CN114590836A - Lead-free halide perovskite nanocrystal, liquid-phase synthesis method thereof and application of perovskite nanocrystal in photoelectric detector - Google Patents
Lead-free halide perovskite nanocrystal, liquid-phase synthesis method thereof and application of perovskite nanocrystal in photoelectric detector Download PDFInfo
- Publication number
- CN114590836A CN114590836A CN202210227370.3A CN202210227370A CN114590836A CN 114590836 A CN114590836 A CN 114590836A CN 202210227370 A CN202210227370 A CN 202210227370A CN 114590836 A CN114590836 A CN 114590836A
- Authority
- CN
- China
- Prior art keywords
- lead
- nano
- halide perovskite
- source
- free halide
- 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.)
- Granted
Links
- 150000004820 halides Chemical class 0.000 title claims abstract description 46
- 239000002159 nanocrystal Substances 0.000 title abstract description 28
- 239000007791 liquid phase Substances 0.000 title abstract description 11
- 238000001308 synthesis method Methods 0.000 title description 6
- 239000000463 material Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000002135 nanosheet Substances 0.000 claims abstract description 45
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 238000010992 reflux Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims description 31
- 229910052792 caesium Inorganic materials 0.000 claims description 23
- 229910052740 iodine Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 18
- 229910052797 bismuth Inorganic materials 0.000 claims description 17
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 16
- 239000011630 iodine Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 13
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 8
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 28
- 239000012071 phase Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 238000001514 detection method Methods 0.000 abstract description 7
- 238000003917 TEM image Methods 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 16
- 238000010586 diagram Methods 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
- C01G29/006—Compounds containing, besides bismuth, 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- 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
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a lead-free halide perovskite material which is Cs3Bi2I9Nanosheets; the Cs3Bi2I9The nano sheets are hexagonal phase nano sheets; the Cs3Bi2I9The diameter of the nano sheet is 14-42 nm. Cs provided by the invention3Bi2I9The nanocrystals have uniform hexagonal plateletsGood appearance, monodispersity, good stability in air and the like. The invention also provides an oil phase reflux method for preparing the lead-free halide perovskite Cs with simple process, mild condition and good repeatability3Bi2I9Nanocrystalline and mixing the prepared Cs3Bi2I9The nano material is constructed into a photoelectric detector with a vertical structure, and the photoelectric detector shows excellent detection performance. The method has the advantages of mild experimental conditions, improved preparation process, greatly shortened preparation time, uniform appearance and good photoelectric property of Cs by a simple liquid phase reflux method3Bi2I9And (3) nano materials.
Description
Technical Field
The invention belongs to the technical field of lead-free halide perovskite materials, relates to a preparation method of a lead-free halide perovskite material and application of the lead-free halide perovskite material in a photoelectric detector, and particularly relates to a lead-free halide perovskite nanocrystal, a liquid phase synthesis method of the lead-free halide perovskite nanocrystal, application of the lead-free halide perovskite nanocrystal in the photoelectric detector and a vertical-structure photoelectric detector.
Background
Metal halide perovskite nanocrystals have the advantages of high absorption coefficient, quasi-quantum well structure, high optical gain, etc., and have attracted much attention in recent years for application in photoelectric detection. However, in the past, most researchers have been working on the synthesis of lead halide perovskites, but these compounds have disadvantages such as poor stability and environmental pollution caused by lead element.
Therefore, the method for preparing the lead-free bismuth-based halide perovskite by adopting the simple process and the mild condition has become one of the focuses of great attention of many prospective researchers in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a lead-free halide perovskite material, a preparation method and an application thereof, and a vertical structure photodetector, especially a Cs photodetector3Bi2I9Nanocrystal and liquid phase synthesis method thereof, and Cs provided by the invention3Bi2I9The nano-crystalline form is uniform in appearance, the synthesis process is simple, and the nano-crystalline form has good stability and monodispersity, and the nano-crystalline form has good prospects in the field of photoelectric detection.
The invention provides a lead-free halide perovskite material which is Cs3Bi2I9Nanosheets;
the Cs3Bi2I9The nano sheets are hexagonal nano sheets;
the Cs3Bi2I9The diameter of the nano sheet is 14-42 nm.
Preferably, said Cs3Bi2I9The nano-sheets have uniform sheet diameter distribution;
the Cs3Bi2I9The relative frequency of the nano-sheets in the range of the sheet diameter interval is 0.018-0.159;
the Cs3Bi2I9In the nano-sheet, Cs, Bi and I elements are uniformly distributed in the whole hexagonal Cs3Bi2I9In a nano-chip.
Preferably, said Cs3Bi2I9Cs prepared by adopting oil phase reflux method by using nanosheet3Bi2I9Nanosheets;
the Cs3Bi2I9The nano sheet is a photosensitive material for preparing a photoelectric detector;
the photodetector comprises a vertical structure photodetector.
The invention provides a preparation method of a lead-free halide perovskite material, which comprises the following steps:
1) mixing a cesium source, a bismuth source and a surfactant to obtain a mixture;
2) heating the mixture obtained in the step under the conditions of protective atmosphere and heating reflux, injecting an iodine source for reaction, and obtaining the lead halide perovskite material Cs3Bi2I9Nanosheets.
