CN106809872A - CsPbBr with quantum size effect3The preparation method of nanometer sheet - Google Patents

CsPbBr with quantum size effect3The preparation method of nanometer sheet Download PDF

Info

Publication number
CN106809872A
CN106809872A CN201710039628.6A CN201710039628A CN106809872A CN 106809872 A CN106809872 A CN 106809872A CN 201710039628 A CN201710039628 A CN 201710039628A CN 106809872 A CN106809872 A CN 106809872A
Authority
CN
China
Prior art keywords
cspbbr
nanometer sheet
oleic acid
quantum size
size effect
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710039628.6A
Other languages
Chinese (zh)
Inventor
杨智
汪敏强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Jiaotong University
Original Assignee
Xian Jiaotong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Jiaotong University filed Critical Xian Jiaotong University
Priority to CN201710039628.6A priority Critical patent/CN106809872A/en
Publication of CN106809872A publication Critical patent/CN106809872A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

CsPbBr with quantum size effect3The preparation method of nanometer sheet, is passed through under conditions of argon gas, and cesium carbonate is dissolved in oleic acid, and the lower stirring of heating is until cesium carbonate dissolving, obtains oleic acid caesium presoma；It is passed through under conditions of argon gas, lead bromide, long-chain Ligand and short chain part are added in octadecylene, reacted at 100~150 DEG C to lead bromide dissolving, after being then heated to 120~150 DEG C, by the injection of oleic acid caesium presoma, 5~15s of reaction continues to react 1~5min after 100~130 DEG C, is then centrifuged for, and the present invention can realize CsPbBr3Nanometer sheet realizes regulation and control of the lateral dimension from 100nm to 1 μm while several atomic layer level thickness are ensured.And thickness can be maintained at below bohr exciton diameter, therefore remain CsPbBr3The quantum size effect of nanometer sheet.

