KR20240075372A - Quantum dot, producing method of quantum dot, photosensitive resin composition, optical film, electric light emitting diode and electronic device - Google Patents

Abstract

The present embodiments include an AgInGaS core containing Ag, In, Ga, and S, a multilayer shell disposed on the AgInGaS core and including at least two layers, and an outermost shell disposed on the multilayer shell, among the multilayer shells. The first shell adjacent to the AgInGaS core contains at least one Group I element, and the outermost shell contains at least one Group II element. Quantum dots, method for manufacturing quantum dots, photosensitive resin composition, optical film, electroluminescent diode, and electronics Devices can be provided.

Description

Quantum dots, manufacturing method of quantum dots, photosensitive resin composition, optical film, electroluminescent diode and electronic device

The present disclosure relates to quantum dots, methods for producing quantum dots, photosensitive resin compositions, optical films, electroluminescent diodes, and electronic devices.

Quantum dots (QDs) are nano-sized semiconductor particles that exhibit excellent optical and electrical properties that bulk semiconductor materials do not possess. For example, quantum dots emit photoluminescence (PL), in which electrons excited by external light emit light as electrons fall from the conduction band to the valence band, or they emit light by external charges. It has the characteristic of emitting light by electroluminescence (EL), and has the characteristic that the color of the emitted light varies depending on the size of the quantum dot even if it is composed of the same material. Due to these characteristics, quantum dots are attracting attention as next-generation high-brightness light emitting diodes (LEDs), bio sensors, lasers, and solar cell nanomaterials.

Meanwhile, when other atoms or molecules approach the core surface of quantum dots, chemical bonds are easily formed, which can cause surface defects and reduce quantum efficiency. Accordingly, in order to prevent a decrease in the quantum efficiency of the core, quantum dots with a core/shell structure in which a shell is formed on the surface of the core were developed.

However, despite the introduction of the shell, there is a problem in that the quantum efficiency of quantum dots is limited to a certain level. In particular, despite the introduction of the shell, there is a problem in which the quantum efficiency of the quantum dot does not reach the expected level due to the stability of the shell for various reasons.

Embodiments of the present disclosure can provide quantum dots and a method of manufacturing quantum dots that can improve quantum efficiency.

In addition, embodiments of the present disclosure can provide quantum dots and a method of manufacturing quantum dots that can not only improve quantum efficiency but also reduce the full width at half maximum.

Additionally, embodiments of the present disclosure can provide photosensitive resin compositions, optical films, electroluminescent diodes, and electronic devices that can improve quantum efficiency.

In one aspect, embodiments of the present disclosure provide quantum dots including an AgInGaS core, a multilayer shell, and an outermost shell.

The AgInGaS core includes Ag, In, Ga, and S, and the multilayer shell is disposed on the AgInGaS core and includes at least two layers, and the outermost shell is disposed on the multilayer shell.

Among the multilayer shells, the first shell adjacent to the AgInGaS core contains at least one Group I element, and the outermost shell contains at least one Group II element.

At least one Group I element included in the first shell may include one or more selected from Cu, Ag, and Au.

The first shell may further include at least one Group III element and at least one Group VI element.

At least one Group III element included in the first shell may include one or more selected from Al, Ga, In, and Tl.

At least one Group VI element included in the first shell may include one or more selected from S, Se, and Te.

The multilayer shell surrounds the first shell and may include a second shell containing at least one Group III element and at least one Group VI element.

At least one Group III element included in the second shell may include one or more selected from Al, Ga, In, and Tl.

At least one Group VI element included in the second shell may include one or more selected from S, Se, and Te.

At least one Group I element included in the first shell includes Ag, and the multilayer shell includes AgGaS/GaS, AgGaS/GaSe, AgGaS/GaTe, AgInS/GaS, AgInS/GaSe, AgInS/GaTe, AgAlS/GaS, AgAlS /GaSe, AgAlS/GaTe, AgTlS/GaS, AgTlS/GaSe, AgTlS/GaTe, AgGaSe/GaS, AgGaSe/GaSe, AgGaSe/GaTe, AgInSe/GaS, AgInSe/GaSe, AgInSe/GaTe, AgAlSe/GaS, AgAlSe/GaSe , AgAlSe/GaTe, AgTlSe/GaS, AgTlSe/GaSe, AgTlSe/GaTe, AgGaTe/GaS, AgGaTe/GaSe, AgGaTe/GaTe, AgInTe/GaS, AgInTe/GaSe, AgInTe/GaTe, AgAlTe/GaS, AgAlTe/GaSe, AgAlTe /GaTe, AgTlTe/GaS, AgTlTe/GaSe, AgTlTe/GaTe, AgGaSSe/GaS, AgGaSSe/GaSe, AgGaSSe/GaTe, AgInSSe/GaS, AgInSSe/GaSe, AgInSSe/GaTe, AgAlSSe/GaS, AgAlSSe/GaSe, AgAlSSe/GaTe , AgTlSSe/GaS, AgTlSSe/GaSe, AgTlSSe/GaTe, AgGaSTe/GaS, AgGaSTe/GaSe, AgGaSTe/GaTe, AgInSTe/GaS, AgInSTe/GaSe, AgInSTe/GaTe, AgAlSTe/GaS, AgAlSTe/GaSe, AgAlSTe/GaTe, AgTlSTe /GaS, AgTlSTe/GaSe, AgTlSTe/GaTe, AgGaSeTe/GaS, AgGaSeTe/GaSe, AgGaSeTe/GaTe, AgInSeTe/GaS, AgInSeTe/GaSe, AgInSeTe/GaTe, AgAlSeTe/GaS, AgAlSeTe/GaSe, AgAlSeTe/GaTe, AgTlSeTe/GaS , AgTlSeTe/GaSe or AgTlSeTe/GaTe.

The molar ratio of Ag included in the AgInGaS core and Ag included in the first shell may be 1:0.5 to 1:1.

At least one Group II element included in the outermost shell may include Zn.

The outermost shell may further include at least one group VI element.

At least one Group VI element included in the outermost shell may include one or more selected from S, Se, and Te.

The multilayer shell is disposed on the first shell and further includes a second shell containing at least one Group III element, Ga, and the molar ratio of Ga contained in the second shell and Zn contained in the outermost shell is 1. :0.55 to 1:1.2.

In another aspect, embodiments of the present disclosure may provide a method of manufacturing quantum dots.

The quantum dot manufacturing method includes an AgInGaS core manufacturing step, a first shell manufacturing step, a second shell manufacturing step, and an outermost shell manufacturing step.

The AgInGaS core manufacturing step is a step of manufacturing an AgInGaS core.

The first shell manufacturing step is a step of manufacturing the first shell by injecting and reacting the AgInGaS core and the sulfur precursor into a first reactor equipped with a silver precursor and a gallium precursor.

The second shell manufacturing step is a step of manufacturing a second shell surrounding the first shell by injecting and reacting the AgInGaS core/first shell prepared in a second reactor equipped with a gallium precursor with a sulfur precursor.

The outermost shell manufacturing step is a step of manufacturing an outermost shell surrounding the second shell by injecting and reacting the AgInGaS core/first shell/second shell, zinc precursor, and sulfur precursor prepared in the third reactor.

In another aspect, embodiments of the present disclosure provide a photosensitive resin composition containing quantum dots.

In another aspect, embodiments of the present disclosure provide an optical film containing a photosensitive resin composition.