Preferably, the cesium source comprises cesium acetate;
the bismuth source comprises bismuth acetate;
the surfactant comprises octadecene, oleylamine and oleic acid;
the molar ratio of the cesium source to the bismuth source is (1-3): (1-2).
Preferably, the ratio of cesium source to surfactant is 1 mg: (0.1-2) mL;
the mixing time is 10-20 min;
the heating temperature is 100-150 ℃;
the heating time is 20-60 min.
Preferably, the iodine source comprises trimethyliodosilane;
the molar ratio of the cesium source to the iodine source is 1: (3-5);
the temperature for injecting the iodine source to carry out the reaction is 100-180 ℃;
the reaction time is 5 s-5 min;
and cooling by a cold water bath after the reaction.
The invention provides an application of the lead-free halide perovskite material or the lead-free halide perovskite material prepared by the preparation method in any one of the above technical schemes in the aspect of a photoelectric detector.
The present invention also provides a vertical structure photodetector, comprising:
a P-type silicon wafer layer;
a photosensitive material layer compounded on the P-type silicon wafer layer;
a graphene layer composited on the photosensitive material layer;
the photosensitive material comprises the lead-free halide perovskite material or the lead-free halide perovskite material prepared by the preparation method of any one of the above technical schemes.
Preferably, the thickness of the P-type silicon wafer layer is 510-540 mu m;
the thickness of the photosensitive material layer is 1-3 mu m;
the thickness of the graphene layer is 0.345 nm;
the graphene layer is a single-layer graphene layer.
The invention provides a lead-free halide perovskite material which is Cs3Bi2I9Nanosheets; the Cs3Bi2I9The nano sheets are hexagonal nano sheets; the Cs3Bi2I9The diameter of the nano sheet is 14-42 nm. Compared with the prior art, the Cs provided by the invention3Bi2I9The nano-crystal has the advantages of uniform hexagonal sheet morphology, good monodispersity, good stability in air and the like. The invention also provides an oil phase reflux method for preparing the lead-free halide with simple process, mild condition and good repeatabilityPerovskite Cs3Bi2I9And (4) nanocrystals. Organic cesium source and bismuth source are used as reaction precursors, and an iodine source is thermally injected at a proper reaction temperature by an oil phase reflux method to obtain Cs with uniform appearance3Bi2I9Method for synthesizing nano material and prepared Cs3Bi2I9The nano material is constructed into a photoelectric detector with a vertical structure, and the photoelectric detector shows excellent detection performance. The method has the advantages of mild experimental conditions, improved preparation process, greatly shortened preparation time, uniform appearance and good photoelectric property of Cs by a simple liquid phase reflux method3Bi2I9And (3) nano materials.
Cs prepared by the present invention3Bi2I9The nanocrystalline synthesis process is simple, has good stability and monodispersity, and has good prospect in the field of photoelectric detection. High performance photodetectors have attracted considerable interest to researchers for their widespread use in the fields of environmental monitoring, biomedicine, imaging, telecommunications, security inspection, and industrial process control. The invention provides the method based on the Cs3Bi2I9The device of the photoelectric detector with the vertical structure of the nano crystal shows wide spectral response and excellent photoelectric performance, and has good application prospect.
Experimental results show that the method can be used for synthesizing Cs with the sheet diameter of about 28.05nm3Bi2I9Hexagonal tablets; the device is constructed into a vertical-structure photoelectric detector, has better light response from ultraviolet to near infrared (254nm-1064nm), and has optimal responsivity of 23.6AW under the irradiation of 650nm wavelength-1The detectivity is up to 1.75X 1013Jones。
Drawings
FIG. 1 shows Cs synthesized in the example of the present invention3Bi2I9An X-ray diffraction (XRD) pattern and raman spectrum of the nanomaterial;
FIG. 2 shows Cs synthesized in the example of the present invention3Bi2I9X-ray photoelectron spectroscopy (XPS) full spectrum of nano material and high resolution of element Cs 3dAn energy spectrum, an element Bi4f high-resolution energy spectrum and an element I3 d high-resolution energy spectrum;
FIG. 3 shows Cs synthesized in the example of the present invention3Bi2I9A Transmission Electron Micrograph (TEM), a particle size distribution diagram, a high-resolution transmission electron micrograph (HRTEM) picture, an electron selective area diffraction diagram and an EDS mapping element distribution picture of the nano material;
FIG. 4 shows Cs synthesized in the example of the present invention3Bi2I9Absorption spectrum of the nano material;
FIG. 5 is a schematic diagram of a photodetector constructed in accordance with an embodiment of the present invention;
FIG. 6 shows that the optical power of the photodetector prepared according to the embodiment of the present invention is 140 μ W/cm at different wavelengths2The I-T diagram of (1);
FIG. 7 is an I-T diagram and a detectivity and responsivity diagram of a photodetector prepared according to an embodiment of the present invention at a wavelength of 650nm and different optical powers;
FIG. 8 shows Cs synthesized in example 2 of the present invention3Bi2I9An X-ray diffraction (XRD) pattern and a TEM pattern of the nanomaterial;
FIG. 9 shows Cs synthesized in example 3 of the present invention3Bi2I9An X-ray diffraction (XRD) pattern and a TEM pattern of the nanomaterial;
FIG. 10 shows Cs synthesized in comparative example 1 of the present invention3Bi2I9X-ray diffraction (XRD) pattern and TEM pattern of the nanomaterial.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
The starting materials used in the present invention are not particularly limited in their purity, and the present invention is preferably analytically pure or of a purity conventional in the art of metal halide material preparation.
