Method for designing novel organic-inorganic hybrid metal halide, method for producing designed novel organic-inorganic hybrid metal halide, and method for manufacturing three-dimensional structure of organic-inorganic hybrid metal halide

Abstract

Provided is a method for designing a novel organic-inorganic hybrid metal halide, the method comprising the steps of: obtaining, from a database related to an organic-inorganic hybrid metal halide represented by the chemical formula below, a reference organic cation at site A and candidate molecular structures for candidate organic cations similar to the reference organic cation; expressing the candidate molecular structures as strings by using a chemical language model; converting the strings into vectors by using a vector conversion model trained through the chemical language model; calculating the similarity between the reference organic cation and the candidate organic cations on the basis of the vectors by using a distance matrix for quantifying molecular similarity; and filtering the candidate organic cations to derive a novel organic cation. <Chemical formula 1> AmMnXm+2n (where, A is at least one selected from an organic material group including C, H, O, P, and N; M is at least one selected from a transition metal group including Cu, Zn, Cd, Sb, Sn, Fe, and Mn; X is at least one selected from a halogen group including F, Cl, Br, and I; and m=n, m=2n, or m=4n)

Description

Novel method for designing organic-inorganic hybrid metal halide, method for manufacturing the designed novel organic-inorganic hybrid metal halide, and method for manufacturing a three-dimensional structure of an organic-inorganic hybrid metal halide

[0001] The present application relates to a method for designing a novel organic-inorganic hybrid metal halide and a method for manufacturing the designed novel organic-inorganic hybrid metal halide. More specifically, it relates to a method for designing a novel organic-inorganic hybrid metal halide that has high molecular similarity to an existing organic-inorganic hybrid metal halide containing a reference organic cation and excellent optical characteristics, and a method for manufacturing the designed novel 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 X3A 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 all at once with conventional non-lead hybrid halides. Furthermore, with conventional non-lead hybrid halides, it may be practically difficult to achieve 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).

[0007] Accordingly, a method to overcome existing limitations is required.

[0008]

[0009] The technical problem that the present application aims to solve is to provide a method for designing a novel organic-inorganic hybrid metal halide and a method for manufacturing the designed novel organic-inorganic hybrid metal halide, which derives a novel cation having high molecular similarity to an existing organic-inorganic hybrid metal halide containing a reference organic cation and manufactures a novel organic-inorganic hybrid metal halide containing said novel cation.

[0010] Another technical problem that the present application aims to solve is to provide a method for manufacturing an organic-inorganic hybrid metal halide filament, a method for manufacturing an organic-inorganic hybrid metal halide filament, and an organic-inorganic hybrid metal halide 3D structure that maximizes processability through a conversion from a crystalline state to a glassy state, solves the problem that previously, substantially non-planar structures, i.e., curved surface processing was impossible, and enables melt-based 3D printing.

[0011] Another technical problem that the present application aims to solve is to provide a method for manufacturing an organic-inorganic hybrid metal halide filament, a method for manufacturing an organic-inorganic hybrid metal halide filament, and an organic-inorganic hybrid metal halide 3D structure, in which the optical performance of the 3D printed structure is restored and maximized by converting the 3D printed structure from a glassy state to a crystalline state through a simple post-processing solution process without substantially a heating process.

[0012] Another technical problem that this application aims to solve is to provide a 3D printing device for printing organic-inorganic hybrid metal halide and a method for manufacturing an organic-inorganic hybrid metal halide 3D structure, which maximizes processability through a conversion from a crystalline state to a glassy state using a 3D printing device, solves the problem that it was previously impossible to process a non-planar structure, i.e., a curved surface, and enables melt-based 3D printing.

[0013] The technical problems that this application aims to solve are not limited to those described above.

[0014]

[0015] To solve the above technical problem, the present application provides a novel method for designing organic-inorganic hybrid metal halides.

[0016] According to one embodiment, the novel organic-inorganic hybrid metal halide design method may include the steps of: obtaining candidate molecular structures for a reference organic cation at site A and candidate organic cations similar to the reference organic cation from a database related to an organic-inorganic hybrid metal halide represented by the following chemical formula; expressing the candidate molecular structures as strings using a chemical language model; converting the strings into vectors using a vector transformation model learned through the chemical language model; calculating similarity between the reference organic cation and the candidate organic cations based on the vectors using a distance matrix for quantifying molecular similarity; and filtering the candidate organic cations to derive novel organic cations.

[0017] Chemical formula

[0018] A m M n X m+2n

[0019] (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)

[0020] According to one embodiment, molecular features including the skeletal structure of a molecule, electron density distribution, substituent effects, and steric hindrance can be learned through the chemical language model.

[0021] According to one embodiment, the distance matrix may include cosine distance, Euclidean distance, and Tanimoto distance.

[0022] According to one embodiment, the organic cation at site A is located between the transition metal halide tetrahedra of the above chemical formula and can be isolated between the transition metals in the transition metal halide tetrahedra.

[0023] According to one embodiment, the organic cation at the A site may have a size and stereovolume that control the distance between adjacent transition metals.

[0024] According to one embodiment, the size and stereovolume of the organic cation at site A can be derived such that the photoluminescence spectrum and photoluminescence quantum yield have maximum values ​​and the full width at half maximum has minimum values.

[0025] According to one embodiment, the chemical formula comprises A2MnBr4, and the organic cation 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 greater than 9.582 Å and less than 10.447 Å.

[0026] According to one embodiment, the reference organic cation comprises a tetraphenylphosphonium cation (PPh4+), and the novel organic cation is a cyclohexyltriphenylphosphonium cation (CHTP) in which one phenyl group of the tetraphenylphosphonium cation (PPh4+) is substituted with cyclohexyl. + , C 24 C 26 P + It may include ).

[0027] According to one embodiment, the reference organic cation comprises a benzyltriphenylphosphonium cation (BzTP+), and the novel organic cation is a 4-methylbenzyltriphenylphosphonium cation (4-MBz) in which a para-methyl group is added to the benzyl group of the benzyltriphenylphosphonium cation (BzTP+). + , C 26 C24 P + It may include ).

[0028] According to one embodiment, through the filtering, molecules having PP or P-Se bonds, hydrolysis-vulnerable groups, and excessive stereovolume can be removed depending on synthesizable, stable, and crystallization compatibility.

[0029]

[0030] To solve the above technical problem, the present application provides a novel method for manufacturing organic-inorganic hybrid metal halides.

[0031] According to one embodiment, the method for manufacturing the designed novel organic-inorganic hybrid metal halide comprises the steps of: obtaining candidate molecular structures for a reference organic cation at site A and candidate organic cations similar to the reference organic cation from a database related to the organic-inorganic hybrid metal halide represented by the following chemical formula; expressing the candidate molecular structures as strings using a chemical language model; converting the strings into vectors using a vector transformation model learned through the chemical language model; calculating similarity between the reference organic cation and the candidate organic cations based on the vectors using a distance matrix for quantifying molecular similarity; filtering the candidate organic cations to derive novel organic cations; dissolving a substance containing the novel organic cation and a transition metal halide of the following chemical formula in a solvent to synthesize a single-crystal organic-inorganic hybrid metal halide; grinding the substance containing the novel organic cation and the transition metal halide of the following chemical formula to form a polycrystalline organic-inorganic hybrid metal halide; and synthesizing the single-crystal or polycrystalline organic-inorganic hybrid metal halide above its melting point. It may include a step of cooling after heat treatment to form a glass-state organic-inorganic hybrid metal halide.

[0032] Chemical formula

[0033] A m M n X m+2n

[0034] (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)

[0035] According to one embodiment, the chemical formula comprises A2MnBr4, the reference organic cation comprises a tetraphenylphosphonium cation (PPh4+), and the novel organic cation may comprise a cyclohexyltriphenylphosphonium cation (CHTP+) in which one phenyl group of the tetraphenylphosphonium cation (PPh4+) is substituted with cyclohexyl.

[0036] According to one embodiment, the reference organic cation comprises a benzyltriphenylphosphonium cation (BzTP+), and the novel organic cation may comprise a 4-methylbenzyltriphenylphosphonium cation (4-MBz+) in which a para-methyl group is added to the benzyl group of the benzyltriphenylphosphonium cation (BzTP+).

[0037] According to one embodiment, the novel organic cation may have a size and stereovolume that control the distance between adjacent Mn and Mn to a range of greater than 9.582 Å and less than 10.447 Å.

[0038]

[0039] To solve the above technical problem, the present application provides a method for manufacturing an organic-inorganic hybrid metal halide three-dimensional structure.

[0040] According to one embodiment, the method for manufacturing the organic-inorganic hybrid metal halide three-dimensional structure may include the steps of providing an organic-inorganic hybrid metal halide represented by the following chemical formula to a three-dimensional printing device and printing it into an organic-inorganic hybrid metal halide three-dimensional printed structure, rapidly cooling the printed organic-inorganic hybrid metal halide three-dimensional printed structure, and post-treating the rapidly cooled organic-inorganic hybrid metal halide three-dimensional printed structure with a solvent.

[0041] Chemical formula

[0042] A m M n X m+2n

[0043] (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)

[0044] According to one embodiment, the organic-inorganic hybrid metal halide is injected into the 3D printing device in the form of a filament mixed with a binder, and the rapidly cooled organic-inorganic hybrid metal halide 3D printing structure is immersed in the solvent to dissolve the binder, wherein the organic-inorganic hybrid metal halide injected in the form of a filament is polycrystalline, and the organic-inorganic hybrid metal halide 3D printing structure is rapidly cooled so that the polycrystalline state is converted into a glass state, and the binder is dissolved in the organic-inorganic hybrid metal halide 3D printing structure by being immersed in the solvent, and the glass state can be reversibly converted back into a polycrystalline state.

[0045] According to one embodiment, the binder may have a higher ratio per volume on the inside than on the surface of the organic-inorganic hybrid metal halide 3D printed structure.

[0046] According to one embodiment, the organic-inorganic hybrid metal halide is injected into the 3D printing device in powder form, and the solvent is provided to the rapidly cooled organic-inorganic hybrid metal halide 3D printed structure.

