CN108910939B - Ultrathin CuInS2Nanosheet and preparation method and application thereof - Google Patents
Ultrathin CuInS2Nanosheet and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000002135 nanosheet Substances 0.000 claims abstract description 56
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229960003151 mercaptamine Drugs 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 239000002096 quantum dot Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000010410 layer Substances 0.000 claims abstract description 10
- 239000002356 single layer Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 6
- 150000002471 indium Chemical class 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- JKNHZOAONLKYQL-UHFFFAOYSA-K tribromoindigane Chemical compound Br[In](Br)Br JKNHZOAONLKYQL-UHFFFAOYSA-K 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- 229910021621 Indium(III) iodide Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- RMUKCGUDVKEQPL-UHFFFAOYSA-K triiodoindigane Chemical compound I[In](I)I RMUKCGUDVKEQPL-UHFFFAOYSA-K 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000002064 nanoplatelet Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 150000004696 coordination complex Chemical class 0.000 description 10
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- -1 aluminum ions Chemical class 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000002159 nanocrystal Substances 0.000 description 4
- 239000002055 nanoplate Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical group [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 3
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 235000013878 L-cysteine Nutrition 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
- C01G15/006—Compounds containing, besides gallium, indium, or thallium, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/39—
-
- B01J35/40—
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- 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
- Y02E10/541—CuInSe2 material PV cells
Abstract
The invention provides an ultrathin CuInS2The nano sheet is a two-dimensional mesomorphic material, has a single-layer or multi-layer structure, has a thickness of 0.65-3 nm and a size of 100-900 nm; the ultra-thin CuInS2A method of making nanoplatelets comprising the steps of: preparation of mercaptoethylamine coordinated Cu+And In3+Precursor solution; preparation of mercaptoethylamine Encapsulated ultra-Small CuInS2Quantum dots; preparation of monolayer or multilayer ultrathin CuInS2Nanosheet, ultrathin CuInS provided by the invention2The nano sheet has a two-dimensional mesomorphic structure and can be used in the fields of solar cells, photocatalysis and the like; the preparation method provided by the invention adopts a water-phase synthesis process, can be used for large-scale preparation, is easy to control the thickness and the size of the nanosheet, and has the advantages of strong controllability, easy control of process parameters, safety, greenness, no pollution and high yield.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to ultrathin CuInS2Nanosheet and preparation method and application thereof.
Background
CuInS2The material is a direct band gap semiconductor material of I-III-VI family, the forbidden band width at room temperature is about 1.53eV, and the material has very high molar extinction coefficient in the visible light region. Because the nano-silver/nano-silver composite material does not contain toxic heavy metal elements such as Cd, Pb and the like, the nano-silver/nano-silver composite material has wide application prospect in the fields of Light Emitting Diodes (LEDs), Solar Cells (Solar Cells), biomarkers, photocatalysis and the like.
In 2009, CuInS is prepared for the first time by taking copper sulfate and indium chloride as metal sources and L-cysteine as a sulfur source in a DMF (dimethyl formamide) solvent thermal reaction2CuInS with nanosheet as construction unit2And (4) nano microspheres. 2015, Michael
By mixing Cu2Heating the O film in ethylene glycol solution of indium chloride and thioacetamide at high temperature, and obtaining CuInS growing on the substrate through ion exchange2Nanoplatelets, leading many scholars to CuInS2Research interest in two-dimensional nanomaterials. In fact, in the fields of photocatalysis, solar cells, light emitting diodes, etc., there is a strong need for solution processable, high quality two-dimensional CuInS2Nanomaterials, which rely on CuInS2Liquid phase synthesis technology of nanocrystalline. Since Cu is easily formed for a long time2Binary phases such as S, CuInS2The nanocrystalline is difficult to be directly synthesized in aqueous solution, and the method of organic heat injection or the method of organic precursor pyrolysis is the CuInS synthesized at present2The main method of nanocrystal. The organic phase has certain advantages in size control, however, on one hand, the organic phase synthesis adopts expensive organic solvent and precursor, the operation temperature is in danger of approaching to the flash point of the solvent and precursor materials, and on the other hand, ultra-thin two-dimensional CuInS is difficult to obtain2A nanostructure. NaInS was synthesized by hydrothermal synthesis in 2015 by the Say Chye Joachim Loo topic group of Nanyang physic2Nanosheets, followed by passage of Cu using this as a template+Ion exchange to obtain CuInS2/NaInS2The research of the two-dimensional nano heterostructure shows that the two-dimensional nano heterostructure contains CuInS after ion exchange2The heterostructure is broken in appearanceBad and severe aggregates are present. To date, CuInS2The low-temperature water phase green synthesis of the two-dimensional nano structure is still an unsolved problem.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides ultrathin CuInS2Nanosheets;
another object of the present invention is to provide the above ultra-thin CuInS2A preparation method and application of the nano-sheet.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
ultrathin CuInS2Nanoplates, the CuInS2The nano-sheet is a two-dimensional mesomorphic material and has a single-layer or multi-layer structure, the thickness is 0.65-3 nm, and the size is 100-900 nm.
