KR101963224B1 - Nanoparticle and method of preparing the same, solution including the nanoparticle, and nanoparticle film and method of preparing the film - Google Patents

Abstract

Nanoparticles and methods for their preparation, solutions containing the nanoparticles, and nanoparticle films and methods for their preparation are disclosed. The disclosed nanoparticles include an inorganic center and an organic-inorganic hybrid ligand bound to the inorganic center.

Description

TECHNICAL FIELD The present invention relates to a nanoparticle and a method for preparing the nanoparticle, a solution including the nanoparticle, a nanoparticle film, and a method for preparing the nanoparticle,

Nanoparticles and methods for their preparation, solutions containing the nanoparticles, and nanoparticle films and methods for their preparation are disclosed. More particularly, the present invention relates to nanoparticles comprising an inorganic center and an organic-inorganic hybrid ligand bound to the inorganic center, a process for producing the nanoparticle, a solution containing the nanoparticle, and a nanoparticle film and a method for producing the same.

Colloidal quantum dots and nanowires passivated with organic ligands (or organic surfactants) are not aggregated in the solution due to steric hinderance of the organic ligand, and maintain a stable structure. Due to passivation of surface defects, excellent light And exhibits a photoluminescence (PL) characteristic. However, such an organic ligand is electrically insulative, and therefore, the nanoparticle film containing the organic ligand has poor electrical characteristics.

One embodiment of the present invention provides nanoparticles comprising a oil-in-water hybrid ligand.

Another embodiment of the present invention provides a method for producing the nanoparticles.

Another embodiment of the present invention provides a solution comprising said nanoparticles.

Another embodiment of the present invention provides a nanoparticle film comprising the nanoparticles.

 Another embodiment of the present invention provides a method for producing the nanoparticle film.

According to an aspect of the present invention,

Inorganic center; And

And an organic-inorganic hybrid ligand bonded to the inorganic center.

The organic-inorganic hybrid ligand may comprise 0.01 to 100 moles of organic ligand per mole of inorganic ligand.

The inorganic center may have a single layer structure, a dual structure of a core / shell, or a triple structure of a core / first shell / second shell.

The inorganic center has a crystalline polyhedral structure, and the organic-inorganic hybrid ligand may include an organic ligand and an inorganic ligand bonded to different crystal planes of the inorganic center.

The inorganic center has an amorphous structure, and the organic-inorganic hybrid ligand may include an organic ligand and an inorganic ligand randomly bonded to the inorganic center.

The inorganic center may be selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgSe, CdHgTe, HgZnS, HgZnSe, CdHgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe; InNb, InNb, InNb, InNb, InNb, InNb, InNb, InNb, InNb, InNb, GaNb, GaNb, InAlSb, InAlNb, InAlNb, InAlNb, InAlNb, InAlNb, InAlNb, GaInNb, SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe; At least one inorganic compound selected from the group consisting of Si, Ge, SiC and SiGe.

The organic-inorganic hybrid ligand may be at least one selected from the group consisting of Sn ₂ S ₆ , Sn ₂ Se ₆ , In ₂ Se ₄ , In ₂ Te ₃ , Ga ₂ Se ₃ , CuInSe ₂ , Cu ₇ S ₄ , Hg ₃ Se ₄ , Sb ₂ Te ₃ And a hydrazine hydrate of ZnTe.

The organic-inorganic hybrid ligand may be selected from organic ligands such as mercapto propionic acid (MPA), cysteamine, mercaptoacetic acid, TOP (trioctylphosphine), TOPO (trioctylphosphine oxide), oleic acid, oleylamine Octadecylamine, hexadecylamine, octanethiol, dodecanethiol, hexylphosphonic acid (HPA), tetradecylphosphonic acid (TDPA), octadecylamine, And at least one organic compound selected from the group consisting of octylphosphinic acid (OPA).

The nanoparticles may have a zero-dimensional structure, a one-dimensional structure, or a two-dimensional structure.

The nanoparticles may be in the form of quantum dots, nanowires, nanorods, nanoplates, or nanosheets.

According to another aspect of the present invention,

Inorganic center;

An organic ligand bound to the inorganic center; And

And an inorganic layer disposed to at least partially cover the inorganic center.

The inorganic layer is made of Sn ₂ S ₆ , Sn ₂ Se ₆ , In ₂ Se ₄ , In ₂ Te ₃ , Ga ₂ Se ₃ , CuInSe ₂ , Cu ₇ S ₄ , Hg ₃ Se ₄ , Sb ₂ Te ₃ and ZnTe And at least one inorganic compound selected from the group consisting of

According to another aspect of the present invention,

Preparing a solution of nanoparticles comprising an organic ligand or an inorganic ligand; And

And a step of exchanging the organic ligand or a part of the inorganic ligand with an inorganic ligand or an organic ligand.

According to another aspect of the present invention,

The nanoparticles; And

And a solvent for dissolving the nanoparticles.

According to another aspect of the present invention,

The nanoparticles; And

And a nanoparticle film comprising an inorganic matrix embedded with the nanoparticles.

