CN114774114A - AgBiS2Preparation method of quantum dot superlattice and photoelectric detector thereof - Google Patents

AgBiS2Preparation method of quantum dot superlattice and photoelectric detector thereof Download PDF

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CN114774114A
CN114774114A CN202210343092.8A CN202210343092A CN114774114A CN 114774114 A CN114774114 A CN 114774114A CN 202210343092 A CN202210343092 A CN 202210343092A CN 114774114 A CN114774114 A CN 114774114A
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朱瑞
纪永强
赵丽宸
龚旗煌
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Abstract

The invention discloses an AgBiS2A preparation method of quantum dot superlattice and a photoelectric detector thereof. The invention obtains high-quality AgBiS by adjusting reaction conditions2Quantum dots, subsequently imparting AgBiS by means of a post-treatment process2Quantum dot 'targeting' function, followed by self-assembly strategy to make single AgBiS2Self-assembly of quantum dots into a superlattice; the nano-scale performance can be transferred to a larger size, and the nano-scale quantum dot has a collector property superior to that of a single quantum dot; the quantum dot superlattice is then used as a functional layer of a photodetector,by adding the interface modification layer, the interface defects of the device are passivated, the energy level structure of the device is optimized, and finally the AgBiS with high sensitivity, high signal-to-noise ratio and environmental protection is obtained2A quantum dot photodetector; AgBiS2The quantum dot superlattice photoelectric detector does not contain heavy metal elements, the whole device adopts a solution processing method, the manufacturing cost is low, and meanwhile, the quantum dot superlattice photoelectric detector has high stability and excellent device performance, so that the quantum dot superlattice photoelectric detector has a good market application prospect.

Description

AgBiS2Preparation method of quantum dot superlattice and photoelectric detector thereof
Technical Field
The invention relates to a preparation technology of photoelectronic components, in particular to an environment-friendly AgBiS2A preparation method of quantum dot superlattice and a photoelectric detector thereof.
Background
Photodetectors are very important electronic components in the field of optoelectronics, and have wide and important applications in various fields of military and national economy. At present, commercial photodetectors are still monocrystalline silicon, but the manufacturing cost of monocrystalline silicon is high, so that the development of some low-cost photodetectors is a hot problem in current social research. Over the past few decades, group II-VI and III-V compounds have shown significant potential applications in the field of photodetectors due to their excellent optoelectronic properties and solution processing characteristics. However, most of the reported II-VI and III-V group photovoltaic materials contain heavy metal elements (lead and cadmium), which are seriously harmful to the health of users. Reported that AgBiS2The quantum dots contain elements which are rich in earth reserves and nontoxic, have high absorption coefficients, adjustable size and components and narrow band gaps, have excellent carrier transport performance, and are stable in air environment, so that the quantum dots are concerned by people. Although the synthesis of AgBiS was successful in 2016 by Konstatatos et al2Quantum dots also show application potential in solar cells, but the synthesized AgBiS2The uniformity and photoelectric properties of quantum dots still need to be further improved,the application range is to be further expanded.
Disclosure of Invention
In order to overcome the defects that II-VI and III-V compound photoelectric detectors contain heavy metals and complicated preparation processes in the prior art and simultaneously increase the spectral detection range and sensitivity of the photoelectric detectors, the invention provides an environment-friendly AgBiS2The preparation method of the quantum dot superlattice and the photoelectric detector thereof can obtain the AgBiS with environmental protection by optimizing the reaction conditions (reaction time, reaction temperature and concentration of the precursor solution)2The photoelectric property of the quantum dots is further improved and the stability of the quantum dots is enhanced through a post-treatment preparation process (ligand or ion exchange and core-shell structure construction), and finally the high-quality AgBiS is added through an induction environment or an inducer2The quantum dots are self-assembled into the superlattice in the solution, and the AgBiS with high sensitivity, high signal-to-noise ratio and wide spectrum detection range is obtained by means of the collective characteristics of the quantum dots in the superlattice2Quantum dot superlattice photodetectors.
One purpose of the invention is to provide an environment-friendly AgBiS2A method for preparing quantum dot superlattice.
