CN110144219A - A kind of nanoscale alkaline earth scandium oxide up-conversion luminescent material and preparation method thereof - Google Patents
A kind of nanoscale alkaline earth scandium oxide up-conversion luminescent material and preparation method thereof Download PDFInfo
- Publication number
- CN110144219A CN110144219A CN201910552788.XA CN201910552788A CN110144219A CN 110144219 A CN110144219 A CN 110144219A CN 201910552788 A CN201910552788 A CN 201910552788A CN 110144219 A CN110144219 A CN 110144219A
- Authority
- CN
- China
- Prior art keywords
- luminescent material
- conversion luminescent
- alkaline earth
- scandium oxide
- preparation
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Biophysics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention relates to a kind of nanoscale alkaline earth scandium oxide up-conversion luminescent material and preparation method thereof, the technical issues of alkaline earth scandium oxide up-conversion luminescent material preparation temperature is high, size is big and bad dispersibility is solved in the prior art.Nanoscale alkaline earth scandium oxide up-conversion luminescent material of the invention, the compound with following below formula: MSc2(1‑x‑y)O4:N3+ 2x,Yb3+ 2y；Wherein, one of M Mg, Sr, Ba；N is one of Er, Ho, Tm；X, y are element molar fraction, value range are as follows: 0.0001≤x≤0.10,0.0001≤y≤0.20.Up-conversion luminescent material of the invention is the light activated nanoscale luminescent material of near-infrared, and compared with the scandium oxide-base up-conversion luminescent material of conventional method preparation, particle is small, morphological rules, good dispersion.The preparation method of up-conversion luminescent material provided by the invention, is the method combined using hydro-thermal and annealing, and this method has many advantages, such as that controllability is good, reaction temperature is low, low for equipment requirements, no pollution to the environment.
Description
Technical field
The invention belongs to luminescent material technical fields, and in particular to a kind of light activated nanoscale alkaline earth scandium oxidation of near-infrared
Object up-conversion luminescent material and preparation method thereof.
Background technique
Up-conversion luminescence is a kind of unique nonlinear optical phenomena, refers to that material absorbs the lower photon of energy and can but send out
The material of higher-energy photon out.Due to its potential application value, not only in basic scientific research field over nearly ten or twenty year,
And in application aspects such as bio-imaging, fluorescence probe, device for non-linear optical, luminescent device, solar battery, photocatalysis,
Cause the especially concern of numerous scientific research personnel.
Compared with conventional fluorescent probe (organic dyestuff and quantum dot etc.), rear-earth-doped up-conversion luminescence nanomaterial tool
Have the advantages that chemical stability is good, illuminant colour is with high purity, toxicity is low and Stokes displacement is big.Meanwhile long wave-near infrared light
Under (800-1300nm) shooting condition, penetration depth is more ultraviolet, visible light has greater advantage, can dissipate to avoid biological sample light
It penetrates and the interference of autofluorescence, so that making to detect background reduces, signal-to-noise ratio is improved.But up-conversion luminescence is multi-photon mistake
The absorption cross section of journey, centre of luminescence rare earth ion is small, is abstinence f-f electric dipole transition and nanocrystal surface in the presence of a large amount of sudden
The latent defects such as center of going out cause up-conversion luminescence efficiency low-intensity weak, constrain the practical application of such material.It is desirable to
By preferred substrate, the methods of ion co-doped raising fluorescence intensity.
Rare earth up-conversion luminescent material can be divided into fluoride, oxide, oxyhalide and sulphur according to the difference of matrix components
Compound etc..In these host materials, with Na (Y, Lu) F4Fluoride for representative is the highest base of transfer efficiency generally acknowledged at present
Material.Fluoride has lower phonon energy, can reduce the damage of the radiationless transition energy as caused by multi-photon relaxation
It loses, so as to cause higher up-conversion luminescence efficiency.But its poor chemical stability, manufacturing conditions are harsh, not easy to control, difficult
The disadvantages of to integrate, is also very prominent, to limit its application to a certain extent.Compared with fluoride, although oxide
Phonon energy is slightly higher, but its preparation process is simple, and environmental condition requires lower, the solubility height of rare earth ion, mechanical strength
It is good with chemical stability.Therefore, from matrix stability, people are more likely to seek to convert material on efficient oxide
Material.
Scandium (Sc) element is located at the top third subgroup (IIIB), is ranked near preceding transition metal element, atomic number
Only 21, so that Sc3+With other rare earth ions (such as Y3+And Lu3+Ion) compared to distinguished physicochemical characteristics.
Sc does not have 4f layers of electronics, while having the smallest radius, therefore Sc3+Ion is easy to enter among the lattice of crystal.Upper conversion hair
Light is highly dependent on crystal field environment and the distance between donor and acceptor ions, and research is found: Sc3+The upper conversion of based compound is sent out
Light property is typically superior to the compound of other rare earth ions composition.Such as: in fluoride system, Na (Y, Lu) F4:Er3+/Yb3+
Up-conversion luminescence efficiency highest, but shine based on green.The study groups such as Zhang Hongjie, Huang Ling, Chen Xueyuan find that scandium base is fluorinated
Object NaxScF4、6:Er3+/Yb3+In up-conversion luminescence based on red, and hexagonal phase NaScF4:Er3+/Yb3+It is red green than high
Up to 13:1, there is the nanocrystalline material of enhancing red emission can more perfectly be applied to inside and outside bio-imaging field.
