CN106753355A - It is a kind of to be applied to one-color fluorescence perovskite material of LED and preparation method thereof - Google Patents
It is a kind of to be applied to one-color fluorescence perovskite material of LED and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 23
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 23
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 23
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000005642 Oleic acid Substances 0.000 claims description 23
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 23
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 235000002639 sodium chloride Nutrition 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 14
- 229910052792 caesium Inorganic materials 0.000 claims description 11
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 9
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 9
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 8
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- -1 octadecylene Chemical group 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000000703 high-speed centrifugation Methods 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical group I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000005349 anion exchange Methods 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000001110 calcium chloride Substances 0.000 claims 1
- 229910001628 calcium chloride Inorganic materials 0.000 claims 1
- 235000011148 calcium chloride Nutrition 0.000 claims 1
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 13
- 150000001450 anions Chemical class 0.000 abstract description 6
- 238000005342 ion exchange Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 11
- 230000006641 stabilisation Effects 0.000 description 9
- 238000011105 stabilization Methods 0.000 description 9
- 238000005538 encapsulation Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 210000004209 hair Anatomy 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910000713 I alloy Inorganic materials 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- SYKNUAWMBRIEKB-UHFFFAOYSA-N [Cl].[Br] Chemical compound [Cl].[Br] SYKNUAWMBRIEKB-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
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- 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
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/006—Compounds containing, besides lead, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
One-color fluorescence perovskite material of LED and preparation method thereof is applied to the invention discloses a kind of, wherein the composition for being applied to the one-color fluorescence perovskite material of LED is represented by below general formula (1)：CsPb(AyB3‑y) (1), wherein A is that Cl, B are that Br or A is that Br, B are I；0≤y≤3.Fluorescent material of the present invention includes fertile material and the material constituted with different anions obtained by ion exchange, and fertile material is synthesized with sol-gal process, and different anion constitute the fluorescence spectrum for determining the material.Gained fluorescent material of the invention has the features such as phototranstormation efficiency is high, light color saturation is high, preparation method is simple.
Description
Technical field
One-color fluorescence perovskite material of LED and preparation method thereof is applied to the present invention relates to a kind of, fluorescence spectrum can cover
Cover whole visible spectrum.
Background technology
Light emitting diode (Light-emitting diodes, LED) be referred to as after incandescent lamp, halogen dove lamp and fluorescent lamp it
Forth generation green illumination light source afterwards.Compared to incandescent lamp and fluorescent lamp, LED has that power consumption is low, energy conversion efficiency is high (no
Limited by incandescent lamp and fluorescent lamp energy conversion efficiency), heat radiation few (reduction greenhouse effects) and environmentally friendly (mercury-free is dirty
Dye) remarkable advantage.Additionally, LED small volumes, shock resistance are good, it is easy to accomplish combined with the application of other energy-saving equipments.At present,
LED oneself be successfully applied to automotive lighting, traffic signals instruction, landscape ornamental, outdoor large screen display screen and display backlight
The aspects such as source, application field is related to present information, household electrical appliances, illumination, traffic, automobile, display, digital image equipment and biological doctor
The various fields such as treatment.Expected future white light LEDs will be expected to replace traditional lighting products, the new main flow as global illumination market.
Realizing the output of white light in the devices has number of ways, such as excites yellow fluorescent powder, blue, gold-tinted by blue chip
White light is mixed to get, or three kinds of fluorescent material of red, green, blue are excited by purple light (or ultraviolet light), red, green, blue is mixed into white
Light；Additionally, it is also a kind of feasible technological approaches to excite green glow and red light fluorescent powder using blue-ray LED.
With developing rapidly for White light LED technology, excite three primary colors fluorescent powder to turn into using near ultraviolet chip and obtain white light
A kind of effective way of LED, thus development high-performance three primary colors fluorescent powder is significant.Inorganic perovskite nano fluorescent material
Material (CsPbX3, X=Cl, Br, I) received much concern in recent years as a kind of novel fluorescent material, due to its have it is high ultraviolet
Absorption efficiency and quantum yield, narrow fluorescence emission spectrum, fluorescence spectrum with its chemical composition is adjustable, the characteristic such as radiation lifetime is short,
Their great potentials in the application of monochromatic LED.
