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 125
- 238000009529 body temperature measurement Methods 0.000 title claims abstract description 33
- 230000003287 optical effect Effects 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 22
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 239000012190 activator Substances 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims description 88
- 239000011572 manganese Substances 0.000 claims description 59
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 38
- 229910052748 manganese Inorganic materials 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 26
- 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 18
- 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
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 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
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 18
- 230000004044 response Effects 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 5
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- 238000002360 preparation method Methods 0.000 description 25
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- 238000004020 luminiscence type Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 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
- 238000005516 engineering process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- 101000827703 Homo sapiens Polyphosphoinositide phosphatase Proteins 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- 102100023591 Polyphosphoinositide phosphatase Human genes 0.000 description 1
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
- 101100233916 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) KAR5 gene Proteins 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
- 230000004913 activation Effects 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 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
- 238000005090 crystal field Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy 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
- 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
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 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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- 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
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- 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
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- 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
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Abstract
本发明提供一种红色荧光材料,以NaNH4TaF7为基质,Mn4+作为激活剂,化学组成为Na(NH4)TaF7:x Mn4+,0.5%≤x≤10%。该红色荧光材料能被紫外或蓝光激发,发射出580~680nm的窄带红光,最强波长位于628.8nm。且该红色荧光材料Na(NH4)TaF7:x Mn4+的发光强度会随着温度的变化而发生明显变化,利用这一温变特性,可以将红色荧光材料应用在光学测温上,并且该红色荧光材料具有响应速度快、测温灵敏度高、测温范围广的特性,在光学测温上的应用前景高。
The present invention provides a red fluorescent material, which uses NaNH 4 TaF 7 as a matrix and Mn 4+ as an activator, and has a chemical composition of Na(NH 4 )TaF 7 :x Mn 4+ , 0.5%≤x≤10%. The red fluorescent material can be excited by ultraviolet or blue light, and emits narrow-band red light of 580-680nm, with the strongest wavelength at 628.8nm. The luminous intensity of the red fluorescent material Na(NH 4 )TaF 7 :x Mn 4+ will change significantly with the change of temperature. By utilizing this temperature-dependent characteristic, the red fluorescent material can be applied to optical temperature measurement, and the red fluorescent material has the characteristics of fast response speed, high temperature measurement sensitivity and wide temperature measurement range, and has a high application prospect in optical temperature measurement.
Description
技术领域Technical Field
本发明属于发光材料领域,具体地,涉及一种红色荧光材料及其光学测温应用、应用方法。The present invention belongs to the field of luminescent materials, and in particular, relates to a red fluorescent material and an optical temperature measurement application and an application method thereof.
背景技术Background Art
近年来,我国工业现代化的进程和电子信息产业连续的高速增长,带动了传感器市场的快速上升。数据显示,2020年中国传感器市场规模2510亿元,同比增长14.7%。随着工业生产对温控需求的提升,对温度传感器的要求也越来越高。常规的基于材料的体积、电阻、磁性等特性与温度的关系来衡量温度,存在低灵敏和响应时间长等缺陷。In recent years, the process of industrial modernization in my country and the continuous high-speed growth of the electronic information industry have driven the rapid rise of the sensor market. Data show that the scale of China's sensor market in 2020 was 251 billion yuan, a year-on-year increase of 14.7%. With the increase in the demand for temperature control in industrial production, the requirements for temperature sensors are also getting higher and higher. Conventional temperature measurement based on the relationship between material properties such as volume, resistance, and magnetism and temperature has defects such as low sensitivity and long response time.
光学测温技术利用发光材料的荧光特性,结合图像处理技术,具有非接触,灵敏度高,响应速度快等优势。光学测温材料广泛应用于以冶金、炼煤为代表的化工生产领域和细胞内热传感类的医学诊断领域。Optical temperature measurement technology uses the fluorescence characteristics of luminescent materials and combines image processing technology. It has the advantages of non-contact, high sensitivity, and fast response speed. Optical temperature measurement materials are widely used in chemical production fields represented by metallurgy and coal refining, and medical diagnosis fields such as intracellular thermal sensing.
然而,目前市面上的无机光学测温材料大多选择f-f跃迁的稀土离子或d-d乐器的过渡金属离子作为激活离子,其测温灵敏度较差、测温范围较窄。中国专利CN113004892A公开了一种基于铈、铕激活硅铝酸盐的发光材料,该发光材料取得的最大绝对灵敏度约为0.0188K-1,取得的最大相对灵敏度约为1.35% K-1,则该发明制备的发光材料的测温灵敏度与测温范围仍有待进一步探索。However, most inorganic optical temperature measurement materials on the market currently use rare earth ions of ff transition or transition metal ions of dd instrument as activation ions, and their temperature measurement sensitivity is poor and the temperature measurement range is narrow. Chinese patent CN113004892A discloses a luminescent material based on cerium and europium activated aluminosilicate, the maximum absolute sensitivity of which is about 0.0188K -1 and the maximum relative sensitivity is about 1.35% K -1 , so the temperature measurement sensitivity and temperature measurement range of the luminescent material prepared by the invention still need to be further explored.
因此,有必要研发一种测温灵敏度高、测温范围广的光学测温材料。Therefore, it is necessary to develop an optical temperature measurement material with high temperature measurement sensitivity and a wide temperature measurement range.
发明内容Summary of the invention
本发明的目的在于克服现有技术存在的缺点,提供一种红色荧光材料及其光学测温应用、应用方法,使该红色荧光材料具有响应速度快、测温灵敏度高、测温范围广的特性,可应用在光学测温上。The purpose of the present invention is to overcome the shortcomings of the prior art and provide a red fluorescent material and its optical temperature measurement application and application method, so that the red fluorescent material has the characteristics of fast response speed, high temperature measurement sensitivity and wide temperature measurement range, and can be applied to optical temperature measurement.
