Organic-inorganic hybrid metal halide optical product and manufacturing method therefor

Abstract

A method for manufacturing an organic-inorganic hybrid metal halide optical product is provided, the method comprising the steps of: preparing an organic-inorganic hybrid metal halide by pulverizing an organic cation material at position A in the following chemical formula and transition metal halides at positions M and X in the following chemical formula; and preparing an organic-inorganic hybrid metal halide optical product by adding a liquid additive to the organic-inorganic hybrid metal halide and imparting viscosity to the organic-inorganic hybrid metal halide. <Chemical formula> AmMnXm+2n (wherein A is at least one selected from an organic material group comprising C, H, O, P, and N, M is at least one selected from a transition metal group comprising Cu, Zn, Cd, Sb, Sn, Fe, and Mn, X is at least one selected from a halogen group comprising F, Cl, Br, and I, and m=n, m=2n, or m=4n)

Description

Organic-inorganic hybrid metal halide optical product and method of manufacturing the same

[0001] The present application relates to an organic-inorganic hybrid metal halide optical product and a method for manufacturing the same, and more specifically, to an organic-inorganic hybrid metal halide optical product and a method for manufacturing the same, which is applied to various optical products by imparting viscosity to the organic-inorganic hybrid metal halide.

[0002]

[0003] Previously, high-efficiency light emitters have been developed to improve the performance of color-conversion layers (CCLs). For example, Korean Patent Publication No. 10-2023-0005998 discloses a method for preparing an oxygen-doped or fluorine-doped perovskite having the chemical formula CsAX3, wherein A represents Pb, or a combination of one or more of Pb and Sn, Si and Ge, and X represents one or more halogen atoms, and the method comprises the chemical formula CsAX3, the chemical formula RbAX3, or the chemical formula Cs 1-x Rb x Pb X3 A method for preparing a lead-based perovskite is disclosed, comprising the step of forming a mixture of a perovskite and a dopant source compound having (wherein 0 < x < 1), wherein A represents Pb, Sn, Si, Ge, or a combination of two or more of these, and X represents one or more halogen atoms, and wherein the dopant source compound comprises PbO, a lead and oxygen-containing compound that decomposes into PbO when heated, PbF2, or a lead and oxygen-containing compound that decomposes into PbF2 when heated; the step of melting the perovskite and the dopant source to form a melt; and the step of crystallizing the oxygen-doped perovskite or the fluorine-doped perovskite from the melt.

[0004] Lead-based perovskites have garnered significant attention as next-generation color conversion materials due to their high photoluminescence quantum yield (PLQY), bandgap tunability, and excellent solution processing characteristics. However, the commercialization of lead-based perovskites has been limited because lead is toxic and has low environmental stability.

[0005] Accordingly, there have been attempts to synthesize non-lead hybrid halides based on copper, tin, bismuth, antimony, and lanthanide elements, in which lead is practically not used.

[0006] However, conventional non-lead hybrid halides have limitations in nanoscale synthesis and patterning, and their application in precision fabrication and high-performance devices may be restricted due to limitations such as reduced crystallinity and increased surface defects. In particular, it may be difficult to achieve light efficiency, structural stability, and heat treatability simultaneously with conventional non-lead hybrid halides. Furthermore, it may be practically difficult to implement uniform color conversion and high-precision patterning on non-planar substrates, such as wearable devices, curved displays, automotive head-up displays (HUDs), and foldable or rollable organic light-emitting diodes (LEDs), with conventional non-lead hybrid halides. Accordingly, a method to overcome these existing limitations is required.

[0007]

[0008] The technical problem that this application aims to solve is to provide an organic-inorganic hybrid metal halide optical product and a method for manufacturing the same, which are applied to various optical products by controlling the viscosity imparted to the organic-inorganic hybrid metal halide.

[0009] The technical problems that this application aims to solve are not limited to those described above.

[0010]

[0011] To solve the above technical problem, the present application provides a method for manufacturing an organic-inorganic hybrid metal halide optical product.

[0012] According to one embodiment, the method for manufacturing an organic-inorganic hybrid metal halide optical product may include the steps of: grinding an organic cation material at the A site in the following chemical formula and a transition metal halide at the M and X sites in the following chemical formula to produce an organic-inorganic hybrid metal halide; and adding a liquid additive to the organic-inorganic hybrid metal halide and imparting viscosity to the organic-inorganic hybrid metal halide to produce an organic-inorganic hybrid metal halide optical product.

[0013] Chemical formula

[0014] A m M n X m+2n

[0015] (wherein A is at least one selected from the group of organic compounds including C, H, O, P, and N, M is at least one selected from the group of transition metals including Cu, Zn, Cd, Sb, Sn, Fe, and Mn, X is at least one selected from the group of halogens including F, Cl, Br, and I, and m=n, m=2n, or m=4n)

[0016] According to one embodiment, the method for manufacturing an organic-inorganic hybrid metal halide optical product may include the step of adding the liquid additive to the organic-inorganic hybrid metal halide and imparting viscosity to the organic-inorganic hybrid metal halide to produce an organic-inorganic hybrid metal halide clay.

[0017] According to one embodiment, the method for manufacturing an organic-inorganic hybrid metal halide optical product may include the step of adding the liquid additive to the organic-inorganic hybrid metal halide and imparting viscosity to the organic-inorganic hybrid metal halide to produce an organic-inorganic hybrid metal halide ink.

[0018] According to one embodiment, the method for manufacturing an organic-inorganic hybrid metal halide optical product may include the steps of: adding the liquid additive to the organic-inorganic hybrid metal halide and imparting viscosity to the organic-inorganic hybrid metal halide to produce a scintillator source; and coating the scintillator source onto a reflector to produce an organic-inorganic hybrid metal halide scintillator.

[0019] According to one embodiment, the method for manufacturing an organic-inorganic hybrid metal halide optical product may include the steps of: adding the liquid additive to the organic-inorganic hybrid metal halide and imparting viscosity to the organic-inorganic hybrid metal halide to manufacture a diode source; and coating the diode source onto a blue LED to manufacture an organic-inorganic hybrid metal halide light-emitting diode.

