CN114958345B - Mn (IV) unequal doped organic-inorganic hybrid fluorescent material and preparation method thereof - Google Patents
Mn (IV) unequal doped organic-inorganic hybrid fluorescent material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic-inorganic hybrid fluorescent material with Mn (IV) unequal doping and a preparation method thereof. The chemical composition of the fluorescent material is A 2 AlF 2 (OH) 3 ·xH 2 O:yMn 4+ Or AAlF 4 ·xH 2 O:yMn 4+ Wherein A is an organic cationic group [ (CH) 3 ) 4 N] + 、[(CH 3 CH 2 ) 4 N] + 、[(CH 3 CH 2 CH 2 CH 2 ) 4 N] + One or a combination of two or more of them; x is the quantity of crystal water contained in the molecular formula, and x is more than or equal to 0 and less than or equal to 3; y is doping ion Mn 4+ Relative to Al 3+ Mole percentage coefficient of ion, 0<y is less than or equal to 40 percent. The fluorescent material can be effectively excited by ultraviolet light, near ultraviolet light and blue light, emits high-color purity narrow-band red light with the wavelength of 631nm, and has the characteristics of high luminous efficiency and short fluorescence lifetime.
Description
Technical Field
The invention belongs to the technical field of luminescent functional materials, and particularly relates to an Mn (IV) unequal doped organic-inorganic hybrid fluorescent material and a preparation method thereof.
Background
The white light LED has the outstanding advantages of long service life, quick response, no stroboscopic effect, energy conservation, environmental protection and the like, and rapidly replaces the traditional illumination light source incandescent lamp and fluorescent lamp, thereby becoming a new generation of solid-state illumination and backlight display light source. Currently, the main stream commercial white light LED is excited by a blue light LED chipYellow fluorescent powder Y 3 Al 5 O 12 :Ce 3+ (YAG:Ce 3+ ) In such a way that white light is obtained, the lack of red light component in the emission spectrum of such white light LED results in a higher color temperature (CCT) of the white light emitted by the device>4500K) Low color rendering index (CRI, ra)<80 It is difficult to meet the requirements of indoor lighting and wide color gamut Liquid Crystal Display (LCD) backlights. In order to improve the light color quality of the white light LED, a proper amount of red light material capable of being excited by the blue light LED needs to be added into the white light LED device of the type.
Current Mn 4+ The red phosphor powder doped with the inorganic fluoride has been reported in a large number and can be mainly divided into Mn 4+ Equivalently doped A 2 MF 6 :Mn 4+ (A:Li、Na、K、Rb、Cs、NH 4 The method comprises the steps of carrying out a first treatment on the surface of the M Si, ge, sn, ti, zr, hf) and Mn 4+ A is not equivalently doped 3 NF 6 :Mn 4+ (A:Li、Na、K、Rb、Cs、NH 4 The method comprises the steps of carrying out a first treatment on the surface of the N: al, ga, in, sc) two major types. Wherein Mn is 4+ Equivalent doping A 2 MF 6 :Mn 4+ Most of the systems have higher luminous efficiency, but the fluorescence life of the systems is too long>5 ms), resulting in severe red smear in backlight display applications, severely affecting display effect (j.mater.chem.c., 2019,7,9203) and user experience. Another kind, mn 4+ Unequal doping A 3 NF 6 :Mn 4+ The system has a short fluorescence lifetime for the majority of the time, but due to Mn 4+ A valence state difference from the replaced trivalent ion, resulting in Mn at the luminescence center 4+ A large number of charge compensation defects are generated around. These defects become fluorescence quenching sites, making Mn 4+ The absorbed excitation energy is quenched in the form of non-radiative relaxation, resulting in a decrease in luminous efficiency. It is reported that large-sized organic cationic groups can make the luminescence centers highly isolated, thereby blocking aggregation between luminescence centers, and blocking Energy transfer of luminescence centers to fluorescence quenching sites, thereby achieving high luminous efficiency (j.phys.chem.lett.2020, 11,5956, ACS Energy lett.2017,3,54.). Therefore, in order to solve the fluorescence quenching problem caused by the charge compensation defect, a light emitting device having high luminous efficiency has been developed(external quantum efficiency is more than 60%) and short fluorescence lifetime<5 ms) of novel Mn 4+ Fluorescent materials are doped to meet the application requirements of high-quality white light LED backlights, and organic cationic groups with large sizes are innovatively introduced into all-inorganic lattices to be Mn 4+ Provides a brand new organic-inorganic hybrid crystal field environment, so that the organic-inorganic hybrid crystal field environment can emit light with high efficiency.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide Mn 4+ Non-equivalently doped organic-inorganic hybrid fluorescent materials. The Mn of 4+ The non-equivalently doped organic-inorganic hybrid fluorescent material can be combined with ultraviolet, near ultraviolet or blue light emitting diodes and commercial fluorescent powder to package high-quality white light LED devices.
The invention also aims to provide the Mn 4+ The preparation method of the non-equivalent doped organic-inorganic hybrid fluorescent material comprises a coprecipitation method and an ion exchange method, and the preparation process is simple and easy to implement, has mild conditions and can be used for large-scale industrial production.
The aim of the invention is achieved by the following technical scheme:
mn (IV) non-equivalently doped organic-inorganic hybrid fluorescent material with chemical composition A 2 AlF 2 (OH) 3 ·xH 2 O:yMn 4+ Or AAlF 4 ·xH 2 O:yMn 4+ The method comprises the steps of carrying out a first treatment on the surface of the Wherein A is an organic cationic group [ (CH) 3 ) 4 N] + 、[(CH 3 CH 2 ) 4 N] + 、[(CH 3 CH 2 CH 2 CH 2 ) 4 N] + One or a combination of two or more of them; x is the quantity of crystal water contained in the molecular formula, and x is more than or equal to 0 and less than or equal to 3; y is doping ion Mn 4+ Relative to Al 3+ Mole percentage coefficient of ion, 0<y≤40％。
Preferably, the fluorescent material can emit narrow-band red light with high color purity and main peak at 625-635 nm under the excitation of ultraviolet light or near ultraviolet light of 300-400 nm and blue light of 400-510 nm; the fluorescent material has a fluorescence lifetime of less than 2ms.
