CN107286924A - Upper conversion nano crystalline material of the infrared ray excited orthogonal fluorescent emission of redgreenblue and preparation method thereof - Google Patents
Upper conversion nano crystalline material of the infrared ray excited orthogonal fluorescent emission of redgreenblue and preparation method thereof Download PDFInfo
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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
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Abstract
The invention belongs to nano fluorescent material technical field, specially a kind of upper conversion nano crystalline material of the orthogonal fluorescent emission of infrared ray excited redgreenblue and preparation method thereof.The material is made up of the shell of up-conversion luminescence centronucleus and two kinds of up-conversion luminescence shells, inert barriers, energy transmission layer and the type of energy-absorbing layer five；Up-conversion luminescence centronucleus absorbs the exciting light of specific wavelength with each energy-absorbing layer；Energy between energy transmission layer transmission energy-absorbing layer and visible luminescent layer；The inert material that inert barriers are prohibited by energy transmission, which isolates each centre of luminescence, makes its fluorescence process be independent of each other；Each energy-absorbing layer thickness is adjusted, to reach filtering infrared excitation luminous intensity so that the energy of each each self-absorption different wave length infrared excitation light of energy-absorbing layer, and the no centre of luminescence of correspondence is eventually transferred to；The present invention realizes the separate fluorescent emission of red green blue tricolor.The nano material can be used for body three-dimensional colour display field.
Description
Technical field
The invention belongs to nano fluorescent material technical field, and in particular to visible light wave range redgreenblue independent orthogonal is glimmering
Photoemissive upper conversion nano crystalline material and preparation method thereof.
Background technology
The importance of advanced information society, visual information transmission and performance progressively strengthens.Wherein show can be i.e. for three-dimensional colour
When show omnibearing angel multidate information, do not influenceed compared with plane is shown by viewing angle.Three-dimensional stereo display technique exists
The fields such as optical information, medical treatment, national defence are with a wide range of applications.Virtual three-dimensional common at present shows main by people's eyes
Parallax, receive image difference by eyes and produce pseudo- Three-dimensional Display.Another aspect hologram technology is done using the diffraction of light
Relate to, real 3-D view is produced in particular space, but hologram technology has compared with the day of one's doom to range of observation and display space
System, and Large-scale Mobile part is needed, be not suitable for complicated display control.In contrast to this, body dimension display technologies are shown
It is the actual stereoscopic images with physical depth.Transparent solid medium is full of three-dimensional spatial area, it is selectable by laser
Fixed point is excited inside display body, can inspire fluorescence.When method of the laser by setting, quickly scan and excite inside display body
During spatial point, the persistence effect of human eye vision is utilized, it is possible to form a width three-dimensional image.Scanning process is with certain frequency
Rate enters line translation, just can obtain dynamic image.
1997, Downing started the dimension display technologies of rare earth fluoride glass, is successfully made up-conversion fluorescence
Stereoscopic display.Using praseodymium is doped with, erbium, the fluoride glass of thulium, each dopant utilizes the suitable laser of a pair of wavelength
Cross-excitation.By commercialized three pairs of infrared lasers in vitreum three dimensions inner focusing, three are realized in centimeter scale
The colored display of dimension.But this method has many limitations so far, on the one hand in order to solve the problems that rare earth element is mixed, use
Be the doping of a large amount of thin layers, be bonded layer by layer by optical adhesive, material manufacture is sufficiently complex, material limited size.Show simultaneously
Show that internal portion's redgreenblue voxel is disconnected from each other, local uneven, by thickness of thin layer control, the resolution limitations of focusing are in thin
Layer yardstick and it is relatively low.On the other hand, this method needs two beam laser accurately to intersect at predetermined position, therefore hot spot is not
Can be too small, otherwise the beam laser of scanning process two be difficult to it is overlapping so that the control accuracy requirement to laser beam position is higher, high point
Resolution requires that volumetric pixel is also more small, and resolution ratio is also therefore limited.Final this method is only capable of obtaining in centimeter scale space, and hundred
The resolution ratio of micron level.
In view of the problem of face two resolution ratio of body three-dimensional imaging, the nano particle one side particle sheet of core shell structure
Body can combine three colour solids element, and imaging voxel is in nanoscale；Another aspect nano material can be filled with substantially uniformity and shown
Body space, has very high application value in terms of body three-dimensional imaging.Conversion nano is glimmering on wherein panchromatic adjustable individual particle
Luminescent material, using the near-infrared laser source excitation of three kinds of different wave lengths, penetration depth is compared to the quantum dot that ultraviolet source is excited
Material is high, thus display space is bigger.While a kind of only a kind of corresponding fluorescent emission of color of near infrared light excitation wavelength, can
See that optical band three primary colors launch separate orthogonal luminous, hot spot can focus on smaller, can effectively improve near infrared light
The resolution ratio that body three-dimensional colour is shown.Three primary colors transmitting can be adjusted by three kinds of exciting light ratios, so as to obtain panchromatic color
Domain shows there is good prospect in new body three-dimensional colour display technology field.
