leadless double perovskite yellow light fluorescent powder is leadless double perovskite Cs 2NaInCl6, the luminescence center is tetravalent Te 4+ ion, the leadless double perovskite yellow light fluorescent powder has very wide excitation spectrum under the excitation of near ultraviolet light of 250-500 nm, can effectively absorb ultraviolet light and partial visible light, the tetravalent Te 4+ ion generates yellow light with peak position of 590nm in the matrix, and the emission spectrum covers 450-800nm, has the advantages of broadband excitation and yellow light emission in ultraviolet-visible light region, and can be potentially applied to the field of white light LED light conversion materials.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a lead-free double perovskite yellow fluorescent powder and a preparation method and application thereof.
Background
Light Emitting Diodes (LEDs) are fourth generation green light sources replacing traditional light sources such as incandescent lamps, fluorescent lamps, tungsten filaments, and the like due to the advantages of high luminous efficiency, low energy consumption, long service life, low operating temperature, high reaction speed, small volume, multiple packaging, high safety reliability, and the like. Although LED has been developed for only decades, it has been widely used in various fields such as indoor and outdoor lighting, plant lamps, backlights, biomedical treatment, sensing, optical communication, food processing, and defense and military industry, and is considered as the most promising new generation of green light source, and is in particular in the context of shortage of global energy, and is highly spotlighted worldwide. For white light illumination devices, there are three methods widely used at present: the first is that the white light device is formed by using the LED chips with three primary colors of red, green and blue, but the cost is high, the feedback of the light color regulating and controlling circuit is complex, and the wide application of the white light device is limited; the second method is to mix the three primary colors of fluorescent materials according to a proper proportion and then combine the mixed materials with an ultraviolet LED chip to realize white light. The white light quality obtained by the method can regulate and control the proportion of three primary colors according to the requirement, and has good color reproducibility and rich materials. However, the current high-power ultraviolet chip has higher cost and low efficiency, and the problem of unstable light color caused by multiple composite fluorescent powder under the condition of reabsorption or long-term use exists among different fluorescent powder. The third is that the yellow fluorescent powder conversion layer is combined with the blue light LED to form a white light device, and the method has the advantages of higher efficiency, low manufacturing cost, simpler packaging process flow, stronger practicability and the like, and is widely applied in actual production and life, so that the method becomes a main implementation mode of the current white light LED light source.
In recent years, lead-free perovskite materials have become a research hotspot for semiconductor luminescent materials in recent years due to a series of unique optical properties such as low toxicity, high stability, flexible preparation, wide emission spectrum, large stokes shift, and the like, compared with lead-halogen perovskite materials. However, most of the lead-free perovskite materials reported at present have high excitation energy and are only suitable for ultraviolet LED chip excitation, so that the lead-free perovskite fluorescent material with broadband excitation is very challenging to obtain. The prior art discloses a Te doped Cs 2ZrCl6 perovskite derivative material, which is synthesized in one step by a solvothermal method by taking cesium-containing compounds, zirconium-containing compounds and tellurium-containing compounds as reactants and concentrated hydrochloric acid as a solution. However, the synthesis method has high equipment requirement and long reaction time, is not suitable for large-batch synthesis, has higher cleaning difficulty of the inner container of the reaction kettle, can have potential safety hazards in high-temperature high-pressure strong-acid solvent experiments, and the like, and the prepared yellow luminous perovskite derivative material only realizes the excitation and yellow emission of a 390nm ultraviolet lamp, so that the excitation spectrum of the lead-free perovskite fluorescent material is not remarkably widened.
Disclosure of Invention
The invention aims to overcome the defects and defects of the existing lead-free perovskite material that the excitation spectrum and the emission spectrum range are narrow and the excitation energy is high, and provides the lead-free double perovskite yellow light fluorescent powder which has the advantages of ultraviolet-visible light region broadband excitation and yellow light emission under the excitation of near ultraviolet light of 250-500 nm.
The invention further aims to provide a preparation method of the leadless double perovskite yellow light fluorescent powder.
The invention further aims to provide an application of the lead-free double perovskite yellow light fluorescent powder in preparing a white light LED light conversion fluorescent powder material.
It is another object of the present invention to provide a white LED.
The above object of the present invention is achieved by the following technical scheme:
The chemical formula of the leadless double perovskite yellow light fluorescent powder is Cs 2NaIn1-xTexCl6, wherein x is the molar percentage content of doped ions Te 4+ relative to matrix ions In 3+, and the value range is as follows: 0.00< x <1.00.
