CN101838534A - Preparation method of single-green up-conversion fluorescent marking material - Google Patents
Preparation method of single-green up-conversion fluorescent marking material Download PDFInfo
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- CN101838534A CN101838534A CN201010207225A CN201010207225A CN101838534A CN 101838534 A CN101838534 A CN 101838534A CN 201010207225 A CN201010207225 A CN 201010207225A CN 201010207225 A CN201010207225 A CN 201010207225A CN 101838534 A CN101838534 A CN 101838534A
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Abstract
The invention relates to a preparation method of a single-green up-conversion fluorescent marking material, in particular to a preparation method of a fluorescent marking material, solving the problems of complicated preparation process, poor chemical stability, easy light injury, toxicity, low detection sensitivity and poor monochromaticity of a traditional preparation method of the fluorescent marking material. The method comprises the following steps of: dissolving Y2O3, Yb2O3, Ho2O3 and Eu2O3 to concentrated sulfuric acid; adding deionized water; adding an LiNO3 solution; adding a complexing agent citric acid; then, adding ammonia to adjust a pH value; drying to obtain dried gel; calcining the dried gel; and naturally cooling to a room temperature to obtain a single-green up-conversion fluorescent marking material. The method has simple preparation process, low reaction temperature and hardly damaged crystal lattice, the single-green up-conversion fluorescent marking material prepared by using the method has high purity, good evenness of particles in 20-50 nm, strong luminescence and favorable monochromaticity.
Description
Technical field
The present invention relates to a kind of preparation method of fluorescence labeling material.
Background technology
Fluorescence labeling material can be widely used in high-tech areas such as cell tracker, ion tunnel detection, DNA detection.Existing fluorescence labeling material mainly is organic dye and quantum dot, and organic dye is poisonous, poor chemical stability, phosphor persistence time short, be not suitable for polychrome observation etc., and quantum dot can produce the intensive autofluorescence and influence detectivity.So they all have separately the intrinsic defective and its further widespread use are restricted.The rare earth up-conversion fluorescent marking material is converted into visible light by the infrared light that will excite and emits, so can obtain the very high transmitance of organizing, realize zero background detection, thereby detectivity is very high; And the matrix of this material is inorganic materials, has good light stability and chemical stability; Through suitable finishing, it can have good bio-compatibility.But it is very high to the monochromaticity specification of quality of its emitting fluorescence to be used as fluorescently-labeled upconverting fluorescent material, at present, and the domestic also relevant report of high monochromaticity up-conversion fluorescence without comparison.
Summary of the invention
It is numerous and diverse to the invention solves existing fluorescence labeling material preparation technology, and poor chemical stability easily produces light injury, and poisonous, detectivity is low, and the problem that monochromaticity is bad provides a kind of preparation method of single-green up-conversion fluorescent marking material.
The preparation method of single-green up-conversion fluorescent marking material of the present invention is as follows: one, with Y
2O
3, Yb
2O
3, Ho
2O
3And Eu
2O
3Add deionized water after being dissolved in concentrated nitric acid, add LiNO again
3Solution, stirring at normal temperatures obtains clear solution, Y in the clear solution
3+Ion and Yb
3+The ionic mol ratio is 1 ﹕ 0 ~ 10, Y
3+Ion and Ho
3+The ionic mol ratio is 1 ﹕ 0.1 ~ 0.5, Y
3+Ion and Eu
3+The ionic mol ratio is 1 ﹕ 0 ~ 2, Y
3+Ion and Li
+The ionic mol ratio is 1 ﹕ 0 ~ 15; Two, the mol ratio according to positively charged ion in the clear solution and citric acid is the ratio of 1 ﹕ 3 ~ 5, adds citric acid (complexing agent) and stir in clear solution, and up to dissolving fully, adding ammoniacal liquor adjusting pH value again is 5 ~ 7; Three, the solution that step 3 is obtained was dried 12 ~ 20 hours under 100 ~ 150 ℃ condition, got xerogel; Four, xerogel was calcined 1 ~ 5 hour under 600 ~ 1000 ℃ of conditions, naturally cooled to room temperature again, promptly get single-green up-conversion fluorescent marking material.
The inventive method preparation technology is simple, temperature of reaction is low, reaction process can realize control fully and accurately, required equipment is cheap, lattice is not destroyed in preparation process, the complexing agent citric acid low price that the present invention adopts, it is very extensive to originate, and production cycle and reaction times are shorter.The single-green up-conversion fluorescent marking material purity height of the present invention's preparation, good uniformity, particle size is between 20 ~ 50nm, and is not only luminous strong, and monochromaticity is fine, doubles than existing monochromaticity up-conversion fluorescent marking material.Li of the present invention
+Ionic mixes and can improve the up-conversion luminescence intensity of single-green up-conversion fluorescent marking material, and red up-conversion fluorescence intensity reduces with respect to green up-conversion fluorescence intensity, and the monochromaticity of green up-conversion fluorescence improves.
