CN112480927B - Quantum dot composite material and preparation method thereof - Google Patents
Quantum dot composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of quantum dot manufacturing, and provides a preparation method of a quantum dot composite material. The invention also provides a quantum dot composite material, a quantum dot composition containing the quantum dot composite material and a quantum dot device containing the quantum dot composite material. The invention has the beneficial effects that: the distance between the first quantum dots is large in spatial arrangement, so that the phenomena of energy transfer and self-absorption between the first quantum dots are greatly avoided; meanwhile, carriers move easily, and the composite material has high photoelectric conversion efficiency; in addition, the blue light absorption is increased, so that the practical use amount of the quantum dots is reduced in some application scenes.
Description
Technical Field
The invention belongs to the technical field of quantum dot manufacturing, and relates to a quantum dot composite material and a preparation method thereof.
Background
Solution semiconductor nanocrystals (solution quantum dots) with sizes in the quantum confinement range are receiving wide attention in the fields of biological imaging and marking, display, solar cells, light emitting diodes, single photon sources and the like due to unique optical properties. In particular, in the fields of biological labeling and imaging, light emitting diodes, lasers, quantum dot photovoltaic devices, and the like, the research work of quantum dots has become one of the hot spots. In the key core fields of display (quantum dot backlight television), illumination and the like which influence the daily life of people, quantum dots are already preliminarily applied in practice. When the inorganic semiconductor quantum dots are applied to the fields of LED, display and the like, the inorganic semiconductor quantum dots are generally required to be prepared into quantum dot films for use, but the distance between the quantum dots is too small, so that energy transfer and self-absorption phenomena occur, and the specific application of the quantum dots is adversely affected.
In recent years, in the fields of solar cells, quantum dot films, light emitting diodes, and the like, perovskite quantum dots have been receiving wide attention due to their various excellent characteristics and low manufacturing costs. By far, the highest photoelectric conversion efficiency of the reported perovskite quantum dots is 23.3%, which is already higher than that of the silicon solar cells widely adopted in the market at present. Meanwhile, the perovskite quantum dot is used as a luminescent material, and the full-color-domain coverage which can be achieved by the traditional inorganic semiconductor quantum dot (such as CdSe quantum dot, cdS quantum dot and the like) can be achieved by adjusting the proportion and the variety of elements in the perovskite quantum dot.
Disclosure of Invention
The invention aims to overcome the defects of excessive energy transfer and self-absorption phenomena of inorganic semiconductor quantum dots when the inorganic semiconductor quantum dots are applied in the prior art.
We know from the following energy transfer equation (where d is the distance between quantum dots): the larger the distance between quantum dots, the smaller the energy transfer.
Therefore, what is needed to overcome the above-mentioned drawbacks is to design and provide a technical solution to increase the relative distance between the inorganic semiconductor quantum dots and to stably maintain the relative distance.
In order to achieve the purpose, the technical scheme provided by the invention relates to a quantum dot composite material, a preparation method of the quantum dot composite material and a corresponding quantum dot device.
More specifically:
the invention provides a preparation method of a quantum dot composite material, which comprises the steps of mixing a first quantum dot with a halogen precursor solution obtained by mixing and reacting a metal halide, aliphatic amine and organic acid in advance, carrying out surface ligand exchange reaction to obtain a mixed solution, and then mixing and reacting the mixed solution with lead carboxylate and cesium carboxylate to obtain the quantum dot composite material.
A preferable embodiment obtained by optimizing the above-described embodiment: the first quantum dots are selected from II-VI compounds, III-V compounds, IV-VI compounds, IV elements or compounds, I-III-VI compounds, I-II-IV-VI compounds or a combination thereof, and more preferably the first quantum dots are selected from one or a combination of CdSe quantum dots, cdSe ZnSeS quantum dots, inP quantum dots, cdSe/CdS quantum dots, inP/ZnSe quantum dots and CdSZnSe quantum dots. The first quantum dots can be core-shell quantum dots, and can also be alloy quantum dots.
A preferable embodiment obtained by optimizing the above-described embodiment: the fatty amine is selected from one or a mixture of more of fatty primary amine and polyamino fatty amine; more preferably the polyamino fatty amines are diamino fatty amines; still preferably, the fatty amine is selected from any one or a combination of several of oleylamine, octylamine, hexylamine, octadecylamine and 1, 4-butanediamine.
