A kind of Er 3+ 、Pr 3+ Co-doped niobate phosphor and its preparation method and application

Abstract

The present invention discloses an Er 3+ 、Pr 3+ Co-doped niobate phosphor and its preparation method and application relate to the technical field of luminescent materials. 3+ 、Pr 3+ Co-doped niobate phosphor, the molecular formula of niobate phosphor is M (1‑x‑y) Er x Pr y Nb2O6, wherein 0≤x≤1, 0≤y≤1, M is one of Zn, Cu, Fe, Ni, and Co. 3+ 、Pr 3+ The co-doped niobate phosphor can be effectively excited by near-ultraviolet light, purple light and blue light, presenting light of different colors, and can achieve a better multi-mode anti-counterfeiting effect. 3+ 、Pr 3+ Co-doped niobate phosphors are temperature-sensitive and can be used in the field of multi-mode temperature measurement.

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent materials, and more particularly to an Er 3+ 、Pr 3+ Co-doped niobate phosphor, preparation method and application thereof. Background Art

[0002] Fluorescent materials, due to their inherent properties, have been widely used in anti-counterfeiting and temperature measurement. Traditional photoluminescence anti-counterfeiting and encryption technologies primarily utilize near-ultraviolet light at 365 nm to excite phosphors. With the continuous advancement of counterfeiting technology, these single-mode anti-counterfeiting materials, with their fixed excitation mode and single-color output, are easily imitated and replicated. Therefore, the development of new multi-mode anti-counterfeiting materials to enhance the confidentiality of anti-counterfeiting and encryption technologies is of great significance. Optical thermometers, which utilize the temperature-dependent optical properties of fluorescent materials (fluorescence intensity ratio, fluorescence lifetime, emission color, bandwidth, etc.) for temperature measurement, have become the most popular type of non-contact thermometer. Currently, the most widely used optical thermometers utilize fluorescence intensity (FI), fluorescence intensity ratio (FIR), and fluorescence lifetime (FL) modes. The FI mode utilizes the temperature-dependent variation of the emission intensity of a single emission peak for temperature measurement. While fluorescent materials based on this mode offer excellent temperature measurement capabilities, their results are easily affected by the test environment, resulting in limited accuracy. The FIR mode utilizes the fluorescence intensity ratio of different emission peaks for temperature detection. Since this mode is less sensitive to measurement conditions and external interference, it has better stability. Therefore, optical thermometers based on FIR mode can have relatively excellent temperature measurement performance in various environments. However, this method also has some shortcomings. When the emission peaks in the emission spectrum overlap, the temperature variation characteristics of the emission peak intensity corresponding to the overlapping area will be affected, which will make the measured S R The value becomes smaller. The FL mode relies on fluorescence lifetime to measure temperature, and its advantage is that it is not easily affected by the external environment. However, the testing conditions using the FL mode are relatively harsh, which is not conducive to widespread use. It can be seen that the single-mode temperature measurement phosphors currently used have shortcomings. In addition, the color coordinate (CIE) mode is also popular. Temperature measurement is achieved through color changes, and the corresponding relative sensitivity can be calculated through color coordinate changes. Combining multiple modes of phosphors can effectively improve temperature measurement performance and self-calibration characteristics. Compared with single-mode temperature sensors, multi-mode thermometers have better performance. Therefore, broadening the excitation mode and color output of luminescent materials plays a vital role in their application in various fields.

[0003] The prior art provides a red phosphor for LED and a preparation method thereof. The phosphor is a praseodymium-activated alkaline earth metal niobate fluorescent material, and its chemical formula is (Ca 1-x-y-2z Srx Ba y A z Pr z )2Nb2O7, where A represents a monovalent alkali metal element selected from at least one of Li, Na, K, and Rb; 0 ≤ x ≤ 0.2; 0 ≤ y ≤ 0.1; 0 < z < 0.1. However, the luminescent color presented by this fluorescent material under different excitation lights is the same, and it cannot achieve multi-color output, nor does it have a certain temperature sensitivity. Summary of the Invention

[0004] The object of the present invention is to overcome the single excitation mode and color output of existing fluorescent luminescent materials, which cannot meet the application requirements of multi-mode excitation and multi-color output, and provide an Er 3+ 、Pr 3+ co-doped niobate phosphor, which can achieve multi-mode excitation, and has different luminescent colors under different excitation modes, and has good temperature sensitivity, and can meet the luminescent material performance requirements of multiple application scenarios.