根据本发明的第一个方面,提供一种红色荧光材料,以NaNH4TaF7为基质,Mn4+作为激活剂,化学组成为Na(NH4)TaF7:x Mn4+,0.5%≤x≤10%。According to a first aspect of the present invention, a red fluorescent material is provided, with NaNH 4 TaF 7 as a matrix and Mn 4+ as an activator, and the chemical composition is Na(NH 4 )TaF 7 :x Mn 4+ , 0.5%≤x≤10%.
本发明提供的红色荧光材料以铵盐氟化物Na(NH4)TaF7为基质,Mn4+为激活剂,使基质中Ta5+可被Mn4+占据,令Mn4+掺杂到Na(NH4)TaF7中,且掺杂量为0.5%~10%,可使制得的红色荧光材料Na(NH4)TaF7:x Mn4+具有发光亮度较强、发光强度对温度响应灵敏的优势。其次,外层电子为3d电子层的Mn4+离子具有极易受晶体场变化所影响的特性,当Mn4+作为激活剂,占据了具有特殊配位的基质中Ta5+离子时,制得的红色荧光材料Na(NH4)TaF7:x Mn4+具有特殊的发光性能,发光强度会随温度的变化而发生明显变化,即本发明提供的红色荧光材料Na(NH4)TaF7:x Mn4+对温度变化具有高灵敏度,且该红色荧光材料在较广的温度范围内均具有温变特性,则该红色荧光材料具有响应速度快、测温灵敏度高、测温范围广的特性。The red fluorescent material provided by the present invention uses ammonium salt fluoride Na(NH 4 )TaF 7 as a matrix and Mn 4+ as an activator, so that Ta 5+ in the matrix can be occupied by Mn 4+ , and Mn 4+ is doped into Na(NH 4 )TaF 7 , and the doping amount is 0.5% to 10%. The prepared red fluorescent material Na(NH 4 )TaF 7 :x Mn 4+ has the advantages of strong luminous brightness and sensitive response of luminous intensity to temperature. Secondly, Mn 4+ ions whose outer electrons are 3d electron layers have the property of being easily affected by changes in the crystal field. When Mn 4+ acts as an activator and occupies Ta 5+ ions in a matrix with special coordination, the prepared red fluorescent material Na(NH 4 )TaF 7 :x Mn 4+ has special luminescence properties, and the luminescence intensity will change significantly with changes in temperature. That is, the red fluorescent material Na(NH 4 )TaF 7 :x Mn 4+ provided by the present invention has high sensitivity to temperature changes, and the red fluorescent material has temperature-dependent characteristics within a wider temperature range. Therefore, the red fluorescent material has the characteristics of fast response speed, high temperature measurement sensitivity and wide temperature measurement range.
优选地,该红色荧光材料由以下步骤制备得到:S1.将钽源与氢氟酸水溶液混合均匀,并于100~180℃下反应7~24小时,制得第一前驱体溶液;S2.再将钠源、铵源、去离子水与第一前驱体溶液混合均匀,并于100~180℃下反应7~24小时,制得Na(NH4)TaF7;S3.锰源与氢氟酸水溶液混合均匀,制得第二前驱体溶液,再向第二前驱体溶液中加入Na(NH4)TaF7使Na(NH4)TaF7部分溶解,并向第二前驱体溶液中加入无水乙醇使Na(NH4)TaF7:x Mn4+重结晶析出,制得红色荧光材料。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 them at 100-180°C for 7-24 hours to obtain a first precursor solution; S2. uniformly mixing a sodium source, an ammonium source, and deionized water with the first precursor solution, and reacting them at 100-180°C for 7-24 hours to obtain Na( NH4 ) TaF7 ; S3. uniformly mixing a manganese source and a hydrofluoric acid aqueous solution to obtain a second precursor solution, and then adding Na( NH4 ) TaF7 to the second precursor solution to partially dissolve Na( NH4 ) TaF7 , and adding anhydrous ethanol to the second precursor solution to recrystallize and precipitate Na( NH4 ) TaF7 :xMn4 + to obtain a red fluorescent material.
本发明采用重结晶法制备红色荧光材料,利用氢氟酸水溶液与无水乙醇对七氟钽酸铵盐Na(NH4)TaF7的溶解度不同,使溶解于第二前驱体溶液中的Na(NH4)TaF7和Mn4+可以通过重结晶的操作,使基质中Ta5+可被Mn4+占据,令Mn4+掺杂到Na(NH4)TaF7中,从而制得具有发光亮度强、发光强度对温度灵敏的红色荧光材料。The present invention adopts a recrystallization method to prepare a red fluorescent material. By utilizing the different solubilities of hydrofluoric acid aqueous solution and anhydrous ethanol to ammonium heptafluorotantalate Na(NH 4 )TaF 7 , Na(NH 4 )TaF 7 and Mn 4+ dissolved in a second precursor solution can be recrystallized so that Ta 5+ in the matrix can be occupied by Mn 4+ , and Mn 4+ is doped into Na(NH 4 )TaF 7 , thereby preparing a red fluorescent material with high luminous brightness and luminous intensity sensitive to temperature.
优选地,在S1中,钽源的加入摩尔量与氢氟酸水溶液的体积之比为1~4mmol/mL。Preferably, in S1, the ratio of the added molar amount of the tantalum source to the volume of the hydrofluoric acid aqueous solution is 1 to 4 mmol/mL.