Description of drawings
Fig. 1 is the XRD figure of embodiment 13 gained single-green up-conversion fluorescent marking materials; Fig. 2 is that 980nmLD excites Different L i in the embodiment one
+Ionic concn doping Y
3O
2: 6Yb
3+, 0.3Ho
3+, 1.0Eu
3+Sample up-conversion fluorescence spectrogram is among the figure
Represent Y
3O
2: 6Yb
3+, 0.3Ho
3+, 1.0Eu
3+Up-conversion fluorescence spectrum,
Represent Y
3O
2: 6Yb
3+, 0.3Ho
3+, 1.0Eu
3+, 6Li
+Up-conversion fluorescence spectrum; Fig. 3 is that 980nmLD excites in the embodiment one, doping Different L i
+The red up-conversion fluorescence spectrogram at the peak, nanocrystal normalization method 550nm place of concentration is in the picture in picture
Represent the normalization method 550nm Y of place
3O
2: 6Yb
3+, 0.3Ho
3+, 1.0Eu
3+, 6Li
+Red up-conversion fluorescence spectrum,
Represent the normalization method 550nm Y of place
3O
2: 6Yb
3+, 0.3Ho
3+, 1.0Eu
3+Red up-conversion fluorescence spectrum.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of single-green up-conversion fluorescent marking material is as follows in the present embodiment: one, with Y
2O
3, Yb
2O
3, Ho
2O
3And Eu
2O
3Add deionized water after being dissolved in concentrated nitric acid, add LiNO again
3Solution, stirring at normal temperatures obtains clear solution, Y in the clear solution
3+Ion and Yb
3+The ionic mol ratio is 1 ﹕ 0 ~ 10, Y
3+Ion and Ho
3+The ionic mol ratio is 1 ﹕ 0.1 ~ 0.5, Y
3+Ion and Eu
3+The ionic mol ratio is 1 ﹕ 0 ~ 2, Y
3+Ion and Li
+The ionic mol ratio is 1 ﹕ 0 ~ 15; Two, the mol ratio according to positively charged ion in the clear solution and citric acid is the ratio of 1 ﹕ 3 ~ 5, adds citric acid and stir in clear solution, and up to dissolving fully, adding ammoniacal liquor adjusting pH value again is 5 ~ 7; Three, the solution that step 3 is obtained was dried 12 ~ 20 hours under 100 ~ 150 ℃ condition, got xerogel; Four, xerogel was calcined 1 ~ 5 hour under 600 ~ 1000 ℃ of conditions, naturally cooled to room temperature again, promptly get single-green up-conversion fluorescent marking material.
Find out Li by Fig. 2
+Ionic mixes and can improve the up-conversion luminescence intensity of single-green up-conversion fluorescent marking material.
Li doped as shown in Figure 3
+Behind the ion, red up-conversion fluorescence intensity reduces with respect to green up-conversion fluorescence intensity, that is to say that the monochromaticity of green up-conversion fluorescence improves.
Embodiment two: that present embodiment and embodiment one are different is Y in the step 1 clear solution
3+Ion and Yb
3+The ionic mol ratio is 1 ﹕ 1 ~ 9, Y
3+Ion and Ho
3+The ionic mol ratio is 1 ﹕ 0.2 ~ 0.4, Y
3+Ion and Eu
3+The ionic mol ratio is 1 ﹕ 1 ~ 1.5, Y
3+Ion and Li
+The ionic mol ratio is 1 ﹕ 1 ~ 14.Other is identical with embodiment one.
Embodiment three: that present embodiment and embodiment one are different is Y in the step 1 clear solution
3+Ion and Yb
3+The ionic mol ratio is 1 ﹕ 8, Y
3+Ion and Ho
3+The ionic mol ratio is 1 ﹕ 0.3, Y
3+Ion and Eu
3+The ionic mol ratio is 1 ﹕ 1.5, Y
3+Ion and Li
+The ionic mol ratio is 1 ﹕ 10.Other is identical with embodiment one.
Embodiment four: that present embodiment and embodiment one are different is Y in the step 1 clear solution
3+Ion, Yb
3+Ion, Ho
3+Ion, Eu
3+Ion and Li
+The ionic mol ratio is 1 ﹕, 0.8 ﹕, 0.3 ﹕, 0.5 ﹕ 1.Other is identical with embodiment one.
