CN105112051A - Synthesis method of ytterbium and thulium doped fluoride used for up-conversion white light - Google Patents
Synthesis method of ytterbium and thulium doped fluoride used for up-conversion white light Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 24
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title abstract description 4
- 229910052775 Thulium Inorganic materials 0.000 title description 3
- 229910052769 Ytterbium Inorganic materials 0.000 title description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 title description 3
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 title 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- ATLJOUJUCRBASY-UHFFFAOYSA-N [Tm].[Yb] Chemical compound [Tm].[Yb] ATLJOUJUCRBASY-UHFFFAOYSA-N 0.000 claims abstract description 12
- LLZBVBSJCNUKLL-UHFFFAOYSA-N thulium(3+);trinitrate Chemical compound [Tm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LLZBVBSJCNUKLL-UHFFFAOYSA-N 0.000 claims abstract description 6
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 fluorine manganese potassium Chemical compound 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- APQQUKGVNQQMJI-UHFFFAOYSA-K potassium manganese(2+) trifluoride Chemical compound [F-].[Mn+2].[K+].[F-].[F-] APQQUKGVNQQMJI-UHFFFAOYSA-K 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 9
- 235000011164 potassium chloride Nutrition 0.000 abstract description 6
- 239000001103 potassium chloride Substances 0.000 abstract description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 abstract description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 abstract description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 abstract description 4
- 235000002867 manganese chloride Nutrition 0.000 abstract description 4
- 239000011565 manganese chloride Substances 0.000 abstract description 4
- 230000004907 flux Effects 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 230000005284 excitation Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000007716 flux method Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- HVCXHPPDIVVWOJ-UHFFFAOYSA-N [K].[Mn] Chemical compound [K].[Mn] HVCXHPPDIVVWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JVWJBBYNBCYSNA-UHFFFAOYSA-N lanthanum(3+) oxygen(2-) yttrium(3+) Chemical compound [O--].[O--].[O--].[Y+3].[La+3] JVWJBBYNBCYSNA-UHFFFAOYSA-N 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Luminescent Compositions (AREA)
Abstract
本发明涉及一种用于上转换白光的镱铥掺杂氟化物的合成方法，属于发光材料领域。将一定比例的氯化钾、氯化亚锰、硝酸镱和硝酸铥与过量的氟氢化氨混合，在180℃条件下反应0.5～24小时，冷却至室温，洗涤，过滤，得到镱铥掺杂氟锰钾。本发明反应体系中，氟氢化氨既作为反应物，同时也作为助熔剂而大过量的存在，这一特殊的反应条件，使得在只存在单个发光离子Tm3+的条件下同时发射红绿蓝三色光，从而在Yb3+和Tm3+共掺杂氟锰钾体系中获得上转换白光。The invention relates to a synthesis method of ytterbium-thulium-doped fluoride used for up-converting white light, and belongs to the field of luminescent materials. Mix a certain proportion of potassium chloride, manganous chloride, ytterbium nitrate and thulium nitrate with excess ammonium hydrofluoride, react at 180°C for 0.5 to 24 hours, cool to room temperature, wash, and filter to obtain ytterbium-thulium doped Potassium manganese fluoride. In the reaction system of the present invention, ammonium hydrofluoride exists in large excess as both a reactant and a flux. This special reaction condition makes it possible to emit red, green and blue at the same time under the condition that only a single luminescent ion Tm3 + exists. Three-color light, so as to obtain up-conversion white light in the Yb 3+ and Tm 3+ co-doped manganese potassium fluoride system.
Description
技术领域 technical field
本发明涉及一种用于上转换白光的镱铥掺杂氟化物的合成方法，具体涉及一种在只存在单个发光离子Tm3+的条件下发射红绿蓝三色光，从而在Yb3+和Tm3+掺杂氟锰钾体系中获得上转换白光的方法，属于发光材料领域。 The present invention relates to a synthesis method of ytterbium-thulium-doped fluoride for up-converting white light, in particular to a method for emitting red, green and blue tricolor light under the condition that only a single luminescent ion Tm 3+ exists, so that Yb 3+ and The invention relates to a method for obtaining up-conversion white light in a Tm 3+ doped manganese potassium fluoride system, which belongs to the field of luminescent materials.