The preparation method of the Mn (IV) non-equivalently doped organic-inorganic hybrid fluorescent material comprises a liquid phase coprecipitation method and an ion exchange method.
Preferably, the preparation is carried out by adopting a coprecipitation method, comprising the following steps:
first, al is contained in 3+ Adding the compound of (2) into HF solution, then adding hexafluoromanganate, and stirring for 5-10 minutes; then adding the compound containing the organic group A, continuously stirring for 5-30 minutes, then dripping a precipitator to separate out yellow precipitate, and collecting, washing and drying the obtained precipitate to obtain the Mn (IV) unequal doped organic-inorganic hybrid fluorescent material.
Further preferably, the precipitant is used in an amount of 0.5 to 2 times that of the HF solution used to obtain A 2 AlF 2 (OH) 3 ·xH 2 O:yMn 4+ The method comprises the steps of carrying out a first treatment on the surface of the The usage amount of the precipitant is 3-10 times of that of the HF solution to obtain AAlF 4 ·xH 2 O:yMn 4+ ；
Further preferably, the drying temperature is 60-80 ℃ to obtain the fluoride fluorescent material containing crystal water; drying at 175-225 deg.c to obtain fluoride fluorescent material without crystal water;
the preparation method adopts an ion exchange method and comprises the following steps:
first, al is contained in 3+ Adding the compound containing the organic group A into an HF solution, stirring for 30-60 minutes, then dripping a precipitator to separate out white precipitate, collecting, washing and drying the obtained precipitate to obtain the organic-inorganic hybrid metal fluoride AAlF 4 ·xH 2 O or A 2 AlF 2 (OH) 3 ·xH 2 An O matrix precursor; then the hexafluoromanganate is dissolved in HF aqueous solution, and then AAlF is added 4 ·xH 2 O or A 2 AlF 2 (OH) 3 ·xH 2 And (3) continuously stirring the O matrix precursor for 5-360 minutes, and collecting, washing and drying the obtained precipitate to obtain the Mn (IV) non-equivalently doped organic-inorganic hybrid fluorescent material.
Further preferably, the precipitant is used in an amount of 0.5 to 2 times that of the HF solution used to obtain A 2 AlF 2 (OH) 3 ·xH 2 An O matrix precursor; the usage amount of the precipitant is 3-10 times of that of the HF solution to obtain AAlF 4 ·xH 2 An O matrix precursor;
further preferably, the temperature of the second drying is 60-80 ℃ to obtain the fluoride fluorescent material containing crystal water; the temperature of the second drying is 175-225 ℃ to obtain the fluoride fluorescent material without crystal water;
further preferably, the organic group A-containing compound is a compound comprising [ (CH) 3 ) 4 N] + 、[(CH 3 CH 2 ) 4 N] + 、[(CH 3 CH 2 CH 2 CH 2 ) 4 N] + One or a combination of two or more of halides, acids, bases and salts;
more preferably, the compound containing the organic group A is one or more than two of tetramethyl ammonium fluoride, tetramethyl ammonium fluoride tetrahydrate, tetramethyl ammonium acetate, tetramethyl ammonium sulfate, tetramethyl ammonium hydroxide and tetraethyl ammonium fluoride;
further preferably, the hexafluoromanganate salt is Li 2 MnF 6 、Na 2 MnF 6 、K 2 MnF 6 、Rb 2 MnF 6 、Cs 2 MnF 6 、(NH 4 ) 2 MnF 6 、[(CH 3 ) 4 N] 2 MnF 6 One or a combination of two or more of them;
further preferably, the Al-containing alloy comprises 3+ The compound of (1) is Al-containing 3+ One or more of oxides, hydroxides, acetates, aluminates, and halides.
More preferably, the Al-containing alloy 3+ The compound of (C) is Al (OH) (CH) 3 COO) 2 、AlF 3 、Al(OH) 3 、NaAlO 2 One or a combination of two or more of them.
Further preferably, the precipitating agent is one or a combination of two or more of organic solvents.
More preferably, the organic solvent is an alcohol, carboxylic acid, aldehyde, ether, lipid, saturated alkane, halogenated hydrocarbon, nitrogen-containing heterocycle, benzene, or a derivative thereof.
Still more preferably, the organic solvent is dimethyl sulfoxide, dimethylformamide, absolute ethyl alcohol, acetone, ethyl acetate, methanol, glacial acetic acid, n-hexane, or tetrahydrofuran.
Further preferably, the preparation method of the hexafluoromanganate salt comprises the following steps:
firstly, dissolving alkali metal fluoride or alkali metal fluorohydride in hydrofluoric acid solution, adding permanganate or manganate, stirring until the mixture is completely dissolved, placing the mixed solution in an ice bath state, then gradually dropwise adding hydrogen peroxide until the solution turns from purple to yellow, immediately stopping dropwise adding, filtering, washing and drying the obtained precipitate to obtain the hexafluoromanganate precursor.
More preferably, the alkali metal fluoride or alkali metal fluorohydride is LiF, naF, KF, rbF, csF, KHF 2 、NaHF 2 One or a combination of two or more of them; the permanganate or manganate is NaMnO 4 、KMnO 4 、BaMnO 4 、CaMnO 4 、Na 2 MnO 4 、K 2 MnO 4 One or a combination of two or more of them.