The following description is needed:
The matrix material of the leadless double perovskite yellow light fluorescent powder material is leadless double perovskite Cs 2NaInCl6, and the luminescence center is tetravalent Te 4+ ions. Under the excitation of near ultraviolet light of 250-500 nm, the ultraviolet light-emitting diode has very wide excitation spectrum, can effectively absorb ultraviolet light and partial visible light in the range of 250-500 nm, is suitable for the current commercial ultraviolet and blue light LED chips, and has the advantages that tetravalent Te 4+ ions generate yellow light with peak positions of 590nm in the matrix, the emission spectrum covers 450-800nm, the ultraviolet-visible light area broadband excitation and yellow light emission are realized, and the ultraviolet-visible light-emitting diode can be used as a potential application in the field of white light LED light conversion materials.
Preferably, the value range of x is: 0.01 to 0.3.
In a specific embodiment, the fluorescent powder can be lead-free double perovskite yellow light fluorescent powder, and has a chemical formula of Cs 2NaIn0.9Te0.1Cl6;
Or lead-free double perovskite yellow light fluorescent powder with a chemical formula of Cs 2NaIn0.8Te0.2Cl6;
Or lead-free double perovskite yellow light fluorescent powder with a chemical formula of Cs 2NaIn0.7Te0.3Cl6;
Or lead-free double perovskite yellow light fluorescent powder with a chemical formula of Cs 2NaIn0.5Te0.5Cl6;
Or lead-free double perovskite yellow light fluorescent powder with a chemical formula of Cs 2NaIn0.3Te0.7Cl6;
or lead-free double perovskite yellow fluorescent powder with a chemical formula of Cs 2NaIn0.2Te0.8Cl6.
The lead-free double perovskite yellow light fluorescent powder is of a face-centered cubic structure. The face-centered cubic structure is beneficial to keeping the half-peak width of the excitation spectrum of the luminescence center of Te 4+ ions not reduced, and meanwhile, the structure is beneficial to controlling the emission wavelength of Te 4+ ions in a yellow light area so as to be matched with a blue light LED chip to directly package a white light LED light source.
The lead-free double perovskite yellow light fluorescent powder is detected by XRD, the XRD spectrograms of the fluorescent powder are all face-centered cubic structures, and the fluorescent powder is high in purity and free of impurity phases.
The invention also specifically protects a preparation method of the leadless double perovskite yellow light fluorescent powder, which specifically comprises the following steps:
Mixing the Na, in and Te-containing compounds according to a certain proportion, adding 0.5-10ml of hydrochloric acid with the mass percentage concentration of 20-37%, dissolving, adding the Cs-containing compound to initiate precipitation, reacting for 2-24h at 30-100 ℃, cleaning and drying to obtain the leadless double perovskite yellow fluorescent powder.
The following description is needed:
The preparation method of the lead-free double perovskite yellow light fluorescent powder is characterized in that hydrochloric acid is added to dissolve the lead-free double perovskite yellow light fluorescent powder, and the lead-free double perovskite yellow light fluorescent powder can be fully stirred and dissolved at the temperature of 30-100 ℃.
Wherein, the cooling is to naturally cool to room temperature; in order to remove the precursor raw materials which are not reacted, the product is also required to be subjected to washing treatment, wherein the washing treatment is carried out by ethanol for 1 to 5 times; the drying is carried out by preserving the temperature at 50-100 ℃ for 1-24h to completely dry.
In a specific embodiment, the preparation method of the lead-free double perovskite yellow light fluorescent powder comprises the following steps:
the compound containing Cs is one or more of Cs oxide, cs carbonate, cs hydroxide, cs nitrate or Cs chloride, preferably Cs chloride;
The Na-containing compound is one or more of Na oxide, na carbonate, na hydroxide, na nitrate and Na chloride, preferably Na chloride;
The compound containing In is one or more of In oxide, in carbonate, in hydroxide, in nitrate and In chloride, preferably In chloride;
the compound containing Te is one or more of Te oxide, te carbonate, te hydroxide, te nitrate and Te chloride, preferably Te chloride.
The invention also specifically protects application of the leadless double perovskite yellow light fluorescent powder in preparation of white light LED light conversion fluorescent powder materials.
The invention also specifically protects a white light LED, and the light conversion fluorescent powder material of the white light LED is the leadless double perovskite yellow fluorescent powder.
