KR102399431B1 - Semiconductor nanoparticle-ligand composite, photosensitive resin composition, optical film, electroluminescent diode and electronic device - Google Patents

Abstract

Embodiments of the present invention relate to a semiconductor nanoparticle-ligand composite, a photosensitive resin composition, an optical film, an electroluminescent diode, and an electronic device. More specifically, the present invention provides the optical film with excellent efficiency which can provide the semiconductor nanoparticle-ligand complex with excellent compatibility by comprising a ligand represented by formula 1, the electroluminescent diode, and the electronic device.

Description

Semiconductor nanoparticle-ligand complex, photosensitive resin composition, optical film, electroluminescent diode and electronic device

The present invention relates to a semiconductor nanoparticle-ligand complex, a photosensitive resin composition, a photosensitive optical film, an electroluminescent diode, and an electronic device.

Liquid crystal display devices, which have been widely used in the past, have low power consumption, are lightweight, and are widely used because they can be implemented in a thin film type. However, there is a problem in that a separate backlight is required because there is no self-luminescence, and it is difficult to realize a perfect black color compared to an organic light emitting diode. In addition, the organic light emitting diode display has difficulty in having wide color reproducibility due to the limitation of the structure of the organic material that emits light.

In order to solve the problem of the liquid crystal display device, a technology using a blue organic light emitting diode that emits blue light as a light source of a backlight unit and a quantum dot, which is a semiconductor nanoparticle-ligand complex that converts blue light into another color, is recently developed. there is.

In order to use quantum dots, a process of patterning a layer containing quantum dots is required, but quantum dots have low compatibility with organic resins used in the patterning process, so the content of quantum dots cannot be increased, so it is difficult to realize excellent color characteristics. am. Therefore, in order to improve quantum dot patterning processability, it is required to improve compatibility with organic resins used in the patterning process.

Embodiments of the present invention can provide a semiconductor nanoparticle-ligand complex having improved compatibility.

In addition, embodiments of the present invention can provide a photosensitive resin composition capable of forming an optical film capable of expressing excellent color characteristics.

In addition, embodiments of the present invention can provide an optical film capable of expressing excellent color characteristics.

In addition, embodiments of the present invention may provide an electric light emitting diode and an electronic device having excellent color characteristics.

In one aspect, embodiments of the present invention provide a semiconductor nanoparticle-ligand complex comprising a ligand represented by the following formula (1).

<Formula 1>

In Formula 1,

X is a functional group bonded to the surface of the semiconductor nanoparticles, -S (H),

R ¹ is a C ₆ ~ C ₃₀ arylene group; O, N, S, Si and P containing at least one heteroatom selected from the group consisting of C ₂ ~ C ₃₀ A heterocyclic group; C ₁ ~ C ₂₀ Alkylene group; C ₁ ~ C ₂₀ An alkoxyl group; C ₁ ~ C ₂₀ Alkylthio group; And it is selected from the group consisting of Formula 2,

The arylene group, heterocyclic group, aliphatic ring group, alkylene group, alkoxyl group, alkylthio group, aryloxy group and arylthio group are each deuterium; C ₆ ~ C ₂₀ Aryl group; C ₂ ~ C ₂₀ A heterocyclic group; C ₃ ~ C ₂₀ An aliphatic ring group; And C ₁ ~ C ₁₀ Alkyl group; may be further substituted with one or more substituents selected from the group consisting of,

Y is the following formula 3,

<Formula 2> <Formula 3> <Formula 4>

In Formula 2,

n1 is an integer from 0 to 12, R ² and R ³ are each independently hydrogen or a methyl group,

In Formula 3,

R ⁴ is Formula 4, R ⁵ is hydrogen or a methyl group,

In Formula 4,

n2 is an integer of 1 to 12, and R ⁶ and R ⁷ are each independently hydrogen or a methyl group.

The semiconductor nanoparticles may have a particle diameter of 1 nm to 30 nm.

In another aspect, according to embodiments of the present invention, (A) a semiconductor nanoparticle-ligand complex comprising Formula 1, (B) a photo-crosslinkable monomer and (C) an initiator; provides a photosensitive resin composition comprising a .

The photocrosslinkable monomer may be represented by the following formula (I).

[Formula I]

In the above formula (I),

R ¹⁰ to R ¹³ are each independently hydrogen or a methyl group,

n3 is an integer from 1 to 15;

The photosensitive resin composition may further include a light diffusing agent.

Here, the light diffusing agent may include barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.

The content of the light diffusing agent may be 0.1 wt% to 10 wt% based on the total amount of the photosensitive resin composition.

The photosensitive resin composition comprises, with respect to the total amount of the photosensitive resin composition, 10 wt% to 60 wt% of the semiconductor nanoparticle-ligand complex (A), 30 wt% to 90 wt% of the photocrosslinkable monomer (B), and the initiator (C) 0.1 wt% to 10 wt% may be included.

In another aspect, according to embodiments of the present invention, the semiconductor nanoparticles-including the ligand complex, and provides an optical film having a thickness of 0.005㎛ to 500㎛.

In another aspect, according to embodiments of the present invention, there is provided an electric light emitting diode comprising the optical film.

In another aspect, according to embodiments of the present invention, there is provided an electronic device including a display device including the optical film and a controller for driving the display device.

In another aspect, according to embodiments of the present invention, there is provided an electronic device including a display device including the electric light emitting diode and a controller for driving the display device.

According to the embodiments of the present invention, it is possible to provide a semiconductor nanoparticle-ligand complex having excellent compatibility with an organic resin by including the ligand represented by Chemical Formula 1.

In addition, according to embodiments of the present invention, by including the semiconductor nanoparticle-ligand complex, it is possible to provide a photosensitive resin composition capable of manufacturing an optical film, an electroluminescent diode, and an electronic device having excellent quantum efficiency.

1 is a diagram showing the compatibility of the semiconductor nanoparticles of Example 1-ligand complex.
2 is a view showing the compatibility of the semiconductor nanoparticles of Comparative Example 1-ligand complex.
FIG. 3 is a view showing the points at which the thickness and optical properties of the film coatings of Example 1 and Comparative Example 1 were evaluated.

Hereinafter, some embodiments of the present invention will be described in detail with reference to exemplary drawings. In adding reference numerals to components of each drawing, the same components may have the same reference numerals as much as possible even though they are indicated in different drawings. In addition, in describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description may be omitted.

In describing the components of the present invention, when "includes", "having", "consisting of", etc. are used, other parts may be added unless "only" is used. When a component is expressed in the singular, it may include a case in which the plural is included unless otherwise explicitly stated.

In addition, in describing the components of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only for distinguishing the elements from other elements, and the essence, order, order, or number of the elements are not limited by the terms.

In the description of the positional relationship of the components, when it is described that two or more components are "connected", "coupled" or "connected", two or more components are directly "connected", "coupled" or "connected" ", but it will be understood that two or more components and other components may be further "interposed" and "connected," "coupled," 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.

