CN112342020A - Holmium-ytterbium co-doped bismuth titanate composite phosphor powder and preparation method thereof - Google Patents

Holmium-ytterbium co-doped bismuth titanate composite phosphor powder and preparation method thereof Download PDF

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CN112342020A
CN112342020A CN201910728167.2A CN201910728167A CN112342020A CN 112342020 A CN112342020 A CN 112342020A CN 201910728167 A CN201910728167 A CN 201910728167A CN 112342020 A CN112342020 A CN 112342020A
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bismuth titanate
sol
composite phosphor
phosphor powder
holmium
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高锋
韦悦周
刘海飞
王友彬
李新生
何春林
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Guangxi University
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Abstract

The invention discloses holmium-ytterbium co-doped bismuth titanate composite phosphor powder, wherein the chemical structural formula of the composite phosphor is Bim‑x‑ yHoxYbyTinOp,0<x≤m，0<y is less than or equal to m, which at least contains Bi4Ti3O12And Bi2Ti2O7Two bismuth titanate phases. The powder presents a honeycomb microstructure, has excellent light absorption and high-efficiency up-conversion luminescence performance, can generate bright up-conversion fluorescence under the excitation of low-power infrared light, and has great application potential in the aspects of laser media, anti-counterfeiting marks, infrared light detection, fluorescence display and the like. Accordingly, the inventor also establishes a corresponding preparation method, namely a sol-gel-combustion method, the method comprises three main steps of sol synthesis, gel preparation and combustion, and the preparation process is simple, efficient and energy-saving.

Description

Holmium-ytterbium co-doped bismuth titanate composite phosphor powder and preparation method thereof
Technical Field
The invention belongs to the technical field of phosphors and composite functional materials, and particularly relates to holmium-ytterbium co-doped bismuth titanate composite phosphor powder and a preparation method thereof.
Background
The rare earth ion doped up-conversion fluorescent material is applied to the aspects of fluorescent marks, laser media, laser anti-counterfeiting, solar cells, photo-thermal physical therapy and the like, particularly the rare earth ion doped fluorohalide up-conversion fluorescent material has lower phonon energy, lower non-radiative relaxation rate, higher up-conversion luminous efficiency and wider application because the host material has lower phonon energy, such as Er3+、Yb3+、Tm3+Doped or co-doped NaYF4(Nature 463(2010) 1061-1065). However, the fluorohalide has poor physical and chemical property stability, is easy to deliquesce and deteriorate in humid air, and seriously affects the up-conversion fluorescence property of the material. Therefore, the search for an oxide phosphor having good stability is still one of the hot spots in the current research of light emitting materials.
Bismuth titanate is a large family of complex oxides, members of which include Bi4Ti3O12、Bi2Ti2O7、Bi20TiO32、Bi12TiO20、Bi2Ti4O11Etc. wherein Bi4Ti3O12And Bi2Ti2O7Most commonly. Rare earth doped Bi4Ti3O12Has a series of special properties of ferroelectric, dielectric, photoluminescence, photovoltaic effect and the like since La3+Doped Bi4Ti3O12The excellent ferroelectric properties of thin films have been reported (Nature 401(1999)682-684) after rare earth doping with Bi4Ti3O12Has become the focus of attention in the ferroelectric field. Rare earth ion Er3+、Er3+-Yb3+、Tm3+-Yb3+、Er3+-Tm3+-Yb3+And Ho3+-Yb3+Doped Bi4Ti3O12All reported. Because of different types of doped rare earth ions, the materials have different up-conversion fluorescence spectrum properties, infrared light can be converted into different colors of light such as red, green and blue, and the color index can be adjusted by controlling the doping amount of various rare earth ions. However, rare earth doped Bi of the prior art4Ti3O12The phosphor exists in the form of a fluorescent thin film, is rarely powdered, and has no Ho3+-Yb3+Doped Bi4Ti3O12The report of the powder limits the application of the powder in the fields of laser materials, anti-counterfeiting materials and fluorescent marking materials. Bi2Ti2O7The phase has good dielectric property and photocatalysis property, and is widely used in dynamic random access memory and gate circuit. Bi20TiO32Is also a material with photocatalytic performance, and often forms a multi-phase structure with other titanate compounds. Bismuth titanate is a compound with relatively stable physicochemical properties, is a phosphor matrix material with excellent performance, and is also a research object of important attention in the development of multifunctional photoelectric materials.