All the materials of the invention, the marks and the acronyms thereof belong to the conventional marks and the acronyms in the field, each mark and the acronyms are clear and definite in the field of the related application, and the technical personnel in the field can purchase the materials from the market or prepare the materials by the conventional method according to the marks, the acronyms and the corresponding application.
All the processes of the invention, the abbreviations thereof belong to the common abbreviations in the art, each abbreviation is clear and definite in the field of its associated use, and the ordinary process steps thereof can be understood by those skilled in the art from the abbreviations.
The invention provides a lead-free halide perovskite material which is Cs3Bi2I9Nanosheets;
the Cs3Bi2I9The nano sheets are hexagonal nano sheets;
the Cs3Bi2I9The diameter of the nano sheet is 14-42 nm.
In the present invention, the Cs3Bi2I9The diameter of the nanosheet is 14-42 nm, preferably 19-37 nm, and preferably 24-32 nm.
In the present invention, the Cs3Bi2I9The nanoplatelets preferably have a uniform distribution of platelet size. Specifically, the Cs3Bi2I9The relative frequency of the nano-sheets in the range of the sheet diameter interval is preferably 0.018-0.159, more preferably 0.048-0.129, and more preferably 0.078-0.099.
In the present invention, the Cs3Bi2I9The thickness of the nano sheet is preferably 10-15 nm, more preferably 11-14 nm, and more preferably 12-13 nm.
In the present invention, the Cs3Bi2I9In the nanosheets, the Cs, Bi and I elements are preferably uniformly distributed throughout the hexagonal Cs3Bi2I9In a nano-chip.
In the present invention, the Cs3Bi2I9The nanosheets are preferablyCs prepared by oil phase reflux method3Bi2I9A nanosheet.
In the present invention, the Cs3Bi2I9The nanoplatelets are preferably photosensitive materials used in the fabrication of photodetectors.
In the present invention, the photodetector preferably includes a photodetector of a vertical structure.
The invention provides a preparation method of a lead-free halide perovskite material, which comprises the following steps:
1) mixing a cesium source, a bismuth source and a surfactant to obtain a mixture;
2) heating the mixture obtained in the step under the conditions of protective atmosphere and heating reflux, injecting an iodine source for reaction, and obtaining the lead halide perovskite material Cs3Bi2I9Nanosheets.
Firstly, cesium source, bismuth source and surfactant are mixed to obtain a mixture.
In the present invention, the cesium source preferably comprises cesium acetate.
In the present invention, the bismuth source preferably includes bismuth acetate.
In the present invention, the surfactant preferably includes octadecene, oleylamine and oleic acid.
In the present invention, the molar ratio of the cesium source to the bismuth source is preferably (1 to 3): (1-2), more preferably (1-3): (1.2-1.8), more preferably (1-3): (1.4-1.6), or (1.2-2.7): (1-2), or (1.5-2.5): (1 to 2)
In the present invention, the ratio of the cesium source to the surfactant is preferably 1 mg: (0.1-2) mL, more preferably 1 mg: (0.3-1.8) mL, more preferably 1 mg: (0.5-1.5) mL, more preferably 1 mg: (0.8-1.2) mL.
In the invention, the mixing time is preferably 10-20 min, more preferably 12-18 min, and more preferably 14-16 min.
The invention heats the mixture obtained in the step under the conditions of protective atmosphere and heating reflux,then injecting an iodine source for reaction to obtain the lead halide perovskite material Cs3Bi2I9Nanosheets.
In the invention, the heating temperature is preferably 100-150 ℃, more preferably 110-140 ℃, and more preferably 120-130 ℃. Wherein the heating step is capable of removing water and other low boiling impurities.
In the invention, the heating time is preferably 20-60 min, more preferably 25-55 min, more preferably 30-50 min, and more preferably 35-45 min.
In the present invention, the iodine source preferably comprises trimethyliodosilane.
In the present invention, the molar ratio of the cesium source to the iodine source is preferably 1: (3-5), more preferably 1: (3.4 to 4.6), more preferably 1: (3.8-4.2).
In the invention, the temperature for injecting the iodine source for reaction is preferably 100-180 ℃, more preferably 115-165 ℃, and more preferably 130-150 ℃.
In the present invention, the reaction time is preferably 5s to 5min, more preferably 5s to 1min, more preferably 10 to 40s, and more preferably 15 to 30 s.
In the present invention, the reaction preferably includes a step of cooling in a cold water bath.
The invention is a complete and refined integral preparation method, and can better ensure Cs3Bi2I9Specific structure and shape of nano sheet to improve Cs3Bi2I9The size uniformity of the nanosheets, and the preparation method of the lead-free halide perovskite material specifically comprises the following steps:
cs is synthesized by adopting a simple one-step heat injection method3Bi2I9Nanosheets.
