CN108190944A - A kind of nanocrystalline preparation method of perovskite - Google Patents
A kind of nanocrystalline preparation method of perovskite Download PDFInfo
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Abstract
The nanocrystalline method of perovskite is synthesized this application discloses a kind of, the method includes at least following steps：S1 the system I containing organic titanium esters) is obtained；S2) under agitation, perovskite presoma is added in into step S1) described in react in system I, obtain the perovskite nanocrystalline material.The method can realize that raw material directly mixes at room temperature, quick and easy, easy to operation, be expected to be widely applied to the synthesis of extensive lead halogen Ca-Ti ore type quantum dot.
Description
Technical field
This application involves a kind of preparation methods of perovskite nanocrystalline material, belong to Material Field.
Background technology
Lead halogen Ca-Ti ore type nanocrystal, since its excellent photoelectric properties becomes the hot spot of Recent study.Its is photic
The yield that shines can reach 90% under conditions of being passivated without any additional surface.Optical characteristics can in entire limit of visible spectrum
To adjust.These optical characteristics make it show up prominently in various optoelectronic applications fields as new material, such as can
Emit the Low threshold single photon of efficient LED of laser and two-photon pumping gain material.
The hot injection method of preparation generally use of traditional lead halogen Ca-Ti ore type quantum dot.But hot injection method need it is more severe
Quarter and cumbersome synthesis condition, such as high temperature, inert gas shielding and local injection operation.These considerably increase it and actually should
Limitation in.Improvement for synthetic method is the research emphasis about lead halogen perovskite at present.
Invention content
According to the one side of the application, the method for providing a kind of nanocrystalline preparation of perovskite, this method can be real
Existing raw material directly mixes at room temperature, quick and easy, easy to operation, is expected to be widely applied to extensive lead halogen Ca-Ti ore type quantum
The synthesis of point.
The nanocrystalline preparation method of the perovskite, which is characterized in that including at least following steps：
S1 the system I containing organic titanium esters) is obtained；
S2) under agitation, perovskite presoma is added in into step S1) described in react in system I, obtain the calcium
Titanium ore nanocrystalline material.
The method is suitable for the nanocrystalline preparation of common perovskite, preferably AMX3Type perovskite nano microcrystalline, preferably
Lead halogen Ca-Ti ore type quantum dot；It is preferred that the perovskite material is CsPbX3；It is further preferred that the perovskite material is
CsPbBr3.Wherein, the A is selected from CH3NH3 +, NH=CHNH3 +Or Cs+At least one of；M is metal ion, the metal
Selected from least one of Sn, Pb；The X is selected from least one of halide anion.Optionally, organic titanium esters are selected from
Commercially available common commodity, can be selected according to actual conditions and present specification.
Optionally, the size of the perovskite nanocrystalline material is 10~100nm.
Optionally, the size of the perovskite nanocrystalline material is 10~80nm.
Optionally, the size of the perovskite nanocrystalline material is 15~50nm.
Optionally, the size of the perovskite nanocrystalline material is 15~25nm.
Optionally, the upper dimension bound of the perovskite nanocrystalline material is selected from 50nm, 60nm, 80nm, 90nm or 100nm；
Lower limit is selected from 10nm, 15nm, 20nm, 25nm or 40nm.
Optionally, the perovskite nanocrystalline material is selected from least one of nanometer sheet, nano cubic block, nanometer rods.
Optionally, the thickness of the nanometer sheet is 3~7nm.
Optionally, the thickness of the nanometer sheet is 5nm.
Optionally, the emission wavelength of the perovskite nanocrystalline material is in 480~520nm.
Optionally, the emission wavelength upper limit of the perovskite nanocrystalline material be selected from 490nm, 495nm, 500nm, 509nm,
510nm or 520nm；Lower limit is selected from 480nm, 485nm or 490nm.
Optionally, step S1) and step S2) reaction condition carried out under room temperature, air conditions.
Optionally, step S1) described in organic titanium esters be selected from isopropyl titanate, tetraethyl titanate, positive four butyl ester of metatitanic acid, titanium
At least one of sour four tert-butyl esters.
Optionally, organic titanium esters in isopropyl titanate, tetraethyl titanate, positive four butyl ester of metatitanic acid at least one
Kind.
Optionally, step S1) described in system I further include solvent and surfactant.
