CN113817465A - Bismuth ion doped germanate base orange long afterglow material and preparation method thereof - Google Patents
Bismuth ion doped germanate base orange long afterglow material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
- C09K11/745—Germanates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
- C01G17/006—Compounds containing, besides germanium, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Abstract
The invention provides a bismuth ion doped germanate base orange long afterglow material, which is prepared from Bi3+The orange long afterglow material is obtained by doping germanate, and the chemical general formula of the orange long afterglow material is as follows: ba1‑xZnGeO4:xBi3+(ii) a Wherein x is more than or equal to 0.01 and less than or equal to 0.04. The invention also provides a preparation method of the bismuth ion doped germanate base orange long afterglow material. Under the excitation of 254nm ultraviolet light, the emission peak of the orange long afterglow material is positioned near 600nm and shows orange emission, so that the conversion from the ultraviolet light to the orange light can be realized; the optical fiber thermometer can be used in the fields of decoration, emergency lighting, optical fiber thermometers and the like; meanwhile, the material of the invention also has the advantages of stable crystal structure performance, high luminous efficiency, good afterglow performance and the like. Compared with the traditional lanthanide ion excitation material, the preparation method has the advantages of simplicity, safety, greenness, no pollution, low cost and the like.
Description
Technical Field
The invention relates to the field of luminescent materials, in particular to a bismuth ion doped germanate base orange long afterglow material and a preparation method thereof.
Background
The long afterglow material is an energy storage material. When irradiated, they can absorb and store the energy of sunlight, ultraviolet light, X-rays, etc., store the trapped carriers (electrons or holes) in energy level traps, and can continue to emit light after the excitation source is removed, and the decay time is prolonged to seconds, minutes or even hours. At present, the main application of the long afterglow material is indication illumination in dark environment, such as emergency passage illumination, indication boards in fire danger and the like. Meanwhile, the long-afterglow luminescent material can also be applied to the fields of decoration, night vision monitoring, optical fiber thermometers, biological imaging, high-energy ray detection and the like. Therefore, the long afterglow material is a material with great application prospect.
The long-afterglow fluorescent powder consists of two parts, namely a substrate and active ions. In the past, under the excitation of ultraviolet light, the substrates of the emitted long afterglow materials mainly have two types: one is sulfide (such as ZnS: Cu, CaS: Bi, ZnCdS: Cu) and aluminate and silicate. The sulfide material has unstable performance and is easy to decompose in air, so that the luminous performance of the fluorescent powder is greatly reduced, and even toxic hydrogen sulfide gas can be decomposed and released, thereby being harmful to the environment and health. With SrAl2O4:Eu2+,Dy3+And Sr2MgSi2O7:Eu2+,Dy3+The aluminate and silicate based second generation long afterglow materials represented by the above are excellent in afterglow performance, but have relatively single luminescent color, high synthesis temperature, large particles and the like, and the application and development of the materials are severely limited. However, the germanate-based material can just overcome the defects, and the application of the long afterglow material is also expanded.
At present, most of active ions of commercial long afterglow fluorescent powder are rare earth ions, but rare earth elements are scarce in resources, limited in supply and expensive in raw material price, so that the cost of relevant industries such as illumination, display and the like is greatly increased. In contrast to rare earths, Bi3+Has the advantages of rich reserves, low price and the like, and more importantly, Bi3+Can be effectively excited in the near ultraviolet region/visible region.
In addition, the current mature commercial long afterglow fluorescent powder is mainly a green long afterglow phosphor (such as SrA 1)2O4:Eu2+,Dy3 +) And blue long persistence materials (e.g., CaA 1)2O4:Eu2+,Nd3+) There are few reports on long-wavelength band long-afterglow materials, such as orange and red long-afterglow materials. Therefore, the research of a novel orange long afterglow material which is activated by non-rare earth ions, has stable performance and no pollution and can be effectively excited by near ultraviolet/visible light becomes the research focus at present.
Disclosure of Invention
The orange long afterglow material does not contain rare earth ions, has good chemical stability and high luminous efficiency, and has an orange long afterglow phenomenon after being irradiated for 10min by an ultraviolet lamp at 254nm and an excitation source is removed.