The leadless double perovskite yellow light fluorescent powder has very wide excitation spectrum, can effectively absorb ultraviolet light and partial visible light within the range of 250-500 nm, and is suitable for the current commercial ultraviolet and blue light LED chips. And the emission spectrum covers 450-800nm, and the white light LED light source device can be obtained by directly carrying out simple packaging with a commercial blue light GaN chip.
The preparation process of the lead-free perovskite fluorescent material is simple, easy to realize, low in cost and low in toxicity, has a wide prospect of large-scale industrial application, and can be widely applied to the preparation of white light LEDs.
Compared with the prior art, the invention has the beneficial effects that:
The matrix material of the leadless double perovskite yellow light fluorescent powder is leadless double perovskite Cs 2NaInCl6, the luminescence center is tetravalent Te 4+ ion, the leadless double perovskite yellow light fluorescent powder has very wide excitation spectrum under the excitation of near ultraviolet light of 250-500 nm, can effectively absorb ultraviolet light and partial visible light, the tetravalent Te 4+ ion generates yellow light with peak position of 590nm in the matrix, and the emission spectrum covers 450-800nm, has the advantages of broadband excitation and yellow light emission in ultraviolet-visible light region, and can be potentially applied to the field of white light LED light conversion materials.
Drawings
FIG. 1 is an XRD pattern for lead-free double perovskite yellow phosphors of examples 1, 2, 3, 4, 5;
FIG. 2 is a graph showing the emission spectra of lead-free double perovskite yellow phosphors of examples 1,2, 3, 4, and 5;
FIG. 3 is a graph showing the excitation spectra of the lead-free double perovskite yellow phosphors of examples 1, 2, 3, 4, and 5;
FIG. 4 is a graph of excitation and emission spectra of the lead-free double perovskite luminescent material of comparative example 1;
FIG. 5 is an electroluminescence spectrum of a white light LED device packaged by the luminescent material of example 3 and a commercial blue light GaN LED chip, and an actual luminescence photograph of the white light LED device after lighting;
fig. 6 is a color graph of a white LED device based on the luminescent material package of example 3.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
Example 1
The chemical formula of the leadless double perovskite yellow light fluorescent powder is Cs 2NaIn0.9Te0.1Cl6.
The preparation method of the leadless double perovskite yellow light fluorescent powder Cs 2NaIn0.9Te0.1Cl6 comprises the following steps:
1mmol of sodium chloride (NaCl), 0.9mmol of indium chloride tetrahydrate (InCl 3·4H2 O) and 0.1mmol of tellurium oxide (TeO 2) are respectively weighed, and the purities of the raw materials are all over 99.9 percent.
The weighed raw materials are poured into a 10ml glass bottle, 5ml hydrochloric acid (35%) is added, the glass bottle is placed on a heating table and heated at a constant temperature of 80 ℃ for 1 hour, and stirring is carried out for dissolution. After dissolution was completed, 2mmol cesium chloride (CsCl) was added to initiate white precipitation, heating was continued at constant temperature for 2 hours, and naturally cooled to room temperature. After cooling to room temperature, the solid in the glass bottle was taken out and rinsed 3 times with ethanol. The rinsed solid material was placed in an oven and baked at 80 ℃ for 8 hours to complete drying.
Example 2
The chemical formula of the leadless double perovskite yellow light fluorescent powder is Cs 2NaIn0.8Te0.2Cl6.
The preparation method of the leadless double perovskite yellow light fluorescent powder Cs 2NaIn0.8Te0.2Cl6 comprises the following steps:
1mmol of sodium chloride (NaCl), 0.8mmol of indium chloride tetrahydrate (InCl 3·4H2 O) and 0.2mmol of tellurium oxide (TeO 2) are respectively weighed, and the purities of the raw materials are all over 99.9 percent. The weighed raw materials are poured into a 10ml glass bottle, 5ml hydrochloric acid (35%) is added, the glass bottle is placed on a heating table and heated at a constant temperature of 80 ℃ for 1 hour, and stirring is carried out for dissolution. After dissolution was completed, 2mmol cesium chloride (CsCl) was added to initiate white precipitation, heating was continued at constant temperature for 2 hours, and naturally cooled to room temperature. After cooling to room temperature, the solid in the glass bottle was taken out and rinsed 3 times with ethanol. The rinsed solid material was placed in an oven and baked at 80 ℃ for 8 hours to complete drying.
Example 3
The chemical formula of the leadless double perovskite yellow light fluorescent powder is Cs 2NaIn0.7Te0.3Cl6.
