CN105505374A - Up-conversion luminescence composite material based on dye sensitization and preparation method of up-conversion luminescence composite material - Google Patents
Up-conversion luminescence composite material based on dye sensitization and preparation method of up-conversion luminescence composite material Download PDFInfo
- Publication number
- CN105505374A CN105505374A CN201610069292.3A CN201610069292A CN105505374A CN 105505374 A CN105505374 A CN 105505374A CN 201610069292 A CN201610069292 A CN 201610069292A CN 105505374 A CN105505374 A CN 105505374A
- Authority
- CN
- China
- Prior art keywords
- conversion
- nano particle
- matrix material
- conversion luminescence
- dye
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/779—Halogenides
- C09K11/7791—Halogenides with alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses an up-conversion luminescence composite material based on dye sensitization and a preparation method of the up-conversion luminescence composite material. The up-conversion luminescence composite material based on dye sensitization comprises up-conversion nano-particles and dye molecules IR-806 according to a mass ratio of (50-2500):1, wherein the chemical formula of the up-conversion nano-particles is NaY0.78F4:Yb0.2, Er0.02@NaY0.9-x1F4:Yb0.1, Ndx1, wherein x1 is 0.1-0.9. The up-conversion luminescence composite material based on dye sensitization is prepared by mixing the up-conversion nano-particles and dye molecules IR-806. The dye molecules IR-806 and up-conversion nano-particles are compounded, the excitation wavelength is moved from 980nm to about 800nm by virtue of a synergistic effect of the dye molecules IR-806 and up-conversion nano-particles, and temperature rise of water caused by long time irradiation of 980nm exciting light is avoided. Moreover, by utilizing energy transfer between the dye molecules IR-806 and the up-conversion nano-particles, compared with the up-conversion nano-particles, the prepared up-conversion luminescence composite material has the advantage that the luminescent intensity is obviously enhanced.
Description
Technical field
The present invention relates to a kind of up-conversion luminescent material and preparation method thereof, particularly a kind of up-conversion luminescence matrix material based on dye sensitization and preparation method thereof.
Background technology
Compare with traditional luminescent material, up-conversion luminescent material can the lower near infrared light of absorb photons energy, sends the visible ray that photon energy is higher.Just based on this special optical property, up-conversion luminescent material has broad application prospects in fields such as biomedicine, solid-state laser, solar cell, stereo displays; Especially be applied in biological diagnosis and biotherapy, up-conversion luminescent material, compared to traditional luminescence probe material, has that chemical stability is good, toxicity is low, investigation depth is high, tissue injury is little, emission band is narrow and signal to noise ratio advantages of higher.
At biomedical sector, also there is certain restriction in the application of up-conversion luminescent material.Such as, the excitation wavelength of most of up-conversion luminescent material is positioned at 980nm, and the absorption peak of the lucky corresponding water of 980nm.Therefore, this will cause cell or tissue (water ratio is very high) under long laser radiation, and temperature raises rapidly, thus biological cells and tissues is destroyed.And up-conversion luminescent material is generally by rare earth ion (Er
3+, Ho
3+or Tm
3+) as luminescence center, but prohibit because rare earth ion exists 4f transition, cause the luminous intensity of up-conversion luminescent material generally on the low side.At present, the quantum yield of up-conversion luminescent material only has about 1%.Therefore, realize the change of the excitation wavelength of up-conversion luminescent material and the raising of its luminous intensity, the application for up-conversion luminescent material has very great meaning simultaneously.
Summary of the invention
Goal of the invention: the first object of the present invention is to provide a kind of up-conversion luminescence matrix material based on dye sensitization that can change excitation wavelength, improve luminous intensity, and the second object of the present invention is to provide the method for this up-conversion luminescence matrix material of preparation.
Technical scheme: a kind of up-conversion luminescence matrix material based on dye sensitization of the present invention, comprise upper conversion nano particle and dye molecule IR-806 that mass ratio is 50 ~ 2500:1, on this, the chemical expression of conversion nano particle is NaY
0.78f
4: Yb
0.2, Er
0.02naY
0.9-x1f
4: Yb
0.1, Nd
x1, wherein, x
1be 0.1 ~ 0.9.
