WO2019105488A1 - Upconversion phosphorescent material, and preparation method therefor and application thereof - Google Patents

Upconversion phosphorescent material, and preparation method therefor and application thereof Download PDF

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WO2019105488A1
WO2019105488A1 PCT/CN2018/126067 CN2018126067W WO2019105488A1 WO 2019105488 A1 WO2019105488 A1 WO 2019105488A1 CN 2018126067 W CN2018126067 W CN 2018126067W WO 2019105488 A1 WO2019105488 A1 WO 2019105488A1
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yyb
xmn
source
upconversion
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宋恩海
魏雨
张勤远
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华南理工大学
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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
    • C09K11/7704—Halogenides
    • C09K11/7705—Halogenides with alkali or alkaline earth metals

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  • the invention relates to the field of luminescent materials, in particular to an up-conversion luminescent material and a preparation method and application thereof.
  • inorganic light functional materials have been widely studied and paid attention to by their unique and excellent luminescent properties and chemical and physical stability.
  • inorganic optical functional materials are favored in the fields of solar cells, anti-counterfeiting, encryption, and bio-fluorescence imaging, and the demand for inorganic optical functional materials is rapidly increasing.
  • the illuminating characteristics of materials have been applied to the anti-counterfeiting field of security articles such as banknotes, documents, and notes of value for a long time.
  • the luminescent materials used are preferably materials that are not commercially available.
  • Chinese patent CN106566547A discloses an up-conversion long afterglow fluorescent material and a preparation method and application thereof. Although the material has good specific up-and-down conversion fluorescence and up-conversion afterglow phenomenon, the material matrix is sulfur oxide.
  • Patent CN1563270A discloses a machine readable fluorescent/phosphorescent anti-counterfeiting material and a method and application for the preparation of the material.
  • this material can only have fluorescence and phosphorescence properties under ultraviolet excitation, and there is no up-conversion fluorescence or phosphorescence.
  • Many inorganic luminescent materials can be realized, and the specificity of the material is not strong. From the point of view of practical application, since the use of valuable documents, particularly banknotes, etc., is various, the luminescent materials used are preferably materials that are not commercially available. In addition, it is also required that the luminescent substance should have obvious specific luminescent characteristics, and the properties of the material after the treatment such as grinding are unchanged.
  • the object of the present invention is to provide a type of upconversion luminescent material, which is an inorganic material having up-conversion fluorescence and phosphorescence characteristics, specifically a kind of fluoride matrix doped with rare earth ions Yb 3+ and transition metal, in view of the deficiencies of the prior art.
  • a class of upconverting phosphorescent materials of ionic Mn 2+ is an inorganic material having up-conversion fluorescence and phosphorescence characteristics, specifically a kind of fluoride matrix doped with rare earth ions Yb 3+ and transition metal
  • A is at least one of the alkali metals Na, K and Rb.
  • B is at least one of the divalent metals Ca, Cd, Zn, and Mg.
  • B ions in the matrix material are jointly replaced by Mn 2+ and Yb 3+ ions, but are not limited to B ions being replaced.
  • the upconverting phosphor material AB 1-xy F 3 :xMn 2+ yYb 3+ is selected from the group consisting of LiSr 1-xy F 3 :xMn 2+ yYb 3+ , NaSr 1-x- y F 3 :xMn 2+ yYb 3+ , KSr 1-xy F 3 :xMn 2+ yYb 3+ , RbSr 1-xy F 3 :xMn 2+ yYb 3+ , CsSr 1-xy F 3 :xMn 2+ yYb 3+ , LiBa 1-xy F 3 : xMn 2+ yYb 3+ , NaBa 1-xy F 3 : xMn 2+ yYb 3+ , KBa 1-xy F 3 : xMn 2+ yYb 3+ , RbBa 1-x- y F 3 : xMn 2+ yYb 3+
  • the upconverting phosphor material AB 1-xy F 3 :xMn 2+ yYb 3+ is selected from the group consisting of KCa 1-xy F 3 :xMn 2+ yYb 3+ , RbCa 1-xy F 3 :xMn 2+ yYb 3+ , KCd 1-xy F 3 :xMn 2+ yYb 3+ , RbCd 1-xy F 3 :xMn 2+ yYb 3+ , NaMg 1-x- y F 3 :xMn 2+ yYb 3+ , KMg 1 -xy F 3 :xMn 2+ yYb 3+ , RbMg 1-xy F 3 :xMn 2+ yYb 3+ , NaZn 1-xy F 3 :xMn 2+ yYb 3+ , KZn 1-xy F 3 :xMn 2+ yYb 3+ , KZn 1-x
  • the upconverting phosphor material AB 1-xy F 3 :xMn 2+ yYb 3+ is excited by 980 nm near-infrared laser, and yttrium Yb 3+ sensitized manganese Mn 2+ obtains bright up-conversion fluorescence; At the time, the material exhibits significant phosphorescence, and the color of the phosphorescence is completely consistent with the color of the fluorescence; and the upconversion fluorescence spectrum or the phosphorescence spectrum is composed of a luminescence peak having a peak position of 500 to 830 nm.
  • step (3) The product obtained in the step (2) is taken out and ground to obtain a colorless product, that is, the up-conversion phosphorescent material.
  • the molar ratio of the fluorine-containing A source, the fluorine-containing B source, the Yb source, the Mn source and the fluorine-containing auxiliary solvent is preferably from 1 to 1.2:0 to 1.0:0.0001 to 0.3:0.0001 to 0.7: 0.001 to 0.30.
  • the fluorine-containing A source is an alkali metal fluoride AF or a difluorohydride AHF 2 .
  • the fluorine-containing A source is at least one of LiF, NaF, KF, RbF, CsF, LiHF 2 , NaHF 2 , KHF 2 , RbHF 2 and CsHF 2 .
  • the fluorine-containing A source is NaF, KF, RbF or CsF.
  • the fluorine-containing B source is a divalent metal fluoride BF 2 .
  • the fluorine-containing B source is at least one of BaF 2 , SrF 2 , CaF 2 , CdF 2 , MgF 2 , ZnF 2 and PbF 2 .
  • the fluorine-containing B source is CaF 2 , CdF 2 , MgF 2 or ZnF 2 .
  • the Yb source is selected from the group consisting of an oxide of Yb, a chloride of Yb, a fluoride of Yb, a carbonate of Yb, a nitrate of Yb, and an acetate of Yb. the above.
  • the fluorine-containing Yb source is selected from the group consisting of Yb 2 O 3 , Yb acetate or Yb fluoride.
  • the fluorine-containing Yb source is Yb 2 O 3 .
  • the Mn source is at least one selected from the group consisting of MnO, Mn chloride, MnF 2 , MnBr 2 , MnCO 3 and Mn acetate.
  • the Mn source is selected from the group consisting of MnO, MnF 2 or MnCO 3 .
  • the Mn source is MnCO 3 .
  • the fluorine-containing flux is one or more of NH 4 F and NH 4 HF 2 .
  • the fluorine-containing flux is NH 4 F.
  • the sufficient grinding is performed in an agate mortar or a ceramic grinding.
  • the sufficient grinding is sufficiently ground in an agate mortar.
  • the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
  • the reducing atmosphere is a nitrogen-hydrogen mixed weak reducing atmosphere.
  • the protective atmosphere that is programmed to be heated and sintered is a nitrogen atmosphere or an argon atmosphere.
  • the temperature is programmed and sintered: heating from room temperature to 200 ° C in 2 hours, and sintering for 1 to 2 hours; then heating to 300 to 900 ° C for 1 to 3 hours, more preferably It is 400-850 ° C and is sintered for 1 to 24 hours, more preferably 1 to 10 hours, still more preferably 2 to 8 hours.
  • the sintering is carried out by holding the mixture in a corundum crucible and placing it in a tubular high-temperature furnace.
  • the upconversion phosphorescent material according to any of the above features has unique up-conversion fluorescence and phosphorescence properties, and can be applied to new fields of anti-counterfeiting, encryption, special display or bio-imaging.
  • the upconversion phosphorescent material AB 1-xy F 3 :xMn 2+ yYb 3+ of the present invention is excited by 980 nm laser, and Yb sensitized manganese Mn obtains bright up-conversion luminescence, turns off the excitation light source, and up-converts the phosphorescent material AB 1 -xy F 3 :xMn 2+ yYb 3+ has a significant phosphorescence phenomenon, and the color of the luminescence can be changed by changing the chemical composition of A or B in AB 1-xy F 3 :xMn 2+ yYb 3+ or the value of x.
  • the luminescent color and excitation power of the upconversion phosphorescent material AB 1-xy F 3 :xMn 2+ yYb 3+ of the present invention are independent of the excitation mode, and the fluorescent color of the material is completely consistent with the phosphorescent color. At the same time, the material itself is colorless.
  • the unique up-conversion fluorescence and phosphorescence mode of the up-conversion phosphor material AB 1-xy F 3 :xMn 2+ yYb 3+ and the unique luminescence property of the present invention it has a novel anti-counterfeiting and cryptographic material applied to valuable documents such as banknotes.
  • the value of encryption and anti-counterfeiting applications, and this unique up-conversion phosphorescence feature can also be used for bioluminescence imaging and labeling with high resolution and high transmission depth.
  • the up-conversion fluorescence spectrum or phosphorescence spectrum of the up-converting phosphor material of the present invention is composed of an emission peak having a peak position of 500 to 830 nm, and the specific peak position can be changed by changing AB 1-xy F 3 : xMn 2+ , yYb 3+ or The chemical composition of B or the value of x is regulated.
  • the present invention has the following beneficial effects:
  • the phosphorescent material of the present invention can be excited by a 980 nm near-infrared laser to obtain up-conversion fluorescence and phosphorescence, and the color of the material can be controlled by the composition of the material or the doping concentration of Mn, and the fluorescence and fluorescent colors are not close.
  • the excitation power of the infrared laser changes and changes;
  • the upconversion fluorescent color of the phosphorescent material of the present invention is completely identical to the upconversion phosphorescent color, and the upconversion fluorescence and phosphorescence characteristics of the material are not changed by grinding;
  • the body color of the phosphorescent material of the present invention tends to be colorless, and as an anti-counterfeiting or encryption application, the naked eye can realize double detection and determination of fluorescence or phosphorescence of the material;
  • the phosphorescent material of the invention has stable performance, simple preparation process, easy realization, low cost, and broad prospects for large-scale industrial production;
  • the excitation process of the phosphorescent material of the invention is fast and stable, and can be quickly recognized by the naked eye or the machine, which is beneficial to practical application and promotion.
  • Example 1 is an XRD pattern of an up-conversion phosphorescent material RbCa 0.85 F 3 :0.05Yb 3+ 0.1Mn 2+ prepared in Example 8;
  • Example 2 is an up-conversion fluorescence spectrum of the up-conversion phosphorescent material RbCa 0.85 F 3 :0.05Yb 3+ 0.1Mn 2+ prepared in Example 8;
  • Example 3 is an emission spectrum diagram of the upconversion phosphorescent material RbCa 0.85 F 3 :0.05Yb 3+ 0.1Mn 2+ prepared in Example 8 under different laser power excitations;
  • Figure 6 is a graph showing the emission spectrum of the upconverting phosphor material KCa 0.92 F 3 : 0.03Yb 3 + 0.05Mn 2+ prepared in Example 17 under different laser power excitations.
  • reagents, methods, and devices employed in the present invention are routine reagents, methods, and devices in the art.
  • RbCa 0.9699 F 3 according to the chemical formula: 0.0001Mn 2+ 0.03Yb 3+, the RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.9699:0.015:0.01:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat.
  • RbCa 0.96 F 3 :0.01Mn 2+ 0.03Yb 3+ RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.96:0.015:0.01:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat.
  • a powder sample is obtained having a chemical composition of RbCa 0.96 F 3 : 0.01 Mn 2+ 0.03 Yb 3+ .
  • the prepared upconversion phosphorescent material RbCa 0.96 F 3 :0.01Mn 2+ 0.03Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located near 560 nm. There is significant phosphorescence after the excitation source is turned off.
  • RbCa 0.92 F 3 0.05Mn 2+ 0.03Yb 3+ , RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.92:0.015:0.05:0.001, and thoroughly ground in an agate mortar, transferred into corundum crucible, and placed in a corundum boat.
  • the prepared upconversion phosphorescent material Rb Ca 0.92 F 3 :0.05Mn 2+ 0.03Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located at 565 nm. Nearby, and there is significant phosphorescence after the excitation source is turned off.
  • RbCa 0.87 F 3 0.1Mn 2+ 0.03Yb 3+ , RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.87:0.015:0.1:0.001, and thoroughly ground in an agate mortar, transferred into a mortar and placed in a corundum boat.
  • the prepared upconversion phosphorescent material RbCa 0.87 F 3 :0.1Mn 2+ 0.03Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by a 980 nm near-infrared laser with bright up-conversion fluorescence, and the emission peak is located near 567 nm. And there is significant phosphorescence after the excitation source is turned off.
  • RbCa 0.77 F 3 0.2Mn 2+ 0.03Yb 3+ , RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above materials were accurately weighed in a molar ratio of 1.05:0.77:0.015:0.2:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat.
  • a powder sample is obtained having a chemical composition of RbCa 0.77 F 3 : 0.2Mn 2+ 0.03Yb 3+ .
  • the prepared upconverting phosphorescent material RbCa 0.77 F 3 :0.2Mn 2+ 0.03Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by a 980 nm near-infrared laser with bright up-conversion fluorescence, and the emission peak is located near 569 nm. And there is significant phosphorescence after the excitation source is turned off.
  • RbCa 0.94 F 3 :0.01Mn 2+ 0.05Yb 3+ RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.94:0.025:0.01:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat.