The environment-friendly AgBiS of the invention2The preparation method of the quantum dot superlattice comprises the following steps:
1) mixing a sulfur source, an organic ligand and a high-boiling-point octadecene solvent, introducing inert gas, stirring to obtain a clear and transparent anion precursor solution, wherein the organic ligand assists in dissolving the sulfur source, so that the temperature and the stirring time required for obtaining the clear and transparent anion precursor solution are reduced, and the energy consumption in the preparation process is reduced;
2) mixing a silver source, a bismuth source, an organic ligand and an octadecylene solvent, reacting at a set temperature and a set vacuum degree, then introducing inert gas for reaction, and obtaining a cation precursor solution when the solution is clear and transparent;
3) adding a set amount of anion precursor liquid into high-boiling point cation precursor liquid, and regulating and controlling reaction time, reaction temperature and concentrations of anion and cation precursor liquid to obtain initial AgBi with different particle sizesS2Quantum dots;
4) addition of exchange ligands or exchange element salts to the original AgBiS2Stirring the quantum dots at high temperature to perform ligand or ion exchange reaction to obtain functional AgBiS2The exchange ligand is multidentate ligand, has multiple coordination groups with quantum dots, and can be chelated at AgBiS2The surface of the quantum dot is added with AgBiS2Environmental stability of quantum dots while passivating AgBiS2Defects generated in the synthesis process of the quantum dots; the exchange elements are small-radius elements, and the function AgBiS is increased through element exchange2The quantum dot size reduces the band gap and widens the spectral range;
5) adding shell precursor solution to functional AgBiS2In the quantum dots, heating and stirring are carried out to obtain functional AgBiS2A layer of shell grows on the outer surface of the quantum dot to obtain AgBiS with a core-shell structure2Quantum dots imparting AgBiS2The quantum dot has a targeting function, and AgBiS with corresponding type I, type II or inverse type I core-shell structure is obtained by selecting different shell precursor solutions2Quantum dots; in functional AgBiS2The shell layer grown on the outer surface of the quantum dot is mainly added with AgBiS2The stability of quantum dots in extreme environments (high temperature, high radiation, strong illumination);
6) AgBiS with core-shell structure2Quantum dots are added with an inducer or an induction environment to induce AgBiS2Self-assembly of quantum dots into a superlattice; AgBiS2The quantum dot superlattice has collective characteristics, and index parameters of key performances such as sensitivity, spectral bandwidth and signal-to-noise ratio of the photoelectric detector can be improved;
7) adding a set amount of anti-solvent to the solution having AgBiS2Centrifuging the original solution of the quantum dot superlattice, adding a solvent into the obtained precipitate for redispersion, repeating the centrifuging step for multiple times, and removing AgBiS2The reaction waste generated in the synthesis process of the quantum dots is finally obtained to obtain clean AgBiS2A quantum dot superlattice product.
Wherein, in the step 1), the sulfur source is one of hexamethyldisilazane, mercaptan, thiourea and elemental sulfur; the organic ligand is one or more of octylamine, oleylamine and trioctylphosphine; the inert gas is nitrogen or argon; the temperature is between room temperature and 200 ℃; the stirring time is 30-180 minutes.
In the step 2), the silver source is one of silver acetate, silver carbonate, silver nitrate and silver halide; the bismuth source is one of bismuth acetate, bismuth carbonate, bismuth nitrate and halogenated bismuth; the organic ligand is one of oleic acid, caprylic acid and trioctylphosphine oxide; the temperature of the mixed reaction of the silver salt, the bismuth salt, the organic ligand and the octadecene is 80-200 ℃, the reaction time is 1-3 hours, and the vacuum degree is 10-300 Torr; and the reaction time after the inert gas is introduced is 2-5 hours.
In step 3), the reaction time, the reaction temperature and the concentration of the anionic and cationic precursor solutions and AgBiS2The relationship between the particle size of the quantum dots is as follows: higher temperature and longer time, AgBiS2The larger the particle size of the quantum dots and the higher the concentration of the anion and cation precursor solutions, the AgBiS2The smaller the particle size of the quantum dots; the concentration of the anion precursor solution is 0.002-0.5 g/mL; the concentration of the cation precursor solution is 0.005-0.8 g/mL.