当钽源与氢氟酸水溶液的添加量满足上述条件时,可以提升Na(NH4)TaF7多晶颗粒的产量。若钽源的加入的摩尔量与HF溶液用量之比小于1mmol/L时,相当于钽源的投料量过少,会导致第一前驱体中钽离子的浓度过低,导致Na(NH4)TaF7多晶颗粒产量过低。若钽源的加入的摩尔量与HF溶液用量之比大于4mmol/L时,则用于溶解钽源的氢氟酸水溶液过少,钽源未完全溶解,但第一前驱体溶液已达到钽的饱和浓度,则同样使得Na(NH4)TaF7的产量过低。When the addition amount of tantalum source and hydrofluoric acid aqueous solution meets the above conditions, the yield of Na(NH 4 )TaF 7 polycrystalline particles can be increased. If the ratio of the added molar amount of tantalum source to the amount of HF solution is less than 1mmol/L, it is equivalent to that the feeding amount of tantalum source is too small, which will cause the concentration of tantalum ions in the first precursor to be too low, resulting in too low yield of Na(NH 4 )TaF 7 polycrystalline particles. If the ratio of the added molar amount of tantalum source to the amount of HF solution is greater than 4mmol/L, the hydrofluoric acid aqueous solution used to dissolve the tantalum source is too small, the tantalum source is not completely dissolved, but the first precursor solution has reached the saturated concentration of tantalum, which also makes the yield of Na(NH 4 )TaF 7 too low.
优选地,钽源的加入摩尔量与氢氟酸水溶液的体积之比为2mmol/mL。Preferably, the ratio of the added molar amount of the tantalum source to the volume of the hydrofluoric acid aqueous solution is 2 mmol/mL.
优选地,氢氟酸水溶液的浓度为20~60wt%。Preferably, the concentration of the hydrofluoric acid aqueous solution is 20 to 60 wt %.
优选地,氢氟酸水溶液的浓度为40wt%。Preferably, the concentration of the hydrofluoric acid aqueous solution is 40 wt %.
优选地,在S2中,钠源、铵源的加入摩尔量之和与去离子水体积之比为1~2.5mmol/mL。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 to 2.5 mmol/mL.
通过调整钠源、铵源、去离子水的投料量,钠源、铵源的加入摩尔量之和与去离子水体积之比为1~2.5mmol/mL,可以提高Na(NH4)TaF7的产量和纯度。若钠源、铵源的加入摩尔量之和与去离子水体积之比小于1mmol/L,则钠离子与铵根离子的浓度过低,影响Na(NH4)TaF7的产量;若钠源、铵源的加入摩尔量之和与去离子水体积之比大于2.5mmol/L,则制得的Na(NH4)TaF7存在较多杂质,从而降低Na(NH4)TaF7的纯度。By adjusting the feeding amount of sodium source, ammonium source and deionized water, the ratio of the sum of the added molar amounts of sodium source and ammonium source to the volume of deionized water is 1-2.5mmol/mL, which can improve the yield and purity of Na(NH 4 )TaF 7. If the ratio of the sum of the added molar amounts of sodium source and ammonium source to the volume of deionized water is less than 1mmol/L, the concentrations of sodium ions and ammonium ions are too low, affecting the yield of Na(NH 4 )TaF 7 ; if the ratio of the sum of the added molar amounts of sodium source and ammonium source to the volume of deionized water is greater than 2.5mmol/L, the obtained Na(NH 4 )TaF 7 contains more impurities, thereby reducing the purity of Na(NH 4 )TaF 7 .
优选地,去离子水的投料量为10~40ml。Preferably, the amount of deionized water added is 10-40 ml.
优选地,去离子水的投料量为20ml。Preferably, the amount of deionized water added is 20 ml.
优选地,在S3中,锰源与Na(NH4)TaF7的投料摩尔比为0.005~0.1:1。Preferably, in S3, the molar ratio of the manganese source to Na(NH 4 )TaF 7 is 0.005 to 0.1:1.
通过调整制备原料的投料量,使Mn4+离子与Na(NH4)TaF7的摩尔比为0.005~0.1:1,从而令红色荧光材料Na(NH4)TaF7:x Mn4+中的Mn4+离子掺杂量为0.5%~10%,使掺杂后的材料可以发出红色荧光。By adjusting the feed amount of the raw materials, the molar ratio of Mn 4+ ions to Na(NH 4 )TaF 7 is set to 0.005-0.1:1, so that the doping amount of Mn 4+ ions in the red fluorescent material Na(NH 4 )TaF 7 :x Mn 4+ is 0.5%-10%, so that the doped material can emit red fluorescence.
优选地,在S3中,锰源与Na(NH4)TaF7的投料摩尔比为0.01:1。Preferably, in S3, the feeding molar ratio of the manganese source to Na(NH 4 )TaF 7 is 0.01:1.
优选地,Na(NH4)TaF7的加入摩尔量与无水乙醇的体积之比为0.025~0.05mmol/mL。Preferably, the ratio of the added molar amount of Na(NH 4 )TaF 7 to the volume of anhydrous ethanol is 0.025 to 0.05 mmol/mL.
通过控制Na(NH4)TaF7与无水乙醇的投料量,使Na(NH4)TaF7的加入摩尔量与无水乙醇的体积之比为0.025~0.05mmol/L,从而使得微量溶解的Na(NH4)TaF7可以通过重结晶析出,制得红色荧光材料Na(NH4)TaF7:x Mn4+。By controlling the feeding amount of Na(NH 4 )TaF 7 and anhydrous ethanol, the ratio of the added molar amount of Na(NH 4 )TaF 7 to the volume of anhydrous ethanol is made to be 0.025-0.05mmol/L, so that the trace dissolved Na(NH 4 )TaF 7 can be precipitated by recrystallization to obtain the red fluorescent material Na(NH 4 )TaF 7 :x Mn 4+ .