The preparation method of the leadless double perovskite yellow light fluorescent powder Cs 2NaIn0.7Te0.3Cl6 comprises the following steps:
1mmol of sodium chloride (NaCl), 0.7mmol of indium chloride tetrahydrate (InCl 3·4H2 O) and 0.3mmol of tellurium oxide (TeO 2) are respectively weighed, and the purities of the raw materials are all over 99.9 percent. The weighed raw materials are poured into a 10ml glass bottle, 5ml hydrochloric acid (35%) is added, the glass bottle is placed on a heating table and heated at a constant temperature of 80 ℃ for 1 hour, and stirring is carried out for dissolution. After dissolution was completed, 2mmol cesium chloride (CsCl) was added to initiate white precipitation, heating was continued at constant temperature for 2 hours, and naturally cooled to room temperature. After cooling to room temperature, the solid in the glass bottle was taken out and rinsed 3 times with ethanol. The rinsed solid material was placed in an oven and baked at 80 ℃ for 8 hours to complete drying.
Example 4
The chemical formula of the leadless double perovskite yellow light fluorescent powder is Cs 2NaIn0.5Te0.5Cl6.
The preparation method of the leadless double perovskite yellow light fluorescent powder Cs 2NaIn0.5Te0.5Cl6 comprises the following steps:
1mmol of sodium chloride (NaCl), 0.5mmol of indium chloride tetrahydrate (InCl 3·4H2 O) and 0.5mmol of tellurium oxide (TeO 2) are respectively weighed, and the purities of the raw materials are all over 99.9 percent. The weighed raw materials are poured into a 10ml glass bottle, 5ml hydrochloric acid (35%) is added, the glass bottle is placed on a heating table and heated at a constant temperature of 80 ℃ for 1 hour, and stirring is carried out for dissolution. After dissolution was completed, 2mmol cesium chloride (CsCl) was added to initiate white precipitation, heating was continued at constant temperature for 2 hours, and naturally cooled to room temperature. After cooling to room temperature, the solid in the glass bottle was taken out and rinsed 3 times with ethanol. The rinsed solid material was placed in an oven and baked at 80 ℃ for 8 hours to complete drying.
Example 5
The chemical formula of the leadless double perovskite yellow light fluorescent powder is Cs 2NaIn0.2Te0.8Cl6.
The preparation method of the leadless double perovskite yellow light fluorescent powder Cs 2NaIn0.2Te0.8Cl6 comprises the following steps:
1mmol of sodium chloride (NaCl), 0.2mmol of indium chloride tetrahydrate (InCl 3·4H2 O) and 0.8mmol of tellurium oxide (TeO 2) are respectively weighed, and the purities of the raw materials are all over 99.9 percent. The weighed raw materials are poured into a 10ml glass bottle, 5ml hydrochloric acid (20-37%) is added, the glass bottle is placed on a heating table and heated at the constant temperature of 80 ℃ for 1 hour, and stirring is carried out for dissolving. After dissolution was completed, 2mmol cesium chloride (CsCl) was added to initiate white precipitation, heating was continued at constant temperature for 2 hours, and naturally cooled to room temperature. After cooling to room temperature, the solid in the glass bottle was taken out and rinsed 3 times with ethanol. The rinsed solid material was placed in an oven and baked at 80 ℃ for 8 hours to complete drying.
Comparative example 1
A leadless double perovskite fluorescent powder has a chemical formula of Cs 2NaInCl6.
The preparation method of the leadless double perovskite yellow light fluorescent powder Cs 2NaInCl6 comprises the following steps:
1mmol of sodium chloride (NaCl) and 1mmol of indium chloride tetrahydrate (InCl 3·4H2 O) are respectively weighed, and the purities of the raw materials are all over 99.9 percent. The weighed raw materials are poured into a10 ml glass bottle, 5ml hydrochloric acid (20-37%) is added, the glass bottle is placed on a heating table and heated at the constant temperature of 80 ℃ for 1 hour, and stirring is carried out for dissolving. After dissolution was completed, 2mmol cesium chloride (CsCl) was added to initiate white precipitation, heating was continued at constant temperature for 2 hours, and naturally cooled to room temperature. After cooling to room temperature, the solid in the glass bottle was taken out and rinsed 3 times with ethanol. The rinsed solid material was placed in an oven and baked at 80 ℃ for 8 hours to complete drying.
Result detection
1. Fig. 1 shows XRD patterns of examples 1, 2, 3,4 and 5, and the detection results are shown in fig. 1, so that the XRD patterns of the phosphors prepared in examples 1, 2, 3,4 and 5 are all face-centered cubic structures, and the purity of the phosphors is high. Wherein the samples prepared in examples 1-3 are consistent with diffraction peaks in the calculated simulated XRD card, no additional diffraction peaks appear, indicating complete absence of impurity phases. However, when x >0.3, a heterogeneous phase will appear in the product of the reaction, which can be confirmed by phase analysis, and too high Te content causes the formation of a heterogeneous phase of NaCl in the material.
2. Fig. 2 is the emission spectra of examples 1,2, 3, 4, and 5, and it can be seen from fig. 2 that as the Te content increases, the yellow emission of the obtained yellow phosphor at 590nm increases.
3. Fig. 3 shows excitation spectra of examples 1,2, 3, 4 and 5, and it can be seen from fig. 3 that the obtained yellow fluorescent powder shows continuous broadband absorption from 250nm to 500nm on the excitation spectra, which shows that the material can meet the requirement of near ultraviolet light to visible light excitation.
4. Fig. 4 shows the excitation and emission spectra of comparative example 1, and it can be seen from fig. 4 that the excitation spectrum of the matrix sample covers only the near ultraviolet region of 300-350nm, and the sample emits a weak blue emission of 440nm under near ultraviolet excitation.
5. Fig. 5 is an electroluminescence spectrum of a white LED device packaged by the luminescent material of example 3 and a commercial blue GaN LED chip, and an actual luminescence photograph of the white LED device after lighting. As can be seen from fig. 4, the color coordinates of the packaged device lie in the white light region and, upon illumination, emit bright white light.
6. As can be seen from fig. 6, the chromaticity coordinate of the white LED device based on the luminescent material package of example 3 is (0.35), which is in the white light region.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (9)
1. A leadless double perovskite yellow light fluorescent powder is characterized In that the chemical formula of the leadless double perovskite yellow light fluorescent powder is Cs 2NaIn1-xTexCl6, wherein x is the molar percentage content of doped ion Te 4+ relative to matrix ion In 3+, the value range x is 0.01-0.8,
The leadless double perovskite yellow light fluorescent powder has a face-centered cubic structure.
2. The lead-free double perovskite yellow phosphor of claim 1, wherein x ranges from: 0.01 to 0.3.
3. A method for preparing the leadless double perovskite yellow light fluorescent powder according to claim 1 or 2, comprising the following steps:
Mixing the Na, in and Te-containing compounds according to a certain proportion, adding 0.5-10ml of hydrochloric acid with the mass percentage concentration of 20-37%, dissolving, adding the Cs-containing compound to initiate precipitation, reacting for 2-24h at 30-100 ℃, cleaning and drying to obtain the leadless double perovskite yellow fluorescent powder.
4. The method for preparing a leadless double perovskite yellow light fluorescent powder according to claim 3, wherein the compound containing Cs is one or more of oxide of Cs, carbonate of Cs, hydroxide of Cs, nitrate of Cs, and chloride of Cs.
5. The method for preparing lead-free double perovskite yellow light fluorescent powder according to claim 3, wherein the Na-containing compound is one or more of Na oxide, na carbonate, na hydroxide, na nitrate and Na chloride.
6. The method for preparing a lead-free double perovskite yellow fluorescent powder according to claim 3, wherein the In-containing compound is one or more of In oxide, in carbonate, in hydroxide, in nitrate and In chloride.
7. The method for preparing a lead-free double perovskite yellow light fluorescent powder according to claim 3, wherein the Te-containing compound is one or more of Te oxide, te carbonate, te hydroxide, te nitrate and Te chloride.
8. Use of the lead-free double perovskite yellow light fluorescent powder according to claim 1 or 2 in preparation of white light LED light conversion fluorescent powder materials.
9. A white LED, wherein the light conversion phosphor material of the white LED is the leadless double perovskite yellow phosphor according to claim 1 or 2.
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| CN112358876A (en) * | 2020-11-17 | 2021-02-12 | 广西大学 | Te-doped Cs2ZrCl6Perovskite derivative material and preparation method and application thereof |
| CN113372905A (en) * | 2021-05-07 | 2021-09-10 | 中山大学 | Lead-free double perovskite for enhancing Er ion photoluminescence and preparation method and application thereof |
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| CN112358876A (en) * | 2020-11-17 | 2021-02-12 | 广西大学 | Te-doped Cs2ZrCl6Perovskite derivative material and preparation method and application thereof |
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