In step 4), the exchange ligand is one or more of polydentate amino ligands, carboxyl ligands, sulfur-based ligands, sulfo ligands, phosphorus-based ligands, such as trioctylphosphine, tributylphosphine, diphenylphosphine, didodecyldimethylammonium bromide, sulfobetaine, phosphorylcholine, amino acids, and the like; the exchange element salt is one or more of transition metal salt, alkali metal salt, rare earth metal salt and equivalent metal salt, such as cesium carbonate, rubidium carbonate, aluminum carbonate, and neodymium carbonate; the temperature is 60-200 ℃, and the stirring time is 0.2-24 hours; for 10mL AgBiS2The quantum dot has 0.1-2 mL of functional exchange ligand and 0.01-2 mmol of exchange element salt.
In step 5), the shell precursor solution is one or more of II-VI, III-V, I-III-VI and perovskite quantum dots, such as ZnS source, InP source, CuInS2Source, CsPbBr3Sources, e.g. synthetic AgBiS2/ZnS、AgBiS2/InP、AgBiS2/CuInS2、AgBiS2/CsPbBr3Core-shell quantumPoint; the stirring temperature is between room temperature and 200 ℃, the stirring time is 1 to 48 hours, the thickness of the shell layer is 3 to 15 nanometers, and the size of the core-shell quantum dot is 10 to 50 nanometers; for 10mL AgBiS2The amount of the shell precursor liquid of the quantum dots is 0.1-10 mL, the more the precursor liquid is, the longer the stirring time is, and the thicker the shell layer is; if the band gap ratio AgBiS of the semiconductor material of the shell layer2The quantum dots are large, the quantum dots with I-shaped core-shell structures are obtained, otherwise, if the band gap ratio of the semiconductor material of the shell layer is AgBiS2The quantum dots are small, and the quantum dots with the inverse I-shaped core-shell structure are obtained; if the valence band edge or the conduction band edge of the semiconductor material of the shell layer is positioned at AgBiS2And quantum dots with II-type core-shell structures are obtained among the band gaps of the quantum dots.
In the step 6), the inducer is one of organic polymer, organic micromolecule, inorganic salt, metal nano-particles and micro-nano structure (nano-alumina template); the induction environment is one of high pressure, illumination (monochromatic light, ultraviolet light, sunlight, laser or X-ray), electric field, magnetic field, high concentration and high temperature; for example, ultraviolet light, template can induce AgBiS2The quantum dots are self-assembled into a one-dimensional superlattice, the power of ultraviolet light is 50-1000W, the distance between a light source and a solution is 10-100 cm, and the particle size of holes of the template is 0.05-10 microns; AgBiS can be induced in high-pressure environment2The quantum dots are self-assembled into a two-dimensional superlattice, and the pressure intensity ranges from 0.1 to 100 gigapascals; high temperature, high concentration or inducer can induce AgBiS2The quantum dots are self-assembled into a three-dimensional superlattice, and the inducer is dodecylamine, tetradecylphosphonic acid, hexadecylamine or ascorbic acid; the temperature range is 100-300 ℃; AgBiS2The concentration of the quantum dots is 50-200 mg/mL; the one-dimensional quantum dot superlattice contains 50-800 AgBiS2The quantum dot and the two-dimensional quantum dot superlattice contain 100-2000 AgBiS2The three-dimensional quantum dot superlattice contains 200-5000 AgBiS2And (4) quantum dots.
In the step 7), the solvent is one of toluene, n-hexane and n-octane, the anti-solvent is one of ethanol, methanol and acetone, and AgBiS2The concentration of the quantum dot product is 5-50 mg/mL, the particle size of the quantum dot is 3-50 nm, and the absorption peak is 600-1600 nm.
The invention also aims to provide a method for preparing the AgBiS based on the environment-friendly AgBiS2A quantum dot superlattice photodetector.
The invention is based on environment-friendly AgBiS2A quantum dot superlattice photodetector comprising: transparent conductive substrate, bottom charge transport layer, AgBiS2The quantum dot superlattice thin film, the top charge transport layer, the interface modification layer and the electrode; wherein a bottom charge transport layer is formed on a transparent conductive substrate; AgBiS2The quantum dot superlattice forms AgBiS on the bottom charge transmission layer by a film forming process2A quantum dot superlattice thin film; in AgBiS2Forming a top charge transport layer on the quantum dot superlattice film; preparing electrodes on the top charge transport layer, on AgBiS2An interface modification layer is added on the upper interface or the lower interface of the quantum dot superlattice film, so that the performance of the device is improved.