[0005] Another object of the present invention is to provide a preparation method of an Er 3+ 、Pr 3+ co-doped niobate phosphor.

[0006] Another object of the present invention is to provide an application of an Er 3+ 、Pr 3+ co-doped niobate phosphor in the preparation of anti-counterfeiting materials.

[0007] Another object of the present invention is to provide an application of an Er 3+ 、Pr 3+ co-doped niobate phosphor in multi-mode temperature measurement.

[0008] The above objects of the present invention are achieved by the following technical solutions:

[0009] An Er 3+ 、Pr 3+ co-doped niobate phosphor, the molecular formula of the niobate phosphor is M (1-x-y) Er x Pr y Nb2O6, where 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, and M is one of Zn, Cu, Fe, Ni, and Co.

[0010] Among them, it should be noted that:

[0011] The luminescent material of the present invention can be effectively excited by near-ultraviolet light, violet light, and blue light. Under 254nm near-ultraviolet light excitation, the phosphor emits a brighter green light; under 365nm near-ultraviolet light excitation, the phosphor emits a brighter yellow light; and under 455nm blue light excitation, the phosphor emits a brighter red light.

[0012] The praseodymium ion and erbium ion co-doped niobate of the present invention integrates multiple modes for temperature measurement and improves the self-calibration characteristics. Compared with single-mode temperature sensing, this material improves temperature measurement performance, has more accurate temperature measurement capabilities and higher sensitivity. The phosphor has temperature-sensitive characteristics. Under 323nm ultraviolet light, when the temperature rises from 300K to 500K, its luminescent color gradually changes from red light to cyan light. In FIR mode, the absolute sensitivity maximum value can be close to 0.049K -1 , the maximum relative sensitivity is as high as 2.78%K -1 In CIE mode, the maximum relative sensitivity is as high as 0.48%K -1 Under 378nm ultraviolet light, when the temperature rises from 300K to 500K, the absolute sensitivity maximum value can be close to 0.063K in FIR mode. -1 , the maximum relative sensitivity is as high as 1.22% K -1 .

[0013] In a specific embodiment, in order to further improve the temperature sensitivity, preferably 0.001≤x≤0.04, for example, X can be 0.005, 0.01, 0.02, 0.03, or 0.04.

[0014] In a specific embodiment, in order to further improve the temperature sensitivity, preferably 0.001≤y≤0.01, more preferably, y is 0.005.

[0015] In a specific embodiment, preferably, the Er 3+ 、Pr 3+ The excitation light sources of the co-doped niobate phosphor are near-ultraviolet light, violet light and blue light, and the excitation spectrum covers a range of 200 to 500 nm.

[0016] In a specific embodiment, preferably, the Er 3+ 、Pr 3+ The strongest emission peaks of the co-doped niobate phosphor are located at 561nm and 606nm.

[0017] The present invention also specifically protects a 3+ 、Pr 3+ The preparation method of co-doped niobate phosphor comprises the following steps:

[0018] According to the stoichiometric ratio of the chemical formula, weigh the compound containing M, the compound containing erbium, the compound containing praseodymium and niobium oxide, mix them evenly, and calcine them in air to obtain Er 3+ 、Pr 3+ Co-doped niobate phosphors.

[0019] In a specific embodiment, the compound M of the present invention is selected from one or more of oxides, carbonates, nitrates, and oxalates.

[0020] In the specific preparation method, the erbium-containing compound of the present invention is selected from one or more of erbium oxide, erbium carbonate, erbium nitrate, and erbium oxalate.

[0021] In the specific preparation method, the praseodymium-containing compound of the present invention is selected from one or more of praseodymium oxide, praseodymium carbonate, praseodymium nitrate and praseodymium oxalate.

