CN109777418A - A kind of Mn4+Adulterate compound fluotitanate red light material of double alkali metal and preparation method thereof - Google Patents
A kind of Mn4+Adulterate compound fluotitanate red light material of double alkali metal and preparation method thereof Download PDFInfo
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- CN109777418A CN109777418A CN201910053674.0A CN201910053674A CN109777418A CN 109777418 A CN109777418 A CN 109777418A CN 201910053674 A CN201910053674 A CN 201910053674A CN 109777418 A CN109777418 A CN 109777418A
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Abstract
The invention discloses a kind of Mn4+Adulterate compound fluotitanate red light material of double alkali metal and preparation method thereof.The chemical composition of the phosphor material powder is NaBTiF6:xMn4+, whereinBFor Li |, any one of K, Rb, Cs, x Mn4+Ion is with respect to Ti4+The molar ratio x of ion is 0.5~10 mol%.The preparation method is as follows: with double alkali metal fluorides, butyl titanate Ti (OR)4As base starting material, K2MnF6The centre of luminescence is provided, at room temperature mix round to complete reaction, filtered, washed, product can be obtained in drying.Product maximum excitation wavelength is located at 467 nm of blue light region, exactly matches with gallium nitride chip institute's blue light-emitting, and launch wavelength range is located at 600~660 nm spectral regions, and excitation purity is high.Preparation method of the present invention is easy to operate, and reaction condition is mild, is suitble to industrialization large-scale production.
Description
Technical field
The present invention relates to luminescent material, in particular to a kind of white light LEDs red light material and preparation method thereof, and in particular to
A kind of excitation wavelength is located at blue region, and launch wavelength is located at the Mn of red light region4+Adulterate the compound fluotitanate hair of double alkali metal
Luminescent material and preparation method thereof.
Background technique
White light LEDs are 21 century most noticeable green light sources, have a vast market with potential illumination application prospect,
Development is swift and violent in recent years, in the permeability of the display fields such as mobile phone, laptop, high definition television nearly 100%.Wide colour gamut, height
Clearly, large scale is the Main Trends of The Development of novel display field.The preparation of prevailing white LED light source currently on the market
Method is combined with yellow fluorescent powder YAG:Ce using blue-light LED chip to realize, so improving the luminescent properties pair of fluorescent powder
It is very important in increasing LED luminous efficiency, and such white light LEDs are lower in low color temperature area colour rendering index, therefore can not expire
The large-scale lighting demand of foot, the reason is that there was only yellow light and blue light ingredient in its white light, and red ingredient is less.
In order to improve the white light LEDs colour rendering index being made of yellow fluorescent powder YAG:Ce and blue chip, some nitride
There is good performance performance in white light LEDs application aspect with nitric oxide fluorescent powder, the colour developing with higher of these fluorescent powders refers to
Several and stable chemical properties can make up YAG:Ce3+ Deficiency.Nitrogen compound rear-earth-doped at present is with [SiN4] or/and
[AlN4] tetrahedron be skeleton, rich and changeful structure type can be formed, be Eu2+/Ce3+Equal rare earth luminescences center provides
The minimum 5d energy level of rare earth ion is effectively reduced in diversified coordination environment, correspondingly, excitation and emission spectra red shift, it can be achieved that
Efficient blue light absorption and red emission meet White-light LED illumination and show demand, such as Sr2-x-yBaxCaySi5N8:Eu2+, matrix
Stability height, Absorber Bandwidth, excitation purity are high, luminous efficiency is high, temperature quenching is unobvious, can effectively optimize the aobvious of two primary colours WLED
Colour index and colour temperature [ X. Q. Piao, T. Horikawa, H. Hanzawa, K. Machida, Appl. Phys.
Lett. 88 (2006) 161908. Y. Q. Li, De With G, H. T. Hintzen, J. Solid State
Chem. 181 (2008) 515-524. ].But most of rare earth ion prices are more expensive, and some rare earth ion doped nitrogen
Compound is toxic, synthesis oxide, nitride condition need high temperature and pressure, condition is more harsh, these problems limit its into
Row large-scale production, constrains the practical application in white light LEDs field.
