CN107384387A - A kind of additive Mn CsPbBr3Perovskite quantum dot and molecular sieve composite luminescent material and preparation method and application - Google Patents
A kind of additive Mn CsPbBr3Perovskite quantum dot and molecular sieve composite luminescent material and preparation method and application Download PDFInfo
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- CN107384387A CN107384387A CN201710765770.9A CN201710765770A CN107384387A CN 107384387 A CN107384387 A CN 107384387A CN 201710765770 A CN201710765770 A CN 201710765770A CN 107384387 A CN107384387 A CN 107384387A
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 84
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000000463 material Substances 0.000 title claims abstract description 63
- 239000002096 quantum dot Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000000654 additive Substances 0.000 title claims abstract description 34
- 230000000996 additive effect Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 39
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 22
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims abstract description 22
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 14
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005642 Oleic acid Substances 0.000 claims abstract description 14
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 14
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims abstract description 13
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims abstract description 13
- -1 octadecylene Chemical group 0.000 claims abstract description 12
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000005119 centrifugation Methods 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 230000007717 exclusion Effects 0.000 claims description 2
- 150000002500 ions Chemical group 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000011572 manganese Substances 0.000 abstract description 33
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910021568 Manganese(II) bromide Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 229910052792 caesium Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000002513 implantation Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 244000283207 Indigofera tinctoria Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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- 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
- C09K11/666—Aluminates; Silicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y40/00—Manufacture or treatment of nanostructures
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- 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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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Abstract
The invention discloses a kind of additive Mn CsPbBr3Perovskite quantum dot and molecular sieve composite luminescent material and preparation method and application, belong to the technical field of luminescent material.This method comprises the following steps：（1）Molecular sieve and cesium bromide solution are stirred, centrifuged, is washed, drying, obtains Cs+The molecular sieve of exchange；（2）Lead bromide and manganous bromide are made by bromide solution using octadecylene, oleic acid and oleyl amine；（3）Under conditions of inert gas and stirring, in octadecylene, by bromide solution and Cs+The molecular sieve of exchange is reacted, and is cooled down, and is washed, and drying, obtains additive Mn CsPbBr3Perovskite quantum dot and molecular sieve composite luminescent material.The composite luminescent material has blue light and the multi-peak emission of green Region, and luminous peak position and each luminous peak intensity can be modulated according to the ratio of manganese ion and lead ion；The composite luminescent material of the present invention has preferable environmental stability, available for white light LEDs field.
Description
Technical field
The invention belongs to field of light emitting materials, and in particular to a kind of additive Mn CsPbBr3 perovskites quantum dot and molecular sieve
Composite luminescent material and preparation method and application.
Background technology
In the research of recent years, full-inorganic Ca-Ti ore type quanta point material (CsPbX3, X=Cl, Br, I) by
In with very narrow transmitting peak width and very high quantum yield, stability is good in solution, while luminous can pass through halogenic ingredient
With two factors of particle size are adjustable in whole visible-range attracts wide attention, these many advantages cause calcium titanium
Ore deposit quantum dot becomes research focus in photoelectric fields such as illumination displays.At the same time, pure quanta point material is to temperature humidity etc.
Environmental factor is more sensitive, and the decay to be lighted under the conditions of the external world limits its further application in fields such as white light LEDs, because
Perovskite quantum dot and other stable compounds are compounded to form relatively stable quantum dot composite material by this also has research more.
On the other hand, the lead element in perovskite quantum dot has certain toxicity as heavy metal, to human body and environment
It is harmful, the production and application of its wider scope are hindered, therefore by adulterating other ionic compartmentation lead in perovskite quantum dot
Also newest research direction is turned into, it is that divalent manganesetion is doped in perovskite quantum dot to study at present more, but due to
The factors such as band gap width, the luminous report of modulation is adulterated in blue violet light perovskite quantum dot only with respect to manganese, and for green glow
The doping of bivalent manganese is studied seldom for luminous modulation in quantum dot.