The fluorescence spectrum of full-inorganic caesium lead halide perovskite material changes with the composition of its anion and changes, chlorion
The fluorescence spectrum of composition is located at violet region, and the fluorescence spectrum that bromide ion is constituted is located at green wavelength, the fluorescence that iodide ion is constituted
Spectrum is located at red light region, and the fluorescence spectrum of chlorine bromine ion alloy material is located at blue light to blue green light region, bromine/iodine alloy material
The fluorescence spectrum of material is located at gold-tinted to orange light region.The perovskite is nanocrystalline with the ionic of height, this cause to its moon from
Son carries out ion exchange and is possibly realized, so that realizing that its fluorescence spectrum is possibly realized visible region is adjustable.
The content of the invention
One-color fluorescence perovskite material of LED and preparation method thereof is applied to it is an object of the invention to provide a kind of, should
Fluorescent material can have high saturation in the range of whole visible light wave range.
The present invention is applied to the one-color fluorescence perovskite material of LED, and its composition is represented by below general formula (1)：
CsPb(AyB3-y) (1),
Wherein A is that Cl, B are that Br or A is that Br, B are I；0≤y≤3；
One-color fluorescence perovskite material of the present invention includes fertile material and exchanges resulting material, and fertile material is CsPbBr3,
Exchanging resulting material includes CsPb (ClyBr3-y)、CsPb(BryI3-y), wherein 0≤y≤3.
The difference that one-color fluorescence perovskite material of the present invention is constituted according to anion, its fluorescence emission spectrum peak covers
Lid visible wavelength range is 410nm to 700nm.Anion constitutes (y) and is regulated and controled by the addition in anion exchange source, adds chlorine
Ion gun makes emission spectrum blue shift；Adding iodide ion source makes red shift of the emission spectra, the material correspondence one that every kind of anion is constituted
Fluorescence emission spectrum peak.
The present invention is applied to the preparation method of the one-color fluorescence perovskite material of LED, including fertile material synthesis and
Exchange the synthesis of resulting material：
1st, fertile material is synthesized using sol-gal process, is comprised the following steps：
The first step：With cesium carbonate, oleic acid as raw material, with octadecylene as solvent, react molten to cesium carbonate in nitrogen atmosphere
Solution is complete, obtains oleic acid caesium presoma, and reaction solution is settled solution；The cesium carbonate is 1 with the mol ratio of oleic acid:2~10, institute
Content of the synthesis oleic acid caesium in reaction solution is not less than 8 × 10-5mol/ml；Reaction temperature is 120-140 DEG C；
Second step：With oleic acid, oleyl amine as ligand, lead bromide is dissolved in octadecylene, reacted in nitrogen atmosphere to
Dissolving is complete；The lead bromide is 1 with the mol ratio of oleic acid:10~20, oleic acid and oleyl amine equimolar amounts, lead bromide is in octadecylene
In content be 3~15 × 10-5mol/ml；Reaction temperature is 100-120 DEG C；
3rd step：At 160 DEG C, in nitrogen atmosphere, first step gained oleic acid caesium presoma reaction solution is expelled to second
In step gained system, reaction is cooled to 0 DEG C after 5 seconds；The mol ratio of the lead bromide added in oleic acid caesium presoma and second step
It is 1:1；
4th step：More than three-step reaction gained product dilution with toluene to 20 times of volumes, it is therefore an objective to molten with toluene
The oil phase substance such as solution octadecylene, excessive oleyl amine, oleic acid through high speed centrifugation (10000r/s, 30min), is done with facilitating it to remove
It is dry, obtain solid phase fluorescent material and be fertile material；
2nd, exchanging resulting material is synthesized using anion exchange method on the basis of fertile material, is comprised the following steps：
The fertile material is dissolved in toluene, the aqueous solution of inorganic salts is subsequently added, 20s is stirred at room temperature, the friendship
Carry out completely, through high speed centrifugation (10000r/s, 30min), drying by changing reaction, acquisition solid phase fluorescent material is exchange and produces
Thing.
