KR20160055092A - Perovskite nanocrystal particle emitters having core-shell structure, method of manufacturing the same and electroluminescence devices using the same - Google Patents

Abstract

The present invention provides a light emitting material including perovskite nanocrystal particles having a core-shell structure, a method for preparing the same and an electroluminescence device using the same. The light emitting material including organic/inorganic hybrid perovskite nanocrystal particles or metal halide perovskite nanocrystal particles can be dispersed in an organic solvent, includes a perovskite nanocrystal structure and has a core-shell structured nanocrystal structure. Therefore, in the light emitting material including perovskite nanocrystal particles according to the present invention, the shell is formed by using a material having a larger band-gap than the core to facilitate confinement of exitons in the core, and perovskite or an inorganic semiconductor or organic polymer stable in the air is used to prevent the core perovskite from being exposed to the air, thereby improving the durability of nanocrystals.

Description

TECHNICAL FIELD The present invention relates to a perovskite nanocrystal particle emitter having a core-shell structure, a method of manufacturing the same, and a light emitting device using the same.

The present invention relates to a phosphor and a light emitting device using the same, and more particularly, to a phosphor-based hybrid perovskite or inorganic metal halide perovskite nanocrystalline phosphor having a core-shell structure, a method for producing the same, .

The megatrend of the display market is shifting to the existing high-efficiency, high-resolution-oriented display and moving to an emotional image quality display aiming at realizing high color purity natural color. From this point of view, organic light emitting diode (OLED) devices based on organic light emitting diodes (OLEDs) have achieved remarkable progress, and inorganic quantum dot LEDs having improved color purity have been actively researched and developed as alternatives. However, both the organic light-emitting material and the inorganic quantum dot light-emitting material have inherent limitations in terms of materials.

 Conventional organic light emitting diodes have the advantages of high efficiency, but they have a wide spectrum and poor color purity. Since the inorganic quantum dot luminous body is known to have good color purity, it is difficult to control the size of the quantum dots uniformly toward the blue side because of the quantum size effect, and thus there is a problem that the color purity decreases. Furthermore, since inorganic quantum dots have a very deep valence band, there is a problem that hole injection barriers in the organic hole injection layer are so large that hole injection is difficult. Also, the two luminous bodies are disadvantageous in that they are expensive. Therefore, there is a need for a new type organic / inorganic hybrid light emitter that compensates for the disadvantages of organic and inorganic light emitters and maintains their merits.

The organic and inorganic hybrid materials have advantages of low manufacturing cost, simple manufacturing and device fabrication processes, advantages of organic materials which are easy to control optical and electrical properties, high charge mobility and mechanical and thermal stability of inorganic materials And it is attracting attention both academically and industrially.

 Among them, the organic / inorganic hybrid perovskite material has a high color purity, has a simple color control, and has a low synthesis cost. High color purity has a layered structure in which the 2D plane of the inorganic material is sandwiched between the 2D planes of the organic material and the dielectric constant difference between the inorganic material and the organic material is large. 2.4, εinorganic ≈ 6.1) are formed because the excitons are bound to the inorganic layer and thus have a high color purity (Full width at half maximum (FWHM) ≈20 nm).

A material having a conventional perovskite structure (ABX ₃ ) is an inorganic metal oxide.

Such an inorganic metal oxide is generally an oxide and may be a metal such as Ti, Sr, Ca, Cs, Ba, Y, Gd, La, Fe, Metal ions of B site are combined with oxygen anions of X site as a corner-sharing octahedron form of 6-fold coordination. It is a substance. Examples thereof include SrFeO ₃ , LaMnO ₃ , CaFeO _3, and the like.

On the other hand, organic hybrids perovskite have organic ammonium (RNH ₃ ) cations in the A site in the ABX ₃ structure and halides (Cl, Br, I) in the X site. So that the composition is completely different from the inorganic metal oxide perovskite material.

In addition, the characteristics of the material vary depending on the difference of the constituent materials. Inorganic metal oxide perovskites typically exhibit superconductivity, ferroelectricity, colossal magnetoresistance, and the like, and thus research has been generally conducted on sensors, fuel cells, and memory devices . For example, yttrium barium copper oxide has superconducting or insulating properties depending on the oxygen contents.

On the other hand, the organic hybrid perovskite (or organometallic halide perovskite) is formed by alternately stacking the organic plane and the inorganic plane, so that the exciton can be bound in the inorganic plane similarly to the lamellar structure, It can be an ideal light emitter which emits light of very high color purity by the crystal structure itself rather than the size of the material.

If the organic hybrid perovskite also contains a chromophore (mainly including a conjugated structure) in which the organic ammonium has a smaller band gap than the central metal and the halogen crystal structure (BX3) , The light of high color purity can not be obtained and the full width at half maximum of the luminescence spectrum becomes wider than 50 nm. Therefore, in this case, it is not very suitable for the high color purity light emitter emphasized in the present patent. Therefore, in order to make a high-purity light-emitting body, it is important that the organic ammonium does not contain a chromophore but occurs in an inorganic lattice where the luminescence is composed of central metal-halogen elements. That is, this patent focuses on the development of a high-purity, high-efficiency light emitting body that emits light in an inorganic lattice. For example, Korean Patent Laid-Open No. 10-2001-0015084 (Mar. 26, 2001) discloses an electroluminescent device in which a dye-containing organic-inorganic hybrid material is formed into a thin film rather than a particle and used as a light emitting layer. Luminescence does not emerge from the lobescite lattice structure. However, since the organic / inorganic hybrid perovskite has a small exciton binding energy, it can emit light at a low temperature. However, at a room temperature, a fundamental problem that excitons can not be emitted due to thermal ionization and delocalization of a charge carrier, have. Further, when free electrons are recombined again to form excitons, there is a problem that the excitons are destroyed by the layer having a high conductivity in the periphery, so that light emission can not occur. Therefore, it is necessary to prevent the quenching of the exciton in order to increase the luminous efficiency and luminance of the organic-hybrid hybrid perovskite-based LED.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a nanocrystalline nanoparticle hybrid nanoparticle hybrid nanoparticle hybrid nanoparticle hybrid nanoparticle hybrid nanoparticle nanoparticle hybrid nanoparticle nanoparticle nanoparticle nanoparticle nanoparticle nanoparticle nanoparticle nanoparticle nanoparticle nanoparticle nanoparticle nanoparticle nanoparticle nanoparticle nanoparticle nanoparticle And a light emitting device using the same.

Further, it is another object of the present invention to provide a nanocrystalline particle illuminant having improved luminous efficiency and durability by forming a shell in a perovskite nanocrystal to form a core-shell structure, and a light emitting device using the same.

According to an aspect of the present invention, there is provided an organic-inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure. The organic-inorganic hybrid perovskite nanocrystalline grain luminescent material having the core-shell structure has a perovskite nanocrystal structure and has a core-shell structure of nanocrystalline grain structure while being dispersible in an organic solvent.

Wherein the organic solvent comprises a protic solvent or aprotic solvent and wherein the protic solvent is selected from the group consisting of dimethylformamide, gamma butyrolactone, N-methylpyrrolidone, Wherein the aprotic solvent is selected from the group consisting of dichloroethylene, trichlorethylene, chloroform, chlorobenzene, dichlorobenzene, styrene, dimethylformamide, dimethylsulfoxide, xylene, toluene , Cyclohexene, or isopropyl alcohol.

The organic / inorganic hybrid perovskite nanocrystalline particles may be spherical, cylindrical, elliptical or polygonal.

The organic / inorganic hybrid perovskite nanocrystalline particles may have a size of 1 nm to 900 nm and may be an organic hybrid perovskite nanocrystal particle emitter having a core-shell structure

The band gap energy of the organic / inorganic hybrid perovskite nanocrystalline grains is determined by the crystal structure without depending on the grain size.

Wherein the organic-inorganic hybrid perovskite nanocrystalline grains of the core-shell structure are composed of a core comprising a first organic-inorganic hybrid perovskite nanocrystal and a core surrounding the core, the first organic hybrid perovskite And may include a shell including a material having a larger bandgap.

The first organic-inorganic hybrid perovskite nanocrystal has a two-dimensional structure or a three-dimensional structure.

Wherein the first organic-inorganic hybrid perovskite includes a structure of ABX _{3 ,} A ₂ BX ₄ , ABX _4, or A _n-1 Pb _n I _{3n + 1} (n is an integer of 2 to 6) Organic ammonium material, B is a metallic material, and X is a halogen element. And A is _{(CH 3 NH 3) n,} ((C x H 2x + 1) n NH 3) 2 (CH 3 NH 3) n, (RNH 3) 2, (C n H 2n + 1 NH 3) 2 _{, (CF 3 NH 3),} (CF 3 NH 3) n, ((C x F 2x + 1) n NH 3) 2 (CF 3 NH 3) n, ((C x F 2x + 1) n NH 3 ) _2, or _{(C n F 2n + 1 NH} 3) 2 and (n is 1 or more integer, x is 1 or more integer), wherein B is a divalent transition metal, rare earth metal, an alkaline earth metal, Pb, Sn, Ge, Ga, In, Al, Sb, Bi, Po or a combination thereof, and X may be Cl, Br, I or a combination thereof.

The shell may be a second organic or inorganic perovskite material. And the shell is a second material other than the organic and inorganic perovskite materials. The present invention also provides an organic / inorganic hybrid perovskite nanocrystal.

The shell may comprise an inorganic semiconductor, an organic polymeric material, or an organic low molecular weight material.

And the shell is a material having an energy band gap larger than that of the organic / inorganic perovskite material existing in the core.

The inorganic semiconductor material may be selected from the group consisting of TiO _x (where x is a real number of 1 to 3), In ₂ O ₃ , SnO ₂ , ZnO, Zinc Tin Oxide, gallium (Ga ₂ O _3), tungsten oxide (WO _3), aluminum, titanium, vanadium oxide oxide _{(V 2 O 5, VO 2} , V 4 O 7, V 5 O 9 or V ₂ O ₃ ), molybdenum oxide (MoO ₃ or MoO _x ), iron oxide, chromium oxide, bismuth oxide, IGZO (indium-gallium zinc oxide), ZrO _{2 ,} nickel oxide (NiO), copper oxide (CuO), copper oxide (CAO) CuAlO _2), zinc oxide rhodium _{(ZincRhodiumOxide: ZRO, ZnRh 2 O} 4) , such as the oxide semiconductor, and hydrogen sulfide (H2S), cadmium sulfide (CdS), carbon disulfide (CS2), lead sulfide (PbS), molybdenum (ZnS), mercury sulphide (HgS), acenic sulphide (AsS), polybenzene sulphide (C6H4S), selenium sulfide (SeS2), selenium sulphide ) Or iron disulfide (FeS2).

