CN112239670A - CuInSe2Ultra-small quantum dot and preparation method and application thereof - Google Patents

CuInSe2Ultra-small quantum dot and preparation method and application thereof Download PDF

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CN112239670A
CN112239670A CN202011062060.8A CN202011062060A CN112239670A CN 112239670 A CN112239670 A CN 112239670A CN 202011062060 A CN202011062060 A CN 202011062060A CN 112239670 A CN112239670 A CN 112239670A
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cuinse
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薛小刚
瞿森林
袁欣
李钰
张小文
袁昌来
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Guilin University of Electronic Technology
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Abstract

The invention discloses CuInSe2The preparation method of the ultra-small quantum dot comprises the following steps: s1:preparing tristhiocyanic acid or sulfydryl coordinated Cu and In ion precursor solution and selenium precursor solution; preparation of CuInSe2A quantum dot precursor solution; preparation of small molecule thiocyanate or sulfydryl-coated ultra-small CuInSe2Quantum dot water solution, preparing target product in water solution by water phase one-pot method with simple process and low temperature to obtain CuInSe2The quantum dot is a cubic-phase ultra-small nanocrystal which is wrapped by micromolecular thiocyanate or sulfydryl and emits light in a near infrared mode. The quantum dot ink is used for printing and preparing the solar cell, so that the optical performance and the electrical performance of the cell can be effectively improved, and the quantum dot has excellent photocatalytic performance.

Description

CuInSe2Ultra-small quantum dot and preparation method and application thereof
Technical Field
The invention relates to the technical field of nano materials, and relates to CuInSe2An ultra-small quantum dot, a preparation method and an application thereof, in particular to a water-soluble CuInSe2Quantum dots, and a water phase synthesis preparation method and application thereof.
Background
CuInSe2The material is a direct band gap semiconductor material of I-III-VI family, the forbidden band width at room temperature is about 1.05eV, and the material has very high molar extinction coefficient and intrinsic dipole moment in a visible light region, thereby facilitating the rapid separation of electron-hole. Such as continuously adjustable emission wavelength, narrow emission wavelength, wide absorption spectrum, high luminous intensity, long fluorescence lifetime, good biocompatibility and the like; because the nano-gold-doped zinc oxide does not contain toxic heavy metal elements such as Cd, Pb and the like, the nano-gold-doped zinc oxide has wide application prospect in the fields of Light Emitting Diodes (LEDs), solar cells (SolarCells), biomarkers, photocatalysis and the like.
At present stage of CuInSe2The preparation method of NCs is single, and the heat injection method is mainly used. In the synthesis of a typical hot injection method, reactants are injected into a solvent in hot coordination for rapid nucleation and growth control. Se was injected into CuCl and InCl at 285 deg.C as Guo, Q, 2008, 8 (see NanoLett.2008, 2982-) -2987 in 20083Obtaining zinc blende nano crystal in oleylamine solution. Further, as in 2013 OlesyaYarema et al (see chem. mater.2013, 25, 3753-3Preparing stock solution and mixing with TOP; reacting TOPSe with LiN (SiMe) at 320 deg.C3) The mixed stock solution was quickly injected into the reaction flask to obtain CuInSe2And (4) nanocrystals. Se powder, copper iodide, indium acetate, paraffin, OAm and DDT were then charged into a three-necked flask as in JunZhu et al 2016 (see Nanoscale, 2016, 8, 10021-; heating to 180 ℃ under argon to prepare CuInSe2And (4) quantum dots. However, these CuInSe2The preparation of nanomaterials requires special equipment or unique precursors and complicated synthetic procedures, uses a large variety of raw materials and is costly to prepare. Water-soluble small molecule coated CuInSe2Nanocrystals, often based on CuInSe of a certain size2Nanocrystals can only be obtained by complex ligand exchange. Therefore, the development of a simple, convenient and cheap preparation method is of great significance. For small molecule thiocyanate or sulfydryl coated CuInSe2Direct aqueous solution synthesis technology of quantum dots, aqueous phase synthesis of CuInSe with near-infrared luminescence2The preparation of quantum dots remains a challenge.