  • the prepared upconversion phosphorescent material RbCa 0.94 F 3 :0.01Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located near 560 nm. And there is significant phosphorescence after the excitation source is turned off.
  • RbCa 0.9 F 3 0.05Mn 2+ 0.05Yb 3+ .
  • RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) were used as raw materials, and the molar ratio was 1.05:0.9:0.025. :0.05:0.001
  • the prepared upconversion phosphorescent material RbCa 0.9 F 3 :0.05Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by a 980 nm near-infrared laser with bright up-conversion fluorescence, and the emission peak is located near 565 nm. And there is significant phosphorescence after the excitation source is turned off.
  • RbCa 0.85 F 3 :0.1Mn 2+ 0.05Yb 3+ RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.85:0.025:0.1:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat.
  • a powder sample is obtained having a chemical composition of RbCa 0.85 F 3 : 0.1Mn 2+ 0.05Yb 3+ .
  • the prepared upconversion phosphorescent material RbCa 0.85 F 3 :0.1Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located near 567 nm. And there is significant phosphorescence after the excitation source is turned off.
  • the XRD pattern of the prepared upconverting phosphor material RbCa 0.85 F 3 :0.1Mn 2+ 0.05Yb 3+ is shown in FIG. 1 . It can be seen from FIG. 1 that the XRD diffraction peak of the prepared sample is substantially identical to the RbCaF 3 standard card, and No other diffraction peaks appeared, indicating that the prepared sample had the same result as RbCaF 3 and was a pure phase target substance.
  • the upconversion fluorescence spectrum of the prepared upconverting phosphorescent material RbCa 0.85 F 3 :0.1Mn 2+ 0.05Yb 3+ is shown in Fig. 2, wherein the inside inset is the upconversion fluorescence of the material under 980 nm laser excitation and the laser off.
  • the phosphorescence pattern of the latter sample, as shown in Fig. 2 shows that the sample produces bright yellow-green upconversion luminescence under the excitation of a 980 nm laser, and its emission spectrum consists of a broadband single peak with a peak at 567 nm.
  • the human eye By moving the sample quickly (or turning off the excitation source), the human eye can see significant upconversion phosphorescence, and the phosphorescence color is consistent with the color of the upconverting fluorescence.
  • This unique upconversion luminescence property is expected to be applied in new fields of anti-counterfeiting, encryption, special display or bio-imaging, to improve the level of anti-counterfeiting or encryption and to reduce damage to organisms during biological imaging.
  • Figure 3 is the emission spectrum of the prepared upconverting phosphorescent material RbCa 0.85 F 3 :0.1Mn 2+ 0.05Yb 3+ under different excitation power laser excitation. It can be seen from Fig. 3 that the sample is excited by 980 nm laser with different power. The emission spectrum is composed of a broadband single peak located near 567 nm. The luminescence intensity of the sample increases with the increase of the laser power, but the shape and peak position of the emission spectrum do not change with the power.
  • RbCa 0.75 F 3 0.2Mn 2+ 0.05Yb 3+ , RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.75:0.025:0.2:0.001, and thoroughly ground in an agate mortar, transferred into corundum crucible, and placed in a corundum boat.
  • a powder sample is obtained having a chemical composition of RbCa 0.75 F 3 : 0.2Mn 2+ 0.05Yb 3+ .
  • the prepared upconversion phosphorescent material RbCa 0.75 F 3 :0.2Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser with bright up-conversion fluorescence, and the emission peak is located near 569 nm. And there is significant phosphorescence after the excitation source is turned off.
  • the preparation of the up-conversion phosphor material RbSr 0.1 Ca 0.9-xy F 3 :0.1Mn 2+ 0.05Yb 3+ comprises the following steps:
  • RbSr 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ RbF (99.1%), SrF 2 (99.0%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) were used as raw materials, and the above substances were accurately weighed in a molar ratio of 1.05:0.1:0.75:0.025:0.1:0.001, and thoroughly ground in an agate mortar and transferred into corundum. In the middle, put it into a corundum boat and place it in a tube furnace. In a N 2 atmosphere, heat the room temperature to 200 ° C for 2 hours.
  • the prepared upconverting phosphorescent material RbSr 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by a 980 nm near-infrared laser with bright up-conversion fluorescence and emission peaks Near 565 nm, there is significant phosphorescence after the excitation source is turned off.
  • the preparation of the up-conversion phosphorescent material RbBa 0.1 Ca 0.9-xy F 3 :0.1Mn 2+ 0.05Yb 3+ comprises the following steps:
  • RbBa 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ RbF (99.1%), BaF 2 (analytical grade), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) were used as raw materials, and the above substances were accurately weighed in a molar ratio of 1.05:0.1:0.75:0.025:0.1:0.001, and thoroughly ground in an agate mortar and transferred into corundum. In the crucible, place it in a corundum boat and place it in a tube furnace. Warm it up to 200 °C from room temperature in N 2 atmosphere for 2 hours.
  • the prepared upconversion phosphorescent material RbBa 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located. Near 565 nm, there is significant phosphorescence after the excitation source is turned off.
  • the preparation of the up-conversion phosphorescent material RbMg 0.1 Ca 0.9-xy F 3 :0.1Mn 2+ 0.05Yb 3+ comprises the following steps:
  • RbMg 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ RbF (99.1%), MgF 2 (99.99%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) were used as raw materials, and the above substances were accurately weighed in a molar ratio of 1.05:0.1:0.75:0.025:0.1:0.001, and thoroughly ground in an agate mortar and transferred into corundum. In the middle, put it into a corundum boat and place it in a tube furnace. In a N 2 atmosphere, heat the room temperature to 200 ° C for 2 hours.
  • the prepared upconverting phosphorescent material RbMg 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located Near 579 nm, there is significant phosphorescence after the excitation source is turned off.
  • the preparation of the up-conversion phosphor material RbZn 0.1 Ca 0.9-xy F 3 :0.1Mn 2+ 0.05Yb 3+ comprises the following steps:
  • RbZn 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ RbF (99.1%), ZnF 2 (99.0%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) were used as raw materials, and the above substances were accurately weighed in a molar ratio of 1.05:0.1:0.75:0.025:0.1:0.001, and thoroughly ground in an agate mortar and transferred into corundum.
  • the crucible put it into a corundum boat and place it in a tube furnace. In a N 2 atmosphere, heat the room temperature to 200 ° C for 2 hours.
  • the prepared up-go phosphorescent material RbZn 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located. Near 565 nm, there is significant phosphorescence after the excitation source is turned off.
  • the preparation of the up-conversion phosphorescent material RbCd 0.1 Ca 0.9-xy F 3 :0.1Mn 2+ 0.05Yb 3+ comprises the following steps:
  • RbCd 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ RbF (99.1%), CdF 2 (99.0%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) were used as raw materials, and the above substances were accurately weighed in a molar ratio of 1.05:0.1:0.75:0.025:0.1:0.001, and thoroughly ground in an agate mortar and transferred into corundum. In the middle, put it into a corundum boat and place it in a tube furnace. In a N 2 atmosphere, heat the room temperature to 200 ° C for 2 hours.
  • the prepared up-go phosphorescent material RbCd 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located. Near 563 nm, there is significant phosphorescence after the excitation source is turned off.
  • KCa 0.9699 F 3 according to the chemical formula: 0.0001Mn 2+ 0.03Yb 3+, the KF (99.9%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.9699:0.015:0.0001:0.01, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat.
  • a powder sample having a chemical composition of KCa 0.96 F 3 : 0.01 Mn 2+ 0.03 Yb 3+ can be obtained .
  • the prepared upconverting phosphor material KCa 0.96 F 3 :0.01Mn 2+ 0.03Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by a 980 nm near-infrared laser with bright up-conversion fluorescence, and the emission peak is located near 576 nm. And there is significant phosphorescence after the excitation source is turned off.
  • KCa 0.92 F 3 0.05Mn 2+ 0.03Yb 3+ , KF (99.9%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.92:0.015:0.05:0.001, and thoroughly ground in an agate mortar, transferred into corundum crucible, and placed in a corundum boat.
  • a powder sample having a chemical composition of KCa 0.92 F 3 : 0.05 Mn 2+ 0.03 Yb 3+ can be obtained .
  • the prepared upconverting phosphor material KCa 0.92 F 3 :0.05Mn 2+ 0.03Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located near 578 nm. And there is significant phosphorescence after the excitation source is turned off.
  • the XRD pattern of the prepared upconverting phosphor material KCa 0.92 F 3 :0.05Mn 2+ 0.03Yb 3+ is shown in FIG. 4 , and as shown in FIG. 4 , the XRD diffraction peak of the prepared sample is substantially identical to the KCaF 3 standard card, and No other diffraction peaks appeared, indicating that the prepared sample had the same result as KCaF 3 and was a pure phase target substance.
  • the upconversion fluorescence spectrum of the prepared upconverting phosphor material KCa 0.92 F 3 :0.05Mn 2+ 0.03Yb 3+ is shown in Fig. 5, wherein the inside inset is the upconversion fluorescence of the material under 980 nm laser excitation and the laser off.
  • the phosphorescence pattern of the latter sample shows that the sample produces bright yellow-green upconversion luminescence under excitation of a 980 nm laser, and its emission spectrum consists of a broadband single peak with a peak at 578 nm.
  • the human eye can see significant upconversion phosphorescence, and the phosphorescence color is consistent with the color of the upconverting fluorescence.
  • This unique upconversion luminescence property is expected to be applied in new fields of anti-counterfeiting, encryption, special display or bio-imaging, to improve the level of anti-counterfeiting or encryption and to reduce damage to organisms during biological imaging.
  • Figure 6 is an emission spectrum of the prepared upconverting phosphor material KCa 0.92 F 3 :0.05Mn 2+ 0.03Yb 3+ under different excitation power laser excitations. It can be seen from Fig. 6 that under the excitation of 980 nm laser with different powers, the emission spectrum of the sample is composed of a broadband single peak located near 578 nm. The luminescence intensity of the sample increases with the increase of laser power, but its emission spectrum shape and peak Bits do not change with power.
  • a powder sample having a chemical composition of KCa 0.87 F 3 : 0.1 Mn 2+ 0.03 Yb 3+ can be obtained .
  • the prepared upconverting phosphor material KCa 0.87 F 3 :0.1Mn 2+ 0.03Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located near 578 nm. And there is significant phosphorescence after the excitation source is turned off.
  • a powder sample was obtained with a chemical composition of KCa 0.77 F 3 : 0.2Mn 2+ 0.03Yb 3+ .
  • the prepared upconverting phosphor material KCa 0.77 F 3 :0.2Mn 2+ 0.03Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located near 580 nm. And there is significant phosphorescence after the excitation source is turned off.
  • the prepared upconverting phosphor material KCa 0.94 F 3 :0.01Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser with bright up-conversion fluorescence, and the emission peak is located near 576 nm. And there is significant phosphorescence after the excitation source is turned off.
  • KCa 0.9 F 3 0.05Mn 2+ 0.05Yb 3+ , KF (99.9%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.9:0.025:0.05:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat.
  • the prepared upconversion phosphor material KCa 0.9 F 3 :0.05Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, with bright up-conversion fluorescence, and the emission peak is located near 577 nm. And there is significant phosphorescence after the excitation source is turned off.
  • a powder sample was obtained with a chemical composition of KCa 0.85 F 3 : 0.1 Mn 2+ 0.05 Yb 3+ .
  • the prepared upconverting phosphor material KCa 0.85 F 3 :0.1Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located near 578 nm. And there is significant phosphorescence after the excitation source is turned off.
  • a powder sample was obtained with a chemical composition of KCa 0.75 F 3 : 0.2Mn 2+ 0.05Yb 3+ .
  • the prepared upconverting phosphor material KCa 0.75 F 3 :0.2Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located near 580 nm. And there is significant phosphorescence after the excitation source is turned off.

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Abstract

Disclosed are an upconversion phosphorescent material, and a preparation method therefor and an application thereof. The chemical composition expression of the upconversion phosphorescent material is AB1-x-yF3:xMn2+yYb3+, wherein A is one or more of the alkali metals Li, Na, K, Rb and Cs, B is one or more of the divalent metals Ba, Sr, Ca, Cd, Mg, Zn and Pb, and x and y are respectively concentrations of the dopant ions Yb3+ and Mn2+, having value ranges of x=0.0001-0.7 and y=0.0001-0.3. Under 980nm near-infrared laser excitation, Yb3+ sensitised Mn2+ of the upconversion phosphorescent material obtains bright upconversion fluorescence, and when the excitation is stopped, the material shows clear phosphorescence, the colour of the phosphorescence being consistent with the colour of the fluorescence. The present invention has potential value for application in the fields of novel anti-counterfeiting, encryption, special displaying or biological imaging.

Description

一类上转换磷光材料及其制备方法与应用Up-conversion phosphorescent material and preparation method and application thereof 技术领域Technical field
本发明涉及发光材料领域，具体涉及上转换发光材料及其制备方法与应用。The invention relates to the field of luminescent materials, in particular to an up-conversion luminescent material and a preparation method and application thereof.