A preferable embodiment obtained by optimizing the above-described embodiment: the metal halide is selected from any one or combination of cadmium halide, zinc halide, indium halide, copper halide, tin halide, manganese halide and iron halide.
A preferable embodiment obtained by optimizing the above-described embodiment: the organic acid is carboxylic acid; more preferably, the organic acid is selected from any one or a combination of oleic acid, formic acid, acetic acid, undecylenic acid, oxalic acid and dodecylbenzene sulfonic acid.
A preferable embodiment obtained by optimizing the above-described embodiment: the molar ratio of the lead carboxylate to the cesium carboxylate is 0.2-5, and the molar ratio of lead element in the lead carboxylate to halogen in the halogen precursor solution is less than 1/3.
A preferable embodiment obtained by optimizing the above-described embodiment: the lead carboxylate is selected from one or a combination of a plurality of lead carboxylates with carbon chain length of 8-22; more preferably, the cesium carboxylate is selected from one or more cesium carboxylate combinations with carbon chain lengths of 8-22.
A preferable embodiment obtained by optimizing the above-described embodiment: the reaction temperature for forming the halogen precursor solution is 100-250 ℃, the reaction temperature for the ligand exchange on the surface of the first quantum dot is 100-250 ℃, and the reaction temperature for mixing and reacting the mixed solution with the lead carboxylate and the cesium carboxylate is 30-250 ℃.
The invention also provides a quantum dot composite material prepared by the preparation method of any quantum dot composite material.
A preferable embodiment obtained by optimizing the above-described embodiment: the quantum dot composite material includes:
a first quantum dot and a perovskite quantum dot;
the surface of the first quantum dot is coated with perovskite quantum dots, and/or
The perovskite quantum dots are doped with first quantum dots.
The invention also provides a quantum dot composition comprising the quantum dot composite material.
In addition, the invention also provides a quantum dot device comprising the quantum dot composite material.
Compared with the prior art, the invention has the beneficial effects that:
by utilizing a special stable structure formed between the first quantum dots and the perovskite quantum dots, the first quantum dots are spaced apart from each other by a large distance, so that the energy transfer and self-absorption phenomena between the first quantum dots are avoided to a large extent; in addition, because the all-inorganic perovskite material belongs to an ionic material, the whole current carrier of the composite material can move very easily, so that the composite material brings new excellent characteristics for the final material, namely the photoelectric conversion efficiency of the composite material is greatly improved; meanwhile, after the first quantum dot and the perovskite quantum dot are combined with each other, the beneficial effect of increasing blue light absorption is also generated, so that the practical application scenes of the material are expanded, such as application scenes that the practical use amount of the quantum dot needs to be reduced.
Drawings
FIG. 1 is an electron micrograph of nuclear CdZnSeS quantum dots;
FIG. 2 is an electron micrograph of the perovskite quantum dots of example 1 in combination with core CdZnSeS quantum dots;
FIG. 3 is an electron micrograph of a nuclear CdSe quantum dot;
FIG. 4 is an electron micrograph of the perovskite quantum dots of example 9 in combination with core CdSe quantum dots.
Detailed Description
For further explanation, the following examples are provided so that those skilled in the art can clearly understand the gist of the present invention. It should be noted that the following embodiments are not intended to limit the technical solutions of the present invention, and those skilled in the art can analyze and understand the embodiments and make a series of modifications and equivalent substitutions on the technical solutions provided by the present invention in combination with the prior knowledge, and new technical solutions obtained by the modifications and equivalent substitutions are also included by the present invention.
Since the present invention cannot be exhaustive, some preferred features and preferred embodiments may be reasonably replaced or combined with each other, and thus the new embodiments are also encompassed by the present invention.
Since the invention relates to material selection, it is within the ability of the person skilled in the art to make reasonable guesses so that the inventive idea is applicable within the scope provided in the solution according to the invention. Therefore, the protection scope of the present invention should not be limited to the materials mentioned in the examples, and can be extended reasonably to other similar materials and related materials.
For the reader to better understand the subject matter of the present invention, a series of experimental data are specifically exemplified. The reader should have the general technical knowledge in the field when reading to facilitate an accurate understanding of the logical relationships included in the data.