Mn4+The appearance of the red light material of doping causes the great interest for carrying out people, due to Mn4+'s2E→4A2Transition issues
Spectrum be located at red area, and its excitation spectrum is located at blue violet light region, and institute's luminous spectrum is relatively narrow feux rouges.According to this spy
Property, make Mn4+The red fluorescence powder of doping can effectively supplement feux rouges in conjunction with blue LED die and YAG:Ce yellow fluorescent powder
Ingredient promotes the illuminating effect of white light LEDs.The feux rouges of efficient transmission can effectively improve the colour rendering index of WLED, obtain low color temperature
The warm white of height colour developing.Mn4+This luminosity with Broad excitation band and narrow transmitting band being had especially applies illumination
It is advantageous.Therefore, Mn4+The red fluorescence powder of doping can be used as the substitute of rear-earth-doped nitride red fluorescent powder,
There is biggish application prospect in warm white LED field.
Current two primary colours gallium nitride base WLED is because lacking feux rouges composition, and it is higher with colour temperature to make colour rendering index relatively low, full
Foot not high-end illumination application requirement, especially in low color temperature region, it is difficult to obtain the warm white of high-color rendering.The study found that Mn4+
The red light material maximum excitation wavelength of doping is located at blue region and matches with gallium nitride chip, and luminous effect with higher
Rate, and raw material is cheap and easy to get, synthesis technology letter, they are packaged in gallium nitride chip with yellow fluorescent powder jointly, is shown
Colour index is greater than 90 warm white.[M. M. Zhu, Y. X. Pan, X. A. Chen, H. Z. Lian and J.
Lin, J. Am. Chem. Soc., 2018, 6, 491-499.] Mn4+The composite oxides of doping, including aluminate, germanium
Hydrochlorate and titanate, wherein Mn4+The octahedra center being coordinated by six oxonium ions is occupied, feux rouges is issued.The study found that Mn4+'s
The fine structure that shines and Mn4+Locating micro have it is closely related, therefore, Mn4+Adulterate double compound fluotitanate of alkali metal because
For the special crystalline field environment of matrix, the high effective percentage that shines, high thermal stability are made it have.
Summary of the invention
The purpose of the invention is to provide it is a kind of can be effectively by ultraviolet excitation, and launch the inorganic light-emitting material of feux rouges
Material, launch feux rouges purity is high, synthesis temperature it is low, maximum excitation wavelength is located at blue light region, can effectively absorb gallium nitride chip
Blue light issues high color purity feux rouges.
The purpose of the present invention is achieved through the following technical solutions:
A kind of Mn4+The compound fluotitanate red light material of double alkali metal is adulterated, the material is with NaBTiF6For matrix, with Mn4+It is sharp
Agent living, chemical composition NaBTiF6:Mn4+, whereinBFor Li |, any one of K, Rb, Cs, Mn4+Part replaces hexa-coordinate eight
Face body center Ti4+The position of place lattice generates the centre of luminescence.
By using above-mentioned technical proposal, according to product principle of luminosity: wherein Mn4+Part replaces Ti4+, occupy positive octahedral
Body [MnF6]2-Lattice center, with six F-Ion coordination, so that the red light material is formed in blue region wider absorption
Band, the centre of luminescence for having sharp emission peak in red light region.
Further, the absorption maximum band in excitation spectrum is located at the blue light region of 420~520 nm, and and gallium nitride
The blue light exact matching that blue chip is issued, emission spectrum are located at the red light region of 600~660 nm；It is corresponding
Chromaticity coordinates is located at: x=0.678, y=0.323.
By using above-mentioned technical proposal, it is bright red, highest under ultraviolet lamp which, which is white under natural light,
Peak is located at 631 nm.
The Mn4+Adulterate the preparation method of the compound fluotitanate red light material of double alkali metal: by double alkali metal fluoride NaF
With any one of LiF, KF, RbF, CsF and butyl titanate Ti (OR)4、K2MnF6Mixing is added in HF solution, HF solution
For reaction medium and fluorization agent, after stirring, reaction obtains white precipitate, filters, dries.
