CN117363352A - Fluorescent powder for information storage and preparation method thereof - Google Patents
Fluorescent powder for information storage and preparation method thereof Download PDFInfo
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- CN117363352A CN117363352A CN202311679102.6A CN202311679102A CN117363352A CN 117363352 A CN117363352 A CN 117363352A CN 202311679102 A CN202311679102 A CN 202311679102A CN 117363352 A CN117363352 A CN 117363352A
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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
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7775—Germanates
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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
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7793—Germanates
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Abstract
The invention belongs to the technical field of luminescent materials, and discloses a fluorescent powder for information storage and a preparation method thereof; the fluorescent powder is prepared by using NaGdGeO 4 The method comprises the steps of (1) introducing doping ions M into a substrate to obtain the matrix; and the molecular formula of the fluorescent powder is NaGdGeO 4 :xM; wherein M is Pb 2+ 、Tb 3+ 、Ln 3+ One or more of the following;xis doped with M in the molar doping concentration of Gd in the matrix and 0 < >xLess than or equal to 3 percent. The invention realizes the regulation and control of fluorescence properties such as photoluminescence, afterglow, thermal excitation fluorescence and the like based on trap regulation and control, especially realizes abnormal thermal quenching phenomenon and thermal capacity-increasing trap filling phenomenon of fluorescent powder, realizes high-capacity information writing and multilevel information reading, and provides a material foundation for fourth-generation optical information storage.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a fluorescent powder for information storage and a preparation method thereof.
Background
With the development of large data, the huge data storage volume will create a storage crisis for existing solid state/magnetic storage technologies, and the development of new high-capacity energy-saving storage materials and storage technologies is urgent.
Long persistence insulating/semiconducting materials are optical information storage materials based on trap storage and release of carriers. It is generally desirable that the trap distribution be narrow, multi-level, and have a suitable depth (0.8-1.6 Ev), which will provide an anti-room temperature tamper energy barrier for optical information storage and a stronger photo/thermal excitation fluorescence for signal readout. At present, the long afterglow material becomes a fourth generation ultrahigh-density ultrafast optical information storage medium with the highest potential by virtue of the advantages of ultrafast speed, no power consumption, large storage capacity, long storage time and the like.
However, the long afterglow materials of the prior art are very important in seeking high storage capacity long afterglow materials because the intensity of the weak photo/thermal excitation fluorescence is not yet sufficient for information storage applications.
To this end, the present invention provides a phosphor for information storage and a method of preparing the same.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides fluorescent powder for information storage and a preparation method thereof. The invention greatly improves the storage capacity by regulating and controlling the energy storage trap of the long afterglow material, researching the control means for inducing the carrier transport path and effectively filling the deep trap and developing the optical storage material of the high-efficiency deep trap, thereby having theoretical significance, practical application value and social significance.
The invention relates to a fluorescent powder for information storage and a preparation method thereof, which are realized by the following technical scheme:
a first object of the present invention is to provide a phosphor for information storage by using NaGdGeO 4 The method comprises the steps of (1) introducing doping ions M into a substrate to obtain the matrix; and the molecular formula of the fluorescent powder is NaGdGeO 4 :xM；
Wherein M is Pb 2+ 、Tb 3+ 、Ln 3+ One or more of the following;
Ln 3+ is Eu 3+ 、Yb 3+ 、Y 3+ 、Ce 3+ 、Dy 3+ 、Nd 3+ 、Tm 3+ 、Er 3+ 、Ho 3+ 、La 3+ 、Lu 3+ 、Sm 3+ 、Pr 3+ 、Sc 3+ Any one of them;
x is the molar doping concentration of doping ion M accounting for Gd in the matrix, and x is more than 0 and less than or equal to 3 percent.
The second object of the present invention is to provide a method for preparing the above phosphor, comprising the steps of:
according to the followingMolecular formula NaGdGeO of fluorescent powder 4 Weighing corresponding mass of each preparation raw material, namely Na source, gd source, ge source, O source and M source;
mixing the weighed Na source, gd source, ge source, O source and doped ion M source, and fully grinding and uniformly mixing to obtain mixed powder;
calcining the mixed powder for the first time at 900-1000 ℃ and grinding the mixed powder into powder to obtain precursor powder;
and (3) calcining the precursor powder for the second time at 1100-1400 ℃ and grinding the precursor powder into powder to obtain the fluorescent powder.
Preferably, the Na source, gd source, ge source, and M source are oxygen-containing compounds containing the corresponding elements; the O source is provided by each of the oxygenates containing the corresponding element.
Preferably, the oxygen-containing compound is any one or more of oxide, carbonate and nitrate.
Preferably, when M employed includes Pb 2+ Or/and Tb 3+ When Pb is added 2+ Or/and Tb 3+ In its corresponding oxide form with other preparation raw materials.
Preferably, when M is employed comprising Ln 3+ When Ln is added 3+ In the form of its nitrate solution, is added after mixing with other preparation materials.
Preferably, the atmosphere of the first calcination is air, and the calcination time is 4-8 hours.
Preferably, the atmosphere of the second calcination is air, the calcination time is 4-8 hours, and the temperature rising rate is 2-4 ℃/min.
Preferably, the grinding time of each grinding is 0.5-1 h.
Compared with the prior art, the invention has the following beneficial effects:
the invention uses NaGdGeO 4 As a matrix, the prepared NaGdGeO is realized by introducing a doped ion M source and regulating the type and the doping concentration of the doped ion M source based on trap regulation 4 Regulating and controlling photoluminescence, afterglow, thermally excited fluorescence and other fluorescence properties of the xM fluorescent powder;particularly, the abnormal thermal quenching phenomenon and the thermal capacity-increasing trap filling phenomenon of the fluorescent powder are realized, the high-capacity information writing and the multi-stage information reading are realized, and a material foundation and a technical scheme are provided for fourth-generation optical information storage.