[0022] In a specific embodiment, preferably, the calcination temperature program is to heat the material to 1100-1400° C. at a rate of 5-30° C. / min, and then calcinate the material in air for 4-10 hours.

[0023] The present invention also specifically protects a 3+ 、Pr 3+ Application of co-doped niobate phosphors in the preparation of anti-counterfeiting materials.

[0024] The fluorescent material of the present invention is a niobate multi-mode anti-counterfeiting fluorescent material co-doped with praseodymium ions and erbium ions. The fluorescent material can be effectively excited by near-ultraviolet light, purple light and blue light, and emits characteristic emission light of different colors under different wavelengths of excitation light, thereby achieving multi-mode anti-counterfeiting and encryption.

[0025] The present invention also specifically protects a 3+ 、Pr 3+ Application of co-doped niobate phosphors in multimode temperature measurement.

[0026] The fluorescent material of this invention is a multi-mode thermometric niobate fluorescent material co-doped with praseodymium and erbium ions. This material can be effectively excited by near-ultraviolet and violet light, enabling efficient fluorescence temperature measurement within the 300K to 500K temperature range and exhibiting high sensitivity in various temperature measurement modes. By combining multiple temperature measurement modes, this material achieves self-calibration and high-precision temperature measurement across a specific temperature range.

[0027] Moreover, the raw materials of the present invention are cheap and easily available, the preparation process is simple, the chemical properties of the finished product are stable, and the temperature measurement sensitivity is high. The prepared niobate fluorescent material is an ideal fluorescent material for multi-mode temperature measurement.

[0028] Preferably, the multi-mode temperature measurement range is 300K to 500K.

[0029] This phosphor is temperature sensitive. When the temperature rises from 300K to 500K under 323nm ultraviolet light, its luminous color gradually changes from red to cyan. In FIR mode, the maximum absolute sensitivity can be close to 0.049K. -1 , the maximum relative sensitivity is as high as 2.78% K -1 In CIE mode, the maximum relative sensitivity is as high as 0.48% K -1 Under 378nm ultraviolet light, when the temperature rises from 300K to 500K, the absolute sensitivity maximum value can be close to 0.063K in FIR mode. -1 , the maximum relative sensitivity is as high as 1.22% K -1 Therefore, the praseodymium ion and erbium ion co-doped niobate can be used in the field of temperature measurement.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] The present invention 3+ 、Pr 3+ The co-doped niobate phosphor can be effectively excited by near-ultraviolet, violet, and blue light. Under 254nm near-ultraviolet light, it emits a brighter green light; under 365nm near-ultraviolet light, it emits a brighter yellow light; and under 455nm blue light, it emits a brighter red light, achieving a strong multi-mode anti-counterfeiting effect.

[0032] And the Er of the present invention 3+ 、Pr 3+ Co-doped niobate phosphors are temperature sensitive. When exposed to 323nm ultraviolet light, their luminescence color gradually changes from red to cyan as the temperature rises from 300K to 500K. In FIR mode, the maximum absolute sensitivity can be close to 0.049K. -1 , the maximum relative sensitivity is as high as 2.78% K -1 In CIE mode, the maximum relative sensitivity is as high as 0.48% K -1 Under 378nm ultraviolet light, when the temperature rises from 300K to 500K, the absolute sensitivity maximum value can be close to 0.063K in FIR mode. -1 , the maximum relative sensitivity is as high as 1.22% K -1 , can be used in the field of temperature measurement. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The Zn prepared in Example 1 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+and Zn prepared in Example 2 0.985 Nb2O6:0.02Er 3+ ,0.005Pr 3+ X-ray powder diffraction patterns of fluorescent materials.

[0034] Figure 2 The Zn prepared in Example 1 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ Fluorescence excitation spectrum of fluorescent materials monitored at different wavelengths.

[0035] Figure 3 The Zn prepared in Example 1 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ Fluorescence emission spectrum of fluorescent materials under excitation of different wavelengths of excitation light.

[0036] Figure 4 The Zn prepared in Example 1 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ Fluorescence emission spectrum of fluorescent material under 254nm ultraviolet light excitation.