Based on the design, the invention designs CuInSe2Ultra-small quantum dots, and a preparation method and application thereof, to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to provide the ultra-small CuInSe coated by small-molecule thiocyanate or small-molecule sulfydryl2The quantum dots and the direct aqueous phase synthesis preparation method thereof are simple, and the prepared quantum dots have near infrared luminescence and narrow size distribution and good water solubility so as to solve the problems.
In order to achieve the purpose, the invention provides the following technical scheme: CuInSe2Ultra-small quantum dots, said CuInSe2The ultra-small quantum dots are wrapped by short-chain micromolecular thiocyanate or sulfydryl, are ultra-small nanoparticles in appearance, and are quasi-zero-dimensional multi-element semiconductor nanocrystals with the size of 0.5-7 nm.
The method is prepared in an aqueous phase and comprises the following steps:
s1: preparing a Cu and In ion precursor solution and a selenium precursor solution of trithiocyanuric acid or sulfydryl coordination:
preparing Cu and In ion precursor solution: dissolving copper salt and indium salt in water according to a certain proportion, adding micromolecular thiocyanic acid or sulfydryl wrapping agent, stirring to obtain white precipitate, adding OH-Until the precipitate is dissolved and the pH value of the solution is adjusted to 7-12;
preparation of Se2-Precursor solution: se powder and small molecular amino ligand2-Selenium precursor solution with the concentration of 0.01-1.00 mol/L;
s2: preparation of CuInSe2Quantum dot precursor solution:
mixing the precursor solution of trimeric thiocyanic acid or Cu and In ions coordinated by sulfydryl with the precursor solution of selenium to obtain CuInSe2A quantum dot precursor solution;
s3: preparation of small molecule thiocyanate or sulfydryl-coated ultra-small CuInSe2Quantum dot aqueous solution:
mixing CuInSe2Putting the quantum dot precursor solution into a hydrothermal kettle, and growing for 1-60 hours at 90-170 ℃ to obtain the CuInSe wrapped by the ultra-small molecular thiocyanate or sulfydryl2And (4) quantum dots.
Preferably, the molar ratio of the copper salt to the indium salt is 1: 1-1: 10, and the copper salt is selected from any one of CuI, CuCl, CuBr, Cu (OAc) and CuSCN.
Preferably, the indium salt is selected from in (OAc)3、InCl3、InBr3、InI3、In(NO3)3Or In2(SO4)2Any one of the above.
Preferably, the molar ratio of the small-molecule thiocyanate wrapping agent to the copper salt is 1: 6-1: 60, and the small-molecule thiocyanate wrapping agent is cyanuric acid.
Preferably, the molar ratio of the small molecule sulfydryl wrapping agent to the copper salt is 1: 6-1: 60, and the small molecule sulfydryl wrapping agent is cysteine, trithiocyanuric acid or TGA.
Preferably, the molar ratio of the small molecular amino ligand to the copper salt is 1: 10-1: 2000, and the small molecular amino ligand is selected from water-soluble amides such as ammonia water, ethylenediamine, hydrazine hydrate, propylenediamine and butylenediamine.
Preferably, the selenium precursor solution is a solution prepared by dissolving selenium powder in a small molecular amino solution, and the concentration of the selenium precursor solution is 0.01-1.00 mol/L.
Preferably, said OH is-Is NaOH.
The CuInSe2The application of the ultra-small quantum dots in quantum dot ink, solar cells and photocatalysis.