[0047] The organic-inorganic hybrid metal halide injected in the form of powder is polycrystalline, and the organic-inorganic hybrid metal halide 3D printed structure is rapidly cooled so that the polycrystalline state is converted into a glassy state, and the solvent is provided so that the glassy state of the organic-inorganic hybrid metal halide 3D printed structure can be reversibly converted back into a polycrystalline state.

[0048] According to one embodiment, the binder may have extrudability at the melting point of the organic-inorganic hybrid metal halide.

[0049] According to one embodiment, the binder comprises at least one selected from the group of thermoplastic polymers including polylactic acid and polyethylene terephthalate glycol, and the solvent may comprise any one selected from the group of solvents including dichloromethane.

[0050]

[0051] According to an embodiment of the present application, a novel organic-inorganic hybrid metal halide design method may be provided, comprising the steps of: obtaining candidate molecular structures for a reference organic cation at site A and candidate organic cations similar to the reference organic cation from a database related to an organic-inorganic hybrid metal halide represented by the following chemical formula; expressing the candidate molecular structures as strings using a chemical language model; converting the strings into vectors using a vector transformation model learned through the chemical language model; calculating similarity between the reference organic cation and the candidate organic cations based on the vectors using a distance matrix for quantifying molecular similarity; and filtering the candidate organic cations to derive novel organic cations.

[0052] Chemical formula

[0053] A m M n X m+2n

[0054] (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)

[0055] According to the novel organic-inorganic hybrid metal halide design method of the embodiment of the present application, a novel cation having high molecular similarity to an existing organic-inorganic hybrid metal halide containing a reference organic cation can be derived.

[0056] Accordingly, according to an embodiment of the present application, a novel organic-inorganic hybrid metal halide designed from the novel organic cation derived therefrom may have a maximum value for the photoluminescence spectrum and photoluminescence quantum yield, and may have a minimum value for the full width at half maximum.

[0057] Furthermore, according to the embodiments of the present application, high-speed mass screening is possible, allowing for the rapid analysis and selection of a large pool of material candidates. Consequently, the time and cost required for experimental preparation and execution can be significantly reduced compared to traditional methods. This enables research on advanced materials by small research teams rather than large laboratories, thereby increasing the accessibility of research.

[0058] Furthermore, according to the embodiments of the present application, screening of material candidates using databases and advanced analytical techniques enables extensive material exploration that was previously impossible. Accordingly, the potential for previously undiscovered materials is significantly expanded, and optimal materials suitable for specific applications can be derived.

[0059] Furthermore, according to an embodiment of the present application, the number of candidate groups requiring experimental verification can be minimized by going through a process of selecting experimental candidate groups through high-speed mass screening, thereby maximizing research efficiency. In addition, according to an embodiment of the present application, the performance of candidate materials can be predicted before experimental verification, which minimizes unnecessary experiments and saves research resources.

[0060] In addition, the novel organic-inorganic hybrid metal halide design method according to the embodiment of the present application and the novel organic-inorganic hybrid metal halide manufactured through said design possess high efficiency and stability, making them suitable for industrial application; accordingly, the time to commercialize the new technology can be shortened, and competitiveness in related industrial fields can be strengthened.

[0061] In addition, according to the method for manufacturing an organic-inorganic hybrid metal halide filament according to an embodiment of the present application, the organic-inorganic hybrid metal halide filament in which the polycrystalline and glassy states are reversibly converted through the distance between adjacent transition metals can be provided.

[0062] According to the organic-inorganic hybrid metal halide filament of the embodiment of the present application, processability can be maximized through the conversion from a crystalline state to a glassy state, and the problem of being unable to process curved surfaces, i.e., a substantially non-planar structure, can be resolved. Furthermore, the organic-inorganic hybrid metal halide filament can enable melt-based 3D printing.

[0063] In addition, according to the 3D printing device for outputting organic-inorganic hybrid metal halide according to an embodiment of the present application, the injection part can be detachably attached to the 3D printing device as an optimized module depending on the form of the organic-inorganic hybrid metal halide, for example, in the form of a filament or a powder.

[0064] Accordingly, the output section, i.e., the nozzle, of the 3D printing device for outputting organic-inorganic hybrid metal halide can not be substantially clogged, the organic-inorganic hybrid metal halide filament or the organic-inorganic hybrid metal halide powder can be easily output, and failure of the 3D printing device for outputting organic-inorganic hybrid metal halide can be minimized.

[0065] In addition, according to the 3D printing device for organic-inorganic hybrid metal halide output according to the embodiment of the present application, since melt-based 3D printing is possible, processability can be maximized through the conversion from a crystalline state to a glassy state, and the problem that it was previously impossible to process a substantially non-planar structure, i.e., a curved surface, can be resolved.

[0066] In addition, a 3D structure printed by a 3D printing device for organic-inorganic hybrid metal halide output according to an embodiment of the present application can be applied as a color conversion layer of an organic light-emitting diode (LED).

[0067] In addition, a 3D structure printed by a 3D printing device for organic-inorganic hybrid metal halide output according to an embodiment of the present application can be applied as an ornament due to its green light emission characteristics.

[0068]

[0069] FIG. 1 is a drawing for explaining a novel organic-inorganic hybrid metal halide design method according to an embodiment of the present application.

[0070] FIG. 2 is a drawing for explaining in more detail a novel organic-inorganic hybrid metal halide design method according to an embodiment of the present application.

[0071] FIG. 3 is a drawing for explaining a novel organic-inorganic hybrid metal halide according to an embodiment of the present application.

[0072] FIG. 4 is a diagram illustrating the optimization of the distance between anions by an organic cation derived from a novel organic-inorganic hybrid metal halide according to an embodiment of the present application.

[0073] FIG. 5 is a diagram illustrating the control of the distance between anions by an organic cation derived according to one embodiment of the present application.

[0074] Figure 6 is a diagram illustrating the distance between anions when the size of the organic cation is small or large according to a comparative example.

[0075] FIG. 7 is a diagram illustrating a novel organic cation derived from a reference organic cation at site A according to one embodiment of the present application.

[0076] FIG. 8 is a diagram illustrating a novel organic cation derived from a reference organic cation at site A according to another embodiment of the present application.

[0077] FIG. 9 is a drawing for illustrating a novel organic-inorganic hybrid metal halide manufacturing method designed according to an embodiment of the present application.

[0078] FIG. 10 is a drawing for explaining in more detail a novel organic-inorganic hybrid metal halide manufacturing method designed according to an embodiment of the present application.

[0079] FIG. 11 is a drawing for explaining a method for manufacturing a filament source according to an embodiment of the present application.

[0080] FIG. 12 is a drawing illustrating a method of providing the filament source to a mold and drying it according to an embodiment of the present application.

[0081] FIG. 13 is a drawing for explaining a 3D printing device for organic-inorganic hybrid metal halide output according to an embodiment of the present application.

[0082] FIG. 14 is a drawing for explaining a 3D printing device for outputting organic-inorganic hybrid metal halide for filament according to an embodiment of the present application.

[0083] FIG. 15 is a drawing for illustrating a 3D printing device for printing organic-inorganic hybrid metal halide powder according to an embodiment of the present application.

[0084] FIG. 16 is a drawing for explaining an organic-inorganic hybrid metal halide 3D printed structure manufactured from an organic-inorganic hybrid metal halide filament according to an embodiment of the present application.

[0085] FIG. 17 is a drawing for explaining an organic-inorganic hybrid metal halide 3D printed structure made of organic-inorganic hybrid metal halide powder according to an embodiment of the present application.

[0086] FIG. 18 is a drawing for explaining the post-processing of an organic-inorganic hybrid metal halide 3D printed structure manufactured with an organic-inorganic hybrid metal halide filament according to an embodiment of the present application.

[0087] FIG. 19 is a drawing for explaining the post-processing of an organic-inorganic hybrid metal halide 3D printed structure manufactured with organic-inorganic hybrid metal halide powder according to an embodiment of the present application.

[0088] FIG. 20 is a diagram illustrating the calculation of similarity between a reference organic cation and a candidate organic cation according to an experimental example of the present application.

[0089] FIG. 21 shows cyclohexyltriphenylphosphonium (C1), a novel organic cation derived according to the experimental example of the present application. 24 H 26 This is the result of the Tanimoto distance similarity test of P).

[0090] FIG. 22 shows cyclohexyltriphenylphosphonium (C12), a novel organic cation derived according to the experimental example of the present application. 24 H 26 This is the result of the cosine distance similarity test of P).

[0091] FIG. 23 shows cyclohexyltriphenylphosphonium (C12), a novel organic cation derived according to the experimental example of the present application. 24 H 26 This is the result of the Euclidean distance similarity test of P).

[0092] FIG. 24 is a diagram for explaining the comparison between a similarity test according to an experimental example of the present application and a conventional similarity test.

[0093] FIG. 25 is the crystal structure of a novel organic-inorganic hybrid metal halide prepared according to an experimental example of the present application.

[0094] Figure 26 shows the results of X-ray diffraction (XRD) analysis and Rietveld refinement of a novel organic-inorganic hybrid metal halide prepared according to the experimental example of the present application.

[0095] FIG. 27 is a graph of the luminescence characteristics of a novel organic-inorganic hybrid metal halide prepared according to an experimental example of the present application.

[0096] FIG. 28 is a design drawing of a mold according to an experimental example of the present application.

[0097] FIG. 29 is a photograph of a mold produced according to an experimental example of the present application.

[0098] FIG. 30 is an organic-inorganic hybrid metal halide filament manufactured using a mold produced according to an experimental example of the present application.

[0099] FIG. 31 is a photograph of an organic-inorganic hybrid metal halide filament before and after light emission according to an experimental example of the present application.

[0100] FIG. 32 is an organic-inorganic hybrid metal halide (C4H) prepared according to the experimental example of the present application. 12 N)MnCl3 and (C 24 H 26 This is a picture of P)2MnBr4.