By using above-mentioned technical proposal, [the MnF in HF solution6]2-With [TiF6]2-Ion exchange, Mn occurs4+Part takes
For Ti4+, so that charge in crystal is kept neutral, wherein the molecular formula of butyl titanate is C16H36O4Ti, Ti (OR)4 For
C16H36O4Ti's writes a Chinese character in simplified form, i.e. Ti (OR)4 Refer to butyl titanate.
Further setting, HF solution are reaction medium and fluorization agent, and concentration is 5~20 wt%, it is preferable that the HF solution
Concentration is 10~15 wt%.
Further setting, K2MnF6Concentration in the reaction system is equivalent to [TiF6]2-0.5~10 mol%, it is preferable that
K2MnF6Concentration is 3~8 mol%, it is further preferred that K2MnF6Concentration is preferably 3~5 mol%.
Further setting, the mixing time be 1 ~ 8 hour, it is preferable that it is described be stirred to react the time be 4~6 hours.
Compared with the existing technology, the present invention have it is following a little and effect:
(1) double alkali metal ions in matrix of the present invention, form asymmetric crystalline field environment, are conducive to Mn4+Radiation transistion,
With high-luminous-efficiency.
(2) present invention has wide excitation wavelength in blue light region, matches with gallium nitride chip, has spike in red light district
Transmitting, excitation purity are high.
(3) present invention is prepared at room temperature, at a normal, is not necessarily to hydro-thermal and high temperature, preparation process is simple and easy, and synthetic technology
Difficulty is low, therefore, is suitble to industrial production.
(4) present invention reaction does not need to use expensive metal simple-substance as raw material, and material is free of rare earth, has significant
Cost advantage.
Detailed description of the invention
Fig. 1 NaCsTiF6:Mn4+The XRD standard card data of (embodiment 1) and the XRD diagram of embodiment product.
Fig. 2 NaCsTiF6:Mn4+The excitation spectrum (a: monitoring wavelength be 631 nm) of (embodiment 1) and emission spectrum (b:
Excitation wavelength is 467 nm).
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described, but the scope of protection of present invention is not
It is confined to the range of embodiment expression.
Embodiment 1
0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol CsF, measure 0.01 mol metatitanic acid, four fourth
Ester Ti (OR)4, it is placed in plastic containers, it is then to be added 1 × 10 in 10 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 4 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The detection of its XRD(Bruker D8 Advance X x ray diffractometer x) as shown in Figure 1, XRD shows that product is pure NaCsTiF6
Phase, trace doped Mn4+And have no significant effect object phase.As shown in Fig. 2, the product luminescent properties of the present embodiment utilize Fluorescence Spectrometer
(HORIBA Jobin Yvon Inc. Fluoromax-4) is studied, and the excitation spectrum of the present embodiment product is close purple by being located at
The wide excitation peak of outskirt (360 nm or so) and blue region (467 nm or so) form, and maximum excitation peak is located at blue light region
Domain, Wavelength matched with White-light LED chip, emission maximum spectrum is located at 631 nm, it is shown that Mn4+Feature at octahedra center
Red emission.
Embodiment 2
0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol CsF, measure 0.01 mol metatitanic acid, four fourth
Ester Ti (OR)4, it is placed in plastic containers, it is then to be added 5 × 10 in 5 wt% HF solution that concentration, which is added,-5 mol K2MnF6,
It is stirred to react 1 hour, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.The white
The XRD diagram of powder body material and fluorescence spectrum are essentially identical with embodiment 1.
Embodiment 3
0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol CsF, measure 0.01 mol metatitanic acid, four fourth
Ester Ti (OR)4, it is placed in plastic containers, it is then to be added 3 × 10 in 10 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 4 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 1.
Embodiment 4
In 0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol CsF, 0.01 mol metatitanic acid four is measured
Butyl ester Ti (OR)4, it is placed in plastic containers, it is then to be added 5 × 10 in 15 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 6 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 1.