Preparing a target product in aqueous solution by adopting a water phase one-pot method with a simpler process and a lower temperature to obtain CuInSe2The quantum dot is a cubic-phase ultra-small nanocrystal which is wrapped by micromolecular thiocyanate or sulfydryl and emits near-infrared light. The quantum dot ink is used for printing and preparing the solar cell, so that the optical performance and the electrical performance of the cell can be effectively improved, and the quantum dot has excellent photocatalytic performance.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention adopts a one-pot method, takes inorganic salt with relatively low price as a precursor, and prepares the CuInSe wrapped by micromolecular thiocyanate or sulfydryl on a large scale by a simple water-phase synthesis process2Quantum dots;
21) the size and band gap of the quantum dot can be controlled by controlling the copper-indium ratio, the growth temperature and the time in the reaction process, and the preparation method has strong controllability, easy control of process parameters, safety, greenness, no pollution and high yield;
3) the invention obtains the ultra-small CuInSe2The quantum dot is a quasi-zero-dimensional semiconductor nano material, has near-infrared luminescence and narrow size distribution compared with the prior method, and can be used in the fields of quantum dot ink, printed solar cells, photocatalysis and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an XRD pattern and cubic phase structure CuInSe of a product prepared in example 1 of the present invention2The abscissa of the pdf card is the diffraction angle and the ordinate is the relative intensity;
FIG. 2 is a graph showing the results of EDS analysis of the composition of the product prepared in example 1 of the present invention;
FIG. 3 is a transmission electron microscope picture and a size distribution analysis result graph of products prepared in examples 1 and 2 of the present invention;
FIG. 4 is a graph showing the UV-VIS absorption spectrum and the fluorescence spectrum of the product prepared in example 1 and example 2 of the present invention;
FIG. 5 is an XRD pattern and tetragonal structure of CuInSe from the product of comparative example 1 of the present invention2Pdf card map of (1);
FIG. 6 is an XRD pattern and tetragonal structure of CuInSe from the product of comparative example 2 of the present invention2Pdf card map of (1);
FIG. 7 is a photocurrent graph of example 1 of the present invention and comparative examples 1 and 2;
FIG. 8 is a schematic diagram of hydrogen production in example 1, comparative example 1 and comparative example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
The technical scheme of the invention uses water as solvent and micromolecule sulfurCyanate or sulfhydryl wrapping agent is used as a coating agent, copper salt and indium salt are respectively a copper source and an indium source, and Cu is prepared firstly+The concentration is 1 mmol/L-20 mmol/L, In3+Preparing Se by dissolving metal ion precursor solution with copper/indium ratio of 1: 1-1: 10 and selenium powder as selenium source in hydrazine hydrate at concentration of 20mmol/L2-Selenium ion precursor solution with concentration of about 0.01-1.00 mol/L, and Cu is inhibited by balancing two ion reaction activities by using soluble small molecular amide2S and In2S3Forming several binary phases, and reacting Se2-Mixing the ion precursor solution and the metal ion precursor solution at normal temperature to obtain CuInSe2The growth time and temperature of the quantum dot precursor solution in a hydrothermal kettle are controlled by a one-pot method to control CuInSe2Size and band gap of quantum dots.
The invention provides CuInSe2Ultra-small quantum dots, CuInSe2The ultra-small quantum dots are wrapped by short-chain small-molecular thiocyanate or sulfydryl, are ultra-small nanoparticles in appearance, and are quasi-zero-dimensional multi-element semiconductor nanocrystals with the size of only 0.5-7 nm.
The invention also provides the ultra-small CuInSe coated by the micromolecule thiocyanate or sulfydryl2The quantum dots are applied to quantum dot ink, solar cells and photocatalysis.
CuInSe2The preparation method of the ultra-small quantum dot is prepared in an aqueous phase and comprises the following steps:
s1: preparing a Cu and In ion precursor solution and a selenium precursor solution of trithiocyanuric acid or sulfydryl coordination:
preparing Cu and In ion precursor solution: dissolving copper salt and indium salt in water according to a certain proportion, adding micromolecular thiocyanic acid or sulfydryl wrapping agent, stirring to obtain white precipitate, adding OH-Until the precipitate is dissolved and the pH value of the solution is adjusted to 7-12;
wherein the molar ratio of copper salt to indium salt is 1: 1-1: 10, and the copper salt is selected from any one of CuI, CuCl, CuBr, Cu (OAc) or CuSCN; the indium salt is selected from in (OAc)3、InCl3、InBr3、InI3、 In(NO3)3Or In2(SO4)2Any one of the above; the molar ratio of the small-molecule thiocyanate-wrapping agent to the copper salt is 1: 6-1: 60, the small-molecule thiocyanate-wrapping agent is cyanuric acid, the molar ratio of the small-molecule sulfydryl-wrapping agent to the copper salt is 1: 6-1: 60, and the small-molecule sulfydryl-wrapping agent is cysteine, cyanuric acid or TGA; OH group-Is NaOH.
