CN114181700A

CN114181700A - Organic-inorganic hybrid fluorine titanium potassium red-light fluorescent powder and preparation method thereof

Info

Publication number: CN114181700A
Application number: CN202111527299.2A
Authority: CN
Inventors: 黄映恒; 廖森; 黄毅; 于艳; 强嘉伟; 李燕; 石云浩
Original assignee: Guangxi Jingzheng Coatings Co ltd; Guangxi University
Current assignee: Guangxi Jingzheng Coatings Co ltd; Guangxi University
Priority date: 2021-12-14
Filing date: 2021-12-14
Publication date: 2022-03-15
Anticipated expiration: 2041-12-14
Also published as: CN114181700B

Abstract

The invention belongs to the technical field of fluorescent powder preparation, and particularly relates to organic-inorganic hybrid fluorine titanium potassium red fluorescent powder, which has a general formula as follows: k₂TiF₆:xMn⁴⁺,ytetaH⁺；tetaH⁺The method comprises the following steps of (1) performing organic-inorganic hybridization by using triethylene tetramine, wherein the hybridized triethylene tetramine exists in a protonated form; x is Mn⁴⁺The doped mole fraction, y is the mole fraction doped with triethylene tetramine, wherein x is more than or equal to 0.01 and less than or equal to 0.12, and y is more than or equal to 0.0 and less than or equal to 0.15. The invention also provides a preparation method of the organic-inorganic hybrid fluorine titanium potassium red fluorescent powder, which comprises the following steps: (1) mixing triethylene tetramine with H₂TiF₆Solution, K₂CO₃The solution reacts and is dried to obtain K₂TiF₆:ytetaH⁺(ii) a (2) KF.2H₂Dissolving O and HFLiquid, K₂MnF₆Solution, K₂TiF₆:ytetaH⁺Reacting, sealing and standing, filtering, washing and drying to obtain K₂TiF₆:xMn⁴⁺,ytetaH⁺. The red fluorescent powder obtained by the invention has the advantages of high luminescence, high intensity, water resistance, thermal stability and the like.

Description

Organic-inorganic hybrid fluorine titanium potassium red-light fluorescent powder and preparation method thereof

Technical Field

The invention belongs to the technical field of fluorescent powder preparation, and particularly relates to organic-inorganic hybrid fluorine titanium potassium red fluorescent powder.

Background

The diodes (white light LEDs) have the advantages of high luminous efficiency, energy conservation, long service life, low energy consumption, environmental protection and the like. Therefore, LEDs are considered as a new generation of solid state light emitting devices. The most mature and commercialized white LEDs are currently manufactured by blue light chips and yellow phosphor YAG: Ce³⁺By a combination of (1) yellow phosphor YAG: Ce³⁺Absorbing blue light emitted by the blue chip generates yellow fluorescent light, and the yellow fluorescent light is combined with the blue light of the chip to obtain white light. The white light has the defects of high color temperature, low color purity and the like due to lack of red light components, so that the white light is difficult to be applied to the backlight source of common illumination and display devices. The red fluorescent powder which can be excited by blue light is added in the packaging process, so that red components which are lacked in the spectrum of the white light LEDs can be compensated, and the color rendering performance of the white light LEDs is improved.

The red fluorescent powder which can be effectively excited by blue light at present is mainly Eu²⁺Nitride or nitrogen oxide doped fluorescent powder, but the preparation conditions of the fluorescent powder are harsh, so that the fluorescent powder is expensive, and the width of the nitride red-light fluorescent powder is wideThe low band emission and color purity severely limits their use in display device backlights. Therefore, the development of novel and efficient fluorescent powder capable of being excited by blue light has important research significance and very wide market application prospect.

At present, Mn⁴⁺The red light fluorescent powder doped with fluoride has very strong wide excitation band and very strong red light narrow-band emission in a blue light region, so that the obtained red light has high color purity, and is suitable for application in a backlight source of a display device, thereby having great application prospect. But now Mn⁴⁺There are also some disadvantages to doped fluoride red phosphors that need to be overcome: (1) the luminous intensity is higher than that of yellow fluorescent powder YAG: Ce³⁺The weight ratio of the yellow-light powder to yellow-light powder is up to 2:1-3:1 when the yellow-light powder is applied; (2) the thermal stability is not high, and the luminous intensity of the white light LED (at about 150 ℃) is reduced to 70-80% of the original luminous intensity due to thermal quenching; (3) poor moisture resistance, Mn in a humid environment⁴⁺Can be easily hydrolyzed into opaque MnO₂And further rapidly deactivated without emitting light. Therefore, by applying an organic-inorganic hybrid matrix, Mn having high luminous intensity, water resistance and thermal stability was developed⁴⁺The doped potassium fluotitanate red-light fluorescent powder and the corresponding preparation method thereof are significant.

Disclosure of Invention

The invention aims to solve the technical problems and provides the organic-inorganic hybrid fluorine titanium potassium red fluorescent powder which has the advantages of high luminescence, high intensity, water resistance, thermal stability and the like.

