CN114854401A - Green fluorophlogopite fluorescent powder with high quantum yield and preparation method and application thereof - Google Patents

Green fluorophlogopite fluorescent powder with high quantum yield and preparation method and application thereof Download PDF

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CN114854401A
CN114854401A CN202210582890.6A CN202210582890A CN114854401A CN 114854401 A CN114854401 A CN 114854401A CN 202210582890 A CN202210582890 A CN 202210582890A CN 114854401 A CN114854401 A CN 114854401A
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fluorophlogopite
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quantum yield
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石士考
刘俊杉
董胜娟
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Hebei Normal University
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Abstract

The invention relates to the technical field of fluorescent materials, and particularly discloses green fluorophlogopite fluorescent powder with high quantum yield, and a preparation method and application thereof. The preparation method of the green fluorophlogopite fluorescent powder comprises the following steps: uniformly mixing potassium fluosilicate, magnesium oxide, aluminum oxide, silicon dioxide, terbium oxide and cerium oxide, and grinding to obtain mixed solid powder; calcining the mixed solid powder for 4.5-5 h at 1030-1070 ℃ under inert atmosphere, cooling and grinding to obtain the green fluorophlogopite fluorescent powder with high quantum yield. The fluorophlogopite fluorescent powder prepared by the invention can clearly show I-III fingerprint characteristics under the excitation of ultraviolet light, realizes the purpose of latent fingerprint display on the surfaces of various substrates, has the fluorescence quantum yield as high as 78 percent, has obvious development effect, and has higher application prospect in the fields of forensic medicine, individual identification and the like.

Description

Green fluorophlogopite fluorescent powder with high quantum yield and preparation method and application thereof
Technical Field
The invention relates to the technical field of fluorescent materials, in particular to green fluorophlogopite fluorescent powder with high quantum yield, and a preparation method and application thereof.
Background
The fingerprint is a unique characteristic of every person, is often regarded as the second 'identity card' of an individual, and is important evidence for confirming identity information of the individual in criminal cases. In general, most of fingerprints left at crime scenes are invisible fingerprints, and certain technical means are needed to enable latent fingerprints to be displayed. The powder display method is a traditional, high-efficiency and widely-applied latent fingerprint display method, and has the advantages of low cost, simplicity in operation, time saving, rapidness and the like. After long-term development, a lot of powder materials can be used for realizing latent fingerprint detection, but currently, fingerprint powder circulating in the market is mostly judged by experience when in use and operation, the contrast and the sensitivity of a fingerprint visual image are low, and identification of I-level fingerprint features (fingerprint ridge flow in common forms such as triangle, ring and spiral) and part of II-level fingerprint features (thin fulcrums for identifying single fingerprint ridges) can be usually only carried out on fingerprints. However, in the case of a damaged fingerprint, the identification of an individual by means of class i fingerprint features and partial class ii fingerprint features alone is often not sufficient, and therefore class iii fingerprint features (finer points on the fingerprint ridges, such as sweat pores and curvatures) need to be identified.
The fluorescence intensity of the fingerprint reagent is an important standard influencing the developing effect of fingerprint images. It is well known that the optic nerve of the human eye is sensitive to different wavelengths of light, the most sensitive to green perception among red, green and blue light. In the existing fingerprint reagent, the green luminous fingerprint reagent has fewer types, and the fluorescence intensity of most fingerprint reagents is relatively low, so that the developing effect of the fingerprint is poor, and the fingerprint reagent is greatly limited in actual latent fingerprint detection. Therefore, it is necessary to develop a new green fluorescent latent fingerprint detection powder with high fluorescence intensity as a fingerprint reagent for accurate identification of latent fingerprints.
Disclosure of Invention
Aiming at the problems that the green luminous latent fingerprint detection powder in the prior art has low fluorescence intensity, causes poor fingerprint development effect and the like, the invention provides the green fluorophlogopite fluorescent powder with high quantum yield and the preparation method and the application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of green fluorophlogopite fluorescent powder with high quantum yield comprises the following steps:
step a, uniformly mixing potassium fluosilicate, magnesium oxide, aluminum oxide, silicon dioxide, terbium oxide and cerium oxide, and grinding to obtain mixed solid powder;
wherein, the total amount of potassium fluosilicate, magnesium oxide, aluminum oxide and silicon dioxide is 100 percent, and the dosage of each component is as follows: 24.5 to 27.5 percent of potassium fluosilicate, 27.1 to 30.1 percent of magnesium oxide, 10.9 to 12.2 percent of aluminum oxide and 33.5 to 37.5 percent of silicon dioxide; the molar ratio of Tb in the terbium oxide to K in the potassium fluosilicate is 0.02-0.04:1, and the molar ratio of Ce in the cerium oxide to K in the potassium fluosilicate is 0.09-0.12: 1;
and b, calcining the mixed solid powder for 4.5-5 h at 1030-1070 ℃ under inert atmosphere, cooling and grinding to obtain the green fluorophlogopite fluorescent powder with high quantum yield.