Description

CsPbBr with quantum size effect3The preparation method of nanometer sheet
Technical field
The invention belongs to field of nano material preparation, and in particular to a kind of CsPbBr with quantum size effect3Nanometer The preparation method of piece.
Background technology
Recently as the fast development of organic inorganic hybridization perovskite solar cell, its photoelectric transformation efficiency is from 2009 The 3.8% of year develops rapidly 22.1% by 2016, and being attributed to perovskite material has strong absorbing ability, carrier high Mobility and exciton migration distance long, while indicating the material also has huge development potentiality.In addition, CH3NH3PbX3 (X=Br, I, Cl) quantum dot shows admirably photoluminescence property, luminous to cover whole visible spectrum, and quantum is produced Rate reaches 70% (Acs Nano, 2015,9 (4):4533-4542；Nano letters,2015,15(6):3692-3696.). But CH3NH3Aerial stability is very poor, it is necessary to process in an inert atmosphere, therefore limits organic inorganic hybridization calcium titanium The application of ore deposit quantum dot.But, researcher has found to use Cs+Substitute CH3NH3 +Perovskite quantum dot can well be solved in sky Stability problem in gas, quantum yield (Advanced Function high are composed while still retaining and can cover total visible light Materials, 2016,26,2435-2445).CsPbBr3Quantum dot is the inorganic perovskite quantum dot of current most study, because For it has the fluorescence quantum yield more than 80%, the halfwidth of emission peak is very narrow, can realize that fluorescence is sent out by sized Regulation of the peak from 430-532nm is penetrated, pattern control is easily realized.Based on CsPbBr3Quantum dot, is not changing the bar of primary morphology Under part, CsPbCl can be obtained by anion exchange reaction3And CsPbI3Quantum dot (J.Am.Chem.Soc.2015,137 (32):10276-10281.)。
The CsPbBr of report synthesis at present3The method of quantum dot is broadly divided into warm injection method high and prepared by normal temperature.Compared to Prepared by normal temperature, traditional warm injection method high can be by regulating and controlling between pre-reaction material, reaction temperature and time, different ligands Volume ratio is obtained various sizes of different morphologies including spherical, cubic block, nano wire and nanometer sheet etc. (J.Am.Chem.Soc.2016,138,7240-7243；Chem.Mater.2016,28,6450-6454).Due to CsPbBr3Amount Son point bohr exciton diameter there was only 7nm, when any one dimension of quantum dot can just be shown less than bohr exciton diameter it is bright Aobvious quantum size effect, shows as fluorescence emission wavelengths and is moved to shortwave length direction.Compared to zero-dimensional quantum dots, two dimension CsPbBr3Nanometer sheet is easier to realize single atomic layer to the regulation and control of several atomic layers on thickness, shows strong quantum chi Very little effect.In addition it has a plane carriers diffusion length long, stronger light absorbs and is easy to prepare the thin of even compact The advantages of film, therefore the two-dimentional CsPbBr for synthesizing3Nanometer sheet is on the one hand for the quantum confined effect of study two-dimensional semiconductor is provided Preferable model, on the other hand can be used to preparing the photoelectric devices such as field-effect transistor, photodetector and light emitting diode. A kind of amine part synthesis CsPbBr of use of report3The method (Adv.Mater.2016,28,4861-4869) of nanometer sheet, one Step reaction, it is impossible to regulate and control to nanometer sheet lateral dimension.
The content of the invention
To overcome the problems of the prior art, it is an object of the invention to provide a kind of with quantum size effect CsPbBr3The preparation method of nanometer sheet, the method added by adjusting long-chain Ligand and short chain part volume ratio, it is nanocrystalline into Core and the temperature and time for growing, it is possible to achieve inorganic perovskite CsPbBr3Nanocrystalline pattern is from spherical to thin layer nanometer sheet Regulation and control.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of CsPbBr with quantum size effect3The preparation method of nanometer sheet, comprises the following steps：
1) it is passed through under conditions of argon gas, cesium carbonate is dissolved in oleic acid, the lower stirring of heating is until cesium carbonate dissolving, obtains Oleic acid caesium presoma；Wherein, the ratio of cesium carbonate and oleic acid is 0.05g：5mL；
2) it is passed through under conditions of argon gas, lead bromide, long-chain Ligand and short chain part is added in octadecylene, 100~ Reacted at 150 DEG C to lead bromide dissolving, obtain mixed solution；Wherein, the ratio of lead bromide and long-chain Ligand is 0.01g~0.1g： 0.5mL；Long-chain Ligand is 1 with the volume ratio of short chain part：(0~1.8)；
3) by step 2) in mixed solution be heated to 120~150 DEG C after, by oleic acid caesium presoma injection, reaction 5~ 15s continues to react 1~5min after 100~130 DEG C, is then cooled to room temperature, is centrifuged, and washing is obtained with quantum size effect CsPbBr3Nanometer sheet；Wherein, the addition of oleic acid caesium presoma and mixed solution is according to cesium carbonate and the mass ratio of lead bromide It is 0.01g：0.01g~0.1g is added.
Of the invention further improvement be, step 1) in the temperature of heating be 120 DEG C, the time of stirring is 0.5h.
Of the invention further improvement be, step 2) in time of reaction be 0.5~2h.
Of the invention further improvement be, the step 2) in long-chain Ligand be that volume ratio is 1:1 oleic acid and oleyl amine Mixture, short chain part be volume ratio be 1:1 octanoic acid and the mixture of octylame.
Of the invention further improvement be, step 2) in the ratio of lead bromide and octadecylene be 0.01g~0.1g：10mL.
Of the invention further improvement be, step 3) in using ice-water bath cooling.
Of the invention further improvement be, step 3) in the speed of centrifugation be 500~10000rpm, the time of centrifugation is 5min。
Of the invention further improvement be, step 3) in centrifugation when, add solvent and anti-solvent；Solvent be n-hexane, Normal octane, toluene or chloroform, anti-solvent are ethyl acetate, isopropanol, butanol or acetone, and solvent is 1 with the volume ratio of anti-solvent: (0~3).
Of the invention further improvement be, step 4) in washing carried out using n-hexane, the number of times of washing for 0~ 4 times.