In order to solve the technical problems, the technical scheme provided by the invention is as follows:

an organic-inorganic hybrid fluorine titanium potassium red fluorescent powder has a general formula as follows: k₂TiF₆:xMn⁴⁺,ytetaH⁺；tetaH⁺The method comprises the following steps of (1) performing organic-inorganic hybridization by using triethylene tetramine, wherein the hybridized triethylene tetramine exists in a protonated form; x is Mn⁴⁺The doped mole fraction, y is the mole fraction doped with triethylene tetramine, wherein x is more than or equal to 0.01 and less than or equal to 0.12, y is more than or equal to 0.0 and less than or equal to 0.15, and x is m_Mn/m(Mn+Ti)，y＝mtetaH⁺/m(Mn+Ti)。

Preferably, in the present invention, x is 0.01, 0.02, 0.04, 0.06, 0.08, 0.10 or 0.12, and y is 0.01, 0.02, 0.04, 0.06, 0.08, 0.10 or 0.15.

Preferably, the invention provides a preparation method of organic-inorganic hybrid fluorine titanium potassium red fluorescent powder, which comprises the following steps:

(1) addition of triethylene tetramine to H₂TiF₆Stirring the solution evenly to obtain H₂TiF₆-tetaH⁺Mixing the solution, and then dropwise adding K₂CO₃Adding the solution into the mixed solution, reacting fully until the pH value is 7.0, continuing stirring, sealing, reacting at constant temperature, and drying to obtain K₂TiF₆:ytetaH⁺；

(2) KF.2H₂Adding O into HF solution, stirring, and adding K into the solution₂MnF₆Stirring to dissolve all solids; then adding K into the solution₂TiF₆:ytetaH⁺Stirring for 20-45 min, sealing and standing for 22-26h, vacuum filtering, washing, and oven drying at 80-100 deg.C for 3-4h to obtain K₂TiF₆:xMn⁴⁺,ytetaH⁺。

In order to fully react the raw materials, the hybridized triethylene tetramine exists in a protonated form, and preferably, in the step (1), the temperature is kept at 80-100 ℃ for 3-4 h.

In order to not waste raw materials and can better stir K₂TiF₆:ytetaH⁺Preferably, in step (2) of the present invention, the volume of the HF solution and K are₂TiF₆:ytetaH⁺The mass ratio of (1.0-3.0) to (1 g). If the ratio is too large, the hydrofluoric acid raw material is wasted; if the ratio is too small, the amount of solid becomes too large, and stirring is not performed during stirring.

The HF solution used in step (2) of the present invention is preferably used in such a manner that if the concentration is too high, it is difficult to obtain a medium-grade product, and if the concentration is too low, the reaction rate is lowered, which affects the conversion rate of the product. Preferably, in step (2) of the present invention, the HF solution has a mass concentration of 40% or more.

To ensure smooth achievement of the targetProduct, preferably, in step (2) of the present invention, the KF and K₂TiF₆:ytetaH⁺The mass ratio of (a) to (b) is z, wherein z is more than 0.7 and more than or equal to 0.1. If the z value is too large, the potassium fluoride raw material is wasted, and if the z value is too small, enough fluorine ions cannot be provided, so that the generation of the target product is influenced.

Preferably, in the step (2), the stirring is performed at 25-35 ℃, that is, the reaction of the invention can be performed at room temperature and normal pressure, and the method is convenient to operate and suitable for large-scale and industrial production.

In the present invention, triethylene tetramine is used as an organic hybridization agent. Triethylene tetramine is a multidentate chelating agent which can react with Mn in the present invention⁴⁺The reaction forms an insoluble coordination polymer, and the formation of the coordination polymer induces improvement in luminescence, thermal stability and water resistance at the same time.

Due to the adoption of the technical scheme, the invention has the beneficial effects that:

1. the organic-inorganic hybrid fluorine titanium potassium red fluorescent powder has strong red light emission (the main emission peak is located at about 631 nm) under the excitation of blue light, and compared with an unhybridized sample, the luminous intensity of the organic-inorganic hybrid fluorine titanium potassium red fluorescent powder is 2.18 times that of the organic-inorganic hybrid fluorine titanium potassium red fluorescent powder.

2. After the organic hybrid modification is carried out by using triethylene tetramine, the internal quantum efficiency of the luminescent of the fluorescent powder is between 86 and 99 percent.

3. After the organic hybrid modification by the triethylene tetramine, the fluorescent powder has higher luminous thermal stability, and the integral luminous intensity at 150 ℃ is 2.3 times or more than the initial value at 30 ℃.

4. After the organic hybrid modification by the triethylene tetramine, the fluorescent powder has better water resistance, the appearance of light yellow light is always kept after the fluorescent powder is soaked in water for 360 minutes (6 hours), and the intensity of the residual emitted light is as high as 85% or more.

5. The preparation method of the organic-inorganic hybrid fluorine titanium potassium red-light fluorescent powder is simple, has low requirements on reaction conditions, is carried out at room temperature and normal pressure, and is suitable for large-scale and industrial production.

Drawings

FIG. 1 shows KTF: xMn prepared according to the present invention⁴⁺,ytetaH⁺(sample No. x 0.01-0.12; y 0.01-0.15, (i) - (vii)) red phosphor and an unhybridized control sample KTF:0.06 Mn)⁴⁺X-ray diffraction pattern (XRD) (sample No. (0)).

FIG. 2 shows KTF:0.06Mn prepared according to the present invention⁴⁺,0.10tetaH⁺0.06Mn of red fluorescent powder and an unhybridized reference sample KTF⁴⁺Excitation spectrogram (PLE).