优选地,Na(NH4)TaF7的加入摩尔量与无水乙醇的体积之比为0.025mmol/mL。Preferably, the ratio of the added molar amount of Na(NH 4 )TaF 7 to the volume of anhydrous ethanol is 0.025 mmol/mL.
优选地,无水乙醇的投料量为5~10mL。Preferably, the feeding amount of anhydrous ethanol is 5 to 10 mL.
优选地,无水乙醇的投料量为10mL。Preferably, the feeding amount of anhydrous ethanol is 10 mL.
优选地,钠源选自氟化钠、氟化氢钠、碳酸钠中至少一种;和/或,铵源选自氟化铵、氟化氢铵、碳酸铵中至少一种;和/或,钽源包括五氧化二钽。Preferably, the sodium source is selected from at least one of sodium fluoride, sodium bifluoride, and sodium carbonate; and/or the ammonium source is selected from at least one of ammonium fluoride, ammonium bifluoride, and ammonium carbonate; and/or the tantalum source includes tantalum pentoxide.
优选地,钠源包括氟化氢钠。Preferably, the sodium source comprises sodium bifluoride.
优选地,铵源包括氟化氢铵。Preferably, the ammonium source comprises ammonium bifluoride.
优选地,锰源包括六氟合锰酸钾。Preferably, the manganese source comprises potassium hexafluoromanganate.
根据本发明的第二个方面,提供一种上述红色荧光材料在光学测温上的应用。According to a second aspect of the present invention, there is provided an application of the above-mentioned red fluorescent material in optical temperature measurement.
该红色荧光材料Na(NH4)TaF7:x Mn4+的发光强度会随着温度的变化而发生明显变化,利用这一温变特性,可以将红色荧光材料应用在光学测温上,利用该红色荧光材料在待测温度下发出的发光强度,可得知待测温度的具体数值。并且该红色荧光材料的可测量的温度范围宽,适用范围广,应用前景高。The luminescence intensity of the red fluorescent material Na(NH 4 )TaF 7 :x Mn 4+ will change significantly with the change of temperature. By utilizing this temperature-dependent characteristic, the red fluorescent material can be applied to optical temperature measurement. By utilizing the luminescence intensity of the red fluorescent material at the temperature to be measured, the specific value of the temperature to be measured can be obtained. In addition, the red fluorescent material has a wide measurable temperature range, a wide range of application, and a high application prospect.
根据本发明的第三个方面,提供一种上述红色荧光材料的应用方法,使用波长300~550nm的紫外光或蓝光对红色荧光材料进行激发。According to a third aspect of the present invention, there is provided an application method of the red fluorescent material, using ultraviolet light or blue light with a wavelength of 300 to 550 nm to excite the red fluorescent material.
本方案采用的红色荧光材料Na(NH4)TaF7:x Mn4+能被波长为300~500nm的光激发,发射出580~680nm的窄带红光,在被应用于光学测温时,需要令红色荧光材料Na(NH4)TaF7:x Mn4+被前述波长的光激发。The red fluorescent material Na(NH 4 )TaF 7 :x Mn 4+ used in this solution can be excited by light with a wavelength of 300-500nm and emit narrow-band red light of 580-680nm. When used in optical temperature measurement, the red fluorescent material Na(NH 4 )TaF 7 :x Mn 4+ needs to be excited by light of the aforementioned wavelength.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例2提供的红色荧光材料的XRD谱图;FIG1 is an XRD spectrum of a red fluorescent material provided in Example 2;
图2为实施例2提供的红色荧光材料的激发和发射光谱图;FIG2 is an excitation and emission spectrum diagram of a red fluorescent material provided in Example 2;
图3为实施例2提供的红色荧光材料在不同温度下的发光光谱;FIG3 is a light-emitting spectrum of the red fluorescent material provided in Example 2 at different temperatures;
图4为实施例2提供的红色荧光材料的发光光谱的积分强度与温度的关系示意图;FIG4 is a schematic diagram showing the relationship between the integrated intensity of the luminescence spectrum of the red fluorescent material provided in Example 2 and the temperature;
图5为实施例2提供的红色荧光材料的温度与灵敏度的关系示意图。FIG. 5 is a schematic diagram showing the relationship between temperature and sensitivity of the red fluorescent material provided in Example 2.
具体实施方式DETAILED DESCRIPTION
为了使本技术领域的人员更好地理解本发明中的技术方案,下面将结合本发明实施例和实施例中的附图对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都应当属于本发明保护的范围。In order to enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention and the drawings in the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.
实施例1Example 1
本实施例提供一种红色荧光材料,其化学组成为Na(NH4)TaF7:0.5% Mn4+。该红色荧光材料选用的钽源为Ta2O5;选用的氢氟酸水溶液浓度为40wt%,选用的钠源为NaHF2;选用的铵源为NH5F2;选用的锰源为K2MnF6。This embodiment provides a red fluorescent material, whose chemical composition is Na(NH 4 )TaF 7 :0.5% Mn 4+ . The tantalum source selected for the red fluorescent material is Ta 2 O 5 ; the concentration of the hydrofluoric acid aqueous solution selected is 40wt%, the sodium source selected is NaHF 2 ; the ammonium source selected is NH 5 F 2 ; and the manganese source selected is K 2 MnF 6 .