Preparation of Se2-Precursor solution: se powder and small molecular amino ligand2-Selenium precursor solution with the concentration of 0.01-1.00 mol/L;
wherein the molar ratio of the micromolecular amino ligand to the copper salt is 1: 10-1: 2000, and the micromolecular amino ligand is selected from water-soluble amides such as ammonia water, ethylenediamine, hydrazine hydrate, propylenediamine, butanediamine and the like. The selenium precursor solution is formed by dissolving selenium powder in a micromolecular amino solution, and the concentration of the selenium precursor solution is 0.01-1.00 mol/L.
S2: preparation of CuInSe2Quantum dot precursor solution:
mixing the precursor solution of trimeric thiocyanic acid or Cu and In ions coordinated by sulfydryl with the precursor solution of selenium to obtain CuInSe2A quantum dot precursor solution;
s3: preparation of small molecule thiocyanate or sulfydryl-coated ultra-small CuInSe2Quantum dot aqueous solution:
mixing CuInSe2Putting the quantum dot precursor solution into a hydrothermal kettle, and growing for 1-60 hours at 90-170 ℃ to obtain the CuInSe wrapped by the ultra-small molecular thiocyanate or sulfydryl2And (4) quantum dots.
Example 1
The preparation method of the ultrasmall CuInSe2 quantum dot wrapped by trithiocyanuric acid comprises the following steps:
s1: preparation of trithiocyanuric acid coordinated Cu and In ions 1:1 precursor solution: 0.004g of Cu (Ac)2And 0.006g In (Ac)3Dissolved in 10mL of H2O, 0.0462g of trithiocyanuric acid was added thereto, and stirred to obtain a white precipitate. Adding NaOH to the precipitate to adjust the pH value of the solution to 7-10. Obtaining the metal complex precursor solution with the copper ion concentration of 2mmol/L and the indium ion concentration of 2 mmol/L.
S2: one-pot method for preparing ultra-small CuInSe wrapped by trithiocyanuric acid2Quantum dot aqueous solution: 0.016g of selenium powder is weighed and dissolved in 1mL of hydrazine hydrate to prepare Se2-Selenium precursor solution such as hydrogen selenide with the concentration of 1mol/L,
s3: mixing the solution with the metal complex precursor solution under stirring, putting the mixture into a hydrothermal kettle, and growing for 1-60 hours at the temperature of 90-170 ℃ to obtain the ultrasmall CuInSe coated with the cyanuric acid2And (4) quantum dots. Taking a certain volume of obtained CuInSe2The quantum dots were washed several times with ethanol and water precipitation to remove impurities and the obtained powder was used for XRD characterization. Washing the CuInSe2The quantum dots are redispersed in a certain volume of water and used for characterization of ultraviolet-visible absorption, emission spectra and transmission electron microscopy.
FIG. 1 is an XRD pattern and cubic phase structure CuInSe of a product prepared in example 1 of the present invention2The pdf card of (1). As can be seen from the figure, a cubic phase structure CuInSe is obtained under the conditions of the present example2And (4) nanocrystals. The crystal size is estimated to be 3-5 nm by the Sherle formula.
