Patent Application
20170342317
The present invention relates to a light emitting body and a light emitting element using the same, and more particularly, to an organic-inorganic hybrid perovskite or inorganic metal halide perovskite nanocrystal particle light emitting body whose content is changed, a method of producing the same, and a light emitting element using the same.
Currently, a mega trend in the display market is moving from existing high-efficiency and high-resolution oriented displays to emotional image quality displays aimed at realizing a natural color having high color purity. From this viewpoint, currently, organic light emitting body based organic light emitting diode (OLED) elements have achieved rapid progress, and inorganic quantum dot light emitting diodes (LEDs) with improved color purity have been actively researched and developed as alternatives. However, both an organic light emitting body and an inorganic quantum dot light emitting body have inherent limitations in terms of materials.
The existing organic light emitting body has high efficiency, but has a wide spectrum and poor color purity. The inorganic quantum dot light emitting body has been known to have good color purity. However, there is a problem in that color purity is reduced since it is difficult to control a size of a quantum dot uniformly toward a blue side because of light emission due to a quantum size effect. Furthermore, since inorganic quantum dots have a very deep valence band, there is a problem in that hole injection barriers in an organic hole injection layer are too large to inject holes. Also, there is a disadvantage in that the two light emitting bodies are expensive. Therefore, there is a need for a new type of organic-inorganic hybrid light emitting body that compensates for the disadvantages of the organic and inorganic light emitting bodies and maintains advantages thereof.
Since organic-inorganic hybrid materials have both advantages of organic materials such as low manufacturing cost, simple producing and element manufacturing processes, and easily controllable optical and electrical properties and advantages of inorganic materials such as high charge mobility and mechanical and thermal stability, the organic-inorganic hybrid materials have been spotlighted both academically and industrially.
Since organic-inorganic hybrid perovskite materials among the organic-inorganic hybrid materials have high color purity, simple color adjustment, and low synthesis cost, the possibility of development as light emitting bodies is very high. Since the organic-inorganic hybrid perovskite materials have a layered structure, in which a two-dimensional (2D) plane of an inorganic material is interposed between 2D planes of an organic material, and a dielectric constant difference between an inorganic material and an organic material is large (∈organic≈2.4, ∈inorganic≈6.1), excitons are confined to the inorganic plane. Therefore, the organic-inorganic hybrid perovskite materials having high color purity (full width at half maximum (FWHM)≈20 nm) are formed.
As a material having a perovskite (ABX3) structure in the related art, there is an inorganic metal oxide.
Such an inorganic metal oxide is generally oxide, and is a material in which cations of metals (such as an alkali metal, an alkaline earth metal, a transition metal, a lanthanide, and the like) such as Ti, Sr, Ca, Cs, Ba, Y, Gd, La, Fe, Mn, and the like having different sizes are located at A and B sites, anions of oxygen are located at an X site, and the cations of metals at the B site are combined with the anions of oxygen at the X site as a corner-sharing octahedron form of 6-fold coordination. As examples of the inorganic metal oxide, there are SrFeO3, LaMnO3, CaFeO3, and the like.
On the other hand, in the organic-inorganic hybrid perovskite, cations of organic ammonium halide (RNH3) are located at an A site and halides (Cl, Br, and I) are located at an X site in an ABX3 structure to form an organic metal halide perovskite material, and thus a composition of the organic metal halide perovskite material is completely different from that of an inorganic metal oxide perovskite material.
Also, properties of the materials are based on the difference of such constituent materials. The inorganic metal oxide perovskite has representative properties such as superconductivity, ferroelectricity, colossal magnetoresistance, and the like. Therefore, the inorganic metal oxide perovskite is generally applied to sensors, fuel cells, memory devices, and the like, and research thereon has been conducted. For example, yttrium barium copper oxide has superconductivity or an insulation property according to oxygen content.
On the other hand, since an organic-inorganic hybrid perovskite (or an organic metal halide perovskite) has a structure, in which an organic plane (or an alkali metal plane) and an inorganic plane are alternately stacked, which is similar to a lamellar structure, excitons may be confined to the inorganic plane. Therefore, an ideal light emitting body which emits light having very high color purity may be formed by a crystalline structure itself rather than a size of the material in essence.
Even in the organic-inorganic hybrid perovskite, since light emission occurs in organic ammonium when the organic ammonium contains a chromophore (mainly including a conjugated structure) having a smaller bandgap than that of a crystalline structure of a central metal and halogen (BX3), light having high color purity cannot be emitted, a FWHM of the light emission spectrum becomes wider than 50 nm, and thus the organic-inorganic hybrid perovskite becomes unsuitable as a light emitting layer. Therefore, in this case, the organic-inorganic hybrid perovskite is not very suitable for a high color purity light emitting body emphasized in the present invention. Therefore, in order to make a high color purity light emitting body, it is important that organic ammonium does not contain a chromophore and light emission occurs in an inorganic material lattice consisting of a central metal and a halogen element. That is, the present invention focuses on the development of a high color purity and high efficiency light emitting body in which light emission occurs in an inorganic material lattice. For example, in Korean Patent Application Publication No. 10-2001-0015084 (Published on Feb. 26, 2001), an electroluminescent element in which a dye-containing organic-inorganic hybrid material is formed in the form of a thin film rather than particles and is used as a light emitting layer is disclosed, but light emission does not occur in a perovskite lattice structure.
However, since the organic-inorganic hybrid perovskite has a small exciton binding energy, there is a fundamental problem in that, at low temperature, light can be emitted but, at room temperature, excitons cannot lead to light emission due to thermal ionization and delocalization of a charge carrier, are separated into free charges, and disappear. Also, when the free charges are recombined to form excitons, there is a problem in that the excitons are destroyed by a layer having a high conductivity around the excitons, so that light emission does not occur. Therefore, it is necessary to prevent quenching of the excitons in order to increase light emission efficiency and luminance of an organic-inorganic hybrid perovskite based LED.
The present invention is directed to providing a nanocrystal particle light emitting body having a light emission efficiency, durability, and stability which are improved by synthesizing an organic-inorganic hybrid perovskite or an inorganic metal halide perovskite as a nanocrystal instead of a thin film in order to prevent thermal ionization, delocalization of a charge carrier, and quenching of excitons, and a light emitting element using the same.
Furthermore, the present invention is directed to providing a nanocrystal particle light emitting body having a light emission efficiency and durability which are further improved by forming a gradient-alloy type organic-inorganic hybrid perovskite or inorganic metal halide perovskite nanocrystal whose content is changed, and a light emitting element using the same.
One aspect of the present invention provides an organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a gradient structure. The organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a gradient structure includes an organic-inorganic hybrid perovskite nanocrystal structure which is dispersible in an organic solvent, wherein the nanocrystal structure has a gradient composition in which a composition is changed from the center thereof to the outside.
