CN108659838A - A kind of nanoscale near-spherical scandium oxide base up-conversion luminescent material and preparation method thereof - Google Patents
A kind of nanoscale near-spherical scandium oxide base up-conversion luminescent material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to luminescent material technical field, it is related to a kind of nanoscale near-spherical scandium oxide base up-conversion luminescent material and preparation method thereof.It is high to solve existing scandium oxide rare earth up-conversion luminescent material preparation temperature, the technical issues of size is big and bad dispersibility.The nanoscale near-spherical scandium oxide base up-conversion luminescent material of the present invention is Sc2(1‑x‑y)O3：M3+ 2x, Yb3+ 2y；Wherein, M is one kind in rare earth element Ho, Er, Tm；X, y are element molar fraction, and value range is：0.0001≤x≤0.10,0.0001≤y≤0.20；Its average diameter is 10~30nm.Compared with scandium oxide base up-conversion luminescent material prepared by conventional method, particle is small, pattern rule, good dispersion；980nm wavelength it is infrared ray excited under the visible light of 400 bright~850nm can be observed.It is smaller to shine more preferably compared with the scandium oxide base up-conversion luminescent material prepared using conventional high-temperature solid phase method.Compared with the sample prepared using hydrothermal method using organic alkali solution modulation, light emission luminance further increases 10 times.
Description
Technical field
The invention belongs to luminescent material technical fields, and in particular to a kind of nanoscale near-spherical scandium oxide base up-conversion luminescence
Material and preparation method thereof.
Background technology
Rare earth up-conversion luminescence is a kind of unique nonlinear optical phenomena.Rare earth up-conversion luminescent material refers to absorbing energy
Measure lower photon but and can send out the material of the photon of higher-energy.Such material is due to distinctive optical property, and very
Various aspects have a good application prospect, especially shows in non-optical device, light, the spy of infrared acquisition, fluorescence falsification preventing, fluorescence
The fields such as needle, biosensor, bio-imaging, solar cell and photocatalysis.
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, the excitation purity that shines is high, toxicity is low and Stokes displacements are big.Meanwhile long wave-near infrared light
Under (800-1300nm) shooting condition, penetration depth is more ultraviolet, visible light has greater advantage, can be dissipated to avoid biological sample light
It penetrates and the interference of autofluorescence, to make the reduction of detection background, signal-to-noise ratio improve.But up-conversion luminescence is multi-photon mistake
The absorption cross section of journey, centre of luminescence rare earth ion is small, is that abstinence f-f electric dipole transitions and nanocrystal surface presence are a large amount of sudden
The latent defects such as center of going out cause that up-conversion luminescence efficiency is low, intensity is 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, fluoride is the highest host material of transfer efficiency generally acknowledged at present.It has lower sound
Sub- energy is reduced due to radiationless transition energy loss caused by multi-photon relaxation, so as to cause higher up-conversion luminescence
Efficiency.But its poor chemical stability, manufacturing conditions are harsh, are difficult to control, it is difficult to and the shortcomings of integrating is also very prominent, to
Its application is limited to a certain extent.Although and oxide is more slightly higher than fluoride phonon energy, its preparation process letter
Single, environmental condition requirement is relatively low, and the solubility of rare earth ion is high, and mechanical strength and chemical stability are good.Therefore, oxide is to answer
With very extensive host material.But it is slightly lower as the upper transfer efficiency of the up-conversion luminescent material of host material using oxide.
Cubic system sesquichloride material (such as Y2O3, Lu2O3, Sc2O3Deng) be concerned because of its distinctive structure.Times
Semi-oxidized closes object and possesses shorter cation-cation distance, and since matrix cation belongs to rare earth ion, other rare earths
Ion can take and replace without charge difference, small ionic radius difference direct in-situ, therefore have higher doping concentration of rare earth ion.This
Outside, sesquialter oxygen compound is also with lower phonon energy, big stoke energy level splitting, the chemical characteristic of stabilization and good
The physical properties such as thermal conduction characteristic.Currently, sesquialter oxygen compound Y2O3、Lu2O3Due to its efficient luminous efficiency, as commercialization
Up-conversion luminescent material be widely used.In sesquichloride material, Sc2O3With minimum lattice parameter, middle-jiao yang, function of the spleen and stomach from
Sub- density is up to 3.338 × 1022cm-1, and Sc-Sc keys bond distance is most short onlySc2O3Shorter Sc-O keys in material
Length can generate stronger crystalline field, cause Doped ions (with Yb3+/Er3+For) there is larger energy level splitting.Sc2O3In material
Shorter Sc-Sc bond distance also makes Yb3+→Er3+Ion pair has closer distance, and then accelerates Yb3+→Er3+Energy transmission speed
Rate.What is more important, in experimenting, we find out that and Y2O3、Lu2O3Sesquichloride material is compared, Yb3+/Er3+Codope
Sc2O3Red emission produces apparent red shift in material.Sesquichloride generally has there are one larger defect：Prepare sample needs
Very high temperature, so usually being prepared by traditional high temperature solid-state method, temperature, which reaches 1600 DEG C, can form pure phase
Sc2O3, the raw material Yb of Doped ions is still had when temperature is 1300 DEG C2O3Crystalline phase.But when temperature reaches 1600 DEG C
When, it is the blocks that a large amount of orbicules are sticked together that luminescent material obtained is caused since temperature is excessively high, and size is big, dispersibility
It is very poor.Simultaneously as activator concentration is unevenly distributed, its luminous efficiency can be also influenced.To limit on scandium oxide base rare earth
Application of the changing luminous material in fields such as biomedical imagings.