背景技术 Background technique
在常规条件下，稀土铥离子Tm3+是典型的能够发射蓝光的稀土离子，通过Tm3+的1D2→3F4和1G4→3H6的能级跃迁能够在450nm和475nm波长区发射明显的蓝光。随着近年来国内外对稀土离子上转换发光的重视，对上转换发光的控制要求越来越多。获得上转换白光最常用的方法是在材料中掺杂Tm3+、Er3+和Yb3+，其中Tm3+发射蓝光，Er3+发射红光和绿光，Yb3+作为敏化离子。从而使材料可以输出450-500nm蓝光、550-560绿光以及650nm红光，通过调节不同稀土离子的掺杂浓度使得发射蓝光、绿光和红光的光强比达到1:1:1，从而得到上转换白光的输出。 Under normal conditions, the rare earth thulium ion Tm 3+ is a typical rare earth ion capable of emitting blue light, and the energy level transitions of 1 D 2 → 3 F 4 and 1 G 4 → 3 H 6 of Tm 3+ can be at 450nm and 475nm The wavelength region emits distinctly blue light. With the emphasis on the upconversion luminescence of rare earth ions at home and abroad in recent years, there are more and more requirements for the control of upconversion luminescence. The most common way to obtain up-conversion white light is to dope Tm 3+ , Er 3+ and Yb 3+ in the material, where Tm 3+ emits blue light, Er 3+ emits red and green light, and Yb 3+ acts as a sensitizing ion . In this way, the material can output 450-500nm blue light, 550-560 green light and 650nm red light. By adjusting the doping concentration of different rare earth ions, the light intensity ratio of blue light, green light and red light can reach 1:1:1, thus An output of up-converted white light is obtained.
目前关于上转换白光材料的合成研究有很多，主要通过掺杂Er3+、Tm3+和Yb3+或者Ho3+、Tm3+和Yb3+来获得上转换白光，其中专利CN104003725A公开了用于上转换白光的Er3+、Tm3+和Yb3+三掺氧化镧钇透明陶瓷的制备方法，采用Er3+和Tm3+为发光离子，需要两种活化剂离子。专利CN1951821A公开了一种钨酸盐基质上转换白光发射材料及其制备方法，采用Ho3+和Tm3+为发光离子，同样需要两种活化剂离子。 At present, there are many researches on the synthesis of up-conversion white light materials, mainly by doping Er 3+ , Tm 3+ and Yb 3+ or Ho 3+ , Tm 3+ and Yb 3+ to obtain up-conversion white light, among which the patent CN104003725A discloses The preparation method of Er 3+ , Tm 3+ and Yb 3+ triple-doped lanthanum yttrium oxide transparent ceramics for up-conversion white light adopts Er 3+ and Tm 3+ as luminescent ions and requires two kinds of activator ions. Patent CN1951821A discloses a tungstate-based up-conversion white light-emitting material and its preparation method. Ho 3+ and Tm 3+ are used as luminescent ions, and two activator ions are also required.
其实，在Tm3+丰富的能级结构中，也同样存在着波长区处于550nm的绿光和处于650nm的红光发射，但由于其极低的跃迁几率，使得在激发过程中只能检测到非常微弱的发射光，甚至完全看不到绿光或红光的发射。如果能够对Tm3+ -的跃迁几率进行改变，我们就可以通过只存在单个发光离子的条件下，获得蓝、绿、红三色光，并通过改变三色光的强度获得白光发射。减少体系中掺杂的发光离子种类不仅能够降低组成多样性造成的产品物理化学性质不稳定，合成体系复杂等一系列的工业生产的问题，而且可以简化上转换荧光激发条件，进一步促进产品在各个领域中的应用。 In fact, in the Tm 3+ rich energy level structure, there are also green light at 550nm and red light emission at 650nm in the wavelength region, but due to its extremely low transition probability, it can only be detected during the excitation process. Very faint emission, even no green or red emission can be seen at all. If the transition probability of Tm 3+ - can be changed, we can obtain blue, green and red three-color light under the condition of only a single luminescent ion, and obtain white light emission by changing the intensity of the three-color light. Reducing the types of luminescent ions doped in the system can not only reduce the instability of the physical and chemical properties of the product caused by the diversity of the composition, and a series of industrial production problems such as the complexity of the synthesis system, but also simplify the excitation conditions for up-conversion fluorescence and further promote the production of products in various fields. applications in the field.
发明内容 Contents of the invention
本发明的目的在于改变Tm3+的不同能级跃迁几率，研究一种用于上转换白光的镱铥掺杂氟化物的合成方法。在反应中加入过量氟氢化氨作为反应物的同时也作为助熔剂，采用助熔剂方法合成镱铥掺杂的氟锰钾，通过化学方法改变Tm3+不同能级的跃迁几率，获得蓝、绿和红光发射，并改变三色光的发光强度比率，从而获得上转换白光。 The purpose of the present invention is to change the transition probability of different energy levels of Tm 3+ , and to study a synthesis method of ytterbium-thulium-doped fluoride for up-conversion white light. In the reaction, excess ammonium hydrofluoride is added as a reactant and also as a flux. The flux method is used to synthesize potassium fluoride manganese potassium doped with ytterbium and thulium. The transition probability of different energy levels of Tm 3+ is changed by chemical methods to obtain blue and green. and red light emission, and change the luminous intensity ratio of the three colors of light to obtain up-converted white light.
本发明的技术方案是：一种助熔剂法制备镱铥掺杂氟锰钾的方法，其步骤为：将氯化钾、氯化亚锰、一定比例的硝酸镱和硝酸铥与过量的氟氢化氨混合，在180℃条件下反应0.5～24小时，冷却至室温，洗涤，过滤，得到镱铥掺杂氟锰钾。本发明的反应体系中，以氯化钾为参照，硝酸镱的摩尔比为5％，硝酸铥的摩尔比为0.5％，氟氢化氨既作为反应物也作为助熔剂，其摩尔用量选择为氯化钾的10倍。 The technical solution of the present invention is: a method for preparing ytterbium thulium doped manganese potassium fluoride by a flux method, the steps of which are: reacting potassium chloride, manganous chloride, a certain proportion of ytterbium nitrate and thulium nitrate with excess hydrofluoride mixed with ammonia, reacted at 180°C for 0.5-24 hours, cooled to room temperature, washed and filtered to obtain ytterbium-thulium-doped manganese potassium fluoride. In the reaction system of the present invention, taking potassium chloride as a reference, the molar ratio of ytterbium nitrate is 5%, the molar ratio of thulium nitrate is 0.5%, ammonium hydrogen fluoride is used as reactant and flux, and its molar dosage is selected as chlorine 10 times that of potassium chloride.
制备镱铥掺杂氟锰钾的具体技术方案如下所述： The specific technical scheme for preparing ytterbium thulium doped manganese potassium fluoride is as follows:
将氯化钾、氯化亚锰、硝酸镱、硝酸铥以及氟氢化氨按摩尔比1:1:5％:0.5％:10的比例混合，在180℃条件下反应0.5～24小时，冷却至室温，洗涤，过滤，得到镱铥掺杂氟锰钾发光材料。 Mix potassium chloride, manganous chloride, ytterbium nitrate, thulium nitrate and ammonium hydrofluoride in a molar ratio of 1:1:5%:0.5%:10, react at 180°C for 0.5 to 24 hours, and cool to room temperature, washing and filtering to obtain ytterbium-thulium-doped fluoromanganese-potassium luminescent material.
在上述的合成方法中，获得白光的反应时间为6～12小时。 In the above synthesis method, the reaction time for obtaining white light is 6-12 hours.
在上述的合成方法中，所述的洗涤，可以用去离子水洗涤除去过量的氟氢化氨。本发明所得到的镱铥掺杂氟锰钾发光材料进行粉末X射线衍射仪和扫描电子显微镜测试，结果表明：所制得的产物为纯相，晶粒尺寸随着反应时间的延长而增大，具体可参见图1的XRD照片和图2的扫描电子显微镜照片。 In the above synthesis method, the washing may be performed with deionized water to remove excess hydrogen fluoride. The ytterbium-thulium-doped manganese potassium luminescent material obtained in the present invention is tested by a powder X-ray diffractometer and a scanning electron microscope, and the results show that the obtained product is a pure phase, and the grain size increases with the prolongation of the reaction time For details, please refer to the XRD photo in Figure 1 and the scanning electron micrograph in Figure 2.
本发明所得到的镱铥掺杂氟锰钾发光材料进行上转换荧光激发测试，结果表明：所得到的镱铥掺杂氟锰钾发光材料具有较强的红绿蓝三色发射光，并且随着反应时间的变化，其三色光强度可调，在6～12小时反应范围内可获得上转换白光，具体可参见图3的荧光激发图和图4的色坐标图。 The ytterbium-thulium-doped manganese-potassium fluoride luminescent material obtained in the present invention is subjected to an up-conversion fluorescence excitation test, and the results show that the obtained ytterbium-thulium-doped manganese-potassium fluoride luminescent material has strong red, green and blue three-color emission light, and With the change of reaction time, the intensities of the three colors of light can be adjusted, and up-converted white light can be obtained within the reaction range of 6-12 hours. For details, please refer to the fluorescence excitation diagram in Figure 3 and the color coordinate diagram in Figure 4.
附图说明 Description of drawings
图1是不同反应时间制得的镱铥掺杂氟锰钾产物的XRD照片 Figure 1 is the XRD photo of ytterbium thulium doped manganese potassium fluoride products prepared at different reaction times
图2是不同反应时间制得的镱铥掺杂氟锰钾产物的扫描电镜照片(A)0.5h,(B)6h,(C)12h,(D)24h。 Fig. 2 is the scanning electron micrographs (A) 0.5h, (B) 6h, (C) 12h, (D) 24h of ytterbium thulium doped manganese potassium fluoride products prepared at different reaction times.