[0037] Figure 5 The Zn prepared in Example 1 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ Fluorescence emission spectrum of the fluorescent material under 365nm near-ultraviolet light excitation.

[0038] Figure 6 The Zn prepared in Example 1 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ Fluorescence emission spectrum of fluorescent material under 455nm blue light excitation.

[0039] Figure 7 The Zn prepared in Example 1 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ Color coordinate diagram of the emitted light of a fluorescent material when excited by excitation light of different wavelengths.

[0040] Figure 8 The Zn prepared in Example 1 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+The temperature-dependent fluorescence emission spectrum of the fluorescent material from 300K to 500K under 323nm near-ultraviolet light excitation.

[0041] Figure 9 The Zn prepared in Example 1 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ The absolute and relative sensitivity results of the fluorescent material's temperature-dependent fluorescence emission from 300K to 500K calculated in FIR mode under 323nm near-ultraviolet light excitation.

[0042] Figure 10 The Zn prepared in Example 1 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ The temperature-dependent fluorescence emission spectrum of the fluorescent material from 300K to 500K under 378nm near-ultraviolet light excitation.

[0043] Figure 11 The Zn prepared in Example 1 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ The absolute and relative sensitivity results of the fluorescence emission of the fluorescent material under 378nm near-ultraviolet light excitation from 300K to 500K calculated in FIR mode.

[0044] Figure 12 The Zn prepared in Example 1 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ Color coordinate diagram of fluorescent materials changing from 300K to 500K under 323nm near-ultraviolet light excitation.

[0045] Figure 13 The Zn prepared in Example 1 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ The relative sensitivity results of the fluorescent material calculated in CIE mode when excited by 323nm near-ultraviolet light from 300K to 500K. DETAILED DESCRIPTION

[0046] The present invention will be further described below in conjunction with specific embodiments, but the examples do not limit the present invention in any form. Unless otherwise specified, the raw materials and reagents used in the examples of the present invention are conventionally purchased raw materials and reagents.

[0047] Example 1

[0048] A praseodymium ion and erbium ion co-doped niobate, the chemical formula of which is:

[0049] Zn 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ .

[0050] The above Zn 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ The preparation method comprises the following steps:

[0051] By element molar ratio Zn 2+ :Nb 5+ :Er 3+ :Pr 3+ =0.985:2:0.01:0.005 Weigh the raw materials separately.

[0052] The raw material contents are zinc oxide (ZnO) 0.1603g, niobium oxide (Nb2O5) 0.5316g, erbium oxide (Er2O3) 0.0038g, praseodymium oxide (Pr6O 11 )0.0017g,

[0053] Add the raw materials to an agate mortar, grind them evenly, and then transfer them to a corundum crucible. Then place the crucible in a high-temperature furnace and calcine it at 1250℃ with a heating rate of 5℃ / min and a holding time of 4 hours. Cool it to room temperature at 5℃ / min, then remove it and grind it evenly to obtain the product.

[0054] Example 2

[0055] A praseodymium ion and erbium ion co-doped niobate, the chemical formula of which is:

[0056] Zn 0.975 Nb2O6:0.02Er 3+ ,0.005Pr 3+

[0057] The above Zn 0.975 Nb2O6:0.02Er 3+ ,0.005Pr 3+ The preparation method comprises the following steps:

[0058] By element molar ratio Zn 2+ :Nb 5+ :Er 3+ :Pr 3+=0.975:2:0.02:0.005 respectively weigh the raw materials. The raw material contents are zinc oxide (ZnO) 0.1603g, niobium oxide (Nb2O5) 0.5316g, erbium oxide (Er2O3) 0.0038g, praseodymium oxide (Pr6O 11 )0.0017g,

[0059] The raw materials were added to an agate mortar, ground evenly, and then transferred to a corundum crucible. The corundum crucible was then placed in a high-temperature furnace and calcined at 1250°C with a heating rate of 5°C / min and a holding time of 4h.

[0060] After cooling to room temperature at 5°C / min, take out and grind evenly to obtain the product.

[0061] Example 3

[0062] A praseodymium ion and erbium ion co-doped niobate, the chemical formula of which is:

[0063] Zn 0.965 Nb2O6:0.03Er 3+ ,0.005Pr 3+ .