The preparation method disclosed by the invention is simple in steps and is favorable for popularization and mass production. The fluorescent powder prepared by the invention has commercial and market values, provides an application foundation for fourth generation information storage, and provides a new thought for regulating and controlling the afterglow material traps by the rare earth micro-doping method.
Drawings
FIG. 1 is XRD patterns of examples 1, 23 and 25 calcined at different temperatures;
FIG. 2 is an XRD refinement of example 1;
FIG. 3 is a schematic diagram of the crystal phase structure of the orthorhombic phosphor of comparative example 1; wherein FIG. 3 (a) shows that Gd and Ge are respectively residing in GdO 6 Octahedron and GeO 4 In a tetrahedral structure; FIG. 3 (b) and FIG. 3 (c) illustrate Na atom NaO 6 In the octahedral structure, the octahedral structure forms a one-dimensional chain structure along the c-axis;
FIG. 4 is the EDS analysis result of the element distribution of example 1; wherein FIG. 4 (a) is the sample of example 1 at 5FIG. 4 (b) is a diagram of the gold phase at 1 +.>Fig. 4 (c) -4 (h) are EDS maps of the elemental distribution of Ge, na, O, gd, pb, tb in fig. 4 (b), respectively, for the gold phase diagram at scale;
FIG. 5 is an ultraviolet-visible absorption spectrum of example 1, and an inset is an absorption spectrum conversion curve of example 1;
FIG. 6 is the emission spectrum and excitation spectrum of comparative example 1, example 2, example 7; wherein, fig. 6 (a) is emission spectra of comparative example 1, example 2, example 7; FIG. 6 (b) shows excitation spectra of comparative example 1, example 2 and example 7;
FIG. 7 shows the afterglow emission spectra and afterglow attenuation curves of comparative example 1, example 2, and example 7; wherein, FIG. 7 (a) shows afterglow emission spectra of comparative example 1, example 2 and example 7, and FIG. 7 (b) shows afterglow attenuation curves of comparative example 1, example 2 and example 7;
FIG. 8 is the emission spectra and afterglow emission spectra of example 1 and examples 23 to 25; wherein FIG. 8 (a) is the emission spectra of example 1, examples 23-25; FIG. 8 (b) shows the afterglow emission spectra of example 1 and examples 23 to 25;
FIG. 9 is the emission spectra and afterglow emission spectra of example 1 and examples 3 to 6; wherein, FIG. 9 (a) is the emission spectra of example 1, examples 3-6; FIG. 9 (b) shows the afterglow emission spectra of example 1 and examples 3 to 6;
FIG. 10 is a graph comparing the integrated intensities of the thermal release curves of the fluorescence at 553nm for examples 8, 10-22 and the integrated intensities of the photoluminescence emission spectra; wherein, the above graph is a comparison graph of the integrated intensities of the pyroelectric curves of the fluorescence at 553nm for examples 8, 10-22; the following figures are graphs comparing the integrated intensities of the photoluminescence emission spectra of example 8, examples 10-22;
FIG. 11 is a thermal release profile of example 1, examples 10-22; wherein, FIG. 11 (a) is the pyroelectric curve of fluorescence at 553nm for example 1, examples 10-13; FIG. 11 (b) is a thermal release profile of fluorescence at 553nm for examples 1, examples 14-18; FIG. 11 (c) is the pyroelectric curves of fluorescence at 553nm for examples 1, 8, and 19-22;
FIG. 12 is a temperature dependent emission spectrum of example 8;
FIG. 13 is a graph showing comparison of heat release curves of examples 1-2, examples 7-9 and comparative example 1; wherein, fig. 13 (a) is a graph comparing the heat release curves of example 1, comparative example 1, example 2, example 7; FIG. 13 (b) is a graph showing comparison of the heat release curves of example 2 and examples 7 to 9; FIG. 13 (c) is a graph comparing the heat release curves of example 1 and example 8;
FIG. 14 is a graph showing the heat release profile of example 8 after waiting for various times after charging at room temperature;
FIG. 15 is an afterglow/thermal excitation fluorescence emission spectrum of example 8 after charging of an ultraviolet lamp;
FIG. 16 example 8 trap filling spectra, photoluminescence excitation spectra, afterglow excitation spectra at 24℃and 80 ℃;
FIG. 17 is a photograph showing the storage and reading of simulated optical information when example 8 is used as an information storage medium; FIGS. 17 (a) and 17 (b) are photographs of temperature-controlled different fluorescence information read out under different thermal stimuli in the case of ultraviolet light writing different trap information; fig. 17 (c) is a multicolor information picture thermally stimulated and read out with the aid of a filter in the case of solar light writing information; fig. 17 (d) is a multicolor information picture read by 980 nm near-infrared excitation with the aid of a filter after ultraviolet light is written into the light information picture;
in fig. 1 to 17, the following description is given:
all English Wavelength (nm) appearing represent wavelength in nanometers;
all english absorptance (a.u.) present represent Absorbance;
all occurrences of Intensity (a.u.) represent Intensity;
all occurrences of Temperature (K) are indicative of temperature in K.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below.
The invention provides a fluorescent powder for information storage, and a preparation method thereof is as follows:
according to the molecular formula NaGdGeO of the fluorescent powder 4 Weighing corresponding mass of each preparation raw material, namely Na source, gd source, ge source, O source and M source;
mixing the weighed Na source, gd source, ge source, O source and doped ion M source, and fully grinding and uniformly mixing to obtain mixed powder; calcining the mixed powder for the first time at 900-1000 ℃ and grinding the mixed powder into powder to obtain precursor powder; and (3) calcining the precursor powder for the second time at 1100-1400 ℃ and grinding the precursor powder into powder to obtain the fluorescent powder.