The following includes the data content of the relevant experiments of examples 1 to 31 and 31. Wherein:
the synthesis procedure of the quantum dot composite materials of examples 1 to 31 was as follows: mixing a preset amount of metal halide, aliphatic amine and organic acid in a solvent ODE in a three-neck flask, and changing the temperature to a first reaction temperature for a first reaction time; injecting the first quantum dots, or changing the temperature to a second reaction temperature, wherein the second reaction time is long, and ligand exchange is carried out; or changing the temperature to a third reaction temperature, adding a preset amount of lead carboxylate and cesium carboxylate solution, reacting for a third reaction time, and stopping the reaction.
The procedure for testing the quantum dot composites of examples 1-31 was as follows: the fluorescence emission peak, the fluorescence half-peak width and the quantum efficiency of the above embodiments were tested using a fluorescence emission spectrometer. The quantum efficiency of the quantum dots of the above embodiments is tested, and the detection method of the quantum efficiency is as follows: the method comprises the steps of using a 450nm blue LED lamp as a light source, using an integrating sphere to respectively test the spectrum of the blue light source and the spectrum after penetrating through a quantum dot solution, and using the integral area of a spectrogram to calculate the luminous efficiency of the quantum dot, wherein the quantum efficiency = the emission peak area of the quantum dot/(the peak area of the blue light source-the area of the blue peak which is not absorbed after penetrating through the quantum dot solution) × 100%.
Example 1:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (3) synthesis of quantum dots. 1mmol of ZnBr 2 Mixing 1.2mL of oleylamine, 1mL of oleic acid and 10mL of ODE in a 100mL three-necked flask, heating to 120 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (the fluorescence peak position is 525 nm) with the absorbance of 50 at 450nm, heating to 200 ℃, reacting for 5 minutes, and exchanging ligands. The temperature is reduced to 150 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 2:
CdZnSeS/Cs-Pb-Cl (CsPbCl) 3 ) And (3) synthesis of quantum dots. 1mmol of ZnCl 2 Mixing 1.2mL of oleylamine, 1mL of oleic acid and 10mL of ODE in a 100mL three-necked flask, heating to 120 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (the fluorescence peak position is 525 nm) with the absorbance of 50 at 450nm, heating to 200 ℃, reacting for 5 minutes, and exchanging ligands. The temperature is reduced to 150 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 3:
CdZnSeS/Cs-Pb iodine (CsPbI) 3 ) And (3) synthesis of quantum dots. 1mmol of ZnI 2 Mixing 1.2mL of oleylamine, 1mL of oleic acid and 10mL of ODE in a 100mL three-necked flask, heating to 120 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (the fluorescence peak position is 525 nm) with the absorbance of 50 at 450nm, heating to 200 ℃, reacting for 5 minutes, and exchanging ligands. Cooling to 150 deg.C, adding 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL oilCesium acid solution, reacted for 5 minutes, and the reaction was stopped.
Example 4:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (3) synthesis of quantum dots. 1mmol of ZnBr 2 Mixing 1.2mL of oleylamine, 1mL of oleic acid and 10mL of ODE in a 100mL three-necked flask, heating to 120 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (the fluorescence peak position is 525 nm) with the absorbance of 50 at 450nm, heating to 200 ℃, reacting for 5 minutes, and exchanging ligands. The temperature is reduced to 50 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 5:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 Mixing 1.2mL of oleylamine, 1mL of oleic acid and 10mL of ODE in a 100mL three-necked flask, heating to 120 ℃ for reaction for 10 minutes, injecting InP/ZnSe alloy quantum dots (the position of a fluorescence peak is 610 nm) with the absorbance of 50 at 450nm, heating to 200 ℃, reacting for 5 minutes, and exchanging ligands. The temperature is reduced to 150 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 6:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (3) synthesis of quantum dots. 1mmol of MnBr 2 Mixing 1.2mL of oleylamine, 1mL of oleic acid and 10mL of ODE in a 100mL three-necked flask, heating to 120 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (the fluorescence peak position is 525 nm) with the absorbance of 50 at 450nm, heating to 200 ℃, reacting for 5 minutes, and exchanging ligands. The temperature is reduced to 150 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 7:
CdZnSeS/Cs lead bromine (CsPbBr) 3 ) And (3) synthesis of quantum dots. 1mmol of InCl 3 Mixing 1.2mL of oleylamine, 1mL of oleic acid and 10mL of ODE in a 100mL three-necked flask, heating to 120 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (the fluorescence peak position is 525 nm) with the absorbance of 50 at 450nm, heating to 200 ℃, reacting for 5 minutes, and exchanging ligands. The temperature is reduced to 150 ℃,0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution were added and the reaction was stopped after 5 minutes.
