CN116656355B - Red fluorescent material and optical temperature measurement application and application method thereof - Google Patents
Red fluorescent material and optical temperature measurement application and application method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 133
- 230000003287 optical effect Effects 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 18
- 238000009529 body temperature measurement Methods 0.000 title abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000012190 activator Substances 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims description 87
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 38
- 239000011572 manganese Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 29
- 229910052715 tantalum Inorganic materials 0.000 claims description 21
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 17
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 3
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004861 thermometry Methods 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 18
- 230000008859 change Effects 0.000 abstract description 12
- 230000004044 response Effects 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 17
- 239000002994 raw material Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000000295 emission spectrum Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000000695 excitation spectrum Methods 0.000 description 3
- 238000001748 luminescence spectrum Methods 0.000 description 3
- -1 rare earth ions Chemical class 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- OJOWXSLGSMTXEO-UHFFFAOYSA-H [Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[K+].[K+].[K+].[K+].[K+].[K+] Chemical compound [Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[K+].[K+].[K+].[K+].[K+].[K+] OJOWXSLGSMTXEO-UHFFFAOYSA-H 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910001460 tantalum ion Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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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
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/674—Halogenides
- C09K11/675—Halogenides with alkali or alkaline earth metals
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
- G01K11/20—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using thermoluminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Luminescent Compositions (AREA)
Abstract
The invention provides a red fluorescent material, which takes NaNH 4TaF7 as a matrix and Mn 4+ as an activator, wherein the chemical composition of the red fluorescent material is Na (NH 4)TaF7:x Mn4+, x is more than or equal to 0.5% and less than or equal to 10%), the red fluorescent material can be excited by ultraviolet or blue light to emit narrowband red light with 580-680 nm, the strongest wavelength is 628.8nm, the luminous intensity of the Na (NH 4)TaF7:x Mn4+) of the red fluorescent material can be obviously changed along with the change of temperature, the red fluorescent material can be applied to optical temperature measurement by utilizing the temperature change characteristic, and the red fluorescent material has the characteristics of high response speed, high temperature measurement sensitivity and wide temperature measurement range and has high application prospect in the optical temperature measurement.
Description
Technical Field
The invention belongs to the field of luminescent materials, and particularly relates to a red fluorescent material, and an optical temperature measurement application and an application method thereof.
Background
In recent years, the progress of industrial modernization and the continuous high-speed growth of electronic information industry in China drive the rapid rise of the sensor market. The data shows that the national sensor market size 2510 hundred million yuan in 2020 is increased by 14.7% comparably. Along with the increase of the temperature control requirements of industrial production, the requirements on the temperature sensor are also higher and higher. The conventional method for measuring the temperature based on the relation between the characteristics of the volume, the resistance, the magnetism and the like of the material and the temperature has the defects of low sensitivity, long response time and the like.
The optical temperature measurement technology utilizes the fluorescence characteristic of the luminescent material and combines with the image processing technology, and has the advantages of non-contact, high sensitivity, high response speed and the like. The optical temperature measurement material is widely applied to the fields of chemical production represented by metallurgy and coal smelting and the medical diagnosis of intracellular heat sensing.
However, most of the inorganic optical temperature measuring materials on the market at present select the rare earth ions of f-f transition or the transition metal ions of d-d musical instrument as activating ions, and the temperature measuring sensitivity is poor and the temperature measuring range is narrow. Chinese patent CN113004892a discloses a luminescent material based on cerium and europium activated aluminosilicate, the maximum absolute sensitivity obtained by the luminescent material is about 0.0188K -1, and the maximum relative sensitivity obtained by the luminescent material is about 1.35% K -1, so that the temperature measurement sensitivity and temperature measurement range of the luminescent material prepared by the invention are still to be further explored.
Therefore, it is necessary to develop an optical temperature measuring material with high temperature measuring sensitivity and wide temperature measuring range.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a red fluorescent material, an optical temperature measurement application and an application method thereof, so that the red fluorescent material has the characteristics of high response speed, high temperature measurement sensitivity and wide temperature measurement range, and can be applied to optical temperature measurement.