Compared with the prior art, the preparation method of the green fluorophlogopite fluorescent powder with high quantum yield provided by the invention takes fluorophlogopite as a substrate and Tb 3+ And Ce 3+ Respectively as an activator and a sensitizer to be jointly doped into the structure of the fluorophlogopite, the unique layered structure of the fluorophlogopite and the excellent ion exchange performance of interlayer cations ensure that Ce 3+ And Tb 3+ Is easier to enter between layers and is Tb 3+ Provides a good luminous environment, and forms stronger Ce in a larger wavelength range with the excitation wavelength of 230-340nm 3+ And Tb 3+ The 4f-5d transition absorption broadband is completely positioned in an ultraviolet region, so that the prepared fluorescent powder can be efficiently excited by ultraviolet light, and the visualization of latent fingerprints is realized in a high-intensity green fluorescence manner; the fluorescence quantum yield of the prepared fluorescent powder is up to 78%, under the excitation of 254nm ultraviolet light, the bright green luminescence and the strong adhesiveness of the fluorescent powder enable the visualized fingerprint image to have higher contrast, sensitivity, selectivity and lower background interference, so that each detail of the fingerprint is clearly and accurately reproduced, the transition area between the ridge and the groove is obvious, the ridge detail characteristics of I-III grades are clearly visible, the latent fingerprint detection on the surfaces of various non-porous and semi-porous substrates is realized,has wide application prospect in the field of latent fingerprint detection.
Preferably, the total amount of the potassium fluosilicate, the magnesium oxide, the aluminum oxide and the silicon dioxide is 100 percent, and the dosage of each component is as follows: 25.6 percent of potassium fluosilicate, 28.1 percent of magnesium oxide, 11.4 percent of aluminum oxide and 34.9 percent of silicon dioxide.
The optimized ratio of the substances is beneficial to fully reacting the components, obtaining the fluorophlogopite fluorescent material with uniform particle size and good crystallinity, and enhancing the luminous intensity of the prepared fluorescent material.
Preferably, the molar ratio of Tb in the terbium oxide to K in the potassium fluosilicate is 0.03: 1.
Preferably, the molar ratio of Ce in the cerium oxide to K in the potassium fluosilicate is 0.12: 1.
Preferred Tb 3+ 、Ce 3+ The doping concentration can improve the fluorescence quantum yield of the fluorescent powder, so that the green fluorescence intensity of the fluorescent powder is enhanced, and the contrast and the sensitivity of a fingerprint image are higher.
Preferably, in the step b, the temperature is raised to 1030-1070 ℃ in a temperature programming manner, and the temperature raising rate is 4-6 ℃/min.
Preferably, in step b, the calcination temperature is 1050 ℃ and the calcination time is 5 h.
Preferably, in the step b, the cooling rate is 2-4 ℃/min.
Preferably, in step b, the cooling rate is 3 ℃/min.
The preferable calcining temperature, heating rate and cooling rate are favorable for obtaining more regular lamellar mica crystals and avoiding the generation of other crystal phases. Meanwhile, the composition is also beneficial to promoting Tb 3+ 、Ce 3+ And the fluorescent powder enters the crystal lattice of the fluorophlogopite, so that the fluorescent quantum yield of the fluorescent powder is improved.
The invention also provides a green fluorophlogopite fluorescent powder with high quantum yield, which is prepared by the preparation method of any one of the green fluorophlogopite fluorescent powder with high quantum yield.
Selection of Ce in the invention 3+ And Tb 3+ As dopant ion, when Tb 3+ 、Ce 3+ After co-doping into the interlayer structure of fluorophlogopite, at Ce 3+ And Tb 3+ The prepared sample shows Tb under the action of energy transfer 3+ Is strong 5 D 4 → 7 F 5 The characteristic transition green emission forms stronger Ce in a larger range of the excitation wavelength of 230-340nm 3+ And Tb 3+ The 4f-5d transition absorbs the broadband, the fluorescence quantum yield is as high as 78%, the ultra-wideband excitation of the high-strength green fluorophlogopite fluorescent powder provides great convenience for acquiring a visual fingerprint image, is favorable for clearly identifying and distinguishing I-level and III-level fingerprint characteristics, and has wide application prospect in the field of latent fingerprint detection.