The invention adopts the following technical scheme to solve the technical problems:
a bismuth ion doped germanate base orange long afterglow material, which is prepared from Bi3+The orange long afterglow material is obtained by doping germanate, and the chemical general formula of the orange long afterglow material is as follows: ba1-xZnGeO4:xBi3+(ii) a Wherein x is more than or equal to 0.01 and less than or equal to 0.04.
In a preferred embodiment of the present invention, the orange long afterglow material has a hexagonal main phase structure; and the chemical general formula of the orange long afterglow phosphor is Ba1-xZnGeO4:xBi3+In the formula, Bi ions substitute Ba ions in the crystal, and x represents a substitution rate.
In a preferred embodiment of the present invention, the orange long afterglow material is formed by mixing and sintering a Ba-containing compound, a Zn-containing compound, a Ge-containing compound, and a Bi-containing compound.
As one of preferable modes of the present invention, the Ba-containing compound is one or a mixture of more of Ba oxide, carbonate, oxalate, acetate, nitrate and hydroxide.
In a preferred embodiment of the present invention, the Zn-containing compound is one or a mixture of more of an oxide, carbonate, oxalate, acetate, nitrate, and hydroxide of Zn.
In a preferred embodiment of the present invention, the Ge-containing compound is one or a mixture of more of an oxide, a nitrate and a hydroxide of Ge.
In a preferred embodiment of the present invention, the Bi-containing compound is one or more of Bi oxide, Bi carbonate, Bi oxalate, Bi acetate, Bi nitrate, and Bi hydroxide.
The preparation method of the bismuth ion doped germanate base orange long afterglow material comprises the following steps: according to the chemical formula Ba1-xZnGeO4:xBi3+Weighing corresponding Ba-containing compound, Zn-containing compound, Ge-containing compound and Bi-containing compound raw materials according to the molar ratio of the Ba, Zn, Ge and Bi elements, and uniformly mixing to obtain a mixture; grinding the mixture in absolute ethyl alcohol, then sintering in an oxygen-containing atmosphere, and cooling along with the furnace to obtain the orange long afterglow material required by the target.
As one of preferable modes of the present invention, the Ba-containing compound is specifically BaCO3The Zn-containing compound is ZnO, and the Bi-containing compound is Bi2O3The Ge-containing compound is GeO2。
In a preferred embodiment of the present invention, the sintering temperature is about 1200 ℃ and the sintering time is about 6 hours.
Compared with the prior art, the invention has the advantages that:
(1) the bismuth ion doped germanate based orange long afterglow material is prepared by a high temperature solid phase method, the preparation process is simple and easy to implement, the requirement on equipment is low, and the repeatability is good;
(2) the bismuth ion doped germanate based orange long afterglow material has high phase purity, and the phase structure can not be changed when the material is placed in the air for a long time, so that the chemical stability is high;
(3) the bismuth ion doped germanate based orange long afterglow material adopts a low-cost compound containing Bi ions as a material source of an activator, reduces the production cost, has no harm to the environment, and is suitable for application scenes such as weak illumination, information display and the like;
(4) the bismuth ion doped germanate base orange long afterglow material of the invention is BaZnGeO4The material is used as a substrate, after ultraviolet/visible light excitation, broadband emission is realized in the wavelength range of 400-800 nm, the highest peak of emission is positioned near 600nm, and orange light emission is realized;
(5) the bismuth ion doped germanate based orange long afterglow material has an orange long afterglow phenomenon after an excitation light source is removed.
Drawings
FIG. 1 shows bismuth ion-doped germanate-based orange long-afterglow materials and BaZnGeO prepared in examples 1 to 54An X-ray diffraction (XRD) pattern of a standard card;
FIG. 2 is an EDS spectrum of the bismuth ion doped germanate based orange long afterglow material prepared in example 3 (in FIG. 2, a is an EDS spectrum analysis diagram, and b is a mapping diagram of SEM);
FIG. 3 is an excitation spectrum of the bismuth ion-doped germanate-based orange long afterglow material prepared in examples 1 to 5;
FIG. 4 is an emission spectrum of the bismuth ion-doped germanate-based orange long afterglow material prepared in examples 1 to 5;
FIG. 5 is a graph showing the decay curve of the long afterglow lifetime of the bismuth ion doped germanate based orange long afterglow materials prepared in examples 1-5.