FIG. 4 is a UV-VIS absorption spectrum and an emission spectrum of a product prepared in example 1 of the present invention. The emission spectrum shows that the emission peak position of the sample is about 800nm, and the result reported by the literature indicates that the luminescence is radiation recombination related to defects. Has good fluorescent labeling application potential. FIG. 3 is a Transmission Electron Microscope (TEM) image of the product prepared in example 1 of the present invention, in which a High Resolution Transmission Electron Microscope (HRTEM) image is embedded, the TEM image confirming that the average size of the synthesized material is about 5nm, and the HRTEM image showing that the lattice spacing is 0.23 nm, consistent with the cubic phase (220) plane spacing. Fig. 2 is an EDX plot of the product prepared In example 1 of the present invention, showing that the ratio of Cu to In of the prepared quantum dots is close to 1:1, and the ratio of the two metals to Se is close to 1:2, the resulting material was confirmed to be CuInSe2。
Example 2
Trithiocyanic acid-coated ultra-small CuInSe2The preparation method of the quantum dot comprises the following steps:
s1: preparation of tris thiocyanic acid coordinated Cu and In ionsSeed 1:10 precursor solution: 0.004g of Cu (Ac)2And 0.06g In (Ac)3Dissolved in 10mL of H2O, 0.0462g of trithiocyanuric acid was added thereto, and stirred to obtain a white precipitate. Adding NaOH to the precipitate to adjust the pH value of the solution to 7-10. Obtaining the metal complex precursor solution with the copper ion concentration of 2mmol/L and the indium ion concentration of 20 mmol/L.
S2: one-pot method for preparing ultra-small CuInSe wrapped by trithiocyanuric acid2Quantum dot aqueous solution: 0.016g of selenium powder is weighed and dissolved in 1mL of hydrazine hydrate,
s3: mixing the solution with the metal complex precursor solution under stirring, putting the mixture into a hydrothermal kettle, and growing for 1-60 hours at the temperature of 90-170 ℃ to obtain the ultrasmall CuInSe coated with the cyanuric acid2And (4) quantum dots. Taking a certain volume of obtained CuInSe2The quantum dots were washed several times with ethanol and water precipitation to remove impurities and the obtained powder was used for XRD characterization. Washing the CuInSe2The quantum dots are redispersed in a certain volume of water and used for characterization of ultraviolet-visible absorption, emission spectra and transmission electron microscopy.
Example 3
Glutathione (GSH) -encapsulated ultra-small CuInS2The preparation method of the quantum dot comprises the following steps:
s1: preparation of GSH-coordinated Cu and In ions 1:1 precursor solution: 0.004g of Cu (Ac)2And 0.006g In (Ac)3Dissolved in 10mL of H2O, to which 0.08g of GSH was added and stirred to give a white precipitate. NaOH was added to the precipitate to adjust the pH of the solution to 9. Obtaining the metal complex precursor solution with the copper ion concentration of 2mmol/L and the indium ion concentration of 2 mmol/L.
S2: one-pot method for preparing GSH-coated ultra-small CuInSe2Quantum dot aqueous solution: 0.016g of selenium powder is weighed and dissolved in 1mL of hydrazine hydrate,
s3: mixing the solution with the metal complex precursor solution under stirring, putting the mixture into a hydrothermal kettle, and growing for 1-60 hours at the temperature of 90-170 ℃ to obtain GSH-coated ultra-small CuInSe2And (4) quantum dots. Taking a certain volume of obtained CuInSe2The quantum dots are precipitated and washed with ethanol and water for multiple times to removeImpurities, the powder obtained was used for XRD characterization. Washing the CuInSe2The quantum dots are redispersed in a volume of water for characterization of ultraviolet-visible absorption, emission spectra and transmission electron microscopy.
Example 4
Glutathione (GSH) -encapsulated ultra-small CuInS2The preparation method of the quantum dot comprises the following steps:
s1: preparation of GSH-coordinated Cu and In ions 1:10, precursor solution: 0.004g of Cu (Ac)2And 0.06g In (Ac)3Dissolved in 10mL of H2O, to which 0.08g of GSH was added and stirred to give a white precipitate. And adding NaOH to the precipitate to adjust the pH value of the solution to 9, thereby obtaining a metal complex precursor solution with the copper ion concentration of 2mmol/L and the indium ion concentration of 20 mmol/L.