红色荧光材料的制备方法包括以下步骤:The preparation method of the red fluorescent material comprises the following steps:
S1.将1.1047g钽源与2.5mL氢氟酸水溶液混合均匀,搅拌20min,并转移至高压反应釜中,于150℃下反应16小时,冷却至室温后,制得第一前驱体溶液。其中,钽源的加入摩尔量与氢氟酸水溶液的体积之比为2mmol/mL。S1. 1.1047 g of tantalum source and 2.5 mL of hydrofluoric acid aqueous solution were mixed evenly, stirred for 20 min, and transferred to a high-pressure reactor, reacted at 150° C. for 16 hours, and cooled to room temperature to obtain a first precursor solution. The ratio of the added molar amount of tantalum source to the volume of hydrofluoric acid aqueous solution was 2 mmol/mL.
S2.再将0.6199g钠源、1.426g铵源与2.5mL第一前驱体溶液依次加入20mL去离子水中,搅拌20min使混合均匀,转移至高压反应釜中,于150℃下反应16小时,冷却至室温,用去离子水与无水乙醇多次洗涤透明多晶,干燥后得到Na(NH4)TaF7。其中,钠源、铵源的加入摩尔量之和与去离子水体积之比为1.75nmol/mL。S2. 0.6199g of sodium source, 1.426g of ammonium source and 2.5mL of the first precursor solution were added to 20mL of deionized water in sequence, stirred for 20min to make the mixture uniform, transferred to a high-pressure reactor, reacted at 150°C for 16 hours, cooled to room temperature, washed the transparent polycrystals with deionized water and anhydrous ethanol for several times, and dried to obtain Na(NH 4 )TaF 7 . The ratio of the sum of the molar amounts of the sodium source and the ammonium source added to the volume of deionized water was 1.75nmol/mL.
S3.将0.0030g锰源溶解于氢氟酸水溶液中,制得第二前驱体溶液,再向第二前驱体溶液中加入0.8874g Na(NH4)TaF7,使Na(NH4)TaF7溶解,再向第二前驱体溶液中滴加10mL无水乙醇,使Na(NH4)TaF7:0.5% Mn4+重结晶析出,对析出物进行离心,将离心得到的沉淀物用无水乙醇洗涤多次,过滤,于70℃烘干8小时,制得红色荧光材料。其中,锰源与Na(NH4)TaF7的投料摩尔比为0.005:1,Na(NH4)TaF7的加入摩尔量与无水乙醇的体积之比为0.025mmol/mL。S3. 0.0030g of manganese source was dissolved in a hydrofluoric acid aqueous solution to obtain a second precursor solution, and then 0.8874g of Na(NH 4 )TaF 7 was added to the second precursor solution to dissolve Na(NH 4 )TaF 7 , and then 10mL of anhydrous ethanol was added to the second precursor solution to recrystallize Na(NH 4 )TaF 7 :0.5% Mn 4+ , and the precipitate was centrifuged, and the precipitate obtained by centrifugation was washed with anhydrous ethanol for multiple times, filtered, and dried at 70°C for 8 hours to obtain a red fluorescent material. The molar ratio of manganese source to Na(NH 4 )TaF 7 was 0.005:1, and the ratio of the added molar amount of Na(NH 4 )TaF 7 to the volume of anhydrous ethanol was 0.025mmol/mL.
实施例2Example 2
本实施例参照实施例1提供的制备方法,制备一种红色荧光材料。本实施例与实施例1的区别在于:在制备红色荧光材料的过程中,锰源与Na(NH4)TaF7的投料摩尔比为0.01:1,则制得的红色荧光材料的化学组成为Na(NH4)TaF7:1%Mn4+。具体为在S3中采用0.0061gK2MnF6代替实施例2采用的锰源。其余原料配比、制备方法与实施例1严格保持一致。This embodiment refers to the preparation method provided in Example 1 to prepare a red fluorescent material. The difference between this embodiment and Example 1 is that in the process of preparing the red fluorescent material, the molar ratio of the manganese source to Na(NH 4 )TaF 7 is 0.01:1, and the chemical composition of the prepared red fluorescent material is Na(NH 4 )TaF 7 :1%Mn 4+ . Specifically, 0.0061gK 2 MnF 6 is used in S3 to replace the manganese source used in Example 2. The rest of the raw material ratios and preparation methods are strictly consistent with Example 1.
实施例3Example 3
本实施例参照实施例1提供的制备方法,制备一种红色荧光材料。本实施例与实施例1的区别在于:在制备红色荧光材料的过程中,锰源与Na(NH4)TaF7的投料摩尔比为0.1:1,则制得的红色荧光材料的化学组成为Na(NH4)TaF7:10%Mn4+。具体为在S3中采用0.0617gK2MnF6代替实施例2采用的锰源。其余原料配比、制备方法与实施例1严格保持一致。This embodiment refers to the preparation method provided in Example 1 to prepare a red fluorescent material. The difference between this embodiment and Example 1 is that in the process of preparing the red fluorescent material, the molar ratio of the manganese source to Na(NH 4 )TaF 7 is 0.1:1, and the chemical composition of the prepared red fluorescent material is Na(NH 4 )TaF 7 :10%Mn 4+ . Specifically, 0.0617gK 2 MnF 6 is used in S3 to replace the manganese source used in Example 2. The rest of the raw material ratios and preparation methods are strictly consistent with Example 1.
实施例4Example 4
本实施例参照实施例2提供的制备方法,制备一种红色荧光材料。本实施例与实施例2的区别在于:在制备红色荧光材料的过程中,钽源的加入摩尔量与氢氟酸水溶液的体积之比为1mmol/L,具体为在S1中,加入0.5523g Ta2O5代替实施例2采用的钽源。其余原料配比、制备方法与实施例2严格保持一致。This example prepares a red fluorescent material with reference to the preparation method provided in Example 2. The difference between this example and Example 2 is that in the process of preparing the red fluorescent material, the ratio of the added molar amount of the tantalum source to the volume of the hydrofluoric acid aqueous solution is 1 mmol/L, specifically, in S1, 0.5523 g Ta 2 O 5 is added to replace the tantalum source used in Example 2. The rest of the raw material ratios and preparation methods are strictly consistent with Example 2.