背景技术Background technique
随着社会和经济的发展，以新能源、新材料、信息、纳米技术等为代表的高新技术逐渐成为全球研究的课题。新材料作为战略新兴产业中最为重要的一部分，起着举足轻重且不可或缺的作用。无机光功能材料凭借其独特而优异的发光性质、化学物理稳定性，使其受到了广泛的研究和关注。尤其是，随着光电子器件的发展，无机光功能材料在太阳能电池、防伪、加密以及生物荧光成像领域备受青睐，对无机光功能材料的需求也迅速增加。其中，将材料的发光特征应用于钞票、证件、有价票据等安全物品的防伪领域已经有很长的时间。符合斯托克斯定律的紫外光或可见光激发发射可见光、红外光的物质，以及符合反斯托克斯效应的上转换发光材料在各国纸币，有价证券，商标，护照，身份证等上都有着较为广泛的应用。然而，随着伪造者获取信息及材料的手段变得越来越容易，很多防伪技术的反防伪效果逐渐减弱。这就对钞票等有价票证的防伪提出了越来越高的要求。因此，发展具有新型发光模式的防伪材料来提高其防伪和保密性具有重要的意义。With the development of society and economy, high-tech represented by new energy, new materials, information and nanotechnology has gradually become a topic of global research. As the most important part of the strategic emerging industry, new materials play an important and indispensable role. Inorganic light functional materials have been widely studied and paid attention to by their unique and excellent luminescent properties and chemical and physical stability. In particular, with the development of optoelectronic devices, inorganic optical functional materials are favored in the fields of solar cells, anti-counterfeiting, encryption, and bio-fluorescence imaging, and the demand for inorganic optical functional materials is rapidly increasing. Among them, the illuminating characteristics of materials have been applied to the anti-counterfeiting field of security articles such as banknotes, documents, and notes of value for a long time. Ultraviolet or visible light in accordance with Stokes's law, which emits visible light and infrared light, and upconverting luminescent materials conforming to the anti-Stokes effect in national banknotes, securities, trademarks, passports, ID cards, etc. Has a wider range of applications. However, as counterfeiters acquire information and materials more and more easily, the anti-counterfeiting effect of many anti-counterfeiting technologies is gradually weakened. This puts higher and higher requirements on the anti-counterfeiting of valuable documents such as banknotes. Therefore, it is of great significance to develop anti-counterfeiting materials with new illumination modes to improve their anti-counterfeiting and confidentiality.
对荧光防伪而言，除了将不同激发条件和发射条件的荧光物质进行编码组合，提高伪造者分析和伪造的难度之外，将适合于钞票等应用要求的新型发光特征引入防伪领域也是一种新的思路。从实际应用考虑，所采用的发光物质最好是市面上购买不到的材料。中国专利CN106566547A公开了一种上转换长余辉荧光材料及其制备方法与应用。该材料虽然具有较好的特异性上下转换荧光以及上转换余辉现象，但是该材料基质为硫氧化物，此类物质化学稳定性差，容易潮解并且不耐紫外光照射，易老化，难以在实际中获得应用。专利CN1563270A公开了一种机器可读荧光/磷光防伪材料以及该材料的制备方法与应用。但是这种材料只有在紫外激发下才会有荧光与磷光性能，无上转换荧光或磷光现象，许多无机发光材料都能够实现，材料的特异性不强。从实际应用的角度考虑，由于有价证件，特别是钞票等的使用场合多种多样，所采用的发光物质最好是市面上购买不到的材料。除此之外，还要求发光物质还应具有明显的特异性发光特征，研磨等处理后材料的性质不变。For fluorescent anti-counterfeiting, in addition to coding and combining fluorescent materials with different excitation conditions and emission conditions to improve the difficulty of forgery analysis and forgery, it is also a new type of new light-emitting features suitable for application requirements such as banknotes. The idea. For practical applications, the luminescent materials used are preferably materials that are not commercially available. Chinese patent CN106566547A discloses an up-conversion long afterglow fluorescent material and a preparation method and application thereof. Although the material has good specific up-and-down conversion fluorescence and up-conversion afterglow phenomenon, the material matrix is sulfur oxide. These materials have poor chemical stability, are easy to deliquesce and are not resistant to ultraviolet light irradiation, and are easy to age, which is difficult in practice. Get the app. Patent CN1563270A discloses a machine readable fluorescent/phosphorescent anti-counterfeiting material and a method and application for the preparation of the material. However, this material can only have fluorescence and phosphorescence properties under ultraviolet excitation, and there is no up-conversion fluorescence or phosphorescence. Many inorganic luminescent materials can be realized, and the specificity of the material is not strong. From the point of view of practical application, since the use of valuable documents, particularly banknotes, etc., is various, the luminescent materials used are preferably materials that are not commercially available. In addition, it is also required that the luminescent substance should have obvious specific luminescent characteristics, and the properties of the material after the treatment such as grinding are unchanged.
发明内容Summary of the invention
本发明的目的在于针对现有技术的不足，提供了一类上转换发光材料，为具有上转换荧光与磷光特性的无机材料，具体为一类氟化物基质掺杂稀土离子Yb 3+和过渡金属离子Mn 2+的一类上转换磷光材料。 The object of the present invention is to provide a type of upconversion luminescent material, which is an inorganic material having up-conversion fluorescence and phosphorescence characteristics, specifically a kind of fluoride matrix doped with rare earth ions Yb 3+ and transition metal, in view of the deficiencies of the prior art. A class of upconverting phosphorescent materials of ionic Mn 2+ .
本发明的目的还在于提供所述的一类上转换磷光材料的制备方法，该制备方法简单且环境友好。It is also an object of the present invention to provide a process for the preparation of such a type of upconversion phosphorescent material which is simple and environmentally friendly.
本发明的另一目的还在于提供所述的一类上转换磷光材料在防伪、加密、显示和生物成像材料方面的潜在应用。It is yet another object of the present invention to provide a potential application of such a type of upconversion phosphor material in anti-counterfeiting, encryption, display and bioimaging materials.
本发明的目的通过如下技术方案实现。The object of the present invention is achieved by the following technical solutions.
一类上转换磷光材料，其化学组成表达式为AB 1-x-yF 3:xMn 2+yYb 3+；其中，A为碱金属Li、Na、K、Rb和Cs中的一种以上，B为二价金属Ba、Sr、Ca、Cd、Mg、Zn和Pb中的一种以上；x，y分别为掺杂离子Mn 2+和的Yb 3+浓度，取值范围：x＝0.0001～0.7，y＝0.0001～0.3。 A type of upconversion phosphorescent material having a chemical composition expression of AB 1-xy F 3 :xMn 2+ yYb 3+ ; wherein A is one or more of the alkali metals Li, Na, K, Rb and Cs, and B is One or more of the divalent metals Ba, Sr, Ca, Cd, Mg, Zn and Pb; x, y are the doping ions Mn 2+ and the Yb 3+ concentration, respectively, ranging from x=0.0001 to 0.7, y=0.0001~0.3.
优选的，A为碱金属Na、K和Rb中的一种以上。Preferably, A is at least one of the alkali metals Na, K and Rb.
优选的，B为二价金属Ca、Cd、Zn和Mg中的一种以上。Preferably, B is at least one of the divalent metals Ca, Cd, Zn, and Mg.
优选的，x＝0.01～0.4，y＝0.01～0.15。Preferably, x = 0.01 to 0.4 and y = 0.01 to 0.15.
本发明的上转换磷光材料，基质材料中主要是B离子被Mn 2+和Yb 3+离子共同替代，但并不限于B离子被替代。 In the upconverting phosphorescent material of the present invention, mainly B ions in the matrix material are jointly replaced by Mn 2+ and Yb 3+ ions, but are not limited to B ions being replaced.
优选的，所述上转换磷光材料AB 1-x-yF 3:xMn 2+yYb 3+选自LiSr 1-x-yF 3:xMn 2+yYb 3+、NaSr 1-x- yF 3:xMn 2+yYb 3+、KSr 1-x-yF 3:xMn 2+yYb 3+、RbSr 1-x-yF 3:xMn 2+yYb 3+、CsSr 1-x-yF 3:xMn 2+yYb 3+、LiBa 1-x-yF 3:xMn 2+yYb 3+、NaBa 1-x-yF 3:xMn 2+yYb 3+、KBa 1-x-yF 3:xMn 2+yYb 3+、RbBa 1-x- yF 3:xMn 2+yYb 3+、CsBa 1-x-yF 3:xMn 2+yYb 3+、LiCa 1-x-yF 3:xMn 2+yYb 3+、NaCa 1-x-yF 3:xMn 2+yYb 3+、KCa 1-x-yF 3:xMn 2+yYb 3+、RbCa 1-x-yF 3:xMn 2+yYb 3+、CsCa 1-x-yF 3:xMn 2+yYb 3+、LiCd 1-x- yF 3:xMn 2+yYb 3+、NaCd 1-x-yF 3:xMn 2+yYb 3+、KCd 1-x-yF 3:xMn 2+yYb 3+、RbCd 1-x-yF 3:xMn 2+yYb 3+、CsCd 1-x-yF 3:xMn 2+yYb 3+、LiMgr 1-x-yF 3:xMn 2+yYb 3+、NaMg 1-x-yF 3:xMn 2+yYb 3+、KMg 1-x- yF 3:xMn 2+yYb 3+、RbMg 1-x-yF 3:xMn 2+yYb 3+、CsMg 1-x-yF 3:xMn 2+yYb 3+、LiZnr 1-x-yF 3:xMn 2+yYb 3+、NaZn 1-x-yF 3:xMn 2+yYb 3+、KZn 1-x-yF 3:xMn 2+yYb 3+、RbZn 1-x-yF 3:xMn 2+yYb 3+、CsZn 1-x- yF 3:xMn 2+yYb 3+、LiPbr 1-x-yF 3:xMn 2+yYb 3+、NaPb 1-x-yF 3:xMn 2+yYb 3+、KPb 1-x-yF 3:xMn 2+yYb 3+、RbPb 1-x-yF 3:xMn 2+yYb 3+或CsPb 1-x-yF 3:xMn 2+yYb 3+。 Preferably, the upconverting phosphor material AB 1-xy F 3 :xMn 2+ yYb 3+ is selected from the group consisting of LiSr 1-xy F 3 :xMn 2+ yYb 3+ , NaSr 1-x- y F 3 :xMn 2+ yYb 3+ , KSr 1-xy F 3 :xMn 2+ yYb 3+ , RbSr 1-xy F 3 :xMn 2+ yYb 3+ , CsSr 1-xy F 3 :xMn 2+ yYb 3+ , LiBa 1-xy F 3 : xMn 2+ yYb 3+ , NaBa 1-xy F 3 : xMn 2+ yYb 3+ , KBa 1-xy F 3 : xMn 2+ yYb 3+ , RbBa 1-x- y F 3 : xMn 2+ yYb 3+ , CsBa 1-xy F 3 :xMn 2+ yYb 3+ , LiCa 1-xy F 3 :xMn 2+ yYb 3+ , NaCa 1-xy F 3 :xMn 2+ yYb 3+ ,KCa 1-xy F 3 :xMn 2+ yYb 3+ , RbCa 1-xy F 3 :xMn 2+ yYb 3+ , CsCa 1-xy F 3 :xMn 2+ yYb 3+ , LiCd 1-x- y F 3 :xMn 2+ yYb 3+ , NaCd 1-xy F 3 :xMn 2+ yYb 3+ , KCd 1-xy F 3 :xMn 2+ yYb 3+ , RbCd 1-xy F 3 :xMn 2+ yYb 3+ , CsCd 1-xy F 3 : xMn 2+ yYb 3+ , LiMgr 1-xy F 3 : xMn 2+ yYb 3+ , NaMg 1-xy F 3 : xMn 2+ yYb 3+ , KMg 1-x- y F 3 : xMn 2+ yYb 3+ , RbMg 1-xy F 3 : xMn 2+ yYb 3+ , CsMg 1-xy F 3 : xMn 2+ yYb 3+ , LiZnr 1-xy F 3 : xMn 2+ yYb 3+ , NaZn 1-xy F 3 : xMn 2+ yYb 3+ , KZn 1-xy F 3 : xMn 2+ yYb 3+ , RbZn 1-xy F 3 : xMn 2+ yYb 3+ , CsZn 1-x- y F 3 : xMn 2+ yYb 3+ , LiPbr 1-xy F 3 : xMn 2+ yYb 3+ , NaPb 1-xy F 3 : xMn 2+ yYb 3+ , KPb 1-xy F 3 : xMn 2+ yYb 3+ , RbPb 1-xy F 3 : xMn 2+ yYb 3+ or CsPb 1-xy F 3 : xMn 2+ yYb 3+ .
更进一步优选的，所述上转换磷光材料AB 1-x-yF 3:xMn 2+yYb 3+选自KCa 1-x-yF 3:xMn 2+yYb 3+、RbCa 1-x-yF 3:xMn 2+yYb 3+、KCd 1-x-yF 3:xMn 2+yYb 3+、RbCd 1-x-yF 3:xMn 2+yYb 3+、NaMg 1-x- yF 3:xMn 2+yYb 3+、KMg 1-x-yF 3:xMn 2+yYb 3+、RbMg 1-x-yF 3:xMn 2+yYb 3+、NaZn 1-x-yF 3:xMn 2+yYb 3+、KZn 1-x-yF 3:xMn 2+yYb 3+、KPb 1-x-yF 3:xMn 2+yYb 3+或RbPb 1-x-yF 3:xMn 2+yYb 3+。 Still more preferably, the upconverting phosphor material AB 1-xy F 3 :xMn 2+ yYb 3+ is selected from the group consisting of KCa 1-xy F 3 :xMn 2+ yYb 3+ , RbCa 1-xy F 3 :xMn 2+ yYb 3+ , KCd 1-xy F 3 :xMn 2+ yYb 3+ , RbCd 1-xy F 3 :xMn 2+ yYb 3+ , NaMg 1-x- y F 3 :xMn 2+ yYb 3+ , KMg 1 -xy F 3 :xMn 2+ yYb 3+ , RbMg 1-xy F 3 :xMn 2+ yYb 3+ , NaZn 1-xy F 3 :xMn 2+ yYb 3+ , KZn 1-xy F 3 :xMn 2+ yYb 3+ , KPb 1-xy F 3 : xMn 2+ yYb 3+ or RbPb 1-xy F 3 : xMn 2+ yYb 3+ .