Compared with prior art, the device have the advantages that：The present invention is used and is rapidly injected oleic acid caesium presoma High temperature nucleation, the scheme of low-temperature epitaxy are carried out after to lead bromide, long-chain Ligand, short chain part, octadecylene mixed solution, while logical Long-chain Ligand and the volume ratio of short chain part, the temperature and time of reaction are overregulated, synthesizes CsPbBr3Nanometer sheet, can realize CsPbBr3Nanometer sheet realizes regulation and control of the lateral dimension from 100nm to 1 μm while several atomic layer level thickness are ensured.And thickness Can be maintained at below bohr exciton diameter, therefore remain CsPbBr3The quantum size effect of nanometer sheet.The present invention can be real Existing CsPbBr3The controllable preparation of nanometer sheet, its lateral dimension is from 100nm to 1 μm, so the big lateral dimension of present invention synthesis CsPbBr3Nanometer sheet be advantageous to for study two-dimensional semiconductor nano piece physical characteristic and prepare field effect transistor The photoelectric devices such as pipe, photodetector and light emitting diode.
Brief description of the drawings
Fig. 1 is the thin layer CsPbBr of the synthesis of the embodiment of the present invention 13The TEM figures of nanometer sheet, lateral dimension is 50nm.
Fig. 2 be the embodiment of the present invention it is 2-in-1 into thin layer CsPbBr3The TEM figures of nanometer sheet, lateral dimension is 100nm.
Fig. 3 is the thin layer CsPbBr of the synthesis of the embodiment of the present invention 33The TEM figures of nanometer sheet, lateral dimension is 200nm.
Fig. 4 is the thin layer CsPbBr of the synthesis of the embodiment of the present invention 43The TEM figures of nanometer sheet, lateral dimension is 300nm.
Fig. 5 is the CsPbBr of the synthesis of the embodiment of the present invention 53The TEM figures of nano spherical particle, size is 10nm.
Fig. 6 is the thick-layer CsPbBr of the synthesis of the embodiment of the present invention 63The TEM figures of nanometer sheet, lateral dimension is 500nm.
Fig. 7 is the CsPbBr of the synthesis of the embodiment of the present invention 1~63The fluorescence spectra of nano-particle.
Fig. 8 is the CsPbBr of the synthesis of the embodiment of the present invention 1~63The abosrption spectrogram of nano-particle.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment is described in further detail to the present invention.
Embodiment 1
1) 0.05g cesium carbonate powder is added in the 50mL three-necked bottles equipped with 5mL oleic acid, the stirring reaction at 120 DEG C 0.5h, cesium carbonate powder is completely dissolved, and obtains oleic acid caesium presoma；Argon gas is passed through in the process and is drained react the water of generation；
2) lead bromide of 0.04g, 0.25mL oleic acid, 0.25mL oleyl amines, 0.15mL octanoic acids and 0.15mL octylames are added successively Enter in 10mL octadecylenes, stirring reaction 0.5h is completely dissolved to lead bromide powder at 120 DEG C, obtains mixed solution；Herein During be passed through argon gas, remain reaction system be inert atmosphere；
3) after step 2) in mixed solution temperature be increased to 120 DEG C after, the 1mL oleic acid caesium presomas of room temperature will be cooled to It is rapidly injected, continuation is reacted during 100 DEG C of oil baths are transferred to after reaction 15s, total reaction time is 5min (total reaction time bags Include the post-reacted 15s of injection oleic acid caesium presoma), then mixed solution is quickly transferred in ice-water bath；
4) solution to be mixed is cooled to room temperature, is transferred into 50mL centrifuge tubes, adds 10mL n-hexanes as solvent With 10mL ethyl acetate as anti-solvent, 5min is centrifuged at 3,000 rpm；
5) supernatant liquid is outwelled, centrifugal sediment is distributed in n-hexane, then repeat step 4) 1 time, had The CsPbBr of quantum size effect3Nanometer sheet.
Embodiment 2
1) 0.05g cesium carbonate powder is added in the 50mL three-necked bottles equipped with 5mL oleic acid, the stirring reaction at 120 DEG C 0.5h, cesium carbonate powder is completely dissolved, and obtains oleic acid caesium presoma；Argon gas is passed through in the process and is drained react the water of generation；
2) lead bromide of 0.04g, 0.25mL oleic acid, 0.25mL oleyl amines, 0.25mL octanoic acids and 0.25mL octylames are added successively Enter in 10mL octadecylene solvents, stirring reaction 0.5h is completely dissolved to lead bromide powder at 120 DEG C, obtains mixed solution； Argon gas is passed through in the process, remains that reaction system is inert atmosphere；
3) after step 2) in mixed solution temperature be increased to 130 DEG C after, the 1mL oleic acid caesium presomas of room temperature will be cooled to It is rapidly injected, continuation is reacted during 110 DEG C of oil baths are transferred to after reaction 15s, total reaction time is 5min (total reaction time bags Include the post-reacted 15s of injection oleic acid caesium presoma), then mixed solution is quickly transferred in ice-water bath；
4) solution to be mixed is cooled to room temperature, is transferred into 50mL centrifuge tubes, adds 10mL n-hexanes as solvent, With 20mL ethyl acetate as anti-solvent, 5min is centrifuged under 2000rpm；
5) supernatant liquid is outwelled, centrifugal sediment is distributed in n-hexane, then repeat step 4) 2 times, had The CsPbBr of quantum size effect3Nanometer sheet.
Embodiment 3
1) 0.05g cesium carbonate powder is added in the 50mL three-necked bottles equipped with 5mL oleic acid, the stirring reaction at 120 DEG C 0.5h, cesium carbonate powder is completely dissolved, and obtains oleic acid caesium presoma；Argon gas is passed through in the process and is drained react the water of generation；
2) lead bromide of 0.04g, 0.25mL oleic acid, 0.25mL oleyl amines, 0.35mL octanoic acids and 0.35mL octylames are added successively Enter in 10mL octadecylene solvents, stirring reaction 0.5h is completely dissolved to lead bromide powder at 120 DEG C, obtains mixed solution； Argon gas is passed through in the process, remains that reaction system is inert atmosphere；
3) after step 2) in mixed solution temperature be increased to 140 DEG C after, the 1mL oleic acid caesium presomas of room temperature will be cooled to It is rapidly injected, continuation is reacted during 120 DEG C of oil baths are transferred to after reaction 10s, total reaction time is 4min (total reaction time bags Include the post-reacted 10s of injection oleic acid caesium presoma), then mixed solution is quickly transferred in ice-water bath；
4) solution to be mixed is cooled to room temperature, is transferred into 50mL centrifuge tubes, adds 10mL n-hexanes as solvent, 5min is centrifuged under 1000rpm；
