CN112646568A - Perovskite metal nonmetal compound core-shell quantum dot and preparation method and application thereof - Google Patents

Perovskite metal nonmetal compound core-shell quantum dot and preparation method and application thereof Download PDF

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CN112646568A
CN112646568A CN202011404302.7A CN202011404302A CN112646568A CN 112646568 A CN112646568 A CN 112646568A CN 202011404302 A CN202011404302 A CN 202011404302A CN 112646568 A CN112646568 A CN 112646568A
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黄胜
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Abstract

The application discloses a perovskite metal nonmetal compound core-shell quantum dot, which consists of a perovskite core, a metal nonmetal compound shell and a ligand; wherein the perovskite core has the structural formula ABX3、A4BX6、AB2X5、A2BX4、A3B2X9、Am‑1Bm+1X3m+1M is not less than 2, andwherein A is CH3NH3 +、NH2CHNH2 +、C(NH2)3 +、Cs+、Li+、Na+、K+、Rb+Or Q; wherein Q is selected from at least one of aryl or alkyl organic amine cation with the carbon atom number not less than 3; b is Pb2+、Cu2+、Bi3+、Sb3+、Tl3+、In3+、Cu+、Ag+At least one of (a); x is selected from anionic Cl‑，Br‑，I‑，SCN‑At least one of (1).

Description

Perovskite metal nonmetal compound core-shell quantum dot and preparation method and application thereof
Technical Field
The invention belongs to the field of perovskite core-shell quantum dots, and particularly relates to a perovskite metal nonmetal compound core-shell quantum dot and a preparation method and application thereof.
Background
Perovskite quantum dot material aspect: at present, perovskite quantum dot materials can be obtained by a thermal injection method and an anti-solvent method, however, halogen anions of the perovskite materials are easy to migrate under the illumination condition, the stability of perovskite lattices is damaged, the photoelectric properties of the perovskite are unstable, the perovskite cannot be put into use for a long time, meanwhile, the perovskite is very sensitive to moisture and oxygen, the properties of the perovskite crystals exposed in the oxygen and the moisture are deteriorated along with the prolonging of time, and the perovskite crystals are difficult to be directly put into use. Various approaches have been tried to address the perovskite stability problem, such as additive strategies, doping with Zn2+Ions promote perovskite formation energy, thereby promoting stability; the surface is coated with a strategy, such as coating a silicon dioxide shell layer on the surface to improve the stability; and the stability of the material can be improved by adding the ionic liquid to improve defect formation energy. However, the above methods have various problems, and the stability problems of water, heat, light, oxygen, etc. cannot be solved at the same time, but only one aspect is to improve the stability of the material system.
Further, the current applications based on perovskite materials mainly focus on solar cells, photodetectors, luminescent displays, pressure sensors and piezoelectric devices, and the functions are mainly realized by existing perovskite quantum dot materials. For example, the perovskite quantum dot-based optical pressure sensor mainly adopts an active resonant cavity strategy, integrates a perovskite quantum dot polymer film with a high-reflectivity Bragg reflector to realize pressure sensing, and has the advantages of complicated pressure testing steps, high cost, complicated required equipment and difficult integration; in the aspect of gas-sensitive detection, only a few gases can be detected at present, the main flow of harmful gases is less at present, the detection mechanism is realized by the change of the fluorescence intensity of a perovskite detector under the gases or the change of photocurrent, and the gas detection is limited in types.
Disclosure of Invention
The technical problem to be solved is as follows:
aiming at the defects of the prior art, the application provides a perovskite metal non-metallic compound core-shell quantum dot and a preparation method and application thereof, and solves the problems that the existing halogen anions are easy to migrate, destroy the perovskite lattice stability, cause the perovskite photoelectric property to be unstable, cannot be put into use for a long time, have complicated pressure testing steps, high cost, complicated required equipment, difficult integration and the like.
The technical scheme is as follows:
in order to achieve the purpose, the application is realized by the following technical scheme:
the perovskite metal nonmetal compound core-shell quantum dot is composed of a perovskite core, a metal nonmetal compound shell layer and a ligand;
wherein the perovskite core has the structural formula ABX3、A4BX6、AB2X5、A2BX4、A3B2X9、Am-1Bm+1X3m+1M is more than or equal to 2;
wherein A is CH3NH3 +、NH2CHNH2 +、C(NH2)3 +、Cs+、Li+、Na+、K+、Rb+Or Q; wherein Q is selected from at least one of aryl or alkyl organic amine cation with the carbon atom number not less than 3;
b is Pb2+、Cu2+、Sn2+、Mn2+、Zn2+、Cd2+、Ge2+、Sr2+、Eu2+、Yb2+、Bi3+、Sb3+、Tl3+、In3+、Cu+、Ag+At least one of (a);
x is selected from anionic Cl-，Br-，I-，SCN-At least one of (1).