进一步地，所述上转换磷光材料AB 1-x-yF 3:xMn 2+yYb 3+在980nm近红外激光激发下，镱Yb 3+敏化锰Mn 2+得到明亮的上转换荧光；当停止激发时，材料呈现出明显的磷光，磷光的颜色与荧光的颜色完全一致；且上转换荧光光谱或磷光光谱由峰位位于500～830nm的发光峰组成。 Further, the upconverting phosphor material AB 1-xy F 3 :xMn 2+ yYb 3+ is excited by 980 nm near-infrared laser, and yttrium Yb 3+ sensitized manganese Mn 2+ obtains bright up-conversion fluorescence; At the time, the material exhibits significant phosphorescence, and the color of the phosphorescence is completely consistent with the color of the fluorescence; and the upconversion fluorescence spectrum or the phosphorescence spectrum is composed of a luminescence peak having a peak position of 500 to 830 nm.
制备上述任一所述的上转换磷光材料的方法，包括如下步骤：A method of preparing the upconverting phosphor material of any of the above, comprising the steps of:
(1)按所述化学组成表达式AB 1-x-yF 3:xMn 2+yYb 3+准确称量含氟A源、含氟B源、Yb源与Mn源，并加入含氟助溶剂，充分研磨混合均匀，得到混合物； (1) Accurately weigh the fluorine-containing A source, the fluorine-containing B source, the Yb source and the Mn source according to the chemical composition expression AB 1-xy F 3 :xMn 2+ yYb 3+ , and add a fluorine-containing auxiliary solvent, fully Grinding and mixing uniformly to obtain a mixture;
(2)将混合物置于空气、惰性气氛或还原气氛保护下程序升温并烧结，自然冷却至室温；(2) The mixture is heated and sintered under the protection of air, an inert atmosphere or a reducing atmosphere, and naturally cooled to room temperature;
(3)将步骤(2)所得产物取出再研磨，得到无色产物，即所述上转换磷光材料。(3) The product obtained in the step (2) is taken out and ground to obtain a colorless product, that is, the up-conversion phosphorescent material.
优选的，步骤(1)中，含氟A源、含氟B源、Yb源、Mn源与含氟助溶剂的摩尔比优选为1～1.2：0～1.0：0.0001～0.3：0.0001～0.7：0.001～0.30。Preferably, in the step (1), the molar ratio of the fluorine-containing A source, the fluorine-containing B source, the Yb source, the Mn source and the fluorine-containing auxiliary solvent is preferably from 1 to 1.2:0 to 1.0:0.0001 to 0.3:0.0001 to 0.7: 0.001 to 0.30.
优选的，步骤(1)中，所述含氟A源为碱金属氟化物AF或二氟氢化物AHF 2。 Preferably, in the step (1), the fluorine-containing A source is an alkali metal fluoride AF or a difluorohydride AHF 2 .
更进一步优选的，步骤(1)中，所述含氟A源为LiF、NaF、KF、RbF、CsF、LiHF 2、NaHF 2、KHF 2、RbHF 2和CsHF 2中的一种以上。 Still more preferably, in the step (1), the fluorine-containing A source is at least one of LiF, NaF, KF, RbF, CsF, LiHF 2 , NaHF 2 , KHF 2 , RbHF 2 and CsHF 2 .
再进一步优选的，步骤(1)中，所述含氟A源为NaF、KF、RbF或CsF。Still further preferably, in the step (1), the fluorine-containing A source is NaF, KF, RbF or CsF.
优选的，步骤(1)中，所述含氟B源为二价金属氟化物BF 2。 Preferably, in the step (1), the fluorine-containing B source is a divalent metal fluoride BF 2 .
更进一步优选的，步骤(1)中，所述含氟B源为BaF 2、SrF 2、CaF 2、CdF 2、MgF 2、ZnF 2和PbF 2中的一种以上。 Still more preferably, in the step (1), the fluorine-containing B source is at least one of BaF 2 , SrF 2 , CaF 2 , CdF 2 , MgF 2 , ZnF 2 and PbF 2 .
再进一步优选的，步骤(1)中，所述含氟B源为CaF 2、CdF 2、MgF 2或ZnF 2。 Still more preferably, in the step (1), the fluorine-containing B source is CaF 2 , CdF 2 , MgF 2 or ZnF 2 .
优选的，步骤(1)中，所述Yb源选自Yb的氧化物、Yb的氯化物、Yb的氟化物、Yb的碳酸盐、Yb的硝酸盐和Yb的醋酸盐中的一种以上。Preferably, in the step (1), the Yb source is selected from the group consisting of an oxide of Yb, a chloride of Yb, a fluoride of Yb, a carbonate of Yb, a nitrate of Yb, and an acetate of Yb. the above.
更进一步优选的，步骤(1)中，所述含氟Yb源选自Yb 2O 3、Yb的醋酸盐或Yb的氟化物。 Still more preferably, in the step (1), the fluorine-containing Yb source is selected from the group consisting of Yb 2 O 3 , Yb acetate or Yb fluoride.
再进一步优选的，步骤(1)中，所述含氟Yb源为Yb 2O 3。 Still more preferably, in the step (1), the fluorine-containing Yb source is Yb 2 O 3 .
优选的，步骤(1)中，所述Mn源选自MnO、Mn的氯化物、MnF 2、MnBr 2、MnCO 3和Mn的醋酸盐中的一种以上。 Preferably, in the step (1), the Mn source is at least one selected from the group consisting of MnO, Mn chloride, MnF 2 , MnBr 2 , MnCO 3 and Mn acetate.
更进一步优选的，步骤(1)中，所述Mn源选自MnO、MnF 2或MnCO 3。 Still more preferably, in the step (1), the Mn source is selected from the group consisting of MnO, MnF 2 or MnCO 3 .
再进一步优选的，步骤(1)中，所述Mn源为MnCO 3。 Still more preferably, in the step (1), the Mn source is MnCO 3 .
优选的，步骤(1)中，所述含氟助熔剂为NH 4F与NH 4HF 2中的一种以上。 Preferably, in the step (1), the fluorine-containing flux is one or more of NH 4 F and NH 4 HF 2 .
再进一步优选的，步骤(1)中，所述含氟助熔剂为NH 4F。 Still more preferably, in the step (1), the fluorine-containing flux is NH 4 F.
优选的，步骤(1)中，所述充分研磨是在玛瑙研钵或陶瓷研磨中充分研磨。Preferably, in the step (1), the sufficient grinding is performed in an agate mortar or a ceramic grinding.
更进一步优选的，步骤(1)中，所述充分研磨是在玛瑙研钵中充分研磨。Still more preferably, in the step (1), the sufficient grinding is sufficiently ground in an agate mortar.
优选的，步骤(2)中，所述惰性气氛为氮气气氛或氩气气氛。Preferably, in the step (2), the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
优选的，步骤(2)中，所述还原气氛为氮气-氢气混合弱还原气氛。Preferably, in the step (2), the reducing atmosphere is a nitrogen-hydrogen mixed weak reducing atmosphere.
更进一步优选的，步骤(2)中，所述程序升温并烧结的保护气氛为氮气气氛或氩气气氛。Still more preferably, in the step (2), the protective atmosphere that is programmed to be heated and sintered is a nitrogen atmosphere or an argon atmosphere.
优选的，步骤(2)中，所述程序升温并烧结是：用2小时从室温升温到200℃，并保温烧结1～2小时；随后用1～3小时升温到300～900℃，更优选为400-850℃，并保温烧结1～24小时，更优选为1～10小时，再优选为2～8小时。Preferably, in the step (2), the temperature is programmed and sintered: heating from room temperature to 200 ° C in 2 hours, and sintering for 1 to 2 hours; then heating to 300 to 900 ° C for 1 to 3 hours, more preferably It is 400-850 ° C and is sintered for 1 to 24 hours, more preferably 1 to 10 hours, still more preferably 2 to 8 hours.
进一步优选的，步骤(2)中，所述烧结是将混合物盛载于刚玉坩埚并置于管式高温炉中进行烧结。Further preferably, in the step (2), the sintering is carried out by holding the mixture in a corundum crucible and placing it in a tubular high-temperature furnace.
上述任一项所述的上转换磷光材料具有独特的上转换荧光与磷光特性，能应用于新型防伪、加密、特种显示或生物成像领域。The upconversion phosphorescent material according to any of the above features has unique up-conversion fluorescence and phosphorescence properties, and can be applied to new fields of anti-counterfeiting, encryption, special display or bio-imaging.
用作加密或防伪的材料要求具有独特的发光特性，且材料不会因为机械研磨而改变性能。本发明的上转换磷光材料AB 1-x-yF 3:xMn 2+yYb 3+在980nm激光激发下，Yb镱敏化锰Mn得到明亮的上转换发光，关掉激发光源，上转换磷光材料AB 1-x-yF 3:xMn 2+yYb 3+有明显的磷光现象，且发光的颜色可以通过改变AB 1-x-yF 3:xMn 2+yYb 3+中A或B的化学成分或x的取值进行调控。本发明上转换磷光材料AB 1-x-yF 3:xMn 2+yYb 3+的发光色与激发功率与激发模式无关，并且材料的荧光颜色与磷光颜色完全一致。与此同时，材料本身无色。鉴于本发明上转换磷光材料AB 1-x-yF 3:xMn 2+yYb 3+的独特上转换荧光与磷光模式以及独特的发光特性，具有作为新型的防伪、加密材料应用于纸币等有价文件的加密与防伪的应用价值，并且这种独特的上转换磷光特性也可用于高分辨率高透射深度的生物荧光成像与标记。 Materials used for encryption or anti-counterfeiting require unique luminescent properties, and the materials do not change performance due to mechanical grinding. The upconversion phosphorescent material AB 1-xy F 3 :xMn 2+ yYb 3+ of the present invention is excited by 980 nm laser, and Yb sensitized manganese Mn obtains bright up-conversion luminescence, turns off the excitation light source, and up-converts the phosphorescent material AB 1 -xy F 3 :xMn 2+ yYb 3+ has a significant phosphorescence phenomenon, and the color of the luminescence can be changed by changing the chemical composition of A or B in AB 1-xy F 3 :xMn 2+ yYb 3+ or the value of x. Regulation. The luminescent color and excitation power of the upconversion phosphorescent material AB 1-xy F 3 :xMn 2+ yYb 3+ of the present invention are independent of the excitation mode, and the fluorescent color of the material is completely consistent with the phosphorescent color. At the same time, the material itself is colorless. In view of the unique up-conversion fluorescence and phosphorescence mode of the up-conversion phosphor material AB 1-xy F 3 :xMn 2+ yYb 3+ and the unique luminescence property of the present invention, it has a novel anti-counterfeiting and cryptographic material applied to valuable documents such as banknotes. The value of encryption and anti-counterfeiting applications, and this unique up-conversion phosphorescence feature can also be used for bioluminescence imaging and labeling with high resolution and high transmission depth.
本发明的上转磷光材料的上转换荧光光谱或磷光光谱由峰位位于500～830nm的发光峰组成，具体峰位可以通过改变AB 1-x-yF 3:xMn 2+,yYb 3+中A或B的化学成分或x的取值进行调控。 The up-conversion fluorescence spectrum or phosphorescence spectrum of the up-converting phosphor material of the present invention is composed of an emission peak having a peak position of 500 to 830 nm, and the specific peak position can be changed by changing AB 1-xy F 3 : xMn 2+ , yYb 3+ or The chemical composition of B or the value of x is regulated.
与现有技术相比，本发具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明的磷光材料可以采用980nm近红外激光激发，得到上转换荧光与磷光，而材料的光色可以通过材料的组分或Mn的掺杂浓度进行调控，且荧光与荧光颜色不随近红外激光的激发功率改变而改变；(1) The phosphorescent material of the present invention can be excited by a 980 nm near-infrared laser to obtain up-conversion fluorescence and phosphorescence, and the color of the material can be controlled by the composition of the material or the doping concentration of Mn, and the fluorescence and fluorescent colors are not close. The excitation power of the infrared laser changes and changes;
(2)本发明的磷光材料的上转换荧光光色与其上转换磷光光色完全一致，且材料的上转换荧光与磷光特性不会因为研磨而发生改变；(2) The upconversion fluorescent color of the phosphorescent material of the present invention is completely identical to the upconversion phosphorescent color, and the upconversion fluorescence and phosphorescence characteristics of the material are not changed by grinding;
(3)本发明磷光材料的本身体色趋近于无色，作为防伪或加密应用时，裸眼就可以实现对材料的荧光或磷光的双重检测与判定；(3) The body color of the phosphorescent material of the present invention tends to be colorless, and as an anti-counterfeiting or encryption application, the naked eye can realize double detection and determination of fluorescence or phosphorescence of the material;
(4)本发明的磷光材料性能稳定，制备工艺简单，易于实现，且成本低廉，大规模工业生产前景广阔；(4) The phosphorescent material of the invention has stable performance, simple preparation process, easy realization, low cost, and broad prospects for large-scale industrial production;
(5)本发明的磷光材料的激发过程快速稳定，可人裸眼或机器快速识别，有利于实际应用与推广。(5) The excitation process of the phosphorescent material of the invention is fast and stable, and can be quickly recognized by the naked eye or the machine, which is beneficial to practical application and promotion.