The invention also provides application of the green fluorophlogopite fluorescent powder with high quantum yield in latent fingerprint detection.
Compared with the existing green fluorescent material, the fluorophlogopite fluorescent powder provided by the invention has a wider excitable range in an ultraviolet region, the absorption broadband range is 230-340nm, the visualization of fingerprints is convenient to realize under the excitation wavelength in a large range, meanwhile, no extra material such as any fluxing agent is required to be added in the synthesis process to enhance the luminescence of a sample, and the unique layered structure of fluorophlogopite is Tb 3+ The excellent green fluorescence emission provides a very suitable environment, and the fluorescence quantum yield of the fluorophlogopite powder prepared by the invention is obviously improved.
When the fluorophlogopite powder provided by the invention is used as a latent fingerprint developing reagent, the fluorophlogopite powder is lightly smeared on the surface of a base material printed with latent fingerprints by using a soft brush, the rest powder is blown off by using a blower, and then the developing is carried out under an 254nm ultraviolet lamp, so that the grade I-grade III ridge-shaped details in a fingerprint image can be accurately identified.
Drawings
FIG. 1 is FP of 3% Tb: 3 prepared in example 1 3+ ,12％Ce 3+ Phosphor samples, FP 3% Tb prepared in comparative example 1 3+ Phosphor samples, FP prepared in comparative example 2 12% Ce 3+ X-ray diffraction patterns of the phosphor samples, the fluorophlogopite substrate prepared in comparative example 7;
FIG. 2 is a 3% Tb FP of example 1 3+ ,12％Ce 3+ SEM picture and TEM picture of the phosphor sample, (a) scanning electron micrograph, (b) transmission electron micrograph;
FIG. 3 is a 3% Tb FP of comparative example 1 3+ An excitation spectrogram and an emission spectrogram of a fluorescent powder sample, (a) the excitation spectrogram and (b) the emission spectrogram;
FIG. 4 is 12% Ce FP prepared in comparative example 2 3+ An excitation spectrogram and an emission spectrogram of a fluorescent powder sample, (a) the excitation spectrogram and (b) the emission spectrogram;
FIG. 5 is FP of 3% Tb: 3 prepared in example 1 3+ ,12％Ce 3+ Phosphor samples, FP 3% Tb prepared in comparative example 3 3 + ,6％Ce 3+ An excitation spectrum of the fluorescent powder sample at a monitoring wavelength of 542 nm;
FIG. 6 is FP of 3% Tb: 3 prepared in example 1 3+ ,12％Ce 3+ Phosphor samples, FP 3% Tb prepared in comparative example 3 3 + ,6％Ce 3+ An emission spectrum of the fluorescent powder sample at an excitation wavelength of 268 nm;
FIG. 7 is a 3% Tb FP of comparative example 1 3+ And FP prepared in example 1 3% Tb 3+ ,12％Ce 3+ A comparison graph of emission spectra of the samples at an excitation wavelength of 254 nm;
FIG. 8 is a 3% Tb FP of example 1 3+ ,12％Ce 3+ Phosphor samples, 3% Tb of Natural FP prepared in comparative example 4 3+ ,12％Ce 3+ An emission spectrum of the fluorescent powder sample under the excitation wavelength of 254 nm;
FIG. 9 is FP of 3% Tb: 3 prepared in example 1 3+ ,12％Ce 3+ Phosphor samples, Sr-FP of 3% Tb 3% prepared in comparative example 5 3+ ,12％Ce 3+ Phosphor samples, and 3% Tb of Ca-FP prepared in comparative example 6 3+ ,12％Ce 3+ An emission spectrum of the fluorescent powder sample under the excitation wavelength of 254 nm;
FIG. 10 is a 3% Tb FP of example 1 3+ ,12％Ce 3+ Phosphor samples, FP 3% Tb prepared in comparative example 1 3 + The fluorescence decay curve of the phosphor sample;
FIG. 11 is FP of 3% Tb: 3 prepared in example 1 3+ ,12％Ce 3+ Phosphor samples, FP prepared in comparative example 2 12% Ce 3+ The fluorescence decay curve of the phosphor sample;
FIG. 12 is a 3% Tb FP of example 1 3+ ,12％Ce 3+ Latent fingerprint images of fluorescent powder samples on the surfaces of objects with different roughness under an ultraviolet lamp of 254nm, wherein the fluorescent powder samples comprise metal (a), glass slides (b), tinfoil (c), plastic (d), common paper (a), (e), common paper (b), (f), common paper (c), (g) and common paper (d), (h);
FIG. 13 is FP of 3% Tb: 3 prepared in example 1 3+ ,12％Ce 3+ An enlarged view of the complete and partial minutiae of the visible fingerprint of the phosphor sample on the slide surface.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to better illustrate the invention, the following examples are given by way of further illustration.
