CN112779012A - Core-shell luminescent quantum dot material and manufacturing method thereof - Google Patents
Core-shell luminescent quantum dot material and manufacturing method thereof Download PDFInfo
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Abstract
A core-shell luminescent quantum dot material comprises at least a core body, an element content decreasing region, a shell body and a zinc blende structure. The core body is an alloy core body, the core body forms a cadmium selenide alloy body, and the element content decreasing region decreases a cadmium element, a selenium element or both from a core part of the core body. The shell is formed by coating the core body, the shell is formed by a cubic crystal material, and the zinc blende structure is formed on the shell. The shell is a polygonal shell, and the sphalerite structure is formed by sphalerite type compounds. The zinc blende structure of the shell provides protection for the alloy type core body, and the zinc blende structure of the shell has water and oxygen corrosion resistance and provides thermal stability, so that the alloy type core body generates luminescence stability and provides quantum efficiency.
Description
Technical Field
The invention relates to a core-shell (core/shell) luminescent quantum dot (quantumdot) material and a manufacturing method thereof; in particular to a luminescent quantum dot material with an alloy core-shell and a manufacturing method thereof; more particularly, to a luminescent quantum dot material having an alloy core and a sphalerite structural shell layer and a method for manufacturing the same.
Background
For example, quantum dot materials are commonly used, such as: 'Quantum dot nanocrystal and quantum dot nanocrystal' of Taiwan patent publication No. TW-I620809Bulk solution the invention patent discloses a quantum dot nanocrystal. The quantum dot nanocrystal includes a core and a shell. The core has a core and an outer core layer, the outer core layer protrudes outward from the core, and the outer core layer is in the shape of an irregular layer on the surface of the core. Wherein the core is formed from compound M1xM21-xA1yA21-y0 < x ≦ 1, 0 < y ≦ 1, and the outer core layer is made of compound M1xM21-xA1yA21-y0 < x ≦ 1, 0 < y ≦ 1, and the energy gap of the outer core layer increasing away from the core, wherein M1 and M2 are selected from metals: zn, Sn, Pb, Cd, In, Ga, Cs, Ge, Ti and Cu, and the M1 is different from the M2. The A1 and A2 are selected from the elements: se, S, Te, P, As, N, O, Cl, Br and I. The shell is used to coat the core and is made of compound M1A2 or M2A 2.
Another commonly used quantum dot material, for example: the invention patent of 'super large quantum dot and forming method thereof' of Taiwan patent publication No. TW-I653318 discloses a super large quantum dot. The super-large quantum dot comprises a core, a shell and an alloy. The core is composed of CdSe and the shell is composed of ZnS, and the shell covers the surface of the core, and the alloy is formed between the core and the shell. The alloy is composed of Cd, Se, Zn and S, and the content of Cd and Se is gradually reduced from the core to the shell, and the content of Zn and S is gradually increased from the core to the shell. The particle size of the super-large quantum dot is larger than 10 nanometers, and the super-large quantum dot can emit light when being excited, and the super-large quantum dot has photoluminescence quantum efficiency larger than 90%.
Another commonly used quantum dot material, for example: the invention discloses a cadmium-free quantum dot ligand material and a manufacturing method thereof in Taiwan patent publication No. TW-I668294, which discloses a manufacturing method of the cadmium-free quantum dot ligand material. The manufacturing method of the cadmium-free quantum dot ligand material comprises the following steps: preparing a plurality of single precursors by using a plurality of metal complexes, mixing the plurality of single precursors according to a preset proportion to obtain a mixed solid precursor, dissolving and thermally cracking the mixed solid precursor in oleylamine liquid to form an uncapped quantum dot solution, performing a shell-coating reaction on the uncapped quantum dot solution in the oleylamine mixed solution to obtain a shell-coated quantum dot solution, and preparing the shell-coated quantum dot solution into a shell-coated quantum dot material.
Another commonly used quantum dot material, for example: the invention patent of 'blue-green light-emitting quantum dot and preparation method thereof' of Chinese patent publication No. CN-105802628 discloses a blue-green light-emitting quantum dot. The blue-green luminescent quantum dot comprises a core and a shell, wherein the core is selected from ZnnCd1-nSmSe1-mA core and the shell is located at the periphery of the core, wherein the ZnnCd1- nSmSe1-mN is more than 0 and less than 1 in the core, and m is more than or equal to 0 and less than or equal to 1. The shell is selected from a ZnS shell, a ZnSe shell or a CdS shell. The blue-green luminescent quantum dot takes ZnnCd1-nX quantum dots as cores to epitaxially grow ZnS, ZnSe or CdS shells, the lattice mismatch degree between core-shell structures is reduced by matching the core-shell structures while the quantum dot structures are simplified, and the blue-green luminescent quantum dot within the wavelength range of 450-550nm is formed, so that the maximum brightness of a QD-LED (light-emitting diode) utilizing the blue-green luminescent quantum dot can reach 4700cd/m2The above.
Another commonly used quantum dot material, for example: PCT patent publication No. WO-2015/117876, entitled "Quantum dots with organic ligands in an organic matrix," discloses a luminescent material based on Quantum dots. The quantum dot-based luminescent material includes a luminescent quantum dot having an inorganic coating agent, and the luminescent material includes a plurality of particles. The particle has an inorganic salt matrix, and the luminescent quantum dot with inorganic coating agent comprises the inorganic salt matrix, and the luminescent quantum dot has an outer layer.