附图说明DRAWINGS
图1是实施例8中制备的上转换磷光材料RbCa 0.85F 3:0.05Yb 3+0.1Mn 2+的XRD图； 1 is an XRD pattern of an up-conversion phosphorescent material RbCa 0.85 F 3 :0.05Yb 3+ 0.1Mn 2+ prepared in Example 8;
图2是实施例8中制备的上转换磷光材料RbCa 0.85F 3:0.05Yb 3+0.1Mn 2+的上转换荧光光谱图； 2 is an up-conversion fluorescence spectrum of the up-conversion phosphorescent material RbCa 0.85 F 3 :0.05Yb 3+ 0.1Mn 2+ prepared in Example 8;
图3是实施例8中制备的上转换磷光材料RbCa 0.85F 3:0.05Yb 3+0.1Mn 2+的在不同激光功率激发下的发射光谱图； 3 is an emission spectrum diagram of the upconversion phosphorescent material RbCa 0.85 F 3 :0.05Yb 3+ 0.1Mn 2+ prepared in Example 8 under different laser power excitations;
图4是实施例17中制备的上转换磷光材料KCa 0.92F 3:0.03Yb 3+0.05Mn 2+的XRD图； 4 is an XRD pattern of the up-conversion phosphor material KCa 0.92 F 3 : 0.03Yb 3+ 0.05Mn 2+ prepared in Example 17;
图5是实施例17中制备的上转换磷光材料KCa 0.92F 3:0.03Yb 3+0.05Mn 2+的上转换荧光光谱图； 5 is an up-conversion fluorescence spectrum of the up-conversion phosphor material KCa 0.92 F 3 : 0.03Yb 3+ 0.05Mn 2+ prepared in Example 17;
图6是实施例17中制备的上转换磷光材料KCa 0.92F 3:0.03Yb 3+0.05Mn 2+的在不同激光功率激发下的发射光谱图。 Figure 6 is a graph showing the emission spectrum of the upconverting phosphor material KCa 0.92 F 3 : 0.03Yb 3 + 0.05Mn 2+ prepared in Example 17 under different laser power excitations.
具体实施方式Detailed ways
以下结合具体实施例及附图对本发明技术方案作进一步详细描述，但本发明的实施方式及保护范围不限于此。The technical solutions of the present invention are further described in detail below with reference to the specific embodiments and the accompanying drawings, but the embodiments and the scope of the present invention are not limited thereto.
除非特别说明，本发明所采用的试剂、方法和设备为本技术领域的常规试剂、方法和设备。Unless otherwise stated, the reagents, methods, and devices employed in the present invention are routine reagents, methods, and devices in the art.
实施例1Example 1
上转换磷光材料RbCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.0001，y＝0.03)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material RbCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.0001, y=0.03) includes the following steps:
按照化学表达式RbCa 0.9699F 3:0.0001Mn 2+0.03Yb 3+，将RbF(99.1％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.9699:0.015:0.01:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为RbCa 0.9699F 3:0.0001Mn 2+0.03Yb 3+。 RbCa 0.9699 F 3 according to the chemical formula: 0.0001Mn 2+ 0.03Yb 3+, the RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.9699:0.015:0.01:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat. tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat up to 850 deg.] C 2.5 hours after incubation 2h, and at this temperature firing 4h, cooled to room temperature, and then grinding, i.e., obtained powder sample, the chemical composition of RbCa 0.9699 F 3: 0.0001Mn 2+ 0.03Yb 3+.
制备的上转换磷光材料RbCa 0.9699F 3:0.0001Mn 2+0.03Yb 3+化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于560nm附近，且关闭激发源后有明显的磷光。 Conversion of the phosphorescent material prepared RbCa 0.9699 F 3: 0.0001Mn 2+ 0.03Yb 3+ chemically stable, non-hazardous to the environment; 980nm can be efficiently excited by near-infrared laser, upconversion bright fluorescence emission peak of 560 nm is located, There is significant phosphorescence after the excitation source is turned off.
实施例2Example 2
上转换磷光材料RbCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.01，y＝0.03)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material RbCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.01, y=0.03) includes the following steps:
按照化学表达式RbCa 0.96F 3:0.01Mn 2+0.03Yb 3+，将RbF(99.1％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.96:0.015:0.01:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至650℃，并于该温度焙烧8h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为RbCa 0.96F 3:0.01Mn 2+0.03Yb 3+。 According to the chemical expression RbCa 0.96 F 3 :0.01Mn 2+ 0.03Yb 3+ , RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.96:0.015:0.01:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat. tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat up to 650 ℃ 2.5 hours incubation 2h, and at this temperature firing 8h, cooled to room temperature, and then grinding, i.e., A powder sample is obtained having a chemical composition of RbCa 0.96 F 3 : 0.01 Mn 2+ 0.03 Yb 3+ .
制备的上转换磷光材料RbCa 0.96F 3:0.01Mn 2+0.03Yb 3+化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于560nm附近，且关闭激发源后有明显的磷光。 The prepared upconversion phosphorescent material RbCa 0.96 F 3 :0.01Mn 2+ 0.03Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located near 560 nm. There is significant phosphorescence after the excitation source is turned off.
实施例3Example 3
上转换磷光材料RbCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.05，y＝0.03)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material RbCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.05, y=0.03) includes the following steps:
按照化学表达式RbCa 0.92F 3:0.05Mn 2+0.03Yb 3+，将RbF(99.1％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.92:0.015:0.05:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至850℃，并于该温度焙烧6h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为RbCa 0.92F 3:0.05Mn 2+0.03Yb 3+。 According to the chemical expression RbCa 0.92 F 3 : 0.05Mn 2+ 0.03Yb 3+ , RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.92:0.015:0.05:0.001, and thoroughly ground in an agate mortar, transferred into corundum crucible, and placed in a corundum boat. tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat up to 850 deg.] C 2.5 hours after incubation 2h, and at this temperature firing 6h, cooled to room temperature, and then grinding, i.e., A powder sample was obtained with a chemical composition of RbCa 0.92 F 3 : 0.05 Mn 2+ 0.03 Yb 3+ .
制备的上转换磷光材料Rb Ca 0.92F 3:0.05Mn 2+0.03Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于565nm附近，且关闭激发源后有明显的磷光。 The prepared upconversion phosphorescent material Rb Ca 0.92 F 3 :0.05Mn 2+ 0.03Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located at 565 nm. Nearby, and there is significant phosphorescence after the excitation source is turned off.
实施例4Example 4
上转换磷光材料RbCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.1，y＝0.03)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material RbCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.1, y=0.03) includes the following steps:
按照化学表达式RbCa 0.87F 3:0.1Mn 2+0.03Yb 3+，将RbF(99.1％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.87:0.015:0.1:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚入坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为RbCa 0.87F 3:0.1Mn 2+0.03Yb 3+。 According to the chemical expression RbCa 0.87 F 3 : 0.1Mn 2+ 0.03Yb 3+ , RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.87:0.015:0.1:0.001, and thoroughly ground in an agate mortar, transferred into a mortar and placed in a corundum boat. in a tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat after 2h insulation over 2.5 hours to 850 ℃, and at this temperature firing 4h, cooled to room temperature, and then grinding, A powder sample was obtained with a chemical composition of RbCa 0.87 F 3 : 0.1 Mn 2+ 0.03 Yb 3+ .
制备的上转换磷光材料RbCa 0.87F 3:0.1Mn 2+0.03Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于567nm附近，且关闭激发源后有明显的磷光。 The prepared upconversion phosphorescent material RbCa 0.87 F 3 :0.1Mn 2+ 0.03Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by a 980 nm near-infrared laser with bright up-conversion fluorescence, and the emission peak is located near 567 nm. And there is significant phosphorescence after the excitation source is turned off.
实施例5Example 5
上转换磷光材料RbCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.2，y＝0.03)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material RbCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.2, y=0.03) includes the following steps:
按照化学表达式RbCa 0.77F 3:0.2Mn 2+0.03Yb 3+，将RbF(99.1％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.77:0.015:0.2:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至450℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为RbCa 0.77F 3:0.2Mn 2+0.03Yb 3+。 According to the chemical expression RbCa 0.77 F 3 : 0.2Mn 2+ 0.03Yb 3+ , RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above materials were accurately weighed in a molar ratio of 1.05:0.77:0.015:0.2:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat. tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat up to 450 deg.] C 2.5 hours after incubation 2h, and at this temperature firing 4h, cooled to room temperature, and then grinding, i.e., A powder sample is obtained having a chemical composition of RbCa 0.77 F 3 : 0.2Mn 2+ 0.03Yb 3+ .
制备的上转换磷光材料RbCa 0.77F 3:0.2Mn 2+0.03Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于569nm附近，且关闭激发源后有明显的磷光。 The prepared upconverting phosphorescent material RbCa 0.77 F 3 :0.2Mn 2+ 0.03Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by a 980 nm near-infrared laser with bright up-conversion fluorescence, and the emission peak is located near 569 nm. And there is significant phosphorescence after the excitation source is turned off.
实施例6Example 6
上转换磷光材料RbCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.01，y＝0.05)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material RbCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.01, y=0.05) comprises the following steps:
按照化学表达式RbCa 0.94F 3:0.01Mn 2+0.05Yb 3+，将RbF(99.1％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.94:0.025:0.01:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至900℃，并于该温度焙烧2h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为RbCa 0.94F 3:0.01Mn 2+0.05Yb 3+。 According to the chemical expression RbCa 0.94 F 3 :0.01Mn 2+ 0.05Yb 3+ , RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.94:0.025:0.01:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat. tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat up to 900 deg.] C 2.5 hours after incubation 2h, and at the baking temperature 2h, cooled to room temperature, and then grinding, i.e., A powder sample was obtained with a chemical composition of RbCa 0.94 F 3 : 0.01 Mn 2+ 0.05 Yb 3+ .
制备的上转换磷光材料RbCa 0.94F 3:0.01Mn 2+0.05Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于560nm附近，且关闭激发源后有明显的磷光。 The prepared upconversion phosphorescent material RbCa 0.94 F 3 :0.01Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located near 560 nm. And there is significant phosphorescence after the excitation source is turned off.
实施例7Example 7
上转换磷光材料RbCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.05，y＝0.05)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material RbCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.05, y=0.05) comprises the following steps:
按照化学表达式RbCa 0.9F 3:0.05Mn 2+0.05Yb 3+。，将RbF(99.1％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.9:0.025:0.05:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至350℃，并于该温度焙烧20h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为RbCa 0.9F 3:0.05Mn 2+0.05Yb 3+。 According to the chemical expression RbCa 0.9 F 3 : 0.05Mn 2+ 0.05Yb 3+ . RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) were used as raw materials, and the molar ratio was 1.05:0.9:0.025. :0.05:0.001 Accurately weigh the above materials, and grind them thoroughly in an agate mortar, transfer them into corundum crucibles, place them in a corundum boat and place them in a tube furnace, and raise the temperature from room temperature in N 2 atmosphere for 2 hours. After heating to 200 ° C for 2 h, continue to heat to 350 ° C for 2.5 hours, and calcine at this temperature for 20 h, naturally cool to room temperature, and then grind to obtain a powder sample with a chemical composition of RbCa 0.9 F 3 : 0.05 Mn 2 + 0.05Yb 3+ .
制备的上转换磷光材料RbCa 0.9F 3:0.05Mn 2+0.05Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于565nm附近，且关闭激发源后有明显的磷光。 The prepared upconversion phosphorescent material RbCa 0.9 F 3 :0.05Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by a 980 nm near-infrared laser with bright up-conversion fluorescence, and the emission peak is located near 565 nm. And there is significant phosphorescence after the excitation source is turned off.
实施例8Example 8
上转换磷光材料RbCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.1，y＝0.05)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material RbCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.1, y=0.05) comprises the following steps:
按照化学表达式RbCa 0.85F 3:0.1Mn 2+0.05Yb 3+，将RbF(99.1％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.85:0.025:0.1:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为RbCa 0.85F 3:0.1Mn 2+0.05Yb 3+。 According to the chemical expression RbCa 0.85 F 3 :0.1Mn 2+ 0.05Yb 3+ , RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.85:0.025:0.1:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat. tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat up to 850 deg.] C 2.5 hours after incubation 2h, and at this temperature firing 4h, cooled to room temperature, and then grinding, i.e., A powder sample is obtained having a chemical composition of RbCa 0.85 F 3 : 0.1Mn 2+ 0.05Yb 3+ .
制备的上转换磷光材料RbCa 0.85F 3:0.1Mn 2+0.05Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于567nm附近，且关闭激发源后有明显的磷光。 The prepared upconversion phosphorescent material RbCa 0.85 F 3 :0.1Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located near 567 nm. And there is significant phosphorescence after the excitation source is turned off.
制备的上转换磷光材料RbCa 0.85F 3:0.1Mn 2+0.05Yb 3+的XRD图如图1所示，由图1可知，所制备的样品的XRD衍射峰与RbCaF 3标准卡片基本一致，且没有其它的衍射峰出现，表明所制备的样品具有RbCaF 3相同的结果，为纯相的目标物质。 The XRD pattern of the prepared upconverting phosphor material RbCa 0.85 F 3 :0.1Mn 2+ 0.05Yb 3+ is shown in FIG. 1 . It can be seen from FIG. 1 that the XRD diffraction peak of the prepared sample is substantially identical to the RbCaF 3 standard card, and No other diffraction peaks appeared, indicating that the prepared sample had the same result as RbCaF 3 and was a pure phase target substance.
制备的上转换磷光材料RbCa 0.85F 3:0.1Mn 2+0.05Yb 3+的上转换荧光光谱图如图2所示，其中，内插图是材料在980nm激光激发下的上转换荧光与关掉激光后样品的磷光图，由图2可知，样品在980nm激光的激发下产生明亮的黄绿色上转换发光，其发射光谱由一个峰位处于567nm宽带单峰组成。快速移动样品(或关掉激发光源)，人裸眼可以看到明显的上转换磷光，且磷光的颜色与上转换荧光的颜色一致。这种独特的上转换发光特性有望应用于新型防伪、加密、特种显示或生物成像等领域，提高防伪或加密的级别以及减小生物成像时对生物体的损害。 The upconversion fluorescence spectrum of the prepared upconverting phosphorescent material RbCa 0.85 F 3 :0.1Mn 2+ 0.05Yb 3+ is shown in Fig. 2, wherein the inside inset is the upconversion fluorescence of the material under 980 nm laser excitation and the laser off. The phosphorescence pattern of the latter sample, as shown in Fig. 2, shows that the sample produces bright yellow-green upconversion luminescence under the excitation of a 980 nm laser, and its emission spectrum consists of a broadband single peak with a peak at 567 nm. By moving the sample quickly (or turning off the excitation source), the human eye can see significant upconversion phosphorescence, and the phosphorescence color is consistent with the color of the upconverting fluorescence. This unique upconversion luminescence property is expected to be applied in new fields of anti-counterfeiting, encryption, special display or bio-imaging, to improve the level of anti-counterfeiting or encryption and to reduce damage to organisms during biological imaging.