FIG. 6 is the prepared bismuth ion doped germanate based orange long afterglow material Ba in example 10.99Bi0.01ZnGeO4The afterglow spectrogram.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Selecting BaCO3、ZnO、Bi2O3、GeO2As starting compound raw materials, respectively weighing four compound raw materials according to the molar ratio of each element to prepare corresponding materials; 5 groups are arranged in total, and as in embodiments 1-5, the mixture ratio is as follows:
(1) ba, Zn, Ge, Bi, 0.990, 1, 0.010, corresponding to x, 1.0%;
(2) ba, Zn, Ge, Bi, 0.985, 1, 0.015, corresponding to x, 1.5%;
(3) ba, Zn, Ge, Bi, 0.980, 1, 0.020, corresponding to x, 2.0%;
(4) ba, Zn, Ge, Bi, 0.970, 1, 0.030, corresponding to x, 3.0%;
(5) ba, Zn, Ge, Bi, 0.960:1:1:0.040, corresponding to x 4.0%.
Example 1
The bismuth ion doped germanate based orange long afterglow phosphor of the present embodiment is prepared from Bi3+Germanate is doped to obtain the compound with the chemical formula: ba0.99Bi0.01ZnGeO4The preparation method comprises the following steps:
with high purity BaCO3(purity 99.99%), ZnO (purity 99.99%), GeO2(purity 99.99%) and Bi2O3(purity 99.99%) as the starting material, accurately weighing the mass of each oxide or carbonate according to the formula, mixing the weighed materials in an agate mortar, adding ethanol, and grinding for 0.5h to obtain a mixture; and (3) placing the crucible filled with the mixture into a high-temperature muffle furnace, sintering for 6h at 1200 ℃, cooling to room temperature along with the furnace, and grinding to obtain the bismuth ion doped orange germanate based long afterglow material.
The luminescent material Ba of this example0.99Bi0.01ZnGeO4The X-ray diffraction (XRD) spectrum is shown in figure 1, the excitation and emission spectra are shown in figures 3 and 4 respectively, the afterglow attenuation curve is shown in figure 5, and the afterglow spectrum is shown in figure6。
As can be seen from fig. 1, the X-ray diffraction peak of the luminescent material of this example is consistent with that of the standard card, and no other impurity phase is seen, indicating that the material obtained by this example is mainly of a hexagonal structure.
As can be seen from fig. 3 and 4, the excitation peaks and emission peaks of the luminescent material of this embodiment are at 254nm and 323nm, respectively, and 447nm and 600nm, respectively, which are orange light emission, and the emission intensities at the highest peak positions of the emission peaks are about 178 and 458 counts, respectively.
As can be seen from FIG. 5, the afterglow initial luminance of the present embodiment is 43.56mcd/m2And the luminance after 10 minutes was 0.84mcd/m2. The decay time is greater than 0.32mcd/m2The sample decay time of this example was 1330 s.
As can be seen from FIG. 6, the emission peak of afterglow after excitation at 254nm for 5min is 600nm, and the sample shows orange emission.
Example 2
The bismuth ion doped germanate based orange long afterglow phosphor of the present embodiment is prepared from Bi3+Germanate is doped to obtain the compound with the chemical formula: ba0.985Bi0.015ZnGeO4The preparation method comprises the following steps:
with high purity BaCO3(purity 99.99%), ZnO (purity 99.99%), GeO2(purity 99.99%) and Bi2O3(purity 99.99%) as an initial raw material, accurately weighing the mass of each oxide or carbonate according to the formula, mixing the weighed raw materials in an agate mortar, adding ethanol, and grinding for 0.5h to obtain a mixture; and (3) placing the crucible filled with the mixture into a high-temperature muffle furnace, sintering for 6h at 1200 ℃, cooling to room temperature along with the furnace, and grinding to obtain the bismuth ion doped orange germanate based long afterglow material.