In the present invention, in order to avoid introducing other elements and impurities, the Na source, gd source, ge source, and M source are preferably used as oxygen-containing compounds containing the corresponding elements; the O isThe sources are provided together by respective oxygenates containing the respective elements; wherein the oxygen-containing compound is any one or more of oxide, carbonate and nitrate. The invention takes the factors of no impurity introduced as much as possible, good chemical stability, moderate price and the like into consideration, and preferably takes Na as 2 CO 3 As Na source, gd 2 O 3 As Gd source, geO 2 As a Ge source.
According to the invention, the fluorescent property of the fluorescent material is regulated and controlled by regulating and controlling the type of the doping ion M and the molar doping concentration of the doping ion M in Gd in the matrix, the fluorescent properties such as photoluminescence, afterglow, thermally excited fluorescence and the like are regulated and controlled, particularly, the abnormal thermal quenching phenomenon and thermal capacity-increasing trap filling phenomenon of the fluorescent powder are realized, the writing of high-capacity information and the reading of multi-stage information are realized, and a material foundation and a technical scheme are provided for fourth-generation optical information storage. And M adopted by the invention is Pb 2+ 、Tb 3+ 、Ln 3+ One or more of the following; ln (Ln) 3+ Is Eu 3+ 、Yb 3+ 、Y 3+ 、Ce 3+ 、Dy 3+ 、Nd 3+ 、Tm 3+ 、Er 3+ 、Ho 3+ 、La 3+ 、Lu 3+ 、Sm 3+ 、Pr 3+ 、Sc 3+ Any one of them; x is the molar doping concentration of doping ion M accounting for Gd in the matrix, and x is more than 0 and less than or equal to 3 percent. Wherein M selected includes Pb 2+ Or/and Tb 3+ When Pb is added 2+ Or/and Tb 3+ Mixing with other raw materials in the form of oxide, namely PbO as Pb source and Tb 4 O 7 Is a Tb source; when M is used to include Ln 3+ When in use, ln is added in consideration of the factors that trace elements are doped in very small amount, very small amount of solid oxide is difficult to weigh and difficult to dissolve in deionized water, nitrate is easy to dissolve in deionized water and the like 3+ The nitrate solution is titrated into other raw material mixture by a burette. In order to fully and uniformly mix the preparation raw materials, the invention preferably adopts a ball milling or manual milling mode for mixing, the milling time is about 0.5-1 h, and the obtained mixed powder is fine and smooth and has the size of 1-2 mu m.
According to the invention, physical factors such as the melting point of the precursor are considered, the mixed powder is calcined in a sectional calcining mode, and the mixed powder is calcined for 4-8 hours at 900-1000 ℃ in an air atmosphere, so that an initial product is obtained. In order to facilitate uniform heating of the material in the subsequent calcination process, the method preferably grinds the first calcination product, namely the precursor, into powder, then calcines the powder in an air atmosphere at 1100-1400 ℃ for 4-8 hours, and ensures that the material can be heated sufficiently and uniformly by the temperature rising rate of 2-4 ℃/min in the second calcination, thereby achieving the optimal crystallinity.
Example 1
This example provides a phosphor for information storage, M used in this example is Pb 2+ And Tb 3+ And Pb 2+ And Tb 3+ Respectively occupy NaGdGeO 4 Gd in matrix 3+ Since the molar concentration was 0.5% and 1%, the molecular formula of the phosphor of this example was NaGdGeO 4 :0.5%Pb 2+ ,1%Tb 3+ . And the preparation method is as follows:
the molar mass ratio according to the chemical formula is weighed 0.2119g Na 2 CO 3 、0.714g Gd 2 O 3 、0.4185g GeO 2 0.0044g PbO and 0.0074g Tb 4 O 7 Mixing the solids, and fully grinding the mixture in an agate mortar for 1h to obtain mixed powder; placing the mixed powder into a crucible, and firing the mixed powder in an air atmosphere at 950 ℃ for 6 hours to obtain precursor powder; grinding the precursor powder into powder, placing in a crucible again, firing in air atmosphere at 1100deg.C for 6 hr, and grinding to obtain NaGdGeO 4 :0.5%Pb 2+ ,1%Tb 3+ Is a fluorescent powder of (a).
Example 2
This embodiment provides a phosphor for information storage, where M is Tb 3+ And Tb 3+ Occupying NaGdGeO 4 Gd in 3+ 1% molar concentration, the molecular formula of the phosphor of this example is NaGdGeO 4 :1%Tb 3+ . And the preparation method is as follows:
will press onThe molar mass ratio of the chemical formula is 0.2119g Na 2 CO 3 、0.717g Gd 2 O 3 、0.4185g GeO 2 And 0.0074g Tb 4 O 7 Mixing the solids, and fully grinding the mixture in an agate mortar for 1h to obtain mixed powder; placing the mixed powder into a crucible, and firing the mixed powder in an air atmosphere at 950 ℃ for 6 hours to obtain precursor powder; grinding the precursor powder into powder, placing into a crucible, firing in air atmosphere at 1100deg.C for 6 hr, and fully grinding to obtain NaGdGeO with molecular formula 4 :1%Tb 3+ Is a fluorescent powder of (a).
Example 3
This example provides a phosphor for information storage, M used in this example is Pb 2+ And Tb 3+ And Pb 2+ And Tb 3+ Respectively occupy NaGdGeO 4 Gd in matrix 3+ 1% and 1% of the molar concentration of the fluorescent powder of the present example, the molecular formula of the fluorescent powder is NaGdGeO 4 :1%Pb 2+ ,1%Tb 3+ . And the preparation method is as follows:
the molar mass ratio according to the chemical formula is weighed 0.2119g Na 2 CO 3 、0.714g Gd 2 O 3 、0.4185g GeO 2 0.0088g PbO and 0.0074g Tb 4 O 7 Mixing the solids, and fully grinding the mixture in an agate mortar for 1h to obtain mixed powder; placing the mixed powder into a crucible, and firing the mixed powder in an air atmosphere at 950 ℃ for 6 hours to obtain precursor powder; grinding the precursor powder into powder, placing into a crucible, firing in air atmosphere at 1100deg.C for 6 hr, and grinding to obtain NaGdGeO 4 :1%Pb 2+ ,1%Tb 3+ Is a fluorescent powder of (a).
