CN111710745B - Manganese-doped pure inorganic perovskite-Au nanocrystalline heterojunction and preparation method and application thereof - Google Patents
Manganese-doped pure inorganic perovskite-Au nanocrystalline heterojunction and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a manganese-doped pure inorganic perovskite-Au nanocrystalline heterojunction and a preparation method and application thereof, belonging to the technical field of nano materials. According to the manganese-doped pure inorganic perovskite-Au nanocrystalline heterojunction, spherical Au particles are directly grown on the nanocrystalline formed by the manganese-doped pure inorganic perovskite to form the heterojunction, so that the heterojunction has the characteristics of good dispersity, good crystallinity and excellent optical performance, has good optical stability, and has wide application prospects in the fields of solar cells, photocatalysis and the like. The preparation method of the manganese-doped pure inorganic perovskite-Au nanocrystalline heterojunction has the advantages of simplicity, controllability and the like, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a manganese-doped pure inorganic perovskite-Au nanocrystalline heterojunction and a preparation method and application thereof.
Background
In recent years, all-inorganic perovskite CsPbX 3 The (X = I, br, cl) nanocrystals, as a novel photovoltaic material, exhibit great potential in the photovoltaic field due to their high luminous efficiency, tunable band gap, low defect density, long carrier lifetime, and environmental stability, and the research heat of the nanocrystals is also continuously increasing. Since 2015, researchers have changed CsPbX 3 The surface ligand, reaction temperature or reaction time of the nanocrystal to prepare CsPbX 3 Nanowires, nanospheres, nanotubes, and nanoplatelets. And with respect to CsPbX 3 Nanocrystalline heterojunctions have been reported less. In 2008, the Banin laboratory invented an experimental method, in which gold (Au) nanoparticles were grown on both ends of a CdSe nanorod to form an Au-CdSe heterostructure, giving the CdSe nanorod new functional characteristics, such as: the Au-CdSe heterostructure exhibits natural contact points and can be used to fabricate nanodevices. Au is known to produce plasmonic field effects in semiconductors, affecting their photocatalytic and photovoltaic properties. Furthermore, exciton-plasmon interaction can also affect the deactivation of excited states as seen from the reduction in the luminous efficiency of semiconductor heterojunctions. Thus, csPbX was synthesized 3 Of an Au heterojunctionMany interesting photovoltaic properties were explored. The related studies are also in progress.
However, there is no report on the heterostructure of doped perovskite nanocrystals and Au. Further research is needed to investigate the method of forming heterostructures from doped perovskite nanocrystals and Au and the optical properties of the structures formed.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a manganese-doped pure inorganic perovskite-Au nanocrystal heterojunction; the second purpose of the invention is to provide a preparation method of a manganese-doped pure inorganic perovskite-Au nanocrystalline heterojunction; the invention also aims to provide application of the manganese-doped pure inorganic perovskite-Au nanocrystalline heterojunction in solar cells or photocatalysis.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a manganese-doped pure inorganic perovskite-Au nanocrystal heterojunction comprising nanocrystals formed in a manganese-doped pure inorganic perovskite material and Au particles grown on the nanocrystals.
Preferably, the pure inorganic perovskite material is CsPbCl 3 A material.
Preferably, the shape of the nanocrystal is square or quasi-square; the Au particles are spherical.
2. The preparation method of the nanocrystalline heterojunction comprises the following steps:
adding trioctylphosphine into a toluene solution of a nanocrystal formed in a manganese-doped pure inorganic perovskite material, and stirring for 30min to form a surface ligand containing trioctylphosphine substitution;
then HAuCl was added 4 ·3H 2 O, stirring for 10min at normal temperature to allow HAuCl 4 ·3H 2 And O is hydrolyzed to obtain the manganese-doped pure inorganic perovskite-Au nanocrystalline heterojunction.
Preferably, the volume-to-mass ratio of the trioctylphosphine to the nanocrystals contained in the solution is 2.
Preferably, the HAuCl is 4 ·3H 2 The mass ratio of O to the nanocrystals in the solution is 1.
Preferably, the nanocrystals formed in the manganese-doped pure inorganic perovskite material are prepared as follows:
(1) Dissolving lead halide and manganese halide in octadecene solution, adding Oleic Acid (OA) and oleylamine (OAm) as stabilizers, stirring for 20min under nitrogen, heating to 120 deg.C, maintaining for 30min, continuing to heat to 170 deg.C, maintaining for 10min, and heating to 200 deg.C, maintaining for 10min;
(2) And (3) injecting oleic acid and oleylamine until the solution is clear, then injecting an oleic acid-cesium precursor for reaction for 10s, cooling in an ice bath, and then purifying to obtain the nanocrystalline formed in the manganese-doped pure inorganic perovskite material.
Preferably, the mass-to-volume ratio of the lead halide, the manganese halide, the oleic acid and the oleylamine in the step (1) is 122.6; the molar ratio of cesium in the oleic acid-cesium precursor in step (2) to the manganese halide in step (1) is 6.
Preferably, the specific operations of the purification are as follows: adding n-hexane and ethyl acetate into the mixed solution cooled by the ice bath according to the volume ratio of 1.
3. Application of nanocrystalline heterojunction in solar cell or photocatalysis
The invention has the beneficial effects that:
1. the invention provides a manganese-doped pure inorganic perovskite-Au nanocrystalline heterojunction, wherein spherical Au particles are directly grown on the manganese-doped pure inorganic perovskite nanocrystalline to form the heterojunction, and the heterojunction has the characteristics of good dispersity, good crystallinity and excellent optical property, and simultaneously has better optical property and stability, thereby having wide application prospect in the fields of solar cells or photocatalysis and the like.
2. The invention also provides a preparation method of the manganese-doped pure inorganic perovskite-Au nanocrystalline heterojunction, which has the advantages of simple and controllable preparation method and the like and is suitable for industrial production.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 shows a manganese-doped pure inorganic perovskite nanocrystal (CsPbMnCl) 3 ) Transmission electron micrographs of (a);
FIG. 2 is CsPbMnCl 3 The high-resolution transmission electron microscope of (1);
FIG. 3 is a manganese-doped pure inorganic perovskite-Au nanocrystalline heterojunction (CsPbMnCl) 3 @ Au);
FIG. 4 is CsPbMnCl 3 @ Au high resolution transmission electron microscope;
FIG. 5 is CsPbMnCl 3 Nanocrystalline and CsPbMnCl 3 X-ray diffraction pattern of @ Au nanocrystalline heterojunction;
FIG. 6 is CsPbMnCl 3 Nanocrystals and CsPbMnCl 3 Picture of @ Au nanocrystalline heterojunction under ultraviolet lamp;
FIG. 7 is CsPbMnCl 3 Nanocrystalline and CsPbMnCl 3 Photoluminescence spectra of @ Au nanocrystalline heterojunctions.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that, in the following embodiments, features in the embodiments may be combined with each other without conflict.
Example 1
Preparation of manganese-doped pure inorganic perovskite (CsPbMnCl) 3 ) -Au nanocrystalline heterojunction (CsPbMnCl) 3 @ Au), the specific preparation method is as follows:
1. mixing 100mg of Cs 2 CO 3 Dissolving in 4mL of octadecene and 0.6mL of oleic acid solution, heating to 120 ℃ under the condition of nitrogen, and keeping for 1h to form a precursor of oleic acid-cesium for later use;
2. dissolving 122mg of lead chloride and 180mg of manganese chloride in 10mL of octadecene solution, adding 1.6mL of oleic acid and 1.6mL of oleylamine as stabilizers, stirring for 20min under nitrogen, continuously heating to 120 ℃, keeping for 30min, heating to 170 ℃, keeping for 10min, heating to 200 ℃, keeping for 10min, then injecting 1.6mL of oleic acid and 1.6mL of oleylamine to clarify the solution, then respectively injecting 0.8mL of the precursor of the oleic acid-cesium prepared in the step (1), reacting for 5s, cooling in an ice bath, finally forming a mixed solvent by using n-hexane and ethyl acetate with the volume ratio of 1 3 )；
3. The prepared manganese-doped pure inorganic perovskite calcium nanocrystal (CsPbMnCl) is added 3 ) Dissolving in toluene solution to form CsPbMnCl with the concentration of 3mg/mL 3 Nanocrystalline toluene solution to 5mL CsPbMnCl 3 Adding 30 mu L of TOP (trioctylphosphine) into the nanocrystalline toluene solution, stirring for 30min to enable the TOP (trioctylphosphine) to partially replace CsPbMnCl 3 The CsPbMnCl is blocked while the ligand (oleic acid or oleylamine) on the surface of the nanocrystal is coordinated 3 Contacting the nanocrystal with moisture;
4. further addition of 5mg of HAuCl 4 ·3H 2 O, stirring for 10min at normal temperature to allow HAuCl 4 ·3H 2 Directly grown in CsPbMnCl after O hydrolysis 3 On the nano crystal, the manganese doped pure inorganic perovskite (CsPbCl) can be obtained 3 ) -Au nanocrystalline heterojunction (CsPbMnCl) 3 @Au)。
Prepared byManganese-doped pure inorganic perovskite nanocrystals (CsPbMnCl) 3 ) The results of the transmission electron microscope examination are shown in fig. 1 and 2, from which it can be seen that the manganese-doped pure inorganic perovskite nanocrystals (CsPbMnCl) prepared by the method of the present invention 3 ) Has a square structure. The final product manganese is doped with pure inorganic perovskite-Au nanocrystalline heterojunction (CsPbMnCl) 3 @ Au) was subjected to transmission electron microscopy, and the results are shown in fig. 3 and 4, from which it can be seen that CsPbMnCl prepared in the present invention 3 In the @ Au nano-gold, spherical Au particles are directly grown in the prepared CsPbMnCl 3 The surface of the material. CsPbMnCl 3 And CsPbMnCl 3 The X-ray diffraction results of @ Au are shown in FIG. 5, and it can be seen that CsPbMnCl 3 The X-ray diffraction pattern of @ Au shows a stronger diffraction peak at 2 theta =38.52 degrees, which corresponds to the (111) crystal face of Au, and other stronger diffraction peaks correspond to manganese-doped pure inorganic perovskite nanocrystals (CsPbMnCl) 3 ) It is proved that Au particles and manganese-doped pure inorganic perovskite nano-crystals (CsPbMnCl) can be really doped by the method 3 ) And combining to form a new nano-gold heterojunction structure. Further, csPbMnCl 3 The formation of @ Au did not affect CsPbMnCl 3 The luminescent color of the nanocrystals, as shown in fig. 6, both showed bright yellow under an ultraviolet lamp; and, csPbMnCl 3 The photoluminescence spectrum of the @ Au heterojunction has no obvious shift, which indicates that the growth of Au particles does not influence CsPbMnCl 3 The luminescence wavelength of the nanocrystals (as shown in fig. 7).
As can be seen from FIGS. 1 to 7, the present invention is obtained by mixing spherical gold particles with manganese-doped pure inorganic perovskite calcium nanocrystals (CsPbMnCl) 3 ) CsPbMnCl prepared by combination 3 The @ Au heterojunction has the characteristics of good dispersibility, good crystallinity and excellent optical property, and also has good optical property and stability, so that the @ Au heterojunction has a wide application prospect in the fields of solar cells, photocatalysis and the like.
Finally, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of a manganese-doped pure inorganic perovskite-Au nanocrystalline heterojunction is characterized by comprising the following steps:
adding trioctylphosphine into a toluene solution of a nanocrystal formed in a manganese-doped pure inorganic perovskite material, and stirring for 30min to form a surface ligand containing trioctylphosphine substitution;
then HAuCl was added 4 ·3H 2 O, stirring for 10min at normal temperature to allow HAuCl 4 ·3H 2 Hydrolyzing O to obtain the manganese-doped pure inorganic perovskite-Au nanocrystalline heterojunction;
the nanocrystalline heterojunction comprises nanocrystals formed in a manganese-doped pure inorganic perovskite material and Au particles grown on the nanocrystals.
2. The method of claim 1, wherein the pure inorganic perovskite material is CsPbCl 3 A nanocrystalline material.
3. The production method according to claim 1, wherein the shape of the nanocrystal is square or quasi-square; the Au particles are spherical.
4. The preparation method according to claim 1, wherein the volume-to-mass ratio of the trioctylphosphine to the nanocrystals contained in the solution is 2.
5. The method of claim 1, wherein the HAuCl is present in the sample 4 ·3H 2 The mass ratio of O to the nanocrystals in the solution is 1.
6. The method according to claim 1, wherein the nanocrystals formed in the manganese-doped pure inorganic perovskite material are prepared as follows:
(1) Dissolving lead halide and manganese halide in octadecylene solution, adding oleic acid and oleylamine as stabilizer, stirring under nitrogen for 20min, heating to 120 deg.C, maintaining for 30min, continuing to heat to 170 deg.C, maintaining for 10min, and heating to 200 deg.C, maintaining for 10min;
(2) And (3) injecting oleic acid and oleylamine until the solution is clear, then injecting an oleic acid-cesium precursor for reaction for 10s, cooling in an ice bath, and then purifying to obtain the nanocrystalline formed in the manganese-doped pure inorganic perovskite material.
7. The preparation method according to claim 6, wherein the molar volume ratio of the lead halide, the manganese halide, the oleic acid and the oleylamine in step (1) is 122.6; the molar ratio of cesium in the oleic acid-cesium precursor in step (2) to the manganese halide in step (1) is 6.
8. The preparation method according to claim 6, characterized in that the specific operations of purification are: adding n-hexane and ethyl acetate into the mixed solution cooled by the ice bath according to the volume ratio of 1.
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| CN110218561A (en) * | 2019-06-14 | 2019-09-10 | 吉林师范大学 | A kind of raising additive Mn CsPbCl3The method of nanocrystalline additive Mn concentration and luminous efficiency |
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| CN104518091A (en) * | 2014-12-23 | 2015-04-15 | 华东师范大学 | Preparation method of organic-inorganic perovskite solar battery |
| CN105609588B (en) * | 2016-01-22 | 2018-01-05 | 南京理工大学 | Au nanoparticle enhanced high-performance inorganic perovskite CsPbX3 nanocrystalline visible light detector |
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| CN110218561A (en) * | 2019-06-14 | 2019-09-10 | 吉林师范大学 | A kind of raising additive Mn CsPbCl3The method of nanocrystalline additive Mn concentration and luminous efficiency |
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