The inorganic salts are villaumite or salt compounded of iodine；The villaumite is the inorganic halides such as zinc chloride, sodium chloride, potassium chloride or calcium chloride
Salt, the salt compounded of iodine is the inorganic halogens such as zinc iodide, sodium iodide, KI or calcium iodide.
When the inorganic salts are villaumite, the mol ratio n (Cl) of villaumite and fertile material：N (Br) is 0~22:1, obtain ripple
The fluorescent emission of a length of 521nm to 410nm；When the inorganic salts are salt compounded of iodine, the mol ratio n (I) of salt compounded of iodine and fertile material:n
(Br) it is 0~13:1, it is the fluorescent emission of 521nm to 700nm to obtain wavelength；The addition of inorganic salts is excessive, is actually only had
Subparticipation is exchanged, but must maintain the addition concentration high could to obtain corresponding exchange capacity, such as CsPb
(ClyBr3-y), as n (Cl)：During n (Br)=0, y=0；As n (Cl)：N (Br)=11:When 1, y=1.5；As n (Cl)：n(Br)
=22:When 1, y=3；Regulated and controled y) by regulating and controlling the addition of villaumite.
Beneficial effects of the present invention are embodied in：
By anion exchange procedures that are simple and quick, can carrying out at room temperature, can obtain high-purity, with various hairs
The fluorescent material of light color, the negative ion source is simple and easy to get；The luminous efficiency of gained fluorescent material of the invention is up to 83lm/W, hair
Light excitation can more than 99%, fluorescence spectrum can covering visible light wavelength 410nm-700nm, while the fluorescent material have system
The features such as Preparation Method is simple, fluorescence property is stable under different driving electric current, the great application on monochromatic light LED and white light LEDs
Potentiality.
Brief description of the drawings
Fig. 1 is the luminous photo that the made product ultraviolet chip of embodiment 1 encapsulates LED；The LED sends out as can be seen from Figure 1
Go out bright green glow, the luminous efficiency for measuring the LED is 83lm/W；
Fig. 2 is the spectral absorption collection of illustrative plates of the made product of embodiment 1；Gained fluorescent material is being less than as can be seen from Figure 2
520nm wave bands have strong absorption, UV absorption efficiency nearly 100%；
Fig. 3 is luminescent spectrums of the LED of the made product of embodiment 1 encapsulation under different driving electric current；As can be seen from Figure 3
In 521nm, half-peak breadth is about 18.4nm to emission peak positions stabilization, illustrates the fluorescent material different under different driving electric current
There are the luminescent properties of stabilization under driving current；
Fig. 4 is that the LED of the made product of embodiment 1 encapsulation lights the position on CIE diagram under different driving electric current, is lighted
Purity is up to 85.8%；
Fig. 5 is the enlarged drawing of coordinate in Fig. 4, and the CIE coordinates that lighted under different driving currents have small change；
Fig. 6 is the luminous photo that the made product ultraviolet chip of embodiment 2 encapsulates LED, it can be seen that the LED sends bright
Blue light, measure the LED luminous efficiency be 64lm/W；
Fig. 7 is the spectral absorption collection of illustrative plates of the made product of embodiment 2, it can be seen that gained fluorescent material is less than 450nm ripples
Section has strong absorption；
Fig. 8 is luminescent spectrums of the LED of the made product of embodiment 2 encapsulation under different driving electric current, it can be seen that not
With emission peak positions stabilization under driving current, in 447nm, half-peak breadth is about 15.3nm, illustrates the fluorescent material in different drivings
There are the luminescent properties of stabilization under electric current；
Fig. 9 is that the LED of the made product of embodiment 2 encapsulation lights the position on CIE diagram under different driving electric current, is lighted