5) supernatant liquid is outwelled, centrifugal sediment is distributed in n-hexane, then repeat step 4) 3 times, had The CsPbBr of quantum size effect3Nanometer sheet.
Embodiment 4
1) 0.05g cesium carbonate powder is added in the 50mL three-necked bottles equipped with 5mL oleic acid, the stirring reaction at 120 DEG C 0.5h, cesium carbonate powder is completely dissolved, and obtains oleic acid caesium presoma；Argon gas is passed through in the process and is drained react the water of generation；
2) lead bromide of 0.04g, 0.25mL oleic acid, 0.25mL oleyl amines, 0.45mL octanoic acids and 0.45mL octylames are added successively Enter in 10mL octadecylene solvents, stirring reaction 0.5h is completely dissolved to lead bromide powder at 120 DEG C, obtains mixed solution； Argon gas is passed through in the process, remains that reaction system is inert atmosphere；
3) after step 2) in mixed solution temperature be increased to 150 DEG C after, the 1mL oleic acid caesium presomas of room temperature will be cooled to It is rapidly injected, continuation is reacted during 130 DEG C of oil baths are transferred to after reaction 5s, total reaction time is 3min (total reaction time bags Include the post-reacted 5s of injection oleic acid caesium presoma), then mixed solution is quickly transferred in ice-water bath；
4) solution to be mixed is cooled to room temperature, is transferred into 50mL centrifuge tubes, adds 10mL n-hexanes as solvent, 5min is centrifuged at 500 rpm；
5) supernatant liquid is outwelled, centrifugal sediment is distributed in n-hexane, then repeat step 4) 4 times, had The CsPbBr of quantum size effect3Nanometer sheet.
Embodiment 5
1) 0.05g cesium carbonate powder is added in the 50mL three-necked bottles equipped with 5mL oleic acid, the stirring reaction at 120 DEG C 0.5h, cesium carbonate powder is completely dissolved, and obtains oleic acid caesium presoma；Argon gas is passed through in the process and is drained react the water of generation；
2) lead bromide of 0.04g, 0.25mL oleic acid and 0.25mL oleyl amines are added in 10mL octadecylene solvents successively, Stirring reaction 0.5h is completely dissolved to lead bromide powder at 120 DEG C, and argon gas is passed through in the process, obtains mixed solution；All the time Holding reaction system is inert atmosphere；
3) after step 2) in mixed solution temperature be increased to 120 DEG C after, the 1mL oleic acid caesium presomas of room temperature will be cooled to It is rapidly injected, continuation is reacted during 100 DEG C of oil baths are transferred to after reaction 5s, total reaction time is 5min (total reaction time bags Include the post-reacted 5s of injection oleic acid caesium presoma), then mixed solution is quickly transferred in ice-water bath；
4) solution to be mixed is cooled to room temperature, is transferred into 50mL centrifuge tubes, adds 10mL n-hexanes as solvent With 30mL ethyl acetate as anti-solvent, 5min is centrifuged under 10000rpm；
5) supernatant liquid is outwelled, centrifugal sediment is distributed in n-hexane, then repeat step 4) 1 time, had The CsPbBr of quantum size effect3Nanometer sheet.
Embodiment 6
1) 0.05g cesium carbonate powder is added in the 50mL three-necked bottles equipped with 5mL oleic acid, the stirring reaction at 120 DEG C 0.5h, cesium carbonate powder is completely dissolved, and obtains oleic acid caesium presoma；Argon gas is passed through in the process and is drained react the water of generation；
2) lead bromide of 0.04g, 0.25mL oleic acid, 0.25mL oleyl amines, 0.15mL octanoic acids and 0.15mL octylames are added successively Enter in 10mL octadecylene solvents, stirring reaction 0.5h is completely dissolved to lead bromide powder at 120 DEG C, obtains mixed solution； Argon gas is passed through in the process, remains that reaction system is inert atmosphere；
3) after step 2) in mixed solution temperature be increased to 150 DEG C after, the 1mL oleic acid caesium presomas of room temperature will be cooled to It is rapidly injected, continuation is reacted during 130 DEG C of oil baths are transferred to after reaction 15s, total reaction time is 5min, then by mixed solution It is quickly transferred in ice-water bath；
4) solution to be mixed is cooled to room temperature, is transferred into 50mL centrifuge tubes, adds 10mL toluene as solvent, 5min is centrifuged under 500rpm；
5) supernatant liquid is outwelled, centrifugal sediment is distributed in toluene, then repeat step 4) 2 times, obtain that there is amount The CsPbBr of sub- dimensional effect3Nanometer sheet.
In embodiment 1, long-chain Ligand is 1 with the volume ratio of short chain part:0.6, hot implantation temperature is 120 DEG C, and total is anti- It is 5min, the CsPbBr for obtaining as can be seen from Figure 1 between seasonable3The lateral length of nanometer sheet is 50nm, as can be seen from Figure 7 main fluorescence Peak position has two secondary peaks of 425nm and 401nm in 458nm, corresponds respectively to the CsPbBr that thickness is 3 layers, 2 layers and 1 layer3 Nanometer sheet, as can be seen from Figure 8 absorbs peak position in 418nm.
In embodiment 2, long-chain Ligand is 1 with the volume ratio of short chain part:1, hot implantation temperature is 130 DEG C, total reaction Time is 5min, the CsPbBr for obtaining as can be seen from Figure 23The lateral length of nanometer sheet is 100nm, as can be seen from Figure 7 main fluorescence Peak position has two secondary peaks of 425nm and 401nm in 452nm, corresponds respectively to the CsPbBr that thickness is 3 layers, 2 layers and 1 layer3 Nanometer sheet, as can be seen from Figure 8, in 424nm, secondary absorption peak position is in 456nm for main absorption peak position.
In embodiment 3, long-chain Ligand is 1 with the volume ratio of short chain part:1.4, hot implantation temperature is 140 DEG C, and total is anti- It is 4min, the CsPbBr for obtaining as can be seen from Figure 3 between seasonable3The lateral length of nanometer sheet is 200nm, is as can be seen from Figure 7 led glimmering Light peak position in 453nm, corresponding to the CsPbBr that thickness is 3 layers3Nanometer sheet, two secondary peaks of short wavelength are not very obvious, show nanometer The thickness of piece is highly uniform, as can be seen from Figure 8 absorbs peak position in 444nm.
In embodiment 4, long-chain Ligand is 1 with the volume ratio of short chain part:1.8, hot implantation temperature is 150 DEG C, and total is anti- It is 3min, the CsPbBr for obtaining as can be seen from Figure 4 between seasonable3The lateral length of nanometer sheet is 300nm, is as can be seen from Figure 7 led glimmering Light peak position has two secondary peaks of 425nm and 401nm in 460nm, and it is 3 layers, 2 layers and 1 layer to correspond respectively to thickness CsPbBr3Nanometer sheet, as can be seen from Figure 8 main absorption peak position is in 458nm.
In embodiment 5, long-chain Ligand is 1 with the volume ratio of short chain part:0, hot implantation temperature is 120 DEG C, total reaction Time is 5min, and spherical CsPbBr is obtained as can be seen from Figure 53The size of nano-particle is 10nm, as can be seen from Figure 7 main fluorescence Peak position has mono- secondary peak of 430nm in 460nm, and as can be seen from Figure 8 main absorption peak position is in 427nm.
In embodiment 6, long-chain Ligand is 1 with the volume ratio of short chain part:0.6, hot implantation temperature is 150 DEG C, and total is anti- It is 5min between seasonable, the CsPbBr of thickness is obtained as can be seen from Figure 63The lateral length of nanometer sheet is 500nm, as can be seen from Figure 7 glimmering Light peak position, corresponding to block materials transmitting, as can be seen from Figure 8 absorbs peak position also in 525nm in 525nm.
It can be seen that, only when the temperature and time for adding volume ratio of the long-chain Ligand with short chain part, reaction is generally noted above Ratio limit when, could generate have quantum size effect thin layer CsPbBr3Nanometer sheet；And embodiment 5 and embodiment 6 do not have Have within this range, so having respectively obtained the spherical CsPbBr with quantum size effect3Nano-particle and without quantum The thick-layer CsPbBr of dimensional effect3Nanometer sheet.
Embodiment 7
1) 0.05g cesium carbonate powder is added in the 50mL three-necked bottles equipped with 5mL oleic acid, the stirring reaction at 120 DEG C 0.5h, cesium carbonate powder is completely dissolved, and obtains oleic acid caesium presoma；Argon gas is passed through in the process and is drained react the water of generation；
2) lead bromide of 0.01g, 0.25mL oleic acid, 0.25mL oleyl amines, 0.2mL octanoic acids and 0.2mL octylames are added successively To in 10mL octadecylenes, stirring reaction 2h is completely dissolved to lead bromide powder at 100 DEG C, obtains mixed solution；In this process In be passed through argon gas, remain reaction system be inert atmosphere；
3) after step 2) in mixed solution temperature be increased to 120 DEG C after, the 1mL oleic acid caesium presomas of room temperature will be cooled to It is rapidly injected, 5min is reacted in continuation during 100 DEG C of oil baths are transferred to after reaction 5s, and mixed solution then is quickly transferred into ice-water bath In；
4) solution to be mixed is cooled to room temperature, is transferred into 50mL centrifuge tubes, adds 10mL normal octanes as solvent, 5min is centrifuged at 500 rpm；
5) supernatant liquid is outwelled, centrifugal sediment is distributed in n-hexane, then repeat step 4) 1 time, had The CsPbBr of quantum size effect3Nanometer sheet.
Embodiment 8
1) 0.05g cesium carbonate powder is added in the 50mL three-necked bottles equipped with 5mL oleic acid, the stirring reaction at 120 DEG C 0.5h, cesium carbonate powder is completely dissolved, and obtains oleic acid caesium presoma；Argon gas is passed through in the process and is drained react the water of generation；
2) lead bromide of 0.1g, 0.25mL oleic acid, 0.25mL oleyl amines, 0.1mL octanoic acids and 0.1mL octylames are added to successively In 10mL octadecylenes, stirring reaction 1h is completely dissolved to lead bromide powder at 130 DEG C, obtains mixed solution；In the process Argon gas is passed through, remains that reaction system is inert atmosphere；
3) after step 2) in mixed solution temperature be increased to 140 DEG C after, the 1mL oleic acid caesium presomas of room temperature will be cooled to It is rapidly injected, 3min is reacted in continuation during 120 DEG C of oil baths are transferred to after reaction 10s, and mixed solution then is quickly transferred into frozen water In bath；
4) solution to be mixed is cooled to room temperature, is transferred into 50mL centrifuge tubes, adds 10mL toluene as solvent, and 10mL acetone is centrifuged 5min as anti-solvent under 5000rpm；
5) supernatant liquid is outwelled, centrifugal sediment is distributed in n-hexane, obtained with quantum size effect CsPbBr3Nanometer sheet.
Embodiment 9
1) 0.05g cesium carbonate powder is added in the 50mL three-necked bottles equipped with 5mL oleic acid, the stirring reaction at 120 DEG C 0.5h, cesium carbonate powder is completely dissolved, and obtains oleic acid caesium presoma；Argon gas is passed through in the process and is drained react the water of generation；
2) lead bromide of 0.07g, 0.25mL oleic acid, 0.25mL oleyl amines are added in 10mL octadecylenes successively, at 150 DEG C Lower stirring reaction 0.5h is completely dissolved to lead bromide powder, obtains mixed solution；Argon gas is passed through in the process, remains anti- It is inert atmosphere to answer system；
3) after step 2) in mixed solution temperature be increased to 150 DEG C after, the 1mL oleic acid caesium presomas of room temperature will be cooled to It is rapidly injected, 1min is reacted in continuation during 130 DEG C of oil baths are transferred to after reaction 15s, and mixed solution then is quickly transferred into frozen water In bath；
4) solution to be mixed is cooled to room temperature, is transferred into 50mL centrifuge tubes, adds 10mL toluene as solvent, and 10mL acetone is centrifuged 5min as anti-solvent under 5000rpm；
5) supernatant liquid is outwelled, centrifugal sediment is distributed in n-hexane, then repeat step 4) 4 times, had The CsPbBr of quantum size effect3Nanometer sheet.
When being centrifuged in the present invention, it can be chloroform that solvent is breathed out, and anti-solvent can also be isopropanol or butanol.
Ratio above-mentioned is broken through when the volume ratio of long-chain Ligand and short chain part, the temperature and time of reaction is added When, possible product is the nanometer sheet (not having quantum size effect) of nano spherical particle or thickness, it is also possible to without generation CsPbBr3.It is an advantage of the invention that：1) can by adjust the volume ratio of long-chain Ligand and short chain part, the temperature of reaction and Time-controllable CsPbBr3The size of nanometer sheet, obtains the ultra-thin CsPbBr with quantum size effect3Nanometer sheet；2) synthesis is big The CsPbBr of lateral dimension3Nanometer sheet is advantageous to physical characteristic and preparation field for study two-dimensional semiconductor nano piece The photoelectric devices such as effect transistor, photodetector and light emitting diode.