The transparent conductive substrate is rigid Indium Tin Oxide (ITO) transparent conductive film glass, Fluorine Tin Oxide (FTO) transparent conductive film glass, Aluminum Zinc Oxide (AZO) transparent conductive film glass or a flexible transparent conductive substrate, for example, silver nanowires are deposited on polyethylene terephthalate (PET), silver nanowires are deposited on Polyimide (PI) film, ITO is deposited on PET film, ITO is deposited on PI film; the transparent electrode needs to be cleaned, the cleaning step comprises the steps of sequentially carrying out ultrasonic treatment on the ITO conductive glass for 15-60 minutes at normal temperature by using soapy water, ultrapure water, acetone and isopropanol, then blowing the ITO by using a nitrogen gun, and carrying out ultraviolet ozone or plasma treatment on the ITO conductive glass for 15-60 minutes;
the bottom charge transport layer is an electron transport layer or a hole transport layer, and the corresponding top charge transport layer is a hole transport layer or an electron transport layer. The electron transport layer is divided into an organic electron transport layer and an inorganic electron transport layer, wherein the organic electron transport layer is 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBi), fullerene and derivatives (C) thereof60、C70PC61BM, PC71BM) with an inorganic electron transport layer of tin oxide (SnO), zinc oxide (ZnO) or titanium oxide (TiO)2). The hole transport layer is divided into an organic hole transport layer and an inorganic hole transport layer, wherein the organic hole transport layer is poly (3-hexylthiophene-2,5-diyl) (P3HT), polysulfonic acid-doped polythiophenes (PEDOT: PSS), [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine](PTAA), Poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) Poly (TFB), (4-butylphenyl diphenylamine) (Poly-TPD) or 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino]-9,9' -spirobifluorene (Spiro-OMeTAD); the inorganic hole transport layer is nickel oxide (NiO) or vanadium pentoxide (V)2O5) Tungsten oxide (WO), cuprous oxide (Cu)2O), molybdenum oxide (MoO)3) Or cuprous thiocyanate (CuSCN).
AgBiS2The thickness of the quantum dot superlattice film is 20-500 nm, and the AgBiS2The annealing temperature of the quantum dot superlattice thin film is 60-150 ℃, and the annealing time is 10-60 minutes. The film forming process is spin coating, blade coating, roll-to-roll, drop coating or screen printing.
The interface modifying layer is Bathocuproine (BCP), Polyethyleneimine (PEI), polyethenoxy ethyleneimine (PEIE), lithium fluoride (LiF) or cesium carbonate (Cs)2CO3) Molybdenum oxide (MoO)3) Polymethyl methacrylate (PMMA) or aluminum 8-hydroxyquinoline (Alq 3); the electrode is one of nickel, titanium, calcium, aluminum, copper, silver, gold, carbon, and graphene.
The invention has the advantages that:
the invention obtains high-quality AgBiS by adjusting reaction conditions (time, temperature and concentration of precursor liquid)2Quantum dots, subsequently imparting AgBiS by a process of post-treatment (ligand or ion exchange, building of core-shell structure)2Quantum dot 'targeting' function, followed by self-assembly strategy to make individual AgBiS2The quantum dots self-assemble into a superlattice. Compare individual AgBiS2Quantum dots, AgBiS2The quantum dot superlattice can transfer the performance of a nanometer level to a larger size, and simultaneously has the collective property superior to that of a single quantum dot; then, the quantum dot superlattice is used as a functional layer of the photoelectric detector, an interface modification layer is added to passivate the interface defects of the device, the energy level structure of the device is optimized, and finally the AgBiS with high sensitivity, high signal-to-noise ratio and environmental protection is obtained2A quantum dot photodetector; AgBiS obtained by the invention2The quantum dot superlattice has good dispersibilityThe size is uniform, the nano-silver/silver composite material can be dispersed in various organic solvents, has high colloid stability and good film forming effect, is suitable for various film deposition methods, and can be used as a functional layer of various photoelectric devices; AgBiS2The quantum dot superlattice photoelectric detector does not contain heavy metal elements, the whole device adopts a solution processing method, the manufacturing cost is low, and meanwhile, the quantum dot superlattice photoelectric detector has high stability and excellent device performance, so that the quantum dot superlattice photoelectric detector has a good market application prospect.