In another aspect, embodiments of the present disclosure provide an electroluminescent diode including an optical film.

In another aspect, embodiments of the present disclosure provide an electronic device including a display device including an optical film and a control unit that drives the display device.

Quantum dots and methods for manufacturing quantum dots according to embodiments of the present disclosure can improve quantum efficiency.

In addition, quantum dots and methods for manufacturing quantum dots according to embodiments of the present disclosure can not only improve quantum efficiency but also reduce the half width.

Additionally, the photosensitive resin composition, optical film, electroluminescent diode, and electronic device according to embodiments of the present disclosure can improve quantum efficiency.

1 is a cross-sectional view of quantum dots according to embodiments of the present disclosure.
Figure 2 is a flowchart showing a method of manufacturing quantum dots according to embodiments of the present disclosure.
Figure 3 is a cross-sectional view of an electronic device according to embodiments of the present disclosure.
Figure 4 is a cross-sectional view of an electrolight-emitting diode according to embodiments of the present disclosure.

Hereinafter, some embodiments of the present disclosure will be described in detail. In describing the present disclosure, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present disclosure, the detailed description may be omitted.

Additionally, in describing the components of the present disclosure, when “includes,” “has,” “consists of,” etc. are used, other parts may be added unless “only” is used. When a component is expressed in the singular, it can also include the plural, unless specifically stated otherwise.

Additionally, in describing the components of the present disclosure, terms such as first, second, A, B, (a), and (b) may be used. These terms are only used to distinguish the component from other components, and the nature, sequence, order, or number of the components are not limited by the term.

In the description of the positional relationship of components, when two or more components are described as being “connected,” “coupled,” or “connected,” the two or more components are directly “connected,” “coupled,” or “connected.” However, it should be understood that two or more components and other components may be further “interposed” and “connected,” “combined,” or “connected.” Here, other components may be included in one or more of two or more components that are “connected,” “coupled,” or “connected” to each other.

Additionally, when a component is said to be “on” or “on” another component, it should be understood that this can include not only “directly above” the other component, but also instances where there is another component in between. something to do. Conversely, when an element is said to be "right on top" of another part, it should be understood to mean that there is no other part in between. In addition, being “on” or “on” a reference part means being located above or below the reference part, and necessarily meaning being located “above” or “on” the direction opposite to gravity. no.

In the explanation of temporal flow relationships related to components, operation methods, production methods, etc., for example, temporal precedence relationships such as “after”, “after”, “after”, “before”, etc. Or, when a sequential relationship is described, non-continuous cases may be included unless “immediately” or “directly” is used.

Meanwhile, when numerical values or corresponding information about a component are mentioned, even if there is no separate explicit statement, the numerical value or corresponding information may be caused by various factors (e.g., process factors, internal or external shocks, noise, etc.). It can be interpreted as including a possible margin of error.

“Diameter” of a nanostructure means the diameter of the cross-section perpendicular to the first axis of the nanostructure, where the first axis has the greatest difference in length with respect to the second and third axes (the second and third axes An axis is the two axes that are closest in length to each other). The first axis is not necessarily the longest axis of the nanostructure; For example, for a disk-shaped nanostructure, the cross-section would be a substantially circular cross-section perpendicular to the minor longitudinal axis of the disk. If the cross section is not circular, the diameter is the average of the major and minor axes of the cross section. For elongated or high aspect ratio nanostructures, such as nanowires, the diameter is measured across a cross-section perpendicular to the longest axis of the nanowire. For spherical nanostructures, the diameter is measured through the center of the sphere from one side to the other.

The term “quantum dot” (or “dot”) refers to a nanocrystal that exhibits quantum confinement or exciton confinement. Quantum dots may be substantially homogeneous in material properties or, in certain embodiments, may be heterogeneous, including, for example, a core and at least one shell. The optical properties of quantum dots can be influenced by their particle size, chemical composition and/or surface composition, and can be determined by appropriate optical testing available in the art. The ability to tailor nanocrystal sizes, for example in the range of about 1 nm to about 15 nm, allows light emission coverage in the entire optical spectrum to provide great versatility in color rendering.

As used herein, the term “shell” refers to a material deposited onto a core or onto a previously deposited shell of the same or different composition and resulting from a single act of deposition of the shell material. The exact shell thickness depends on the material as well as precursor input and conversion and can be reported in nanometers or monolayers. “Target shell thickness” refers to the intended shell thickness used for calculation of the required precursor amount, and “actual shell thickness” refers to the actual deposited amount of shell material after synthesis and can be measured by methods known in the art. You can. As an example, actual shell thickness can be measured by comparing particle diameters determined from transmission electron microscopy (TEM) images of nanocrystals before and after shell synthesis.

Additionally, in describing embodiments of the present disclosure, “Group” refers to a group of the periodic table of elements. Additionally, in describing embodiments of the present disclosure, “cycle” refers to a period of the periodic table of elements.

Here, “Group I” may include Group IA (or 1A) and Group IB (or 1B), and Group I elements may include Li, Na, K, Rb, Cs Cu, Ag and Au. Not limited.

“Group II” may include Group IIA (or 2A) and Group IIB (or 2B), and Group II elements may include, but are not limited to, Be, Mg, Ca, Sr, Zn, Cd, and Hg. .

“Group III” may include Group IIIA (or 3A) and Group IIIB (or 3B), and Group III elements may include, but are not limited to, In, Ga, Al, and Tl.

“Group V” may include group VA (or 5A), and group V elements may include, but are not limited to, P, As, Sb, Bi, and N.

“Group VI” may include group VIA (or 6A), and group VI elements may include, but are not limited to, S, Se, and Te.

In describing embodiments of the present disclosure, a precursor is a chemical substance prepared in advance to react quantum dots, and is a concept referring to all compounds including metals, ions, elements, compounds, complexes, complexes, and clusters. It is not limited to the final material of the reaction, and may mean a material that can be obtained at an arbitrarily determined stage.

Quantum dots according to embodiments of the present disclosure will be described in detail below with reference to the drawings.

1 is a cross-sectional view of quantum dots according to embodiments of the present disclosure.

Referring to FIG. 1, quantum dots 10 according to embodiments of the present disclosure include an AgInGaS core 12, multilayer shells 14 and 16, and an outermost shell 18.

AgInGaS core 12 includes Ag, In, Ga, and S. That is, the AgInGaS core 12 is a quaternary element compound containing Ag, which is a group I element, In and Ga, which are group III elements, and S, which is a group VI element.

AgInGaS core 12 may be doped with a metal or non-metal. Additionally, the AgInGaS core 12 may be filtered to remove precipitates from the core solution and purified prior to deposition of the multilayer shells 14 and 16.

Multilayer shells 14, 16 may be disposed on AgInGaS core 12. For example, the first shell 14, which is the inner shell of the multilayer shells 14 and 16, may be arranged in a structure surrounding the AgInGaS core 12, and the second shell, which is the outer shell of the multilayer shells 14 and 16, may be disposed in a structure that surrounds the AgInGaS core 12. (16) may be arranged in a structure surrounding the first shell (14).

The multilayer shells 14 and 16 may include at least two layers. For example, the multi-layer shells 14 and 16 may be provided with two layers, including a first shell 14 and a second shell 16, as shown in FIG. 1, but are not limited thereto. . For example, the multi-layer shells 14 and 16 may be provided with three or more layers.

The outermost shell 18 may be disposed on the multilayer shells 14 and 16. For example, the outermost shell 18 may be arranged to surround the second shell 16, which is the outer shell of the multi-layer shells 14 and 16.