Example 4
This embodiment provides a phosphor for information storage, where M is Tb 3+ And Tb 3+ Occupying NaGdGeO 4 Gd in matrix 3+ Since the molar concentration is 0.5%, the molecular formula of the fluorescent powder of this example is NaGdGeO 4 :0.5%Tb 3+ Fluorescent powder. And the preparation method is as follows:
the molar mass ratio according to the chemical formula is weighed 0.2119g Na 2 CO 3 、0.714g Gd 2 O 3 、0.4185g GeO 2 、0.0037g Tb 4 O 7 Mixing the solids, and fully grinding the mixture in an agate mortar for 1h to obtain mixed powder; placing the mixed powder into a crucible, and firing the mixed powder in an air atmosphere at 950 ℃ for 6 hours to obtain precursor powder; grinding the precursor powder into powder, placing into a crucible, firing in air atmosphere at 1100deg.C for 6 hr, and grinding to obtain NaGdGeO 4 :0.5%Tb 3+ Is a fluorescent powder of (a).
Example 5
This example provides a phosphor for information storage, M used in this example is Pb 2+ And Tb 3+ And Pb 2+ And Tb 3+ Respectively occupy NaGdGeO 4 Gd in 3+ Since the molecular formula of the phosphor of this example is NaGdGeO, the molar concentration of the phosphor is 0.5% and 2% 4 :0.5%Pb 2+ ,2%Tb 3+ . And the preparation method is as follows:
the molar mass ratio according to the chemical formula is weighed 0.2119g Na 2 CO 3 、0.714g Gd 2 O 3 、0.4185g GeO 2 0.0044g PbO and 0.00148g Tb 4 O 7 Mixing the solids, and fully grinding the mixture in an agate mortar for 1h to obtain mixed powder; placing the mixed powder into a crucible, and firing the mixed powder in an air atmosphere at 950 ℃ for 6 hours to obtain precursor powder; grinding the precursor powder into powder, placing in a crucible again, firing in air atmosphere at 1100deg.C for 6 hr, and grinding to obtain NaGdGeO 4 :0.5%Pb 2+ ,2%Tb 3+ Is a fluorescent powder of (a).
Example 6
This example provides a phosphor for information storage, M used in this example is Pb 2+ And Tb 3+ And Pb 2+ And Tb 3+ Respectively occupy NaGdGeO 4 Gd in matrix 3+ 0.5% of the molar concentration of NaGdGeO of the formula 4 :0.5%Pb 2+ ,0.5%Tb 3+ Fluorescent powder. And preparation thereofThe method comprises the following steps:
the molar mass ratio according to the chemical formula is weighed 0.2119g Na 2 CO 3 、0.717g Gd 2 O 3 、0.4185g GeO 2 0.0044g PbO and 0.0037g Tb 4 O 7 Mixing the solids, and fully grinding the mixture in an agate mortar for 1h to obtain mixed powder; placing the mixed powder into a crucible, and firing the mixed powder in an air atmosphere at 950 ℃ for 6 hours to obtain precursor powder; grinding the precursor powder into powder, placing in a crucible again, firing in air atmosphere at 1100deg.C for 6 hr, and grinding to obtain NaGdGeO 4 :0.5%Pb 2+ ,0.5%Tb 3+ Is a fluorescent powder of (a).
Example 7
This example provides a phosphor for information storage, M used in this example is Pb 2+ And Pb 2+ Occupying NaGdGeO 4 Gd in matrix 3+ Since the molecular formula of the phosphor of this example is NaGdGeO, the molar concentration of the phosphor is 0.5% 4 :0.5%Pb 2 + Fluorescent powder. And the preparation method is as follows:
the molar mass ratio according to the chemical formula is weighed 0.2119g Na 2 CO 3 、0.714g Gd 2 O 3 、0.4185g GeO 2 Mixing 0.0044g of PbO solid, and fully grinding for 1h in an agate mortar to obtain mixed powder; placing the mixed powder into a crucible, and firing the mixed powder in an air atmosphere at 950 ℃ for 6 hours to obtain precursor powder; grinding the precursor powder into powder, placing in a crucible again, firing in air atmosphere at 1100deg.C for 6 hr, and grinding to obtain NaGdGeO 4 :0.5%Pb 2+ Is a fluorescent powder of (a).
Example 8
This example provides a phosphor for information storage, M used in this example is Pb 2+ 、Tb 3+ 、Sm 3+ And Pb 2+ 、Tb 3+ And Sm 3+ Respectively occupy NaGdGeO 4 Gd in matrix 3+ The molar doping concentrations of (2) are 0.5%, 1% and 0.0000025% of the molar concentration, and the phosphor of this example is dividedThe sub-formula is NaGdGeO 4 :0.5%Pb 2+ ,1%Tb 3+ ,Sm 3+ Fluorescent powder. And the preparation method is as follows:
the molar mass ratio according to the chemical formula is weighed 0.2119g Na 2 CO 3 、0.714g Gd 2 O 3 、0.4185g GeO 2 0.0044g PbO and 0.0074g Tb 4 O 7 Mixing the solids, and adding dropwise 10 containing 0.1ml -7 Sm (NO) 3 ) 3 Aqueous solutions, i.e. Sm 3+ Total mole number of 10 -8 After mmol, fully grinding for 1h in an agate mortar to obtain mixed powder; placing the mixed powder into a crucible, and firing the mixed powder in an air atmosphere at 950 ℃ for 6 hours to obtain precursor powder; grinding the precursor powder into powder, placing in a crucible again, firing in air atmosphere at 1100deg.C for 6 hr, and grinding to obtain NaGdGeO 4 :0.5%Pb 2+ ,1%Tb 3+ ,Sm 3+ Is a fluorescent powder of (a).