Embodiment 5
In 0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol CsF, 0.01 mol metatitanic acid four is measured
Butyl ester Ti (OR)4, it is placed in plastic containers, it is then to be added 1 × 10 in 20 wt% HF solution that concentration, which is added,-3 mol
K2MnF6, it is stirred to react 8 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 1.
Embodiment 6
In 0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol CsF, 0.01 mol metatitanic acid four is measured
Butyl ester Ti (OR)4, it is placed in plastic containers, it is then to be added 2 × 10 in 8 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 3 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 1.
Embodiment 7
In 0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol CsF, 0.01 mol metatitanic acid four is measured
Butyl ester Ti (OR)4, it is placed in plastic containers, it is then to be added 8 × 10 in 12 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 7 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 1.
Embodiment 8
0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol LiF, measure 0.01 mol metatitanic acid, four fourth
Ester Ti (OR)4, it is placed in plastic containers, it is then to be added 1 × 10 in 10 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 4 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
Its XRD(Bruker D8 Advance X x ray diffractometer x detection) XRD show product be pure NaLiTiF6Phase, it is trace doped
Mn4+And have no significant effect object phase.Mn is shown in the product of the present embodiment4+Feature red emission at octahedra center.
Embodiment 9
0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol LiF, measure 0.01 mol metatitanic acid, four fourth
Ester Ti (OR)4, it is placed in plastic containers, it is then to be added 5 × 10 in 5 wt% HF solution that concentration, which is added,-5 mol K2MnF6,
It is stirred to react 1 hour, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.The white
The XRD diagram of powder body material and fluorescence spectrum are essentially identical with embodiment 8.
Embodiment 10
0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol LiF, measure 0.01 mol metatitanic acid, four fourth
Ester Ti (OR)4, it is placed in plastic containers, it is then to be added 3 × 10 in 10 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 4 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 8.
Embodiment 11
In 0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol LiF, 0.01 mol metatitanic acid four is measured
Butyl ester Ti (OR)4, it is placed in plastic containers, it is then to be added 5 × 10 in 15 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 6 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 8.
Embodiment 12
In 0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol LiF, 0.01 mol metatitanic acid four is measured
Butyl ester Ti (OR)4, it is placed in plastic containers, it is then to be added 1 × 10 in 20 wt% HF solution that concentration, which is added,-3 mol
K2MnF6, it is stirred to react 8 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 8.
Embodiment 13
In 0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol LiF, 0.01 mol metatitanic acid four is measured
Butyl ester Ti (OR)4, it is placed in plastic containers, it is then to be added 2 × 10 in 8 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 3 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 8.
Embodiment 14
In 0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol LiF, 0.01 mol metatitanic acid four is measured
Butyl ester Ti (OR)4, it is placed in plastic containers, it is then to be added 8 × 10 in 12 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 7 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 8.
Embodiment 15
0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol KF, measure 0.01 mol butyl titanate
Ti(OR)4, it is placed in plastic containers, it is then to be added 1 × 10 in 10 wt% HF solution that concentration, which is added,-4 mol K2MnF6,
It is stirred to react 4 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.Its XRD
(detection of Bruker D8 Advance X x ray diffractometer x) XRD shows that product is pure NaKTiF6Phase, trace doped Mn4+And
Have no significant effect object phase.Mn is shown in the product of the present embodiment4+Feature red emission at octahedra center.
Embodiment 16
0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol KF, measure 0.01 mol butyl titanate
Ti(OR)4, it is placed in plastic containers, it is then to be added 5 × 10 in 5 wt% HF solution that concentration, which is added,-5 mol K2MnF6,
It is stirred to react 1 hour, filters under room temperature, drying obtains white powder.Product sends out bright red in the UV lamp.The white powder
The XRD diagram of body material and fluorescence spectrum are essentially identical with embodiment 15.
Embodiment 17
0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol KF, measure 0.01 mol butyl titanate
Ti(OR)4, it is placed in plastic containers, it is then to be added 3 × 10 in 10 wt% HF solution that concentration, which is added,-4 mol K2MnF6,
It is stirred to react 4 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.The white
The XRD diagram of powder body material and fluorescence spectrum are essentially identical with embodiment 15.