According to a first aspect of the present invention, there is provided a red fluorescent material having a chemical composition of Na (NH 4)TaF7:x Mn4+, 0.5% or more and 10% or less) using NaNH 4TaF7 as a matrix and Mn 4+ as an activator.
The red fluorescent material provided by the invention takes ammonium salt fluoride Na (NH 4)TaF7 as a matrix and Mn 4+ as an activator, so that Ta 5+ in the matrix can be occupied by Mn 4+, mn 4+ is doped into Na (NH 4)TaF7, the doping amount is 0.5% -10%, the prepared red fluorescent material Na (NH 4)TaF7:x Mn4+ has the advantages of strong luminous brightness and sensitive luminous intensity to temperature response, and secondly, mn 4+ ions of a 3d electronic layer serving as outer electrons have the characteristic of being very easily influenced by crystal field change, and when Mn 4+ is taken as the activator, ta 5+ ions in the matrix with special coordination are occupied, the prepared red fluorescent material Na (NH 4)TaF7:x Mn4+ has special luminous performance, the luminous intensity can be obviously changed along with temperature change, namely, the prepared red fluorescent material Na (NH 4)TaF7:x Mn4+ has high sensitivity to temperature change, and has the characteristic of temperature change in a wider temperature range, the red fluorescent material has the characteristics of quick response speed, high sensitivity and wide temperature measurement range).
Preferably, the red fluorescent material is prepared by the following steps: s1, uniformly mixing a tantalum source and a hydrofluoric acid aqueous solution, and reacting for 7-24 hours at 100-180 ℃ to prepare a first precursor solution; s2, uniformly mixing a sodium source, an ammonium source, deionized water and a first precursor solution, reacting for 7-24 hours at 100-180 ℃ to obtain Na (NH 4)TaF7; S3, uniformly mixing a manganese source and a hydrofluoric acid aqueous solution to obtain a second precursor solution, adding Na (NH 4)TaF7 to enable Na (NH 4)TaF7) to be partially dissolved, and adding absolute ethyl alcohol to the second precursor solution to enable Na (NH 4)TaF7:x Mn4+) to be recrystallized and separated out, thus obtaining the red fluorescent material.
The invention adopts a recrystallization method to prepare the red fluorescent material, utilizes the difference of solubility of hydrofluoric acid aqueous solution and absolute ethyl alcohol to heptafluorotantalate ammonium salt Na (NH 4)TaF7), so that Na (NH 4)TaF7 and Mn 4+) dissolved in the second precursor solution can be occupied by Mn 4+ by Ta 5+ in a matrix through recrystallization operation, and Mn 4+ is doped into Na (NH 4)TaF7), thereby preparing the red fluorescent material with strong luminous brightness and sensitive luminous intensity to temperature.
Preferably, in S1, the ratio of the molar amount of tantalum source added to the volume of the aqueous hydrofluoric acid solution is 1 to 4mmol/mL.
When the amount of the tantalum source added to the aqueous solution of hydrofluoric acid satisfies the above conditions, the yield of Na (NH 4)TaF7 polycrystalline particles) can be increased, if the ratio of the amount of the tantalum source added to the amount of the HF solution is less than 1mmol/L, the amount of the tantalum source added is excessively small, which results in an excessively low concentration of tantalum ions in the first precursor, and in an excessively low yield of Na (NH 4)TaF7 polycrystalline particles), if the ratio of the amount of the tantalum source added to the amount of the HF solution is greater than 4mmol/L, the aqueous solution of hydrofluoric acid used for dissolving the tantalum source is excessively small, the tantalum source is not completely dissolved, but the first precursor solution has reached the saturation concentration of tantalum, and the yield of Na (NH 4)TaF7) is also excessively low.
Preferably, the ratio of the molar amount of tantalum source added to the volume of the aqueous hydrofluoric acid solution is 2mmol/mL.
Preferably, the concentration of the aqueous hydrofluoric acid solution is 20 to 60wt%.
Preferably, the concentration of the aqueous hydrofluoric acid solution is 40wt%.
Preferably, in S2, the ratio of the sum of the added molar amounts of the sodium source and the ammonium source to the volume of deionized water is 1-2.5 mmol/mL.