The organic polymer material may be a conjugated polymer including polyfluorene, poly (p-phenylee), poly (spirofluorene), and derivatives thereof. As the liquid polymer, there may be used poly (methyl methacrylate) (PMMA), poly (N-vinylcarbazole) (PVK), polyethylene glycol, polyethylene oxide, Polyvinylpyrrolidone, polyethyleneimine, or polyvinyl alcohol (PVA). And may include all kinds of conjugated polymers and non-conjugated polymers and is not limited to a particular chemical structure.

The organic small molecule material may be a conjugated material such as 4,4'-bis (N-carbazolyl) -1,1'-biphenyl (CBP), 2,8- bis (diphenylphosphoryl) dibenzo [b, d] thiophene N, N-dicarbazolyl-3,5-benzene (mCP). May include all kinds of conjugated polymers and non-conjugated low molecular weight and is not limited to a particular chemical structure.

It may further comprise a plurality of organic ligands surrounding the shell. The organic ligand may comprise an alkyl halide. The alkyl structure of the alkyl halide may be an acyclic alkyl having a structure of C _n H _{2n + 1} , a primary alcohol, a secondary alcohol, a tertiary alcohol, an alkylamine ), p-substituted aniline, phenyl ammonium, or fluorine ammonium.

Further, the surfactant may be at least one selected from the group consisting of 4,4'-azobis (4-cyanovaleric acid), 4'-azobis (4-cyanovaleric acid), acetic acid, But are not limited to, 5-aminosalicylic acid, acrylic acid, L-Aspentic acid, 6-Bromohexanoic acid, Bromoacetic acid, Dichloro acetic acid, Ethylenediaminetetraacetic acid, Isobutyric acid, Itaconic acid, Maleic acid, r-Malay acid, Maleimidobutyric acid, L-Malic acid, 4-Nitrobenzoic acid, 1-pyrenecarboxylic acid, or It may include, but is not limited to, carboxylic acids (COOH), such as oleic acid. It is not.

According to another aspect of the present invention, there is provided a metal halide perovskite nanocrystal particle emitter having a core-shell structure. The metal halide perovskite nanocrystal particle emitter of the core-shell structure can be dispersed in an organic solvent and has a perovskite nanocrystal structure and can have a core-shell nanocrystalline grain structure.

According to another aspect of the present invention, there is provided a solar cell. The solar cell may include a first electrode, a second electrode, and a photoactive layer positioned between the first electrode and the second electrode and including perovskite nanocrystalline particles of the core-shell structure described above.

In addition, the metal halide perovskite nanocrystalline grains of the core-shell structure may include a core comprising a first metal halide perovskite nanocrystal; And a shell surrounding the core, the shell including a material having a larger bandgap than the first metal halide perovskite.

Also, the first metal halide perovskite includes a structure of ABX _{3 ,} A ₂ BX ₄ , ABX _4, or A _n-1 Pb _n I _{3n + 1} (n is an integer of 2 to 6) Is an alkali metal substance, B is a metal substance, and X may be a halogen element.

Further, A is Na, K, Rb, Cs or Fr.

It may further comprise a plurality of organic ligands surrounding the shell.

According to another aspect of the present invention, there is provided a method of manufacturing an organic / inorganic hybrid perovskite nanocrystal particle phosphor having a core-shell structure. The method for manufacturing an organic / inorganic hybrid perovskite nanocrystalline particle luminescent material having a core-shell structure is characterized in that a first solution in which a first organic hybrid polybeat complex is dissolved in a protonic solvent and a second solution in which a surfactant is dissolved in an aprotic solvent Preparing a second solution; Mixing the first solution with the second solution to form a core comprising a first organic-inorganic hybrid perovskite nanocrystal; And a third solution containing a second organic hybrid perovskite or an inorganic semiconductor material having a larger bandgap than the first organic-inorganic hybrid perovskite is dissolved in the second solution to form a second solution, Organic hybrid perovskite nanocrystals, or inorganic semiconductor material, as described above.

According to another aspect of the present invention, there is provided a method of manufacturing an organic / inorganic hybrid perovskite nanocrystal particle phosphor having a core-shell structure. The method for manufacturing an organic / inorganic hybrid perovskite nanocrystalline particle luminescent material having a core-shell structure is characterized in that a first solution in which a first organic hybrid polybeat complex is dissolved in a protonic solvent and a second solution in which a surfactant is dissolved in an aprotic solvent Preparing a second solution; Mixing the first solution with the second solution to form a core comprising a first organic-inorganic hybrid perovskite nanocrystal; And adding an organic ammonium halide solution to the second solution, followed by stirring to form a shell having a band gap larger than that of the core surrounding the core.

According to another aspect of the present invention, there is provided a method of manufacturing an organic / inorganic hybrid perovskite nanocrystal particle phosphor having a core-shell structure. The method for manufacturing an organic / inorganic hybrid perovskite nanocrystalline particle luminescent material having a core-shell structure is characterized in that a first solution in which a first organic hybrid polybeat complex is dissolved in a protonic solvent and a second solution in which a surfactant is dissolved in an aprotic solvent Preparing a second solution; Mixing the first solution with the second solution to form a core comprising a first organic-inorganic hybrid perovskite nanocrystal; Thermally decomposing the surface of the core by heat treating the second solution; And adding an organic ammonium halide solution to the heat-treated second solution to form a shell having a larger bandgap than the core surrounding the core.

According to another aspect of the present invention, there is provided a light emitting device. The light emitting device includes a first electrode; A second electrode; And an inorganic metal halide perovskite nanocrystal particle emitter positioned between the first electrode and the second electrode, wherein the organic-metal hybridide perovskite nanocrystal particle emitter having the core-shell structure, the organic perovskite nanocrystal particle emitter, or the core- Emitting layer.

The nanocrystalline particle illuminant comprising the organic-inorganic hybrid perovskite nanocrystals or the inorganic metal halide perovskite nanocrystals according to the present invention is a nanocomposite particle emitter comprising an inorganic hybrid perovolume having a crystal structure of FCC and BCC combined in a nanocrystal particle emitter A skeletal or inorganic metal halide perovskite is formed, and a lamellar structure in which the organic plane and the inorganic plane are alternately stacked is formed, and the exciton is constrained to the inorganic plane to give a high color purity.

In addition, the exciton diffusion length is reduced and the exciton binding energy is increased in nanocrystals of 900 nm or less, thereby preventing thermal ionization and destruction of excitons due to delamination of the charge carriers, The light emitting efficiency can be obtained.

Further, the band gap energy of the organic-inorganic hybrid perovskite nanocrystal particle or the inorganic metal halide perovskite nanocrystal particle depends on the structure of the perovskite crystal, .

In addition, by synthesizing the two-dimensional organic / inorganic hybrid perovskite with nanocrystals in comparison with the three-dimensional organic-inorganic hybrid perovskite, the exciton binding energy can be increased to further improve the luminous efficiency and increase the durability-stability .

In addition, the organic-inorganic hybrid perovskite nanocrystal particle emitter or the inorganic metal halide perovskite nanocrystal particle emitter having a core-shell structure formed according to the present invention may form a shell with a material having a band gap larger than that of the core, It is possible to improve the durability of the nanocrystal by preventing the core perovskite from being exposed to the air by using a perovskite stable in the air or an inorganic semiconductor or organic polymer in the air.

The technical effects of the present invention are not limited to those mentioned above, and other technical effects not mentioned can be clearly understood by those skilled in the art from the following description.

1 is a schematic diagram of a perovskite nanocrystal structure according to an embodiment of the present invention.
FIG. 2 is a flowchart showing a method of manufacturing an organic-inorganic hybrid perovskite nanocrystalline particle illuminant having a core-shell structure according to an embodiment of the present invention.
3 is a schematic view showing a method of manufacturing an organic / inorganic hybrid perovskite nanocrystal particle phosphor according to an embodiment of the present invention.
4 is a schematic diagram showing an organic-inorganic hybrid perovskite nanocrystal particle emitter and an inorganic metal halide perovskite nanocrystal particle emitter according to an embodiment of the present invention.
FIG. 5 is a schematic diagram showing a partial cut of an organic-inorganic hybrid perovskite nanocrystal having a core-shell structure according to an embodiment of the present invention and a band diagram therefor.
6 is a schematic diagram illustrating a method of forming a shell according to an embodiment of the present invention.
7 is a fluorescence image in which luminescent light according to Production Example 1, Comparative Example 1, and Comparative Example 2 is irradiated with ultraviolet light.
8 is a schematic diagram of a light emitting device according to Production Example 1 and Comparative Example 1. Fig.
9 is an image of a photoluminescence matrix of the light emitting body according to Production Example 1 and Comparative Example 1 taken at normal temperature and low temperature, respectively.
FIG. 10 is a graph of photoluminescence of the phosphor according to Production Example 1 and Comparative Example 1. FIG.
11 is a conceptual diagram showing a method of manufacturing an organic-inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure according to the present invention.
12 is a graph showing the luminescence intensity characteristics of an organic-inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure according to the present invention.
13 is a view showing band gaps of shell materials according to the present invention.
FIG. 14 is a graph showing the luminescence intensity characteristics of an organic-inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure according to the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. Rather, the intention is not to limit the invention to the particular forms disclosed, but rather, the invention includes all modifications, equivalents and substitutions that are consistent with the spirit of the invention as defined by the claims.

It will be appreciated that when an element such as a layer, region or substrate is referred to as being present on another element "on," it may be directly on the other element or there may be an intermediate element in between .

Although the terms first, second, etc. may be used to describe various elements, components, regions, layers and / or regions, such elements, components, regions, layers and / And should not be limited by these terms.

Organic hybrid perovskite nanocrystal particles according to an embodiment of the present invention will be described.

The organic-inorganic hybrid perovskite nanocrystal particles according to an embodiment of the present invention may include a perovskite nanocrystal structure while being dispersible in an organic solvent.

1 shows a structure of a perovskite nanocrystal according to an embodiment of the present invention.