Example 9
This example provides a phosphor for information storage, M used in this example is Pb 2+ And Sm 3+ And Pb 2+ And Sm 3+ Respectively occupy NaGdGeO 4 Gd in matrix 3+ Since the molecular formula of the phosphor of this example was NaGdGeO, the molar concentration was 0.5% and 0.0000025% 4 :0.5%Pb 2+ ,Sm 3+ . And the preparation method is as follows:
the molar mass ratio according to the chemical formula is weighed 0.2119g Na 2 CO 3 、0.714g Gd 2 O 3 、0.4185g GeO 2 Mixing with 0.0044g PbO solid, and dripping 10 containing 0.1ml -7 Sm (NO) 3 ) 3 Aqueous solutions, i.e. Sm 3+ Total mole number of 10 -8 After mmol, fully grinding for 1h in an agate mortar to obtain mixed powder; placing the mixed powder into a crucible, and firing the mixed powder in an air atmosphere at 950 ℃ for 6 hours to obtain precursor powder; grinding the precursor powder into powder, placing in a crucible again, firing in air atmosphere at 1100deg.C for 6 hr, and grinding to obtain NaGdGeO 4 :0.5%Pb 2+ ,Sm 3+ Is a fluorescent powder of (a).
Example 10
The present embodiment provides a phosphor for information storage, and the difference between the present embodiment and embodiment 8 is that: eu used in this example 3+ Substitute for Sm 3+ 。
Example 11
The present embodiment provides a phosphor for information storage, and the difference between the present embodiment and embodiment 8 is that: yb used in the present example 3+ Substitute for Sm 3+ 。
Example 12
The present embodiment provides a phosphor for information storage, and the difference between the present embodiment and embodiment 8 is that: ce employed in the present example 3+ Substitute for Sm 3+ 。
Example 13
The present embodiment provides a phosphor for information storage, and the difference between the present embodiment and embodiment 8 is that: y employed in the present embodiment 3+ Substitute for Sm 3+ 。
Example 14
The present embodiment provides a phosphor for information storage, and the difference between the present embodiment and embodiment 8 is that: nd used in this example 3+ Substitute for Sm 3+ 。
Example 15
The present embodiment provides a phosphor for information storage, and the difference between the present embodiment and embodiment 8 is that: er used in this example 3+ Substitute for Sm 3+ 。
Example 16
The present embodiment provides a phosphor for information storage, and the difference between the present embodiment and embodiment 8 is that: tm used in the present example 3+ Substitute for Sm 3+ 。
Example 17
The present embodiment provides a phosphor for information storage, and the difference between the present embodiment and embodiment 8 is that: ho adopted in the embodiment 3+ Substitute for Sm 3+ 。
Example 18
The present embodiment provides a phosphor for information storage, and the difference between the present embodiment and embodiment 8 is that: dy used in this embodiment 3+ Substitute for Sm 3+ 。
Example 19
The present embodiment provides a phosphor for information storage, and the difference between the present embodiment and embodiment 8 is that: lu used in this example 3+ Substitute for Sm 3+ 。
Example 20
The present embodiment provides a phosphor for information storage, and the difference between the present embodiment and embodiment 8 is that: pr adopted in the embodiment 3+ Substitute for Sm 3+ 。
Example 21
The present embodiment provides a phosphor for information storage, and the difference between the present embodiment and embodiment 8 is that: la employed in the present example 3+ Substitute for Sm 3+ 。
Example 22
The present embodiment provides a phosphor for information storage, and the difference between the present embodiment and embodiment 8 is that: sc adopted in the embodiment 3+ Substitute for Sm 3+ 。
Example 23
The present embodiment provides a phosphor for information storage, and the difference between the present embodiment and embodiment 1 is that: the second calcination temperature in this example was 1000 ℃.
Example 24
The present embodiment provides a phosphor for information storage, and the difference between the present embodiment and embodiment 1 is that: the second calcination temperature in this example was 1200 ℃.
Example 25
The present embodiment provides a phosphor for information storage, and the difference between the present embodiment and embodiment 1 is that: the second calcination temperature in this example was 1300℃and the calcination time was 4 hours.
Comparative example 1
This comparative example provides a NaGdGeO 4 The preparation method of the fluorescent powder comprises the following steps:
will be according to the chemical formula NaGdGeO 4 The molar mass ratio of the mixture is respectively weighed 0.2119g Na 2 CO 3 、0.72g 5Gd 2 O 3 And 0.4185g GeO 2 Grinding the mixed solids for 1h by an agate mortar to obtain mixed powder; placing the mixed powder into a crucible, and firing for 6 hours at the temperature of 950 ℃ to obtain precursor powder; grinding the precursor powder into powder, placing in a crucible again, firing in air atmosphere at 1100deg.C for 6 hr, and grinding into powder to obtain NaGdGeO 4 Fluorescent powder.
Test section
Structural analysis
The present invention was XRD tested using examples 1, 23 and 25, and the test results are shown in FIG. 1. The lowermost XRD patterns in FIG. 1 are PDF#88-1776 standard cards of pure orthorhombic NGGO, and as can be seen by comparing the standard cards of pure orthorhombic NGGO, the XRD patterns of examples 1, 23 and 25 are all shown as pure orthorhombic NGGO, demonstrating that examples 1, 23-25 successfully incorporate dopant ions into the matrix and do not affect the structure thereof. And the XRD pattern of the invention is refined by taking example 1 as an example, and the refined XRD pattern is shown in figure 2, and it can be seen that the doped ions are successfully doped into the matrix, and no second phase is generated.