The present invention is by carrying out compound by dye molecule IR-806 and upper conversion nano particle, the excitation wavelength of gained up-conversion luminescence matrix material moves to about 800nm, and, and single upper conversion nano Particle Phase ratio, up-conversion luminescence matrix material luminous intensity is obviously promoted.
Preferably, the mass ratio of upper conversion nano particle and dye molecule IR-806 is 200 ~ 600:1.Now, and single upper conversion nano Particle Phase ratio, the luminous intensity of up-conversion luminescence matrix material strengthens 5 ~ 18 times.
Further, x
1be 0.1 ~ 0.7.Now, with single upper conversion nano Particle Phase ratio, the luminous intensity of up-conversion luminescence matrix material strengthens 18 ~ 41 times.
The preparation method of a kind of up-conversion luminescence matrix material based on dye sensitization of the present invention, comprises the steps:
(1) modification is carried out to dye molecule IR-780, prepare dye molecule IR-806;
Dye molecule IR-780 is 2-[2-[the chloro-3-[(1 of 2-, 3-dihydro-3,3-dimethyl-1-propyl group-2H-indoles-2-subunit) ethylidene]-1-tetrahydrobenzene-1-base] vinyl]-3,3-dimethyl-1-propyl indole iodide, chemical formula is C
36h
44clIN
2.
(2) conversion nano particle NaY in preparation
0.78f
4: Yb
0.2, Er
0.02naY
0.9-x1f
4: Yb
0.1, Nd
x1;
(3) be that 50 ~ 2500:1 is dissolved in trichloromethane by obtained upper conversion nano particle and dye molecule IR-806 according to mass ratio, obtain the up-conversion luminescence matrix material based on dye sensitization.
Concrete, in step (1), the method preparing dye molecule IR-806 is:
A. IR-780 dye molecule is stoichiometrically taken and 4-Thiosalicylic acid is dissolved in DMF, under argon atmosphere, stirring at room temperature 12 ~ 15 hours;
B. above-mentioned mixing solutions is heated to 50 ~ 60 DEG C, removes DMF, remaining green colored residue is dissolved in methylene dichloride, use metre filter gained solution;
C. add ether sedimentation in solution after filtration, and use ether to clean 2 ~ 3 times, drying obtains golden crystal.
In above-mentioned steps (2), in preparation, the method for conversion nano particle comprises:
D. the lanthanon acetate taking Y, Yb and Er by chemical constitution and stoichiometric ratio is dissolved in the mixing solutions of oleic acid and octadecylene, is heated to 110 ~ 150 DEG C and stirs the mixing solutions that 30 ~ 40min form clear homogeneous;
E. above-mentioned mixing solutions is cooled to 50 ~ 60 DEG C, adds wherein and be dissolved with NH
4the methanol solution of F and NaOH, stirs 30 ~ 50min, wherein, and NH
4the mol ratio of F, NaOH and lanthanon acetate is respectively 4:1 and 2.5:1;
F. the methyl alcohol in removing step E gained solution, raises solution temperature to 300 ~ 310 DEG C reaction 90 ~ 120min, is cooled to room temperature subsequently;
G. the lanthanon acetate taking Y, Yb and Nd by chemical constitution and stoichiometric ratio is dissolved in the mixing solutions of oleic acid and octadecylene, is heated to 110 ~ 150 DEG C and stirs the mixing solutions that 30 ~ 40min form clear homogeneous;
H. above-mentioned mixing solutions is cooled to 50 ~ 60 DEG C, first adds step F gained solution wherein, then add wherein and be dissolved with NH
4the methanol solution of F and NaOH, stirs 30 ~ 50min, wherein, and NH
4the mol ratio of F and NaOH and lanthanon acetate is respectively 4:1 and 2.5:1;
I. the methyl alcohol in removing step H gained solution, raises solution temperature to 300 ~ 310 DEG C reaction 90 ~ 120min, is cooled to room temperature subsequently, eccentric cleaning, obtains conversion nano particle.