Optionally, the solvent, which is selected from, has at least one of compound of chemical formula shown in formula (I)：
R13- CH=CH2Formula (I)
Wherein, R13Selected from C1~C20Alkyl, C1~C20Unsaturated alkyl.
Optionally, the surfactant be selected from formula (II), in the compound of chemical formula shown in formula (III) extremely
Few one kind：
R11-NH2Formula (II)
R12- COOH formulas (III)
Wherein, R11、R12Separately it is selected from C1~C20Alkyl, C1~C20Unsaturated alkyl.
Optionally, the solvent is octadecylene, and the surfactant is selected from least one of oleic acid, oleyl amine.
Optionally, the volume ratio of the solvent, surfactant and organic titanium esters meets：
Solvent：Surfactant：Organic titanium esters=8~12:0.5~2:0.5~2.
Optionally, the volume ratio of the solvent, surfactant and organic titanium esters meets：
Solvent：Surfactant：Organic titanium esters=8~12:1~2:0.5~2.
Optionally, the R13- CH=CH2、R11-NH2、R12- COOH, organic titanium esters volume ratio be 8~12：0.5~1:
0.5~1:0.5~2.
Optionally, aforementioned proportion range (R13- CH=CH2、R11-NH2、R12- COOH, organic titanium esters volume ratio for 8~
12：0.5~1:0.5~1:0.5~2) the volume ratio upper limit of organic titanium esters is selected from 1,1.2,1.5,1.8 or 2 in；Lower limit is selected from
0.5th, 0.6,0.8 or 1.When the volume ratio upper limit such as organic titanium esters is 1, the R13- CH=CH2、R11-NH2、R12It is-COOH, organic
The volume ratio of titanium esters is 8~12：0.5~1:0.5~1:0.5~1.
Optionally, the R13- CH=CH2、R11-NH2、R12- COOH, organic titanium esters volume ratio be 10：0.5：0.5：1.
Optionally, step S2) described in perovskite be selected from have at least one of chemical formula shown in formula (IV)：
AMX3Formula (IV)
Wherein, A is selected from CH3NH3 +, NH=CHNH3 +Or Cs+At least one of；
M is metal ion, and the metal is selected from least one of Sn, Pb；
The X is selected from least one of halide anion.
Optionally, it is CsPbBr that the perovskite is nanocrystalline3It is nanocrystalline.
Optionally, the perovskite presoma includes salt compounds AX1With MX2；Wherein, A and M such as formulas (IV) are described；
The X1、X2Independently selected from halide anion, CO3 2-At least one of；Wherein, X1、X2In at least one be
Halide anion.
Optionally, the X2Selected from Cl-、Br-Or I-, X1Selected from CO3 2-。
Optionally, AX1Selected from Cs2CO3, at least one of CsBr.
Optionally, AX1Selected from Cs2CO3。
Optionally, MX2Selected from PbBr2。
Optionally, the X1、X2Independently selected from Cl-、Br-Or I-。
Optionally, step S2) described in AX1With MX2Molar ratio be 1:1~5.
Optionally, step S2) described in AX1With MX2Molar ratio be 1:1~4.
Optionally, step S2) described in AX1With MX2Molar ratio be 1:3.
Optionally, step S2) described in AX1With step S1) described in organic titanium esters ratio be 1mol：0.5~2ml.
Optionally, step S2) described in reaction condition in mechanical agitation, magnetic agitation, high speed dispersion, oscillation extremely
Few one kind.
Optionally, the rate of the stirring is 400~640rpm/min.
Optionally, the frequency of oscillation is per minute for 560.
Optionally, step S2) described in the reaction time be 5~240 minutes.
Optionally, the upper limit in the reaction time is selected from 180 minutes, 200 minutes, 220 minutes, 240 minutes；Lower limit is selected from
5 minutes, 15 minutes, 30 minutes, 60 minutes, 80 minutes, 100 minutes, 120 minutes, 140 minutes, 160 minutes.
Optionally, step S2) described in the reaction time be 30~180 minutes.
Optionally, the upper limit in the reaction time be selected from 80 minutes, 100 minutes, 120 minutes, 140 minutes, 160 minutes,
180 minutes；Lower limit is selected from 30 minutes, 60 minutes, 80 minutes, 100 minutes, 120 minutes, 140 minutes, 160 minutes.
Optionally, the step S2) be that perovskite presoma is added in into step S1) described in react in system I, reaction solution
Isolated precipitation, and disperseed with toluene to obtain the perovskite nanocrystalline material.
