CN1908115A - High light red alkaline earth titanate fluorescent powder and method of processing and preparing reducing ambience thereof - Google Patents

Abstract

The invention discloses a high-brightness red alkaline-earth titanate fluorescent powder and a preparation method thereof. Different atmosphere conditions are used to regulate matrix defects of the alkaline-earth titanate fluorescent powder, thereby improving the luminous brightness of the ultraviolet excitation and electron beam excitation. Its main technical feature is that the mixture prepared by the solid phase mixture or wet chemical method is fired by high temperature solid phase reaction under reducing atmosphere conditions, or the post-treatment process of reducing atmosphere is introduced after air firing to activate rare earth ions The defect state of the alkaline earth titanate fluorescent powder matrix is regulated, so that the fluorescent powder has high luminous brightness and good material performance when excited by ultraviolet rays and low-voltage electron beams. The material has the characteristics of high stability, no toxic and side effects, simple operation process and low cost, and can be widely used in information display fields such as electron beam excited display screens.

Description

High-brightness red alkaline earth titanate phosphor and its preparation method by reducing atmosphere treatment

technical field

The invention relates to a high-brightness rare earth ion-activated red alkaline earth titanate fluorescent powder and a preparation method thereof, in particular to high-brightness rare earth ion-activated red alkaline earth titanate obtained by introducing a reducing atmosphere treatment means in the firing process or post-treatment process The salt fluorescent powder and a preparation method thereof belong to the technical field of material science.

Background technique

With the rapid development of modern science and technology, luminescent materials have developed from general photoluminescence, display and lighting materials to luminescence excited by various excitation sources such as electricity, sound, heat, chemistry, biology, mechanical energy and high-energy rays, and are widely used. Key display materials used in high-tech products such as ultra-thin TVs, liquid crystal and plasma displays, micro-monitors and precision sensors and probes.

Recently, Field Emission Display (FED) has developed vigorously as a new flat panel display technology, and is expected to replace the traditional cathode ray tube (CRT) display technology. The phosphor powder used in FED requires to work under low voltage and high current density conditions. Phosphor powder for CRT, such as commonly used red Y ₂ O ₃ :Eu phosphor powder, is not suitable for FED display occasions. At present, the red phosphor used for low-voltage (10V ~ 100V) electron beam excitation is mainly Zn _1-x Cd _x S (0≤x≤1) system phosphor, which has been widely used in vacuum fluorescent display devices ( VFD) and other occasions. However, there are some obvious problems in the use of sulfide Zn _1-x Cd _x S phosphors, such as the sulfide phosphors are easy to decompose after long-time electron beam irradiation, and the S or SO ₂ produced by the decomposition reduces the electron source The electron emission capability of the oxide cathode; in addition, the red chromaticity regulator component Cd ion used in a large amount in the sulfide phosphor is harmful to the human body. From the perspective of environmental protection, the European Union stipulated that this type of Zn should be banned from July 2006. _1-x Cd _x S red phosphor, which leads to the great limitation of the application field of traditional Zn _1-x Cd _x S red phosphor, and there is an urgent need to find and develop a new type of non-toxic, efficient and stable environment-friendly red FED Use fluorescent powder.

In 1994, Vecht et al. discovered that CaTiO ₃ :Pr ³⁺ with a perovskite structure was a new type of red phosphor with potential display applications. In 1996, Toki et al. found that co-doping of Al(OH) ₃ or Ga ₂ O ₃ components could enhance the photoluminescence and cathodoluminescence intensity of SrTiO ₃ :Pr ³⁺ by about two orders of magnitude, which can be used as a field emission display (FED) and vacuum electron luminescent display (VFD) and other red phosphor materials. Therefore, the research and development of titanate-based phosphors has attracted the attention of the industry. Compared with Zn _1-x Cd _x S sulfide phosphors, the material chemical properties of titanate-based phosphors are very stable. When rare earth ions are used as luminescent central ions, the phosphors have a single luminescence peak and better color purity, such as The color coordinates of the photoluminescence and cathode ray red light of CaTiO ₃ :Pr ³⁺ are x=0.680, y=0.311, which are very close to the ideal red color specified by the US NTSC system. Considering material stability and luminescent color, this kind of rare earth ion-activated titanate phosphor is expected to replace Zn _1-x Cd _x S sulfide red phosphor, and become a new generation of non-toxic, highly stable and environmentally friendly red phosphor for FED. powder material.

However, this kind of material still has the fundamental problem of low luminance, which limits its application. So far, there are very few patent applications for this type of phosphor. For example, Hideki Oshima applied for patents 2004-097738 and 200510069719.1 in Japan and China in 2004 and 2005, respectively. In addition, for the research on the relationship between the material structure and luminescent properties of CaTiO ₃ fluorescent materials, there are many non-patent literature reports, such as non-patent literature 1 (Vecht et al., "New electron excited light emitting materials", J.Vac.Sci. Tehcnol.B, 12(2)(1994) p.781), non-patent literature 2 (Diallo et al., "Improvement of theoptical performances of Pr ³⁺ in CaTiO ₃ ", J.Alloys.Comp., 323-324(2001 ) p.218); or non-patent literature 3 (Kang et al., "The influence of Li addition on Cathodoluminescence of CaTiO ₃ :Pr ³⁺ ", Eurodisplay (2002) p.777).

Summarizing the existing patent literature and non-patent literature reports, it is found that all literature research works use the traditional high-temperature reaction firing process under the atmosphere, and the research work mainly involves doping different types of monovalent, divalent or trivalent Use valence auxiliary ions to improve the luminous brightness of red titanate fluorescent materials, and analyze and study the material structure and luminescent properties. Although some documents and patents have reported that the luminance of phosphors under photoluminescence and electron beam excitation has been significantly improved, the large amount of dopant ions doped for this will easily lead to phase transition of the matrix and the hardening of phosphor materials after firing. Disadvantages such as reduced material life expectancy.

Generally speaking, the luminous brightness of this kind of material is still low at present, and needs to be further improved and improved; for this kind of alkaline earth titanate luminous matrix, there are no special preparation process conditions to control the structural defects so as to obtain high luminance There is no relevant patent application for the research report on phosphor powder.