Drawings
FIG. 1 is an environmentally friendly AgBiS according to the present invention2Example of a method of preparing a Quantum dot superlattice2A transmission electron microscope topography of the quantum dots;
FIG. 2 is an environmentally friendly AgBiS according to the present invention2Example of a method of making a Quantum dot superlattice2An X-ray diffraction spectrum of the quantum dots;
FIG. 3 is an environmentally friendly AgBiS according to the present invention2Example of a method of making a Quantum dot superlattice2Ultraviolet-visible absorption spectrogram of the quantum dots;
FIG. 4 is an environmentally friendly AgBiS according to the present invention2Example of a method of making a Quantum dot superlattice2A band gap diagram of the quantum dots;
FIG. 5 is an environmentally friendly AgBiS according to the present invention2Example one of preparation methods of quantum dot superlattice2An X-ray photoelectron energy spectrum of the quantum dots;
FIG. 6 shows an AgBiS based on environmental friendly type of the present invention2A schematic diagram of one embodiment of a quantum dot superlattice photodetector.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings.
Example one
One-dimensional AgBiS of the present example2Environment-friendly AgBiS of/ZnSe2Preparation method and package of quantum dot superlatticeThe method comprises the following steps:
1) adding 1mmol of hexamethyldisilathiane into 5mL of octadecene, adding 0.5mL of oleylamine, introducing nitrogen, and stirring at room temperature for 30 minutes to obtain an anion precursor solution with a concentration of 0.032 g/mL;
2) adding 1mmol of bismuth acetate and 0.8mmol of silver acetate into 10mL of oleic acid and 5mL of octadecene, exhausting for 3 hours to obtain an anhydrous and oxygen-free environment with the vacuum degree of 100Torr, then introducing nitrogen, reacting for 3 hours at 100 ℃, and obtaining 0.033g/mL of cation precursor solution when the solution is clear and transparent;
3) 5mL of the anion precursor solution was injected into 10mL of the cation precursor solution, and the reaction was carried out at 100 ℃ for 30 seconds to obtain an initial AgBiS having an average particle diameter of 5nm2Quantum dots, shown in FIG. 1, initial AgBiS2The quantum dot has high crystallinity, and XRD diffraction peak and AgBiS2(PDF #21-2278) to indicate that the synthesized quantum dots are AgBiS2As shown in fig. 2; the cut-off edge of absorption is at 1200 nm, and simultaneously, the band gap of 1.0eV is shown in FIGS. 3 and 4, and the quantum dots contain Ag, Bi and S elements through the characterization of X-ray photoelectron spectroscopy, as shown in FIG. 5;
4) 1mL of tributylphosphine ligand was added to 10mL of the initial AgBiS2Stirring the quantum dots for 2 hours at the temperature of 60 ℃ to obtain functional AgBiS modified by tributyl phosphine ligand2Quantum dots;
5) dissolving 0.15g of zinc acetate in 2mL of oleic acid and 0.5mL of octadecene to obtain a cationic shell precursor solution, simultaneously dissolving 0.1g of selenium powder in 2mL of trioctylphosphine to obtain an anionic shell precursor solution, and then injecting the anionic shell precursor solution and the cationic shell precursor solution into 10mL of functional AgBiS modified by tributylphosphine ligand2In the quantum dots, stirring is carried out for 5 hours at 100 ℃ to obtain AgBiS with a core-shell structure2/ZnSe quantum dots;
6) 10mL of AgBiS with a core-shell structure2Putting the/ZnSe quantum dot solution under the irradiation of an ultraviolet lamp, wherein the power of the ultraviolet lamp is 100W, the irradiation time is 5 hours (the distance between the ultraviolet lamp and the quantum dot solution is 20cm, and the wavelength of the ultraviolet lamp is 365nm),obtaining AgBiS2a/ZnSe one-dimensional quantum dot superlattice;
7) AgBiS centrifugally purified for many times by taking acetone as precipitator and toluene as solvent2the/ZnSe quantum dot superlattice is dispersed in toluene, and the purification step is repeated for three times to obtain clean AgBiS2a/ZnSe quantum dot superlattice product.