Optionally, the 11000rpm that is separated into is centrifuged 5 minutes.
Optionally, the method includes at least：
Step a1：Surfactant is added in solvent, then adds in organic titanium esters, is stirred；
Step a2：Perovskite presoma is added in the solution stirred in step a1 and is reacted；
Step a3：Solution after being reacted in step a2 is centrifuged, retains lower sediment to get to the perovskite nanometer
It is brilliant；
Optionally, the method includes at least：
Step c1：By 10ml R13- CH=CH2It is added in the reagent bottle of 20ml, adds in the R of 0.5-1ml12- COOH and
The R of 0.5-1ml11-NH2, organic titanium esters of 0.5-2ml are then added in, are stirred continuously；
Step c2：Weigh the MX of 0.1-0.4mmol2With the AX of 0.1mmol1It is added in the above-mentioned solution being stirred continuously anti-
It should；
Step c3：Solution after reaction under the conditions of 11000rpm is centrifuged 5 minutes, is retained nanocrystalline in lower sediment
And with toluene distributed and saved to get nanocrystalline to the perovskite.
Optionally, the method includes at least：
Step b1：10ml octadecylenes are added in the reagent bottle of 20ml, add in the oleic acid and 0.5-1ml of 0.5-1ml
Then oleyl amine adds in organic titanium esters of 0.5-2ml, is stirred continuously；
Step b2：Weigh the PbBr of 0.1-0.4mmol2With the Cs of 0.1mmol2CO3It is added to the above-mentioned solution being stirred continuously
Middle reaction；
Step b3：Solution after reaction under the conditions of 11000rpm is centrifuged 5 minutes, is retained in lower sediment
CsPbBr3It is nanocrystalline and with toluene distributed and saved to get nanocrystalline to the perovskite.
After reactant is expanded 20 times in the application, this method is still effective, remains to synthesize perovskite nanocrystalline (preferably
CsPbX3It is nanocrystalline).
After reactant is expanded 20 times in the application, this method is still effective, remains to synthesize CsPbX3It is nanocrystalline.
This application provides a kind of CsPbBr3Nanocrystalline, preparation method and its application in fluorescent material.It is described
CsPbBr3It is nanocrystalline to pass through the catalysis Fast back-projection algorithm of organic titanium esters.This method only needs single stepping, and can largely synthesize.
Nanocrystalline pattern, such as nanometer sheet, nano cubic block can be changed by the type for changing organic titanium esters.The CsPbBr3It receives
Meter Jing can be used for the photoelectric devices such as LED, have broad application prospects in LED field.
Specifically, one of the object of the invention is for current CsPbX3Compare in (X=Cl, Br, I) nanocrystalline material system
Compared with the Fast back-projection algorithm of shortage, a kind of CsPbBr is provided3Nanocrystalline fast preparation method, this method directly by solid reactant and
Reagent directly mixes, and then under the catalytic action of organic titanium esters, by directly synthesis is stirred at room temperature, to have obtained luminescent properties excellent
Different perovskite is nanocrystalline, this is current synthesis CsPbX3Nanocrystalline most fast most easy method.And reactant is expanded 20
After times, this method is still effective, remains to synthesize CsPbX3It is nanocrystalline.Organic titanium esters play the role of catalyst, and change
The CsPbX of different-shape can be obtained by becoming the type of organic titanium esters3It is nanocrystalline.The material emission spectral coverage is big,
Quantum efficiency is high, and the scale of being easy to is combined to, and has in the fields such as White-light LED illumination and display, optical detector, solar cell wide
Wealthy application prospect.
Specifically, the method includes at least following steps：
Step 1：10ml octadecylenes are added in the reagent bottle of 20ml, add in the oleic acid of 0.5-1ml and the oil of 0.5-1ml
Then amine adds in organic titanium esters of 0.5-2ml, is stirred continuously；
Step 2：Weigh the PbBr of 0.1-0.4mmol2With the Cs of 0.1mmol2CO3It is added to the above-mentioned solution being stirred continuously
In, solution colour can be observed in room temperature and air environment, after a few minutes and become yellow, under ultraviolet lamp (365nm) irradiation
Bright green light can be observed；
Step 3：Solution after reaction under the conditions of 11000rpm is centrifuged 5 minutes, retains the CsPbBr in lower sediment3
It is nanocrystalline and with toluene distributed and saved.