Contents of the invention

The purpose of the present invention is to propose the use of reducing atmosphere firing or reducing atmosphere post-treatment in order to improve the material use characteristics such as the luminous brightness of the phosphor material, in addition to the technical route of improving the material formula by doping with different valence ions that has been extensively studied at present. Process for preparing high-brightness red alkaline earth titanate fluorescent powder and a preparation method thereof.

The high-brightness red alkaline-earth titanate phosphor powder and the preparation method thereof provided by the invention regulate and control the matrix defects of the red alkaline-earth titanate phosphor powder through different atmosphere conditions, thereby improving its ultraviolet excitation and electron beam excitation brightness. Its main technological innovation feature is that the mixture prepared by solid-phase mixing or wet chemical method is subjected to a high-temperature solid-phase reaction firing process in a reducing atmosphere, or a post-treatment process in a reducing atmosphere after firing in an atmospheric atmosphere, to activate rare earth ions The matrix defect state of the alkaline earth titanate phosphor is regulated, and the phosphor has high luminous brightness and good material performance when excited by low-voltage electron beams and ultraviolet rays.

The invention provides a high-brightness red alkaline-earth titanate fluorescent powder that regulates material defects through a reducing atmosphere, and its formula composition formula is: ATiO ₃ : xRe, yM; wherein A is one of alkaline-earth elements Ca, Sr, and Ba, That is, CaTiO ₃ , SrTiO ₃ or BaTiO ₃ alkaline earth titanate is used as the luminescent matrix; Re is the doped rare earth luminescent center ion (or rare earth ion activator), which is cerium Ce, praseodymium Pr, europium Eu, terbium Tb, erbium One or both of Er or thulium Tm; 0<x<0.15, 0≤y<0.4, M is an auxiliary doping element, which is boron B, aluminum Al, gallium Ga, indium In or lithium Li, sodium Na, One or more of potassium K.

A preparation method of high-brightness red alkaline earth titanate fluorescent powder, comprising the following steps:

1) Prepare the mixture for firing with a solid phase mixing method or a wet chemical reaction method;

2) Using a high-temperature reducing atmosphere firing process or a reducing atmosphere post-treatment process to perform firing treatment on the firing mixture to obtain fired fluorescent powder;

3) Add absolute ethanol according to the weight ratio of fired fluorescent powder and absolute ethanol as 1:0.5~2.5, ball mill and mix in a planetary ball mill at a speed of 50~250r/min for 4~24h, and ball mill at 50~150°C Dry in an oven for 6 to 24 hours, and obtain the dried material after sieving.

The solid phase reaction method is as follows: using alkaline earth carbonate, titanium dioxide, rare earth nitrate, and auxiliary doping element M compounds as raw materials, and weighing each raw material according to the atomic ratio of ATiO ₃ : xRe, yM, wherein A is Ca , Sr or Ba, Re is a doped rare earth luminescent center ion, which is one or two of cerium Ce, praseodymium Pr, europium Eu, terbium Tb, erbium Er or thulium Tm; 0<x<0.15, 0≤y <0.4; M is an auxiliary doping element, which is one or more of boron B, aluminum Al, gallium Ga, indium In, lithium Li, sodium Na or potassium K; the weight ratio of raw materials to deionized water is 1 : 0.5 to 1.5, add deionized water, ball mill and mix in a planetary ball mill at a speed of 200r/min for 2 to 36 hours, and dry the ball mill in an oven at 50 to 150°C for 6 to 36 hours to obtain a mixture for firing.

The wet chemical reaction method is as follows: using alkaline earth nitrate, butyl phthalate, rare earth nitrate and the compound of auxiliary doping element M as raw materials, and using cyclohexane, polyethylene glycol octyl ether and acetylacetone as Auxiliary chemical reagent; according to the atomic ratio of ATiO ₃ : xRe, yM, each raw material is weighed, wherein A is Ca, Sr or Ba, and Re is a doped rare earth luminescent center ion, which is cerium Ce, praseodymium Pr, europium Eu, terbium Tb , one or both of erbium Er or thulium Tm; 0<x<0.15, 0≤y<0.4; M is an auxiliary doping element, which is boron B, aluminum Al, gallium Ga, indium In, lithium Li, sodium One or more of Na or potassium K; add appropriate amount of deionized water to the rare earth nitrate raw material to prepare a rare earth nitrate solution with a rare earth ion concentration of 0.5-2.0mol/L and a pH of 2-6; take 50 ～150ml of cyclohexane, add 10～50ml of surfactant polyethylene glycol octyl ether under stirring condition, then add 2～10ml of rare earth nitrate solution mixed according to atomic ratio, alkaline earth nitrate solution and auxiliary doping element compound nitric acid diluent, add isoamyl alcohol until the solution is transparent, and continue to stir for 10 to 60 minutes; then add butyl titanate raw materials weighed according to the proportion to carry out hydrolysis and polycondensation reactions, and control its dispersion through the dispersion of water in the microemulsion. Hydrolysis speed, and finally form a uniform and transparent gel body, which is dried at 50-250 ° C, and the dried xerogel is ground to obtain a mixture for firing.

The alkaline earth carbonate is one or more of CaCO ₃ , SrCO ₃ or BaCO ₃ .

The alkaline earth nitrate is one or more of Ca(NO ₃ ) ₂ , Sr(NO ₃ ) ₂ or Ba(NO ₃ ) ₂ .

The rare earth nitrate is one of Pr(NO ₃ ) ₃ , Ce(NO ₃ ) ₃ , Eu(NO ₃ ) ₃ , Tb(NO ₃ ) ₃ , Er(NO ₃ ) ₃ or Tm(NO ₃ ) ₃ one or two.

The compound of the auxiliary doping element M is an oxide, hydroxide or carbonate compound of the auxiliary doping element M.

The high-temperature reducing atmosphere firing process is as follows: directly put the firing mixture into a graphite crucible or a corundum tube furnace with good sealing performance, and pass a gas of CO, N ₂ , H ₂ or NH ₃ Or its mixed gas, such as nitrogen/hydrogen mixed gas reducing gas, starts from room temperature at 10°C/min to 800-1400°C, and keeps at the set firing temperature for 1-6 hours to carry out sufficient high-temperature reaction. , keep the reducing atmosphere and cool down to room temperature with the furnace to obtain fired phosphor material.