Example 8:
CdZnSeS/Cs lead bromine (CsPbBr) 3 ) And (3) synthesis of quantum dots. 1mmol of CuBr 2 1.2mL oleylamine, 1mL oleic acid and 10mL ODE were mixed in a 100mL three-necked flask, heated to 120 ℃ for 10 minutes of reaction, cdZnSeS alloy quantum dots with absorbance of 50 at 450nm (fluorescence peak position 525 nm) were injected, the temperature was raised to 200 ℃ for 5 minutes of reaction, and ligand exchange was performed. The temperature is reduced to 150 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 9:
CdSe/cesium lead bromide (CsPbBr) 3 ) And (4) synthesis of quantum dots. Adding 1mmol SnI 2 Mixing 1.2mL of oleylamine, 1mL of oleic acid and 10mL of ODE in a 100mL three-necked flask, heating to 120 ℃ for reaction for 10 minutes, injecting CdSe alloy quantum dots (the fluorescence peak position is 550 nm) with the absorbance of 50 at 450nm, heating to 200 ℃, reacting for 5 minutes, and exchanging ligands. The temperature is reduced to 150 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 10:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 Mixing 1.2mL of hexylamine, 1mL of oleic acid and 10mL of ODE in a 100mL three-neck flask, heating to 120 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (the fluorescence peak position is 525 nm) with the absorbance of 50 at 450nm, heating to 150 ℃, reacting for 5 minutes, and exchanging ligands. The temperature is reduced to 100 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 11:
CdZnSeS/Cs lead bromine (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 1.2mL of octadecylamine (solid at room temperature, added after heating), 1mL of oleic acid and 10mL of ODE were mixed in a 100mL three-necked flask, heated to 120 ℃ for reaction for 10 minutes, and the amount of CdZnSeS alloy with an absorbance of 50 at 450nm was injectedThe sub-spot (fluorescence peak position 525 nm), raise the temperature to 200 deg.C, react for 5 minutes, ligand exchange. The temperature is reduced to 150 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 12:
CdZnSeS/Cs lead bromine (CsPbBr) 3 ) And (3) synthesis of quantum dots. 1mmol of ZnBr 2 1.2mL of 1, 4-butanediamine, 1mL of oleic acid and 10mL of ODE were mixed in a 100mL three-necked flask, the mixture was heated to 120 ℃ to react for 10 minutes, cdZnSeS alloy quantum dots (fluorescence peak position 525 nm) having an absorbance of 50 at 450nm were injected to react for 5 minutes, ligand exchange was performed, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution were added to react for 5 minutes, and the reaction was stopped.
Example 13:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 Mixing 1.2mL oleylamine, 1mL formic acid and 10mL ODE in a 100mL three-necked flask, heating to 120 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (fluorescence peak position 525 nm) with absorbance of 100 at 450nm, reducing the temperature to 100 ℃, reacting for 5 minutes, carrying out ligand exchange, cooling to 30 ℃, adding 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution, reacting for 5 minutes, and stopping the reaction.
Example 14:
CdZnSeS/Cs lead bromine (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 Mixing 1.2mL oleylamine, 1mL oxalic acid and 10mL ODE in a 100mL three-necked flask, heating to 120 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (fluorescence peak position 525 nm) with absorbance of 100 at 450nm, heating to 150 ℃, reacting for 5 minutes, ligand exchanging, adding 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution, reacting for 5 minutes, and stopping the reaction.