The present invention was carried out by taking comparative example 1 as an example, and the results are shown in FIG. 3, wherein FIG. 3 (a) shows that Gd and Ge are respectively contained in GdO 6 Octahedron and GeO 4 In a tetrahedral structure. FIG. 3 (b) and FIG. 3 (c) illustrate Na atom NaO 6 In the octahedral structure, the octahedral structure forms a one-dimensional chain structure along the c-axis; the crystal phase structure provides Gd for doped ions 3+ 、Na + And Ge (Ge) 4+ Three different cationic sites.
The present invention was carried out by EDS analysis using example 1, and the results are shown in FIG. 4. In FIG. 4, FIG. 4 (a) shows that example 1 shows that the ratio of the components is 5A gold phase diagram under the scale of the method,FIG. 4 (b) shows that example 1 is at 1 +.>The gold phase diagrams at scale, fig. 4 (c) -4 (h) are EDS maps of the element distribution of Ge, na, O, gd, pb, tb in fig. 4 (b), respectively. As can be seen from FIG. 4, na, gd, ge, O, pb, tb and other elements are uniformly distributed in the fluorescent powder in example 1, which shows that NaGdGeO is successfully synthesized 4 :Pb 2+ ,Tb 3+ 。
(II) analysis of fluorescence Properties
The ultraviolet-visible absorption spectrum test is carried out on the fluorescent powder of the embodiment 1, the result is shown in fig. 5, and the inset in fig. 5 is the absorption spectrum conversion curve of the embodiment 1. It can be seen that the phosphor of example 1 is a wide bandgap semiconductor with a bandgap width of about 5.51eV, which proves that the material is a wide bandgap semiconductor.
The emission spectrum and excitation spectrum of comparative example 1, example 2, example 7 were tested according to the present invention, and the test results are shown in fig. 6. Wherein, FIG. 6 (a) is the emission spectra of comparative example 1, example 2 and example 7 under excitation at 274 nm; fig. 6 (b) shows excitation spectra of comparative example 1, example 2, and example 7. As can be seen from FIG. 6 (a), from the emission spectra of comparative example 1 and example 7, a weak Gd-derived source can be observed at 312nm 3+ And at 616nm, matrix defect related transitions can be observed. As can be seen from comparison with comparative example 1, in example 2, strong multi-band fluorescence emission can be observed, which is analyzed to be derived from Tb 3+ A kind of electronic device 5 D 3,4 Energy level to 7 F J Transition of energy level. As can be seen in comparison with example 2, in example 1, it is derived from Tb 3+ Is enhanced without Pb 2+ To account for Pb 2+ The auxiliary dopant is introduced as only one defect, i.e. in Pb 2+ Based on (a), further dope Tb 3+ And is more beneficial to improving the fluorescence performance of the matrix material. In FIG. 6 (b), it can be seen that the excitation spectra of comparative example 1 and example 7 at the emission wavelength of 616nm, and example 1 and example 2 at 553nmExcitation spectra at emission wavelength, it can be seen that the intensities of comparative example 1 and example 7 are lower, while Gd is observed in the excitation spectra of example 1 and example 2 3+ Is (Gd at 274 and 312 nm) 3+ A kind of electronic device 8 S 7/2 → 6 I J Transition), tb 3+ 4 f-5 d transition (261 nm), tb 3+ F-f transitions of (337-400 nm and 481 nm, these Gd) 3+ Transition, confirm Gd 3+ To Tb 3+ Is provided for the energy transfer of (a). Pb-free 2+ Description of emission of Pb 2+ The auxiliary dopant is introduced as only one defect.
The afterglow emission spectra and afterglow decay curves of comparative example 1, example 2 and example 7 were tested, and the results are shown in FIG. 7. Wherein FIG. 7 (a) is the afterglow emission spectra of comparative example 1, example 2 and example 7 at excitation of 274 nm; FIG. 7 (b) is an afterglow decay curve at 274nm excitation, at 616nm for comparative example 1, at 552nm for example 2, and at 616nm for example 7. As can be seen from FIG. 7 (a), example 1 shows strong Tb-derived 3+ Is a multi-band afterglow emission. As can be seen from FIG. 7 (b), the afterglow intensity and duration of example 1 were longer than those of examples 2 and 7, and the afterglow duration was about 360 s more.
Taking the example 1 and the examples 23-25 as examples, the emission spectrum and the afterglow emission spectrum of the invention are respectively tested, and the test results are shown in figure 8, wherein figure 8 (a) is the emission spectrum of the example 1 and the examples 23-25 under the excitation of 274 nm; FIG. 8 (b) shows the afterglow emission spectra of example 1 and examples 23 to 25 at excitation of 274 nm. As can be seen, example 1 has better fluorescence properties than examples 23-25, so that the present invention prepares NaGdGeO with the formula 4 :0.5%Pb 2+ ,1%Tb 3+ The second calcination temperature is preferably 1100 ℃.
Taking the example 1 and the examples 3-6 as examples, the emission spectrum and the afterglow emission spectrum of the invention are respectively tested, and the test results are shown in figure 9, wherein figure 9 (a) is the emission spectrum of the example 1 and the examples 3-6 under the excitation of 274 nm; FIG. 9 (b) shows a process of example 1 and example 3-6 afterglow emission spectrum at 274nm excitation. It can be seen that when M is Pb 2+ And Tb 3+ And Pb 2+ And Tb 3+ At 0.5% and 1%, respectively, of the NaGdGeO obtained 4 :0.5%Pb 2+ ,1%Tb 3+ The fluorescent powder has better fluorescent performance than other Pb 2+ ,Tb 3+ Concentration doped NaGdGeO 4 Fluorescent powder.