A preparation method of perovskite metal nonmetal compound core-shell quantum dots comprises the following steps:
the first step is as follows: reacting CX1-3In a molar ratio of 1: (0.1-4), wherein CX1-3Selected from C1X, C2X2、C3X3Wherein C1 in C1X is selected from Cu+、Ag+At least one of (1), C2X2Wherein C2 is selected from Pb2+、Cu2+、Sn2+、Mn2+、Zn2 +、Cd2+、Ge2+、Sr2+、Eu2+、Yb2+At least one of (1), C3X3Wherein C3 is selected from Bi3+、Sb3+、Tl3+、In3+X is selected from Cl-，Br-，I-，SCN-At least one of; then adding the solvent, CX1-3The molar ratio to the solvent is 1: (20-1100), adding into a 5 mL glass bottle; then respectively dripping 20 mu L of oleylamine and 500 mu L of oleic acid into a glass bottle by using a liquid-transferring gun, then putting the glass bottle into a magnetic stirrer for stirring until the solution is clear and transparent, filtering the clear and transparent mixed solution by using a polytetrafluoroethylene filter tip with the diameter of 200 nanometers, and taking the filtered solution as the perovskite precursor solution A;
the second step is that: putting the perovskite precursor solution A into a 100 mL beaker, carrying out magnetic stirring, dropwise adding an anti-solvent into the solution by using a liquid-transferring gun while stirring, wherein the dropping speed is 5 mu L-2 mL/min, and the added volume ratio is that of the perovskite precursor: antisolvent = 1: (2-200), continuously stirring for 3 hours to obtain a perovskite material suspension;
the third step: 10 mL of perovskite material suspension is taken out and put into a centrifuge tube for centrifugal separation, the first centrifuge rotation speed is 6000 plus 10000 rpm, the time is 1-15 minutes, after centrifugation, a lower precipitate is obtained, then an antisolvent (2-50 mL) is added into the lower precipitate, after ultrasonic dispersion for 30 minutes, second centrifugation is carried out, the second centrifuge rotation speed is 4000-5000 rpm, the time is 1-15 minutes, after centrifugation, a supernatant is obtained, and the perovskite quantum dot solution B is obtained;
the fourth step: and then taking the perovskite quantum dot solution B in a nitrogen atmosphere, and slowly adding a metal or nonmetal organic compound into the perovskite quantum dot solution B for multiple times, wherein the addition amount of each time is that the mass ratio of the perovskite quantum dot solution to the metal or nonmetal organic compound is 1: (0.00001-0.1), the adding rate is 1 muL-3 mL/min, oxygen or sulfur powder is added after each addition, and the molar ratio of the oxygen or sulfur powder to the metal or nonmetal organic compound is 1: (0.5-3), continuously and circularly adding a metal or nonmetal organic compound and oxygen or sulfur powder until the mass ratio of the perovskite quantum dot solution to the metal or nonmetal organic compound is 1: (0.0001-0.5); then filtering the solution by using a polytetrafluoroethylene filter with the diameter of 200 nanometers, wherein the solution obtained by filtering is a perovskite metal nonmetal compound core-shell quantum dot solution;
the fifth step: distilling the perovskite metal nonmetal compound core-shell quantum dot solution in the fourth step, removing the organic solvent, and drying the remained solid for 12 hours at 50 ℃ under the pressure of-0.1 MPa in a vacuum drying oven to obtain the perovskite metal nonmetal compound core-shell quantum dot material.
Further, the solvent is: at least one of Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), butyrolactone, and tetrahydrofuran.
Further, the anti-solvent is: at least one of toluene, xylene and n-hexane.
Further, the ligand is selected from at least one of carboxylate molecules and amine radical molecules;
the carboxylate-containing molecule is selected from saturated alkyl acids C comprising at least 3 carbon atomsnH2n+1COOH, n is more than or equal to 2 or unsaturated alkyl acid CnH2n-1COOH, n is more than or equal to 2; the carboxylate-containing molecule is at least one selected from acetic acid, stearic acid, formic acid, carbonic acid, isovaleric acid, valeric acid, trimethylacetic acid, basic acetic acid, tartaric acid and lauric acid;
the chemical formula of the molecule containing amine radical is RNH2Wherein R is a saturated straight-chain alkyl group or a saturated branched-chain alkyl group, orUnsaturated straight chain alkyl group or unsaturated branched chain alkyl group, or selected from aromatic base or alkylamine or aromatic amine with 2-25 carbon atoms.
Further, the metal or nonmetal organic compound: at least one of dimethyl zinc, diethyl zinc, dimethyl mercury, methyl lithium, methyl potassium, butyl lithium, ethyl methyl stannane, tetraethyl tin, dimethyl beryllium, tetramethyl germanium, trimethyl gallium, dimethyl cadmium, alkyl phosphine and alkyl indium;
the alkyl phosphine is composed of at least one of tri-n-octyl phosphine, triethyl phosphine, trimethyl phosphine, triisopropyl phosphine, diethyl phosphine, tri-n-propyl phosphine, diisobutyl phosphine, bis (dimethyl phosphine) methane, 1, 3-bis (biphenyl phosphine) propane, trivinyl phosphine and tert-butyl diethyl phosphine;
the alkyl indium is composed of at least one of trimethyl indium and triethyl indium.