Example 15:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 Mixing 1.2mL oleylamine, 1mL undecylenic acid and 10mL ODE in a 100mL three-necked flask, heating to 120 deg.C, reacting for 10 min, and injecting the mixture with absorbance of 50 at 450nmCdZnSeS alloy quantum dots (fluorescence peak position 525 nm), raising the temperature to 200 ℃, reacting for 5 minutes, and exchanging ligands. The temperature is reduced to 150 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 16:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 Mixing 1.2mL of oleylamine, 1mL of oleic acid and 10mL of ODE in a 100mL three-necked flask, heating to 120 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (the fluorescence peak position is 525 nm) with the absorbance of 50 at 450nm, heating to 200 ℃, reacting for 5 minutes, and exchanging ligands. The temperature is reduced to 150 ℃, 0.08mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 17:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 1.2mL oleylamine, 1mL oleic acid and 10mL ODE were mixed in a 100mL three-necked flask, heated to 120 ℃ for 10 minutes of reaction, cdZnSeS alloy quantum dots with absorbance of 50 at 450nm (fluorescence peak position 525 nm) were injected, the temperature was raised to 200 ℃ for 5 minutes of reaction, and ligand exchange was performed. The temperature is reduced to 150 ℃, 0.4mL of 0.5mmol/mL lead oleate and 0.2mL of 0.2mmol/mL cesium oleate solution are added, the reaction is carried out for 5 minutes, and the reaction is stopped.
Example 18:
CdZnSeS/Cs lead bromine (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 1.2mL oleylamine, 1mL oleic acid and 10mL ODE were mixed in a 100mL three-necked flask, heated to 120 ℃ for 10 minutes of reaction, cdZnSeS alloy quantum dots with absorbance of 50 at 450nm (fluorescence peak position 525 nm) were injected, the temperature was raised to 200 ℃ for 5 minutes of reaction, and ligand exchange was performed. The temperature is reduced to 150 ℃, 0.5mL of 0.5mmol/mL lead oleate and 0.5mL of 0.2mmol/mL cesium oleate solution are added, the reaction is carried out for 5 minutes, and the reaction is stopped.
Example 19:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 1.2mL oleylamine, 1mL oleic acid, and 10mL ODE in a 100mL three-necked flaskHeating to 120 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (the position of a fluorescence peak is 525 nm) with the absorbance of 50 at 450nm, reducing the temperature to 100 ℃, reacting for 5 minutes, and exchanging ligands. The temperature was raised to 150 ℃ and 0.5mL of 0.5mmol/mL lead oleate and 0.5mL of 0.2mmol/mL cesium oleate solution were added to react for 5 minutes, and the reaction was stopped.
Example 20:
CdZnSeS/Cs lead bromine (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 1.2mL oleylamine, 1mL oleic acid and 10mL ODE were mixed in a 100mL three-necked flask, heated to 120 ℃ for 10 minutes of reaction, cdZnSeS alloy quantum dots with absorbance of 50 at 450nm (fluorescence peak position 525 nm) were injected, the temperature was raised to 200 ℃ for 5 minutes of reaction, and ligand exchange was performed. The temperature is reduced to 30 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 21:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (3) synthesis of quantum dots. 1mmol of ZnBr 2 Mixing 1.2mL of oleylamine, 1mL of oleic acid and 10mL of ODE in a 100mL three-necked flask, heating to 120 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (the fluorescence peak position is 525 nm) with the absorbance of 50 at 450nm, heating to 200 ℃, reacting for 5 minutes, and exchanging ligands. The temperature is reduced to 100 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 22:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 Mixing 1.2mL oleylamine, 1mL oleic acid and 10mL ODE in a 100mL three-necked flask, heating to 120 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (fluorescence peak position 525 nm) with absorbance of 50 at 450nm, heating to 200 ℃, reacting for 5 minutes, ligand exchanging, adding 0.4mL 0.5mmol/mL lead oleate and 1mL 0.2mmol/mL cesium oleate solution, reacting for 5 minutes, and stopping the reaction.
Example 23:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 1.2mL oleylamine, 1mMixing L oleic acid and 10mL ODE in a 100mL three-neck flask, heating to 120 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (the position of a fluorescence peak is 525 nm) with the absorbance of 50 at 450nm, raising the temperature to 200 ℃, reacting for 5 minutes, and exchanging ligands. The temperature was raised to 250 ℃ and 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution were added to react for 5 minutes, and the reaction was stopped.