The thickness of the outermost shell 18 may be provided in a certain spherical shape as shown in FIG. 1, but is not limited thereto. For example, the thickness of the outermost shell 18 may be provided in a different shape combining thick and thin parts.

Among the multilayer shells 14 and 16, the first shell 14 adjacent to the AgInGaS core 12 may include at least one Group I element. For example, at least one Group I element included in the first shell 14 may include one or more selected from Cu, Ag, and Au, but is not limited thereto.

Additionally, the first shell 14 may further include at least one Group III element and at least one Group VI element. For example, at least one Group III element included in the first shell 14 may include one or more selected from Al, Ga, In, and Tl, and at least one Group Ⅵ element included in the first shell 14 The group element may include one or more selected from S, Se, and Te, but is not limited thereto.

For example, the first shell 14 includes CuAlS, CuAlSe, CuAlTe, CuGaS, CuGaSe, CuGaTe, CuInS, CuInSe, CuInTe, CuTlS, CuTlSe, CuTlTe, AgAlS, AgAlSe, AgAlTe, AgGaS, AgGaSe, AgGaTe, AgInS, AgInSe, AgInTe, AgTlS, AgTlSe, AgTlTe, AuAlS, AuAlSe, AuAlTe, AuGaS, AuGaSe, AuGaTe, AuInS, AuInSe, AuInTe, AuTlS, AuTlSe, AuTlTe, CuAlSSe, CuGaSSe, CuInSSe, CuTlSSe, CuAlSTe, CuGaSTe, CuInSTe, CuTlSTe, CuAlSeTe, CuGaSeTe, CuInSeTe, CuTlSeTe, AgAlSSe, AgGaSSe, AgInSSe, AgTlSSe, AgAlSTe, AgGaSTe, AgInSTe, AgTlSTe, AgAlSeTe, AgGaSeTe, AgInSeTe, AgTlSeTe, AuAlSSe, AuGaSSe, AuInSSe, AuTlSSe, AuAlSTe, AuGaSTe, AuInSTe, AuTlSTe, SeTe, AuGaSeTe, It may include, but is not limited to, AuInSeTe or AuTlSeTe.

As another example, the first shell 14 may include four elements selected from two group I elements, one element from group III elements, and one element from group VI elements. That is, the first shell 14 may include all combinations of elements that can be selected from group I elements, group III elements, and group VI elements.

The first shell 14 included in the multilayer shells 14 and 16 contains at least one Group I element and is provided in a structure surrounding the AgInGaS core 12, and the first shell 14 containing the Group I element Since the AgInGaS core and the lattice structure are similar, and thus the structural fit between the AgInGaS core and the first shell is well achieved, the quantum efficiency of the quantum dot 10 can be improved.

Meanwhile, the multilayer shells 14 and 16 preferably surround the first shell 14 on the first shell 14 and include a second shell including at least one Group III element and at least one Group VI element. It may include a shell 16.

For example, the at least one Group Ⅲ element forming the second shell 16 may include one or more selected from Al, Ga, In, and Tl, and the at least one Group Ⅵ element forming the second shell 16 may be S , may include one or more selected from Se and Te, but are not limited thereto.

For example, the second shell 16 may include, but is not limited to, AlS, AlSe, AlTe, GaS, GaSe, GaTe, InS, InSe, InTe, TlS, TlSe, or TlTe.

As another example, the second shell 16 may include three elements by selecting two elements from group III elements and one element from group VI elements. That is, the second shell 16 may include all combinations of elements that can be selected from group III elements and group VI elements.

Meanwhile, the quantum dot 10 includes Ag at least one group I element included in the first shell 14, and the multilayer shells 14/16 include AgGaS/GaS, AgGaS/GaSe, AgGaS/GaTe, and AgInS. /GaS, AgInS/GaSe, AgInS/GaTe, AgAlS/GaS, AgAlS/GaSe, AgAlS/GaTe, AgTlS/GaS, AgTlS/GaSe, AgTlS/GaTe, AgGaSe/GaS, AgGaSe/GaSe, AgGaSe/GaTe, AgInSe/GaS , AgInSe/GaSe, AgInSe/GaTe, AgAlSe/GaS, AgAlSe/GaSe, AgAlSe/GaTe, AgTlSe/GaS, AgTlSe/GaSe, AgTlSe/GaTe, AgGaTe/GaS, AgGaTe/GaSe, AgGaTe/GaTe, AgInTe/GaS, AgInTe /GaSe, AgInTe/GaTe, AgAlTe/GaS, AgAlTe/GaSe, AgAlTe/GaTe, AgTlTe/GaS, AgTlTe/GaSe, AgTlTe/GaTe, AgGaSSe/GaS, AgGaSSe/GaSe, AgGaSSe/GaTe, AgInSSe/GaS, AgInSSe/GaSe , AgInSSe/GaTe, AgAlSSe/GaS, AgAlSSe/GaSe, AgAlSSe/GaTe, AgTlSSe/GaS, AgTlSSe/GaSe, AgTlSSe/GaTe, AgGaSTe/GaS, AgGaSTe/GaSe, AgGaSTe/GaTe, AgInSTe/GaS, AgInSTe/GaSe, AgInSTe /GaTe, AgAlSTe/GaS, AgAlSTe/GaSe, AgAlSTe/GaTe, AgTlSTe/GaS, AgTlSTe/GaSe, AgTlSTe/GaTe, AgGaSeTe/GaS, AgGaSeTe/GaSe, AgGaSeTe/GaTe, AgInSeTe/GaS, AgInSeTe/GaSe, AgInSeTe/GaTe , AgAlSeTe/GaS, AgAlSeTe/GaSe, AgAlSeTe/GaTe, AgTlSeTe/GaS, AgTlSeTe/GaSe or AgTlSeTe/GaTe, but is not limited thereto.

In the quantum dot 10, at least one Group I element included in the first shell 14 includes Ag, and the multilayer shells 14/16 are preferably AgGaS/GaS, AgGaS/GaSe, AgGaS/ GaTe, AgInS/GaS, AgInS/GaSe, AgInS/GaTe, AgAlS/GaS, AgAlS/GaSe, AgAlS/GaTe, AgTlS/GaS, AgTlS/GaSe, AgTlS/GaTe, AgGaSe/GaS, AgGaSe/GaSe, AgGaSe/GaTe, AgInSe/GaS, AgInSe/GaSe, AgInSe/GaTe, AgAlSe/GaS, AgAlSe/GaSe, AgAlSe/GaTe, AgTlSe/GaS, AgTlSe/GaSe, AgTlSe/GaTe, AgGaTe/GaS, AgGaTe/GaSe, AgGaTe/GaTe, AgInTe/ It may include, but is not limited to, GaS, AgInTe/GaSe, AgInTe/GaTe, AgAlTe/GaS, AgAlTe/GaSe, AgAlTe/GaTe, AgTlTe/GaS, AgTlTe/GaSe or AgTlTe/GaTe.

Quantum dots 10 include Ag as at least one group I element included in the first shell 14, and the multilayer shells 14/16 are more preferably AgGaS/GaS, AgGaS/GaSe, or AgGaS. /GaTe, AgInS/GaS, AgInS/GaSe, AgInS/GaTe, AgAlS/GaS, AgAlS/GaSe, AgAlS/GaTe, AgTlS/GaS, AgTlS/GaSe or AgTlS/GaTe.