[0020] According to one embodiment, the liquid additive may be added in the order of the ink, the scintillator, the clay, and the light-emitting diode.

[0021] According to one embodiment, the liquid additive may be added in an amount of 0.3 mL or more to 3 mL or less.

[0022] According to one embodiment, the liquid additive is added so that the organic-inorganic hybrid metal halide can be melted and recrystallized and have cohesive force.

[0023] According to one embodiment, the chemical formula comprises A2MnBr4, and the organic cation at the A site is a cyclohexyltriphenylphosphonium cation (CHTP). + , C 24 C 26 P + ) and 4-methylbenzyltriphenylphosphonium cation (4-MBz + , C 26 C 24 P + It comprises any one selected from the group of organic cations including ), and the organic cation at site A is a manganese bromide anion (MnBr4 2- It is located between the tetrahedrons and can isolate the Mn center.

[0024] According to one embodiment, the organic cation at the A site controls the distance between adjacent Mn and Mn according to size and stereovolume, and depending on the distance between Mn and Mn, the photoluminescence spectrum, full width at half maximum, and photoluminescence quantum yield can be controlled.

[0025] According to one embodiment, the organic cation at the A site controls the distance between adjacent Mn and Mn to a range greater than 9.582 Å and less than 10.447 Å, and within the range, the photoluminescence spectrum and photoluminescence quantum yield may have a maximum value, and the full width at half maximum may have a minimum value.

[0026] According to one embodiment, the cyclohexyltriphenylphosphonium cation (CHTP) at the A site + ) is a tetraphenylphosphonium cation (PPh4 + It includes one phenyl group of which is substituted with cyclohexyl, and the 4-methylbenzyltriphenylphosphonium cation (4-MBz) at the A site. + ) is a benzyltriphenylphosphonium cation (BzTP +It may include a para-methyl group added to the benzyl group of ).

[0027]

[0028] To solve the above technical problem, the present application provides an organic-inorganic hybrid metal halide optical product.

[0029] According to one embodiment, the organic-inorganic hybrid metal halide optical product may include an organic-inorganic hybrid metal halide optical viscous agent represented by the following chemical formula.

[0030] Chemical formula

[0031] A m M n X m+2n

[0032] (wherein A is at least one selected from the group of organic compounds including C, H, O, P, and N, M is at least one selected from the group of transition metals including Cu, Zn, Cd, Sb, Sn, Fe, and Mn, X is at least one selected from the group of halogens including F, Cl, Br, and I, and m=n, m=2n, or m=4n)

[0033] According to one embodiment, the optical product may include ink, a scintillator, clay, and a light-emitting diode.

[0034]

[0035] According to an embodiment of the present application, a method for manufacturing an organic-inorganic hybrid metal halide optical product may be provided, comprising the steps of: grinding an organic cationic substance at the A site in the following chemical formula and a transition metal halide at the M and X sites in the following chemical formula to produce an organic-inorganic hybrid metal halide; and adding a liquid additive to the organic-inorganic hybrid metal halide and imparting viscosity to the organic-inorganic hybrid metal halide to produce an organic-inorganic hybrid metal halide optical product.

[0036] Chemical formula

[0037] A m M n X m+2n

[0038] (wherein A is at least one selected from the group of organic compounds including C, H, O, P, and N, M is at least one selected from the group of transition metals including Cu, Zn, Cd, Sb, Sn, Fe, and Mn, X is at least one selected from the group of halogens including F, Cl, Br, and I, and m=n, m=2n, or m=4n)

[0039] According to the method for manufacturing an organic-inorganic hybrid metal halide optical product according to an embodiment of the present application, the liquid additive is added so that the organic-inorganic hybrid metal halide can be melted and recrystallized and have cohesive force.

[0040] Accordingly, by providing the liquid additive and then evaporating the liquid additive to recrystallize the molten organic-inorganic hybrid metal halide through a simple process, the processability of the organic-inorganic hybrid metal halide is maximized without substantially any additional processes, and it can be applied to various optical products.

[0041]

[0042] FIG. 1 is a drawing illustrating a method for manufacturing organic-inorganic hybrid metal halide clay according to an embodiment of the present application.

[0043] FIG. 2 is a drawing for explaining a method for manufacturing an organic-inorganic hybrid metal halide ink according to an embodiment of the present application.

[0044] FIG. 3 is a drawing illustrating a method for manufacturing an organic-inorganic hybrid metal halide scintillator according to an embodiment of the present application.

[0045] FIG. 4 is a drawing for explaining a method for manufacturing an organic-inorganic hybrid metal halide light-emitting diode according to an embodiment of the present application.

[0046] FIG. 5 is a drawing for explaining an organic-inorganic hybrid metal halide according to an embodiment of the present application.

[0047] FIG. 6 is a diagram illustrating the optimization of the distance between anions by an organic cation derived from an organic-inorganic hybrid metal halide according to an embodiment of the present application.

[0048] FIG. 7 is a diagram illustrating the control of the distance between anions by an organic cation derived according to one embodiment of the present application.

[0049] Figure 8 is a diagram illustrating the distance between anions when the size of the organic cation is small or large according to a comparative example.

[0050] Figure 9 is a photograph of an organic-inorganic hybrid metal halide prepared according to an experimental example of the present application.

[0051] FIG. 10 is a photograph of an organic-inorganic hybrid metal halide clay prepared according to an experimental example of the present application.

[0052] FIG. 11 is a photograph of a drawing made with organic-inorganic hybrid metal halide ink prepared according to the experimental example of the present application.

[0053] FIG. 12 is an image of an organic-inorganic hybrid metal halide scintillator manufactured according to an experimental example of the present application.

[0054] FIG. 13 is an x-ray transmission image taken with an organic-inorganic hybrid metal halide scintillator prepared according to the experimental example of the present application.