The yield and purity of Na (NH 4)TaF7) can be improved by adjusting the feeding amount of the sodium source, the ammonium source and the deionized water, wherein the ratio of the sum of the adding molar amounts of the sodium source and the ammonium source to the volume of the deionized water is 1-2.5 mmol/mL, and if the ratio of the sum of the adding molar amounts of the sodium source and the ammonium source to the volume of the deionized water is less than 1mmol/L, the concentration of sodium ions and ammonium ions is too low to influence the yield of Na (NH 4)TaF7), and if the ratio of the sum of the adding molar amounts of the sodium source and the ammonium source to the volume of the deionized water is more than 2.5mmol/L, the prepared Na (NH 4)TaF7 has more impurities, so that the purity of Na (NH 4)TaF7) is reduced.
Preferably, the dosage of deionized water is 10-40 ml.
Preferably, the dosage of deionized water is 20ml.
Preferably, in S3, the molar ratio of manganese source to Na (NH 4)TaF7) is 0.005-0.1:1.
The molar ratio of Mn 4+ ions to Na (NH 4)TaF7) is 0.005-0.1:1 by adjusting the feeding amount of the preparation raw materials, so that the doping amount of Mn 4+ ions in the Na (NH 4)TaF7:x Mn4+) of the red fluorescent material is 0.5-10%, and the doped material can emit red fluorescence.
Preferably, in S3, the molar ratio of manganese source to Na (NH 4)TaF7 fed in is 0.01:1.
Preferably, the ratio of the added molar amount of Na (NH 4)TaF7) to the volume of absolute ethanol is 0.025-0.05 mmol/mL.
Na (NH 4)TaF7 and absolute ethyl alcohol are added in a controlled amount, so that the ratio of the added molar amount of Na (NH 4)TaF7) to the volume of absolute ethyl alcohol is 0.025-0.05 mmol/L, and a trace amount of dissolved Na (NH 4)TaF7) can be separated out through recrystallization, so that the red fluorescent material Na (NH 4)TaF7:x Mn4+) is prepared.
Preferably, the ratio of the molar amount of Na (NH 4)TaF7 added to the volume of absolute ethanol) is 0.025mmol/mL.
Preferably, the dosage of the absolute ethyl alcohol is 5-10 mL.
Preferably, the dosage of the absolute ethyl alcohol is 10mL.
Preferably, the sodium source is selected from at least one of sodium fluoride, sodium bifluoride, sodium carbonate; and/or the ammonium source is at least one selected from ammonium fluoride, ammonium bifluoride and ammonium carbonate; and/or the tantalum source comprises tantalum pentoxide.
Preferably, the sodium source comprises sodium hydrogen fluoride.
Preferably, the ammonium source comprises ammonium bifluoride.
Preferably, the manganese source comprises potassium hexafluoromanganate.
According to a second aspect of the present invention, there is provided an application of the above red fluorescent material in optical thermometry.
The red fluorescent material Na (NH 4)TaF7:x Mn4+) has the advantages that the luminous intensity can be obviously changed along with the change of temperature, the red fluorescent material can be applied to optical temperature measurement by utilizing the temperature change characteristic, the specific value of the temperature to be measured can be obtained by utilizing the luminous intensity of the red fluorescent material emitted by the temperature to be measured, and the red fluorescent material has wide measurable temperature range, wide application range and high application prospect.
According to a third aspect of the present invention, there is provided a method for applying the above red fluorescent material, wherein the red fluorescent material is excited by ultraviolet light or blue light having a wavelength of 300 to 550 nm.
The red fluorescent material Na (NH 4)TaF7:x Mn4+ can be excited by light with the wavelength of 300-500 nm and emits 580-680 nm narrow-band red light), and when the red fluorescent material Na is applied to optical temperature measurement, the red fluorescent material Na (NH 4)TaF7:x Mn4+ is required to be excited by the light with the wavelength.