图3是不同反应时间制得的镱铥掺杂氟锰钾产物的荧光激发图(A,B)0.5h,(C,D)6h,(D,E)12h,(G)24h，其中B,D,F为放大可见光部分。 Figure 3 is the fluorescence excitation diagram of ytterbium-thulium doped manganese potassium fluoride products prepared at different reaction times (A, B) 0.5h, (C, D) 6h, (D, E) 12h, (G) 24h, where B , D, F are the enlarged visible light part.
图4是不同反应时间制得的镱铥掺杂氟锰钾产物的色坐标图(A)0.5h,(B)6h,(C)12h,(D)24h。 Fig. 4 is the color coordinate diagram of (A) 0.5h, (B) 6h, (C) 12h, (D) 24h of ytterbium thulium doped manganese potassium fluoride products prepared at different reaction times.
具体实施方式 Detailed ways
通过下列实例对本发明进行进一步阐述。 The present invention is further illustrated by the following examples.
实施例1： Example 1:
取0.0746g氯化钾(KCl)、0.1980g氯化亚锰(MnCl2·4H2O)、0.0225g硝酸镱(Yb(NO3)3·6H2O)、0.0023g硝酸铥(Tm(NO3)3·6H2O)与0.5704g氟氢化氨(NH4HF2)混合，(摩尔比1:1:5％:0.5％:10)，充分研磨后放入反应容器中，180℃反应0.5小时，取出冷却至室温，洗涤，过滤。得到镱铥掺杂氟锰钾产物，产物的XRD如图1所示，扫描电子显微镜照片如图2A所示，荧光激发如图3A，3B所示，色坐标如图4所示。 Take 0.0746g potassium chloride (KCl), 0.1980g manganese chloride (MnCl 2 4H 2 O), 0.0225g ytterbium nitrate (Yb(NO 3 ) 3 6H 2 O), 0.0023g thulium nitrate (Tm(NO 3 ) Mix 3 6H 2 O) with 0.5704g ammonium hydrogen fluoride (NH 4 HF 2 ), (molar ratio 1:1:5%:0.5%:10), grind thoroughly and put it into a reaction vessel, and react at 180°C After 0.5 hour, take it out and cool to room temperature, wash and filter. The obtained ytterbium-thulium-doped manganese potassium fluoride product has XRD as shown in Figure 1, scanning electron microscope photo as shown in Figure 2A, fluorescence excitation as shown in Figures 3A and 3B, and color coordinates as shown in Figure 4.
实施例2： Example 2:
反应原料按实施例1比例混合，充分研磨后放入反应容器中，180℃反应6小时，取出冷却至室温，洗涤，过滤。得到镱铥掺杂氟锰钾产物，产物的XRD如图1所示，扫描电子显微镜照片如图2B所示，荧光激发如图3C，3D所示，色坐标如图4所示。 The reaction raw materials were mixed according to the ratio of Example 1, thoroughly ground, put into a reaction vessel, reacted at 180°C for 6 hours, taken out, cooled to room temperature, washed, and filtered. The obtained Ytterbium Thulium-doped Manganese Potassium Fluoride product was obtained. The XRD of the product is shown in Figure 1, the scanning electron micrograph is shown in Figure 2B, the fluorescence excitation is shown in Figures 3C and 3D, and the color coordinates are shown in Figure 4.
实施例3： Example 3:
反应原料按实施例1比例混合，充分研磨后放入反应容器中，180℃反应12小时，取出冷却至室温，洗涤，过滤。得到镱铥掺杂氟锰钾产物，产物的XRD如图1所示，扫描电子显微镜照片如图2C所示，荧光激发如图3E，3F所示，色坐标如图4所示。 The reaction raw materials were mixed according to the ratio of Example 1, thoroughly ground, put into a reaction vessel, reacted at 180°C for 12 hours, taken out, cooled to room temperature, washed, and filtered. Ytterbium-thulium-doped manganese potassium fluoride product was obtained. The XRD of the product is shown in FIG. 1 , the scanning electron micrograph is shown in FIG. 2C , the fluorescence excitation is shown in FIG. 3E and 3F , and the color coordinates are shown in FIG. 4 .
实施例4： Example 4:
反应原料按实施例1比例混合，充分研磨后放入反应容器中，180℃反应24小时，取出冷却至室温，洗涤，过滤。得到镱铥掺杂氟锰钾产物，产物的XRD如图1所示，扫描电子显微镜照片如图2D所示，荧光激发如图3G所示，色坐标如图4所示。 The reaction raw materials were mixed according to the ratio of Example 1, thoroughly ground, put into a reaction vessel, reacted at 180°C for 24 hours, taken out, cooled to room temperature, washed, and filtered. The obtained ytterbium-thulium-doped manganese potassium fluoride product is shown in Figure 1 for XRD, as shown in Figure 2D for scanning electron micrographs, as shown in Figure 3G for fluorescence excitation, and as shown in Figure 4 for the color coordinates.
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