CN108359460B - Mn (IV) -activated fluoride red fluorescent powder and preparation method thereof - Google Patents
Mn (IV) -activated fluoride red fluorescent powder and preparation method thereof Download PDFInfo
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Abstract
The invention discloses Mn (IV) -activated fluoride red fluorescent powder and a preparation method thereof, wherein the red fluorescent powder uses a chemical general formula AMF7:Mn4+ yIn the formula, A represents any one of Sr, Ca and Ba, M represents Nb or Ta, and y has a value of 0.005-0.1. The invention uses A (CH)3COO)2And Nb2O5Or Ta2O5Taking Nb as raw material2O5Or Ta2O5Dissolving in hydrofluoric acid completely, adding A (CH)3COO)2And K2MnF6Thus obtaining the AMF7 Mn4+ y fluoride red fluorescent powder. The phosphor of the present invention is AMF7As a matrix, Mn4+The red fluorescent powder is a luminescent center, the preparation method is simple and safe, the reaction temperature is low, the content of the activator is controllable, the prepared red fluorescent powder has good luminescent performance, the wavelength of the emitted light is not changed, and the red fluorescent powder is suitable for the fields of white light LED illuminating devices, backlight sources and the like which have high requirements on luminescent materials.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to Mn (IV) -activated fluoride red fluorescent powder and a preparation method thereof.
Background
Nowadays, luminescent materials have become support materials in the fields of information display, lighting source, photoelectric device, etc., and the high luminous intensity and good microscopic shape of the phosphor can effectively improve the performance of the display, so the research and application of new fluorescent materials has been one of the important research fields of material chemistry and material physics.
Since the invention of White Light Emitting Diodes (WLEDs) in 1996, the characteristics of energy saving and environmental friendliness make people hope about the WLEDs infinitely, and luminescent materials play a very important role in various properties of the WLEDs, such as color coordinates, relevant temperature coefficients and the like. The commercial white light LED mainly comprises a blue light LED chip and yellow fluorescent powder Y3Al5O12:Ce3+(YAG) are combined. However, since the phosphor YAG is Ce3+The insufficient red light component in the spectrum results in the low color rendering index (CRI, Ra) of the current white light LED<80) High color temperature (CCT)>4000K) It is difficult to apply to backlights of general illumination and display devices.
Despite the pertinence of the researchersRed phosphors such as nitride and fluoride have been developed, but the manufacturing cost is high due to the severe preparation conditions, and the application of the nitride red phosphor in the backlight of the display device is severely restricted by the broad band emission and the low color purity of the nitride red phosphor. The composition, heat treatment time and temperature of the fluoride phosphor are important factors determining the luminescent properties of the phosphor. By controlling the composition, heat treatment temperature and time of the fluorescent powder, the fluoride fluorescent powder with high luminous intensity, regular powder particles and smooth particle surfaces can be prepared. In recent years, a series of Mn (IV) -activated fluoride red fluorescent powder (general formula is A)a-xBxMX6:Mn4+ yThe material composition is shown in the formula, wherein M represents Si, Ge, Ti, Sn or Zr, X represents halogen, and y represents Mn4 +The number of moles of (a) y is 0.01 to 0.10, and a is 1 or 2, wherein when a is 2, x is 0 to 1, A, B represents Na, K, Cs or Rb independently, and when a is 1, x is 0 to 2, A, B represents Mg, Ba or Zn independently, and A, B is different) has attracted attention.
The existing preparation methods of Mn (IV) -activated fluoride red fluorescent powder generally have 4 types: (1) chemical erosion at room temperature; (2) hydrothermal method; (3) ion exchange method; (4) coprecipitation synthesis method. By adopting the methods, high-quality Mn (IV) -activated fluoride red fluorescent powder can be synthesized, however, the research on VB group elements is relatively less, and Mn (IV) -activated fluoroniobate (tantalate) red fluorescent powder also attracts attention.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of Mn (IV) -activated fluoride red fluorescent powder with high luminous intensity, controllable granularity and long service life, and provide a preparation method which is simple and safe to operate and has controllable concentration of an activator for the red fluorescent powder.