Drawings
FIG. 1 is an XRD spectrum of a red fluorescent material provided in example 2;
FIG. 2 is a graph showing the excitation and emission spectra of the red fluorescent material provided in example 2;
FIG. 3 is the luminescence spectrum of the red fluorescent material provided in example 2 at different temperatures;
FIG. 4 is a graph showing the relationship between the integrated intensity and the temperature of the luminescence spectrum of the red fluorescent material provided in example 2;
Fig. 5 is a schematic diagram showing the relationship between the temperature and the sensitivity of the red fluorescent material provided in example 2.
Detailed Description
In order that the manner in which the above-recited embodiments of the invention are attained and can be readily understood by those skilled in the art, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
The embodiment provides a red fluorescent material, which has a chemical composition of Na (NH 4)TaF7:0.5％ Mn4+. The tantalum source selected by the red fluorescent material is Ta 2O5, the concentration of hydrofluoric acid aqueous solution selected by the red fluorescent material is 40wt%, the sodium source selected by the red fluorescent material is NaHF 2, the ammonium source selected by the red fluorescent material is NH 5F2, and the manganese source selected by the red fluorescent material is K 2MnF6.
The preparation method of the red fluorescent material comprises the following steps:
S1, evenly mixing 1.1047g of tantalum source with 2.5mL of hydrofluoric acid aqueous solution, stirring for 20min, transferring into a high-pressure reaction kettle, reacting for 16 hours at 150 ℃, and cooling to room temperature to obtain a first precursor solution. Wherein the ratio of the molar amount of tantalum source added to the volume of the aqueous hydrofluoric acid solution is 2mmol/mL.
S2, sequentially adding 0.6199g of sodium source, 1.426g of ammonium source and 2.5mL of first precursor solution into 20mL of deionized water, stirring for 20min to uniformly mix, transferring into a high-pressure reaction kettle, reacting for 16 hours at 150 ℃, cooling to room temperature, washing the transparent polycrystal with deionized water and absolute ethyl alcohol for multiple times, and drying to obtain Na (NH 4)TaF7, wherein the ratio of the sum of the added molar amounts of the sodium source and the ammonium source to the volume of deionized water is 1.75nmol/mL.
S3, dissolving 0.0030g of manganese source in hydrofluoric acid aqueous solution to prepare a second precursor solution, adding 0.8874g of Na (NH 4)TaF7 to dissolve Na (NH 4)TaF7), dropwise adding 10mL of absolute ethyl alcohol to the second precursor solution to recrystallize and separate out Na (NH 4)TaF7:0.5％ Mn4+), centrifuging the precipitate, washing the precipitate obtained by centrifugation with absolute ethyl alcohol for multiple times, filtering, and drying at 70 ℃ for 8 hours to prepare the red fluorescent material, wherein the molar ratio of manganese source to Na (NH 4)TaF7) is 0.005:1, and the volume ratio of the added molar amount of Na (NH 4)TaF7) to the absolute ethyl alcohol is 0.025mmol/mL.
Example 2
This example refers to the preparation method provided in example 1 to prepare a red fluorescent material. This embodiment differs from embodiment 1 in that: in the process of preparing the red fluorescent material, the chemical composition of the prepared red fluorescent material is Na (NH 4)TaF7:1％Mn4+, specifically, 0.0061g K 2MnF6 is adopted in S3 to replace the manganese source adopted in the embodiment 2, and the proportion of the rest raw materials is strictly consistent with that of the embodiment 1, wherein the feeding molar ratio of the manganese source to Na (NH 4)TaF7 is 0.01:1).
Example 3
This example refers to the preparation method provided in example 1 to prepare a red fluorescent material. This embodiment differs from embodiment 1 in that: in the process of preparing the red fluorescent material, the chemical composition of the prepared red fluorescent material is Na (NH 4)TaF7:10％Mn4+, specifically, 0.0617g K 2MnF6 is adopted in S3 to replace the manganese source adopted in the embodiment 2, and the proportion of the rest raw materials and the preparation method are strictly consistent with those of the embodiment 1, wherein the feeding molar ratio of the manganese source to Na (NH 4)TaF7 is 0.1:1).
Example 4
This example refers to the preparation method provided in example 2 to prepare a red fluorescent material. This embodiment differs from embodiment 2 in that: in the preparation of the red fluorescent material, the ratio of the molar amount of tantalum source added to the volume of the aqueous hydrofluoric acid solution was 1mmol/L, specifically, 0.5523g of Ta 2O5 was added in S1 in place of the tantalum source used in example 2. The proportions of the other raw materials and the preparation method are strictly consistent with those of the embodiment 2.