Invention content
The invention solves the height of scandium oxide rare earth up-conversion luminescent material preparation temperature in the prior art, size is big and disperses
Property difference technical problem, a kind of nanoscale near-spherical scandium oxide base up-conversion luminescent material and preparation method thereof is provided.The present invention
By green hydrothermal synthesis method, Yb is obtained under cryogenic3+/Er3+、Ho3+Or Tm3+Codope Sc2O3Material has strong
Red up-conversion luminescence, and size is smaller, good dispersion.
In order to solve the above-mentioned technical problem, technical scheme of the present invention is specific as follows：
A kind of nanoscale near-spherical scandium oxide base up-conversion luminescent material, is the compound with following below formula：
Sc2(1-x-y)O3：M3+ 2x, Yb3+ 2y；
Wherein, M is one kind in rare earth element Ho, Er, Tm；X, y are element molar fraction, and value range is：
0.0001≤x≤0.10,0.0001≤y≤0.20.
In the above-mentioned technical solutions, the up-conversion luminescent material is evengranular near-spherical, and average diameter is
10~30nm.
In the above-mentioned technical solutions, the up-conversion luminescent material is cubic system sesquichloride.
The present invention also provides a kind of preparation method of nanoscale near-spherical scandium oxide base up-conversion luminescent material, including it is following
Step：
(1) expression formula Sc is pressed2(1-x-y)O3：M3+ 2x, Yb3+ 2y, x, y are element molar fraction, and value range is：0.0001
≤ x≤0.10,0.0001≤y≤0.20, in the stoichiometric ratio of each substance measure Sc (NO respectively3)3、Yb(NO3)3, Yi Jiliang
Take Tm (NO3)3、Er(NO3)3、Ho(NO3)3In one kind, be added ethanol solution, preparation obtain mixed alkoxide solution；
(2) sodium hydrate aqueous solution is added dropwise while stirring in the mixed alkoxide solution prepared to step (1), continues to stir；
(3) oleic acid is added dropwise in the solution obtained to step (2) to be sufficiently stirred, obtains uniform and stable suspension；
(4) suspension that step (3) 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, uses deionized water and ethyl alcohol eccentric cleaning respectively, it is dry, it obtains anti-
Object presoma is answered to precipitate；
(5) the reactant presoma obtained in step (4) precipitation is put into corundum crucible and is capped, is placed in high temperature furnace,
It is roasted, calcination temperature is 700~1000 DEG C, and roasting time is 1~3 hour, takes out grinding and obtains final product nanoscale
Near-spherical scandium oxide base up-conversion luminescent material.
In the above-mentioned technical solutions, the step (2) is specially：
The hydrogen-oxygen of a concentration of 3.75mol/L of 1.5mL-2.0mL is added dropwise in the mixed alkoxide solution prepared to step (1)
Change sodium water solution, is stirred 30min.
In the above-mentioned technical solutions, the step (3) is specially：
The oleic acid of 315 μ L-1.0mL is added dropwise in the solution obtained to step (2), is sufficiently stirred 1~2 hour, obtains
Suspension.
In the above-mentioned technical solutions, the reaction temperature of step (4) is 180 DEG C, and the time is 24 hours.
In the above-mentioned technical solutions, the sediment of gained first uses deionized water eccentric cleaning 3~5 times in step (4), then uses
Ethyl alcohol eccentric cleaning 3~5 times；It places into baking oven, in 60~90 DEG C of freeze-day with constant temperature 8~15 hours, obtains reactant presoma
Precipitation.