Specifically, the reaction time has a certain impact to pattern, and 5-240min can obtain the nanocrystalline of high quality,
30-180min is best time.
Specifically, the additive amount of organic titanium esters has a certain impact to pattern, and 0.5-2ml can obtain luminous
CsPbBr3Nanocrystalline, 1ml is optimum addition.
Specifically, the addition of different organic titanium esters can obtain the CsPbBr of different-shape3It is nanocrystalline.Tetraethyl titanate
It can obtain the CsPbBr of nanometer sheet pattern3It is nanocrystalline；Isopropyl titanate can obtain the nano cubic block pattern of size uniformity
CsPbBr3It is nanocrystalline；Positive four butyl ester of metatitanic acid can obtain the CsPbBr of the nano cubic block pattern of size unevenness3It is nanocrystalline.
The CsPbBr that the application provides3Nanocrystalline preparation method, it is characterised in that：Reaction process only needs a step, extremely
It is simple and efficient.
The CsPbBr that the application provides3Nanocrystalline preparation method, it is characterised in that：Organic titanium esters play catalyst work
With, and change its type and can adjust pattern.
CsPbBr provided by the invention3Nanocrystalline preparation method, it is characterised in that：It can be combined to again, for industrializing
Production.
According to the another aspect of the application, a kind of luminescent material is provided, the perovskite being prepared comprising the above method
Nanocrystalline material.
Optionally, the size of the perovskite nanocrystalline material is 10~100nm.
Optionally, the size of the perovskite nanocrystalline material is 15~25nm.
Optionally, the upper dimension bound of the perovskite nanocrystalline material is selected from 50nm, 60nm, 80nm, 90nm or 100nm；
Lower limit is selected from 10nm, 15nm, 20nm, 25nm or 40nm.
Optionally, the emission wavelength of the perovskite nanocrystalline material is in 480~520nm.
Optionally, the emission wavelength upper limit of the perovskite nanocrystalline material be selected from 490nm, 495nm, 500nm, 509nm,
510nm or 520nm；Lower limit is selected from 480nm, 485nm or 490nm.
The condition that numberical range is related in the application can be independently selected from the arbitrary point value in the numberical range.
" C in the application1~C20”、“C1~C10" etc. refer both to the carbon atom number that group is included.
In the application, " alkyl " is the group formed by losing any one hydrogen atom on alkane compound molecule.
In the application, " alkyl " is loses the group formed after a hydrogen atom on carbon atom in hydrocarbon molecule.The hydrocarbon
For carbohydrate, such as alkane, alkene, alkynes are hydrocarbon.
In the application, " aryl " is to lose what is formed after any one hydrogen atom on aromatic rings in aromatic compound molecule
Group.
The advantageous effect that the application can generate includes：
1) preparation method of perovskite crystallite provided herein succeeds at ambient temperature, in urging for organic titanium esters
Reaction has synthesized CsPbBr in next step for change effect3It is nanocrystalline, possibility is provided for its industrialized production, makes it in photoelectric device
Field has broad application prospects.
2) preparation method of perovskite crystallite provided herein, have to be combined to again, for industrialized production.
3) preparation method of perovskite crystallite provided herein, reaction process only needs a step, extremely simple quick, instead
It is 30~180min between seasonable.
4) preparation method of perovskite crystallite provided herein, organic titanium esters play catalyst action, and change
Pattern can be adjusted by becoming its type.
Description of the drawings
Fig. 1 is the isopropyl titanate that 1ml is added in embodiment 1, stirs the CsPbBr that 60min is obtained at room temperature3It is nanocrystalline
XRD diagram.
Fig. 2 is the isopropyl titanate that 1ml is added in embodiment 1, stirs the CsPbBr that 60min is obtained at room temperature3It is nanocrystalline
Transmission electron microscope picture, the nanometer sheet erect is represented wherein in box.
Fig. 3 is the tetraethyl titanate that 1ml is added in embodiment 2, stirs the CsPbBr that 60min is obtained at room temperature3It is nanocrystalline
Transmission electron microscope picture.
Fig. 4 is positive four butyl ester of metatitanic acid that 1ml is added in embodiment 3, stirs the CsPbBr that 60min is obtained at room temperature3Nanometer
Brilliant transmission electron microscope picture.
Fig. 5 is that the fluorescence spectrum of sample and the light absorption spectrogram that different organic titanium esters obtain are added in embodiment 1-3, wherein
(a) corresponding embodiment 1；(b) corresponding embodiment 2；(c) corresponding embodiment 3.