Further, the perovskite core has a size in at least one dimension of 2 to 60 nm.
Further, the metal nonmetal compound shell layer is formed by MxNy, wherein M is at least one of Zn, Cd, In, Sn, Hg, Li, Be, Ge, Ga and P, and N is at least one of O, S; the value range of x and y is 0.01-10;
the size of the metal compound shell layer in at least one dimension is 0.1-40 nm.
The application also discloses application of the perovskite metal nonmetal compound core-shell quantum dots in gas sensors, pressure sensors and luminescent films.
Has the advantages that:
the application provides a perovskite metal nonmetal compound core-shell quantum dot and a preparation method and application thereof, and the perovskite metal nonmetal compound core-shell quantum dot has the following beneficial effects:
1. the application improves the water stability of the perovskite material, and the coated perovskite core-shell quantum dots MAPbBr32 mg of @ ZnO core-shell quantum dot is dissolved in 2 mL of aqueous solution, ultrasonic treatment is carried out for 30 min, the dispersion is uniform, then the obtained product is placed at room temperature for 30 days, the quantum yield is tested every other day, and the quantum yield is found to be from the first day92% of the total amount of the quantum dots, and 91% of the total amount of the quantum dots, the reduction is little, the fluorescence peak is 531.4 nm at the first day, and 531.5 nm at the thirtieth day, and basically no shift exists, but the non-coated quantum dots can be destroyed when being put into water, the fluorescence is quenched, and the quantum yield is reduced to almost 0. Therefore, the water stability of the perovskite quantum dot material is greatly improved by coating the shell layers of the metal and the non-metal compounds.
2. The application promotes the thermal stability of the perovskite material, and the coated perovskite core-shell quantum dot CsSnI3Putting 1 mg of @ ZnS core-shell quantum dot in an environment of 120 ℃, preserving heat for 24 hours, testing the quantum yield before and after heating, wherein the quantum yield before heating is 67 percent, the quantum yield after heating is 65 percent, the reduction degree is small, and directly putting CsSnI3The quantum dots are placed in an environment of 120 ℃, and the quantum yield is reduced from 58% to 9%, and the reduction range is large. Therefore, the coating of the metal or nonmetal compound improves the thermal stability of the perovskite quantum dot material.
Drawings
FIG. 1 shows GAPbI according to example 1 of the present application3@In2O3 (GA+: C(NH2)3 +Guanidine cation) core-shell quantum dots with a scale of 5 nm.
FIG. 2 shows a GAPbI according to example 4 of the present application3@Al2O3EPDM polymer flexible film pressure-resistance plot.
FIG. 3 shows CsSnI at different methane concentrations in example 5 of the present application3The @ ZnS core-shell quantum dot resistance-methane concentration curve.
FIG. 4 shows MAPbBr in example 6 of the present application3@ ZnO core-shell quantum dot luminescent film fluorescence spectrogram.
Fig. 5 is a structural diagram of a perovskite metal nonmetal compound core-shell quantum dot.
Detailed Description
The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings in the specification.
As shown in FIG. 5, the perovskite metal nonmetal compound core-shell quantum dot is composed of a perovskite core, a metal nonmetal compound shell and a ligand(ii) a Wherein the perovskite core has the structural formula ABX3、A4BX6、AB2X5、A2BX4、A3B2X9、Am- 1Bm+1X3m+1M is more than or equal to 2; wherein A is CH3NH3 +、NH2CHNH2 +、C(NH2)3 +、Cs+、Li+、Na+、K+、Rb+Or Q; wherein Q is selected from at least one of aryl or alkyl organic amine cation with the carbon atom number not less than 3; b is Pb2+、Cu2+、Sn2+、Mn2+、Zn2+、Cd2+、Ge2+、Sr2+、Eu2+、Yb2+、Bi3+、Sb3+、Tl3+、In3+、Cu+、Ag+At least one of (a); x is selected from anionic Cl-，Br-，I-，SCN-At least one of (1).
The perovskite core has a size in at least one dimension of 2-60 nm.
The metal nonmetal compound shell layer is formed by MxNy, wherein M is at least one of Zn, Cd, In, Sn, Hg, Li, Be, Ge, Ga and P, and N is at least one of O, S; the value range of x and y is 0.01-10;
the size of the metal compound shell layer in at least one dimension is 0.1-40 nm.