The content of the invention
Simple it is an object of the invention to provide a kind of preparation technology, 980 nm, 808 nm, tri- kinds of 1532 nm are orthogonal red
Outer light excites upper conversion nano crystalline material of redgreenblue independent fluorescence transmitting and preparation method thereof.
980 nm that the present invention is provided, 808 nm, the orthogonal infrared ray excited redgreenblue independent fluorescences of tri- kinds of 1532 nm
The upper conversion nano crystalline material of transmitting, the core shell structure constituted with a core, seven shells, wherein, a core is up-conversion luminescence
Centronucleus, 1532 nm near-infrared laser energy can be absorbed simultaneously；Seven shells are followed successively by from inside to outside：In inert barriers, internal layer
Change luminescent layer, energy transmission layer, 808 nm near-infrared lasers energy-absorbing layers, inert barriers, outer layer up-conversion luminescence layer
It is also simultaneously 980 nm near-infrared lasers energy-absorbing layers, inert barriers；
By adjusting the thickness of each energy-absorbing layer, the infrared excitation luminous intensity of filtering corresponding wavelength can be reached so that each
Individual energy-absorbing layer absorbs the energy of different wave length infrared excitation light independently of one another, and it is different to be eventually transferred to correspondence
The centre of luminescence；980 nm that the present invention is provided, 808 nm, the orthogonal infrared ray excited redgreenblues of tri- kinds of 1532 nm are independently glimmering
Photoemissive upper conversion nano crystalline material, will provide a kind of new method for body three-dimensional colour Display Technique, can effectively carry
High-resolution, has broad application prospects in Modern three-dimensional field of stereoscopic display.
The present invention is planted, and up-conversion luminescence centronucleus is used for the exciting light for absorbing 1532 nm wavelength, and launches visible light wave
The feux rouges of section；The up-conversion luminescence shell of inner layer is used for the energy for receiving energy transmission layer, and launches visible light wave range
Green glow；Energy transmission layer is used to transmit the energy between energy-absorbing layer and up-conversion luminescence shell and play to isolate energy suction
The effect of layer and up-conversion luminescence shell is received, to prevent energy to be quenched；Energy-absorbing layer is used for the infrared light for absorbing 808nm wavelength
Energy, and it is transferred into energy transmission layer；The up-conversion luminescence shell of outer layer is used for the infrared light for absorbing 980 nm wavelength
Energy and the blue light for launching visible light wave range；Inert barriers play a part of energy transmission between isolation shell, to prevent
Unnecessary energy transmission；Respectively can mistake by the shell thickness for adjusting energy-absorbing layer and the up-conversion luminescence layer of outer layer
Filter the infrared energy of 808 nm wavelength and the infrared energy of 980 nm wavelength so that excite the energy of infrared light as few as possible
Ground enters nanocrystal interior shell, and the fluorescence of other shells is not influenceed, realize three kinds of different wave lengths it is infrared ray excited under
The mutually orthogonal independence of fluorescent emission.
In the present invention, the up-conversion luminescence centronucleus, up-conversion luminescence shell, including matrix and the centre of luminescence；Wherein,
Host material is：Fluoride, oxide, oxysulfide or halide；The fluoride is selected from：CaF2、BaF2、LaF3、YF3、
ZnF2、NaYF4、NaYbF4、LiYF4、KYF4、NaGdF4Or NaLuF4；The oxide is selected from：La2O3、Y2O3、Yb2O3、Gd2O3
Or Lu2O3；The oxysulfide is selected from Y2O2S、CaS2Or La2S3；The halide is selected from Cs3Lu2Br9；Centre of luminescence rare earth from
Son is selected from Ce3+、Pr3+、Nd3+、Sm3+、Eu3+、Tb3+、Dy3+、Ho3+、Er3+、Tm3+、Yb3+In one or several kinds；In luminous
The molar content of the heart is 0.01% ~ 100%（It is without host luminescent center only containing a kind of rare earth ion if for 100%）；On described
The conversion centre of luminescence can launch corresponding up-conversion fluorescence under the exciting of certain wavelength.For example 980 nm are excited down,
Tm3+It can launch the blue light based on 475nm, Er for the material of the centre of luminescence3+It can launch for the material of the centre of luminescence
Green glow and feux rouges based on 550nm and 650nm.