Example 5
This example refers to the preparation method provided in example 2 to prepare a red fluorescent material. This embodiment differs from embodiment 2 in that: in the preparation of the red fluorescent material, the ratio of the molar amount of tantalum source added to the volume of the aqueous hydrofluoric acid solution was 4mmol/L, specifically, 2.2094g of Ta 2O5 was added in S1 in place of the tantalum source used in example 2. The proportions of the other raw materials and the preparation method are strictly consistent with those of the embodiment 2.
Example 6
This example refers to the preparation method provided in example 2 to prepare a red fluorescent material. This embodiment differs from embodiment 2 in that: in the process of preparing the red fluorescent material, the ratio of the sum of the added molar amounts of the sodium source and the ammonium source to the volume of deionized water is 1.25mmol/L, specifically, 0.3099gNaHF 2、1.1408g NH5F2 is adopted in S2 to replace the sodium source and the ammonium source adopted in the embodiment 2. The proportions of the other raw materials and the preparation method are strictly consistent with those of the embodiment 2.
Example 7
This example refers to the preparation method provided in example 2 to prepare a red fluorescent material. This embodiment differs from embodiment 2 in that: in the preparation of the red fluorescent material, the ratio of the sum of the added molar amounts of the sodium source and the ammonium source to the volume of deionized water was 2.5mmol/L, specifically, 1.5497g of NaHF 2 was added in S2 in place of the sodium source used in example 2. The proportions of the other raw materials and the preparation method are strictly consistent with those of the embodiment 2.
Example 8
This example refers to the preparation method provided in example 2 to prepare a red fluorescent material. This embodiment differs from embodiment 2 in that: in the process of preparing the red fluorescent material, naF is used as a sodium source. The proportions of the other raw materials and the preparation method are strictly consistent with those of the embodiment 2.
Example 9
This example refers to the preparation method provided in example 2 to prepare a red fluorescent material. This embodiment differs from embodiment 2 in that: in the process of preparing the red fluorescent material, NH 4 F is used as a sodium source. The proportions of the other raw materials and the preparation method are strictly consistent with those of the embodiment 2.
Example 10
This example refers to the preparation method provided in example 2 to prepare a red fluorescent material. This embodiment differs from embodiment 2 in that: in the process of preparing the red fluorescent material, the reaction temperature and the reaction time in S1 and S2 are changed, and specifically, the reaction in S1 and S2 is carried out for 10 hours at 180 ℃. The proportions of the other raw materials and the preparation method are strictly consistent with those of the embodiment 2.
Example 11
This example refers to the preparation method provided in example 2 to prepare a red fluorescent material. This embodiment differs from embodiment 2 in that: in the process of preparing the red fluorescent material, the reaction temperature and the reaction time in S1 and S2 are changed, and specifically, the reaction in S1 and S2 is carried out for 24 hours at 100 ℃. The proportions of the other raw materials and the preparation method are strictly consistent with those of the embodiment 2.
Comparative example 1
This comparative example was prepared as a red fluorescent material with reference to the preparation method provided in example 2. The difference between this comparative example and example 2 is that: in the process of preparing the red fluorescent material, the chemical composition of the prepared red fluorescent material is Na (NH 4)TaF7:0.1％ Mn4+, specifically, 0.002. 0.002g K 2MnF6 is adopted in S3 to replace the manganese source adopted in the example 2, and the proportion of the rest raw materials and the preparation method are strictly consistent with those of the example 2, wherein the feeding molar ratio of the manganese source to Na (NH 4)TaF7 is 0.001:1).
Comparative example 2
This comparative example a red fluorescent material was prepared with reference to the method for preparing a red fluorescent material provided in example 2. The difference between this comparative example and example 2 is that: in the process of preparing the red fluorescent material, the molar ratio of the manganese source to Na (NH 4)TaF7) is n (Mn 4+): n (Ta) =0.15:1, and the chemical composition of the prepared red fluorescent material is Na (NH 4)TaF7:15％ Mn4+. Specifically, 0.0927g K 2MnF6 is adopted in S3 to replace the manganese source adopted in the example 2. The other raw material ratios and the preparation method are strictly consistent with the example 2.