But the usual melt temperature of oxide is very high, 2000 DEG C or so, it is previously reported in, scandium base oxide generallys use
High temperature solid-state method preparation.The oxide luminescent material of high temperature preparation is the aggregate of a large amount of spherical particles, size is big, dispersibility very
Difference, cluster cause ion concentration distribution uneven, influence the raising of luminous efficiency.
Summary of the invention
The present invention is that alkaline earth scandium oxide up-conversion luminescent material preparation temperature is high in the prior art, size is big and divides for solution
The technical problem for dissipating property difference, provides that a kind of morphological rules, good dispersion, size be smaller, the good nanoscale alkaline earth of luminescent properties
Scandium oxide up-conversion luminescent material and preparation method thereof.
In order to solve the above-mentioned technical problem, technical solution of the present invention is specific as follows:
The present invention provides a kind of nanoscale alkaline earth scandium oxide up-conversion luminescent material, the chemical combination with following below formula
Object: MSc2(1-x-y)O4:N3+ 2x,Yb3+ 2y；
Wherein, one of M Mg, Sr, Ba；N is one of Er, Ho, Tm；X, y are element molar fraction, value
Range are as follows: 0.0001≤x≤0.10,0.0001≤y≤0.20.
In the above-mentioned technical solutions,
When M is Mg, the up-conversion luminescent material is the near-spherical of morphological rules；
When M is Sr, the up-conversion luminescent material is that the length of morphological rules is rodlike；
When M is Ba, the up-conversion luminescent material is the corynebacterium of morphological rules.
In the above-mentioned technical solutions,
The up-conversion luminescent material chemical formula is MgSc1.88O4:Er3+ 0.02,Yb3+ 0.1, it is the class ball of morphological rules
Shape, diameter are 25~30nm；
The up-conversion luminescent material chemical formula is SrSc1.88O4:Er3+ 0.02,Yb3+ 0.1, it is the long stick of morphological rules
Shape is highly 420~450nm, and width is 40~60nm；
The up-conversion luminescent material chemical formula is BaSc1.88O4:Er 3+ 0.02,Yb3+ 0.1, it is the stub of morphological rules
Shape is highly 80~100nm, and width is 30~50nm.
In the above-mentioned technical solutions, the up-conversion luminescent material is rhombic system, has CaFe2O4The alkaline earth scandium of structure
Oxide.
The present invention also provides a kind of preparation methods of nanoscale alkaline earth scandium oxide up-conversion luminescent material, including following step
It is rapid:
(1) expression formula MSc is pressed2(1-x-y)O4:N3+ 2x,Yb3+ 2y, one of M Mg, Sr, Ba；N is one in Er, Ho, Tm
Kind；X, y are element molar fraction, value range are as follows: 0.0001≤x≤0.10,0.0001≤y≤0.20, in each substance
Stoichiometric ratio measures Sc (NO respectively3)3, Yb (NO3)3And Er (NO3)3、Ho(NO3)3、Tm3(NO)3One of and Mg
(NO3)2、Sr(NO3)2、Ba(NO3)2One of be put in beaker, be added dehydrated alcohol, be sufficiently stirred using magnetic stirring apparatus,
Uniform mixed solution is obtained, then proceedes to stir；
(2) pH for the mixed solution prepared with alkaline aqueous solution regulating step (1) is 11~13, and stirring obtains suspension；
(3) suspension that step (2) obtains is placed in hydrothermal reaction kettle, the isothermal reaction 12 in 160~190 DEG C of baking ovens
~48 hours；Sediment in reaction kettle is centrifuged and is taken out, cleaning, drying obtain reactant presoma precipitating；
(4) precipitating of reactant presoma obtained in step (3) is put into corundum crucible and is covered, is placed in high temperature furnace,
It is roasted, maturing temperature is 600~800 DEG C, and calcining time is 1~3 hour, takes out grinding and obtains final product nanoscale alkali
Native scandium oxide up-conversion luminescent material.
In the above-mentioned technical solutions, alkaline aqueous solution used in step (2) is sodium hydroxide, potassium hydroxide, hydroxide
One of lithium aqueous solution.
In the above-mentioned technical solutions, specific as follows the step of cleaning, drying in step (3):
Sediment is first used deionized water eccentric cleaning 3~5 times, then with dehydrated alcohol eccentric cleaning 3~5 times, placed into
In baking oven, in 60~90 DEG C freeze-day with constant temperature 8~15 hours.
In the above-mentioned technical solutions, the temperature of hydro-thermal reaction is 180 DEG C in step (3), and the time is 24 hours.
In the above-mentioned technical solutions, maturing temperature is 600 DEG C in step (4), and the time is 2 hours.
The beneficial effects of the present invention are:
A kind of nanoscale alkaline earth scandium oxide up-conversion luminescent material provided by the invention is the light activated nanometer of near-infrared
The luminescent material of grade, compared with the scandium oxide-base up-conversion luminescent material of conventional method preparation, particle is small, morphological rules, divides
It is good to dissipate property.The transmission electron microscope photo of the sample prepared such as embodiment 1,2,3 is it is found that wherein MgSc1.88O4:Er3+ 0.02,Yb3+ 0.1Sample
Product pattern is near-spherical, a diameter of 25~30nm；SrSc1.88O4:Er3+ 0.02,Yb3+ 0.1Sample topography is long rodlike, height
For 420~450nm, width is 40~60nm；BaSc1.88O4:Er3+ 0.02,Yb3+ 0.1Sample topography is corynebacterium, height 80
~100nm, width are 30~50nm.