Claims (9)

1. a kind of CsPbBr with quantum size effect3The preparation method of nanometer sheet, it is characterised in that comprise the following steps：
1) it is passed through under conditions of argon gas, cesium carbonate is dissolved in oleic acid, the lower stirring of heating is until cesium carbonate dissolving, obtains oleic acid Caesium presoma；Wherein, the ratio of cesium carbonate and oleic acid is 0.05g：5mL；
2) it is passed through under conditions of argon gas, lead bromide, long-chain Ligand and short chain part is added in octadecylene, at 100~150 DEG C Lower reaction obtains mixed solution to lead bromide dissolving；Wherein, the ratio of lead bromide and long-chain Ligand is 0.01g~0.1g：0.5mL； Long-chain Ligand is 1 with the volume ratio of short chain part：(0~1.8)；
3) by step 2) in mixed solution be heated to 120~150 DEG C after, by oleic acid caesium presoma injection, reaction 5~15s after Continue to react 1~5min in 100~130 DEG C, be then cooled to room temperature, be centrifuged, washing is obtained with quantum size effect CsPbBr3Nanometer sheet；Wherein, oleic acid caesium presoma is with the mass ratio of lead bromide according to cesium carbonate with the addition of mixed solution 0.01g：0.01g~0.1g is added.
2. a kind of CsPbBr with quantum size effect according to claim 13The preparation method of nanometer sheet, its feature Be, step 1) in heating temperature for 120 DEG C, the time of stirring is 0.5h.
3. a kind of CsPbBr with quantum size effect according to claim 13The preparation method of nanometer sheet, its feature Be, step 2) in reaction time be 0.5~2h.
4. a kind of CsPbBr with quantum size effect according to claim 13The preparation method of nanometer sheet, its feature Be, the step 2) in long-chain Ligand be volume ratio be 1:1 oleic acid and the mixture of oleyl amine, short chain part are that volume ratio is 1:1 octanoic acid and the mixture of octylame.
5. a kind of CsPbBr with quantum size effect according to claim 13The preparation method of nanometer sheet, its feature Be, step 2) in lead bromide and octadecylene ratio be 0.01g~0.1g：10mL.
6. a kind of CsPbBr with quantum size effect according to claim 13The preparation method of nanometer sheet, its feature It is, step 3) it is middle using ice-water bath cooling.
7. a kind of CsPbBr with quantum size effect according to claim 13The preparation method of nanometer sheet, its feature Be, step 3) in centrifugation speed for 500~10000rpm, the time of centrifugation is 5min.
8. a kind of CsPbBr with quantum size effect according to claim 13The preparation method of nanometer sheet, its feature Be, step 3) in centrifugation when, add solvent and anti-solvent；Solvent is n-hexane, normal octane, toluene or chloroform, and anti-solvent is Ethyl acetate, isopropanol, butanol or acetone, solvent are 1 with the volume ratio of anti-solvent:(0~3).
9. a kind of CsPbBr with quantum size effect according to claim 13The preparation method of nanometer sheet, its feature Be, step 4) in washing carried out using n-hexane, the number of times of washing is 0~4 time.
CN201710039628.6A 2017-01-19 2017-01-19 CsPbBr with quantum size effect3The preparation method of nanometer sheet Pending CN106809872A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710039628.6A CN106809872A (en) 2017-01-19 2017-01-19 CsPbBr with quantum size effect3The preparation method of nanometer sheet