Cesium acetate and bismuth acetate were weighed into a three-necked flask at room temperature, then octadecene, oleylamine and oleic acid solutions (surfactant or synthetic ligand) were injected and sonicated until the mixture was completely mixed.
The mixture was first heated under a stream of argon and magnetic stirring to remove water and other low boiling impurities. And simultaneously injecting the iodotrimethylsilane into a three-mouth bottle at the temperature, quickly reacting for several seconds, and cooling the three-mouth bottle to room temperature in a cold water bath. Transferring the obtained orange-red product into a centrifuge tube, adding n-hexane, centrifuging at 8000RPM, and separating the product.
The invention provides an application of the lead-free halide perovskite material or the lead-free halide perovskite material prepared by the preparation method in any one of the above technical schemes in the aspect of a photoelectric detector.
The invention provides a vertical structure photodetector, comprising:
a P-type silicon wafer layer;
a photosensitive material layer compounded on the P-type silicon wafer layer;
a graphene layer composited on the photosensitive material layer;
the photosensitive material comprises the lead-free halide perovskite material according to any one of the above technical schemes or the lead-free halide perovskite material prepared by the preparation method according to any one of the above technical schemes.
In the invention, the thickness of the P-type silicon wafer layer is preferably 510-540 μm, more preferably 515-535 μm, and more preferably 520-530 μm.
In the invention, the thickness of the photosensitive material layer is preferably 1-3 μm, more preferably 1.4-2.6 μm, and more preferably 1.8-2.2 μm.
In the present invention, the thickness of the graphene layer is preferably 0.345 nm.
In the present invention, the graphene layer is preferably a single graphene layer.
The invention is a complete and detailed integral preparation method, which better ensures the performance of a vertical structure photoelectric detector, and the preparation method of the vertical structure photoelectric detector can specifically comprise the following steps:
the Cs prepared by a liquid phase reflux method3Bi2I9The nano material is uniformly coated on a p-type silicon wafer in a spinning way through a spin coater to form a film, then single-layer graphene with relatively small size is transferred to the surface of the film, and a p-n junction is formed between the silicon wafer and a sample to obtain more than oneGraphite and silicon chip are vertical structure detectors of the electrode.
The invention provides the lead-free halide perovskite nanocrystal, the liquid phase synthesis method thereof, the application of the lead-free halide perovskite nanocrystal in the photoelectric detector and the vertical-structure photoelectric detector. Cs provided by the invention3Bi2I9The nano-crystal has the advantages of uniform hexagonal sheet morphology, good monodispersity, good stability in air and the like. The invention also provides an oil phase reflux method for preparing the lead-free halide perovskite Cs with simple process, mild condition and good repeatability3Bi2I9And (4) nanocrystals. Organic cesium source and bismuth source are used as reaction precursors, and an iodine source is thermally injected at a proper reaction temperature by an oil phase reflux method to obtain Cs with uniform appearance3Bi2I9Method for synthesizing nano material and prepared Cs3Bi2I9The nano material is constructed into a photoelectric detector with a vertical structure, and the photoelectric detector shows excellent detection performance. The method has the advantages of mild experimental conditions, improved preparation process, greatly shortened preparation time, uniform appearance and good photoelectric property of Cs by a simple liquid phase reflux method3Bi2I9And (3) nano materials.
Cs prepared by the present invention3Bi2I9The nanocrystalline synthesis process is simple, has good stability and monodispersity, and has good prospect in the field of photoelectric detection. High performance photodetectors have attracted considerable interest to researchers for their widespread use in the fields of environmental monitoring, biomedicine, imaging, telecommunications, security inspection, and industrial process control. The invention provides the method based on the Cs3Bi2I9The device of the photoelectric detector with the vertical structure of the nano crystal shows wide spectral response and excellent photoelectric performance, and has good application prospect.
Experimental results show that the method can be used for synthesizing Cs with the sheet diameter of about 28.05nm3Bi2I9Hexagonal tablets; the device is constructed into a vertical-structure photoelectric detector, and the device has better light response from ultraviolet to near infrared (254nm-1064nm)It should be noted that, under irradiation of 650nm wavelength, the optimal responsivity is 23.6A W-1The detectivity is up to 1.75X 1013Jones。
For further illustration of the present invention, the following will describe in detail a lead-free halide perovskite material and a method for preparing the same, application thereof, and a vertical structure photodetector provided by the present invention with reference to examples, but it should be understood that these examples are carried out on the premise of the technical solution of the present invention, and that the detailed embodiments and specific procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
The preparation method of the perovskite nano material comprises the following steps:
cs is synthesized by adopting a simple one-step heat injection method3Bi2I9And (4) nanocrystals. In a typical procedure, 28mg cesium acetate and 38mg bismuth acetate are weighed into a three-necked flask at room temperature, then 6ml of a solution of octadecene, oleylamine and oleic acid (surfactant or synthetic ligand) in defined proportions are injected and sonication continued for 10 minutes until the mixture is completely mixed. The mixture was first heated to 100 ℃ for 30 minutes under a stream of argon and magnetic stirring to remove water and other low boiling impurities. At the same time, 70. mu.L of iodotrimethylsilane was poured into a three-necked flask at this temperature, reacted rapidly for several seconds, and then cooled to room temperature in a cold water bath. Transferring the obtained orange-red product into a centrifuge tube, adding n-hexane, centrifuging at 8000RPM for 5min, and separating the product.