The post-treatment process in a reducing atmosphere is as follows: put the mixture for firing into a high-temperature electric furnace, raise the temperature from room temperature to 1000-1400°C at 10°C/min, and keep it at the set firing temperature for 1-6 hours. Sufficient high-temperature reaction, after the heat preservation is completed, the phosphor powder is obtained by cooling with the furnace; then the phosphor powder is put into a well-sealed graphite crucible or corundum tube furnace, and one of CO, N ₂ , H ₂ or NH ₃ is passed through Gas or its mixed gas, such as nitrogen/hydrogen mixed gas, reducing gas, start from room temperature at 10°C/min to 600-1100°C, keep at the set post-treatment temperature for 2-10 hours to carry out sufficient reducing atmosphere post-treatment reaction After the heat preservation is over, keep the reducing atmosphere and cool down to room temperature with the furnace to obtain the fired phosphor material.

The invention can introduce reducing atmosphere treatment means in the firing treatment process to regulate the structural defects of the red alkaline earth titanate fluorescent powder matrix, and improve the luminous intensity of electron beam excitation and ultraviolet excitation of the fluorescent powder. The red alkaline earth titanate fluorescent powder prepared by the invention has material characteristics such as excellent red light-emitting performance, and is a promising red fluorescent powder material. Compared with the preparation method and material properties of the current domestic and foreign research and use of electron beams to excite red phosphors, the present invention has the following characteristics:

1) Compared with the traditional Zn _1-x Cd _x S phosphor, it has the advantages of high material stability, no toxic side effects, and no environmental pollution, and has broad application prospects.

2) Compared with the red alkaline earth titanate phosphor fired in ordinary atmospheric atmosphere, the luminous intensity of phosphor fired by high-temperature reduction process or reducing atmosphere post-treatment process is increased by an order of magnitude, which can overcome the doping of a large number of auxiliary ions and higher burning. The phosphor matrix caused by the formation temperature is prone to phase change, and the material is hard and difficult to grind.

3) The material process is stable, and the type and number of point traps in the luminescent matrix can be effectively controlled by adjusting the atmosphere type, proportion and air flow conditions, and the luminous intensity and afterglow characteristics of the material can be adjusted and optimized.

4) Based on this reduction firing process, a new phosphor powder preparation process that can effectively improve the luminescence performance of this type of phosphor without doping ions can be developed.

Detailed ways

The present invention will be further described below in conjunction with embodiment. Among them, Examples 1-12 are firing processes in a reducing atmosphere, and Examples 13-24 are post-treatment processes using a reducing atmosphere.

Example 1

Chemically pure or analytically pure calcium carbonate CaCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Ca:Ti:Pr is 1:1:0.002. Weigh each raw material to prepare a mixture, mix Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/min for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed according to 5g each, and pressed into a Φ22mm×3mm disc under 150MPa uniaxial pressure. To obtain the fired fluorescent powder, add absolute ethanol according to the weight ratio of the fired fluorescent powder to absolute ethanol as 1:1.5, ball mill and mix in a planetary ball mill at a speed of 150r/min for 24 hours, and dry the ball mill in an oven at 100°C After drying for 24 hours, the dried material was sieved to obtain the CaTiO ₃ :0.002Pr phosphor material fired in a CO reducing atmosphere.

Example 2

Chemically pure or analytically pure strontium carbonate SrCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Sr:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/min for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed according to 5g each, and pressed into a Φ22mm×3mm disc under 150MPa uniaxial pressure. To obtain the fired fluorescent powder, add absolute ethanol according to the weight ratio of the fired fluorescent powder to absolute ethanol as 1:1.5, ball mill and mix in a planetary ball mill at a speed of 150r/min for 24 hours, and dry the ball mill in an oven at 100°C After drying for 24 hours, the dried material was sieved to obtain the SrTiO ₃ :0.002Pr fluorescent material fired in a CO reducing atmosphere.

Example 3

Chemically pure or analytically pure barium carbonate BaCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Ba:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/mi for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed according to 5g each, and pressed into a Φ22mm×3mm disc under 150MPa uniaxial pressure. To obtain the fired fluorescent powder, add absolute ethanol according to the weight ratio of the fired fluorescent powder to absolute ethanol as 1:1.5, ball mill and mix in a planetary ball mill at a speed of 150r/min for 24 hours, and dry the ball mill in an oven at 100°C After drying for 24 hours, the dried material was sieved to obtain the BaTiO ₃ :0.002Pr fluorescent material fired in a CO reducing atmosphere.

Example 4

Chemically pure or analytically pure strontium carbonate SrCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Sr:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/min for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed by 5g each, and pressed into a Φ22mm×3mm disc under 150MPa uniaxial pressure. The disc is placed in an alumina crucible, placed in a sealed corundum ceramic tube, and N ₂ : H ₂ = 9:1 mixed atmosphere, the total flow rate is 100ml/min, the temperature is raised to 1200°C at 10°C/min, kept for 2 to 3 hours for firing, and after cooling, the fired fluorescent powder is obtained. The weight ratio of water to ethanol is 1:1.5, adding absolute ethanol, ball milling and mixing in a planetary ball mill at a speed of 150r/min for 24 hours, and drying the ball mill in an oven at 100°C for 24 hours _. SrTiO ₃ :0.002Pr fluorescent material fired in mixed reducing atmosphere of /H ₂ .

Example 5

Chemically pure or analytically pure strontium carbonate SrCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Sr:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/min for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed at 5g per portion, pressed into a disc of Φ22mm×3mm under 150MPa uniaxial pressure, placed in an alumina crucible, placed in a sealed corundum ceramic tube, and fed with N ₂ : H ₂ =1 : 9 mixed atmosphere, the total flow rate is 100ml/min, the temperature is raised to 1200°C at 10°C/min, the heat preservation is fired for 3 hours, and the fired fluorescent powder is obtained after cooling, according to the weight of the fired fluorescent powder and absolute ethanol Add absolute ethanol at a ratio of 1:1.5, ball mill and mix in a planetary ball mill at a speed of 150r/min for 24 hours, and dry the ball mill in an oven at 100°C for 24 hours. After the dried material is sieved, it can be mixed in N ₂ /H ₂ SrTiO ₃ :0.002Pr fluorescent material fired in reducing atmosphere.