The inorganic matrix is made of Sn ₂ S ₆ , Sn ₂ Se ₆ , In ₂ Se ₄ , In ₂ Te ₃ , Ga ₂ Se ₃ , CuInSe ₂ , Cu ₇ S ₄ , Hg ₃ Se ₄ , Sb ₂ Te ₃ and ZnTe And at least one inorganic compound selected from the group consisting of

According to another aspect of the present invention,

Mixing a solution of the nanoparticles with an inorganic matrix precursor to prepare a composition for forming a nanoparticle film;

Applying the composition for forming a nanoparticle film on a substrate; And

And heat treating the composition for forming a nanoparticle film applied on the substrate.

The inorganic matrix precursor may comprise a metal chalcogenide complex.

Wherein the inorganic matrix precursor is selected from the group consisting of Sn ₂ S ₆ , Sn ₂ Se ₆ , In ₂ Se ₄ , In ₂ Te ₃ , Ga ₂ Se ₃ , CuInSe ₂ , Cu ₇ S ₄ , Hg ₃ Se ₄ , Sb ₂ Te ₃ , And at least one inorganic compound selected from the group consisting of hydrazine hydrates thereof.

The heat treatment may be performed at a temperature ranging from 100 to 300 ° C.

The nanoparticles according to one embodiment of the present invention include an inorganic core and an organic-inorganic hybrid ligand bonded to the inorganic center, thereby exhibiting excellent optical properties such as charge transportability and photoluminescence efficiency, The oxidation state and the reduction state, the surface dipole and the energy band level are controlled, the miscibility with the solvent is improved, the solution processability is excellent, and various functions can be obtained by controlling the kind and concentration of the organic ligand.

1A is a schematic cross-sectional view of a nanoparticle according to one embodiment of the present invention.
1B is a schematic cross-sectional view of a nanoparticle according to another embodiment of the present invention.
2A is a schematic cross-sectional view of a nanoparticle according to another embodiment of the present invention.
Figure 2b is a schematic cross-sectional view of a nanoparticle according to another embodiment of the present invention.
3A is a view for explaining a method for producing nanoparticles according to an embodiment of the present invention.
FIG. 3B is a view for explaining a method for producing nanoparticles according to another embodiment of the present invention.
4 is a graph showing an optical density spectrum of each nanoparticle-containing solution prepared in Example 1. FIG.
5 is a graph showing a photoluminescence spectrum of each nanoparticle-containing solution prepared in Example 1. FIG.

Hereinafter, nanoparticles according to one embodiment of the present invention, a method for producing the nanoparticles, a solution containing the nanoparticles, a nanoparticle film, and a method for producing the nanoparticle film will be described in detail.

Nanoparticles according to one embodiment of the present invention include an inorganic center and an organic-inorganic hybrid ligand bound (e.g., coordinately bound) to the inorganic center. As used herein, " nanoparticle " means a particle having a maximum particle size of less than 1 nanometer and less than 100 nanometers. Also, in the present specification, the term "organic-inorganic hybrid ligand" means a mixed ligand of an organic ligand and an inorganic ligand.

Since the organic ligand has electrical insulation, the flow of the charge carrier (electron or hole) through it is restricted. However, since the organic ligand has functionality, it can be used as a factor for controlling the physical properties of the nanoparticles. By appropriately selecting and / or controlling, for example, the kind and content of the organic ligand and / or the ratio of the organic ligand to the inorganic ligand, the dipole moment, oxidation state and reduction state of the nanoparticle, photoluminescence efficiency , Compatibility with solvents, solution processibility, polarity and charge can be controlled. In addition, various functionalities can be imparted to the organic ligand.

The inorganic ligand is low in electric resistance, so that the flowability of the charge carrier through the inorganic ligand is good. Thus, most of the charge carriers flow through the inorganic ligand rather than the organic ligand. In addition, the inorganic ligand can lower the energy barrier at the interface between the nanoparticles and the inorganic matrix in the nanoparticle film described later, and improve the electrical characteristics of the nanoparticle film. The electrical properties may include bandgap or band level, P-type or n-type characteristics and conductivity. However, such inorganic ligands themselves can not impart functionality to the nanoparticles, and functionality can be imparted to the nanoparticles by the organic ligands as described above.

The organic-inorganic hybrid ligand may comprise from 0.01 to 100 moles, for example, from 0.1 to 10 moles, for example, from 0.2 to 1.5 moles, of the organic ligand per mole of the inorganic ligand. When the mole of the organic ligand per 1 mole of the inorganic ligand is within the above range (i.e., 0.01 to 100 moles), nanoparticles having excellent electrical and optical properties and various functionalities can be obtained.

The inorganic center may have a single layer structure (e.g., CdSe), a dual structure of core / shell (e.g., CdSe / CdS) or a triple structure of core / first shell / second shell / CdS / ZnS).

The inorganic center has a crystalline polyhedral structure, and the organic-inorganic hybrid ligand may include an organic ligand and an inorganic ligand bonded to different crystal planes of the inorganic center (see FIG. 1A). For example, the nanoparticles of rocksalt or zinc blende have (100) and (111) crystal faces, respectively, and the (111) crystal face has a narrower surface area than the (100) crystal face. Such nanoparticles may be passivated with an inorganic ligand such as a metal calcogenide complex (MCC), and the inorganic ligand may be partially converted into an organic ligand (for example, TOP: trioctylphosphine) When the ligand is exchanged, the organic ligand can not bind well to the (111) crystal face due to steric hindrance and selectively bind to the (100) face. On the other hand, the organic ligand can be selectively bonded to the (100) crystal face or the (111) crystal face by appropriately selecting terminal linking groups (for example, -NH ₂ , -S, -COO, -O-) have. By using the property of the organic ligand selectively binding to a specific crystal plane as described above, the molar ratio of the organic ligand to the inorganic ligand bound to the inorganic center can be controlled by appropriately selecting the crystal form of the inorganic center. For example, the crystal shape of the inorganic center may be a cube, a truncated cube, a cuboctahedron, a truncated cuboctahedron, an octahedron or a tetrahedron, The ratio of the surface area between the (100) crystal face and the (111) crystal face differs depending on the shape of each crystal. Also, in this case, the ratio of the inorganic ligand may be adjusted by controlling the ratio of the ligand exchange during the production of the nanoparticles.