图3是所制备的上转换磷光材料RbCa 0.85F 3:0.1Mn 2+0.05Yb 3+在不同激发功率激光激发下的发射光谱，由图3可知，样品在不同功率的980纳米激光的激发下，其发射光谱都由一个位于567nm附近的宽带单峰组成，样品的发光强度随激光功率的增加而增加，但是其发射光谱形状和峰位不会随功率变化而变化。 Figure 3 is the emission spectrum of the prepared upconverting phosphorescent material RbCa 0.85 F 3 :0.1Mn 2+ 0.05Yb 3+ under different excitation power laser excitation. It can be seen from Fig. 3 that the sample is excited by 980 nm laser with different power. The emission spectrum is composed of a broadband single peak located near 567 nm. The luminescence intensity of the sample increases with the increase of the laser power, but the shape and peak position of the emission spectrum do not change with the power.
实施例9Example 9
上转换磷光材料RbCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.2，y＝0.05)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material RbCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.2, y=0.05) comprises the following steps:
按照化学表达式RbCa 0.75F 3:0.2Mn 2+0.05Yb 3+，将RbF(99.1％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.75:0.025:0.2:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h 后继续用2.5小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为RbCa 0.75F 3:0.2Mn 2+0.05Yb 3+。 According to the chemical expression RbCa 0.75 F 3 : 0.2Mn 2+ 0.05Yb 3+ , RbF (99.1%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.75:0.025:0.2:0.001, and thoroughly ground in an agate mortar, transferred into corundum crucible, and placed in a corundum boat. tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat up to 850 deg.] C 2.5 hours after incubation 2h, and at this temperature firing 4h, cooled to room temperature, and then grinding, i.e., A powder sample is obtained having a chemical composition of RbCa 0.75 F 3 : 0.2Mn 2+ 0.05Yb 3+ .
制备的上转换磷光材料RbCa 0.75F 3:0.2Mn 2+0.05Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于569nm附近，且关闭激发源后有明显的磷光。 The prepared upconversion phosphorescent material RbCa 0.75 F 3 :0.2Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser with bright up-conversion fluorescence, and the emission peak is located near 569 nm. And there is significant phosphorescence after the excitation source is turned off.
实施例10Example 10
上转换磷光材料RbSr 0.1Ca 0.9-x-yF 3:0.1Mn 2+0.05Yb 3+的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material RbSr 0.1 Ca 0.9-xy F 3 :0.1Mn 2+ 0.05Yb 3+ comprises the following steps:
按照化学表达式RbSr 0.1Ca 0.75F 3:0.1Mn 2+0.05Yb 3+，将RbF(99.1％)、SrF 2(99.0％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.1:0.75:0.025:0.1:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为RbSr 0.1Ca 0.75F 3:0.1Mn 2+0.05Yb 3+。 According to the chemical expression RbSr 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ , RbF (99.1%), SrF 2 (99.0%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) were used as raw materials, and the above substances were accurately weighed in a molar ratio of 1.05:0.1:0.75:0.025:0.1:0.001, and thoroughly ground in an agate mortar and transferred into corundum. In the middle, put it into a corundum boat and place it in a tube furnace. In a N 2 atmosphere, heat the room temperature to 200 ° C for 2 hours. After 2 hours of heat preservation, continue to heat up to 850 ° C for 2.5 hours and bake at this temperature for 4 hours. It is naturally cooled to room temperature and then ground to obtain a powder sample having a chemical composition of RbSr 0.1 Ca 0.75 F 3 : 0.1Mn 2+ 0.05Yb 3+ .
制备的上转换磷光材料RbSr 0.1Ca 0.75F 3:0.1Mn 2+0.05Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于565nm附近，且关闭激发源后有明显的磷光。 The prepared upconverting phosphorescent material RbSr 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by a 980 nm near-infrared laser with bright up-conversion fluorescence and emission peaks Near 565 nm, there is significant phosphorescence after the excitation source is turned off.
实施例11Example 11
上转换磷光材料RbBa 0.1Ca 0.9-x-yF 3:0.1Mn 2+0.05Yb 3+的制备，具体包括如下步骤： The preparation of the up-conversion phosphorescent material RbBa 0.1 Ca 0.9-xy F 3 :0.1Mn 2+ 0.05Yb 3+ comprises the following steps:
按照化学表达式RbBa 0.1Ca 0.75F 3:0.1Mn 2+0.05Yb 3+，将RbF(99.1％)、BaF 2(分析纯)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.1:0.75:0.025:0.1:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至750℃，并于该温度焙烧10h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为RbBa 0.1Ca 0.75F 3:0.1Mn 2+0.05Yb 3+。 According to the chemical expression RbBa 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ , RbF (99.1%), BaF 2 (analytical grade), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) were used as raw materials, and the above substances were accurately weighed in a molar ratio of 1.05:0.1:0.75:0.025:0.1:0.001, and thoroughly ground in an agate mortar and transferred into corundum. In the crucible, place it in a corundum boat and place it in a tube furnace. Warm it up to 200 °C from room temperature in N 2 atmosphere for 2 hours. After heating for 2 h, continue to heat up to 750 ° C for 2.5 hours, and roast at this temperature for 10 h. It is naturally cooled to room temperature and then ground to obtain a powder sample having a chemical composition of RbBa 0.1 Ca 0.75 F 3 : 0.1Mn 2+ 0.05Yb 3+ .
制备的上转换磷光材料RbBa 0.1Ca 0.75F 3:0.1Mn 2+0.05Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于565nm附近，且关闭激发源后有明显的磷光。 The prepared upconversion phosphorescent material RbBa 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located. Near 565 nm, there is significant phosphorescence after the excitation source is turned off.
实施例12Example 12
上转换磷光材料RbMg 0.1Ca 0.9-x-yF 3:0.1Mn 2+0.05Yb 3+的制备，具体包括如下步骤： The preparation of the up-conversion phosphorescent material RbMg 0.1 Ca 0.9-xy F 3 :0.1Mn 2+ 0.05Yb 3+ comprises the following steps:
按照化学表达式RbMg 0.1Ca 0.75F 3:0.1Mn 2+0.05Yb 3+，将RbF(99.1％)、MgF 2(99.99％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.1:0.75:0.025:0.1:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为RbMg 0.1Ca 0.75F 3:0.1Mn 2+0.05Yb 3+。 According to the chemical expression RbMg 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ , RbF (99.1%), MgF 2 (99.99%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) were used as raw materials, and the above substances were accurately weighed in a molar ratio of 1.05:0.1:0.75:0.025:0.1:0.001, and thoroughly ground in an agate mortar and transferred into corundum. In the middle, put it into a corundum boat and place it in a tube furnace. In a N 2 atmosphere, heat the room temperature to 200 ° C for 2 hours. After 2 hours of heat preservation, continue to heat up to 850 ° C for 2.5 hours and bake at this temperature for 4 hours. It is naturally cooled to room temperature and then ground to obtain a powder sample having a chemical composition of RbMg 0.1 Ca 0.75 F 3 : 0.1Mn 2+ 0.05Yb 3+ .
制备的上转换磷光材料RbMg 0.1Ca 0.75F 3:0.1Mn 2+0.05Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于579nm附近，且关闭激发源后有明显的磷光。 The prepared upconverting phosphorescent material RbMg 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located Near 579 nm, there is significant phosphorescence after the excitation source is turned off.
实施例13Example 13
上转换磷光材料RbZn 0.1Ca 0.9-x-yF 3:0.1Mn 2+0.05Yb 3+的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material RbZn 0.1 Ca 0.9-xy F 3 :0.1Mn 2+ 0.05Yb 3+ comprises the following steps:
按照化学表达式RbZn 0.1Ca 0.75F 3:0.1Mn 2+0.05Yb 3+，将RbF(99.1％)、ZnF 2(99.0％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.1:0.75:0.025:0.1:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温1.5h后继续用2.5小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为RbZn 0.1Ca 0.75F 3:0.1Mn 2+0.05Yb 3+。 According to the chemical expression RbZn 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ , RbF (99.1%), ZnF 2 (99.0%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) were used as raw materials, and the above substances were accurately weighed in a molar ratio of 1.05:0.1:0.75:0.025:0.1:0.001, and thoroughly ground in an agate mortar and transferred into corundum. In the crucible, put it into a corundum boat and place it in a tube furnace. In a N 2 atmosphere, heat the room temperature to 200 ° C for 2 hours. After heating for 1.5 h, continue to heat up to 850 ° C for 2.5 hours, and roast at this temperature. After 4 h, it was naturally cooled to room temperature, and then ground to obtain a powder sample having a chemical composition of RbZn 0.1 Ca 0.75 F 3 : 0.1 Mn 2+ 0.05 Yb 3+ .
制备的上转磷光材料RbZn 0.1Ca 0.75F 3:0.1Mn 2+0.05Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于565nm附近，且关闭激发源后有明显的磷光。 The prepared up-go phosphorescent material RbZn 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located. Near 565 nm, there is significant phosphorescence after the excitation source is turned off.
实施例14Example 14
上转换磷光材料RbCd 0.1Ca 0.9-x-yF 3:0.1Mn 2+0.05Yb 3+的制备，具体包括如下步骤： The preparation of the up-conversion phosphorescent material RbCd 0.1 Ca 0.9-xy F 3 :0.1Mn 2+ 0.05Yb 3+ comprises the following steps:
按照化学表达式RbCd 0.1Ca 0.75F 3:0.1Mn 2+0.05Yb 3+，将RbF(99.1％)、CdF 2(99.0％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.1:0.75:0.025:0.1:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为RbCd 0.1Ca 0.75F 3:0.1Mn 2+0.05Yb 3+。 According to the chemical expression RbCd 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ , RbF (99.1%), CdF 2 (99.0%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) were used as raw materials, and the above substances were accurately weighed in a molar ratio of 1.05:0.1:0.75:0.025:0.1:0.001, and thoroughly ground in an agate mortar and transferred into corundum. In the middle, put it into a corundum boat and place it in a tube furnace. In a N 2 atmosphere, heat the room temperature to 200 ° C for 2 hours. After 2 hours of heat preservation, continue to heat up to 850 ° C for 2.5 hours and bake at this temperature for 4 hours. It is naturally cooled to room temperature and then ground to obtain a powder sample having a chemical composition of RbCd 0.1 Ca 0.75 F 3 : 0.1Mn 2+ 0.05Yb 3+ .
制备的上转磷光材料RbCd 0.1Ca 0.75F 3:0.1Mn 2+0.05Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于563nm附近，且关闭激发源后有明显的磷光。 The prepared up-go phosphorescent material RbCd 0.1 Ca 0.75 F 3 :0.1Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located. Near 563 nm, there is significant phosphorescence after the excitation source is turned off.
实施例15Example 15
上转换磷光材料KCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.0001，y＝0.03)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material KCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.0001, y=0.03) includes the following steps:
按照化学表达式KCa 0.9699F 3:0.0001Mn 2+0.03Yb 3+，将KF(99.9％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.9699:0.015:0.0001:0.01准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为KCa 0.9699F 3:0.0001Mn 2+0.03Yb 3+。 KCa 0.9699 F 3 according to the chemical formula: 0.0001Mn 2+ 0.03Yb 3+, the KF (99.9%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.9699:0.015:0.0001:0.01, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat. tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat up to 850 deg.] C 2.5 hours after incubation 2h, and at this temperature firing 4h, cooled to room temperature, and then grinding, i.e., obtained powder sample, the chemical composition of KCa 0.9699 F 3: 0.0001Mn 2+ 0.03Yb 3+.
制备的上转换磷光材料KCa 0.9699F 3:0.0001Mn 2+0.03Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于572nm附近，且关闭激发源后有明显的磷光。 Conversion of the phosphorescent material prepared KCa 0.9699 F 3: 0.0001Mn 2+ 0.03Yb 3+ chemically stable, non-hazardous to the environment; 980nm can be efficiently excited by near-infrared laser, upconversion bright fluorescence emission peak near 572nm And there is significant phosphorescence after the excitation source is turned off.
实施例16Example 16
上转换磷光材料KCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.01，y＝0.03)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material KCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.01, y=0.03) includes the following steps:
按照化学表达式KCa 0.96F 3:0.01Mn 2+0.03Yb 3+，将KF(99.9％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.96:0.015:0.01:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为KCa 0.96F 3:0.01Mn 2+0.03Yb 3+。 According to the chemical expression KCa 0.96 F 3 :0.01Mn 2+ 0.03Yb 3+ , KF (99.9%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.96:0.015:0.01:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat. tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat up to 850 deg.] C 2.5 hours after incubation 2h, and at this temperature firing 4h, cooled to room temperature, and then grinding, i.e., A powder sample having a chemical composition of KCa 0.96 F 3 : 0.01 Mn 2+ 0.03 Yb 3+ can be obtained .
制备的上转换磷光材料KCa 0.96F 3:0.01Mn 2+0.03Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于576nm附近，且关闭激发源后有明显的磷光。 The prepared upconverting phosphor material KCa 0.96 F 3 :0.01Mn 2+ 0.03Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by a 980 nm near-infrared laser with bright up-conversion fluorescence, and the emission peak is located near 576 nm. And there is significant phosphorescence after the excitation source is turned off.