The preparation method of the perovskite metal nonmetal compound core-shell quantum dot comprises the following steps:
the first step is as follows: reacting CX1-3In a molar ratio of 1: (0.1-4), wherein CX1-3Selected from C1X, C2X2、C3X3Wherein C1 in C1X is selected from Cu+、Ag+At least one of (1), C2X2Wherein C2 is selected from Pb2+、Cu2+、Sn2+、Mn2+、Zn2 +、Cd2+、Ge2+、Sr2+、Eu2+、Yb2+At least one of (1), C3X3Wherein C3 is selected from Bi3+、Sb3+、Tl3+、In3+X is selected from Cl-，Br-，I-，SCN-At least one of; then adding the solvent, CX1-3The molar ratio to the solvent is 1: (20-1100), adding into a 5 mL glass bottle; then respectively dripping 20 mu L of oleylamine and 500 mu L of oleic acid into a glass bottle by using a liquid-transferring gun, then putting the glass bottle into a magnetic stirrer for stirring until the solution is clear and transparent, filtering the clear and transparent mixed solution by using a polytetrafluoroethylene filter tip with the diameter of 200 nanometers, and taking the filtered solution as the perovskite precursor solution A;
the second step is that: putting the perovskite precursor solution A into a 100 mL beaker, carrying out magnetic stirring, dropwise adding an anti-solvent into the solution by using a liquid-transferring gun while stirring, wherein the dropping speed is 5 mu L-2 mL/min, and the added volume ratio is that of the perovskite precursor: antisolvent = 1: (2-200), continuously stirring for 3 hours to obtain a perovskite material suspension;
the third step: 10 mL of perovskite material suspension is taken out and put into a centrifuge tube for centrifugal separation, the first centrifuge rotation speed is 6000 plus 10000 rpm, the time is 1-15 minutes, after centrifugation, a lower precipitate is obtained, then an antisolvent (2-50 mL) is added into the lower precipitate, after ultrasonic dispersion for 30 minutes, second centrifugation is carried out, the second centrifuge rotation speed is 4000-5000 rpm, the time is 1-15 minutes, after centrifugation, a supernatant is obtained, and the perovskite quantum dot solution B is obtained;
the fourth step: and then taking the perovskite quantum dot solution B in a nitrogen atmosphere, and slowly adding a metal or nonmetal organic compound into the perovskite quantum dot solution B for multiple times, wherein the addition amount of each time is that the mass ratio of the perovskite quantum dot solution to the metal or nonmetal organic compound is 1: (0.00001-0.1), the adding rate is 1 muL-3 mL/min, oxygen or sulfur powder is added after each addition, and the molar ratio of the oxygen or sulfur powder to the metal or nonmetal organic compound is 1: (0.5-3), continuously and circularly adding a metal or nonmetal organic compound and oxygen or sulfur powder until the mass ratio of the perovskite quantum dot solution to the metal or nonmetal organic compound is 1: (0.0001-0.5); then filtering the solution by using a polytetrafluoroethylene filter with the diameter of 200 nanometers, wherein the solution obtained by filtering is a perovskite metal nonmetal compound core-shell quantum dot solution;
the fifth step: distilling the perovskite metal nonmetal compound core-shell quantum dot solution in the fourth step, removing the organic solvent, and drying the remained solid for 12 hours at 50 ℃ under the pressure of-0.1 MPa in a vacuum drying oven to obtain the perovskite metal nonmetal compound core-shell quantum dot material.
The solvent is at least one of Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and butyrolactone.
The antisolvent is at least one of toluene, xylene and n-hexane.
The ligand is selected from at least one of carboxylate molecules and amine radical molecules;
the carboxylate-containing molecule is selected from saturated alkyl acids C comprising at least 3 carbon atomsnH2n+1COOH, n is more than or equal to 2 or unsaturated alkyl acid CnH2n-1COOH, n is more than or equal to 2; the carboxylate-containing molecule is at least one selected from acetic acid, stearic acid, formic acid, carbonic acid, isovaleric acid, valeric acid, trimethylacetic acid, basic acetic acid, tartaric acid and lauric acid;
the chemical formula of the molecule containing amine radical is RNH2Wherein R is a saturated straight-chain alkyl group or a saturated branched-chain alkyl group, or an unsaturated straight-chain alkyl group or an unsaturated branched-chain alkyl group, or is selected from an aromatic base or an alkylamine or aromatic amine with 2-25 carbon atoms.
The metal or nonmetal organic compound: at least one of triethyl aluminum, trimethyl aluminum, dimethyl zinc, diethyl zinc, dimethyl mercury, methyl lithium, methyl potassium, butyl lithium, ethyl methyl stannane, tetraethyl tin, dimethyl beryllium, tetramethyl germanium, trimethyl gallium, dimethyl cadmium, alkyl phosphine, and alkyl indium;
the alkyl phosphine is composed of at least one of tri-n-octyl phosphine, triethyl phosphine, trimethyl phosphine, triisopropyl phosphine, diethyl phosphine, tri-n-propyl phosphine, diisobutyl phosphine, bis (dimethyl phosphine) methane, 1, 3-bis (biphenyl phosphine) propane, trivinyl phosphine and tert-butyl diethyl phosphine;
the alkyl indium is composed of at least one of trimethyl indium and triethyl indium.