In the present invention, the energy transmission layer, including matrix and energy transfer center two parts；Wherein, host material is selected
From：Fluoride, oxide, oxysulfide or halide；The fluoride is selected from：CaF2、BaF2、LaF3、YF3、ZnF2、NaYF4、
NaYbF4、LiYF4、KYF4、NaGdF4Or NaLuF4；The oxide is selected from：La2O3、Y2O3、Yb2O3、Gd2O3Or Lu2O3；It is described
Oxysulfide is selected from Y2O2S、CaS2Or La2S3；The halide is selected from Cs3Lu2Br9；Energy transfer center material is Nd3+、Yb3+
In one or two kinds of；The molar content at energy transfer center is 0.01% ~ 50%；The energy transmission center can transmit energy
The approximately equal to energy of 980 nm photons.
In the present invention, the energy-absorbing layer includes energy absorption center and energy transfer center two parts；Wherein, it is described
Energy absorption center material is Nd3+、Yb3+In one or two kinds of；The molar content at energy absorption center is 10% ~ 90%；Should
Energy absorption center utilizes rare earth ion in the absorption of near infrared region（Such as Nd3+At 800 nm, Yb3+At 900 ~ 1000 nm）
It is enriched with energy；The energy transfer center material is Nd3+、Yb3+In one or two kinds of；Energy transfer center mole contains
Measure as 0.01% ~ 50%；The energy transmission center can absorb energy and be approximately equal to the energy of 800 nm photons, and convert it to energy
Amount is approximately equal to the energy of 980 nm photons, is then passed to energy transmission layer.
It is independently glimmering that the present invention provides above-mentioned 980 nm, 808 nm, the orthogonal infrared ray excited redgreenblues of tri- kinds of 1532 nm
The preparation method of photoemissive upper conversion nano crystalline material, is comprised the following steps that：
（1）The preparation of shell presoma：
A, earth solution presoma preparation：Rare-earth salts is dissolved among high boiling solvent under elevated temperature in vacuo；Its
In, rare-earth salts is selected from：Chloride, nitrate, acetate, oxide, trifluoroacetate, acetylacetonate, including rare earth member
Element is Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu；High boiling solvent is：Oleic acid, stearic acid,
One or several kinds in capric acid, laurate, myristic acid, palmitic acid, octadecylene, atoleine, olive oil；Solution temperature is
20-150 degrees Celsius；The concentration of final resulting solution is 0.01 mol/L to 5 mol/L；
B, sodium trifluoroacetate/potassium/lithium/barium solution preparation：By sodium trifluoroacetate or trifluoroacetic acid potassium or trifluoroacetic acid lithium or three
Fluoroacetic acid barium, is dissolved in high boiling solvent；High boiling solvent is：Oleic acid, stearic acid, capric acid, laurate, myristic acid, palm fibre
One or several kinds in palmitic acid acid, octadecylene, atoleine, olive oil；Solution temperature is 20-150 degrees Celsius；Final gained is molten
The concentration of liquid is 0.01 mol/L to 5 mol/L；
（2）Up-conversion luminescence center is synthesized：Rare-earth salts is dissolved among high boiling solvent under elevated temperature in vacuo, added
Remaining reaction thing, reacts under 200-320 degrees Celsius, inert gas atmosphere, that is, obtains dispersiveness and the preferable rare earth of uniformity
Nanocrystal.Wherein, rare-earth salts is selected from：Rare earth-iron-boron, rare earth trifluoroacetate, rare earth nitrades or lanthanon acetate；
Remaining reaction thing includes：One kind in ammonium fluoride, sodium fluoride, lithium fluoride, potassium fluoride, sodium hydroxide, potassium hydroxide, lithium hydroxide
Or it is several；The high-temperature solvent is the one or more in oleic acid, oleyl amine, trioctylphosphine, octadecylene or atoleine；
（3）The synthesis of core, the nano-crystal with core-shell structure body of@shells 1：The up-conversion luminescence center prepared using in previous step as nucleus,
Under hot conditions, according to the composition needs of shell, earth solution presoma is continually introduced into, incorporation way is is added dropwise, and temperature is
150-340 degrees Celsius, the thickness of shell, presoma and centre of luminescence core can be changed by adjusting the amount of the material of the presoma added
Material amount ratio be 1:5 to 10:1, it is preferably in a proportion of 1:3 to 5:1；Every time introduce higher boiling earth solution presoma with
The volume ratio of sodium trifluoroacetate/potassium/lithium/barium solution is 10:1 to 1:10, it is preferably in a proportion of 2:1 to 1:2；
（4）Core ,@shells 1, the synthesis of the nano-crystal with core-shell structure body of@shells 2：With the structure nano crystal of core shell 1 prepared in previous step
For nucleus, under the high temperature conditions, according to the composition needs of shell, shell precursor solution is continually introduced into, incorporation way is dropwise addition,
Temperature is 150-340 degrees Celsius；The body of higher boiling earth solution presoma and sodium trifluoroacetate/potassium/lithium/barium solution is introduced every time
Product ratio is 10:1 to 1:10；
（5）Core ,@shells 1 ,@shells 2, the synthesis of@...@shell n nano-crystal with core-shell structure bodies：Core, shell to be prepared in back
1st ,@shells 2 ,@...@shell n-1 structure nanos crystal are nucleus, under the high temperature conditions, according to the composition needs of shell, continuous alternating
Shell precursor solution is introduced, incorporation way is is added dropwise, and temperature is 150-340 degrees Celsius；Higher boiling earth solution is introduced every time
The volume ratio of presoma and sodium trifluoroacetate/potassium/lithium/barium solution is 10:1 to 1:10；Until n+7.