Compared with the prior art, the invention has the advantages and positive effects that:
(1) Mn of the present invention 4+ The organic-inorganic hybrid fluorescent material with non-equivalent doping has high luminous efficiency and short fluorescence life, can be used in a white light LED to effectively improve the light color quality of output white light, and improves the product performance based on the white light LED, in particular to the use experience in a backlight display device;
(2) Mn of the present invention 4+ The organic-inorganic hybrid fluorescent material with non-equivalent doping is in a powder form with uniform particle size, is easy to be mixed with other fluorescent materials and dispersed in epoxy resin or silica gel, and can be widely and commercially applied to the fields of white light LED illumination and backlight display;
(3) The preparation method comprises a liquid phase coprecipitation method and an ion exchange method, and the preparation process is simple and feasible, mild in condition and low in cost, and can be used for large-scale industrial production.
Drawings
FIG. 1 is a graph of [ (CH) prepared in example 1 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ XRD powder diffraction patterns of the organic-inorganic hybrid fluorescent material and corresponding standard card patterns;
FIG. 2 is a graph of [ (CH) prepared in example 1 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ The room temperature excitation spectrum and the emission spectrum of the organic-inorganic hybrid hydroxyl-containing fluoride fluorescent material;
FIG. 3 is a graph of [ (CH) prepared in example 1 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ Scanning electron microscope images of organic-inorganic hybrid hydroxyl-containing fluoride fluorescent materials;
FIG. 4 is a graph of [ (CH) prepared in example 1 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ Organic-inorganic hybrid fluorescent material and commercial beta-sialon Eu 2+ An electroluminescence spectrogram of a warm white light LED device packaged by the green fluorescent powder and the blue light LED chip under excitation of 20mA current;
FIG. 5 is a graph of [ (CH) prepared in example 3 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ XRD powder diffraction patterns of the organic-inorganic hybrid fluorescent material and corresponding standard card patterns;
FIG. 6 is a graph of [ (CH) prepared in example 3 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ Room temperature excitation spectrum and emission spectrum of organic-inorganic hybrid fluoride fluorescent material;
FIG. 7 is a graph of [ (CH) prepared in example 3 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ Scanning electron microscope images of organic-inorganic hybrid fluoride fluorescent materials;
FIG. 8 is a graph of [ (CH) prepared in example 3 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ Organic-inorganic hybrid fluorescent material and commercial beta-sialon Eu 2+ An electroluminescence spectrogram of a warm white light LED device packaged by the green fluorescent powder and the blue light LED chip under excitation of 20mA current;
FIG. 9 is a graph of [ (CH) prepared in example 5 3 ) 4 N]AlF 4 :Mn 4+ XRD powder diffraction patterns of the organic-inorganic hybrid fluorescent material and corresponding standard card patterns;
FIG. 10 is a graph of [ (CH) prepared in example 5 3 ) 4 N]AlF 4 :Mn 4+ Room temperature excitation spectrum and emission spectrum of organic-inorganic hybrid fluoride fluorescent material;
FIG. 11 is a graph of [ (CH) prepared in example 5 3 ) 4 N]AlF 4 :Mn 4+ Organic-inorganic hybrid fluorescent material and commercial beta-sialon Eu 2+ Electroluminescent spectrogram of warm white LED device packaged by green fluorescent powder and blue LED chip under excitation of 20mA current.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples and drawings, but the following examples are only for enhancing the description of the technical solution of the present invention, and should not be construed as any limitation on the scope of the claimed invention, and the described examples are only some examples of the present invention, not all examples. All other embodiments, modifications, equivalents, improvements, etc., which are apparent to those skilled in the art without the benefit of this disclosure, are intended to be included within the scope of this invention.
In a specific embodiment of the invention, the preparation process of hexafluoromanganate salt specifically comprises the following steps:
according to X 2 MnF 6 The chemical composition of the fluoromanganate (X is alkali metal cation), alkali metal (X) fluoride or alkali metal (X) fluorohydride is weighed and dissolved in hydrofluoric acid solution with the mass fraction of 49%, then permanganate (X) or manganate (X) is added, after the mixture is completely dissolved, the ice bath of the mixed solution is cooled to 0 ℃, and then 30wt% of hydrogen peroxide is gradually added dropwise until the mixture is dissolvedImmediately stopping dripping from purple to yellow, filtering, washing the obtained precipitate with acetone, and drying at 80deg.C for 2 hr to obtain hexafluoromanganate X 2 MnF 6 A precursor.
In a specific embodiment of the invention, mn 4+ The non-equivalent doped organic-inorganic hybrid fluorescent material is prepared by adopting a liquid phase coprecipitation method or an ion exchange method, and specifically comprises the following steps:
and (3) preparing by a coprecipitation method:
(1) Will contain Al 3+ The ionic compound is added to the HF solution, then hexafluoromanganate is added and stirred for 5-10 minutes.
(2) Then adding the compound containing the organic group A, continuously stirring for 5-30 minutes, then dripping a proper amount of precipitant to separate out yellow precipitate, collecting, washing and drying the obtained precipitate to obtain the Mn 4+ An organic-inorganic hybrid fluorescent material is not equivalently doped.
Ion exchange method preparation:
(1) Will contain Al 3+ Adding ionic compound into HF solution, adding compound containing organic group A, stirring for 30-60 min, dripping appropriate amount of precipitant to separate out white precipitate, collecting the precipitate, washing, and drying to obtain organic-inorganic hybridized metal fluoride AAlF 4 ·xH 2 O or A 2 AlF 2 (OH) 3 ·xH 2 And O matrix.
(2) Dissolving hexafluoromanganate in a small amount of HF aqueous solution, and then adding AAlF 4 ·xH 2 O or A 2 AlF 2 (OH) 3 ·xH 2 Continuously stirring the O matrix precursor for 5-360 minutes, collecting, washing and drying the obtained precipitate to obtain the Mn 4+ Non-equivalently doped organic-inorganic hybrid fluorescent materials.