The ultrathin CuInS2A method of making nanoplatelets comprising the steps of:
(1) preparation of mercaptoethylamine coordinated Cu+And In3+Precursor solution: according to Cu+And In3+The molar ratio is 1: 1.6-16, weighing copper salt and indium salt, adding the copper salt and the indium salt into deionized water, adding mercaptoethylamine, stirring to obtain white precipitate, and adding an alkali solution into the system to adjust the pH value to 7-12 to obtain a solution A;
(2) preparation of mercaptoethylamine Encapsulated ultra-Small CuInS2Quantum dot: dissolving a sulfur precursor into deionized water to prepare a solution B, heating the solution B to 70-100 ℃, and then adding the solution B into the solution A under stirring to obtain mercaptoethylamine-coated ultra-small CuInS2Quantum dots;
(3) preparation of monolayer or multilayer ultrathin CuInS2Nanosheet: ultra-small CuInS wrapped in mercaptoethylamine2Adding soluble aluminum salt into the quantum dot aqueous solution, carrying out hydrothermal reaction for 10-40 hours at the temperature of 150-250 ℃, and separating and drying after the reaction is finished to obtain the single-layer or multi-layer ultrathin CuInS2Nanosheets.
Preferably, the copper salt in the step (1) is one or more of CuI, CuCl, CuBr, Cu (OAc) or CuSCN; the indium saltIs in (OAc)3、InCl3、InBr3、 InI3、In(NO3)3Or In2(SO4)2One or more of them.
Preferably, Cu in the solution A in the step (1)+The concentration of (b) is 3 to 20 mmol/L.
Preferably, In said step (1)3+And mercaptoethylamine at a molar ratio of 1: 6 to 7.
Preferably, the sulfur precursor in step (2) is one or more of sodium sulfide, potassium sulfide, ammonium sulfide or thiourea.
Preferably, the sulfur precursor and In the step (2)3+In a molar ratio of 1: 5.
preferably, the soluble aluminum salt in step (3) is Al (NO)3)3、Al2(SO4)3Or AlCl3。
Preferably, Al in said step (3)3+And In3+In a molar ratio of 1: 1.6 to 16.
The ultra-thin CuInS2The nano sheet is applied to the preparation of solar cells or photocatalysis.
The invention has the beneficial effects that: 1. the invention provides single-layer or multi-layer ultrathin CuInS2The nano-sheet is made of CuInS2The quantum dot is obtained by assembling and crystallizing, is a two-dimensional mesomorphic material, has multiple absorption edges and exciton absorption splitting, and can be used in the fields of solar cells, photocatalysis and the like; 2. the preparation method provided by the invention adopts a negative ion reverse phase hot injection method, takes relatively low-price inorganic salt as a precursor, takes aluminum ions as a two-dimensional assembly growth promoter, and prepares single-layer or multi-layer CuInS in a large batch manner by a simple water phase synthesis process2Ultrathin nanosheets; the thickness and the size of the nanosheets can be controlled by controlling the copper-indium ratio, the aluminum ion concentration, the growth temperature and the growth time in the reaction process, and the preparation method has the advantages of strong controllability, easy control of process parameters, safety, greenness, no pollution and high yield.