Example 24:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 1.2mL of octylamine, 1mL of oleic acid and 10mL of ODE are mixed in a 100mL three-neck flask, the temperature is raised to 120 ℃ for reaction for 10 minutes, cdZnSeS alloy quantum dots (the position of a fluorescence peak is 525 nm) with the absorbance of 50 at 450nm are injected, the temperature is raised to 150 ℃ for reaction for 5 minutes, and ligand exchange is carried out. 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium stearate solution were added and the reaction was stopped after 5 minutes.
Example 25:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 Mixing 1.2mL of oleylamine, 1mL of oleic acid and 10mL of ODE in a 100mL three-necked flask, heating to 120 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (the fluorescence peak position is 525 nm) with the absorbance of 100 at 450nm, heating to 250 ℃, reacting for 5 minutes, and exchanging ligands. The temperature is reduced to 150 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 26:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 Mixing 1.2mL oleylamine, 1mL acetic acid and 10mL ODE in a 100mL three-necked flask, heating to 120 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (fluorescence peak position 525 nm) with absorbance of 100 at 450nm, heating to 150 ℃, reacting for 5 minutes, ligand exchanging, adding 0.4mL of 0.5mmol/mL lead stearate and 1mL of 0.2mmol/mL cesium oleate solution, reacting for 5 minutes, and stopping the reaction.
Example 27:
CdZnSeS/Cs lead bromine (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of the active ingredient CdBr 2 1.2mL oleylamine, 1mL oleic acid and 10mL ODE were mixed in a 100mL three-necked flask, heated to 120 ℃ for 10 minutes of reaction, cdZnSeS alloy quantum dots with absorbance of 50 at 450nm (fluorescence peak position 525 nm) were injected, the temperature was raised to 200 ℃ for 5 minutes of reaction, and ligand exchange was performed. The temperature is reduced to 150 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 28:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 1.2mL oleylamine, 1mL oleic acid and 10mL ODE were mixed in a 100mL three-necked flask, heated to 100 ℃ for 10 minutes, and CdZnSeS alloy quantum dots (fluorescence peak position 525 nm) with absorbance of 50 at 450nm were injected, heated to 200 ℃ for 5 minutes, and subjected to ligand exchange. The temperature is reduced to 150 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 29:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 1.2mL oleylamine, 1mL oleic acid and 10mL ODE were mixed in a 100mL three-necked flask, heated to 200 ℃ and reacted for 10 minutes, cdZnSeS alloy quantum dots (fluorescence peak position 525 nm) with absorbance 50 at 450nm were injected, reacted for 5 minutes, and ligand exchange was performed. The temperature is reduced to 150 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 30:
CdZnSeS/Cs lead bromine (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 Mixing 1.2mL of oleylamine, 1mL of oleic acid and 10mL of ODE in a 100mL three-necked flask, heating to 250 ℃ for reaction for 10 minutes, injecting CdZnSeS alloy quantum dots (the position of a fluorescence peak is 525 nm) with the absorbance of 50 at 450nm, cooling to 200 ℃, reacting for 5 minutes, and exchanging ligands. The temperature is reduced to 150 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Example 31:
CdZnSeS/Cs-Pb-Br (CsPbBr) 3 ) And (4) synthesis of quantum dots. 1mmol of ZnBr 2 1.2mL oleylamine, 1mL dodecylbenzene sulfonic acid and 10mL ODE were mixed in a 100mL three-necked flask, heated to 150 ℃ for 10 minutes, injected with CdZnSeS alloy quantum dots (fluorescence peak position 525 nm) with absorbance of 50 at 450nm, heated to 200 ℃ for 5 minutes, and subjected to ligand exchange. The temperature is reduced to 150 ℃, 0.4mL of 0.5mmol/mL lead oleate and 1mL of 0.2mmol/mL cesium oleate solution are added for reaction for 5 minutes, and the reaction is stopped.