Example 1
Preparation of [ (CH) by coprecipitation method 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ The organic-inorganic hybrid hydroxyl-containing fluoride fluorescent material specifically comprises the following steps:
weigh 0.4863g Al(OH)C 4 H 6 O 4 Adding into 3ml hydrofluoric acid solution with mass fraction of 49%, and then adding 0.0519g K 2 MnF 6 Stirring for 2 minutes. Subsequently, 5g of tetramethyl ammonium fluoride tetrahydrate was added and stirring was continued for 5 minutes, followed by dropwise addition of 3ml of absolute ethanol and stirring continued for 30 minutes. Finally, centrifugally collecting a precipitate sample by adopting a centrifugal machine, washing the precipitate sample for 3 times by using acetone or ethanol, and drying the precipitate sample at 60 ℃ for 5 hours to obtain Mn 4+ Inequivalence doped organic-inorganic hybrid [ (CH) 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ Fluorescent material.
FIG. 1 shows [ (CH) 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ XRD powder diffraction pattern of organic-inorganic hybridization fluorescent material, diffraction peak of sample is identical to standard card diffraction pattern, and diffraction peak intensity is high, half-width is very narrow, which indicates that the synthesized organic-inorganic hybridization [ (CH) 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ The fluorescent material sample has good crystallinity.
FIG. 2 shows [ (CH) 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ Room temperature excitation spectrum and emission spectrum of organic-inorganic hybrid fluorescent material. The sample has strong wide excitation band in ultraviolet and near ultraviolet light region (320-420 nm) and blue light region (420-500 nm). Under the excitation of 470nm blue light, the sample emits 631nm (strongest emission peak) narrow-band red light composed of multiple sharp line peaks, and the color purity is high and is close to 100%.
FIG. 3 shows [ (CH) 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ Scanning electron microscope image of organic-inorganic hybrid fluorescent material. From the figure, it can be seen that the sample consisted of octahedral morphology particles with distinct edges and corners and good crystallinity.
FIG. 4 shows the developed [ (CH) 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ And commercial beta-sialon Eu 2+ Electroluminescent spectrogram of warm white LED device packaged by green fluorescent powder and blue LED chip under excitation of 20mA current. As can be seen from the graph, the blue light emission peak at-460 nm is derived from the emission of the LED chip, and the emission peak at-530 nm is derived from green phosphor beta-sialon Eu 2+ Is a novel organic-inorganic hybrid [ (CH) 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ The fluorescent material emits light in red light area with the strongest emission peak at 631nm, and the white light emitted by the white light LED is standard white light with wide color gamut.
Example 2
Preparation of [ (CH) by ion exchange 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ The organic-inorganic hybrid hydroxyl-containing fluoride fluorescent material specifically comprises the following steps:
(1)[(CH 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 preparation of O matrix precursor: 0.4863g of Al (OH) C are weighed 4 H 6 O 4 To 3ml of a 49% strength by mass hydrofluoric acid solution, 5g of tetramethyl ammonium fluoride tetrahydrate was added and stirred for 5 minutes, and then 3ml of absolute ethanol was added dropwise and stirring was continued for 30 minutes. Finally, centrifugally collecting a precipitate sample by adopting a centrifugal machine, washing the precipitate sample for 3 times by using acetone or ethanol, and drying the precipitate sample at 60 ℃ for 5 hours to obtain [ (CH) 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O organic-inorganic hybrid hydroxyl-containing fluoride matrices.
(2)[(CH 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ Preparation of the hybrid fluorescent material: weighing 0.0519gK 2 MnF 6 Dissolving in 1ml hydrofluoric acid solution with mass fraction of 49%, and adding 1.4127g [ (CH) 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 After continuously stirring the O matrix precursor for 30 minutes, centrifugally collecting a sediment sample by adopting a centrifugal machine, washing 3 times by using acetone or ethanol, and placingDrying at 60deg.C for 5 hr to obtain [ (CH) 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ Organic-inorganic hybrid fluorescent materials.
[ (CH) prepared by ion exchange method 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ The structure and luminescence properties of the organic-inorganic hybrid fluorescent material were the same as those of example 1.
Example 3
Preparation of [ (CH) by coprecipitation method 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ The organic-inorganic hybrid fluoride fluorescent material specifically comprises the following steps:
0.4863g of Al (OH) C are weighed 4 H 6 O 4 Adding into 3ml hydrofluoric acid solution with mass fraction of 49%, and then adding 0.0519g K 2 MnF 6 Stirring for 2 minutes. Subsequently, 5g of tetramethyl ammonium fluoride tetrahydrate was added and stirring was continued for 5 minutes, followed by dropwise addition of 15ml of absolute ethanol and stirring continued for 30 minutes. Finally, centrifugally collecting a precipitate sample by adopting a centrifugal machine, washing the precipitate sample for 3 times by using acetone or ethanol, and drying the precipitate sample at 60 ℃ for 5 hours to obtain Mn 4+ Inequivalence doped organic-inorganic hybrid [ (CH) 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ Fluorescent material.
FIG. 5 shows [ (CH) 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ XRD powder diffraction pattern of organic-inorganic hybrid fluorescent material, diffraction peak of sample is identical to standard card diffraction pattern, and diffraction peak signal of impurity phase is not observed, so that it shows that the synthesized organic-inorganic hybrid [ (CH) 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ The fluorescent material sample is in a pure phase.
FIG. 6 shows [ (CH) 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ Room temperature excitation spectrum and emission spectrum of organic-inorganic hybrid fluorescent material. The sample has strong wide excitation band in ultraviolet and near ultraviolet light region (320-420 nm) and blue light region (420-500 nm). At 470nmThe sample emits narrow-band red light with the wavelength of 631nm (the strongest emission peak) and composed of a plurality of sharp line peaks, and the color purity is high and is close to 100%.