The inorganic center has an amorphous structure (e.g., a spherical structure), and the organic-inorganic hybrid ligand may include an organic ligand and an inorganic ligand randomly bonded to the inorganic center (see FIG. 1B). In this case, the ratio of the organic ligand and the inorganic ligand bound to the inorganic center can be controlled by controlling the ligand exchange ratio in the process of manufacturing the nanoparticles.

The inorganic center may include a II-VI semiconductor compound, a III-V semiconductor compound, a IV-VI semiconductor compound, a Group IV element or compound, or a combination thereof. For example, the inorganic center may be CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, CdHgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe; InNb, InNb, InNb, InNb, InNb, InNb, InNb, InNb, InNb, InNb, GaNb, GaNb, InAlSb, InAlNb, InAlNb, InAlNb, InAlNb, InAlNb, InAlNb, GaInNb, SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe; At least one inorganic compound selected from the group consisting of Si, Ge, SiC and SiGe.

The organic-inorganic hybrid ligand may include a hydrazine hydrate of a metal chalcogenide complex as an inorganic ligand. For example, the organic-inorganic hybrid ligand may be selected from the group consisting of Sn ₂ S ₆ , Sn ₂ Se ₆ , In ₂ Se ₄ , In ₂ Te ₃ , Ga ₂ Se ₃ , CuInSe ₂ , Cu ₇ S ₄ , Hg ₃ Se ₄ , Sb ₂ Te ₃ And a hydrazine hydrate of ZnTe. As used herein, the term " hydrazine hydrate " refers to hydrazine monohydrate, hydrazine dihydrate, hydrazine trihydrate, tetrahydrate, hydrazine pentahydrate or hexahydrate, .

The organic-inorganic hybrid ligand may be selected from organic ligands such as mercapto propionic acid (MPA), cysteamine, mercaptoacetic acid, TOP (trioctylphosphine), TOPO (trioctylphosphine oxide), oleic acid, oleylamine Octadecylamine, hexadecylamine, octanethiol, dodecanethiol, hexylphosphonic acid (HPA), tetradecylphosphonic acid (TDPA), octadecylamine, And at least one organic compound selected from the group consisting of octylphosphinic acid (OPA).

The nanoparticles may have a zero-dimensional structure, a one-dimensional structure, or a two-dimensional structure. In the present specification, the term " zero-dimensional structure " means a structure exhibiting a quantum confinement effect in all directions in the x-, y-, and z-axis directions, refers to a structure that exhibits a quantum confinement effect in two directions of a y-axis direction and a z-axis direction, and a "two-dimensional structure" refers to a structure that exhibits a quantum confinement effect in one of x-axis direction, y- . In the present specification, the term " quantum confinement effect " means that when a particle is less than several tens of nanometers, specifically when the particle size is smaller than the wavefunction of the electron, it forms a discontinuous energy state by the space wall, The smaller the size of the electron, the higher the energy state of the electron and the greater the energy of the band. The nanoparticles of the zero-dimensional structure may include a quantum dot shape, the one-dimensional nanoparticles may include nanowires, and the two-dimensional nanoparticles may include nanorods, nanoplates, Or a triangular plate) or nanosheet form.

Hereinafter, nanoparticles according to one embodiment of the present invention will be described in more detail with reference to FIGS. 1A and 1B. Figures 1A and 1B are schematic cross-sectional views of nanoparticles according to embodiments of the present invention.

In the present specification, the same reference numerals as in the drawings shown above refer to the same or a part of the same member.

1A, nanoparticles 10 include an inorganic center 11, an organic ligand 12, and an inorganic ligand 13. The inorganic center 11 has a crystalline polyhedral structure. The organic ligand 12 and the inorganic ligand 13 are bonded to different crystal planes of the inorganic center 11.

Referring to FIG. 1B, the nanoparticles 20 include an inorganic center 21, an organic ligand 22, and an inorganic ligand 23. The inorganic center 21 has a spherical amorphous structure. The organic ligand 12 and the inorganic ligand 13 are bonded to the inorganic center 21 at random.

Hereinafter, nanoparticles according to another embodiment of the present invention will be described in detail.

The nanoparticle according to another embodiment of the present invention comprises an inorganic center, an organic ligand bound to the inorganic center, and an inorganic layer arranged to at least partially cover the inorganic center. Thus, the nanoparticles containing an inorganic layer instead of the inorganic ligand may be obtained by heat-treating the nanoparticles containing the organic-inorganic hybrid ligand as shown in FIG. 1A or 1B described above. That is, by the heat treatment, the organic ligands bound to the nanoparticles containing the organic-inorganic hybrid ligand described above are preserved without changing the shape, but the inorganic ligand is converted into a film form to form an inorganic layer. The heat treatment may be performed at a temperature ranging from 100 to 300 ° C. When the heat treatment temperature is within the above range, the inorganic ligand can be effectively converted to the inorganic layer without damaging the inorganic center by heat.

The inorganic layer may comprise a metal chalcogenide complex. For example, the inorganic layer may include at least one of Sn ₂ S ₆ , Sn ₂ Se ₆ , In ₂ Se ₄ , In ₂ Te ₃ , Ga ₂ Se ₃ , CuInSe ₂ , Cu ₇ S ₄ , Hg ₃ Se ₄ , Sb ₂ Te ₃ And at least one inorganic compound selected from the group consisting of ZnTe.

Hereinafter, nanoparticles containing an inorganic layer will be described in detail with reference to FIGS. 2A and 2B. 2A and 2B are schematic cross-sectional views of nanoparticles according to other embodiments of the present invention.

2A, the nanoparticles 30 include an inorganic center 11, an organic ligand 12, and an inorganic layer 33. [ The inorganic center 11 has a polyhedral crystal structure. The organic ligand 12 is bonded to a specific crystal face of the inorganic center 11 and the inorganic layer 33 is arranged to at least partially cover the inorganic center 11. [ In addition, the inorganic layer 33 may cover a part of the organic ligand 12.

Referring to FIG. 2B, the nanoparticles 40 include an inorganic center 21, an organic ligand 22, and an inorganic layer 43. The inorganic center 21 has a spherical amorphous structure. The organic ligand 22 is bonded randomly (or uniformly) to the inorganic center 20 and the inorganic layer 43 is arranged to at least partially cover the inorganic center 21. In addition, the inorganic layer 43 may cover a part of the organic ligand 22.

Hereinafter, a method for producing nanoparticles according to one embodiment of the present invention will be described in detail.

A method of preparing nanoparticles according to an embodiment of the present invention comprises the steps of preparing a solution of nanoparticles comprising an organic ligand or an inorganic ligand and a step of exchanging the organic ligand or a part of the inorganic ligand with an inorganic ligand or an organic ligand .

In the method for producing nanoparticles, the step of preparing a solution of nanoparticles containing an organic ligand can be carried out by a method of manufacturing a quantum dot disclosed in Korean Patent Publication No. 2010-0050271 or a method similar to the above method. Korean Patent Publication No. 2010-0050271 is incorporated herein by reference.

Meanwhile, in the method for producing nanoparticles, the step of preparing a solution of nanoparticles containing an inorganic ligand includes an organic ligand by the method of manufacturing a quantum dot disclosed in Korean Patent Publication No. 2010-0050271 or a method similar to the method (I. E., Components other than inorganic centers and inorganic ligands) from the resultant product, and a step of removing impurities including residual organic ligands (i. E., Components other than inorganic centers and inorganic ligands) from the resultant product can do.

In the method for producing nanoparticles, the step of exchanging a part of the organic ligand or the inorganic ligand with an inorganic ligand or an organic ligand may be carried out by a method of manufacturing a quantum dot disclosed in Korean Patent Application No. 2011-0106637 or Korean Patent Application No. 2011-0134001 Method or a method analogous to each of the above methods. Korean Patent Application No. 2011-0106637 and Korean Patent Application No. 2011-0134001 are incorporated herein by reference.

Hereinafter, a method for producing nanoparticles according to one embodiment of the present invention will be described in detail with reference to FIGS. 3A and 3B.

3A, a nanoparticle 10 'in which an organic ligand 12 is bonded to an inorganic center 11 having a crystalline polyhedral structure or an inorganic ligand 13 is bonded to the inorganic center 11 (10 "). ≪ / RTI > A portion of the organic ligand 12 or the inorganic ligand 13 bonded to the inorganic center 11 is exchanged with the inorganic ligand 13 or the organic ligand 12 to form the organic ligand 12 and the inorganic ligand 13 ) Are selectively bonded to specific crystal faces, respectively. Next, the nanoparticles 10 are heat-treated to selectively bind the organic ligand 12 to a specific crystal plane of the inorganic center 11, and the inorganic layer 33 at least partially covers the inorganic center 11 Nanoparticles 30 are obtained.

3B, a nanoparticle 20 'having an inorganic ligand 22 bonded to an inorganic center 21 having an amorphous spherical structure, or an inorganic ligand 23 bonded to the inorganic center 21 Nanoparticles 20 " A portion of the organic ligand 22 or the inorganic ligand 23 bonded to the inorganic center 21 is exchanged with the inorganic ligand 23 or the organic ligand 22 to form the organic ligand 22 and the inorganic ligand 23 ) Are randomly bonded to each other to obtain nanoparticles (20). Next, the nanoparticles 20 are thermally treated to randomly bind the organic ligand 22 to the inorganic center 21, and the inorganic layer 43 is bonded to the nanoparticles at least partially covering the inorganic center 21 40).

The nanoparticle solution according to an embodiment of the present invention includes nanoparticles containing the above-described organic-inorganic ligand and a solvent for dissolving the nanoparticles.

The solvent may include at least one selected from the group consisting of water, ethanolamine, dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), and formamide.

The nanoparticle film according to an embodiment of the present invention includes nanoparticles including the above-described organic-inorganic ligand and an inorganic matrix embedded with the nanoparticles.