FIG. 1 also shows the structures of organic hybrid perovskite nanocrystals and inorganic metal halide perovskite nanocrystals.

Referring to FIG. 1, the present organic / inorganic hybrid perovskite nanocrystals have a center metal as a center, an inorganic halide material (X) in face centered cubic (FCC), six on all surfaces of a hexahedron , Body centered cubic (BCC), and organic ammonium (OA) are formed at eight corners of the hexahedron. An example of the center metal at this time is Pb.

Further, the inorganic metal halide perovskite nanocrystals have a center metal as a center, six face-centered cubic (FCC) inorganic halide materials (X) on all the surfaces of the hexahedral body, body centered cubic (BCC), which forms a structure in which eight alkali metals are located at every vertex of the hexahedron. An example of the center metal at this time is Pb.

In this case, not only a cubic structure in which all the faces of the hexahedron form 90 °, a width, a length and a height have the same length but also a tetragonal structure having the same width and height but different height.

Accordingly, the two-dimensional structure according to the present invention is a two-dimensional structure in which the center metal is in the center, and the inorganic halide material is a face-centered cubic structure in which six inorganic substances are located on all the surfaces of the hexahedron, and eight organic amoniums are located at all vertices of the hexahedron The term " hybrid perovskite nanocrystal structure " is defined as a structure having the same lateral length and longitudinal length but a height of at least 1.5 times longer than the transverse length and the longitudinal length.

A method of manufacturing an organic-inorganic hybrid perovskite nanocrystal particle phosphor according to an embodiment of the present invention will be described.

FIG. 2 is a flowchart showing a method of manufacturing an organic-inorganic hybrid perovskite nanocrystalline particle illuminant having a core-shell structure according to an embodiment of the present invention.

Referring to FIG. 2, the method for manufacturing an organic-inorganic hybrid perovskite nanocrystalline particle light emitting body having a core-shell structure according to the present invention includes the steps of mixing a first solution in which a first organic binder hybrid perovskite is dissolved in a protic solvent, Preparing a second solution in which a surfactant is dissolved in a protic solvent (S100); mixing the first solution with the second solution to form a core containing a first organic-inorganic hybrid perovskite nanocrystal (S200) and forming a shell surrounding the core and including a material having a bandgap larger than that of the core (S300).

More specifically,

First, a first solution in which a first organic group hybrid perovskite is dissolved in a protic solvent and a second solution in which a surfactant is dissolved in an aprotic solvent are prepared (S100).

The protic solvent may include dimethylformamide, gamma butyrolactone or N-methylpyrrolidone, dimethylsulfoxide, but is not limited thereto. It is not.

The first organic / inorganic hybrid perovskite nanocrystal has a two-dimensional structure or a three-dimensional structure.

For example, an organic-inorganic hybrid perovskite having a three-dimensional crystal structure may be an ABX ₃ structure. In addition, the organic / inorganic hybrid perovskite having a two-dimensional crystal structure may be a structure of ABX ₃ , A ₂ BX ₄ , ABX ₄ or A _{n- 1} Pb _n I _{3n +1} (n is an integer of 2 to 6) have.

In this case, A is an organic ammonium substance, B is a metallic substance, and X is a halogen element.

For example, A is _{(CH 3 NH 3) n,} ((C x H 2x + 1) n NH 3) 2 (CH 3 NH 3) n, (RNH 3) 2, (C n H 2n + 1 _{NH 3) 2, (CF 3} NH 3), (CF 3 NH 3) n, ((C x F 2x + 1) n NH 3) 2 (CF 3 NH 3) n, ((C x F 2x + 1 ) _n NH ₃ ) ₂ or (C _n F _{2n + 1} NH ₃ ) ₂ (n is an integer of 1 or more and x is an integer of 1 or more), B is a divalent transition metal, a rare earth metal, Sn, Ge, Ga, In, Al, Sb, Bi, Po or a combination thereof, and X may be Cl, Br, I or a combination thereof. The rare earth metal may be, for example, Ge, Sn, Pb, Eu or Yb. The alkaline earth metal may be Ca or Sr, for example.

On the other hand, such a perovskite can be prepared by combining AX and BX ₂ at a certain ratio. That is, the first solution may be formed by dissolving AX and BX ₂ in a proton magnetic solvent at a predetermined ratio. For example, AX and BX ₂ may be dissolved in a protic solvent at a ratio of 2: 1 to prepare a first solution in which an A ₂ BX ₃ organic / organic hybrid perovskite is dissolved.

It is more preferable that the organic / inorganic hybrid perovskite uses a material having a two-dimensional crystal structure rather than a three-dimensional crystal structure.

This is because formation of an organic hybrid perovskite having a two-dimensional structure as a nanocrystal in comparison with the case of forming an organic-inorganic hybrid perovskite having a three-dimensional structure as a nanocrystal is a separation of an inorganic plane and an organic plane , The exciton to the inorganic plane due to the organic plane can be more surely restrained and the exciton binding energy can be increased to improve the luminous efficiency as well as increase the durability-stability and achieve a higher color purity.

Also, the aprotic solvent may be dichloroethylene, trichlorethylene, chloroform, chlorobenzene, dichlorobenzene, styrene, dimethylformamide, dimethylsulfoxide, xylene, toluene, cyclohexene or isopropyl alcohol But is not limited thereto.

The surfactant may also be an alkyl halide surfactant, such as alkyl-X. The halogen element corresponding to X at this time may include Cl, Br, I, or the like. At this time, the structure of the alkyl primary alcohol (primary alcohol) having a structure such as acyclic alkyl _{(acyclic alkyl), C n H} 2n + 1 OH having the structure C _n H _{2n +1,} secondary alcohol (secondary alcohol) Tertiary alcohols, alkylamines having a structure of alkyl-N (ex. Hexadecyl amine, 9-Octadecenylamine 1-Amino-9-octadecene (C ₁₉ H ₃₇ N)), p- but are not limited to, p-substituted aniline, phenyl ammonium, and fluorine ammonium.

Surfactants include 4,4'-Azobis (4-cyanovaleric acid), Acetic acid, 5-Aminosalicylic acid, Acrylic acid, L-Aspentic acid, 6-Bromohexanoic acid, Bromoacetic acid, Dichloro acetic acid, Ethylenediaminetetraacetic acid, Isobutyric but are not limited to, carboxylic acids (COOH) such as maleic acid, itaconic acid, maleic acid, r-maleimidobutyric acid, L-malic acid, 4-nitrobenzoic acid, 1-pyrenecarboxylic acid and oleic acid.

Next, the first solution is mixed with the second solution to form a core containing the first organic-inorganic hybrid perovskite nanocrystal (S200).

In the step of mixing the first solution with the second solution to form a core, it is preferable that the first solution is mixed dropwise with the second solution. Further, the second solution at this time may be subjected to stirring. For example, a second solution in which an organic hybrid perovskite (OIP) is dissolved is slowly added dropwise to a second solution in which an alkyl halide surfactant strongly stirring is dissolved to form a first organic hybrid peak perovskite nano A core containing crystals can be synthesized.

In this case, when the first solution is mixed with the second solution, the organic hybrid perovskite (OIP) precipitates in the second solution due to the difference in solubility. The organic hybrid perovskite (OIP) precipitated in the second solution is then alkyl halide surfactant stabilized on the surface to produce a well dispersed organic perovskite nanocrystal (OIP-NC) core. Thus, in this case, the resulting organic or inorganic perovskite nanocrystals are surrounded by a plurality of alkyl halide organic ligands.

On the other hand, the size of such an organic hybrid perovskite nanocrystal can be controlled by adjusting the length or shape factor of the alkyl halide surfactant. For example, shape factor control can be controlled through a linear, tapered or inverted shape of surfactant.

In addition, the size of such organic perovskite nanocrystalline particles can be from 1 nm to 900 nm. On the other hand, the size of the nanocrystal particles at this time means the size without considering the length of the ligand described later, that is, the size of the remaining portion excluding the ligand.

If the size of the organic perovskite nanocrystalline particles is larger than 900 nm, the exciton can not emit light due to thermal ionization and delamination of the charge carriers in the large nanocrystals, .

Next, a shell including a material having a band gap larger than that of the core is formed (S300).

For example, the shell at this time may comprise a second organic-based hybrid perovskite material. In addition, the shell may include an inorganic semiconductor or an organic polymer material.

For example, a solution in which a second organic hybrid perovskite having a larger bandgap than the first organic-inorganic hybrid perovskite, an inorganic semiconductor material, an organic polymeric substance or an organic low-molecular substance is dissolved in the second solution is added A second organic-inorganic hybrid perovskite nanocrystal, an inorganic semiconductor material, an organic polymeric material or an organic low-molecular material surrounding the core may be formed.

In this case, the second organic-inorganic hybrid perovskite is preferably selected to have a larger band gap than the first organic-inorganic hybrid perovskite. Such a second organic-inorganic hybrid perovskite may be a structure of ABX ₃ , A ₂ BX ₄ , ABX ₄ or A _{n- 1} Pb _n I _{3n +1} (n is an integer of 2 to 6). Wherein A is an organic ammonium material, B is a metallic material, and X is a halogen element.

For example, A is _{(CH 3 NH 3) n,} ((C x H 2x + 1) n NH 3) 2 (CH 3 NH 3) n, (RNH 3) 2, (C n H 2n + 1 _{NH 3) 2, (CF 3} NH 3), (CF 3 NH 3) n, ((C x F 2x + 1) n NH 3) 2 (CF 3 NH 3) n, ((C x F 2x + 1 ) _n NH ₃ ) ₂ or (C _n F _{2n + 1} NH ₃ ) ₂ (n is an integer of 1 or more and x is an integer of 1 or more), B is a divalent transition metal, a rare earth metal, Sn, Ge, Ga, In, Al, Sb, Bi, Po or a combination thereof, and X may be Cl, Br, I or a combination thereof. The rare earth metal may be, for example, Ge, Sn, Pb, Eu or Yb. The alkaline earth metal may be Ca or Sr, for example.

Examples of the inorganic semiconductor material include TiO _x (where x is a real number of 1 to 3), indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), zinc oxide (ZnO), zinc tin oxide ), gallium oxide (Ga ₂ O _3), tungsten oxide (WO _3), aluminum, titanium, vanadium oxide oxide _{(V 2 O 5, VO 2} , V 4 O 7, V 5 O 9 , or V ₂ O ₃ ), molybdenum oxide (MoO ₃ or MoO _x ), iron oxide, chromium oxide, bismuth oxide, IGZO (indium-gallium zinc oxide), ZrO ₂ , nickel oxide (NiO), copper oxide (CuO), copper oxide (CAO) CuAlO ₂ ) or an oxide semiconductor such as zinc rhodium oxide (ZRO, ZnRh ₂ O ₄ ).