However, there is still a need to provide a quantum dot material with improved luminescent stability, quantum efficiency, thermal stability or resistance to water and oxygen attack. The patents or patent applications of the aforementioned taiwan patent publication nos. TW-I620809, TW-I653318, TW-I668294, chinese patent publication No. CN-105802628 and PCT patent publication No. WO-2015/117876 are only for reference of the background of the present invention and to illustrate the current state of the art, and are not intended to limit the scope of the present invention.
Accordingly, the present invention is directed to a core-shell luminescent quantum dot material and a method for manufacturing the same, in which a cadmium selenide alloy body is formed on a core, the cadmium selenide alloy body has an element content decreasing region, a cadmium element, a selenium element or both are decreased from the core of the core, a shell is formed on the core, the shell is formed of a cubic material, and a zinc blende structure is formed on the shell, so as to improve the technical defects of poor luminescent stability, quantum efficiency, thermal stability or water and oxygen corrosion resistance of the conventional core-shell luminescent quantum dot material.
Disclosure of Invention
It is a primary objective of preferred embodiments of the present invention to provide a core-shell luminescent quantum dot material and a method for manufacturing the same, wherein a cadmium selenide alloy body is formed on a core, the cadmium selenide alloy body has an element content decreasing region, a cadmium element, a selenium element or both are decreased from the core of the core to the outside, a shell is formed on the core, the shell is formed of a cubic material, and a zinc blende structure is formed on the shell, so as to achieve the purpose of improving the luminescent stability, quantum efficiency, thermal stability or resistance to water and oxygen erosion.
In order to achieve the above objects, the core-shell luminescent quantum dot material according to the preferred embodiment of the present invention comprises:
at least one core body which is an alloy core body, wherein the core body is provided with a core part and forms a cadmium selenide alloy body;
an element content decreasing region that decreases an element of cadmium, an element of selenium, or both, outward from the core of the core;
a shell, which is formed on the core body in a coating way, and the shell is provided with a shell layer and an outer surface, the outer surface is positioned outside the shell layer, and the shell is formed by a cubic crystal system material; and
at least one sphalerite structure formed on the shell layer and the outer surface of the shell, wherein the shell is a polygonal shell and the sphalerite structure is formed by sphalerite type compounds;
the zinc blende structure of the shell provides protection for the alloy type core body, and has water and oxygen corrosion resistance and provides thermal stability, so that the alloy type core body generates luminescence stability and provides quantum efficiency.
The cadmium selenide alloy body of the alloy core body of the preferred embodiment of the invention is selected from a CdZnSe alloy body, an alloy body made of CdZnSe alloy, a CdZnSeS alloy body, an alloy body made of CdZnSeS alloy, a CdSeS alloy body, an alloy body made of CdSeS alloy or an alloy body of any combination thereof.
In the preferred embodiment of the present invention, the ratio of the cadmium element or the selenium element in the decreasing element content region is 0.1 mol% to 50 mol%, 10 mol% to 50 mol%, 30 mol% to 50 mol%, or other ranges.
The shell of the preferred embodiment of the invention is formed by a ZnS shell, a ZnSe shell, a ZnSeS shell, a CdS shell, a CdZnS shell, a CdSe shell or any combination thereof.
The outer surface of the housing of the preferred embodiment of the present invention has an angular polygonal surface.
The shell of the preferred embodiment of the present invention is a multi-layer composite shell including a plurality of shell thicknesses, the shell thicknesses decreasing in thickness from the core of the core.
In order to achieve the above objects, a method for manufacturing a core-shell luminescent quantum dot material according to a preferred embodiment of the present invention comprises:
performing a misfit activation on a first metal precursor solution to form an activated first metal precursor solution, wherein the activated first metal precursor solution comprises an activated first metal precursor, and the activated first metal precursor is an activated cadmium precursor;
adding a second metal precursor into the activated first metal precursor solution for misfit activation to form an activated first and second metal precursor solution;
adding a third metal ion solution into the activated first and second metal precursor solutions to perform a core particle reaction, wherein the third metal ion solution contains a third metal ion, and the third metal ion is a selenium ion, so as to form an alloy type core solution and a cadmium selenide alloy body, and the cadmium selenide alloy body has an element content decreasing area, and the element content decreasing area decreases a cadmium element, a selenium element or both from the core part of the core body;
adding a fourth ion solution into the alloy type core body solution to perform a first shell coating reaction so as to obtain an alloy type core-shell quantum dot solution; and
the alloy type nuclear-cladding quantum dot solution is prepared into an alloy type nuclear-cladding quantum dot material.
In order to achieve the above object, a method for manufacturing a core-shell luminescent quantum dot material according to another preferred embodiment of the present invention comprises:
performing a misfit activation on a first metal precursor solution to form an activated first metal precursor solution, wherein the activated first metal precursor solution comprises an activated first metal precursor, and the activated first metal precursor is an activated cadmium precursor;
adding a second metal precursor into the activated first metal precursor solution for misfit activation to form an activated first and second metal precursor solution;
adding a third metal ion solution into the activated first and second metal precursor solutions to perform a core particle reaction, wherein the third metal ion solution contains a third metal ion, and the third metal ion is a selenium ion, so as to form an alloy type core solution and a cadmium selenide alloy body, and the cadmium selenide alloy body has an element content decreasing area, and the element content decreasing area decreases a cadmium element, a selenium element or both from the core part of the core body;
adding a fourth ion solution into the alloy type core body solution to perform a first shell coating reaction so as to obtain an alloy type core-shell quantum dot solution, wherein the first shell coating reaction generates an alloy type core-shell quantum dot material;
mixing another second metal precursor and oleic acid to form a second metal precursor mixed solution, and adding the second metal precursor mixed solution into the alloy type core body solution to perform a second shell-wrapping reaction to obtain an alloy type core-multilayer shell quantum dot solution; and
the alloy type nuclear-multilayer cladding quantum dot solution is prepared into an alloy type nuclear-multilayer cladding quantum dot material.