[0101] FIG. 33 is an organic-inorganic hybrid metal halide (C) prepared according to the experimental example of the present application. 24 H 26 This is a photograph of P)2MnBr4 dissolved in a thermoplastic polymer.

[0102] FIG. 34 is an organic-inorganic hybrid metal halide (C4H) prepared according to the experimental example of the present application. 12 N)MnCl3 and (C 24 H 26This is a photograph of an organic-inorganic hybrid metal halide filament prepared from P)2MnBr4.

[0103] FIG. 35 is a photograph of a 3D printing device for organic-inorganic hybrid metal halide output manufactured according to an experimental example of the present application.

[0104] FIG. 36 is a photograph of an organic-inorganic hybrid metal halide 3D structure printed using a 3D printing device for printing organic-inorganic hybrid metal halide according to an experimental example of the present application.

[0105] FIG. 37 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 halides according to Experimental Examples 1-1 to 1-4 of the present application.

[0106] FIG. 38 is a diagram illustrating the distance (Mn-Mn) between adjacent Mn and Mn of organic-inorganic hybrid metal halides according to Experimental Examples 1-1 to 1-4 of the present application.

[0107] FIG. 39 is a diagram illustrating the photoluminescence quantum yield (PLQY) of organic-inorganic hybrid metal halides according to Experimental Examples 1-3 and 1-4 of the present application.

[0108] FIG. 40 is a diagram illustrating the band gap of organic-inorganic hybrid metal halides according to Experimental Examples 2-1 to 2-3 of the present application.

[0109] FIG. 41 is a diagram illustrating the stability over time of organic-inorganic hybrid metal halides according to Experimental Examples 2-1 to 2-3 of the present application.

[0110] FIG. 42 is a diagram illustrating the symmetry of organic-inorganic hybrid metal halides according to Experimental Example 2-1 and Experimental Example 2-3 of the present application.

[0111] FIG. 43 is a drawing for explaining the degree of disorder of organic-inorganic hybrid metal halides according to Experimental Examples 2-1 to 2-3 of the present application.

[0112]

[0113]

[0114]

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121]

[0122] FIG. 1 is a drawing for explaining a novel organic-inorganic hybrid metal halide design method according to an embodiment of the present application, FIG. 2 is a drawing for explaining a novel organic-inorganic hybrid metal halide design method according to an embodiment of the present application in more detail, FIG. 3 is a drawing for explaining a novel organic-inorganic hybrid metal halide according to an embodiment of the present application, FIG. 4 is a drawing for explaining the optimization of the distance between anions by an organic cation derived from a novel organic-inorganic hybrid metal halide according to an embodiment of the present application, FIG. 5 is a drawing for explaining the control of the distance between anions by an organic cation derived according to one embodiment of the present application, FIG. 6 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, FIG. 7 is a drawing for explaining a novel organic cation derived from a reference organic cation at site A according to one embodiment of the present application, and FIG. 8 is a drawing for explaining a novel organic cation derived from a reference organic cation at site A according to another embodiment of the present application.

[0123] Referring to FIGS. 1 and 2, in a database related to organic-inorganic hybrid metal halides represented by the following chemical formula, a reference organic cation at site A (11r: 11ra, 11rb, see FIGS. 7 and 8) and candidate molecular structures for candidate organic cations similar to said reference organic cation (11r: 11ra, 11rb) can be obtained (S110).

[0124] Chemical formula

[0125] A m M n X m+2n

[0126] 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.

[0127] According to one embodiment, molecular similarity can be analyzed based on a large language model (LLM). Specifically, a database such as ChemSpider and / or PubChem may be used to obtain candidate molecular structures for candidate organic cations similar to the reference organic cation (11r: 11ra, 11rb).

[0128] Referring further to FIGS. 1 and FIGS. 2, a chemical language model is used so that the candidate molecular structure can be expressed as a string (S120). Specifically, as a chemical language model, for example, a string of a simplified molecular input line entry system (SMILES) is used so that the candidate molecular structure can be expressed as a string.

[0129] Referring further to FIGS. 1 and FIGS. 2, a vector transformation model learned through the chemical language model can be used to convert the string into a vector (S130). Specifically, for example, MoLFormer can be used as the vector transformation model to convert the string into a vector. MoLFormer may be a transformer model learned through large-scale SMILES data and can convert input SMILES into a vector.

[0130] According to one embodiment, molecular features including the skeleton structure, electron density distribution, substituent effects, and steric hindrance of the molecule can be learned through the chemical language model.

[0131] Accordingly, a vector transformation model learned through the chemical language model is used, and the accuracy and efficiency of converting the string into a vector can be improved.

[0132] Referring further to FIGS. 1 and FIGS. 2, a distance matrix for quantifying molecular similarity is used so that the similarity between the reference organic cation (11r: 11ra, 11rb) and the candidate organic cation can be calculated based on the vector (S140). Specifically, the distance matrix may include a cosine distance, a Euclidean distance, and a Tanimoto distance, and through the distance matrix, the similarity between the reference organic cation (11r: 11ra, 11rb) and the candidate organic cation can be quantified based on the vector.

[0133] Referring further to FIGS. 1 and FIGS. 2, the candidate organic cations can be filtered to derive new organic cations (S150). Specifically, through the filtering, molecules with PP or P-Se bonds, hydrolysis-vulnerable groups, and excessive stereovolume can be removed depending on synthesizable, stable, and crystallization compatibility.

[0134] Accordingly, the synthesis yield and efficiency of the novel organic cation derived through the above-described novel organic-inorganic hybrid metal halide design method can be maximized.

[0135] Referring to FIGS. 3 and 4, 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.

[0136] 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 novel 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. 5, 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.

[0137] Accordingly, the novel 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.

[0138] Unlike the embodiment of the present application, as shown in FIG. 6(a), if the size of the organic cation (11) at the A site is excessively small, the distance between adjacent transition metals is shortened, and a non-radiative energy transfer path can be activated.

[0139] Accordingly, the luminescence characteristics and luminescence efficiency of the new organic-inorganic hybrid metal halide may be reduced.

[0140] On the other hand, as shown in FIG. 6(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.

[0141] Accordingly, the luminescence characteristics and luminescence efficiency of the new organic-inorganic hybrid metal halide may be reduced.

[0142] 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 novel organic-inorganic hybrid metal halide (10) represented by the above 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.

[0143] Referring to FIG. 7, according to one embodiment of the present application, when the reference organic cation (11ra) is a tetraphenylphosphonium cation (PPh4+), the novel organic cation (11a) can be derived as a cyclohexyltriphenylphosphonium cation (CHTP+) in which one phenyl group of the tetraphenylphosphonium cation (PPh4+) is substituted with cyclohexyl.

[0144] Due to the size and stereovolume of the novel cyclohexyltriphenylphosphonium cation (CHTP+, 11a) derived above, the distance between adjacent Mn and Mn in the novel organic-inorganic hybrid metal halide (10) represented by the above chemical formula can be controlled to 9.794 Å.

[0145] Accordingly, the novel organic-inorganic hybrid metal halide (10) represented by the above chemical formula can have a maximum photoluminescence quantum yield.

[0146] Referring to FIG. 8, according to another embodiment of the present application, when the reference organic cation (11rb) is a benzyltriphenylphosphonium cation (BzTP+), the novel organic cation (11b) can be derived as a 4-methylbenzyltriphenylphosphonium cation (4-MBz+) in which a para-methyl group is added to the benzyl group of the benzyltriphenylphosphonium cation (BzTP+).

[0147] Due to the size and stereovolume of the novel cyclohexyltriphenylphosphonium cation (4-MBz+, 11b) derived above, the distance between adjacent Mn and Mn in the novel organic-inorganic hybrid metal halide (10) represented by the above chemical formula can be controlled to 9.922 Å.

[0148] Accordingly, the novel organic-inorganic hybrid metal halide (10) represented by the above chemical formula may have a maximum photoluminescence spectrum and a minimum full width at half maximum.

[0149]

[0150] According to the novel organic-inorganic hybrid metal halide design method according to the embodiment of the present application described above, a novel cation (11) having high molecular similarity to an existing organic-inorganic hybrid metal halide containing a reference organic cation can be derived.

[0151] Accordingly, according to an embodiment of the present application, a novel organic-inorganic hybrid metal halide (10) designed from the novel organic cation (11) derived therefrom may have a maximum value for photoluminescence spectrum and photoluminescence quantum yield, and may have a minimum value for full width at half maximum.

[0152] Hereinafter, a method for manufacturing a novel organic-inorganic hybrid metal halide designed from a novel organic cation (11) derived through the novel organic-inorganic hybrid metal halide design method described above is explained.

[0153]

[0154] FIG. 9 is a drawing for explaining a novel organic-inorganic hybrid metal halide manufacturing method designed according to an embodiment of the present application, and FIG. 10 is a drawing for explaining a novel organic-inorganic hybrid metal halide manufacturing method designed according to an embodiment of the present application in more detail.

[0155] Referring to FIG. 9, the novel organic-inorganic hybrid metal halide manufacturing method may include steps S110 to S150 described above.

[0156] Specifically, with reference to FIGS. 1 and FIGS. 2, in a database related to organic-inorganic hybrid metal halide represented by the chemical formula, a reference organic cation at site A (11r: 11ra, 11rb, see FIGS. 7 and FIGS. 8) and a candidate molecular structure for a candidate organic cation similar to the reference organic cation (11r: 11ra, 11rb) can be obtained (S110).

[0157] Referring further to FIGS. 1 and FIGS. 2, a chemical language model is used so that the candidate molecular structure can be represented as a string. Specifically, for example, a string of the simplified molecular input line entry system (SMILES) is used as the chemical language model so that the candidate molecular structure can be represented as a string (S120).

[0158] Referring further to FIGS. 1 and FIGS. 2, a vector transformation model learned through the chemical language model can be used to convert the string into a vector. Specifically, for example, MoLFormer can be used as the vector transformation model to convert the string into a vector. MoLFormer may be a transformer model learned through large-scale SMILES data and can convert input SMILES into a vector (S130).