Purity is 78.3%；
Figure 10 is the enlarged drawing of coordinate in Fig. 9, and the CIE coordinates that lighted under different driving currents have small change；
Figure 11 is the luminous photo that the made product ultraviolet chip of embodiment 3 encapsulates LED, it can be seen that the LED sends bright
Bright feux rouges, the luminous efficiency for measuring the LED is 78lm/W；
Figure 12 is the spectral absorption collection of illustrative plates of the made product of embodiment 3, it can be seen that gained fluorescent material is less than 450nm ripples
Section has strong absorption；
Figure 13 is luminescent spectrums of the LED of the made product of embodiment 3 encapsulation under different driving electric current, it can be seen that not
With emission peak positions stabilization under driving current, in 675nm, half-peak breadth is about 29nm, illustrates the fluorescent material in different driving electricity
Flow down the luminescent properties with stabilization；
Figure 14 is that the LED of the made product of embodiment 3 encapsulation lights the position on CIE diagram under different driving electric current, hair
Optical purity is up to 99.2%；
Figure 15 is the enlarged drawing of coordinate in Figure 14, and the CIE coordinates that lighted under different driving currents have small change.
Specific embodiment
Embodiment 1：
Using liquid phase method synthesis green fluorescence CsPbBr3It is nanocrystalline.
1st, cesium carbonate 0.08g, octadecylene 3ml are put into double-neck flask, 120 DEG C is warming up under nitrogen protection, measure oleic acid
0.25ml is put into double-neck flask and dissolves cesium carbonate, oleic acid caesium presoma is obtained standby；
2nd, lead bromide 0.13g, octadecylene 5ml are put into three-neck flask, 120 DEG C is warming up under nitrogen protection；Measure respectively
Oleic acid 1.68ml, oleyl amine 1.71ml are added in three-neck flask, and reaction is complete to dissolving at 120 DEG C；
3rd, the reaction solution of step 2 is warming up to 160 DEG C, measures the oleic acid caesium presoma reaction solution of 1.24ml steps 1 preparation
Injection enters in three-neck flask, and 0 DEG C is cooled to ice-water bath after reacting 5s in nitrogen atmosphere；Added in products therefrom
150ml toluene, (10000r/s, 30min) is centrifuged with supercentrifuge, throws away supernatant and dry sediment, obtains green glimmering
Luminescent material.
The performance test results such as Fig. 1-5 of the material and the LED using the material package, the as can be seen from the figure fluorescence
Material has strong UV absorption, and lighting, collection of illustrative plates half-peak breadth is narrower, and with color saturation higher, its luminosity is not
Varied less under same driving current, luminosity stabilization.
Embodiment 2：
On the basis of embodiment 1 obtains fertile material, blue light CsPb (Cl are prepared using ion-exchange1.6Br1.4) receive
Meter Jing.
4th, the fertile material prepared by embodiment 1 is dissolved in toluene；Weigh 1.16g zinc chloride and be dissolved in 0.25ml
In ionized water, the toluene solution of fertile material is added, 20s (stirring is to promote exchange reaction) is stirred at room temperature, through at a high speed
Centrifugation (10000r/s, 30min), dry, acquisition blue fluorescent material.(inorganic salts are 12 with the mol ratio of fertile material:1)
The performance test results such as Fig. 6-10 of the material and the LED using the material package, as can be seen from the figure this is glimmering
Luminescent material has strong UV absorption, and lighting, collection of illustrative plates half-peak breadth is narrower, and with color saturation higher, its luminosity exists
Varied less under different driving currents, luminosity stabilization.
Embodiment 3：
On the basis of embodiment 1 obtains fertile material, feux rouges CsPb (I are prepared using ion-exchange2.1Br0.9) nanometer
It is brilliant.