The content of the invention
The shortcomings that in order to overcome prior art and deficiency, also for the doping by manganese to green glow perovskite quantum dot light emitting
It is modulated, primary and foremost purpose of the invention is to provide a kind of CsPbBr of additive Mn3Perovskite quantum dot and molecular sieve are compound
The preparation method of luminescent material.The method that the present invention uses fabricated in situ, Cs first is carried out to molecular sieve+-Na+Ion exchange, obtain
Cs+The molecular sieve of ion exchange；Then there will be a certain proportion of lead bromide PbBr2With manganous bromide MnBr2Solution, with containing Cs+
Molecular sieve reacted, obtain the CsPbBr of manganese ion doping3Perovskite quantum dot and molecular sieve composite luminescent material, and lead to
Cross and change the ratio of lead ion and manganese ion and luminous to composite be modulated.The calcium titanium that the present invention adulterates divalent manganesetion
Ore deposit quanta point material is compound with molecular sieve, reduces the ratio of green glow perovskite quanta point material Poisoning lead ion, and passes through
CsPbBr of the doping of manganese ion to unimodal green glow originally3Perovskite quantum dot light emitting is modulated, and is had in blue light and green Region
Multimodal lights, and the relative intensity of each transmitting peak position is adjustable.Molecular sieve makes the ring of perovskite quantum dot as matrix material simultaneously
Border stability is improved.
Another object of the present invention is to provide the additive Mn CsPbBr obtained by above-mentioned preparation method3Perovskite quantum dot with
Molecular sieve composite luminescent material.
Still a further object of the present invention is to provide a kind of additive Mn CsPbBr3Perovskite quantum dot and molecular sieve recombination luminescence material
Material is applied in white light LEDs.
The purpose of the present invention is realized by following proposal.
A kind of additive Mn CsPbBr3The preparation method of perovskite quantum dot and molecular sieve composite luminescent material, including it is following
Step：
（1）Ion exchange-Size exclusion：Molecular sieve and cesium bromide solution are stirred, centrifuged, is washed, drying, obtains Cs+Exchange
Molecular sieve；
（2）The preparation of bromide solution：Under conditions of stirring, by octadecylene（ODE）, oleic acid（OA）, oleyl amine（OAm）、
（PbBr2）And manganous bromide（MnBr2）Mixing, is vacuumized, and stirring is until solid all dissolvings, obtain bromide in an inert atmosphere
Solution；
（3）The preparation of composite luminescent material：By step（1）Cs+The molecular sieve of exchange is scattered in octadecylene, then is taken out true
Sky, under conditions of inert gas and stirring, add step（2）Bromide solution reacted at 130 ~ 200 DEG C, after having reacted
Cooling, wash, drying, obtain the CsPbBr of additive Mn3Perovskite quantum dot and molecular sieve composite luminescent material.
Preferably, step（1）Described in molecular sieve be in Y type molecular sieve, A type molecular sieve and X-type molecular sieve it is a kind of with
On, more preferably Y type molecular sieve.
Preferably, step（1）Described in Cs in cesium bromide solution+Concentration be 0.1 ~ 1mol/L；The molecular sieve and bromine
It is 1g to change caesium amount ratio：(0.001~0.01)mol.
Preferably, step（1）Described in time for stirring be 8 ~ 36h, the temperature of stirring is 25 ~ 80 DEG C, the rotating speed of stirring
For 300 ~ 600r/min；The rotating speed of the centrifugation is 3000 ~ 6000r/min, and the time is 3 ~ 10min；The washing refers to use
Distill water washing 1 ~ 3 time；The temperature of the drying is 60 ~ 120 DEG C, and the time is 5 ~ 24 hours.
Preferably, step（2）Described in Mn in bromide solution2+And Pb2+Mol ratio be（0.5~8）:1, Mn2+And Pb2+
Total concentration in bromide solution is 0.01 ~ 0.03mol/L；The volume ratio of the octadecylene, oleic acid and oleyl amine is（5~10）:
1:1。
Preferably, step（2）Described in vacuumize and refer to vacuumize 5 ~ 30min at 80 ~ 120 DEG C；The rotating speed of the stirring
For 200 ~ 600r/min；The temperature stirred under the inert atmosphere is 100 ~ 150 DEG C；The inert atmosphere is N2Or Ar atmosphere.
Preferably, step（3）Described in Cs+The molecular sieve of exchange and the amount ratio of bromide solution are (0.01 ~ 0.2) g:
1mL。
Preferably, step（3）Described in Cs+The quality of the molecular sieve of exchange and the volume ratio of octadecylene are 1g:(5~20)
mL。
Preferably, step（3）Described in inert gas be N2Or Ar；The rotating speed of the stirring is 200 ~ 600r/min；Institute
The time for stating reaction is 5 ~ 30min；The reagent of the washing is isopropanol and n-hexane；The cooling refers to that ice-water bath is cooled to
Normal temperature；The drying is that 5 ~ 12h is dried in vacuo at 50 ~ 100 DEG C.