[0159] Referring further to FIGS. 1 and FIGS. 2, a distance matrix for quantifying molecular similarity is used so that the similarity between the reference organic cation (11r: 11ra, 11rb) and the candidate organic cation can be calculated based on the vector (S140). Specifically, the distance matrix may include a cosine distance, a Euclidean distance, and a Tanimoto distance, and through the distance matrix, the similarity between the reference organic cation (11r: 11ra, 11rb) and the candidate organic cation can be quantified based on the vector.

[0160] Referring further to FIGS. 1 and FIGS. 2, the candidate organic cations can be filtered to derive new organic cations (S150). Specifically, through the filtering, molecules with PP or P-Se bonds, hydrolysis-vulnerable groups, and excessive stereovolume can be removed depending on synthesizable, stable, and crystallization compatibility.

[0161] Accordingly, the synthesis yield and efficiency of the novel organic cation derived through the above-described novel organic-inorganic hybrid metal halide design method can be maximized.

[0162] Referring further to FIGS. 9 and FIGS. 10, an organic cationic material (11) containing the novel organic cation and a transition metal halide (12) are dissolved in a solvent (5) to synthesize a single-crystal organic-inorganic hybrid metal halide (10) (S160). Specifically, referring to FIG. 10, the organic cationic material (11) and the transition metal halide (12) are dissolved in a first solvent (5a) to produce a single-crystal source solution. Specifically, for example, the transition metal halide (12) may be manganese(IV) bromide (MnBr4).

[0163] According to one embodiment, the single crystal source solution can be stirred in a heated atmosphere.

[0164] Accordingly, the dissolution of the organic cationic substance (11) and the transition metal halide (12) in the first solvent (5a) can be facilitated.

[0165] Continuing with reference to FIG. 10, the single crystal source solution may be provided in a sealed atmosphere formed with a second solvent (5b) having lower polarity than the first solvent (5a). Specifically, for example, the first solvent (5a) may be selected from the group of solvents including N,N-dimethylformamide (DMF) or methanol, and the second solvent (5b) may be selected from the group of solvents including dichloromethane (DCM) or ethanol. More specifically, for example, when the organic cationic substance (11) is a cyclohexyltriphenylphosphonium cation (CHTP+), the first solvent (5a) may be N,N-dimethylformamide (DMF) and the second solvent (5b) may be dichloromethane (DCM). When the above organic cationic substance (11) is a 4-methylbenzyltriphenylphosphonium cation (4-MBz+), the above first solvent (5a) may be methanol and the above second solvent (5b) may be ethanol.

[0166] According to one embodiment, in the sealed atmosphere, the second solvent (5b) is evaporated to form vapor, and the vapor penetrates into the single crystal source solution to form a concentration gradient. Due to the concentration gradient, the solubility of the single crystal source is reduced, nucleation occurs, and crystals can grow.

[0167] Thus, the above single crystal organic-inorganic hybrid metal halide (10) can be synthesized.

[0168] Referring further to FIGS. 9 and FIGS. 10, the organic cationic material (11) and the transition metal halide (12) may be crushed to form a polycrystalline organic-inorganic hybrid metal halide (20) (S170).

[0169] According to one embodiment, a liquid additive may be added during the grinding of the organic cationic material (11) and the transition metal halide (12). Specifically, for example, anhydrous ethanol may be added as the liquid additive during the grinding.

[0170] Accordingly, 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. In addition, 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.

[0171] Referring further to FIG. 9 and FIG. 10, the single crystal or polycrystalline organic-inorganic hybrid metal halide (10, 20) may be cooled after being heat-treated above its melting point to form a glassy organic-inorganic hybrid metal halide (30) (S180).

[0172] According to one embodiment, the heat treatment of the polycrystalline organic-inorganic hybrid metal halide (20) can be performed in an inert gas atmosphere.

[0173] Accordingly, the influence of oxygen and / or moisture in the atmosphere is minimized during the melting process of the single crystal or polycrystalline organic-inorganic hybrid metal halide (10, 20), thereby minimizing the oxidation and / or thermal decomposition reactions of the glassy organic-inorganic hybrid metal halide (30) being manufactured. In addition, the generation of unnecessary by-products is minimized during the melting process of the single crystal or polycrystalline organic-inorganic hybrid metal halide (10, 20), so that the glassy organic-inorganic hybrid metal halide (30) being manufactured can be formed uniformly and with high purity. Furthermore, the loss of optical performance of the glassy organic-inorganic hybrid metal halide (30) after heat treatment can be minimized.

[0174] According to one embodiment, the single crystal or polycrystalline organic-inorganic hybrid metal halide (10, 20) can be rapidly cooled after the heat treatment.

[0175] As a result, there may be insufficient time for atoms in the single crystal or polycrystalline organic-inorganic hybrid metal halide (10, 20) to form a regular arrangement. Accordingly, it may be easy to convert from the single crystal or polycrystalline, i.e., crystalline state to the glassy state.

[0176] That is, according to an embodiment of the present application, the single crystal or polycrystalline organic-inorganic hybrid metal halide (10, 20) can be converted into a liquid state through the heat treatment and into a glassy organic-inorganic hybrid metal halide (30) through the rapid cooling. The glassy organic-inorganic hybrid metal halide (30) is more disordered than the crystalline state but can maintain a solid state.

[0177] As a result, according to an embodiment of the present application, three-dimensional printing based on melting may be possible.

[0178] Furthermore, through the rapid cooling described above, the return of the glass state to a crystalline state is minimized, and the formation of a new low-temperature phase can be minimized.

[0179] Accordingly, the above glass-state organic-inorganic hybrid metal halide (30) can remain in an intermediate state for maximizing performance through post-processing in a subsequent process.

[0180] In other words, according to an embodiment of the present application, formula A designed through the novel organic-inorganic hybrid metal halide design method m M n X m+2nIn the novel organic-inorganic hybrid metal halide (10) described above, the organic cation material (11) is designed so that the distance between adjacent transition metals is optimized, and thus the distance between adjacent transition metals in the substantially manufactured organic-inorganic hybrid metal halide (10, 20, 30) can be reversibly converted into a single crystal, polycrystalline, and glassy state.

[0181] As a result, according to the embodiments of the present application, not only can processability be maximized through the conversion from a crystalline state to a glassy state, but the problem of being unable to process a substantially non-planar structure, i.e., a curved surface, can also be resolved, and melt-based 3D printing can be made possible.

[0182]

[0183] According to the novel organic-inorganic hybrid metal halide manufacturing method designed according to the embodiments of the present application described above, the organic-inorganic hybrid metal halide (10, 20, 30) in which the single crystal, polycrystalline, and glassy states are reversibly converted through the distance between adjacent transition metals can be provided.

[0184] According to the organic-inorganic hybrid metal halide (10, 20, 30) of the embodiment of the present application, processability can be maximized through the conversion from a crystalline state to a glassy state, and the problem of being unable to process curved surfaces, i.e., having a substantially non-planar structure, can be resolved. Furthermore, the organic-inorganic hybrid metal halide (10, 20, 30) can enable melt-based 3D printing.

[0185] Hereinafter, a method for manufacturing an organic-inorganic hybrid metal halide filament for applying the above organic-inorganic hybrid metal halide (10, 20, 30) to a 3D printer is described.

[0186]

[0187] FIG. 11 is a drawing for explaining a method for manufacturing a filament source according to an embodiment of the present application, and FIG. 12 is a drawing for explaining a method for providing the filament source to a mold and drying it according to an embodiment of the present application.

[0188] Referring to FIG. 11, the organic-inorganic hybrid metal halide (20) and the thermoplastic polymer (31) represented by the above chemical formula are dissolved in a solvent to produce a filament source (32). For example, the solvent may be any one selected from the group of solvents including dichloromethane (DCM). More specifically, for example, the solvent may be dichloromethane (DCM).

[0189] According to one embodiment, the thermoplastic polymer (31) may have extrudability at the melting point of the organic-inorganic hybrid metal halide (20). For example, the thermoplastic polymer (31) may include at least one selected from the group of thermoplastic polymers including polylactic acid (PLA) and polyethylene terephthalate glycol (PETG). More specifically, for example, the thermoplastic polymer (31) may be polylactic acid (PLA). When the thermoplastic polymer (31) is polylactic acid (PLA), the output temperature of the organic-inorganic hybrid metal halide filament (41, see FIG. 12) produced from the filament source (32) may be lowered. Specifically, the output temperature of the organic-inorganic hybrid metal halide filament (41) made of the organic-inorganic hybrid metal halide (20) and polylactic acid (PLA, 31) through a 3D printer is 150°C or higher and 180°C or lower, which may be lower than the melting point of the organic-inorganic hybrid metal halide (20), which is 206.5°C.

[0190] Accordingly, when the thermoplastic polymer (31) is polylactic acid (PLA), the organic-inorganic hybrid metal halide filament (41) may have uniform dispersion and excellent loading stability. For example, even when the organic-inorganic hybrid metal halide filament (41) is loaded up to 50 wt% into the 3D printer, the nozzle of the 3D printer does not substantially clog, and failure of the 3D printing device can be minimized.

[0191] As another example, the thermoplastic polymer (31) may be polyethylene terephthalate glycol (PETG). When the thermoplastic polymer (31) is polyethylene terephthalate glycol (PETG), the output temperature of the organic-inorganic hybrid metal halide filament (41) produced from the filament source (32) may be relatively higher than when it is polylactic acid (PLA). Specifically, the output temperature of the organic-inorganic hybrid metal halide filament (41) produced from the organic-inorganic hybrid metal halide (20) and polyethylene terephthalate glycol (PETG, 31) through a 3D printer may be 220°C or higher and 260°C or lower, which is similar to the melting point of the organic-inorganic hybrid metal halide (20), which is 206.5°C.

[0192] Accordingly, when the thermoplastic polymer (31) is polyethylene terephthalate glycol (PETG), the organic-inorganic hybrid metal halide filament (41) may have excellent mixability and mechanical stability at relatively high temperatures.