The organic solvent may include a protic solvent or an aprotic solvent, wherein the protic solvent may include dimethylformamide, gamma butyrolactone, N-methylpyrrolidone, or dimethyl sulfoxide, and the aprotic solvent may include dichloroethylene, trichlorethylene, chloroform, chlorobenzene, dichlorobenzene, styrene, dimethylformamide, dimethyl sulfoxide, xylene, toluene, cyclohexene, or isopropyl alcohol.
The organic-inorganic hybrid perovskite nanocrystal particle may have a spherical, cylindrical, elliptical pillar, or polygonal pillar shape.
A size of the nanocrystal particle may range from 1 nm to 900 nm.
A bandgap energy of the organic-inorganic hybrid perovskite nanocrystal particle may be determined by a crystalline structure without depending on the size of the particle.
The organic-inorganic hybrid perovskite may have a structure of ABX3-mX′m, A2BX4-lX′l or ABX4-kX′k, wherein A may be an organic ammonium material, B is a metal material, X is Br, X′ is Cl, and values of m, l, and k may be increased from a center of the nanocrystal structure to the outside.
The A may be (CH3NH3)n, ((CxH2x+1)nNH3)2(CH3NH3)n, (RNH3)2, (CnH2n+1NH3)2, (CF3NH3), (CF3NH3)n, ((CxF2x+1)nNH3)2(CF3NH3)n, ((CxF2x+1)nNH3)2, or (CnF2n+1NH3)2 (here, n and x are integers greater than or equal to 1), and the B may be a bivalent transition metal, a rare-earth metal, an alkaline-earth metal, Pb, Sn, Ge, Ga, In, Al, Sb, Bi, Po, or a combination thereof.
The values of m, l, and k may be gradually increased from the center of the nanocrystal structure to the outside.
The values of m, l, and k may be increased stepwise from the center of the nanocrystal structure to the outside.
The organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a gradient structure may further include a plurality of organic ligands configured to surround the perovskite nanocrystal structure.
The organic ligands may include an alkyl halide. An alkyl structure of the alkyl halide may include an acyclic alkyl having a structure of CnH2n+1, a primary alcohol, a secondary alcohol, a tertiary alcohol, an alkylamine, p-substituted aniline, phenyl ammonium, or fluorine ammonium.
Another aspect of the present invention provides a method of producing an organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a gradient structure. The method includes preparing an organic-inorganic hybrid perovskite nanocrystal particle having a core-shell structure in which a composition of a core is different from a composition of a shell, and forming the organic-inorganic hybrid perovskite nanocrystal particle having a core-shell structure so as to have a gradient composition through interdiffusion by performing heat treatment thereon.
The preparing of the organic-inorganic hybrid perovskite nanocrystal particle having a core-shell structure may include preparing a first solution in which a first organic-inorganic hybrid perovskite is dissolved in a protic solvent and a second solution in which an alkyl halide surfactant is dissolved in an aprotic solvent, forming a core including a first organic-inorganic hybrid perovskite nanocrystal by mixing the first solution with the second solution, and forming a shell, which includes a second organic-inorganic hybrid perovskite nanocrystal and surrounds the core, by adding a third solution, in which a second organic-inorganic hybrid perovskite having a larger bandgap than that of the first organic-inorganic hybrid perovskite is dissolved, to the second solution.
The first organic-inorganic hybrid perovskite may have a structure of ABX3, A2BX4 or ABX4 and the second organic-inorganic hybrid perovskite may have a structure of ABX′ 3, A2BX′4 or ABX′4, wherein A may be an organic ammonium material, B may be a metal material, X may be Br, and X′ may be Cl.
The preparing of the organic-inorganic hybrid perovskite nanocrystal particle having a core-shell structure may include preparing a first solution in which a first organic-inorganic hybrid perovskite is dissolved in a protic solvent and a second solution in which an alkyl halide surfactant is dissolved in an aprotic solvent, forming a core including a first organic-inorganic hybrid perovskite nanocrystal by mixing the first solution with the second solution, and forming a shell, which has a larger bandgap than that of the core and surrounds the core, by adding an organic ammonium halide solution to the second solution and then stirring.
The preparing of the organic-inorganic hybrid perovskite nanocrystal particle having a core-shell structure may include preparing a first solution in which a first organic-inorganic hybrid perovskite is dissolved in a protic solvent and a second solution in which an alkyl halide surfactant is dissolved in an aprotic solvent, forming a core including a first organic-inorganic hybrid perovskite nanocrystal by mixing the first solution with the second solution, thermally decomposing a surface of the core by performing heat treatment on the second solution, and forming a shell, which has a larger bandgap than that of the core and surrounds the core, by adding an organic ammonium halide solution to the heat-treated second solution.
Still another aspect of the present invention provides a method of producing an organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a gradient structure. The method includes preparing a first solution in which a first organic-inorganic hybrid perovskite is dissolved in a protic solvent and a second solution in which an alkyl halide surfactant is dissolved in an aprotic solvent, forming a core including a first organic-inorganic hybrid perovskite nanocrystal by mixing the first solution with the second solution, and forming a shell, which has a larger bandgap than that of the core and surrounds the core, by adding a third solution, in which a second organic-inorganic hybrid perovskite is dissolved, to the second solution while changing a composition of the second organic-inorganic hybrid perovskite.
The second organic-inorganic hybrid perovskite may have a structure of ABX3-mX′m, A2BX4-lX′l, or ABX4-kX′k, wherein A may be an organic ammonium material, B may be a metal material, X may be Br, and X′ may be Cl, and the third solution in which the second organic-inorganic hybrid perovskite is dissolved may be added to the second solution while increasing a value of m, l, or k.
Yet another aspect of the present invention provides a light emitting element. The light emitting element includes a first electrode, a second electrode, and a light emitting layer, which is located between the first electrode and the second electrode and includes the organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a gradient structure.
Yet another aspect of the present invention provides an inorganic metal halide perovskite nanocrystal particle light emitting body having a gradient structure. The inorganic metal halide perovskite nanocrystal particle light emitting body having a gradient structure includes an inorganic metal halide perovskite nanocrystal structure which is dispersible in an organic solvent, wherein the nanocrystal structure has a gradient composition in which a composition is changed from the center thereof to the outside. The inorganic metal halide perovskite may have a structure of ABX3-mX′m, A2BX4-lX′l, or ABX4-kX′k, wherein A may be an alkali metal, B may be a metal material, X may be Br, and X′ may be Cl, and values of m, l, and k may be increased from a center of the nanocrystal structure to the outside.
The A may be Na, K, Rb, Cs, or Fr, and the B may be a bivalent transition metal, a rare-earth metal, an alkaline-earth metal, Pb, Sn, Ge, Ga, In, Al, Sb, Bi, Po, or a combination thereof.
Values of m, l, and k may be gradually increased from the center of the nanocrystal structure to the outside.
The values of m, l, and k may be increased stepwise from the center of the nanocrystal structure to the outside.
The inorganic metal halide perovskite nanocrystal particle light emitting body having a gradient structure may further include a plurality of organic ligands configured to surround the perovskite nanocrystal structure.