A kind of additive Mn CsPbBr obtained by above-described preparation method3Perovskite quantum dot and the compound hair of molecular sieve
Luminescent material.
A kind of above-described additive Mn CsPbBr3Perovskite quantum dot is applied to white light with molecular sieve composite luminescent material
LED field.
The present invention mechanism be：
First by ion exchange process, by existing Na in molecular sieve pore passage+Replace with Cs+, be perovskite quantum dot in hole
Fabricated in situ provides Cs in road+Source；Then make lead bromide and bromination manganese solution and Cs+The molecular sieve of exchange is reacted, and can be obtained
To Mn2+The CsPbBr of doping3The compound molecular sieve of perovskite quantum dot, Mn2+Doping may change CsPbBr3Quantum dot band
Gap structure, and then had an impact to luminous；Composite glow peak can be realized by the change of the ratio of manganese ion and lead ion
Position and the modulation of luminous intensity.Meanwhile molecular sieve is as additive Mn CsPbBr3Carrier existing for perovskite quantum dot, it is quantum
Point provides a protective effect, makes more stable in the environment under its solid-state.
Molecular sieve is many luminous as a kind of aluminosilicate with regular pore canal structure, its unique hole and basket structure
Material provides good luminous environment and carrier, and there is the scattered centre of luminescence to reduce concentration quenching or increase the work of stability
With it is perovskite quantum dot being stabilized and forming the micron order composite luminescent material with superior luminescent properties wherein
Provide possibility.On the other hand, divalent manganesetion studies extensive transition metal ions as a kind of, has similar to lead ion
Ionic radius and identical valence state so that it can adulterate in perovskite quantum dot and be sent out by the change modulates of concentration
Light.
Relative to prior art, the present invention has the following advantages that and beneficial effect：
（1）Additive Mn CsPbBr prepared by the present invention3Perovskite quantum dot has indigo plant, green Region with molecular sieve composite luminescent material
Multi-peak emission, and luminous peak position and each luminous peak intensity can be modulated according to the ratio of manganese ion and lead ion；
（2）Additive Mn CsPbBr prepared by the present invention3Perovskite quantum dot is made with molecular sieve composite luminescent material based on molecular sieve
For carrier existing for quantum dot, there is preferable environmental stability；
（3）Additive Mn CsPbBr prepared by the present invention3Titanium ore quantum dot reduces perovskite amount with molecular sieve composite luminescent material
The usage ratio of son point Poisoning lead ion, it is more green, it is environmentally friendly composite；
（4）Additive Mn CsPbBr prepared by the present invention3Perovskite quantum dot is outstanding in illumination display with molecular sieve composite luminescent material
It is that the fields such as white light LEDs have good application prospect.
Brief description of the drawings
Fig. 1 is additive Mn CsPbBr prepared by embodiment 13The XRD of perovskite quantum dot and molecular sieve composite luminescent material
Diffracting spectrum；
Fig. 2 is additive Mn CsPbBr prepared by embodiment 13The emission spectrum of perovskite quantum dot and molecular sieve composite luminescent material
Figure；
Fig. 3 is additive Mn CsPbBr prepared by embodiment 23The emission spectrum of perovskite quantum dot and molecular sieve composite luminescent material
Figure；
Fig. 4 is additive Mn CsPbBr prepared by embodiment 33The emission spectrum of perovskite quantum dot and molecular sieve composite luminescent material
Figure；
Fig. 5 is additive Mn CsPbBr prepared by embodiment 43The emission spectrum of perovskite quantum dot and molecular sieve composite luminescent material
Figure.