[0193] Referring further to FIGS. 11 and 12, the filament source (32) is provided to a mold (md) and dried to produce an organic-inorganic hybrid metal halide filament (41). The mold (md) shown in FIG. 12 is merely an example and is not limited thereto.

[0194] According to one embodiment, the organic-inorganic hybrid metal halide filament (41) may be polycrystalline. On the other hand, when the organic-inorganic hybrid metal halide filament (41) is printed into a three-dimensional structure through a three-dimensional printing device, the polycrystalline state may be converted into a glassy state. More specifically, the polycrystalline organic-inorganic hybrid metal halide filament (41) may be provided to a three-dimensional printing device, printed, and rapidly cooled.

[0195] As a result, there may be insufficient time for atoms to form a regular arrangement in the polycrystalline organic-inorganic hybrid metal halide filament (41). Accordingly, the transition from the polycrystalline state to the glassy state may be easy.

[0196] That is, according to an embodiment of the present application, when the polycrystalline organic-inorganic hybrid metal halide (20) is printed through a 3D printer, at least a portion of it becomes liquid, and it can be converted into the glass state through rapid cooling. The 3D structure in the glass state is more disordered than the crystalline state, but it can maintain a solid state.

[0197] As a result, according to an embodiment of the present application, three-dimensional printing based on melting may be possible.

[0198] Furthermore, through the rapid cooling described above, the return of the glass state to a crystalline state is minimized, and the formation of a new low-temperature phase can be minimized.

[0199] Accordingly, the above-mentioned glass-state three-dimensional structure can remain in an intermediate state for maximizing performance through post-processing in a subsequent process.

[0200] In other words, according to the embodiments of the present application, not only can processability be maximized through the conversion from a crystalline state to a glassy state, but the problem of being unable to process curved surfaces, which is a substantially non-planar structure, can also be resolved, and melt-based 3D printing can be made possible.

[0201]

[0202] According to an embodiment of the present application, a 3D printing device for 3D printing of organic-inorganic hybrid metal halide output using a conversion from a crystalline state to a glass state may be provided.

[0203] Hereinafter, a 3D printing device for organic-inorganic hybrid metal halide output according to an embodiment of the present application is described.

[0204]

[0205] FIG. 13 is a drawing for explaining a 3D printing device for printing organic-inorganic hybrid metal halide according to an embodiment of the present application, FIG. 14 is a drawing for explaining a 3D printing device for printing organic-inorganic hybrid metal halide for filament according to an embodiment of the present application, and FIG. 15 is a drawing for explaining a 3D printing device for printing organic-inorganic hybrid metal halide for powder according to an embodiment of the present application.

[0206] Referring to FIGS. 13 to 15, the 3D printing device (100) for outputting an organic-inorganic hybrid metal halide may include an injection part (110: 110a, 110b) into which an organic-inorganic hybrid metal halide (41, 42) represented by the chemical formula A2MnBr4 is injected, an output part (120) into which the organic-inorganic hybrid metal halide (41, 42) injected into the injection part (110) is output, and a stage (130) that supports and rotates relative to an organic-inorganic hybrid metal halide 3D printed structure (51, 52) into which the organic-inorganic hybrid metal halide (41, 42) is output through the output part (120) while the injection part (110) is fixed.

[0207] According to one embodiment, the injection part (110: 110a, 110b) can be detachably attached to the 3D printing device (100) as shown in FIG. 14 and FIG. 15. More specifically, the injection part (110: 110a, 110b) can be detachably attached to the 3D printing device (100) as an optimized module depending on the form of the organic-inorganic hybrid metal halide, for example, a filament form (41) or a powder form (42).

[0208] Accordingly, referring to FIG. 14, when the organic-inorganic hybrid metal halide is in the form of a filament (41), the injection part (110a) may include an injection port (111a) into which the organic-inorganic hybrid metal halide filament (41) is injected, and a rotary gear (112a) that moves the organic-inorganic hybrid metal halide filament (41) injected through the injection port (111a) toward the output part (120).

[0209] Accordingly, the organic-inorganic hybrid metal halide filament (41) can be easily printed through the organic-inorganic hybrid metal halide output 3D printing device (100).

[0210] Additionally, referring to FIG. 15, when the organic-inorganic hybrid metal halide is in powder form (42), the injection unit (110b) may include a hopper (111b) in which the organic-inorganic hybrid metal halide powder (42) is contained, and a motor (not shown) and a screw (112a) for moving the organic-inorganic hybrid metal halide powder (42) contained in the hopper (111b) toward the output unit (120).

[0211] Accordingly, the organic-inorganic hybrid metal halide powder (42) can be easily printed through the 3D printing device (100) for printing the organic-inorganic hybrid metal halide.

[0212] According to one embodiment, the 3D printing device (100) for outputting an organic-inorganic hybrid metal halide may further include a heating block (140, see FIG. 35) mounted on the injection unit (110) to heat the organic-inorganic hybrid metal halide (41, 42) injected into the injection unit (110).

[0213] As a result, the output section (120), i.e., the nozzle of the 3D printing device (100) for outputting the organic-inorganic hybrid metal halide, is not substantially clogged, and the organic-inorganic hybrid metal halide filament (41) or the organic-inorganic hybrid metal halide powder (42) can be easily output.

[0214] Accordingly, failures of the above-mentioned organic-inorganic hybrid metal halide output 3D printing device (100) can be minimized.

[0215] Additionally, according to an embodiment of the present application, the thermoplastic polymer (31) may have extrudability at the melting point of the organic-inorganic hybrid metal halide (20). For example, the thermoplastic polymer (31) may include at least one selected from the group of thermoplastic polymers including polylactic acid (PLA) and polyethylene terephthalate glycol (PETG). More specifically, for example, the thermoplastic polymer (31) may be polylactic acid (PLA). When the thermoplastic polymer (31) is polylactic acid (PLA), the output temperature of the organic-inorganic hybrid metal halide filament (41, see FIG. 12) produced from the filament source (32) may be lowered. Specifically, the output temperature of the organic-inorganic hybrid metal halide filament (41) made of the organic-inorganic hybrid metal halide (20) and polylactic acid (PLA, 31) through the 3D printing device (100) for outputting the organic-inorganic hybrid metal halide is 150°C or higher and 180°C or lower, which may be lower than the melting point of the organic-inorganic hybrid metal halide (20), which is 206.5°C.

[0216] Accordingly, when the thermoplastic polymer (31) is polylactic acid (PLA), the organic-inorganic hybrid metal halide filament (41) may have uniform dispersion and excellent loading stability. For example, even when the organic-inorganic hybrid metal halide filament (41) is loaded at a maximum of 50 wt% into the organic-inorganic hybrid metal halide output 3D printing device (100), the output section (120), i.e., the nozzle, of the organic-inorganic hybrid metal halide output 3D printing device (100) is not substantially clogged, and failure of the organic-inorganic hybrid metal halide output 3D printing device (100) can be minimized.

[0217] As another example, the thermoplastic polymer (31) may be polyethylene terephthalate glycol (PETG). When the thermoplastic polymer (31) is polyethylene terephthalate glycol (PETG), the output temperature of the organic-inorganic hybrid metal halide filament (41) produced from the filament source (32) may be relatively higher than when it is polylactic acid (PLA). Specifically, the output temperature of the organic-inorganic hybrid metal halide filament (41) produced from the organic-inorganic hybrid metal halide (20) and polyethylene terephthalate glycol (PETG, 31) through the 3D printing device (100) for organic-inorganic hybrid metal halide output may be 220°C or higher and 260°C or lower, which is similar to the melting point of the organic-inorganic hybrid metal halide (20), which is 206.5°C.

[0218] Accordingly, when the thermoplastic polymer (31) is polyethylene terephthalate glycol (PETG), the organic-inorganic hybrid metal halide filament (41) may have excellent mixability and mechanical stability at relatively high temperatures.

[0219]

[0220] According to the 3D printing device for outputting organic-inorganic hybrid metal halide according to the embodiment of the present application described above, the injection part (110: 110a, 110b) can be attached and detached from the 3D printing device (100) as an optimized module depending on the form of the organic-inorganic hybrid metal halide, for example, filament form (41) or powder form (42).

[0221] Accordingly, the output section (120), i.e., the nozzle, of the 3D printing device (100) for outputting organic-inorganic hybrid metal halide can be substantially not clogged, and the organic-inorganic hybrid metal halide filament (41) or the organic-inorganic hybrid metal halide powder (42) can be easily output, and the failure of the 3D printing device (100) for outputting organic-inorganic hybrid metal halide can be minimized.

[0222] Hereinafter, a method for manufacturing a 3D structure of an organic-inorganic hybrid metal halide using a 3D printing device for outputting organic-inorganic hybrid metal halides according to an embodiment of the present application is described.

[0223]

[0224] FIG. 16 is a drawing for explaining an organic-inorganic hybrid metal halide 3D printed structure manufactured with an organic-inorganic hybrid metal halide filament according to an embodiment of the present application, FIG. 17 is a drawing for explaining an organic-inorganic hybrid metal halide 3D printed structure manufactured with an organic-inorganic hybrid metal halide powder according to an embodiment of the present application, FIG. 18 is a drawing for explaining the post-processing of an organic-inorganic hybrid metal halide 3D printed structure manufactured with an organic-inorganic hybrid metal halide filament according to an embodiment of the present application, and FIG. 19 is a drawing for explaining the post-processing of an organic-inorganic hybrid metal halide 3D printed structure manufactured with an organic-inorganic hybrid metal halide powder according to an embodiment of the present application.

[0225] Referring to FIGS. 16 and 17, the organic-inorganic hybrid metal halide filament (41) or the organic-inorganic hybrid metal halide powder (42) is provided to the 3D printing device (100), and an organic-inorganic hybrid metal halide 3D printed structure (51, 52) can be printed.

[0226] The above-mentioned organic-inorganic hybrid metal halide 3D printed structures (51, 52) can be rapidly cooled.