FIG. 3 shows KTF 0.06Mn prepared according to the invention⁴⁺,0.10tetaH⁺0.06Mn of red fluorescent powder and an unhybridized reference sample KTF⁴⁺Emission spectrum (PL).

FIG. 4 shows KTF: xMn prepared according to the present invention⁴⁺,ytetaH⁺(sample No. x 0.01-0.12; y 0.01-0.15, (i) - (vii)) color coordinate diagram of red phosphor.

FIG. 5 shows KTF:0.06Mn prepared according to the present invention⁴⁺,0.10tetaH⁺0.06Mn of red fluorescent powder and an unhybridized reference sample KTF⁴⁺The water resistance test integrated intensity of (2) is plotted against the soaking time.

FIG. 6 shows KTF:0.06Mn prepared according to the present invention⁴⁺,0.10tetaH⁺0.06Mn of red fluorescent powder and an unhybridized reference sample KTF⁴⁺Integrated intensity versus temperature curve.

FIG. 7 shows an assembled white LED (KTF:0.06 Mn) of the present invention⁴⁺,0.10tetaH⁺⁺YAG04) (chip drive current of 20 mA).

FIG. 8 is a white LED (KTF:0.06 Mn) assembled according to the present invention⁴⁺,0.10tetaH⁺⁺YAG04) (chip drive current 20 mA).

In the figure, KTF represents K₂TiF₆。

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

KTF is K in the following examples₂TiF₆The abbreviation of (1); the used chemical raw materials are pure chemical raw materials; teta is abbreviated as triethylene tetramine.

Example 1: preparation of [ KTF:0.06Mn⁴⁺,0.10tetaH⁺]

(1) First, 1.4623g (10mmol) of teta were added dropwise with stirring to 48.01g (100mmol) of 50% H₂TiF₆In solution to obtain H₂TiF₆-tetaH⁺The solution was mixed and 11.06g (80.0mmol) of K were added₂CO₃Adding into 30mL deionized water, stirring to dissolve completely to obtain K₂CO₃The solution of (1); then, the K is stirred₂CO₃To the above H₂TiF₆-tetaH⁺Dripping the mixed solution into the solution until the pH value is 7.0, continuing stirring for 30 minutes, sealing the opening of a beaker by using a preservative film, and placing the beaker in an oven to perform heat preservation reaction for 3 hours at the temperature of 90 ℃; finally, the preservative film is removed and is placed in an oven to be dried for 4 hours at the temperature of 120 ℃, and an intermediate K is obtained₂TiF₆:0.10tetaH⁺；

(2) Taking 12.39mLHF solution (mass concentration is 40%) (V)_HF/W_Substrate＝3.0mL/g)，0.413g KF·2H₂O(W_KF/W_Substrate＝0.1)，0.2966g(1.2mmol)K₂MnF₆Putting the powder into a 50mL plastic beaker, and stirring the powder by using a magnetic stirrer at room temperature and normal pressure until the solid raw material is completely dissolved to obtain a yellow solution; 4.13g (18.8mmol) of K are subsequently added with stirring₂TiF₆:0.10tetaH⁺The powder was added to the above solution ((Mn/(T)⁺Mn), and x is 0.06), sealing the opening of the beaker by using a preservative film, and stirring and reacting for 30min at room temperature and normal pressure to obtain a reaction mixture; then keeping the mixture in the original beaker, standing at room temperature for 24h, filtering, washing with anhydrous ethanol, and drying at 80 deg.C for 4h to obtain K₂TiF₆:0.06Mn⁴⁺,0.10tetaH⁺Red light phosphor crystal.

Unhybridized control [ KTF:0.06Mn ]⁴⁺]The synthesis method comprises the following steps: taking 12.39mLHF solution (mass concentration is 40%) (V)_HF/W_Substrate＝3.0mL/g)，0.413g KF·2H₂O(W_KF/W_Substrate＝0.1)，0.2966g(1.2mmol)K₂MnF₆Putting the powder into a 50mL plastic beaker, and stirring the powder by using a magnetic stirrer at room temperature and normal pressure until the solid raw material is completely dissolved to obtain a yellow solution; 4.513g (18.8mmol) of KTF powder were then added to the above solution with stirring ((Mn/(T)⁺Mn), and x is 0.06), sealing the opening of the beaker by using a preservative film, and stirring and reacting for 30min at room temperature and normal pressure to obtain a reaction mixture; then keeping the mixture in the original beaker, standing at room temperature for 24h, filtering, washing with anhydrous ethanol, and drying at 80 deg.C for 4h to obtain K₂TiF₆:0.06Mn⁴⁺Unhybridized control red phosphor crystals.

FIG. 1 shows the spectrum of KTF:0.06Mn prepared according to the present invention⁴⁺,0.10tetaH⁺X-ray diffraction pattern (XRD) of red phosphor. As can be seen from FIG. 1, the peak and K of the sample₂TiF₆The standard spectra of (1) are consistent (PDF #08-0488), which shows that the synthesized sample has a single phase K₂TiF₆The structure of (1).