In addition, the molar ratio of Ag contained in the AgInGaS core 12 and Ag contained in the first shell 14 in the quantum dot 10 is 1:0.5 to 1:1, preferably 1:0.5 to 1:0.75, More preferably, it may be 1:0.5 to 1:0.6.

When the molar ratio of Ag included in the AgInGaS core 12 and Ag included in the first shell 14 is within the range of 1:0.5 to 1:1, the quantum efficiency of the quantum dots 10 can be improved.

In addition, when the molar ratio of Ag contained in the AgInGaS core 12 and Ag contained in the first shell 14 is within the range of 1:0.5 to 1:0.75, the quantum dot 10 not only has improved quantum efficiency, but also has a half width at half maximum. can also be reduced.

In particular, when the molar ratio of Ag contained in the AgInGaS core 12 and Ag contained in the first shell 14 is within the range of 1:0.5 to 1:0.6, the quantum dot 10 not only improves quantum efficiency, but also has a half width at half maximum. can also be further reduced.

Meanwhile, at least one Group II element included in the outermost shell 18 may include Zn, and the outermost shell 18 may further include at least one Group VI element.

For example, at least one Group VI element included in the outermost shell 18 may include one or more selected from S, Se, and Te, but is not limited thereto.

For example, the outermost shell 18 may include, but is not limited to, ZnS, ZnSe, or ZnTe.

As another example, the outermost shell 18 may include three elements such as Zn from group II elements, one element other than Zn from group II elements, and one element from group VI elements. That is, the second shell 16 may include all combinations of elements that can be selected from group II elements and group VI elements, including Zn among group II elements but excluding Zn.

In addition, in the quantum dot 10, the multilayer shells 14 and 16 are disposed on the first shell 14 and further include a second shell 16 containing at least one Group III element, Ga, and the second shell 16 includes Ga. The molar ratio of Ga included in the shell 16 and Zn included in the outermost shell 18 may be 1:0.55 to 1:1.2, preferably 1:0.55 to 1:0.7.

When the molar ratio of Ga included in the second shell 16 and Zn included in the outermost shell 18 is within the range of 1:0.55 to 1:1.2, the quantum efficiency of the quantum dots 10 can be improved.

In addition, when the molar ratio of Ga contained in the second shell 16 and Zn contained in the outermost shell 18 is 1:0.55 to 1:0.7, the quantum dot 10 not only improves quantum efficiency, but also has a half width at half maximum. can also be reduced.

Figure 2 is a flowchart showing a method of manufacturing quantum dots according to embodiments of the present disclosure.

In the quantum dot manufacturing method according to the embodiments of the present disclosure, matters regarding the AgInGaS core, first shell, second shell, and outermost shell are in the quantum dot 10 according to the above-described embodiments unless otherwise specified. It is the same as that for the AgInGaS core 12, first shell 14, second shell 16, and outermost shell 18 described above.

Referring to FIG. 2, the method of manufacturing quantum dots according to embodiments of the present disclosure includes an AgInGaS core manufacturing step (S22).

The AgInGaS core manufacturing step (S22) may be a step of manufacturing an AgInGaS core by injecting a silver precursor, indium precursor, gallium precursor, sulfur precursor, and solvent into a reactor and heating them.

Silver precursors injected into the reactor include, for example, silver (Ⅰ) acetylacetonate, silver (Ⅰ) chloride, silver (Ⅰ) bromide, and silver iodide (silver (Ⅰ) chloride). It may be one or more selected from the group consisting of (Ⅰ) iodide, silver(Ⅰ) acetate, silver(Ⅰ) nitrate, and silver(Ⅰ) myristate, but is limited thereto. It doesn't work.

Indium precursors injected into the reactor include, for example, indium (Ⅲ) acetylacetonate, indium (Ⅲ) chloride, indium (Ⅲ) acetate, and trimethyl indium. , may be one or more selected from the group consisting of alkyl indium, aryl indium, indium (Ⅲ) myristate, and indium (Ⅲ) myristate acetate. Not limited.

Gallium precursors injected into the reactor include, for example, gallium(Ⅲ) acetylacetonate, gallium(Ⅲ) chloride, gallium(Ⅲ) iodide, and gallium bromide (gallium (Ⅲ)). It may be one or more selected from the group consisting of (Ⅲ) bromide, gallium (Ⅲ) acetate, and gallium (Ⅲ) nitrate, but is not limited thereto.

Sulfur precursors injected into the reactor include, for example, n-butanethiol, isobutane thiol, n-haxanethiol, and 1-octanethiol. , alkylthiols such as decanethiol, 1-dodecanethiol, hexadecanethiol, and octadecanethiol, sulfur chloride, elemental sulfur (S), sulfur -Trioctylphosphine (S-TOP), sulfur-octadecene (S-ODE), sulfur-toluene (S-toluene), sulfur-oleylamine (S-OLA), N It may be one or more selected from the group consisting of ,N-N,N-dimethylthiourea(N,N-dimethylthiourea), etc., but is not limited thereto.

The solvent injected into the reactor may be one or more selected from oleylamine, 1-octadecene, and trioctylamine, but is not limited thereto.

Each of the silver precursor, indium precursor, gallium precursor, and sulfur precursor injected into the reactor may be a precursor solution mixed with a solvent.

An AgInGaS core can be manufactured by reacting a silver precursor, an indium precursor, a gallium precursor, and a sulfur precursor in a reactor.

The AgInGaS core is centrifuged with the addition of a purification solvent, and the precipitate separated through centrifugation can be dispersed in a dispersion solvent.

The purification solvent may be methanol, ethanol, acetone, isopropanol (2-propanol, IPA), etc., and the dispersion solvent may be hexane, toluene, or octadecane. , heptane, oleylamine, 1-octadecene, etc.

Referring to FIG. 2, the method of manufacturing quantum dots according to embodiments of the present disclosure includes a first shell manufacturing step (S24).

The first shell manufacturing step is a step of manufacturing the first shell by injecting and reacting the AgInGaS core and the sulfur precursor into a first reactor equipped with a silver precursor and a gallium precursor.

Exemplary compounds of the silver precursor and gallium precursor provided in the first reactor are as described above in the AgInGaS core manufacturing step, and the silver precursor and gallium precursor provided in the first reactor are the same as the silver precursor and gallium precursor in the AgInGaS core manufacturing step. Or it may be different.

In addition, the example compound of the sulfur precursor injected into the first reactor is the same as described above in the AgInGaS core manufacturing step, and the sulfur precursor injected into the first reactor may be the same as or different from the sulfur precursor in the AgInGaS core manufacturing step.

The silver precursor and gallium precursor provided in the first reactor, and the sulfur precursor injected into the first reactor may each be a precursor solution mixed with a solvent.

In the first reactor, the silver precursor, gallium precursor, and sulfur precursor react to surround the AgInGaS core and produce a first shell containing AgGaS.

The AgInGaS core/first shell is centrifuged with the addition of a purification solvent, and the precipitate separated through centrifugation can be dispersed in a dispersion solvent.

Referring to FIG. 2, the method of manufacturing quantum dots according to embodiments of the present disclosure includes a second shell manufacturing step (S26).

The second shell manufacturing step is a step of manufacturing a second shell surrounding the first shell by injecting and reacting the AgInGaS core/first shell prepared in a second reactor equipped with a gallium precursor with a sulfur precursor.