Embodiment 18
In 0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol KF, 0.01 mol metatitanic acid, four fourth is measured
Ester Ti (OR)4, it is placed in plastic containers, it is then to be added 5 × 10 in 15 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 6 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 15.
Embodiment 19
In 0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol KF, 0.01 mol metatitanic acid, four fourth is measured
Ester Ti (OR)4, it is placed in plastic containers, it is then to be added 1 × 10 in 20 wt% HF solution that concentration, which is added,-3 mol
K2MnF6, it is stirred to react 8 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 15.
Embodiment 20
In 0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol KF, 0.01 mol metatitanic acid, four fourth is measured
Ester Ti (OR)4, it is placed in plastic containers, it is then to be added 2 × 10 in 8 wt% HF solution that concentration, which is added,-4 mol K2MnF6,
It is stirred to react 3 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.The white
The XRD diagram of powder body material and fluorescence spectrum are essentially identical with embodiment 15.
Embodiment 21
In 0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol KF, 0.01 mol metatitanic acid, four fourth is measured
Ester Ti (OR)4, it is placed in plastic containers, it is then to be added 8 × 10 in 12 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 7 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 15.
Embodiment 22
0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol RbF, measure 0.01 mol metatitanic acid, four fourth
Ester Ti (OR)4, it is placed in plastic containers, it is then to be added 1 × 10 in 10 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 4 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
Its XRD(Bruker D8 Advance X x ray diffractometer x detection) XRD show product be pure NaKTiF6Phase, it is trace doped
Mn4+And have no significant effect object phase.Mn is shown in the product of the present embodiment4+Feature red emission at octahedra center.
Embodiment 23
0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol RbF, measure 0.01 mol metatitanic acid, four fourth
Ester Ti (OR)4, it is placed in plastic containers, it is then to be added 5 × 10 in 5 wt% HF solution that concentration, which is added,-5 mol K2MnF6,
It is stirred to react 1 hour, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.The white
The XRD diagram of powder body material and fluorescence spectrum are essentially identical with embodiment 22.
Embodiment 24
0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol RbF, measure 0.01 mol metatitanic acid, four fourth
Ester Ti (OR)4, it is placed in plastic containers, it is then to be added 3 × 10 in 10 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 4 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 22.
Embodiment 25
In 0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol RbF, 0.01 mol metatitanic acid four is measured
Butyl ester Ti (OR)4, it is placed in plastic containers, it is then to be added 5 × 10 in 15 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 6 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 22.
Embodiment 26
In 0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol RbF, 0.01 mol metatitanic acid four is measured
Butyl ester Ti (OR)4, it is placed in plastic containers, it is then to be added 1 × 10 in 20 wt% HF solution that concentration, which is added,-3 mol
K2MnF6, it is stirred to react 8 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 22.
Embodiment 27
In 0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol RbF, 0.01 mol metatitanic acid four is measured
Butyl ester Ti (OR)4, it is placed in plastic containers, it is then to be added 2 × 10 in 8 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 3 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 22.
Embodiment 28
In 0.01 mol NaF of the double alkali metal fluorides of precise solid, 0.01 mol RbF, 0.01 mol metatitanic acid four is measured
Butyl ester Ti (OR)4, it is placed in plastic containers, it is then to be added 8 × 10 in 12 wt% HF solution that concentration, which is added,-4 mol
K2MnF6, it is stirred to react 7 hours, filters at normal temperature, drying obtains white powder.Product sends out bright red in the UV lamp.
The XRD diagram of the white powder material and fluorescence spectrum are essentially identical with embodiment 22.
From above-described embodiment as it can be seen that the present invention is compared with the titanate of known tetravalence additive Mn, woth no need to high temperature sintering,
Because woth no need to use noble metal titanium, whole depress in Room is carried out, and material pattern due to no sintering is evenly dispersed.
Because material is free of rare earth, preparation process whole process carries out in air, keeps away oxygen without keeping away water, without high temperature sintering,
Therefore, cost is far below business nitride rouge and powder.