Comparative example 3
The comparative example was prepared as a material containing Na (NH 4)TaF7) by the method for preparing a red fluorescent material provided in example 2. The comparative example was different from example 2 in that the recrystallization in S3 was omitted, specifically, the step of adding absolute ethanol to the second precursor solution was omitted. The prepared material contained Na (NH 4)TaF7, but Mn 4+ was not doped to Na (NH 4)TaF7. The remaining raw material ratios, preparation method were strictly consistent with example 2.
Test case
A reference subject: the red fluorescent materials obtained in examples 1 to 11 and the materials obtained in comparative examples 1 to 3.
Test items and test methods:
(1) X-ray powder diffraction
An X-ray diffraction spectrum (XRD) of a reference object is acquired by using a Bruker D8 advanced X-ray diffractometer, a Cu-K alpha target is adopted as a radiation source (lambda= 0.15406 nm), the working voltage is 40kV, the working current is 40mA, and the 2 theta scanning range is 5-90 degrees.
(2) Fluorescence spectrum
Excitation of the reference sample at 83-448K and emission spectra were collected on a Edinburgh Instrument FS steady-state-transient fluorescence spectrometer, equipped with a 450W xenon lamp and an SC-05 temperature change controller.
Test results: comparing the test results of the red fluorescent materials provided in examples 1 to 11 with those of the materials prepared in comparative examples 1 to 3, it was found that the red fluorescent materials prepared in comparative examples 1 to 2 had lower luminous intensities than those measured in examples 1 to 11. Wherein, the red fluorescent material provided in comparative example 1 has too little Mn 4+ doping amount, and the red fluorescent material provided in comparative example 2 has too much Mn 4+ doping amount. Therefore, if the doping amount of Mn 4+ in the material is too small, the optimal concentration which can be contained in the material is not reached, and the luminous intensity of the material is low; if the doping amount of Mn 4+ in the material is too large, concentration quenching easily occurs, so that the luminous intensity of the material is low. Since the resolution of temperature measurement depends on the luminous intensity of the material, the optical applications of the red fluorescent materials provided in comparative examples 1 to 2 may be limited. The red fluorescent materials provided in the comparative example 3 can be excited by ultraviolet light or blue light with the wavelength of 300-550 nm, emit narrow-band red light with the wavelength of 580-680 nm and have the highest luminous intensity due to the fact that Mn 4+ cannot be successfully doped into Na (NH 4)TaF7, which is equivalent to the doping amount being 0% or less) and the material provided in the comparative example 3 cannot emit light, and the red fluorescent materials provided in the examples 1-11 have the characteristics of high response speed, high temperature measurement sensitivity and wide temperature measurement range and have the potential of being applied to the field of optical temperature measurement because NaNH 4TaF7 is used as a matrix, mn 4+ is used as an activator, the luminous intensity of the red fluorescent materials is 0.5% -x-10% or less and can emit red light, and the red fluorescent materials have the characteristic of temperature change in a wide temperature range.
Among the red fluorescent materials prepared in examples 1 to 11, na (NH 4)TaF7:1％ Mn4+) prepared in example 2 had the best temperature measurement sensitivity and the widest temperature measurement range, and the test patterns of the provided red fluorescent material Na (NH 4)TaF7:1％ Mn4+) in example 2 are shown in FIGS. 1 to 5.
Fig. 1 shows the XRD spectrum of the red fluorescent material Na (NH 4)TaF7:1％ Mn4+) provided in example 2 as shown in fig. 1, the XRD diffraction peaks of the obtained material were identical to those of the standard card pdf#00-057-0546, indicating that the Na (NH 4)TaF7:1％ Mn4+ is pure phase) obtained in example 2.
Fig. 2 is a graph of excitation and emission spectra of the red fluorescent material Na (NH 4)TaF7:1％ Mn4+. As can be seen from fig. 2, the excitation spectrum of the red fluorescent material Na (NH 4)TaF7:1％ Mn4+) consists of two broad peaks with center wavelengths of 358nm and 473nm, wherein the strongest excitation is at 473nm, the emission is 580-680 nm of narrow-band red light, and the strongest wavelength is at 628.8nm.
Fig. 3 is a light emission spectrum of the red fluorescent material provided in example 2 at different temperatures. As can be seen from fig. 3, the red fluorescent material Na (NH 4)TaF7:1％ Mn4+) has a tendency to significantly decrease the total emission intensity with increasing temperature.
Fig. 4 is a graph showing the relationship between the integrated intensity and the temperature of the luminescence spectrum of the red fluorescent material provided in example 2. It can be more intuitively found from fig. 4 that the red fluorescent material has high sensitivity to temperature change, and the red fluorescent material has temperature change characteristics in the temperature range of 240-440K.
Fig. 5 is a schematic diagram showing the relationship between the temperature and the sensitivity of the red fluorescent material provided in example 2. As can be seen from fig. 5, the red fluorescent material Na provided in example 2 (NH 4)TaF7:1％ Mn4+ achieved the highest absolute sensitivity of 0.0122K -1 at 323K and the highest relative sensitivity of 2.48% K -1 at 348K).
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. A red fluorescent material is characterized in that NaNH 4TaF7 is used as a matrix, mn 4+ is used as an activator, the chemical composition is Na (NH 4)TaF7:x Mn4+, x is more than or equal to 0.5% and less than or equal to 10%), and the red fluorescent material is prepared by the following steps:
s1, uniformly mixing a tantalum source and a hydrofluoric acid aqueous solution, and reacting for 7-24 hours at 100-180 ℃ to prepare a first precursor solution;
S2, uniformly mixing a sodium source, an ammonium source, deionized water and the first precursor solution, and reacting at 100-180 ℃ for 7-24 hours to prepare Na (NH 4)TaF7;
s3, uniformly mixing a manganese source with the hydrofluoric acid aqueous solution to obtain a second precursor solution, adding Na (NH 4)TaF7 to dissolve Na (NH 4)TaF7), and adding absolute ethyl alcohol to the second precursor solution to recrystallize Na (NH 4)TaF7:x Mn4+) to obtain the red fluorescent material.
2. The red fluorescent material according to claim 1, wherein in S1, a ratio of an addition molar amount of the tantalum source to a volume of the aqueous hydrofluoric acid solution is 1 to 4mmol/mL.
3. The red fluorescent material of claim 2, wherein the concentration of the aqueous hydrofluoric acid solution is 20 to 60wt%.
4. The red fluorescent material of claim 1, wherein in S2, a ratio of a sum of added molar amounts of the sodium source and the ammonium source to a volume of the deionized water is 1 to 2.5mmol/mL.
5. The red fluorescent material of claim 1, wherein in S3, a feed molar ratio of the manganese source to the Na (NH 4)TaF7) is 0.005 to 0.1:1.
6. The red fluorescent material according to claim 1, wherein a ratio of an addition molar amount of Na (NH 4)TaF7) to a volume of the absolute ethyl alcohol is 0.25 to 0.05mmol/mL.
7. The red fluorescent material of claim 1, wherein the sodium source is selected from at least one of sodium fluoride, sodium bifluoride, sodium carbonate;
and/or the ammonium source is at least one selected from ammonium fluoride, ammonium bifluoride and ammonium carbonate;
and/or, the tantalum source comprises tantalum pentoxide.
8. Use of a red fluorescent material according to any one of claims 1 to 7 for optical thermometry.
9. The method of using a red fluorescent material according to any one of claims 1 to 7, wherein the red fluorescent material is excited by ultraviolet light or blue light having a wavelength of 300 to 550 nm.
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| "From CsKTaF7 to CsNaTaF7: Alkali Metal Cations Regulation to Generate SHG Activity";Ru-Ling Tang et al.;Chem. Eur. J.;20220803;第28卷;第e202201588(1-7)页 * |
| "Mn(Ⅳ)激活的K3TaO2F4/BMF7红色荧光粉";周洋;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20200615(06);第B016-606页 * |
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