FIG. 10 is a graph comparing the integrated intensities of the thermal release curves of the fluorescence at 553nm for examples 8, 10-22 and the integrated intensities of the photoluminescence emission spectra; wherein, the comparison graph of the integral intensity of the pyroelectric curve of the fluorescence of the embodiment 8 and the embodiments 10-22 at 553nm is shown, wherein the horizontal line represents the integral intensity of the pyroelectric curve of the embodiment 1 as a comparison reference standard; the following figures are graphs comparing the integrated intensities of the photoluminescence emission spectra of example 8 and examples 10-22, wherein the horizontal line represents the photoluminescence intensity of example 1 as a reference for comparison. Obviously, compared with example 1, the rare earth micro-doped samples of examples 8 and 10-22 have slightly reduced photoluminescence intensity, but the afterglow/thermal excitation fluorescence intensity is sharply increased, wherein NaGdGeO 4 :0.5%Pb 2+ ,1%Tb 3+ ,Sm 3+ The samples exhibited the greatest thermal excitation fluorescence intensity suggesting their suitability as information storage medium materials.
FIG. 11 is the thermal release profile of the fluorescence at 553nm for examples 1, 8, 10-22, wherein FIG. 11 (a) is the thermal release profile of the fluorescence at 553nm for examples 1, 10-13; FIG. 11 (b) is a thermal release profile of fluorescence at 553nm for examples 1, examples 14-18; FIG. 11 (c) shows the thermal release curves of fluorescence at 553nm for examples 1, 8, and 19-22. As can be seen from fig. 11, the thermally stimulated fluorescence of example 8 was the strongest, and the integrated intensity of the pyroelectric curve was increased by 6 times relative to example 1.
FIG. 12 is a graph showing the temperature dependent emission spectrum of example 8 at 274nm excitation, and it can be seen that the fluorescence peak intensities of the photoluminescence emission spectrum are substantially unchanged with temperature, indicating that example 8 has good thermal stability.
The present invention was carried out by taking examples 1-2, examples 7-9 and comparative example 1 as examples, and the results of the tests are shown in FIG. 13. Fig. 13 (a) is a graph showing the heat release curves of comparative examples 1, 2 and 7, and fig. 13 (b) is a graph showing the heat release curves of examples 2, 7, 8 and 9; FIG. 13 (c) is a graph showing comparison of the heat release curves of example 1 and example 8.
And in FIG. 13 (a), the upper graph shows the pyroelectric curves at 553nm for example 1 and example 2 under 254nm excitation; the middle plot shows the thermal release profile at 404nm and 616nm for example 7, respectively, under 254nm excitation; the lower graph shows the pyroelectric profile at 616nm for comparative example 1 under excitation at 274 nm; from fig. 13 (a), it can be seen that the doping Tb 3+ Deepen the traps of the phosphor.
And in FIG. 13 (b), the upper graph shows the pyroelectric curves at 400nm for example 7 and example 9 under excitation at 274 nm; the lower graph shows the thermal release curves at 553nm for example 2 and example 8 at 274nm excitation. FIG. 13 (c) shows the thermal release curves at 553nm for examples 1 and 8 at 274nm excitation. As can be seen from FIGS. 13 (b) and 13 (c), the trace Sm 3+ Trap II in the doped sample is much deeper than its counterpart, especially the comparison of example 1 and example 8 is more evident. Average depth of trap I and trap II uses equation e=t m The/500 estimates, yielding values of 0.64 eV and 0.83 eV, respectively, conclude that example 8 has the best stored energy and the strongest thermal stimulus signal. Wherein, the trap I and the trap II respectively refer to a left peak value and a right peak value in the pyroelectric curve, and the peak temperature of the pyroelectric curve reflects the depth of the trap releasing the carrier.
The present invention was carried out by taking example 8 as an example, and the test results are shown in FIG. 14, wherein the heat release curve at 553nm under excitation of 274nm is tested after waiting for different times after charging at room temperature. And as can be seen from fig. 14, the trap preservation information of embodiment 8 remains relatively stable within a delay time of 3 min to 1h. However, as the delay time is prolonged, the decay rates of the stored energy of trap I and trap II are different, the stored energy of trap I is finally dissipated by ambient temperature, and after the trap II is decayed for a longer time, the stored energy retention rate is higher than 50%, and then the trap II is basically lossless in a room temperature darkroom environment, which indicates that example 8 can be used as an information storage medium with a high information retention rate.
The invention is exemplified in example 8, for which Gd is excited in ultraviolet 3+ A kind of electronic device 6 I J Afterglow/thermal excitation fluorescence emission spectra at 274nm after energy level were tested and the test results are shown in FIG. 15. As can be seen from FIG. 15, example 8 thermally stimulated fluorescence emission spectrum is a multi-band emission from the ultraviolet to the visible region, attributable to Tb 3+ A kind of electronic device 5 D 3,4 → 7 F J (j= 6,5,4,3) energy level transitions. The strongest thermally-stimulated fluorescence emission spectrum of example 8 was obtained upon heating to 140 ℃.
In order to evaluate the effectiveness of the different excitation wavelengths in generating afterglow in example 8, the invention uses a monochromatic xenon lamp to irradiate the fluorescent powder of example 8 to obtain the photoluminescence excitation spectrum and the afterglow excitation spectrum of example 8 as shown in fig. 16, and it can be seen that when the excitation wavelength spans the range of 200-400 nm, the afterglow intensity of example 8 can be effectively obtained. Taking example 8 as an example, trap filling spectra (namely a pyroelectric excitation spectrum) at 24 ℃ and 80 ℃ are tested, and the test results are shown in fig. 16, so that the filling of the fluorescent powder of example 8 at 80 ℃ is obviously enhanced compared with room temperature, and the abnormal thermal compatibilization phenomenon of example 8 is shown.
The optical information storage process comprises three basic steps: empty traps are set by thermal/optical (clear process), recharged (written) by burn-in process, and signal extraction process (read). Thus, in the present invention, taking example 8 as an example, a fluorescence photograph is read by using the information storage medium to simulate the storage of optical information, and the obtained fluorescence photograph is shown in fig. 17.