The inorganic matrix may comprise a metal chalcogenide complex. For example, the inorganic matrix may be selected from the group consisting of Sn ₂ S ₆ , Sn ₂ Se ₆ , In ₂ Se ₄ , In ₂ Te ₃ , Ga ₂ Se ₃ , CuInSe ₂ , Cu ₇ S ₄ , Hg ₃ Se ₄ , Sb ₂ Te ₃ And at least one inorganic compound selected from the group consisting of ZnTe.

Hereinafter, a method for producing a nanoparticle film according to an embodiment of the present invention will be described in detail.

The method for producing a nanoparticle film according to an embodiment of the present invention includes the steps of preparing a composition for forming a nanoparticle film by mixing an inorganic matrix precursor with the nanoparticle solution described above, And heat treating the composition for forming a nanoparticle film applied on the substrate. The method of manufacturing the nanofilm may be the same as or similar to the method of manufacturing the quantum dot-matrix thin film disclosed in Korean Patent Application No. 2011-0134001.

The inorganic matrix precursor may comprise a metal chalcogenide complex. For example, the inorganic matrix precursor may be selected from the group consisting of Sn ₂ S ₆ , Sn ₂ Se ₆ , In ₂ Se ₄ , In ₂ Te ₃ , Ga ₂ Se ₃ , CuInSe ₂ , Cu ₇ S ₄ , Hg ₃ Se ₄ , Sb ₂ Te ₃ , ZnTe, and their hydrazine hydrates. The inorganic matrix precursor may be the same as or different from the above-mentioned inorganic ligand.

The heat treatment may be performed at a temperature ranging from 100 to 300 ° C. When the heat treatment temperature is within the above range, the inorganic ligand can be effectively converted to the inorganic layer without damaging the inorganic center by heat.

Hereinafter, the present invention will be described with reference to the following examples, but the present invention is not limited thereto.

Example

Manufacturing example  One: Sn ₂ S ₆ of Hydrazine Monohydrate  Preparation of solution

0.32 g of sulfur (S) powder was dissolved in 10 mL of an aqueous solution of 64.5 wt% hydrazine monohydrate (N ₂ H ₄ .H ₂ O) to prepare a 1 M aqueous solution of sulfur-hydrazine monohydrate. 1 mL of an aqueous solution of hydrazine monohydrate of 64.5 wt% and 120 mg of tin (Sn) powder were added to 3 mL of the aqueous solution of sulfur-hydrazine monohydrate (concentration of sulfur: 1M) and reacted. The reaction was carried out at room temperature (25 ° C) and stirred for about 1 hour. The remaining precipitate was removed from the reaction solution by centrifugation to obtain a hydrazine monohydrate solution of Sn ₂ S ₆ . Hydrazine monohydrate solution of Sn ₂ S ₆ comprises a hydrazine mono-hydrate of Sn ₂ S ₆ with hydrazine monohydrate is combined Sn ₂ S _6.

Manufacturing example  2: Sn ₂ S ₆ of Hydrazine Monohydrate Ethanolamine  Solution preparation

The hydrazine monohydrate solution of Sn ₂ S ₆ prepared in Preparation Example 1 was dried with N ₂ gas to remove only the Sn ₂ S ₆ hydrazine monohydrate and remove the solvent. The separated hydrazine monohydrate of Sn ₂ S ₆ was dissolved in ethanolamine to prepare a 16 mg / mL Sn ₂ S ₆ hydrazine monohydrate ethanolamine solution.

Example  One: CdSe - Sn ₂ S ₆ Hydrazine Monohydrate  Structure nanoparticles and the preparation of the nanoparticle solution

(Preparation of nanoparticle solution of CdSe-organic ligand structure)

First, CdO powder (1.6 mmol, 0.206 g; Aldrich, +99.99 wt%) and oleic acid (6.4 mmol, 1.8 g; Aldrich, 95 wt%) were mixed in 40 mL of trioctylamine (TOA, Aldrich, 95 wt% Containing solution. The Cd-containing solution was heat-treated at 150 캜 for 10 minutes while vigorously stirring, and the temperature was raised to 300 캜 while flowing N ₂ gas. Subsequently, 0.2 mL of 2.0 M Se (Alfa Aesar) added to trioctylphosphine (TOP, Strem, 97 wt%) was added to the Cd-containing solution heated to 300 ° C., and the reaction was performed for 90 seconds to obtain a CdSe-organic ligand Structure nanoparticle solution was prepared. On the surface of the final nanoparticles, oleic acid, TOA and TOP are present as organic ligands.

(Preparation of nanoparticle solution of CdSe-Sn ₂ S ₆ hydrazine monohydrate structure)

The hydrazine monohydrate ethanolamine solution of Sn ₂ S ₆ prepared in Preparation Example 2 was added to the nanoparticle solution of the CdSe-organic ligand structure, followed by conducting a ligand exchange reaction with stirring at room temperature for 8 hours. Most of the organic ligands in the nanoparticle solution of the CdSe-organic ligand structure were exchanged with the Sn ₂ S ₆ hydrazine monohydrate ligands by the ligand exchange reaction. As a result, a nanoparticle solution of the CdSe-Sn ₂ S ₆ hydrazine monohydrate structure was obtained.