The up-conversion rare earth ions mainly comprise Er3+、Ho3+、Tm3+、Sm3+And Yb3+Wherein Er3+、Ho3+、Tm3+、Sm3+Usually as the luminescence center ion, and Yb3+Typically as sensitizing ions. These ions have a specific 4f layer electronic configuration, showing their specific properties and applications in the field of photoluminescence. At present, Ho3+-Yb3+Co-doped Bi4Ti3O12Up-conversion fluorescent film (Journal of Applied Physics 109(2011)123101), Bi2Ti2O7Up-conversion fluorescent films (J.Am.Ceram. Soc., 96(2013) 3768-3774) have been reported, however, Ho3+、Yb3+Co-doped bismuth titanate composite phosphor powder (made of Bi)4Ti3O12、Bi2Ti2O7、Bi20TiO32Two-phase or three-phase composition) has not been reported, and synthesis of Bi by sol-gel-combustion has not been reported4Ti3O12、Bi2Ti2O7And Bi20TiO32And (5) reporting materials.
Disclosure of Invention
The invention aims to solve the technical problem of providing holmium-ytterbium co-doped bismuth titanate composite phosphor powder with adjustable structure and stable performance and a preparation method thereof, wherein the obtained product has excellent light absorption and high-efficiency up-conversion luminescence performance, and the preparation process is simple, high-efficiency and energy-saving.
In order to solve the technical problems, the invention adopts the following technical scheme:
the holmium-ytterbium co-doped bismuth titanate composite phosphor powder has a chemical structural formula of Bim-x- yHoxYbyTinOp(abbreviated as BTO: Ho, Yb or BTO: x Ho, y Yb), wherein m, n, p represent Bi respectively4Ti3O12、Bi2Ti2O7、Bi20TiO32、Bi12TiO20、Bi2Ti4O11Ion numbers of Bi, Ti and O in bismuth titanate phase, wherein x represents Ho3+Number of ions of (2) at a value of 0<x is less than or equal to m, and y represents Yb3+Number of ions of (2) at a value of 0<y is less than or equal to m; which at least comprises Bi4Ti3O12And Bi2Ti2O7Two bismuth titanate phases.
The holmium-ytterbium co-doped bismuth titanate composite phosphor powder also comprises Bi20TiO32A bismuth titanate phase.
The composite phosphor powder is a solid solution having stable properties and formed of bismuth titanate phases constituting the composite phosphor, and has a honeycomb-like microstructure.
The preparation method of the holmium-ytterbium co-doped bismuth titanate composite phosphor powder is a sol-gel-combustion method, and comprises three main steps of sol synthesis, gel preparation and combustion.
The preparation method comprises the following steps:
(1) nitrate, chloride or oxide of Bi, Ho and Yb is used as precursor of Bi, Ho and Yb, titanium-containing organic matter or inorganic matter is used as precursor of Ti, and the proportion is Bi4Ti3O12、Bi2Ti2O7、Bi20TiO32、Bi12TiO20、Bi2Ti4O11One or more ofDesigning a plurality of types;
(2) preparing a solution by using glacial acetic acid or inorganic acid and an organic solvent as solvents and acetylacetone as a stabilizer;
(3) taking the precursor obtained in the step (1) as a solute and the solution obtained in the step (2) as a solvent, and mixing and stirring the two solutions uniformly to obtain sol;
(4) heating the sol obtained in the step (3) to volatilize the solvent to obtain gel;
(5) igniting the gel obtained in the step (4), and then fully burning to generate a bismuth titanate compound (like paper ash, which is easy to break);
(6) and (5) grinding the bismuth titanate compound obtained in the step (5) to obtain the holmium-ytterbium co-doped bismuth titanate composite phosphor powder.
The nitrate is (hydrated) bismuth nitrate, (hydrated) holmium nitrate, and (hydrated) ytterbium nitrate; the titanium-containing organic or inorganic substance is butyl titanate, titanium isopropoxide and titanium dioxide; the inorganic acid is nitric acid or aqua regia, and the organic solvent is ethylene glycol monomethyl ether, ethanol, methanol or chloroform.
The volume ratio of the glacial acetic acid to the ethylene glycol monomethyl ether is 0.1-20, and the volume mass ratio of the acetylacetone to the butyl titanate is 0.1-5.
In the step (3), the temperature is 10-100 ℃, the mixing and stirring speed is 20-1500 r/min, the mixing and stirring time is 5-480 min, and the concentration of the obtained sol (Bi is used as the reference of Bi)4Ti3O12、Bi2Ti2O7、Bi20TiO32、Bi12TiO20、Bi2Ti4O11Any one of the above) is 0.01 to 0.5 mol/L; in the step (4), the heating temperature of the sol is 25-250 ℃, and the heating time is 10-300 min.
In the step (3), the temperature is 20-70 ℃ during mixing, the mixing and stirring speed is 200-750 r/min, the mixing and stirring time is 10-150 min, and the concentration of the obtained sol is 0.04-0.2 mol/L; in the step (4), the heating temperature of the sol is 60-160 ℃, and the heating time is 30-200 min.