The material of 6@shells of core@shell 1@shells, 2@shells, 3@shells, 4@shells, 5@shells 7 synthesized by the present invention, the design of eight Rotating fields is realized
1532nm infrared ray excited rare earth ion Er3+Launch 650nm red fluorescences, the infrared ray excited lower generation Nd of 808 nm3+→Yb3 +→Ho3+Or Er3+Energy transfer process launches 550 nm green fluorescences, and 980 nm infrared lights swash lower generation Yb3+→Tm3+Energy is passed
The nm blue-fluorescences of procedure transmission 450 are passed, and just may filter that its correspondence absorbs ripple by adjusting the thickness of increase energy-absorbing layer
Long infrared light, for example, increase the nm energy-absorbing layers of outer layer 980, and 980 nm's of filtering correspondence excites infrared light it is not influenceed
The fluorescent emission of internal layer up-conversion luminescence layer, is achieved in the separate fluorescent emission of red green blue tricolor.Pass through regulation
1532 nm, 980 nm, 808 nm, tri- kinds of infrared excitation light ratios and intensity, it is possible to achieve the regulation of a wide range of colour gamut and difference
The regulation of brightness, the nano material can be used for body three-dimensional colour display field.
Brief description of the drawings
Fig. 1 is 980 nm, 808 nm, the orthogonal infrared ray excited redgreenblue independent fluorescence transmittings of tri- kinds of 1532 nm
The basic structure schematic diagram of upper conversion nano crystalline material.
Fig. 2 is the prepared nm hexagonal phases NaErF of particle diameter 1104@NaYF4@NaGdF4:Yb,Er@NaGdF4：Yb@
NaNdF4:Yb@NaYF4@NaGdF4:Yb,Tm@NaYF4 The nano-crystal with core-shell structure of 6@shells of core@shell 1@shells, 2@shells, 3@shells, 4@shells, 5@shells 7
The transmission electron microscope photo of body.
Fig. 3 is the prepared nm hexagonal phases NaErF of particle diameter 1104@NaYF4@NaGdF4:Yb,Er@NaGdF4：Yb@
NaNdF4:Yb@NaYF4@NaGdF4:Yb,Tm@NaYF4 The nano-crystal with core-shell structure of 6@shells of core@shell 1@shells, 2@shells, 3@shells, 4@shells, 5@shells 7
Fluorescence emission spectrum of the body under different excitation wavelengths.
Label in figure：1 is that up-conversion luminescence centronucleus absorbs 1532 nm near-infrared laser energy simultaneously；2nd, 6,8 be inertia
Separation layer；3 be internal layer up-conversion luminescence layer；4 be energy transmission layer；5 be 808 nm near-infrared laser energy-absorbing layers；7 be outer
Layer up-conversion luminescence layer is also simultaneously 980 nm near-infrared laser energy-absorbing layers.
Embodiment
（1）The preparation of the rare earth precursor grown for shell.
Y-OA（0.1 M）The preparation of presoma：5 mmol YCl are sequentially added in 250 mL three-necked bottles3, 20 mL oil
Acid（OA）, 30 mL octadecylenes（ODE）.140 degrees Celsius of reactions are heated under the conditions of vacuum and magnetic agitation and remove knot within 1 hour
Brilliant water and low boiling point solvent molecule, obtain the oleic acid complex Y-OA of clear（0.1 M）Presoma.
Gd,Yb,Er-OA （0.1M）The preparation of presoma：Gd,Yb,Er -OA（0.1M）Presoma preparation and it is above-mentioned
Y-OA（0.1 M）The preparation method of presoma is similar, will be above-mentioned in 5 mmol YCl3, replace with 3.9 mmol GdCl3,
1mmol YbCl3, 0.1 mmol ErCl3, synthetic method is identical.