Example 1:
preparation of GAPbI by perovskite metal nonmetal compound core-shell quantum dot3@In2O3The core-shell quantum dot comprises the following steps:
the first step is as follows: 0.2 mmol of GAI and 0.2 mmol of PbI2And 1mL of Dimethylformamide (DMF) was added to a 5 mL glass bottle, wherein GAI was guanidine iodide (CAS number: 19227-70-4, chemical formula: CH)6N3I) (ii) a Then respectively dripping 20 mu L of oleylamine and 500 mu L of oleic acid into the glass bottle by using a liquid-transferring gun, and then putting the glass bottle into a magnetic stirrer for stirring until the solution is clear and transparent to obtain a perovskite precursor solution A; putting the perovskite precursor solution A into a 100 mL beaker, performing magnetic stirring, slowly dropwise adding 80 mL of toluene solution into the beaker while stirring, after dropwise adding, putting the beaker into a centrifuge tube, centrifuging the centrifuge tube in a centrifuge with the rotation speed of 8000 rpm, taking down the precipitate, and performing ultrasonic dispersion for 30 min by using 10 mL of toluene solution; putting the perovskite quantum dot into a centrifugal tube, centrifuging the perovskite quantum dot in a centrifugal machine at the rotating speed of 4000 rpm, and taking supernate to obtain perovskite quantum dot solution B;
the second step is that: and then slowly adding 1 mu L of triethyl indium into the perovskite quantum dot solution B, carrying out magnetic stirring in the adding process, uniformly dispersing once, and gradually connecting the triethyl indium with the surface of the perovskite quantum dot along with the reaction to obtain the perovskite quantum dot solution C. Then In the process of magnetic stirring, slowly introducing oxygen into the perovskite quantum dot solution C at the introduction rate of 0.1 mL/min, and forming In with surface triethyl indium after the oxygen is introduced2O3Introducing into shell for 2 min to obtain GAPbI3@In2O3Core-shell quantum dot colloidal solution D, then filtering the solution D by a polytetrafluoroethylene filter head with the diameter of 0.2 mu m, putting the obtained filtrate at 30 DEG CDistilling under reduced pressure of 0.1 MPa, and removing solvent to obtain GAPbI3@In2O3A core-shell quantum dot powder material. A photograph thereof under a transmission scanning electron microscope (TEM, model: JEOL JEM-2100, Japan Electron Ltd.) is shown in FIG. 1, and it can be seen that the size thereof is about 5 nm, wherein the core layer is about 4 nm and the shell layer is about 1 nm.
Example 2:
perovskite metal nonmetal compound core-shell quantum dot for preparing CsSnI3The @ ZnS core-shell quantum dot comprises the following steps:
the first step is as follows: adding 0.2 mmol CsI and 0.2 mmol SnI2And 1mL of dimethyl sulfoxide (DMSO) was added to a 5 mL glass vial; then respectively dripping 20 mu L of oleylamine and 500 mu L of oleic acid into the glass bottle by using a liquid-transferring gun, and then putting the glass bottle into a magnetic stirrer for stirring until the solution is clear and transparent to obtain a perovskite precursor solution A; putting the perovskite precursor solution A into a 100 mL beaker, performing magnetic stirring, slowly dropwise adding 80 mL of toluene solution into the beaker while stirring, after dropwise adding, putting the beaker into a centrifuge tube, centrifuging the centrifuge tube in a centrifuge with the rotation speed of 8000 rpm, taking down the precipitate, and performing ultrasonic dispersion for 30 min by using 10 mL of toluene solution; putting the perovskite quantum dot into a centrifugal tube, centrifuging the perovskite quantum dot in a centrifugal machine at the rotating speed of 4000 rpm, and taking supernate to obtain perovskite quantum dot solution B;
the second step is that: and then slowly adding 1 mu L of dimethyl zinc into the perovskite quantum dot solution B, carrying out magnetic stirring in the adding process, uniformly dispersing once, and gradually connecting the dimethyl zinc with the surface of the perovskite quantum dot along with the reaction to obtain the perovskite quantum dot solution C. Then slowly adding elemental sulfur powder into the perovskite quantum dot solution C in the process of magnetic stirring, wherein the adding amount is 1 mmol, and after the elemental sulfur powder is added, forming a ZnS shell layer with surface dimethyl zinc to obtain CsSnI3The @ ZnS core-shell quantum dot colloidal solution D is filtered by a polytetrafluoroethylene filter head with the diameter of 0.2 mu m, the obtained filtrate is put at 30 ℃ and under the pressure of-0.1 MPa, reduced pressure distillation is carried out, the solvent is removed, and the CsSnI is obtained3The material is a @ ZnS core-shell quantum dot powder material.