Embodiment
The present invention is done with reference to embodiment and accompanying drawing and is further described in detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
A kind of additive Mn CsPbBr3The preparation method of perovskite quantum dot and molecular sieve composite luminescent material, is specifically included following
Step：
（1）Accurately weigh 2.13g cesium bromides（CsBr）, it is dissolved in 10mL distilled water, obtains 1mol/L cesium bromide solution；Will
1.0g Y type molecular sieve（SiO2/ Al2O3=5.1, Alfa Aesar brands）Add in cesium bromide solution, 60 DEG C of stirring in water bath
20h（The rotating speed of stirring is 400r/min）, centrifugation（The rotating speed of centrifugation is 3500r/min）5min, remove a layer sample, distillation washing
Wash twice, and Cs is obtained after dry 12h at 60 DEG C+The Y type molecular sieve of exchange；
（2）By octadecylene（ODE）5mL, oleic acid (OA) 1mL, oleyl amine（OAm）1mL, lead bromide（PbBr2）0.012g
（0.033mmol）, manganous bromide（MnBr2）0.035g（0.167mmol）It is mixed in container, 30min is vacuumized at 120 DEG C,
N2The lower 120 DEG C of stirrings of atmosphere（The rotating speed of stirring is 250r/min）Untill solid is completely dissolved, bromide solution is obtained；
（3）By 0.5g Cs+The Y type molecular sieve of exchange and 5mL octadecylenes（ODE）It is mixed in container, is vacuumized at 120 DEG C
30min, N2150 DEG C are warming up under atmosphere, implantation step（2）Bromide solution, stir 15min（The rotating speed of stirring is 250r/
min）Afterwards, ice-water bath is cooled to normal temperature, adds 2.5mL isopropanols and the centrifugation of 2.5mL n-hexanes（Rotating speed is 3500r/min, the time
For 5min）, remove layer sample addition 2.5mL n-hexanes and the washing centrifugation of 5.0mL isopropanols be repeated twice；50 DEG C of vacuum drying
12h, obtain the CsPbBr of additive Mn3Perovskite quantum dot and Y type molecular sieve composite luminescent material.It is manufactured in the present embodiment compound
The XRD diffracting spectrums of luminescent material are as shown in figure 1, it can be seen that composite luminescent material maintains the base of Y type molecular sieve carrier
This structure.
The launching light spectrogram of composite luminescent material manufactured in the present embodiment as shown in Fig. 2 visible material in 430nm,
460nm, 480nm and 490nm have multiple blue lights and the emission peak of green range respectively.
Embodiment 2
A kind of additive Mn CsPbBr3The preparation method of perovskite quantum dot and molecular sieve composite luminescent material, is specifically included following
Step：
（1）Accurately weigh 0.213g cesium bromides（CsBr）, it is dissolved in 10mL distilled water, obtains 0.1mol/L cesium bromide solution；
By 1.0g Y type molecular sieves（SiO2/ Al2O3=5.1, Alfa Aesar brands）Add in cesium bromide solution, 80 DEG C of water-baths are stirred
Mix 20h（The rotating speed of stirring is 400r/min）, centrifugation（The rotating speed of centrifugation is 3500r/min）5min, remove a layer sample, distilled water
Wash twice, and Cs is obtained after dry 12h at 80 DEG C+The Y type molecular sieve of exchange；
（2）By octadecylene（ODE）5mL, oleic acid (OA) 1mL, oleyl amine（OAm）1mL, lead bromide（PbBr2）0.018g
（0.05mmol）, manganous bromide（MnBr2）0.032g（0.15mmol）It is mixed in container, 30min, N is vacuumized at 100 DEG C2
The lower 120 DEG C of stirrings of atmosphere（The rotating speed of stirring is 200r/min）Untill solid is completely dissolved, bromide solution is obtained；
（3）By 1.0g Cs+The Y type molecular sieve of exchange and 5mL octadecylenes（ODE）It is mixed in container, is vacuumized at 120 DEG C
30min, N2130 DEG C are warming up under atmosphere, implantation step（2）Bromide solution, stir 15min（The rotating speed of stirring is 200r/
min）Afterwards, ice-water bath is cooled to room temperature, adds 2.5mL isopropanols and the centrifugation of 2.5mL n-hexanes（Rotating speed is 3500r/min, the time
For 5min）, remove layer sample addition 2.5mL n-hexanes and the washing centrifugation of 5.0mL isopropanols be repeated twice；60 DEG C of vacuum drying
8h, obtain the CsPbBr of additive Mn3Perovskite quantum dot and Y type molecular sieve composite luminescent material.It is manufactured in the present embodiment compound
The XRD diffracting spectrums of luminescent material are similar with Fig. 1, it can be seen that composite luminescent material maintains the base of Y type molecular sieve carrier
This structure.
The launching light spectrogram of composite luminescent material manufactured in the present embodiment as shown in figure 3, visible material in 430nm,
463nm, 494nm and 524nm have multiple blue lights and the emission peak of green range respectively.