In the step (5), the gel is ignited by adopting open fire, such as matches, lighters or other ignition tools; the ignition can be directly carried out during ignition, and the ignition can also be carried out after a small amount of alcohol is poured. Before the gel is ignited, a corundum crucible can be used as a combustion reaction vessel, and other heat-resisting devices such as a beaker and the like can also be used as a reactor. However, the combustion preparation cannot be carried out after the heating device is slowly heated to the ignition point, which results in insufficient organic matter for supporting the combustion reaction in the combustion process, and more impurities, especially C impurities, are generated in the product. In the step (6), the grinding is carried out by finger-pinching, mortar-grinding, mechanical-grinding or ethanol solvent-dispersing to obtain dispersed and fine particles.
Aiming at the current Ho3+、Yb3+The co-doped bismuth titanate composite phosphor powder has the problem of technical blank, and the inventor develops the holmium-ytterbium co-doped bismuth titanate composite phosphor powder, wherein the chemical structural formula of the composite phosphor is Bim-x- yHoxYbyTinOp,0<x≤m，0<y is less than or equal to m, which at least contains Bi4Ti3O12And Bi2Ti2O7Two bismuth titanate phases. The product is holmium-ytterbium co-doped bismuth titanate composite phosphor powder with adjustable structure and stable performance, and mainly comprises Bi4Ti3O12And Bi2Ti2O7Also contains a small amount of Bi20TiO32And (4) phase(s). The powder presents a honeycomb microstructure, has excellent light absorption and high-efficiency up-conversion luminescence performance, and can convert 980nm infrared light into 530-580 nm green light and 630-690 nm red light. Under 0.1W low-power infrared excitation, bright spots on the sample surface can still be observed. Particularly, the phase structure, light absorptivity, up-conversion fluorescence intensity and up-conversion life of the phosphor can be changed by changing Ho3+、Yb3+The ion concentration is effectively adjusted. The invention relates to a bismuth titanate composite fluorescent powder, in particular to a bismuth titanate composite fluorescent powder, which is prepared by mixing various pure bismuth titanate phases, is prepared by a rapid combustion reaction and is compounded by different bismuth titanate phasesAnd (4) co-melting the components.
Compared with the prior art, the invention has the outstanding advantages that:
(1) the bismuth titanate composite phosphor powder has a unique honeycomb microstructure, good crystallization performance and high crystallinity. The bismuth titanate phases constituting the composite phosphor are formed into a solid solution phase during combustion, and are not simply mixed, and the properties thereof are stable.
(2) The fluorescent body has efficient up-conversion photoluminescence performance, can generate bright up-conversion fluorescence under the excitation of low-power infrared light, and has great application potential in the aspects of laser media, anti-counterfeiting marks, infrared light detection, fluorescence display and the like.
(3) The phosphor is prepared by adopting an efficient and energy-saving sol-gel-combustion method, the preparation process is simple, the preparation is carried out at a low temperature, the whole preparation process does not need high-temperature heat treatment, the phase transformation (within one minute or even within ten seconds) can be completed by natural combustion after the gel is ignited, and the production efficiency is high.
Drawings
FIG. 1 is an XRD pattern of BTO: Ho, Yb phosphor powder synthesized by the sol-gel-combustion method of the present invention, in which: (a) xHo, 0.2Yb, where x is 0, 0.02, 0.04, 0.06, 0.08 or 0.1; (c) 0.02Ho, yYb, where y is 0.1, 0.2, 0.3, 0.5, 0.7 or 0.9; (b) and (d) represent magnified images of diffraction in the 2 θ region of 36 ° to 41 ° for BTO: xHo, 0.2Yb, and BTO:0.02Ho, yYb, respectively.
FIG. 2 is a SEM photograph and EDS spectrum analysis result chart of BTO 0.02Ho, 0.5Yb phosphor powder, in which: (a) SEM images at low magnification; (b) SEM images at high magnification; (c) is the EDS spectrum at point 1 in (b); (d) is the EDS spectrum at point 2 in (b).
Fig. 3 is a graph comparing undoped BTO and doped BTO, where: (a) uv-vis-nir diffuse reflectance spectra of undoped BTO and doped BTO 0.02Ho, yYb (y 0.2, 0.5, 0.9); (b) undoped BTO and doped BTO 0.02Ho, yYb (y 0.2, 0.5, 0.9) [ F (R) hv]1/2And hv.
FIG. 4 shows the upconversion of the BTO Ho Yb phosphor powder of the present inventionEmission energy spectrum and green and red light emission band integrated intensity and Ho3+、Yb3+Graph of the relationship between concentrations, in which: (a) xHo, 0.2Yb of upconversion emission spectra; (c) 0.02Ho, yYb for BTO; (b) and (d) corresponding to the integrated intensities of green and red emission bands and Ho of the BTO: Ho, Yb phosphor powders in (a) and (b), respectively3+、Yb3+Graph of the relationship between concentrations.