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710039628.6A CN106809872A (en) 2017-01-19 2017-01-19 CsPbBr with quantum size effect3The preparation method of nanometer sheet

Publications (1)

Publication Number Publication Date
CN106809872A true CN106809872A (en) 2017-06-09

Family

ID=59112848

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710039628.6A Pending CN106809872A (en) 2017-01-19 2017-01-19 CsPbBr with quantum size effect3The preparation method of nanometer sheet

Country Status (1)

Country Link
CN (1) CN106809872A (en)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107418570A (en) * 2017-07-03 2017-12-01 苏州虹霞晶体科技有限公司 A kind of zero dimension perovskite structure high efficient luminous material and reversal temperature production method
CN107522225A (en) * 2017-09-18 2017-12-29 河北工业大学 A kind of synthetic method of inorganic perovskite nanometer sheet
CN107792877A (en) * 2017-10-27 2018-03-13 华南理工大学 A kind of centrifugal mixer synthesizes CsPbBr3The method of nanocrystal
CN107915250A (en) * 2017-11-29 2018-04-17 南京理工大学 A kind of Ca-Ti ore type nanotube and preparation method thereof
CN108300465A (en) * 2018-03-21 2018-07-20 中山大学 A kind of preparation method of additive Mn full-inorganic lead chlorine perovskite nanometer sheet
CN108585030A (en) * 2018-04-26 2018-09-28 吉林大学 A kind of small size Mn of Color tunable:CsPbCl3Nanocrystalline preparation method
CN110357148A (en) * 2019-07-09 2019-10-22 济南大学 A kind of preparation method of overstable CsPbBr3 nanometer sheet and its application in terms of the scintillation screen of x-ray imaging
CN110407479A (en) * 2019-07-09 2019-11-05 济南大学 A kind of production method of the solar concentrator based on zero dimension perovskite
CN110589878A (en) * 2019-09-30 2019-12-20 上海应用技术大学 Hexagonal phase CsPbBr3Nanocrystalline and preparation method thereof
CN110649160A (en) * 2018-06-26 2020-01-03 华中科技大学鄂州工业技术研究院 Inorganic charge transport layer, preparation method thereof and application of perovskite solar cell
CN110982523A (en) * 2019-12-11 2020-04-10 西南交通大学 Copper-doped quasi-two-dimensional all-inorganic perovskite material and preparation method thereof
CN111646496A (en) * 2020-04-30 2020-09-11 南京理工大学 Highly ordered perovskite nanosheet film with high polarization characteristic and preparation method thereof
CN112429762A (en) * 2020-11-24 2021-03-02 北京交通大学 Preparation method of inorganic cesium-lead halogen perovskite nanorod with adjustable width and length
US11091693B2 (en) * 2016-08-12 2021-08-17 Boe Technology Group Co., Ltd. Method of preparing luminescent nano-sheet, luminescent nano-sheet material, luminescent nano-sheet film, back light, and liquid crystal display apparatus
CN114316944A (en) * 2021-12-07 2022-04-12 西安交通大学 Method for preparing high-stability zirconium oxide coated quantum dots
CN116970392A (en) * 2023-08-01 2023-10-31 上海工程技术大学 In-situ ligand modified CsPbBr 3 Preparation method and application of nanosheet material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105441074A (en) * 2015-11-18 2016-03-30 重庆大学 Preparation method based on regulating and controlling CsPbBr3 perovskite quantum dots from blue light to green light
CN105523581A (en) * 2016-02-25 2016-04-27 吉林大学 Single-size CsPbX3 perovskite nanocrystalline preparation method
CN105621477A (en) * 2016-01-31 2016-06-01 南京理工大学 Inorganic perovskite CsPbX3 nanosheet synthesis method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105441074A (en) * 2015-11-18 2016-03-30 重庆大学 Preparation method based on regulating and controlling CsPbBr3 perovskite quantum dots from blue light to green light
CN105621477A (en) * 2016-01-31 2016-06-01 南京理工大学 Inorganic perovskite CsPbX3 nanosheet synthesis method
CN105523581A (en) * 2016-02-25 2016-04-27 吉林大学 Single-size CsPbX3 perovskite nanocrystalline preparation method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JAVAD SHAMSI等: "Colloidal Synthesis of Quantum Confined Single Crystal CsPbBr3 Nanosheets with Lateral Size Control up to the Micrometer Range", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 *