Drawings
FIG. 1 is an XRD pattern of the product prepared in example 1And chalcopyrite structure CuInS2The pdf card of (1);
FIG. 2 is a transmission electron micrograph (a) and a power spectrum analysis result (d) of the product prepared in example 1, and FIGS. 2b and 2c are high resolution transmission electron micrographs of a square area of FIG. 2 a;
FIG. 3 is a graph (a) of the UV-VIS absorption spectrum and a graph (b) of the forbidden band width obtained from the UV-VIS absorption spectrum data of the product prepared in example 1;
FIG. 4 is a transmission electron micrograph of the product prepared in example 2;
FIG. 5 is a graph (a) of the UV-VIS absorption spectrum and a graph (b) of the forbidden band width obtained from the UV-VIS absorption spectrum data of the product prepared in example 2;
FIG. 6 is a High Resolution Transmission Electron Micrograph (HRTEM) of the product prepared in comparative example 1;
fig. 7 is a graph (a) of the uv-vis absorption spectrum of the product prepared in the comparative example and a graph (b) of the forbidden band width obtained from the uv-vis absorption spectrum data.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described below clearly and completely, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Ultra-thin CuInS2The preparation method of the nanosheet comprises the following steps:
(1) preparation of mercaptoethylamine coordinated Cu+And In3+Precursor solution: 0.02g of Cu (OAc) and 0.234g of In (OAc)3Dissolving in water, adding mercaptoethylamine surface coating agent 0.401g, stirring to obtain white precipitate, adding NaOH solution to adjust pH to 9 to obtain Cu+The concentration is 3.2mmol/L, In3+The concentration is 16mmol/L, Cu+And In3+In a molar ratio of 1:5, a metal complex precursor solution;
(2) preparation of mercaptoethylamine Encapsulated ultra-Small CuInS2Quantum dot: 0.96g of Na was weighed2S·9H2Dissolving O in 200ml deionized water, heating to 90 deg.C and keeping the temperature for half an hour, rapidly injecting the solution into the metal complex precursor solution under stirring to obtain mercaptoethylamine-coated ultra-small CuInS2Quantum dots;
(3) preparation of ultra-thin CuInS2Nanosheet: ultra-small CuInS wrapped in mercaptoethylamine2Adding 0.125mmol of aluminum ions into the quantum dot aqueous solution, carrying out hydrothermal reaction at 180 ℃ for 20 hours, and after the reaction is finished, carrying out precipitation, centrifugal separation and drying on the reaction solution by using ethanol to obtain a product.
FIG. 1 shows CuInS prepared in this example2XRD (X-ray diffraction) spectrum of nanosheet and chalcopyrite structure CuInS2The pdf card of (1). As can be seen from the figure, the CuInS with chalcopyrite structure is prepared in the embodiment2And (3) nanocrystals with a crystal size below 2nm as estimated by the scherrer equation.
FIG. 2 shows CuInS prepared in this example2The transmission electron microscope image of the nano sheet, FIG. 2a shows that the product is an ultrathin nano sheet, the size of the ultrathin nano sheet is about 100nm, and the embedded electron diffraction pattern is between single crystal and nanocrystalline; fig. 2b and 2c are high-resolution transmission electron microscope images of the nanosheets, fig. 2b shows that the nanosheets are formed by uniformly aligning and partially bonding nanocrystalline lattices with the sizes of about 2nm, which is consistent with an electron diffraction result, and shows that the nanosheets are mesomorphic structures, and fig. 2c shows that the thickness of folds of the nanosheets is 1.5nm, so that the thickness of the nanosheets is presumed to be less than 0.75nm and is a diatomic layer ultrathin structure. FIG. 2d shows CuInS2The energy spectrum analysis result of the nano-sheet shows that the nano-sheet comprises Cu, In and S, and the atomic ratio of the nano-sheet is consistent with the results of the implementation case.
The CuInS prepared in this example is shown in FIG. 32Uv-vis absorption spectra and calculated band gaps of the nanoplates, fig. 3a shows that the sample has double absorption edges, further confirming CuInS2The mesomorphic structure of the ultrathin structure is characterized, meanwhile, exciton absorption and splitting also show the formation of the mesomorphic state of the ultrathin structure, and fig. 3b is a forbidden bandwidth diagram of a sample.
Example 2
Ultra-thin CuInS2The preparation method of the nanosheet comprises the following steps:
(1) preparation of mercaptoethylamine coordinated Cu+And In3+Precursor solution: 0.02g of Cu (OAc) and 0.234g of In (OAc)3Dissolving in water, adding mercaptoethylamine surface coating agent 0.401g, stirring to obtain white precipitate, adding NaOH solution to adjust pH to 9 to obtain Cu+The concentration is 3.2mmol/L, In3+The concentration is 16mmol/L, Cu+And In3+In a molar ratio of 1:5, a metal complex precursor solution;
(2) preparation of mercaptoethylamine Encapsulated ultra-Small CuInS2Quantum dot: 0.96g of Na was weighed2S·9H2Dissolving O in 200ml deionized water, heating to 90 deg.C and keeping the temperature for half an hour, rapidly injecting the solution into the metal complex precursor solution under stirring to obtain mercaptoethylamine-coated ultra-small CuInS2Quantum dots;
(3) preparation of ultra-thin CuInS2Nanosheet: to step (ii) mercaptoethylamine coated ultra-small CuInS2Adding 0.25mmol of aluminum ions into the quantum dot aqueous solution, carrying out hydrothermal reaction for 20 hours at 180 ℃, precipitating the reaction solution by using ethanol after the reaction is finished, carrying out centrifugal separation, and drying to obtain the product.