In the above-mentioned technical solutions, calcination temperature is 700 DEG C in step (5), and the time is 2 hours.
The beneficial effects of the invention are as follows：
Nanoscale near-spherical scandium oxide base up-conversion luminescent material provided by the invention is the light activated nanoscale of near-infrared
The luminescent material of near-spherical, compared with scandium oxide base up-conversion luminescent material prepared by conventional method, particle is small, pattern rule,
Good dispersion.Sample is nanoscale near-spherical, and average diameter is 10~30nm, and dispersibility is preferably.
The present invention nanoscale near-spherical scandium oxide base up-conversion luminescent material, 980nm wavelength it is infrared ray excited under
The visible light of 400 bright~850nm can be observed.With the scandium oxide base up-conversion luminescence prepared using conventional high-temperature solid phase method
Material is compared, smaller to shine more preferably.In addition, prepared using hydrothermal method using organic alkali solution modulation with document report
Sample is compared, and light emission luminance further increases 10 times.
The preparation method of nanoscale near-spherical scandium oxide base up-conversion luminescent material provided by the invention, be using hydro-thermal and
Annealing is combined, have controllability it is good, reaction temperature is low, low for equipment requirements, it is environmentally safe the advantages that.
In preparation process, reactant is adjusted with sodium hydrate aqueous solution and oleic acid, reactant is made to form pure phase；At annealing
When reason, roasting only need to reach 700~1000 DEG C, when good dispersion can be prepared at 700 DEG C in temperature, be not easy to reunite,
The smaller near-spherical scandium oxide base up-conversion luminescent material of particle size.Such as see transmission electron microscope photo Fig. 1, the nanometer near-spherical of synthesis
A diameter of 10~30nm, dispersibility is preferably.
Description of the drawings
Invention is further described in detail with reference to the accompanying drawings and detailed description.
Fig. 1 is embodiment 1：Sc1.88O3:Er3+ 0.02, Yb3+ 0.1Transmission electron microscope photo.
Fig. 2 is embodiment 1：Sc1.88O3:Er3+ 0.02,Yb3+ 0.1Up-conversion emission spectrum under 980nm excitations.
Fig. 3 is embodiment 1：Sc1.88O3:Er3+ 0.02, Yb3+ 0.1XRD diffracting spectrums.
Fig. 4 is embodiment 2：Sc1.79O3:Er3+ 0.01, Yb3+ 0.2XRD diffracting spectrums.
Fig. 5 is embodiment 3：Sc1.78O3:Er3+ 0.02, Yb3+ 0.2Up-conversion emission spectrum under 980nm excitations.
Fig. 6 is embodiment 4：Sc1.88O3:Er3+ 0.02, Yb3+ 0.1Up-conversion emission spectrum under 980nm excitations.
Fig. 7 is embodiment 5：Sc1.88O3:Er3+ 0.02,Yb3+ 0.1Up-conversion emission spectrum under 980nm excitations.
Fig. 8 is embodiment 6：Sc1.88O3:Er3+ 0.02, Yb3+ 0.1Transmission electron microscope photo.
Fig. 9 is embodiment 7：Sc1.88O3:Er3+ 0.02,Yb3+ 0.1Transmission electron microscope photo.
Figure 10 is embodiment 8：Sc1.88O3:Tm3+ 0.02,Yb3+ 0.1Up-conversion emission spectrum under 980nm excitations.
Figure 11 is embodiment 9:Sc1.88O3:Ho3+ 0.02, Yb3+ 0.1Up-conversion emission spectrum under 980nm excitations.
Specific implementation mode
The present invention provides a kind of nanoscale near-spherical scandium oxide base up-conversion luminescent material, has following below formula
Compound：Sc2(1-x-y)O3：M3+ 2x, Yb3+ 2y；Wherein, M is one kind in rare earth element Ho, Er, Tm；X, y are element mole point
Number, value range are：0.0001≤x≤0.10,0.0001≤y≤0.20.The up-conversion luminescent material is cubic crystal
It is sesquichloride, evengranular near-spherical, average diameter is 10~30nm.