Example 1
The embodiment of the invention provides a preparation method of green fluorophlogopite fluorescent powder with high quantum yield, which at least comprises the following steps:
step one, 0.1307g K 2 SiF 6 、0.1435g MgO、0.0581g Al 2 O 3 、0.1783g SiO 2 、0.0067g Tb 4 O 7 And 0.0246g of CeO 2 After mixing, fully grinding in an agate mortar for 20min to obtain mixed solid powder;
step two, placing the mixed solid powder in a corundum crucible, heating the mixed solid powder to 1050 ℃ at the speed of 5 ℃/min in a tube furnace under the nitrogen atmosphere, calcining for 5.0h, cooling to room temperature at the speed of 3 ℃/min, and grinding to obtain the green fluorophlogopite fluorescent powder (FP: 3% Tb) with high quantum yield 3+ ,12％Ce 3+ A phosphor).
Example 2
The embodiment of the invention provides a preparation method of green fluorophlogopite fluorescent powder with high quantum yield, which at least comprises the following steps:
step one, 0.1285g K 2 SiF 6 、0.1565g MgO、0.0628g Al 2 O 3 、0.1751g SiO 2 、0.0045g Tb 4 O 7 And 0.0182g of CeO 2 After mixing, fully grinding in an agate mortar for 20min to obtain mixed solid powder;
step two, placing the mixed solid powder in a corundum crucible, heating to 1030 ℃ at the speed of 4 ℃/min in a tube furnace under the nitrogen atmosphere, calcining for 5.0h, cooling to room temperature at the speed of 2 ℃/min, and grinding to obtain the green fluorophlogopite fluorescent powder (FP: 2% Tb) with high quantum yield 3+ ,9％Ce 3+ A phosphor).
Example 3
The embodiment of the invention provides a preparation method of green fluorophlogopite fluorescent powder with high quantum yield, which at least comprises the following steps:
step one, 0.1405g K 2 SiF 6 、0.1449g MgO、0.0576g Al 2 O 3 、0.1916g SiO 2 、0.0095g Tb 4 O 7 And 0.0242g of CeO 2 After mixing, fully grinding in an agate mortar for 20min to obtain mixed solid powder;
step two, placing the mixed solid powder in a corundum crucible, heating to 1070 ℃ at the speed of 6 ℃/min in a tube furnace in the nitrogen atmosphere, calcining for 4.5h, cooling to room temperature at the speed of 4 ℃/min, and grinding to obtain the green fluorophlogopite fluorescent powder (FP: 4% Tb) with high quantum yield 3+ ,11％Ce 3+ A phosphor).
Comparative example 1
Comparative example of the present invention provides a method for preparing fluorophlogopite phosphor, which is completely the same as example 1 except that only Tb is doped 3+ The preparation method comprises the following steps:
step one, 0.1307g K 2 SiF 6 、0.1435g MgO、0.0581g Al 2 O 3 、0.1783g SiO 2 、0.0067g Tb 4 O 7 After mixing, fully grinding in an agate mortar for 20min to obtain mixed solid powder;
step two, placing the mixed solid powder in a corundum crucible, heating to 1050 ℃ at the speed of 5 ℃/min in a tube furnace under the nitrogen atmosphere, calcining for 5.0h, cooling to room temperature at the speed of 3 ℃/min, and grinding to obtain fluorophlogopite fluorescent powder (FP: 3% Tb) 3+ A phosphor).
Comparative example 2
The comparative example of the invention provides a preparation method of fluorophlogopite fluorescent powder, which is completely the same as the example 1 except that only Ce is doped 3+ The preparation method comprises the following steps:
step one, 0.1307g K 2 SiF 6 、0.1435g MgO、0.0581g Al 2 O 3 、0.1783g SiO 2 And 0.0246g of CeO 2 After mixing, fully grinding in an agate mortar for 20min to obtain mixed solid powder;
step two, placing the mixed solid powder in a corundum crucible, heating to 1050 ℃ at the speed of 5 ℃/min in a tube furnace under the nitrogen atmosphere, calcining for 5.0h, cooling to room temperature at the speed of 3 ℃/min, and grinding to obtain fluorophlogopite fluorescent powder (FP: 12% Ce) 3+ A phosphor).