Example compounds of the gallium precursor provided in the second reactor are the same as those described above in the AgInGaS core manufacturing step, and the gallium precursor provided in the second reactor may be the same as or different from the gallium precursor in the AgInGaS core manufacturing step.

In addition, the example compound of the sulfur precursor injected into the second reactor is the same as described above in the AgInGaS core manufacturing step, and the sulfur precursor injected into the second reactor may be the same as or different from the sulfur precursor in the AgInGaS core manufacturing step.

Each of the gallium precursor provided in the second reactor and the sulfur precursor injected into the second reactor may be a precursor solution mixed with a solvent.

The gallium precursor and the sulfur precursor react in the second reactor to produce a second shell that surrounds the first shell and includes GaS.

The AgInGaS core/first shell/second shell is centrifuged with the addition of a purification solvent, and the precipitate separated through centrifugation can be dispersed in a dispersion solvent.

Referring to FIG. 2, the method of manufacturing quantum dots according to embodiments of the present disclosure includes an outermost shell manufacturing step (S28).

The outermost shell manufacturing step may be a step of manufacturing an outermost shell surrounding the second shell by injecting and reacting the AgInGaS core/first shell/second shell, zinc precursor, and sulfur precursor manufactured in the third reactor.

The zinc precursors injected into the third reactor include dimethylzinc, diethylzinc, zinc acetate, zinc acetylacetonate, zinc iodide, and zinc bromide. (zinc bromide), zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, zinc nitrate, zinc oxide, It may be one or more selected from the group consisting of compounds such as zinc peroxide, zinc perchlorate, zinc sulfate, zinc stearate, and zinc oleate. However, it is not limited to this.

In addition, the example compound of the sulfur precursor injected into the third reactor is the same as described above in the AgInGaS core manufacturing step, and the sulfur precursor injected into the second reactor may be the same as or different from the sulfur precursor in the AgInGaS core manufacturing step.

Each of the zinc precursor and sulfur precursor injected into the third reactor may be a precursor solution mixed with a solvent.

In the third reactor, the zinc precursor and the sulfur precursor react to surround the second shell and produce an outermost shell containing ZnS.

The AgInGaS core/first shell/second shell/outermost shell is centrifuged with the addition of a purification solvent, and the precipitate separated through centrifugation can be dispersed in the dispersion solvent.

In another aspect, embodiments of the present disclosure provide a photosensitive resin composition containing quantum dots.

In describing the photosensitive resin composition according to the embodiments of the present disclosure, unless otherwise specified, details regarding the quantum dots are the same as those described for the quantum dots according to the embodiments of the present disclosure, and will therefore be omitted.

The photosensitive resin composition may include a quantum dot-ligand complex containing quantum dots, a photocrosslinkable monomer, an initiator, and a light diffuser.

Ligands include, for example, oleic acid, lauric acid, palmitic acid, myristic acid, 2-(2-methoxyethoxy)acetic acid, It may be 2-[2-(2-methoxyethoxy)ethoxy]acetic acid, and succinic acid mono-[2-(2-methoxy-ethoxy)-ethyl]ester, but is not limited thereto.

Quantum dot-ligand complexes can be prepared by coordinating a ligand to the surface of a quantum dot.

Photocrosslinkable monomers include, for example, monofunctional esters such as ethylene glycol methacrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, N-butyl methacrylate, T-butyl methacrylate, and hexyl. Methacrylate, ethylhexyl methacrylate, lauryl methacrylate, octyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, tetracyclodecyl methacrylate, N-phenylmaleimide, N-cyclohexyl maleimide Examples include mead, methacrylic acid, isobornyl methacrylate, styrene, vinyl acetic acid, and vinyl pyrrolidone, and multifunctional esters such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and diethylene glycol diacrylate. , triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, Dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol, dimethacrylate pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexa Acrylate, bisphenol A epoxy acrylate, ethylene glycol monomethyl ether acrylate, trimethylolpropane triacrylate, etc., and multi-acrylate with ethyleneoxy group or γ or ε-lactone chain linked. It is not limited to this.

The initiator may be one or more of a photopolymerization initiator and a thermal polymerization initiator.

The photopolymerization initiator may be, for example, one or more of an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, an oxime ester-based compound, a phosphorus-based compound, and a triazine-based compound.

As a thermal polymerization initiator, for example, a peroxide-based compound, an azobis-based compound, etc. can be used.

An initiator may be used with a photosensitizer that absorbs light, becomes excited, and then transfers the energy to cause a chemical reaction.

Examples of photosensitizers include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, etc. I can hear it.

In another aspect, embodiments of the present disclosure provide an optical film containing a photosensitive resin composition.

In describing the optical film according to the embodiments of the present disclosure, matters regarding the photosensitive resin composition are the same as those described for the photosensitive resin composition according to the embodiments of the present disclosure described above, unless otherwise specified. Decided to omit it.

The optical film may be, for example, a wavelength conversion film or a color filter that converts light of a specific wavelength into light of another specific wavelength. For example, the optical film according to embodiments of the present disclosure may be used as a color filter that converts the wavelength of light emitted from a backlight including a light emitting diode, but the optical film according to embodiments of the present disclosure may be used as a color filter. However, it is not limited to wavelength conversion films.

For example, an optical film can be positioned between the cathode and anode electrodes of an electroluminescent diode and used as a layer that emits light by electrons and holes arriving from the cathode and anode electrodes.

In another aspect, embodiments of the present disclosure provide an electronic device including an optical film.

Figure 3 is a cross-sectional view of an electronic device according to embodiments of the present disclosure.

Referring to FIG. 3, the electronic device 100 according to embodiments of the present disclosure includes a substrate 110, a light source 120 disposed on the substrate 110, and a light source 120 disposed in a path of light emitted from the light source 120. It includes a color conversion member 130, and the color conversion member 130 may be formed using the optical film described above.

The light source 120 included in the electronic device 100 may be a light emitting device. For example, the light source 12 may be an organic light emitting diode (OLED) or an inorganic light emitting diode (QLED or ILED).

In another aspect, according to embodiments of the present disclosure, an electroluminescent diode including an optical film is provided.

Figure 4 is a cross-sectional view of an electrolight-emitting diode according to embodiments of the present disclosure.

Referring to FIG. 4, the electroluminescent diode 200 includes, for example, a cathode electrode 210, an anode electrode 230, and an intermediate layer 220 located between the cathode electrode 210 and the anode electrode 230. and the intermediate layer 200 may include the optical film described above. The electroluminescent diode 200 may further include one or more functional layers such as a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer.

In describing the electroluminescent diode according to the embodiments of the present disclosure, matters regarding the optical film are the same as those described for the optical film according to the above-described embodiments of the present disclosure, unless otherwise specified, and will therefore be omitted. do.

In another aspect, according to embodiments of the present disclosure, an electronic device is provided including a display device including an optical film and a control unit that drives the display device.

In describing the electronic device according to the embodiments of the present disclosure, unless otherwise specified, matters regarding the electroluminescent diode are the same as those described for the electroluminescence diode according to the embodiments of the present disclosure described above, and will therefore be omitted. Do this.

Electronic devices include, for example, display devices, lighting devices, solar cells, portable or mobile terminals (e.g. smart phones, tablets, PDAs, electronic dictionaries, PMPs, etc.), navigation terminals, game consoles, various TVs, various computer monitors, etc. It may include all, but is not limited to this, and any type of device may be included as long as it includes the above component(s).