The luminescent material Ba of this example0.985Bi0.015ZnGeO4The X-ray diffraction (XRD) spectrum of the compound is shown in figure 1, the excitation spectrum and the emission spectrum are respectively shown in figures 3 and 4, and the afterglow attenuation curve is shown in figure 5.
As can be seen from fig. 1, the X-ray diffraction peak of the luminescent material of this example is consistent with that of the standard card, and no other impurity phase is seen, indicating that the material obtained by this example is mainly of a hexagonal structure.
As can be seen from fig. 3 and 4, the excitation peaks and emission peaks of the luminescent material of the present embodiment are at 254nm and 324nm, and 453nm and 600nm, respectively, and the emission intensity at the highest peak position of the emission peaks is about 200 and 477 counts.
As can be seen from FIG. 5, the afterglow initial luminance of this embodiment is 26.19mcd/m2And the luminance after 10 minutes was 0.63mcd/m2. The decay time is greater than 0.32mcd/m2The sample decay time of this example was 1040 s.
Example 3
The bismuth ion doped germanate based orange long afterglow phosphor of the present embodiment is prepared from Bi3+Germanate is doped to obtain the compound with the chemical formula: ba0.98Bi0.02ZnGeO4The preparation method comprises the following steps:
with high purity BaCO3(purity 99.99%), ZnO (purity 99.99%), GeO2(purity 99.99%) and Bi2O3(purity 99.99%) as an initial raw material, accurately weighing the mass of each oxide or carbonate according to the formula, mixing the weighed raw materials in an agate mortar, adding ethanol, and grinding for 0.5h to obtain a mixture; and (3) placing the crucible filled with the mixture into a high-temperature muffle furnace, sintering for 6h at 1200 ℃, cooling to room temperature along with the furnace, and grinding to obtain the bismuth ion doped orange germanate based long afterglow material.
The luminescent material Ba of this example0.98Bi0.02ZnGeO4The X-ray diffraction (XRD) spectrum of the compound is shown in figure 1, the EDS energy spectrum is shown in figure 2, the excitation spectrum and the emission spectrum are respectively shown in figures 3 and 4, and the afterglow attenuation curve is shown in figure 5.
As can be seen from fig. 1, the X-ray diffraction peak of the luminescent material of this example is consistent with that of the standard card, and no other impurity phase is seen, indicating that the material obtained by this example is mainly of a hexagonal structure.
As can be seen from FIG. 2, Ba0.98Bi0.02ZnGeO4The elements of the phosphor powder Ba, Zn, Ge, Bi, O and the like are uniformly distributed in the whole phosphor powder particle, and the phenomena of element aggregation and phase separation are avoided.
As can be seen from FIGS. 3 and 4, the excitation peaks and emission peaks of the luminescent material of this example are at 254nm and 324nm, respectively, and at 451nm and 600nm, respectively, the emission intensity of the luminescent material is orange light emission, and the emission intensity at the highest peak position of the emission peak is about 253 count intensity and 620 count intensity, respectively.
As can be seen from FIG. 5, the afterglow initial luminance of this embodiment is 10.66mcd/m2And the luminance after 10 minutes was 0.34mcd/m2. The decay time is greater than 0.32mcd/m2The sample decay time of this example was 650 s.
Example 4
The bismuth ion doped germanate based orange long afterglow phosphor of the present embodiment is prepared from Bi3+Germanate is doped to obtain the compound with the chemical formula: ba0.97Bi0.03ZnGeO4The preparation method comprises the following steps:
with high purity BaCO3(purity 99.99%), ZnO (purity 99.99%), GeO2(purity 99.99%) and Bi2O3(purity 99.99%) as an initial raw material, accurately weighing the mass of each oxide or carbonate according to the formula, mixing the weighed raw materials in an agate mortar, adding ethanol, and grinding for 0.5h to obtain a mixture; and (3) placing the crucible filled with the mixture into a high-temperature muffle furnace, sintering for 6h at 1200 ℃, cooling to room temperature along with the furnace, and grinding to obtain the bismuth ion doped orange germanate based long afterglow material.