[0227] According to one embodiment, the organic-inorganic hybrid metal halide filament (41) and the organic-inorganic hybrid metal halide powder (42) may be polycrystalline. On the other hand, when the organic-inorganic hybrid metal halide filament (41) and the organic-inorganic hybrid metal halide powder (42) are output into a three-dimensional structure through the three-dimensional printing device (100), the polycrystalline state may be converted into a glass state. More specifically, the polycrystalline organic-inorganic hybrid metal halide filament (41) or the organic-inorganic hybrid metal halide powder (42) may be provided to the three-dimensional printing device, output, and rapidly cooled.

[0228] As a result, there may be insufficient time for atoms in the polycrystalline organic-inorganic hybrid metal halide filament (41) and the organic-inorganic hybrid metal halide powder (42) to form a regular arrangement. Accordingly, the transition from the polycrystalline state to the glassy state may be easy.

[0229] That is, according to an embodiment of the present application, when the organic-inorganic hybrid metal halide filament (41) and the organic-inorganic hybrid metal halide powder (42) are output through the 3D printing device (100), at least a portion of them become liquid, and can be converted into the glass state through the rapid cooling. The organic-inorganic hybrid metal halide 3D printed structure (51, 52) in the glass state is more disordered than the crystalline state, but can maintain a solid state.

[0230] As a result, according to an embodiment of the present application, three-dimensional printing based on melting may be possible.

[0231] Furthermore, through the rapid cooling described above, the return of the glass state to a crystalline state is minimized, and the formation of a new low-temperature phase can be minimized.

[0232] Accordingly, the above-mentioned organic-inorganic hybrid metal halide 3D printed structure (51, 52) in a glass state can remain in an intermediate state for maximizing performance through post-processing in a subsequent process.

[0233] In other words, according to the embodiments of the present application, not only can processability be maximized through the conversion from a crystalline state to a glassy state, but the problem of being unable to process curved surfaces, which is a substantially non-planar structure, can also be resolved, and melt-based 3D printing can be made possible.

[0234] Referring further to FIGS. 18 and 19, the rapidly cooled organic-inorganic hybrid metal halide 3D printed structures (51, 52) can be post-treated (60) with a solvent (7). Specifically, the post-treatment solvent (7) for post-treating the rapidly cooled organic-inorganic hybrid metal halide 3D printed structures (51, 52) may be dichloromethane (DCM).

[0235] Referring to FIG. 18, the organic-inorganic hybrid metal halide 3D printed structure (51) manufactured as a filament is immersed in the post-treatment solvent (7) and post-treated (60), so that the thermoplastic polymer (31), i.e., the binder, contained in the organic-inorganic hybrid metal halide filament (41) can be dissolved.

[0236] Accordingly, the glass state of the post-processed organic-inorganic hybrid metal halide 3D printed structure (60) can be converted into a crystalline state.

[0237] That is, according to an embodiment of the present application, the organic-inorganic hybrid metal halide (41) injected in the form of a filament is polycrystalline, and the organic-inorganic hybrid metal halide 3D printing structure (51) is rapidly cooled so that the polycrystalline state is converted into a glassy state, and the binder (31) is selectively dissolved in the organic-inorganic hybrid metal halide 3D printing structure (51) by immersion in the post-treatment solvent (7), and the glassy state is reversibly converted back into a polycrystalline state, so the post-treated organic-inorganic hybrid metal halide 3D printing structure (60) may be polycrystalline.

[0238] Accordingly, according to an embodiment of the present application, the optical performance of the 3D printed structure can be restored and maximized by converting it from a glass state to a crystalline state through a simple post-processing solution process without substantially a heating process. More specifically, the brightness, color purity, and luminescence efficiency of the post-processed organic-inorganic hybrid metal halide 3D printed structure (60) can be maximized.

[0239] According to one embodiment, the organic-inorganic hybrid metal halide 3D printed structure (51) is immersed in the post-treatment solvent (7), so that the binder (31) can be selectively dissolved on the surface rather than on the inside.

[0240] As a result, the binder (31) may have a higher ratio per volume on the inside than on the surface of the organic-inorganic hybrid metal halide 3D printed structure (60).

[0241] Accordingly, the structure of the organic-inorganic hybrid metal halide 3D printing structure (60) can be easily maintained by the binder (31) which has a relatively high ratio on the inside, and the brightness, color purity, and luminous efficiency of the organic-inorganic hybrid metal halide 3D printing structure (60) can be maximized by the binder (31) which has a relatively low ratio on the surface.

[0242] Referring to FIG. 19, in the case of an organic-inorganic hybrid metal halide 3D printed structure (52) manufactured as a powder, the glass state can be converted into a crystalline state by providing the post-treatment solvent (7) and performing post-treatment (60).

[0243] That is, according to an embodiment of the present application, the organic-inorganic hybrid metal halide (42) injected in powder form is polycrystalline, and the organic-inorganic hybrid metal halide 3D printing structure (52) is rapidly cooled so that the polycrystalline state is converted into a glassy state, and the solvent (7) is provided so that the glassy state of the organic-inorganic hybrid metal halide 3D printing structure (52) can be reversibly converted back into a polycrystalline state.

[0244] Accordingly, according to an embodiment of the present application, the optical performance of the 3D printed structure can be restored and maximized by converting it from a glass state to a crystalline state through a simple post-processing solution process without substantially a heating process. More specifically, the brightness, color purity, and luminescence efficiency of the post-processed organic-inorganic hybrid metal halide 3D printed structure (60) can be maximized.

[0245]

[0246] According to the organic-inorganic hybrid metal halide three-dimensional structure according to the embodiment of the present application described above, the three-dimensional printed structure can be converted from a glassy state to a crystalline state through a simple post-processing solution process without substantially a heating process, thereby restoring and maximizing the optical performance of the three-dimensional printed structure.

[0247] In particular, when the above organic-inorganic hybrid metal halide 3D printing structure (60) is manufactured with the above organic-inorganic hybrid metal halide filament (41), the binder (31) can be selectively dissolved on the surface rather than the inside by the above post-treatment solvent (7).

[0248] As a result, the organic-inorganic hybrid metal halide three-dimensional structure (60) containing a binder with a higher volume ratio on the inside than on the surface can be provided.

[0249] Accordingly, the structure of the organic-inorganic hybrid metal halide 3D printing structure (60) can be easily maintained by the binder (31) which has a relatively high ratio on the inside, and the brightness, color purity, and luminous efficiency of the organic-inorganic hybrid metal halide 3D printing structure (60) can be maximized by the binder (31) which has a relatively low ratio on the surface.

[0250]

[0251] Specific experimental examples and characteristic evaluation results according to the embodiments of the present application are described below.

[0252]

[0253] Design of a Novel Organic-Inorganic Hybrid Metal Halide According to Experimental Examples

[0254] The process of data mining organic cation data was carried out by accessing the PubChem and ChemSpider databases. PubChem is a database of chemical, molecular, and biological research activities managed under the leadership of the National Center for Biotechnology Information within the U.S. Library of Medicine, containing approximately 110 million registered compounds. ChemSpider is a chemical structure-centric database built by RSC Publishers in collaboration with the University of Manchester, providing rapid access to approximately 26 million chemical structures, properties, and related information. By using "phosphonium" within PubChem and ChemSpider as a reference organic cation keyword among the organic cations corresponding to the A position of the above chemical formulas, approximately 50,000 candidate molecular structures of candidate organic cations similar to the reference organic cations were obtained.

[0255] The above candidate molecular structure was represented as a string using SMILES' string.

[0256] The above string was converted into a vector using the MoLFormer Large Language Model as the vector conversion model.

[0257] Among the reference materials represented by the above chemical formulas, the materials of the following chemical formulas A and B, which are reported as high-performance luminescent materials and have photoluminescence quantum yields (PLQY) of 100% and 99.8%, respectively, were selected as reference organic-inorganic hybrid metal halides, and molecular similarity tests were performed.

[0258] <Chemical Formula A>

[0259] (C 24 H 20 P)2MnBr4

[0260] <Chemical Formula B>

[0261] (C 25 H 22 P)2MnBr4

[0262] Based on the above vectors, the similarity between the reference organic cation and the candidate organic cation in the reference organic-inorganic hybrid metal halides of the above chemical formulas A and B was calculated.

[0263]

[0264] FIG. 20 is a diagram illustrating the calculation of similarity between a reference organic cation and a candidate organic cation according to an experimental example of the present application.

[0265] Referring to Fig. 20, a similarity test was performed by comparing the vectorized candidate organic cation SMILES data based on a large language model with the A-position organic cations of chemical formulas A and B. By including the reference organic cation at the A-position in the query and targeting the candidate organic cation data, a total of three similarity tests were performed for Tanimoto distance, cosine distance, and Euclidean distance.

[0266] As shown in FIG. 20, a similarity check was performed by setting a query and a target, and a vectorization method using the existing RDKit and a method based on a large language model according to the experimental example of the present application were compared.

[0267] Through Fig. 20, it can be seen that the reliability of the data preprocessed using the large language model according to the experimental example of the present application is higher than that of the vectorization method using the existing RDKit.

[0268] Accordingly, based on the results of the molecular similarity test above, the top compositions were selected in descending order as the candidate molecular structures. Classification and synthesis experiments were conducted starting from the top-ranked candidate molecular structures, and through this, a novel organic-inorganic hybrid metal halide represented by Chemical Formula 1 below was derived.

[0269] <Chemical Formula 1>

[0270] (C 24 H 26P)2MnBr4

[0271]

[0272] FIG. 21 shows cyclohexyltriphenylphosphonium (C1), a novel organic cation derived according to the experimental example of the present application. 24 H 26 Figure 22 shows the results of the Tanimoto distance similarity test of P), and cyclohexyltriphenylphosphonium (C) is a novel organic cation derived according to the experimental example of the present application. 24 H 26 Figure 23 shows the results of a cosine distance similarity test of P), and cyclohexyltriphenylphosphonium (C) is a novel organic cation derived according to the experimental example of the present application. 24 H 26 P) is the result of a Euclidean distance similarity test, and FIG. 24 is a diagram for comparing and explaining the similarity test according to the experimental example of the present application and the existing similarity test.