实施例17Example 17
上转换磷光材料KCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.05，y＝0.03)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material KCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.05, y=0.03) includes the following steps:
按照化学表达式KCa 0.92F 3:0.05Mn 2+0.03Yb 3+，将KF(99.9％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.92:0.015:0.05:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为KCa 0.92F 3:0.05Mn 2+0.03Yb 3+。 According to the chemical expression KCa 0.92 F 3 : 0.05Mn 2+ 0.03Yb 3+ , KF (99.9%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.92:0.015:0.05:0.001, and thoroughly ground in an agate mortar, transferred into corundum crucible, and placed in a corundum boat. tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat up to 850 deg.] C 2.5 hours after incubation 2h, and at this temperature firing 4h, cooled to room temperature, and then grinding, i.e., A powder sample having a chemical composition of KCa 0.92 F 3 : 0.05 Mn 2+ 0.03 Yb 3+ can be obtained .
制备的上转换磷光材料KCa 0.92F 3:0.05Mn 2+0.03Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于578nm附近，且关闭激发源后有明显的磷光。 The prepared upconverting phosphor material KCa 0.92 F 3 :0.05Mn 2+ 0.03Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located near 578 nm. And there is significant phosphorescence after the excitation source is turned off.
制备的上转换磷光材料KCa 0.92F 3:0.05Mn 2+0.03Yb 3+的XRD图如图4所示，由图4可知，所制备的样品的XRD衍射峰与KCaF 3标准卡片基本一致，且没有其它的衍射峰出现，表明所制备的样品具有KCaF 3相同的结果，为纯相的目标物质。 The XRD pattern of the prepared upconverting phosphor material KCa 0.92 F 3 :0.05Mn 2+ 0.03Yb 3+ is shown in FIG. 4 , and as shown in FIG. 4 , the XRD diffraction peak of the prepared sample is substantially identical to the KCaF 3 standard card, and No other diffraction peaks appeared, indicating that the prepared sample had the same result as KCaF 3 and was a pure phase target substance.
制备的上转换磷光材料KCa 0.92F 3:0.05Mn 2+0.03Yb 3+的上转换荧光光谱图如图5所示，其中，内插图是材料在980nm激光激发下的上转换荧光与关掉激光后样品的磷光图，由图5可知，样品在980nm激光的激发下产生明亮的黄绿色上转换发光，其发射光谱由一个峰位处于578nm宽带单峰组成。快速移动样品(或关掉激发光源)，人裸眼可以看到明显的上转换磷光，且磷光的颜色与上转换荧光的颜色一致。这种独特的上转换发光特性有望应用于新型防伪、加密、特种显示或生物成像等领域，提高防伪或加密的级别以及减小生物成像时对生物体的损害。 The upconversion fluorescence spectrum of the prepared upconverting phosphor material KCa 0.92 F 3 :0.05Mn 2+ 0.03Yb 3+ is shown in Fig. 5, wherein the inside inset is the upconversion fluorescence of the material under 980 nm laser excitation and the laser off. The phosphorescence pattern of the latter sample, as shown in Fig. 5, shows that the sample produces bright yellow-green upconversion luminescence under excitation of a 980 nm laser, and its emission spectrum consists of a broadband single peak with a peak at 578 nm. By moving the sample quickly (or turning off the excitation source), the human eye can see significant upconversion phosphorescence, and the phosphorescence color is consistent with the color of the upconverting fluorescence. This unique upconversion luminescence property is expected to be applied in new fields of anti-counterfeiting, encryption, special display or bio-imaging, to improve the level of anti-counterfeiting or encryption and to reduce damage to organisms during biological imaging.
图6是所制备的上转换磷光材料KCa 0.92F 3:0.05Mn 2+0.03Yb 3+在不同激发功率激光激发下的发射光谱。由图6可知，样品在不同功率的980nm激光的激发下，其发射光谱都由一个位于578nm附近的宽带单峰组成，样品的发光强度随激光功率的增加而增加，但是其发射光谱形状和峰位不会随功率变化而变化。 Figure 6 is an emission spectrum of the prepared upconverting phosphor material KCa 0.92 F 3 :0.05Mn 2+ 0.03Yb 3+ under different excitation power laser excitations. It can be seen from Fig. 6 that under the excitation of 980 nm laser with different powers, the emission spectrum of the sample is composed of a broadband single peak located near 578 nm. The luminescence intensity of the sample increases with the increase of laser power, but its emission spectrum shape and peak Bits do not change with power.
实施例18Example 18
上转换磷光材料KCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.1，y＝0.03)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material KCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.1, y=0.03) includes the following steps:
按照化学表达式KCa 0.87F 3:0.1Mn 2+0.03Yb 3+，将KF(99.9％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.87:0.015:0.1:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h 后继续用3小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为KCa 0.87F 3:0.1Mn 2+0.03Yb 3+。 According to the chemical expression KCa 0.87 F 3 :0.1Mn 2+ 0.03Yb 3+ , KF (99.9%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.87:0.015:0.1:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat. tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat up to 850 deg.] C over 3 hours incubation 2h, and at this temperature firing 4h, cooled to room temperature, and then grinding, i.e., A powder sample having a chemical composition of KCa 0.87 F 3 : 0.1 Mn 2+ 0.03 Yb 3+ can be obtained .
制备的上转换磷光材料KCa 0.87F 3:0.1Mn 2+0.03Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于578nm附近，且关闭激发源后有明显的磷光。 The prepared upconverting phosphor material KCa 0.87 F 3 :0.1Mn 2+ 0.03Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located near 578 nm. And there is significant phosphorescence after the excitation source is turned off.
实施例19Example 19
上转换磷光材料KCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.2，y＝0.03)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material KCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.2, y=0.03) specifically includes the following steps:
按照化学表达式KCa 0.77F 3:0.2Mn 2+0.03Yb 3+，将KF(99.9％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.77:0.015:0.2:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为KCa 0.77F 3:0.2Mn 2+0.03Yb 3+。 According to the chemical expression KCa 0.77 F 3 :0.2Mn 2+ 0.03Yb 3+ , KF (99.9%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above materials were accurately weighed in a molar ratio of 1.05:0.77:0.015:0.2:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat. tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat up to 850 deg.] C 2.5 hours after incubation 2h, and at this temperature firing 4h, cooled to room temperature, and then grinding, i.e., A powder sample was obtained with a chemical composition of KCa 0.77 F 3 : 0.2Mn 2+ 0.03Yb 3+ .
制备的上转换磷光材料KCa 0.77F 3:0.2Mn 2+0.03Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于580nm附近，且关闭激发源后有明显的磷光。 The prepared upconverting phosphor material KCa 0.77 F 3 :0.2Mn 2+ 0.03Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located near 580 nm. And there is significant phosphorescence after the excitation source is turned off.
实施例20Example 20
上转换磷光材料KCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.01，y＝0.05)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material KCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.01, y=0.05) comprises the following steps:
按照化学表达式KCa 0.94F 3:0.01Mn 2+0.05Yb 3+，将KF(99.9％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.94:0.025:0.01:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用1小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为KCa 0.94F 3:0.01Mn 2+0.05Yb 3+。 According to the chemical expression KCa 0.94 F 3 :0.01Mn 2+ 0.05Yb 3+ , KF (99.9%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.94:0.025:0.01:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat. tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat up to 850 deg.] C over 1 hour incubation 2h, and at this temperature firing 4h, cooled to room temperature, and then grinding, i.e., A powder sample having a chemical composition of KCa 0.94 F 3 : 0.01 Mn 2+ 0.05 Yb 3+ was obtained .
制备的上转换磷光材料KCa 0.94F 3:0.01Mn 2+0.05Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于576nm附近，且关闭激发源后有明显的磷光。 The prepared upconverting phosphor material KCa 0.94 F 3 :0.01Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser with bright up-conversion fluorescence, and the emission peak is located near 576 nm. And there is significant phosphorescence after the excitation source is turned off.
实施例21Example 21
上转换磷光材料KCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.05，y＝0.05)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material KCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.05, y=0.05) comprises the following steps:
按照化学表达式KCa 0.9F 3:0.05Mn 2+0.05Yb 3+，将KF(99.9％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.9:0.025:0.05:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为KCa 0.9F 3:0.05Mn 2+0.05Yb 3+。 According to the chemical expression KCa 0.9 F 3 : 0.05Mn 2+ 0.05Yb 3+ , KF (99.9%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.9:0.025:0.05:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat. tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat up to 850 deg.] C 2.5 hours after incubation 2h, and at this temperature firing 4h, cooled to room temperature, and then grinding, i.e., A powder sample having a chemical composition of KCa 0.9 F 3 : 0.05 Mn 2+ 0.05 Yb 3+ was obtained .
制备的上转换磷光材料KCa 0.9F 3:0.05Mn 2+0.05Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于577nm附近，且关闭激发源后有明显的磷光。 The prepared upconversion phosphor material KCa 0.9 F 3 :0.05Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, with bright up-conversion fluorescence, and the emission peak is located near 577 nm. And there is significant phosphorescence after the excitation source is turned off.
实施例22Example 22
上转换磷光材料KCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.1，y＝0.05)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material KCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.1, y=0.05) comprises the following steps:
按照化学表达式KCa 0.85F 3:0.1Mn 2+0.05Yb 3+，将KF(99.9％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.85:0.025:0.1:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温1h后继续用2.5小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为KCa 0.85F 3:0.1Mn 2+0.05Yb 3+。 According to the chemical expression KCa 0.85 F 3 :0.1Mn 2+ 0.05Yb 3+ , KF (99.9%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.85:0.025:0.1:0.001, and thoroughly ground in an agate mortar, transferred into a corundum crucible, and placed in a corundum boat. tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat up to 850 deg.] C 2.5 hours after incubation IH, and at this temperature firing 4h, cooled to room temperature, and then grinding, i.e., A powder sample was obtained with a chemical composition of KCa 0.85 F 3 : 0.1 Mn 2+ 0.05 Yb 3+ .
制备的上转换磷光材料KCa 0.85F 3:0.1Mn 2+0.05Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于578nm附近，且关闭激发源后有明显的磷光。 The prepared upconverting phosphor material KCa 0.85 F 3 :0.1Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located near 578 nm. And there is significant phosphorescence after the excitation source is turned off.
实施例23Example 23
上转换磷光材料KCa 1-x-yF 3:xMn 2+yYb 3+(x＝0.2，y＝0.05)的制备，具体包括如下步骤： The preparation of the up-conversion phosphor material KCa 1-xy F 3 :xMn 2+ yYb 3+ (x=0.2, y=0.05) comprises the following steps:
按照化学表达式KCa 0.75F 3:0.2Mn 2+0.05Yb 3+，将KF(99.9％)、CaF 2(99.99％)、Yb 2O 3(99.99％)、MnCO 3(99.95％)和NH 4HF 2(98.5％)作为原料，按摩尔比1.05:0.75:0.025:0.2:0.001准确称取以上物质，并在玛瑙研钵中充分研磨均匀，移入刚玉坩埚中，再放入刚玉舟中置于管式炉中，在N 2气氛中，用2小时从室温升温至200℃，保温2h后继续用2.5小时升温至850℃，并于该温度焙烧4h，自然冷却至室温，然后进行研磨，即可得到粉末样品，其化学组成为KCa 0.75F 3:0.2Mn 2+0.05Yb 3+。 According to the chemical expression KCa 0.75 F 3 :0.2Mn 2+ 0.05Yb 3+ , KF (99.9%), CaF 2 (99.99%), Yb 2 O 3 (99.99%), MnCO 3 (99.95%) and NH 4 HF 2 (98.5%) was used as the raw material, and the above substances were accurately weighed in a molar ratio of 1.05:0.75:0.025:0.2:0.001, and thoroughly ground in an agate mortar, transferred into corundum crucible, and placed in a corundum boat. tube furnace, in a N 2 atmosphere, over 2 hours from room temperature to 200 ℃, continue to heat up to 850 deg.] C 2.5 hours after incubation 2h, and at this temperature firing 4h, cooled to room temperature, and then grinding, i.e., A powder sample was obtained with a chemical composition of KCa 0.75 F 3 : 0.2Mn 2+ 0.05Yb 3+ .
制备的上转换磷光材料KCa 0.75F 3:0.2Mn 2+0.05Yb 3+的化学性质稳定，对环境无危害；可被980nm近红外激光有效激发，有明亮的上转换荧光，发射峰位于580nm附近，且关闭激发源后有明显的磷光。 The prepared upconverting phosphor material KCa 0.75 F 3 :0.2Mn 2+ 0.05Yb 3+ is chemically stable and harmless to the environment; it can be effectively excited by 980 nm near-infrared laser, has bright up-conversion fluorescence, and the emission peak is located near 580 nm. And there is significant phosphorescence after the excitation source is turned off.
显而易见地，所述描述的仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，根据本发明获得的其他可替代、改变、修饰、组合、简化或同等变形等，均在本发明保护范围内。Obviously, the description is only some of the embodiments of the present invention, and other alternatives, modifications, modifications, combinations, and simplifications obtained according to the present invention will be made by those skilled in the art without any inventive effort. Or equivalent deformation, etc., are within the scope of the present invention.