4th, the fertile material prepared by embodiment 1 is dissolved in toluene；Weigh 2.03g zinc iodides and be dissolved in 0.25ml
In ionized water, the toluene solution of fertile material is added, 20s is stirred at room temperature, through high speed centrifugation (10000r/s, 30min), done
It is dry, obtain red fluorescence material.(inorganic salts are 9 with the mol ratio of fertile material:1)
The performance test results such as Figure 11-15 of the material and the LED using the material package, as can be seen from the figure this is glimmering
Luminescent material has strong UV absorption, and lighting, collection of illustrative plates half-peak breadth is narrower, and with high color saturation, its luminosity exists
Varied less under different driving currents, luminosity stabilization.
Claims (9)
1. a kind of one-color fluorescence perovskite material for being applied to LED, it is characterised in that its composition is represented by below general formula (1)：
CsPb(AyB3-y) (1),
Wherein A is that Cl, B are that Br or A is that Br, B are I；0≤y≤3.
2. a kind of preparation method of the one-color fluorescence perovskite material for being applied to LED described in claim 1, including fertile material
Synthesis and exchange resulting material synthesis, it is characterised in that：
(1) fertile material is synthesized using sol-gal process, is comprised the following steps：
The first step：With cesium carbonate, oleic acid as raw material, with octadecylene as solvent, reacted to cesium carbonate in nitrogen atmosphere and dissolved
Entirely, oleic acid caesium presoma is obtained, reaction solution is settled solution；
Second step：With oleic acid, oleyl amine as ligand, lead bromide is dissolved in octadecylene, reaction is extremely dissolved in nitrogen atmosphere
Completely；
3rd step：At 160 DEG C, in nitrogen atmosphere, first step gained oleic acid caesium presoma reaction solution is expelled to second step institute
In the system of obtaining, reaction is cooled to 0 DEG C after 5 seconds；
4th step：More than three-step reaction gained product dilution with toluene to 20 times of volumes, through high speed centrifugation, drying, obtain
Obtain solid phase fluorescent material and be fertile material；
(2) exchanging resulting material is synthesized using anion exchange method on the basis of fertile material, is comprised the following steps：
The fertile material is dissolved in toluene, the aqueous solution of inorganic salts is subsequently added, 20s is stirred at room temperature, the exchange is anti-
Should carry out completely, through high speed centrifugation, drying, obtain solid phase fluorescent material and be exchange product；The inorganic salts are villaumite
Or salt compounded of iodine.
3. preparation method according to claim 2, it is characterised in that：
Cesium carbonate described in the first step is 1 with the mol ratio of oleic acid:2~10, content of the synthesized oleic acid caesium in reaction solution is not
Less than 8 × 10-5mol/ml。
4. preparation method according to claim 2, it is characterised in that：
Reaction temperature in the first step is 120-140 DEG C.
5. preparation method according to claim 2, it is characterised in that：
Lead bromide described in second step is 1 with the mol ratio of oleic acid:10~20, oleic acid and oleyl amine equimolar amounts, lead bromide is ten
Content in eight alkene is 3~15 × 10-5mol/ml。
6. preparation method according to claim 2, it is characterised in that：
Reaction temperature in second step is 100-120 DEG C.
7. preparation method according to claim 2, it is characterised in that：
The mol ratio of the lead bromide added in oleic acid caesium presoma and second step in the 3rd step is 1:1.
8. preparation method according to claim 2, it is characterised in that：
The villaumite is zinc chloride, sodium chloride, potassium chloride or calcium chloride, and the salt compounded of iodine is zinc iodide, sodium iodide, KI or iodine
Change calcium.
9. the preparation method according to claim 2 or 8, it is characterised in that：
When the inorganic salts are villaumite, the mol ratio n (Cl) of villaumite and fertile material：N (Br) is 0~22:1, obtaining wavelength is
The fluorescent emission of 521nm to 410nm；When the inorganic salts are salt compounded of iodine, the mol ratio n (I) of salt compounded of iodine and fertile material:N (Br) is 0
~13:1, it is the fluorescent emission of 521nm to 700nm to obtain wavelength.
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