FIG. 4 shows CuInS prepared in this example2The transmission electron microscope picture of the nano-sheet shows that the nano-sheet is an ultrathin nano-sheet, and the size of the ultrathin nano-sheet is about 150 nm.
FIG. 5 shows CuInS prepared in this example2The uv-vis absorption spectrum and the calculated band gap of the nanoplate, fig. 5a shows that the nanoplate has double absorption edges, indicating that it has both quantum dots and absorption characteristics of a large size single crystal, further confirming CuInS2Mesomorphic structure of (a). And meanwhile, exciton absorption and splitting at the peak positions of 412 and 465nm indicate that the nano sheet with the mesomorphic structure is a double-layer or multi-layer ultrathin structure. The red shift of the absorption edge shows that the size and the thickness of the nano sheet are higher than those of the nano sheet in example 1, the thickness and the size of the sample can be adjusted through the concentration of aluminum ions, and FIG. 5b shows the forbidden band of the sampleWidth diagram.
Example 3
Ultra-thin CuInS2The preparation method of the nanosheet comprises the following steps:
(1) preparation of mercaptoethylamine coordinated Cu+And In3+Precursor solution: 0.03g of Cu (OAc) and 0.234g of In (OAc)3Dissolving in water, adding mercaptoethylamine surface coating agent 0.401g, stirring to obtain white precipitate, adding NaOH solution to adjust pH to 9 to obtain Cu+The concentration is 4.8mmol/L, In3+The concentration is 16mmol/L, Cu+And In3+A metal complex precursor solution with a molar ratio of 3: 10;
(2) preparation of mercaptoethylamine Encapsulated ultra-Small CuInS2Quantum dot: 0.96g of Na was weighed2S·9H2Dissolving O in 200ml deionized water, heating to 90 deg.C and keeping the temperature for half an hour, rapidly injecting the solution into the metal complex precursor solution under stirring to obtain mercaptoethylamine-coated ultra-small CuInS2Quantum dots;
(3) preparation of ultra-thin CuInS2Nanosheet: ultra-small CuInS wrapped in mercaptoethylamine2Adding 0.125mmol of aluminum ions into the quantum dot aqueous solution, carrying out hydrothermal reaction at 180 ℃ for 20 hours, and after the reaction is finished, carrying out precipitation, centrifugal separation and drying on the reaction solution by using ethanol to obtain a product.
Example 4
Ultra-thin CuInS2The preparation method of the nanosheet comprises the following steps:
(1) preparation of mercaptoethylamine coordinated Cu+And In3+Precursor solution: 0.016g of CuCl and 0.234g of In (OAc)3Dissolving in water, adding mercaptoethylamine surface coating agent 0.401g, stirring to obtain white precipitate, adding NaOH solution to adjust pH to 9 to obtain Cu+The concentration is 3.2mmol/L, In3+The concentration is 16mmol/L, Cu+And In3+The molar ratio of (1: 5) of the metal complex precursor solution;
(2) preparation of mercaptoethylamine Encapsulated ultra-Small CuInS2Quantum dot: 0.96g of Na was weighed2S·9H2Dissolving O in 200mlHeating the solution in ionized water to 90 ℃ and preserving heat for half an hour, and quickly injecting the solution into the metal complex precursor solution under stirring to obtain the ultra-small CuInS wrapped by mercaptoethylamine2Quantum dots;
(3) preparation of ultra-thin CuInS2Nanosheet: ultra-small CuInS wrapped in mercaptoethylamine2Adding 0.25mmol of aluminum ions into the quantum dot aqueous solution, heating for 20 hours at 180 ℃ under a hydrothermal condition, precipitating the reaction solution by using ethanol after the reaction is finished, carrying out centrifugal separation, and drying to obtain a product.