[0055] FIGS. 14 and 15 illustrate the process of manufacturing an organic-inorganic hybrid metal halide light-emitting diode according to an experimental example of the present application, for white light emission by 450 nm excitation (C 21 H 20P)2MnBr4 and K2SiF6:Mn 4+ This is a diagram to explain the optimal ratio of.

[0056] FIG. 16 is a diagram showing a blue LED coating in the manufacturing process of an organic-inorganic hybrid metal halide light-emitting diode according to an experimental example of the present application.

[0057] FIG. 17 is a diagram evaluating the optical characteristics of an organic-inorganic hybrid metal halide light-emitting diode manufactured according to an experimental example of the present application.

[0058] FIG. 18 is a diagram illustrating the distance between adjacent Mn and Mn (Mn-Mn), photoluminescence quantum yield (PLQY), photoluminescence spectrum (PL peak), and full width at half maximum (FWHM) of organic-inorganic hybrid metal halide optical products according to Experimental Examples 1-1 to 1-4 of the present application.

[0059] FIG. 19 is a diagram illustrating the distance (Mn-Mn) between adjacent Mn and Mn of an organic-inorganic hybrid metal halide optical product according to Experimental Examples 1-1 to 1-4 of the present application.

[0060] FIG. 20 is a diagram illustrating the photoluminescence quantum yield (PLQY) of organic-inorganic hybrid metal halide optical products according to Experimental Examples 1-3 and 1-4 of the present application.

[0061] FIG. 21 is a drawing for explaining the bandgap of an organic-inorganic hybrid metal halide optical product according to Experimental Examples 2-1 to 2-3 of the present application.

[0062] FIG. 22 is a drawing illustrating the stability over time of organic-inorganic hybrid metal halide optical products according to Experimental Examples 2-1 to 2-3 of the present application.

[0063] FIG. 23 is a drawing for illustrating the symmetry of organic-inorganic hybrid metal halide optical products according to Experimental Example 2-1 and Experimental Example 2-3 of the present application.

[0064] FIG. 24 is a drawing for explaining the degree of disorder of organic-inorganic hybrid metal halide optical products according to Experimental Examples 2-1 to 2-3 of the present application.

[0065]

[0066] Hereinafter, preferred embodiments of the present application will be described in detail with reference to the attached drawings. However, the technical concept of the present application is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed content is thorough and complete and to ensure that the concept of the present application is sufficiently conveyed to those skilled in the art.

[0067] In this specification, when a component is described as being on another component, it means that it may be formed directly on the other component or that a third component may be interposed between them. Additionally, in the drawings, the thicknesses of shapes and regions are exaggerated for the effective description of the technical content.

[0068] Additionally, although terms such as first, second, third, etc., have been used to describe various components in the various embodiments of this specification, these components should not be limited by such terms. These terms are used merely to distinguish one component from another. Accordingly, what is referred to as the first component in one embodiment may be referred to as the second component in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiment. Furthermore, in this specification, "and / or" is used to mean including at least one of the components listed before and after it.

[0069] In the specification, singular expressions include plural expressions unless the context clearly indicates otherwise. Furthermore, terms such as "include" or "have" are intended to specify the existence of the features, numbers, steps, components, or combinations thereof described in the specification, and should not be understood as excluding the existence or addition of one or more other features, numbers, steps, components, or combinations thereof. Additionally, in this specification, "connection" is used to include both indirectly connecting multiple components and directly connecting them.

[0070] Additionally, terms such as “…part,” “…unit,” and “module” described in the specification refer to a unit that processes at least one function or operation, and this may be implemented in hardware, software, or a combination of hardware and software.

[0071] Furthermore, in describing the present application below, if it is determined that a detailed description of related known functions or configurations could unnecessarily obscure the essence of the application, such detailed description will be omitted.

[0072]

[0073] FIG. 1 is a drawing for explaining a method for manufacturing organic-inorganic hybrid metal halide clay according to an embodiment of the present application, FIG. 2 is a drawing for explaining a method for manufacturing organic-inorganic hybrid metal halide ink according to an embodiment of the present application, FIG. 3 is a drawing for explaining a method for manufacturing an organic-inorganic hybrid metal halide scintillator according to an embodiment of the present application, FIG. 4 is a drawing for explaining a method for manufacturing an organic-inorganic hybrid metal halide light-emitting diode according to an embodiment of the present application, FIG. 5 is a drawing for explaining an organic-inorganic hybrid metal halide according to an embodiment of the present application, FIG. 6 is a drawing for explaining the optimization of the distance between anions by an organic cation derived from an organic-inorganic hybrid metal halide according to an embodiment of the present application, FIG. 7 is a drawing for explaining the control of the distance between anions by an organic cation derived according to an embodiment of the present application, and FIG. 8 is a drawing for explaining the distance between anions when the size of the organic cation is small or large according to a comparative example.

[0074] Referring to FIGS. 1 to 5, various organic-inorganic hybrid metal halide optical products can be manufactured by a simple process comprising the steps of: grinding an organic cationic substance (11) at the A position in the following chemical formula and a transition metal halide (12) at the M and X positions in the following chemical formula to produce an organic-inorganic hybrid metal halide (10); adding a liquid additive to the organic-inorganic hybrid metal halide (10) and imparting viscosity to the organic-inorganic hybrid metal halide (10) to produce an organic-inorganic hybrid metal halide optical product.

[0075] Chemical formula

[0076] A m M n X m+2n

[0077] Here, A is at least one selected from the group of organic materials including C, H, O, P, and N, M is at least one selected from the group of transition metals including Cu, Zn, Cd, Sb, Sn, Fe, and Mn, X is at least one selected from the group of halogens including F, Cl, Br, and I, and m=n, m=2n, or m=4n.

[0078] According to one embodiment, the amount of the liquid additive added during the manufacturing process of the organic-inorganic hybrid metal halide optical product can be controlled. For example, the liquid additive may be anhydrous ethanol.