FIG. 2 shows KTF:0.06Mn prepared according to the present invention⁴⁺,0.10tetaH⁺0.06Mn of red fluorescent powder and an unhybridized reference sample KTF⁴⁺Excitation spectrum (PLE) diagram of (d); as can be seen from FIG. 2, there is a strong broadband excitation peak at 467nm, whose peak width at half height is about 51nm, which is much larger than the peak width at half height of 20nm emitted by the blue light chip, so that it can form a good match with the blue light chip.

FIG. 3 shows KTF:0.06Mn prepared according to the present invention⁴⁺,0.10tetaH⁺0.06Mn of red fluorescent powder and an unhybridized reference sample KTF⁴⁺Emission spectrum (PL). As can be seen from FIG. 3, the emission spectrum is a narrow-band spectrum with a main emission peak at 632 nm. It can also be seen from fig. 3 that the intensity of the hybridized sample PL is about 2.18 times that of the unhybridized sample.

FIG. 4 is a color coordinate diagram of seven samples (i) - (vii), seven color coordinates being superimposedThe positions of the emission spectrum peaks of the seven samples are not obviously shifted. (i) The number is KTF:0.06Mn prepared by the invention⁴⁺,0.10tetaH⁺And (3) a color coordinate graph of the red fluorescent powder. As can be seen from fig. 4, the phosphor emits deep red light (x is 0.6923, y is 0.3075), and the color coordinate values of the phosphor are close to the standard values of the red color coordinate (x is 0.67, y is 0.33) set by the international television standards committee (NTSC).

FIG. 5 shows KTF:0.06Mn prepared according to the present invention⁴⁺,0.10tetaH⁺0.06Mn of red fluorescent powder and an unhybridized reference sample KTF⁴⁺The water resistance test of (2) is a curve of the relationship between the integral luminous intensity and the soaking time. As can be seen in fig. 5, after soaking in water for 360 minutes (6 days), the integrated luminescence intensity of the hybrid was 88.4% of the initial value before soaking; the integrated luminous intensity of the unhybridized sample is only 9.9% of the initial value before soaking, which shows that the water resistance of the hybridized sample is greatly improved.

FIG. 6 shows KTF:0.06Mn prepared according to the present invention⁴⁺,0.10tetaH⁺0.06Mn of red fluorescent powder and an unhybridized reference sample KTF⁴⁺Integrated luminescence intensity versus temperature curve. As can be seen in FIG. 6, the integrated luminescence intensities at 150 ℃ for the two samples are 233.7 and 87.8% of the initial values at room temperature (30 ℃), respectively, indicating that the thermal stability of the hybridized samples is much higher than that of the unhybridized samples.

FIG. 7 shows an assembled white LED (KTF:0.06 Mn) of the present invention⁴⁺,0.10tetaH⁺⁺YAG04) (chip drive current of 20 mA). Fig. 7 shows a complete spectrum consisting of three colors, blue, yellow and red (CCT 3766K, Ra 90.7). FIG. 8 is a white LED (KTF:0.06 Mn) assembled according to the present invention⁴⁺0.10tetaH + + YAG04) (0.3680,0.3054) (the driving current of the chip is 20 mA). Fig. 8 shows that the resulting white light is warm white.

Example 2: preparation of [ KTF:0.01Mn⁴⁺,0.02tetaH⁺]

(1) First, 0.2925g (2mmol) of teta were added dropwise with stirring to 48.01g (100mmol) of 50% strength by mass H₂TiF₆In solution to obtain H₂TiF₆-tetaH⁺The solution was mixed and 13.27g (96.0mmol) of K were added₂CO₃Adding 30mL of deionized water, stirring until the mixture is completely dissolved to obtain K₂CO₃The solution of (1); then, the K is stirred₂CO₃To the above H₂TiF₆-tetaH⁺Dripping the mixed solution into the solution until the pH value is 7.0, continuing stirring for 20 minutes, sealing the opening of a beaker by using a preservative film, and placing the beaker in an oven to perform heat preservation reaction for 3.5 hours at 85 ℃; finally, the preservative film is removed and is placed in an oven to be dried for 3 hours at the temperature of 130 ℃ to obtain an intermediate K₂TiF₆:0.02tetaH⁺；

(2) Taking 4.4mLHF solution (mass concentration is 40%) (V)_HF/W_Substrate＝1.0mL/g)，0.872g KF·2H₂O(W_KF/W_Substrate＝0.2)，0.0494g(0.2mmol)K₂MnF₆Putting the powder into a 50mL plastic beaker, and stirring the powder by using a magnetic stirrer at room temperature and normal pressure until the solid raw material is completely dissolved to obtain a yellow solution; 4.359g (19.6mmol) of K are then introduced with stirring₂TiF₆:0.02tetaH⁺The powder was added to the above solution ((Mn/(T)⁺Mn), and x is 0.01), sealing the opening of the beaker by using a preservative film, and stirring and reacting for 25min at room temperature and normal pressure to obtain a reaction mixture; then keeping the mixture in the original beaker, standing at room temperature for 24h, filtering, washing with anhydrous ethanol, and drying at 80 deg.C for 4h to obtain K₂TiF₆:0.01Mn⁴⁺,0.02tetaH⁺Red light phosphor crystal.