Experimental data:
electron microscopy results:
based on the principle that the contrast on an electron microscope is different due to the difference of elements between the first quantum dot material and the perovskite quantum dot, so that the first quantum dot material and the perovskite quantum dot can be visually distinguished, SEM scanning is respectively performed on example 1 and example 9, and the following results are obtained through observation: as can be seen from the comparison between fig. 1 and 2, and between fig. 3 and 4, the first quantum dots are successfully combined with the perovskite quantum dots, and the distance between the first quantum dots is effectively increased. In addition, as can be seen from fig. 4, in the material of example 9, most of the CdSe quantum dots contained in a single perovskite quantum dot are concentrated in the range of 1 to 4, which has a positive significance for increasing the distance between the first quantum dots.
In addition:
the halogen precursor solution obtained by mixing and reacting the metal halide, the aliphatic amine and the organic acid can exchange the ligand on the surface of the first quantum dot, and the main reasons are that: reacting organic acid with metal halide to generate metal salt and hydrogen halide, and further reacting hydrogen halide with aliphatic amine to obtain the compound with the general formula of R-NH 3 + X - Salts (X represents Cl, br,I, etc.). The salt comprising the above formula is capable of forming a halogen-containing ligand on the surface of the first quantum dot. The first quantum dot having the halogen ligand on the surface provides a function as a halogen precursor when the perovskite quantum dot is subsequently synthesized, so that the first quantum dot is combined with the perovskite quantum dot.
For what is shown above we can know: the specific kind and structure of the first quantum dot are not limited, and thus it may be arbitrarily selected from among group II-VI compounds, group III-V compounds, group IV-VI compounds, group IV elements or compounds, group I-III-VI compounds, group I-II-IV-VI compounds, or combinations thereof. More specifically, the quantum dots are selected from CdSe quantum dots, cdSnZnSeS quantum dots, inP quantum dots, cdSe/CdS quantum dots, inP/ZnSe quantum dots, cdSnZnSe quantum dots and the like singly or in combination. The specific structure can also be core-shell quantum dots or alloy quantum dots. The first quantum dot original surface ligand should be a series of ligands capable of being exchanged by amine, such as carboxylate ligand, phosphate ligand, phosphonic acid ligand, and the like.
The fatty amine is selected from one or more of fatty primary amine and polyamino fatty amine, such as saturated or unsaturated primary amine commonly used in the field; and the polyamino fatty amines are preferably diamino fatty amines; further preferably, the aliphatic amine is selected from any one or a combination of several of oleylamine, octylamine, hexylamine, octadecylamine and 1, 4-butanediamine. The fatty amine having the above chain length range is advantageous for improving the activity of the perovskite growth reaction.
The selection of the metal halide should follow the following principles: various types of metal halides that are soluble in the organic acids and aliphatic amines of the present invention at the various reaction temperatures mentioned herein, such as cadmium halides, zinc halides, indium halides, copper halides, tin halides, manganese halides, iron halides, and the like. The metal halides can thus be selected according to the above-mentioned principles, in any single choice or in combination among the substances mentioned.
The organic acid is preferably selected from carboxylic acid, more preferably, any one or combination of several of oleic acid, formic acid, acetic acid, undecylenic acid, oxalic acid and dodecylbenzene sulfonic acid, compared with other organic acid, the selection is favorable for improving the activity of perovskite growth reaction.
The molar ratio of the lead carboxylate to the cesium carboxylate is 0.2-5, and the molar ratio of the lead element in the lead carboxylate to the halogen in the halogen precursor solution is less than 1/3. Limiting the molar ratio of lead carboxylate and cesium carboxylate and the molar ratio of lead element and halogen within the above ranges is advantageous for improving the fluorescence quantum yield of the perovskite quantum dots.
In addition to the above examples, the lead carboxylate and cesium carboxylate may be arbitrarily selected within the following ranges: the lead carboxylate is selected from one or a combination of a plurality of lead carboxylates with carbon chain length of 8-22; meanwhile, preferably, the cesium carboxylate is selected from one or a combination of several of cesium carboxylate with carbon chain length of 8-22. The use of lead carboxylate and cesium carboxylate having the above chain length ranges is advantageous in improving the activity of the perovskite-forming reaction.
ODE is one of the solvents, and other solvents commonly used in the field can be selected as the substitute. The bonding mode between the first quantum dot and the perovskite quantum dot is mainly embodied in one or two of the following two aspects: the surface of the first quantum dot is coated with the perovskite quantum dot, and the first quantum dot is doped in the perovskite quantum dot.