Containing double alkali metal ions in matrix, asymmetrical crystalline field environment is formed, centre of luminescence Mn is conducive to4+Radiation jump
It moves.
Claims (8)
1. a kind of Mn4+Adulterate the compound fluotitanate red light material of double alkali metal, it is characterised in that: the material is with NaBTiF6As
Matrix uses Mn4+For active ions, related chemistry formula is NaBTiF6:xMn4+, whereinBFor Li |, any one of K, Rb, Cs,
Mn4+Part replaces hexa-coordinate octahedron center Ti4+The position of place lattice generates the centre of luminescence.
2. a kind of Mn according to claim 14+Adulterate the compound fluotitanate red light material of double alkali metal, it is characterised in that:
Adulterate Mn4+Ion is with respect to Ti4+Molar ratio x shared by ion is 0.5~10 mol%.
3. a kind of Mn according to claims 1 to 24+The compound fluotitanate red light material of double alkali metal is adulterated, feature exists
In: the absorption maximum band in its excitation spectrum is located at the blue region of 420~520 nm, and is sent out with gallium-nitride blue chip
Blue light exact matching out, emission spectrum are located at the red light region of 600~660 nm；Corresponding chromaticity coordinates is located at: x
=0.678, y=0.323.
4. a kind of Mn described according to claim 1 ~ 34+The preparation method of the compound fluotitanate red light material of double alkali metal is adulterated,
It is characterized by: by any one of double alkali metal fluoride NaF and LiF, KF, RbF, CsF and butyl titanate Ti
(OR)4、K2MnF6Mixing is added in HF solution, and after stirring, reaction obtains white precipitate, filters, dries.
5. a kind of Mn according to claim 44+The preparation method of the compound fluotitanate red light material of double alkali metal is adulterated,
Be characterized in that: HF solution is reaction medium and fluorization agent, and concentration is 5~20 wt%.
6. a kind of Mn according to claim 44+The preparation method of the compound fluotitanate red light material of double alkali metal is adulterated,
It is characterized in that: K2MnF6Concentration in the reaction system is equivalent to [TiF6]2-0.5~10 mol%.
7. a kind of Mn according to claim 44+The preparation method of the compound fluotitanate red light material of double alkali metal is adulterated,
Be characterized in that: the mixing time is 1 ~ 8 hour.
8. a kind of Mn according to claim 44+The preparation method of the compound fluotitanate red light material of double alkali metal is adulterated,
Be characterized in that: the whipping process carries out under room temperature normal air.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791282A (en) * | 2019-10-31 | 2020-02-14 | 云南民族大学 | Mn-doped steel wire4+Alkali metal fluoferrite red luminescent material and preparation method thereof |
| WO2021213900A1 (en) * | 2020-04-22 | 2021-10-28 | Osram Opto Semiconductors Gmbh | Red luminescent material and conversion led |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275711A (en) * | 2013-06-08 | 2013-09-04 | 温州大学 | Fluorine titanium salt red-light material for white LED with two primary colors and preparation method of material |
| CN103429701A (en) * | 2011-03-23 | 2013-12-04 | 通用电气公司 | Color stable manganese-doped phosphors |
| CN103429702A (en) * | 2011-12-16 | 2013-12-04 | 皇家飞利浦有限公司 | Mn-activated hexafluorosilicates for LED applications |
| CN103980896A (en) * | 2014-04-29 | 2014-08-13 | 中国科学院福建物质结构研究所 | Preparation method of fluoride fluorescent powder material |
| CN105505384A (en) * | 2015-12-03 | 2016-04-20 | 河北利福光电技术有限公司 | Red-light fluorescent powder with narrow band and preparation method of red-light fluorescent powder |