The luminescent material Ba of this example0.97Bi0.03ZnGeO4The X-ray diffraction (XRD) spectrum of the compound is shown in figure 1, the excitation spectrum and the emission spectrum are respectively shown in figures 3 and 4, and the afterglow attenuation curve is shown in figure 5.
As can be seen from fig. 1, the X-ray diffraction peak of the luminescent material of this example is consistent with that of the standard card, and no other impurity phase is seen, indicating that the material obtained by this example is mainly of a hexagonal structure.
As can be seen from fig. 3 and 4, the excitation peaks and emission peaks of the luminescent material of this embodiment are at 252nm and 323nm and at 464nm and 600nm, respectively, and are orange light emission, and the emission intensities at the highest peak positions of the emission peaks are about 53 and 142 count intensities, respectively.
As can be seen from FIG. 5, the afterglow initial luminance of the present embodiment4.00mcd/m2And the luminance after 5 minutes was 0.4mcd/m2. The decay time is greater than 0.32mcd/m2The sample decay time of this example was 395 s.
Example 5
The bismuth ion doped germanate based orange long afterglow phosphor of the present embodiment is prepared from Bi3+Germanate is doped to obtain the compound with the chemical formula: ba0.96Bi0.04ZnGeO4The preparation method comprises the following steps:
with high purity BaCO3(purity 99.99%), ZnO (purity 99.99%), GeO2(purity 99.99%) and Bi2O3(purity 99.99%) as an initial raw material, accurately weighing the mass of each oxide or carbonate according to the formula, mixing the weighed raw materials in an agate mortar, adding ethanol, and grinding for 0.5h to obtain a mixture; and (3) placing the crucible filled with the mixture into a high-temperature muffle furnace, sintering for 6h at 1200 ℃, cooling to room temperature along with the furnace, and grinding to obtain the bismuth ion doped orange germanate based long afterglow material.
The luminescent material Ba of this example0.96Bi0.04ZnGeO4The X-ray diffraction (XRD) spectrum of the compound is shown in figure 1, the excitation spectrum and the emission spectrum are respectively shown in figures 3 and 4, and the afterglow attenuation curve is shown in figure 5.
As can be seen from fig. 1, the X-ray diffraction peak of the luminescent material of this example is consistent with that of the standard card, and no other impurity phase is seen, indicating that the material obtained by this example is mainly of a hexagonal structure.
As can be seen from fig. 3 and 4, the excitation peaks and emission peaks of the luminescent material of this embodiment are at 253nm and 318nm, 469nm and 599nm, respectively, and are orange light emission, and the emission intensities at the highest peak positions of the emission peaks are about 8 and 19 count intensities, respectively.
As can be seen from FIG. 5, the afterglow initial luminance of this embodiment is 3.22mcd/m2And after 2 minutes the luminance was 0.95mcd/m2. The decay time is greater than 0.32mcd/m2The sample decay time of this example was 203 s.
And (4) analyzing results:
FIG. 1 is an X-ray diffraction pattern of the orange long-afterglow phosphor in examples 1 to 5.As shown in FIG. 1, the bismuth-doped orange germanate long-afterglow luminescent material Ba1-xZnGeO4:xBi3+XRD pattern of (A) and BaZnGeO4The standard cards (PDF #35-1139) match consistently, indicating that the samples obtained by the methods employed in the various embodiments of the present invention are predominantly hexagonal in structure.
FIG. 2 is the EDS spectrum of the orange long afterglow material in example 3, wherein a is the EDS spectrum analysis chart, and b is the mapping chart of SEM. As can be seen from FIG. 2, Ba0.98Bi0.02ZnGeO4The elements of the fluorescent material, such as Ba, Zn, Ge, Bi, O, and the like, are uniformly distributed in the whole fluorescent powder particles, and the phenomena of element aggregation and phase separation are avoided.
FIG. 3 is an emission spectrum of the orange long afterglow materials of examples 1-5 under 330nm wavelength excitation. As can be seen from FIG. 3, all samples have two distinct emission peaks at 450nm and 600nm, the intensity of the emission peaks is different, the positions of the emission peaks are approximately the same, and all the emission peaks belong to Bi3+Characteristic emission peak of (1). The emission peak at 600nm is dominant, which indicates that the fluorescent material powder can be excited by ultraviolet light to emit orange light. The luminous intensity of the luminescent material of the invention is firstly increased and then reduced along with the increase of the Bi ion doping concentration, and the luminous intensity is strongest when the Bi ion doping concentration is 0.02.