As another example of the inorganic semiconductor material, there may be mentioned a material such as hydrogen sulfide (H ₂ S), cadmium sulfide (CdS), carbon disulfide (CS ₂ ), lead sulfide (PbS), molybdenum disulfide (MoS ₂ ) (S ₂ S), sodium sulfide (Na ₂ S), zinc sulfide (ZnS), mercury sulfide (HgS), asynic sulfide (AsS), polybenzene sulfide (C ₆ H ₄ S), selenium sulfide SeS ₂ ) or iron disulfide (FeS ₂ ).

The organic polymer material may be a conjugated polymer including polyfluorene, poly (p-phenylee), poly (spirofluorene), and derivatives thereof. As the liquid polymer, there may be used poly (methyl methacrylate) (PMMA), poly (N-vinylcarbazole) (PVK), polyethylene glycol, polyethylene oxide, Polyvinylpyrrolidone, polyethyleneimine, or polyvinyl alcohol (PVA). And may include all kinds of conjugated polymers and non-conjugated polymers and is not limited to a particular chemical structure.

The organic small molecule material may be a conjugated material such as 4,4'-bis (N-carbazolyl) -1,1'-biphenyl (CBP), 2,8- bis (diphenylphosphoryl) dibenzo [b, d] thiophene N, N-dicarbazolyl-3,5-benzene (mCP). May include all kinds of conjugated polymers and non-conjugated low molecular weight and is not limited to a particular chemical structure.

3 is a schematic view showing a method of manufacturing an organic / inorganic hybrid perovskite nanocrystal particle phosphor according to an embodiment of the present invention.

Referring to FIG. 3 (a), a first solution in which an organic hybrid perovskite is dissolved in a protonic solvent is added dropwise to a second solution in which an alkyl halide surfactant is dissolved in an aprotic solvent.

Referring to FIG. 3 (b), when the first solution is added to the second solution, the organic hybrid perovskite is precipitated in the second solution due to the difference in solubility, and the precipitated organic hybrid perovskite An organic halide perovskite nanocrystal particle emitter 100 including an organic hybrid perovskite nanocrystal core 110 that is well dispersed while the surface of the organic halide surfactant is surrounded is stabilized. Wherein the nanocrystal core 110 is surrounded by alkyl halide organic ligands.

The organic / inorganic hybrid perovskite nanocrystal particle emitter constituting the core according to an embodiment of the present invention will be described first with reference to FIG.

4 is a schematic view showing an organic-inorganic hybrid perovskite nanocrystal particle illuminant and inorganic metal halide perovskite nanocrystal particles according to an embodiment of the present invention. 4 shows an organic hybrid hybrid perovskite nanocrystal particle emitter. When the organic hybrid of FIG. 4 is replaced with an inorganic metal halide perovskite, perovskite is an inorganic metal halide nanocrystal particle emitter. same.

Referring to FIG. 4, the phosphor according to an embodiment of the present invention is an organic-inorganic hybrid perovskite nanocrystal particle emitter or an inorganic metal halide perovskite nanocrystalline particle emitter, which is an inorganic or organic hybrid dispersible in an organic solvent Perovskite nanocrystal structure or an inorganic metal halide perovskite nanocrystal structure 110. This nanocrystal structure 110 becomes the nanocrystal core 110 of the phosphor according to the present invention.

The organic or inorganic metal halide perovskite at this time may be a material having a three-dimensional crystal structure or a two-dimensional crystal structure.

For example, an organic-inorganic hybrid perovskite having a three-dimensional crystal structure may be an ABX ₃ structure. In addition, the organic / inorganic hybrid perovskite having a two-dimensional crystal structure may be a structure of ABX ₃ , A ₂ BX ₄ , ABX ₄ or A _{n- 1} Pb _n I _{3n +1} (n is an integer of 2 to 6) have.

At this time, A is _{(CH 3 NH 3) n,} ((C x H 2x + 1) n NH 3) 2 (CH 3 NH 3) n, (RNH 3) 2, (C n H 2n + 1 NH 3 _{) 2, (CF 3 NH 3} ), (CF 3 NH 3) n, ((C x F 2x + 1) n NH 3) 2 (CF 3 NH 3) n, ((C x F 2x + 1) n NH _{3) 2} or _{(C n F 2n + 1 NH} 3) 2 and (n is 1 or more integer), wherein B is a divalent transition metal, rare earth metal, an alkaline earth metal, Pb, Sn, Ge, Ga, In, Al, Sb, Bi, Po or a combination thereof, and X may be Cl, Br, I or a combination thereof. The rare earth metal may be, for example, Ge, Sn, Pb, Eu or Yb. The alkaline earth metal may be Ca or Sr, for example.

For example, an inorganic metal halide perovskite having a three-dimensional crystal structure may be an ABX ₃ structure. The inorganic metal halide perovskite having a two-dimensional crystal structure may be a structure of ABX ₃ , A ₂ BX ₄ , ABX ₄ or A _{n- 1} Pb _n I _{3n +1} (n is an integer of 2 to 6) have.

Wherein A is an alkali metal, B is a bivalent transition metal, a rare earth metal, an alkaline earth metal, Pb, Sn, Ge, Ga, In, Al, Sb, Bi, Po, , Br, I, or a combination thereof. The rare earth metal may be, for example, Ge, Sn, Pb, Eu or Yb. The alkaline earth metal may be Ca or Sr, for example.

The organic-inorganic hybrid perovskite nanocrystal particle emitter 100 according to the present invention further includes a plurality of organic ligands 120 surrounding the organic hybrid perovskite nanocrystal core 110 can do.

Such an organic ligand 120 may comprise an alkyl halide. For example, the alkyl halide may be a structure of alkyl-X. The halogen element corresponding to X at this time may include Cl, Br, I, or the like. At this time, the structure of the alkyl primary alcohol (primary alcohol) having a structure such as acyclic alkyl _{(acyclic alkyl), C n H} 2n + 1 OH having the structure C _n H _{2n +1,} secondary alcohol (secondary alcohol) Tertiary alcohols, alkylamines having a structure of alkyl-N (ex. Hexadecyl amine, 9-Octadecenylamine 1-Amino-9-octadecene (C ₁₉ H ₃₇ N)), p- but are not limited to, p-substituted aniline, phenyl ammonium, or fluorine ammonium.

Referring again to FIG. 3 (c), the shell 130 surrounding the core 110 and including a material having a larger bandgap than the core 110 may be formed.

The core-shell structure according to an embodiment of the present invention will be described first with reference to FIG.

The organic-inorganic hybrid perovskite nanocrystal particle emitter of the core-shell structure according to an embodiment of the present invention includes a perovskite nanocrystal structure dispersible in an organic solvent, and a core-shell structure nanocrystal Particle structure. The organic solvent may be a protonic solvent or an aprotic solvent.

In addition, the nanocrystalline particles may be spherical, cylindrical, elliptical or polygonal.

In addition, the size of such nanocrystalline particles can be from 1 nm to 900 nm. On the other hand, the size of the nanocrystal particles at this time means the size without considering the length of the ligand described later, that is, the size of the remaining portion excluding the ligand. For example, if the nanocrystals are spherical, the diameter of the nanocrystals may be between 1 nm and 900 nm.

In addition, it may further comprise a plurality of organic ligands surrounding such organic or inorganic hybrid perovskite nanocrystals.

5 is a schematic diagram showing an organic-inorganic hybrid perovskite nanocrystal having a core-shell structure according to an embodiment of the present invention and its band diagram.

Referring to FIG. 5 (a), it can be seen that the nanocrystal particle emitter according to the present invention has a structure of a shell 130 surrounding the core 110 and the core 130. Referring to FIG. 5 (b), the energy band gap of the shell is larger than the energy band gap of the core, so that the exciton can be more constrained to the core perovskite.

Again, methods of forming such a shell will be described in detail with reference to FIG.

6 is a schematic diagram illustrating a method of forming a shell according to an embodiment of the present invention.

Referring to FIG. 6, a first organic-inorganic hybrid perovskite nanocrystal 120 is formed as a core. At this time, the first organic-inorganic hybrid perovskite is described with MAPbBr ₃ as an example. In this case, MA means methyl ammonium.

The method of forming such a core can be performed by an inverse nano-emulsion method. For example, a method of forming a core includes the steps of: preparing a first solution in which a first organic-inorganic hybrid perovskite is dissolved in a protonic solvent and a second solution in which an alkyl halide surfactant is dissolved in an aprotic solvent; And mixing the first solution with the second solution to form a core comprising a first organic-inorganic hybrid perovskite nanocrystal.

The following three methods can be used to form a shell on the surface of such a core.

As a first method, a shell may be formed using a second organic hybrid perovskite solution or an inorganic semiconductor material solution. That is, a second solution containing a second organic hybrid perovskite or an inorganic semiconductor material having a larger band gap than that of the first organic-inorganic hybrid perovskite is added to the second solution, 2 < / RTI > organic hybrid perovskite nanocrystals or inorganic semiconductor material.

For example, an organic hybrid perovskite (MAPbBr ₃ ) solution produced through the above-described method (inverse nano-emulsion method) is stirred vigorously and an organic hybrid perovskite having a larger band gap than MAPbBr ₃ MAPbCl ₃ ) solution or a solution of an inorganic semiconductor material such as ZnS or a metal oxide is slowly dropped to form a shell containing a second organic hybrid perovskite nanocrystal (MAPbCl ₃ ) or an inorganic semiconductor material .

This is because the core perovskite and the shell perovskite are mixed with each other to form or stick to each other, so that a hybrid perovskite having a core-shell structure can be synthesized.

Therefore, an organic hybrid perovskite nanocrystal particle emitter having a MAPbBr ₃ / MAPbCl ₃ core-shell structure can be formed.

As a second method, an organic ammonium halide solution can be used to form a shell. That is, a large amount of the organic ammonium halide solution may be added to the second solution and then stirred to form a shell having a band gap larger than that of the core surrounding the core.

For example, a MACl solution is added to an organic / inorganic hybrid perovskite (MAPbBr ₃ ) solution produced by the above-described method (inverse nano-emulsion method) and stirred vigorously to produce MAPbBr ₃ on the surface of MAPbBr _{3 - x} Cl _x to form a shell.

Therefore, an organic-inorganic hybrid perovskite nanocrystal particle emitter having a MAPbBr ₃ / MAPbBr _{3 - x C x} core-shell structure can be formed.

As a third method, a shell can be formed using a decomposition / alloying method. That is, the surface of the core is thermally decomposed by heat treatment of the second solution, and an organic ammonium halide solution is added to the heat-treated second solution to synthesize the surface again to form a bandgap than the core surrounding the core A large shell can be formed.

For example, the organic / inorganic hybrid perovskite (MAPbBr ₃ ) solution produced through the above-described method (inverse nano-emulsion method) is heat-treated to pyrolyze the surface to change into PbBr ₂ , And the surface is again MAPbBr ₂ Cl to form a shell.

That is, at this time, MAPbBr3 can be pyrolyzed into MABr and PbBr2 through thermal decomposition.

Thus, an organic hybrid perovskite nanocrystal particle emitter of the MAPbBr ₃ / MAPbBr ₂ Cl core-shell structure can be formed.

In a fourth method, a shell can be formed using a solution of an organic semiconductor material. That is, in the second solution, the organic semiconductor material having a band gap larger than that of the organic hybrid perovskite is preliminarily melted, and the first solution in which the above-mentioned first organic hybrid peak perovskite is dissolved is added to the second solution Thereby forming a core including the first organic-inorganic hybrid perovskite nanocrystal and a shell including an organic semiconductor material surrounding the core.

Since the organic semiconducting material sticks to the core perovskite surface, it is possible to synthesize an organic / inorganic hybrid perovskite having a core-shell structure.

Thus, an organic hybrid perovskite nanocrystal particle emitter of the MAPbBr ₃ - organic semiconductor core-shell structure can be formed.

As a fifth method, a shell may be formed using a selective excretion method. That is, by adding a small amount of IPA solvent to the second solution in which the core containing the first organic-inorganic hybrid perovskite nanocrystal is formed, MABr is selectively extracted from the nanocrystal surface to form PbBr ₂ alone, A shell having a band gap larger than that of the surrounding core can be formed.

For example, by adding a small amount of IPA to the organic or hybrid hybrid perovskite (MAPbBr ₃ ) solution produced through the above-described method (inverse nano-emulsion method), only the MABr on the surface of the nanocrystals is selectively dissolved to form PbBr 2 So that the PbBr2 shell can be formed.

That is, at this time, MABr on the surface of MAPbBr3 can be removed through selective extraction.

Thus, an organic hybrid perovskite nanocrystal particle emitter of the MAPbBr ₃ -PbBr ₂ core-shell structure can be formed.

An inorganic metal halide perovskite nanocrystal particle emitter having a core-shell structure according to an embodiment of the present invention will be described.

The inorganic metal halide perovskite nanocrystalline particle emitter having a core-shell structure can be dispersed in an organic solvent and has a perovskite nanocrystal structure and can have a core-shell nanocrystalline grain structure.

Such an inorganic metal halide perovskite nanocrystalline particle illuminant is the same except that in the above organic-inorganic hybrid perovskite nanocrystalline particle illuminant, an alkali metal material is contained in A site instead of an organic ammonium material. The alkali metal material may be, for example, A, Na, K, Rb, Cs or Fr.

For example, the inorganic metal halide perovskite nanocrystalline grains of the core-

A core comprising a first inorganic metal halide perovskite nanocrystal and a shell surrounding the core and comprising a material having a larger bandgap than the first inorganic metal halide perovskite. The first inorganic metal halide perovskite at this time includes a structure of ABX _{3 ,} A ₂ BX ₄ , ABX ₄ or A _{n- 1} Pb _n I _{3n +1} (n is an integer of 2 to 6) , A is an alkali metal substance, B is a metal substance, and X may be a halogen element. It may further comprise a plurality of organic ligands surrounding the shell. In addition, the shell may include a second inorganic halide, an inorganic metal halide perovskite nanocrystal material, an inorganic semiconductor or an organic polymeric material.

The "inorganic metal halide" perovskite nanocrystalline grains of such a core-shell structure have a structure in which the A site material is an alkali metal and the "organic hybrid" perovskite nanocrystalline grains of the core- The only difference is the ammonium material and the rest are the same. Therefore, a detailed description of inorganic-metal halide perovskite nanocrystalline particles having a core-shell structure and a method for producing the same is described in detail in detail with respect to an organic-inorganic hybrid perovskite nanocrystal particle having a core- As described, it is redundant and will be omitted.

A light emitting device according to an embodiment of the present invention will be described.

The light emitting device according to one embodiment of the present invention includes the inorganic-metal halide perovskite nanocrystal particle emitter of the core-shell structure organic-organic hybrid perovskite nanocrystal particle emitter or the core-shell structure described above, May be used. The organic-inorganic hybrid perovskite nanocrystal particle emitter or the inorganic metal halide perovskite nanocrystalline particle emitter having the core-shell structure at this time may be one produced by the above-described production method.

For example, the light emitting device according to the present invention may include a first electrode, a second electrode, and an organic-inorganic hybrid perovskite nanocrystal particle positioned between the first electrode and the second electrode, Emitting layer or an inorganic metal halide perovskite nanocrystal particle emitter.

As another example, the photoactive layer including the inorganic-metal halide perovskite nanocrystalline particles having the core-shell structure, the organic perovskite nanocrystalline grains or the core-shell structure described above may be applied to a solar cell . The solar cell may include a first electrode, a second electrode, and a photoactive layer disposed between the first electrode and the second electrode and including the perovskite nanocrystalline particles described above.

Production Example 1

Thereby forming an organic-inorganic hybrid perovskite nanocrystal particle emitter having a three-dimensional structure according to an embodiment of the present invention. Inverse nano-emulsion method.

Specifically, the organic solvent hybrid perovskite was dissolved in the protic solvent to prepare a first solution. In this case, dimethylformamide was used as the proton magnetic solvent, and organic hybrid perovskite CH ₃ NH ₃ PbBr ₃ was used. The CH ₃ NH ₃ PbBr ₃ used here was a mixture of CH ₃ NH ₃ Br and PbBr ₂ in a ratio of 1: 1.

And a second solution in which an alkyl halide surfactant was dissolved in an aprotic solvent was prepared. Toluene was used as the aprotic solvent and octadecylammonium bromide (CH ₃ (CH ₂ ) ₁₇ NH ₃ Br) was used as the alkyl halide surfactant.

Then, the first solution was slowly and dropwise added to the strongly stirring second solution to form an organic / inorganic hybrid perovskite nanocrystal particle emitter having a three-dimensional structure.

Then, organic hybrid hybrid perovskite nanocrystalline particles were spin-coated on the glass substrate to form an organic hybrid perovskite nanocrystal particle thin film (OIP-NP film).

The size of the organic / inorganic hybrid perovskite nanocrystalline grains formed at this time is about 20 nm.

Production Example 2

Except that the alkyl halide surfactant was changed to CH ₃ (CH ₂ ) ₁₃ NH ₃ Br in the same manner as in Production Example 1 to obtain an organic hybrid perovskite nanocrystal particle having a three-dimensional structure according to an embodiment of the present invention To form a light emitting body.

At this time, the size of the organic / inorganic hybrid perovskite nanocrystal particles formed is about 100 nm.

Production Example 3

Except that the alkyl halide surfactant was used in the same manner as in Production Example 1 except that CH ₃ (CH ₂ ) ₁₀ NH ₃ Br was used to form an organic-inorganic hybrid perovskite nanocrystal particle having a three-dimensional structure according to an embodiment of the present invention To form a light emitting body.

The size of the formed organic perovskite nanocrystalline particles is about 300 nm.

Production Example 4

Except that the alkyl halide surfactant was used in the same manner as in Production Example 1 except that CH ₃ (CH ₂ ) ₇ NH ₃ Br was used to form an organic-inorganic hybrid perovskite nanocrystal particle having a three-dimensional structure according to an embodiment of the present invention To form a light emitting body.

At this time, the size of the formed organic hybrid perovskite nanocrystal particles is about 500 nm.

Production Example 5

The procedure of Preparation Example 1 was repeated except that the alkyl halide surfactant was dispersed in an organic-inorganic hybrid perovskite nanocrystal particle having a three-dimensional structure according to an embodiment of the present invention using CH ₃ (CH ₂ ) ₄ NH ₃ Br To form a light emitting body.

The size of the organic / inorganic hybrid perovskite nanocrystals formed at this time is about 700 nm.

Production Example 6

The same procedure as in Preparation Example 1 was carried out except that the alkyl halide surfactant was formed by using CH ₃ CH ₂ NH ₃ Br to form an organic hybrid perovskite nanocrystal particle emitter having a three-dimensional structure according to an embodiment of the present invention Respectively.

The size of the formed organic hybrid perovskite nanocrystal particles is about 800 nm.

Production Example 7

An organic hybrid perovskite nanocrystal particle emitter having a three-dimensional structure according to an embodiment of the present invention was formed using CH ₃ NH ₃ Br as an alkyl halide surfactant in the same manner as in Production Example 1.

The size of the formed organic perovskite nanocrystalline particles is about 900 nm.

Production Example 8

The organic / inorganic hybrid perovskite nanocrystals according to Preparation Example 1 are used as cores. Then, a solution of a second organic hybrid hybrid perovskite (MAPbCl ₃ ) having a large bandgap was slowly dropped one by one in a solution containing the organic-inorganic hybrid perovskite nanocrystal core to form a second hybrid organic perovskite (MAPbCl ₃ ) was formed to form an organic-inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure according to an embodiment of the present invention.

Production Example 9

The organic / inorganic hybrid perovskite nanocrystals according to Production Example 2 are used as the core. Then, a solution of a second organic hybrid hybrid perovskite (MAPbCl ₃ ) having a large bandgap was slowly dropped one by one in a solution containing the organic-inorganic hybrid perovskite nanocrystal core to form a second hybrid organic perovskite (MAPbCl ₃ ) was formed to form an organic-inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure according to an embodiment of the present invention.