FIG. 5 is a time relaxation curve of the fluorescence intensity converted at 551nm for BTO: Ho, Yb samples of the invention, in which: (a) xHo, 0.2Yb (x ═ 0.02, 0.04, 0.06, and 0.1) samples, (b) 0.02Ho, yYb (y ═ 0.2, 0.5, 0.7, and 0.9) samples.
Detailed Description
Example 1
This example is an example of a BTO 0.02Ho, 0.5Yb composite phosphor powder prepared by the following steps:
with 3.5290g of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O), 0.0165g of holmium nitrate hexahydrate (Ho (NO)3)3·6H2O), 0.4207g ytterbium nitrate hexahydrate (Yb (NO)3)3·6H2O), 1.8562g of butyl titanate (C)16H36O4Ti) as the precursor of Bi, Ho, Yb and Ti in the proportion of Bi4Ti3O12And (4) weighing. The precursors are used as solutes, 13ml of glacial acetic acid and 13ml of ethylene glycol monomethyl ether are used as solvents, 3.84ml of acetylacetone is used as a stabilizer, the analytically pure drugs and chemical reagents are mixed in a beaker, stirred for 30min at the room temperature of 500r/min on a constant temperature magnetic stirrer, and finally a small amount of ethylene glycol monomethyl ether is dropped to adjust the concentration of the solution, so that 30ml of sol with the concentration of 0.06mol/L is formed. The obtained sol was heated in a drying oven at 120 ℃ for 120min to obtain a gel. Igniting the gel with match, burning to obtain loose yellow-white product, and grinding to obtain final bismuth titanate composite phosphor powder.
Example 2
This example is an example of a BTO 0.04Ho, 0.2Yb composite phosphor powder prepared by the following steps:
3.8130g of pentahydrateBismuth nitrate (Bi (NO))3)3·5H2O), 0.0330g of holmium nitrate hexahydrate (Ho (NO)3)3·6H2O), 0.1683g ytterbium nitrate hexahydrate (Yb (NO)3)3·6H2O), 1.8562g of butyl titanate (C)16H36O4Ti) as the precursor of Bi, Ho, Yb and Ti, and the proportion can be according to Bi4Ti3O12And (4) weighing. The precursors are used as solutes, 13ml of glacial acetic acid and 13ml of ethylene glycol monomethyl ether are used as solvents, 1.92ml of acetylacetone is used as a stabilizer, the analytically pure drugs and chemical reagents are mixed in a beaker, stirred for 30min at the room temperature of 500r/min on a constant temperature magnetic stirrer, and finally a small amount of ethylene glycol monomethyl ether is dropped to adjust the concentration of the solution, so that 30ml of sol with the concentration of 0.06mol/L is formed. The obtained sol was heated in a drying oven at 150 ℃ for 90min to obtain a gel. The gel was ignited with a lighter and then burned sufficiently to obtain a loose yellowish white product, which was ground to obtain the final bismuth titanate composite phosphor powder.
Example 3
This example is an example of a BTO 0.04Ho, 0.7Yb composite phosphor powder prepared by the following steps:
with 6.3550g of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O), 0.0330g of holmium nitrate hexahydrate (Ho (NO)3)3·6H2O), 0.9818g ytterbium nitrate hexahydrate (Yb (NO)3)3·6H2O), 1.8562g of butyl titanate (C)16H36O4Ti) as the precursor of Bi, Ho, Yb and Ti, and the proportion can be according to Bi4Ti3O12And (4) weighing. The precursors are used as solutes, 18ml of glacial acetic acid and 8ml of ethylene glycol monomethyl ether are used as solvents, 1.75ml of acetylacetone is used as a stabilizer, the analytically pure drugs and chemical reagents are mixed in a beaker, stirred for 15min at the room temperature of 750r/min on a constant temperature magnetic stirrer, and finally a small amount of ethylene glycol monomethyl ether is dropped to adjust the concentration of the solution, so that 30ml of sol with the concentration of 0.1mol/L is formed. The obtained sol was heated in a drying oven at 250 ℃ for 240min to obtain a gel. Igniting the gel with igniter, and burning to obtain loose yellowish white productThe resultant was ground to obtain a final bismuth titanate composite phosphor powder.