| CN106244143A (en) * | 2015-06-04 | 2016-12-21 | 隆达电子股份有限公司 | Fluorescent powder with preferred direction, preparation method thereof and light-emitting element packaging structure comprising fluorescent powder |
| CN106367066A (en) * | 2016-09-06 | 2017-02-01 | 华南理工大学 | Fluo-germanate red fluorescent material for white LED (light-emitting diode) and preparation method of material |
| CN106433626A (en) * | 2016-09-22 | 2017-02-22 | 陕西师范大学 | Method for preparing Mn(IV)-activated fluoride red fluorescent powder |
| CN106433624A (en) * | 2015-08-04 | 2017-02-22 | 云南民族大学 | Uniform-appearance and high-color-purity Mn4+ activated red fluoride luminescent material prepared by using micro-emulsion method |
| CN106687562A (en) * | 2014-07-22 | 2017-05-17 | 通用电气公司 | Fluorescent organic light emitting elements having high efficiency |
| CN107057695A (en) * | 2017-06-14 | 2017-08-18 | 温州大学 | A kind of fluostannic acid potassium sodium mixes Mn4+Red light material and preparation method thereof |
| CN107686726A (en) * | 2017-09-29 | 2018-02-13 | 温州大学 | A kind of white light LEDs lithium fluorosilicate sodium red light material and preparation method thereof |
-
2019
- 2019-01-21 CN CN201910053674.0A patent/CN109777418A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103429701A (en) * | 2011-03-23 | 2013-12-04 | 通用电气公司 | Color stable manganese-doped phosphors |
| CN103429702A (en) * | 2011-12-16 | 2013-12-04 | 皇家飞利浦有限公司 | Mn-activated hexafluorosilicates for LED applications |
| CN103275711A (en) * | 2013-06-08 | 2013-09-04 | 温州大学 | Fluorine titanium salt red-light material for white LED with two primary colors and preparation method of material |
| CN103980896A (en) * | 2014-04-29 | 2014-08-13 | 中国科学院福建物质结构研究所 | Preparation method of fluoride fluorescent powder material |
| CN106687562A (en) * | 2014-07-22 | 2017-05-17 | 通用电气公司 | Fluorescent organic light emitting elements having high efficiency |
| CN106244143A (en) * | 2015-06-04 | 2016-12-21 | 隆达电子股份有限公司 | Fluorescent powder with preferred direction, preparation method thereof and light-emitting element packaging structure comprising fluorescent powder |
| CN106433624A (en) * | 2015-08-04 | 2017-02-22 | 云南民族大学 | Uniform-appearance and high-color-purity Mn4+ activated red fluoride luminescent material prepared by using micro-emulsion method |
| CN105505384A (en) * | 2015-12-03 | 2016-04-20 | 河北利福光电技术有限公司 | Red-light fluorescent powder with narrow band and preparation method of red-light fluorescent powder |
| CN106367066A (en) * | 2016-09-06 | 2017-02-01 | 华南理工大学 | Fluo-germanate red fluorescent material for white LED (light-emitting diode) and preparation method of material |
| CN106433626A (en) * | 2016-09-22 | 2017-02-22 | 陕西师范大学 | Method for preparing Mn(IV)-activated fluoride red fluorescent powder |
| CN107057695A (en) * | 2017-06-14 | 2017-08-18 | 温州大学 | A kind of fluostannic acid potassium sodium mixes Mn4+Red light material and preparation method thereof |
| CN107686726A (en) * | 2017-09-29 | 2018-02-13 | 温州大学 | A kind of white light LEDs lithium fluorosilicate sodium red light material and preparation method thereof |
Non-Patent Citations (7)
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791282A (en) * | 2019-10-31 | 2020-02-14 | 云南民族大学 | Mn-doped steel wire4+Alkali metal fluoferrite red luminescent material and preparation method thereof |
| WO2021213900A1 (en) * | 2020-04-22 | 2021-10-28 | Osram Opto Semiconductors Gmbh | Red luminescent material and conversion led |
| CN115516063A (en) * | 2020-04-22 | 2022-12-23 | 艾迈斯-欧司朗国际有限责任公司 | Red phosphor and conversion LED |
| DE112021002599B4 (en) | 2020-04-22 | 2024-02-01 | Ams-Osram International Gmbh | RED FLUORESCENT, METHOD FOR PRODUCING A FLUORESCENT AND CONVERSION LED |
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