Example 6

Chemically pure or analytically pure strontium carbonate SrCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Sr:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/min for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed by 5g each, pressed into a disc of Φ22mm×3mm under 150MPa uniaxial pressure, placed in an alumina crucible, placed in a sealed corundum ceramic tube, and fed with N ₂ : H ₂ =9 : 1 mixed atmosphere, the total flow rate is 300ml/min, the temperature is raised to 1200°C at 10°C/min, and the heat preservation is fired for 3 hours to obtain the fired phosphor material, according to the weight ratio of the fired phosphor powder to absolute ethanol Add absolute ethanol at a ratio of 1:1.5, ball mill and mix in a planetary ball mill at a speed of 150r/min for 24 hours, dry the ball mill in an oven at 100°C for 24 hours, and sieve the dried material to obtain a N ₂ /H ₂ mixed reducing atmosphere Sintered SrTiO ₃ :0.002Pr fluorescent material.

Example 7

Chemically pure or analytically pure strontium carbonate SrCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Sr:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/min for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed according to 5g per portion, pressed into a disc of Φ22mm×3mm under 150MPa uniaxial pressure, placed in an alumina crucible, put into a sealed corundum ceramic tube, and filled with pure _N2 atmosphere, the total flow rate to 100ml/min, raise the temperature to 1200°C at 10°C/min, keep it warm for 3 hours and burn it, and obtain the fired phosphor material after cooling, add anhydrous Ethanol, ball milled and mixed in a planetary ball mill at a speed of 150r/min for 24 hours, and the ball mill was dried in an oven at 100°C for 24 hours. After _the dried material was sieved, SrTiO ₃ :0.002Pr fluorescent Material.

Example 8

Chemically pure or analytically pure strontium carbonate SrCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Sr:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/min for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed according to 5g each, and pressed into a Φ22mm×3mm disc under 150MPa uniaxial pressure, placed in an alumina crucible, put into a sealed corundum ceramic tube, and filled with pure H ₂ atmosphere, the total flow rate to 100ml/min, raise the temperature to 1200°C at 10°C/min, keep it warm for 3 hours and burn it, and obtain the fired phosphor material after cooling, add anhydrous Ethanol, ball milled and mixed in a planetary ball mill at a speed of 150r/min for 24 hours, and the ball mill was dried in an oven _{at 100°C for 24 hours, and the dried material was sieved to obtain SrTiO 3 :} 0.002Pr fluorescent Material.

Example 9

Chemically pure or analytically pure calcium carbonate CaCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Ca:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/min for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed according to 5g each, and pressed into a Φ22mm×3mm disc under 150MPa uniaxial pressure, placed in an alumina crucible, put into a sealed corundum ceramic tube, and filled with pure H ₂ atmosphere, the total flow rate to 100ml/min, raise the temperature to 1200°C at 10°C/min, keep it warm for 3 hours and burn it, and obtain the fired phosphor material after cooling, add anhydrous Ethanol, ball milled and mixed in a planetary ball mill at a speed of 150r/min for 24 hours, and the ball mill was dried in an oven at 100°C for 24 hours, and _the dried material was sieved to obtain CaTiO ₃ :0.002Pr fluorescent Material.

Example 10

Using chemically pure or analytically pure calcium carbonate CaCO ₃ , titanium dioxide TiO ₂ , hydroxide Al(OH ₃ ) ₃ and praseodymium nitrate Pr(NO ₃ ) ₃ as raw materials, the atomic ratio is Ca:Ti:Pr:Al 1:1 : 0.002: 0.25 Weigh each raw material to prepare the batching material, the mixture is put into the agate ball mill jar of 200ml, and the weight ratio of the mixture and the agate ball milling medium is 1: 1 to add the agate ball milling medium with the size ratio, press the mixture Add an appropriate amount of deionized water at a weight ratio of 1:1, mill in a planetary ball mill at a rotational speed of 200r/min for 4 hours, and dry the ball mill in an oven at 80°C for 24 hours. The drying material is weighed according to 5g per portion, pressed into a disc of Φ22mm×3mm under 150MPa uniaxial pressure, placed in a graphite crucible, heated to 1200°C at 10°C/min, kept for 3 hours, and obtained after cooling. To form fluorescent powder, add absolute ethanol according to the weight ratio of fired fluorescent powder and absolute ethanol as 1:1.5, ball mill and mix in a planetary ball mill with a rotation speed of 150r/min for 24 hours, and dry the ball abrasive in an oven at 100°C for 24 hours. Hours, after sieving the dried material, the CaTiO ₃ : 0.002Pr, 0.25Al fluorescent material fired in a CO reducing atmosphere is obtained.

Example 11

Chemically or analytically pure cyclohexane, polyethylene glycol octyl ether, praseodymium nitrate Pr(NO ₃ ) ₃ , strontium nitrate Sr(NO ₃ ) ₂ , butyl titanate, aluminum nitrate Al(NO ₃ ) ₃ and Acetylacetone is used as a raw material, and each raw material is weighed to prepare a batch according to the ratio of Sr:Ti:Pr:Al 1:1:0.002:0.25. Dissolve praseodymium nitrate Pr(NO ₃ ) ₃ in a 100ml beaker, add an appropriate amount of deionized water and heat until completely dissolved, adjust the pH to 3-4, and set the Pr ion concentration of the solution to 1.0mol/L. Add 100ml of cyclohexane, add 20ml of surfactant polyethylene glycol octyl ether under stirring condition, then add and mix 10ml of Pr(NO ₃ ) ₃ solution and appropriate amount of Sr(NO ₃ ) ₂ and Al(NO ₃ ) ₃ solution, add a small amount of isoamyl alcohol until the solution is transparent, and continue to stir for 30 minutes. Add butyl titanate for hydrolysis and polycondensation reaction, control the hydrolysis rate through the dispersion of water in the microemulsion, and finally form a uniform and transparent gel, dry the gel at 80°C, take out the dried dry gel and grind it to obtain The wet mixture used for firing, the mixture is placed in an alumina crucible, put into a sealed corundum ceramic tube, and pure H ₂ gas is introduced at a flow rate of 100ml/min, fired at 1100°C for 3 hours, and obtained after cooling Burn the fluorescent powder, add absolute ethanol according to the weight ratio of the fired fluorescent powder and absolute ethanol as 1:1.5, ball mill and mix in a planetary ball mill at a speed of 150r/min for 24 hours, and dry the ball mill in an oven at 100°C After 24 hours, the dried material was sieved to obtain the SrTiO ₃ : 0.002Pr, 0.25Al phosphor material fired in a reducing atmosphere of pure H ₂ .