Example 4
This example is an example of a BTO 0.02Ho, 0.5Yb composite phosphor powder prepared by the following steps:
with 11.7637g of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O), 0.0550g of holmium nitrate hexahydrate (Ho (NO)3)3·6H2O), 1.40233g ytterbium nitrate hexahydrate (Yb (NO)3)3·6H2O), 1.8562g of butyl titanate (C)16H36O4Ti) as the precursor of Bi, Ho, Yb and Ti, and the proportion can be according to Bi4Ti3O12And (4) weighing. The precursors are used as solutes, 4ml of glacial acetic acid and 24ml of ethylene glycol monomethyl ether are used as solvents, 3.84ml of acetylacetone is used as a stabilizer, the analytically pure drugs and chemical reagents are mixed in a beaker, stirred for 10min at the room temperature of 1500r/min on a constant temperature magnetic stirrer, and finally a small amount of ethylene glycol monomethyl ether is dropped to adjust the concentration of the solution, so that 30ml of sol with the concentration of 0.2mol/L is formed. The obtained sol was heated in a drying oven at 250 ℃ for 120min to obtain a gel. Igniting the gel with match, burning to obtain loose yellow-white product, and grinding to obtain final bismuth titanate composite phosphor powder.
Example 5
This example is an example of a BTO 0.02Ho, 0.5Yb composite phosphor powder prepared by the following steps:
with 29.4092g of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O), 0.1375g of holmium nitrate hexahydrate (Ho (NO)3)3·6H2O), 3.5058g ytterbium nitrate hexahydrate (Yb (NO)3)3·6H2O), 1.8562g of butyl titanate (C)16H36O4Ti) as the precursor of Bi, Ho, Yb and Ti, and the proportion can be according to Bi4Ti3O12And (4) weighing. Using the precursors as solute, 13ml glacial acetic acid and 13ml ethylene glycol methyl ether as solvent, 3.84ml acetylacetone as stabilizer, mixing the analytically pure medicines and chemical reagents in beaker, and then magnetic force at constant temperatureStirring the mixture for 150min at the room temperature of 200r/min on a stirrer, and finally dripping a small amount of ethylene glycol monomethyl ether to adjust the concentration of the solution to form 30ml of sol with the concentration of 0.5 mol/L. The obtained sol was heated in a drying oven at 60 ℃ for 240min to obtain a gel. After adding 5mL of alcohol into the gel, igniting the gel with a match and then fully burning the gel to obtain a loose yellowish white product, and grinding the product to obtain the final bismuth titanate composite phosphor powder.
Example 6
This example is an example of a BTO 0.04Ho, 0.2Yb composite phosphor powder prepared by the following steps:
with 3.8130g of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O), 0.0330g of holmium nitrate hexahydrate (Ho (NO)3)3·6H2O), 0.1683g ytterbium nitrate hexahydrate (Yb (NO)3)3·6H2O), 1.8562g of butyl titanate (C)16H36O4Ti) as the precursor of Bi, Ho, Yb and Ti, and the proportion can be according to Bi4Ti3O12And (4) weighing. The precursors are used as solutes, 19ml of glacial acetic acid and 7ml of ethylene glycol monomethyl ether are used as solvents, 0.48ml of acetylacetone is used as a stabilizer, the analytically pure drugs and chemical reagents are mixed in a beaker, stirred for 70min at the room temperature of 300r/min on a constant temperature magnetic stirrer, and finally a small amount of ethylene glycol monomethyl ether is dropped to adjust the concentration of the solution, so that 30ml of sol with the concentration of 0.06mol/L is formed. The obtained sol was heated in a drying oven at 240 ℃ for 30min to obtain a gel. The gel was ignited with a lighter and then burned sufficiently to obtain a loose yellowish white product, which was ground to obtain the final bismuth titanate composite phosphor powder.
Example 7
This example is an example of a BTO 0.02Ho, 0.9Yb composite phosphor powder prepared by the following steps:
with 1.5730g of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O), 0.0917g holmium nitrate hexahydrate (Ho (NO)3)3·6H2O), 1.2622g ytterbium nitrate hexahydrate (Yb (NO)3)3·6H2O), 2.0625g of butyl titanate (C)16H36O4Ti) as BiHo, Yb and Ti in Bi2Ti2O7And (4) weighing. The precursors are used as solutes, 8ml of glacial acetic acid and 18ml of ethylene glycol monomethyl ether are used as solvents, 2.1333ml of acetylacetone is used as a stabilizer, the analytically pure drugs and chemical reagents are mixed in a beaker, stirred on a constant temperature magnetic stirrer at the room temperature of 600r/min for 30min, and finally a small amount of ethylene glycol monomethyl ether is dropped to adjust the concentration of the solution, so that 30ml of sol with the concentration of 0.1mol/L is formed. The obtained sol was heated in a drying oven at 150 ℃ for 120min to obtain a gel. Igniting the gel with match, burning to obtain loose yellow-white product, and grinding to obtain final bismuth titanate composite phosphor powder.