FIG. 1 shows the spectrum (ii) of KTF:0.01Mn prepared according to the present invention⁴⁺,0.02tetaH⁺X-ray diffraction pattern (XRD) of red phosphor. As can be seen from FIG. 1, the peak and K of the sample₂TiF₆The standard spectra of (1) are consistent (PDF #08-0488), which shows that the synthesized sample has a single phase K₂TiF₆The structure of (1).

FIG. 4 is a color coordinate graph of (i) - (vii) seven samples, with the seven color coordinates superimposed, illustrating that the emission spectrum peaks of the seven samples are not significantly shifted in position. (ii) The number is KTF of 0.01Mn prepared by the invention⁴⁺,0.02tetaH⁺And (3) a color coordinate graph of the red fluorescent powder. As can be seen from fig. 4, the phosphor emits deep red light (x is 0.6923, y is 0.3075), and the color coordinate values of the phosphor are close to the standard values of the red color coordinate (x is 0.67, y is 0.33) set by the international television standards committee (NTSC).

Example 3: preparation of [ KTF:0.02Mn⁴⁺,0.06tetaH⁺]

(1) First, 0.8774g (6mmol) of teta were added dropwise with stirring to 48.01g (100mmol) of 50% strength by mass H₂TiF₆In solution to obtain H₂TiF₆-tetaH⁺The solution was mixed and 12.16g (88.0mmol) of K were added₂CO₃Adding 30mL of deionized water, stirring until the mixture is completely dissolved to obtain K₂CO₃The solution of (1); then, the K is stirred₂CO₃To the above H₂TiF₆-tetaH⁺Dripping the mixed solution into the solution until the pH value is 7.0, continuing stirring for 25 minutes, sealing the opening of a beaker by using a preservative film, and placing the beaker in an oven to perform heat preservation reaction for 4 hours at the temperature of 95 ℃; finally, the preservative film is removed and is placed in an oven to be dried for 3.5 hours at the temperature of 130 ℃ to obtain an intermediate K₂TiF₆:0.06tetaH⁺；

(2) 19.63mL of HF solution (40% by mass) (V)_HF/W_Substrate＝4.0mL/g)，1.4723g KF·2H₂O(W_KF/W_Substrate＝0.3)，0.0989g(0.4mmol)K₂MnF₆Putting the powder into a 50mL plastic beaker, and stirring the powder by using a magnetic stirrer at room temperature and normal pressure until the solid raw material is completely dissolved to obtain a yellow solution; 4.310g (19.6mmol) of K are then introduced with stirring₂TiF₆:0.06tetaH⁺The powder was added to the above solution ((Mn/(T)⁺Mn), and x is 0.02), sealing the opening of the beaker by using a preservative film, and stirring and reacting for 30min at room temperature and normal pressure to obtain a reaction mixture; then keeping the mixture in the original beaker, standing at room temperature for 27h, filtering, washing with anhydrous ethanol, and drying at 95 deg.C for 4h to obtain K₂TiF₆:0.02Mn⁴⁺,0.06tetaH⁺Red light phosphor crystal.

Figure 1 (iii) is a chart of the present inventionKTF prepared from Ming prepared 0.02Mn⁴⁺,0.06tetaH⁺X-ray diffraction pattern (XRD) of red phosphor. As can be seen from FIG. 1, the peak and K of the sample₂TiF₆The standard spectra of (1) are consistent (PDF #08-0488), which shows that the synthesized sample has a single phase K₂TiF₆The structure of (1).

FIG. 4 is a color coordinate graph of (i) - (vii) seven samples, with the seven color coordinates superimposed, illustrating that the emission spectrum peaks of the seven samples are not significantly shifted in position. (iii) The number point is KTF 0.02Mn prepared by the invention⁴⁺,0.06tetaH⁺And (3) a color coordinate graph of the red fluorescent powder. As can be seen from fig. 4, the phosphor emits deep red light (x is 0.6923, y is 0.3075), and the color coordinate values of the phosphor are close to the standard values of the red color coordinate (x is 0.67, y is 0.33) set by the international television standards committee (NTSC).

Example 4: preparation of [ KTF:0.04Mn⁴⁺,0.15tetaH⁺]

(1) First, 2.1935g (15mmol) of teta were added dropwise with stirring to 48.01g (100mmol) of 50% strength by mass H₂TiF₆In solution to obtain H₂TiF₆-tetaH⁺The solution was mixed and 9.674g (70.0mmol) of K were added₂CO₃Adding 30mL of deionized water, stirring until the mixture is completely dissolved to obtain K₂CO₃The solution of (1); then, the K is stirred₂CO₃To the above H₂TiF₆-tetaH⁺Dripping the mixed solution into the solution until the pH value is 7.0, continuing stirring for 30 minutes, sealing the opening of a beaker by using a preservative film, and placing the beaker in an oven to perform heat preservation reaction for 3 hours at the temperature of 100 ℃; finally, removing the preservative film, and drying the preservative film in an oven at 125 ℃ for 4 hours to obtain an intermediate K₂TiF₆:0.15tetaH⁺；

(2) Taking 8.42mL of HF solution (with the mass concentration of 40%) (V)_HF/W_Substrate＝2.0mL/g)，2.94g KF·2H₂O(W_KF/W_Substrate＝0.7)，0.1977g(0.8mmol)K₂MnF₆Putting the powder into a 50mL plastic beaker, and stirring the powder by using a magnetic stirrer at room temperature and normal pressure until the solid raw material is completely dissolved to obtain a yellow solution; 4.212g (19) were then added with stirring.2mmol)K₂TiF₆:0.04tetaH⁺The powder was added to the above solution ((Mn/(T)⁺Mn), and x is 0.04), sealing the opening of the beaker by using a preservative film, and stirring and reacting for 35min at room temperature and normal pressure to obtain a reaction mixture; then keeping the mixture in the original beaker, standing at room temperature for 23h, filtering, washing with anhydrous ethanol, and oven drying at 100 deg.C for 3h to obtain K₂TiF₆:0.04Mn⁴⁺,0.15tetaH⁺Red light phosphor crystal.