Yet another aspect of the present invention provides a solar cell. The solar cell includes a first electrode, a second electrode, and a photoactive layer, which is located between the first electrode and the second electrode and includes the organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a gradient structure or the inorganic metal halide perovskite nanocrystal particle light emitting body having a gradient structure.
In a nanocrystal particle light emitting body including an organic-inorganic hybrid perovskite (or an organic metal halide perovskite) nanocrystal according to the present invention, an organic-inorganic hybrid perovskite having a crystalline structure in which a face centered cubic (FCC) structure and a body centered cubic (BCC) structure are combined can be formed in the nanocrystal particle light emitting body, a lamellar structure in which an organic plane and an inorganic plane are alternately stacked can be formed, and excitons can be confined to the inorganic plane to show high color purity.
Also, an exciton diffusion length can be reduced and an exciton binding energy can be increased in a nanocrystal within a size of 900 nm, and thus exciton destruction due to thermal ionization and delocalization of a charge carrier can be prevented and light emission efficiency can be obtained at a high room temperature.
Also, a bandgap energy of the organic-inorganic hybrid perovskite nanocrystal particle is determined by a crystalline structure without depending on the size of the particle.
Also, a two-dimensional (2D) organic-inorganic hybrid perovskite is synthesized as a nanocrystal in comparison to a three-dimensional (3D) organic-inorganic hybrid perovskite, and thus an exciton binding energy can be increased not only to further improve the light emission efficiency but also to increase durability and stability.
Also, an organic-inorganic hybrid perovskite or an inorganic metal halide perovskite nanocrystal is made in a gradient-alloy type, and thus a content of perovskite present in large quantities outside the nanocrystal and a content of perovskite present in large quantities inside the nanocrystal can be gradually changed. Such gradual change in the content inside the nanocrystal can be used to uniformly adjust a fraction in the nanocrystal, to reduce surface oxidation, and to improve exciton confinement in the perovskite existing in large quantities inside the nanocrystal, and thus light emission efficiency can be improved and durability and stability can also be increased.
Technical effects of the present invention are not limited to the above-described effects and other unmentioned technical effects may be clearly understood by those skilled in the art from the following descriptions.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
While the present invention can be modified in various ways and take on various alternative forms, specific embodiments thereof are shown in the drawings and described in detail below as examples. However, there is no intent to limit the invention to the particular forms disclosed. On the contrary, the present invention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present invention as defined by the appended claims.
It will be understood that when an element such as a layer, an area, or a substrate is referred to as being present “on” another element, it can be directly present on the other element or an intervening element can be present.
Although the terms “first,” “second,” etc. can be used to describe various elements, components, areas, layers, and/or regions, it will be understood that such elements, components, areas, layers, and/or regions are not limited to these terms.
In
Referring to
Also, the inorganic metal halide perovskite nanocrystal is formed to have a structure in which a central metal is in the center thereof, six inorganic halide materials (X) are located on all surfaces of a hexahedron in a FCC structure, and eight alkali metals are located at all vertexes of a hexahedron in a BCC structure. In this case, Pb is illustrated as an example of the central metal.
In this case, all the surfaces of the hexahedron form 90°, and the hexahedron includes a cubic structure in which a horizontal length, a vertical length, and a height are the same, and a tetragonal structure in which a horizontal length and a vertical length are the same and a height is different therefrom.
Therefore, a two-dimensional (2D) structure according to the present invention is a structure of an organic-inorganic hybrid perovskite nanocrystal in which a central metal is in the center thereof, six inorganic halide materials are located on all surfaces of a hexahedron in a FCC structure, and eight organic ammonium are located at all vertexes of a hexahedron in a BCC structure, and is defined as a structure in which a horizontal length and a vertical length are the same and a height is at least 1.5 times longer than the horizontal length and vertical length.
An organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a gradient structure according to one embodiment of the present invention will be described.
Referring to
Also, in this case, the nanocrystal particle may have a spherical, cylindrical, elliptical pillar, or polygonal pillar shape.
Also, a size of the nanocrystal particle may range from 1 nm to 900 nm. Meanwhile, in this case, the size of the nanocrystal particle refers to a size without considering a length of a ligand to be described below, that is, a size of the remaining portion excluding the ligand.
For example, when the nanocrystal particle has a spherical shape, a diameter of the nanocrystal particle may range from 1 nm to 900 nm.
Also, in this case, the organic-inorganic hybrid perovskite may have a structure of ABX3-mX′m, A2BX4-lX′l, or ABX4-kX′k, wherein A may be an organic ammonium material, B may be a metal material, X may be Br, and X′ may be Cl. Also, values of m, l, and k are increased from the center of the nanocrystal structure 140 to the outside.
Therefore, the organic-inorganic hybrid perovskite structure becomes a structure in which an energy bandgap is increased from the center of the nanocrystal structure 140 to the outside.
The A may be (CH3NH3)n, ((CxH2x+1)nNH3)2(CH3NH3)n, (RNH3)2, (CnH2n+1NH3)2, (CF3NH3), (CF3NH3)n, ((CxF2x+1)nNH3)2(CF3NH3)n, ((CxF2x+1)nNH3)2, or (CnF2n+1NH3)2 (here, n and x are integers greater than or equal to 1), and the B may be a bivalent transition metal, a rare-earth metal, an alkaline-earth metal, Pb, Sn, Ge, Ga, In, Al, Sb, Bi, Po, or a combination thereof.
Meanwhile, the values of m, l, and k may be gradually increased from the center of the nanocrystal structure 140 to the outside. Therefore, an energy bandgap may be gradually increased according to such a composition change.
As another example, the values of m, l, and k may be increased stepwise from the center of the nanocrystal structure 140 to the outside. Therefore, an energy bandgap may be increased stepwise according to such a composition change.
Also, the organic-inorganic hybrid perovskite nanocrystal particle light emitting body 100″ may further include a plurality of organic ligands 120 which surround the organic-inorganic hybrid perovskite nanocrystal structure 140. The organic ligands may include an alkyl halide. The alkyl halide may have a structure of alkyl-X. In this case, a halogen element corresponding to X may include Cl, Br, I, or the like. Also, in this case, the alkyl structure may include an acyclic alkyl having a structure of CnH2n+1, a primary alcohol, a secondary alcohol, or a tertiary alcohol having a structure of CnH2n+1OH etc., an alkylamine (e.g., hexadecyl amine and 9-octadecenylamine 1-amino-9-octadecene (C19H37N)) having a structure of alkyl-N, p-substituted aniline, phenyl ammonium, or fluorine ammonium, but the present invention is not limited thereto.
Referring to
A method of producing an organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a gradient structure according to one embodiment of the present invention will be described.
The method of producing the organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a gradient structure according to the embodiment of the present invention will be described in detail with reference to
Referring to
First, an organic-inorganic hybrid perovskite nanocrystal particle having a core-shell structure is prepared (S100).
