CN101838534A - Preparation method of single-green up-conversion fluorescent marking material - Google Patents

Preparation method of single-green up-conversion fluorescent marking material Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
ion
mol ratio
green
marking material
fluorescent marking
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201010207225A
Other languages
Chinese (zh)
Inventor
刘娟
盛艳秋
张治国
曹文武
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN201010207225A priority Critical patent/CN101838534A/en
Publication of CN101838534A publication Critical patent/CN101838534A/en
Pending legal-status Critical Current

Links

Images

Landscapes

  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Luminescent Compositions (AREA)

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

The preparation method of single-green up-conversion fluorescent marking material
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
Figure 230797DEST_PATH_IMAGE001
Represent Y 3O 2: 6Yb 3+, 0.3Ho 3+, 1.0Eu 3+Up-conversion fluorescence spectrum,
Figure 798176DEST_PATH_IMAGE002
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
Figure 535187DEST_PATH_IMAGE001
Represent the normalization method 550nm Y of place 3O 2: 6Yb 3+, 0.3Ho 3+, 1.0Eu 3+, 6Li +Red up-conversion fluorescence spectrum,
Figure 120890DEST_PATH_IMAGE002
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.
CN201010207225A 2010-06-23 2010-06-23 Preparation method of single-green up-conversion fluorescent marking material Pending CN101838534A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201010207225A CN101838534A (en) 2010-06-23 2010-06-23 Preparation method of single-green up-conversion fluorescent marking material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201010207225A CN101838534A (en) 2010-06-23 2010-06-23 Preparation method of single-green up-conversion fluorescent marking material

Publications (1)

Publication Number Publication Date
CN101838534A true CN101838534A (en) 2010-09-22

Family

ID=42742213

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201010207225A Pending CN101838534A (en) 2010-06-23 2010-06-23 Preparation method of single-green up-conversion fluorescent marking material

Country Status (1)

Country Link
CN (1) CN101838534A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
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

Cited By (4)

* Cited by examiner, † Cited by third party
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

Similar Documents

Publication Publication Date Title
Wang et al. Pechini-type sol–gel synthesis and multicolor-tunable emission properties of GdY (MoO4) 3: RE3+ (RE= Eu, Dy, Sm, Tb) phosphors
CN102851027B (en) Green environment-friendly method for preparing BCNO fluorescent powder
CN103086394B (en) Preparation method of high-quantum-efficiency blue-light-emitting BCNO phosphor
CN101760198B (en) Gallate luminous material and preparation method thereof
CN102585828B (en) Yb3+-doped vanadate up-conversion fluorescent material and preparation method thereof
CN101838534A (en) Preparation method of single-green up-conversion fluorescent marking material
CN107365582A (en) Europium red fluorescence powder and preparation method thereof is mixed suitable for the molybdic acid alkali of white light LEDs
CN105018087B (en) Eu3+Adulterate laminated perovskite structure La2CuO4The preparation method of fluorescent powder
CN102703071A (en) Method for preparing lithium-based double tungstate/molybdate red phosphor
CN105462589A (en) Core-shell structured Fe3O4@GdVO4:Eu<3+> magnetic nanometer luminescent material and preparation method thereof
CN102268258A (en) Strontium aluminate based up-conversion luminescent material and preparation method thereof
CN103865533B (en) A kind of preparation method of rare earth oxide micron bar
CN103224794A (en) Near ultraviolet excitation type red phosphor and preparation method thereof
CN102942932B (en) Preparation method of rare earth doped fluoride nano dispersion liquid
CN102660286B (en) Vanadate up-conversion light-emitting material activated by erbium ions Er<3+> and preparation method thereof
CN102344807A (en) Solvothermal synthesis method for NaLn(MoO4)2 micron crystal
CN106010528B (en) Bismuth and manganese doped blue fluorescent powder and preparation method and application thereof
CN104830344B (en) A kind of Er3+,Yb3+The preparation method being co-doped with YOF redness upconverting fluorescent material
CN109180711A (en) A kind of organic boronic-rare earth-HPAs complex and preparation method thereof and the application in photo luminescent devices
CN103333689A (en) Method of thermosynthesis of SrWO4:Ln3<+> nanoribbon with solvent
CN103911154B (en) Micro nanocrystalline of a kind of single dispersing up-conversion luminescence and preparation method thereof
CN103113893B (en) A kind of Yb 3+boron tungstate up-conversion luminescent material activated and preparation method thereof
CN107794042B (en) Rare earth element Sm-doped phosphotungstate luminescent material and preparation method thereof
CN101586027A (en) Novel gadolinium gallate white light nanometer luminescent material activated by rare-earth ions
CN105419800A (en) Preparation method of yttrium phosphate vanadate europium-doped or samarium-doped luminescent microspheres

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20100922