FIG. 4 is an excitation spectrum of the orange long afterglow materials of examples 1 to 5 under 600nm monitoring. As can be seen from FIG. 4, the excitation spectrum is composed of two broad bands with wavelength ranges of 220-280 nm and 280-380 nm, and peaks at 254nm and 324nm, respectively, due to Bi3+Different transition processes of the ions.
FIG. 5 is an afterglow decay curve of the orange long afterglow phosphors of examples 1 and 5. As can be seen from FIG. 5, the afterglow attenuation decreases as the doping concentration of Bi ions increases, and Ba0.99Bi0.01ZnGeO4The decay time of afterglow is longest and reaches 1330 s.
Fig. 6 is an afterglow spectrum of the orange long afterglow material of example 1. As can be seen from FIG. 6, Ba was observed after excitation at 254nm for 5min0.99Bi0.01ZnGeO4The emission peak of afterglow is 600nm, and the sample has the phenomenon that the emitted light is orange.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A bismuth ion doped germanate base orange long afterglow material, which is characterized in that Bi is used3+The orange long afterglow material is obtained by doping germanate, and the chemical general formula of the orange long afterglow material is as follows: ba1-xZnGeO4:xBi3+(ii) a Wherein x is more than or equal to 0.01 and less than or equal to 0.04.
2. The bismuth ion doped germanate based orange long afterglow material of claim 1, wherein the main phase structure of the orange long afterglow material is hexagonal system; the orange long afterglow phosphor has the chemical general formula Ba1-xZnGeO4:xBi3+In the formula, Bi ions substitute Ba ions in the crystal, and x represents a substitution rate.
3. The bismuth ion doped germanate based orange long afterglow material of claim 1, wherein the orange long afterglow material is formed by mixing a Ba-containing compound, a Zn-containing compound, a Ge-containing compound and a Bi-containing compound and then sintering.
4. The bismuth ion doped germanate based orange long afterglow material of claim 3, wherein the Ba containing compound is one or more of Ba oxide, Ba carbonate, Ba oxalate, Ba acetate, Ba nitrate, Ba hydroxide mixture.
5. The bismuth ion doped germanate based orange long afterglow material of claim 3, wherein the Zn containing compound is one or more mixture of Zn oxide, carbonate, oxalate, acetate, nitrate and hydroxide.
6. The bismuth ion doped germanate based orange long afterglow material of claim 3, wherein the Ge containing compound is one or more mixture of Ge oxide, nitrate and hydroxide.
7. The bismuth ion doped germanate based orange long afterglow material of claim 3, wherein the Bi containing compound is one or more of Bi oxide, carbonate, oxalate, acetate, nitrate and hydroxide.
8. The preparation method of the bismuth ion doped germanate based orange long afterglow material as claimed in any one of claims 1 to 7, which comprises the following steps: according to the chemical formula Ba1-xZnGeO4:xBi3+Weighing corresponding Ba-containing compound, Zn-containing compound, Ge-containing compound and Bi-containing compound raw materials according to the molar ratio of the Ba, Zn, Ge and Bi elements, and uniformly mixing to obtain a mixture; grinding the mixture in absolute ethyl alcohol, then sintering in an oxygen-containing atmosphere, and cooling along with the furnace to obtain the orange long afterglow material required by the target.
9. The method for preparing bismuth ion doped germanate based orange long afterglow material as claimed in claim 8, wherein said Ba containing compound is BaCO3The Zn-containing compound is ZnO and the Bi-containing compound is Bi2O3The Ge-containing compound is GeO2。
10. The method for preparing the bismuth ion doped germanate based orange long afterglow material of claim 8, wherein the sintering temperature is 1200 ℃ and the sintering time is 6 h.
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| CN115873594A (en) * | 2022-12-06 | 2023-03-31 | 济南大学 | Low-temperature solution method synthesis process of transparent cadmium-based long-afterglow crystal |
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