As a first method, the preparing of the organic-inorganic hybrid perovskite nanocrystal particle having a core-shell structure (S100) may include preparing a first solution in which a first organic-inorganic hybrid perovskite is dissolved in a protic solvent and a second solution in which an alkyl halide surfactant is dissolved in an aprotic solvent, forming a core including a first organic-inorganic hybrid perovskite nanocrystal by mixing the first solution with the second solution, and forming a shell, which includes a second organic-inorganic hybrid perovskite nanocrystal and surrounds the core, by adding a third solution, in which a second organic-inorganic hybrid perovskite having a larger bandgap than that of the first organic-inorganic hybrid perovskite is dissolved, to the second solution.
More specifically, first, the first solution in which the first organic-inorganic hybrid perovskite is dissolved in the protic solvent and the second solution in which the alkyl halide surfactant is dissolved in the aprotic solvent are prepared.
In this case, the protic solvent may include dimethylformamide, gamma butyrolactone N-methylpyrrolidone, or dimethyl sulfoxide, but the present invention is not limited thereto.
In this case, the first organic-inorganic hybrid perovskite has a 2D structure or a three-dimensional (3D) structure.
For example, the organic-inorganic hybrid perovskite having a 3D crystalline structure may have a structure of ABX3. Also, the organic-inorganic hybrid perovskite having a 2D crystalline structure may have a structure of ABX3, A2BX4, or ABX4.
Here, A is an organic ammonium material, B is a metal material, and X is a halogen element.
For example, the A may be (CH3NH3)n, ((CxH2x+1)nNH3)2(CH3NH3)n, (RNH3)2, (CnH2n+1 NH3)2, (CF3NH3), (CF3NH3)n, ((CxF2x+1)nNH3)2(CF3NH3)n, ((CxF2x+1)nNH3)2, or (CnF2n+1NH3)2, the B may be a bivalent transition metal, a rare-earth metal, an alkaline-earth metal, Pb, Sn, Ge, Ga, In, Al, Sb, Bi, Po, or a combination thereof, and the X may be Cl, Br, I, or a combination thereof. In this case, the rare-earth metal may be, for example, Ge, Sn, Pb, Eu, or Yb. Also, the alkaline-earth metal may be, for example, Ca or Sr.
Meanwhile, the perovskite may be prepared by combining AX and BX2 at a certain ratio. That is, the first solution may be formed by dissolving AX and BX2 in the protic solvent at a certain ratio. For example, the first solution in which an organic-inorganic hybrid perovskite having a structure of A2BX3 is dissolved may be prepared by dissolving AX and BX2 in the protic solvent in a ratio of 2:1.
Also, in this case, a material having a 2D crystalline structure rather than a 3D crystalline structure is more preferably used as the organic-inorganic hybrid perovskite.
This is because, in comparison to in a case in which the organic-inorganic hybrid perovskite having a 3D structure is formed as a nanocrystal, in a case in which the organic-inorganic hybrid perovskite having a 2D structure is formed as a nanocrystal, stacked inorganic and organic planes are clearly distinguished from each other and exciton confinement to the inorganic plane due to the organic plane becomes further certain. Therefore, an exciton binding energy may be increased to improve light emission efficiency, durability and stability may be increased, and high color purity may be shown.
Also, in this case, the aprotic solvent may include dichloroethylene, trichlorethylene, chloroform, chlorobenzene, dichlorobenzene, styrene, dimethylformamide, dimethyl sulfoxide, xylene, toluene, cyclohexene, or isopropyl alcohol, but the present invention is not limited thereto.
Also, the alkyl halide surfactant may have a structure of alkyl-X. In this case, a halogen element corresponding to X may include Cl, Br, or I. Also, in this case, the alkyl structure may include an acyclic alkyl having a structure of CnH2n+1, a primary alcohol, a secondary alcohol, or a tertiary alcohol having a structure of CnH2n+1OH, etc., an alkylamine (e.g., hexadecyl amine and 9-octadecenylamine 1-amino-9-octadecene (C19H37N)) having a structure of alkyl-N, p-substituted aniline, phenyl ammonium, or fluorine ammonium, but the present invention is not limited thereto.
Meanwhile, a carboxylic acid (COOH) surfactant may be used in place of the alkyl halide surfactant.
For example, the surfactant may include a carboxylic acid (COOH) such as 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 acid, itaconic acid, maleic acid, r-maleimidobutyric acid, L-malic acid, 4-nitrobenzoic acid, 1-pyrenecarboxylic acid, or oleic acid, but the present invention is not limited thereto.
Then, the first solution is mixed with the second solution to form a core including a first organic-inorganic hybrid perovskite nanocrystal.
The mixing of the first solution with the second solution to form the core preferably includes by dropwise mixing the first solution with the second solution. Also, in this case, the second solution may be stirred. For example, the core including the first organic-inorganic hybrid perovskite nanocrystal may be synthesized by slowly dropwise adding the second solution, in which the organic-inorganic hybrid perovskite (OIP) is dissolved, to the strongly stirring second solution in which the alkyl halide surfactant is dissolved.
In this case, when the first solution is dropped and mixed with the second solution, the organic-inorganic hybrid perovskite is precipitated from the second solution due to a difference in solubility. While a surface of the organic-inorganic hybrid perovskite precipitated from the second solution is stabilized by the alkyl halide surfactant, a well-dispersed organic-inorganic perovskite nanocrystal (OIP-NC) core is generated. Therefore, in this case, the generated organic-inorganic perovskite nanocrystal core is surrounded by a plurality of alkyl halide organic ligands.
Meanwhile, a size of the organic-inorganic hybrid perovskite nanocrystal particle may be controlled by adjusting a length or shape factor of the alkyl halide surfactant. For example, the size of the organic-inorganic perovskite nanocrystal particle may be controlled through shape factor adjustment, that is, a linear, tapered, or inverted triangular surfactant.
Also, the size of the organic-inorganic hybrid perovskite nanocrystal particle generated in this manner may range from 1 nm to 900 nm. When the size of the organic-inorganic hybrid perovskite nanocrystal particle is greater than 900 nm, there may be a fundamental problem in that excitons may not lead to light emission due to thermal ionization and delocalization of a charge carrier in the large nanocrystal, are separated into free charges, and disappear.
Then, a shell, which includes a second organic-inorganic hybrid perovskite nanocrystal and surrounds the core, is formed by adding a third solution, in which a second organic-inorganic hybrid perovskite having a larger bandgap than that of the first organic-inorganic hybrid perovskite is dissolved, to the second solution.
For example, a shell, which includes a second organic-inorganic hybrid perovskite nanocrystal and surrounds the core, may be formed by adding a third solution, in which a second organic-inorganic hybrid perovskite having a larger bandgap than that of the first organic-inorganic hybrid perovskite, to the second solution.
In this case, a material having a larger bandgap than that of the first organic-inorganic hybrid perovskite is preferably selected as the second organic-inorganic hybrid perovskite. The second organic-inorganic hybrid perovskite may have a structure of ABX3, A2BX4, or ABX4. Here, A is an organic ammonium material, B is a metal material, and X is a halogen element.