Quantum dots and methods for manufacturing quantum dots according to embodiments of the present disclosure can improve quantum efficiency.

In addition, quantum dots and methods for manufacturing quantum dots according to embodiments of the present disclosure can not only improve quantum efficiency but also reduce the half width.

Additionally, the photosensitive resin composition, optical film, electroluminescent diode, and electronic device according to embodiments of the present disclosure can improve quantum efficiency.

Hereinafter, examples according to the present disclosure will be specifically described as experimental examples, but the present disclosure is not limited to the following examples.

[Example]

Ⅰ. Quantum dot manufacturing

(1) Example 1 production (AgInGaS/AgGaS/GaS/ZnS quantum dots)

(1-1) AgInGaS core fabrication

1) In a 50 mL three-necked round flask equipped with a reflux, 5 mL of octadecene (ODE), 0.06M silver(I) acetate-oleylamine, 0.1 g of silver acetate, and 10 mL of oleylamine. mixture) 2 mL, 0.0487 g of indium chloride, 0.1284 g of gallium acetylacetonate, 1 M sulfur-oleylamine (S-OLA), a mixture of 0.305 g of sulfur and 9.5 mL of oleylamine ) Add 1 mL and 0.5 mL of dodecanethiol (DDT) and react at 120°C for 30 minutes while reducing the pressure of the mixture.

2) The reactant is replaced with N ₂ atmosphere, maintained at 210°C for 10 minutes, cooled to 180°C, and 5 mL of trioctylphosphine (TOP) is added to the cooled mixture.

3) Cool the reactant to room temperature, purify it with ethanol, obtain AgInGaS core precipitate, and redisperse the precipitate in toluene.

(1-2) Fabrication of AgGaS first shell

1) Add 16 mL of oleylamine, 0.014 g of silver iodide, and 1 g of gallium acetylacetonate to a 50 mL three-necked round flask equipped with a reflux and simmer at 120°C for 30 minutes while reducing pressure. react while

2) After replacing the reactant with N ₂ atmosphere, AgInGaS core prepared in step (1-1) and dispersed in toluene and 3.4 mL of 1M sulfur-oleylamine (S-OLA) were injected and incubated at 240°C for 10 minutes. react.

3) After the reaction mixture was cooled to 180°C, 5 mL of trioctylphosphine (TOP) was injected. After cooling to room temperature, ethanol was added, centrifuged, and redispersed in toluene.

(1-3) GaS second shell fabrication

1) Add 16 mL of oleylamine and 1 g of gallium acetylacetonate to a 50 mL three-necked round flask equipped with a reflux and react at 120°C for 30 minutes while reducing pressure.

2) After replacing the reactant with N ₂ atmosphere, AgInGaS quantum dots (AgInGaS core/AgGaS first shell) prepared in step (1-2) and dispersed in toluene and 3.4 mL of 1M sulfur-oleylamine (S-OLA) After injection, react at 240°C for 2 hours.

3) After the reaction is completed, the mixture is cooled to 180°C and 5 mL of trioctylphosphine (TOP) is injected. After cooling to room temperature, ethanol is added, centrifuged, and redispersed in toluene.

(1-4) Manufacturing of ZnS outermost shell

1) AgInGaS quantum dots (AgInGaS core/AgGaS first shell/GaS second shell) prepared in step (1-3) and dispersed in toluene and 10mL of octadecene (ODE) in a 50 mL three-necked round flask equipped with a reflux. , 1.5 mmol of zinc acetate, 1.5 mL of 1 M sulfur-oleylamine (a mixture of 0.305 g of sulfur and 9.5 mL of oleylamine), and 3 mmol of lauric acid were added, the pressure was reduced, and N ₂ was added. After replacing with the atmosphere, react at 180°C for 10 minutes.

2) The mixture is cooled to room temperature, ethanol is added, centrifuged, and then redispersed in toluene.

(2) Example 2 production (AgInGaS/AgGaS/GaS/ZnS quantum dots)

(2-1) AgInGaS core manufacturing

Prepared in the same manner as (1-1) of Example 1.

(2-2) Fabrication of AgGaS first shell

It was prepared in the same manner as (1-2) of Example 1, except that 0.021 g of silver iodide was used in (1-2) of Example 1.

(2-3) Fabrication of GaS second shell

Prepared in the same manner as (1-3) of Example 1.

(2-4) Manufacturing of ZnS outermost shell

Prepared in the same manner as (1-4) of Example 1.

(3) Example 3 production (AgInGaS/AgGaS/GaS/ZnS quantum dots)

(3-1) AgInGaS core manufacturing

Prepared in the same manner as (1-1) of Example 1.

(3-2) Fabrication of AgGaS first shell

It was prepared in the same manner as (1-2) of Example 1, except that 0.028 g of silver iodide was used in (1-2) of Example 1.

(3-3) GaS second shell production

Prepared in the same manner as (1-3) of Example 1.

(3-4) Manufacturing of ZnS outermost shell

Prepared in the same manner as (1-4) of Example 1.

(4) Example 4 Production (AgInGaS/AgGaS/GaS/ZnS quantum dots)

(4-1) AgInGaS core manufacturing

Prepared in the same manner as (1-1) of Example 1.

(4-2) Fabrication of AgGaS first shell

Prepared in the same manner as (1-2) of Example 1.

(4-3) GaS second shell production

Prepared in the same manner as (1-3) of Example 1.

(4-4) Manufacturing of ZnS outermost shell

In (1-4) of Example 1, except that 2.0 mmol of zinc acetate and 2 mL of 1 M sulfur-oleylamine (a mixture of 0.305 g of sulfur and 9.5 mL of oleylamine) were used. Prepared in the same manner as (1-4) of Example 1.

(5) Example 5 Preparation (AgInGaS/AgGaS/GaS/ZnS quantum dots)

(5-1) AgInGaS core manufacturing

Prepared in the same manner as (1-1) of Example 1.

(5-2) Fabrication of AgGaS first shell

Prepared in the same manner as (1-2) of Example 1.

(5-3) GaS second shell production

Prepared in the same manner as (1-3) of Example 1.

(5-4) Manufacturing of ZnS outermost shell

In (1-4) of Example 1, except that 2.5 mmol of zinc acetate and 2.5 mL of 1 M sulfur-oleylamine (a mixture of 0.305 g of sulfur and 9.5 mL of oleylamine) were used. Prepared in the same manner as (1-4) of Example 1.

(6) Example 6 Preparation (AgInGaS/AgGaS/GaS/ZnS quantum dots)

(6-1) AgInGaS core manufacturing

Prepared in the same manner as (1-1) of Example 1.

(6-2) Fabrication of AgGaS first shell

Prepared in the same manner as (1-2) of Example 1.

(6-3) GaS second shell production

Prepared in the same manner as (1-3) of Example 1.

(6-4) Manufacturing of ZnS outermost shell

In (1-4) of Example 1, except that 3.0 mmol of zinc acetate and 3 mL of 1 M sulfur-oleylamine (a mixture of 0.305 g of sulfur and 9.5 mL of oleylamine) were used. Prepared in the same manner as (1-4) of Example 1.

(7) Comparative example 1 production (AgInGaS/GaS/GaS/ZnS quantum dots)

(7-1) AgInGaS core manufacturing

Prepared in the same manner as (1-1) of Example 1.

(7-2) GaS first shell production

It was prepared in the same manner as in (1-2) of Example 1, except for silver iodide.

(7-3) GaS second shell production

Prepared in the same manner as (1-3) of Example 1.

