CN108314077A - The simple method for preparing full-inorganic perovskite nanostructure - Google Patents

The simple method for preparing full-inorganic perovskite nanostructure Download PDF

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CN108314077A
CN108314077A CN201810101903.7A CN201810101903A CN108314077A CN 108314077 A CN108314077 A CN 108314077A CN 201810101903 A CN201810101903 A CN 201810101903A CN 108314077 A CN108314077 A CN 108314077A
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oleic acid
quantum dot
octadecylene
pbbr
hour
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陈海涛
郭安琪
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Yangzhou University
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Yangzhou University
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    • 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
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • 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
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/664—Halogenides
    • C09K11/665—Halogenides with alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • 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
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

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Abstract

The invention discloses a kind of simple method for preparing full-inorganic perovskite nanostructure, step is：By Cs2CO3It is mixed with octadecylene and oleic acid, is reacted 1 ~ 2 hour at 120 ± 10 DEG C and be configured to oleic acid caesium precursor solution；In air, by PbBr2It reacts 1 ~ 2 hour, oleyl amine and oleic acid is added as ligand, and be warming up to 180 ± 10 DEG C at 120 ± 10 DEG C with octadecylene；It is then slowly injected into oleic acid caesium precursor solution, after injecting 5 ~ 15s, ice bath cooling is carried out to reactant immediately, centrifugation takes precipitation to be dissolved in toluene and obtains CsPbBr3Quantum dot solution.The present invention directly prepares CsPbBr under air conditions3Quantum dot, using toluene to the passivation of perovskite quantum dot, can get has higher fluorescence quantum efficiency（~90%）, emission wavelength cover entire visible spectrum（400‑700 nm）, halfwidth relative narrower（12‑42 nm）, many advantages, such as fluorescence lifetime is long quantum dot.