[0079] Accordingly, an optimized formulation is provided for each optical product, which not only improves processability but also maximizes luminescence efficiency. Specifically, for example, if the optical products are clay, ink, scintillator, and light-emitting diode, the liquid additive may be added in the order of the ink, scintillator, clay, and light-emitting diode.

[0080] Accordingly, processability and luminous efficiency can be maximized.

[0081] Specifically, referring to FIG. 1, the organic cation (11) material and the transition metal halide (12) can be crushed to produce the organic-inorganic hybrid metal halide (10) (S111).

[0082] Referring further to FIG. 1, the liquid additive is added to the organic-inorganic hybrid metal halide (10), and viscosity is imparted to the organic-inorganic hybrid metal halide (10) so that an organic-inorganic hybrid metal halide clay can be produced (S112). Specifically, the liquid additive may be added in an amount of 0.3 mL or more and 3 mL or less. More specifically, the liquid additive may be added in an amount of 1 mL.

[0083] Accordingly, the organic-inorganic hybrid metal halide (10) may have a viscosity suitable for manufacturing the organic-inorganic hybrid metal halide clay, and the organic-inorganic hybrid metal halide clay may be easily manufactured.

[0084] Referring to FIG. 2, the organic cationic material (11) and the transition metal halide (12) can be crushed to produce the organic-inorganic hybrid metal halide (10) (S112).

[0085] Referring further to FIG. 2, the liquid additive is added to the organic-inorganic hybrid metal halide (10), and viscosity is imparted to the organic-inorganic hybrid metal halide (10), thereby producing an organic-inorganic hybrid metal halide ink (S122). Specifically, the liquid additive may be added in an amount of 0.3 mL or more and 3 mL or less. More specifically, the liquid additive may be added in an amount of 3 mL.

[0086] Accordingly, the organic-inorganic hybrid metal halide (10) may have a viscosity suitable for the organic-inorganic hybrid metal halide ink, and the organic-inorganic hybrid metal halide ink may be easily manufactured.

[0087] Referring to FIG. 3, the organic cationic material (11) and the transition metal halide (12) can be crushed to produce the organic-inorganic hybrid metal halide (10) (S113).

[0088] Referring further to FIG. 3, the liquid additive is added to the organic-inorganic hybrid metal halide (10), and viscosity is imparted to the organic-inorganic hybrid metal halide (10) so that a scintillator source can be manufactured (S123). Specifically, the liquid additive may be added in an amount of 1 mL or more to 3 mL or less. More specifically, the liquid additive may be added in an amount of 2 mL or less.

[0089] Accordingly, the organic-inorganic hybrid metal halide (10) may have a viscosity suitable for the organic-inorganic hybrid metal halide scintillator, and the organic-inorganic hybrid metal halide scintillator may be easily manufactured.

[0090] Referring further to FIG. 3, the scintillator source is coated onto a reflector, and an organic-inorganic hybrid metal halide scintillator can be manufactured (S133).

[0091] Referring to FIG. 4, the organic cationic material (11) and the transition metal halide (12) can be crushed to produce the organic-inorganic hybrid metal halide (10) (S114).

[0092] Referring further to FIG. 4, the liquid additive is added to the organic-inorganic hybrid metal halide (10), and viscosity is imparted to the organic-inorganic hybrid metal halide (10), so that a diode source can be manufactured (S124). Specifically, the liquid additive can be added in an amount of 0.3 mL or more and 1 mL or less. More specifically, the liquid additive can be added in an amount of 0.3 mL.

[0093] Accordingly, the organic-inorganic hybrid metal halide (10) may have a viscosity suitable for the organic-inorganic hybrid metal halide light-emitting diode, and the organic-inorganic hybrid metal halide light-emitting diode may be easily manufactured.

[0094] Referring further to FIG. 4, the diode source can be coated onto a blue LED to manufacture an organic-inorganic hybrid metal halide light-emitting diode (S134).

[0095] According to an embodiment of the present application, the liquid additive is added so that the organic-inorganic hybrid metal halide (10) can be melted and recrystallized and have cohesive force.

[0096] Accordingly, by providing the liquid additive to melt the organic-inorganic hybrid metal halide (10) and then evaporating the liquid additive to recrystallize the melted organic-inorganic hybrid metal halide (10), the processability of the organic-inorganic hybrid metal halide (10) is maximized without substantially any additional processes, and it can be applied to various optical products.

[0097] In addition, the liquid additive added to the grinding of the organic cationic material (11) and the transition metal halide (12), i.e., the solid-solid mechanochemical reaction, can make the mixing uniform and promote the reaction. Furthermore, the heat generated during the grinding process is absorbed by the liquid additive, so that an excessive rise in the reaction temperature can be minimized.

[0098] Referring to FIGS. 5 and 6, the organic cation (11) at the A site is located between the tetrahedrons of the transition metal halide (12) of the chemical formula and can be isolated between the transition metals in the tetrahedrons of the transition metal halide (12). The organic cation (11) at the A site may have a size and stereovolume that control the distance between adjacent transition metals.

[0099] According to an embodiment of the present application, the size and stereovolume of the organic cation (11) at the A site can be derived such that the organic-inorganic hybrid metal halide (10) represented by the chemical formula has a maximum value for the photoluminescence spectrum and photoluminescence quantum yield, and a minimum value for the full width at half maximum. Specifically, for example, referring to FIG. 7, when the chemical formula is A2MnBr4, the organic cation (11) at the A site can be derived such that it has a size and stereovolume that control the distance between adjacent Mn and Mn to a range greater than 9.582 Å and less than 10.447 Å. More specifically, for example, the organic cation (11) at the A site can be derived such that it has a size and stereovolume that control the distance between adjacent Mn and Mn to a range greater than 9.794 Å and less than 9.922 Å. More preferably, the organic cation (11) at the A site can be derived to have a size and stereovolume that control the distance between adjacent Mn and Mn to a range of 9.794 Å or 9.922 Å.