It should also be understood that when a component is referred to as being “on” or “on” another component, this may include instances where another component is “directly above” as well as intervening with another component. something to do. Conversely, when it is said that an element is "on top of" another part, it should be understood to mean that there is no other part in the middle. In addition, to be "on" or "on" the reference part means to be located above or below the reference part, and to necessarily mean to be located "on" or "on" in the direction opposite to the gravity not.

In the description of the temporal flow relationship related to the components, the operation method or the production method, for example, the temporal precedence relationship such as "after", "after", "after", "before", etc. Alternatively, when a flow precedence relationship is described, it may include a case where it is not continuous unless "immediately" or "directly" is used.

On the other hand, if numerical values or corresponding information for components are mentioned, even if there is no separate explicit description, the numerical values or corresponding information may be caused by various factors (eg process factors, internal or external shock, noise, etc.) It may be interpreted as including a possible error range.

As used herein, the term “halo” or “halogen” refers to fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), unless otherwise specified.

The term "alkyl", "alkyl group" or "alkylene group" as used herein, unless otherwise specified, has 1 to 60 carbons linked by a single bond, straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group , a radical of saturated aliphatic functional groups including alkyl-substituted cycloalkyl groups, cycloalkyl-substituted alkyl groups.

As used herein, the terms "alkenyl", "alkenyl group", "alkenyl" or "alkenyl group" each have a double bond, and include a straight or branched chain group, and 2 to 60 unless otherwise specified. may have a carbon number of

As used herein, the terms "alkynyl", "alkynyl group", "alkynyl", "alkynyl group", "alkynyl" or "alkynyl group" each have a triple bond and are straight-chain or It includes a branched chain group and may have 2 to 60 carbon atoms.

As used herein, the term “cycloalkyl” refers to an alkyl forming a ring having 3 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

As used herein, the term "alkoxyl group", "alkoxy group" or "alkyloxy group" refers to an alkyl group to which an oxygen radical is bonded, and may have 1 to 60 carbon atoms unless otherwise specified, but is limited herein. it is not As used herein, the term "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and unless otherwise specified, 2 to 60 It may have a carbon number of, but is not limited thereto.

As used herein, the term "alkylthio group" refers to an alkyl group to which a sulfur radical is attached, and may have 1 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

As used herein, the terms "aryl group" and "arylene group" each have 6 to 60 carbon atoms unless otherwise specified, but are not limited thereto. In embodiments of the present invention, the aryl group or the arylene group refers to a monocyclic or multicyclic aromatic compound. For example, the aryl group may be a phenyl group, a monovalent functional group of biphenyl, a monovalent functional group of naphthalene, a fluorenyl group, or a spirofluorenyl group.

As used herein, the prefix “aryl” or “ar” refers to a radical substituted with an aryl group. For example, an arylalkyl group is an alkyl group substituted with an aryl group, an arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the number of carbon atoms described herein. Also, when prefixes are named consecutively, it is meant that the substituents are listed in the order listed first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group and wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

As used herein, the term "fluorenyl group" or "fluorenylene group" may mean a monovalent or divalent functional group of fluorene, respectively, unless otherwise specified. "Substituted fluorenyl group" or "substituted fluorenylene group" may refer to a monovalent or divalent functional group of substituted fluorene. "Substituted fluorene" means that at least one of the following substituents R, R', R" and R'" is a functional group other than hydrogen, and R and R' are bonded to each other to form a spiro compound together with the carbon to which they are attached. Including cases where

As used herein, the term "spiro compound" has a 'spiro union', and the spiro linkage refers to a connection formed by sharing only one atom in two rings. At this time, the atoms shared by the two rings are called 'spiro atoms', and they are respectively 'monospiro-', 'dispiro-', 'trispiro-', depending on the number of spiro atoms in a compound. ' It can be called a compound.

The term "heterocyclic group" as used herein includes not only an aromatic ring, such as a "heteroaryl group" or "heteroarylene group", but also an aliphatic ring, and unless otherwise specified, each containing at least one heteroatom having 2 carbon atoms To 60 means a single ring and a polycyclic ring, but is not limited thereto.

As used herein, the term “aliphatic” refers to an aliphatic hydrocarbon having 1 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

As used herein, the term “aliphatic ring” refers to an aliphatic hydrocarbon ring having 3 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

As used herein, the term “heteroatom” refers to N, O, S, P or Si, unless otherwise specified.

In addition, the "heterocyclic group" may include a ring containing SO ₂ instead of carbon forming the ring. For example, "heterocyclic group" may include the following compounds.

As used herein, the term “ring” includes monocyclic and polycyclic rings, and includes hydrocarbon rings as well as heterocycles including at least one heteroatom, and may include aromatic and aliphatic rings.

The terms "polycyclic" and "polycyclic" as used herein include ring assemblies such as biphenyls, terphenyls, etc., fused multiple ring systems and spiro compounds, both aromatic as well as aliphatic It may include a heterocycle including at least one heteroatom as well as a hydrocarbon ring.

In addition, unless otherwise explicitly stated, as used herein, in the term "substituted or unsubstituted", "substitution" means deuterium, halogen, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ Alkoxy group, C ₁ -C ₂₀ Alkylamine group, C ₁ -C ₂₀ Alkylthiophene group, C ₆ -C ₂₀ Arylthiophene group, C ₂ -C ₂₀ Alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, C ₆ -C ₂₀ aryl group substituted with deuterium, C ₈ -C ₂₀ arylalkenyl group, silane group, boron group, germanium group, and O, N, S, Si and P containing at least one heteroatom selected from the group consisting of C ₂ -C ₂₀ heterocyclic group means substituted with one or more substituents selected from the group consisting of and is not limited to these substituents.

In this application, the 'functional group name' corresponding to the aryl group, arylene group, heterocyclic group, etc. exemplified as examples of each symbol and its substituents in the present application may be described as 'the name of the functional group reflecting the valence', but is described as the 'name of the parent compound' You may. For example, in the case of 'phenanthrene', a type of aryl group, the monovalent 'group' is 'phenanthryl (group)', and the divalent group is 'phenanthrylene (group)', etc. However, regardless of the valence, it can be written as the name of the parent compound, 'phenanthrene'. Similarly, in the case of pyrimidine, regardless of the valence, it is described as 'pyrimidine', It can also be written as 'name'. Therefore, in the present application, when the type of the substituent is described as the name of the parent compound, it may mean an n-valent 'group' formed by the detachment of a hydrogen atom bonding to a carbon atom and/or a hetero atom of the parent compound.

In the present specification, in describing the compound name or the substituent name, numbers or alphabets indicating positions may be omitted. For example, pyrido[4,3-d]pyrimidine to pyridopyrimidine, benzofuro[2,3-d]pyrimidine to benzofuropyrimidine, 9,9-dimethyl-9H-flu Orene can be described as dimethylfluorene and the like. Therefore, both benzo[g]quinoxaline and benzo[f]quinoxaline can be described as benzoquinoxaline.