[0273] Referring to FIGS. 21 to 24, the results of the molecular similarity test of the novel organic-inorganic hybrid metal halide represented by Chemical Formula 1 can be confirmed.

[0274] Through FIGS. 21 to 24, it can be confirmed that the novel organic-inorganic hybrid metal halide represented by Chemical Formula 1 is within the top 0.1% in all molecular similarity tests performed with Chemical Formulas A and B.

[0275] Thus, the high similarity of the novel organic-inorganic hybrid metal halide derived according to the experimental examples of the present application can be demonstrated.

[0276]

[0277] Preparation of novel organic-inorganic hybrid metal halides designed according to experimental examples

[0278] In order to prepare a novel organic-inorganic hybrid metal halide represented by the derived chemical formula 1, AX and MX2 powders (wherein A is C, H, P, M is Mn, and X is Br) were quantified according to stoichiometric equivalent ratios as raw materials, and then mixed and ground using an agate pestle for 5 minutes while adding anhydrous ethanol in a mortar to prepare a novel organic-inorganic hybrid metal halide designed according to experimental examples.

[0279]

[0280] FIG. 25 is the crystal structure of a novel organic-inorganic hybrid metal halide prepared according to the experimental example of the present application, FIG. 26 is the result of X-ray diffraction (XRD) analysis and Rietveld refinement of a novel organic-inorganic hybrid metal halide prepared according to the experimental example of the present application, and FIG. 27 is a graph of the luminescence characteristics of a novel organic-inorganic hybrid metal halide prepared according to the experimental example of the present application.

[0281] Through FIG. 25, the crystal structure of a novel organic-inorganic hybrid metal halide prepared according to the experimental example of the present application can be confirmed.

[0282] In addition, through FIG. 26, it can be confirmed that the novel organic-inorganic hybrid metal halide prepared according to the experimental example of the present application has a polycrystalline structure and has the same phase as a single crystal.

[0283] In addition, through FIG. 27, it can be confirmed that the novel organic-inorganic hybrid metal halide prepared according to the experimental example of the present application emits green light when irradiated with an ultraviolet wavelength of 365 nm as an excitation source.

[0284]

[0285] Mold manufacturing according to experimental example

[0286] After designing a mold through 3D modeling, the object prototype was obtained by printing it with a 3D printer, placed in a mold, and provided with silicone and a hardener to manufacture the mold according to the experimental example.

[0287]

[0288] FIG. 28 is a design drawing of a mold according to an experimental example of the present application, and FIG. 29 is a photograph of a mold produced according to an experimental example of the present application.

[0289] Referring to FIGS. 28 and 29, it can be seen that a mold (md) designed through three-dimensional modeling according to the experimental example of the present application is manufactured into a finished product using silicone and a curing agent.

[0290]

[0291] FIG. 30 is an organic-inorganic hybrid metal halide filament manufactured using a mold produced according to an experimental example of the present application, and FIG. 31 is a photograph of the organic-inorganic hybrid metal halide filament according to an experimental example of the present application before and after light emission.

[0292] Referring to FIG. 30, it can be seen that a mold (md) manufactured according to the experimental example of the present application is used to manufacture an organic-inorganic hybrid metal halide filament (41) according to the experimental example.

[0293] Additionally, referring to FIG. 31, it can be seen that the organic-inorganic hybrid metal halide filament (41) manufactured according to the experimental example of the present application emits green light when irradiated with an ultraviolet wavelength of 365 nm as an excitation source.

[0294]

[0295] Preparation of organic-inorganic hybrid metal halide filaments according to experimental examples

[0296] (C4H 12 N)MnCl3 and (C 24 H 26A source powder for the preparation of P)2MnBr4 is prepared, and while adding anhydrous ethanol in a mortar, it is mixed and ground using an agate pestle (C4H 12 N)MnCl3 and (C 24 H 26 P)2MnBr4 was prepared.

[0297] Polyethylene terephthalate glycol (PETG) was placed in a vial, and a dichloromethane (DCM) solution was added to the vial in an amount equivalent to 10 times the mass of the PETG. Subsequently, after stirring for 30 minutes to completely dissolve the PETG in the DCM solvent, the above (C4H 12 N)MnCl3 and (C 24 H 26 P)2MnBr4 was added to a vial in an amount equal to twice the mass of PETG and further stirred to prepare the filament source.

[0298] Using a syringe, 3 ml of the above filament source was placed and injected into a silicone tube with an inner diameter of 1.8 mm and a length of 30 cm, and the opposite end of the silicone tube was sealed with Teflon tape. Since DCM is highly volatile, the internal mixed solution solidified due to the PETG that had evaporated and dissolved, thereby producing an organic-inorganic hybrid metal halide filament according to the experimental example.

[0299]

[0300] FIG. 32 is an organic-inorganic hybrid metal halide (C4H) prepared according to the experimental example of the present application. 12 N)MnCl3 and (C 24 H 26 This is a picture of P)2MnBr4.

[0301] Referring to Fig. 32, (C4H 12 N)MnCl3 is red, and (C 24 H 26 It can be confirmed that P)2MnBr4 is green.

[0302]

[0303] FIG. 33 is an organic-inorganic hybrid metal halide (C) prepared according to the experimental example of the present application. 24 H 26 This is a photograph of P)2MnBr4 dissolved in a thermoplastic polymer.

[0304] Referring to Fig. 33, the green (C 24 H 26 It can be confirmed that P)2MnBr4 is dissolved in the DCM solvent in which PETG is dissolved.

[0305]

[0306] FIG. 34 is an organic-inorganic hybrid metal halide (C4H) prepared according to the experimental example of the present application. 12 N)MnCl3 and (C 24 H 26 This is a photograph of an organic-inorganic hybrid metal halide filament prepared from P)2MnBr4.

[0307] Referring to Fig. 34, (C4H 12 Organic-inorganic hybrid metal halide filaments prepared from N)MnCl3 are red, and (C 24 H 26 It can be confirmed that the organic-inorganic hybrid metal halide filament prepared from P)2MnBr4 is green.

[0308]

[0309] FIG. 35 is a photograph of a 3D printing device for printing organic-inorganic hybrid metal halide according to an experimental example of the present application, and FIG. 36 is a photograph of an organic-inorganic hybrid metal halide 3D structure printed through a 3D printing device for printing organic-inorganic hybrid metal halide according to an experimental example of the present application.

[0310] Referring to FIG. 35, it can be seen that a 3D printing device (100) for printing organic-inorganic hybrid metal halide is manufactured, comprising an injection part (110) manufactured to be detachably attached to and attached to the 3D printing device (100) for a filament (110a) and a powder (110b), a heating block (140) mounted on the injection part (110), an output part (120), and a stage (130).

[0311] In addition, referring to FIG. 36, it can be seen that the organic-inorganic hybrid metal halide 3D structure manufactured using the 3D printing device for outputting organic-inorganic hybrid metal halide according to the experimental example of the present application emits green light when irradiated with an ultraviolet wavelength of 365 nm as an excitation source.

[0312]

[0313] Preparation of organic-inorganic hybrid metal halide (ex1-1) according to Experimental Example 1-1

[0314] 1 mmol of (PPh4)Br and 1 mmol of MnBr2, which are organic cation-containing substances, were mixed and ground using an agate pestle for 5 minutes while adding 0.5 mL of anhydrous ethanol in a mortar, and then dried at room temperature (25 °C) for 1 hour to prepare an organic-inorganic hybrid metal halide (ex1-1) according to Experimental Example 1-1.

[0315]

[0316] Preparation of organic-inorganic hybrid metal halide (ex1-2) according to Experimental Example 1-2

[0317] 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 (ex1-2) according to Experimental Example 1-2.

[0318]

[0319] Preparation of organic-inorganic hybrid metal halide (ex1-3) according to Experimental Example 1-3

[0320] 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 prepare an organic-inorganic hybrid metal halide (ex1-3) according to Experimental Example 1-3.

[0321]

[0322] Preparation of organic-inorganic hybrid metal halide (ex1-4) according to Experimental Example 1-4

[0323] 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 prepare an organic-inorganic hybrid metal halide (ex1-4) according to Experimental Example 1-4.

[0324]

[0325] Experimental Examples 1-1 to 1-4 described above can be summarized as shown in Table 1 below.

[0326]

[0327] Classification: Organic Cations

[0328] Experimental Example 1-1 (ex1-1) Tetraphenylphosphonium (PPh4)

[0329] Experimental Example 1-2 (ex1-2) Benzyltriphenylphosphonium (BzTP)

[0330] Experimental Example 1-3 (ex1-3) Cyclohexyltriphenylphosphonium (CHTP)

[0331] Experimental Example 1-4 (ex1-4) 4-methylbenzyltriphenylphosphonium (4-MBz)

[0332]

[0333] FIG. 37 is a figure for explaining 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 halides according to Experimental Examples 1-1 to 1-4 of the present application, FIG. 38 is a figure for explaining the distance between adjacent Mn and Mn (Mn-Mn) of organic-inorganic hybrid metal halides according to Experimental Examples 1-1 to 1-4 of the present application, and FIG. 39 is a figure for explaining the photoluminescence quantum yield (PLQY) of organic-inorganic hybrid metal halides according to Experimental Examples 1-3 and 1-4 of the present application.

[0334] FIGS. 37 to 39 can be summarized as shown in Table 2 below.

[0335] Table 2

[0336] Classification Experiment Examples 1-1(ex1-1) 1-2(ex1-2) 1-3(ex1-3) 1-4(ex1-4)

[0337] Mn-Mn(Å) 9.528 9.794 9.922 10.447

[0338] PLQY(%) 99.79 99.8 98.2 98.2

[0339] PL peak(λ em ) 511 514 516 515

[0340] FWHM(nm) 41 43 42 45

[0341]

[0342]

[0343] Referring to FIGS. 37 to 39 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.

[0344] 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.

[0345] In addition, referring to FIGS. 37 to 39 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.

[0346] 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.

[0347]

[0348] Preparation of organic-inorganic hybrid metal halide (ex2-1) according to Experimental Example 2-1

[0349] 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.

[0350] 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.

[0351] 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.

[0352] 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 (ex2-1) according to Experimental Example 2-1.

[0353]

[0354] Preparation of organic-inorganic hybrid metal halide (ex2-2) according to Experimental Example 2-2

[0355] In the above-described Experimental Example 2-1, an organic-inorganic hybrid metal halide (ex2-2) according to Experimental Example 2-2 was prepared by melting at 400 K.

[0356]

[0357] Preparation of organic-inorganic hybrid metal halide (ex2-3) according to Experimental Example 2-3

[0358] In the above-described Experimental Example 2-1, an organic-inorganic hybrid metal halide (ex2-3) according to Experimental Example 2-3 was prepared by melting at 700 K.

[0359]

[0360] Experimental Examples 2-1 to 2-3 described above can be summarized as shown in Table 3 below.

[0361] Table 3

[0362] Differential temperature

[0363] Experimental Example 2-1 (ex2-1) 300 K

[0364] Experimental Example 2-2 (ex2-2) 400 K

[0365] Experimental Example 2-3 (ex2-3) 500 K

[0366]

[0367] FIG. 40 is a diagram illustrating the band gap of organic-inorganic hybrid metal halides according to Experimental Examples 2-1 to 2-3 of the present application, FIG. 41 is a diagram illustrating the stability over time of organic-inorganic hybrid metal halides according to Experimental Examples 2-1 to 2-3 of the present application, FIG. 42 is a diagram illustrating the symmetry of organic-inorganic hybrid metal halides according to Experimental Examples 2-1 and 2-3 of the present application, and FIG. 43 is a diagram illustrating the disorder of organic-inorganic hybrid metal halides according to Experimental Examples 2-1 to 2-3 of the present application.

[0368] FIGS. 40 to 43 were derived from the simulation results of the present application.

[0369] Referring to Fig. 40, 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).

[0370] In addition, referring to Fig. 41, 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.

[0371] In addition, referring to Fig. 42, 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).

[0372] In addition, referring to Fig. 43, 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). In addition, 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).

[0373] Thus, the critical significance of a temperature of 400 K according to the above experimental example 2-2 (ex2-2) can be proven.

[0374]

[0375] 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 obtaining candidate molecular structures for a reference organic cation at site A and candidate organic cations similar to the reference organic cation from a database related to organic-inorganic hybrid metal halides represented by the following chemical formula; A step of representing the above candidate molecular structure as a string using a chemical language model; A step of converting the string into a vector using a vector transformation model learned through the chemical language model; A step of calculating the similarity between the reference organic cation and the candidate organic cation based on the vector using a distance matrix for quantifying molecular similarity; and A method for designing a novel organic-inorganic hybrid metal halide, comprising the step of filtering the above candidate organic cations to derive a novel organic cation. 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 novel method for designing organic-inorganic hybrid metal halides, comprising learning molecular features including the skeletal structure, electron density distribution, substituent effects, and steric hindrance of the molecule through the chemical language model above.

3. In Paragraph 1, The above distance metrics are, A novel organic-inorganic hybrid metal halide design method including cosine distance, Euclidean distance, and Tanimoto distance.

4. In Paragraph 1, A novel organic-inorganic hybrid metal halide design method comprising the organic cation at site A being located between the transition metal halide tetrahedra of the above chemical formula and separating the transition metals in the transition metal halide tetrahedra.

5. In Paragraph 1, A novel method for designing organic-inorganic hybrid metal halides, wherein the organic cation at the A site has a size and stereovolume that controls the distance between adjacent transition metals.

6. In Paragraph 5, A novel method for designing organic-inorganic hybrid metal halide, comprising deriving the size and stereovolume of the organic cation at site A such that the photoluminescence spectrum and photoluminescence quantum yield have maximum values ​​and the full width at half maximum has minimum values.

7. In Paragraph 5, The above chemical formula includes A2MnBr4, and A novel method for designing an organic-inorganic hybrid metal halide, comprising deriving the organic cation at the A site to have a size and stereovolume that control the distance between adjacent Mn and Mn to a range of greater than 9.582 Å and less than 10.447 Å.

8. In Paragraph 7, The above-mentioned reference organic cation is a tetraphenylphosphonium cation (PPh4 + Includes ), The novel organic cation mentioned above is a tetraphenylphosphonium cation (PPh4 + Cyclohexyltriphenylphosphonium cation (CHTP) in which one phenyl group of ) is substituted with cyclohexyl + A novel organic-inorganic hybrid metal halide design method including ).

9. In Paragraph 7, The above-mention referenced organic cation is the benzyltriphenylphosphonium cation (BzTP). + Includes ), The above novel organic cation is a benzyltriphenylphosphonium cation (BzTP). + 4-methylbenzyltriphenylphosphonium cation (4-MBz) with a para-methyl group added to the benzyl group of ) + A novel organic-inorganic hybrid metal halide design method including ).

10. In Paragraph 7, A novel method for designing organic-inorganic hybrid metal halides, comprising removing PP or P-Se bonds, hydrolysis-vulnerable groups, and molecules with excessive stereovolume through the above filtering, depending on synthesizability, stability, and crystallization compatibility.

11. A step of obtaining candidate molecular structures for a reference organic cation at site A and candidate organic cations similar to the reference organic cation from a database related to organic-inorganic hybrid metal halides represented by the following chemical formulas; A step of representing the above candidate molecular structure as a string using a chemical language model; A step of converting the string into a vector using a vector transformation model learned through the chemical language model; A step of calculating the similarity between the reference organic cation and the candidate organic cation based on the vector using a distance matrix for quantifying molecular similarity; A step of filtering the above candidate organic cations to derive a new organic cation; A step of synthesizing a single-crystal organic-inorganic hybrid metal halide by dissolving a substance containing the novel organic cation and a transition metal halide of the following chemical formula in a solvent; A step of forming a polycrystalline organic-inorganic hybrid metal halide by grinding the material containing the novel organic cation and the transition metal halide of the following chemical formula; and A novel method for manufacturing an organic-inorganic hybrid metal halide, comprising the step of heat-treating the single crystal or polycrystalline organic-inorganic hybrid metal halide above its melting point and then cooling it to form a glassy organic-inorganic hybrid metal halide. 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) 12. In Paragraph 11, The above chemical formula includes A2MnBr4, and The above-mentioned reference organic cation is a tetraphenylphosphonium cation (PPh4 + Includes ), The novel organic cation mentioned above is a tetraphenylphosphonium cation (PPh4 + Cyclohexyltriphenylphosphonium cation (CHTP) in which one phenyl group of ) is substituted with cyclohexyl + A novel method for manufacturing organic-inorganic hybrid metal halides designed to include ).

13. In Paragraph 12, The above-mention referenced organic cation is the benzyltriphenylphosphonium cation (BzTP). + Includes ), The above novel organic cation is a benzyltriphenylphosphonium cation (BzTP). + 4-methylbenzyltriphenylphosphonium cation (4-MBz) with a para-methyl group added to the benzyl group of ) + A novel method for manufacturing organic-inorganic hybrid metal halides designed to include ).

14. In Paragraph 13, A method for manufacturing a designed novel organic-inorganic hybrid metal halide, comprising the novel organic cation having a size and stereovolume that controls the distance between adjacent Mn and Mn to a range of greater than 9.582 Å and less than 10.447 Å.

15. A step of providing an organic-inorganic hybrid metal halide represented by the following chemical formula to a 3D printing device and printing it as an organic-inorganic hybrid metal halide 3D printed structure; A step of rapidly cooling the outputted organic-inorganic hybrid metal halide 3D printed structure; and A method for manufacturing an organic-inorganic hybrid metal halide 3D structure, comprising the step of post-treating the rapidly cooled organic-inorganic hybrid metal halide 3D printed structure with a solvent. 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) 16. In Paragraph 15, The above organic-inorganic hybrid metal halide is injected into the 3D printing device in the form of a filament mixed with a binder, and the rapidly cooled organic-inorganic hybrid metal halide 3D printed structure is immersed in the solvent so that the binder dissolves. A method for manufacturing an organic-inorganic hybrid metal halide 3D structure, comprising: the organic-inorganic hybrid metal halide injected in the form of a filament is polycrystalline; the organic-inorganic hybrid metal halide 3D printed structure is rapidly cooled to convert the polycrystalline state into a glassy state; the structure is immersed in a solvent to dissolve the binder in the organic-inorganic hybrid metal halide 3D printed structure; and the glassy state is reversibly converted back into a polycrystalline state.

17. In Paragraph 16, A method for manufacturing an organic-inorganic hybrid metal halide 3D structure, wherein the binder comprises having a higher ratio per volume on the inner side than on the surface of the organic-inorganic hybrid metal halide 3D printed structure.

18. In Paragraph 15, The above organic-inorganic hybrid metal halide is injected into the 3D printing device in powder form, and the solvent is provided to the rapidly cooled organic-inorganic hybrid metal halide 3D printed structure. A method for manufacturing an organic-inorganic hybrid metal halide 3D structure, comprising: the organic-inorganic hybrid metal halide injected in powder form is polycrystalline; the organic-inorganic hybrid metal halide 3D printed structure is rapidly cooled to convert the polycrystalline state into a glassy state; and the solvent is provided to reversibly convert the glassy state of the organic-inorganic hybrid metal halide 3D printed structure back into a polycrystalline state.

19. In Paragraph 16, A method for manufacturing a three-dimensional structure of an organic-inorganic hybrid metal halide, wherein the binder comprises having extrudability at the melting point of the organic-inorganic hybrid metal halide.

20. In Paragraph 16, The above binder comprises at least one selected from the group of thermoplastic polymers including polylactic acid and polyethylene terephthalate glycol, and A method for manufacturing a three-dimensional organic-inorganic hybrid metal halide structure, wherein the solvent comprises any one selected from the group of solvents including dichloromethane.

Images