Example 8
This example is an example of a BTO 0.06Ho, 0.4Yb composite phosphor powder prepared by the following steps:
with 2.2430g of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O), 0.2751g holmium nitrate hexahydrate (Ho (NO)3)3·6H2O), 0.5610g ytterbium nitrate hexahydrate (Yb (NO)3)3·6H2O), 2.0625g of butyl titanate (C)16H36O4Ti) as the precursor of Bi, Ho, Yb and Ti, and the proportion can be according to Bi2Ti2O7And (4) weighing. The precursors are used as solutes, 6ml of glacial acetic acid and 20ml of ethylene glycol monomethyl ether are used as solvents, 2.1333ml of acetylacetone is used as a stabilizer, the analytically pure drugs and chemical reagents are mixed in a beaker, stirred on a constant temperature magnetic stirrer at the room temperature of 500r/min for 40min, and finally a small amount of ethylene glycol monomethyl ether is dropped to adjust the concentration of the solution, so that 30ml of sol with the concentration of 0.1mol/L is formed. The obtained sol was heated in a drying oven at 250 ℃ for 120min to obtain a gel. Igniting the gel with match, burning to obtain loose yellow-white product, and grinding to obtain final bismuth titanate composite phosphor powder.
Example 9
This example is an example of a BTO 0.06Ho, 0.4Yb composite phosphor powder prepared by the following steps:
with 11.215g of nitric acid pentahydrateBismuth (Bi (NO)3)3·5H2O), 1.3755g holmium nitrate hexahydrate (Ho (NO)3)3·6H2O), 2.8050g ytterbium nitrate hexahydrate (Yb (NO)3)3·6H2O), 10.3125g of butyl titanate (C)16H36O4Ti) as the precursor of Bi, Ho, Yb and Ti, and the proportion can be according to Bi2Ti2O7And (4) weighing. The precursors are used as solutes, 8ml of glacial acetic acid and 18ml of ethylene glycol monomethyl ether are used as solvents, 1.6665ml of acetylacetone is used as a stabilizer, the analytically pure drugs and chemical reagents are mixed in a beaker, stirred for 20min at the room temperature of 600r/min on a constant temperature magnetic stirrer, and finally a small amount of ethylene glycol monomethyl ether is dropped to adjust the concentration of the solution, so that 30ml of sol with the concentration of 0.5mol/L is formed. The obtained sol was heated in a drying oven at 120 ℃ for 230min to obtain a gel. Igniting the gel with match, burning to obtain loose yellow-white product, and grinding to obtain final bismuth titanate composite phosphor powder.
Example 10
This example is an example of a BTO 0.06Ho, 0.4Yb composite phosphor powder prepared by the following steps:
with 0.8972g of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O), 0.1100g of holmium nitrate hexahydrate (Ho (NO)3)3·6H2O), 0.2244g ytterbium nitrate hexahydrate (Yb (NO)3)3·6H2O), 0.8250g of butyl titanate (C)16H36O4Ti) as the precursor of Bi, Ho, Yb and Ti, and the proportion can be according to Bi2Ti2O7And (4) weighing. The precursors are used as solutes, 18ml of glacial acetic acid and 8ml of ethylene glycol monomethyl ether are used as solvents, 1.2455ml of acetylacetone is used as a stabilizer, the analytically pure drugs and chemical reagents are mixed in a beaker, stirred for 40min at the room temperature of 450r/min on a constant temperature magnetic stirrer, and finally a small amount of ethylene glycol monomethyl ether is dropped to adjust the concentration of the solution, so that 30ml of sol with the concentration of 0.04mol/L is formed. The obtained sol was heated in a drying oven at 180 ℃ for 280min to obtain a gel. Igniting the gel with match, burning to obtain loose yellowish white product, and grindingCrushing to obtain final bismuth titanate composite phosphor powder.
Example 11
This example is a BTO 2Ho, 6Yb composite phosphor powder, which is prepared by the following steps:
with 2.0099g of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O), 0.2757g holmium nitrate hexahydrate (Ho (NO)3)3·6H2O), 0.8414g ytterbium nitrate hexahydrate (Yb (NO)3)3·6H2O), 0.1031g of butyl titanate (C)16H36O4Ti) as the precursor of Bi, Ho, Yb and Ti in the proportion of Bi20TiO32And (4) weighing. The precursors are used as solutes, 13ml of glacial acetic acid and 13ml of ethylene glycol monomethyl ether are used as solvents, 0.21ml of acetylacetone is used as a stabilizer, the analytically pure drugs and chemical reagents are mixed in a beaker, stirred for 50min at the room temperature of 350r/min on a constant temperature magnetic stirrer, and finally a small amount of ethylene glycol monomethyl ether is dropped to adjust the concentration of the solution, so that 30ml of sol with the concentration of 0.01mol/L is formed. The obtained sol was heated in a drying oven at 100 ℃ for 300min to obtain a gel. Igniting the gel with match, burning to obtain loose yellow-white product, and grinding to obtain final bismuth titanate composite phosphor powder.