(Preparation of nanoparticles of CdSe-Sn ₂ S ₆ hydrazine monohydrate structure)

To the nanoparticle solution of the CdSe-Sn ₂ S ₆ hydrazine monohydrate structure prepared above After the addition of butanol, the resultant is centrifuged to obtain a precipitate containing nanoparticles, the solvent (i.e., water and butanol) is removed from the precipitate, and the solvent-removed precipitate is redispersed in water to remove residual organic ligands To obtain nanoparticles of the CdSe-Sn ₂ S ₆ hydrazine monohydrate structure.

(Preparation of a solution of nanoparticles containing an organic-inorganic hybrid ligand)

The CdSe-Sn ₂ S ₆ hydrazine monohydrate aqueous solution of a nanoparticle structure nanoparticles dissolve in water CdSe-Sn ₂ S ₆ hydrazine monohydrate structure prepared above was prepared. 3-mercaptopropionic acid (MPA) was added to the nanoparticle aqueous solution to prepare three kinds of nanoparticle solutions having MPA concentrations of 0.01M, 0.03M and 0.05M. Then, each nanoparticle solution was stirred at room temperature for 3 hours to carry out partial ligand exchange reaction. As a result, a solution of the nanoparticles containing the organic-inorganic hybrid ligand was obtained.

Example  2: CdSe / CdS / ZnS - Sn ₂ S ₆ Hydrazine Monohydrate  Preparation of nanoparticles and nanoparticle solution

(Preparation of nanoparticle solution of CdSe / CdS / ZnS-organic ligand structure)

First, CdO powder (1.6 mmol, 0.206 g; Aldrich, +99.99 wt%) and oleic acid (6.4 mmol, 1.8 g; Aldrich, 95 wt%) were mixed in 40 mL of trioctylamine (TOA, Aldrich, 95 wt% Containing solution. The Cd-containing solution was heat-treated at 150 캜 for 10 minutes while vigorously stirring, and the temperature was raised to 300 캜 while flowing N ₂ gas. Then, 0.2 mL of 2.0 M Se (Alfa Aesar) added to trioctylphosphine (TOP, Strem, 97 wt%) was added to the Cd-containing solution heated to 300 ° C. After 90 seconds, 1.2 mmol of n-octanethiol (210 μL in 6 mL) added to TOA was added to the Cd-containing solution at a rate of 1 mL / min using a syringe pump and reacted for 40 minutes.

On the other hand, it was dissolved under N ₂ gas atmosphere, the zinc acetate and 2.8g of oleic acid 0.92g of from 200 ℃ in 20mL of TOA was prepared 0.25M Zn precursor solution. A 16 mL aliquot of Zn precursor solution was heated to 100 DEG C and then added to the Cd containing solution at a rate of 2 mL / min. From the point of addition of Se, the total reaction proceeded for 2 hours. After completion of the reaction, the product was cooled to about 55 DEG C and organic sludge was removed by centrifugation at a speed of 5,600 rpm. Then, ethanol (Fischer, HPLC grade) was added until the opaque mass disappears. Thereafter, the resultant was centrifuged to obtain a precipitate. The precipitate contains colloidal quantum dots in which oleic acid, TOP (trioctylphosphine), TOPO (trioctylphosphine oxide) and trioctylphosphine oxide are coordinated to an inorganic center of a CdSe / CdS / ZnS structure (see Evaluation Example 2) . The precipitate was then dissolved in cyclohexane to obtain a nanoparticle solution of the CdSe / CdS / ZnS-organic ligand structure.

(Preparation of nanoparticle solution of CdSe / CdS / ZnS-Sn ₂ S ₆ hydrazine monohydrate structure)

The hydrazine monohydrate ethanolamine solution of Sn ₂ S ₆ prepared in Preparation Example 2 was added to the nanoparticle solution of the CdSe / CdS / ZnS-organic ligand structure, followed by conducting a ligand exchange reaction with stirring at room temperature for 8 hours. Most of the organic ligands in the nanoparticle solution of the CdSe / CdS / ZnS-organic ligand structure were exchanged with the Sn ₂ S ₆ hydrazine monohydrate ligands by the ligand exchange reaction. As a result, a nanoparticle solution of a CdSe / CdS / ZnS-Sn ₂ S ₆ hydrazine monohydrate structure was obtained.

(Preparation of nanoparticles of CdSe / CdS / ZnS-Sn ₂ S ₆ hydrazine monohydrate structure)

After butanol was added to the nanoparticle solution of the CdSe / CdS / ZnS-Sn2S6 hydrazine monohydrate structure prepared above, the resultant was centrifuged to obtain a precipitate containing nanoparticles, and the precipitate was dissolved in a solvent (i.e., water and butanol CdS / ZnS-Sn ₂ S ₆ hydrazine monohydrate structure nanoparticles were obtained by removing impurities including residual organic ligands by redispersing the solvent-removed precipitate in water.

(Preparation of a solution of nanoparticles containing an organic-inorganic hybrid ligand)

A _{CdSe / CdS / ZnS-Sn 2} S 6 hydrazine mono hydrate structure to melt the nanoparticles in water, _{CdSe / CdS / ZnS-Sn 2} S 6 hydrazine monohydrate aqueous solution of a nanoparticle structure produced in was prepared. 3-mercaptopropionic acid (MPA) was added to the nanoparticle aqueous solution to prepare a nanoparticle solution having a MPA concentration of 0.03M. Then, the nanoparticle solution was stirred at room temperature for 3 hours to carry out partial ligand exchange reaction. As a result, a solution of the nanoparticles containing the organic-inorganic hybrid ligand was obtained.