For example, the A may be (CH3NH3)n, ((CxH2x+1)nNH3)2(CH3NH3)n, (RNH3)2, (CnH2n+1NH3)2, (CF3NH3), (CF3NH3)n, ((CxF2x+1)nNH3)2(CF3NH3)n, ((CxF2x+1)nNH3)2 or (CnF2n+1NH3)2 (here, n and x are integers greater than or equal to 1), the B may be a bivalent transition metal, a rare-earth metal, an alkaline-earth metal, Pb, Sn, Ge, Ga, In, Al, Sb, Bi, Po, or a combination thereof, and the X may be Cl, Br, I, or a combination thereof. In this case, the rare-earth metal may be, for example, Ge, Sn, Pb, Eu, or Yb. Also, the alkaline-earth metal may be, for example, Ca or Sr.
For example, a shell including a second organic-inorganic hybrid perovskite (MAPbCl3) nanocrystal may be formed by slowly dropping a solution of an organic-inorganic hybrid perovskite (MAPbCl3) having a larger bandgap than that of an organic-inorganic hybrid perovskite (MAPbBr3) solution which is generated through the above-described method (an inverse nano-emulsion method) thereinto drop by drop while strongly stirring the MAPbBr3 solution.
Since the core perovskite and the shell perovskite are mixed with each other to form an alloy form or stick to each other, an organic-inorganic hybrid perovskite having a core-shell structure may be synthesized.
Therefore, an organic-inorganic hybrid perovskite nanocrystal having a core-shell structure of MAPbBr3/MAPbCl3 may be formed.
Meanwhile, preferably, the first organic-inorganic hybrid perovskite may have a structure of ABX3, A2BX4, or ABX4 and the second organic-inorganic hybrid perovskite may have a structure of ABX′3, A2BX′4, or ABX′4, wherein A may be an organic ammonium material, B may be a metal material, X may be Br, and X′ may be Cl.
As a second method, the preparing of the organic-inorganic hybrid perovskite nanocrystal particle having a core-shell structure (S100) may include preparing a first solution in which a first organic-inorganic hybrid perovskite is dissolved in a protic solvent and a second solution in which an alkyl halide surfactant is dissolved in an aprotic solvent, forming a core including a first organic-inorganic hybrid perovskite nanocrystal by mixing the first solution with the second solution, and forming a shell, which has a larger bandgap than that of the core and surrounds the core, by adding an organic ammonium halide solution to the second solution and then stirring.
That is, the shell may be formed using the organic ammonium halide solution. That is, a large amount of the organic ammonium halide solution may be added to the second solution and the resulting mixed solution is then stirred to form the shell which has a larger bandgap than that of the core and surrounds the core.
For example, a shell may be formed by adding a MACl solution to the organic-inorganic hybrid perovskite (MAPbBr3) solution which is generated through the above-described method (an inverse nano-emulsion method), strongly stirring the resulting mixed solution, and converting MAPbBr3 on the surface thereof into MAPbBr3-xClx by excess MACl.
Therefore, an organic-inorganic hybrid perovskite nanocrystal having a core-shell structure of MAPbBr3/MAPbBr3-xClx may be formed.
As a third method, the preparing of the organic-inorganic hybrid perovskite nanocrystal particle having a core-shell structure (S100) may include preparing a first solution in which a first organic-inorganic hybrid perovskite is dissolved in a protic solvent and a second solution in which an alkyl halide surfactant is dissolved in an aprotic solvent, forming a core including a first organic-inorganic hybrid perovskite nanocrystal by mixing the first solution with the second solution, thermally decomposing a surface of the core by performing heat treatment on the second solution, and forming a shell, which has a larger bandgap than that of the core and surrounds the core, by adding an organic ammonium halide solution to the heat-treated second solution.
That is, the shell may be formed using a decomposition/alloying method. That is, after the surface of the core is thermally decomposed by performing heat treatment on the second solution, the shell, which has a larger bandgap than that of the core and surrounds the core, may be formed by adding the organic ammonium halide solution to the heat-treated second solution and by synthesizing the surface thereof again.
For example, after the organic-inorganic hybrid perovskite (MAPbBr3) solution which is generated through the above-described method (an inverse nano-emulsion method) is thermally decomposed so that the surface thereof is converted into PbBr2 by performing heat treatment thereon, the shell may be formed by adding an MACl solution to the organic-inorganic hybrid perovskite (MAPbBr3) solution and by synthesizing the surface thereof again so that the surface becomes MAPbBr2Cl.
That is, in this case, MAPbBr3 may be thermally decomposed into MABr and PbBr2 through the thermal decomposition.
Therefore, an organic-inorganic hybrid perovskite nanocrystal having a core-shell structure of MAPbBr3/MAPbBr2Cl may be formed.
Then, the organic-inorganic hybrid perovskite nanocrystal particle having a core-shell structure is formed so as to have a gradient composition through interdiffusion by performing heat treatment thereon (S200).
For example, after the organic-inorganic hybrid perovskite having a core-shell structure is made to a solid solution state by performing annealing thereon at high temperature, the organic-inorganic hybrid perovskite having a core-shell structure is formed so as to have a gradient composition through interdiffusion by performing heat treatment thereon.
For example, the heat treatment temperature may range from 100° C. to 150° C. The interdiffusion may be induced by performing annealing thereon at such a heat treatment temperature.
The above-described methods will be described once again with reference to a schematic diagram of
Referring to
Meanwhile, each of cores 110 is surrounded by a plurality of organic ligands 120.
Referring to
Referring to
Referring to
First, a first organic-inorganic hybrid perovskite nanocrystal core is formed (S100′). Since the method of forming the first organic-inorganic hybrid perovskite nanocrystal core is the same as the above-described method of forming the nanocrystal core, detailed description thereof will be omitted.
Then, a second organic-inorganic hybrid perovskite nanocrystal shell which has a gradient composition and surrounds the core is formed (S200′).
A second organic-inorganic hybrid perovskite may have a structure of ABX3-mX′m, A2BX4-lX′l, or ABX4-kX′k, wherein A may be an organic ammonium material, B may be a metal material, X may be Br, and X′ may be Cl.
Therefore, a third solution in which the second organic-inorganic hybrid perovskite is dissolved may be added to a second solution while increasing a value of m, l, or k.
That is, a solution in which a composition of ABX3-mX′m, A2BX4-lX′l, or ABX4-kX′k is controlled may be continuously dropped to form a shell whose composition is continuously changed.
An inorganic metal halide perovskite nanocrystal particle light emitting body having a gradient structure according to the embodiment of the present invention will be described.
The inorganic metal halide perovskite nanocrystal particle light emitting body having a gradient structure includes an inorganic metal halide perovskite nanocrystal structure which is dispersible in an organic solvent, and the nanocrystal structure has a gradient composition in which a composition is changed from the center thereof to the outside.
An inorganic metal halide perovskite may have a structure of ABX3-mX′m, A2BX4-lX′l, or ABX4-kX′k, wherein A is an alkali metal, B is a metal material, X is Br, X′ is Cl, and values of m, l, and k are increased from the center of the nanocrystal structure to the outside.