Example 12

Chemically or analytically pure cyclohexane, polyethylene glycol octyl ether, praseodymium nitrate Pr(NO ₃ ) ₃ , strontium nitrate Sr(NO ₃ ) ₂ , butyl titanate, aluminum nitrate Al(NO ₃ ) ₃ and Acetylacetone is used as a raw material, and each raw material is weighed to prepare a batch according to the ratio of Sr:Ti:Pr:Al 1:1:0.002:0.25. Dissolve praseodymium nitrate Pr(NO ₃ ) ₃ in a 50ml beaker, add an appropriate amount of deionized water and heat until completely dissolved, adjust the pH to 3-4, and set the Pr ion concentration of the solution to 1.0mol/L. Add 100ml of cyclohexane, add 20ml of surfactant polyethylene glycol octyl ether under stirring condition, then add and mix 10ml of Pr(NO ₃ ) ₃ solution and appropriate amount of Sr(NO ₃ ) ₂ and Al(NO ₃ ) ₃ solution, add a small amount of isoamyl alcohol until the solution is transparent, and continue to stir for 30 minutes. Add butyl titanate for hydrolysis and polycondensation reaction, control the hydrolysis rate through the dispersion of water in the microemulsion, and finally form a uniform and transparent gel, dry the gel at 80°C, take out the dried dry gel and grind it to obtain The wet mixture for firing, the mixture is placed in a graphite crucible, the temperature is raised to 1100°C at 10°C/min, and the temperature is kept for 3 hours. Add absolute ethanol at a weight ratio of 1:1.5, ball mill and mix in a planetary ball mill at a speed of 150r/min for 24 hours, and dry the ball mill in an oven at 100°C for 24 hours. SrTiO ₃ : 0.002Pr, 0.25Al phosphor material.

Example 13

Chemically pure or analytically pure calcium carbonate CaCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Ca:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/min for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed according to 5g each, and pressed into a Φ22mm×3mm disc under 150MPa uniaxial pressure. Insulated in the air for 3 hours to obtain the phosphor powder that has not been post-treated in a reducing atmosphere. Then the fluorescent powder is ground into powder, put into a sealed carbon box and heat-preserved at 800° C. for 6 hours, and the obtained fluorescent powder is added with absolute ethanol according to the weight ratio of fluorescent powder and absolute ethanol as 1: 1.5. Mixed by ball milling in a 150r/min planetary ball mill for 24 hours, and dried in an oven at 100°C for 24 hours. After the dried material was sieved, the CaTiO ₃ :0.002Pr phosphor material that was annealed in a CO reducing atmosphere was obtained.

Example 14

Chemically pure or analytically pure strontium carbonate SrCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Sr:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/min for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed according to 5g each, and pressed into a Φ22mm×3mm disc under 150MPa uniaxial pressure. Insulated in the air for 3 hours to obtain the phosphor powder that has not been post-treated in a reducing atmosphere. Then the fluorescent powder is ground into powder, put into a sealed carbon box and heat-preserved at 850° C. for 6 hours, and the obtained fluorescent powder is added with absolute ethanol according to the weight ratio of fluorescent powder and absolute ethanol as 1: 1.5. Mixed by ball milling in a planetary ball mill at 150r/min for 24 hours, and dried in an oven at 100°C for 24 hours. After the dried material was sieved, the SrTiO ₃ :0.002Pr phosphor material that was annealed in a CO reducing atmosphere was obtained.

Example 15

Chemically pure or analytically pure barium carbonate BaCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Ba:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/mi for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed according to 5g each, and pressed into a Φ22mm×3mm disc under 150MPa uniaxial pressure. Insulate in the air for 2 to 3 hours to obtain the phosphor powder that has not been post-treated in a reducing atmosphere. Then the fluorescent powder is ground into powder, put into a sealed carbon box and heat-preserved at 900°C for 6 hours, the obtained fluorescent powder is added with absolute ethanol according to the weight ratio of fluorescent powder and absolute ethanol as 1:1.5, and the Mixed by ball milling in a planetary ball mill at 150r/min for 24 hours, and dried in an oven at 100°C for 24 hours. After the dried material was sieved, the BaTiO ₃ :0.002Pr phosphor material that was annealed in a CO reducing atmosphere was obtained.

Example 16

Chemically pure or analytically pure strontium carbonate SrCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Sr:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/min for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed according to 5g each, and pressed into a Φ22mm×3mm disc under 150MPa uniaxial pressure. Insulated in the air for 3 hours to obtain the phosphor powder that has not been post-treated in a reducing atmosphere. Then grind the fluorescent powder into powder, place it in an alumina crucible, put it into a sealed corundum ceramic tube, and pass it into a mixed atmosphere of N ₂ : H ₂ =9:1, with a total flow rate of 100ml/min and a temperature of 10°C/min. Heat up to 850°C for heat preservation for 6 hours, add absolute ethanol to the fluorescent powder material obtained after cooling according to the weight ratio of fluorescent powder material and absolute ethanol as 1:1.5, ball mill and mix in a planetary ball mill at a speed of 150r/min for 24 hours, ball mill The material was dried in an oven at 100°C for 24 hours, and the dried material was sieved to obtain the SrTiO ₃ :0.002Pr fluorescent material after treatment in a N ₂ /H ₂ mixed reducing atmosphere.