The chemical general formula AMF for the fluorescent powder used for solving the technical problems is7:Mn4+ yIn the formula, A represents any one of Sr, Ca and Ba, M represents Nb or Ta, and y is 0.005-0.1.
Nb is preferable as M.
The value of y is preferably 0.01 to 0.06.
The preparation method of the Mn (IV) -activated fluoride red fluorescent powder comprises the following steps: according to AMF7:Mn4+ yAt a stoichiometric ratio of M2O5Adding hydrofluoric acid and hydrofluoric acid into a reaction kettle with a polytetrafluoroethylene lining, preserving the heat for 30-120 minutes at 80-120 ℃ under a closed condition, cooling to normal temperature, and then adding A (CH)3COO)2And K2MnF6And stirring for 30-60 minutes at normal temperature, washing the product with acetone, deionized water and absolute ethyl alcohol in sequence, and drying to obtain the Mn (IV) -activated fluoride red fluorescent powder.
In the preparation method, the temperature is preferably kept for 30-60 minutes at 110-120 ℃ under a closed condition.
In the preparation method, the mass fraction of the hydrogen fluoride in the hydrofluoric acid is 30-49%.
The invention adopts a two-step synthesis method, and Nb is dissolved by a hydrothermal method2O5Or Ta2O5Then, adopting a coprecipitation method to synthesize Mn (IV) -activated fluoride red fluorescent powder, compared with other Mn4+The activated fluoride red phosphor has the following advantages:
1. the red fluorescent powder has the advantages of low preparation temperature, simple operation, short reaction period, easy control of the reaction process and great commercial potential.
2. The proportion of the activator in the preparation method is controllable, the waste of the raw material of the activator is avoided, the medicine is saved, and the cost is low.
3. The red fluorescent powder prepared by the invention has high stability, high fluorescence intensity and long service life, is completely suitable for the requirements of white light LED devices, and has important industrial application value.
Drawings
FIG. 1 is BaNbF prepared in example 17:Mn4+ 0.01X-ray diffraction pattern of red phosphor.
FIG. 2 is BaNbF prepared in example 17:Mn4+ 0.01Scanning electrode of red fluorescent powderMirror photograph (solid line is excitation spectrum, dashed line is emission spectrum).
FIG. 3 is BaNbF prepared in example 17:Mn4+ 0.01X-ray energy analysis of red phosphor.
FIG. 4 shows BaNbF prepared in examples 1 to 37:Mn4+ 0.01、BaNbF7:Mn4+ 0.03And BaNbF7:Mn4+ 0.06Emission spectrum of red phosphor.
FIG. 5 is CaNbF prepared in example 47:Mn4+ 0.03Emission spectrum of red phosphor.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
K used in the examples below2MnF6The preparation method comprises the following steps: 6.4g of KMnO4And 128.0g KHF2Placing the mixture into a 1000mL plastic measuring cup, adding 420mL of 49% hydrogen fluoride aqueous solution by mass, stirring in ice bath under a closed condition until the solid is completely dissolved, and then dropwise adding 5.10mL of 30% H by mass2O2Stirring the aqueous solution at normal temperature for 30 minutes after the dropwise addition is finished, standing for layering, pouring out supernatant, washing the precipitate for 3 times by using hydrofluoric acid and acetone with the mass fraction of 20%, and drying for 4 hours at 60 ℃ to obtain K2MnF6。
Example 1
According to BaNbF7:Mn4+ 0.011.3290g Nb2O5Adding into a reaction kettle with polytetrafluoroethylene lining containing 4mL of hydrofluoric acid (the mass fraction of hydrogen fluoride is 49%), keeping the temperature at 120 ℃ for 30 minutes under a closed condition, naturally cooling to normal temperature, and adding 2.554g of Ba (CH)3COO)2And 0.0247g K2MnF6Stirring for 30 minutes at normal temperature, washing the product with acetone, deionized water and absolute ethyl alcohol in sequence, and drying at 60 ℃ to obtain BaNbF7:Mn4+ 0.01And (4) red fluorescent powder.