Comparative example 3
The comparative example provides a preparation method of fluorophlogopite fluorescent powder, which at least comprises the following steps:
step one, 0.1307g K 2 SiF 6 、0.1435g MgO、0.0581g Al 2 O 3 、0.1783g SiO 2 、0.0067g Tb 4 O 7 And 0.0123g of CeO 2 After mixing, fully grinding in an agate mortar for 20min to obtain mixed solid powder;
step two, placing the mixed solid powder in a corundum crucible, heating to 1050 ℃ at the speed of 5 ℃/min in a tube furnace under the nitrogen atmosphere, calcining for 5.0h, cooling to room temperature at the speed of 3 ℃/min, and grinding to obtain fluorophlogopite fluorescent powder (FP: 3% Tb) 3+ ,6％Ce 3+ A phosphor).
Comparative example 4
The comparative example provides a preparation method of fluorophlogopite fluorescent powder, which at least comprises the following steps:
step one, crushing, grinding and drying a commercially available fluorophlogopite sheet to obtain natural mica powder;
step two, weighing 0.5g of natural mica powder and 0.0067g of Tb 4 O 7 And 0.0246g of CeO 2 After mixing, fully grinding in an agate mortar for 20min to obtain mixed solid powder;
step two, placing the mixed solid powder in a corundum crucible, heating to 1050 ℃ at the speed of 5 ℃/min in a tubular furnace under the conditions of nitrogen atmosphere and carbon powder reduction, calcining for 5.0h, cooling to room temperature at the speed of 3 ℃/min, and grinding to obtain fluorophlogopite fluorescent powder (natural FP: 3% Tb: 3%) 3+ ,12％Ce 3+ A phosphor).
Comparative example 5
The invention provides a preparation method of fluorophlogopite fluorescent powder, which at least comprises the following steps:
step one, 0.0855g of SrCO 3 、0.0684g MgO、0.0595g Al 2 O 3 、0.2015g SiO 2 、0.1062g MgF 2 、0.0067g Tb 4 O 7 And 0.0246g of CeO 2 After mixing, fully grinding in an agate mortar for 20min to obtain mixed solid powder;
step two, placing the mixed solid powder in a corundum crucible, heating to 1050 ℃ at the speed of 5 ℃/min in a tube furnace under the nitrogen atmosphere, calcining for 5.0h, cooling to room temperature at the speed of 3 ℃/min, and grinding to obtain fluorophlogopite fluorescent powder (Sr-FP: 3% Tb) 3+ ,12％Ce 3+ A phosphor).
Comparative example 6
The invention provides a preparation method of fluorophlogopite fluorescent powder, which at least comprises the following steps:
step one, 0.0348g of CaO, 0.0756g of MgO and 0.0648g of Al 2 O 3 、0.2256g SiO 2 、0.1142g MgF 2 、0.0067g Tb 4 O 7 And 0.0246g of CeO 2 After mixing, fully grinding in an agate mortar for 20min to obtain mixed solid powder;
step two, placing the mixed solid powder in a corundum crucible, heating to 1050 ℃ at the speed of 5 ℃/min in a tube furnace under the nitrogen atmosphere, calcining for 5.0h, cooling to room temperature at the speed of 3 ℃/min, and grinding to obtain fluorophlogopite fluorescent powder (Ca-FP: 3% Tb) 3+ ,12％Ce 3+ A phosphor).
Comparative example 7
The preparation method of the fluorophlogopite substrate comprises the following steps:
step one, 0.1307g K 2 SiF 6 、0.1435g MgO、0.0581g Al 2 O 3 、0.1783g SiO 2 After mixing, fully grinding in an agate mortar for 20min to obtain mixed solid powder;
and step two, placing the mixed solid powder in a corundum crucible, heating the mixed solid powder to 1050 ℃ at the speed of 5 ℃/min in a tubular furnace under the nitrogen atmosphere, calcining for 5.0h, cooling to room temperature at the speed of 3 ℃/min, and grinding to obtain the fluorophlogopite substrate.
Material characterization
FIG. 1 is FP of 3% Tb: 3 prepared in example 1 3+ ,12％Ce 3+ Phosphor sample, FP prepared in comparative example 1 3% Tb 3+ Phosphor samples, FP prepared in comparative example 2 12% Ce 3+ X-ray diffraction pattern of the phosphor sample, fluorophlogopite substrate prepared in comparative example 7. As can be seen from the figure, all diffraction peaks of each sample map are very close in shape and position, are matched with the diffraction peak height in the characteristic standard card JCPDS #16-0344, belong to a monoclinic crystal structure, and have a space group of C 2/m . The characteristic diffraction peaks at 8.9 °, 19.3 °, 26.8 °, 34.3 ° and 45.4 ° (2 θ) correspond to the (001), (020), (003), (200) and (005) crystal planes, respectively. Among them, the diffraction angles corresponding to the (001), (003) and (005) planes exhibited good fold relationships, indicating that the sample had a lamellar structure. At Tb 3+ 、Ce 3+ And Tb 3+ And Ce 3+ No Tb was observed after co-doping 4 O 7 And CeO 2 Is substantially the same as the structure of the fluorophlogopite substrateThus, it indicates Tb 3+ And Ce 3+ The doping of (a) hardly changes the structure of the sample.