Embodiment five: that present embodiment and embodiment one are different is Y in the step 1 clear solution
3+Ion, Yb
3+Ion, Ho
3+Ion, Eu
3+Ion and Li
+The ionic mol ratio is 1 ﹕, 5 ﹕, 0.4 ﹕, 1.5 ﹕ 14.Other is identical with embodiment one.
Embodiment six: present embodiment and embodiment one to five are different be in the step 2 in the clear solution mol ratio of positively charged ion and citric acid be 1 ﹕ 4.Other is identical with embodiment one to five.
Embodiment seven: present embodiment and embodiment one to six are different is to add ammoniacal liquor in the step 2 to regulate pH value be 6.Other is identical with embodiment one to six.
Embodiment eight: present embodiment and embodiment one to seven are different be in the step 3 under 140 ℃ condition, dried 18 hours.Other is identical with embodiment one to seven.
Embodiment nine: what present embodiment and embodiment one to eight were different is in the step 4 xerogel to be calcined 2 ~ 4 hours under 700 ~ 900 ℃ of conditions.Other is identical with embodiment one to eight.
Embodiment ten: what present embodiment and embodiment one to nine were different is in the step 4 xerogel to be calcined 3 hours under 800 ℃ of conditions.Other is identical with embodiment one to nine.
Embodiment 11: the preparation method of single-green up-conversion fluorescent marking material is as follows in the present embodiment: one, with Y
2O
3, Yb
2O
3, Ho
2O
3And Eu
2O
3Add deionized water after being dissolved in concentrated nitric acid, add LiNO again
3Solution, stirring at normal temperatures obtains clear solution, Y in the clear solution
3+Ion and Yb
3+The ionic mol ratio is 1 ﹕ 10, Y
3+Ion and Ho
3+The ionic mol ratio is 1 ﹕ 0.5, Y
3+Ion and Eu
3+The ionic mol ratio is 1 ﹕ 2, Y
3+Ion and Li
+The ionic mol ratio is 1 ﹕ 15; Two, the mol ratio according to positively charged ion in the clear solution and citric acid is the ratio of 1 ﹕ 5, adds the complexing agent citric acid and stir in clear solution, and up to dissolving fully, adding ammoniacal liquor adjusting pH value again is 7; Three, the solution that step 3 is obtained was dried 20 hours under 150 ℃ condition, got xerogel; Four, xerogel was calcined 5 hours under 1000 ℃ of conditions, naturally cooled to room temperature again, promptly get single-green up-conversion fluorescent marking material.
Embodiment 12: the preparation method of single-green up-conversion fluorescent marking material is as follows in the present embodiment: one, with Y
2O
3, Yb
2O
3, Ho
2O
3And Eu
2O
3Add deionized water after being dissolved in concentrated nitric acid, add LiNO again
3Solution, stirring at normal temperatures obtains clear solution, Y in the clear solution
3+Ion and Yb
3+The ionic mol ratio is 1 ﹕ 0.1, Y
3+Ion and Ho
3+The ionic mol ratio is 1 ﹕ 0.1, Y
3+Ion and Eu
3+The ionic mol ratio is 1 ﹕ 0.2, Y
3+Ion and Li
+The ionic mol ratio is 1 ﹕ 0.5; Two, the mol ratio according to positively charged ion in the clear solution and citric acid is the ratio of 1 ﹕ 3, adds the complexing agent citric acid and stir in clear solution, and up to dissolving fully, adding ammoniacal liquor adjusting pH value again is 5; Three, the solution that step 3 is obtained was dried 12 hours under 100 ℃ condition, got xerogel; Four, xerogel was calcined 1 hour under 600 ℃ of conditions, naturally cooled to room temperature again, promptly get single-green up-conversion fluorescent marking material.
Embodiment 13: the preparation method of single-green up-conversion fluorescent marking material is as follows in the present embodiment: one, with Y
2O
3, Yb
2O
3, Ho
2O
3And Eu
2O
3Add deionized water after being dissolved in concentrated nitric acid, add LiNO again
3Solution, stirring at normal temperatures obtains clear solution, Y in the clear solution
3+Ion, Yb
3+Ion, Ho
3+Ion, Eu
3+Ion and Li
+The ionic mol ratio is 1 ﹕, 5 ﹕, 0.4 ﹕, 1.5 ﹕ 14; Two, the mol ratio according to positively charged ion in the clear solution and citric acid is the ratio of 1 ﹕ 3.5, adds the complexing agent citric acid and stir in clear solution, and up to dissolving fully, adding ammoniacal liquor adjusting pH value again is 7; Three, the solution that step 3 is obtained was dried 20 hours under 150 ℃ condition, got xerogel; Four, xerogel was calcined 1.5 hours under 800 ℃ of conditions, naturally cooled to room temperature again, promptly get single-green up-conversion fluorescent marking material.