Also, the A may be Na, K, Rb, Cs, or Fr, and the B may be a bivalent transition metal, a rare-earth metal, an alkaline-earth metal, Pb, Sn, Ge, Ga, In, Al, Sb, Bi, Po, or a combination thereof.
Also, the values of m, l, and k are gradually increased from the center of the nanocrystal structure to the outside.
Also, the values of m, l, and k are increased stepwise from the center of the nanocrystal structure to the outside.
Also, the inorganic metal halide perovskite nanocrystal particle light emitting body having a gradient structure may further include a plurality of organic ligands which surround the perovskite nanocrystal structure.
The inorganic metal halide perovskite nanocrystal particle is the same as the inorganic-inorganic hybrid perovskite nanocrystal particle except that a material of an A site is an alkali metal in the former and an organic ammonium material in the latter. Therefore, since the inorganic metal halide perovskite nanocrystal particle having a gradient structure and a method of producing the same are the same as the organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a gradient structure and the method of producing the same, detailed description thereof will be omitted.
A light emitting element according to one embodiment of the present invention will be described.
The light emitting element according to the embodiment of the present invention may be an element using a light emitting layer including the above-described organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a gradient structure or inorganic metal halide perovskite nanocrystal particle light emitting body having a gradient structure. In this case, the organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a gradient structure or the inorganic metal halide perovskite nanocrystal particle light emitting body having a gradient structure may be produced by the above-described production methods.
For example, the light emitting element according to the present invention may include a first electrode, a second electrode, and a light emitting layer, which is located between the first electrode and the second electrode and includes the above-described organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a gradient structure or inorganic metal halide perovskite nanocrystal particle light emitting body having a gradient structure.
As another example, the light emitting element according to the present invention may be applied to a solar cell by using a photoactive layer including the above-described organic-inorganic hybrid perovskite nanocrystal particle having a gradient structure or inorganic metal halide perovskite nanocrystal particle having a gradient structure. The solar cell may include a first electrode, a second electrode, and a photoactive layer, which is located between the first electrode and the second electrode and includes the above-described perovskite nanocrystal particle.
An organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a 3D structure according to one embodiment of the present invention was formed. The organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a 3D structure was formed through an inverse nano-emulsion method.
Specifically, a first solution was prepared by dissolving an organic-inorganic hybrid perovskite in a protic solvent. In this case, dimethylformamide was used as the protic solvent, and CH3NH3PbBr3 was used as the organic-inorganic hybrid perovskite. The CH3NH3PbBr3 used herein was a mixture of CH3NH3Br and PbBr2 in a ratio of 1:1.
A second solution was prepared by dissolving an alkyl halide surfactant in an aprotic solvent. In this case, toluene was used as the aprotic solvent, and octadecylammonium bromide (CH3(CH2)17NH3Br) was used as the alkyl halide surfactant.
Then, the organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a 3D structure was formed by slowly dropwise adding the first solution to the strongly stirring second solution.
Then, an organic-inorganic hybrid perovskite nanocrystal particle (OIP-NP) thin film was formed by spin-coating a glass substrate with the organic-inorganic hybrid perovskite nanocrystal particle in a solution state.
In this case, a size of the formed organic-inorganic hybrid perovskite nanocrystal particle is about 20 nm.
Production Example 2 was performed in the same manner as Production Example 1 except that an organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a 3D structure according to one embodiment of the present invention was formed by using CH3(CH2)13NH3Br as an alkyl halide surfactant.
In this case, a size of the formed organic-inorganic hybrid perovskite nanocrystal particle is about 100 nm.
Production Example 3 was performed in the same manner as Production Example 1 except that an organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a 3D structure according to one embodiment of the present invention was formed by using CH3(CH2)10NH3Br as an alkyl halide surfactant.
In this case, a size of the formed organic-inorganic hybrid perovskite nanocrystal particle is about 300 nm.
Production Example 4 was performed in the same manner as Production Example 1 except that an organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a 3D structure according to one embodiment of the present invention was formed by using CH3(CH2)7NH3Br as an alkyl halide surfactant.
In this case, a size of the formed organic-inorganic hybrid perovskite nanocrystal particle is about 500 nm.
Production Example 5 was performed in the same manner as Production Example 1 except that an organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a 3D structure according to one embodiment of the present invention was formed by using CH3(CH2)4NH3Br as an alkyl halide surfactant.
In this case, a size of the formed organic-inorganic hybrid perovskite nanocrystal particle is about 700 nm.
Production Example 6 was performed in the same manner as Production Example 1 except that an organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a 3D structure according to one embodiment of the present invention was formed by using CH3CH2NH3Br as an alkyl halide surfactant.
In this case, a size of the formed organic-inorganic hybrid perovskite nanocrystal particle is about 800 nm.
Production Example 7 was performed in the same manner as Production Example 1 except that an organic-inorganic hybrid perovskite nanocrystal particle light emitting body having a 3D structure according to one embodiment of the present invention was formed by using CH3NH3Br as an alkyl halide surfactant.
In this case, a size of the formed organic-inorganic hybrid perovskite nanocrystal particle is about 900 nm.
The organic-inorganic hybrid perovskite nanocrystal according to Production Example 1 was used as a core. Also, a shell including a second organic-inorganic hybrid perovskite nanocrystal (MAPbCl3) was formed by slowly dropwise adding a second organic-inorganic hybrid perovskite (MAPbCl3) solution having a large bandgap to a solution containing the organic-inorganic hybrid perovskite nanocrystal core.
Then, an organic-inorganic hybrid perovskite nanocrystal particle light emitting body, whose content is changed, according to one embodiment of the present invention was formed by annealing at a temperature of 150° C.
The organic-inorganic hybrid perovskite nanocrystal according to Production Example 2 was used as a core. Also, a shell including a second organic-inorganic hybrid perovskite nanocrystal (MAPbCl3) was formed by slowly dropwise adding a second organic-inorganic hybrid perovskite (MAPbCl3) solution having a large bandgap to a solution containing the organic-inorganic hybrid perovskite nanocrystal core.
Then, an organic-inorganic hybrid perovskite nanocrystal particle light emitting body, whose content is changed, according to one embodiment of the present invention was formed by annealing at a temperature of 150° C.
The organic-inorganic hybrid perovskite nanocrystal according to Production Example 3 was used as a core. Also, a shell including a second organic-inorganic hybrid perovskite nanocrystal (MAPbCl3) was formed by slowly dropwise adding a second organic-inorganic hybrid perovskite (MAPbCl3) solution having a large bandgap to a solution containing the organic-inorganic hybrid perovskite nanocrystal core.
Then, an organic-inorganic hybrid perovskite nanocrystal particle light emitting body, whose content is changed, according to one embodiment of the present invention was formed by annealing at a temperature of 150° C.
The organic-inorganic hybrid perovskite nanocrystal according to Production Example 4 was used as a core. Also, a shell including a second organic-inorganic hybrid perovskite nanocrystal (MAPbCl3) was formed by slowly dropwise adding a second organic-inorganic hybrid perovskite (MAPbCl3) solution having a large bandgap to a solution containing the organic-inorganic hybrid perovskite nanocrystal core.
Then, an organic-inorganic hybrid perovskite nanocrystal particle light emitting body, whose content is changed, according to one embodiment of the present invention was formed by annealing at a temperature of 150° C.
The organic-inorganic hybrid perovskite nanocrystal according to Production Example 5 was used as a core. Also, a shell including a second organic-inorganic hybrid perovskite nanocrystal (MAPbCl3) was formed by slowly dropwise adding a second organic-inorganic hybrid perovskite (MAPbCl3) solution having a large bandgap to a solution containing the organic-inorganic hybrid perovskite nanocrystal core.
Then, an organic-inorganic hybrid perovskite nanocrystal particle light emitting body, whose content is changed, according to one embodiment of the present invention was formed by annealing at a temperature of 150° C.
The organic-inorganic hybrid perovskite nanocrystal according to Production Example 6 was used as a core. Also, a shell including a second organic-inorganic hybrid perovskite nanocrystal (MAPbCl3) was formed by slowly dropwise adding a second organic-inorganic hybrid perovskite (MAPbCl3) solution having a large bandgap to a solution containing the organic-inorganic hybrid perovskite nanocrystal core.
Then, an organic-inorganic hybrid perovskite nanocrystal particle light emitting body, whose content is changed, according to one embodiment of the present invention was formed by annealing at a temperature of 150° C.
The organic-inorganic hybrid perovskite nanocrystal according to Production Example 7 was used as a core. Also, a shell including a second organic-inorganic hybrid perovskite nanocrystal (MAPbCl3) was formed by slowly dropwise adding a second organic-inorganic hybrid perovskite (MAPbCl3) solution having a large bandgap to a solution containing the organic-inorganic hybrid perovskite nanocrystal core.
Then, an organic-inorganic hybrid perovskite nanocrystal particle light emitting body, whose content is changed, according to one embodiment of the present invention was formed by annealing at a temperature of 150° C.
Production Example 15 was performed in the same manner as Production Example 8 except that (CH3NH3)2PbBr4 was used as an organic-inorganic hybrid perovskite core. The (CH3NH3)2PbBr4 used herein was a mixture of CH3NH3Br and PbBr2 in a ratio of 2:1.
In this case, the formed organic-inorganic hybrid perovskite nanocrystal particle light emitting body whose content is changed emits light near ultraviolet or blue. An emission spectrum of the light is located at about 520 nm.
Production Example 16 was performed in the same manner as Production Example 8 except that (CH3NH3)2PbI4 was used as an organic-inorganic hybrid perovskite core. The (CH3NH3)2PbI4 used herein was a mixture of CH3NH3I and PbI2 in a ratio of 2:1.
In this case, the formed organic-inorganic hybrid perovskite nanocrystal particle whose content is changed emits light near ultraviolet or red. An emission spectrum of the light is located at about 780 nm.
Production Example 17 was performed in the same manner as Production Example 8 except that (CH3NH3)2PbClxBr4-x was used as an organic-inorganic hybrid perovskite core. The (CH3NH3)2PbClxBr4-x used herein was a mixture of CH3NH3Cl and PbBr2 in a predetermined ratio.
In this case, an emission spectrum of light emitted from the formed organic-inorganic hybrid perovskite nanocrystal particle whose content is changed is located between 380 nm and 520 nm.
Production Example 18 was performed in the same manner as Production Example 8 except that (CH3NH3)2PbIxBr4-x was used as an organic-inorganic hybrid perovskite core. The (CH3NH3)2PbIxBr4-x used herein was a mixture of CH3NH3I and PbBr2 in a predetermined ratio.
In this case, an emission spectrum of light emitted from the formed organic-inorganic hybrid perovskite nanocrystal particle whose content is changed is located between 520 nm and 780 nm.
Production Example 19 was performed in the same manner as Production Example 8 except that (CH(NH2)2)2PbI4 was used as an organic-inorganic hybrid perovskite core. The (CH(NH2)2)2PbI4 used herein was a mixture of CH(NH2)2I and PbI2 in a ratio of 2:1.
In this case, an emission spectrum of light emitted from the formed organic-inorganic hybrid perovskite nanocrystal particle whose content is changed is located at about 800 nm.
Production Example 20 was performed in the same manner as Production Example 8 except that (CH3NH3)2PbxSn1-xI4 was used as an organic-inorganic hybrid perovskite core. The (CH3NH3)2PbxSn1-xI4 used herein was a mixture of CH3NH3I and PbxSn1-xI2 in a ratio of 2:1.
In this case, an emission spectrum of light emitted from the formed organic-inorganic hybrid perovskite nanocrystal particle whose content is changed is located between 820 nm and 1120 nm.
Production Example 21 was performed in the same manner as Production Example 8 except that (CH3NH3)2PbxSn1-xBr4 was used as an organic-inorganic hybrid perovskite core. The (CH3NH3)2PbxSn1-xBr4 used herein was a mixture of CH3NH3Br and PbxSn1-xBr2 in a ratio of 2:1.
In this case, an emission spectrum of light emitted from the formed organic-inorganic hybrid perovskite nanocrystal particle whose content is changed is located between 540 nm and 650 nm.
Production Example 22 was performed in the same manner as Production Example 8 except that (CH3NH3)2PbxSn1-xCl4 was used as an organic-inorganic hybrid perovskite core. The (CH3NH3)2PbxSn1-xCl4 used herein was a mixture of CH3NH3Cl and PbxSn1-xCl2 in a ratio of 2:1.
In this case, an emission spectrum of light emitted from the formed organic-inorganic hybrid perovskite nanocrystal particle whose content is changed is located between 400 nm and 460 nm.
Production Example 23 was performed in the same manner as Production Example 8 except that (C4H9NH3)PbBr4 was used as an organic-inorganic hybrid perovskite core. The (C4H9NH3)PbBr4 used herein was a mixture of (C4H9NH3)Br and PbBr2 in a ratio of 2:1.
In this case, an emission spectrum of light emitted from the formed organic-inorganic hybrid perovskite nanocrystal particle whose content is changed is located at about 411 nm.
Production Example 24 was performed in the same manner as Production Example 8 except that (C5H11NH3)PbBr4 was used as an organic-inorganic hybrid perovskite core. The (C5H11NH3)PbBr4 used herein was a mixture of (C5H11NH3)Br and PbBr2 in a ratio of 2:1.
In this case, an emission spectrum of light emitted from the formed organic-inorganic hybrid perovskite nanocrystal particle whose content is changed is located at about 405 nm.
Production Example 25 was performed in the same manner as Production Example 8 except that (C7H15NH3)PbBr4 was used as an organic-inorganic hybrid perovskite core. The (C7H15NH3)PbBr4 used herein was a mixture of (C7H15NH3)Br and PbBr2 in a ratio of 2:1.