Example 17

Chemically pure or analytically pure strontium carbonate SrCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Sr:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/min for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed according to 5g per portion, and pressed into a Φ22mm×3mm disc under 150MPa uniaxial pressure. The disc is placed in an alumina crucible and placed in a high-temperature electric furnace to heat up to 1200°C at 10°C/min. Insulated in the air for 3 hours to obtain the phosphor powder that has not been post-treated in a reducing atmosphere. Then grind the fluorescent powder into powder, put it in an alumina crucible, put it into a sealed corundum ceramic tube, and pass it into a mixed atmosphere of N ₂ : H ₂ =1:9, with a total flow rate of 100ml/min and a temperature of 10°C/min. Heat up to 850°C for heat preservation for 6 hours, add absolute ethanol to the fluorescent powder material obtained after cooling according to the weight ratio of fluorescent powder material and absolute ethanol as 1:1.5, ball mill and mix in a planetary ball mill at a speed of 150r/min for 24 hours, ball mill The material was dried in an oven at 100°C for 24 hours, and the dried material was sieved to obtain the SrTiO ₃ :0.002Pr fluorescent material after treatment in a N ₂ /H ₂ mixed reducing atmosphere.

Example 18

Chemically pure or analytically pure strontium carbonate SrCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Sr:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/min for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed according to 5g per portion, and pressed into a Φ22mm×3mm disc under 150MPa uniaxial pressure. The disc is placed in an alumina crucible and placed in a high-temperature electric furnace to heat up to 1200°C at 10°C/min. Insulated in the air for 3 hours to obtain the phosphor powder that has not been post-treated in a reducing atmosphere. Then grind the fluorescent powder into powder, place it in an alumina crucible, put it into a sealed corundum ceramic tube, and pass it into a mixed atmosphere of N ₂ : H ₂ =9:1, with a total flow rate of 300ml/min and a temperature of 10°C/min. Heat up to 850°C for heat preservation for 6 hours, add absolute ethanol to the fluorescent powder material obtained after cooling according to the weight ratio of fluorescent powder material and absolute ethanol as 1:1.5, ball mill and mix in a planetary ball mill at a speed of 150r/min for 24 hours, ball mill The material was dried in an oven at 100°C for 24 hours, and the dried material was sieved to obtain the SrTiO ₃ :0.002Pr fluorescent material after treatment in a N ₂ /H ₂ mixed reducing atmosphere.

Example 19

Chemically pure or analytically pure strontium carbonate SrCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Sr:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/min for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed according to 5g per portion, and pressed into a Φ22mm×3mm disc under 150MPa uniaxial pressure. The disc is placed in an alumina crucible and placed in a high-temperature electric furnace to heat up to 1200°C at 10°C/min. Insulated in the air for 3 hours to obtain the phosphor powder that has not been post-treated in a reducing atmosphere. Then grind the fluorescent powder into powder, place it in an alumina crucible, put it into a sealed corundum ceramic tube, feed pure _N2 gas with a total flow rate of 100ml/min, and heat it up to 850°C at 10°C/min for 6 hours. After cooling, add absolute ethanol to the fluorescent powder material obtained after cooling according to the weight ratio of fluorescent powder material and absolute ethanol as 1:1.5, ball mill and mix in a planetary ball mill at a speed of 150r/min for 24 hours, and dry the ball mill in an oven at 100°C After 24 hours, the dried material was sieved to obtain the SrTiO ₃ :0.002Pr fluorescent material after treatment in a pure N ₂ atmosphere.

Example 20

Chemically pure or analytically pure strontium carbonate SrCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Sr:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/min for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed according to 5g per portion, and pressed into a Φ22mm×3mm disc under 150MPa uniaxial pressure. The disc is placed in an alumina crucible and placed in a high-temperature electric furnace to heat up to 1200°C at 10°C/min. Insulated in the air for 3 hours to obtain the phosphor powder that has not been post-treated in a reducing atmosphere. Then grind the fluorescent powder into powder, place it in an alumina crucible, put it into a sealed corundum ceramic tube, feed pure _H2 gas with a total flow rate of 100ml/min, and heat it at 10°C/min to 850°C for 6 hours. After cooling, add absolute ethanol to the fluorescent powder material obtained after cooling according to the weight ratio of fluorescent powder material and absolute ethanol as 1:1.5, ball mill and mix in a planetary ball mill at a speed of 150r/min for 24 hours, and dry the ball mill in an oven at 100°C After 24 hours, the dried material was sieved to obtain the SrTiO ₃ :0.002Pr fluorescent material post-treated in a pure H ₂ atmosphere.

Example 21

Chemically pure or analytically pure calcium carbonate CaCO ₃ , titanium dioxide TiO ₂ and praseodymium nitrate Pr(NO ₃ ) ₃ are used as raw materials, and the atomic ratio of Ca:Ti:Pr is 1:1:0.002. Put the material into a 200ml agate ball mill jar, add the agate ball milling medium with a size ratio according to the weight ratio of the mixture and the agate ball milling medium as 1:1, add an appropriate amount according to the weight ratio of the mixture and deionized water as 1:1 Deionized water was used for ball milling in a planetary ball mill at a controlled speed of 200r/min for 4 hours, and the ball mill was dried in an oven at 80°C for 24 hours. The drying material is weighed according to 5g each, and pressed into a Φ22mm×3mm disc under 150MPa uniaxial pressure. The disc is placed in an alumina crucible and placed in a high-temperature electric furnace at 10°C/min. ℃, keep warm in the air for 2-3 hours, and obtain the phosphor powder that has not been post-treated in the reducing atmosphere. Then grind the fluorescent powder into powder, place it in an alumina crucible, put it into a sealed corundum ceramic tube, feed pure _H2 gas with a total flow rate of 100ml/min, and heat it at 10°C/min to 850°C for 6 hours. After cooling, the fluorescent powder material is obtained by adding absolute ethanol according to the weight ratio of the fluorescent powder material and absolute ethanol as 1:1.5, ball milling and mixing in a planetary ball mill at a speed of 150r/min for 24 hours, and the ball grinding material is dried in an oven at 100°C for 24 hours. Hours, the dried material is sieved to obtain CaTiO ₃ :0.002Pr fluorescent material after treatment in pure H ₂ atmosphere.