Gd,Yb-OA（0.1M）The preparation of presoma：Gd,Yb -OA（0.1M）The preparation of presoma and above-mentioned Y-OA
（0.1 M）The preparation method of presoma is similar, will be above-mentioned in 5 mmol YCl3, replace with 4.9 mmol GdCl3, 1mmol
YbCl3, synthetic method is identical.
Nd, Yb-OA（0.1M）The preparation of presoma：Nd, Yb-OA（0.1M）The preparation of presoma and above-mentioned Y-OA
（0.1 M）The preparation method of presoma is similar, will be above-mentioned in 2.5 mmol YCl3, replace with 2 mmol NdCl3, 0.5
mmol YbCl3, synthetic method is identical.
Gd,Yb,Tm（0.1M）The preparation of presoma：Gd,Yb,Tm -OA（0.1M）The preparation of presoma and above-mentioned Y-OA
（0.1 M）The preparation method of presoma is similar, will be above-mentioned in 5 mmol YCl3, replace with 2.5 mmol GdCl3,
2.45mmol YbCl3, 0.05 mmol ErCl3, synthetic method is identical.
Na-TFA-OA（0.4M）The preparation of presoma：10 mmol sodium trifluoroacetates and 25 are added in 250 mL three-necked bottles
ML oleic acid, the room-temperature dissolution under vacuum and stirring condition obtains water white transparency clarification Na-TFA-OA precursor solutions.
（2）NaErF4The synthesis of nanocrystal.
It is reaction vessel to take 250 mL three neck round bottom flask, adds 1 mmol ErCl3, 6 mL oleic acid（OA）, 15 mL ten
Eight alkene（ODE）, water and oxygen that 140 DEG C and holding are removed in solution for 60 minutes are heated with stirring under vacuo, obtain transparent mixed
Close solution and be cooled to room temperature.By 2.5 mmol NaOH and 4 mmol NH4F is dissolved in 10 mL methanol solutions, is injected above-mentioned
Reaction solution is simultaneously warming up to 50 DEG C and continuously stirs curing in 30 minutes.After curing terminates, 100 DEG C are heated with stirring under vacuum condition simultaneously
Keep removing methanol, water, oxygen in 10 minutes, be warming up to 285 DEG C simultaneously under high-purity argon gas protection with 10 DEG C/min speed afterwards
Insulation reaction 90 minutes.After reaction terminates, reaction mother liquor is cooled to room temperature and taken out, adding isometric ethanol makes product from solution
Middle Precipitation.By centrifuging discrete obtained solid, absolute ethyl alcohol is reused by solid supersound washing and is centrifuged again, wash
Dry after 3-5 times, product is dissolved in standby in 10 mL hexamethylenes repeatedly.
（3）NaErF4@NaYF4The synthesis of the nano-crystal with core-shell structure of core@shells 1.
Take the above-mentioned purification liquid of 5 mL（~ 0.5 mmol）In 8 mL oleic acid（OA）, 12 mL octadecylenes（ODE）Mixing, true
100 DEG C are heated under empty condition to keep removing hexamethylene and oxygen in 30 minutes.Afterwards by reaction system with 20 DEG C/min speed
It is warming up to 280 DEG C.Then the mL Y-OA precursor solutions of alternate dropwise addition 1 and 0.5 mL Na-TFA-OA forerunners into reaction bulb
Body.Be added dropwise every time at intervals of 20 minutes.It is 8 times that total degree, which is added dropwise, and 280 DEG C of holding reacts 30 points after the completion of introducing presoma
Clock.After question response terminates, reaction solution is cooled to room temperature and taken out, adding isometric ethanol makes product Precipitation from solution.
By centrifuging discrete obtained solid, absolute ethyl alcohol being reused by solid supersound washing and is centrifuged again, washing is repeatedly after 3-5 times
Dry, product is dissolved in standby in 10 mL hexamethylenes.
（4）NaErF4 @NaYF4@NaGdF4:The synthesis of the nano-crystal with core-shell structure of 1@shells of Yb20%, Er2% core@shells 2.
Synthesis with the above-mentioned nano-crystal with core-shell structure of core@shells 1 is similar.By previous cyclohexane solution (~ 0.5
Mmol) with 8 mL oleic acid（OA）, 12 mL octadecylenes（ODE）Mixing, synthetic method is same as described above, only by Y-OA（0.1M)）
Precursor solution replaces with Gd, Yb, Er-OA（0.1M）Precursor solution, while the dropwise addition total degree for changing introducing presoma is
6 times, NaErF4@NaYF4@NaGdF4 can be prepared:The nano-crystal with core-shell structure of 1@shells of Yb20%, Er2% core@shells 2.