Fig. 6 is embodiment 1, the isopropyl titanate of 1ml added in 4-6, be stirred at room temperature 60 respectively, 15,30,180min
Obtained CsPbBr3Nanocrystalline transmission electron microscope picture, wherein (a) corresponding embodiment 4；(b) corresponding embodiment 5；(c) it is corresponding to implement
Example 1；(d) corresponding embodiment 6.
Fig. 7 is embodiment 1, add 1 in 7-9 respectively, 0.5,1.5, the isopropyl titanate of 2ml, stir 60min at room temperature and obtain
The CsPbBr arrived3Nanocrystalline transmission electron microscope picture, wherein (a) corresponding embodiment 7；(b) corresponding embodiment 2；(c) corresponding embodiment
8；(d) corresponding embodiment 9.
Specific embodiment
The application is described in detail, but the application is not limited to these embodiments with reference to embodiment.
Unless otherwise instructed, the raw material in embodiments herein and solvent are bought by commercial sources.
Analysis method is as follows in embodiments herein：
XRD tests, test scope are carried out using Rigaku MiniFlex II X-ray powder diffractions instrument：10-70 degree,
Sweep speed is 2 degree mins, and scanning step is 0.02 degree.
Pattern test is carried out using Tecnai G2S-Twin F20 Flied emissions transmission electron microscope.
Fluorescence property test is carried out using Varian Cary 500scan Fluorescence Spectrometer.
Ultraviolet test is carried out using Hitachi UV-2450 Ultraviolet visible absorption spectrums instrument.
1 sample 1 of embodiment#Preparation
Step 1：10ml octadecylenes are added in the reagent bottle of 20ml, add in the oleic acid of 0.5ml and the oleyl amine of 0.5ml,
Then the isopropyl titanate of 1ml is added in, is stirred continuously and (is vibrated with 560 frequency shaking tables per minute, shaking table modelKS
130basic)；
Step 2：Weigh the PbBr of 0.3mmol2With the Cs of 0.1mmol2CO3It is added in the above-mentioned solution being stirred continuously,
In room temperature and air environment, i.e. solution colour, which can be observed, becomes yellow after a few minutes, persistently stirs 60min ultraviolet lamps
Bright green light can be observed under (365nm) irradiation；
Step 3：Solution after reaction under the conditions of 11000rpm is centrifuged 5 minutes, retains the CsPbBr in lower sediment3
It is nanocrystalline and with toluene distributed and saved, obtained CsPbBr3It is nanocrystalline to be denoted as 1#。
2 sample 2 of embodiment#Preparation
For other steps with embodiment 1, the difference lies in the isopropyl titanates in step 1 to be changed to tetraethyl titanate, obtains
CsPbBr3It is nanocrystalline to be denoted as 2#。
3 sample 3 of embodiment#Preparation
For other steps with embodiment 1, the difference lies in the isopropyl titanates in step 1 to be changed to positive four butyl ester of metatitanic acid, obtains
The CsPbBr arrived3It is nanocrystalline to be denoted as 3#。
4 sample 4 of embodiment#Preparation
For other steps with embodiment 1, the difference lies in the mixings time in step 2 to be changed to 15min by 60min, obtains
CsPbBr3It is nanocrystalline to be denoted as 4#。
5 sample 5 of embodiment#Preparation
For other steps with embodiment 1, the difference lies in the mixings time in step 2 to be changed to 30min by 60min, obtains
CsPbBr3It is nanocrystalline to be denoted as 5#。
6 sample 6 of embodiment#Preparation
For other steps with embodiment 1, the difference lies in the mixings time in step 2 to be changed to 180min by 60min, obtains
CsPbBr3It is nanocrystalline to be denoted as 6#。
7 sample 7 of embodiment#Preparation
For other steps with embodiment 1, the amount the difference lies in the isopropyl titanate in step 1 becomes 0.5ml from 1ml,
Obtained CsPbBr3It is nanocrystalline to be denoted as 7#。
8 sample 8 of embodiment#Preparation
For other steps with embodiment 1, the amount the difference lies in the isopropyl titanate in step 1 becomes 1.5ml from 1ml,
Obtained CsPbBr3It is nanocrystalline to be denoted as 8#。
9 sample 9 of embodiment#Preparation
With embodiment 1, the amount the difference lies in the isopropyl titanate in step 1 becomes 2ml from 1ml, obtains other steps
The CsPbBr arrived3It is nanocrystalline to be denoted as 9#。
10 sample 1 of embodiment#~9#Structural characterization
To sample 1#~9#XRD tests are carried out, XRD spectrum shows to be a cube phase structure.Typical CsPbBr3It is nanocrystalline
XRD spectra as shown in Figure 1, sample 1 in corresponding embodiment 1#.Sample 1#It is a cube phase structure (PDF#75-0412).