Example 3:
preparation of MAPbBr by perovskite metal nonmetal compound core-shell quantum dot3@ ZnO core-shell quantum dot comprises the following steps:
the first step is as follows: 0.2 mmol of MABr (methylamine bromide) and 0.2 mmol of PbBr2And 1mL of dimethyl sulfoxide (DMSO) was added to a 5 mL glass vial; then respectively dripping 20 mu L of n-octylamine and 500 mu L of oleic acid into a glass bottle by using a liquid-transferring gun, and then putting the glass bottle into a magnetic stirrer for stirring until the solution is clear and transparent to obtain a perovskite precursor solution A; putting the perovskite precursor solution A into a 100 mL beaker, performing magnetic stirring, slowly dropwise adding 80 mL of toluene solution into the beaker while stirring, after dropwise adding, putting the beaker into a centrifuge tube, centrifuging the centrifuge tube in a centrifuge with the rotation speed of 8000 rpm, taking down the precipitate, and performing ultrasonic dispersion for 30 min by using 10 mL of toluene solution; putting the perovskite quantum dot into a centrifugal tube, centrifuging the perovskite quantum dot in a centrifugal machine at the rotating speed of 4000 rpm, and taking supernate to obtain perovskite quantum dot solution B;
the second step is that: and then slowly adding 1 mu L of diethyl zinc into the perovskite quantum dot solution B, carrying out magnetic stirring in the adding process, uniformly dispersing once, and gradually connecting the diethyl zinc with the surface of the perovskite quantum dot along with the reaction to obtain the perovskite quantum dot solution C. Then in the process of magnetic stirring, slowly introducing oxygen into the perovskite quantum dot solution C at the introduction rate of 0.1 mL/min, forming a ZnO shell layer with the surface diethyl zinc after the oxygen is introduced, and introducing for 1 min to obtain MAPbBr3@ ZnO core-shell quantum dot colloidal solution D, filtering the solution D with a polytetrafluoroethylene filter head with the diameter of 0.2 μm, distilling the obtained filtrate at 30 ℃ and-0.1 MPa under reduced pressure, and removing the solvent to obtain MAPbBr3@ ZnO core-shell quantum dot powder material.
Example 4:
a perovskite metal non-metallic compound core-shell quantum dot and a pressure sensor are applied, and the method comprises the following steps:
the first step is as follows: for the GAPbI obtained in example 13@In2O3The core-shell quantum dots are subjected to a pressure-resistance test,the testing instrument is an SHK-A101 electronic universal material testing machine, namely a METRAHIT 2+ digital multimeter. The results are shown in FIG. 4, from which it can be seen that GAPbI3@In2O3The resistance value of the core-shell quantum dot has a very good linear relation with the change of pressure, and the resistance value is gradually reduced with the increase of the pressure. Meanwhile, the composition has good recovery, and 10000 times of cyclic pressure test in the range of 0-500N show that the GAPbI3@In2O3Compared with the first time, the error of the resistance value of the core-shell quantum dot along with the pressure change is less than 0.1 percent, which shows that the GAPbI3@In2O3The core-shell quantum dots can well sense the pressure, and the pressure is in the GAPbI3@In2O3When the core-shell quantum dots bear different pressures, the GAPbI is measured3@In2O3The core-shell quantum dot resistance value can obtain the pressure, and the pressure sensor can be used as a pressure sensor.
Example 5:
the application of the perovskite metal nonmetal compound core-shell quantum dot and the methane gas sensor comprises the following steps:
the first step is as follows: the CsSnI obtained in example 23Putting the @ ZnS core-shell quantum dots into air atmosphere with different methane concentrations, and collecting CsSnI under the irradiation of a 365 nm ultraviolet lamp with 5W power3The resistance value of the @ ZnS core-shell quantum dot is changed. The testing instrument is an AGILENT 7890A/5975C gas chromatography-mass spectrometer and a METRAHIT 2+ digital multimeter. The results are shown in FIG. 5, CsSnI3The linear relation that the resistance value of the @ ZnS core-shell quantum dot is reduced along with the increase of the methane gas content, the resistance value variation is good along with the change of the methane gas content, the linear relation is good because the linear relation can be used for preparing a methane gas sensor, the methane concentration in the air at the moment can be obtained through the resistance value under the methane atmosphere with different concentrations, and the linear relation is based on CsSnI3The @ ZnS core-shell quantum dot methane gas sensor has good recoverability, and when gas is charged and discharged 6000 times, the film resistance is 125K omega and 125.1K omega respectively at the beginning and 6000 times of the film resistance under the concentration of 1%, and basically has no change, which indicates that the recoverability is good and can be used for a long time.
Example 6:
a perovskite metal non-metallic compound core-shell quantum dot is applied to an optical film and comprises the following steps:
the first step is as follows: take MAPbBr in example 33@ ZnO core-shell quantum dot 1 mg dissolved in 1mL toluene solution, ultrasonically treated for 30 min, uniformly dispersed, then spin-coated on a glass substrate at the rotating speed of 4000 rpm, placed on a 50 ℃ hot stage, heated and volatilized for 1 hour, and MAPbBr is obtained after the toluene solvent is completely volatilized3The @ ZnO core-shell quantum dot light-emitting film is aligned and subjected to spectrum testing, and a fluorescence spectrophotometer (model: FLS980, Edinburgh instruments) is adopted for testing, wherein the fluorescence light-emitting peak of the light-emitting film is 531.6 nm, and the half-peak width (FWHM) is 14.67 nm.
Finally, it should be understood that the above-described preferred embodiments are merely illustrative of the technical solutions of the present application and are not intended to limit the present application, and although the present application has been described in detail through the above-described preferred embodiments, it should be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the present application, and any changes, equivalents, improvements, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (9)

1. A perovskite metal non-metallic compound core-shell quantum dot is characterized in that: the perovskite metal nonmetal compound core-shell quantum dot is composed of a perovskite core, a metal nonmetal compound shell and a ligand;
wherein the perovskite core has the structural formula ABX3、A4BX6、AB2X5、A2BX4、A3B2X9、Am-1Bm+1X3m+1M is more than or equal to 2,
wherein A is CH3NH3 +、NH2CHNH2 +、C(NH2)3 +、Cs+、Li+、Na+、K+、Rb+Or Q;
wherein Q is selected from at least one of aryl or alkyl organic amine cation with the carbon atom number not less than 3;
b is Pb2+、Cu2+、Sn2+、Mn2+、Zn2+、Cd2+、Ge2+、Sr2+、Eu2+、Yb2+、Bi3+、Sb3+、Tl3+、In3+、Cu+、Ag+At least one of (a);
x is selected from anionic Cl-，Br-，I-，SCN-At least one of (1).
2. A preparation method of perovskite metal nonmetal compound core-shell quantum dots is characterized by comprising the following steps:
the first step is as follows: reacting CX1-3In a molar ratio of 1: (0.1-4), wherein CX1-3Selected from C1X, C2X2、C3X3Wherein C1 in C1X is selected from Cu+、Ag+At least one of (1), C2X2Wherein C2 is selected from Pb2+、Cu2+、Sn2+、Mn2+、Zn2+、Cd2 +、Ge2+、Sr2+、Eu2+、Yb2+At least one of (1), C3X3Wherein C3 is selected from Bi3+、Sb3+、Tl3+、In3+X is selected from Cl-，Br-，I-，SCN-At least one of; then adding the solvent, CX1-3The molar ratio to the solvent is 1: (20-1100), adding into a 5 mL glass bottle; then respectively dripping 20 mu L of oleylamine and 500 mu L of oleic acid into a glass bottle by using a liquid-transferring gun, then putting the glass bottle into a magnetic stirrer for stirring until the solution is clear and transparent, filtering the clear and transparent mixed solution by using a polytetrafluoroethylene filter tip with the diameter of 200 nanometers, and taking the filtered solution as the perovskite precursor solution A;
the second step is that: putting the perovskite precursor solution A into a 100 mL beaker, carrying out magnetic stirring, dropwise adding an anti-solvent into the solution by using a liquid-transferring gun while stirring, wherein the dropping speed is 5 mu L-2 mL/min, and the added volume ratio is that of the perovskite precursor: antisolvent = 1: (2-200), continuously stirring for 3 hours to obtain a perovskite material suspension;
the third step: 10 mL of perovskite material suspension is taken out and put into a centrifuge tube for centrifugal separation, the first centrifuge rotation speed is 6000 plus 10000 rpm, the time is 1-15 minutes, after centrifugation, a lower precipitate is obtained, then an antisolvent (2-50 mL) is added into the lower precipitate, after ultrasonic dispersion for 30 minutes, second centrifugation is carried out, the second centrifuge rotation speed is 4000-5000 rpm, the time is 1-15 minutes, after centrifugation, a supernatant is obtained, and the perovskite quantum dot solution B is obtained;
the fourth step: and then taking the perovskite quantum dot solution B in a nitrogen atmosphere, and slowly adding a metal or nonmetal organic compound into the perovskite quantum dot solution B for multiple times, wherein the addition amount of each time is that the mass ratio of the perovskite quantum dot solution to the metal or nonmetal organic compound is 1: (0.00001-0.1), the adding rate is 1 muL-3 mL/min, oxygen or sulfur powder is added after each addition, and the molar ratio of the oxygen or sulfur powder to the metal or nonmetal organic compound is 1: (0.5-3), continuously and circularly adding a metal or nonmetal organic compound and oxygen or sulfur powder until the mass ratio of the perovskite quantum dot solution to the metal or nonmetal organic compound is 1: (0.0001-0.5); then filtering the solution by using a polytetrafluoroethylene filter with the diameter of 200 nanometers, wherein the solution obtained by filtering is a perovskite metal nonmetal compound core-shell quantum dot solution;
the fifth step: distilling the perovskite metal nonmetal compound core-shell quantum dot solution in the fourth step, removing the organic solvent, and drying the remained solid for 12 hours at 50 ℃ under the pressure of-0.1 MPa in a vacuum drying oven to obtain the perovskite metal nonmetal compound core-shell quantum dot material.