In a preferred embodiment of the invention, the second shell reaction is carried out by adding additional dodecanethiol to the solution of the alloy core body.
In the preferred embodiment of the present invention, the first metal precursor solution is activated by adding oleylamine liquid and oleic acid solution.
The activated first and second metal precursor solutions of the preferred embodiment of the invention include an activated second metal precursor, and the second activated metal precursor is an activated zinc precursor.
The first metal precursor solution of the preferred embodiment of the present invention is selected from a cadmium-containing metal precursor solution.
The second metal precursor of the preferred embodiment of the present invention is selected from a zinc-containing metal precursor.
The third metal ion solution of the preferred embodiment of the present invention is selected from a mixed solution of third metal ions and fourth ions.
In the preferred embodiment of the present invention, the third metal ion solution is selected from a selenium-containing metal ion solution.
The fourth ionic solution of the preferred embodiment of the present invention is selected from a sulfur-containing anionic solution, a sulfur-containing and TOP anionic solution or a sulfur-containing and TBP anionic solution.
The invention has the beneficial effects that:
the invention provides a core-shell luminescent quantum dot material and a manufacturing method thereof, wherein a core body is formed into a cadmium selenide alloy body, the cadmium selenide alloy body is provided with an element content decreasing area, a cadmium element, a selenium element or both are decreased outwards from the core part of the core body in the element content decreasing area, a shell is coated on the core body and is formed by a cubic crystal material, and a zinc blende structure is formed on the shell, so that the purposes of improving the luminescent stability, the quantum efficiency, the thermal stability or the water and oxygen corrosion resistance of the shell are achieved.
Drawings
Fig. 1 is a schematic diagram of a core-shell luminescent quantum dot material according to a first preferred embodiment of the invention.
Fig. 2 is a block diagram illustrating a method for manufacturing a core-shell luminescent quantum dot material according to a first preferred embodiment of the invention.
Fig. 3 is a schematic view of a core-shell luminescent quantum dot material according to a second preferred embodiment of the invention.
Fig. 4 is a block diagram illustrating a method for manufacturing a core-shell luminescent quantum dot material according to a second preferred embodiment of the invention.
Fig. 5 is a schematic view of a core-shell luminescent quantum dot material according to a third preferred embodiment of the invention.
Fig. 6A is a transmission electron microscope image of the core-shell light-emitting quantum dot material according to the preferred embodiment of the invention.
Fig. 6B is a schematic view of a particle size distribution of the core-shell luminescent quantum dot material according to the preferred embodiment of the invention.
Fig. 6C is a schematic diagram of a diffraction pattern of an X-ray diffractometer of the core-shell luminescent quantum dot material according to the preferred embodiment of the present invention.
Fig. 7A is a transmission electron microscope image of the core-shell light-emitting quantum dot material according to another preferred embodiment of the invention.
Fig. 7B is a schematic view of a particle size distribution of a core-shell luminescent quantum dot material according to another preferred embodiment of the invention.
Fig. 7C is a schematic diagram of a diffraction pattern of an X-ray diffractometer for the core-shell luminescent quantum dot material according to another preferred embodiment of the present invention.
Fig. 8A is a schematic spectrum diagram of the relationship between different cadmium metal precursor concentrations and photoluminescence of the core-shell luminescent quantum dot material according to the preferred embodiment of the invention.
Fig. 8B is a schematic diagram illustrating a relationship between different cadmium metal precursor concentrations and photoluminescence wavelengths of the core-shell luminescent quantum dot material according to the preferred embodiment of the invention.
Fig. 9A is an image of cadmium and selenium displayed by scanning through an electron microscope-X-ray energy spectrum-two-dimensional element distribution manner by using a single core-shell luminescent quantum dot of the core-shell luminescent quantum dot material according to the preferred embodiment of the present invention.
Fig. 9B is an image of a single core-shell luminescent quantum dot of the core-shell luminescent quantum dot material displaying zinc and sulfur in a scanning transmission electron microscope-X-ray energy spectrum-two-dimensional element distribution manner according to the preferred embodiment of the present invention.
Fig. 9C is a schematic diagram of an X-ray mass spectrometer display element distribution image of a single core-shell luminescent quantum dot of the core-shell luminescent quantum dot material according to the preferred embodiment of the invention along the detection lines of fig. 9A and 9B.
Fig. 10 is a scanning transmission electron microscope image-high angle annular dark field image of the core-shell light-emitting quantum dot material according to the preferred embodiment of the invention.
Fig. 11 is a schematic diagram of a sphalerite structure of a core-shell luminescent quantum dot material according to a preferred embodiment of the invention.
Reference numerals
1: a core body; 11: an element content decreasing region; 2: a housing; 21: a first outer shell layer; 22: a second outer shell layer; 3: a sphalerite structure; a: cd element; b: se element; c: zn element; d: and (5) an S element.
Detailed Description
In order that the invention may be fully understood, there will now be described by way of example only preferred embodiments with reference to the accompanying drawings, in which the invention is not limited.
The core-shell luminescent quantum dot material and the manufacturing method thereof of the preferred embodiment of the invention can be applied to various fluorescent luminescent materials, light diffusion mixed materials, light diffusion film structures and devices thereof (such as displays or lighting devices); furthermore, the core-shell luminescent quantum dot material and the manufacturing method thereof according to the preferred embodiment of the present invention can be suitably used as a surface stabilizer, an adsorbent or a dispersion carrier of a quantum dot material or a fluorescent luminescent material, or can be selectively applied to the fields of materials, image display, optics or biomedicine or other technologies, but the present invention is not limited thereto.
Fig. 1 shows a schematic view of a core-shell luminescent quantum dot material according to a first preferred embodiment of the invention. Please refer to
As shown in fig. 1, for example, the core-shell luminescent quantum dot material according to the first preferred embodiment of the present invention comprises at least one core body 1, at least one element content decreasing region 11 (as schematically shown in the depth variation region of fig. 1), at least one shell 2, and a sphalerite structure 3 (as schematically shown in the fine dot of fig. 1).
Referring to fig. 1 again, for example, the core body 1 is an alloy type core body, and the core body 1 has a core portion in configuration, and the core body 1 forms a cadmium selenide alloy body. In addition, the cadmium selenide alloy body of the alloy core body is selected from a CdZnSe alloy body, an alloy body made of CdZnSe alloy, a CdZnSeS alloy body, an alloy body made of CdZnSeS alloy, a CdSeS alloy, or an alloy body made of CdSeS alloy or any combination thereof.
Referring again to FIG. 1, for example, the element content decreasing region 11 decreases a cadmium element, a selenium element, or both, outward from the core of the core 1. In addition, the proportion of the cadmium element or the selenium element in the decreasing element content region 11 is 0.1 mol% to 50 mol%, 10 mol% to 50 mol%, 30 mol% to 50 mol%, or other ranges.
Referring to fig. 1 again, for example, the shell 2 is formed on the core body 1, the shell 2 has a shell layer and an outer surface, the outer surface is located outside the shell layer 2, and the shell 2 is formed of a cubic material. The outer surface of the housing 2 has an angular polygonal surface. In addition, the housing 2 can be selected from a ZnS housing, a ZnSe housing, a ZnSeS housing, a CdS housing, a CdZnS housing, a CdSe housing, or any combination thereof.
Referring again to fig. 1, for example, the zincblende structure 3 is formed on the shell and the outer surface of the shell 2, the shell 2 is a polygonal shell, and the zincblende structure 3 is formed of a zincblende-type compound. The zincblende structure 3 of the shell 2 functionally provides protection for the alloy core, and the zincblende structure 3 of the shell 2 has a water and oxygen corrosion resistance and provides a thermal stability so that the alloy core produces a luminescence stability and provides a quantum efficiency (e.g., a quantum efficiency greater than 90% or 95%).
Fig. 2 is a block diagram illustrating a method for manufacturing a core-shell luminescent quantum dot material according to a first preferred embodiment of the invention, which corresponds to the core-shell luminescent quantum dot material shown in fig. 1. Referring to fig. 1 and fig. 2, a method for manufacturing (synthesizing) a core-shell luminescent quantum dot material according to a first preferred embodiment of the invention includes a first step S1: first, for example, a first metal precursor solution is subjected to a misfit activation to form an activated first metal precursor solution, and the activated first metal precursor solution includes an activated first metal precursor, and the activated first metal precursor is an activated cadmium precursor, i.e., the first metal precursor solution is optionally a cadmium-containing metal precursor solution.
Referring again to fig. 1 and 2, for example, the cadmium concentration of the cadmium-containing metal precursor solution may be selected from 0.04 mmol, 0.08 mmol, 0.14 mmol, 0.20 mmol, 0.42 mmol, 1.00 mmol, or other suitable concentrations.
Referring to fig. 1 and 2 again, for example, the first metal precursor solution is subjected to complexing activation by adding an oleylamine (oleylamine) liquid and an oleic acid (oleic acid) solution or other primary amine or oleylamine mixed solution. Alternatively, the first metal precursor solution may be prepared by adding a predetermined amount (e.g., a suitable small amount) of primary alkylamine (primary alkylamine), 12 amine (dedocylamine), 15 amine (pentadecylamine), 16 amine (hexadecylamine) or oleylamine (olecylamine) to the first metal precursor solution at a reaction temperature of 150 ℃ to 180 ℃ or other suitable reaction temperature.
Referring to fig. 1 and fig. 2 again, the method for manufacturing the core-shell luminescent quantum dot material according to the first preferred embodiment of the present invention includes a second step S2: then, for example, a second metal precursor is added to the activated first metal precursor solution to perform a misfit activation (e.g., at a reaction temperature between 300 ℃ and 320 ℃ or other suitable reaction temperature) to form an activated first and second metal precursor solution. The activated first and second metal precursor solutions include an activated second metal precursor, and the second activated metal precursor is an activated zinc precursor, i.e., the second metal precursor may be selected from a zinc-containing metal precursor (e.g., zinc at a concentration of 2.9 millimolar).
Referring to fig. 1 and fig. 2 again, the method for manufacturing the core-shell luminescent quantum dot material according to the first preferred embodiment of the present invention includes a third step S3: then, for example, a third metal ion solution is added to the activated first and second metal precursor solutions to perform a core particle reaction (e.g., 10 minutes or other reaction time), such as: the cadmium selenide alloy body is provided with an element content decreasing area, and the element content decreasing area decreases a cadmium element, a selenium element or both from the core part of the core body.
Referring to fig. 1 and 2 again, for example, the third metal ion solution is selected from a selenium-containing metal ion solution (e.g., selenium concentration of 1.5 mmol). Alternatively, the third metal ion solution may optionally comprise sulfur (e.g., sulfur concentration of 2.2 mmol), selenium and n-Trioctylphosphine (TOP) or sulfur, selenium and Tributylphosphine (TBP).
Referring again to fig. 1 and 2, for example, the third metal ion solution of another preferred embodiment of the present invention is selected from a mixed solution of third metal ions and fourth ions, so that a CdSeZnS core quantum dot or a similar CdSeZnS core quantum dot is selectively formed on the reaction of the core particles.
Referring to fig. 1 and fig. 2 again, the method for manufacturing a core-shell luminescent quantum dot material according to a first preferred embodiment of the present invention includes a fourth step S4: then, for example, a fourth ion solution is added to the alloy-type core-body solution to perform a first shell-covering reaction (e.g., 15 to 20 minutes or other reaction time) to obtain an alloy-type core-shell quantum dot solution.
Referring again to fig. 1 and 2, for example, the fourth ionic solution is selected from a stock solution of sulfur-containing anions, a solution of sulfur-containing and TOP anions (e.g., sulfur concentration of 2.0 mmol), or a solution of sulfur-containing and TBP anions. In addition, the first shell-coating reaction can be selected from the reaction temperature of 240 ℃ to 290 ℃ or other suitable reaction temperature.
Referring to fig. 1 and fig. 2 again, the method for manufacturing a core-shell luminescent quantum dot material according to a first preferred embodiment of the present invention includes a fifth step S5: then, for example, the alloy-type core-shell quantum dot solution is made into an alloy-type core-shell quantum dot material with a huge grain size (>13nm or >15 nm). For example, the present invention may choose to use a variety of different cladding materials, such as: various Zn salt cladding materials or other suitable salt cladding materials.
Fig. 3 is a schematic diagram of a core-shell luminescent quantum dot material according to a second preferred embodiment of the invention, which corresponds to the core-shell luminescent quantum dot material structure shown in fig. 1. Referring to fig. 3, for example, compared to the first embodiment, the core-shell luminescent quantum dot material of the second preferred embodiment of the present invention further includes a first shell layer 21 (e.g., ZnS), and the first shell layer 21 is suitably coated on the shell 2 (e.g., ZnS).
Referring to fig. 3, the shell 2 and the first outer shell 21 are formed as a multi-layer composite shell, and the shell 2 includes a plurality of shell thicknesses, and the plurality of shell thicknesses may be selected to decrease in thickness from the core of the core 1 or may be selected to increase in thickness from the core of the core 1.
Fig. 4 is a block diagram illustrating a method for manufacturing (synthesizing) a core-shell luminescent quantum dot material according to a second preferred embodiment of the invention, which corresponds to the core-shell luminescent quantum dot material of fig. 3. Referring to fig. 3 and 4, a method for manufacturing a core-shell luminescent quantum dot material according to a second preferred embodiment of the invention includes a first step S1: first, for example, a first metal precursor solution is subjected to a misfit activation to form an activated first metal precursor solution, and the activated first metal precursor solution includes an activated first metal precursor, and the activated first metal precursor is an activated cadmium precursor, i.e., the first metal precursor solution is optionally a cadmium-containing metal precursor solution.
Referring again to fig. 3 and 4, for example, the cadmium concentration of the cadmium-containing metal precursor solution may be selected from 0.04 mmol, 0.08 mmol, 0.14 mmol, 0.20 mmol, 0.42 mmol, 1.00 mmol, or other suitable concentrations.
Referring to fig. 3 and 4, for example, the first metal precursor solution is activated by adding oleylamine liquid and oleic acid solution or other primary amine or oleylamine mixed solution. Alternatively, the first metal precursor solution may be prepared by adding a predetermined amount of primary alkylamine (primary alkylamine), 12 amine (dedocylamine), 15 amine (pentacyclamine), 16 amine (hexacanamine) or oleylamine (oleylamine) at a reaction temperature of 150 ℃ to 180 ℃ or other suitable reaction temperature.
Referring to fig. 3 and 4 again, the method for manufacturing the core-shell luminescent quantum dot material according to the second preferred embodiment of the invention includes a second step S2: then, for example, a second metal precursor is added to the activated first metal precursor solution to perform a misfit activation (e.g., at a reaction temperature between 300 ℃ and 320 ℃ or other suitable reaction temperature) to form an activated first and second metal precursor solution. The activated first and second metal precursor solutions include an activated second metal precursor, and the second activated metal precursor is an activated zinc precursor, i.e., the second metal precursor may be selected from a zinc-containing metal precursor (e.g., zinc at a concentration of 2.9 millimolar).
Referring to fig. 3 and 4 again, the method for manufacturing the core-shell luminescent quantum dot material according to the second preferred embodiment of the invention includes a third step S3: then, for example, a third metal ion solution is added to the activated first and second metal precursor solutions to perform a core particle reaction (e.g., 10 minutes or other reaction time), and the third metal ion solution includes a third metal ion, and the third metal ion is a selenium ion, so as to form an alloy type core solution and a cadmium selenide alloy body, and the cadmium selenide alloy body has an element content decreasing region, and the element content decreasing region decreases a cadmium element, a selenium element or both from the core portion of the core body.
Referring to fig. 3 and 4 again, for example, the third metal ion solution is selected from a selenium-containing metal ion solution (e.g., selenium concentration of 1.5 mmol). Alternatively, the third metal ion solution may optionally comprise sulfur (e.g., 2.2 mmoles sulfur concentration), selenium and n-Trioctylphosphine Oxide (TOP) or comprise sulfur, selenium and Tributylphosphine (TBP).
Referring again to fig. 3 and 4, for example, in another preferred embodiment of the present invention, the third metal ion solution is selected from a mixed solution of third metal ions and fourth ions, so that a CdSeZnS core quantum dot or a similar CdSeZnS core quantum dot is selectively formed on the reaction of the core particles.
Referring to fig. 3 and 4 again, the method for manufacturing a core-shell luminescent quantum dot material according to a second preferred embodiment of the present invention includes a fourth step S4: then, for example, a fourth ion solution is added to the alloy-type core-body solution to perform a first shell-wrapping reaction (e.g., 15 to 20 minutes or other reaction time) to obtain an alloy-type core-shell quantum dot solution, and the first shell-wrapping reaction generates an alloy-type core-shell quantum dot material.
Referring again to fig. 3 and 4, for example, the fourth ionic solution is selected from a stock solution containing sulfur anions, a solution containing sulfur (e.g., sulfur concentration of 2.0 mmol) and TOP anions, or a solution containing sulfur and TBP anions. In addition, the first shell-coating reaction can be selected from the reaction temperature of 240 ℃ to 290 ℃ or other suitable reaction temperature.
Referring to fig. 3 and 4 again, the method for manufacturing a core-shell luminescent quantum dot material according to a second preferred embodiment of the invention includes a fifth (a) step S5A: then, for example, another second metal precursor and an oleic acid are mixed to form a second metal precursor mixed solution, and the second metal precursor mixed solution is added into the alloy-type core body solution to perform a second shell-wrapping reaction (for example, 30 minutes or other reaction time) to obtain an alloy-type core-multilayer cladding quantum dot solution.
Referring to fig. 3 and 4, the second metal precursor mixed solution is a zinc oleate (Zn-oleate) solution (transparent light yellow solution), and the reaction temperature of the second metal precursor mixed solution may be selected from 180 ℃ to 220 ℃ or other suitable reaction temperatures. In addition, the second shell-coating reaction can be carried out at a reaction temperature of 240-290 ℃ or at other suitable reaction temperatures.
Referring to fig. 3 and 4 again, the method for manufacturing a core-shell luminescent quantum dot material according to a second preferred embodiment of the present invention further includes the steps of: the second shell reaction is optionally carried out by adding additional dodecanethiol to the solution of the alloy core body at a reaction temperature between 180 c and 220 c or other suitable reaction temperature (e.g., 30 minutes or other reaction time).
Referring to fig. 3 and 4 again, the method for manufacturing a core-shell luminescent quantum dot material according to a second preferred embodiment of the present invention includes a sixth step S6: then, for example, the alloy type core-multilayer cladding quantum dot solution is made into an alloy type core-multilayer cladding quantum dot material with huge grain size (>13nm or >15 nm). For example, the present invention may choose to use a variety of different cladding materials, such as: various Zn salt cladding materials or other suitable salt cladding materials.
Fig. 5 is a schematic diagram of a core-shell luminescent quantum dot material according to a third preferred embodiment of the invention, which corresponds to the core-shell luminescent quantum dot material structures shown in fig. 1 and fig. 3. Referring to fig. 5, for example, compared to the first and second embodiments, the core-shell luminescent quantum dot material of the third preferred embodiment of the present invention further includes a second shell layer 22 (e.g., ZnS), and the second shell layer 22 is suitably wrapped on the shell 2 and the first shell layer 21.
Fig. 6A shows a Transmission Electron Microscope (TEM) image of the core-shell luminescent quantum dot material according to the preferred embodiment of the invention. Referring to fig. 6A, for example, the core-shell luminescent quantum dot material according to the preferred embodiment of the present invention generates a giant cdsenna quantum dot with the addition of hexadecylamine (hexadecaaniline).
Fig. 6B is a schematic diagram showing a particle size distribution of the core-shell luminescent quantum dot material according to the preferred embodiment of the invention, which corresponds to fig. 6A. Referring to fig. 6B, for example, the dispersion degree of the particle size of the core-shell luminescent quantum dot material according to the preferred embodiment of the invention is less than about 10%, and the average value of the particle size is about 15.36 ± 1.46nm, and the size is relatively uniform.
Fig. 6C shows a schematic diagram of an X-ray diffractometer (XRD) of the core-shell luminescent quantum dot material according to the preferred embodiment of the present invention, which corresponds to fig. 6A and 6B. Referring to fig. 6C, for example, the core-shell luminescent quantum dot material according to the preferred embodiment of the invention has a zinc-blend structure, as shown in the black bar of fig. 6C.
FIG. 7A shows a transmission electron microscope image of a core-shell light-emitting quantum dot material according to another preferred embodiment of the invention. Referring to fig. 7A, for example, the core-shell luminescent quantum dot material according to the preferred embodiment of the present invention still generates a huge CdSeZnS quantum dot without adding hexadecylamine.
Fig. 7B is a schematic diagram showing a particle size distribution of a core-shell luminescent quantum dot material according to another preferred embodiment of the invention, which corresponds to fig. 7A. Referring to fig. 7B, for example, the average particle size of the core-shell luminescent quantum dot material according to the preferred embodiment of the invention is about 13.87 ± 1.41nm, the dispersion degree of the particle size is about slightly larger than 10%, and the size of the particle size can be regarded as being relatively close to uniform.
Fig. 7C shows a diffraction pattern diagram of an X-ray diffractometer for the core-shell luminescent quantum dot material according to another preferred embodiment of the present invention, which corresponds to fig. 7A and 7B. Referring to fig. 7C, for example, the core-shell luminescent quantum dot material according to the preferred embodiment of the invention further has wurtzite (wurtzite) structure, as shown in the black bar of fig. 7C.
Fig. 8A shows a spectrum diagram of the relationship between different concentrations of cadmium metal precursor (concentration) and Photoluminescence (PL) of the core-shell luminescent quantum dot material according to the preferred embodiment of the invention. Referring to fig. 8A, for example, the core-shell luminescent quantum dot material according to the preferred embodiment of the invention selects three cadmium metal precursor concentrations, wherein the cadmium metal precursor concentrations are selected to be 0.14 mmol, 0.28 mmol and 1.00 mmol, and the corresponding luminescence wavelengths are 519nm (the leftmost peak in fig. 8A), 533nm (the middle peak in fig. 8A) and 625nm (the rightmost peak in fig. 8A).
Fig. 8B is a schematic diagram showing a relationship between different cadmium metal precursor concentrations and photoluminescence wavelengths of the core-shell luminescent quantum dot material according to the preferred embodiment of the invention, which corresponds to fig. 8A. Referring to fig. 8A, for example, the core-shell luminescent quantum dot material according to the preferred embodiment of the present invention generates red shift (519nm, 533nm, and 625nm) of luminescence with increasing concentration of the cadmium metal precursor (0.14 mmol, 0.28 mmol, and 1.00 mmol), and the maximum red shift is 620nm to 625 nm.
Fig. 9A shows a single (single) core-shell luminescent quantum dot of the core-shell luminescent quantum dot material according to the preferred embodiment of the invention, which displays an image of cadmium (Cd) element and selenium (Se) element by using the core-shell luminescent quantum dot in a scanning transmission electron microscope-X-ray energy spectrum-two-dimensional element distribution (STEM-EDS elemental mapping) manner. Referring to fig. 9A, for example, in a microstructure analysis, the core body of the single core-shell luminescent quantum dot of the preferred embodiment of the present invention has cadmium element a (red) and selenium element B (blue), and the core body mainly contains Cd, Zn, Se and S (e.g., radius ≦ 3 nm).
Fig. 9B shows an image of a single core-shell luminescent quantum dot of the core-shell luminescent quantum dot material according to the preferred embodiment of the invention, which shows zinc (Zn) and sulfur (S) in a scanning transmission electron microscope-X-ray energy spectrum-two-dimensional element distribution manner, which corresponds to fig. 9A. Referring to fig. 9B, for example, in a microstructure analysis, the shell of the single core-shell light-emitting quantum dot of the preferred embodiment of the present invention has zinc element C (actually showing green color) and sulfur element D (actually showing yellow color), and the shell mainly includes Zn and S.
Fig. 9C shows a schematic diagram of a single core-shell luminescent quantum dot of the core-shell luminescent quantum dot material according to the preferred embodiment of the invention along the probe line (probe line) of fig. 9A and 9B, which corresponds to fig. 9A and 9B, showing an element distribution image (elemental map) by an X-ray mass spectrometer (EDS). Referring to fig. 9A, 9B and 9C, for example, the core-shell luminescent quantum dot material according to the preferred embodiment of the present invention emits light with a red shift phenomenon as the concentration of the cadmium metal precursor increases.
Fig. 10 shows a scanning transmission electron microscope image-high angle annular dark field image (STEM-HAADF image) of the core-shell light-emitting quantum dot material according to the preferred embodiment of the present invention. Referring to fig. 10, for example, in a microstructure analysis, the core-shell luminescent quantum dot material according to a preferred embodiment of the present invention has various atoms arranged in a hexagonal form or a nearly hexagonal form.
Fig. 11 is a schematic diagram of a sphalerite structure of a core-shell luminescent quantum dot material according to a preferred embodiment of the invention, which corresponds to fig. 10. Referring to fig. 11, for example, in the micro-structure analysis, the core-shell luminescent quantum dot material according to the preferred embodiment of the present invention has a sphalerite structure from [110] direction in the simulation, i.e., is arranged in a hexagonal form.
The experimental data are preliminary experimental results obtained under specific conditions, which are only used for easy understanding or reference of the technical contents of the present invention, and other relevant experiments are required. The experimental data and the results are not intended to limit the scope of the present invention.
The foregoing description of the preferred embodiments is merely exemplary of the invention and its technical features, and the techniques of the embodiments may be suitably modified and/or substituted in various substantially equivalent manners; therefore, the scope of the present invention is subject to the scope defined by the appended claims.
Claims (10)
1. A core-shell luminescent quantum dot material, comprising:
at least one core body which is an alloy core body, wherein the core body is provided with a core part and forms a cadmium selenide alloy body;
an element content decreasing region that decreases an element of cadmium, an element of selenium, or both, outward from the core of the core;
a shell, which is formed on the core body in a coating way, and the shell is provided with a shell layer and an outer surface, the outer surface is positioned outside the shell layer, and the shell is formed by a cubic crystal system material; and
at least one sphalerite structure formed on the shell layer and the outer surface of the shell, wherein the shell is a polygonal shell and the sphalerite structure is formed by sphalerite type compounds;
the zinc blende structure of the shell provides protection for the alloy type core body, and has water and oxygen corrosion resistance and provides thermal stability, so that the alloy type core body generates luminescence stability and provides quantum efficiency.
2. The core-shell luminescent quantum dot material of claim 1, wherein the cadmium selenide alloy body of the alloy core is selected from a CdZnSe alloy body, an alloy body with a CdZnSe alloy, a CdZnSeS alloy body, an alloy body with a CdZnSeS alloy, a CdSeS alloy body, an alloy body with a CdSeS alloy, or an alloy body of any combination thereof.
3. The core-shell luminescent quantum dot material of claim 1, wherein the shell is selected from a ZnS shell, a ZnSe shell, a ZnSeS shell, a CdS shell, a CdZnS shell, a CdSe shell, or any combination thereof.
4. The core-shell luminescent quantum dot material of claim 1, wherein the outer surface of the shell has an angular polygonal surface.
5. The core-shell luminescent quantum dot material of claim 1, wherein the shell is a multilayer composite shell comprising a plurality of shell thicknesses, and wherein the shell thicknesses decrease from the core portion of the core body outward.
6. A method for manufacturing a core-shell luminescent quantum dot material, comprising:
performing a misfit activation on a first metal precursor solution to form an activated first metal precursor solution, wherein the activated first metal precursor solution comprises an activated first metal precursor, and the activated first metal precursor is an activated cadmium precursor;
adding a second metal precursor into the activated first metal precursor solution for misfit activation to form an activated first and second metal precursor solution;
adding a third metal ion solution into the activated first and second metal precursor solutions to perform a core particle reaction, wherein the third metal ion solution contains a third metal ion, and the third metal ion is a selenium ion, so as to form an alloy type core solution and a cadmium selenide alloy body, and the cadmium selenide alloy body has an element content decreasing area, and the element content decreasing area decreases a cadmium element, a selenium element or both from the core part of the core body;
adding a fourth ion solution into the alloy type core body solution to perform a first shell coating reaction so as to obtain an alloy type core-shell quantum dot solution; and
the alloy type nuclear-cladding quantum dot solution is prepared into an alloy type nuclear-cladding quantum dot material.
7. A method for manufacturing a core-shell luminescent quantum dot material, comprising:
performing a misfit activation on a first metal precursor solution to form an activated first metal precursor solution, wherein the activated first metal precursor solution comprises an activated first metal precursor, and the activated first metal precursor is an activated cadmium precursor;
adding a second metal precursor into the activated first metal precursor solution for misfit activation to form an activated first and second metal precursor solution;
adding a third metal ion solution into the activated first and second metal precursor solutions to perform a core particle reaction, wherein the third metal ion solution contains a third metal ion, and the third metal ion is a selenium ion, so as to form an alloy type core solution and a cadmium selenide alloy body, and the cadmium selenide alloy body has an element content decreasing area, and the element content decreasing area decreases a cadmium element, a selenium element or both from the core part of the core body;
adding a fourth ion solution into the alloy type core body solution to perform a first shell coating reaction so as to obtain a first alloy type-shell quantum dot solution, wherein the first shell coating reaction generates an alloy type core-shell quantum dot material; and
mixing another second metal precursor and oleic acid to form a second metal precursor mixed solution, and adding the second metal precursor mixed solution into the alloy type core body solution to perform a second shell-wrapping reaction to obtain an alloy type core-multilayer shell quantum dot solution; and
the alloy type nuclear-multilayer cladding quantum dot solution is prepared into an alloy type nuclear-multilayer cladding quantum dot material.
8. The method of manufacturing a core-shell luminescent quantum dot material according to claim 7, wherein dodecanethiol is additionally added to the alloy type core body solution to perform the second shell-wrapping reaction.
9. The method of claim 6 or 7, wherein the first metal precursor solution is activated by complexing by adding oleylamine liquid and oleic acid solution.
10. The method of claim 6 or 7, wherein the activated first and second metal precursor solutions comprise an activated second metal precursor, and the second activated metal precursor is an activated zinc precursor; or, the third metal ion solution is selected from a selenium-containing metal ion solution or a mixed solution of a third metal ion and a fourth ion.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101835875A (en) * | 2007-10-29 | 2010-09-15 | 伊斯曼柯达公司 | Making colloidal ternary nanocrystals |
| CN101901827A (en) * | 2010-07-16 | 2010-12-01 | 南京大学 | Core/shell type wurtzite/blende ZnS hetero nano structure and preparation method thereof |
| CN108822853A (en) * | 2017-05-26 | 2018-11-16 | 优美特创新材料股份有限公司 | Super large quantum dot and forming method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101835875A (en) * | 2007-10-29 | 2010-09-15 | 伊斯曼柯达公司 | Making colloidal ternary nanocrystals |
| CN101901827A (en) * | 2010-07-16 | 2010-12-01 | 南京大学 | Core/shell type wurtzite/blende ZnS hetero nano structure and preparation method thereof |
| CN108822853A (en) * | 2017-05-26 | 2018-11-16 | 优美特创新材料股份有限公司 | Super large quantum dot and forming method thereof |
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