In addition, unless there is an explicit explanation, the formula used in the present application may be applied the same as the definition of the substituent by the exponential definition of the following formula.

Here, when a is 0, the substituent R ¹ is absent, when a is 1, one substituent R ¹ is bonded to any one carbon of the carbons forming the benzene ring, and when a is 2 or 3, respectively, In this case, R ¹ may be the same or different from each other, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the indication of the hydrogen bonded to the carbon forming the benzene ring may be omitted. can

In the present application, the fact that substituents are bonded to each other to form a ring means that a plurality of substituents bonded to each other share an arbitrary atom, for example, at least one atom among carbon atoms and heteroatoms O, N, S, Si, and P to form a saturated or unsaturated ring. For example, in the case of naphthalene, an adjacent methyl group substituted on one benzene ring and a butadienyl group share one carbon to form an unsaturated ring, or a vinyl group and a propyleneyl group share one carbon to form an unsaturated ring It can be seen that a ring is formed. In addition, in the case of fluorene, it may be viewed as an aryl group having 13 carbon atoms, but two methyl groups substituted with a biphenyl group may be bonded to each other to share one carbon to form a ring.

In the present application, the organic electric device may mean a component(s) between the anode and the cathode, or may refer to an organic light emitting diode including the anode and the cathode, and the component(s) positioned therebetween.

In addition, in some cases, the organic electric device in the present application may mean an organic light emitting diode and a panel including the same, or may mean an electronic device including a panel and a circuit. Here, for example, the electronic device includes a display device, a lighting device, a solar cell, a portable or mobile terminal (eg, a smart phone, a tablet, a PDA, an electronic dictionary, a PMP, etc.), a navigation terminal, a game machine, various TVs, and various computers. It may include all monitors and the like, but is not limited thereto, and may be any type of device as long as it includes the component(s).

As used herein, the term "precursor" is a chemical substance prepared in advance to react semiconductor nanoparticles, and refers to all compounds including metals, ions, elements, compounds, complexes, complexes, and clusters. am. It is not necessarily limited to the final material of a certain reaction, but refers to a material that can be obtained in any step arbitrarily determined.

As used herein, the term “cluster” refers to particles in which single atoms, molecules, or other types of atoms are aggregated or combined within tens to thousands of atoms.

The semiconductor nanoparticle-ligand complex according to embodiments of the present invention includes a ligand represented by the following formula (1).

<Formula 1>

Hereinafter, Chemical Formula 1 will be described.

X is a functional group bonding to the surface of the semiconductor nanoparticles, and is -S(H). Since the ligand represented by Formula 1 forms a coordination bond with the inorganic atoms of the semiconductor nanoparticles, for example, X is -SH or H is detached from -SH to form a coordination bond with the semiconductor nanoparticles as -S.

R ¹ is a C ₆ ~ C ₃₀ arylene group; O, N, S, Si and P containing at least one heteroatom selected from the group consisting of C ₂ ~ C ₃₀ A heterocyclic group; C ₁ ~ C ₂₀ Alkylene group; C ₁ ~ C ₂₀ An alkoxyl group; C ₁ ~ C ₂₀ Alkylthio group; And it is selected from the group consisting of the following formula (2).

When R ¹ is an arylene group, for example, R ¹ may be a C ₆ -C ₂₀ arylene group, or a C ₆ -C ₁₈ arylene group. For example, R ¹ may be phenyl, biphenyl, naphthyl, and terphenyl.

When R ¹ is a heterocyclic group, for example, R ¹ may be a C ₂ ~ C ₂₀ heterocyclic group, or a C ₂ ~ C ₁₈ heterocyclic group. For example, R ¹ may be pyridine, pyrimidine, benzofuran, benzothiophene, dioxin, dibenzofuran, dibenzothiophene, naphthobenzothiophene, naphthobenzofuran, or the like.

When R ¹ is an alkylene group, for example, R ¹ may be a C ₁ to C ₁₀ alkylene group. For example, R ¹ may be a methylene group, an ethylene group, or a t-butylene group.

When R ¹ is an alkoxyl group, for example, R ¹ may be a C ₁ to C ₁₀ alkoxyl group. For example, R ¹ may be methoxy, t-butoxy, or the like.

When R ¹ is an alkylthio group, for example, R ¹ may be a C ₁ to C ₁₀ alkylthio group. For example, R ¹ may be a methylthio group or a t-butylthio group.

The arylene group, the heterocyclic group, the alkylene group, the alkoxyl group and the alkylthio group are each deuterium; C ₆ ~ C ₂₀ Aryl group; C ₂ ~ C ₂₀ A heterocyclic group; C ₃ ~ C ₂₀ An aliphatic ring group; And C ₁ ~ C ₂₀ Alkyl group; may be further substituted with one or more substituents selected from the group consisting of.

Y is the following formula (3).

<Formula 2> <Formula 3> <Formula 4>

In Formula 2, n1 is an integer of 0 to 12, and R ² and R ³ are each independently hydrogen or a methyl group.

In Formula 3, R ⁴ is Formula 4, and R ⁵ is hydrogen or a methyl group.

In Formula 4, n2 is an integer of 1 to 12, and R ⁶ and R ⁷ are each independently hydrogen or a methyl group.

Specifically, the ligand represented by Formula 1 may be one of the following L-1 to L-32, but is not limited thereto.

The semiconductor nanoparticles may include a central particle. The central particle may have a single-layer or multi-layer structure. The central particle may be composed of a group II-VI compound, a group II-V compound, a group III-V compound, a group III-IV compound, a group III-VI compound, a group IV-VI compound, or a mixture thereof. In addition, a dopant may be doped or alloyed with the central particle. The "mixture" includes not only a simple mixture of the compounds, but also a ternary compound, a quaternary compound, and a case in which a dopant is doped into the mixture.

One or more of the Group II element may be selected from the group consisting of Zn, Cd, Hg and Mg, and the Group III element may be one or more selected from the group consisting of Al, Ga, In and Ti.

The group IV element may be one or more selected from the group consisting of Si, Ge, Sn and Pb, the group VI element may be one or more selected from the group consisting of O, S, Se and Te, and group V One or more elements may be selected from the group consisting of P, As, Sb and Bi.

Group II-VI compounds include, for example, magnesium sulfide (MgS), magnesium selenide (MgSe), magnesium telluride (MgTe), calcium sulfide (CaS), calcium selenide (CaSe), calcium telluride (CaTe) , strontium sulfide (SrS), strontium selenide (SrSe), strontium telluride (SrTe), cadmium sulfide (CdS), cadmium selenide (CdSe), cadmium telluride (CdTe), zinc sulfide (ZnS), zinc selenide ( ZnSe), zinc telluride (ZnTe), mercury sulfide (HgS), mercury selenide (HgSe), or mercury telluride (HgTe).