3. The preparation method of the perovskite metal nonmetal compound core-shell quantum dot according to claim 2, characterized in that: the solvent is at least one of Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and butyrolactone.
4. The preparation method of the perovskite metal nonmetal compound core-shell quantum dot according to claim 2, characterized in that: the antisolvent is at least one of toluene, xylene and n-hexane.
5. The preparation method of the perovskite metal nonmetal compound core-shell quantum dot according to claim 2, characterized in that: the ligand is selected from at least one of carboxylate molecules and amine radical molecules;
the carboxylate-containing molecule is selected from saturated alkyl acids C comprising at least 3 carbon atomsnH2n+1COOH, n is more than or equal to 2 or unsaturated alkyl acid CnH2n-1COOH, n is more than or equal to 2; the carboxylate-containing molecule is at least one selected from acetic acid, stearic acid, formic acid, carbonic acid, isovaleric acid, valeric acid, trimethylacetic acid, basic acetic acid, tartaric acid and lauric acid;
the chemical formula of the molecule containing amine radical is RNH2Wherein R is a saturated straight-chain alkyl group or a saturated branched-chain alkyl group, or an unsaturated straight-chain alkyl group or an unsaturated branched-chain alkyl group, or is selected from an aromatic base or an alkylamine or aromatic amine with 2-25 carbon atoms.
6. The preparation method of the perovskite metal nonmetal compound core-shell quantum dot according to claim 2, characterized in that: the metal or nonmetal organic compound is: at least one of dimethyl zinc, diethyl zinc, dimethyl mercury, methyl lithium, methyl potassium, butyl lithium, ethyl methyl stannane, tetraethyl tin, dimethyl beryllium, tetramethyl germanium, trimethyl gallium, dimethyl cadmium, alkyl phosphine and alkyl indium;
the alkyl phosphine is composed of at least one of tri-n-octyl phosphine, triethyl phosphine, trimethyl phosphine, triisopropyl phosphine, diethyl phosphine, tri-n-propyl phosphine, diisobutyl phosphine, bis (dimethyl phosphine) methane, 1, 3-bis (biphenyl phosphine) propane, trivinyl phosphine and tert-butyl diethyl phosphine;
the alkyl indium is composed of at least one of trimethyl indium and triethyl indium.
7. The perovskite metal nonmetal compound core-shell quantum dot according to claim 1, characterized in that: the perovskite core has a size in at least one dimension of 2-60 nm.
8. The perovskite metal nonmetal compound core-shell quantum dot according to claim 1, characterized in that: the metal nonmetal compound shell layer is formed by MxNy, wherein M is at least one of Zn, Cd, In, Sn, Hg, Li, Be, Ge, Ga and P, and N is at least one of O, S; the value range of x and y is 0.01-10;
the size of the metal compound shell layer in at least one dimension is 0.1-40 nm.
9. An application of the perovskite metal non-metal compound core-shell quantum dot in gas sensors, pressure sensors and luminescent films.
CN202011404302.7A 2020-12-04 2020-12-04 Perovskite metal nonmetal compound core-shell quantum dot and preparation method and application thereof Pending CN112646568A (en)

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CN114540024A (en) * 2022-02-22 2022-05-27 江苏烨湫传感科技有限公司 Perovskite quantum dot material with gas-sensitive property and application thereof
CN114637057A (en) * 2022-03-01 2022-06-17 中国矿业大学 High-stability perovskite quantum dot lens and preparation method thereof
CN114702949A (en) * 2022-04-06 2022-07-05 中国矿业大学 Perovskite quantum dot-polymer composite film and preparation method thereof
CN115627162A (en) * 2022-11-14 2023-01-20 兰州城市学院 Preparation method of high-stability overlong one-dimensional perovskite quantum dot array

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CN113881432A (en) * 2021-10-27 2022-01-04 河南科技大学 Ligand modified CsPbBr3Preparation method of quantum dot material
CN114540024A (en) * 2022-02-22 2022-05-27 江苏烨湫传感科技有限公司 Perovskite quantum dot material with gas-sensitive property and application thereof
CN114637057A (en) * 2022-03-01 2022-06-17 中国矿业大学 High-stability perovskite quantum dot lens and preparation method thereof
CN114702949A (en) * 2022-04-06 2022-07-05 中国矿业大学 Perovskite quantum dot-polymer composite film and preparation method thereof
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CN115627162A (en) * 2022-11-14 2023-01-20 兰州城市学院 Preparation method of high-stability overlong one-dimensional perovskite quantum dot array

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