Inventive principle: traditional upper conversion nano particle excitation optical wavelength is positioned at 980nm, and traditionally conversion nano particle outer cladding one deck contains Nd
3+shell after, just can utilize Nd
3+absorption peak at the feature of 800nm and Nd
3+with Yb
3+between transmission ofenergy, excitation wavelength is moved to about 800nm.Under 800nm excites, there is a wider emission peak at 800 ~ 900nm in IR-806 dye molecule, and Nd
3+an absorption peak is there is respectively at about 800nm and 850nm; Therefore, utilize dye molecule emission peak and the peak-to-peak overlap of upper conversion nano particulate absorbent, the transmission ofenergy of the two can be realized.Meanwhile, dye molecule is very high to the specific absorption of light, therefore by after itself and upper conversion nano Particles dispersed, by transmission ofenergy therebetween, can improve upper conversion nano particle to the absorption of light, thus improve its luminous intensity.
Beneficial effect: compared with prior art, remarkable advantage of the present invention is: dye molecule IR-806 and upper conversion nano particle are carried out compound by (1) the present invention, utilize the transmission ofenergy between dye molecule IR-806 and upper conversion nano particle, the upper conversion nano particle that the luminous intensity of gained up-conversion luminescence matrix material is more single significantly strengthens; And, by the synergy of dye molecule IR-806 and upper conversion nano particle, successfully achieve and the excitation wavelength of up-conversion luminescence matrix material is moved to about 800nm by 980nm, avoid the temperature rise that 980nm exciting light irradiates the water caused for a long time; (2) by regulating the content of Nd in upper conversion nano particle or regulating the mass ratio of dye molecule and upper conversion nano particle, the luminous intensity of up-conversion luminescence matrix material can obtain enhancing in various degree, and luminous intensity is the highest strengthens 41 times for it.
Accompanying drawing explanation
Fig. 1 is the mass ratio of upper conversion nano particle and dye molecule IR-806 is 200:1, and x
1the Up-conversion emission spectrum of the up-conversion luminescence matrix material obtained when being 0.1;
Fig. 2 is the mass ratio of upper conversion nano particle and dye molecule IR-806 is 400:1, and x
1the Up-conversion emission spectrum of the up-conversion luminescence matrix material obtained when being 0.1;
Fig. 3 is the mass ratio of upper conversion nano particle and dye molecule IR-806 is 600:1, and x
1the Up-conversion emission spectrum of the up-conversion luminescence matrix material obtained when being 0.1;
Fig. 4 is the mass ratio of upper conversion nano particle and dye molecule IR-806 is 50:1, and x
1the Up-conversion emission spectrum of the up-conversion luminescence matrix material obtained when being 0.1;
Fig. 5 is the mass ratio of upper conversion nano particle and dye molecule IR-806 is 2500:1, and x
1the Up-conversion emission spectrum of the up-conversion luminescence matrix material obtained when being 0.1;
Fig. 6 is the mass ratio of upper conversion nano particle and dye molecule IR-806 is 4000:1, and x
1the Up-conversion emission spectrum of the up-conversion luminescence matrix material obtained when being 0.1;
Fig. 7 is the mass ratio of upper conversion nano particle and dye molecule IR-806 is 10:1, and x
1the Up-conversion emission spectrum of the up-conversion luminescence matrix material obtained when being 0.1;
Fig. 8 is the mass ratio of upper conversion nano particle and dye molecule IR-806 is 200:1, and x
1the Up-conversion emission spectrum of the up-conversion luminescence matrix material obtained when being 0.3;
Fig. 9 is the mass ratio of upper conversion nano particle and dye molecule IR-806 is 200:1, and x
1the Up-conversion emission spectrum of the up-conversion luminescence matrix material obtained when being 0.5;
Figure 10 is the mass ratio of upper conversion nano particle and dye molecule IR-806 is 200:1, and x
1the Up-conversion emission spectrum of the up-conversion luminescence matrix material obtained when being 0.7;
Figure 11 is the mass ratio of upper conversion nano particle and dye molecule IR-806 is 200:1, and x
1be the Up-conversion emission spectrum of the up-conversion luminescence matrix material that 0.9 obtains;
Figure 12 is the mass ratio of upper conversion nano particle and dye molecule IR-806 is 200:1, and x
1be the Up-conversion emission spectrum of the up-conversion luminescence matrix material that 0 obtains.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is described further.