Production Example 10

The organic / inorganic hybrid perovskite nanocrystals according to Production Example 3 were used as cores. Then, a solution of a second organic hybrid hybrid perovskite (MAPbCl ₃ ) having a large bandgap was slowly dropped one by one in a solution containing the organic-inorganic hybrid perovskite nanocrystal core to form a second hybrid organic perovskite (MAPbCl ₃ ) was formed to form an organic-inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure according to an embodiment of the present invention.

Production Example 11

The organic / inorganic hybrid perovskite nanocrystals according to Production Example 4 are used as cores. Then, a solution of a second organic hybrid hybrid perovskite (MAPbCl ₃ ) having a large bandgap was slowly dropped one by one in a solution containing the organic-inorganic hybrid perovskite nanocrystal core to form a second hybrid organic perovskite (MAPbCl ₃ ) was formed to form an organic-inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure according to an embodiment of the present invention.

Production Example 12

The organic / inorganic hybrid perovskite nanocrystals according to Production Example 5 are used as cores. Then, a solution of a second organic hybrid hybrid perovskite (MAPbCl ₃ ) having a large bandgap was slowly dropped one by one in a solution containing the organic-inorganic hybrid perovskite nanocrystal core to form a second hybrid organic perovskite (MAPbCl ₃ ) was formed to form an organic-inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure according to an embodiment of the present invention.

Production Example 13

The organic / inorganic hybrid perovskite nanocrystals according to Production Example 6 are used as the core. Then, a solution of a second organic hybrid hybrid perovskite (MAPbCl ₃ ) having a large bandgap was slowly dropped one by one in a solution containing the organic-inorganic hybrid perovskite nanocrystal core to form a second hybrid organic perovskite (MAPbCl ₃ ) was formed to form an organic-inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure according to an embodiment of the present invention.

Production Example 14

The organic / inorganic hybrid perovskite nanocrystals according to Preparation Example 7 were used as cores. Then, a solution of a second organic hybrid hybrid perovskite (MAPbCl ₃ ) having a large bandgap was slowly dropped one by one in a solution containing the organic-inorganic hybrid perovskite nanocrystal core to form a second hybrid organic perovskite (MAPbCl ₃ ) was formed to form an organic-inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure according to an embodiment of the present invention.

Production Example 15

(CH ₃ NH ₃ ) ₂ PbBr ₄ was used in the same manner as in Production Example 8 except that the core organic hybrid perovskite (CH ₃ NH ₃ ) ₂ PbBr ₄ was used. The (CH ₃ NH ₃ ) ₂ PbBr ₄ used was a mixture of CH ₃ NH ₃ Br and PbBr ₂ in a ratio of 2: 1.

At this time, the organic / inorganic hybrid perovskite nanocrystal particle emitter formed in the core-shell form emits light near ultraviolet ray or blue. The emission spectrum is located at about 520 nm.

Production Example 16

(CH ₃ NH ₃ ) ₂ PbI ₄ was carried out in the same manner as in Production Example 8 except that the core organic phase hybrid perovskite (CH ₃ NH ₃ ) ₂ PbI ₄ was used. The (CH ₃ NH ₃ ) ₂ PbI ₄ used here was a mixture of CH ₃ NH ₃ I and PbI ₂ in a ratio of 2: 1.

At this time, the formed organic perovskite nanocrystalline particles in the form of a core-shell type emits light in the vicinity of infrared rays or red light. The emission spectrum is located at about 780 nm.

Production Example 17

(CH ₃ NH ₃ ) ₂ PbCl _x Br _4-x was used in the same manner as in Production Example 8, except that the core organic phase hybrid perovskite (CH ₃ NH ₃ ) ₂ PbCl _x Br _4-x was used. The (CH ₃ NH ₃ ) ₂ PbCl _x Br _{4 -x} used here was a mixture of CH ₃ NH ₃ Cl and PbBr ₂ in a certain ratio.

At this time, the emission spectrum of the organic-base hybrid perovskite nanocrystalline particles formed in the core-shell form is located between 380 nm and 520 nm.

Production Example 18

(CH ₃ NH ₃ ) ₂ PbI _x Br _4-x was carried out in the same manner as in Production Example 8 except that a core organic hybrid perovskite (CH ₃ NH ₃ ) ₂ PbI _x Br _4-x was used. The (CH ₃ NH ₃ ) ₂ PbI _x Br _{4 -x} used here was a mixture of CH ₃ NH ₃ I and PbBr ₂ in a certain ratio.

At this time, the emission spectrum of the organic-base hybrid perovskite nanocrystalline particles formed in the core-shell form is located between 520 nm and 780 nm.

Production Example 19

(CH (NH ₂ ) ₂ ) ₂ PbI ₄ was used in the same manner as in Production Example 8 except that the core organic hybrid perovskite (CH (NH ₂ ) ₂ ) ₂ PbI ₄ was used. The (CH (NH ₂ ) ₂ ) ₂ PbI ₄ used here was a mixture of CH (NH ₂ ) ₂ I and PbI ₂ in a ratio of 2: 1.

At this time, the formed organic-hybrid perovskite nanocrystalline particles in the core-shell form emits infrared light and the emission spectrum is located at about 800 nm.

Production example 20

(CH ₃ NH ₃ ) ₂ Pb _x Sn _1-x I ₄ was used in the same manner as in Production Example 8, except that the core organic hybrid perovskite (CH ₃ NH ₃ ) ₂ Pb _x Sn _1-x I ₄ was used. The (CH ₃ NH ₃ ) ₂ Pb _x Sn _{1 - x} I ₄ used was a mixture of CH ₃ NH ₃ I and Pb _x Sn _{1 -x} I ₂ in a ratio of 2: 1.

At this time, the emission spectrum of the organic-hybrid hybrid perovskite nanocrystalline grains formed in the core-shell form is located at 820 nm and 1120 nm.

Production Example 21

(CH ₃ NH ₃ ) ₂ Pb _x Sn _1-x Br ₄ was performed in the same manner as in Production Example 8, except that the core organic phase hybrid perovskite (CH ₃ NH ₃ ) ₂ Pb _x Sn _1-x Br ₄ was used. The (CH ₃ NH ₃ ) ₂ Pb _x Sn _{1 - x} Br ₄ used was a mixture of CH ₃ NH ₃ Br and Pb _x Sn _1-x Br ₂ in a ratio of 2: 1.

At this time, the emission spectrum of the organic-base hybrid perovskite nanocrystalline particles in the core-shell type formed is located at 540 nm and 650 nm.

Production Example 22

(CH ₃ NH ₃ ) ₂ Pb _x Sn _1-x Cl ₄ was used in the same manner as in Production Example 8, except that the core organic phase hybrid perovskite (CH ₃ NH ₃ ) ₂ Pb _x Sn _1-x Cl ₄ was used. The (CH ₃ NH ₃ ) ₂ Pb _x Sn _{1 - x} Cl ₄ used was a mixture of CH ₃ NH ₃ Cl and Pb _x Sn ₁ -xCl ₂ in a ratio of 2: 1.

At this time, the emission spectrum of the organic-base hybrid perovskite nanocrystalline particles formed in the core-shell form is located at 400 nm and 460 nm.

Production Example 23

(C ₄ H ₉ NH ₃ ) PbBr ₄ was used in the same manner as in Production Example 8, except that the core organic phase hybrid perovskite (C ₄ H ₉ NH ₃ ) PbBr ₄ was used. The (C ₄ H ₉ NH ₃ ) PbBr _{4 used here} was a mixture of (C ₄ H ₉ NH ₃ ) Br and PbBr ₂ in a ratio of 2: 1.

At this time, the emission spectrum of the organic-base hybrid perovskite nanocrystalline grains formed in the core-shell form is located at about 411 nm.

Production Example 24

(C ₅ H ₁₁ NH ₃ ) PbBr ₄ was used in the same manner as in Production Example 8, except that the core organic phase hybrid perovskite (C ₅ H ₁₁ NH ₃ ) PbBr ₄ was used. The (C ₅ H ₁₁ NH ₃ ) PbBr _{4 used here} was a mixture of (C ₅ H ₁₁ NH ₃ ) Br and PbBr ₂ in a ratio of 2: 1.

The emission spectrum of the organic-base hybrid perovskite nanocrystalline particle having the core-shell structure formed at this time is located at about 405 nm.

Production example 25

(C ₇ H ₁₅ NH ₃ ) PbBr ₄ was carried out in the same manner as in Production Example 8, except that the core organic phase hybrid perovskite (C ₇ H ₁₅ NH ₃ ) PbBr ₄ was used. The (C ₇ H ₁₅ NH ₃ ) PbBr _{4 used here} was a mixture of (C ₇ H ₁₅ NH ₃ ) Br and PbBr ₂ in a ratio of 2: 1.

The emission spectrum of the organic-base hybrid perovskite nanocrystalline particle having the core-shell structure formed at this time is located at about 401 nm.

Production Example 26

(C ₁₂ H ₂₅ NH ₃ ) PbBr ₄ was used in the same manner as in Production Example 8 except that a core organic hybrid perovskite (C ₁₂ H ₂₅ NH ₃ ) PbBr ₄ was used. The (C ₁₂ H ₂₅ NH ₃ ) PbBr _{4 used here} was a mixture of (C ₁₂ H ₂₅ NH ₃ ) Br and PbBr ₂ in a ratio of 2: 1.

At this time, the emission spectrum of the organic-base hybrid perovskite nanocrystalline particle of the formed core-shell structure is located at about 388 nm.

Production Example 27

Thereby forming an inorganic metal halide perovskite nanocrystal particle emitter having a three-dimensional structure according to an embodiment of the present invention. Inverse nano-emulsion method.

Specifically, a third solution was prepared by adding cesium carbonate (Cs2CO3) and oleic acid to octadecene (ODE) as an aprotic solvent and reacting at a high temperature. Prepare a fourth solution containing PbBr2, oleic acid and oleylamine in an aprotic solvent and reacting at high temperature (120 ° C) for one hour.

Then, the first solution was slowly added dropwise to the strongly stirring second solution to form an inorganic metal halide perovskite nanocrystal particle emitter having a three-dimensional structure.

Then, inorganic metal halide perovskite nanocrystalline particles in such a solution state were spin-coated on a glass substrate to form an inorganic metal halide perovskite nanocrystal particle thin film (OIP-NP film).

The size of the formed inorganic metal halide perovskite nanocrystalline grains is about 20 nm.