(7-4) Manufacturing of ZnS outermost shell

Prepared in the same manner as (1-4) of Example 1.

(8) Comparative example 2 production (AgInGaS/GaS/GaS/GaS quantum dots)

(8-1) AgInGaS core manufacturing

Prepared in the same manner as (1-1) of Example 1.

(8-2) GaS first shell production

Prepared in the same manner as (7-2) of Comparative Example 1.

(8-3) GaS second shell production

Prepared in the same manner as (1-3) of Example 1.

(8-4) Manufacturing of ZnS outermost shell

Prepared in the same manner as (7-3) of Comparative Example 1.

Table 1 shows the results measured with Otsuka Electronics' QE-2000 equipment, and shows the optical characteristics of the manufactured quantum dots (Emission Peak, Quantum Yield, Full Width at Half Maximum, FWHM). Shows the results of confirmation.

Shell configuration Emission peak (nm) FWHM (nm) QY (%) Comparative Example 1 GaS/GaS/ZnS 530.6 33.1 74.3 Comparative Example 2 GaS/GaS/GaS 529.7 32.6 76.8 Example 1 AgGaS/GaS/ZnS 530.2 32.1 83.0 Example 2 AgGaS/GaS/ZnS 530.2 32.6 82.7 Example 3 AgGaS/GaS/ZnS 530.1 33.1 82.8 Example 4 AgGaS/GaS/ZnS 530.3 33.0 82.9 Example 5 AgGaS/GaS/ZnS 530.8 33.4 82.8 Example 6 AgGaS/GaS/ZnS 531.6 33.7 82.7

In Table 1, comparing Comparative Examples 1 and 2 with Examples 1 to 6, it can be seen that quantum efficiency is improved when Ag is included in the first shell. This is believed to be due to the fact that when the first shell is wrapped on the AgInGaS core, the first shell containing Ag has a similar lattice structure to the AgInGaS core, and thus the structural match between the AgInGaS core and the first shell is well achieved.

In addition, in Table 1, comparing Examples 1 and 2 with Comparative Example 1, when the mole ratio of Ag contained in the AgInGaS core and Ag contained in the first shell is within a certain range, Ag is included in the first shell. It can be seen that not only is the quantum efficiency superior to Comparative Example 1, but the half width is also reduced. This is believed to be due to the fact that Ag contained in a specific amount in the first shell reduced surface defects of the AgInGaS core.

Meanwhile, in Table 1, comparing Example 1 and Examples 4 to 6, when the molar ratio of Ga contained in the second shell and Zn contained in the outermost shell exceeds a certain range, the half width increases. You can check that. This is believed to be due to the fact that Zn in the outermost shell acts as a defect when it contains more than a certain amount.

Ⅱ. Manufacture of photosensitive resin compositions and optical films

P1 below can be synthesized by the reaction route suggested in Deoksan Neolux Co., Ltd.'s Korean Patent No. 10-2399434 (registration notice dated May 13, 2022), but the method of synthesizing P1 is not limited thereto.

(1) Example 7 (Photosensitive resin composition and optical film comprising Example 1)

(1-1) Preparation of photosensitive resin composition

In a 20 mL vial, 35 parts by weight of the quantum dot-ligand complex P1 containing the quantum dots prepared in Example 1, 57 parts by weight of a photocrosslinkable monomer (Eternal, EM224), and 5 parts by weight of phosphine oxide (Irgacure TPO) as an initiator. Add 3 parts by weight of Titanium(IV) oxide (SMS) as a light diffuser and stir at room temperature for 2 hours to prepare a photosensitive resin composition.

(1-2) Optical film manufacturing

Using the photosensitive resin composition prepared in ( _1-1 ), the photosensitive resin composition prepared above was added dropwise to a 50mm Pre-bake for 1 minute at ℃ late to form a film.

(2) Example 8 (Photosensitive resin composition and optical film comprising Example 2)

A photosensitive resin composition and a quantum dot film were prepared in the same manner as Example 7, except that the quantum dots prepared in Example 2 were used.

(3) Example 9 (Photosensitive resin composition and optical film comprising Example 3)

A photosensitive resin composition and a quantum dot film were prepared in the same manner as Example 7, except that the quantum dots prepared in Example 3 were used.

(4) Example 10 (Photosensitive resin composition and optical film comprising Example 4)

A photosensitive resin composition and a quantum dot film were prepared in the same manner as Example 7, except that the quantum dots prepared in Example 4 were used.

(5) Example 11 (photosensitive resin composition and optical film comprising Example 5)

A photosensitive resin composition and a quantum dot film were prepared in the same manner as in Example 7, except that the quantum dots prepared in Example 5 were used.

(6) Example 12 (Photosensitive resin composition and optical film comprising Example 6)

A photosensitive resin composition and a quantum dot film were prepared in the same manner as in Example 7, except that the quantum dots prepared in Example 6 were used.

(7) Comparative Example 3 (Photosensitive resin composition and optical film comprising Comparative Example 1)

A photosensitive resin composition and a quantum dot film were prepared in the same manner as in Example 7, except that the quantum dots prepared in Comparative Example 1 were used.

Table 2 shows the results measured with Otsuka Electronics' QE-2100 equipment, and shows the optical characteristics results of the optical film using the photosensitive resin composition (Emission Peak, Film Quantum Yield, Full Width at Shows the results of checking [Half Maximum, FWHM), thickness].

Emission peak (nm) FWHM (nm) Film QY (%) Thickness (㎛) Comparative Example 3 536.1 35.0 17.8 8.2 Example 7 535.2 34.4 23.9 8.3 Example 8 535.3 34.7 24.0 8.2 Example 9 535.2 34.9 23.9 8.4 Example 10 535.0 35.1 24.0 8.2 Example 11 535.1 35.4 23.8 8.1 Example 12 535.2 35.7 24.1 8.3

Meanwhile, according to the examples of the present disclosure and the above-described Comparative Example 1, quantum dots whose outermost shells contain Zn could be manufactured from a photosensitive resin composition. On the other hand, quantum dots that do not contain Zn in the outermost shell, as in Comparative Example 2 described above, could not be manufactured with a photosensitive resin composition. This is believed to be a result of the high affinity between the Zn element and the S element contained in the outermost shell of the quantum dot when the S element is included in the ridand as in P1 above.

In Table 2, comparing Comparative Example 3 and Examples 7 to 12, it can be seen that the quantum efficiency of the optical film is improved when Ag is included in the first shell. This is believed to be due to the fact that the first shell containing Ag has a similar lattice structure to the AgInGaS core, similar to the results in Table 1 above, and thus the lattice match between the AgInGaS core and the first shell is well achieved.

Additionally, in Table 2, comparing Examples 7 and 8 with Comparative Example 3, when the mole ratio of Ag contained in the AgInGaS core and Ag contained in the first shell is within a certain range, the optical film has It can be seen that not only is the quantum efficiency superior to that of the optical film of Comparative Example 3 that does not contain Ag, but the full width at half maximum is also reduced. This is believed to be due to the fact that Ag contained in a specific amount in the first shell reduced surface defects of the AgInGaS core.

Meanwhile, in Table 2, when comparing the optical film of Example 7 with the optical film of Examples 10 to 12, the mole ratio of Ga contained in the second shell and Zn contained in the outermost shell exceeds a certain range. In this case, it can be seen that the half width increases. This is believed to be due to the fact that Zn in the outermost shell acts as a defect when it contains more than a certain amount.