Example 12
This example takes BTO 4Ho, 12Yb composite phosphor powder as an example, and the preparation steps are as follows:
with 12.0594g of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O), 1.6542g holmium nitrate hexahydrate (Ho (NO)3)3·6H2O), 4.8864g ytterbium nitrate hexahydrate (Yb (NO)3)3·6H2O), 0.3094g of butyl titanate (C)16H36O4Ti) as the precursor of Bi, Ho, Yb and Ti in the proportion of Bi20TiO32And (4) weighing. Mixing the above analytical pure drugs and chemical reagents in a beaker with 13ml glacial acetic acid and 13ml ethylene glycol methyl ether as solvents and 0.32ml acetylacetone as stabilizer, stirring at 350r/min room temperature for 50min on a constant temperature magnetic stirrer, and drippingA small amount of ethylene glycol methyl ether is added to adjust the concentration of the solution, and 30ml of sol with the concentration of 0.03mol/L is formed. The obtained sol was heated in a drying oven at 100 ℃ for 300min to obtain a gel. Igniting the gel with match, burning to obtain loose yellow-white product, and grinding to obtain final bismuth titanate composite phosphor powder.
Fig. 1 to 5 are graphs showing the results of detection of the holmium-ytterbium co-doped bismuth titanate composite phosphor powder prepared according to the present invention and examples. Wherein the content of the first and second substances,
as shown in FIG. 1, the phosphor powder produced by the sol-gel-combustion method of the present invention is a bismuth titanate composite composed of relatively large amount of Bi4Ti3O12And Bi2Ti2O7Phase composition also containing a small amount of Bi20TiO32And (4) phase(s). It can be seen from FIGS. 1(c) and 1(d) that Yb is dependent on Yb3+Increase in doping concentration, Bi4Ti3O12Has a partial diffraction peak of (B) disappeared, Bi2Ti2O7The phase ratio of the BTO to Ho to Yb phosphor can be adjusted by the doping concentration of the rare earth ions.
As shown in FIG. 2, FIG. 2(a) shows that the BTO: Ho, Yb phosphor powder of the present invention has a honeycomb-like porous structure which is advantageous in light absorption and emission. FIG. 2(b) reflects that the powder is well crystalline and dense in texture on the nanometer scale. As is clear from the energy spectra of (c) and (d), the phosphor is mainly composed of Bi, Ti, O and Yb elements, and contains a very small amount of Ho element, and the element distributions at both points 1 and 2 are uniform. This result is consistent with XRD results.
FIG. 3(a) shows undoped Ho3+And Yb3+The bismuth titanate complex (BTO) has no absorption near 975nm, and is doped with Yb3+After which an absorption peak clearly appears. FIG. 3(b) illustrates that the forbidden bandwidth of BTO Ho, Yb phosphor powders generally varies with Yb3+The doping concentration increases with increasing concentration. In the figure, the intersection point of the fitting straight line and the abscissa axis is the forbidden bandwidth of the material, and the visible bandwidth and the undoped Ho bandwidth3+And Yb3+Compared with BTO, the forbidden band width of the doped BTO can be increased from 3.53eV to 4.03eV, which shows that the forbidden band of the BTO: Ho, Yb phosphorThe width can be adjusted by the doping concentration of the rare earth ions.
As shown in FIG. 4, the BTO, Ho, Yb phosphor of the present invention generates two emission bands of red light and green light under the excitation of infrared light, and the emission band positions thereof are in accordance with Ho3+、Yb3+Independent of the doping concentration, Ho for optimum performance of the fluorescence3+、Yb3+All have a suitable doping concentration. The insert in the upper left corner of fig. 4(c) is a bright upconversion fluorescent spot on the surface of a sample under excitation of 980nm infrared light, and the spot is a photograph taken when an infrared laser is adjusted to 0.1W for excitation, which shows that the BTO: Ho, Yb composite phosphor powder has efficient upconversion performance. As can be seen, for the BTO: xHo, 0.2Yb phosphor, when the x value is increased from 0.02(0.5 mol%) to 0.1(2.5 mol%), both the intensity of the green emission band and the intensity of the red emission band are affected by Ho3+The doping concentration has great influence, and the green light integral intensity value is 3.41 multiplied by 106～8.59×106C.p.s. and integrated intensity of red light at 2.03 × 106～3.71×106C.p.s. was varied. Similarly, in the BTO:0.02Ho, yYb sample, the emission intensity varied with Yb3+The doping concentration of the phosphor also changes obviously, which shows that the emission intensity of the BTO: Ho, Yb phosphor can be changed by changing rare earth ions (Ho)3+、Yb3+) The doping concentration of (a) is adjusted.