Fig. 17 (a) and 17 (b) are fluorescence photographs of information stored in traps of different depths, which are read out at different thermal stimuli (temperatures), after patterned uv light is written into different trap information at different temperatures. In fig. 17 (a), the pear pattern was written by light irradiation of 274nm at 150 ℃ through a patterned photomask. Subsequently, peach patterns were written at 80 ℃. Finally, the banana pattern was written at room temperature. Thus, three different patterns are stored in traps of different depths. As shown in fig. 17, by temperature management, "bananas" stored in advance in shallow traps, "peaches" stored in middle-deep traps, and "pears" stored in only deep partial traps can be visualized. This stored information can only be released when the phosphor film is provided with sufficient activation energy (heat or photons). The recorded banana patterns can be individually extracted and read out at 60 ℃. The peach pattern can be clearly obtained by raising the temperature to 120 ℃. The temperature was raised to 180℃and the pear pattern was obtained. Therefore, different information can be stored and read out in the same space, and multi-level optical information storage is realized. Likewise, digital information can also be stored and extracted by the above-described modes, as shown in fig. 17 (b). Fig. 17 (c) is a multicolor information picture read by thermal excitation with the aid of a filter in the case of solar light writing information, showing simultaneous information reading and trichromatic encryption under thermal excitation at 130 ℃ after solar charging. Fig. 17 (d) is a picture of the multi-color information read out by near infrared light excitation with the aid of a filter after writing the letter information by ultraviolet light. Fig. 17 (d) shows that: in addition to the extraction of stored information using thermal excitation in fig. 17 (a) -17 (c), information can also be read by photoexcitation. The above results indicate that: the thermal excitation fluorescent powder can be successfully applied to multistage information storage and synchronous encryption.
The present invention summarizes the luminescence properties of the phosphors of comparative example 1 and examples 1 to 22 according to the above-described fluorescence property test results as shown in table 1.
And the properties of phosphors doped with different ions and different concentrations can be seen from table 1.
TABLE 1 luminescence properties of phosphors
In summary, the fluorescence performance of example 8 was optimal.
It should be apparent that the embodiments described above are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (9)
1. A fluorescent powder for information storage is characterized by using NaGdGeO 4 The method comprises the steps of (1) introducing doping ions M into a substrate to obtain the matrix; and the molecular formula of the fluorescent powder is NaGdGeO 4 :xM；
Wherein M is Pb 2+ 、Tb 3+ 、Ln 3+ One or more of the following;
Ln 3+ is Eu 3+ 、Yb 3+ 、Y 3+ 、Ce 3+ 、Dy 3+ 、Nd 3+ 、Tm 3+ 、Er 3+ 、Ho 3+ 、La 3+ 、Lu 3+ 、Sm 3+ 、Pr 3+ 、Sc 3+ Any one of them;
xis doped with M in the molar doping concentration of Gd in the matrix and 0 < >x≤3%。
2. A method of preparing the phosphor of claim 1, comprising the steps of:
NaGdGeO according to the molecular formula of the fluorescent powder 4 :xThe stoichiometric ratio in M, weighing each preparation raw material with corresponding mass, namely Na source, gd source, ge source, O source and M source;
mixing the weighed Na source, gd source, ge source, O source and doped ion M source, and fully grinding and uniformly mixing to obtain mixed powder;
calcining the mixed powder for the first time at 900-1000 ℃ and grinding the mixed powder into powder to obtain precursor powder;
and (3) calcining the precursor powder for the second time at 1100-1400 ℃ and grinding the precursor powder into powder to obtain the fluorescent powder.
3. The method of claim 2, wherein the Na source, gd source, ge source, and M source are oxygen-containing compounds containing the corresponding elements;
the O source is provided by each of the oxygenates containing the corresponding element.
4. The method of claim 3, wherein the oxygen-containing compound is any one or more of an oxide, a carbonate, and a nitrate.
5. The process according to claim 4, wherein M comprises Pb 2+ Or/and Tb 3+ When Pb is added 2+ Or/and Tb 3+ In its corresponding oxide form with other preparation raw materials.
6. The method of claim 4, wherein M comprises Ln 3+ When Ln is added 3+ In the form of its nitrate solution, is added after mixing with other preparation materials.
7. The method according to claim 2, wherein the atmosphere for the first calcination is air and the calcination time is 4 to 8 hours.
8. The preparation method according to claim 2, wherein the atmosphere of the second calcination is air, the calcination time is 4-8 hours, and the temperature rising rate is 2-4 ℃/min.
9. The method of claim 2, wherein the polishing time per polishing is 0.5 to 1 hour.
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| US20110038947A1 (en) * | 2007-12-14 | 2011-02-17 | Basf Se | Inorganic phosphor, obtainable by wet milling |
| EP3623449A1 (en) * | 2018-09-14 | 2020-03-18 | Seaborough IP I B.V. | Method for preparing a luminescent composition |
| EP3623448A1 (en) * | 2018-09-14 | 2020-03-18 | Seaborough IP I B.V. | Method for treating a luminescent material comprising organic ligands |
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| US20110038947A1 (en) * | 2007-12-14 | 2011-02-17 | Basf Se | Inorganic phosphor, obtainable by wet milling |
| EP3623449A1 (en) * | 2018-09-14 | 2020-03-18 | Seaborough IP I B.V. | Method for preparing a luminescent composition |
| EP3623448A1 (en) * | 2018-09-14 | 2020-03-18 | Seaborough IP I B.V. | Method for treating a luminescent material comprising organic ligands |
| WO2023111247A1 (en) * | 2021-12-16 | 2023-06-22 | Seaborough Ip I B.V. | Microjet reactor based synthesis of nanophosphors |
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