The above description is merely an illustrative description of the present disclosure, and those skilled in the art will be able to make various modifications without departing from the essential characteristics of the present disclosure. Accordingly, the embodiments disclosed in this specification are for illustrative purposes rather than limiting the present disclosure, and the spirit and scope of the present disclosure are not limited by these embodiments. The scope of protection of this disclosure should be interpreted in accordance with the claims below, and all technologies within the equivalent scope should be interpreted as being included in the scope of rights of this disclosure.

10: Quantum dots
12: AgInGaS core
14: first shell
16: second shell
18: Outermost shell
100: Electronic device
110: substrate
120: light source
130: Absence of color conversion
200: electroluminescent diode
210: cathode electrode
220: middle layer
230: anode electrode

Claims (21)

AgInGaS core containing Ag, In, Ga and S;
a multilayer shell disposed on the AgInGaS core and including at least two layers; and
It includes an outermost shell disposed on the multi-layer shell,
Among the multilayer shells, a first shell adjacent to the AgInGaS core contains at least one Group I element,
The outermost shell is a quantum dot containing at least one group II element. According to paragraph 1,
A quantum dot wherein at least one Group I element included in the first shell includes one or more selected from Cu, Ag, and Au. According to paragraph 1,
The first shell is a quantum dot further comprising at least one Group III element and at least one Group VI element. According to paragraph 3,
A quantum dot wherein at least one Group III element included in the first shell includes one or more selected from Al, Ga, In, and Tl. According to paragraph 3,
A quantum dot wherein at least one Group VI element included in the first shell includes one or more selected from S, Se, and Te. According to paragraph 3,
The first shell is CuAlS, CuAlSe, CuAlTe, CuGaS, CuGaSe, CuGaTe, CuInS, CuInSe, CuInTe, CuTlS, CuTlSe, CuTlTe, AgAlS, AgAlSe, AgAlTe, AgGaS, AgGaSe, AgGaTe, AgInS, AgInSe, AgInTe, AgTlS, AgTlSe , AgTlTe, AuAlS, AuAlSe, AuAlTe, AuGaS, AuGaSe, AuGaTe, AuInS, AuInSe, AuInTe, AuTlS, AuTlSe, AuTlTe, CuAlSSe, CuGaSSe, CuInSSe, CuTlSSe, CuAlSTe, CuGaSTe, CuInSTe, CuTlSTe, CuAlSeTe, CuGaSeTe, CuInSeTe, CuTlSeTe , AgAlSSe, AgGaSSe, AgInSSe, AgTlSSe, AgAlSTe, AgGaSTe, AgInSTe, AgTlSTe, AgAlSeTe, AgGaSeTe, AgInSeTe, AgTlSeTe, AuAlSSe, AuGaSSe, AuInSSe, AuTlSSe, AuAlSTe, AuGaSTe, AuInSTe, AuTlSTe, AuAlSeTe, AuGaSeTe, AuInSeTe or Au Includes TlSeTe Quantum dots. According to paragraph 1,
The multilayer shell surrounds the first shell and includes a second shell including at least one Group III element and at least one Group VI element. In clause 7,
A quantum dot wherein at least one Group III element included in the second shell includes one or more selected from Al, Ga, In, and Tl. In clause 7,
A quantum dot wherein at least one Group VI element included in the second shell includes one or more selected from S, Se, and Te. In clause 7,
The second shell is a quantum dot comprising AlS, AlSe, AlTe, GaS, GaSe, GaTe, InS, InSe, InTe, TlS, TlSe or TlTe. According to paragraph 1,
At least one Group I element included in the first shell includes Ag,
The multilayer shell is AgGaS/GaS, AgGaS/GaSe, AgGaS/GaTe, AgInS/GaS, AgInS/GaSe, AgInS/GaTe, AgAlS/GaS, AgAlS/GaSe, AgAlS/GaTe, AgTlS/GaS, AgTlS/GaSe, AgTlS/ GaTe, AgGaSe/GaS, AgGaSe/GaSe, AgGaSe/GaTe, AgInSe/GaS, AgInSe/GaSe, AgInSe/GaTe, AgAlSe/GaS, AgAlSe/GaSe, AgAlSe/GaTe, AgTlSe/GaS, AgTlSe/GaSe, AgTlSe/GaTe, AgGaTe/GaS, AgGaTe/GaSe, AgGaTe/GaTe, AgInTe/GaS, AgInTe/GaSe, AgInTe/GaTe, AgAlTe/GaS, AgAlTe/GaSe, AgAlTe/GaTe, AgTlTe/GaS, AgTlTe/GaSe, AgTlTe/GaTe, AgGaSSe/ GaS, AgGaSSe/GaSe, AgGaSSe/GaTe, AgInSSe/GaS, AgInSSe/GaSe, AgInSSe/GaTe, AgAlSSe/GaS, AgAlSSe/GaSe, AgAlSSe/GaTe, AgTlSSe/GaS, AgTlSSe/GaSe, AgTlSSe/GaTe, AgGaSTe/GaS, AgGaSTe/GaSe, AgGaSTe/GaTe, AgInSTe/GaS, AgInSTe/GaSe, AgInSTe/GaTe, AgAlSTe/GaS, AgAlSTe/GaSe, AgAlSTe/GaTe, AgTlSTe/GaS, AgTlSTe/GaSe, AgTlSTe/GaTe, AgGaSeTe/GaS, AgGaSeTe/ Quantum dots comprising GaSe, AgGaSeTe/GaTe, AgInSeTe/GaS, AgInSeTe/GaSe, AgInSeTe/GaTe, AgAlSeTe/GaS, AgAlSeTe/GaSe, AgAlSeTe/GaTe, AgTlSeTe/GaS, AgTlSeTe/GaSe or AgTlSeTe/GaTe. According to clause 11,
A quantum dot wherein the molar ratio of Ag included in the AgInGaS core and Ag included in the first shell is 1:0.5 to 1:1. According to paragraph 1,
At least one Group II element included in the outermost shell includes Zn, and the outermost shell further includes at least one Group VI element. According to clause 13,
A quantum dot wherein at least one Group VI element included in the outermost shell includes one or more selected from S, Se, and Te. According to clause 13,
The outermost shell is a quantum dot containing ZnS, ZnSe or ZnTe. According to clause 13,
The multilayer shell is disposed on the first shell and further includes a second shell containing at least one Group III element, Ga,
The molar ratio of the Ga included in the second shell and the Zn included in the outermost shell is 1:0.55 to 1:1.2. AgInGaS core manufacturing step of manufacturing an AgInGaS core;
A first shell manufacturing step of manufacturing a first shell by injecting the AgInGaS core and a sulfur precursor into a first reactor equipped with a silver precursor and a gallium precursor and reacting them;
A second shell manufacturing step of injecting the prepared AgInGaS core/first shell and a sulfur precursor into a second reactor equipped with a gallium precursor and reacting to produce a second shell surrounding the first shell; and
Quantum dots comprising an outermost shell manufacturing step of injecting and reacting the prepared AgInGaS core/first shell/second shell, zinc precursor, and sulfur precursor into a third reactor to produce an outermost shell surrounding the second shell. Manufacturing method. A photosensitive resin composition comprising the quantum dots of claim 1. An optical film comprising the photosensitive resin composition of claim 18. An electroluminescent diode comprising the optical film of claim 19. A display device comprising the optical film of claim 19; and a control unit that drives the display device.