For Cs prepared in example 1 of the present invention3Bi2I9And (5) carrying out characterization on the nanocrystals.
Referring to FIG. 1, FIG. 1 shows Cs synthesized in the examples of the present invention3Bi2I9An X-ray diffraction (XRD) pattern and a raman spectrum of the nanomaterial. Wherein, a is an XRD pattern, and b is a Raman spectrum.
All peaks detected in the XRD pattern are very consistent with hexagonal phase Cs3Bi2I9The space group was P63/mmc (JCPDS No. 73-0707), and high-quality Cs was confirmed3Bi2I9Successful synthesis of nanocrystals. In addition, 146.67cm in Raman image-1The strongest peak at (A) represents the symmetric stretching frequency (A1') of the terminal Bi-I bond, and the asymmetric vibration is 119.78cm-1E' of (E); observed 104.37cm-1The peak at (A) is then due to the weakly symmetrical stretching mode of the bridged Bi-I bond1 1)。
Referring to FIG. 2, FIG. 2 shows Cs synthesized in the example of the present invention3Bi2I9An X-ray photoelectron spectroscopy (XPS) full spectrum, an element Cs 3d high resolution energy spectrum, an element Bi4f high resolution energy spectrum and an element I3 d high resolution energy spectrum of the nano material. Wherein, (a) is an X-ray photoelectron spectroscopy (XPS) full spectrum, (b) is an element Cs 3d high resolution energy spectrum; (c) is a Bi4f high-resolution energy spectrogram; (d) is an element I3 d high-resolution energy spectrum.
To further analyze the elemental composition and state of the prepared samples, the XPS spectra in fig. 2 were analyzed. As can be seen in the XPS survey spectrum of fig. 2a, only the signals of Cs, Bi, I, C and O elements were detected in the nanocrystals prepared in the examples; observing elemental high resolution XPS plots, in the Cs 3d spectrum, both 724.4 and 738.2eV were contributed by 3d5/2 and 3d3/2, respectively; the peak at the position of 156.88eV is from Bi4f 7/2, the peak at 162.16eV is from 4f5/2, and the standard spectrum of Bi (III) is met; furthermore, the observed values of 618.9 and 630.3eV are caused by 3d5/2 and 3d3/2 in the I3 d spectrum. In general, highly pure Cs can be prepared by this example3Bi2I9A nanocrystal.
Referring to FIG. 3, FIG. 3 shows Cs synthesized in the examples of the present invention3Bi2I9Transmission Electron Micrograph (TEM), particle size distribution, High Resolution Transmission Electron Micrograph (HRTEM), selective electron diffraction pattern, and EDS mapping elemental distribution. Wherein (a) is a Transmission Electron Micrograph (TEM); (b) is a particle size distribution diagram; (c-d) is a High Resolution Transmission Electron Microscope (HRTEM) photograph; (e) is an electron selective diffraction pattern; (f-i) is an EDS mapping element distribution photograph.
FIG. 3a synthetic Cs3Bi2I9TEM image of nanostructures, watchThe uniform hexagonal shape and good dispersibility of the synthesized nanocrystals are clear. The size distribution plot further illustrates that the monodisperse hexagonal nanostructures have an average particle size of only 28.05nm (fig. 3 b). In addition, high resolution tem (hrtem) images showed that the observed interplanar spacing of 0.42 nm corresponded to the (110) crystallographic plane of the nanostructure, the presence of which was further confirmed in the electron extraction diffractogram. Then, typical single Cs were studied3Bi2I9The elemental map of the nano hexagonal plate shows that Cs, Bi and I are constituent elements and are uniformly distributed throughout hexagonal Cs3Bi2I9In a nano-chip.
Referring to FIG. 4, FIG. 4 shows Cs synthesized in the examples of the present invention3Bi2I9Absorption spectrum of the nano material.
The ultraviolet-visible-near infrared absorption spectrum of the product prepared in this experimental example is shown in fig. 4, and as can be seen from the results of the inset fitting, the band gap of the product can be estimated to be 2.0 eV.
The manufacturing method of the photoelectric detector comprises the following steps:
the Cs prepared by a liquid phase reflux method3Bi2I9The nano material is uniformly coated on a 1cm multiplied by 1cm square p-type silicon wafer in a spinning mode through a spin coater to form a film, then single-layer graphene with relatively small size is transferred to the surface of the film, a p-n junction is formed between the silicon wafer and a sample, a vertical structure detector with graphite and the silicon wafer as electrodes is obtained, and then a semiconductor testing system is used for testing photoelectric performance.
Referring to fig. 5, fig. 5 is a schematic structural diagram of a photodetector constructed in accordance with an embodiment of the present invention.