Example 22

Using chemically pure or analytically pure calcium carbonate CaCO ₃ , titanium dioxide TiO ₂ , hydroxide Al(OH ₃ ) ₃ and praseodymium nitrate Pr(NO ₃ ) ₃ as raw materials, the atomic ratio is Ca:Ti:Pr:Al 1:1 : 0.002: 0.25 Weigh each raw material to prepare the batching material, the mixture is put into the agate ball mill jar of 200ml, and the weight ratio of the mixture and the agate ball milling medium is 1: 1 to add the agate ball milling medium with the size ratio, press the mixture Add an appropriate amount of deionized water at a weight ratio of 1:1, mill in a planetary ball mill at a rotational speed of 200r/min for 4 hours, and dry the ball mill in an oven at 80°C for 24 hours. The drying material is weighed according to 5g each, and pressed into a Φ22mm×3mm disc under 150MPa uniaxial pressure. Insulated in the air for 3 hours to obtain the phosphor powder that has not been post-treated in a reducing atmosphere. Then the fluorescent powder is ground into powder, put into a sealed carbon box and heat-preserved at 800° C. for 6 hours, and the obtained fluorescent powder is added with absolute ethanol according to the weight ratio of fluorescent powder and absolute ethanol as 1: 1.5. The ball mill was mixed in a 150r/min planetary ball mill for 24 hours, and the ball mill was dried in an oven at 100°C for 24 hours. After the dried material was sieved, the CaTiO ₃ : 0.002Pr, 0.25Al phosphor material that was annealed in a CO reducing atmosphere was obtained.

Example 23

Chemically or analytically pure cyclohexane, polyethylene glycol octyl ether, praseodymium nitrate Pr(NO ₃ ) ₃ , strontium nitrate Sr(NO ₃ ) ₂ , butyl titanate, aluminum nitrate Al(NO ₃ ) ₃ and Acetylacetone is used as a raw material, and each raw material is weighed to prepare a batch according to the ratio of Sr:Ti:Pr:Al 1:1:0.002:0.25. Dissolve praseodymium nitrate Pr(NO ₃ ) ₃ in a 100ml beaker, add an appropriate amount of deionized water and heat until completely dissolved, adjust the pH to 4-5, and set the Pr ion concentration of the solution to 1.0mol/L. Add 100ml of cyclohexane, add 20ml of surfactant polyethylene glycol octyl ether under stirring condition, then add and mix 5ml of Pr(NO ₃ ) ₃ solution and appropriate amount of Sr(NO ₃ ) ₂ and Al(NO ₃ ) ₃ solution, add a small amount of isoamyl alcohol until the solution is transparent, and continue to stir for 30 minutes. Add butyl titanate for hydrolysis and polycondensation reaction, control the hydrolysis rate through the dispersion of water in the microemulsion, and finally form a uniform and transparent gel, dry the gel at 100°C, take out the dried dry gel and grind it to obtain The wet mixture for firing, the mixture is placed in an alumina crucible, placed in a high-temperature electric furnace to raise the temperature to 1050°C at 10°C/min, and kept in the air for 3 hours to obtain a phosphor powder that has not been post-treated in a reducing atmosphere . Then grind the fluorescent powder into powder, put it into a sealed corundum ceramic tube, feed pure _H2 gas, the flow rate is 100ml/min, and heat it at 800°C for 6 hours. The weight ratio of water to ethanol is 1:1.5, add absolute ethanol, ball mill and mix for 24 hours in a planetary ball mill with a rotating speed of 150r/min, dry the ball mill in an oven at 100°C for 24 hours, and sieve the dried material to obtain pure H ₂ Atmosphere annealed SrTiO ₃ :0.002Pr, 0.25Al phosphor material.

Example 24

Chemically or analytically pure cyclohexane, polyethylene glycol octyl ether, praseodymium nitrate Pr(NO ₃ ) ₃ , strontium nitrate Sr(NO ₃ ) ₂ , butyl titanate, aluminum nitrate Al(NO ₃ ) ₃ and Acetylacetone is used as a raw material, and each raw material is weighed to prepare a batch according to the ratio of Sr:Ti:Pr:Al 1:1:0.002:0.25. Dissolve praseodymium nitrate Pr(NO ₃ ) ₃ in a 100ml beaker, add an appropriate amount of deionized water and heat until completely dissolved, adjust the pH to 4-5, and set the Pr ion concentration of the solution to 1.0mol/L. Add 100ml of cyclohexane, add 20ml of surfactant polyethylene glycol octyl ether under stirring condition, then add and mix 5ml of Pr(NO ₃ ) ₃ solution and appropriate amount of Sr(NO ₃ ) ₂ and Al(NO ₃ ) ₃ solution, add a small amount of isoamyl alcohol until the solution is transparent, and continue to stir for 30 minutes. Add butyl titanate for hydrolysis and polycondensation reaction, control the hydrolysis rate through the dispersion of water in the microemulsion, and finally form a uniform and transparent gel, dry the gel at 100°C, take out the dried dry gel and grind it to obtain The wet mixture used for firing is placed in a high-temperature electric furnace and raised to 1050°C at a rate of 10°C/min, and kept in air for 2 to 3 hours to obtain phosphor powder without post-treatment in a reducing atmosphere. Then the fluorescent powder is ground into powder, put into a graphite crucible, and heat-preserved at 800° C. for 6 hours, and the phosphor material obtained after cooling is added with absolute ethanol according to the weight ratio of the fluorescent powder and absolute ethanol as 1:1.5, and then Ball milling and mixing in a planetary ball mill at a rotational speed of 150r/min for 24 hours. The ball mill material was dried in an oven at 100°C for 24 hours. After the dried material was sieved, the SrTiO ₃ : 0.002Pr, 0.25Al phosphor material annealed in a CO atmosphere was obtained.

Claims (10)

1. high brightness red alkaline earth titanate fluorescent powder, the composition formula that it is characterized in that filling a prescription is: ATiO ₃: xRe, yM; Wherein A is a kind of of alkaline earths Ca, Sr, Ba element, promptly with CaTiO ₃, SrTiO ₃Or BaTiO ₃Alkaline earth titanate is a luminous host; Re is a Doped Rare Earth luminescence center ion, is among cerium Ce, praseodymium Pr, europium Eu, terbium Tb, erbium Er or the thulium Tm one or both; 0＜x＜0.15,0≤y＜0.4; M is the supplementary doping element, is among boron, aluminium Al, gallium Ga, indium In, lithium Li, sodium Na or the potassium K one or more.