Up-conversion luminescent material prepared by the present invention, 980nm wavelength it is infrared ray excited under bright 400 can be observed
The visible light of~850nm.Compared with using the scandium oxide-base up-conversion luminescent material of conventional high-temperature solid phase method preparation, size is more
Small, luminescent properties are more preferable.
A kind of preparation method of nanoscale alkaline earth scandium oxide up-conversion luminescent material provided by the invention is using hydro-thermal
With the method that combines of annealing, this method has that controllability is good, reaction temperature is low, low for equipment requirements, no pollution to the environment etc.
Advantage.
The present invention during the preparation process, is adjusted with one of sodium hydroxide, potassium hydroxide, lithium hydroxide aqueous solution and is reacted
Object makes reactant form pure phase；When annealing, roasting only need to reach 600~800 DEG C, when temperature can be prepared at 600 DEG C
Obtain good dispersion, not easy to reunite, the lesser nanoscale alkaline earth scandium oxide up-conversion luminescent material of crystalline size.
Detailed description of the invention
Invention is further described in detail with reference to the accompanying drawings and detailed description.
Fig. 1 is embodiment 1:MgSc1.88O4:Er3+ 0.02,Yb3+ 0.1Transmission electron microscope photo.
Fig. 2 is embodiment 1:MgSc1.88O4:Er3+ 0.02,Yb3+ 0.1Up-conversion emission spectrum under 980nm excitation.
Fig. 3 is embodiment 1:MgSc1.88O4:Er3+ 0.02,Yb3+ 0.1XRD diffracting spectrum.
Fig. 4 is embodiment 2:SrSc1.88O4:Er3+ 0.02,Yb3+ 0.1Transmission electron microscope photo.
Fig. 5 is embodiment 2:SrSc1.88O4:Er3+ 0.02,Yb3+ 0.1Up-conversion emission spectrum under 980nm excitation.
Fig. 6 is embodiment 2:SrSc1.88O4:Er3+ 0.02,Yb3+ 0.1XRD diffracting spectrum.
Fig. 7 is embodiment 3:BaSc1.88O4:Er3+ 0.02,Yb3+ 0.1Transmission electron microscope photo.
Fig. 8 is embodiment 3:BaSc1.88O4:Er3+ 0.02,Yb3+ 0.1Up-conversion emission spectrum under 980nm excitation.
Fig. 9 is embodiment 3:BaSc1.88O4:Er3+ 0.02,Yb3+ 0.1XRD diffracting spectrum.
Figure 10 is embodiment 4:MgSc1.798O4:Ho3+ 0.002,Yb3+ 0.2Up-conversion emission spectrum under 980nm excitation.
Figure 11 is embodiment 5:SrSc1.796O4:Tm3+ 0.004,Yb3+ 0.2Up-conversion emission spectrum under 980nm excitation.
Figure 12 is embodiment 6:SrSc1.88O4:Er3+ 0.02,Yb3+ 0.1XRD diffracting spectrum.
Figure 13 is embodiment 7:SrSc1.88O4:Er3+ 0.02,Yb3+ 0.1XRD diffracting spectrum.
Specific embodiment
The present invention is directed to scandium oxide M Sc2O4(M=Mg, Sr, Ba) material adjusts the size distribution of material and pattern
Control, obtains that appearance and size is uniform, mono-dispersed nano grade alkaline earth scandium oxide material.
The present invention provides a kind of nanoscale alkaline earth scandium oxide up-conversion luminescent material, the chemical combination with following below formula
Object: MSc2(1-x-y)O4:N3+ 2x,Yb3+ 2y；
Wherein, one of M Mg, Sr, Ba；N is one of Er, Ho, Tm；X, y are element molar fraction, value
Range are as follows: 0.0001≤x≤0.10,0.0001≤y≤0.20.
When M is Mg, the up-conversion luminescent material is the near-spherical of morphological rules；When M is Sr, the upper conversion hair
Luminescent material is that the length of morphological rules is rodlike；When M is Ba, the up-conversion luminescent material is the corynebacterium of morphological rules.
The up-conversion luminescent material chemical formula is MgSc1.88O4:Er3+ 0.02,Yb3+ 0.1, it is the class ball of morphological rules
Shape, diameter are 25~30nm；
The up-conversion luminescent material chemical formula is SrSc1.88O4:Er3+ 0.02,Yb3+ 0.1, it is the long stick of morphological rules
Shape is highly 420~450nm, and width is 40~60nm；
The up-conversion luminescent material chemical formula is BaSc1.88O4:Er3+ 0.02,Yb3+ 0.1, it is the stub of morphological rules
Shape is highly 80~100nm, and width is 30~50nm.
The up-conversion luminescent material is rhombic system, has CaFe2O4The alkaline earth scandium oxide of structure.
The present invention also provides a kind of preparation methods of nanoscale alkaline earth scandium oxide up-conversion luminescent material, including following step
It is rapid:
(1) expression formula MSc is pressed2(1-x-y)O4:N3+ 2x,Yb3+ 2y, (0.0001≤x≤0.10；0.0001≤y≤0.20) in it is each
The stoichiometric ratio of substance measures Sc (NO respectively3)3、Yb(NO3)3And Er (NO3)3、Ho(NO3)3、Tm3(NO)3One of,
And Mg (NO3)2、Sr(NO3)2、Ba(NO3)2One of be put in beaker, be added dehydrated alcohol, filled using magnetic stirring apparatus
Divide stirring, obtain uniform mixed solution, continues to stir 30min；
Sc(NO3)3、Yb(NO3)3、Er(NO3)3、Ho(NO3)3And Tm (NO3)3The preparation of standard solution:
4-5N Sc is accurately weighed respectively2O3, Yb2O3, Er2O3, Ho2O3, Tm2O3It is put into clean beaker, is added a little
Dust technology is added dropwise in deionized water while stirring, and stirring and dissolving is clear solution under 60~80 DEG C of heating conditions, sets volumetric flask
In, it is made into Sc (NO respectively3)3Concentration is 1mol/L, Yb (NO3)3Concentration is 0.2mol/L, Tm (NO3)3Concentration is 0.2mol/L,
Ho(NO3)3Concentration is 0.02mol/L, Er (NO3)3Concentration is the nitrate standard aqueous solution of 0.2mol/L；
Wherein dust technology dosage should be calculated according to chemical equivalent, and allow appropriate excessive 10%.Dust technology used is excellent
The pure concentrated nitric acid of grade is formulated with deionized water, and the ratio of concentrated nitric acid and deionized water is (1~1.5): 1；
M(NO3)2The preparation of (M=Mg, Sr, Ba) standard solution:
A certain amount of Mg (NO is weighed respectively3)2·6H2O、Sr(NO3)2、Ba(NO3)2Solid powder is put into clean beaker
In, it is added in deionization and is stirred, until solution becomes transparent solution, set in volumetric flask, be made into M (NO3)2Concentration is
1mol/L。
(2) sodium hydroxide, potassium hydroxide, lithium hydroxide water are added dropwise while stirring in the mixed solution prepared to step (1)
One of solution, the pH for adjusting mixed solution is 11~13, is stirred 1~2 hour, obtains suspension；
(3) suspension that step (2) obtains is placed in hydrothermal reaction kettle, the isothermal reaction 12 in 160~190 DEG C of baking ovens
~48 hours；By in reaction kettle sediment be centrifuged take out, first use deionized water eccentric cleaning 3~5 times, then with dehydrated alcohol from
The heart cleans 3~5 times；Place into baking oven, in 60~90 DEG C freeze-day with constant temperature 8~15 hours, obtain reactant presoma precipitating；This
The temperature of preferred hydro-thermal reaction is 180 DEG C in step, and the time is 24 hours；
(4) reactant presoma precipitating will be obtained in step (3) to be put into corundum crucible and cover, and is placed in high temperature furnace, into
Row roasting, maturing temperature are 600~800 DEG C, and calcining time is 1~3 hour, and taking-up grinds and obtains final product nanoscale alkaline earth
Scandium oxide up-conversion luminescent material；Preferred maturing temperature is 600 DEG C in this step, and the time is 2 hours.
Embodiment 1
By expression formula MgSc1.88O4:Er3+ 0.02,Yb3+ 0.1In each substance stoichiometric ratio into 100mL small beaker respectively
Measure 940 μ L Sc (NO3)3, 250 μ L Yb (NO3)3, 50 μ L Er (NO3)3, 500 μ L Mg (NO3)2Add the anhydrous second of about 20mL
Alcohol is stirred 30min；Then sodium hydrate aqueous solution 2mL is added dropwise to above-mentioned mixed liquor while stirring, adjusts pH value of solution
Value is located at 11~13, and 1~2h is sufficiently stirred.Gained suspension is put into hydrothermal reaction kettle and is reacted for 24 hours for 180 DEG C, natural cooling,
Sediment is centrifuged and is taken out, first uses deionized water, then distinguished centrifuge washing 3 times with dehydrated alcohol.It is put into baking oven, 80 DEG C of dryings
15h obtains reactant presoma precipitating；Reactant presoma precipitating is put into corundum crucible and is covered, is placed in high temperature furnace, is roasted
Burning temperature is 600 DEG C, calcining time 2h, takes out to grind and obtains infrared ray excited near-spherical, in nanoscale scandium acid magnesium-based
Changing luminous material MgSc1.88O4:Er3+ 0.02,Yb3+ 0.1。
Pattern, upconversion emission and the XRD diffracting spectrum of the embodiment sample are as follows:
Transmission electron microscope photo is shown in that Fig. 1, pattern are near-spherical, and a diameter of 25~30nm, dispersibility is preferably；
Up-conversion emission spectrum under 980nm excitation is shown in Fig. 2, is 7mW/mm in exciting power density2980nm excitation under,
Clearly red up-conversion luminescence can be observed in naked eyes；
XRD diffracting spectrum is shown in Fig. 3, with MgSc2O4Standard diffraction composes (JCPDS card 74-0101) unanimously, and diffraction maximum
Half-peak breadth is larger, illustrates that particle size is smaller.
Embodiment 2
By expression formula SrSc1.88O4:Er3+ 0.02,Yb3+ 0.1In each substance stoichiometric ratio into 100mL small beaker respectively
Measure 940 μ L Sc (NO3)3, 250 μ L Yb (NO3)3, 50 μ L Er (NO3)3, 500 μ L Sr (NO3)2Add the anhydrous second of about 20mL
Alcohol is stirred 30min；Then sodium hydrate aqueous solution 2mL is added dropwise to above-mentioned mixed liquor while stirring, adjusts pH value of solution
Value is located at 11~13, and 1~2h is sufficiently stirred.Gained suspension is put into hydrothermal reaction kettle and is reacted for 24 hours for 180 DEG C, natural cooling,
Sediment is centrifuged and is taken out, first uses deionized water, then distinguished centrifuge washing 3 times with dehydrated alcohol.It is put into baking oven, 80 DEG C of dryings
15h obtains reactant presoma precipitating；Reactant presoma precipitating is put into corundum crucible and is covered, is placed in high temperature furnace, is roasted
Burning temperature is 600 DEG C, calcining time 2h, take out grind obtain infrared ray excited length is rodlike, on nanoscale scandium acid strontium base
Changing luminous material SrSc1.88O4:Er3+ 0.02,Yb3+ 0.1。
Pattern, upconversion emission and the XRD diffracting spectrum of the embodiment sample are as follows:
Transmission electron microscope photo is shown in Fig. 4, and pattern is long club shaped structure, and height is 420~450nm, width is 40~
60nm；
Up-conversion emission spectrum under 980nm excitation is shown in Fig. 5, is 7mW/mm in exciting power density2980nm excitation under,
Clearly red up-conversion luminescence can be observed in naked eyes；
XRD diffracting spectrum is shown in Fig. 6, with SrSc2O4Standard diffraction composes (JCPDS card 20-1213) unanimously, and diffraction maximum
Half-peak breadth is larger, illustrates that particle size is smaller.
Embodiment 3
By expression formula BaSc1.88O4:Er3+ 0.02,Yb3+ 0.1In each substance stoichiometric ratio into 100mL small beaker respectively
Measure 940 μ L Sc (NO3)3, 250 μ L Yb (NO3)3, 50 μ L Er (NO3)3, 500 μ L Ba (NO3)2Add the anhydrous second of about 20mL
Alcohol is stirred 30min；Then sodium hydrate aqueous solution 2mL is added dropwise to above-mentioned mixed liquor while stirring, adjusts pH value of solution
Value is located at 11~13, and 1~2h is sufficiently stirred.Gained suspension is put into hydrothermal reaction kettle and is reacted for 24 hours for 180 DEG C, natural cooling,
Sediment is centrifuged and is taken out, first uses deionized water, then distinguished centrifuge washing 3 times with dehydrated alcohol.It is put into baking oven, 80 DEG C of dryings
15h obtains reactant presoma precipitating；Reactant presoma precipitating is put into corundum crucible and is covered, is placed in high temperature furnace, is roasted
Burning temperature is 600 DEG C, calcining time 2h, takes out to grind and obtains infrared ray excited corynebacterium, on nanoscale scandium acid barium base
Changing luminous material BaSc1.88O4:Er3+ 0.02,Yb3+ 0.1。
Pattern, upconversion emission and the XRD diffracting spectrum of the embodiment sample are as follows:
Transmission electron microscope photo is shown in Fig. 7, and pattern is corynebacterium structure, and height is 80~100nm, width is 30~
50nm；
Up-conversion emission spectrum under 980nm excitation is shown in Fig. 8, is 7mW/mm in exciting power density2980nm excitation under,
Red up-conversion luminescence can be observed in naked eyes；
XRD diffracting spectrum is shown in Fig. 9, with BaSc2O4Standard diffraction composes (JCPDS card 44-0259) unanimously, and diffraction maximum
Half-peak breadth is larger, illustrates that particle size is smaller.
Embodiment 4
By expression formula MgSc1.798O4:Ho3+ 0.002,Yb3+ 0.2In each substance stoichiometric ratio into 100mL small beaker point
899 μ L Sc (NO are not measured3)3, 500 μ L Yb (NO3)3, 50 μ L Ho (NO3)3, 500 μ L Mg (NO3)2It is anhydrous to add about 20mL
Ethyl alcohol is stirred 30min；Then sodium hydrate aqueous solution 2mL is added dropwise to above-mentioned mixed liquor while stirring, adjusts solution
PH value is located at 11~13, and 1~2h is sufficiently stirred.It is for 24 hours, naturally cold that gained suspension is put into 180 DEG C of reactions in hydrothermal reaction kettle
But, sediment is centrifuged and is taken out, first use deionized water, then distinguished centrifuge washing 3 times with dehydrated alcohol.It is put into baking oven, 80 DEG C dry
Dry 15h obtains reactant presoma precipitating；Reactant presoma precipitating is put into corundum crucible and is covered, is placed in high temperature furnace,
Maturing temperature is 600 DEG C, calcining time 2h, takes out grinding and obtains infrared ray excited near-spherical, nanoscale scandium acid magnesium-based
Up-conversion luminescent material MgSc1.798O4:Ho3+ 0.002,Yb3+ 0.2。
Up-conversion emission spectrum under 980nm excitation is shown in Figure 10, is 7mW/mm in exciting power density2980nm excitation under,
Red green up-conversion luminescence can be observed in naked eyes；
Embodiment 5
By expression formula SrSc1.796O4:Tm3+ 0.004,Yb3+ 0.2In each substance stoichiometric ratio into 100mL small beaker point
948 μ L Sc (NO are not measured3)3, 500 μ L Yb (NO3)3, 10 μ L Tm3+(NO3)3, 500 μ L Sr (NO3)2Add about 20mL without
Water-ethanol is stirred 30min；Then sodium hydrate aqueous solution 2mL is added dropwise to above-mentioned mixed liquor while stirring, adjusts molten
Liquid pH value is located at 11~13, and 1~2h is sufficiently stirred.It is for 24 hours, natural that gained suspension is put into 180 DEG C of reactions in hydrothermal reaction kettle
It is cooling, sediment is centrifuged and is taken out, first uses deionized water, then distinguished centrifuge washing 3 times with dehydrated alcohol.It is put into baking oven, 80 DEG C
Dry 15h obtains reactant presoma precipitating；Reactant presoma precipitating is put into corundum crucible and is covered, high temperature furnace is placed in
In, maturing temperature is 600 DEG C, calcining time 2h, takes out to grind and obtains that infrared ray excited length is rodlike, nanoscale scandium acid strontium
Base up-conversion luminescent material SrSc1.796O4:Tm3+ 0.004,Yb3+ 0.2。
Up-conversion emission spectrum under 980nm excitation is shown in Figure 11, is 7mW/mm in exciting power density2980nm excitation under,
Naked eyes can be observed clearly blue up-conversion luminous.
Embodiment 6
By expression formula SrSc1.88O4:Er3+ 0.01,Yb3+ 0.2In each substance stoichiometric ratio into 100mL small beaker respectively
Measure 940 μ L Sc (NO3)3, 250 μ L Yb (NO3)3, 50 μ L Er (NO3)3, 500 μ L Mg (NO3)2, it is respectively put into three beakers
In, about 20mL dehydrated alcohol is added, 30min is stirred；Then hydroxide is added dropwise to above-mentioned mixed liquor while stirring
Aqueous solutions of potassium 2.5mL adjusts solution ph and is located at 11~13,1~2h is sufficiently stirred.Gained suspension is put into hydrothermal reaction kettle
In 180 DEG C of reactions for 24 hours, sediment is centrifuged and takes out by natural cooling, first uses deionized water, then is centrifuged and is washed respectively with dehydrated alcohol
It washs 3 times.It is put into baking oven, 80 DEG C of dry 15h obtain reactant presoma precipitating；Reactant presoma precipitating is put into corundum earthenware
It covers, is placed in high temperature furnace in crucible, maturing temperature is 600 DEG C, calcining time 2h, takes out grinding and obtains infrared ray excited receive
Meter level scandium oxide up-conversion luminescent material SrSc1.88O4:Er3+ 0.02,Yb3+ 0.1。
XRD diffracting spectrum is shown in Figure 12, with SrSc2O4Standard diffraction composes (JCPDS card 20-1213) unanimously, and diffraction maximum
Half-peak breadth is larger, illustrates that particle size is smaller.
Embodiment 7
By expression formula SrSc1.88O4:Er3+ 0.02,Yb3+ 0.1In each substance stoichiometric ratio into 100mL small beaker respectively
Measure 940 μ L Sc (NO3)3, 250 μ L Yb (NO3)3, 50 μ L Er (NO3)3, 500 μ L Ba (NO3)2, it is anhydrous to add about 20mL
Ethyl alcohol is stirred 30min；Then lithium hydroxide aqueous solution 2mL is added dropwise to above-mentioned mixed liquor while stirring, adjusts solution
PH value is located at 11~13, and 1~2h is sufficiently stirred.Gained suspension is put into hydrothermal reaction kettle 160 DEG C of reaction 48h, it is naturally cold
But, sediment is centrifuged and is taken out, first use deionized water, then distinguished centrifuge washing 5 times with dehydrated alcohol.It is put into baking oven, 90 DEG C dry
Dry 8h obtains reactant presoma precipitating；Reactant presoma precipitating is put into corundum crucible and is covered, is placed in high temperature furnace,
Maturing temperature is 600 DEG C, calcining time 1h, takes out to grind and obtains that infrared ray excited length is rodlike, nanoscale scandium acid strontium base
Up-conversion luminescent material SrSc1.88O4:Er3+ 0.02,Yb3+ 0.1。
XRD diffracting spectrum is shown in Figure 13, with SrSc2O4Standard diffraction composes (JCPDS card 20-1213) unanimously, and diffraction maximum
Half-peak breadth is larger, illustrates that particle size is smaller.
Embodiment 8
By expression formula BaSc1.88O4:Er3+ 0.02,Yb3+ 0.1In each substance stoichiometric ratio into 100mL small beaker respectively
Measure 940 μ L Sc (NO3)3, 250 μ L Yb (NO3)3, 50 μ L Er (NO3)3, 500 μ L Ba (NO3)2, it is anhydrous to add about 20mL
Ethyl alcohol is stirred 30min；Then potassium hydroxide aqueous solution 2.5mL is added dropwise to above-mentioned mixed liquor while stirring, adjusts molten
Liquid pH value is located at 11~13, and 1~2h is sufficiently stirred.Gained suspension is put into 190 DEG C of reaction 12h in hydrothermal reaction kettle, it is natural
It is cooling, sediment is centrifuged and is taken out, first uses deionized water, then distinguished centrifuge washing 4 times with dehydrated alcohol.It is put into baking oven, 60 DEG C
Dry 15h obtains reactant presoma precipitating；Reactant presoma precipitating is put into corundum crucible and is covered, high temperature furnace is placed in
In, maturing temperature is 800 DEG C, calcining time 3h, takes out grinding and obtains infrared ray excited near-spherical, nanoscale scandium acid magnesium
Base up-conversion luminescent material BaSc1.88O4:Er3+ 0.02,Yb3+ 0.1。
The sample of the present embodiment is 7mW/mm in exciting power density2980nm excitation under, red can be observed in naked eyes
Up-conversion luminescence.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (9)
1. a kind of nanoscale alkaline earth scandium oxide up-conversion luminescent material, which is characterized in that its chemical combination with following below formula
Object: MSc2(1-x-y)O4:N3+ 2x,Yb3+ 2y；
Wherein, one of M Mg, Sr, Ba；N is one of Er, Ho, Tm；X, y are element molar fraction, value range
Are as follows: 0.0001≤x≤0.10,0.0001≤y≤0.20.
2. nanoscale alkaline earth scandium oxide up-conversion luminescent material according to claim 1, which is characterized in that
When M is Mg, the up-conversion luminescent material is the near-spherical of morphological rules；
When M is Sr, the up-conversion luminescent material is that the length of morphological rules is rodlike；
When M is Ba, the up-conversion luminescent material is the corynebacterium of morphological rules.
3. nanoscale alkaline earth scandium oxide up-conversion luminescent material according to claim 1, which is characterized in that
The up-conversion luminescent material chemical formula is MgSc1.88O4:Er3+ 0.02,Yb3+ 0.1, it is the near-spherical of morphological rules, diameter
For 25~30nm；
The up-conversion luminescent material chemical formula is SrSc1.88O4:Er3+ 0.02,Yb3+ 0.1, it is that the length of morphological rules is rodlike, height
For 420~450nm, width is 40~60nm；
The up-conversion luminescent material chemical formula is BaSc1.88O4:Er3+ 0.02,Yb3+ 0.1, it is the corynebacterium of morphological rules, height
For 80~100nm, width is 30~50nm.
4. nanoscale alkaline earth scandium oxide up-conversion luminescent material according to claim 1, which is characterized in that described upper turn
Changing luminescent material is rhombic system, has CaFe2O4The alkaline earth scandium oxide of structure.
5. a kind of preparation method of nanoscale alkaline earth scandium oxide up-conversion luminescent material, which comprises the following steps:
(1) expression formula MSc is pressed2(1-x-y)O4:N3+ 2x,Yb3+ 2y, one of M Mg, Sr, Ba；N is one of Er, Ho, Tm；
X, y be element molar fraction, value range are as follows: 0.0001≤x≤0.10,0.0001≤y≤0.20, in each substance chemistry
Metering than measuring Sc (NO respectively3)3, Yb (NO3)3And Er (NO3)3、Ho(NO3)3、Tm3(NO)3One of and Mg
(NO3)2、Sr(NO3)2、Ba(NO3)2One of be put in beaker, be added dehydrated alcohol, be sufficiently stirred using magnetic stirring apparatus,
Uniform mixed solution is obtained, then proceedes to stir；
(2) pH for the mixed solution prepared with alkaline aqueous solution regulating step (1) is 11~13, and stirring obtains suspension；
(3) suspension that step (2) obtains is placed in hydrothermal reaction kettle, the isothermal reaction 12~48 in 160~190 DEG C of baking ovens
Hour；Sediment in reaction kettle is centrifuged and is taken out, cleaning, drying obtain reactant presoma precipitating；
(4) precipitating of reactant presoma obtained in step (3) is put into corundum crucible and is covered, is placed in high temperature furnace, carried out
Roasting, maturing temperature are 600~800 DEG C, and calcining time is 1~3 hour, take out grinding and obtain final product nanoscale alkaline earth scandium
Oxide up-conversion luminescent material.
6. preparation method according to claim 5, which is characterized in that alkaline aqueous solution used in step (2) is hydrogen-oxygen
Change one of sodium, potassium hydroxide, lithium hydroxide aqueous solution.
7. preparation method according to claim 5, which is characterized in that in step (3) the step of cleaning, drying specifically such as
Under:
Sediment is first used deionized water eccentric cleaning 3~5 times, then with dehydrated alcohol eccentric cleaning 3~5 times, places into baking oven
In, in 60~90 DEG C freeze-day with constant temperature 8~15 hours.
8. preparation method according to claim 5, which is characterized in that the temperature of hydro-thermal reaction is 180 DEG C in step (3),
Time is 24 hours.
9. preparation method according to claim 5, which is characterized in that maturing temperature is 600 DEG C in step (4), the time 2
Hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910552788.XA CN110144219A (en) | 2019-06-25 | 2019-06-25 | A kind of nanoscale alkaline earth scandium oxide up-conversion luminescent material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910552788.XA CN110144219A (en) | 2019-06-25 | 2019-06-25 | A kind of nanoscale alkaline earth scandium oxide up-conversion luminescent material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110144219A true CN110144219A (en) | 2019-08-20 |
Family
ID=67596603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910552788.XA Pending CN110144219A (en) | 2019-06-25 | 2019-06-25 | A kind of nanoscale alkaline earth scandium oxide up-conversion luminescent material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110144219A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785850A (en) * | 2020-07-16 | 2020-10-16 | 京东方科技集团股份有限公司 | Light emitting device and display device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108297A (en) * | 2009-12-29 | 2011-06-29 | 北京有色金属研究总院 | Red fluorescent powder, preparation method thereof and luminescent device prepared therefrom |
| CN102994084A (en) * | 2012-12-12 | 2013-03-27 | 中国科学院长春光学精密机械与物理研究所 | Submicron rodlike calcium scandate-based up-conversion luminescent material and preparation method thereof |
| CN106978176A (en) * | 2017-05-18 | 2017-07-25 | 济南大学 | A kind of yellow fluorescent powder and preparation method and its application in luminescent device |
| CN108659838A (en) * | 2018-05-02 | 2018-10-16 | 长春工业大学 | A kind of nanoscale near-spherical scandium oxide base up-conversion luminescent material and preparation method thereof |
-
2019
- 2019-06-25 CN CN201910552788.XA patent/CN110144219A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108297A (en) * | 2009-12-29 | 2011-06-29 | 北京有色金属研究总院 | Red fluorescent powder, preparation method thereof and luminescent device prepared therefrom |
| CN102994084A (en) * | 2012-12-12 | 2013-03-27 | 中国科学院长春光学精密机械与物理研究所 | Submicron rodlike calcium scandate-based up-conversion luminescent material and preparation method thereof |
| CN106978176A (en) * | 2017-05-18 | 2017-07-25 | 济南大学 | A kind of yellow fluorescent powder and preparation method and its application in luminescent device |
| CN108659838A (en) * | 2018-05-02 | 2018-10-16 | 长春工业大学 | A kind of nanoscale near-spherical scandium oxide base up-conversion luminescent material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JING LI ET AL.: "Synthesis, morphology, and upconversion luminescence of Tm3+/Yb3+ codoped bulk and submicro-rod CaSc2O4 phosphors", 《INORGANIC CHEMISTRY COMMUNICATIONS》 * |
| 李静: "Tm3+/Yb3+及Ho3+/Yb3+共掺钪酸盐氧化物材料发光性质的研究", 《中国优秀博硕士学位论文全文数据库（博士）基础科学辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785850A (en) * | 2020-07-16 | 2020-10-16 | 京东方科技集团股份有限公司 | Light emitting device and display device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100378192C (en) | Luminescent material converted in nano level with yttrium oxide as matrix and preparation method | |
| Phogat et al. | Crystallographic and judd-ofelt parametric investigation into Ca9Bi (VO4) 7: Eu3+ nanophosphor for NUV-WLEDs | |
| CN110093154B (en) | Mg2+/Si4+Substituted Ga3+Doped with Cr3+Zinc gallate based near-infrared long afterglow material and preparation method thereof | |
| CN104818023B (en) | Rare earth luminescent material preparation method and its product containing crystal defect renovation technique | |
| Chen et al. | Yolk–shell structured Bi 2 SiO 5: Yb 3+, Ln 3+(Ln= Er, Ho, Tm) upconversion nanophosphors for optical thermometry and solid-state lighting | |
| Fu et al. | Highly luminescent red light phosphor CaTiO3: Eu3+ under near-ultraviolet excitation | |
| Pushpendra et al. | NaBi0. 9Eu0. 1 (MoO4) 2 nanomaterials: tailoring the band gap and luminescence by La3+ substitution for light-emitting diodes | |
| Raju et al. | Synthesis and luminescent properties of low concentration Dy3+: GAP nanophosphors | |
| CN109266346A (en) | Superfine nano luminescent material and its preparation and application are converted on the wolframic acid double salt of rare earth ion doping | |
| CN104927863A (en) | Method for preparing rare earth metal co-doped hexagonal NaYF4 nanocrystalline by use of discarded fluorescent powder | |
| CN110628431B (en) | Bismuth orthosilicate nano luminescent material with yolk-eggshell structure and preparation method thereof | |
| Yogananda et al. | Lysine assisted hydrothermal synthesis and formation process of MoO3: Sm3+ phosphors with hierarchical structures and its electron trapping luminescence properties | |
| Wang et al. | A new method for preparing cubic-shaped Sr2MgSi2O7: Eu2+, Dy3+ phosphors and the effect of sintering temperature | |
| Bhagyalekshmi et al. | Luminescence dynamics of Eu3+ activated and co-activated defect spinel zinc titanate nanophosphor for applications in WLEDs | |
| Sridhar et al. | Cr-doped ZnGa2O4: Simple synthesis of intense red-NIR emitting nanoparticles with enhanced quantum efficiency | |
| Qingqing et al. | Facile sol-gel combustion synthesis and photoluminescence enhancement of CaZrO3: Sm3+ nanophosphors via Gd3+ doping | |
| Makhija et al. | Green emission from trivalent cerium doped LaAlO 3/MgO nano-composite for photonic and latent finger printing applications | |
| Yang et al. | Crystal structure and up-conversion luminescence properties of K3ScF6: Er3+, Yb3+ cryolite | |
| Gowri et al. | Phase dependent photoluminescence and thermoluminescence properties of Y2SiO5: Sm3+ nanophosphors and its advanced forensic applications | |
| CN102994084B (en) | Submicron rodlike calcium scandate-based up-conversion luminescent material and preparation method thereof | |
| CN110144219A (en) | A kind of nanoscale alkaline earth scandium oxide up-conversion luminescent material and preparation method thereof | |
| Deng et al. | Sol-gel combustion synthesis and near-infrared luminescence of Ni2+-doped MgAl2O4 spinel phosphor | |
| CN108659838A (en) | A kind of nanoscale near-spherical scandium oxide base up-conversion luminescent material and preparation method thereof | |
| CN101439860A (en) | Preparation of manganese-doped willemite yellow fluorescent powder | |
| CN107903899B (en) | Yb-erbium co-doped KGdF4Method for synthesizing nano-particles and nano-belts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190820 |
|
| WD01 | Invention patent application deemed withdrawn after publication |