Referring to FIG. 6, FIG. 6 shows the optical power of 140 μ W/cm at different wavelengths of a photodetector prepared according to an embodiment of the present invention2I-T diagram of (1).
From the device of FIG. 6 at a light intensity of 140. mu.W/cm2I-T diagrams of different wavelengths show that the device shows excellent wide-spectrum response (254nm-1064nm) and has the strongest optical response signal when the incident light wave is 650 nm.
Based on the above, the invention fixes the incident light wave at 650nm, and selects I-T curves obtained by different optical powers.
Referring to fig. 7, fig. 7 is an I-T diagram and a detectivity and responsivity diagram of different optical powers at a wavelength of 650nm for a photodetector prepared according to an embodiment of the present invention. Wherein (a) is an I-T diagram; (b) is a diagram of detectivity and responsivity.
As shown in fig. 7, since the concentration of carriers is positively correlated with the light intensity, the photocurrent increases with the increase in incident light power; however, as the power is further increased, the increase in photocurrent decreases due to increased photon-generated carrier recombination in the photoactive layer of the device. In addition, the optimal responsivity of the detector is 23.6A W-1The detectivity is up to 1.75X 1013Jones. These results show that the photodetector prepared by the invention has wide spectral response, excellent properties and great potential.
Example 2
Cs is synthesized by adopting a simple one-step heat injection method3Bi2I9And (3) nanoparticles. In a typical procedure, 30mg cesium acetate and 40mg bismuth acetate were weighed into a three-necked flask at room temperature, then 6ml of a solution of octadecene, oleylamine and oleic acid in the defined ratio was injected and sonication continued for 10 minutes until the mixture was completely mixed. The mixture was first heated to 100 ℃ for 30 minutes under a stream of argon and magnetic stirring to remove water and other low boiling impurities. At the same time, 70. mu.L of iodotrimethylsilane was poured into a three-necked flask at 180 ℃ and reacted rapidly for several seconds, after which the reaction mixture was cooled to room temperature with cold water. Transferring the obtained orange-red product into a centrifuge tube, adding n-hexane, centrifuging at 8000RPM for 5min, and separating the product. As can be seen from comparison of example 1, pure Cs can still be prepared at this temperature3Bi2I9The nanocrystalline and the relatively high iodine source heat injection temperature are beneficial to improving the crystallinity of the nano material.
For Cs prepared in example 2 of the present invention3Bi2I9And (5) carrying out characterization on the nanocrystals.
Referring to FIG. 8, FIG. 8 shows Cs synthesized in example 2 of the present invention3Bi2I9X-ray diffraction (XRD) and TEM images of the nanomaterials. Wherein, a is an XRD image, and b is a TEM image.
Example 3
Cs is synthesized by adopting a simple one-step heat injection method3Bi2I9And (3) nanoparticles. In a typical procedure, 30mg cesium acetate and 40mg bismuth acetate were weighed into a three-necked flask at room temperature, then 6ml of a solution of octadecene, oleylamine and oleic acid in the proportions identified were injected and sonication continued for 10 minutes until the mixture was completely mixed. The mixture was first heated to 150 ℃ for 30 minutes under a stream of argon and magnetic stirring to remove water and other low boiling impurities. At the same time, 70. mu.L of iodotrimethylsilane was poured into a three-necked flask at 100 ℃ and reacted rapidly for several seconds, after which the reaction mixture was cooled to room temperature in cold water. Transferring the obtained orange-red product into a centrifuge tube, adding n-hexane, centrifuging at 8000RPM for 5min, and separating the product. As can be seen from comparison with example 1, pure Cs can still be prepared at this temperature for removal of impurities3Bi2I9And the temperature is higher than 100 ℃, so that the purity and the appearance of the product are not greatly influenced.
For Cs prepared in example 3 of the present invention3Bi2I9And (5) carrying out characterization on the nanocrystals.
Referring to FIG. 9, FIG. 9 shows Cs synthesized in example 3 of the present invention3Bi2I9X-ray diffraction (XRD) and TEM images of the nanomaterials. Wherein, a is an XRD image, and b is a TEM image.
Comparative example 1
In a typical procedure, 30mg cesium acetate and 40mg bismuth acetate were weighed into a three-necked flask at room temperature, then 6ml of a solution of octadecene, oleylamine and oleic acid in the proportions identified were injected and sonication continued for 10 minutes until the mixture was completely mixed. The mixture was first heated to 150 ℃ for 30 minutes under a stream of argon and magnetic stirring to remove water and other low boiling impurities. At the same time, 70. mu.L of iodotrimethylsilane was poured into a three-necked flask at 100 ℃ and allowed to react for 10min before cooling to room temperature. Transferring the obtained orange-red product into a centrifuge tube, adding n-hexane, centrifuging at 8000RPM for 5min, and separating the product. As can be seen from the comparison of the examples, pure Cs can be prepared by prolonging the reaction time to 100min3Bi2I9Nanocrystalline but will be on the productThe uniformity and dispersion of the morphology of (a) has an adverse effect.
For Cs prepared in comparative example 1 of the present invention3Bi2I9And (5) carrying out characterization on the nanocrystals.