11 sample 1 of embodiment#~9#Morphology characterization
To sample 1#~9#Morphology characterization is carried out, typical transmission electron microscope photo is as shown in Fig. 2~4, Fig. 6~7.Fig. 2 is to add
The CsPbBr that tetraethyl titanate (corresponding embodiment 2) is added to prepare3Nanocrystalline transmission electron microscope picture, the results showed that the pattern of sample is
Nanometer sheet is mixed with a small amount of small cubic block, the nanometer sheet erect wherein is represented in box, shows that its thickness only has about 5nm.Figure
3 be to add CsPbBr prepared by metatitanic acid isopropyl ester (corresponding embodiment 1)3Nanocrystalline transmission electron microscope picture, the results showed that sample
Pattern is uniform nano cubic block.Fig. 4 is to add CsPbBr prepared by positive four butyl ester (corresponding embodiment 3) of metatitanic acid3It is nanocrystalline
Transmission electron microscope picture, pattern is also for nano cubic block, but size difference is larger between particle.Sample 1#~9#1#10~
100nm；Wherein sample 2#Size is in 15~25nm；Wherein sample 3#Size is in 50~100nm；Wherein sample 4#Size 10~
20nm；Wherein sample 5#Size is in 15~25nm；Wherein sample 6#Size is in 15~25nm；Wherein sample 7#Size 20~
40nm；Wherein sample 8#Size is in 20~100nm；Wherein sample 9#Size is in 20~100nm.
The CsPbBr for being prepared for pattern by changing mixing time and being slightly different3It is nanocrystalline, to CsPbBr3Nanocrystalline progress
Transmissioning electric mirror test.Fig. 6 is the transmission electron microscope picture (corresponding embodiment 4~6) obtained under four kinds of different mixings time, can be with
Sample particle when finding out 15min is smaller and thinner thickness, and with the increase of mixing time, particle gradually grows up to nano cubic
Block, with a small amount of nanometer sheet.But since 30min, the size of particle is substantially constant, is maintained at 20nm or so.So
Particle sustainable growth will not be made by increasing mixing time, and 30-180min is the rational reaction time.
CsPbBr has been regulated and controled by the additive amount for changing isopropyl titanate3Nanocrystalline pattern, to CsPbBr3It is nanocrystalline into
Transmissioning electric mirror test is gone.Fig. 7 is the transmission electron microscope picture (corresponding embodiment 7~9) obtained under four kinds of Different adding amounts, can be with
Sample particle when finding out 0.5ml is small-sized and without cube pattern, the little particle for no pattern.It is obtained during the additive amount of 1ml
Good uniform cubic block pattern is arrived.Continue to increase with isopropyl titanate, particle surface, which covers some, does not have shape
The substance of looks.These substances are the titanyl substances that isopropyl titanate hydrolysis generates, so as to which product be made not to be pure CsPbBr3Nanometer
It is brilliant.Therefore, most suitable additive amount is 1ml, can obtain good nanocrystalline of pattern at this time.
12 sample 1 of embodiment#~9#Fluorescence spectrum and UV absorption test
To sample 1#~9#Fluorescence spectrum and UV absorption test are carried out, typical spectrogram is as shown in figure 5, corresponding implement
Example 1~3.By further looking at fluorescence spectrum, it is known that, the position consistency of the position of emission peak all with absorption spectrum ABSORPTION EDGE.
The CsPbBr that tetraethyl titanate and isopropyl titanate obtain3Nanocrystalline emission peak half-peak breadth is small.And positive four butyl ester of metatitanic acid
CsPbBr3Nanocrystalline half-peak breadth is very big, and absorption spectrum ABSORPTION EDGE slows down, this is related with the homogeneity of pattern.Sample 1#~9#Hair
Optical wavelength is in 480~520nm.Wherein, the emission wavelength of sample is 495nm in Fig. 5 a；The emission wavelength of sample is in Fig. 5 b
509nm；The emission wavelength of sample is 500nm in Fig. 5 c.
According to result above, it can be seen that it is adjustable that method proposed by the present invention has successfully quickly prepared pattern
CsPbBr3It is nanocrystalline, the CsPbBr3The Best Times of Syntheses are 30~180min, and best organic titanium esters additive amount is
1ml.This method has filled up CsPbBr3The scarcity of nanocrystalline synthetic technology at room temperature.Present invention determine that CsPbBr3Nanocrystalline
Industrialization production basic condition.
The amplification production of 13 Examples 1 to 9 of embodiment
After launching 20 times of quality amplification to the reactant of Examples 1 to 9, same effect is still obtained.
Those skilled in the art select mechanical agitation, magnetic agitation, high speed dispersion, at least one item vibrated as needed
The technical solution in the application can be achieved in part (rate is 400~640rpm/min), reaches the technique effect.Above to this
Illustrative description has been done in invention, it should it says, in the case of the core for not departing from the present invention, any simple deformation,
Modification or other skilled in the art can not spend the equivalent replacement of creative work to each fall within protection model of the invention
It encloses.
Unaccomplished matter of the present invention is known technology.
The above is only several embodiments of the application, any type of limitation is not done to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in the range of technical solution.
Claims (10)
1. a kind of synthesize the nanocrystalline method of perovskite, which is characterized in that including at least following steps：
S1 the system I containing organic titanium esters) is obtained；
S2) under agitation, perovskite presoma is added in into step S1) described in react in system I, obtain the perovskite
Nanocrystalline material.
2. according to the method described in claim 1, it is characterized in that, step S1) and step S2) under room temperature, air conditions
It carries out.
3. according to the method described in claim 1, it is characterized in that, step S1) described in organic titanium esters be selected from isopropyl titanate,
At least one of positive four butyl ester of tetraethyl titanate, metatitanic acid, four tert-butyl ester of metatitanic acid.
4. according to the method described in claim 1, it is characterized in that, solvent and table are further included in system I described in step (S1)
Face activating agent；
Preferably, the solvent, which is selected from, has at least one of compound of chemical formula shown in formula (I)：
R13- CH=CH2Formula (I)
Wherein, R13Selected from C1~C20Alkyl, C1~C20Unsaturated alkyl；
Preferably, the surfactant is selected from at least one in the compound of chemical formula shown in formula (II), formula (III)
Kind：
R11-NH2Formula (II)
R12- COOH formulas (III)
Wherein, R11、R12Independently selected from C1~C20Alkyl, C1~C20Unsaturated alkyl；
Preferably, the solvent is octadecylene；The surfactant is selected from least one of oleic acid, oleyl amine；
Preferably, the volume ratio of the solvent, surfactant and organic titanium esters meets：
Solvent：Surfactant：Organic titanium esters=8~12:0.5~2:0.5~2；
Preferably, the volume ratio of the solvent, surfactant and organic titanium esters meets：
Solvent：Surfactant：Organic titanium esters=8~12:1~2:0.5~2；
Preferably, the R13- CH=CH2、R11-NH2、R12- COOH, organic titanium esters volume ratio be 8~12：0.5~1:0.5~
1:0.5~2；
Preferably, the R13- CH=CH2、R11-NH2、R12- COOH, organic titanium esters volume ratio be 10：0.5：0.5：1.
5. according to the method described in claim 1, it is characterized in that, step S2) described in perovskite be selected from there is formula (IV) institute
Show at least one of chemical formula：
AMX3Formula (IV)
Wherein, A is selected from CH3NH3 +, NH=CHNH3 +Or Cs+At least one of；
M is metal ion, and the metal is selected from least one of Sn, Pb；
The X is selected from least one of halide anion；
Preferably, it is CsPbBr that the perovskite is nanocrystalline3It is nanocrystalline；
Preferably, the step S2) in perovskite presoma include salt compounds AX1With MX2；Wherein, A and M such as formulas (IV) institute
It states；
The X1、X2Independently selected from halide anion, CO3 2-At least one of；Wherein, X1、X2In it is at least one cloudy for halogen
Ion；
Preferably, the X2Selected from Cl-、Br-Or I-, X1Selected from CO3 2-。
6. according to the method described in claim 5, it is characterized in that, step S2) described in AX1With MX2Molar ratio be 1:1~
5；
Preferably, step S2) described in AX1With MX2Molar ratio be 1:1~4；
Preferably, step S2) described in AX1With MX2Molar ratio be 1:3；
Preferably, step S2) described in AX1With step S1) described in organic titanium esters ratio be 1mmol：0.5~2ml；
Preferably, step S2) described in reaction condition in mechanical agitation, magnetic agitation, high speed dispersion, oscillation at least one
Kind；
Wherein, the rate of the stirring is 400~640rpm/min.