Production Example 28

An inorganic metal halide perovskite (CsPbBr ₃ ) nanocrystal according to Production Example 27 is used as a core. Then, a solution of the second inorganic metal halide perovskite (CsPbCl ₃ ) having a large band gap was slowly dropped one by one in the solution containing the inorganic metal halide perovskite nanocrystal core to form the second inorganic metal halide perovskite (CsPbCl ₃ ) to form an inorganic metal halide perovskite nanocrystal particle emitter of a core-shell structure according to an embodiment of the present invention.

Production Example 29

Thereby manufacturing a light emitting device according to an embodiment of the present invention.

First, an ITO substrate (a glass substrate coated with ITO anode) was prepared, and then a conductive material PEDOT: PSS (AI4083 from Heraeus) was spin-coated on the ITO anode and heat-treated at 150 ° C for 30 minutes to form a hole injection Layer.

Coating a solution of the organic-inorganic hybrid perovskite nanocrystal particles having the core-shell structure according to Production Example 8 on the hole injection layer by spin coating and then heat-treating the hybrid organic perovskite nanocrystal particles at 80 ° C for 20 minutes to form an organic hybrid perovskite nanocrystal Thereby forming a particle-emitting layer.

Subsequently, a 50 nm-thick 1,3,5-Tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI) was deposited on the organic hybrid perovskite nanocrystalline grain luminescent layer at 1 × 10 ^-7 Torr , And then an electron injection layer was formed thereon by depositing LiF having a thickness of 1 nm thereon. Aluminum was deposited to a thickness of 100 nm on the electron injection layer to form a negative electrode, thereby forming an organic hybrid perovskite nano- A crystal grain luminescent device was fabricated.

Production Example 30

A solar cell according to an embodiment of the present invention was manufactured.

First, an ITO substrate (ITO anode coated glass substrate) was prepared, and then a conductive material PEDOT: PSS (CLEVIOS PH manufactured by Heraeus Co., Ltd.) was spin-coated on the ITO anode and heat-treated at 150 to 30 minutes to form holes with a thickness of 40 nm Layer.

The organic-inorganic hybrid perovskite nanocrystals of core-shell structure according to Preparation Example 1 were mixed with Phenyl-C61-butyric acid methyl ester (PCBM) on the hole extraction layer to form a photoactive layer, And 100 nm thick Al was deposited thereon to prepare a perovskite nanocrystal particle solar cell.

Comparative Example 1

The first solution was prepared by dissolving CH ₃ NH ₃ PbBr ₃ in dimethylformamide, which is a protic solvent.

Then, the spin-coating a first solution on a glass plate CH ₃ NH ₃ PbBr ₃ (OIP film) was prepared.

Comparative Example 2

The first solution was prepared by dissolving CH ₃ NH ₃ PbCl ₃ in dimethylformamide, which is a protic solvent.

Then, the spin-coating a first solution on a glass plate CH ₃ NH ₃ PbCl ₃ (OIP film) was prepared.

Experimental Example

7 is a fluorescence image in which luminescent light according to Production Example 1, Comparative Example 1, and Comparative Example 2 is irradiated with ultraviolet light.

Referring to FIG. 7, a bulk organic-inorganic hybrid perovskite solution according to Comparative Example 1 and Comparative Example 2, which is not a nanocrystalline type, emits dark light, while the nanocrystal type according to Production Example 1 It can be confirmed that the light emitting body emits very bright green light.

As a result of measurement of absolute photoluminescence quantum yield (PLQY), it was confirmed that the organic / inorganic hybrid perovskite nanocrystal particle emitter according to Preparation Example 1 had a very high value of 52%.

On the other hand, in Comparative Example 1 and Comparative Example 2, a thin organic hybrid coating perovskite formed by spin coating on a glass substrate exhibited a low PLQY value of about 1%.

8 is a schematic diagram of a light emitting device according to Production Example 1 and Comparative Example 1. Fig.

FIG. 8A is a schematic view of a phosphor thin film (OIP film) according to Comparative Example 1, and FIG. 8B is a schematic diagram of a phosphor thin film (OIP-NP film) according to Production Example 1. Referring to FIG. 8 (a), Comparative Example 1 is a thin film formed by spin coating a first solution on a glass substrate. Referring to FIG. 8 (b), the light emitting body according to Production Example 1 includes a nanocrystal structure 110, Is a nanocrystal type.

9 is an image of a photoluminescence matrix of the light emitting body according to Production Example 1 and Comparative Example 1 taken at normal temperature and low temperature, respectively.

9 (a) is an image taken at a low temperature (70 K) of a photoluminescence matrix of a thin film organic / inorganic hybrid perovskite (OIP film) according to Comparative Example 1, and FIG. 9 FIG. 4 is an image of a light emitting matrix of a thin film organic / inorganic hybrid perovskite (OIP film) according to Example 1 taken at room temperature. FIG.

9 (c) is an image of a light emitting matrix of an organic-inorganic hybrid perovskite nanocrystal particle thin film (OIP-NP film) according to Production Example 1 at a low temperature (70 K) (OIP-NP film) organic-based hybrid perovskite nanocrystal particle thin film according to Example 1 at room temperature.

9 (a) to 9 (d), in the case of the organic hybrid perovskite nanocrystal particle thin film (OIP-NP film) according to Production Example 1, the organic / inorganic hybrid It shows photoluminescence at the same position as the perovskite (OIP film) and shows higher color purity. Also, the OIP-NP film according to Production Example 1 exhibits high color purity light emission at the same position as that at a low temperature at room temperature, and the luminescence intensity is not reduced. On the other hand, in the thin film organic / inorganic hybrid perovskite according to Comparative Example 1, not only the color purity and the luminescent position were different at room temperature and low temperature, but the exciton could not emit light due to thermal ionization and delocalization of the charge carrier at room temperature, And it shows low emission intensity.

FIG. 10 is a graph of photoluminescence of the phosphor according to Production Example 1 and Comparative Example 1. FIG.

10, in the case of a solution state in which the organic / inorganic hybrid perovskite nanocrystal particle emitter according to Production Example 1 is placed in a solution and a thin film state in which a thin film layer is formed using such a nanocrystalline particle emitter, 1 shows the photoluminescence at the same position as that of the organic / inorganic hybrid perovskite according to the present invention, and shows higher color purity.

11 is a conceptual diagram showing a process of forming a core-shell structure using an IPA (isopropyl alcohol) solution in an organic-inorganic hybrid perovskite nanocrystal particle emitter according to Production Example 1. FIG.

11, a small amount of an IPA solution is dropped into a second solution in which an organic-inorganic hybrid perovskite nanocrystal particle emitter (MAPbBr ₃ ) according to Production Example 1 is formed, and the mixture is stirred. In this case, MA was CH ₃ NH ₃ in Production Example 1. In this case, only CH ₃ NH ₃ Br on the surface of the nanocrystal particle emitter is selectively extracted by IPA to leave a surface of PbBr ₂ to form a shell, thereby forming a core-shell nanocrystalline particle luminescent article.

12 is a graph showing the luminescence intensity characteristics of an organic-inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure according to the present invention.

The organic / inorganic hybrid perovskite nanocrystal particle emitter according to Production Example 1 is referred to as Reference.

20 μl, 40 μl, and 60 μl of IPA solution were added to a second solution (about 5 ml) having 0.6 mol of the organic perovskite nanoparticle particle emitter prepared according to Preparation Example 1 and stirred to prepare Core-shell (1) structure , A core-shell (2) structure, and a core-shell (3) structure.

It can be seen that the nanocrystal particle emitters of the core-shell (1) structure, the core-shell (2) structure and the core-shell (3) structure exhibit brighter light emission than the nanoparticle particle emitters of Production Example 1 .

13 is a view showing band gaps of shell materials according to the present invention.

13, an organic material such as CBP, mCP, PVK, PPT or PMMA having a larger bandgap than nanocrystals on the surface of the organic-inorganic hybrid perovskite nanocrystal particle illuminant (OIP-NCs) according to Production Example 1 It is possible to form nanocrystals of a core (nanocrystal particle) -shell (organic material) structure.

FIG. 14 is a graph showing photoluminescence (PL) intensity characteristics of an organic-inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure according to the present invention.

The organic / inorganic hybrid perovskite nanocrystal particle emitter according to Production Example 1 is referred to as Reference.

Then, the same procedure as in Preparation Example 1 was carried out except that an organic substance for a shell material was dissolved together in a second solution in which an alkyl halide surfactant was dissolved in an aprotic solvent, and then the first solution was slowly added dropwise to the organic solution, (Nanocrystal particle) -shell (organic substance) structure of the perovskite nanocrystal particle emitter was formed on the surface of the perovskite nanocrystal particle emitter with an organic material having a band gap larger than that of the nanocrystal.

At this time, 0.01 g of CBP, mCP, PMMA, PPT, and PVK were added as an organic substance for the shell material to be added to form a core-shell structure nanoparticle particle emitter.

As a result, it can be seen that the nanocrystalline particle illuminant of the core (nanocrystal particle) -shell (organic material) structure exhibits brighter light emission (PL) than the nanocrystal particle illuminant of Production Example 1.

The nanocrystalline particle illuminant comprising the organic-inorganic hybrid perovskite nanocrystals or the inorganic metal halide perovskite nanocrystals according to the present invention is a nanocomposite particle emitter comprising an inorganic hybrid perovolume having a crystal structure of FCC and BCC combined in a nanocrystal particle emitter A skeletal or inorganic metal halide perovskite is formed, and a lamellar structure in which the organic plane and the inorganic plane are alternately stacked is formed, and the exciton is constrained to the inorganic plane to give a high color purity.

In addition, the exciton diffusion length is reduced and the exciton binding energy is increased in nanocrystals of 900 nm or less, thereby preventing thermal ionization and destruction of excitons due to delamination of the charge carriers, The light emitting efficiency can be obtained.

In addition, the band gap energy of the organic-inorganic hybrid perovskite nanocrystal particle or the inorganic metal halide perovskite nanocrystal particle is determined by the crystal structure without depending on the particle size.

In addition, by synthesizing the two-dimensional organic / inorganic hybrid perovskite with nanocrystals in comparison with the three-dimensional organic-inorganic hybrid perovskite, the exciton binding energy can be increased to further improve the luminous efficiency and increase the durability-stability .