The present invention also provides a kind of preparation method of nanoscale near-spherical scandium oxide base up-conversion luminescent material, including it is following
Step：
(1) expression formula Sc is pressed2(1-x-y)O3：M3+ 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 Tm (NO3)3、Er(NO3)3、Ho(NO3)3In one kind
In beaker, absolute ethyl alcohol is added, absolute ethyl alcohol volume is about the 70% of reactor volume, is fully stirred using magnetic stirring apparatus
It mixes, obtains uniform mixed solution；
Sc(NO3)3、Yb(NO3)3、Tm(NO3)3、Ho(NO3)3And Er (NO3)3The preparation of standard solution：
4-5N Sc are accurately weighed respectively2O3, Yb2O3, Tm2O3, Ho2O3, Er2O3, it 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)3A concentration of 1mol/L, Yb (NO3)3A concentration of 0.2mol/L, Tm (NO3)3A concentration of 0.2mol/L,
Ho(NO3)3A concentration of 0.2mol/L, Er (NO3)3The nitrate standard aqueous solution of a concentration 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.
(2) sodium hydrate aqueous solution is added dropwise while stirring in the mixed solution prepared to step (1), is stirred 30min,
A concentration of 3.75mol/L of the wherein described sodium hydroxide；
(3) step (2) is obtained suspension oleic acid is added dropwise to be sufficiently stirred 1~2 hour, obtain uniform and stable suspended
Liquid；
(4) suspension that step (3) 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, first uses deionized water eccentric cleaning 3~5 times, then is centrifuged clearly with ethyl alcohol
It washes 3~5 times；It places into baking oven, in 60~90 DEG C of freeze-day with constant temperature 8~15 hours, obtains reactant presoma precipitation；
(5) reactant presoma precipitation will be obtained in step (4) to be put into corundum crucible and be capped, and is placed in high temperature furnace, into
Row roasting, calcination temperature are 700~1000 DEG C, and roasting time is 1~3 hour, and taking-up grinds and obtains final product nanoscale class
Spherical scandium oxide base up-conversion luminescent material.
Sc (NO used in following embodiment3)3A concentration of 1mol/L, Yb (NO3)3A concentration of 0.2mol/L, Tm (NO3)3It is dense
Degree is 0.2mol/L, Ho (NO3)3A concentration of 0.2mol/L, Er (NO3)3A concentration of 0.2mol/L, naoh concentration are
3.75mol/L。
Embodiment 1
By expression formula Sc2(1-x-y)O4：M3+ 2x, Yb3+ 2yIn the stoichiometric ratio of each substance measured respectively into 100mL small beakers
Take 940 μ L Sc (NO3)3, 250 μ L Yb (NO3)3, 50 μ L Er (NO3)3, add about 20mL absolute ethyl alcohols；Then while stirring
Sodium hydrate aqueous solution 1.7mL is added dropwise to above-mentioned mixed liquor, is stirred 30min, oleic acid 1mL is then added dropwise, fills
Divide stirring 1~2 hour.Gained suspension is put into hydrothermal reaction kettle and is reacted 24 hours for 180 DEG C, natural cooling, by sediment
Centrifugation is taken out, and first uses deionized water, then distinguish centrifuge washing 3 times with absolute ethyl alcohol.It is put into baking oven, 80 DEG C of dryings 15 hours obtain
It is precipitated to reactant presoma；Reactant presoma precipitation is put into corundum crucible and is capped, is placed in high temperature furnace, calcination temperature
It it is 700 DEG C, roasting time is 2 hours, takes out grinding and obtains converting on infrared ray excited nanoscale near-spherical scandium oxide base
Luminescent material Sc1.88O3:Er3+ 0.02, Yb3+ 0.1。
Pattern, upconversion emission and the XRD of the embodiment sample, which are scanned, is：
Transmission electron microscope photo is shown in Fig. 1, and the nanoscale near-spherical average diameter of synthesis is 10~30nm, and dispersibility is preferably；
Up-conversion emission spectrum under 980nm excitations 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 spectrums are shown in Fig. 3, with Sc2O4Standard diffraction composes (JCPDS card 84-1844) unanimously, and diffraction maximum half
Peak width is larger, illustrates that particle size is smaller；
Embodiment 2
By expression formula Sc2(1-x-y)O3：M3+ 2x, Yb3+ 2yIn the stoichiometric ratio of each substance measured respectively into 100mL small beakers
Take 895 μ L Sc (NO3)3, 500 μ L Yb (NO3)3, 25 μ L Er (NO3)3, about 20mL absolute ethyl alcohols are added, then while stirring
Sodium hydrate aqueous solution 2mL is added dropwise to above-mentioned mixed liquor, is stirred 30min, oleic acid 1mL is then added dropwise, fully
Stir 1~2h.Gained suspension is put into hydrothermal reaction kettle and is reacted 24 hours for 180 DEG C, natural cooling, by sediment centrifuging and taking
Go out, first uses deionized water, then distinguish centrifuge washing 3 times with absolute ethyl alcohol.It is put into baking oven, 80 DEG C of dryings 15 hours are reacted
Object presoma precipitates；Reactant presoma precipitation is put into corundum crucible and is capped, is placed in high temperature furnace, calcination temperature 700
DEG C, roasting time is 2 hours, takes out grinding and obtains infrared ray excited nanoscale near-spherical scandium oxide base up-conversion luminescence material
Expect Sc1.79O3:Er3+ 0.01, Yb3+ 0.2。
Embodiment sample XRD diffracting spectrums are shown in Fig. 4, with Sc2O4Standard diffraction composes (JCPDS card 84-1844) one
It causes, and diffraction maximum half-peak breadth is larger, illustrates that particle size is smaller.