Evaluation example

Evaluation example  1: Optical characterization

The optical density spectrum and the photoluminescence intensity (PL intensity) spectrum of the solution of the nanoparticles of the CdSe-Sn ₂ S ₆ hydrazine monohydrate structure prepared in Example 1 and the nanoparticle solution containing the organic-inorganic hybrid ligand were measured , And Fig. 4 and Fig. 5, respectively. Spectrophotometer (HITACHI, F7000) was used as a photoluminescence intensity meter. The UV / Vis spectrometer (Agilent technology, Carry5000) was used as the optical density meter.

Referring to FIG. 4, there was no change in the optical density spectrum according to the concentration change of MPA. From this, it can be seen that each solution has the same concentration of nanoparticles.

Referring to FIG. 5, it can be seen that there is an optimum MPA concentration indicating the maximum photoluminescence intensity.

Evaluation example  2: Analysis of components of nanoparticles

The solution of the nanoparticles containing the organic-inorganic hybrid ligand prepared in Example 2 was dried with N ₂ gas to remove only liquid components including water, leaving only the nanoparticles. Then, the nanoparticles were analyzed by high-angle annular dark-field (HAADF) -STEM (FEI, TitanG2) and ICP (SHIMAZU, ICP-8100) to calculate the volume ratio of each component. Respectively.

CdSe CdS ZnS Sn HAADF-STEM One 3.98 6.89 - ICP One 4.03 7.06 0.56

Referring to Table 1, the nanoparticles containing the organic-inorganic hybrid ligand prepared in Example 2 had an inorganic center having a triple structure of CdSe / CdS / ZnS and an inorganic ligand coordinately bound to the inorganic center (I.e., Sn ₂ S ₆ hydrazine monohydrate). Also. HAADF-STEM analysis results and ICP analysis results were found to agree with each other.

Evaluation example  3: Weapons Ligand and  abandonment Ligand  Ratio analysis

A solution of the nanoparticles of the CdSe-Sn ₂ S ₆ hydrazine monohydrate structure prepared in Example 1 and the nanoparticles containing the organic-inorganic hybrid ligands prepared in Examples 1 and 2 was dried with N ₂ gas Thereby removing liquid components including moisture, leaving only nanoparticles. Then, the moles of the organic ligand, the moles of the inorganic ligand, and the moles of the organic ligand per 1 mole of the inorganic ligand contained in one nanoparticle were determined in the following manner. The results are shown in Table 2 below.

≪ Calculation method of organic ligand / inorganic ligand molar ratio >

First, the number of inorganic ligands per nanoparticle was determined from the results of the inorganic component analysis of ICP using CdSe / CdS / ZnS-Sn ₂ S ₆ as an example. That is, the molar ratios of Cd, Se, Zn, S and Sn components were determined from ICP. Then, the volume ratios of CdSe, CdS, and ZnS were determined from the molar ratios of Cd, Se, Zn, and S excluding Sn. That is, the mass ratio can be known from the molar ratio, and since the density of CdSe, CdS, and ZnS is known, the mass ratio is converted to the volume ratio using the relationship of 'density = mass / volume'. The diameters of the outermost ZnS measured by HAADF-STEM were 6.5 nm and the diameters of CdSe, CdS and ZnS were 4/3 πa ³ , respectively (a, b, c) / 3 πb ³ - 4 / 3πa ³ ), (4 / 3πc ³ - 4/3 πb ³ ), where c is 3.25 nm (= 6.5 / 2). Cd and Zn contribute only to the volume of CdSe and ZnS, respectively, Cd contributes to the volume of CdSe and CdS, and S contributes to the volume of CdS and ZnS. Therefore, the volume ratio of Se: Zn is 4/3 πa ³ : (4 / 3πc ³ -4/3 πb ³ ), and the volume ratio of Cd: S is 4/3 πb ³ : 4/3 πc ³ . From these procedures, a and b values can be calculated from the volume ratios of Cd, Se, Zn, and S, respectively. Therefore, the size of CdSe, CdS, and ZnS in CdSe / CdS / ZnS nanoparticles, the total number of atoms per nanoparticle, and the number of atoms of each component can be obtained. For example, since the ratio of the number of atoms of Cd: Sn is obtained from ICP, the number of Sn atoms per nanoparticle is determined. Since the molecular formula of the inorganic ligand is Sn ₂ S ₆ , , Several moieties) of inorganic ligands are combined.

Similarly, in the case of CdSe-Sn ₂ S ₆ , the number of Sn ₂ S ₆ (ie, the number of moles) per nanoparticle can be obtained assuming the CdSe size (4 nm) from the molar ratio of Cd: Sn.

The number of organic ligands was determined from organic mass analysis by TGA analysis (thermogravimetric analysis). The number of organic ligands (ie, number of moles) per nanoparticle was calculated by assuming the average value of the molecular weight of TOA and the molecular weight of oleic acid (318) as the molecular weight of the organic material.

Example 1 Example 2 Sn ₂ S ₆ + 0.01M MPA Sn ₂ S ₆ + 0.03M MPA Sn ₂ S ₆ + 0.05M MPA Sn ₂ S ₆ + 0.03M MPA Moles of organic ligand 15 34 42 54 Moles of inorganic ligand 52 45 41 70 Organic ligands / inorganic ligands
(Molar ratio)
0.29 0.76 1.02 0.77

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, . Accordingly, the scope of protection of the present invention should be determined by the appended claims.