As can be seen from FIG. 5(a), Ho in 0.2Yb when BTO is xHo3+When the concentration of (2) is increased from 0.5 mol% to 2.5 mol%, the lifetime of the up-converted green light can be reduced from 88 to 41 μ s. For the BTO 0.02Ho, yYb sample, it follows Yb3+The fluorescence lifetime can be reduced from 88 mus to 53 mus due to the change of doping concentration. It can be seen that the fluorescence lifetime of BTO Ho, Yb phosphor can be improved by changing the rare earth ion (Ho)3+、Yb3+) The doping concentration of (a) is adjusted.
In conclusion, the phase structure, the light absorption rate, the up-conversion fluorescence intensity and the up-conversion service life of the holmium-ytterbium co-doped bismuth titanate composite phosphor powder can be changed by changing Ho3+、Yb3+The ion concentration is effectively adjusted.

Claims (10)

1. The holmium-ytterbium co-doped bismuth titanate composite phosphor powder is characterized in that: the chemical structural formula of the composite phosphor is Bim-x-yHoxYbyTinOp,0<x≤m，0<y is less than or equal to m, which at least contains Bi4Ti3O12And Bi2Ti2O7Two bismuth titanate phases.
2. The holmium-ytterbium co-doped bismuth titanate composite phosphor powder according to claim 1, characterized by further comprising Bi20TiO32A bismuth titanate phase.
3. The holmium-ytterbium co-doped bismuth titanate composite phosphor powder according to claim 1, characterized in that: the composite phosphor powder is a solid solution formed of bismuth titanate phases constituting the composite phosphor and has a honeycomb-like microstructure.
4. The method for preparing the holmium-ytterbium codoped bismuth titanate composite phosphor powder as claimed in claim 1, which is characterized by being a sol-gel-combustion method comprising three main steps of sol synthesis, gel preparation and combustion.
5. The method according to claim 4, characterized by comprising the steps of:
(1) nitrate, chloride or oxide of Bi, Ho and Yb is used as precursor of Bi, Ho and Yb, titanium-containing organic matter or inorganic matter is used as precursor of Ti, and the proportion is Bi4Ti3O12、Bi2Ti2O7、Bi20TiO32、Bi12TiO20、Bi2Ti4O11One or more of them are designed;
(2) preparing a solution by using glacial acetic acid or inorganic acid and an organic solvent as solvents and acetylacetone as a stabilizer;
(3) taking the precursor obtained in the step (1) as a solute and the solution obtained in the step (2) as a solvent, and mixing and stirring the two solutions uniformly to obtain sol;
(4) heating the sol obtained in the step (3) to volatilize the solvent to obtain gel;
(5) igniting the gel obtained in the step (4), and then fully burning to generate a bismuth titanate compound;
(6) and (5) grinding the bismuth titanate compound obtained in the step (5) to obtain the holmium-ytterbium co-doped bismuth titanate composite phosphor powder.
6. The method of claim 5, wherein: the nitrate is bismuth nitrate, holmium nitrate and ytterbium nitrate; the titanium-containing organic or inorganic substance is butyl titanate, titanium isopropoxide and titanium dioxide; the inorganic acid is nitric acid or aqua regia, and the organic solvent is ethylene glycol monomethyl ether, ethanol, methanol or chloroform.
7. The method of claim 6, wherein: the volume ratio of the glacial acetic acid to the ethylene glycol monomethyl ether is 0.1-20, and the volume mass ratio of the acetylacetone to the butyl titanate is 0.1-5.
8. The method of claim 5, wherein: in the step (3), the temperature is 10-100 ℃ during mixing, the mixing and stirring speed is 20-1500 r/min, the mixing and stirring time is 5-480 min, and the concentration of the obtained sol is 0.01-0.5 mol/L; in the step (4), the heating temperature of the sol is 25-250 ℃, and the heating time is 10-300 min.
9. The method of claim 8, wherein: in the step (3), the temperature is 20-70 ℃ during mixing, the mixing and stirring speed is 200-750 r/min, the mixing and stirring time is 10-150 min, and the concentration of the obtained sol is 0.04-0.2 mol/L; in the step (4), the heating temperature of the sol is 60-160 ℃, and the heating time is 30-200 min.
10. The method of claim 5, wherein: in the step (5), igniting the gel by adopting open fire; in the step (6), the grinding is carried out by finger kneading, mortar grinding, mechanical grinding or ethanol solvent dispersion.
CN201910728167.2A 2019-08-08 2019-08-08 Holmium-ytterbium co-doped bismuth titanate composite phosphor powder and preparation method thereof Pending CN112342020A (en)

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