In this case, an emission spectrum of light emitted from the formed organic-inorganic hybrid perovskite nanocrystal particle whose content is changed is located at about 401 nm.
Production Example 26 was performed in the same manner as Production Example 8 except that (C12H25NH3)PbBr4 was used as an organic-inorganic hybrid perovskite core. The (C12H25NH3)PbBr4 used herein was a mixture of (C12H25NH3)Br and PbBr2 in a ratio of 2:1.
In this case, an emission spectrum of light emitted from the formed organic-inorganic hybrid perovskite nanocrystal particle whose content is changed is located at about 388 nm.
An inorganic metal halide perovskite nanocrystal particle light emitting body according to one embodiment of the present invention was formed. The inorganic metal halide perovskite nanocrystal particle light emitting body was formed through an inverse nano-emulsion method.
Specifically, a third solution was prepared by adding cesium carbonate (Cs2CO3) and oleic acid to octadecene (ODE) which is an aprotic solvent and reacting them at high temperature. A fourth solution was prepared by adding PbBr2, oleic acid, and oleylamine to an aprotic solvent and reacting them at high temperature (120° C.) for an hour.
Then, an inorganic halide perovskite (CsPbBr3) nanocrystal particle light emitting body having a 3D structure was formed by slowly dropwise adding the third solution to the strongly stirring fourth solution.
Then, an inorganic halide perovskite nanocrystal particle thin film was formed by spin-coating a glass substrate with the inorganic metal halide perovskite nanocrystal particle in a state of being dispersed in such a solution.
In this case, a size of the formed inorganic metal halide perovskite nanocrystal particle is about 20 nm.
The inorganic metal halide perovskite nanocrystal according to Production Example 27 was used as a core. Also, a shell including a second inorganic metal halide perovskite nanocrystal (CsPbCl3) was formed by slowly dropwise adding a second inorganic metal halide perovskite (CsPbCl3) solution having a large bandgap to a solution containing the inorganic metal halide perovskite nanocrystal core.
Then, an inorganic metal halide perovskite nanocrystal particle light emitting body, whose content is changed, according to one embodiment of the present invention was formed by annealing at a temperature of 150° C.
A light emitting element according to one embodiment of the present invention was prepared.
First, an indium tin oxide (ITO) substrate (a glass substrate in which an ITO positive electrode is coated) was prepared, the ITO positive electrode was then spin-coated with PEDOT:PSS (AI4083 produced by Heraeus) which is a conductive material, and a hole injection layer having a thickness of 40 nm was formed by performing heat treatment thereon at a temperature of 150° C. for 30 minutes.
The hole injection layer was then spin-coated with a solution in which the organic-inorganic hybrid perovskite nanocrystal particle whose content is changed according to Production Example 8 was dissolved, and an organic-inorganic hybrid perovskite nanocrystal particle light emitting layer was formed by performing heat treatment thereon at a temperature of 80° C. for 20 minutes.
Then, an electron transport layer was formed by depositing 1,3,5-Tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBI) having a thickness of 50 nm on the organic-inorganic hybrid perovskite nanocrystal particle light emitting layer in a high vacuum of 1×10−7 Torr or less, an electron injection layer was formed by depositing LiF having a thickness of 1 nm thereon, a negative electrode was formed by depositing aluminum having a thickness of 100 nm thereon, and an organic-inorganic hybrid perovskite nanocrystal particle light emitting element was prepared.
A solar cell according to one embodiment of the present invention was prepared.
First, an ITO substrate (a glass substrate in which an ITO positive electrode is coated) was prepared, the ITO positive electrode was then spin-coated with PEDOT:PSS (CLEVIOS PH produced by Heraeus) which is a conductive material, and a hole extraction layer having a thickness of 40 nm was formed by performing heat treatment thereon at a temperature of 150° C. for 30 minutes.
A photoactive layer was formed by mixing the organic-inorganic hybrid perovskite nanocrystal particle having a gradient structure according to Production Example 1 with phenyl-C61-butyric acid methyl ester (PCBM) and by coating the hole extraction layer with the resulting mixture, and a perovskite nanocrystal particle solar cell was formed by depositing Al having a thickness of 100 nm directly on the photoactive layer.
A first solution was prepared by dissolving CH3NH3PbBr3 in dimethylformamide which is a protic solvent.
Then, a CH3NH3PbBr3 thin film (an OIP film) was prepared by spin-coating a glass substrate with the first solution.
A first solution was prepared by dissolving CH3NH3PbCl3 in dimethylformamide which is a protic solvent.
Then, a CH3NH3PbCl3 thin film (an OIP film) was prepared by spin-coating a glass substrate with the first solution.
Referring to
Also, as a result of measuring a photoluminescence quantum yield (PLQY), it was confirmed that the organic-inorganic hybrid perovskite nanocrystal particle light emitting bodies according to Production Example 1 had a very high PLQY value of 52%.
On the other hand, in Comparative Example 1 and Comparative Example 2, the organic-inorganic hybrid perovskites in the form of a thin film which were produced by spin-coating a glass substrate had a low PLQY value of about 1%.
Referring to
Referring to
In the nanocrystal particle light emitting body including the organic-inorganic hybrid perovskite nanocrystal according to the present invention, an organic-inorganic hybrid perovskite having a crystalline structure in which a FCC structure and a BCC structure are combined may be formed in a nanocrystal particle light emitting body, a lamellar structure in which an organic plane and an inorganic plane are alternately stacked may be formed, and excitons may be confined to the inorganic plane to show high color purity.
Also, an exciton diffusion length may be reduced and an exciton binding energy may be increased in a nanocrystal within a size of 300 nm, and thus exciton destruction due to thermal ionization and delocalization of a charge carrier may be prevented and light emission efficiency may be obtained at a high room temperature.
Also, a 2D organic-inorganic hybrid perovskite is synthesized as a nanocrystal in comparison to a 3D organic-inorganic hybrid perovskite, and thus an exciton binding energy may be increased not only to further improve the light emission efficiency but also to increase durability and stability.
Also, a nanocrystal is made in a gradient-alloy type, and thus a content of the perovskite present in large quantities outside the nanocrystal and a content of the perovskite present in large quantities inside the nanocrystal may be gradually changed. Such a gradual change in the content inside the nanocrystal may be used to uniformly adjust a fraction in the nanocrystal, to reduce surface oxidation, and to improve exciton confinement in the perovskite present in large quantities inside the nanocrystal, and thus light emission efficiency may be improved and durability and stability may be increased.
Meanwhile, the embodiments disclosed in this specification and drawings are only examples for the sake of understanding and the invention is not limited thereto. It is clear to those skilled in the art that various modifications based on the technological scope of the invention in addition to the embodiments disclosed herein can be made.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2014-0153973 | Nov 2014 | KR | national |
| 10-2015-0156170 | Nov 2015 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2015/011962 | 11/6/2015 | WO | 00 |