Referring to FIG. 10, FIG. 10 shows Cs synthesized in comparative example 1 according to the present invention3Bi2I9X-ray diffraction (XRD) pattern and TEM pattern of the nanomaterial. Wherein, a is an XRD image, and b is a TEM image.
The above detailed description of the lead halide-free perovskite nanocrystals and the liquid phase synthesis method thereof, the application in photodetectors, and the vertical structure photodetectors provided by the present invention, and the specific examples used herein to illustrate the principles and embodiments of the present invention, are provided only to help understand the method of the present invention and its core ideas, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any device or system, and implementing any combination of methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A lead-free halide perovskite material, wherein the lead-free halide perovskite material is Cs3Bi2I9Nanosheets;
the Cs3Bi2I9The nano sheets are hexagonal nano sheets;
the Cs3Bi2I9The diameter of the nano sheet is 14-42 nm.
2. The lead-free halide perovskite material of claim 1, wherein Cs3Bi2I9The nano-sheets have uniform sheet diameter distribution;
the Cs3Bi2I9The relative frequency of the nano-sheets in the range of the sheet diameter interval is 0.018-0.159;
the Cs3Bi2I9In the nano-sheet, Cs, Bi and I elements are uniformly distributed in the whole hexagonal Cs3Bi2I9In a nano-chip.
3. The lead-free halide perovskite material of claim 1, wherein Cs is3Bi2I9Cs prepared by adopting oil phase reflux method by using nanosheet3Bi2I9Nanosheets;
the Cs3Bi2I9The nano sheet is a photosensitive material for preparing the photoelectric detector;
the photodetector comprises a vertical structure photodetector.
4. A preparation method of a lead-free halide perovskite material is characterized by comprising the following steps:
1) mixing a cesium source, a bismuth source and a surfactant to obtain a mixture;
2) heating the mixture obtained in the step under the conditions of protective atmosphere and heating reflux, injecting an iodine source for reaction, and obtaining the lead halide perovskite material Cs3Bi2I9A nanosheet.
5. The method of claim 4, wherein the cesium source comprises cesium acetate;
the bismuth source comprises bismuth acetate;
the surfactant comprises octadecene, oleylamine and oleic acid;
the molar ratio of the cesium source to the bismuth source is (1-3): (1-2).
6. The method of claim 4, wherein the ratio of cesium source to surfactant is 1 mg: (0.1-2) mL;
the mixing time is 10-20 min;
the heating temperature is 100-150 ℃;
the heating time is 20-60 min.
7. The method of claim 4, wherein the iodine source comprises trimethyliodosilane;
the molar ratio of the cesium source to the iodine source is 1: (3-5);
the temperature for injecting the iodine source to carry out the reaction is 100-180 ℃;
the reaction time is 5 s-5 min;
and cooling by a cold water bath after the reaction.
8. Use of the lead-free halide perovskite material according to any one of claims 1 to 3 or the lead-free halide perovskite material prepared by the preparation method according to any one of claims 4 to 7 in a photodetector.
9. A vertical structure photodetector, comprising:
a P-type silicon wafer layer;
a photosensitive material layer compounded on the P-type silicon wafer layer;
a graphene layer composited on the photosensitive material layer;
the photosensitive material comprises the lead-free halide perovskite material as defined in any one of claims 1 to 3 or the lead-free halide perovskite material prepared by the preparation method as defined in any one of claims 4 to 7.
10. The vertical structure photodetector as claimed in claim 9, wherein the P-type silicon wafer layer has a thickness of 510 to 540 μm;
the thickness of the photosensitive material layer is 1-3 mu m;
the thickness of the graphene layer is 0.345 nm;
the graphene layer is a single-layer graphene layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210227370.3A CN114590836B (en) | 2022-03-08 | 2022-03-08 | Lead-free halide perovskite nanocrystalline, liquid phase synthesis method thereof and application thereof in photoelectric detector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210227370.3A CN114590836B (en) | 2022-03-08 | 2022-03-08 | Lead-free halide perovskite nanocrystalline, liquid phase synthesis method thereof and application thereof in photoelectric detector |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114590836A true CN114590836A (en) | 2022-06-07 |
| CN114590836B CN114590836B (en) | 2023-04-21 |
Family
ID=81818372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210227370.3A Active CN114590836B (en) | 2022-03-08 | 2022-03-08 | Lead-free halide perovskite nanocrystalline, liquid phase synthesis method thereof and application thereof in photoelectric detector |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114590836B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108946808A (en) * | 2018-06-25 | 2018-12-07 | 中山大学 | A kind of full-inorganic caesium-bismuth/antimony halide perovskite is nanocrystalline and preparation method thereof |
| WO2018231909A1 (en) * | 2017-06-13 | 2018-12-20 | Board Of Trustees Of Michigan State University | Method for fabricating epitaxial halide perovskite films and devices |