Example 2
According to BaNbF7:Mn4+ 0.031.3290g Nb2O5Adding into a reaction kettle with polytetrafluoroethylene lining containing 4mL of hydrofluoric acid (the mass fraction of hydrogen fluoride is 49%), keeping the temperature at 120 ℃ for 30 minutes under a closed condition, naturally cooling to normal temperature, and adding 2.554g of Ba (CH)3COO)2And 0.0741g K2MnF6Stirring for 30 minutes at normal temperature, washing the product with acetone, deionized water and absolute ethyl alcohol in sequence, and drying at 60 ℃ to obtain BaNbF7:Mn4+ 0.03And (4) red fluorescent powder.
Example 3
According to BaNbF7:Mn4+ 0.061.3290g Nb2O5Adding into a reaction kettle with polytetrafluoroethylene lining containing 4mL of hydrofluoric acid (the mass fraction of hydrogen fluoride is 49%), keeping the temperature at 120 ℃ for 30 minutes under a closed condition, naturally cooling to normal temperature, and adding 2.554g of Ba (CH)3COO)2And 0.1482g K2MnF6Stirring for 30 minutes at normal temperature, washing the product with acetone, deionized water and absolute ethyl alcohol in sequence, and drying at 60 ℃ to obtain BaNbF7:Mn4+ 0.06And (4) red fluorescent powder.
Crystals were selected from the phosphor prepared in example 1, and subjected to single crystal test using a Bruker D8Quest single crystal instrument (test conditions: CuK alpha radiation,
) Performing single crystal analysis on the obtained single crystal data, which belongs to the cubic system and has unit cell parameters
α＝90°，
And Z is 8.0. The analyzed single crystal data was subjected to X-ray diffraction simulation using a Rigaku mini flex 6000X-ray powder diffractometer manufactured by Nippon chemical Co., LtdThe phosphor powder was subjected to phase analysis (test conditions: CuK. alpha. radiation, voltage 40KV, current 15mA, scanning range 10 to 70 degrees, scanning speed 10/min, step size 0.02 degree), and the results are shown in FIG. 1. As can be seen from FIG. 1, the diffraction peak of the prepared phosphor is consistent with the simulated diffraction peak of the crystal, which indicates that the prepared phosphor is pure phase.
The phosphor particles prepared in example 1 were subjected to morphology characterization and energy spectrum testing using a Quanta 200-type environmental Scanning Electron Microscope (SEM) manufactured by FEI, usa, and the results are shown in fig. 2 to 3. As can be seen from FIG. 2, the prepared phosphor has a uniform particle size of about 10-25 μm. As can be seen from FIG. 3, the prepared phosphor contains four elements of Ba, Nb, F and Mn. Combining the results of FIG. 1 and FIG. 3, the BaNbF is shown to be prepared7:Mn4+ 0.01。
The phosphor powders prepared in examples 1 to 3 were subjected to a luminescence property test using an F-4600 fluorescence spectrometer manufactured by Hitachi, and the results are shown in FIG. 4. As can be seen from FIG. 4, the emission peak of the phosphor prepared in examples 1 to 3 is at 630nm under 460nm excitation light, and belongs to Mn4+Is/are as follows2Eg→4A2gAnd (3) characteristic transition emission shows that the sample emits red light, has high luminous intensity and good color purity, and can be used for a white light LED.
Example 4
According to CaNbF7:Mn4+ 0.031.3290g Nb2O5Adding into a reaction kettle with polytetrafluoroethylene lining containing 4mL of hydrofluoric acid (49 mass percent of hydrogen fluoride), keeping the temperature at 120 ℃ for 30 minutes under a closed condition, naturally cooling to normal temperature, and then adding 1.5817g of Ca (CH)3COO)2And 0.0741g K2MnF6Stirring for 30 minutes at normal temperature, washing the product with acetone, deionized water and absolute ethyl alcohol in sequence, and drying at 60 ℃ to obtain CaNbF7:Mn4+ 0.03And (4) red fluorescent powder. As can be seen from FIG. 5, the emission peak of the phosphor prepared in example 4 under 460nm excitation light is at 630nm, which is Mn4+Is/are as follows2Eg→4A2gCharacteristic transition emission, descriptionThe sample emits red light, has high luminous intensity and good color purity, and can be used for a white light LED.
Example 5
According to SrTaF7:Mn4+ 0.012.2095g Ta2O5Adding into a reaction kettle with polytetrafluoroethylene lining containing 4mL of hydrofluoric acid (the mass fraction of hydrogen fluoride is 49%), keeping the temperature at 120 ℃ for 30 minutes under a closed condition, naturally cooling to normal temperature, and adding 2.0571Sr (CH)3COO)2And 0.0247g K2MnF6Stirring for 30 minutes at normal temperature, washing the product with acetone, deionized water and absolute ethyl alcohol in sequence, and drying at 60 ℃ to obtain SrTaF7:Mn4+ 0.01And (4) red fluorescent powder.
Example 6
According to BaTaF7:Mn4+ 0.032.2095g Ta2O5Adding into a reaction kettle with polytetrafluoroethylene lining containing 4mL of hydrofluoric acid (hydrogen fluoride mass fraction of 49%), keeping the temperature at 120 ℃ for 0.5 hour under a closed condition, naturally cooling to normal temperature, and adding 2.554g of Ba (CH)3COO)2And 0.0741g K2MnF6Stirring for 30 minutes at normal temperature, washing the product with acetone, deionized water and absolute ethyl alcohol in sequence, and drying at 60 ℃ to obtain BaTaF7:Mn4+ 0.03And (4) red fluorescent powder.
Example 7
According to CaTaF7:Mn4+ 0.062.2095g Ta2O5Adding into a reaction kettle with polytetrafluoroethylene lining containing 4mL of hydrofluoric acid (hydrogen fluoride mass fraction of 49%), keeping the temperature at 120 ℃ for 0.5 h under a closed condition, naturally cooling to normal temperature, and adding 1.5817g of Ca (CH)3COO)2And 0.1482g K2MnF6Stirring for 30 minutes at normal temperature, washing the product with acetone, deionized water and absolute ethyl alcohol in sequence, and drying at 60 ℃ to obtain CaTaF7:Mn4+ 0.06And (4) red fluorescent powder.
Claims (6)
1. An Mn (IV) -activated fluoride red phosphor, characterized by: the chemical general formula AMF for the fluorescent powder7:Mn4+ yIn the formula, A represents any one of Sr, Ca and Ba, M represents Nb or Ta, and y is 0.005-0.1.
2. A mn (iv) activated fluoride red phosphor according to claim 1, characterized in that: and M represents Nb.
3. A mn (iv) -activated fluoride red phosphor according to claim 1 or 2, characterized in that: and the value of y is 0.01-0.06.
4. A method of preparing a mn (iv) -activated fluoride red phosphor of claim 1, characterized in that: according to AMF7:Mn4+ yAt a stoichiometric ratio of M2O5Adding hydrofluoric acid and hydrofluoric acid into a reaction kettle with a polytetrafluoroethylene lining, preserving the heat for 30-120 minutes at 80-120 ℃ under a closed condition, cooling to normal temperature, and then adding A (CH)3COO)2And K2MnF6And stirring for 30-60 minutes at normal temperature, washing the product with acetone, deionized water and absolute ethyl alcohol in sequence, and drying to obtain the Mn (IV) -activated fluoride red fluorescent powder.
5. The method of claim 4 for preparing a Mn (IV) -activated fluoride red phosphor, wherein: and preserving the heat for 30-60 minutes at 110-120 ℃ under a closed condition.
6. The reverse preparation method of Mn (IV) -activated fluoride red phosphor according to claim 4, wherein: the mass fraction of the hydrogen fluoride in the hydrofluoric acid is 30-49%.
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