Example two
Three-dimensional AgBiS of the present example2InP-friendly AgBiS2The preparation method of the quantum dot superlattice comprises the following steps:
1) adding 1mmol of sulfur powder into 2mL of trioctylphosphine and 1mL of octadecene, introducing nitrogen, stirring for 1 hour at 120 ℃, and obtaining an anion precursor solution with the concentration of 0.013g/mL when the solution is clear;
2) adding 1mmol of bismuth carbonate and 0.8mmol of silver carbonate into 10mL of oleic acid and 5mL of octadecene, exhausting for 3 hours to obtain an anhydrous and oxygen-free environment with the vacuum degree of 100Torr, introducing nitrogen, reacting for 5 hours at 120 ℃, and obtaining a cation precursor solution with the concentration of 0.093g/mL when the solution is clear and transparent;
3) injecting 5mL of anion precursor solution into 10mL of cation precursor solution, and reacting at 100 ℃ for 30 seconds under the nitrogen environment to obtain initial AgBiS with the average particle size of 8nm2Quantum dots;
4) 0.1mmol rubidium carbonate was added to 10mL of initial AgBiS2Stirring the quantum dots for 2 hours at 100 ℃ to obtain functional AgBiS for rubidium ion exchange2(Rb:AgBiS2) Quantum dots;
5) dissolving 0.05g of indium chloride in 2.5mL of oleylamine to obtain a cationic shell precursor solution, then dissolving 0.15g of trimethylsilylphosphine in 1mL of oleylamine to obtain an anionic shell precursor solution, and then injecting the anionic shell precursor solution and the cationic shell precursor solution into 10mL of Rb: AgBiS2In the quantum dots, stirring is carried out for 5 hours at 120 ℃ to obtain Rb AgBiS2/InP core-shell quantum dots;
6) 10mL of Rb AgBiS2Adding tetradecyl phosphonic acid into InP core-shell quantum dot solution, stirring for 24 hours at 60 ℃ to obtain the tri-n-propyl naphthaleneAgBiS as vitamin Rb2An InP quantum dot superlattice;
8) centrifugal purification of three-dimensional Rb AgBiS by using ethanol as precipitator and n-hexane as solvent2The InP quantum dot superlattice is dispersed in toluene, and the purification step is repeated three times to obtain clean three-dimensional Rb AgBiS2A superlattice product of InP quantum dots.
EXAMPLE III
Environment-friendly AgBiS-based method of the embodiment2The preparation method of the quantum dot superlattice photoelectric detector comprises the following steps:
1) ultrasonically treating the ITO conductive glass for 15 minutes at normal temperature by using soapy water, ultrapure water, acetone and isopropanol in sequence, then drying the ITO conductive glass by using a nitrogen gun, and treating the ITO conductive glass for 15 minutes by using ultraviolet ozone;
2) spin-coating a ZnO (15mg/mL, ethanol as a solvent) solution on transparent conductive glass to prepare an electron transmission layer film, wherein the spin-coating speed is 3000rpm, the rotation time is 60 seconds, then transferring the film on a hot table, annealing at 60 ℃ for 15 minutes, and obtaining an ITO/ZnO substrate, wherein the thickness of the electron transmission layer film is 30 nm;
3) carrying out spin coating on an ITO/ZnO substrate by using Polyethenoxy Ethylene Imine (PEIE), wherein the solvent of the PEIE is isopropanol, the concentration of the isopropanol is 0.4 wt.%, the spin coating rotating speed is 5000rpm, and the rotating time is 60 seconds, so as to obtain the ITO/ZnO/PEIE substrate;
4) AgBiS2The quantum dot superlattice solution is coated on an ITO/ZnO/PEIE substrate in a spinning way, and AgBiS2The concentration of the quantum dot superlattice is 20mg/mL, the solvent is anhydrous toluene, the spin-coating rotating speed is 2000rpm, and the rotating time is 45 seconds;
5) then carrying out dynamic spin-coating of tetramethylammonium iodide/methanol solution (volume ratio is 1% v/v) for ligand exchange reaction, and then sequentially carrying out spin-coating cleaning on AgBiS by using methanol and toluene2Quantum dot superlattice film, annealing at 120 deg.C for 10 min, and repeatedly treating for three times to obtain ITO/ZnO/PEIE/AgBiS2A substrate;
6) ITO/ZnO/PEIE/AgBiS obtained in the step 5)2Putting the substrate into a glove box in a nitrogen environment, carrying out spin coating of TFB at the rotating speed of 3000rpm for 45 seconds, and then placing the film on a hot bench 1Annealing at 20 ℃ for 30 minutes to obtain ITO/ZnO/PEIE/AgBiS2/TFB substrate
7) ITO/ZnO/PEIE/AgBiS obtained in the step 6)2/TFB substrate gold-evaporated, gold film thickness of 100nm, finally obtaining AgBiS2The quantum dot superlattice photoelectric detector and the schematic diagram of the photoelectric detector are shown in FIG. 6, and the photoelectric detector comprises a transparent conductive substrate 1, a bottom charge transmission layer 2, an interface modification layer 3 and AgBiS2A quantum dot superlattice thin film 4, a top charge transport layer 5, and an electrode 6.