Claims (6)
1. the preparation method of single-green up-conversion fluorescent marking material is characterized in that the preparation method of single-green up-conversion fluorescent marking material is as follows: one, with Y
2O
3, Yb
2O
3, Ho
2O
3And Eu
2O
3Add deionized water after being dissolved in concentrated nitric acid, add LiNO again
3Solution, stirring at normal temperatures obtains clear solution, Y in the clear solution
3+Ion and Yb
3+The ionic mol ratio is 1 ﹕ 0 ~ 10, Y
3+Ion and Ho
3+The ionic mol ratio is 1 ﹕ 0.1 ~ 0.5, Y
3+Ion and Eu
3+The ionic mol ratio is 1 ﹕ 0 ~ 2, Y
3+Ion and Li
+The ionic mol ratio is 1 ﹕ 0 ~ 15; Two, the mol ratio according to positively charged ion in the clear solution and citric acid is the ratio of 1 ﹕ 3 ~ 5, adds citric acid and stir in clear solution, and up to dissolving fully, adding ammoniacal liquor adjusting pH value again is 5 ~ 7; Three, the solution that step 3 is obtained was dried 12 ~ 20 hours under 100 ~ 150 ℃ condition, got xerogel; Four, xerogel was calcined 1 ~ 5 hour under 600 ~ 1000 ℃ of conditions, naturally cooled to room temperature again, promptly get single-green up-conversion fluorescent marking material.
2. the preparation method of single-green up-conversion fluorescent marking material according to claim 1 is characterized in that Y in the step 1 clear solution
3+Ion and Yb
3+The ionic mol ratio is 1 ﹕ 1 ~ 9, Y
3+Ion and Ho
3+The ionic mol ratio is 1 ﹕ 0.2 ~ 0.4, Y
3+Ion and Eu
3+The ionic mol ratio is 1 ﹕ 1 ~ 1.5, Y
3+Ion and Li
+The ionic mol ratio is 1 ﹕ 1 ~ 14.
3. the preparation method of single-green up-conversion fluorescent marking material according to claim 1 is characterized in that Y in the step 1 clear solution
3+Ion and Yb
3+The ionic mol ratio is 1 ﹕ 8, Y
3+Ion and Ho
3+The ionic mol ratio is 1 ﹕ 0.3, Y
3+Ion and Eu
3+The ionic mol ratio is 1 ﹕ 1.5, Y
3+Ion and Li
+The ionic mol ratio is 1 ﹕ 10.
4. the preparation method of single-green up-conversion fluorescent marking material according to claim 1 is characterized in that Y in the step 1 clear solution
3+Ion, Yb
3+Ion, Ho
3+Ion, Eu
3+Ion and Li
+The ionic mol ratio is 1 ﹕, 0.8 ﹕, 0.3 ﹕, 0.5 ﹕ 1.
5. the preparation method of single-green up-conversion fluorescent marking material according to claim 1 is characterized in that Y in the step 1 clear solution
3+Ion, Yb
3+Ion, Ho
3+Ion, Eu
3+Ion and Li
+The ionic mol ratio is 1 ﹕, 5 ﹕, 0.4 ﹕, 1.5 ﹕ 14.
6. according to the preparation method of claim 1,2,3,4 or 5 described single-green up-conversion fluorescent marking materials, it is characterized in that in the step 2 that the mol ratio of positively charged ion and citric acid is 1 ﹕ 4 in the clear solution.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102660278A (en) * | 2012-05-15 | 2012-09-12 | 东北林业大学 | Green up-conversion nanometer fluorescent powder and preparation method thereof |
CN104178157A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Dysprosium-ytterbium-codoped yttrium oxide up-conversion luminescent material, preparation method and organic light-emitting diode |
CN105567233A (en) * | 2016-01-15 | 2016-05-11 | 江苏省电力公司电力科学研究院 | Preparation method of fluorescent powder for optical fiber temperature sensor |
-
2010
- 2010-06-23 CN CN201010207225A patent/CN101838534A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102660278A (en) * | 2012-05-15 | 2012-09-12 | 东北林业大学 | Green up-conversion nanometer fluorescent powder and preparation method thereof |
CN102660278B (en) * | 2012-05-15 | 2013-10-16 | 东北林业大学 | Preparation method of green up-conversion nanometer fluorescent powder |
CN104178157A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Dysprosium-ytterbium-codoped yttrium oxide up-conversion luminescent material, preparation method and organic light-emitting diode |
CN105567233A (en) * | 2016-01-15 | 2016-05-11 | 江苏省电力公司电力科学研究院 | Preparation method of fluorescent powder for optical fiber temperature sensor |
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Application publication date: 20100922 |