CN109777418A - A kind of Mn4+ doped double alkali metal composite fluorotitanate red light material and preparation method thereof - Google Patents
A kind of Mn4+ doped double alkali metal composite fluorotitanate red light material and preparation method thereof Download PDFInfo
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- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002905 metal composite material Substances 0.000 title claims abstract 10
- 229910001438 Mn4+ Inorganic materials 0.000 title description 22
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract 2
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Abstract
本发明公开了一种Mn4+掺杂双碱金属复合氟钛酸盐红光材料及其制备方法。该荧光粉材料的化学组成为NaBTiF6:xMn4+,其中B为Li|、K、Rb、Cs中的任何一种，x为Mn4+离子相对Ti4+离子的摩尔比例x为0.5～10 mol%。制备方法如下：用双碱金属氟化物、钛酸四丁酯Ti(OR)4作为基质原料，K2MnF6提供发光中心，在室温条件下搅拌完成反应，抽滤，洗涤，烘干，即可得到产品。产品最大激发波长位于蓝光区467 nm处，与氮化镓芯片所发蓝光完全匹配，其发射波长范围位于600～660 nm光谱区，色纯度高。本发明制备方法操作简便，反应条件温和，适合工业化大规模生产。
The invention discloses a Mn 4+ doped double alkali metal composite fluorotitanate red light material and a preparation method thereof. The chemical composition of the phosphor material is Na B TiF 6 : xMn 4+ , wherein B is any one of Li|, K, Rb, Cs, and x is the molar ratio of Mn 4+ ions to Ti 4+ ions, and x is 0.5～10 mol%. The preparation method is as follows: using double alkali metal fluoride and tetrabutyl titanate Ti(OR) 4 as matrix raw materials, K 2 MnF 6 providing a luminescent center, stirring at room temperature to complete the reaction, suction filtration, washing, drying, namely product available. The maximum excitation wavelength of the product is located at 467 nm in the blue light region, which completely matches the blue light emitted by the gallium nitride chip. Its emission wavelength range is located in the 600-660 nm spectral region, with high color purity. The preparation method of the invention has simple operation and mild reaction conditions, and is suitable for industrialized 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)
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