It is finally noted that the disclosed embodiments are intended to aid in the further understanding of the invention, but that those skilled in the art will appreciate that: various substitutions and modifications are possible without departing from the spirit and scope of the invention and the appended claims. Therefore, the invention should not be limited to the embodiments disclosed, but the scope of the invention is defined by the appended claims.

Claims (9)

1. Environment-friendly AgBiS2The preparation method of the quantum dot superlattice is characterized by comprising the following steps of:
1) mixing a sulfur source, an organic ligand and a high-boiling octadecylene solvent, introducing inert gas, stirring to obtain a clear and transparent anion precursor solution, wherein the organic ligand assists in dissolving the sulfur source, so that the temperature and the stirring time required for obtaining the clear and transparent anion precursor solution are reduced, and the energy consumption in the preparation process is reduced;
2) mixing a silver source, a bismuth source, an organic ligand and an octadecylene solvent, reacting at a set temperature and a set vacuum degree, then introducing inert gas for reaction, and obtaining a cation precursor solution when the solution is clear and transparent;
3) adding a set amount of anion precursor solution into high-boiling point cation precursor solution, and regulating and controlling reaction time, reaction temperature and concentrations of anion precursor solution and cation precursor solution to obtain initial AgBiS with different particle sizes2Quantum dots;
4) addition of exchange ligands or exchange element salts to the original AgBiS2In the quantum dots, stirring is carried out at a high temperatureLigand or ion exchange reaction to obtain functional AgBiS2The quantum dot and the exchange ligand are polydentate ligands, have a plurality of coordination groups with the quantum dot, and can be chelated in AgBiS2The surface of the quantum dot is added with AgBiS2Environmental stability of quantum dots with simultaneous AgBiS passivation2Defects generated in the synthesis process of the quantum dots; the exchange elements are elements of small radius,
augmenting functionality AgBiS through element exchange2The quantum dot size reduces the band gap and widens the spectral range;
5) adding shell precursor solution to functional AgBiS2In the quantum dots, heating and stirring are carried out to obtain the functional AgBiS2Growing a shell on the outer surface of the quantum dot to obtain AgBiS with a core-shell structure2Quantum dots endowed with AgBiS2The quantum dot has a targeting function, and AgBiS with corresponding type I, type II or inverse type I core-shell structure is obtained by selecting different shell precursor solutions2Quantum dots; in a functional AgBiS2The shell layer grown on the outer surface of the quantum dot is mainly added with AgBiS2The stability of the quantum dots in extreme environments;
6) AgBiS with core-shell structure2Quantum dot is added with inducer or induction environment to induce AgBiS2Self-assembly of quantum dots into a superlattice; AgBiS2The quantum dot superlattice has collective characteristics, and index parameters of key performances such as sensitivity, spectral bandwidth and signal-to-noise ratio of the photoelectric detector can be improved;
7) adding a set amount of anti-solvent to the solution having AgBiS2Centrifuging the original solution of the quantum dot superlattice, adding solvent into the obtained precipitate for redispersion, repeating the centrifuging step for multiple times, and removing AgBiS2The reaction waste generated in the synthesis process of the quantum dots is finally obtained to obtain clean AgBiS2A quantum dot superlattice product.