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11091693B2 (en) * 2016-08-12 2021-08-17 Boe Technology Group Co., Ltd. Method of preparing luminescent nano-sheet, luminescent nano-sheet material, luminescent nano-sheet film, back light, and liquid crystal display apparatus
CN107418570A (en) * 2017-07-03 2017-12-01 苏州虹霞晶体科技有限公司 A kind of zero dimension perovskite structure high efficient luminous material and reversal temperature production method
CN107522225A (en) * 2017-09-18 2017-12-29 河北工业大学 A kind of synthetic method of inorganic perovskite nanometer sheet
CN107522225B (en) * 2017-09-18 2019-06-14 河北工业大学 A kind of synthetic method of inorganic perovskite nanometer sheet
CN107792877A (en) * 2017-10-27 2018-03-13 华南理工大学 A kind of centrifugal mixer synthesizes CsPbBr3The method of nanocrystal
CN107915250A (en) * 2017-11-29 2018-04-17 南京理工大学 A kind of Ca-Ti ore type nanotube and preparation method thereof
CN107915250B (en) * 2017-11-29 2019-05-07 南京理工大学 A kind of Ca-Ti ore type nanotube and preparation method thereof
CN108300465A (en) * 2018-03-21 2018-07-20 中山大学 A kind of preparation method of additive Mn full-inorganic lead chlorine perovskite nanometer sheet
CN108585030A (en) * 2018-04-26 2018-09-28 吉林大学 A kind of small size Mn of Color tunable:CsPbCl3Nanocrystalline preparation method
CN108585030B (en) * 2018-04-26 2019-09-17 吉林大学 A kind of small size Mn:CsPbCl of Color tunable3Nanocrystalline preparation method
CN110649160A (en) * 2018-06-26 2020-01-03 华中科技大学鄂州工业技术研究院 Inorganic charge transport layer, preparation method thereof and application of perovskite solar cell
CN110649160B (en) * 2018-06-26 2021-06-25 华中科技大学鄂州工业技术研究院 Inorganic charge transport layer, preparation method thereof and application of perovskite solar cell
CN110407479A (en) * 2019-07-09 2019-11-05 济南大学 A kind of production method of the solar concentrator based on zero dimension perovskite
CN110357148A (en) * 2019-07-09 2019-10-22 济南大学 A kind of preparation method of overstable CsPbBr3 nanometer sheet and its application in terms of the scintillation screen of x-ray imaging
CN110589878A (en) * 2019-09-30 2019-12-20 上海应用技术大学 Hexagonal phase CsPbBr3Nanocrystalline and preparation method thereof
CN110589878B (en) * 2019-09-30 2022-06-24 上海应用技术大学 Hexagonal phase CsPbBr3Nanocrystalline and preparation method thereof
CN110982523A (en) * 2019-12-11 2020-04-10 西南交通大学 Copper-doped quasi-two-dimensional all-inorganic perovskite material and preparation method thereof
CN111646496A (en) * 2020-04-30 2020-09-11 南京理工大学 Highly ordered perovskite nanosheet film with high polarization characteristic and preparation method thereof
CN111646496B (en) * 2020-04-30 2023-05-23 南京理工大学 Highly ordered perovskite nano sheet film with high polarization characteristic and preparation method thereof
CN112429762A (en) * 2020-11-24 2021-03-02 北京交通大学 Preparation method of inorganic cesium-lead halogen perovskite nanorod with adjustable width and length
CN114316944A (en) * 2021-12-07 2022-04-12 西安交通大学 Method for preparing high-stability zirconium oxide coated quantum dots
CN114316944B (en) * 2021-12-07 2023-11-21 西安交通大学 Method for preparing high-stability zirconia coated quantum dot
CN116970392A (en) * 2023-08-01 2023-10-31 上海工程技术大学 In-situ ligand modified CsPbBr 3 Preparation method and application of nanosheet material

Similar Documents

Publication Publication Date Title
CN106809872A (en) CsPbBr with quantum size effect3The preparation method of nanometer sheet
CN108502918B (en) Synthesis method of inorganic perovskite nanowire
CN105441074B (en) One kind is based on to CsPbBr3The preparation method that perovskite quantum dot regulates and controls from blue light to green glow
CN110564416B (en) High-stability perovskite quantum dot composite material and preparation method thereof
CN105621477A (en) Inorganic perovskite CsPbX3 nanosheet synthesis method
CN108531172B (en) Preparation method and application of hybrid perovskite microcrystalline luminescent material
CN106833635B (en) Large scale perovskite CsPbBr3The preparation method of six square pieces-circular piece
CN110589878B (en) Hexagonal phase CsPbBr3Nanocrystalline and preparation method thereof
CN107474823A (en) With core shell structure perovskite nanocrystalline material and preparation method thereof
KR101788240B1 (en) Preparation of copper selenide nanoparticles
CN108314077A (en) The simple method for preparing full-inorganic perovskite nanostructure
CN112251221B (en) Method for preparing cesium-lead halogen perovskite quantum dots based on in-situ mercaptosilane passivation
CN108753289A (en) Inorganic halide lead perovskite quantum dot and preparation method, nano wire and preparation method
CN106118216B (en) Ga-doped ZnO nano ink and preparation method thereof
CN102503161A (en) SnS nanocrystalline thin film preparation method
CN106566553A (en) Methods for synthesizing ZnxCd1-xSe, ZnxCd1-xSe/ZnS and ZnxCd1-xSe/ZnS/ZnS alloy quantum dots
CN113845142A (en) Cesium-lead-iodine perovskite nanocrystal and preparation method and application thereof
CN105154086A (en) Method for preparing CdSe/CdS nuclear shell semiconductor quantum dots at normal temperature
CN110808335B (en) Preparation method and application of tin-lead binary perovskite film with preferred orientation growth
CN106929920A (en) The nanocrystalline preparation method of inorganic perovskite based on doping thiocyanate
CN113061434A (en) Perovskite quantum dot, preparation method thereof and photoelectric device
CN103694997B (en) A kind of bluish violet that synthesizes shines the method for ZnCdS/ZnS nano-crystal with core-shell structure
CN112391164A (en) Method for realizing optical property conversion of intermediate band gap semiconductor nanocrystalline
CN102101653A (en) Cu2ZnSnSe4 nano material as well as preparation method and application of thereof
CN111303882A (en) Cadmium-free quantum dot and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20170609

RJ01 Rejection of invention patent application after publication