2. the preparation method of a high brightness red alkaline earth titanate fluorescent powder as claimed in claim 1 is characterized in that: may further comprise the steps:

1) preparation of solid phase batch mixing method or wet-chemical reaction method is burnt till and is used compound;

2) high temperature reduction atmosphere firing process or reducing atmosphere aftertreatment technology burn till processing to burning till with compound, obtain to burn till the fluorescence powder;

3) be 1: 0.5～2.5 adding dehydrated alcohols by the weight ratio of burning till fluorescence powder and dehydrated alcohol, at rotating speed is that ball milling mixes 4～24h in 50～250r/min planetary ball mill, the ball milling material was dried 6～24 hours in 50～150 ℃ of baking ovens, after oven dry material sieves promptly.

3. preparation method according to claim 2 is characterized in that: described solid phase batch mixing method is: the compound with alkaline earth carbonate, titanium dioxide, rare earth nitrate, supplementary doping element M is a raw material, is ATiO by atomic ratio ₃: xRe, yM take by weighing each raw material, and wherein A is Ca, Sr or Ba, and Re is a Doped Rare Earth luminescence center ion, are among cerium Ce, praseodymium Pr, europium Eu, terbium Tb, erbium Er or the thulium Tm one or both; 0＜x＜0.15,0≤y＜0.4; M is the supplementary doping element, is among boron, aluminium Al, gallium Ga, indium In, lithium Li, sodium Na or the potassium K one or more; Weight ratio by raw material and deionized water is 1: 0.5～1.5, adds deionized water, and ball milling mixes 2～36h in rotating speed 200r/min planetary ball mill, and the ball milling material was dried 6～36 hours in 50～150 ℃ of baking ovens, promptly got to burn till to use compound.

4. preparation method according to claim 2, it is characterized in that: described wet-chemical reaction method is: adopting the compound of alkaline earth nitrate, Butyl Phthalate, rare earth nitrate and supplementary doping element M is raw material, and is assistant chemical reagent with hexanaphthene, polyoxyethylene glycol Octyl Ether and methyl ethyl diketone; By atomic ratio is ATiO ₃: xRe, yM take by weighing each raw material, and wherein A is Ca, Sr or Ba, and Re is a Doped Rare Earth luminescence center ion, are among cerium Ce, praseodymium Pr, europium Eu, terbium Tb, erbium Er or the thulium Tm one or both; 0＜x＜0.15,0≤y＜0.4; M is the supplementary doping element, is among boron, aluminium Al, gallium Ga, indium In, lithium Li, sodium Na or the potassium K one or more; The rare earth nitrate raw material is added appropriate amount of deionized water, and being mixed with rare earth ion concentration is that 0.5～2.0mol/L, pH are 2～6 rare earth nitrate solution; Get 50～150ml hexanaphthene, agitation condition adds 10～50ml surfactant polyethylene Octyl Ether down, add the nitric acid diluent of pressing atom proportioning blended rare earth nitrate solution 2～10ml, alkaline earth nitrate solution and supplementary doping element compound then, add again primary isoamyl alcohol to solution transparent till, continue to stir 10～60 minutes; The butyl (tetra) titanate raw material that adds again by the proportioning weighing is hydrolyzed and polycondensation, control its hydrolysis rate by the dissemination of water in the microemulsion, form the gelinite of homogeneous transparent at last, it 50～250 ℃ of dryings, is promptly got to burn till after the exsiccant xerogel grinds and use compound.

5. preparation method according to claim 3 is characterized in that: the alkaline earth carbonate in the described solid phase batch mixing method is CaCO ₃, SrCO ₃Or BaCO ₃In one or more.

6. preparation method according to claim 4 is characterized in that: the alkaline earth nitrate in the described wet-chemical reaction method is Ca (NO ₃) ₂, Sr (NO ₃) ₂Or Ba (NO ₃) ₂In one or more.

7. according to claim 3 or 4 described preparation methods, it is characterized in that: described rare earth nitrate is Pr (NO ₃) ₃, Ce (NO ₃) ₃, Eu (NO ₃) ₃, Tb (NO ₃) ₃, Er (NO ₃) ₃Or Tm (NO ₃) ₃In one or both.

8. according to claim 3 or 4 described preparation methods, it is characterized in that: the compound of described supplementary doping element M is oxide compound, oxyhydroxide or the carbonate cpds of supplementary doping element M.

9. preparation method according to claim 2 is characterized in that: described high temperature reduction atmosphere firing process is: will burn till plumbago crucible or the corundum matter tube furnace of directly putting into favorable sealing property with compound, logical CO, N ₂, H ₂Or NH ₃In a kind of gas or its mixed gas, begin to be warming up to 800～1400 ℃ from room temperature with 10 ℃/min, carried out sufficient pyroreaction in 1～6 hour in the firing temperature insulation of setting, after insulation finishes, keep the reducing atmosphere furnace cooling to obtain to burn till the fluorescence powder to room temperature.

10. preparation method according to claim 2, it is characterized in that: described reducing atmosphere aftertreatment technology is: will burn till with compound and put into high-temperature electric resistance furnace, begin to be warming up to 1000～1400 ℃ from room temperature with 10 ℃/min, carried out sufficient pyroreaction in 1～6 hour in the firing temperature insulation of setting, insulation finishes the back furnace cooling and obtains fluorescent material; Then fluorescent material is put into the plumbago crucible or the corundum matter tube furnace of favorable sealing property, logical CO, N ₂, H ₂Or NH ₃In a kind of gas or its mixed gas, begin to be warming up to 600～1100 ℃ from room temperature with 10 ℃/min, carried out sufficient reducing atmosphere aftertreatment reaction in 2～10 hours in the post-processing temperature insulation of setting, insulation finishes the back and keeps the reducing atmosphere furnace cooling to obtain to burn till the fluorescence powder to room temperature.