[0064] The above Zn 0.965 Nb2O6:0.02Er 3+ ,0.005Pr 3+ The preparation method comprises the following steps:

[0065] By element molar ratio Zn 2+ :Nb 5+ :Er 3+ :Pr 3+ =0.965:2:0.03:0.005 respectively weigh the raw materials. The raw material contents are 0.1603g zinc oxide (ZnO), 0.5316g niobium oxide (Nb2O5), 0.0115g erbium oxide (Er2O3), 0.0115g praseodymium oxide (Pr6O 11 )0.0017g,

[0066] The raw materials were added to an agate mortar, ground evenly, and then transferred to a corundum crucible. The corundum crucible was then placed in a high-temperature furnace and calcined at 1250°C with a heating rate of 5°C / min and a holding time of 4h.

[0067] After cooling to room temperature at 5°C / min, take out and grind evenly to obtain the product.

[0068] Example 4

[0069] A praseodymium ion and erbium ion co-doped niobate, the chemical formula of which is:

[0070] Zn0.955 Nb2O6:0.04Er 3+ ,0.005Pr 3+ .

[0071] The above Zn 0.955 Nb2O6:0.04Er 3+ ,0.005Pr 3+ The preparation method comprises the following steps:

[0072] By element molar ratio Zn 2+ :Nb 5+ :Er 3+ :Pr 3+ =0.955:2:0.04:0.005 respectively weigh the raw materials. The raw material contents are zinc oxide (ZnO) 0.1603g, niobium oxide (Nb2O5) 0.5316g, erbium oxide (Er2O3) 0.0157g, praseodymium oxide (Pr6O 11 )0.0017g,

[0073] The raw materials were added to an agate mortar, ground evenly, and then transferred to a corundum crucible. The corundum crucible was then placed in a high-temperature furnace and calcined at 1250°C with a heating rate of 5°C / min and a holding time of 4h.

[0074] After cooling to room temperature at 5°C / min, take out and grind evenly to obtain the product.

[0075] Example 5

[0076] A praseodymium ion and erbium ion co-doped niobate, the chemical formula of which is:

[0077] Zn 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ .

[0078] The above Zn 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ The preparation method comprises the following steps:

[0079] By element molar ratio Zn 2+ :Nb 5+ :Er 3+ :Pr 3+ =0.985:2:0.01:0.005 respectively weigh the raw materials. The raw material contents are 0.2471g zinc carbonate (ZnCO3), 0.5316g niobium oxide (Nb2O5), 0.0051g erbium carbonate (Er2(CO3)3), 0.0023g praseodymium carbonate (Pr2(CO3)3),

[0080] The raw materials were added to an agate mortar, ground evenly, and then transferred to a corundum crucible. The corundum crucible was then placed in a high-temperature furnace and calcined at 1250°C with a heating rate of 5°C / min and a holding time of 4h.

[0081] After cooling to room temperature at 5°C / min, take out and grind evenly to obtain the product.

[0082] Example 6

[0083] A praseodymium ion and erbium ion co-doped niobate, the chemical formula of which is:

[0084] Zn 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ .

[0085] The above Zn 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ The preparation method comprises the following steps:

[0086] By element molar ratio Zn 2+ :Nb 5+ :Er 3+ :Pr 3+ =0.985:2:0.01:0.005 respectively weigh the raw materials. The raw material contents are 0.3732g of zinc oxalate (ZnC2O4·2H2O), 0.5316g of niobium oxide (Nb2O5), 0.0078g of erbium oxalate (Er2(C2O4)3·10H2O), and 0.0036g of praseodymium oxalate (Pr2(C2O4)3·10H2O).

[0087] Add the raw materials to an agate mortar, grind them evenly, and transfer them to a corundum crucible. Place the crucible in a high-temperature furnace and pre-sinter at 600°C with a heating rate of 5°C / min and a holding time of 2 hours. Cool naturally to room temperature, remove, grind them evenly, and transfer them to a corundum crucible. Place the crucible in a high-temperature furnace and sinter at 1250°C with a heating rate of 5°C / min and a holding time of 4 hours.