Embodiment 1
(1) dye molecule IR-806 is prepared
A. 100mgIR-780 dye molecule is taken and 46.2mg4-Thiosalicylic acid is dissolved in 10mlN, in dinethylformamide, dye molecule IR-780 is 2-[2-[the chloro-3-[(1 of 2-, 3-dihydro-3,3-dimethyl-1-propyl group-2H-indoles-2-subunit) ethylidene]-1-tetrahydrobenzene-1-base] vinyl]-3,3-dimethyl-1-propyl indole iodide, chemical formula is C
36h
44clIN
2; Under argon atmosphere, stirring at room temperature 12 hours;
B. gained mixing solutions is heated to 50 DEG C, remove DMF, remaining green colored residue is dissolved in q. s. methylene chloride, uses metre filter gained solution;
C. slowly add ether sedimentation in solution after filtration, and use ether to clean 2 times, dry and obtain golden crystal.
(2) conversion nano particle in preparation
D. 0.02mmolEr (CH is taken
3cOO)
3, 0.2mmolYb (CH
3cOO)
3, 0.78mmolY (CH
3cOO)
3with 6ml oleic acid, the mixed solvent mixing of 15ml1-octadecylene, stirs under vacuum and is heated to 110 DEG C, and insulation 40min, obtains the rare-earth ion solution of clear;
E. then pass into argon gas, under argon atmosphere, be cooled to 50 DEG C, will containing 2.5mmolNaOH and 4mmolNH
4the methanol solution of F adds in above-mentioned rare-earth ion solution, passes into argon gas, under 50 DEG C of conditions, stir 30min;
F. then gained mixing solutions is warming up to 70 DEG C, pumps methyl alcohol wherein, then be rapidly heated to 310 DEG C and be incubated 90min; After insulating process terminates, solution is cooled to 90 DEG C, adds ethanol in proper amount eccentric cleaning, obtain the upper conversion nano particle that diameter is about 24nm, by this Granular composite in solvent hexane;
G. 0.1mmolNd (CH is taken
3cOO)
3, 0.1mmolYb (CH
3cOO)
3, 0.8mmolY (CH
3cOO)
3mix with the mixed solvent of 6ml oleic acid and 15ml1-octadecylene, stir under vacuum and be heated to 110 DEG C, insulation 40min, obtains the rare-earth ion solution of clear;
H. pass into argon gas, under argon atmosphere, rare-earth ion solution is cooled to 50 DEG C, will containing 2.5mmolNaOH and 4mmolNH
4the NaYF be scattered in normal hexane prepared by the methanol solution of F and 1mmol step e
4: Yb, Er upper conversion nano particle adds in above-mentioned rare-earth ion solution, passes into argon gas, under 50 DEG C of conditions, stirs 30min;
I. then gained mixing solutions is warming up to 70 DEG C, pumps methyl alcohol wherein and normal hexane, then be rapidly heated to 310 DEG C and be incubated 90min; After insulating process terminates, solution is cooled to 90 DEG C, adds ethanol in proper amount eccentric cleaning, obtain the upper conversion nano particle that a diameter is about 32nm.
(3) configuration concentration is the upper conversion nano particle solution of 2mg/ml, adds IR-806 dye molecule wherein, and the mass ratio making conversion nano particle and dye molecule is 200:1, at room temperature stirs 1 ~ 2h, obtains up-conversion luminescence matrix material.
Embodiment 2
(1) dye molecule IR-806 is prepared
A. 100mgIR-780 dye molecule is taken and 46.2mg4-Thiosalicylic acid is dissolved in 10mlN, in dinethylformamide, dye molecule IR-780 is 2-[2-[the chloro-3-[(1 of 2-, 3-dihydro-3,3-dimethyl-1-propyl group-2H-indoles-2-subunit) ethylidene]-1-tetrahydrobenzene-1-base] vinyl]-3,3-dimethyl-1-propyl indole iodide, chemical formula is C
36h
44clIN
2; Under argon atmosphere, stirring at room temperature 15 hours;
B. gained mixing solutions is heated to 60 DEG C, remove DMF, remaining green colored residue is dissolved in q. s. methylene chloride, uses metre filter gained solution;
C. slowly add ether sedimentation in solution after filtration, and use ether to clean 3 times, dry and obtain golden crystal.