实施例5Example 5
本实施例参照实施例2提供的制备方法,制备一种红色荧光材料。本实施例与实施例2的区别在于:在制备红色荧光材料的过程中,钽源的加入摩尔量与氢氟酸水溶液的体积之比为4mmol/L,具体为在S1中,加入2.2094g Ta2O5代替实施例2采用的钽源。其余原料配比、制备方法与实施例2严格保持一致。This example prepares a red fluorescent material with reference to the preparation method provided in Example 2. The difference between this example and Example 2 is that in the process of preparing the red fluorescent material, the ratio of the added molar amount of the tantalum source to the volume of the hydrofluoric acid aqueous solution is 4 mmol/L, specifically, in S1, 2.2094 g Ta 2 O 5 is added to replace the tantalum source used in Example 2. The rest of the raw material ratios and preparation methods are strictly consistent with Example 2.
实施例6Example 6
本实施例参照实施例2提供的制备方法,制备一种红色荧光材料。本实施例与实施例2的区别在于:在制备红色荧光材料的过程中,钠源、铵源的加入摩尔量之和与去离子水体积之比为1.25mmol/L,具体为在S2中,采用0.3099gNaHF2、1.1408g NH5F2代替实施例2采用的钠源和铵源。其余原料配比、制备方法与实施例2严格保持一致。This example prepares a red fluorescent material with reference to the preparation method provided in Example 2. The difference between this example and Example 2 is 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 1.25 mmol/L, specifically, in S2, 0.3099 g NaHF 2 and 1.1408 g NH 5 F 2 are used to replace the sodium source and ammonium source used in Example 2. The rest of the raw material ratios and preparation methods are strictly consistent with Example 2.
实施例7Example 7
本实施例参照实施例2提供的制备方法,制备一种红色荧光材料。本实施例与实施例2的区别在于:在制备红色荧光材料的过程中,钠源、铵源的加入摩尔量之和与去离子水体积之比为2.5mmol/L,具体为在S2中,加入1.5497g NaHF2代替实施例2采用的钠源。其余原料配比、制备方法与实施例2严格保持一致。This example prepares a red fluorescent material by referring to the preparation method provided in Example 2. The difference between this example and Example 2 is 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 2.5 mmol/L, specifically, in S2, 1.5497 g NaHF 2 is added to replace the sodium source used in Example 2. The rest of the raw material ratios and preparation methods are strictly consistent with Example 2.
实施例8Example 8
本实施例参照实施例2提供的制备方法,制备一种红色荧光材料。本实施例与实施例2的区别在于:在制备红色荧光材料的过程中,采用NaF作为钠源。其余原料配比、制备方法与实施例2严格保持一致。This example prepares a red fluorescent material by referring to the preparation method provided in Example 2. The difference between this example and Example 2 is that NaF is used as a sodium source in the process of preparing the red fluorescent material. The rest of the raw material ratios and preparation methods are strictly consistent with those in Example 2.
实施例9Embodiment 9
本实施例参照实施例2提供的制备方法,制备一种红色荧光材料。本实施例与实施例2的区别在于:在制备红色荧光材料的过程中,采用NH4F作为钠源。其余原料配比、制备方法与实施例2严格保持一致。This example prepares a red fluorescent material by referring to the preparation method provided in Example 2. The difference between this example and Example 2 is that NH 4 F is used as the sodium source in the process of preparing the red fluorescent material. The other raw material ratios and preparation methods are strictly consistent with those in Example 2.
实施例10Example 10
本实施例参照实施例2提供的制备方法,制备一种红色荧光材料。本实施例与实施例2的区别在于:在制备红色荧光材料的过程中,改变S1与S2中的反应反应温度和反应时间,具体为S1、S2中均于180℃下反应10小时。其余原料配比、制备方法与实施例2严格保持一致。This example prepares a red fluorescent material with reference to the preparation method provided in Example 2. The difference between this example and Example 2 is that in the process of preparing the red fluorescent material, the reaction temperature and reaction time in S1 and S2 are changed, specifically, both S1 and S2 are reacted at 180°C for 10 hours. The rest of the raw material ratios and preparation methods are strictly consistent with Example 2.
实施例11Embodiment 11
本实施例参照实施例2提供的制备方法,制备一种红色荧光材料。本实施例与实施例2的区别在于:在制备红色荧光材料的过程中,改变S1与S2中的反应反应温度和反应时间,具体为S1、S2中均于100℃下反应24小时。其余原料配比、制备方法与实施例2严格保持一致。This example prepares a red fluorescent material with reference to the preparation method provided in Example 2. The difference between this example and Example 2 is that in the process of preparing the red fluorescent material, the reaction temperature and reaction time in S1 and S2 are changed, specifically, both S1 and S2 are reacted at 100°C for 24 hours. The rest of the raw material ratios and preparation methods are strictly consistent with Example 2.
对比例1Comparative Example 1
本对比例参照实施例2提供的制备方法,制备一种红色荧光材料。本对比例与实施例2的区别在于:在制备红色荧光材料的过程中,锰源与Na(NH4)TaF7的投料摩尔比为0.001:1,则制得的红色荧光材料的化学组成为Na(NH4)TaF7:0.1% Mn4+。具体为在S3中采用0.002g K2MnF6代替实施例2采用的锰源。其余原料配比、制备方法与实施例2严格保持一致。This comparative example refers to the preparation method provided in Example 2 to prepare a red fluorescent material. 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 )TaF 7 is 0.001:1, and the chemical composition of the prepared red fluorescent material is Na(NH 4 )TaF 7 :0.1% Mn 4+ . Specifically, 0.002g K 2 MnF 6 is used in S3 to replace the manganese source used in Example 2. The rest of the raw material ratios and preparation methods are strictly consistent with Example 2.