FIG. 1 shows the spectrum (iv) of KTF:0.04Mn prepared according to the present invention⁴⁺,0.15tetaH⁺X-ray diffraction pattern (XRD) of red phosphor. As can be seen from FIG. 1, the peak and K of the sample₂TiF₆The standard spectra of (1) are consistent (PDF #08-0488), which shows that the synthesized sample has a single phase K₂TiF₆The structure of (1).

FIG. 4 is a color coordinate graph of (i) - (vii) seven samples, with the seven color coordinates superimposed, illustrating that the emission spectrum peaks of the seven samples are not significantly shifted in position. (iv) The number is KTF of 0.04Mn prepared by the invention⁴⁺,0.15tetaH⁺And (3) a color coordinate graph of the red fluorescent powder. As can be seen from fig. 4, the phosphor emits deep red light (x is 0.6923, y is 0.3075), and the color coordinate values of the phosphor are close to the standard values of the red color coordinate (x is 0.67, y is 0.33) set by the international television standards committee (NTSC).

Example 5: preparation of [ KTF:0.08Mn⁴⁺,0.01tetaH⁺]

(1) First, 0.1462g (1mmol) of teta was added dropwise to 48.01g (100mmol) of 50% H with stirring₂TiF₆In solution to obtain H₂TiF₆-tetaH⁺The solution was mixed and 13.54g (98.0mmol) of K were added₂CO₃Adding 30mL of deionized water, stirring until the mixture is completely dissolved to obtain K₂CO₃The solution of (1); then, the K is stirred₂CO₃To the above H₂TiF₆-tetaH⁺Dropping the mixed solution until the pH value is 7.0, continuing stirring for 35 minutes, sealing the opening of the beaker by using a preservative film, placing the beaker in an oven, and preserving heat for reaction at 80 DEG C4 h; finally, removing the preservative film, and drying the preservative film in an oven at 125 ℃ for 3 hours to obtain an intermediate K₂TiF₆:0.01tetaH⁺；

(2) Taking 10.13mLHF solution (mass concentration is 40%) (V)_HF/W_Substrate＝2.5mL/g)，0.4052g KF·2H₂O(W_KF/W_Substrate＝0.1)，0.3954g(1.6mmol)K₂MnF₆Putting the powder into a 50mL plastic beaker, and stirring the powder by using a magnetic stirrer at room temperature and normal pressure until the solid raw material is completely dissolved to obtain a yellow solution; 4.052g (18.4mmol) of K are then added with stirring₂TiF₆:0.08tetaH⁺The powder was added to the above solution ((Mn/(T)⁺Mn), and x is 0.08), sealing the opening of the beaker by using a preservative film, and stirring and reacting for 40min at room temperature and normal pressure to obtain a reaction mixture; then keeping the mixture in the original beaker, standing at room temperature for 26h, filtering, washing with anhydrous ethanol, and drying at 80 deg.C for 4h to obtain K₂TiF₆:0.08Mn⁴⁺,0.01tetaH⁺Red light phosphor crystal.

FIG. 1 shows the spectrum (v) of KTF:0.08Mn prepared according to the present invention⁴⁺,0.01tetaH⁺X-ray diffraction pattern (XRD) of red phosphor. As can be seen from FIG. 1, the peak and K of the sample₂TiF₆The standard spectra of (1) are consistent (PDF #08-0488), which shows that the synthesized sample has a single phase K₂TiF₆The structure of (1).

FIG. 4 is a color coordinate graph of (i) - (vii) seven samples, with the seven color coordinates superimposed, illustrating that the emission spectrum peaks of the seven samples are not significantly shifted in position. (v) The number point is KTF:0.08Mn prepared by the invention⁴⁺,0.01tetaH⁺And (3) a color coordinate graph of the red fluorescent powder. As can be seen from fig. 4, the phosphor emits deep red light (x is 0.6923, y is 0.3075), and the color coordinate values of the phosphor are close to the standard values of the red color coordinate (x is 0.67, y is 0.33) set by the international television standards committee (NTSC).

Example 6: preparation of [ KTF:0.10Mn⁴⁺,0.04tetaH⁺]

(1) First, 0.5849g (4mmol) of teta were added dropwise to 48.01g (100mmol) of mass under stirringH concentration of 50%₂TiF₆In solution to obtain H₂TiF₆-tetaH⁺The solution was mixed and 12.72g (92.0mmol) of K were added₂CO₃Adding 30mL of deionized water, stirring until the mixture is completely dissolved to obtain K₂CO₃The solution of (1); then, the K is stirred₂CO₃To the above H₂TiF₆-tetaH⁺Dripping the mixed solution into the solution until the pH value is 7.0, continuing stirring for 40 minutes, sealing the mouth of the beaker by using a preservative film, and placing the beaker in an oven to perform heat preservation reaction for 3 hours at the temperature of 90 ℃; finally, the preservative film is removed and is placed in an oven to be dried for 3.5 hours at the temperature of 120 ℃ to obtain an intermediate K₂TiF₆:0.04tetaH⁺；

(2) Taking 11.88mLHF solution (mass concentration is 40%) (V)_HF/W_Substrate＝3.0mL/g)，1.188g KF·2H₂O(W_KF/W_Substrate＝0.3)，0.4943g(2.0mmol)K₂MnF₆Putting the powder into a 50mL plastic beaker, and stirring the powder by using a magnetic stirrer at room temperature and normal pressure until the solid raw material is completely dissolved to obtain a yellow solution; then 3.960g (18.0mmol) of K are stirred₂TiF₆:0.04tetaH⁺The powder was added to the above solution ((Mn/(T)⁺Mn), and x is 0.10), sealing the opening of the beaker by using a preservative film, and stirring and reacting for 45min at room temperature and normal pressure to obtain a reaction mixture; then keeping the mixture in the original beaker, standing at room temperature for 22h, filtering, washing with anhydrous ethanol, and oven drying at 90 deg.C for 3h to obtain K₂TiF₆:0.10Mn⁴⁺,0.04tetaH⁺Red light phosphor crystal.

FIG. 1 shows the spectrum (vi) of KTF:0.10Mn prepared according to the present invention⁴⁺,0.04tetaH⁺X-ray diffraction pattern (XRD) of red phosphor. As can be seen from FIG. 1, the peak and K of the sample₂TiF₆The standard spectra of (1) are consistent (PDF #08-0488), which shows that the synthesized sample has a single phase K₂TiF₆The structure of (1).

FIG. 4 is a color coordinate diagram of (i) - (vii) seven samples, with the seven color coordinates superimposed, illustrating the position of the peaks of the emission spectra of the seven samplesSignificant drift occurs. (vi) The number is KTF of 0.10Mn prepared by the invention⁴⁺,0.04tetaH⁺And (3) a color coordinate graph of the red fluorescent powder. As can be seen from fig. 4, the phosphor emits deep red light (x is 0.6923, y is 0.3075), and the color coordinate values of the phosphor are close to the standard values of the red color coordinate (x is 0.67, y is 0.33) set by the international television standards committee (NTSC).

Example 7: preparation of [ KTF:0.12Mn⁴⁺,0.08tetaH⁺]

(1) First, 1.1699g (8mmol) of teta were added dropwise with stirring to 48.01g (100mmol) of 50% strength by mass H₂TiF₆In solution to obtain H₂TiF₆-tetaH⁺The solution was mixed and 11.61g (84.0mmol) of K were added₂CO₃Adding 30mL of deionized water, stirring until the mixture is completely dissolved to obtain K₂CO₃The solution of (1); then, the K is stirred₂CO₃To the above H₂TiF₆-tetaH⁺Dripping the mixed solution into the solution until the pH value is 7.0, continuing stirring for 45 minutes, sealing the opening of a beaker by using a preservative film, and placing the beaker in an oven to perform heat preservation reaction for 3.5 hours at the temperature of 100 ℃; finally, the preservative film is removed and is placed in an oven to be dried for 4 hours at the temperature of 120 ℃ to obtain an intermediate K₂TiF₆:0.08tetaH⁺；

(2) Taking a 13.54mLHF solution (with the mass concentration of 40%) (V)_HF/W_Substrate＝3.5mL/g)，1.934g KF·2H₂O(W_KF/W_Substrate＝0.5)，0.5931g(2.4mmol)K₂MnF₆Putting the powder into a 50mL plastic beaker, and stirring the powder by using a magnetic stirrer at room temperature and normal pressure until the solid raw material is completely dissolved to obtain a yellow solution; 3.8681g (17.6mmol) of K are then introduced with stirring₂TiF₆:0.08tetaH⁺The powder was added to the above solution ((Mn/(T)⁺Mn), and x is 0.12), sealing the opening of the beaker by using a preservative film, and stirring and reacting for 50min at room temperature and normal pressure to obtain a reaction mixture; then keeping the mixture in the original beaker, standing at room temperature for 25h, filtering, washing with anhydrous ethanol, and oven drying at 100 deg.C for 3.5h to obtain K₂TiF₆:0.12Mn⁴⁺,0.08tetaH⁺Red light phosphor crystal.

FIG. 1 shows the spectrum of KTF:0.12Mn in FIG. 1⁴⁺,0.08tetaH⁺X-ray diffraction pattern (XRD) of red phosphor. As can be seen from FIG. 1, the peak and K of the sample₂TiF₆The standard spectra of (1) are consistent (PDF #08-0488), which shows that the synthesized sample has a single phase K₂TiF₆The structure of (1).

FIG. 4 is a color coordinate graph of (i) - (vii) seven samples, with the seven color coordinates superimposed, illustrating that the emission spectrum peaks of the seven samples are not significantly shifted in position. (vii) The number is KTF of 0.12Mn prepared by the invention⁴⁺,0.08tetaH⁺And (3) a color coordinate graph of the red fluorescent powder. As can be seen from fig. 4, the phosphor emits deep red light (x is 0.6923, y is 0.3075), and the color coordinate values of the phosphor are close to the standard values of the red color coordinate (x is 0.67, y is 0.33) set by the international television standards committee (NTSC).