[0100] Accordingly, the organic-inorganic hybrid metal halide (10) represented by the above chemical formula may have a maximum value for the photoluminescence spectrum and photoluminescence quantum yield, and a minimum value for the full width at half maximum.

[0101] Unlike the embodiment of the present application, as shown in FIG. 8(a), if the size of the organic cation (11) at site A is excessively small, the distance between adjacent transition metals is shortened, and a non-radiative energy transfer path can be activated.

[0102] Accordingly, the luminescence characteristics and luminescence efficiency of organic-inorganic hybrid metal halides may be reduced.

[0103] On the other hand, as shown in FIG. 8(b), if the size of the organic cation (11) at site A is excessively large, the phonon-assisted nonradiative transition may be enhanced due to increased molecular mobility and structural distortion.

[0104] Accordingly, the luminescence characteristics and luminescence efficiency of organic-inorganic hybrid metal halides may be reduced.

[0105] However, according to an embodiment of the present application, the organic cation (11) at the A site can be derived to have a size and stereovolume that control the distance between adjacent transition metals, namely adjacent Mn and Mn, to a range of greater than 9.582 Å and less than 10.447 Å, and as a result, the organic-inorganic hybrid metal halide (10) represented by the chemical formula can have a maximum value for the photoluminescence spectrum and photoluminescence quantum yield, and a minimum value for the full width at half maximum.

[0106] Accordingly, the luminous efficiency of various optical products manufactured from the organic-inorganic hybrid metal halide (10) described above can be maximized.

[0107]

[0108] Specific experimental examples and characteristic evaluation results according to the embodiments of the present application are described below.

[0109]

[0110] Preparation of organic-inorganic hybrid metal halides according to experimental examples

[0111] (C 21 H 20 Prepare the source powder for the preparation of P)2MnBr4, and mix and grind using an agate pestle for 5 minutes while adding 0.5 mL of anhydrous ethanol in a mortar, (C 21 H 20 P)2MnBr4 was prepared.

[0112]

[0113] Preparation of organic-inorganic hybrid metal halide clay according to experimental example

[0114] (C prepared according to the above experimental example 21 H 201 mL of anhydrous ethanol was added per 1 g of 2MnBr and mixed, and then the anhydrous ethanol was evaporated to prepare an organic-inorganic hybrid metal halide clay according to the experimental example.

[0115]

[0116] Preparation of organic-inorganic hybrid metal halide ink according to experimental example

[0117] (C prepared according to the above experimental example 21 H 20 3 mL of anhydrous ethanol was added and mixed per 1 g of 2 MnBr to prepare an organic-inorganic hybrid metal halide ink according to the experimental example.

[0118]

[0119] Preparation of an organic-inorganic hybrid metal halide scintillator according to experimental example

[0120] (C prepared according to the above experimental example 21 H 20 A scintillator source was prepared by adding 2 mL of anhydrous ethanol to 41 g of 2 MnBr and mixing.

[0121] After coating the scintillator source on a TiO2 reflector, the anhydrous ethanol was evaporated to produce an organic-inorganic hybrid metal halide scintillator according to the experimental example.

[0122]

[0123] Fabrication of organic-inorganic hybrid metal halide light-emitting diodes according to experimental examples

[0124] (C prepared according to the above experimental example 21 H 20 P)2MnBr4 and commercial red phosphor K2SiF6:Mn 4+ A diode source was prepared by adding 0.3 mL of anhydrous ethanol per 1 g of material prepared by grinding and mixing at a mass ratio of 9:1 and mixing.

[0125] After coating the above diode source 0.3 g / ml onto a 450 nm blue LED, the above anhydrous ethanol was evaporated to produce an organic-inorganic hybrid metal halide light-emitting diode according to the experimental example.

[0126]

[0127] Figure 9 is a photograph of an organic-inorganic hybrid metal halide prepared according to an experimental example of the present application.

[0128] Referring to Fig. 9, the above organic-inorganic hybrid metal halide, which is a green polycrystalline phosphor, was obtained by evaporating anhydrous ethanol, and green luminescence can be confirmed when irradiated with an ultraviolet wavelength of 365 nm as an excitation source.

[0129]

[0130] FIG. 10 is a photograph of an organic-inorganic hybrid metal halide clay prepared according to an experimental example of the present application.

[0131] Referring to FIG. 10, when anhydrous ethanol is mixed with the organic-inorganic hybrid metal halide, which is a fluorescent material, and as time passes, the organic-inorganic hybrid metal halide partially melts, becomes viscous, and turns into clay.

[0132] The organic-inorganic hybrid metal halide clay prepared according to the experimental example can be plastically deformed and produced into a desired shape, and after producing the desired shape, anhydrous ethanol evaporates over time, and it can be confirmed that the material recrystallizes in the produced product and hardens.

[0133]

[0134] FIG. 11 is a photograph of a drawing made with organic-inorganic hybrid metal halide ink prepared according to the experimental example of the present application.

[0135] Referring to Fig. 11, during the process of mixing anhydrous ethanol with the organic-inorganic hybrid metal halide, most of the organic-inorganic hybrid metal halide dissolves in anhydrous ethanol, and the remaining materials are evenly mixed in the solvent.

[0136] After applying the above organic-inorganic hybrid metal halide ink prepared according to the experimental example to a brush and drawing, anhydrous ethanol evaporated over time, causing recrystallization of the above organic-inorganic hybrid metal halide.

[0137] After all the anhydrous ethanol has evaporated, 365 nm ultraviolet light is irradiated to excite the image, and luminescence can be confirmed in the picture drawn with the organic-inorganic hybrid metal halide ink.

[0138]

[0139] FIG. 12 is an image of an organic-inorganic hybrid metal halide scintillator manufactured according to an experimental example of the present application, and FIG. 13 is an X-ray transmission image taken with an organic-inorganic hybrid metal halide scintillator manufactured according to an experimental example of the present application.

[0140] Referring to FIGS. 12 and 13, it can be confirmed that X-ray transmission is possible using the organic-inorganic hybrid metal halide scintillator according to the experimental example prepared by coating the scintillator source onto a TiO2 reflector and then evaporating the anhydrous ethanol.

[0141]

[0142] FIGS. 14 and 15 illustrate the process of manufacturing an organic-inorganic hybrid metal halide light-emitting diode according to an experimental example of the present application, for white light emission by 450 nm excitation (C 21 H 20 P)2MnBr4 and K2SiF6:Mn 4+Figure 16 is a drawing illustrating the optimal ratio of an organic-inorganic hybrid metal halide light-emitting diode according to an experimental example of the present application, and Figure 17 is a drawing evaluating the optical characteristics of an organic-inorganic hybrid metal halide light-emitting diode manufactured according to an experimental example of the present application.

[0143] Referring to FIGS. 14 to 17, it can be seen that a white light-emitting diode is realized by the conversion of green and red light emitted through the organic-inorganic hybrid metal halide light-emitting diode according to the experimental example, which is prepared by coating the diode source onto a 450 nm blue LED and then evaporating the anhydrous ethanol.

[0144] In particular, referring to FIG. 14, (C 21 H 20 P)2MnBr4 and K2SiF6:Mn 4+ It can be confirmed that the white light emission characteristics are best when the mass ratio is 9:1, and outside the above mass ratio, K2SiF6:Mn 4+ Contrast (C 21 H 20 It can be observed that when the mass ratio of P)2MnBr4 is reduced or increased, the white light emission characteristics actually deteriorate.

[0145] Thus, the above (C 21 H 20 P)2MnBr4 and K2SiF6:Mn 4+ The critical significance of a mass ratio of 9:1 can be proven.

[0146]

[0147] Preparation of an organic-inorganic hybrid metal halide optical product (ex1-1) according to Experimental Example 1-1

[0148] Organic-inorganic hybrid metal halide was prepared by mixing and grinding 1 mmol of (PPh4)Br and 1 mmol of MnBr2, which are organic cation-containing substances, in a mortar with an agate pestle for 5 minutes while adding 0.5 mL of anhydrous ethanol.

[0149] The above organic-inorganic hybrid metal halide was filled into a mold prepared according to the above experimental example, and after heat treatment at 260°C for 1 hour in a quartz furnace under a vacuum and argon atmosphere, air-cooled to produce an organic-inorganic hybrid metal halide optical product (ex1-1) according to experimental example 1-1.

[0150]

[0151] Preparation of an organic-inorganic hybrid metal halide optical product (ex1-2) according to Experimental Example 1-2

[0152] In the above-described Experimental Example 1-1, 1 mmol of (BzTP)Br and 1 mmol of MnBr were mixed as organic cation-containing materials to prepare an organic-inorganic hybrid metal halide optical product (ex1-2) according to Experimental Example 1-2.

[0153]

[0154] Preparation of an organic-inorganic hybrid metal halide optical product (ex1-3) according to Experimental Example 1-3

[0155] In the above-described Experimental Example 1-1, 1 mmol of (CHTP)Br and 1 mmol of MnBr were mixed with the novel organic cation derived therefrom to produce an organic-inorganic hybrid metal halide optical product (ex1-3) according to Experimental Example 1-3.

[0156]

[0157] Preparation of organic-inorganic hybrid metal halide optical product (ex1-4) according to Experimental Example 1-4

[0158] In the above-described Experimental Example 1-1, 1 mmol of (4-MBz)Br and 1 mmol of MnBr were mixed with the novel organic cation derived therefrom to produce an organic-inorganic hybrid metal halide optical product (ex1-4) according to Experimental Example 1-4.

[0159]

[0160] Experimental Examples 1-1 to 1-4 described above can be summarized as shown in Table 1 below.

[0161]

[0162] Classification: Organic Cations

[0163] Experimental Example 1-1 (ex1-1) Tetraphenylphosphonium (PPh4)

[0164] Experimental Example 1-2 (ex1-2) Benzyltriphenylphosphonium (BzTP)

[0165] Experimental Example 1-3 (ex1-3) Cyclohexyltriphenylphosphonium (CHTP)

[0166] Experimental Example 1-4 (ex1-4) 4-methylbenzyltriphenylphosphonium (4-MBz)

[0167]

[0168] FIG. 18 is a diagram illustrating the distance between adjacent Mn and Mn (Mn-Mn), photoluminescence quantum yield (PLQY), photoluminescence spectrum (PL peak), and full width at half maximum (FWHM) of organic-inorganic hybrid metal halide optical products according to Experimental Examples 1-1 to 1-4 of the present application, FIG. 19 is a diagram illustrating the distance between adjacent Mn and Mn (Mn-Mn) of organic-inorganic hybrid metal halide optical products according to Experimental Examples 1-1 to 1-4 of the present application, and FIG. 20 is a diagram illustrating the photoluminescence quantum yield (PLQY) of organic-inorganic hybrid metal halide optical products according to Experimental Examples 1-3 and 1-4 of the present application.

[0169] FIGS. 18 to 20 can be summarized as shown in Table 2 below.

[0170] Table 2

[0171] Classification Experiment Examples 1-1(ex1-1) 1-2(ex1-2) 1-3(ex1-3) 1-4(ex1-4)

[0172] Mn-Mn(Å) 9.528 9.794 9.922 10.447

[0173] PLQY(%) 99.79 99.8 98.2 98.2

[0174] PL peak(λ em ) 511 514 516 515

[0175] FWHM(nm) 41 43 42 45

[0176]

[0177] Referring to FIGS. 18 to 20 and Table 2, it can be seen that the photoluminescence quantum yield (PLQY) increased when the distance between adjacent Mn and Mn (Mn-Mn) was increased from 9.528 Å to 9.794 Å according to Experimental Example 1-2 (ex1-2) and Experimental Example 1-3 (ex1-3). Additionally, it can be seen that the photoluminescence quantum yield (PLQY) was highest when the distance between adjacent Mn and Mn (Mn-Mn) was 9.794 Å according to Experimental Example 1-3 (ex1-3). On the other hand, when the distance between adjacent Mn and Mn (Mn-Mn) exceeds that of Experimental Example 1-3 (ex1-3) and is increased to 9.922 Å according to Experimental Example 1-4 (ex1-4), it can be seen that the photoluminescence quantum yield (PLQY) is actually reduced.

[0178] Thus, the critical significance of the distance (Mn-Mn) of 9.794 Å between adjacent Mn and Mn according to the above experimental example 1-3 (ex1-3) can be proven.

[0179] In addition, referring to FIGS. 18 to 20 and Table 2, it can be seen that when the distance between adjacent Mn and Mn (Mn-Mn) is increased from 9.794 Å to 9.922 Å according to Experimental Example 1-3 (ex1-3) and Experimental Example 1-4 (ex1-4), the photoluminescence spectrum (PL peak) increases and the full width at half maximum (FWHM) decreases. In addition, it can be seen that when the distance between adjacent Mn and Mn (Mn-Mn) is 9.922 Å according to Experimental Example 1-4 (ex1-4), the photoluminescence spectrum (PL peak) is highest and the full width at half maximum (FWHM) is lowest. On the other hand, when the distance between adjacent Mn and Mn (Mn-Mn) exceeds that of Experimental Example 1-4 (ex1-4) and is increased to 10.447 Å according to Experimental Example 1-1 (ex1-1), it can be seen that the photoluminescence spectrum (PL peak) is reduced and the full width at half maximum (FWHM) is increased.

[0180] Thus, the critical significance of the distance (Mn-Mn) of 9.922 Å between adjacent Mn and Mn according to the above experimental example 1-4 (ex1-4) can be proven.

[0181]

[0182] Preparation of an organic-inorganic hybrid metal halide optical product (ex2-1) according to Experimental Example 2-1

[0183] A single-crystal source solution was prepared by dissolving 2 mmol of (CHTP)Br and 1 mmol of MnBr2, which are substances containing the derived novel organic cation, in 1 mL of N,N-dimethylformamide (DMF) using a magnetic stirrer at 300 K for 10 minutes.

[0184] The single crystal source solution was placed in the first vial, the opening of the first vial was sealed with Parafilm, and a hole was made in the sealed area.

[0185] 8 mL of dichloromethane (DCM) was added to a second vial larger than the first vial, and the first vial containing the single crystal source solution was placed inside the second vial.

[0186] The opening of the second vial was sealed, and antisolvent vapor diffusion was performed at room temperature (25 ℃) for 24 hours to produce an organic-inorganic hybrid metal halide.

[0187] The above organic-inorganic hybrid metal halide was filled into a mold prepared according to the above experimental example, and after heat treatment at 260°C for 1 hour in a quartz furnace under a vacuum and argon atmosphere, air-cooled to produce an organic-inorganic hybrid metal halide optical product (ex2-1) according to experimental example 2-1.

[0188]

[0189] Preparation of an organic-inorganic hybrid metal halide optical product (ex2-2) according to Experimental Example 2-2

[0190] In the above-described Experimental Example 2-1, an organic-inorganic hybrid metal halide optical product (ex2-2) according to Experimental Example 2-2 was prepared by melting at 400 K.

[0191]

[0192] Preparation of an organic-inorganic hybrid metal halide optical product (ex2-3) according to Experimental Example 2-3

[0193] In the above-described Experimental Example 2-1, an organic-inorganic hybrid metal halide optical product (ex2-3) according to Experimental Example 2-3 was prepared by melting at 700 K.

[0194]

[0195] Experimental Examples 2-1 to 2-3 described above can be summarized as shown in Table 3 below.

[0196] Table 3

[0197] Differential temperature

[0198] Experimental Example 2-1 (ex2-1) 300 K

[0199] Experimental Example 2-2 (ex2-2) 400 K

[0200] Experimental Example 2-3 (ex2-3) 500 K

[0201]

[0202] FIG. 21 is a diagram illustrating the bandgap of an organic-inorganic hybrid metal halide optical product according to Experimental Examples 2-1 to 2-3 of the present application, FIG. 22 is a diagram illustrating the stability over time of an organic-inorganic hybrid metal halide optical product according to Experimental Examples 2-1 to 2-3 of the present application, FIG. 23 is a diagram illustrating the symmetry of an organic-inorganic hybrid metal halide optical product according to Experimental Examples 2-1 and 2-3 of the present application, and FIG. 24 is a diagram illustrating the disorder of an organic-inorganic hybrid metal halide optical product according to Experimental Examples 2-1 to 2-3 of the present application.

[0203] FIGS. 21 to 24 were derived from the simulation results of the present application.

[0204] Referring to Fig. 21, it can be seen that the band gap is the same at 2.39 eV when the temperature is 300 K to 400 K according to Experimental Example 2-1 (ex2-1) and Experimental Example 2-2 (ex2-2). On the other hand, it can be seen that the band gap is reduced to 2.26 eV when the temperature is increased to 700 K according to Experimental Example 2-3 (ex2-3).

[0205] In addition, referring to Fig. 22, it can be seen that when the temperature is 300 K to 400 K according to Experimental Example 2-1 (ex2-1) and Experimental Example 2-2 (ex2-2), the structure is preserved and equilibrium is reached. On the other hand, when the temperature is increased to 700 K according to Experimental Example 2-3 (ex2-3), it can be seen that disorder is maximized.

[0206] In addition, referring to Fig. 23, it can be seen that the structure is maintained when the temperature is 300 K according to Experimental Example 2-1 (ex2-1). On the other hand, it can be seen that the structure collapses when the temperature is increased to 700 K according to Experimental Example 2-3 (ex2-3).

[0207] Additionally, referring to FIG. 24, it can be seen that the peak increased when the temperature was increased from 300 K to 400 K according to Experimental Example 2-1 (ex2-1) and Experimental Example 2-2 (ex2-2). Furthermore, it can be seen that the peak was highest when the temperature was 400 K according to Experimental Example 2-2 (ex2-2). On the other hand, it can be seen that the peak actually decreased when the temperature was increased to 700 K according to Experimental Example 2-3 (ex2-3), exceeding Experimental Example 2-2 (ex2-2).

[0208] Thus, the critical significance of a temperature of 400 K according to the above experimental example 2-2 (ex2-2) can be proven.

[0209]

[0210] Although the present application has been described in detail using preferred embodiments, the scope of the present application is not limited to specific embodiments and should be interpreted by the appended claims. Furthermore, those skilled in the art will understand that many modifications and variations are possible without departing from the scope of the present application.

Claims

1. A step of preparing an organic-inorganic hybrid metal halide by grinding an organic cation substance at the A site in the following chemical formula and a transition metal halide at the M and X sites in the following chemical formula; and A method for manufacturing an organic-inorganic hybrid metal halide optical product, comprising the step of adding a liquid additive to the organic-inorganic hybrid metal halide and imparting viscosity to the organic-inorganic hybrid metal halide to manufacture an organic-inorganic hybrid metal halide optical product. Chemical formula A m M n X m+2n (wherein A is at least one selected from the group of organic compounds including C, H, O, P, and N, M is at least one selected from the group of transition metals including Cu, Zn, Cd, Sb, Sn, Fe, and Mn, X is at least one selected from the group of halogens including F, Cl, Br, and I, and m=n, m=2n, or m=4n) 2. In Paragraph 1, A method for manufacturing an organic-inorganic hybrid metal halide optical product, comprising the step of adding the liquid additive to the organic-inorganic hybrid metal halide and imparting viscosity to the organic-inorganic hybrid metal halide to produce an organic-inorganic hybrid metal halide clay.

3. In Paragraph 1, A method for manufacturing an organic-inorganic hybrid metal halide optical product, comprising the step of adding the liquid additive to the organic-inorganic hybrid metal halide and imparting viscosity to the organic-inorganic hybrid metal halide to produce an organic-inorganic hybrid metal halide ink.

4. In Paragraph 1, A step of preparing a scintillator source by adding the liquid additive to the organic-inorganic hybrid metal halide and imparting viscosity to the organic-inorganic hybrid metal halide; and A method for manufacturing an organic-inorganic hybrid metal halide optical product, comprising the step of manufacturing an organic-inorganic hybrid metal halide scintillator by coating the scintillator source on a reflector.

5. In Paragraph 1, A step of manufacturing a diode source by adding the liquid additive to the organic-inorganic hybrid metal halide and imparting viscosity to the organic-inorganic hybrid metal halide; and A method for manufacturing an organic-inorganic hybrid metal halide optical product, comprising the step of manufacturing an organic-inorganic hybrid metal halide light-emitting diode by coating the above diode source onto a blue LED.

6. In any one of paragraphs 2 through 5, The above liquid additive is, A method for manufacturing an organic-inorganic hybrid metal halide optical product, comprising the above-mentioned ink, the above-mentioned scintillator, the above-mentioned clay, and the above-mentioned light-emitting diode in increasing amounts in that order.

7. In Paragraph 6, A method for manufacturing an organic-inorganic hybrid metal halide optical product, comprising adding the above liquid additive in an amount of 0.3 mL or more to 3 mL or less.

8. In Paragraph 1, The above liquid additive is added, A method for manufacturing an organic-inorganic hybrid metal halide optical product, comprising melting and recrystallizing the above organic-inorganic hybrid metal halide and having cohesive force.

9. In Paragraph 1, The above chemical formula includes A2MnBr4, and The organic cation at site A above is a cyclohexyltriphenylphosphonium cation (CHTP + ) and 4-methylbenzyltriphenylphosphonium cation (4-MBz + It comprises any one selected from the group of organic cations including ), The organic cation at site A above is a manganese bromide anion (MnBr4 2- A method for manufacturing an organic-inorganic hybrid metal halide optical product, comprising isolating an Mn center located between tetrahedrons.

10. In Paragraph 9, The organic cation at the above A site controls the distance between adjacent Mn and Mn depending on its size and stereovolume, and A method for manufacturing an organic-inorganic hybrid metal halide optical product, comprising controlling the photoluminescence spectrum, full width at half maximum, and photoluminescence quantum yield according to the distance between the above Mn and Mn.

11. In Paragraph 10, The organic cation at the above A site controls the distance between adjacent Mn and Mn to a range greater than 9.582 Å and less than 10.447 Å, and A method for manufacturing an organic-inorganic hybrid metal halide optical product, wherein, within the above range, the photoluminescence spectrum and photoluminescence quantum yield have maximum values ​​and the full width at half maximum has minimum values.

12. In Paragraph 9, The cyclohexyltriphenylphosphonium cation (CHTP) at the above A site + ) is a tetraphenylphosphonium cation (PPh4 + It includes one phenyl group of which is substituted with cyclohexyl, and The 4-methylbenzyltriphenylphosphonium cation (4-MBz) at the above A site + ) is a benzyltriphenylphosphonium cation (BzTP + A method for manufacturing an organic-inorganic hybrid metal halide optical product comprising a para-methyl group added to a benzyl group.

13. An organic-inorganic hybrid metal halide optical product comprising an organic-inorganic hybrid metal halide optical viscosizing agent represented by the following chemical formula. Chemical formula A m M n X m+2n (wherein A is at least one selected from the group of organic compounds including C, H, O, P, and N, M is at least one selected from the group of transition metals including Cu, Zn, Cd, Sb, Sn, Fe, and Mn, X is at least one selected from the group of halogens including F, Cl, Br, and I, and m=n, m=2n, or m=4n) 14. In Paragraph 13, The above optical product is an organic-inorganic hybrid metal halide optical product comprising ink, a scintillator, clay, and a light-emitting diode.

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