Claims (10)

  1. 一类上转换磷光材料，其特征在于，化学组成表达式为AB 1-x-yF 3:xMn 2+yYb 3+；其中，A为碱金属Li、Na、K、Rb和Cs中的一种以上，B为二价金属Ba、Sr、Ca、Cd、Mg、Zn和Pb中的一种以上，x，y分别为掺杂离子Yb 3+和Mn 2+的浓度，取值范围：x＝0.0001～0.7，y＝0.0001～0.3。 A type of upconversion phosphorescent material characterized in that the chemical composition expression is AB 1-xy F 3 :xMn 2+ yYb 3+ ; wherein A is one or more of alkali metals Li, Na, K, Rb and Cs B is one or more of the divalent metals Ba, Sr, Ca, Cd, Mg, Zn and Pb, and x, y are the concentrations of the doping ions Yb 3+ and Mn 2+ , respectively, and the range of values is x=0.0001 ～0.7, y=0.0001~0.3.
  2. 根据权利要求1所述的一类上转换磷光材料，其特征在于，A为碱金属Na、K和Rb中的一种以上；B为二价金属Ca、Cd、Zn和Mg中的一种以上；x，y分别为掺杂离子Mn 2+和的Yb 3+浓度，取值范围：x＝0.01～0.4，y＝0.01～0.15。 The up-conversion phosphorescent material according to claim 1, wherein A is one or more of alkali metals Na, K and Rb; and B is one or more of divalent metals Ca, Cd, Zn and Mg. ;x,y are the concentrations of the doping ions Mn 2+ and Yb 3+ , respectively, ranging from x=0.01 to 0.4, y=0.01 to 0.15.
  3. 根据权利要求1所述的一类上转换磷光材料，其特征在于，所述AB 1-x- yF 3:xMn 2+yYb 3+选自LiSr 1-x-yF 3:xMn 2+yYb 3+、NaSr 1-x-yF 3:xMn 2+yYb 3+、KSr 1-x-yF 3:xMn 2+yYb 3+、RbSr 1-x-yF 3:xMn 2+yYb 3+、CsSr 1-x-yF 3:xMn 2+yYb 3+、LiBa 1-x-yF 3:xMn 2+yYb 3+、NaBa 1-x- yF 3:xMn 2+yYb 3+、KBa 1-x-yF 3:xMn 2+yYb 3+、RbBa 1-x-yF 3:xMn 2+yYb 3+、CsBa 1-x-yF 3:xMn 2+yYb 3+、LiCa 1-x-yF 3:xMn 2+yYb 3+、NaCa 1-x-yF 3:xMn 2+yYb 3+、KCa 1-x-yF 3:xMn 2+yYb 3+、RbCa 1-x- yF 3:xMn 2+yYb 3+、CsCa 1-x-yF 3:xMn 2+yYb 3+、LiCd 1-x-yF 3:xMn 2+yYb 3+、NaCd 1-x-yF 3:xMn 2+yYb 3+、KCd 1-x-yF 3:xMn 2+yYb 3+、RbCd 1-x-yF 3:xMn 2+yYb 3+、CsCd 1-x-yF 3:xMn 2+yYb 3+、LiMgr 1-x- yF 3:xMn 2+yYb 3+、NaMg 1-x-yF 3:xMn 2+yYb 3+、KMg 1-x-yF 3:xMn 2+yYb 3+、RbMg 1-x-yF 3:xMn 2+yYb 3+、CsMg 1-x-yF 3:xMn 2+yYb 3+、LiZnr 1-x-yF 3:xMn 2+yYb 3+、NaZn 1-x-yF 3:xMn 2+yYb 3+、KZn 1-x- yF 3:xMn 2+yYb 3+、RbZn 1-x-yF 3:xMn 2+yYb 3+、CsZn 1-x-yF 3:xMn 2+yYb 3+、LiPbr 1-x-yF 3:xMn 2+yYb 3+、NaPb 1-x-yF 3:xMn 2+yYb 3+、KPb 1-x-yF 3:xMn 2+yYb 3+、RbPb 1-x-yF 3:xMn 2+yYb 3+或CsPb 1-x- yF 3:xMn 2+yYb 3+。 The upconversion phosphorescent material according to claim 1, wherein said AB 1-x- y F 3 :xMn 2+ yYb 3+ is selected from the group consisting of LiSr 1-xy F 3 :xMn 2+ yYb 3+ NaSr 1-xy F 3 :xMn 2+ yYb 3+ , KSr 1-xy F 3 :xMn 2+ yYb 3+ , RbSr 1-xy F 3 :xMn 2+ yYb 3+ , CsSr 1-xy F 3 : xMn 2+ yYb 3+ , LiBa 1-xy F 3 :xMn 2+ yYb 3+ , NaBa 1-x- y F 3 :xMn 2+ yYb 3+ , KBa 1-xy F 3 :xMn 2+ yYb 3+ , RbBa 1-xy F 3 : xMn 2+ yYb 3+ , CsBa 1-xy F 3 : xMn 2+ yYb 3+ , LiCa 1-xy F 3 : xMn 2+ yYb 3+ , NaCa 1-xy F 3 : xMn 2+ yYb 3+ , KCa 1-xy F 3 :xMn 2+ yYb 3+ , RbCa 1-x- y F 3 :xMn 2+ yYb 3+ , CsCa 1-xy F 3 :xMn 2+ yYb 3+ LiCd 1-xy F 3 :xMn 2+ yYb 3+ , NaCd 1-xy F 3 :xMn 2+ yYb 3+ , KCd 1-xy F 3 :xMn 2+ yYb 3+ , RbCd 1-xy F 3 : xMn 2+ yYb 3+ , CsCd 1-xy F 3 :xMn 2+ yYb 3+ , LiMgr 1-x- y F 3 :xMn 2+ yYb 3+ , NaMg 1-xy F 3 :xMn 2+ yYb 3+ KMg 1-xy F 3 :xMn 2+ yYb 3+ , RbMg 1-xy F 3 :xMn 2+ yYb 3+ , CsMg 1-xy F 3 :xMn 2+ yYb 3+ , LiZnr 1-xy F 3 : xMn 2+ yYb 3+ , NaZn 1-xy F 3 :xMn 2+ yYb 3+ , KZn 1-x- y F 3 :x Mn 2+ yYb 3+ , RbZn 1-xy F 3 : xMn 2+ yYb 3+ , CsZn 1-xy F 3 : xMn 2+ yYb 3+ , LiPbr 1-xy F 3 : xMn 2+ yYb 3+ , NaPb 1-xy F 3 :xMn 2+ yYb 3+ , KPb 1-xy F 3 :xMn 2+ yYb 3+ , RbPb 1-xy F 3 :xMn 2+ yYb 3+ or CsPb 1-x- y F 3 : xMn 2+ yYb 3+ .
  4. 根据权利要求1所述的一类上转换磷光材料，其特征在于，所述AB 1-x- yF 3:xMn 2+yYb 3+选自KCa 1-x-yF 3:xMn 2+yYb 3+、RbCa 1-x-yF 3:xMn 2+yYb 3+、KCd 1-x-yF 3:xMn 2+yYb 3+、RbCd 1-x-yF 3:xMn 2+yYb 3+、NaMg 1-x-yF 3:xMn 2+yYb 3+、KMg 1-x-yF 3:xMn 2+yYb 3+、RbMg 1-x- yF 3:xMn 2+yYb 3+、NaZn 1-x-yF 3:xMn 2+yYb 3+、KZn 1-x-yF 3:xMn 2+yYb 3+、KPb 1-x-yF 3:xMn 2+yYb 3+或RbPb 1-x-yF 3:xMn 2+yYb 3+。 A type of upconversion phosphorescent material according to claim 1 wherein said AB 1-x- y F 3 :xMn 2+ yYb 3+ is selected from the group consisting of KCa 1-xy F 3 :xMn 2+ yYb 3+ , RbCa 1-xy F 3 : xMn 2+ yYb 3+ , KCd 1-xy F 3 : xMn 2+ yYb 3+ , RbCd 1-xy F 3 : xMn 2+ yYb 3+ , NaMg 1-xy F 3 : xMn 2+ yYb 3+ , KMg 1-xy F 3 :xMn 2+ yYb 3+ , RbMg 1-x- y F 3 :xMn 2+ yYb 3+ , NaZn 1-xy F 3 :xMn 2+ yYb 3+ KZn 1-xy F 3 : xMn 2+ yYb 3+ , KPb 1-xy F 3 : xMn 2+ yYb 3+ or RbPb 1-xy F 3 : xMn 2+ yYb 3+ .
  5. 根据权利要求1～4任一项所述的一类上转换磷光材料，其特征在于，材料在980nm近红外激光激发下，镱Yb 3+敏化锰Mn 2+得到明亮的上转换荧光；当停止激发时，材料呈现出明显的磷光，磷光的颜色与荧光的颜色完全一致；且上转换荧光光谱或磷光光谱由峰位位于500～830nm的发光峰组成。 The above-mentioned type of up-conversion phosphorescent material according to any one of claims 1 to 4, wherein the material is excited by 980 nm near-infrared laser, and yttrium Yb 3+ sensitized manganese Mn 2+ obtains bright up-conversion fluorescence; When the excitation is stopped, the material exhibits obvious phosphorescence, and the color of the phosphorescence is completely consistent with the color of the fluorescence; and the up-conversion fluorescence spectrum or the phosphorescence spectrum is composed of a luminescence peak having a peak position of 500 to 830 nm.
  6. 制备权利要求1～6任一项所述的上转换磷光材料的方法，其特征在于，包括如下步骤：A method of preparing the upconverting phosphor material according to any one of claims 1 to 6, comprising the steps of:
    (1)按所述化学组成表达式AB 1-x-yF 3:xMn 2+yYb 3+准确称量含氟A源、含氟B源、Yb源与Mn源，并加入含氟助溶剂，充分研磨混合均匀，得到混合物； (1) Accurately weigh the fluorine-containing A source, the fluorine-containing B source, the Yb source and the Mn source according to the chemical composition expression AB 1-xy F 3 :xMn 2+ yYb 3+ , and add a fluorine-containing auxiliary solvent, fully Grinding and mixing uniformly to obtain a mixture;
    (2)将混合物置于空气、惰性气氛或还原气氛保护下程序升温并烧结，自然冷却至室温；(2) The mixture is heated and sintered under the protection of air, an inert atmosphere or a reducing atmosphere, and naturally cooled to room temperature;
    (3)将步骤(2)所得产物取出再研磨，得到无色产物，即所述上转换磷光材料。(3) The product obtained in the step (2) is taken out and ground to obtain a colorless product, that is, the up-conversion phosphorescent material.
  7. 根据权利要求6所述的制备方法，其特征在于，步骤(1)中，所述含氟A源为碱金属氟化物AF或二氟氢化物AHF 2；所述含氟B源为二价金属氟化物BF 2；所述Yb源选自Yb的氧化物、Yb的氯化物、Yb的氟化物、Yb的碳酸盐、Yb的硝酸盐和Yb的醋酸盐中的一种以上；所述Mn源选自MnO、Mn的氯化物、MnF 2、MnBr 2、MnCO 3和Mn的醋酸盐中的一种以上；所述含氟助熔剂为NH 4F与NH 4HF 2中的一种以上；所述充分研磨是在玛瑙研钵或陶瓷研磨中充分研磨。 The preparation method according to claim 6, wherein in the step (1), the fluorine-containing A source is an alkali metal fluoride AF or a difluorohydride AHF 2 ; and the fluorine-containing B source is a divalent metal. Fluoride BF 2 ; the Yb source is selected from the group consisting of an oxide of Yb, a chloride of Yb, a fluoride of Yb, a carbonate of Yb, a nitrate of Yb, and an acetate of Yb; The Mn source is one or more selected from the group consisting of MnO, Mn chloride, MnF 2 , MnBr 2 , MnCO 3 and Mn acetate; the fluorine-containing flux is one of NH 4 F and NH 4 HF 2 Above; the full grinding is fully ground in an agate mortar or ceramic grinding.
  8. 根据权利要求6所述的制备方法，其特征在于，步骤(1)中，所述含氟A源为LiF、NaF、KF、RbF、CsF、LiHF 2、NaHF 2、KHF 2、RbHF 2和CsHF 2中的一种以上；所述含氟B源为BaF 2、SrF 2、CaF 2、CdF 2、MgF 2、ZnF 2和PbF 2中的一种以上；所述含氟Yb源选自Yb 2O 3、Yb的醋酸盐或Yb的氟化物；所述Mn源选自MnO、MnF 2或MnCO 3。 The preparation method according to claim 6, wherein in the step (1), the fluorine-containing A source is LiF, NaF, KF, RbF, CsF, LiHF 2 , NaHF 2 , KHF 2 , RbHF 2 and CsHF. One or more of 2 ; the fluorine-containing B source is one or more of BaF 2 , SrF 2 , CaF 2 , CdF 2 , MgF 2 , ZnF 2 and PbF 2 ; the fluorine-containing Yb source is selected from Yb 2 An acetate of O 3 , Yb or a fluoride of Yb; the source of Mn is selected from the group consisting of MnO, MnF 2 or MnCO 3 .
  9. 根据权利要求6所述的制备方法，其特征在于，步骤(2)中，所述惰性气氛为氮气气氛或氩气气氛；所述还原气氛为氮气-氢气混合弱还原气氛；所述程序升温并烧结是：用2小时从室温升温到200℃，并保温烧结1～2小时；随后用1～3小时升温到300～900℃，并保温烧结1～24小时。The preparation method according to claim 6, wherein in the step (2), the inert atmosphere is a nitrogen atmosphere or an argon atmosphere; the reducing atmosphere is a nitrogen-hydrogen mixed weak reducing atmosphere; Sintering is: heating from room temperature to 200 ° C in 2 hours, and sintering for 1 to 2 hours; then heating to 300 to 900 ° C for 1 to 3 hours, and sintering for 1 to 24 hours.
  10. 权利要求1～5任一项所述的上转换磷光材料应用于新型防伪、加密、特种显示或生物成像领域。The upconverting phosphor material according to any one of claims 1 to 5 is applied to a novel anti-counterfeiting, encryption, special display or bio-imaging field.
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