FIG. 7 shows [ (CH) 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ Scanning electron microscope image of organic-inorganic hybrid fluorescent material. As can be seen from the figure, the sample consisted of particles in a block shape, the edges and corners were clear, and the crystallinity was good.
FIG. 8 shows the developed [ (CH) 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ And commercial beta-sialon Eu 2+ Electroluminescent spectrogram of warm white LED device packaged by green fluorescent powder and blue LED chip under excitation of 20mA current. As can be seen from the graph, the blue light emission peak at-460 nm is derived from the emission of the LED chip, and the emission peak at-530 nm is derived from green phosphor beta-sialon Eu 2+ Is a novel organic-inorganic hybrid [ (CH) 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ The fluorescent material emits light in red light area with the strongest emission peak at 631nm, and the white light emitted by the white light LED is standard white light with wide color gamut.
Example 4
Preparation of [ (CH) by ion exchange 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ The organic-inorganic hybrid fluoride fluorescent material specifically comprises the following steps:
(1)[(CH 3 ) 4 N]AlF 4 ·H 2 preparation of O matrix precursor: 0.4863g of Al (OH) C are weighed 4 H 6 O 4 To 3ml of a 49% strength by mass hydrofluoric acid solution, 5g of tetramethyl ammonium fluoride tetrahydrate was added and stirred for 5 minutes, and then 15ml of absolute ethanol was added dropwise and stirring was continued for 30 minutes. Finally, centrifugally collecting a precipitate sample by adopting a centrifugal machine, washing the precipitate sample for 3 times by using acetone or ethanol, and drying the precipitate sample at 60 ℃ for 5 hours to obtain [ (CH) 3 ) 4 N]AlF 4 ·H 2 O organic-inorganic hybrid fluoride matrices.
(2)[(CH 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ Preparation of the hybrid fluorescent material: weighing 0.0519g K 2 MnF 6 Dissolving in 1ml of 49% hydrofluoric acid solution, and adding 1.257g [ (CH) 3 ) 4 N]AlF 4 ·H 2 Continuously stirring the O matrix precursor for 30 minutes, centrifuging by adopting a centrifuge to collect a precipitate sample, washing 3 times by adopting acetone or ethanol, and drying at 60 ℃ for 5 hours to obtain [ (CH) 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ Organic-inorganic hybrid fluorescent materials.
[ (CH) prepared by ion exchange method 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ The structure and luminescence properties of the organic-inorganic hybrid fluorescent material were the same as those of example 3.
Example 5
Preparation of [ (CH) by coprecipitation method 3 ) 4 N]AlF 4 :Mn 4+ The organic-inorganic hybrid fluoride fluorescent material specifically comprises the following steps:
0.4863g of Al (OH) C are weighed 4 H 6 O 4 Adding into 3ml hydrofluoric acid solution with mass fraction of 49%, and then adding 0.0519g K 2 MnF 6 Stirring for 2 minutes. Subsequently, 5g of tetramethyl ammonium fluoride tetrahydrate was added and stirring was continued for 5 minutes, then 15ml of absolute ethanol was added dropwise and stirring was continued for 30 minutes, and after that, a precipitated sample was collected by centrifugation with a centrifuge and washed 3 times with acetone or ethanol. Finally, drying for 4 hours at 60 ℃ and then drying for 1 hour in a vacuum drying oven at 200 ℃ to obtain Mn 4+ Heterovalent doped organic-inorganic hybrid [ (CH) 3 ) 4 N]AlF 4 :Mn 4+ Fluorescent material.
FIG. 9 shows [ (CH) 3 ) 4 N]AlF 4 :Mn 4+ XRD powder diffraction pattern of organic-inorganic hybrid fluorescent material, diffraction peak of sample is identical to standard card diffraction pattern, and diffraction peak signal of impurity phase is not observed, which indicates synthesized [ (CH) 3 ) 4 N]AlF 4 :Mn 4+ The organic-inorganic hybrid fluorescent material sample is a pure phase.
FIG. 10 shows [ (CH) 3 ) 4 N]AlF 4 :Mn 4+ Room temperature excitation spectrum and emission spectrum of organic-inorganic hybrid fluorescent material. The sample has strong wide excitation band in ultraviolet and near ultraviolet light region (320-420 nm) and blue light region (420-500 nm). Under the excitation of 470nm blue light, the sample emits 631nm (strongest emission peak) narrow-band red light composed of multiple sharp line peaks, and the color purity is high and is close to 100%.
FIG. 11 shows the developed [ (CH) 3 ) 4 N]AlF 4 :Mn 4+ And commercial beta-sialon Eu 2+ Electroluminescent spectrogram of warm white LED device packaged by green fluorescent powder and blue LED chip under excitation of 20mA current. As can be seen from the graph, the blue light emission peak at-460 nm is derived from the emission of the LED chip, and the emission peak at-530 nm is derived from green phosphor beta-sialon Eu 2+ Is a novel organic-inorganic hybrid [ (CH) 3 ) 4 N]AlF 4 :Mn 4+ The fluorescent material emits light in red light area with the strongest emission peak at 631nm, and the white light emitted by the white light LED is standard white light with wide color gamut.