10, 10 ', 10 ", 20, 20', 20", 30, 40:
11, 21: inorganic center 12, 22: organic ligand
13, 23: inorganic ligand 33, 43: inorganic layer

Claims (20)

Inorganic center; And
And an organic-inorganic hybrid ligand bonded to the inorganic center,
Wherein the organic-inorganic hybrid ligand comprises an organic ligand directly bonded to the inorganic center and an inorganic ligand directly bonded to the inorganic center,
Wherein the inorganic ligand comprises a hydrazine hydrate of a metal chalcogenide complex. The method according to claim 1,
Wherein the organic-inorganic hybrid ligand comprises 0.01 to 100 moles of the organic ligand per mole of the inorganic ligand. The method according to claim 1,
The inorganic center has a single layer structure, a double structure of core / shell, or a triple structure of core / first shell / second shell. The method according to claim 1,
Wherein the inorganic center has a crystalline polyhedral structure, and the organic ligand and the inorganic ligand are bonded to different crystal planes of the inorganic center. The method according to claim 1,
Wherein the inorganic center has an amorphous structure, and the organic ligand and the inorganic ligand are randomly bonded to the inorganic center. The method according to claim 1,
The inorganic center may be selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgSe, CdHgTe, HgZnS, HgZnSe, CdHgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe; InNb, InNb, InNb, InNb, InNb, InNb, InNb, InNb, InNb, InNb, GaNb, GaNb, InAlSb, InAlNb, InAlNb, InAlNb, InAlNb, InAlNb, InAlNb, GaInNb, SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe; At least one inorganic compound selected from the group consisting of Si, Ge, SiC and SiGe. The method according to claim 1,
The inorganic ligand is a hydrazine of Sn ₂ S ₆ , Sn ₂ Se ₆ , In ₂ Se ₄ , In ₂ Te ₃ , Ga ₂ Se ₃ , CuInSe ₂ , Cu ₇ S ₄ , Hg ₃ Se ₄ , Sb ₂ Te _3, And at least one inorganic compound selected from the group consisting of hydrates. The method according to claim 1,
The organic ligand may be selected from the group consisting of mercapto propionic acid (MPA), cysteamine, mercaptoacetic acid, TOP (trioctylphosphine), TOPO (trioctylphosphine oxide), oleic acid, oleylamine, octylamine ), Trioctyl amine, hexadecylamine, octanethiol, dodecanethiol, hexylphosphonic acid (HPA), tetradecylphosphonic acid (TDPA) and octylphosphinic acid (OPA ). ≪ / RTI > The method according to claim 1,
The nanoparticles have a zero-dimensional structure, a one-dimensional structure, or a two-dimensional structure. 10. The method of claim 9,
The nanoparticles are nanoparticles in the form of quantum dots, nanowires, nanorods, nanoplates or nanosheets. Inorganic center;
An organic ligand directly bonded to the inorganic center; And
And an inorganic layer disposed at least partially covering the inorganic center,
Wherein at least a portion of the inorganic layer is bonded directly to the inorganic center,
Wherein the inorganic layer comprises a metal chalcogenide complex. 12. The method of claim 11,
The inorganic layer is made of Sn ₂ S ₆ , Sn ₂ Se ₆ , In ₂ Se ₄ , In ₂ Te ₃ , Ga ₂ Se ₃ , CuInSe ₂ , Cu ₇ S ₄ , Hg ₃ Se ₄ , Sb ₂ Te ₃ and ZnTe At least one inorganic compound selected from the group consisting of: delete 12. A nanoparticle according to any one of claims 1 to 12; And
A solution of nanoparticles comprising a solvent that dissolves the nanoparticles. 12. A nanoparticle according to any one of claims 1 to 12; And
Wherein the nanoparticle film comprises an inorganic matrix embedded with the nanoparticles. 16. The method of claim 15,
The inorganic matrix may be selected from the group consisting of Sn ₂ S ₆ , Sn ₂ Se ₆ , In ₂ Se ₄ , In ₂ Te ₃ , Ga ₂ Se ₃ , CuInSe ₂ , Cu ₇ S ₄ , Hg ₃ Se ₄ , Sb ₂ Te ₃ , ZnTe, By weight of at least one inorganic compound selected from the group consisting of hydrazine hydrate. Mixing a solution of the nanoparticles according to claim 14 with an inorganic matrix precursor to prepare a composition for forming a nanoparticle film;
Applying the composition for forming a nanoparticle film on a substrate; And
And heat treating the composition for forming a nanoparticle film applied on the substrate. 18. The method of claim 17,
Wherein the inorganic matrix precursor comprises a metal chalcogenide complex. 19. The method of claim 18,
The inorganic matrix precursor may be selected from the group consisting of Sn ₂ S ₆ , Sn ₂ Se ₆ , In ₂ Se ₄ , In ₂ Te ₃ , Ga ₂ Se ₃ , CuInSe ₂ , Cu ₇ S ₄ , Hg ₃ Se ₄ , Sb ₂ Te ₃ And at least one inorganic compound selected from the group consisting of ZnTe. 18. The method of claim 17,
Wherein the heat treatment is performed in a temperature range of 100 to 300 ° C.

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