Embodiment 3
By expression formula Sc2(1-x-y)O3：M3+ 2x, Yb3+ 2yIn the stoichiometric ratio of each substance measured respectively into 100mL small beakers
Take 890 μ L Sc (NO3)3, 500 μ L Yb (NO3)3, 50 μ L Er (NO3)3, about 20mL absolute ethyl alcohols are added, then while stirring
Sodium hydrate aqueous solution 2mL is added dropwise to above-mentioned mixed liquor, is stirred 30min, oleic acid 1mL is then added dropwise, fully
Stir 1~2h.Gained suspension is put into hydrothermal reaction kettle and is reacted 24 hours for 180 DEG C, natural cooling, by sediment centrifuging and taking
Go out, first uses deionized water, then distinguish centrifuge washing 3 times with absolute ethyl alcohol.It is put into baking oven, 80 DEG C of dryings 15 hours are reacted
Object presoma precipitates；Reactant presoma precipitation is put into corundum crucible and is capped, is placed in high temperature furnace, calcination temperature 700
DEG C, roasting time is 2 hours, takes out grinding and obtains infrared ray excited nanoscale near-spherical scandium oxide base up-conversion luminescence material
Expect Sc1.78O3:Er3+ 0.02, Yb3+ 0.2。
The upconversion emission of the embodiment sample is：
Up-conversion emission spectrum under 980nm excitations 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.
Embodiment 4
By expression formula Sc2(1-x-y)O3：M3+ 2x, Yb3+ 2yIn the stoichiometric ratio of each substance measured respectively into 100mL small beakers
Take 940 μ L Sc (NO3)3, 250 μ L Yb (NO3)3, 50 μ L Er (NO3)3, about 20mL absolute ethyl alcohols are added, then while stirring
Sodium hydrate aqueous solution 2mL is added dropwise to above-mentioned mixed liquor, is stirred 30min, oleic acid 1mL is then added dropwise, fully
Stir 1~2h.Gained suspension is put into hydrothermal reaction kettle and is reacted 24 hours for 180 DEG C, natural cooling, by sediment centrifuging and taking
Go out, first uses deionized water, then distinguish centrifuge washing 3 times with absolute ethyl alcohol.It is put into baking oven, 80 DEG C of dryings 15 hours are reacted
Object presoma precipitates；Reactant presoma precipitation is put into corundum crucible and is capped, is placed in high temperature furnace, calcination temperature 700
DEG C, roasting time is 2 hours, takes out grinding and obtains infrared ray excited nanoscale near-spherical scandium oxide base up-conversion luminescence material
Expect Sc1.88O3:Er3+ 0.02, Yb3+ 0.1。
The embodiment sample upconversion emission is：
Up-conversion emission spectrum under 980nm excitations is shown in Fig. 6, is 7mW/mm in exciting power density2980nm excitation under,
Clearly red up-conversion luminescence can be observed in naked eyes.
Embodiment 5
By expression formula Sc2(1-x-y)O3：M3+ 2x, Yb3+ 2yIn the stoichiometric ratio of each substance measured respectively into 100mL small beakers
Take 940 μ L Sc (NO3)3, 250 μ L Yb (NO3)3, 50 μ L Er (NO3)3, about 20mL absolute ethyl alcohols are added, then while stirring
Sodium hydrate aqueous solution 1.5mL is added dropwise to above-mentioned mixed liquor, is stirred 30min, oleic acid 1mL is then added dropwise, fills
Divide stirring 1~2h.Gained suspension is put into hydrothermal reaction kettle and is reacted 24 hours for 180 DEG C, natural cooling centrifuges sediment
It takes out, first uses deionized water, then distinguish centrifuge washing 3 times with absolute ethyl alcohol.It is put into baking oven, 80 DEG C of dryings 15 hours obtain anti-
Object presoma is answered to precipitate；Reactant presoma precipitation is put into corundum crucible and is capped, is placed in high temperature furnace, calcination temperature is
700 DEG C, roasting time is 2 hours, takes out grinding and obtains converting hair on infrared ray excited nanoscale near-spherical scandium oxide base
Luminescent material Sc1.88O3:Er3+ 0.02,Yb3+ 0.1。
The embodiment sample upconversion emission is：
Up-conversion emission spectrum under 980nm excitations is shown in Fig. 7, is 7mW/mm in exciting power density2980nm excitation under,
Clearly red up-conversion luminescence can be observed in naked eyes.