Example 6
Preparation of [ (CH) by ion exchange 3 ) 4 N]AlF 4 :Mn 4+ The organic-inorganic hybrid fluoride fluorescent material specifically comprises the following steps:
(1)[(CH 3 ) 4 N]AlF 4 liquid phase method preparation of matrix precursor: 0.4863g of Al (OH) C are weighed 4 H 6 O 4 Adding into 3ml hydrofluoric acid solution with the mass fraction of 49%, adding 5g tetramethyl ammonium fluoride tetrahydrate, stirring for 5 minutes, then dripping 15ml absolute ethanol, stirring for 30 minutes, centrifuging by adopting a centrifuge, collecting a precipitate sample, and washing 3 times by acetone or ethanol. Finally, drying for 4 hours at 60 ℃, and then drying for 1 hour in a vacuum drying oven at 200 ℃ to obtain [ (CH) 3 ) 4 N]AlF 4 An organic-inorganic hybrid fluoride matrix.
(2)[(CH 3 ) 4 N]AlF 4 :Mn 4+ Preparation of the hybrid fluorescent material: weighing 0.0519g K 2 MnF 6 Dissolving in 1ml of 49% hydrofluoric acid solution, and adding 1.126g [ (CH) 3 ) 4 N]AlF 4 After stirring the matrix precursor for 30 minutes, centrifuging and collecting a precipitate sample by adopting a centrifugal machine, and washing 3 times by using acetone or ethanol. Finally, drying for 4 hours at 60 ℃, and then drying for 1 hour in a vacuum drying oven at 200 ℃ to obtain [ (CH) 3 ) 4 N]AlF 4 :Mn 4+ Organic-inorganic hybrid fluorescent materials.
[ (CH) prepared by ion exchange method 3 ) 4 N]AlF 4 :Mn 4+ The structure and luminescence properties of the organic-inorganic hybrid fluorescent material were the same as those of example 5.
[ (CH) synthesized according to the above liquid phase method 3 ) 4 N]AlF 4 :Mn 4+ The organic-inorganic hybrid fluorescent material has longer fluorescence lifetime than that of all-inorganic Mn 4+ The doped fluoride fluorescent material and certain organic-inorganic hybrid fluorescent materials have more excellent performance, specifically, the organic-inorganic hybrid fluoroaluminate has shorter fluorescence life, is in hundreds of subtle levels, and is more suitable for high-quality backlight source display application with quick response. Organic-inorganic hybrid fluoroaluminate fluorescent materials synthesized according to examples 1-6 with a portion of typical Mn 4+ The optical characteristics of the doped inorganic fluoride fluorescent material and the organic-inorganic hybrid fluoromanganate fluorescent material in terms of fluorescence lifetime, relative brightness, etc. are compared in table 1 below.
TABLE 1
[ (CH) synthesized in examples 1-6 3 ) 4 N]AlF 4 :Mn 4+ The fluorescence lifetime and the relative brightness of the organic-inorganic hybrid fluorescent material and a part of typical inorganic fluoride fluorescent material.
| Sample number | Chemical formula | Fluorescence lifetime | Relative brightness |
| Example 1 | [(CH 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ | 0.36ms | 0.6834 |
| Example 2 | [(CH 3 ) 4 N] 2 AlF 2 (OH) 3 ·H 2 O:Mn 4+ | 0.46ms | 0.7591 |
| Example 3 | [(CH 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ | 1.18ms | 1.0160 |
| Example 4 | [(CH 3 ) 4 N]AlF 4 ·H 2 O:Mn 4+ | 1.39ms | 1.1241 |
| Example 5 | [(CH 3 ) 4 N]AlF 4 :Mn 4+ | 0.71ms | 0.8894 |
| Example 6 | [(CH 3 ) 4 N]AlF 4 :Mn 4+ | 0.58ms | 0.8065 |
| Comparative example 1 | [(CH 3 ) 4 N] 2 MnF 6 | 3.1ms | 1.0000 |
| Comparative example 2 | [(CH 3 ) 4 N] 2 MnF 6 | 3.6ms | 1.5160 |
| Comparative example 3 | K 2 SiF 6 :Mn 4+ | 8.6ms | 0.8110 |
| Comparative example 4 | K 2 TiF 6 :Mn 4+ | 5.9ms | 0.7712 |
| Comparative example 5 | K 2 GeF 6 :Mn 4+ | 6.6ms | 0.7956 |
| Comparative example 6 | Na 2 SiF 6 :Mn 4+ | 5.8ms | 0.3531 |
| Comparative example 7 | Na 2 TiF 6 :Mn 4+ | 6.1ms | 0.4042 |
| Comparative example 8 | Na 2 GeF 6 :Mn 4+ | 6.5ms | 0.4312 |
| Comparative example 9 | Cs 2 SiF 6 :Mn 4+ | 7.8ms | 0.6133 |
| Comparative example 10 | Cs 2 TiF 6 :Mn 4+ | 4.2ms | 0.5832 |
| Comparative example 11 | Cs 2 GeF 6 :Mn 4+ | 7.5ms | 0.6219 |
| Comparative example 12 | Rb 2 SiF 6 :Mn 4+ | 8.2ms | 0.6838 |
| Comparative example 13 | Rb 2 TiF 6 :Mn 4+ | 5.3ms | 0.5891 |
| Comparative example 14 | Rb 2 GeF 6 :Mn 4+ | 6.1ms | 0.6194 |
| Comparative example 15 | Rb 2 MnF 6 | 1.5ms | 0.1376 |
| Comparative example 16 | Cs 2 MnF 6 | 3.8ms | 0.2081 |
Note that: the data are obtained by testing under excitation of blue light (470 nm)
The various Mn of the comparative examples in the above tables are described in detail below 4+ A method for synthesizing doped all-inorganic or organic-inorganic hybrid fluoride fluorescent material.
Comparative example 1 fluorescent Material [ (CH) 3 ) 4 N] 2 MnF 6 The synthesis method of (2) is as follows:
300g of tetramethyl ammonium fluoride and 5g of KMnO were weighed 4 Dissolved in 300ml of hydrogen with a mass fraction of 49%Stirring in fluoric acid solution until the solid is completely dissolved, cooling the mixed solution to 0 ℃ by adopting an ice bath, gradually dropwise adding hydrogen peroxide solution with the mass fraction of 30 percent until the solution is changed from purple to orange yellow, immediately stopping dropwise adding, standing, aging, collecting a precipitate sample, washing 3 times by glacial acetic acid, acetone or ethanol, and drying at 60 ℃ for 4 hours to obtain [ (CH) 3 ) 4 N] 2 MnF 6 An organic-inorganic hybrid fluoromanganate polycrystalline powder fluorescent material.
Comparative example 2 fluorescent Material [ (CH) 3 ) 4 N] 2 MnF 6 The synthesis method of (2) is as follows:
60g of tetramethyl ammonium fluoride is weighed and dissolved in 5ml of hydrofluoric acid solution with the mass fraction of 49% to prepare solution A, and then 0.5. 0.5g K is weighed 2 MnF 6 Adding 10ml hydrofluoric acid solution with mass fraction of 49%, stirring to dissolve completely to obtain solution B, adding solution A into solution B, stirring for 30 min, standing, aging, collecting precipitate sample, washing with glacial acetic acid, acetone or ethanol for 3 times, and drying at 60deg.C for 4 hr to obtain [ (CH) 3 ) 4 N] 2 MnF 6 An organic-inorganic hybrid fluoromanganate polycrystalline powder fluorescent material.
Comparative example 3 fluorescent Material K 2 SiF 6 :Mn 4+ The synthesis method of (2) is as follows:
S1、K 2 SiF 6 preparing a matrix precursor: 4ml of H is measured 2 SiF 6 Adding into 2ml hydrofluoric acid solution with mass fraction of 49%, adding 1.4525g potassium fluoride, stirring for 30-360 min, centrifuging with centrifuge to collect precipitate sample, washing with glacial acetic acid, acetone or ethanol for 3 times, and drying at 70deg.C for 4 hr to obtain K 2 SiF 6 An all inorganic fluoride matrix.
S2、K 2 SiF 6 :Mn 4+ Preparation of an inorganic fluoride fluorescent material: weigh 0.247 and 0.247g K 2 MnF 6 Dissolving in 4ml of 49% hydrofluoric acid solution, and adding 2.2. 2.2g K 2 SiF 6 Continuously stirring matrix precursor for 5-360 min, and centrifuging with centrifuge to collect precipitateWashing with glacial acetic acid, acetone or ethanol for 3 times, and drying at 70deg.C for 4 hr to obtain K 2 SiF 6 :Mn 4+ An all-inorganic fluoride fluorescent material.
Mn of comparative examples 4 to 14 4+ The preparation steps of the doped all-inorganic or organic-inorganic hybrid fluoride fluorescent material are the same as those of comparative example 3 except that the relevant raw materials are weighed according to the chemical formula composition and the stoichiometric ratio thereof.
The per-inorganic fluoromanganate fluorescent materials of comparative examples 15 and 16 were in accordance with fluoromanganate X 2 MnF 6 Is prepared by the preparation method as follows:
comparative example 15
Fluorescent material Rb 2 MnF 6 The synthesis method of (2) is as follows:
100g of RbF and 4.28g of RbMnO were weighed out 4 Adding into 300ml hydrofluoric acid solution with 49% by mass, stirring until completely dissolving, ice-bath cooling the mixed solution to 0deg.C, then dropwise adding 30wt% hydrogen peroxide until the solution turns from purple to yellow, immediately stopping dropwise adding, filtering, washing the obtained yellow precipitate with acetone or ethanol for 3 times, and drying at 70deg.C for 4 hr to obtain Rb 2 MnF 6 An all-inorganic fluoride fluorescent material.
Comparative example 16
Fluorescent material Cs 2 MnF 6 The synthesis method of (2) is as follows:
120g CsF and 5g CsMnO were weighed 4 Adding into 250ml hydrofluoric acid solution with mass fraction of 49%, stirring until completely dissolving, ice-bath cooling the mixed solution to 0deg.C, then dropwise adding 30wt% hydrogen peroxide until the solution turns from purple to yellow, immediately stopping dropwise adding, filtering, washing the obtained yellow precipitate with acetone or ethanol for 3 times, and drying at 70deg.C for 4 hr to obtain Cs 2 MnF 6 An all-inorganic fluoride fluorescent material.
It should be understood that any modification, substitution, variation, etc. of the specific embodiments of the present invention, which are based on the true spirit of the present invention, should be covered by the present invention.
Claims (10)
1. An organic-inorganic hybrid fluorescent material with Mn (IV) non-equivalent doping, which is characterized in that the chemical composition is A 2 AlF 2 (OH) 3 ·xH 2 O:yMn 4+ ，x=1; or AAlF 4 ·xH 2 O:yMn 4+ ，x=0 or 1; wherein A is an organic cationic group [ (CH) 3 ) 4 N] + ；yIs doped with ion Mn 4+ Relative to Al 3+ Mole percentage coefficient of ion, 0< y ≤ 40%。
2. The Mn (IV) non-equivalently doped organic-inorganic hybrid fluorescent material according to claim 1, wherein the fluorescent material emits narrow-band red light with a main peak at 625-635 nm and high color purity under excitation of ultraviolet or near ultraviolet light of 300-400 nm and blue light of 400-510 nm; the fluorescent material has a fluorescence lifetime of less than 2ms.
3. The method for preparing the Mn (IV) non-equivalently doped organic-inorganic hybrid fluorescent material according to claim 1 or 2, which is characterized by comprising a liquid phase coprecipitation method and an ion exchange method.