Description

The simple method for preparing full-inorganic perovskite nanostructure
Technical field
The invention belongs to quantum dots to show, the technical field of lighting engineering and solar cell preparation, under air environment Prepare full-inorganic perovskite nanostructure.
Background technology
In recent years, hybrid inorganic-organic perovskite（CH3NH3PbX3, X=Cl, Br, I）Material is at low cost with its, carrier The advantages that mobility is high, the absorption coefficient of light is big as area of solar cell research hotspot.Its photoelectricity turns since two thousand nine Efficiency is changed from less than 4% rapid promotion to 22.1%.However, since the problems such as environmental stability and poor thermal stability, has constrained Application of the machine-inorganic hybridization perovskite in field of solar energy.
At this point, a kind of new quantum dot system --- full-inorganic perovskite quantum dot（CsPbX3, X = Cl, Br, I） Cause the extensive concern of industrial circle.The system can get stable cubic crystal structure under high―temperature nuclei, with high Fluorescence quantum efficiency（Up to 90%）, wavelength of fluorescence is adjustable and the entire visible light wave range of covering（400-700 nm）, halfwidth compared with It is narrow（12-42 nm）, fluorescence lifetime it is long, be expected to be applied to quantum dot of new generation show in lighting engineering, at present in solar-electricity It is most widely used in pond.
The CsPbX of report synthesis at present3The method of nanostructure is mainly high warm injection method, it can be by regulating and controlling to react Predecessor, reaction temperature and time, different ligands obtain different sizes, the nanostructure of different-shape（Nanometer sheet, nanometer rods, Nano wire, nanosphere etc.）.However, the preparation condition of high warm injection method is harsher, and other than needing hot conditions, overall process It needs long-time rare gas atmosphere to protect, is hardly formed the batch production of commercial Application.
Invention content
The object of the present invention is to provide a kind of simple preparation methods of full-inorganic perovskite nanostructure.
Realizing the technical solution of the object of the invention is：The simple method for preparing full-inorganic perovskite nanostructure, packet Include following steps：
（1）By Cs2CO3With octadecylene（1-ODE）And oleic acid（OA）It is mixed, is reacted 1 ~ 2 hour at 120 ± 10 DEG C It is configured to oleic acid caesium precursor solution；
（2）In air, by PbBr2It is reacted 1 ~ 2 hour at 120 ± 10 DEG C with octadecylene, by oleyl amine（OAm）With oleic acid conduct Ligand is added, and is increased to 180 ± 10 DEG C；
（3）Then it is slowly injected into step（1）The oleic acid caesium precursor solution after injecting 5 ~ 15s, carries out ice to reactant immediately Bath cooling, centrifugation take precipitation to be dissolved in toluene and obtain CsPbBr3Quantum dot solution.
Further, step（1）In, Cs2CO3, octadecylene and oleic acid three mass ratio be 2:80:5（Molar ratio is 1: 50:3）.
Further, step（2）In, PbBr2Mass ratio with octadecylene is 2:23（Molar ratio is 1:50）；PbBr2And oil The mass ratio of amine is 1.7:1（Molar ratio is 1.2:1）；PbBr2Mass ratio with oleic acid is 3:2（Molar ratio is 1.2:1）.
Further, step（3）In, mixture of ice and water is used when ice bath cools down.
Compared with prior art, it is an advantage of the invention that：
（1）In traditional CsPbBr3In quantum dot preparation process, all processes need under vacuum or inert gas environment into Row, the present invention directly can prepare CsPbBr under air conditions3Quantum dot makees the passivation of perovskite quantum dot using toluene With can get has higher fluorescence quantum efficiency（~90%）, emission wavelength cover entire visible spectrum（400-700 nm）, it is half high Wide relative narrower（12-42 nm）, many advantages, such as fluorescence lifetime is long quantum dot.
（2）Further, since this preparation method is simple to operation, it can be used for large-scale industrial production.
Description of the drawings
Fig. 1 is CsPbBr prepared by the present invention3The XRD spectra of perovskite nanostructure.
Fig. 2 is CsPbBr prepared by the present invention3The TEM of perovskite nanostructure schemes.
Fig. 3 is CsPbBr prepared by the present invention3The PL spectrograms of perovskite nanostructure.
Fig. 4 is CsPbBr of the present invention3The preparation process schematic diagram of perovskite nanostructure.
Specific implementation mode
Such as Fig. 4, CsPbBr of the present invention3The preparation process of perovskite nanostructure is as follows：
（1）The preparation of oleic acid caesium precursor solution：
0.407g Cs are added in three-necked flask2CO3 With 20ml octadecylenes and 1.2ml oleic acid, it is heated to 120 DEG C and keeps 1 hour, mixture is then warming up to 150 DEG C and is kept for 30 minutes, until all Cs2CO3Reaction finishes.
（2）CsPbBr3The synthesis of quantum dot：
By 1.378g PbBr2With 20ml octadecylenes at 120 DEG C continuous heating 1 hour, by 1ml drying oleyl amine and 1ml dry Oleic acid be added solution in, the temperature of solution is risen to 180 DEG C, is then slowly injected into 1ml oleic acid caesium precursor solutions（This mistake Cheng Jun is completed under air environment）.After injecting 5s, ice bath cooling is carried out to reactant immediately.
（3）The thick solution that ice bath cools down is centrifuged 10 minutes under the rotating speed of 7000 rpm/min.After centrifugation, discard supernatant Precipitation particle is dispersed in toluene by liquid.
Fig. 1 is to prepare CsPbBr under air environment3The XRD spectra of perovskite nanostructure.We can from figure Go out, the CsPbBr prepared by the present invention3The XRD spectra of perovskite nanostructure and the XRD spectra of standard（PDF#54-0752）One It causes.
Fig. 2 is to utilize CsPbBr prepared by the present invention3The TEM of perovskite nanostructure schemes.As can be seen from the figure it prepares Nanostructure size be 8-10 nm.The size of the nanostructure can further be regulated and controled by the adjusting to temperature, from several Nanometer is differed to tens nanometers.
Fig. 3 is the CsPbBr synthesized under 180 DEG C of air environments3The PL spectrograms of perovskite nanostructure.We in phase Synthermal Ar2The sample prepared in environment is compared, it can be seen from the figure that sample prepared by the present invention is with higher glimmering Photo-quantum efficiency；The transmitting peak position of the two is almost unchanged, in 509nm, illustrates in air environment and Ar2The calcium prepared in environment Titanium ore nanostructure structure having the same and size.

Claims (4)