Example 8

The red fluorescent powder K prepared by the invention₂TiF₆:0.06Mn⁴⁺,0.10tetaH⁺Commercial yellow phosphor YAG: Ce³⁺(Intemet YAG04) with an epoxy resin in the formula K₂TiF₆:0.06Mn⁴⁺,0.10tetaH⁺Mixing the/YAG 04/epoxy resin at a mass ratio of 1:4:16, coating the mixture on a GaN blue light chip after uniform mixing to assemble a white light LED lamp, and then carrying out related tests under the condition that the driving current of the chip is 20 mA.

FIG. 7 is an assembled LED of the present invention (KTF:0.06 Mn)⁴⁺,0.10tetaH⁺YAG04) (chip drive current of 20 mA). As can be seen from FIG. 7, the peak around 460nm is contributed by the blue spectral band transmitted by the blue light chip, the broad band peak around 550nm is the peak of AGY04 yellow phosphor, and the seven narrow band peaks in the range of 600-660nm are red phosphor KTF:0.06Mn⁴⁺,0.10tetaH⁺Spectrum peak of (2).

FIG. 8 assembled white light LED (KTF:0.06 Mn) of the present invention⁴⁺,0.10tetaH⁺YAG04) (chip drive current 20 mA). As can be seen in FIG. 8, the LED emits white light (0.3680,0.3054), which is in turn reflected by the LEDThe color temperature corresponding to the color coordinates is 3766K, the color rendering index is 90.7 and the efficiency of the LED is 106.4 lm/W.

It can be seen from this that: the invention has the following advantages: (1) the luminescence intensity of the former was 2.18 for the latter compared to the unhybridized sample; (2) after soaking in water for 360 minutes (6 hours), the luminous intensity of the former is 88% or more than that before soaking, while the latter is only less than 10%; (c) the integrated luminescence intensity of the hybridized sample at 150 ℃ is 2.3 times or more the initial value at room temperature (30 ℃). The invention relates to a method for preparing triethylene tetramine hybridized potassium fluotitanate by hybridizing triethylene tetramine and potassium fluotitanate, and then obtaining Mn⁴⁺The red phosphor powder doped with organic-inorganic hybrid potassium fluotitanate has high luminous intensity, water resistance and thermal stability.

The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.

Claims

1. An organic-inorganic hybrid fluorine titanium potassium red fluorescent powder is characterized in that: the general formula is as follows: k₂TiF₆:xMn⁴⁺,ytetaH⁺；tetaH⁺The method comprises the following steps of (1) performing organic-inorganic hybridization by using triethylene tetramine, wherein the hybridized triethylene tetramine exists in a protonated form; x is Mn⁴⁺The doped mole fraction, y is the mole fraction doped with triethylene tetramine, wherein x is more than or equal to 0.01 and less than or equal to 0.12, and y is more than or equal to 0.01 and less than or equal to 0.15.

2. The organic-inorganic hybrid fluorine titanium potassium red phosphor as claimed in claim 1, wherein: x is 0.01, 0.02, 0.04, 0.06, 0.08, 0.10 or 0.12, and y is 0.01, 0.02, 0.04, 0.06, 0.08, 0.10 or 0.15.

3. The preparation method of the organic-inorganic hybrid potassium titanium fluoride red-light phosphor as claimed in claim 1 or 2, which comprises the following steps:

(1) addition of triethylene tetramine to H₂TiF₆Stirring the solution evenly to obtain H₂TiF₆-tetaH⁺Mixing the solution, and then dropwise adding K₂CO₃Adding the solution into the mixed solution, fully reacting until the pH value is 7.0, continuously stirring, sealing, reacting at a constant temperature, and drying to obtain K₂TiF₆:ytetaH⁺；

4. The preparation method of the organic-inorganic hybrid fluorine titanium potassium red fluorescent powder as claimed in claim 3, which is characterized in that: in the step (1), the reaction is carried out for 3 to 4 hours at the temperature of 80 to 100 ℃.

5. The preparation method of the organic-inorganic hybrid fluorine titanium potassium red fluorescent powder as claimed in claim 3, which is characterized in that: in the step (2), the volume of the HF solution and K₂TiF₆:ytetaH⁺The mass ratio of (1.0-3.0) to (1 g).

6. The preparation method of the organic-inorganic hybrid fluorine titanium potassium red fluorescent powder as claimed in claim 3, which is characterized in that: in the step (2), the mass concentration of the HF solution is equal to or more than 40%.

7. The preparation method of the organic-inorganic hybrid fluorine titanium potassium red fluorescent powder as claimed in claim 3, which is characterized in that: in the step (2), the KF and the K₂TiF₆:ytetaH⁺⁺The mass ratio of (a) to (b) is z, wherein z is more than 0.7 and more than or equal to 0.1.

8. The preparation method of the organic-inorganic hybrid fluorine titanium potassium red fluorescent powder as claimed in claim 3, which is characterized in that: in the step (2), the stirring is carried out at 25-35 ℃.