4. The method for preparing an Mn (IV) non-equivalently doped organic-inorganic hybrid fluorescent material according to claim 3, wherein the method comprises the steps of:
first, al is contained in 3+ Adding the compound of (2) into HF solution, then adding hexafluoromanganate, and stirring for 5-10 minutes; then adding the compound containing the organic group A, continuously stirring for 5-30 minutes, then dripping a precipitator to separate out yellow precipitate, and collecting, washing and drying the obtained precipitate to obtain the Mn (IV) unequal doped organic-inorganic hybrid fluorescent material.
5. The method for preparing an Mn (IV) non-equivalently doped organic-inorganic hybrid fluorescent material according to claim 3, wherein the method comprises the steps of:
first, al is contained in 3+ Adding the compound containing the organic group A into an HF solution, stirring for 30-60 minutes, then dripping a precipitator to separate out white precipitate, collecting, washing and drying the obtained precipitate to obtain the organic-inorganic hybrid metal fluoride AAlF 4 ·xH 2 O or A 2 AlF 2 (OH) 3 ·xH 2 An O matrix precursor; then the hexafluoromanganate is dissolved in HF aqueous solution, and then AAlF is added 4 ·xH 2 O or A 2 AlF 2 (OH) 3 ·xH 2 And (3) continuously stirring the O matrix precursor for 5-360 minutes, and collecting, washing and drying the obtained precipitate to obtain the Mn (IV) non-equivalently doped organic-inorganic hybrid fluorescent material.
6. The method for preparing an Mn (IV) non-equivalently doped organic-inorganic hybrid fluorescent material according to any one of claims 4 to 5, wherein the compound containing the organic group A is a compound containing [ (CH) 3 ) 4 N] + One or a combination of two or more of halides, acids, bases and salts;
the hexafluoromanganate salt is Li 2 MnF 6 、Na 2 MnF 6 、K 2 MnF 6 、Rb 2 MnF 6 、Cs 2 MnF 6 、(NH 4 ) 2 MnF 6 、[(CH 3 ) 4 N] 2 MnF 6 One or a combination of two or more of them;
the Al containing 3+ The compound of (1) is Al-containing 3+ One or more of oxides, hydroxides, acetates, aluminates, and halides.
7. The method for preparing an Mn (IV) non-equivalent doped organic-inorganic hybrid fluorescent material according to claim 6, wherein the compound containing the organic group A is one or a combination of more than two of tetramethyl ammonium fluoride, tetramethyl ammonium fluoride tetrahydrate, tetramethyl ammonium acetate, tetramethyl ammonium sulfate and tetramethyl ammonium hydroxide;
the Al containing 3+ The compound of (C) is Al (OH) (CH) 3 COO) 2 、AlF 3 、Al(OH) 3 、NaAlO 2 One or a combination of two or more of them.
8. The method for preparing an Mn (IV) non-equivalent doped organic-inorganic hybrid fluorescent material according to any one of claims 4 to 5, wherein the precipitant is one or a combination of two or more organic solvents.
9. The method for preparing an Mn (IV) non-equivalent doped organic-inorganic hybrid fluorescent material according to claim 8, wherein the organic solvent is alcohols, carboxylic acids, aldehydes, ethers, lipids, saturated alkanes, halogenated hydrocarbons, nitrogen-containing heterocycles, benzene or derivatives thereof.
10. The method for preparing an Mn (IV) non-equivalent doped organic-inorganic hybrid fluorescent material according to claim 9, wherein the organic solvent is dimethyl sulfoxide, dimethylformamide, absolute ethyl alcohol, acetone, ethyl acetate, methanol, glacial acetic acid, n-hexane, tetrahydrofuran.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713827A (en) * | 2019-10-31 | 2020-01-21 | 云南民族大学 | Mn4+ doped hexafluoride compound red fluorescent powder and synthetic method thereof |
| CN112521935A (en) * | 2020-09-18 | 2021-03-19 | 中国计量大学 | Quadrivalent manganese ion doped quaternary ammonium salt red light material and preparation method and application thereof |
| WO2021092723A1 (en) * | 2019-11-11 | 2021-05-20 | 南京大学 | Manganese-halogen fluorescent powder material and preparation method, and light emitting device using manganese-halogen fluorescent powder material |
| CN113583656A (en) * | 2021-08-23 | 2021-11-02 | 中国计量大学 | Oleamidooleic acid modified tetravalent manganese doped fluoride red light material and preparation method thereof |
| CN114181700A (en) * | 2021-12-14 | 2022-03-15 | 广西经正涂料有限公司 | Organic-inorganic hybrid fluorine titanium potassium red-light fluorescent powder and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713827A (en) * | 2019-10-31 | 2020-01-21 | 云南民族大学 | Mn4+ doped hexafluoride compound red fluorescent powder and synthetic method thereof |
| WO2021092723A1 (en) * | 2019-11-11 | 2021-05-20 | 南京大学 | Manganese-halogen fluorescent powder material and preparation method, and light emitting device using manganese-halogen fluorescent powder material |
| CN112521935A (en) * | 2020-09-18 | 2021-03-19 | 中国计量大学 | Quadrivalent manganese ion doped quaternary ammonium salt red light material and preparation method and application thereof |
| CN113583656A (en) * | 2021-08-23 | 2021-11-02 | 中国计量大学 | Oleamidooleic acid modified tetravalent manganese doped fluoride red light material and preparation method thereof |
| CN114181700A (en) * | 2021-12-14 | 2022-03-15 | 广西经正涂料有限公司 | Organic-inorganic hybrid fluorine titanium potassium red-light fluorescent powder and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Luminescence of Mn4+ in a Hexafluorogermanate with the Complex Organic Cation Guanidinium [C(NH2)3]2GeF6:Mn4+;Florian Baur et al.;《ECS Journal of Solid State Science and Technology》;第9卷;第046003页 * |
| Mn4+ doped zero-dimensional organic-inorganic hybrid material with narrow-red emission;Peiqing Cai et al.;《Journal of Luminescence》;第228卷;第117661(1-7)页 * |
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