Group II-V compounds include, for example, zinc phosphide (Zn ₃ P ₂ ), zinc arsenide (Zn ₃ As ₂ ), cadmium phosphide (Cd ₃ P ₂ ), cadmium arsenide (Cd ₃ As ₂ ), nitride It may be cadmium (Cd ₃ N ₂ ) or zinc nitride (Zn ₃ N ₂ ).

Group III-V compounds include, for example, boron phosphide (BP), aluminum phosphide (AlP), aluminum arsenide (AlAs), aluminum antimonide (AlSb), gallium nitride (GaN), gallium phosphide (GaP), Gallium arsenide (GaAs), gallium antimonide (GaSb), indium nitride (InN), indium phosphide (InP), indium arsenide (InAs), indium antimonide (InSb), aluminum nitride (AlN) or boron nitride (BN).

The group III-IV compound may be, for example, boron carbide (B ₄ C), aluminum carbide (Al ₄ C ₃ ), or gallium carbide (Ga ₄ C).

Group III-VI compounds are, for example, aluminum sulfide (Al ₂ S ₃ ), aluminum selenide (Al ₂ Se ₃ ), aluminum telluride (Al ₂ Te ₃ ), gallium sulfide (Ga ₂ S ₃ ), selenium It may be gallium sulfide (Ga ₂ Se ₃ ), indium sulfide (In ₂ S ₃ ), indium selenide (In ₂ Se ₃ ), gallium telluride (Ga ₂ Te ₃ ), or indium telluride (In ₂ Te ₃ ). .

The group IV-VI compound may be, for example, lead sulfide (PbS), lead selenide (PbSe), lead telluride (PbTe), tin sulfide (SnS), tin selenide (SnSe) or tin telluride (SnTe). there is.

When the central particle has a multi-layered structure, for example, the central particle may include a core/shell structure. In this case, the core and the shell of the central particle are a group II-IV compound, a group II-V compound, a group III-V compound, a group III-IV compound, a group III-VI compound, a group IV-VI compound, or a mixture thereof and a dopant may be doped or alloyed with the core or shell of the central atom, and the compound constituting the core and the compound constituting the shell may be different from each other. For example, the central particle may have a CdZnS/ZnS (core/shell) structure having a core including CdZnS and a shell including ZnS. In another example, the central particle may have an InZnP/ZnSeS (core/shell) structure having a core including InZnP and a shell including ZnSeS.

In another aspect, when the central particle has a multi-layered structure, for example, the central particle may have a core/multi-shell structure having a shell of at least two or more layers. In this case, the core and the shell of the central particle are a group II-IV compound, a group II-V compound, a group III-V compound, a group III-IV compound, a group III-VI compound, a group IV-VI compound, or a mixture thereof. may be made, a dopant may be doped or alloyed with the core or shell of the central atom, and the compound constituting the core and the compound constituting the shell may be different from each other. For example, the central particle is CdZnS/ZnS/ZnS having a core including CdZnS, a first shell surrounding the surface of the core and including ZnS, and a second shell surrounding the surface of the first shell and including ZnS It may have a (core/first shell/second shell) structure.

The central particle may be a single layer rather than a multi-layered structure (core/shell structure), and for example, may be formed of only a group II-IV compound.

The central particle may further include a cluster molecule as a seed. The cluster molecule is a compound serving as a seed in the process of manufacturing the central particle, and the central particle may be formed by growing precursors of the compound constituting the central particle on the cluster molecule.

The semiconductor nanoparticles may have a particle diameter of 1 nm to 30 nm, or 5 nm to 15 nm.

The semiconductor nanoparticle-ligand complex according to embodiments of the present invention may further include a ligand other than the ligand represented by Formula 1 above. For example, an amine-based compound having an alkyl group having 6 to 30 carbon atoms, (poly)ethyleneoxy, or an aryl group, a thiol compound or a carboxylic acid compound may be included as a ligand. Examples of the amine-based compound having an alkyl group include hexadecylamine or octylamine. As another example of the ligand, an amine compound or a carboxylic acid compound having an alkenyl group having 6 to 30 carbon atoms may be mentioned. Alternatively, as another example of the ligand, a phosphine compound including trioctylphosphine, triphenolphosphine, t-butylphosphine, and the like; phosphine oxides such as trioctylphosphine oxide; and pyridine or thiophene.

The types of ligands that can be used together with the ligands proposed in the present invention are not limited to those exemplified above.

The ligand of the semiconductor nanoparticle-ligand complex can prevent the central particles adjacent to each other from being agglomerated and quenched. The ligand binds to the central particle and may have hydrophobic properties.

In another aspect, embodiments of the present invention may provide a photosensitive resin composition.

The photosensitive resin composition includes (A) a semiconductor nanoparticle-ligand complex, (B) a photocrosslinkable monomer, and (C) an initiator.

In describing the photosensitive resin composition according to the embodiments of the present invention, the semiconductor nanoparticle-ligand complex is described above, unless otherwise specified, the semiconductor nanoparticle-ligand complex according to the above-described embodiments of the present invention. Since it is the same as described, it will be omitted.

The photosensitive resin composition may include 10 wt% to 60 wt% of the semiconductor nanoparticle-ligand complex based on the total amount of the photosensitive resin composition. The lower limit of the content of the semiconductor nanoparticle-ligand complex may be 20 wt% or more or 30 wt% or more. The upper limit of the content of the semiconductor nanoparticle-ligand complex may be 50% by weight or less. When the photosensitive resin composition contains the semiconductor nanoparticle-ligand complex in the above content, it may have sufficient luminescent effect and a viscosity suitable for coating and inkjetting.

The photocrosslinkable monomer may be a monofunctional ester of (meth)acrylic acid having one ethylenically unsaturated double bond or a polyfunctional ester of (meth)acrylic acid having at least two ethylenically unsaturated double bonds. The polyfunctional ester may be, for example, a difunctional ester, a trifunctional ester, or a tetrafunctional ester.

In the present invention, one type of the photocrosslinkable monomer may be used, or two or more types may be mixed.

Since the photocrosslinkable monomer has the ethylenically unsaturated double bond, sufficient polymerization occurs during exposure to light in the pattern forming process to form a pattern having excellent heat resistance, light resistance and chemical resistance.

Specific examples of the photo-crosslinkable monomer include monofunctional esters of ethylene glycol methacrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, N-butyl methacrylate, T-butyl methacrylate, hexyl Methacrylate, ethylhexyl methacrylate, lauryl methacrylate, octyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, tetracyclodecyl methacrylate, N-phenylmaleimide, N-cyclohexyl maleate Mead, methacrylic acid, isobornyl methacrylate, styrene, vinyl acetic acid, vinyl pyrrolidone, etc. are mentioned, Polyfunctional ester ethylene glycol diacrylate, ethylene glycol dimethacrylate, 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. However, the present invention is not limited thereto.

Commercially available products of the photocrosslinkable monomer are as follows.

Examples of the bifunctional ester of (meth)acrylic acid include Aronix M-210, M-240, M-6200 of Toagosei Chemical Co., Ltd. and KAYARAD HDDA, HX-220 of Nihon Kayaku Co., Ltd., R-604 and the like and V-260, V-312, V-335 HP, V-1000, V-802 manufactured by Osaka Yuki Chemical High School Co., Ltd. are mentioned.

Examples of the trifunctional ester of (meth)acrylic acid, Toagosei Chemical Co., Ltd. Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, M- 8060, Nihon Kayaku Co., Ltd.'s KAYARAD TMPTA, DPCA-20, DPCA-60, DPCA-120, etc. and Osaka Yuki Kayaku High School's V-295, V-300, V-360, etc. are mentioned.

The photocrosslinkable monomer may be represented by the following formula (I).

[Formula I]

In Formula I, R ¹⁰ to R ¹³ are, each independently, hydrogen or a methyl group.

In Formula I, n3 is an integer of 1 to 15.

Specifically, the compound represented by Formula I may be one of the following M-1 to M-10, but is not limited thereto.

The photo-crosslinkable monomer may be used after treatment with an acid anhydride in order to provide better developability. The photo-crosslinkable monomer may be included in an amount of 30 wt% to 90 wt%, or 35 wt% to 85 wt%, based on the total amount of the photosensitive resin composition. When the photo-crosslinkable monomer is included within the above range, the semiconductor nanoparticles and the initiator can be sufficiently put thereinto, thereby exhibiting a sufficient amount of light emission and high reliability.

The photosensitive resin composition may further include a binder resin.

The binder resin may be at least one selected from the group consisting of an acrylic resin and an epoxy resin.

As the initiator, at least one of a photopolymerization initiator and a thermal polymerization initiator may be used.

The photopolymerization initiator may be, for example, at least one 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.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloroacetophenone, p-t-Butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethyl amino)benzophenone, 4,4 '-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc. are mentioned.

Examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diiso and propyl thioxanthone and 2-chlorothioxanthone.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethyl ketal.

Examples of the oxime ester compound include 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime)-1-[9 -Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, 2-dimethylamino- 2-(4-Methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione2- Oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-one Oxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime-O-acetate, 1-(4-methylsulfanyl-phenyl)-butan-1-oneoxime-O-acetate , hydroxyimino-(4-methylsulfanyl-phenyl)-acetic acid ethyl ester-O-acetate, hydroxyimino-(4-methylsulfanyl-phenyl)-acetic acid ethyl ester-O-benzoate, and the like. .

Examples of the phosphorus compound include diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, benzyl (diphenyl) phosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and the like. can be heard

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3', 4'- Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine; 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho1-yl)-4,6 -bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho1-yl)-4,6-s(trichloromethyl)-s-triazine, 2-4-trichloromethyl (piperonyl)-6-triazine, 2-4-trichloromethyl(4'-methoxystyryl)-6-triazine, etc. are mentioned.

As the photopolymerization initiator, a carbazole-based compound, a diketone-based compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, or a biimidazole-based compound may be used in addition to the above compound.

As the thermal polymerization initiator, a peroxide-based compound, an azobis-based compound, or the like may be used.

Examples of the peroxide-based compound include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, and acetylacetone peroxide; diacyl peroxides such as isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, and bis-3,5,5-trimethylhexanoyl peroxide; hydroperoxides such as 2,4,4,-trimethylpentyl-2-hydroperoxide, diisopropylbenzenehydroperoxide, cumene hydroperoxide, and t-butylhydroperoxide; Dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butyloxyisopropyl)benzene, n-butyl t-butylperoxyvalerate dialkyl peroxides such as esters; alkyl peresters such as 2,4,4-trimethylpentyl peroxyphenoxyacetate, α-cumyl peroxyneodecanoate, t-butyl peroxybenzoate, and di-t-butyl peroxytrimethyl adipate; Di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis-4-t-butylcyclohexyl peroxydicarbonate, diisopropyl peroxydicarbonate, acetylcyclohexylsulfonyl peroxide, t -Percarbonates, such as butyl peroxyaryl carbonate, etc. are mentioned.

Examples of the azobis-based compound include 1,1'-azobiscyclohexane-1-carbonitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2,-azobis( methylisobutyrate), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), α,α′-azobis(isobutylnitrile) and 4,4′-azobis(4 -cyanovaleic acid) and the like.

The initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light to enter an excited state and then transferring the energy.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like. can be heard

The content of the initiator may be 0.1 wt% to 10 wt%, or 0.1 wt% to 8 wt% based on the total amount of the photosensitive resin composition. When the content of the initiator satisfies the above-mentioned range, curing occurs sufficiently during exposure or heating in the pattern forming process using the photosensitive resin composition to obtain excellent reliability, and the pattern has excellent heat resistance, light resistance and chemical resistance, and resolution and adhesion It is also excellent, and it is possible to prevent a decrease in transmittance due to an unreacted initiator.

The photosensitive resin composition may further include a light diffusing agent, for example, the light diffusing agent may include barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.

In this case, the content of the light diffusing agent may be 0.1 wt% to 10 wt%, or 0.1 wt% to 8 wt%, based on the total amount of the photosensitive resin composition. When the content of the light-diffusing agent satisfies the above-mentioned range, it may have a viscosity suitable for coating and inkjetting while having a sufficient light-diffusion effect.

In another aspect, according to embodiments of the present invention, it is possible to provide an optical film comprising a semiconductor nanoparticle-ligand complex.

In describing the optical film according to the embodiments of the present invention, the semiconductor nanoparticles-ligand complex is described for the semiconductor nanoparticles-ligand complex according to the above-described embodiments of the present invention unless otherwise specified. Since it is the same as that, we will omit it.

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

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

The optical film may be formed on the bare glass through spin coating, exposure, or heating process using a photosensitive resin composition. In this case, the spin coating, exposure, or heating process is merely an example, and the optical film may be formed by any method capable of forming the film without being limited to the spin coating, exposure or heating process.

In describing the optical film according to the embodiments of the present invention, the details of the photosensitive resin composition are the same as those described for the photosensitive resin composition according to the above-described embodiments of the present invention, unless otherwise specified, and thus omitted. do it with

The thickness of the optical film may be 0.005 μm to 500 μm, or 1 μm to 11 μm.

In another aspect, according to embodiments of the present invention, it is possible to provide an electric light emitting diode including an optical film. The electroluminescent diode may include, for example, a cathode electrode, an anode electrode, and an optical film positioned between the cathode electrode and the anode electrode. The electroluminescent diode may further include one or more of 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 diodes according to the embodiments of the present invention, the details of the optical film are the same as those described for the optical films according to the above-described embodiments of the present invention, unless otherwise specified, and thus will be omitted. do.

Since the optical film according to embodiments of the present invention is formed using a semiconductor nanoparticle-ligand complex having excellent compatibility, the electroluminescent diode may have excellent quantum efficiency.

In another aspect, embodiments of the present invention may provide an electronic device including a display device including an optical film and a controller for driving the display device.

In describing the electronic device according to the embodiments of the present invention, the optical film is the same as that described for the optical film according to the above-described embodiments of the present invention unless otherwise specified, and thus will be omitted. .

The electronic device may be used as a wavelength conversion film or a color filter for converting an optical film to a wavelength. Since the optical film according to the embodiments of the present invention is formed using a semiconductor nanoparticle-ligand complex having excellent compatibility, the electronic device according to the embodiments of the present invention may have excellent quantum efficiency.

In another aspect, embodiments of the present invention may provide an electronic device including a display device including an electric light emitting diode and a controller for driving the display device.

In describing the electronic device according to the embodiments of the present invention, the details of the electric light emitting diode are the same as those described for the electric light emitting diode according to the above-described embodiments of the present invention, unless otherwise specified, and thus will be omitted. do it with

Hereinafter, examples will be given with respect to the synthesis examples of the compounds according to the present invention and the manufacturing examples of the electric device will be described in detail, but the present invention is not limited to the following examples.

<Synthesis example>

The semiconductor nanoparticle-ligand complex (final product) represented by Formula 1 according to the present invention may be synthesized by reacting Sub1 and Sub2 as shown in Scheme 1 below, but is not limited thereto.

<Scheme 1>

X to Z and R ¹ are the same as defined in Formula 1 above.

I. Synthesis of semiconductor nanoparticles (Z)

1. Synthesis of semiconductor nanoparticles Z-1 (InZnP/ZnSeS)

Put 0.05 g of indium acetate, 1.14 g of zinc acetate, 3.7 g of oleic acid, and 15 mL of 1-Octadecene in a 50 mL three-necked round flask with a reflux device, heated to 110 °C, and maintained at about 0.1 torr using a vacuum pump for 1 hour. Remove the vacuum, put N ₂ gas, and heat to 280 ℃. Add 0.43 g of Tris(trimethylsilyl)phosphine at once. Agitation is maintained for 10 minutes after input. After dissolving 0.17 g of selenium and 0.07 g of sulfur in 5 mL of trioctyl phosphine, it was added to the reactor and stirred for 30 minutes. After dissolving 0.07 g of sulfur in 2 mL of Trioctyl phosphine, it is put back into the reactor and stirred for 10 minutes. The temperature was lowered to 240° C., maintained for 3 hours, cooled to room temperature, 100 ml of ethanol was added, stirred for 5 minutes, and the precipitate was prepared using a centrifugal separator to prepare semiconductor nanoparticles Z-1.

2. Synthesis of semiconductor nanoparticles Z-2 (CdZnSe/ZnSe/ZnS)

Cadmium acetate 0.097 g (Sigma-Aldrich), Zn acetate 1.878 g (Sigma-Aldrich), oleic acid 21 ml (Sigma-Aldrich), and 1-octadecene 45 ml (Sigma-Aldrich) were added to 250 with a reflux group. After putting in a ml 3-neck round-bottom reactor, the temperature is raised to 110 °C, and 0.1 torr is maintained for 1 hour using a vacuum pump. After that, the inside of the reactor is changed to an N ₂ atmosphere and the temperature is raised to 290 °C. After dissolving 0.65 g of selenium (Sigma-Aldrich) and 0.16 g of sulfur (Sigma-Aldrich) in 6 ml of trioctylphosphine (Sigma-Aldrich), temporarily put into the reactor and hold for 20 minutes. After dissolving 0.15 g of sulfur (Sigma-Aldrich) in 6 ml of trioctylphosphine, it is temporarily added to the reactor and maintained for 20 minutes. 1.6 g of Zn acetate and 5.4 g of oleic acid were placed in a 50 ml three-necked round-bottomed reactor equipped with 24 ml of 1-octadecene and a reflux device, the temperature was raised to 110 °C, and 0.1 torr was maintained for 1 hour using a vacuum pump, and then this solution was drained. Temporarily added to the reactor and maintained for 20 minutes. After cooling the reactor to room temperature, 100 ml of ethanol (Sigma-Aldrich) was added to the reaction solution, and then semiconductor nanoparticles Z-2 were prepared using a centrifuge.

II. Synthesis of Sub1

Sub1 of Scheme 1 is synthesized by the reaction route of Scheme 2 below, but is not limited thereto. In this case, Hal ¹ is I, Br, or Cl.

<Scheme 2>

1. Synthesis example of Sub1-1

After dissolving 6-Bromo-1-hexanol (20.0 g, 111 mmol) in THF (221 mL), the mixture was stirred at -10°C. Then (TMS) ₂ S (23.7 g, 133 mmol), TBAF 1M Solution in THF (122 mL) was added and stirred at room temperature for 30 minutes. When the reaction is completed, extraction is performed with CH ₂ Cl ₂ and NH ₄ Cl aqueous solution, and the organic layer is dried over MgSO ₄ and concentrated. Thereafter, the resulting compound was subjected to a silica gel column to obtain 12.8 g (yield: 86%) of the product.

2. Synthesis example of Sub1-2

4-Bromo-1-butanol (20.0 g, 131 mmol), (TMS) ₂ S (28.0 g, 157 mmol), TBAF 1M Solution in THF (144 mL) was prepared using the above method for the synthesis of Sub1-1 to 12.4 g of the product (Yield: 89%) was obtained.

3. Synthesis example of Sub1-7

2-[2-(2-Chloroethoxy)ethoxy]ethanol (20.0 g, 119 mmol), (TMS) ₂ S (25.4 g, 142 mmol), TBAF 1M Solution in THF (131 mL) Synthesis of Sub1-1 was used to obtain 16.0 g (yield: 81%) of the product.

4. Synthesis example of Sub1-14

4-Hydroxyphenethyl bromide (20.0 g, 99.5 mmol), (TMS) ₂ S (21.3 g, 119 mmol), TBAF 1M Solution in THF (109 mL) was prepared using the above method for the synthesis of Sub1-1 to 11.5 g of the product (Yield: 75%) was obtained.

4. Synthesis example of Sub1-15

4-(Chloromethyl)benzyl alcohol (20.0 g, 128 mmol), (TMS) ₂ S (27.3 g, 153 mmol), TBAF 1M Solution in THF (141 mL) was synthesized using the method of Sub1-1 above to synthesize 14.2 g of the product (Yield: 72%) was obtained.

On the other hand, the compound belonging to Sub1 may be a compound as follows, but is not limited thereto, and Table 1 shows FD-MS (Field Desorption-Mass Spectrometry) values of the following compounds.

Ⅲ. Synthesis of Sub2

Sub2 of Scheme 1 may be synthesized by the reaction route presented in Korean Patent No. 10-1140086 (registration dated April 18, 2012) and Japanese Patent No. 5165815 (published on December 28, 2012) by Showa Denko, but is limited thereto. not.

On the other hand, the compound belonging to Sub2 may be a compound as follows, but is not limited thereto, and Table 2 shows FD-MS (Field Desorption-Mass Spectrometry) values of the following compounds.

IV. Synthesis of final product

1. Synthesis example of P-1

(1) Synthesis example of Inter1-1

Z-1 (6 g) obtained in the above synthesis was dissolved in 60 ml of toluene, the temperature was raised to 150° C., Sub1-1 (3 g) was added, and the mixture was stirred for 2 hours. After adding 200 ml of toluene to the reaction solution, the mixture was stirred for 5 minutes, and the precipitate was centrifuged to obtain 6 g of Inter1-1.

(2) Synthesis example of P-1

Inter1-1 (3 g) obtained in the above synthesis was dissolved in 30 ml of acetone, Sub2-1 (1.5 g, Showa denko, AOI-EG) was added thereto and stirred for 2 hours to obtain semiconductor nanoparticle-ligand complex P-1 prepared. By measuring ¹ H-NMR (JEOL), it was confirmed that the reaction proceeded as three peaks appeared in the range of 6 to 6.5 ppm.

2. Synthesis example of P-2

Inter1-1 (3 g) and Sub2-2 (1.5 g, Showa denko, MOI-EG) obtained in the above synthesis were used for the synthesis of P-1 to prepare a semiconductor nanoparticle-ligand complex P-2. By measuring ¹ H-NMR, it was confirmed that the reaction proceeded with two peaks in the 6-6.5 ppm region and one peak in the 0.9 ppm region.

3. Synthesis example of P-14

(1) Synthesis example of Inter1-7

Z-1 (3 g) and Sub1-7 (1.5 g) obtained in the above synthesis were used for the above synthesis of Inter1-1 to obtain 3 g of Inter1-7.

(2) Synthesis example of P-14

Inter1-7 (3 g) and Sub2-2 (1.5 g, Showa denko, MOI-EG) obtained in the above synthesis were used for the synthesis of P-1 to prepare a semiconductor nanoparticle-ligand complex P-14. By measuring ¹ H-NMR, it was confirmed that the reaction proceeded with two peaks in the 6-6.5 ppm region and one peak in the 0.9 ppm region.

4. Synthesis example of P-28

(1) Synthesis example of Inter1-15

Z-1 (3 g) and Sub1-15 (1.5 g) obtained in the above synthesis were used for the above synthesis of Inter1-1 to obtain 2 g of Inter1-15.

(2) Synthesis example of P-28

Inter1-15 (2 g) and Sub2-2 (1 g, Showa denko, MOI-EG) obtained in the above synthesis were used for the synthesis of P-1 to prepare a semiconductor nanoparticle-ligand complex P-28. By measuring ¹ H-NMR, it was confirmed that the reaction proceeded with two peaks in the 6-6.5 ppm region and one peak in the 0.9 ppm region.

5. Synthesis example of P-32

(1) Synthesis example of Inter1-21

Z-1 (3 g) and Sub1-21 (1.5 g) obtained in the above synthesis were used for the synthesis of Inter1-1, to obtain 2 g of Inter1-21.

(2) Synthesis example of P-32

Inter1-21 (2 g) and Sub2-2 (1 g, Showa denko, MOI-EG) obtained in the above synthesis were used for the synthesis of P-1 to prepare a semiconductor nanoparticle-ligand complex P-32. By measuring ¹ H-NMR, it was confirmed that the reaction proceeded with two peaks in the 6-6.5 ppm region and one peak in the 0.9 ppm region.

Referring to the above-described synthesis method, semiconductor nanoparticles-ligand complexes such as the following P-1 to P-32 may be prepared, but the semiconductor nanoparticles-ligand complexes according to embodiments of the present invention include the following P-1 to It is not limited to the P-32. In the following P-1 to P-32, Z means the surface of the semiconductor nanoparticles. The following P-1 to P-32 indicate that one ligand coordinates with Z for convenience. can

Preparation of photosensitive resin composition

[Example 1]

In a 20 mL vial, 35 parts by weight of the semiconductor nanoparticle-ligand complex P-2 of the present invention as a semiconductor nanoparticle-ligand complex, 60 parts by weight of M-1 (Eternal, EM224) as a photocrosslinking monomer, Ingacure TPO ( Basf) was added in 5 parts by weight and stirred at room temperature for 2 hours to prepare a photosensitive resin composition.

[Example 2]

In a 20 mL vial, 35 parts by weight of the semiconductor nanoparticle-ligand complex P-14 of the present invention as a semiconductor nanoparticle-ligand complex, 60 parts by weight of M-1 as a photo-crosslinking monomer, and 5 parts by weight of Ingacure TPO as an initiator 2 A photosensitive resin composition was prepared by stirring at room temperature for a period of time.

[Example 3]

In a 20 mL vial, 35 parts by weight of the semiconductor nanoparticle-ligand complex P-14 of the present invention as a semiconductor nanoparticle-ligand complex, 57 parts by weight of M-1 as a photo-crosslinking monomer, 5 parts by weight of Ingacure TPO as an initiator, light diffusion A photosensitive resin composition was prepared by adding 3 parts by weight of zero titanium(IV) oxide (SMS) and stirring at room temperature for 2 hours.

[Comparative Example 1]

In a 20 mL vial, 35 parts by weight of the following comparative semiconductor nanoparticle-ligand complex C-1, 60 parts by weight of M-1 as a photo-crosslinking monomer, and 5 parts by weight of Ingacure TPO as an initiator, and stirring at room temperature for 2 hours, photosensitive resin composition was prepared.

[Comparative Example 2]

In a 20 mL vial, 35 parts by weight of the following comparative semiconductor nanoparticle-ligand complex C-2, 60 parts by weight of M-1 as a photo-crosslinking monomer, and 5 parts by weight of Ingacure TPO as an initiator, and stirred at room temperature for 2 hours to create a photosensitive resin composition was prepared.

[Comparative semiconductor nanoparticle-ligand complex C-1] [Comparative semiconductor nanoparticle-ligand complex C-2]

In the structure, Z is a semiconductor nanoparticle Z-1 (InZnP/ZnSeS).

Viscosity measurement method

In Yellow Room conditions, 0.5 mL of the photosensitive resin compositions of Examples and Comparative Examples prepared above were added dropwise to the specimen holder of a viscometer (Brookfield) and measured at 20 rpm for 1 minute.

Film formation method

Under N ₂ condition, the photosensitive resin compositions of Examples and Comparative Examples prepared above were added dropwise to 50mm x 50mm bare glass, coated at 500 rpm for 30 seconds using a spin coater, and then pre-baked at 100℃ on a hot plate for 1 minute to form a film.

How to measure thickness

Film coating properties and thicknesses of the films prepared in Examples and Comparative Examples prepared above were measured at five different points in the same glass as shown in FIG. 3 using a 3D profiler (Nano system) equipment. The measurement results are shown in Table 3 below.

Film Quantum Efficiency (Film QY) Measurement Method

Film quantum efficiencies at five different points in the same glass were measured for the films prepared in Examples and Comparative Examples prepared above as shown in FIG. 3 using QE-2100 of Otsuka Corporation. The measurement results are shown in Table 3 below.

The measurement results of the viscosity, thickness, and Film QY of the photosensitive resin composition and the film using the photosensitive resin composition in Examples and Comparative Examples prepared as described above are shown in Table 3 below.

Compatibility evaluation of semiconductor nanoparticles-ligand complexes

The photosensitive resin compositions prepared in Examples and Comparative Examples were visually observed to evaluate the compatibility of the semiconductor nanoparticle-ligand complex according to the following criteria, and the results are shown in Table 4 below.

○: No aggregation phenomenon of semiconductor nanoparticle-ligand complex

△: Aggregation of the semiconductor nanoparticle-ligand complex appears

×: The aggregation phenomenon of the semiconductor nanoparticle-ligand complex is large.

As can be seen from the results in Table 3, the photosensitive resin composition of the present invention has a viscosity of 20 cps or less lower than the photosensitive resin compositions of Comparative Examples 1 and 2, and Comparative Examples 1 and 2 have a viscosity higher than 20 cps. will have Such a low viscosity has excellent properties in the process, and if it has a high viscosity, it is impossible to make a uniform film due to problems such as clogging of the nozzle during the process and poor spreadability of the substrate when applied to inkjetting.

Referring to FIGS. 1, 2 and 3 , the semiconductor nanoparticle-ligand complex included in the photosensitive resin composition according to embodiments of the present invention is judged to have high compatibility.

Conversely, in the case of Comparative Example 1, compatibility is very poor, and Comparative Example 2 is also inferior in compatibility. For this reason, it is judged that the aggregation phenomenon of the semiconductor nanoparticle-ligand complex increases. If the aggregation of the semiconductor nanoparticle-ligand complex increases, it is expected that the quantum efficiency will be affected due to the interaction between the semiconductor nanoparticle-ligand complex.

In the case of Comparative Example 2, although it mixes well with the raw materials of other photosensitive resin compositions, it shows a high viscosity that is difficult to form a film because it has a low polarity compared to Examples 1 to 3, and thus the difference in thickness for each location in the same film is large. can check that

In addition, when compatibility is increased, it is possible to uniformly manufacture a desired thickness during film formation. When the thickness and quantum efficiency of the bare glass of Example 1 having high compatibility and Comparative Example 1 having low compatibility were measured, it was confirmed that in Example 1, uniform thickness and quantum efficiency were exhibited at each point. On the contrary, in the case of Comparative Examples 1 and 2, non-uniform thickness and quantum efficiency for each point are shown.

As a result, it is possible to prepare a photosensitive resin composition having a low viscosity and high compatibility with the semiconductor nanoparticle-ligand composite of the present invention, and thus it is judged to have a uniform film and remarkably excellent quantum efficiency.

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in the present specification are intended to illustrate, not to limit the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be construed by the following claims, and all descriptions within the scope equivalent thereto should be construed as being included in the scope of the present invention.

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in the present specification are intended to illustrate, not to limit the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be construed by the following claims, and all descriptions within the scope equivalent thereto should be construed as being included in the scope of the present invention.

Claims (13)

A semiconductor nanoparticle comprising the following formula (1)-ligand complex:
<Formula 1>

In Formula 1,
X is a functional group bonded to the surface of the semiconductor nanoparticles, -S (H),
R ¹ is a C ₆ ~ C ₃₀ arylene group; O, N, S, Si and P containing at least one heteroatom selected from the group consisting of C ₂ ~ C ₃₀ A heterocyclic group; C ₁ ~ C ₂₀ Alkylene group; C ₁ ~ C ₂₀ An alkoxyl group; C ₁ ~ C ₂₀ Alkylthio group; And it is selected from the group consisting of Formula 2,
The arylene group, the heterocyclic group, the alkylene group, the alkoxyl group and the alkylthio group are each deuterium; C ₆ ~ C ₂₀ Aryl group; C ₂ ~ C ₂₀ A heterocyclic group; C ₃ ~ C ₂₀ An aliphatic ring group; And C ₁ ~ C ₁₀ Alkyl group; may be further substituted with one or more substituents selected from the group consisting of,
Y is the following formula 3,
<Formula 2><Formula3><Formula4>

In Formula 2,
n1 is an integer from 0 to 12, R ² and R ³ are, independently of each other, hydrogen or a methyl group;
In Formula 3,
R ⁴ is Formula 4, R ⁵ is hydrogen or a methyl group,
In Formula 4,
n2 is an integer of 1 to 12, and R ⁶ and R ⁷ are, each independently, hydrogen or a methyl group. According to claim 1,
The ligand represented by Formula 1 is any one of the following compounds semiconductor nanoparticles-ligand complex:

. According to claim 1,
The semiconductor nanoparticles have a particle diameter of 1 nm to 30 nm, characterized in that the semiconductor nanoparticles-ligand complex. (A) the semiconductor nanoparticles of claim 1-ligand complex;
(B) a photocrosslinkable monomer; and
(C) an initiator;
A photosensitive resin composition comprising a. 5. The method of claim 4,
A photosensitive resin composition wherein the photocrosslinkable monomer is a compound represented by the following formula (I):
[Formula I]

In the above formula (I),
R ¹⁰ to R ¹³ are each independently hydrogen or a methyl group,
n3 is an integer from 1 to 15; 5. The method of claim 4,
A photosensitive resin composition further comprising a light diffusing agent. 7. The method of claim 6,
The light diffusing agent is a photosensitive resin composition comprising barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof. 7. The method of claim 6,
The content of the light diffusing agent is 0.1 wt% to 10 wt% of the photosensitive resin composition based on the total amount of the photosensitive resin composition. 5. The method of claim 4,
With respect to the total amount of the photosensitive resin composition,
The semiconductor nanoparticle-ligand complex (A) 10% to 60% by weight, the photo-crosslinkable monomer (B) 30% to 85% by weight, and the initiator (C) 0.1% to 10% by weight A photosensitive resin comprising composition. An optical film comprising the semiconductor nanoparticle-ligand complex of claim 1 and having a thickness of 0.005 μm to 500 μm. An electric light emitting diode comprising the optical film of claim 10 . A display device comprising the optical film of claim 10; and a controller configured to drive the display device. A display device comprising the electroluminescent diode of claim 11; and a controller configured to drive the display device.

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