Embodiment 6
By expression formula Sc2(1-x-y)O3：M3+ 2x, Yb3+ 2yIn the stoichiometric ratio of each substance measured respectively into 100mL small beakers
Take 940 μ L Sc (NO3)3, 250 μ L Yb (NO3)3, 50 μ L Er (NO3)3, about 20mL absolute ethyl alcohols are added, then while stirring
Sodium hydrate aqueous solution 2mL is added dropwise to above-mentioned mixed liquor, is stirred 30min, 315 μ L of oleic acid are then added dropwise, fill
Divide stirring 1~2h.Gained suspension is put into hydrothermal reaction kettle and is reacted 24 hours for 180 DEG C, natural cooling centrifuges sediment
It takes out, first uses deionized water, then distinguish centrifuge washing 3 times with absolute ethyl alcohol.It is put into baking oven, 80 DEG C of dryings 15 hours obtain anti-
Object presoma is answered to precipitate；Reactant presoma precipitation is put into corundum crucible and is capped, is placed in high temperature furnace, calcination temperature is
700 DEG C, roasting time is 2 hours, takes out grinding and obtains converting hair on infrared ray excited nanoscale near-spherical scandium oxide base
Luminescent material Sc1.88O3:Er3+ 0.02,Yb3+ 0.1。
The embodiment sample transmission electron microscope photo is shown in that Fig. 8 is：The nanoscale near-spherical average diameter of synthesis is 10~30nm,
It is dispersed preferable；
Embodiment 7
By expression formula Sc2(1-x-y)O3：M3+ 2x, Yb3+ 2yIn the stoichiometric ratio of each substance measured respectively into 100mL small beakers
Take 940 μ L Sc (NO3)3, 250 μ L Yb (NO3)3, 50 μ L Er (NO3)3, about 20mL absolute ethyl alcohols are added, then while stirring
Sodium hydrate aqueous solution 2mL is added dropwise to above-mentioned mixed liquor, is stirred 30min, 631 μ L of oleic acid are then added dropwise, fill
Divide stirring 1~2h.Gained suspension is put into hydrothermal reaction kettle and is reacted 24 hours for 180 DEG C, natural cooling centrifuges sediment
It takes out, first uses deionized water, then distinguish centrifuge washing 3 times with absolute ethyl alcohol.It is put into baking oven, 80 DEG C of dryings 15 hours obtain anti-
Object presoma is answered to precipitate；Reactant presoma precipitation is put into corundum crucible and is capped, is placed in high temperature furnace, calcination temperature is
700 DEG C, roasting time is 2 hours, takes out grinding and obtains converting hair on infrared ray excited nanoscale near-spherical scandium oxide base
Luminescent material Sc1.88O3:Er3+ 0.02,Yb3+ 0.1。
The embodiment sample transmission electron microscope photo is shown in that Fig. 9 is：The nanoscale near-spherical average diameter of synthesis is 10~30nm,
It is dispersed preferable；
Embodiment 8
By expression formula Sc2(1-x-y)O3：M3+ 2x, Yb3+ 2yIn the stoichiometric ratio of each substance measured respectively into 100mL small beakers
Take 940 μ L Sc (NO3)3, 250 μ L Yb (NO3)3, 50 μ L Tm (NO3)3, about 20mL absolute ethyl alcohols are added, then while stirring
Sodium hydrate aqueous solution 2mL is added dropwise to above-mentioned mixed liquor, is stirred 30min, oleic acid 1mL is then added dropwise, fully
Stir 1~2h.Gained suspension is put into hydrothermal reaction kettle and is reacted 48 hours for 190 DEG C, natural cooling, by sediment centrifuging and taking
Go out, first uses deionized water, then distinguish centrifuge washing 3 times with absolute ethyl alcohol.It is put into baking oven, 90 DEG C of dryings 8 hours obtain reactant
Presoma precipitates；Reactant presoma precipitation is put into corundum crucible and is capped, is placed in high temperature furnace, calcination temperature is 700 DEG C,
Roasting time is 3 hours, takes out grinding and obtains infrared ray excited nanoscale near-spherical scandium oxide base up-conversion luminescent material
Sc1.88O3:Tm 3+ 0.02, Yb3+ 0.1。
The embodiment sample upconversion emission is：
Up-conversion emission spectrum under 980nm excitations is shown in Figure 10, is 7mW/mm in exciting power density2980nm excitation under,
Naked eyes can be observed blue up-conversion luminous.