（5）NaErF4 @NaYF4@NaGdF4:Yb20%,Er2%@NaGdF4:The core shell structure of 2@shells of Yb20% core@1@shells of shell 3
The synthesis of nanocrystal.
Synthesis with the nano-crystal with core-shell structure of 1@shells of above-mentioned core@shells 2 is similar.By previous cyclohexane solution (~ 0.5
Mmol) with 8 mL oleic acid（OA）, 12 mL octadecylenes（ODE）Mixing, synthetic method is same as described above, only by Gd, Yb, Er-OA
（0.1M)）Precursor solution replaces with Gd, Yb-OA（0.1M）Precursor solution, while the dropwise addition for changing introducing presoma is always secondary
Number is 2 times, can prepare NaErF4@NaYF4@NaGdF4:Yb20%,Er2%@NaGdF4:The@shells 3 of 1@shells of Yb20% core@shells 2
Nano-crystal with core-shell structure.
（6）NaErF4 @NaYF4@NaGdF4:Yb20%,Er2%@NaGdF4:Yb20%@NaNdF4:The@of 1@shells of Yb20% core@shells 2
The synthesis of the nano-crystal with core-shell structure body of 3@shells of shell 4.
Synthesis with the nano-crystal with core-shell structure of 1@shells of above-mentioned core@shells, 2@shells 3 is similar.By previous cyclohexane solution (~
0.5 mmol) and 8 mL oleic acid（OA）, 12 mL octadecylenes（ODE）Mixing, synthetic method is same as described above, only by Gd, Yb-OA
（0.1M)）Precursor solution replaces with Nd, Yb-OA（0.1M）Precursor solution, while the dropwise addition for changing introducing presoma is always secondary
Number is 8 times, can be prepared：
NaErF4 @NaYF4@NaGdF4:Yb20%,Er2%@NaGdF4:Yb20%@NaNdF4:The@of 2@shells of Yb20% core@1@shells of shell 3
The nano-crystal with core-shell structure of shell 4.
（7）
NaErF4 @NaYF4@NaGdF4:Yb20%,Er2%@NaGdF4:Yb20%@NaNdF4:Yb20%@NaYF4The@of 1@shells of core@shells 2
The synthesis of the nano-crystal with core-shell structure body of 3@shells of shell, 4@shells 5.
Synthesis with the nano-crystal with core-shell structure of 3@shells of above-mentioned core@shells 1@shells, 2@shells 4 is similar.Previous hexamethylene is molten
Liquid (~ 0.5 mmol) and 8 mL oleic acid（OA）, 12 mL octadecylenes（ODE）Mixing, synthetic method is same as described above, only by Nd,
Yb-OA（0.1M)）Precursor solution replaces with Y-OA（0.1M）Precursor solution, while the dropwise addition for changing introducing presoma is total
Number of times is 4 times, can be prepared：
NaErF4 @NaYF4@NaGdF4:Yb20%,Er2%@NaGdF4:Yb20%@NaNdF4:Yb20%@NaYF4The@of 1@shells of core@shells 2
The nano-crystal with core-shell structure body of 3@shells of shell, 4@shells 5.
（8）
NaErF4@NaYF4@NaGdF4:Yb20%,Er2%@NaGdF4:Yb20%@NaNdF4:Yb20%@NaYF4@ NaGdF4:
The synthesis of the nano-crystal with core-shell structure body of 5@shells of Yb49%, Tm1% core@shell 1@shells, 2@shells, 3@shells, 4@shells 6.
Synthesis with the nano-crystal with core-shell structure of 4@shells of above-mentioned core@shells 1@shells, 2@shells, 3@shells 5 is similar.By previous hexamethylene
Alkane solution (~ 0.5 mmol) and 8 mL oleic acid（OA）, 12 mL octadecylenes（ODE）Mixing, synthetic method is same as described above, only will
Y-OA（0.1M)）Precursor solution replaces with Gd, Yb, Tm-OA（0.1M）Precursor solution, presoma is introduced while changing
It is 10 times that total degree, which is added dropwise, can prepare NaErF4 @ NaYF4 @ NaGdF4:Yb20%,Er2% @ NaGdF4:Yb20%@
NaNdF4:Yb20% @ NaYF4 @ NaGdF4:The core shell structure of 5@shells of Yb49%, Tm1% core@shell 1@shells, 2@shells, 3@shells, 4@shells 6 is received
Meter Jing.