| CN109052470A (en) * | 2018-10-15 | 2018-12-21 | 郑州大学 | A kind of inorganic non-lead caesium bismuth halogen Cs3Bi2X9Perovskite micron disk and its synthetic method |
| CN113562763A (en) * | 2021-06-22 | 2021-10-29 | 中国科学技术大学 | Preparation method of InAs nano-particles and preparation method of photoelectric detector |
| CN114005564A (en) * | 2021-11-02 | 2022-02-01 | 山东大学 | Flexible polymer-bismuth-based halide nanoparticle composite X-ray protection material and preparation method and application thereof |
-
2022
- 2022-03-08 CN CN202210227370.3A patent/CN114590836B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018231909A1 (en) * | 2017-06-13 | 2018-12-20 | Board Of Trustees Of Michigan State University | Method for fabricating epitaxial halide perovskite films and devices |
| CN108946808A (en) * | 2018-06-25 | 2018-12-07 | 中山大学 | A kind of full-inorganic caesium-bismuth/antimony halide perovskite is nanocrystalline and preparation method thereof |
| CN109052470A (en) * | 2018-10-15 | 2018-12-21 | 郑州大学 | A kind of inorganic non-lead caesium bismuth halogen Cs3Bi2X9Perovskite micron disk and its synthetic method |
| CN113562763A (en) * | 2021-06-22 | 2021-10-29 | 中国科学技术大学 | Preparation method of InAs nano-particles and preparation method of photoelectric detector |
| CN114005564A (en) * | 2021-11-02 | 2022-02-01 | 山东大学 | Flexible polymer-bismuth-based halide nanoparticle composite X-ray protection material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| SIDNEY E. CREUTZ ET AL.: "Structural Diversity in Cesium Bismuth Halide Nanocrystals", 《CHEM. MATER.》 * |
| YUJIN LIU ET AL.: "All-inorganic lead-free NiOx/Cs3Bi2Br9 perovskite heterojunction photodetectors for ultraviolet multispectral imaging", 《NANO RESEARCH》 * |
| ZHAOYANG QI ET AL.: "Highly stable lead-free Cs3Bi2I9 perovskite nanoplates for photodetection applications", 《NANO RESEARCH》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114590836B (en) | 2023-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hu et al. | A microwave-assisted rapid route to synthesize ZnO/ZnS core–shell nanostructures via controllable surface sulfidation of ZnO nanorods | |
| Chen et al. | Non-injection gram-scale synthesis of cesium lead halide perovskite quantum dots with controllable size and composition | |
| Aldwayyan et al. | Synthesis and characterization of CdO nanoparticles starting from organometalic dmphen-CdI2 complex | |
| Raoufi | Synthesis and microstructural properties of ZnO nanoparticles prepared by precipitation method | |
| Wang et al. | Cu 2− x Se nanooctahedra: controllable synthesis and optoelectronic properties | |
| Li et al. | Au@ HgxCd1-xTe core@ shell nanorods by sequential aqueous cation exchange for near-infrared photodetectors | |
| Li et al. | Synthesis of colloidal SnSe quantum dots by electron beam irradiation | |
| Murugadoss | ZnO/CdS nanocomposites: synthesis, structure and morphology | |
| Murugadoss et al. | Structural and optical properties of highly crystalline Ce, Eu and co-doped ZnO nanorods | |
| CN112484851B (en) | Perovskite lanthanide series composite nano material, preparation method thereof and application of perovskite lanthanide series composite nano material in broadband photoelectric detector | |
| Shi et al. | Phosphate-free synthesis, optical absorption and photoelectric properties of Cu 2 ZnGeS 4 and Cu 2 ZnGeSe 4 uniform nanocrystals | |
| WO2012121515A2 (en) | Copper indium selenide nanoparticles and preparation method thereof | |
| Nasi et al. | Mesoporous single-crystal ZnO nanobelts: supported preparation and patterning | |
| Khan et al. | From Zn microspheres to hollow ZnO microspheres: A simple route to the growth of large scale metallic Zn microspheres and hollow ZnO microspheres | |
| Malevu et al. | Phase transformations of high-purity PbI2 nanoparticles synthesized from lead-acid accumulator anodes | |
| Chen et al. | Wafer‐scale growth of vertical‐structured SnSe2 nanosheets for highly sensitive, fast‐response UV–Vis–NIR broadband photodetectors | |
| Gokarna et al. | On the origin of the enhancement of defect related visible emission in annealed ZnO micropods | |
| Qu et al. | Preparation and optical property of porous ZnO nanobelts | |
| Wang et al. | Preparation and characteristics of CuInSe2 thin films by dip-coating method using its nanocrystal ink | |
| Wang et al. | Isovalent bismuth ion-induced growth of highly-disperse Sb 2 S 3 nanorods and their composite with p-CuSCN for self-powered photodetectors | |
| Mazloumi et al. | Self-assembly of ZnO nanoparticles and subsequent formation of hollow microspheres | |
| Vahidshad et al. | Synthesis and characterization of copper indium sulfide chalcopyrite structure with hot injection method | |
| He et al. | Universal Vapor‐Phase Synthesis of Large‐Scale Ultrathin Perovskites with Superior Stability for Photodetectors and Image Sensors | |
| CN114590836A (en) | Lead-free halide perovskite nanocrystal, liquid-phase synthesis method thereof and application of perovskite nanocrystal in photoelectric detector | |
| Patel et al. | A facile route towards the preparation of ZnSe nanocrystals |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |