TWI720671B - Core/shell quantum dot material and manufacturing method thereof - Google Patents

Abstract

A core/shell quantum dot material includes at least one core, an element descending portion, a shell and a zinc-blende structure. The core is an alloyed core as a CdSe-alloyed core. The element descending portion has a Cd element, a Se element or both descending from a center of the core to exterior. The shell is formed to cover the core and made from a material of cubic system. The shell is a polygon shell formed from a zinc-blende compound. The zinc-blende structure of the shell provides to protect the alloyed core, with the zinc-blende structure enhancing resistance capabilities of water or oxidation erosion and thermal stability which can provide stabilities of light emitting and further enhance QD efficiencies.

Description

Core-shell luminous quantum dot material and manufacturing method thereof

The present invention relates to a core-shell (core/shell) light-emitting quantum dot material and its manufacturing method; in particular, it relates to an alloy core-shell light-emitting quantum dot material and its manufacturing method; more particularly to a composite Gold core-luminescent quantum dot material with zinc blende structure shell and manufacturing method thereof.

For example, conventional quantum dot materials, such as the invention patent of "Quantum Dot Nanocrystals and Quantum Dot Nanocrystal Solutions" in the Republic of China Patent Publication No. TW-I620809, which 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, and the outer core layer protrudes outward from the core, and the outer core layer is an irregular layer shape on the surface of the core. The core is composed of compound M1 _x M2 _1-x A1 _y A2 _1-y , 0<x≦1, 0<y≦1, and the outer core layer is composed of compound M1 _x M2 _1-x A1 _y A2 _1-y , 0<x≦1, 0<y≦1, and the energy gap of the outer core layer gradually increases away from the core, wherein the M1 and M2 are selected from metals: Zn, Sn, Pb, Cd, In, Ga , Cs, Ge, Ti, and Cu, and the M1 and M2 are different. The A1 and A2 are selected from one of the elements: Se, S, Te, P, As, N, O, Cl, Br, and I. The shell is used to coat the core, and the shell is composed of the compound M1A2 or M2A2.

Another conventional quantum dot material, for example, the invention patent of "Super large number of dots and its formation method" of the Republic of China Patent Publication No. TW-I653318, which discloses a kind of ultra large number of dots. The super large number of sub-dots includes a core, a shell, and an alloy. The core is made of CdSe, and the shell is made 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 gradually decreases from the core to the shell, and the content of Zn and S gradually increases from the core to the shell. The particle size of the super large number of dots is greater than 10 nanometers, and the super large number of dots can emit light when excited, and it has a photoluminescence quantum efficiency greater than 90%.

Another conventional quantum dot material, such as the invention patent of "Cadmium-free Quantum Dot Ligand Material and Its Manufacturing Method" of the Republic of China Patent Publication No. TW-I668294, discloses a method for manufacturing a cadmium-free quantum dot ligand material. The manufacturing method of the cadmium-free quantum dot ligand material comprises: preparing several single precursors using several metal complexes, and mixing the several single precursors in a predetermined ratio to obtain a mixed solid precursor, and The mixed solid precursor is dissolved and thermally cracked in an oleylamine liquid to form an unencapsulated quantum dot solution, and then the unencapsulated quantum dot solution is subjected to an encapsulation reaction in an oleylamine mixed solution, A cladding quantum dot solution is obtained, and then the cladding quantum dot solution is made into a cladding quantum dot material.

m

1。該外殼選自一ZnS殼、一ZnSe殼或一CdS殼。該藍綠色發光量子點通過以ZnnCd1-nX量子點為核外延生長ZnS、ZnSe或CdS外殼，在簡化量子點結構的同時，通過匹配核殼結構，降低核殼結構間的晶格失配度，形成在450-550nm波長範圍內的藍綠色發光量子點，使得由利用該藍綠色發光量子點的QD-LED的最高亮度可達到4700cd/m²以上。 Another conventional quantum dot material, such as the invention patent of "Blue-green light-emitting quantum dots and its preparation method" of China Patent Publication No. CN-105802628, which discloses a blue-green light-emitting quantum dot. The blue-green light-emitting quantum dot includes a core and a shell, and the core is selected from a Zn _n Cd _1-n S _m Se _1-m core, and the shell is located on the periphery of the core, wherein the Zn _n Cd _{1- n} S _m Se _1-m core 0<n<1, 0

m

1. The shell is selected from a ZnS shell, a ZnSe shell or a CdS shell. The blue-green light-emitting quantum dots epitaxially grow ZnS, ZnSe or CdS shells with ZnnCd1-nX quantum dots as the core. While simplifying the structure of the quantum dots, by matching the core-shell structure, the lattice mismatch between the core-shell structures is reduced, The blue-green light-emitting quantum dots formed in the wavelength range of 450-550nm enable the highest brightness of the QD-LED using the blue-green light-emitting quantum dots to reach 4700 cd/m ² or more.

Another conventional quantum dot material, for example: PCT Patent Publication No. WO-2015/117876 "Quantum dots with inorganic ligands in an inorganic matrix" invention patent application, which discloses a quantum dot-based luminescent material. The quantum dot-based luminescent material includes a luminescent quantum dot, and the luminescent quantum dot has an inorganic coating agent, and the luminescent material includes a plurality of particles. The particles have an inorganic salt matrix, and the luminescent quantum dots with inorganic coatings include the inorganic salt matrix, and the luminescent quantum dots have an outer layer.

However, conventional quantum dot materials still have a potential need to further improve their luminescence stability, quantum efficiency, thermal stability, or resistance to water and oxygen. The aforementioned ROC Patent Publication No. TW-I620809, No. TW-I653318, No. TW-I668294, China Patent Publication No. CN-105802628 and PCT Patent Publication No. WO-2015/117876 patents or patent applications are only The reference to the technical background of the present invention and the description of the current state of technology development are only, and are not intended to limit the scope of the present invention.

In view of this, in order to meet the above requirements, the present invention provides a core-shell light-emitting quantum dot material and a manufacturing method thereof. A core body is formed into a cadmium selenide alloy body, and the cadmium selenide alloy body has an element content Decrease area, and the decrease area of element content decreases a cadmium element, a selenium element or both from the core part of the core body, and a shell is formed on the core body, and the shell is made of a cubic The crystal system material is formed, and a zinc blende structure is formed on the shell to improve the luminescence stability, quantum efficiency, thermal stability, or poor resistance to water and oxygen of conventional core-shell luminescent quantum dot materials.

The main purpose of the preferred embodiments of the present invention is to provide a core-shell luminescent quantum dot material and a manufacturing method thereof. A core body is formed into a cadmium selenide alloy body, and the cadmium selenide alloy body has a region of decreasing element content , And the decreasing element content area decreases a cadmium element, a selenium element or both from the core part of the core body, and a shell is formed on the core body, and the shell The body is formed of a cubic crystal system material, and a zinc blende structure is formed on the shell, thereby achieving the purpose of improving its luminescence stability, quantum efficiency, thermal stability, or resistance to water and oxygen erosion.

In order to achieve the above objective, the core-shell luminescent quantum dot material of a preferred embodiment of the present invention includes:

At least one core body, which is an alloy core body, and the core body has a core part, and the core body forms a cadmium selenide alloy body;

A zone of decreasing element content, which decreases a cadmium element, a selenium element or both from the core part of the core body;

A shell covering the core body, the shell having a shell layer and an outer surface, the outer surface is located outside the shell layer, and the shell is formed of a cubic material; and

At least one sphalerite structure formed on the shell and outer surface of the shell, and the shell is a polygonal shell, and the sphalerite structure is formed of a sphalerite type compound;

The zinc blende structure of the shell provides protection for the alloy core body, and the zinc blende structure of the shell has a resistance to water and oxygen erosion and provides a thermal stability, so that the alloy type core body produces a luminescence Stability and provide a quantum efficiency.

The cadmium selenide alloy body of the alloy core body of the preferred embodiment of the present invention is selected from a CdZnSe alloy body, an alloy body made of a CdZnSe alloy, a CdZnSeS alloy body, an alloy body with a CdZnSeS alloy, and a CdSeS alloy Body, an alloy body with CdSeS alloy or any combination of alloy bodies.

In a preferred embodiment of the present invention, the ratio of cadmium or selenium in the element content decreasing area 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 present invention is selected from a ZnS shell Body, a ZnSe shell, a ZnSeS shell, a CdS shell, a CdZnS shell, a CdSe shell, or any combination thereof to form the shell.

In the preferred embodiment of the present invention, the outer surface of the casing has an angular polygonal surface.

In a preferred embodiment of the present invention, the shell is a multi-layer composite shell, and the shell includes a plurality of shell thicknesses, and the thickness of the shell layers decreases gradually from the core part of the core body.

In order to achieve the above objective, the manufacturing method of the core-shell luminescent quantum dot material of the preferred embodiment of the present invention includes:

A first metal precursor solution is complex activated 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 solution A metal precursor is an activated cadmium precursor;

Adding a second metal precursor to the activated first metal precursor solution for complex activation to form an activated first and second metal precursor solution;

A third metal ion solution is added to the activated first and second metal precursor solutions to perform a core particle reaction, and the third metal ion solution includes a third metal ion, and the third metal ion is a Selenium ions to form an alloy core solution and a cadmium selenide alloy body, and the cadmium selenide alloy body has a decreasing element content area, and the decreasing element content area decreases by one from the core part of the core body Cadmium, selenium or both;

Adding a fourth ion solution to the alloy-type core body solution to perform a first cladding reaction to obtain an alloy-type core-cladding quantum dot solution; and

The alloy core-clad quantum dot solution is made into an alloy core-clad quantum dot material.

In order to achieve the above object, another preferred embodiment of the present invention The manufacturing method of core-shell luminescent quantum dot material includes:

A first metal precursor solution is complex activated 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 solution A metal precursor is an activated cadmium precursor;

Adding a second metal precursor to the activated first metal precursor solution for complex activation to form an activated first and second metal precursor solution;

A third metal ion solution is added to the activated first and second metal precursor solutions to perform a core particle reaction, and the third metal ion solution includes a third metal ion, and the third metal ion is a Selenium ions to form an alloy core solution and a cadmium selenide alloy body, and the cadmium selenide alloy body has a decreasing element content area, and the decreasing element content area decreases by one from the core part of the core body Cadmium, selenium or both;

A fourth ion solution is added to the alloy-type core body solution to perform a first cladding reaction to obtain an alloy-type core-cladding quantum dot solution, and the first cladding reaction produces an alloy-type core-cladding solution Shell quantum dot material;

Mixing another second metal precursor and an oleic acid to form a second metal precursor mixed solution, and adding the second metal precursor mixed solution to the alloy core solution to perform a second cladding reaction, To obtain an alloy-type core-multilayer cladding quantum dot solution; and

The alloy type core-multilayer cladding quantum dot solution is made into an alloy type core-multilayer cladding quantum dot material.

In a preferred embodiment of the present invention, dodecanethiol is additionally added to the alloy-type core solution to perform the second cladding reaction.

In the preferred embodiment of the present invention, the first metal precursor solution is activated by adding an oleylamine liquid and an oleic acid solution.

The activated first and second gold in the preferred embodiment of the present invention The precursor solution includes an activated second metal precursor, and the second activated metal precursor is an activated zinc precursor.

The first metal precursor solution in a preferred embodiment of the present invention is selected from a cadmium-containing metal precursor solution.

The second metal precursor in a preferred embodiment of the present invention is selected from a zinc-containing metal precursor.

The third metal ion solution in a preferred embodiment of the present invention is selected from a mixed solution of a third metal ion and a fourth ion.

The third metal ion solution in a preferred embodiment of the present invention is selected from a selenium-containing metal ion solution.

The fourth ion solution in the preferred embodiment of the present invention is selected from a sulfur-containing anion solution, a sulfur-containing and TOP anion solution, or a sulfur-containing and TBP anion solution.

1‧‧‧nucleus body

11‧‧‧Decreasing element content area

2‧‧‧Shell

21‧‧‧First shell layer

22‧‧‧Second shell layer

3‧‧‧Sphalerite structure

A‧‧‧Cd element

B‧‧‧Se element

C‧‧‧Zn element

D‧‧‧S element

Figure 1: A schematic diagram of the core-shell luminescent quantum dot material of the first preferred embodiment of the present invention.

Figure 2: A schematic block diagram of the manufacturing method of the core-shell light-emitting quantum dot material according to the first preferred embodiment of the present invention.

Figure 3: A schematic diagram of the core-shell luminescent quantum dot material of the second preferred embodiment of the present invention.

Figure 4: A schematic block diagram of a method for manufacturing a core-shell light-emitting quantum dot material according to a second preferred embodiment of the present invention.

Figure 5: A schematic diagram of the core-shell luminescent quantum dot material of the third preferred embodiment of the present invention.

Fig. 6A: A transmission electron microscope image of a core-shell luminescent quantum dot material according to a preferred embodiment of the present invention.

Fig. 6B: A schematic diagram of the particle size distribution of the core-shell luminescent quantum dot material according to a preferred embodiment of the present invention.

Fig. 6C: A schematic diagram of the diffraction spectrum of the X-ray diffractometer of the core-shell luminescent quantum dot material of the preferred embodiment of the present invention.

Fig. 7A: A transmission electron microscope image of a core-shell luminescent quantum dot material according to another preferred embodiment of the present invention.

Fig. 7B: A schematic diagram of the particle size distribution of a core-shell luminescent quantum dot material according to another preferred embodiment of the present invention.

Fig. 7C: A schematic diagram of the diffraction spectrum of an X-ray diffractometer of a core-shell luminescent quantum dot material according to another preferred embodiment of the present invention.

Fig. 8A: A schematic diagram of the spectrum of the relationship between the concentration of different cadmium metal precursors and the photoluminescence of the core-shell luminescent quantum dot material of the preferred embodiment of the present invention.

Fig. 8B: A schematic diagram of the relationship between the concentration of different cadmium metal precursors and the photoluminescence wavelength of the core-shell luminescent quantum dot material of the preferred embodiment of the present invention.

Fig. 9A: The single core-shell luminescent quantum dot of the core-shell luminescent quantum dot material of the preferred embodiment of the present invention shows the image of cadmium and selenium in a scanning transmission electron microscope-X-ray energy spectrum-two-dimensional element distribution method .

Figure 9B: The single core-shell luminescent quantum dot of the core-shell luminescent quantum dot material of the preferred embodiment of the present invention shows the image of zinc and sulfur by scanning transmission electron microscope-X-ray energy spectrum-two-dimensional element distribution .

Figure 9C: A schematic diagram of a single core-shell luminescent quantum dot of a core-shell luminescent quantum dot material according to a preferred embodiment of the present invention along the detection lines of Figures 9A and 9B, showing the element distribution image by X-ray mass spectrometer.

Figure 10: A scanning transmission electron microscope image of a core-shell luminescent quantum dot material according to a preferred embodiment of the present invention-a high-angle ring-shaped dark field image.

Figure 11: A schematic diagram of the zinc blende structure of the core-shell luminescent quantum dot material according to a preferred embodiment of the present invention.

In order to fully understand the present invention, preferred embodiments are exemplified below and described in detail with the accompanying drawings, and they are not intended to limit the present invention.

The core-shell luminescent quantum dot material of the preferred embodiment of the present invention and The manufacturing method can be applied to various fluorescent light-emitting materials, light-diffusing mixed materials, light-diffusing film structures and their devices (such as displays or lighting devices); furthermore, the core-shell light-emitting quantum dot material of the preferred embodiment of the present invention Its manufacturing method can be suitably used as quantum dot material or fluorescent material surface stabilizer, adsorbent or dispersion carrier, or it can be applied to materials, image display, optics or biomedicine or other technical fields, but it is not used To limit the scope of application of the present invention.

Figure 1 shows a schematic diagram of the core-shell luminescent quantum dot material of the first preferred embodiment of the present invention. Please refer to Figure 1. For example, the core-shell luminescent quantum dot material of the first preferred embodiment of the present invention includes at least one core body 1 and at least one element content decreasing region 11 (as shown in the depth change region in Figure 1 Schematic diagram], at least one shell 2 and a zinc blende structure 3 [as shown in the schematic diagram of the fine points in Figure 1].

Please refer to FIG. 1 again. For example, the core body 1 is an alloy core body, and the core body 1 has a core part in structure, 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, a CdZnSe alloy body, a CdZnSeS alloy body, a CdZnSeS alloy body, a CdSeS alloy body, and a CdSeS alloy body. Alloy body of alloy or any combination of alloy body.

Please refer to FIG. 1 again. For example, the decreasing element content region 11 decreases a cadmium element, a selenium element, or both from the core portion of the core body 1 outward. In addition, the ratio of cadmium or selenium in the element content decreasing region 11 is 0.1 mol% to 50 mol%, 10 mol% to 50 mol%, 30 mol% to 50 mol%, or other ranges.

Please refer to Figure 1 again. For example, the shell 2 is formed on the core body 1, and the shell 2 has a shell layer and an outer surface, and the outer surface is located on the shell layer 2. Outside, and the shell 2 is made of a cubic crystal system Material formation. The outer surface of the shell 2 has an angular polygonal surface. In addition, the casing 2 can be formed of a ZnS casing, a ZnSe casing, a ZnSeS casing, a CdS casing, a CdZnS casing, a CdSe casing, or any combination thereof.

Please refer to Figure 1 again. For example, the sphalerite structure 3 is formed on the shell and outer surface of the shell 2, and the shell 2 is a polygonal shell, and the zinc blende structure 3 is formed by a zinc blende type compound. Functionally, the zinc blende structure 3 of the shell 2 provides protection for the alloy core body, and the zinc blende structure 3 of the shell 2 has a resistance to water and oxygen erosion and provides a thermal stability, so that the alloy The core body produces a luminescence stability and provides a quantum efficiency (for example, the quantum efficiency is greater than 90% or 95%).

FIG. 2 shows a schematic block diagram of the core-shell light-emitting quantum dot material manufacturing method according to the first preferred embodiment of the present invention, which corresponds to the core-shell light-emitting quantum dot material of FIG. 1. Please refer to Figures 1 and 2, the method for manufacturing [synthesizing] a core-shell luminescent quantum dot material in the first preferred embodiment of the present invention includes a first step S1: First, for example, a first metal precursor solution Perform complex 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 The cadmium precursor, that is, the first metal precursor solution can be selected as a cadmium-containing metal precursor solution.

Please refer to Figures 1 and 2. For example, the cadmium concentration of the cadmium-containing metal precursor solution can be selected from 0.04 millimoles, 0.08 millimoles, 0.14 millimoles, 0.20 millimoles, and 0.42 millimoles. Molar, 1.00 millimolar or other appropriate concentration.

Please refer to Figures 1 and 2, for example, the first metal precursor solution is added with an oleyl amine liquid and an oleic acid solution or a mixed solution of other primary amines or oleyl amine The way to carry out the complex activation. In addition, the first metal precursor solution can be optionally added with a predetermined amount [e.g. a suitable small amount] of primary alkylamine [primary Alkylamine], 12 amine [dodecylamine], 15 amine [pentadecylamine], 16 amine [hexadecanamine] or [oleylamine] are activated at a reaction temperature between 150°C and 180°C or other appropriate reaction temperature.

Please refer to Figures 1 and 2, the method for manufacturing the core-shell light-emitting quantum dot material of the first preferred embodiment of the present invention includes a second step S2: Then, for example, a second metal precursor is added to the Perform complex activation in the activated first metal precursor solution (for example, the reaction temperature is between 300°C and 320°C or other appropriate 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, that is, the second metal precursor can be selected from A metal precursor containing zinc (for example: zinc concentration of 2.9 millimoles).

Please refer to Figures 1 and 2, the method for manufacturing the core-shell light-emitting quantum dot material of 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 A nuclear body particle reaction (for example: 10 minutes or other reaction time) is performed in the activated first and second metal precursor solutions, such as CdZnSeS nuclear body, and the third metal ion solution contains a third metal ion, and the The third metal ion is a selenium ion to form an alloy core solution and a cadmium selenide alloy body, and the cadmium selenide alloy body has a decreasing element content area, and the decreasing element content area is from the core body At the core, a cadmium element, a selenium element, or both are decremented outward.

Please refer to Figures 1 and 2, for example, the third metal ion solution is selected from a selenium-containing metal ion solution (for example, the selenium concentration is 1.5 millimoles). Or, the third metal ion solution can optionally contain sulfur (for example, a sulfur concentration of 2.2 millimoles), selenium and n-trioctylphosphine oxide [TOP, trioctylphosphine] or contain sulfur, selenium and tributylphosphine [TBP, tributylphosphine]. ].

Please refer to Figures 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 a third metal ion and a fourth ion. The particle reaction can choose to form a CdSeZnS core quantum dot or a similar CdSeZnS core quantum dot.

Please refer to Figures 1 and 2, the method for manufacturing the core-shell light-emitting quantum dot material of the first preferred embodiment of the present invention includes a fourth step S4: Then, for example, a fourth ion solution is added to the alloy Perform a first cladding reaction (for example: 15 to 20 minutes or other reaction time) in the core solution to obtain an alloy core-clad quantum dot solution.

Please refer to Figures 1 and 2. For example, the fourth ion solution is selected from a stock solution containing sulfur anions [stock solution], a sulfur and TOP anion solution [for example: sulfur concentration of 2.0 millimetres Mole] or a solution containing sulfur and TBP anion. In addition, the first cladding reaction can select a reaction temperature between 240°C and 290°C or other appropriate reaction temperature.

Please refer to Figures 1 and 2, the method for manufacturing the core-shell light-emitting quantum dot material of the first preferred embodiment of the present invention includes a fifth step S5: Then, for example, the alloy core-clad quantum dot The solution is made into an alloy core-clad quantum dot material, which has a huge particle size [>13nm or>15nm]. For example, various cladding materials can be selected in the present invention, such as various Zn salt cladding materials or other suitable salt cladding materials.

FIG. 3 shows a schematic diagram of the core-shell light-emitting quantum dot material according to the second preferred embodiment of the present invention, which corresponds to the structure of the core-shell light-emitting quantum dot material in FIG. 1. Please refer to FIG. 3, with respect to the first embodiment, for example, the core-shell light-emitting quantum dot material of the second preferred embodiment of the present invention further includes a first shell layer 21 (e.g., ZnS), and the The first shell layer 21 is appropriately coated on the shell 2 (for example: ZnS).

Please refer to Figure 3, the shell 2 and the first shell layer 21 It is composed of a multi-layer composite shell, and the shell 2 includes several shell thicknesses, and several shell thicknesses can be selected from the core portion of the core body 1 to decrease in thickness or can be selected from the core body 1 The core part increases in thickness outwards.

FIG. 4 shows a block diagram of the core-shell light-emitting quantum dot material manufacturing (synthesis) method of the second preferred embodiment of the present invention, which corresponds to the core-shell light-emitting quantum dot material in FIG. 3. Please refer to Figures 3 and 4, the method for manufacturing the core-shell light-emitting quantum dot material of the second preferred embodiment of the present invention includes a first step S1: First, for example, a first metal precursor solution is staggered 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 That is, the first metal precursor solution can be selected as a cadmium-containing metal precursor solution.

Please refer to Figures 3 and 4 again. For example, the cadmium concentration of the cadmium-containing metal precursor solution can be selected from 0.04 millimoles, 0.08 millimoles, 0.14 millimoles, 0.20 millimoles, and 0.42 millimoles. Molar, 1.00 millimolar or other appropriate concentration.

Please refer to Figures 3 and 4 again. For example, the first metal precursor solution is activated by adding an oleylamine liquid and an oleic acid solution or a mixed solution of other primary amines or oleylamine. In addition, the first metal precursor solution can be optionally added with a predetermined amount of primary alkylamine [primary alkylamine], 12 amine [dodecylamine], 15 amine [pentadecylamine], 16 amine [hexadecanamine] or [oleylamine] at the reaction temperature in advance. Perform complex activation between 150°C and 180°C or other appropriate reaction temperature.

Please refer to FIGS. 3 and 4 again. The method for manufacturing the core-shell light-emitting quantum dot material of the second preferred embodiment of the present invention includes a second step S2: Then, for example, a second metal precursor is added to the Perform complex activation in the solution of the activated first metal precursor (for example, the reaction temperature is between 300°C and 320°C or other appropriate reaction temperature) to form an activated first metal precursor solution. One and the 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, that is, the second metal precursor can be selected from A metal precursor containing zinc (for example: zinc concentration of 2.9 millimoles).

Please refer to FIGS. 3 and 4 again. The manufacturing method of the core-shell light-emitting quantum dot material of the second preferred embodiment of the present invention includes a third step S3: Then, for example, a third metal ion solution is added to the A nucleus particle reaction is carried out in the activated first and second metal precursor solutions (for example: 10 minutes or other reaction time), and the third metal ion solution contains a third metal ion, and the third metal ion is a Selenium ions to form an alloy core solution and a cadmium selenide alloy body, and the cadmium selenide alloy body has a decreasing element content area, and the decreasing element content area decreases by one from the core part of the core body Cadmium, selenium or both.

Please refer to Figures 3 and 4 again. For example, the third metal ion solution is selected from a selenium-containing metal ion solution (for example, a selenium concentration of 1.5 millimoles). Or, the third metal ion solution can optionally contain sulfur (for example, a sulfur concentration of 2.2 millimoles), selenium and n-trioctylphosphine oxide [TOP] or contain sulfur, selenium and tributylphosphine [TBP].

Please refer to Figures 3 and 4 again. For example, the third metal ion solution of another preferred embodiment of the present invention is selected from a mixed solution of a third metal ion and a fourth ion. The particle reaction can choose to form a CdSeZnS core quantum dot or a similar CdSeZnS core quantum dot.

Please refer to FIGS. 3 and 4 again, the method for manufacturing the core-shell light-emitting quantum dot material of the second preferred embodiment of the present invention includes a fourth step S4: Then, for example, a fourth ion solution is added to the alloy A first cladding reaction (for example, 15 to 20 minutes or other reaction time) is performed in the core solution to obtain an alloy core-clad quantum dot solution, and the first cladding reaction produces an alloy core -Encapsulated quantum dot material.

Please refer to Figures 3 and 4 again. For example, the fourth ion solution is selected from a stock solution containing sulfur anions, a sulfur containing (for example: sulfur concentration of 2.0 millimoles) and a TOP anion solution or A solution containing sulfur and TBP anion. In addition, the first cladding reaction can select a reaction temperature between 240°C and 290°C or other appropriate reaction temperature.

Please refer to FIGS. 3 and 4 again. The method for manufacturing the core-shell light-emitting quantum dot material of the second preferred embodiment of the present invention includes the 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 to the alloy core solution for a second cladding reaction (for example: 30 minutes or other reaction Time] to obtain an alloy-type core-multilayer cladding quantum dot solution.

Please refer to Figures 3 and 4 again, the second metal precursor mixed solution is a zinc oleate [Zn-oleate] solution [transparent light yellow solution], and the second metal precursor mixed solution can select the reaction temperature Between 180°C and 220°C or other appropriate reaction temperature. In addition, the second cladding reaction can select a reaction temperature between 240°C and 290°C or other appropriate reaction temperature.

Please refer to Figures 3 and 4 again. The manufacturing method of the core-shell light-emitting quantum dot material of the second preferred embodiment of the present invention further includes the step of selecting a reaction temperature between 180°C and 220°C or other appropriate reaction temperature. Dodecyl mercaptan is additionally added to the alloy core solution to perform the second cladding reaction (for example: 30 minutes or other reaction time).

Please refer to Figures 3 and 4 again. The method for manufacturing the core-shell light-emitting quantum dot material of the second preferred embodiment of the present invention includes a sixth step S6: Then, for example, the alloy core-multilayer cladding quantum dot material The dot solution is made into an alloy-type core-multilayer cladding quantum dot material, which has a huge particle size [>13nm or>15nm]. For example, the present invention can choose to use various cladding materials, such as various Zn salt cladding materials or other appropriate salt cladding materials. material.

FIG. 5 shows a schematic diagram of the core-shell light-emitting quantum dot material according to the third preferred embodiment of the present invention, which corresponds to the structure of the core-shell light-emitting quantum dot material in FIGS. 1 and 3. Please refer to FIG. 5, with respect to the first and second embodiments, for example, the core-shell light-emitting quantum dot material of the third preferred embodiment of the present invention further includes a second outer shell 22 [e.g., ZnS] , And the second shell layer 22 is appropriately covered on the housing 2 and the first shell layer 21.

FIG. 6A shows a transmission electronic microscopy [TEM, transmission electronic microscopy] image of the core-shell luminescent quantum dot material of the preferred embodiment of the present invention. Please refer to FIG. 6A. For example, the core-shell light-emitting quantum dot material of the preferred embodiment of the present invention produces a giant CdSeZnS quantum dot with appropriate addition of hexadecanamine.

Fig. 6B shows a schematic diagram of the particle size distribution of the core-shell light-emitting quantum dot material according to a preferred embodiment of the present invention, which corresponds to Fig. 6A. Please refer to Figure 6B. For example, the particle size dispersion of the core-shell light-emitting quantum dot material of the preferred embodiment of the present invention is about less than 10%, and the average particle size is about 15.36±1.46nm. And its size is quite uniform.

Fig. 6C shows a schematic diagram of the diffraction pattern of the X-ray diffratometer [XRD, X-ray diffratometer] of the core-shell luminescent quantum dot material of the preferred embodiment of the present invention, which corresponds to Figs. 6A and 6B. Please refer to FIG. 6C. For example, the core-shell luminescent quantum dot material of the preferred embodiment of the present invention has a zinc-blende structure, as shown in the black rod in 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 present invention. Referring to FIG. 7A, for example, the core-shell light-emitting quantum dot material of the preferred embodiment of the present invention still produces a huge CdSeZnS quantum dot without adding hexadecylamine.

Figure 7B discloses another preferred embodiment of the present invention core-shell hair A schematic diagram of the particle size distribution of the light quantum dot material, which corresponds to Figure 7A. Please refer to Figure 7B. For example, the average particle diameter of the core-shell light-emitting quantum dot material of the preferred embodiment of the present invention is about 13.87±1.41 nm, and the dispersion of the particle diameter is about slightly larger than 10%, its size can be regarded as approximately fairly close to uniform.

FIG. 7C shows a schematic diagram of the diffraction pattern of an X-ray diffractometer of a core-shell luminescent quantum dot material according to another preferred embodiment of the present invention, which corresponds to FIGS. 7A and 7B. Please refer to FIG. 7C. For example, the core-shell luminescent quantum dot material of the preferred embodiment of the present invention has a wurtzite structure, as shown in the black rod in FIG. 7C.

FIG. 8A shows the spectral diagram of the relationship between different cadmium metal precursor concentration [concentration] and photoluminescence [PL, photoluminescence] of the core-shell luminescent quantum dot material of the preferred embodiment of the present invention. Please refer to Figure 8A. For example, the core-shell light-emitting quantum dot material of the preferred embodiment of the present invention selects three cadmium metal precursor concentrations, and the cadmium metal precursor concentrations are selected as 0.14 millimoles and 0.28 millimoles And 1.00 millimoles, and its corresponding emission wavelengths are 519nm [the leftmost peak in Figure 8A], 533nm [the middle peak in Figure 8A], and 625nm [the rightmost peak in Figure 8A].

FIG. 8B shows a schematic diagram of the relationship between the concentration of different cadmium metal precursors and the photoluminescence wavelength of the core-shell luminescent quantum dot material of the preferred embodiment of the present invention, which corresponds to FIG. 8A. Please refer to Figure 8A. For example, the core-shell luminescent quantum dot material of the preferred embodiment of the present invention increases with the concentration of the cadmium metal precursor [0.14 millimoles, 0.28 millimoles, and 1.00 millimoles] Its luminescence produces red shift phenomenon [519nm, 533nm and 625nm], and its maximum red shift is 620nm to 625nm.

3nm〕為主要包含Cd、Zn、Se及S。 Figure 9A shows the single core-shell luminescent quantum dot material of the core-shell luminescent quantum dot material of the preferred embodiment of the present invention. The core-shell luminescent quantum dot is used for scanning penetration electron microscope-X-ray energy spectrum-two-dimensional element distribution [ STEM-EDS elemental mapping] displays the image of cadmium (Cd) and selenium (Se). Please refer to Figure 9A. For example, in terms of microstructure analysis, the core body of the single-core-shell light-emitting quantum dot of the preferred embodiment of the present invention has cadmium element A (display red) and selenium element B (display blue) , At its core (e.g. radius

3nm] mainly contains Cd, Zn, Se and S.

Figure 9B shows that a single core-shell luminescent quantum dot of a core-shell luminescent quantum dot material of a preferred embodiment of the present invention displays zinc (Zn) and sulfur in a scanning transmission electron microscope-X-ray energy spectrum-two-dimensional element distribution method. S] the image of the element, which corresponds to image 9A. Please refer to Figure 9B. For example, in terms of microstructure analysis, the shell of the single-core-shell light-emitting quantum dot according to the preferred embodiment of the present invention has zinc element C (in fact, it displays green) and sulfur element D (in Actually it shows yellow], and its shell mainly contains Zn and S.

Figure 9C shows the core-shell luminescent quantum dot material of the preferred embodiment of the present invention. The single core-shell luminescent quantum dot of the core-shell luminescent quantum dot material along the probed line of Figure 9A and Figure 9B shows the element distribution by X-ray mass spectrometer (EDS) Image [elemental map] schematic diagram, which corresponds to images 9A and 9B. Please refer to Figures 9A, 9B and 9C. For example, the core-shell light-emitting quantum dot material of the preferred embodiment of the present invention produces a red shift phenomenon in its light emission as the concentration of the cadmium metal precursor increases.

Figure 10 shows a scanning transmission electron microscope image of a core-shell luminescent quantum dot material according to a preferred embodiment of the present invention-a high-angle ring-shaped dark field image [STEM-HAADF image]. Please refer to FIG. 10, for example, in terms of microstructure analysis, the core-shell light-emitting quantum dot material of the preferred embodiment of the present invention has various atoms arranged in a hexagonal form or an approximate hexagonal form.

FIG. 11 shows a schematic diagram of the zinc blende structure of the core-shell luminescent quantum dot material according to a preferred embodiment of the present invention, which corresponds to FIG. 10. Please refer As shown in Figure 11, for example, in the analysis of the microstructure, the core-shell light-emitting quantum dot material of the preferred embodiment of the present invention shows a sphalerite structure from the [110] direction in the simulation, that is, in the form of a hexagon arrangement.

The above-mentioned experimental data are preliminary experimental results obtained under specific conditions, which are only used to easily understand or refer to the technical content of the present invention, and other related experiments are needed. The experimental data and results are not intended to limit the scope of rights of the present invention.

The foregoing preferred embodiments only illustrate the present invention and its technical features. The technology of this embodiment can still be implemented with various substantially equivalent modifications and/or alternatives; therefore, the scope of rights of the present invention shall be subject to a patent application. The scope defined by the scope shall prevail. The copyright in this case is restricted to the use of patent applications in the Republic of China.

1‧‧‧nucleus body

11‧‧‧Decreasing element content area

2‧‧‧Shell

3‧‧‧Sphalerite structure

Claims (10)

A core-shell luminescent quantum dot material, which comprises: At least one core body, which is an alloy core body, and the core body has a core part, and the core body forms a cadmium selenide alloy body; A zone of decreasing element content, which decreases a cadmium element, a selenium element or both from the core part of the core body; A shell covering the core body, the shell having a shell layer and an outer surface, the outer surface is located outside the shell layer, and the shell is formed of a cubic material; and At least one sphalerite structure formed on the shell and outer surface of the shell, and the shell is a polygonal shell, and the sphalerite structure is formed of a sphalerite type compound; The zinc blende structure of the shell provides protection for the alloy core body, and the zinc blende structure of the shell has a resistance to water and oxygen erosion and provides a thermal stability, so that the alloy type core body produces a luminescence Stability and provide a quantum efficiency. According to the core-shell luminescent quantum dot material described in item 1 of the scope of patent application, wherein the cadmium selenide alloy body of the alloy core body is selected from a CdZnSe alloy body, a CdZnSe alloy body, and a CdZnSeS alloy body , An alloy body with CdZnSeS alloy, a CdSeS alloy body, an alloy body with CdSeS alloy or any combination of alloy bodies. According to the core-shell luminescent quantum dot material described in item 1 of the scope of patent application, the shell is selected from a ZnS shell, a ZnSe shell, a ZnSeS shell, a CdS shell, a CdZnS shell, and a The CdSe shell or any combination thereof forms the shell. According to the core-shell light-emitting quantum dot material described in item 1 of the scope of patent application, the outer surface of the shell has an angular polygonal surface. According to the core-shell light-emitting quantum dot material according to the first item of the scope of patent application, the shell is a multi-layer composite shell, and the shell includes a plurality of shell thicknesses, and the shell thicknesses are from the The core of the nucleus body decreases in thickness outward. A method for manufacturing a core-shell luminescent quantum dot material, which comprises: A first metal precursor solution is complex activated 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 solution A metal precursor is an activated cadmium precursor; Adding a second metal precursor to the activated first metal precursor solution for complex activation to form an activated first and second metal precursor solution; A third metal ion solution is added to the activated first and second metal precursor solutions to perform a core particle reaction, and the third metal ion solution includes a third metal ion, and the third metal ion is a Selenium ions to form an alloy core solution and a cadmium selenide alloy body, and the cadmium selenide alloy body has a decreasing element content area, and the decreasing element content area decreases by one from the core part of the core body Cadmium, selenium or both; Adding a fourth ion solution to the alloy-type core body solution to perform a first cladding reaction to obtain an alloy-type core-cladding quantum dot solution; and The alloy core-clad quantum dot solution is made into an alloy core-clad quantum dot material. A method for manufacturing a core-shell luminescent quantum dot material, which comprises: A first metal precursor solution is complex activated 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 solution A metal precursor is an activated cadmium precursor; Adding a second metal precursor to the activated first metal precursor solution for complex activation to form an activated first and second metal precursor solution; A third metal ion solution is added to the activated first and second metal precursor solutions to perform a core particle reaction, and the third metal ion solution includes a third metal ion, and the third metal ion is a Selenium ions to form an alloy core solution and a cadmium selenide alloy body, and the cadmium selenide The alloy body has a decreasing element content area, and the decreasing element content area decreases a cadmium element, a selenium element, or both from the core part of the core body; A fourth ion solution is added to the alloy-type core body solution to perform a first cladding reaction to obtain a first alloy-type-clad quantum dot solution, and the first cladding reaction produces an alloy-type core- Encapsulated quantum dot material; and Mixing another second metal precursor and an oleic acid to form a second metal precursor mixed solution, and adding the second metal precursor mixed solution to the alloy core solution to perform a second cladding reaction, To obtain an alloy-type core-multilayer cladding quantum dot solution; and The alloy type core-multilayer cladding quantum dot solution is made into an alloy type core-multilayer cladding quantum dot material. According to the manufacturing method of core-shell luminescent quantum dot material according to item 7 of the scope of patent application, dodecanethiol is additionally added to the alloy core solution to perform the second cladding reaction. According to the method for manufacturing the core-shell light-emitting quantum dot material according to item 6 or 7 of the scope of patent application, the first metal precursor solution is complex activated by adding an oleylamine liquid and an oleic acid solution. According to the method for manufacturing the core-shell light-emitting quantum dot material according to item 6 or 7 of the scope of patent application, wherein the activated first and second metal precursor solutions include an activated second metal precursor, and the second The 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 third metal ion and fourth ion mixed solution.

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