2. The method of claim 1, wherein in step 1), the sulfur source is one of hexamethyldisilathiane, thiol, thiourea, and elemental sulfur; the organic ligand is one or more of octylamine, oleylamine and trioctylphosphine; the inert gas is nitrogen or argon; the temperature is between room temperature and 200 ℃; the stirring time is 30-180 minutes.
3. The method of claim 1, wherein in the step 2), the silver source is one of silver acetate, silver carbonate, silver nitrate and silver halide; the bismuth source is one of bismuth acetate, bismuth carbonate, bismuth nitrate and halogenated bismuth; the organic ligand is one of oleic acid, caprylic acid and trioctylphosphine oxide; the temperature of the mixed reaction of the silver source, the bismuth source, the organic ligand and the octadecene is 80-200 ℃, and the reaction time is 1-3 hours; and the reaction time after the inert gas is introduced is 2-5 hours.
4. The method of claim 1, wherein in step 3), the reaction time, the reaction temperature, and the concentrations of the anionic and cationic precursor solutions with AgBiS2The relationship between the particle size of the quantum dots is as follows: higher temperature and longer time, AgBiS2The larger the particle size of the quantum dot and the larger the concentration of the anion and cation precursor solution, the AgBiS2The smaller the particle size of the quantum dots is; the concentration of the anion precursor solution is 0.002-0.5 g/mL; the concentration of the cation precursor solution is 0.005-0.8 g/mL.
5. The method of claim 1, wherein in step 4), the exchange ligand is one or more of a multidentate amino ligand, carboxyl ligand, thio ligand, sulfo ligand, and phospho ligand; the exchange element salt is one or more of transition metal salt, alkali metal salt, rare earth metal salt and equivalent metal salt; the temperature is 60-200 ℃, and the stirring time is 0.2-24 hours.
6. The method of claim 1, wherein in step 5), the shell precursor solution is one or more of group II-VI, group III-V, group I-III-VI, and perovskite quantum dots; the stirring temperature is between room temperature and 200 ℃, the stirring time is 1 to 48 hours, the thickness of the shell layer is 3 to 15 nanometers, and the size of the core-shell quantum dot is 10 to 50 nanometers; if the semiconductor material of the shell layerBand gap ratio AgBiS2The quantum dots are large, and the quantum dots with I-type core-shell structures are obtained; if the band gap ratio AgBiS of the semiconductor material of the shell layer2The quantum dots are small, and the quantum dots with the inverse I-shaped core-shell structure are obtained; if the valence band edge or the conduction band edge of the semiconductor material of the shell layer is positioned at AgBiS2And obtaining the quantum dots with the II-type core-shell structure among the band gaps of the quantum dots.
7. The preparation method of claim 1, wherein in the step 6), the inducer is one of an organic polymer, an organic small molecule, an inorganic salt, a metal nanoparticle, and a micro-nano structure; the induction environment is one of high voltage, light, electric field, magnetic field, high concentration and high temperature.
8. The method of claim 1, wherein in step 7), the solvent is one of toluene, n-hexane and n-octane, and the anti-solvent is one of ethanol, methanol and acetone, AgBiS2The concentration of the quantum dot product is 5-50 mg/mL, the particle size of the quantum dot is 3-50 nm, and the absorption peak is 600-1600 nm.
9. Environment-friendly AgBiS obtained based on the preparation method of claim 12A quantum dot superlattice photodetector, comprising: transparent conductive substrate, bottom charge transport layer, AgBiS2The quantum dot superlattice thin film, the top charge transport layer, the interface modification layer and the electrode; wherein a bottom charge transport layer is formed on a transparent conductive substrate; AgBiS2Forming AgBiS on the bottom charge transport layer of the quantum dot superlattice by film forming process2A quantum dot superlattice thin film; in AgBiS2Forming a top charge transport layer on the quantum dot superlattice thin film; preparing electrodes on the top charge transport layer, on AgBiS2An interface modification layer is added on the upper interface or the lower interface of the quantum dot superlattice film, so that the performance of the device is improved.
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