S2: one-pot method for preparing ultra-small CuInSe wrapped by trithiocyanuric acid2Quantum dot aqueous solution: 0.032g of selenium powder is weighed and dissolved in 1mL of hydrazine hydrate,
s3: mixing the solution with the metal complex precursor solution under stirring, putting the mixture into a hydrothermal kettle, and growing for 1-60 hours at the temperature of 90-170 ℃ to obtain the ultrasmall CuInSe coated with the cyanuric acid2And (4) quantum dots. Taking a certain volume of obtained CuInSe2The quantum dots were washed several times with ethanol and water precipitation to remove impurities and the obtained powder was used for XRD characterization. Washing the CuInSe2The quantum dots are redispersed in a certain volume of water and used for characterization of ultraviolet-visible absorption, emission spectra and transmission electron microscopy.
Comparative example 1
CuInSe2The one-pot synthesis of quantum dots comprises the following steps:
in a typical synthesis, 0.004g of Cu (Ac) is taken2And 0.006g In (Ac)3And 0.016g of selenium powder, adding 5mL of mixed solvent of ethanol and ethylenediamine, mixing uniformly, and filling into a stainless steel autoclave with a polytetrafluoroethylene lining. The autoclave was sealed, kept at 180 ℃ for 3 hours, and then cooled to room temperature to be natural. The resulting precipitate was centrifuged and washed several times with distilled water and absolute ethanol to remove any material soluble by-products. Vacuum at 60 deg.CAfter drying for 6 hours, a black powder collection product is finally obtained.
Fig. 5 is an XRD spectrum and a tetragonal crystal structure pdf card of the product synthesized in comparative example 1. As can be seen from the figure, a tetragonal crystal structure CuInSe was obtained under the conditions of this example2And (4) nanocrystals. The crystal size is estimated to be 7-10 nm by the Sherle formula. The product obtained is free of fluorescence.
Comparative example 2
Organic phase one-pot method for preparing CuInSe2The preparation method of the quantum dot comprises the following steps:
in a typical synthesis, 0.004g of Cu (Ac) is taken2And 0.006g In (Ac)3And 0.016g of selenium powder, adding 10mL of oleylamine, mixing uniformly, and putting into a stainless steel high-pressure hydrothermal kettle with a polytetrafluoroethylene lining. Hydrothermal growth at 180 ℃ for 3 hours. And naturally cooling the reaction container to room temperature and taking out. Separation of Black CuInSe by addition of chloroform2Nanocrystals, ethanol precipitation, in 10000rpm speed centrifugation for 5 minutes. The precipitate was then redispersed in chloroform. This precipitation/centrifugation/dispersion cycle was repeated twice to eliminate by-products and unreacted precursors. The suspension was thus dried in a vacuum oven at 60 ℃ to give black CuInSe2A nanocrystalline powder.
Fig. 6 is an XRD spectrum and a tetragonal crystal structure pdf card of the product synthesized in comparative example 2. As can be seen from the figure, a tetragonal structure CuInSe was obtained under the conditions of this example2And (4) nanocrystals. The crystal size is estimated to be 3-5 nm by the Sherle formula. The product obtained is free of fluorescence.
FIG. 7 shows the photocurrent of the products obtained from example 1 and comparative examples 1 and 2 when used as quantum dot inks printed on ITO. It can be seen from the graph that the optical response of the example is 3 times that of the comparative example 1, and the optical response of the comparative example 2 is almost zero. The synthetic method of the invention and other methods have better photoelectric properties.
FIG. 8 shows the hydrogen production of the products of example 1 and comparative examples 1 and 2 under visible light (. lamda. >430nm) 10mg in 50ml of an aqueous solution of 0.5M sodium thionate nonahydrate and 0.25M sodium sulfite. Example 1 has excellent hydrogen generation performance due to its affinity with water and its excellent electron transport and photoelectric properties.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, a schematic representation of the above terms does not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (10)

1. CuInSe2Ultra-small quantum dots, characterized in that: the CuInSe2The ultra-small quantum dots are wrapped by short-chain micromolecular thiocyanate or sulfydryl, are ultra-small nanoparticles in appearance, and are quasi-zero-dimensional multi-element semiconductor nanocrystals with the size of 0.5-7 nm.