(2) conversion nano particle in preparation
D. 0.02mmolEr (CH is taken
3cOO)
3, 0.2mmolYb (CH
3cOO)
3, 0.78mmolY (CH
3cOO)
3with 6ml oleic acid, the mixed solvent mixing of 15ml1-octadecylene, stirs under vacuum and is heated to 150 DEG C, and insulation 30min, obtains the rare-earth ion solution of clear;
E. then pass into argon gas, under argon atmosphere, be cooled to 60 DEG C, will containing 2.5mmolNaOH and 4mmolNH
4the methanol solution of F adds in above-mentioned rare-earth ion solution, passes into argon gas, under 60 DEG C of conditions, stir 50min;
F. then gained mixing solutions is warming up to 70 DEG C, pumps methyl alcohol wherein, then be rapidly heated to 300 DEG C and be incubated 120min; After insulating process terminates, solution is cooled to 90 DEG C, adds ethanol in proper amount eccentric cleaning, obtain the upper conversion nano particle that diameter is about 24nm, by this Granular composite in solvent hexane;
G. 0.1mmolNd (CH is taken
3cOO)
3, 0.1mmolYb (CH
3cOO)
3, 0.8mmolY (CH
3cOO)
3mix with the mixed solvent of 6ml oleic acid and 15ml1-octadecylene, stir under vacuum and be heated to 150 DEG C, insulation 30min, obtains the rare-earth ion solution of clear;
H. pass into argon gas, under argon atmosphere, rare-earth ion solution is cooled to 60 DEG C, will containing 2.5mmolNaOH and 4mmolNH
4the NaYF be scattered in normal hexane prepared by the methanol solution of F and 1mmol step F
4: Yb, Er upper conversion nano particle adds in above-mentioned rare-earth ion solution, passes into argon gas, under 60 DEG C of conditions, stirs 50min;
I. then gained mixing solutions is warming up to 70 DEG C, pumps methyl alcohol wherein and normal hexane, then be rapidly heated to 300 DEG C and be incubated 120min; After insulating process terminates, solution is cooled to 90 DEG C, adds ethanol in proper amount eccentric cleaning, obtain the upper conversion nano particle that a diameter is about 32nm.
(3) configuration concentration is the upper conversion nano particle solution of 2mg/ml, adds IR-806 dye molecule wherein, and the mass ratio making conversion nano particle and dye molecule is 200:1, at room temperature stirs 1 ~ 2h, obtains up-conversion luminescence matrix material.
Embodiment 3
7 groups of parallel laboratory tests are set, method with reference to embodiment 1 prepares up-conversion luminescence matrix material, wherein, in step (3), the mass ratio of upper conversion nano particle and dye molecule IR-806 is respectively 200:1,400:1,600:1,50:1,2500:1,4000:1,10:1, and the Up-conversion emission spectrum of obtained up-conversion luminescence matrix material is as Fig. 1 ~ Fig. 7.
As shown in Fig. 1 ~ Fig. 7, by a certain amount of IR-806 dye molecule of compound in upper conversion nano particle, the luminescence enhancement of up-conversion luminescence matrix material can be realized; By regulating the mass ratio adding upper conversion nano particle and IR-806 dye molecule, the luminous intensity of up-conversion luminescence matrix material can be strengthened to some extent.
Concrete, under the irradiation of 800nm exciting light, when the mass ratio of upper conversion nano particle and IR-806 dye molecule is for being less than 50:1, because dye molecule content is higher, major part incident light absorb by dye molecule, cannot produce effective transmission ofenergy, the luminous intensity of the more single upper conversion nano particle of luminous intensity of obtained up-conversion luminescence matrix material promotes and not quite even produces decline; When both mass ratioes are 50 ~ 2500:1, the upper conversion nano particle that the luminous intensity of up-conversion luminescence matrix material is more single, has obvious enhancing; Wherein, when both mass ratioes are 200 ~ 600:1, the luminous intensity of gained up-conversion luminescence matrix material significantly strengthens, and is 5 ~ 18 times of single upper conversion nano particle; When both mass ratioes are 200:1, the luminous intensity of up-conversion luminescence matrix material reaches the highest, comparatively goes up the enhancing 18 times of conversion nano particle.And when the mass ratio of upper conversion nano particle and IR-806 dye molecule is more than 2500:1, along with the amount of IR-806 dye molecule reduces gradually, the transmission ofenergy produced reduces thereupon, the luminous intensity of up-conversion luminescence matrix material is weakened gradually, close with upper conversion nano particle.