[0088] After cooling to room temperature at 5°C / min, take out and grind evenly to obtain the product.

[0089] Example 7

[0090] A praseodymium ion and erbium ion co-doped niobate, the chemical formula of which is:

[0091] Zn 0.985 Nb2O6:0.01Er 3+,0.005Pr 3+ .

[0092] The above Zn 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ The preparation method comprises the following steps:

[0093] By element molar ratio Zn 2+ :Nb 5+ :Er 3+ :Pr 3+ =0.985:2:0.01:0.005 respectively weigh the raw materials. The raw material contents are 0.3731g zinc nitrate (Zn(NO3)2), 0.5316g niobium oxide (Nb2O5), 0.0035g erbium nitrate (Er(NO3)3), 0.0022g praseodymium nitrate (Pr(NO3)3·6H2O),

[0094] Add the raw materials to an agate mortar and grind them evenly. Then transfer them to a corundum crucible. Place the crucible in a high-temperature furnace and pre-sinter at 600°C with a heating rate of 5°C / min and a holding time of 2 hours. After cooling naturally to room temperature, remove them, grind them evenly again, and transfer them to a corundum crucible. Place the crucible in a high-temperature furnace and sinter at 1250°C with a heating rate of 5°C / min and a holding time of 4 hours.

[0095] After cooling to room temperature at 5°C / min, take out and grind evenly to obtain the product.

[0096] Example 8

[0097] A praseodymium ion and erbium ion co-doped niobate, the chemical formula of which is:

[0098] Cu 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ .

[0099] The above Cu 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ The preparation method comprises the following steps:

[0100] According to the element molar ratio Cu 2+ :Nb 5+ :Er 3+ :Pr 3+=0.985:2:0.01:0.005 respectively weigh the raw materials. The raw material contents are 0.1567g of copper oxide (CuO), 0.5316g of niobium oxide (Nb2O5), 0.0038g of erbium oxide (Er2O3), 0.0038g of praseodymium oxide (Pr6O 11 )0.0017g,

[0101] The raw materials were added to an agate mortar, ground evenly, and then transferred to a corundum crucible. The corundum crucible was then placed in a high-temperature furnace and calcined at 1250°C with a heating rate of 5°C / min and a holding time of 4h.

[0102] After cooling to room temperature at 5°C / min, take out and grind evenly to obtain the product.

[0103] Example 9

[0104] A praseodymium ion and erbium ion co-doped niobate, the chemical formula of which is:

[0105] Fe 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ .

[0106] The above Fe 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ The preparation method comprises the following steps:

[0107] By element molar ratio Fe 2+ :Nb 5+ :Er 3+ :Pr 3+ =0.985:2:0.01:0.005 respectively weigh the raw materials. The raw material contents are 0.1573g of iron oxide (Fe2O3), 0.5316g of niobium oxide (Nb2O5), 0.0038g of erbium oxide (Er2O3), 0.0038g of praseodymium oxide (Pr6O 11 )0.0017g,

[0108] The raw materials were added to an agate mortar, ground evenly, and then transferred to a corundum crucible. The corundum crucible was then placed in a high-temperature furnace and calcined in an inert gas at 1250°C with a heating rate of 5°C / min and a holding time of 4h.

[0109] After cooling to room temperature at 5°C / min, take out and grind evenly to obtain the product.

[0110] Example 10

[0111] A praseodymium ion and erbium ion co-doped niobate, the chemical formula of which is:

[0112] Ni0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ .

[0113] The above Ni 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ The preparation method comprises the following steps:

[0114] According to the element molar ratio Ni 2+ :Nb 5+ :Er 3+ :Pr 3+ =0.985:2:0.01:0.005 respectively weigh the raw materials. The raw material contents are nickel oxide (NiO) 0.1431g, niobium oxide (Nb2O5) 0.5316g, erbium oxide (Er2O3) 0.0038g, praseodymium oxide (Pr6O 11 )0.0017g,

[0115] The raw materials were added to an agate mortar, ground evenly, and then transferred to a corundum crucible. The corundum crucible was then placed in a high-temperature furnace and calcined at 1250°C with a heating rate of 5°C / min and a holding time of 4h.

[0116] After cooling to room temperature at 5°C / min, take out and grind evenly to obtain the product.

[0117] Example 11

[0118] A praseodymium ion and erbium ion co-doped niobate, the chemical formula of which is:

[0119] Co 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ .

[0120] The above Co 0.985 Nb2O6:0.01Er 3+ ,0.005Pr 3+ The preparation method comprises the following steps:

[0121] According to the element molar ratio Co 2+ :Nb 5+ :Er 3+ :Pr 3+ =0.985:2:0.01:0.005 respectively weigh the raw materials. The raw material contents are 0.1476g of cobalt oxide (CoO), 0.5316g of niobium oxide (Nb2O5), 0.0038g of erbium oxide (Er2O3), 0.0038g of praseodymium oxide (Pr6O 11 )0.0017g,

[0122] The raw materials were added to an agate mortar, ground evenly, and then transferred to a corundum crucible. The corundum crucible was then placed in a high-temperature furnace and calcined at 1250°C with a heating rate of 5°C / min and a holding time of 4h.

[0123] After cooling to room temperature at 5°C / min, take out and grind evenly to obtain the product.

[0124] Result detection

[0125] Detection method:

[0126] 1. Test method

[0127] (1) X-ray powder diffraction method (instrument used and test conditions) X-ray powder diffraction uses a D-MAX2200VPC instrument with a fixed Cu target, a test voltage of 40 kV, and a current of 26 mA.

[0128] (2) Emission spectrum test method (instruments used and test conditions) Excitation and emission spectra were tested using Edinburgh FLS980, and the light source was a xenon lamp.

[0129] (3) Luminous intensity test method (instrument used and test conditions) FLS980 spectrum test is used to directly read the luminous intensity at different wavelengths.

[0130] (4) Using the color purity calculation software CIE1931 with version number V.1.6.0.2, the color coordinates of the light emitted by the product obtained in Example 1 were calculated.

[0131] 2. Test results

[0132] The X-ray powder diffraction results of Example 1 are as follows: Figure 1 As shown in spectrum line 1, all diffraction peaks are basically the same as those in the standard card ZnNb2O6 (ICSD#36290), indicating that the introduction of praseodymium ions and erbium ions does not significantly affect the original phase.

[0133] The X-ray powder diffraction results of Example 2 are as follows: Figure 1 As shown in spectrum line 2, all diffraction peaks are basically the same as those in the standard card ZnNb2O6 (ICSD#36290), indicating that the introduction of different concentrations of ions does not significantly affect the original phase.

[0134] The fluorescence excitation spectrum of Example 1 is shown in FIG. Figure 2As shown in the figure, the excitation spectrum of the obtained fluorescent material under the monitoring wavelength of 561nm covers the ultraviolet and violet light in the range of 200-400nm, and the highest point of its excitation peak is located at a wavelength of 378nm; the excitation spectrum under the monitoring wavelength of 606nm covers the ultraviolet, violet and blue light in the range of 200-500nm, and the highest point of its excitation peak is located at a wavelength of 490nm.

[0135] The X-ray powder diffraction results of Examples 5 to 11 show that the phases of Examples 5 to 11 are basically consistent with those of Example 1, and the structures are consistent, indicating that the emission spectra and excitation spectra of Examples 5 to 11 are close to those of Example 1.

[0136] The fluorescence emission spectrum of Example 1 is shown in FIG. Figure 3 As shown in FIG. , it can be seen that the emission spectrum of the obtained fluorescent material changes with the change of the excitation wavelength.

[0137] Example 1 The fluorescence emission spectra under the excitation of different wavelengths of excitation light are as follows Figure 4 , Figure 5 , Figure 6 As shown. Figure 4 Under the excitation of 254nm ultraviolet light, the strongest emission peak of the phosphor is located at 561nm, showing a brighter green light. Figure 5 Under the excitation of 365nm near-ultraviolet light, the strongest emission peaks of the phosphor are located at 561nm and 606nm, showing a brighter yellow light. Figure 6 Under the excitation of 455nm blue light, the strongest emission peak of the phosphor is located at 606nm, showing a brighter red light.

[0138] Example 1 Color coordinate diagram under the excitation of different wavelengths of excitation light. Figure 7 As shown in the figure, under the irradiation of 254nm, 365nm, and 455nm excitation light, the color coordinates of the green light are (0.2857, 0.4939), the yellow light is (0.492, 0.4929), and the red light is (0.5867, 0.3937), respectively.

[0139] Figure 9 The absolute sensitivity and relative sensitivity calculation results of the FIR mode of the temperature-variable fluorescence emission from 300K to 500K under 323nm near-ultraviolet light excitation in Example 1 are shown. The emission intensity of erbium ions and praseodymium ions is compared. In the FIR mode, the maximum absolute sensitivity can be close to 0.049K. -1 , the maximum relative sensitivity is as high as 2.78% K -1 .

[0140] Figure 10 This is the temperature-dependent fluorescence emission spectrum of Example 1 from 300K to 500K under 378nm near-ultraviolet light excitation.

[0141] Figure 11 The absolute sensitivity and relative sensitivity calculation results of the FIR mode for the temperature-dependent fluorescence emission from 300K to 500K under 378nm near-ultraviolet light excitation. In FIR mode, the emission intensity at wavelengths of 536nm and 561nm is compared, and the maximum absolute sensitivity is close to 0.064K. -1 , the maximum relative sensitivity is as high as 1.22%K -1 .

[0142] Figure 12 This is a temperature-varying color coordinate diagram from 300K to 500K of Example 1 under 323nm near-ultraviolet light excitation.

[0143] Figure 13 The relative sensitivity calculation results in CIE mode. When the temperature rises from 300K to 500K, its luminous color gradually changes from red to cyan, and the color coordinates change from (0.657, 0.3418) at 300K to (0.4101, 0.573) at 500K. In CIE mode, the maximum relative sensitivity is as high as 0.48% K. -1 .

[0144] Obviously, the above embodiments of the present invention are merely examples for the purpose of clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Those skilled in the art will appreciate that other variations or modifications can be made based on the above description. It is not necessary and impossible to enumerate all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the claims of the present invention.

Claims

1. A kind of Er 3+ 、Pr 3+ Co-doped niobate phosphor, characterized in that: The molecular formula of niobate phosphor is M (1-x-y) Er x Pr y Nb2O6, where 0.005≤x≤0.04, y=0.005, and M is Zn.

2. The method according to claim 1 3+ 、Pr 3+ Co-doped niobate phosphor, characterized in that: The Er 3+ 、Pr 3+ The excitation light sources of the co-doped niobate phosphor are near-ultraviolet light, violet light and blue light, and the excitation spectrum covers the range of 200 ~ 500 nm.

3. The method according to claim 2 3+ 、Pr 3+ Co-doped niobate phosphor, characterized in that: The Er 3+ 、Pr 3+ The strongest emission peaks of the co-doped niobate phosphor are located at 561 nm and 606 nm.

4. The Er according to any one of claims 1 to 2 3+ 、Pr 3+ The preparation method of co-doped niobate phosphor is characterized in that: The steps include: According to the stoichiometric ratio of the chemical formula, weigh the compound containing M, the compound containing erbium, the compound containing praseodymium and niobium oxide, mix them evenly, and calcine them in air to obtain Er 3+ 、Pr 3+ Co-doped niobate phosphors.

5. The method according to claim 4 3+ 、Pr 3+ The preparation method of co-doped niobate phosphor is characterized in that: The calcination temperature program is to increase the temperature to 1100-1400°C at a rate of 5-30°C / min, and then calcine in air for a holding time of 4-10 hours.

6. The Er according to any one of claims 1 to 2 3+ 、Pr 3+ Application of co-doped niobate phosphors in the preparation of anti-counterfeiting materials.

7. The Er according to any one of claims 1 to 2 3+ 、Pr 3+ Application of co-doped niobate phosphors in multimode temperature measurement.

8. The use according to claim 7, characterized in that The range of the multi-mode temperature measurement is 300 K ~ 500 K.

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