1. the simple method for preparing full-inorganic perovskite nanostructure, which is characterized in that include the following steps：
（1）By Cs2CO3It is mixed with octadecylene and oleic acid, is reacted 1 ~ 2 hour at 120 ± 10 DEG C and be configured to oleic acid caesium Precursor solution；
（2）In air, by PbBr2It is reacted 1 ~ 2 hour at 120 ± 10 DEG C with octadecylene, oleyl amine and oleic acid is added as ligand Enter, and is warming up to 180 ± 10 DEG C；
（3）Then it is slowly injected into step（1）The oleic acid caesium precursor solution after injecting 5 ~ 15s, carries out ice to reactant immediately Bath cooling, centrifugation take precipitation to be dissolved in toluene and obtain CsPbBr3Quantum dot solution.
2. the method as described in claim 1, which is characterized in that step（1）In, Cs2CO3, octadecylene and oleic acid three matter Amount is than being 2:80:5.
3. the method as described in claim 1, which is characterized in that step（2）In, PbBr2Mass ratio with octadecylene is 2:23； PbBr2Mass ratio with oleyl amine is 1.7:1；PbBr2Mass ratio with oleic acid is 3:2.
4. the method as described in claim 1, which is characterized in that step（3）In, mixture of ice and water is used when ice bath cools down.
CN201810101903.7A 2018-02-01 2018-02-01 The simple method for preparing full-inorganic perovskite nanostructure Pending CN108314077A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111204797A (en) * 2020-01-17 2020-05-29 南京工业大学 Morphology-controllable all-inorganic CsPbBr3Preparation method of perovskite nanocrystal
CN112028117A (en) * 2020-09-17 2020-12-04 昆明理工大学 Wet chemical annealing method for preparing fully inorganic CsPbBr3Method and application of nanocrystalline
CN113257932A (en) * 2021-05-12 2021-08-13 常熟理工学院 High-performance photoelectric detector and preparation method thereof
CN113308245A (en) * 2021-05-27 2021-08-27 南京邮电大学 Preparation method and application of blue-violet light-free perovskite nano material
CN113604220A (en) * 2021-08-17 2021-11-05 东北电力大学 Perovskite quantum dot material and preparation method and application thereof
CN114891505A (en) * 2022-05-26 2022-08-12 天津大学 Preparation method and application of blue-light dodecahedral perovskite quantum dot material

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CN105331362A (en) * 2015-12-07 2016-02-17 南京理工大学 High-yield preparing method for inorganic halogen perovskite fluorescent quantum dots at room temperature
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
CN105838366A (en) * 2016-04-11 2016-08-10 武汉保丽量彩科技有限公司 A fluorescent caesium-lead-halogen group perovskite quantum dot material, a preparing method thereof and applications of the material
CN106830060A (en) * 2016-12-07 2017-06-13 青岛海信电器股份有限公司 A kind of CsPbX3Quantum dot, CsPbX3/SiO2Composite quantum dot and preparation method and backlight module
CN106833635A (en) * 2017-01-22 2017-06-13 山东工商学院 Large scale perovskite CsPbBr3The preparation method of six square piece circular pieces
CN107474833A (en) * 2017-07-26 2017-12-15 华东理工大学 The quick device and method for continuously synthesizing more pattern caesium lead halogen cluster perovskite quantum dots
CN107619485A (en) * 2017-09-08 2018-01-23 福建师范大学 Inorganic perovskite quantum dot syndiotactic polytyrene laminated film and preparation method thereof

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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
CN105441074B (en) * 2015-11-18 2018-03-09 重庆大学 One kind is based on to CsPbBr3The preparation method that perovskite quantum dot regulates and controls from blue light to green glow
CN105331362A (en) * 2015-12-07 2016-02-17 南京理工大学 High-yield preparing method for inorganic halogen perovskite fluorescent quantum dots at room temperature
CN105838366A (en) * 2016-04-11 2016-08-10 武汉保丽量彩科技有限公司 A fluorescent caesium-lead-halogen group perovskite quantum dot material, a preparing method thereof and applications of the material
CN106830060A (en) * 2016-12-07 2017-06-13 青岛海信电器股份有限公司 A kind of CsPbX3Quantum dot, CsPbX3/SiO2Composite quantum dot and preparation method and backlight module
CN106833635A (en) * 2017-01-22 2017-06-13 山东工商学院 Large scale perovskite CsPbBr3The preparation method of six square piece circular pieces
CN107474833A (en) * 2017-07-26 2017-12-15 华东理工大学 The quick device and method for continuously synthesizing more pattern caesium lead halogen cluster perovskite quantum dots
CN107619485A (en) * 2017-09-08 2018-01-23 福建师范大学 Inorganic perovskite quantum dot syndiotactic polytyrene laminated film and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111204797A (en) * 2020-01-17 2020-05-29 南京工业大学 Morphology-controllable all-inorganic CsPbBr3Preparation method of perovskite nanocrystal
CN112028117A (en) * 2020-09-17 2020-12-04 昆明理工大学 Wet chemical annealing method for preparing fully inorganic CsPbBr3Method and application of nanocrystalline
CN112028117B (en) * 2020-09-17 2022-01-25 昆明理工大学 Wet chemical annealing method for preparing fully inorganic CsPbBr3Method and application of nanocrystalline
CN113257932A (en) * 2021-05-12 2021-08-13 常熟理工学院 High-performance photoelectric detector and preparation method thereof
CN113308245A (en) * 2021-05-27 2021-08-27 南京邮电大学 Preparation method and application of blue-violet light-free perovskite nano material
CN113604220A (en) * 2021-08-17 2021-11-05 东北电力大学 Perovskite quantum dot material and preparation method and application thereof
CN114891505A (en) * 2022-05-26 2022-08-12 天津大学 Preparation method and application of blue-light dodecahedral perovskite quantum dot material

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Application publication date: 20180724