对比例2Comparative Example 2
本对比例参照实施例2提供的用于制备红色荧光材料的方法,制备一种红色荧光材料。本对比例与实施例2的区别在于:在制备红色荧光材料的过程中,锰源与Na(NH4)TaF7的投料摩尔比为n(Mn4+):n(Ta)=0.15:1,则制得的红色荧光材料的化学组成为Na(NH4)TaF7:15% Mn4+。具体为在S3中采用0.0927g K2MnF6代替实施例2采用的锰源。其余原料配比、制备方法与实施例2严格保持一致。This comparative example refers to the method for preparing a red fluorescent material provided in Example 2 to prepare a red fluorescent material. 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 )TaF 7 is n(Mn 4+ ):n(Ta)=0.15:1, and the chemical composition of the prepared red fluorescent material is Na(NH 4 )TaF 7 :15% Mn 4+ . Specifically, 0.0927g K 2 MnF 6 is used in S3 to replace the manganese source used in Example 2. The rest of the raw material ratios and preparation methods are strictly consistent with Example 2.
对比例3Comparative Example 3
本对比例参照实施例2提供的用于制备红色荧光材料的方法,制备一种含Na(NH4)TaF7的材料。本对比例与实施例2的区别在于:省略S3中重结晶的操作,具体为省略向第二前驱体溶液中加入无水乙醇的操作步骤。则制得的材料中包含Na(NH4)TaF7,但Mn4+未掺杂到Na(NH4)TaF7之中。其余原料配比、制备方法与实施例2严格保持一致。This comparative example refers to the method for preparing a red fluorescent material provided in Example 2 to prepare a material containing Na(NH 4 )TaF 7. The difference between this comparative example and Example 2 is that the recrystallization operation in S3 is omitted, specifically, the operation step of adding anhydrous ethanol to the second precursor solution is omitted. The prepared material contains Na(NH 4 )TaF 7 , but Mn 4+ is not doped into Na(NH 4 )TaF 7. The rest of the raw material ratios and preparation methods are strictly consistent with those in Example 2.
测试例Test Case
参试对象:实施例1~11制得的红色荧光材料、对比例1~3制得的材料。Test objects: red fluorescent materials prepared in Examples 1 to 11, and materials prepared in Comparative Examples 1 to 3.
测试项目及测试方法:Test items and test methods:
(1)X-射线粉末衍射(1) X-ray powder diffraction
利用Bruker D8 Advance X射线衍射仪采集参试对象的X射线衍射图谱(XRD),采用Cu-Kα靶为辐射源(λ=0.15406nm),工作电压为40kV,工作电流为40mA,2θ扫描范围为5~90°。The X-ray diffraction patterns (XRD) of the test objects were collected by Bruker D8 Advance X-ray diffractometer, using Cu-Kα target as the radiation source (λ=0.15406nm), working voltage of 40kV, working current of 40mA, and 2θ scanning range of 5-90°.
(2)荧光光谱(2) Fluorescence spectroscopy
在83~448K的温度下对参试样品进行激发、发射光谱是在Edinburgh InstrumentFS5稳态-瞬态荧光光谱仪上收集,设备配备了450W的氙灯和SC-05变温控制器。The samples were excited at temperatures ranging from 83 to 448 K, and the emission spectra were collected on an Edinburgh Instrument FS5 steady-state-transient fluorescence spectrometer equipped with a 450 W xenon lamp and an SC-05 variable temperature controller.
测试结果:将实施例1~11提供的红色荧光材料与对比例1~3制得的材料对应的测试结果进行对比,可以发现,与实施例1~11测得的发光强度相比,对比例1~2制得的红色荧光材料的发光强度较低。其中,对比例1提供的红色荧光材料中Mn4+掺杂量过少,对比例2提供的红色荧光材料中Mn4+掺杂量过多。由此说明,若材料中Mn4+的掺杂量过少,则未达到材料可容纳的最优浓度,材料的发光强度较低;若材料中Mn4+的掺杂量过多,则容易发生浓度猝灭,使得材料的发光强度较低。由于测温分辨率依赖于材料的发光强度,因此对比例1~2所提供的红色荧光材料的光学应用会受到限制。对比例3提供的材料由于没有采用重结晶法制备,导致Mn4+无法顺利掺杂到Na(NH4)TaF7之中,相当于掺杂量接近为0%,因此对比例3提供的材料也无法发光。而实施例1~11提供的红色荧光材料均可以被波长为300~550nm的紫外光或蓝光激发,发射出波长为580~680nm的窄带红光,且波长为628.8nm的光具有最高的发光强度。由此说明,实施例1~11提供的以NaNH4TaF7为基质,Mn4+作为激活剂,化学组成为Na(NH4)TaF7:xMn4+,且0.5%≤x≤10%的红色荧光材料可以发出红光,且其发光强度对温度变化表现灵敏的响应,并且在较广的温度范围内均具有温变特性,该红色荧光材料具有响应速度快、测温灵敏度高、测温范围广的特性,具有应用于光学测温领域的潜力。Test results: By comparing the test results of the red fluorescent materials provided in Examples 1 to 11 with the corresponding test results of the materials prepared in Comparative Examples 1 to 3, it can be found that the luminescence intensity of the red fluorescent materials prepared in Comparative Examples 1 to 2 is lower than that measured in Examples 1 to 11. Among them, the Mn 4+ doping amount in the red fluorescent material provided in Comparative Example 1 is too small, and the Mn 4+ doping amount in the red fluorescent material provided in Comparative Example 2 is too large. This shows that if the doping amount of Mn 4+ in the material is too small, the optimal concentration that the material can accommodate is not reached, and the luminescence intensity of the material is low; if the doping amount of Mn 4+ in the material is too much, concentration quenching is likely to occur, resulting in a low luminescence intensity of the material. Since the temperature measurement resolution depends on the luminescence intensity of the material, the optical application of the red fluorescent materials provided in Comparative