2. The CuInSe of claim 12The preparation method of the ultra-small quantum dot is characterized by comprising the following steps: the method is prepared in an aqueous phase and comprises the following steps:
s1: preparing a Cu and In ion precursor solution and a selenium precursor solution of trithiocyanuric acid or sulfydryl coordination:
preparing Cu and In ion precursor solution: dissolving copper salt and indium salt in water according to a certain proportion, adding small moleculeStirring thiocyanic acid or sulfydryl wrapping agent to obtain white precipitate, adding OH-Until the precipitate is dissolved and the pH value of the solution is adjusted to 7-12;
preparation of Se2-Precursor solution: se powder and small molecular amino ligand2-Selenium precursor solution with the concentration of 0.01-1.00 mol/L;
s2: preparation of CuInSe2Quantum dot precursor solution:
mixing the precursor solution of trimeric thiocyanic acid or Cu and In ions coordinated by sulfydryl with the precursor solution of selenium to obtain CuInSe2A quantum dot precursor solution;
s3: preparation of small molecule thiocyanate or sulfydryl-coated ultra-small CuInSe2Quantum dot aqueous solution:
mixing CuInSe2Putting the quantum dot precursor solution into a hydrothermal kettle to grow for 1-60 hours at the temperature of 90-170 ℃ to obtain the CuInSe wrapped by the ultra-small molecular thiocyanate or sulfydryl2And (4) quantum dots.
3. The CuInSe of claim 22The preparation method of the ultra-small quantum dot is characterized by comprising the following steps: the molar ratio of the copper salt to the indium salt is 1: 1-1: 10, and the copper salt is selected from any one of CuI, CuCl, CuBr, Cu (OAc) or CuSCN.
4. The CuInSe of claim 22The preparation method of the ultra-small quantum dot is characterized by comprising the following steps: the indium salt is selected from in (OAc)3、InCl3、InBr3、InI3、In(NO3)3Or In2(SO4)2Any one of the above.
5. The CuInSe of claim 22The preparation method of the ultra-small quantum dot is characterized by comprising the following steps: the mole ratio of the micromolecular thiocyanate wrapping agent to the copper salt is 1: 6-1: 60, and the micromolecular thiocyanate wrapping agent is cyanuric acid.
6. The CuInS of claim 2e2The preparation method of the ultra-small quantum dot is characterized by comprising the following steps: the molar ratio of the small molecule sulfydryl wrapping agent to the copper salt is 1: 6-1: 60, and the small molecule sulfydryl wrapping agent is cysteine, trithiocyanuric acid and TGA.
7. The CuInSe of claim 22The preparation method of the ultra-small quantum dot is characterized by comprising the following steps: the molar ratio of the small-molecule amino ligand to the copper salt is 1: 10-1: 2000, and the small-molecule amino ligand is selected from water-soluble amides such as ammonia water, ethylenediamine, hydrazine hydrate, propylenediamine and butanediamine.
8. The CuInSe of claim 22The preparation method of the ultra-small quantum dot is characterized by comprising the following steps: the selenium precursor solution is obtained by dissolving selenium powder in a micromolecular amino solution, and the concentration of the selenium precursor solution is 0.01-1.00 mol/L.
9. The CuInSe of claim 22The preparation method of the ultra-small quantum dot is characterized by comprising the following steps: the OH group-Is NaOH.
10. The CuInSe of claim 12The application of the ultra-small quantum dots is characterized in that: the CuInSe2The application of the ultra-small quantum dots in quantum dot ink, solar cells and photocatalysis.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104513663A (en) * 2013-09-27 2015-04-15 深圳先进技术研究院 Near-infrared copper-indium-selenium quantum dot and preparation method thereof
CN109021970A (en) * 2018-08-06 2018-12-18 桂林电子科技大学 A kind of AgInS2Or CuInS2Extra small quantum dot and its preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104513663A (en) * 2013-09-27 2015-04-15 深圳先进技术研究院 Near-infrared copper-indium-selenium quantum dot and preparation method thereof
CN109021970A (en) * 2018-08-06 2018-12-18 桂林电子科技大学 A kind of AgInS2Or CuInS2Extra small quantum dot and its preparation method and application

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