Embodiment 3
A kind of additive Mn CsPbBr3The preparation method of perovskite quantum dot and molecular sieve composite luminescent material, is specifically included following
Step：
（1）Accurately weigh 1.065g cesium bromides（CsBr）, it is dissolved in 10mL distilled water, obtains 0.5mol/L cesium bromide solution；
By 1.0g Y type molecular sieves（SiO2/ Al2O3=5.1, Alfa Aesar brands）Add in cesium bromide solution, 25 DEG C of water-baths are stirred
Mix 36h（The rotating speed of stirring is 400r/min）, centrifugation（The rotating speed of centrifugation is 3500r/min）5min, remove a layer sample, distilled water
Wash twice, and Cs is obtained after dry 5h at 120 DEG C+The Y type molecular sieve of exchange；
（2）By octadecylene（ODE）5mL, oleic acid (OA) 1mL, oleyl amine（OAm）1mL, lead bromide（PbBr2）0.037g
（0.1mmol）, manganous bromide（MnBr2）0.022g（0.1mmol）It is mixed in container, 30min, N is vacuumized at 120 DEG C2Gas
The lower 150 DEG C of stirrings of atmosphere（The rotating speed of stirring is 200r/min）Untill solid is completely dissolved, bromide solution is obtained；
（3）By 0.5g Cs+The Y type molecular sieve of exchange and 5mL octadecylenes（ODE）It is mixed in container, is vacuumized at 120 DEG C
30min, N2200 DEG C are warming up under atmosphere, implantation step（2）Bromide solution, stir 30min（The rotating speed of stirring is 400r/
min）Afterwards, ice-water bath is cooled to room temperature, adds 2.5mL isopropanols and the centrifugation of 2.5mL n-hexanes（Rotating speed is 3500r/min, the time
For 5min）, remove layer sample addition 2.5mL n-hexanes and the washing centrifugation of 5.0mL isopropanols be repeated twice；100 DEG C of vacuum drying
5h, obtain the CsPbBr of additive Mn3Perovskite quantum dot and Y type molecular sieve composite luminescent material.It is manufactured in the present embodiment compound
The XRD diffracting spectrums of luminescent material are similar with Fig. 1, it can be seen that composite luminescent material maintains the base of Y type molecular sieve carrier
This structure.
The launching light spectrogram of composite luminescent material manufactured in the present embodiment as shown in figure 4, visible material in 430nm and
516nm has blue light and the emission peak of green range respectively.
Embodiment 4
A kind of additive Mn CsPbBr3The preparation method of perovskite quantum dot and molecular sieve composite luminescent material, is specifically included following
Step：
（1）Accurately weigh 2.13g cesium bromides（CsBr）, it is dissolved in 10mL distilled water, obtains 1mol/L cesium bromide solution；Will
1.0g Y type molecular sieve（SiO2/ Al2O3=5.1, Alfa Aesar brands）Add in cesium bromide solution, 70 DEG C of stirring in water bath
24h（The rotating speed of stirring is 400r/min）, centrifugation（The rotating speed of centrifugation is 3500r/min）5min, remove a layer sample, distillation washing
Wash twice, and Cs is obtained after dry 20h at 70 DEG C+The Y type molecular sieve of exchange；
（2）By octadecylene（ODE）10mL, oleic acid (OA) 1mL, oleyl amine（OAm）1mL, lead bromide（PbBr2）0.049g
（0.13mmol）, manganous bromide（MnBr2）0.014g（0.067mmol）It is mixed in container, 30min, N is vacuumized at 80 DEG C2
The lower 100 DEG C of stirrings of atmosphere（The rotating speed of stirring is 200r/min）Untill solid is completely dissolved, bromide solution is obtained；
（3）By 0.1g Cs+The Y type molecular sieve of exchange and 2mL octadecylenes（ODE）It is mixed in container, is vacuumized at 120 DEG C
30min, N2150 DEG C are warming up under atmosphere, implantation step（2）Bromide solution, stir 5min（The rotating speed of stirring is 600r/
min）Afterwards, ice-water bath is cooled to room temperature, adds 2.5mL isopropanols and the centrifugation of 2.5mL n-hexanes（Rotating speed is 3500r/min, the time
For 5min）, remove layer sample addition 2.5mL n-hexanes and the washing centrifugation of 5.0mL isopropanols be repeated twice；60 DEG C of vacuum drying
8h, obtain the CsPbBr of additive Mn3Perovskite quantum dot and Y type molecular sieve composite luminescent material.It is manufactured in the present embodiment compound
The XRD diffracting spectrums of luminescent material are similar with Fig. 1, it can be seen that composite luminescent material maintains the base of Y type molecular sieve carrier
This structure.
The launching light spectrogram of composite luminescent material manufactured in the present embodiment as shown in figure 5, visible material in 430nm and
519nm has blue light and the emission peak of green range respectively.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not limited by examples detailed above
System, it is other it is any without departing from spirit of the invention with made under principle change, modification, replacement, combine, simplification is
Effect.
Claims (10)
- A kind of 1. additive Mn CsPbBr3The preparation method of perovskite quantum dot and molecular sieve composite luminescent material, it is characterised in that Comprise the following steps：（1）Ion exchange-Size exclusion：Molecular sieve and cesium bromide solution are stirred, centrifuged, is washed, drying, obtains Cs+Exchange Molecular sieve；（2）The preparation of bromide solution：Under conditions of stirring, octadecylene, oleic acid, oleyl amine, lead bromide and manganous bromide are mixed, Vacuumize, stirring is until solid all dissolvings, obtain bromide solution under an inert atmosphere；（3）The preparation of composite luminescent material：By step（1）Cs+The molecular sieve of exchange is scattered in octadecylene, then is vacuumized, Under conditions of inert gas and stirring, step is added（2）Bromide solution reacted at 130 ~ 200 DEG C, reacted after it is cold But, wash, drying, obtain the CsPbBr of additive Mn3Perovskite quantum dot and molecular sieve composite luminescent material.
- 2. preparation method according to claim 1, it is characterised in that step（1）Described in molecular sieve be Y type molecular sieve, A One or more of type molecular sieve and X-type molecular sieve.
- 3. preparation method according to claim 1, it is characterised in that step（1）Described in Cs in cesium bromide solution+It is dense Spend for 0.1 ~ 1mol/L；The molecular sieve and cesium bromide amount ratio are 1g：(0.001~0.01)mol.
- 4. preparation method according to claim 1, it is characterised in that：Step（1）Described in time for stirring be 8 ~ 36h, The temperature of stirring is 25 ~ 80 DEG C, and the rotating speed of stirring is 300 ~ 600r/min；The rotating speed of the centrifugation is 3000 ~ 6000r/min, Time is 3 ~ 10min；The washing refers to use distillation water washing 1 ~ 3 time；The temperature of the drying is 60 ~ 120 DEG C, and the time is 5 ~ 24 hours.
- 5. preparation method according to claim 1, it is characterised in that step（2）Described in Mn in bromide solution2+With Pb2+Mol ratio be（0.5~8）:1, Mn2+And Pb2+Total concentration in bromide solution is 0.01 ~ 0.03mol/L；Described ten The volume ratio of eight alkene, oleic acid and oleyl amine is（5~10）:1:1.
- 6. preparation method according to claim 1, it is characterised in that：Step（2）Described in vacuumize and refer to 80 ~ 120 DEG C Under vacuumize 5 ~ 30min；The rotating speed of the stirring is 200 ~ 600r/min；The temperature stirred under the inert atmosphere be 100 ~ 150℃；The inert atmosphere is N2Or Ar atmosphere.
- 7. preparation method according to claim 1, it is characterised in that：Step（3）Described in Cs+The matter of the molecular sieve of exchange Amount and the volume ratio of octadecylene are 1g:(5~20)mL；The Cs+The molecular sieve of exchange and the amount ratio of bromide solution are (0.01~0.2)g:1mL。
- 8. preparation method according to claim 1, it is characterised in that：Step（3）Described in inert gas be N2Or Ar；Institute The rotating speed for stating stirring is 200 ~ 600r/min；The time of the reaction is 5 ~ 30min；The reagent of the washing is for isopropanol and just Hexane；The cooling refers to that ice-water bath is cooled to normal temperature；The drying is that 5 ~ 12h is dried in vacuo at 50 ~ 100 DEG C.
- A kind of 9. additive Mn CsPbBr obtained as the preparation method described in any one of claim 1 ~ 83Perovskite quantum dot is with dividing Son sieve composite luminescent material.
- A kind of 10. additive Mn CsPbBr described in claim 93Perovskite quantum dot is applied to molecular sieve composite luminescent material In white light LEDs.
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| CN110317607A (en) * | 2019-06-04 | 2019-10-11 | 华南理工大学 | A kind of perovskite quantum dot and low-dimensional-oxide composite luminescent material and preparation and application |
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