Examples 1 to 2 will be limited. Since the material provided in Comparative Example 3 is not prepared by the recrystallization method, Mn 4+ cannot be smoothly doped into Na(NH 4 )TaF 7 , which is equivalent to a doping amount close to 0%, so the material provided in Comparative Example 3 cannot emit light either. The red fluorescent materials provided in Examples 1 to 11 can be excited by ultraviolet light or blue light with a wavelength of 300 to 550 nm, and emit narrow-band red light with a wavelength of 580 to 680 nm, and the light with a wavelength of 628.8 nm has the highest luminous intensity. This shows that the red fluorescent materials provided in Examples 1 to 11 with NaNH 4 TaF 7 as a matrix, Mn 4+ as an activator, a chemical composition of Na(NH 4 )TaF 7 :xMn 4+ , and 0.5%≤x≤10% can emit red light, and their luminous intensity responds sensitively to temperature changes, and has temperature-dependent characteristics in a wide temperature range. The red fluorescent material has the characteristics of fast response speed, high temperature measurement sensitivity, and a wide temperature measurement range, and has the potential to be applied in the field of optical temperature measurement.
其中,实施例2制得的Na(NH4)TaF7:1% Mn4+在实施例1~11制得的红色荧光材料中,具有最佳的测温灵敏度和最广的测温范围。实施例2的提供的红色荧光材料Na(NH4)TaF7:1% Mn4+的测试图谱如图1~5所示。Among them, Na(NH 4 )TaF 7 :1% Mn 4+ prepared in Example 2 has the best temperature measurement sensitivity and the widest temperature measurement range among the red fluorescent materials prepared in Examples 1 to 11. The test spectra of the red fluorescent material Na(NH 4 )TaF 7 :1% Mn 4+ provided in Example 2 are shown in FIGS.
图1为实施例2提供的红色荧光材料Na(NH4)TaF7:1% Mn4+的XRD谱图。从图1中可知,制得的材料的XRD衍射峰与标准卡片PDF#00-057-0546一致,说明实施例2制得的Na(NH4)TaF7:1% Mn4+为纯相。Figure 1 is an XRD spectrum of the red fluorescent material Na( NH4 ) TaF7 :1%Mn4 + provided in Example 2. As can be seen from Figure 1, the XRD diffraction peaks of the prepared material are consistent with the standard card PDF#00-057-0546, indicating that the Na( NH4 ) TaF7 :1%Mn4 + prepared in Example 2 is a pure phase.
图2为实施例2提供的红色荧光材料Na(NH4)TaF7:1% Mn4+的激发和发射光谱图。从图2中可知,红色荧光材料Na(NH4)TaF7:1% Mn4+的激发光谱由中心波长为358nm和473nm的两个宽峰组成,其中最强激发位于473nm,发射为580~680nm的窄带红光,最强波长位于628.8nm。Figure 2 is an excitation and emission spectrum diagram of the red fluorescent material Na(NH 4 )TaF 7 :1% Mn 4+ provided in Example 2. As can be seen from Figure 2, the excitation spectrum of the red fluorescent material Na(NH 4 )TaF 7 :1% Mn 4+ consists of two broad peaks with central wavelengths of 358nm and 473nm, wherein the strongest excitation is at 473nm, and the emission is a narrow-band red light of 580-680nm, with the strongest wavelength at 628.8nm.
图3为实施例2提供的红色荧光材料在不同温度下的发光光谱。从图3中可知,随着温度的升高,红色荧光材料Na(NH4)TaF7:1% Mn4+的总发光强度呈明显下降的趋势。Figure 3 is the luminescence spectrum at different temperatures of the red fluorescent material provided in Example 2. As can be seen from Figure 3, with the increase of temperature, the total luminescence intensity of the red fluorescent material Na(NH 4 )TaF 7 :1% Mn 4+ shows a significant downward trend.
图4为实施例2提供的红色荧光材料的发光光谱的积分强度与温度的关系示意图。从图4中可更直观地发现该红色荧光材料对温度变化具有高灵敏度,且该红色荧光材料在240~440K的温度范围内均具有温变特性。Figure 4 is a schematic diagram showing the relationship between the integrated intensity of the luminescence spectrum and temperature of the red fluorescent material provided in Example 2. From Figure 4, it can be more intuitively found that the red fluorescent material has high sensitivity to temperature changes, and the red fluorescent material has temperature variation characteristics within the temperature range of 240-440K.
图5为实施例2提供的红色荧光材料的温度与灵敏度的关系示意图。由图5可知,实施例2提供的红色荧光材料Na(NH4)TaF7:1% Mn4+在323K取得最高绝对灵敏度0.0122K-1,在348K取得最高相对灵敏度2.48%K-1。Figure 5 is a schematic diagram showing the relationship between temperature and sensitivity of the red fluorescent material provided in Example 2. As shown in Figure 5, the red fluorescent material Na( NH4 ) TaF7 :1%Mn4 + provided in Example 2 achieves the highest absolute sensitivity of 0.0122K -1 at 323K and the highest relative sensitivity of 2.48%K -1 at 348K.
以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。The above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.
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