Comparative example
CuInS2The preparation of the nanocrystalline comprises the following steps:
(1) preparation of mercaptoethylamine coordinated Cu+And In3+Precursor solution: 0.02g of Cu (OAc) and 0.234g of In (OAc)3Dissolving in water, adding mercaptoethylamine surface coating agent 0.401g, stirring to obtain white precipitate, adding NaOH solution to adjust pH to 9 to obtain Cu+The concentration is 3.2mmol/L, In3+The concentration is 16mmol/L, Cu+And In3+The molar ratio of (1: 5) of the metal complex precursor solution;
(2) preparation of mercaptoethylamine Encapsulated ultra-Small CuInS2Quantum dot: 0.96g of Na was weighed2S·9H2Dissolving O in 200ml deionized water, heating to 90 deg.C and keeping the temperature for half an hour, rapidly injecting the solution into the metal complex precursor solution under stirring to obtain mercaptoethylamine-coated ultra-small CuInS2Quantum dots;
(3) preparation of CuInS2Nano-crystalline: the mercapto ethylamine is wrapped by ultra-small CuInS2The quantum dot aqueous solution is directly heated for 20 hours under the hydrothermal condition of 180 ℃, and after the reaction is finished, the reaction solution is precipitated by ethanol, centrifugally separated and dried to obtain a product.
FIG. 6 is a CuInS prepared by this comparative example2The picture of a high-resolution transmission electron microscope of the nano-crystal is known to be an ultra-small nano-crystal aggregate without the appearance of an ultra-thin nano-sheet and a crystal lattice ordered arrangement structure.
FIG. 7 shows the preparation of this comparative exampleCuInS of2Ultraviolet visible absorption spectrum of nanocrystalline without ultrathin CuInS absorption2The features of the nanosheets cleave exciton absorption peaks.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. Ultrathin CuInS2Preparation method of nanosheet, CuInS2The nano-sheet is a two-dimensional mesomorphic material and has a single-layer or multi-layer structure, the thickness is 0.65-3 nm, and the size is 100-900 nm, and the method is characterized by comprising the following steps:
(1) preparation of mercaptoethylamine coordinated Cu+And In3+Precursor solution: according to Cu+And In3+The molar ratio is 1: 1.6-16, weighing copper salt and indium salt, adding the copper salt and the indium salt into deionized water, adding mercaptoethylamine, stirring to obtain white precipitate, and adding an alkali solution into the system to adjust the pH value to 7-12 to obtain a solution A;
(2) preparation of mercaptoethylamine Encapsulated ultra-Small CuInS2Quantum dot: dissolving a sulfur precursor into deionized water to prepare a solution B, heating the solution B to 70-100 ℃, and then adding the solution B into the solution A under stirring to obtain mercaptoethylamine-coated ultra-small CuInS2Quantum dots;
(3) preparation of monolayer or multilayer ultrathin CuInS2Nanosheet: ultra-small CuInS wrapped in mercaptoethylamine2Adding soluble aluminum salt into the quantum dot aqueous solution, carrying out hydrothermal reaction for 10-40 hours at the temperature of 150-250 ℃, and separating and drying after the reaction is finished to obtain the single-layer or multi-layer ultrathin CuInS2Nanosheets.
2. The method of claim 1Ultra-thin CuInS2The preparation method of the nanosheet is characterized in that the copper salt in the step (1) is one or more of CuI, CuCl, CuBr, Cu (OAc) or CuSCN; the indium salt is in (OAc)3、InCl3、InBr3、InI3、In(NO3)3Or In2(SO4)2One or more of them.
3. The ultra-thin CuInS of claim 12The preparation method of the nano sheet is characterized in that Cu in the solution A in the step (1)+The concentration of (b) is 3 to 20 mmol/L.
4. The ultra-thin CuInS of claim 12A process for producing a nanosheet, wherein In the step (1)3+And mercaptoethylamine at a molar ratio of 1: 6 to 7.
5. The ultra-thin CuInS of claim 12The preparation method of the nanosheet is characterized in that the sulfur precursor in the step (2) is one or more of sodium sulfide, potassium sulfide, ammonium sulfide or thiourea.
6. The ultra-thin CuInS of claim 12The preparation method of the nano sheet is characterized In that the sulfur precursor and In the step (2)3+In a molar ratio of 1: 1 to 5.
7. The ultra-thin CuInS of claim 12A process for producing a nanosheet, wherein the soluble aluminum salt in step (3) is Al (NO)3)3、Al2(SO4)3Or AlCl3。
8. The ultra-thin CuInS of claim 12The preparation method of the nano-sheet is characterized in that Al in the step (3)3+And In3+In a molar ratio of 1: 1.6 to 16.
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Application publication date: 20181130 Assignee: Guilin Sensing Material Technology Co.,Ltd. Assignor: GUILIN University OF ELECTRONIC TECHNOLOGY Contract record no.: X2022450000575 Denomination of invention: An ultra-thin CuInS2nano sheet and its preparation method and application Granted publication date: 20201110 License type: Common License Record date: 20221230 |