In addition, the organic-inorganic hybrid perovskite nanocrystal particle emitter or the inorganic metal halide perovskite nanocrystal particle emitter having a core-shell structure formed according to the present invention may form a shell with a material having a band gap larger than that of the core, It is possible to improve the durability of the nanocrystal by preventing the core perovskite from being exposed to the air by using a perovskite stable in the air or an inorganic semiconductor or organic polymer in the air.

It should be noted that the embodiments of the present invention disclosed in the present specification and drawings are only illustrative of specific examples for the purpose of understanding and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that other modifications based on the technical idea of the present invention are possible in addition to the embodiments disclosed herein.

100: organic / inorganic hybrid perovskite nanocrystal particle emitter
100 ': organic / organic hybrid perovskite nanocrystal particle emitter with core-shell structure
110: Organic-inorganic hybrid perovskite nanocrystal core
120: organic ligand 130: shell

Claims (29)

Which comprises a perovskite nanocrystal structure capable of being dispersed in an organic solvent,
An organic / inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure having a nanocrystalline particle structure of a core-shell structure. The method according to claim 1,
Wherein the organic solvent comprises a protic solvent or aprotic solvent,
Wherein the protonic solvent comprises dimethylformamide, gamma butyrolactone, N-methylpyrrolidone or dimethylsulfoxide, wherein the protonic solvent is selected from the group consisting of dimethylformamide, gamma butyrolactone, N-methylpyrrolidone,
Wherein the aprotic solvent is selected from the group consisting of dichloroethylene, trichlorethylene, chloroform, chlorobenzene, dichlorobenzene, styrene, dimethylformamide, dimethylsulfoxide, xylene, toluene, cyclohexene or isopropyl alcohol An organic / inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure. The method according to claim 1,
The organic / inorganic hybrid perovskite nanocrystal particle is a spherical, cylindrical, elliptic column or polygonal columnar core-shell structure organic / organic hybrid perovskite nanocrystal particle emitter. The method according to claim 1,
Wherein the organic / inorganic hybrid perovskite nanocrystal particle size is 1 nm to 900 nm. The method according to claim 1,
Wherein the band gap energy of the organic / inorganic hybrid perovskite nanocrystalline grains is determined by the crystal structure without depending on the grain size, and the organic / inorganic hybrid perovskite nanocrystal particle emitter . The method according to claim 1,
The organic-inorganic hybrid perovskite nanocrystalline grains of the core-shell structure may be prepared by,
A core comprising a first organic-inorganic hybrid perovskite nanocrystal; And
And a shell surrounding the core, the shell including a material having a bandgap larger than that of the first organic-inorganic hybrid perovskite, the inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure. The method according to claim 6,
Wherein the first organic-inorganic hybrid perovskite nanocrystals have a two-dimensional structure or a three-dimensional structure, wherein the first organic-inorganic hybrid perovskite nanocrystals have a two-dimensional structure or a three-dimensional structure. The method according to claim 6,
Wherein the first organic-inorganic hybrid perovskite includes a structure of ABX _{3 ,} A ₂ BX ₄ , ABX ₄ or A _n-1 Pb _n I _{3n + 1} (n is an integer of 2 to 6)
Wherein A is an organic ammonium material, B is a metallic material, and X is a halogen element. 9. The method of claim 8,
And A is _{(CH 3 NH 3) n,} ((C x H 2x + 1) n NH 3) 2 (CH 3 NH 3) n, (RNH 3) 2, (C n H 2n + 1 NH 3) 2 _{, (CF 3 NH 3),} (CF 3 NH 3) n, ((C x F 2x + 1) n NH 3) 2 (CF 3 NH 3) n, ((C x F 2x + 1) n NH 3 ) ₂ or (C _n F _{2n + 1} NH ₃ ) ₂ (n is an integer of 1 or more, x is an integer of 1 or more)
Wherein B is a divalent transition metal, a rare earth metal, an alkaline earth metal, Pb, Sn, Ge, Ga, In, Al, Sb, Bi, Po,
Wherein X is Cl, Br, I or a combination thereof.
An organic / inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure. The method according to claim 6,
Wherein the shell comprises a second organic-inorganic hybrid perovskite nanocrystal. 2. The organic / inorganic hybrid perovskite nanocrystal particle emitter according to claim 1, wherein the shell comprises a second organic-inorganic hybrid perovskite nanocrystal. The method according to claim 6,
Wherein the shell comprises an inorganic halide or an organic low-molecular material. The phosphor-based hybrid perovskite nanocrystal particle emitter of the core-shell structure is characterized in that the shell comprises an inorganic halide or an organic low-molecular material. The method according to claim 6,
Wherein the shell comprises an inorganic semiconductor or an organic polymeric substance, wherein the shell is a core-shell structure. 13. The method of claim 12,
Wherein the inorganic semiconductor material is selected from the group consisting of TiO _x (x is a real number of 1 to 3), indium oxide, tin oxide, zinc oxide, tin oxide, gallium oxide, tungsten oxide, aluminum oxide, vanadium oxide, molybdenum oxide , Iron oxide, chromium oxide, bismuth oxide, IGZO (indium-gallium zinc oxide), ZrO ₂ , nickel oxide, copper oxide, copper aluminum oxide, zinc oxide rhodium, hydrogensulfide, cadmium sulfide, carbon disulfide, lead sulfide, mol Organic hybrid perovskite nanocrystalline particles having a core-shell structure containing at least one member selected from the group consisting of rubidium disulfide, silver sulfide, sodium sulfide, zinc sulfide, mercury sulfide, acenic sulfide, polybenzylene sulfide, selenium sulfide or iron disulfide. illuminant. 13. The method of claim 12,
The organic polymeric material may be a polymer having a core-shell structure including polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, polyethyleneimine or polyvinyl alcohol (PVA) Hybrid perovskite nanocrystalline particle emitter. 13. The method of claim 12,
Wherein the organic polymeric substance includes any one selected from the group consisting of polyfluorene, poly (p-phenylee), poly (spirofluorene), and derivatives thereof An organic / inorganic hybrid perovskite nanocrystal particle emitter having a core-shell structure. 13. The method of claim 12,
The organic polymeric material may be an organic or inorganic hybrid material having a core-shell structure including poly (methyl methacrylate) (PMMA) or poly (N-vinylcarbazole) (PVK) Twin nanocrystal particle emitter. The method according to claim 6,
Further comprising a plurality of organic ligands surrounding said shell, said core-shell structure further comprising a plurality of organic ligands surrounding said shell. 18. The method of claim 17,
Wherein the organic ligand comprises an alkyl halide, and wherein the organic ligand comprises an alkyl halide. 19. The method of claim 18,
The alkyl structure of the alkyl halide may be an acyclic alkyl having a structure of C _n H _{2n + 1} , a primary alcohol, a secondary alcohol, a tertiary alcohol, an alkylamine ), a p-substituted aniline, phenyl ammonium, or fluorine ammonium. The phosphor-based hybrid perovskite nanocrystal particle emitter has a core-shell structure. Which comprises a perovskite nanocrystal structure capable of being dispersed in an organic solvent,
An inorganic metal halide perovskite nanocrystalline particle emitter of a core-shell structure having a nanocrystalline grain structure of a core-shell structure. 21. The method of claim 20,
The inorganic metal halide perovskite nanocrystalline grains of the core-
A core comprising a first inorganic metal halide perovskite nanocrystal; And
An inorganic metal halide perovskite nanocrystalline particle emitter of a core-shell structure including a shell surrounding the core and including a material having a band gap larger than that of the first inorganic metal halide perovskite. 22. The method of claim 21,
Wherein said first inorganic metal halide perovskite comprises a structure of ABX _{3 ,} A ₂ BX ₄ , ABX ₄ or A _n-1 Pb _n I _{3n + 1} , wherein n is an integer between 2 and 6,
The inorganic metal halide perovskite nanocrystalline particle emitter of the core-shell structure wherein A is an alkali metal substance, B is a metal substance, and X is a halogen element. 23. The method of claim 22,
The inorganic metal halide perovskite nanocrystalline particle emitter of the core-shell structure, wherein A is Na, K, Rb, Cs or Fr. 22. The method of claim 21,
Wherein the inorganic metal halide perovskite nanocrystal particle emitter further comprises a plurality of organic ligands surrounding the shell. Preparing a first solution in which a first organic group hybrid perovskite is dissolved in a protic solvent and a second solution in which an alkyl halide surfactant is dissolved in an aprotic solvent;
Mixing the first solution with the second solution to form a core comprising a first organic-inorganic hybrid perovskite nanocrystal; And
A second solution containing a second organic hybrid perovskite or an inorganic semiconductor material having a larger bandgap than that of the first organic-inorganic hybrid perovskite is added to the second solution to form a second solution And forming a shell comprising a plurality of hybrid perovskite nanocrystals or inorganic semiconductor materials. The method of claim 1, wherein the phosphor-perovskite nanocrystalline particle emitter has a core-shell structure. Preparing a first solution in which a first organic group hybrid perovskite is dissolved in a protic solvent and a second solution in which an alkyl halide surfactant is dissolved in an aprotic solvent;
Mixing the first solution with the second solution to form a core comprising a first organic-inorganic hybrid perovskite nanocrystal; And
And adding a solution of an organic ammonium halide solution to the second solution and stirring to form a shell having a band gap larger than that of the core surrounding the core, Lt; / RTI > Preparing a first solution in which a first organic group hybrid perovskite is dissolved in a protic solvent and a second solution in which an alkyl halide surfactant is dissolved in an aprotic solvent;
Mixing the first solution with the second solution to form a core comprising a first organic-inorganic hybrid perovskite nanocrystal;
Thermally decomposing the surface of the core by heat treating the second solution; And
And adding an organic ammonium halide solution to the heat-treated second solution to form a shell having a larger bandgap than the core surrounding the core, wherein the core- Gt; A first electrode;
A second electrode; And
An inorganic metal halide emitter of a core-shell structure having an organic-inorganic hybrid perovskite nanocrystal particle emitter or a core-shell structure of the core-shell structure according to any one of claims 1 to 24, which is located between the first electrode and the second electrode. A luminescent device comprising a luminescent layer comprising a lobb- cate nanocrystalline particle emitter. A first electrode;
A second electrode; And
An inorganic metal halide emitter of a core-shell structure having an organic-inorganic hybrid perovskite nanocrystal particle emitter or a core-shell structure of the core-shell structure according to any one of claims 1 to 24, which is located between the first electrode and the second electrode. A solar cell comprising a photoactive layer comprising a lobescite nanocrystalline particle emitter.

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