7. according to the method described in claim 1, it is characterized in that, step S2) described in the reaction time be 5~240 minutes；
Preferably, step S2) described in the reaction time be 30~180 minutes.
8. according to the method described in claim 1, it is characterized in that, the method includes at least：
Step a1：Surfactant is added in solvent, then adds in organic titanium esters, is stirred；
Step a2：Perovskite presoma is added in the solution stirred in step a1 and is reacted；
Step a3：Solution after being reacted in step a2 is centrifuged, retains lower sediment to get nanocrystalline to the perovskite；
Preferably, the method includes at least：
Step b1：10ml octadecylenes are added in the reagent bottle of 20ml, add in the oleic acid of 0.5-1ml and the oleyl amine of 0.5-1ml,
Then organic titanium esters of 0.5-2ml are added in, are stirred continuously；
Step b2：Weigh the PbBr of 0.1-0.4mmol2With the Cs of 0.1mmol2CO3It is added in the above-mentioned solution being stirred continuously anti-
It should；
Step b3：Solution after reaction under the conditions of 11000rpm is centrifuged 5 minutes, retains the CsPbBr in lower sediment3Nanometer
It is brilliant and with toluene distributed and saved to get nanocrystalline to the perovskite.
9. according to the method described in claim 1, it is characterized in that, the size of the perovskite nanocrystalline material for 10~
100nm；
Preferably, the size of the perovskite nanocrystalline material is 15~50nm；
Preferably, the emission wavelength of the perovskite nanocrystalline material is in 480~520nm.
10. a kind of luminescent material, which is characterized in that include the calcium being prepared according to any one of claim 1 to 9 the method
Titanium ore nanocrystalline material.
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| CN109030380A (en) * | 2018-07-25 | 2018-12-18 | 佛山科学技术学院 | A kind of detection method and device of the nanocrystalline Random Laser emission mechanism of perovskite |
| CN109516496A (en) * | 2018-12-18 | 2019-03-26 | 江南大学 | A kind of full-inorganic perovskite CsPbBr of stable dispersion3Nanocrystalline preparation method |
| CN110304651A (en) * | 2019-06-27 | 2019-10-08 | 浙江大学 | A kind of perovskite with clad structure is nanocrystalline and preparation method thereof |
| CN110387223A (en) * | 2019-07-11 | 2019-10-29 | 浙江大学 | A kind of hydroxyl halogen lead ore/lead halogen perovskite composite micro-nano rice material and preparation method thereof |
| CN111117601A (en) * | 2019-12-30 | 2020-05-08 | 上海大学 | Red light perovskite quantum dot with stable luminescence property and preparation method thereof |
| CN111171814A (en) * | 2020-01-08 | 2020-05-19 | 上海大学 | Synthesis method of perovskite nanorod |
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| CN109030380A (en) * | 2018-07-25 | 2018-12-18 | 佛山科学技术学院 | A kind of detection method and device of the nanocrystalline Random Laser emission mechanism of perovskite |
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| CN110304651A (en) * | 2019-06-27 | 2019-10-08 | 浙江大学 | A kind of perovskite with clad structure is nanocrystalline and preparation method thereof |
| CN110304651B (en) * | 2019-06-27 | 2020-05-26 | 浙江大学 | Perovskite nanocrystalline with cladding structure and preparation method thereof |
| CN110387223A (en) * | 2019-07-11 | 2019-10-29 | 浙江大学 | A kind of hydroxyl halogen lead ore/lead halogen perovskite composite micro-nano rice material and preparation method thereof |
| CN111117601A (en) * | 2019-12-30 | 2020-05-08 | 上海大学 | Red light perovskite quantum dot with stable luminescence property and preparation method thereof |
| CN111117601B (en) * | 2019-12-30 | 2022-12-23 | 上海大学 | Red light perovskite quantum dot with stable luminescence property and preparation method thereof |
| CN111171814A (en) * | 2020-01-08 | 2020-05-19 | 上海大学 | Synthesis method of perovskite nanorod |
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