Embodiment 4
Arrange 6 groups of parallel laboratory tests, the method with reference to embodiment 1 prepares up-conversion luminescence matrix material, and wherein, the content of the neodymium added in step G is as follows:
1st group, take 0.1mmolNd (CH
3cOO)
3, 0.1mmolYb (CH
3cOO)
3, 0.7mmolY (CH
3cOO)
3;
2nd group: take 0.3mmolNd (CH
3cOO)
3, 0.1mmolYb (CH
3cOO)
3, 0.6mmolY (CH
3cOO)
3;
3rd group: take 0.5mmolNd (CH
3cOO)
3, 0.1mmolYb (CH
3cOO)
3, 0.4mmolY (CH
3cOO)
3;
4th group: take 0.7mmolNd (CH
3cOO)
3, 0.1mmolYb (CH
3cOO)
3, 0.2mmolY (CH
3cOO)
3;
5th group: take 0.9mmolNd (CH
3cOO)
3, 0.1mmolYb (CH
3cOO)
3;
6th group: take 0.1mmolYb (CH
3cOO)
3, 0.9mmolY (CH
3cOO)
3.
As shown in Fig. 1, Fig. 8 ~ 12, as Nd in upper conversion nano particle
3+content when being 0.1 ~ 0.9, compound IR-806 dye molecule in upper conversion nano particle, on gained, the luminous intensity of conversion nano compound material is all significantly increased; And work as Nd
3+when content is less than 0.1, although prepared up-conversion luminescence matrix material also can be luminous, luminous intensity is very weak, lower than single upper conversion nano particle.Meanwhile, Nd in upper conversion nano particle is added by regulating
3+content, the luminous intensity of up-conversion luminescence matrix material can be strengthened to some extent; Concrete, work as Nd
3+when content is 0.1 ~ 0.7, the luminous intensity of gained up-conversion luminescence matrix material strengthens the most remarkable, is 18 ~ 41 times of single upper conversion nano particle; Wherein, Nd is worked as
3+when content is 0.5, luminescence enhancement effect is best, can reach 41 times.
Claims (6)
1. based on a up-conversion luminescence matrix material for dye sensitization, it is characterized in that, comprise upper conversion nano particle and dye molecule IR-806 that mass ratio is 50 ~ 2500:1, on this, the chemical expression of conversion nano particle is NaY
0.78f
4: Yb
0.2, Er
0.02naY
0.9-x1f
4: Yb
0.1, Nd
x1, wherein, x
1be 0.1 ~ 0.9.
2. the up-conversion luminescence matrix material based on dye sensitization according to claim 1, is characterized in that, the mass ratio of described upper conversion nano particle and dye molecule IR-806 is 200 ~ 600:1.
3. the up-conversion luminescence matrix material based on dye sensitization according to claim 1, is characterized in that, described x
1be 0.1 ~ 0.7.
4. described in claim 1 based on a preparation method for the up-conversion luminescence matrix material of dye sensitization, it is characterized in that, comprise the steps:
(1) modification is carried out to dye molecule IR-780, prepare dye molecule IR-806;
(2) conversion nano particle NaY in preparation
0.78f
4: Yb
0.2, Er
0.02naY
0.9-x1f
4: Yb
0.1, Nd
x1;
(3) be that 50 ~ 2500:1 is dissolved in trichloromethane by obtained upper conversion nano particle and dye molecule IR-806 according to mass ratio, obtain the up-conversion luminescence matrix material based on dye sensitization.
5. the preparation method of the up-conversion luminescence matrix material based on dye sensitization according to claim 4, is characterized in that, in step (1), the method preparing dye molecule IR-806 is:
A. IR-780 dye molecule is stoichiometrically taken and 4-Thiosalicylic acid is dissolved in DMF, under argon atmosphere, stirring at room temperature 12 ~ 15 hours;
B. above-mentioned mixing solutions is heated to 50 ~ 60 DEG C, removes DMF, remaining green colored residue is dissolved in methylene dichloride, use metre filter gained solution;
C. add ether sedimentation in solution after filtration, and use ether to clean 2 ~ 3 times, drying obtains golden crystal.