FIG. 2 is a 3% Tb FP of example 1 3+ ,12％Ce 3+ SEM image (a) and TEM image (b) of the phosphor sample. As can be seen from FIG. 2, though Tb was incorporated in the fluorophlogopite matrix 3+ 、Ce 3+ The two ions, but the appearance of the sample still presents an obvious lamellar structure, the layering effect is obvious, and the result is consistent with the analysis result of the X-ray diffraction. The average grain size of the sample is 3-4 mu m, and the crystallinity is higher, so that the grain size requirement of the lamellar fingerprint reagent is met.
FIG. 3 is a 3% Tb FP of comparative example 1 3+ The excitation spectrum (a) and the emission spectrum (b) of the phosphor sample show that a strong absorption band exists in the range of 220-280nm, the central value is at 242nm, which is mainly derived from Tb 3+ Characteristic 4f-5d transition. In addition, there is a weak broad band of absorption in the 290-340nm range, which is mainly attributed to Tb 3+ Characteristic 4f-4f transitions. Since the sample has the strongest absorption at 242nm, 242nm is taken as FP:3 mol% Tb 3+ Excitation wavelength of the sample. Under the excitation wavelength of 242nm, a series of sharp emission peaks exist in the region of 450-650nm of the sample, and correspond to Tb at 487nm, 542nm, 584nm and 621nm respectively 3+ Is characterized by 5 D 4 → 7 F J (J-6, 5, 4, 3) transition emission, at 542nm 5 D 4 → 7 F 5 The transition takes a dominant position.
FIG. 4 is 12% Ce FP prepared in comparative example 2 3+ The excitation spectrum (a) and the emission spectrum (b) of the phosphor sample show that two distinct absorption broad bands exist at 268nm and 300nm, corresponding to Ce 3+ 4f → 5d electric dipole characteristic transition. The emission spectrum mainly consists of a broad band (with a central value of 400nm) in the range of 330nm-530nm, corresponding to Ce 3+ The 5d → 4f characteristic transition of (A), the sample exhibits bright blue emission, demonstrating that Ce is present 3+ Can be used as an effective activator for promoting Tb 3+ Green fluorescence emission of (2).
FIG. 5 is FP of 3% Tb: 3 prepared in example 1 3+ ,12％Ce 3+ Phosphor samples, FP 3% Tb prepared in comparative example 3 3 + ,6％Ce 3+ The excitation spectrum of the phosphor sample at the monitoring wavelength of 542nm is shown in the figure, and it can be seen that there are two distinct absorption broad bands at the central positions of 268nm and 297m, which are assigned to Ce 3+ Is a characteristic absorption of the molecular sieve, demonstrates a conversion from Ce 3+ To Tb 3+ There is an efficient energy transfer therebetween. And FP 3% Tb 3+ In comparison with the excitation spectrum of Ce (FIG. 3) 3+ And Tb 3+ The broadband absorption peak at 268nm for the co-doped sample became clearly broader, indicating that Ce is present 3+ 4f-5d excitation band and Tb 3+ The excitation bands of 4f-5d have overlapping effect at 242 nm. In addition, the excitation intensity of the sample at 268nm is stronger than that at 297nm, which indicates that the sample has better excitation effect under 268nm ultraviolet light. Ce 3+ And Tb 3+ The codoped FP sample is suitable for the application of realizing latent fingerprint detection under the excitation of a wide ultraviolet range (230-340 nm). And the excitation intensity of the phosphor sample prepared in example 1 was higher compared to that of comparative example 3.
FIG. 6 is FP of 3% Tb: 3 prepared in example 1 3+ ,12％Ce 3+ Phosphor samples, FP 3% Tb prepared in comparative example 3 3 + ,6％Ce 3+ The emission spectrum of the phosphor sample at an excitation wavelength of 268nm can be seen from the graph, at Ce 3+ After doping, the emission spectrum of the sample and FP: Tb 3+ The emission spectra (FIG. 3) were of uniform shape and were greatly enhanced in luminous intensity, again demonstrating Ce 3+ And Tb 3+ The effective energy transfer function exists. The emission spectra correspond to Tb at 487nm, 542nm, 584nm and 621nm respectively 3+ Is characterized by 5 D 4 → 7 F J (J ═ 6, 5, 4, 3) transition emission. And the luminescence intensity of the sample prepared in example 1 was significantly increased compared to that of comparative example 3.
To observe Ce more intuitively 3+ For Tb 3+ FIG. 7 presents FP: 3% Tb prepared in comparative example 1 3+ And example 1FP prepared 3% Tb 3+ ,12％Ce 3+ Emission spectra of the samples at an excitation wavelength of 254nm are compared. FP 3% Tb 3 + Sample doped with Tb alone 3+ The luminescence intensity at time is very low, at Ce 3+ And Tb 3+ After co-doping, the luminous intensity of the sample is greatly enhanced and is about FP: 3% Tb 3+ 16 times of that of fluorophlogopite, indicating that Ce is contained in fluorophlogopite 3+ And Tb 3+ The energy transfer effect between the two parts is remarkable.
FIG. 8 is a 3% Tb FP of example 1 3+ ,12％Ce 3+ Phosphor samples, 3% Tb of Natural FP prepared in comparative example 4 3+ ,12％Ce 3+ The emission spectrum of the phosphor sample at the excitation wavelength of 254nm can be seen from the figure when Ce is used 3 + ,Tb 3+ Co-doping into natural fluorophlogopite, the sample showed only weak green luminescence, while 3% Tb in the synthesized FP 3+ ,12％Ce 3+ In the sample, the luminous intensity of the sample is greatly enhanced, which indicates that the rare earth ions are in the synthetic mica (FP: 3% Tb) 3+ ,12％Ce 3+ ) The micro environment in (1) has more obvious promotion effect on the luminescence.
FIG. 9 is FP of 3% Tb: 3 prepared in example 1 3+ ,12％Ce 3+ Phosphor samples, Sr-FP of 3% Tb 3% prepared in comparative example 5 3+ ,12％Ce 3+ Phosphor samples, and 3% Tb of Ca-FP prepared in comparative example 6 3+ ,12％Ce 3+ The emission spectrum of the phosphor sample at the excitation wavelength of 254nm shows that at the excitation wavelength of 254nm, the mica with different interlayer cation types presents similar spectral characteristics, but has obvious difference in emission intensity. FP prepared in example 1 3% Tb 3+ ,12％Ce 3+ The sample had the strongest fluorescence intensity and the emission intensity was about 3% Tb and Sr-FP prepared in comparative example 5 3+ ,12％Ce 3+ Sample and Ca-FP 3% Tb prepared in comparative example 6 3+ ,12％Ce 3+ About 2 times of the sample, thus indicating that fluorophlogopite is a compound which can be Tb 3+ Most suitable host materials that provide a good light emitting environment.
FIG. 10 is a 3% Tb FP of example 1 3+ ,12％Ce 3+ Phosphor samples, FP 3% Tb prepared in comparative example 1 3 + Fluorescence decay Curve (lambda) of the phosphor sample ex ＝268nm，λ em 542nm) it can be seen that their decay traces all follow a bi-exponential decay pattern. Although Tb was present in the sample 3+ In the same concentration, but at Ce 3+ And Tb 3+ Tb in co-doped samples 3+ Is significantly slower than at Tb 3+ In the sample doped alone. Calculated FP: 3% Tb 3+ Sample and FP 3% Tb 3+ ,12％Ce 3+ The lifetime values of the samples were 0.96ms and 1.15ms, respectively, indicating Ce 3+ As a suitable donor, the energy is effectively transferred to Tb 3+ 。
FIG. 11 is FP of 3% Tb: 3 prepared in example 1 3+ ,12％Ce 3+ Phosphor samples, FP prepared in comparative example 2 12% Ce 3+ Fluorescence decay Curve (lambda) of the phosphor sample ex ＝268nm，λ em 400nm), it can be seen that their decay traces all follow a bi-exponential decay pattern. At the same Ce 3+ At a concentration of Ce 3+ And Tb 3+ Ce in Co-doped samples 3+ Is significantly higher than the rate of decay of Ce 3+ The decay rate in the singly doped samples was fast. Calculating FP to 12 percent Ce by life fitting 3+ Sample and FP 3% Tb 3+ ,12％Ce 3+ The lifetime values of the samples were 43.98ns and 8.96ns, respectively, further confirming Ce 3+ And Tb 3+ The energy transfer efficiency is 79.6 percent.
Latent fingerprint detection
The surfaces of various objects of different roughness were pressed with a clean finger and the FP of 3% Tb from example 1 was applied 3+ ,12％Ce 3+ And slightly coating the fluorescent powder sample on the surface of the object printed with the latent fingerprints by using a soft brush, blowing away the residual powder by using a blower, and observing the developing effect of the latent fingerprints under 254nm ultraviolet light.
Wherein FIG. 12 is the FP of 3% Tb prepared in example 1 3+ ,12％Ce 3+ Phosphor samples on the surface of various objects of different roughness under a 254nm ultraviolet lampLatent fingerprint image, wherein non-porous substrates (metal (a), glass slide (b), tinfoil (c), plastic (d)), semi-porous substrates (plain paper a (e), plain paper b (f), plain paper c (g) and plain paper d (h)). As can be seen from the figure, the fingerprint area of the attached sample can be observed to show green fluorescence through the image, and the color is pure. The bright fluorescence effect of the sample enables the transition characteristics between the convex ridge and the concave groove to be obvious, the contrast between the fingerprint area and the background is high, the interference effect of the background on the surface of the base material on the visual fingerprint image is low, and the fingerprint image can be clearly shown. Meanwhile, the material has a wide application range, and the latent fingerprints can be visualized even on a semi-rough substrate.
To further confirm the precise identification of latent fingerprints, FIG. 13 shows FP 3% Tb prepared in example 1 3+ ,12％Ce 3+ An enlarged view of the complete and partial minutiae of the visible fingerprint of the phosphor sample on the slide surface. Generally, better identification is achieved by combining the level i-iii minutiae in the ridge pattern of the fingerprint with analysis. In the complete fingerprint visual image, the I-level integral ridge flow characteristic of the fingerprint is annular, and in addition, a plurality of II-level single ridge detail characteristics such as bifurcation, ridge end, bridge, island, lake and the like are very easy to distinguish. Most importantly, fine level III local detail features such as sweat pores can be clearly seen after the local detail features are enlarged. All the presented I-III level detail characteristics show the high selectivity and high sensitivity of the fluorescent powder sample prepared in the embodiment 1 of the invention to the fingerprint residues, so that the novel green fluorescent powder with high fluorescence intensity and high quantum yield has wide application prospect in the future latent fingerprint detection application.
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 or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A preparation method of green fluorophlogopite fluorescent powder with high quantum yield is characterized by comprising the following steps:
step a, uniformly mixing potassium fluosilicate, magnesium oxide, aluminum oxide, silicon dioxide, terbium oxide and cerium oxide, and grinding to obtain mixed solid powder;
wherein, the total amount of potassium fluosilicate, magnesium oxide, aluminum oxide and silicon dioxide is 100 percent, and the dosage of each component is as follows: 24.5 to 27.5 percent of potassium fluosilicate, 27.1 to 30.1 percent of magnesium oxide, 10.9 to 12.2 percent of aluminum oxide and 33.5 to 37.5 percent of silicon dioxide; the molar ratio of Tb in the terbium oxide to K in the potassium fluosilicate is 0.02-0.04:1, and the molar ratio of Ce in the cerium oxide to K in the potassium fluosilicate is 0.09-0.12: 1;
and b, calcining the mixed solid powder for 4.5-5 h at 1030-1070 ℃ under inert atmosphere, cooling and grinding to obtain the green fluorophlogopite fluorescent powder with high quantum yield.
2. The method of claim 1 for preparing high quantum yield green fluorphlogopite phosphor in the amount of 100% total of potassium fluorosilicate, magnesium oxide, aluminum oxide and silicon dioxide as follows: 25.6 percent of potassium fluosilicate, 28.1 percent of magnesium oxide, 11.4 percent of aluminum oxide and 34.9 percent of silicon dioxide.
3. The method of claim 1, wherein the molar ratio of Tb in terbium oxide to K in potassium fluosilicate is 0.03: 1.
4. The method of claim 1, wherein the molar ratio of Ce in the cerium oxide to K in the potassium fluosilicate is 0.12: 1.
5. The method of claim 1, wherein in step b, the temperature is raised to 1030-1070 ℃ by temperature programming at a rate of 4-6 ℃/min.
6. The method for preparing high quantum yield green fluorphlogopite phosphor according to claim 1, wherein the calcination temperature is 1050 ℃ and the calcination time is 5h in step b.
7. The method of claim 1, wherein in step b, the temperature reduction rate is 2 ℃/min to 4 ℃/min.
8. The method for preparing high quantum yield green fluorphlogopite phosphor according to claim 7, wherein the temperature decrease rate in step b is 3 ℃/min.
9. A high quantum yield green fluorophlogopite fluorescent powder, which is prepared by the preparation method of the high quantum yield green fluorophlogopite fluorescent powder as claimed in any one of claims 1 to 8.
10. Use of the high quantum yield green fluorphlogopite phosphor of claim 9 for latent fingerprint detection.
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