The reaction temperature for forming the halogen precursor solution may be selected to be any value of 100 to 250 ℃.
The temperature of the first quantum dot surface ligand exchange reaction can be selected to be any value in the range of 100-250 ℃.
The reaction temperature at which the mixed solution is mixed with lead carboxylate and cesium carboxylate and reacted may be any value from 30 to 250 ℃.
The distance between the first quantum dots of the quantum dot composite material is larger in spatial arrangement, so that the phenomena of energy transfer and self-absorption between the first quantum dots are greatly avoided; meanwhile, carriers move easily, and the composite material has high photoelectric conversion efficiency; in addition, the blue light absorption is increased, so that the practical use amount of the quantum dots is reduced in some application scenes.
Example 32
In view of the above examples 1 to 31, the present example provides a quantum dot composition of a quantum dot composite material.
Example 33:
in view of the above embodiments 1 to 31, the present embodiment provides a quantum dot device of a quantum dot composite material. The quantum dot device may be a thermal sensor, an image sensor, a display device, an optical device, or the like.
Based on the characteristics that the quantum dot composite material has high photoelectric conversion efficiency, and simultaneously has good blue light absorption performance. Therefore, the quantum dot device containing the quantum dot composite material has high luminous efficiency.
Claims (12)
1. A preparation method of a quantum dot composite material is characterized in that a first quantum dot and a halogen precursor solution obtained by mixing and reacting a metal halide, aliphatic amine and organic acid in advance are mixed and subjected to surface ligand exchange reaction to obtain a mixed solution, and then the mixed solution is mixed with lead carboxylate and cesium carboxylate and subjected to reaction to obtain the quantum dot composite material; the metal halide is selected from any one or combination of cadmium halide, zinc halide, indium halide, copper halide, tin halide, manganese halide and iron halide; the organic acid is carboxylic acid; the first quantum dot is selected from a group II-VI compound, a group III-V compound, a group IV-VI compound, a group IV element or compound, a group I-III-VI compound, a group I-II-IV-VI compound, or a combination thereof.
2. The preparation method of the quantum dot composite material according to claim 1, wherein the first quantum dot is selected from one or more of CdSe quantum dot, cdSnSeS quantum dot, inP quantum dot, cdSe/CdS quantum dot, inP/ZnSe quantum dot and CdSnZnSe quantum dot.
3. The preparation method of the quantum dot composite material according to claim 1, wherein the aliphatic amine is selected from one or a mixture of aliphatic primary amine and polyamino aliphatic amine.
4. The method of preparing a quantum dot composite material according to claim 3, wherein the polyamino fatty amine is a diamino fatty amine.
5. The method for preparing the quantum dot composite material according to claim 1, wherein the organic acid is selected from one or more of oleic acid, formic acid, acetic acid, undecylenic acid, oxalic acid and dodecylbenzene sulfonic acid.
6. The method for preparing the quantum dot composite material as claimed in claim 1, wherein the molar ratio of the lead carboxylate to the cesium carboxylate is 0.2 to 5, and the molar ratio of the lead element in the lead carboxylate to the halogen in the halogen precursor solution is less than 1/3.
7. The preparation method of the quantum dot composite material according to claim 1, wherein the lead carboxylate is selected from one or a combination of several of lead carboxylates with carbon chain length of 8-22; the cesium carboxylate is one or a combination of several of cesium carboxylate with carbon chain length of 8-22.
8. The method for preparing the quantum dot composite material according to claim 1, wherein the reaction temperature for forming the halogen precursor solution is 100 to 250 ℃, the reaction temperature for the ligand exchange reaction on the surface of the first quantum dot is 100 to 250 ℃, and the reaction temperature for mixing and reacting the mixed solution with the lead carboxylate and the cesium carboxylate is 30 to 250 ℃.
9. A quantum dot composite material, which is prepared by the preparation method of any one of claims 1 to 8.
10. The quantum dot composite of claim 9, comprising:
a first quantum dot and a perovskite quantum dot;
the surface of the first quantum dot is coated with perovskite quantum dots, and/or
The perovskite quantum dots are doped with first quantum dots.
11. A quantum dot composition comprising the quantum dot composite of claim 9 or 10.
12. A quantum dot device comprising the quantum dot composite material of claim 9 or 10.
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