Embodiment 9
By expression formula Sc2(1-x-y)O3：M3+ 2x, Yb3+ 2yIn the stoichiometric ratio of each substance measured respectively into 100mL small beakers
Take 940 μ L Sc (NO3)3, 250 μ L Yb (NO3)3, 50 μ L Ho (NO3)3, about 20mL absolute ethyl alcohols are added, then while stirring
Sodium hydrate aqueous solution 2mL is added dropwise to above-mentioned mixed liquor, is stirred 30min, oleic acid 1mL is then added dropwise, fully
Stir 1~2h.Gained suspension is put into hydrothermal reaction kettle and is reacted 12 hours for 160 DEG C, natural cooling, by sediment centrifuging and taking
Go out, first uses deionized water, then distinguish centrifuge washing 5 times with absolute ethyl alcohol.It is put into baking oven, 60 DEG C of dryings 15 hours are reacted
Object presoma precipitates；Reactant presoma precipitation is put into corundum crucible and is capped, is placed in high temperature furnace, calcination temperature 700
DEG C, roasting time is 1 hour, takes out grinding and obtains infrared ray excited nanoscale near-spherical scandium oxide base up-conversion luminescence material
Expect Sc1.88O3:Ho 3+ 0.02, Yb3+ 0.1。
The embodiment sample upconversion emission is：
Up-conversion emission spectrum under 980nm excitations is shown in Figure 11, is 7mW/mm in exciting power density2980nm excitation
Under, clearly red green up-conversion luminescence can be observed in naked eyes.
Embodiment 10
By expression formula Sc2(1-x-y)O4：M3+ 2x, Yb3+ 2yIn the stoichiometric ratio of each substance measured respectively into 100mL small beakers
Take 940 μ L Sc (NO3)3, 0.25 μ L Yb (NO3)3, 0.5 μ L Er (NO3)3, add about 20mL absolute ethyl alcohols；Then side is stirred
While sodium hydrate aqueous solution 1.7mL is added dropwise to above-mentioned mixed liquor, it is stirred 30min, oleic acid 1mL is then added dropwise,
It is sufficiently stirred 1~2 hour.Gained suspension is put into hydrothermal reaction kettle and is reacted 24 hours for 180 DEG C, natural cooling will precipitate
Object centrifugation is taken out, and first uses deionized water, then distinguish centrifuge washing 3 times with absolute ethyl alcohol.It is put into baking oven, 80 DEG C of dryings 15 hours,
Obtain reactant presoma precipitation；Reactant presoma precipitation is put into corundum crucible and is capped, is placed in high temperature furnace, roasting temperature
Degree is 1000 DEG C, and roasting time is 2 hours, takes out grinding and obtains turning on infrared ray excited nanoscale near-spherical scandium oxide base
Change luminescent material Sc1.9996O3:Er3+ 0.0002, Yb3+ 0.0002。
Embodiment 11
By expression formula Sc2(1-x-y)O4：M3+ 2x, Yb3+ 2yIn the stoichiometric ratio of each substance measured respectively into 100mL small beakers
Take 940 μ L Sc (NO3)3, 1000 μ L Yb (NO3)3, 250 μ L Er (NO3)3, add about 20mL absolute ethyl alcohols；Then side is stirred
While sodium hydrate aqueous solution 1.7mL is added dropwise to above-mentioned mixed liquor, it is stirred 30min, oleic acid 1mL is then added dropwise,
It is sufficiently stirred 1~2 hour.Gained suspension is put into hydrothermal reaction kettle and is reacted 24 hours for 180 DEG C, natural cooling will precipitate
Object centrifugation is taken out, and first uses deionized water, then distinguish centrifuge washing 3 times with absolute ethyl alcohol.It is put into baking oven, 80 DEG C of dryings 15 hours,
Obtain reactant presoma precipitation；Reactant presoma precipitation is put into corundum crucible and is capped, is placed in high temperature furnace, roasting temperature
Degree is 600 DEG C, and roasting time is 2 hours, takes out grinding and obtains turning on infrared ray excited nanoscale near-spherical scandium oxide base
Change luminescent material Sc1.4O3:Er3+ 0.2, Yb3+ 0.4。
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 near-spherical scandium oxide base up-conversion luminescent material, which is characterized in that it has following below formula
Compound：Sc2(1-x-y)O3：M3+ 2x, Yb3+ 2y；
Wherein, M is one kind in rare earth element Ho, Er, Tm；X, y are element molar fraction, and value range is：0.0001≤x
≤ 0.10,0.0001≤y≤0.20.
2. nanoscale near-spherical scandium oxide base up-conversion luminescent material according to claim 1, which is characterized in that it is
The uniform near-spherical of grain, average diameter are 10~30nm.
3. nanoscale near-spherical scandium oxide base up-conversion luminescent material according to claim 1, which is characterized in that it is vertical
Prismatic crystal system sesquichloride.
4. a kind of preparation method of nanoscale near-spherical scandium oxide base up-conversion luminescent material described in claim 1, feature
It is, includes the following steps：
(1) expression formula Sc is pressed2(1-x-y)O3：M3+ 2x, Yb3+ 2y, x, y are element molar fraction, and value range is：0.0001≤x≤
0.10,0.0001≤y≤0.20, in the stoichiometric ratio of each substance measure Sc (NO respectively3)3、Yb(NO3)3, and measure Tm
(NO3)3、Er(NO3)3、Ho(NO3)3In one kind, be added ethanol solution, preparation obtain mixed alkoxide solution；
(2) sodium hydrate aqueous solution is added dropwise while stirring in the mixed alkoxide solution prepared to step (1), continues to stir；
(3) oleic acid is added dropwise in the solution obtained to step (2) to be sufficiently stirred, obtains uniform and stable suspension；
(4) suspension that step (3) 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, uses deionized water and ethyl alcohol eccentric cleaning respectively, it is dry, obtain reactant
Presoma precipitates；
(5) the reactant presoma obtained in step (4) precipitation is put into corundum crucible and is capped, is placed in high temperature furnace, carried out
Roasting, calcination temperature are 700~1000 DEG C, and roasting time is 1~3 hour, take out grinding and obtain final product nanoscale class ball
Shape scandium oxide base up-conversion luminescent material.
5. the preparation method of nanoscale near-spherical scandium oxide base up-conversion luminescent material according to claim 4, feature
It is, the step (2) is specially：
The sodium hydroxide of a concentration of 3.75mol/L of 1.5mL-2.0mL is added dropwise in the mixed alkoxide solution prepared to step (1)
Aqueous solution is stirred 30min.
6. the preparation method of nanoscale near-spherical scandium oxide base up-conversion luminescent material according to claim 4, feature
It is, the step (3) is specially：
The oleic acid of 315 μ L-1.0mL is added dropwise in the solution obtained to step (2), is sufficiently stirred 1~2 hour, obtains suspended
Liquid.
7. the preparation method of nanoscale near-spherical scandium oxide base up-conversion luminescent material according to claim 4, feature
It is, the reaction temperature of step (4) is 180 DEG C, and the time is 24 hours.
8. the preparation method of nanoscale near-spherical scandium oxide base up-conversion luminescent material according to claim 4, feature
It is, the sediment of gained first uses deionized water eccentric cleaning 3~5 times in step (4), then with ethyl alcohol eccentric cleaning 3~5 times；
It places into baking oven, in 60~90 DEG C of freeze-day with constant temperature 8~15 hours, obtains reactant presoma precipitation.
9. the preparation method of nanoscale near-spherical scandium oxide base up-conversion luminescent material according to claim 4, feature
It is, calcination temperature is 700 DEG C in step (5), and the time is 2 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110144219A (en) * | 2019-06-25 | 2019-08-20 | 长春工业大学 | A kind of nanoscale alkaline earth scandium oxide up-conversion luminescent material and preparation method thereof |
| CN110699080A (en) * | 2019-11-11 | 2020-01-17 | 长春工业大学 | Ultra-small scandium oxide based up-conversion luminescent material and preparation method thereof |
-
2018
- 2018-05-02 CN CN201810409968.8A patent/CN108659838A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| DAGUANG LI等: "Synthesis and luminescence properties of RE3+ (RE=Yb,Er,Tm,Eu,Tb)-doped Sc2O3 microcrystals", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110144219A (en) * | 2019-06-25 | 2019-08-20 | 长春工业大学 | A kind of nanoscale alkaline earth scandium oxide up-conversion luminescent material and preparation method thereof |
| CN110699080A (en) * | 2019-11-11 | 2020-01-17 | 长春工业大学 | Ultra-small scandium oxide based up-conversion luminescent material and preparation method thereof |
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