6. the preparation method of the up-conversion luminescence matrix material based on dye sensitization according to claim 4, is characterized in that, in step (2), in preparation, the method for conversion nano particle comprises:
D. the lanthanon acetate taking Y, Yb and Er by chemical constitution and stoichiometric ratio is dissolved in the mixing solutions of oleic acid and octadecylene, is heated to 110 ~ 150 DEG C and stirs the mixing solutions that 30 ~ 40min form clear homogeneous;
E. above-mentioned mixing solutions is cooled to 50 ~ 60 DEG C, adds wherein and be dissolved with NH
4the methanol solution of F and NaOH, stirs 30 ~ 50min, wherein, and NH
4the mol ratio of F, NaOH and lanthanon acetate is respectively 4:1 and 2.5:1;
F. the methyl alcohol in removing step E gained solution, raises solution temperature to 300 ~ 310 DEG C reaction 90 ~ 120min, is cooled to room temperature subsequently;
G. the lanthanon acetate taking Y, Yb and Nd by chemical constitution and stoichiometric ratio is dissolved in the mixing solutions of oleic acid and octadecylene, is heated to 110 ~ 150 DEG C and stirs the mixing solutions that 30 ~ 40min form clear homogeneous;
H. above-mentioned mixing solutions is cooled to 50 ~ 60 DEG C, first adds step F gained solution wherein, then add wherein and be dissolved with NH
4the methanol solution of F and NaOH, stirs 30 ~ 50min, wherein, and NH
4the mol ratio of F and NaOH and lanthanon acetate is respectively 4:1 and 2.5:1;
I. the methyl alcohol in removing step H gained solution, raises solution temperature to 300 ~ 310 DEG C reaction 90 ~ 120min, is cooled to room temperature subsequently, eccentric cleaning, obtains up-conversion luminescence nano particle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610069292.3A CN105505374B (en) | 2016-02-01 | 2016-02-01 | A kind of up-conversion luminescence composite material based on dye sensitization and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610069292.3A CN105505374B (en) | 2016-02-01 | 2016-02-01 | A kind of up-conversion luminescence composite material based on dye sensitization and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105505374A true CN105505374A (en) | 2016-04-20 |
| CN105505374B CN105505374B (en) | 2018-06-19 |
Family
ID=55713684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610069292.3A Active CN105505374B (en) | 2016-02-01 | 2016-02-01 | A kind of up-conversion luminescence composite material based on dye sensitization and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105505374B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106867509A (en) * | 2017-03-08 | 2017-06-20 | 杭州电子科技大学 | A kind of Nd3+Conversion nano crystalline substance material and preparation method thereof and water detect application on sensitization nucleocapsid |
| CN109735325A (en) * | 2019-02-28 | 2019-05-10 | 湖北大学 | A kind of composite material using quantum dot enhancing up-conversion luminescence |
| CN110184063A (en) * | 2019-05-30 | 2019-08-30 | 西北大学 | A kind of rare earth luminescent material and the preparation method and application thereof |
| US11066598B2 (en) * | 2018-09-07 | 2021-07-20 | Korea Institute Of Science And Technology | Dye-sensitized upconversion nanophosphor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130287703A1 (en) * | 2012-04-27 | 2013-10-31 | Korea Institute Of Science And Technology | Core/shell multifunctional magnetic nanophosphor having core/shell structure and synthetic method thereof |
| CN103865538A (en) * | 2014-02-23 | 2014-06-18 | 复旦大学 | Up/down conversion dual-mode fluorescent nanomaterial for Nd<3+> sensitization and synthesis method thereof |
-
2016
- 2016-02-01 CN CN201610069292.3A patent/CN105505374B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130287703A1 (en) * | 2012-04-27 | 2013-10-31 | Korea Institute Of Science And Technology | Core/shell multifunctional magnetic nanophosphor having core/shell structure and synthetic method thereof |
| CN103865538A (en) * | 2014-02-23 | 2014-06-18 | 复旦大学 | Up/down conversion dual-mode fluorescent nanomaterial for Nd<3+> sensitization and synthesis method thereof |
Non-Patent Citations (2)
| Title |
|---|
| L. MARCINIAK等: "A broadening temperature sensitivity range with a core–shell YbEr@YbNd double ratiometric optical nanothermometer", 《NANOSCALE》 * |