（9）NaErF4 @ NaYF4 @ NaGdF4:Yb20%,Er2% @ NaGdF4:Yb20%@NaNdF4:Yb20% @
NaYF4 @ NaGdF4:Yb49%,Tm1%@NaYF4The nano-crystal with core-shell structure body of 6@shells of core@shell 1@shells, 2@shells, 3@shells, 4@shells, 5@shells 7
Synthesis.
Synthesis with the nano-crystal with core-shell structure of 1@shells of above-mentioned core@shells 2 is similar.By previous cyclohexane solution (~ 0.5
Mmol) with 8 mL oleic acid（OA）, 12 mL octadecylenes（ODE）Mixing, synthetic method is same as described above, only by Gd, Yb, Tm-OA
（0.1M)）Precursor solution replaces with Y-OA（0.1M）Precursor solution, while the dropwise addition total degree for changing introducing presoma is
4 times, NaErF can be prepared4 @ NaYF4 @ NaGdF4:Yb20%,Er2% @ NaGdF4:Yb20%@NaNdF4:Yb20% @
NaYF4 @ NaGdF4:Yb49%,Tm1%@NaYF4The nano-crystal with core-shell structure of 6@shells of core@shell 1@shells, 2@shells, 3@shells, 4@shells, 5@shells 7.
The design of eight Rotating fields, realizes the infrared ray excited rare earth ion Er of 1532nm3+Launch 650nm red fluorescences,
The infrared ray excited lower generation Nd of 808 nm3+→Yb3+→Ho3+Or Er3+Energy transfer process launches 550 nm green fluorescences, 980
Nm infrared lights swash lower generation Yb3+→Tm3+Energy transfer process launches 450 nm blue-fluorescences, and by adjusting energy absorption
What the thickness of layer just may filter that respective wavelength excites infrared light, it is not absorbed by internal layer energy-absorbing layer and is caused internal layer fluorescence
Transmitting, so as to realize the separate fluorescent emission of red green blue tricolor.
Claims (5)
1. a kind of upper conversion nano crystalline material of the orthogonal fluorescent emission of infrared ray excited redgreenblue, excites infrared light to distinguish
For 1532 nm, 808 nm, 980 nm；Characterized in that, the core shell structure with a core, seven shells, wherein, a core is upper turn
Light center core is changed, 1532 nm near-infrared laser energy can be absorbed simultaneously；Seven shells are followed successively by from inside to outside：Inert barriers,
Internal layer up-conversion luminescence layer, energy transmission layer, change on 808 nm near-infrared lasers energy-absorbing layers, inert barriers, outer layer
Luminescent layer is also 980 nm near-infrared lasers energy-absorbing layers, inert barriers simultaneously；
By adjusting the thickness of each energy-absorbing layer, the infrared excitation luminous intensity of filtering corresponding wavelength can be reached so that each
Individual energy-absorbing layer absorbs the energy of different wave length infrared excitation light independently of one another, and it is different to be eventually transferred to correspondence
The centre of luminescence.
2. the upper conversion nano crystal material of the orthogonal fluorescent emission of infrared ray excited redgreenblue according to claim 1
Material, it is characterised in that described up-conversion luminescence centronucleus includes matrix and the centre of luminescence with up-conversion luminescence shell；Wherein,
Host material is selected from：Fluoride, oxide, oxysulfide or halide；The fluoride is selected from：CaF2、BaF2、LaF3、YF3、
ZnF2、NaYF4、NaYbF4、LiYF4、KYF4、NaGdF4Or NaLuF4；The oxide is selected from：La2O3、Y2O3、Yb2O3、Gd2O3
Or Lu2O3；The oxysulfide is selected from Y2O2S、CaS2Or La2S3；The halide is selected from Cs3Lu2Br9；Centre of luminescence rare earth from
Attached bag includes Ce3+、Pr3+、Nd3+、Sm3+、Eu3+、Tb3+、Dy3+、Ho3+、Er3+、Tm3+、Yb3+In one or several kinds；In luminous
The molar content of the heart is 0.01% ~ 100%.
3. the upper conversion nano crystal of the orthogonal fluorescent emission of infrared ray excited redgreenblue according to claim 1 or 2
Material, it is characterised in that described energy transmission layer includes matrix and energy transfer center two parts；Wherein, host material bag
Include：Fluoride, oxide, oxysulfide or halide；The fluoride is selected from：CaF2、BaF2、LaF3、YF3、ZnF2、NaYF4、
NaYbF4、LiYF4、KYF4、NaGdF4Or NaLuF4；The oxide is selected from：La2O3、Y2O3、Yb2O3、Gd2O3Or Lu2O3；It is described
Oxysulfide is selected from Y2O2S、CaS2Or La2S3；The halide is selected from Cs3Lu2Br9；Energy transfer center material is Nd3+、Yb3+
In one or two kinds of；The molar content at energy transfer center is 0.01% ~ 50%.
4. the upper conversion nano crystal material of the orthogonal fluorescent emission of infrared ray excited redgreenblue according to claim 3
Material, it is characterised in that described energy-absorbing layer includes energy absorption center and energy transfer center two parts；Wherein, energy
Absorbent core material is Nd3+、Yb3+In one or two kinds of；The molar content at energy absorption center is 10% ~ 90%；Energy is moved
Shifting center material is Nd3+、Yb3+In one or two kinds of；The molar content at energy transfer center is 0.01% ~ 50%.
5. a kind of upper conversion of orthogonal fluorescent emission of infrared ray excited redgreenblue as described in one of claim 1-4 is received
The preparation method of rice crystalline material, it is characterised in that comprise the following steps that：
（1）The preparation of shell presoma：
A, earth solution presoma preparation：Rare-earth salts is dissolved among high boiling solvent under elevated temperature in vacuo；Its
In, rare-earth salts is selected from：Chloride, nitrate, acetate, oxide, trifluoroacetate, acetylacetonate, including rare earth member
Element is Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu；High boiling solvent is：Oleic acid, stearic acid,
One or several kinds in capric acid, laurate, myristic acid, palmitic acid, octadecylene, atoleine, olive oil；Solution temperature is
20-150 degrees Celsius；The concentration of final resulting solution is 0.01 mol/L to 5 mol/L；
B, sodium trifluoroacetate/potassium/lithium/barium solution preparation：By sodium trifluoroacetate or trifluoroacetic acid potassium or trifluoroacetic acid lithium or three
Fluoroacetic acid barium, is dissolved in high boiling solvent；High boiling solvent is：Oleic acid, stearic acid, capric acid, laurate, myristic acid, palm fibre
One or several kinds in palmitic acid acid, octadecylene, atoleine, olive oil；Solution temperature is 20-150 degrees Celsius；Final gained is molten
The concentration of liquid is 0.01 mol/L to 5 mol/L；
（2）Up-conversion luminescence center is synthesized：Rare-earth salts is dissolved among high boiling solvent under elevated temperature in vacuo, added
Remaining reaction thing, reacts under 200-320 degrees Celsius, inert gas atmosphere, that is, obtains dispersiveness and the preferable rare earth of uniformity
Nanocrystal；Wherein, rare-earth salts is selected from：Rare earth-iron-boron, rare earth trifluoroacetate, rare earth nitrades or lanthanon acetate；
Remaining reaction thing includes：One kind in ammonium fluoride, sodium fluoride, lithium fluoride, potassium fluoride, sodium hydroxide, potassium hydroxide, lithium hydroxide
Or it is several；The high-temperature solvent is the one or more in oleic acid, oleyl amine, trioctylphosphine, octadecylene or atoleine；
（3）The synthesis of core, the nano-crystal with core-shell structure body of@shells 1：The rare earth nano crystal prepared using in previous step is nucleus, in height
Under the conditions of temperature, according to the composition needs of shell, earth solution presoma is introduced, incorporation way is is added dropwise, and temperature is taken the photograph for 150-340
Family name's degree；The volume ratio for introducing higher boiling earth solution presoma and sodium trifluoroacetate/potassium/lithium/barium solution is 10:1 to 1:10；
Obtained material is designated as the nano-crystal with core-shell structure body of@shells 1；
（4）Core ,@shells 1, the synthesis of the nano-crystal with core-shell structure body of@shells 2：With the structure nano crystal of core shell 1 prepared in previous step
For nucleus, under the high temperature conditions, according to the composition needs of shell, shell precursor solution is introduced, incorporation way is is added dropwise, temperature
For 150-340 degrees Celsius；The volume ratio of higher boiling earth solution presoma and sodium trifluoroacetate/potassium/lithium/barium solution is introduced every time
Example is 10:1 to 1:10；Obtained material is designated as the nano-crystal with core-shell structure body of@shells 2；
（5）Core ,@shells 1 ,@shells 2, the synthesis of@...@shell n nano-crystal with core-shell structure bodies：Core, shell to be prepared in back
1st ,@shells 2 ,@...@shell n-1 structure nanos crystal are nucleus, under the high temperature conditions, according to the composition needs of shell, introduce shell
Precursor solution, incorporation way is is added dropwise, and temperature is 150-340 degrees Celsius；Every time introduce higher boiling earth solution presoma with
The volume ratio of sodium trifluoroacetate/potassium/lithium/barium solution is 10:1 to 1:10；Until n+7.
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