| 王丹: "808 nm激发的上转换纳米粒子的合成及生物应用", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106867509A (en) * | 2017-03-08 | 2017-06-20 | 杭州电子科技大学 | A kind of Nd3+Conversion nano crystalline substance material and preparation method thereof and water detect application on sensitization nucleocapsid |
| US11066598B2 (en) * | 2018-09-07 | 2021-07-20 | Korea Institute Of Science And Technology | Dye-sensitized upconversion nanophosphor |
| CN109735325A (en) * | 2019-02-28 | 2019-05-10 | 湖北大学 | A kind of composite material using quantum dot enhancing up-conversion luminescence |
| CN109735325B (en) * | 2019-02-28 | 2021-12-28 | 湖北大学 | Composite material for enhancing up-conversion luminescence by using quantum dots |
| CN110184063A (en) * | 2019-05-30 | 2019-08-30 | 西北大学 | A kind of rare earth luminescent material and the preparation method and application thereof |
| CN110184063B (en) * | 2019-05-30 | 2021-09-07 | 西北大学 | Rare earth luminescent material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105505374B (en) | 2018-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103450875B (en) | 800-nanometer continuous laser excited rare earth upconversion nanoparticles (UCNPs), and preparation method and application thereof | |
| CN105505374A (en) | Up-conversion luminescence composite material based on dye sensitization and preparation method of up-conversion luminescence composite material | |
| CN107739603A (en) | Conversion nano particle and preparation method thereof on a kind of red green luminescence rare earth of exciting light regulation and control | |
| US20150238638A1 (en) | Coated up-conversion nanoparticles | |
| CN103254495B (en) | Nano silver fluorescence enhanced rare earth oxide nano crystal composite EVA (Ethylene Vinyl Acetate) adhesive film and preparation method thereof | |
| CN103865538A (en) | Up/down conversion dual-mode fluorescent nanomaterial for Nd<3+> sensitization and synthesis method thereof | |
| CN102517019B (en) | Method for improving photoluminescence efficiency of upconversion material | |
| CN110878207A (en) | Up-conversion nanometer optical switch material and preparation method thereof | |
| CN111303879B (en) | Efficient single-spectrum band-up-conversion red light nanocrystalline material | |
| Lee et al. | Origin of strong red emission in Er 3+-based upconversion materials: role of intermediate states and cross relaxation | |
| CN104083777A (en) | Upconversion composite nano-material as well as preparation method and application thereof | |
| CN105713612A (en) | Up-conversion fluorescent powder with substantially increased red-green ratio and preparation method of up-conversion fluorescent powder with substantially increased red-green ratio | |
| CN112940726A (en) | Blue-violet and near-infrared two-region dual-mode luminescent nanocrystal and preparation method thereof | |
| CN105368444B (en) | Converting system on a kind of efficient green dim light based on protonic solvent | |
| CN105670628A (en) | Up-conversion fluorescent powder with greatly improved red light and excellent monochromaticity and method for preparing up-conversion fluorescent powder | |
| CN104388088B (en) | Conversion nano granule and preparation method thereof on the water solublity of a kind of Fluorescence Increasing | |
| CN103666474A (en) | Red light/near-infrared light double-color up-conversion luminescence nanomaterial and preparation method thereof | |
| CN107286197B (en) | A kind of complex of iridium and its preparation method and application with phosphorescence ion-pair structure | |
| CN104232091A (en) | Up-conversion nano-material NaYbF4: Tm and preparation method thereof | |
| Ye et al. | Pure red visible emission via three-photon excitation of colloidal Na 3 ZrF 7: Er nanoparticles using a telecom-band laser | |
| CN104031635A (en) | Preparation method of rare earth complex functionalized up/down-conversion luminescent nano mesoporous material and bioimaging application thereof | |
| CN101899038B (en) | Near-infrared light emitting ionic complex and preparation method thereof | |
| CN102604391A (en) | Preparation method of silicone rubber composite material with fluorescence | |
| CN103450884A (en) | Luminous xerogel grafted with rare earth/diketone derivatives and preparation method thereof | |
| CN103007295A (en) | Medical imaging material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |