Organic-inorganic hybrid metal halide glass and manufacturing method thereof

Abstract

Provided is a method of preparing an organic-inorganic hybrid metal halide glass, the method including: preparing a glass source by pulverizing an organic cationic material of the potion A in the following chemical formula and transition metal halides of the potions M and X in the following chemical formula; and preparing an organic-inorganic hybrid metal halide glass by heat-treating the glass source at the melting point or higher and then cooling same. Chemical Formula 1 AmMnXm+2n (wherein, 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

Organic-inorganic hybrid metal halide glass and its manufacturing method

[0001] The present application relates to organic-inorganic hybrid metal halide glass and a method for manufacturing the same, and more specifically, to organic-inorganic hybrid metal halide glass and a method for manufacturing the same, which has maximized processability and excellent luminescence properties through a reversible conversion of polycrystalline and glassy states.

[0002]

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

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

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

[0006] However, conventional non-lead hybrid halides have limitations in nanoscale synthesis and patterning, and their application in precision fabrication and high-performance devices may be restricted due to limitations such as reduced crystallinity and increased surface defects. In particular, it may be difficult to achieve light efficiency, structural stability, and heat treatability 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 this application aims to solve is to provide an organic-inorganic hybrid metal halide glass that maximizes processability through a transition from a crystalline state to a glassy state, solves the problem of previously being practically non-planar structures, i.e., impossible to process curved surfaces, and enables melt-based 3D printing.

[0010] Another technical problem that this application aims to solve is to provide an organic-inorganic hybrid metal halide glass having excellent photoluminescence spectrum, full width at half maximum, and photoluminescence quantum yield characteristics, and a method for manufacturing the same.

[0011] The technical problems that this application aims to solve are not limited to those described above.

[0012]

[0013] To solve the above technical problem, the present application provides a method for manufacturing organic-inorganic hybrid metal halide glass.

[0014] According to one embodiment, the method for manufacturing an organic-inorganic hybrid metal halide glass may include the steps of: grinding an organic cationic substance at the A position in the following chemical formula and a transition metal halide at the M and X positions in the following chemical formula to produce a glass source; and heat-treating the glass source above its melting point and then cooling it to produce an organic-inorganic hybrid metal halide glass.

[0015] Chemical formula

[0016] A m M n X m+2n

[0017] (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)

[0018] According to one embodiment, the chemical formula comprises A2MnBr4, and the organic cation at the A site is a cyclohexyltriphenylphosphonium cation (CHTP). + , C24 C 26 P + ) and 4-methylbenzyltriphenylphosphonium cation (4-MBz + , C 26 C 24 P + It comprises any one selected from the group of organic cations including ), and the organic cation at site A is a manganese bromide anion (MnBr4 2- It is located between the tetrahedrons and can isolate the Mn center.

[0019] According to one embodiment, the organic cation at the A site controls the distance between adjacent Mn and Mn according to size and stereovolume, and depending on the distance between Mn and Mn, the photoluminescence spectrum, full width at half maximum, and photoluminescence quantum yield can be controlled.

[0020] According to one embodiment, the organic cation at the A site controls the distance between adjacent Mn and Mn to a range greater than 9.582 Å and less than 10.447 Å, and within the range, the photoluminescence spectrum and photoluminescence quantum yield may have a maximum value, and the full width at half maximum may have a minimum value.

[0021] According to one embodiment, the polycrystalline and glassy states can be reversibly converted through the distance between the adjacent Mn and Mn.

[0022] According to one embodiment, the cyclohexyltriphenylphosphonium cation (CHTP) at the A site + ) is a tetraphenylphosphonium cation (PPh4 + It includes one phenyl group of which is substituted with cyclohexyl, and the 4-methylbenzyltriphenylphosphonium cation (4-MBz) at the A site. + ) is a benzyltriphenylphosphonium cation (BzTP + It may be that a para-methyl group has been added to the benzyl group of ).

[0023] According to one embodiment, the glass source can be rapidly cooled after the heat treatment.

[0024] According to one embodiment, the glass source is polycrystalline, and after the heat treatment, the organic-inorganic hybrid metal halide glass may be in a glass state.

[0025] According to one embodiment, the melting point may be greater than 200°C and less than 300°C.

[0026]

[0027] To solve the above technical problem, the present application provides an organic-inorganic hybrid metal halide glass.

[0028] According to one embodiment, the organic-inorganic hybrid metal halide glass reversibly changes between a polycrystalline and glassy state and can be represented by the following chemical formula.

[0029] Chemical formula

[0030] A2MX4

[0031] (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, and X is at least one selected from the group of halogens including F, Cl, Br, and I)

[0032] According to one embodiment, the chemical formula comprises A2MnBr4, and the organic cation at the A site is a cyclohexyltriphenylphosphonium cation (CHTP). + , C 24 C 26 P + ) and 4-methylbenzyltriphenylphosphonium cation (4-MBz + , C26 C 24 P + It comprises any one selected from the group of organic cations including ), and the organic cation at site A is a manganese bromide anion (MnBr4 2- It is located between the tetrahedrons and can isolate the Mn center.

[0033] According to one embodiment, the organic cation at the A site controls the distance between adjacent Mn and Mn according to size and stereovolume, and controls the photoluminescence spectrum, full width at half maximum, and photoluminescence quantum yield according to the distance between Mn and Mn, wherein the organic cation at the A site controls the distance between adjacent Mn and Mn to a range greater than 9.582 Å and less than 10.447 Å, and in the range, the photoluminescence spectrum and photoluminescence quantum yield may have a maximum value and the full width at half maximum may have a minimum value.

[0034] According to one embodiment, the polycrystalline and glassy states can be reversibly converted through the distance between the adjacent Mn and Mn.

[0035] According to one embodiment, the cyclohexyltriphenylphosphonium cation (CHTP) at the A site + ) is a tetraphenylphosphonium cation (PPh4 + It includes one phenyl group of which is substituted with cyclohexyl, and the 4-methylbenzyltriphenylphosphonium cation (4-MBz) at the A site. + ) is a benzyltriphenylphosphonium cation (BzTP + A para-methyl group can be added to the benzyl group of ).

[0036]

[0037] According to an embodiment of the present application, a method for manufacturing an organic-inorganic hybrid metal halide glass may be provided, comprising the steps of: grinding an organic cationic substance at the A position in the following chemical formula and a transition metal halide at the M and X positions in the following chemical formula to produce a glass source; and heat-treating the glass source above its melting point and then cooling it to produce an organic-inorganic hybrid metal halide glass.

[0038] Chemical formula

[0039] A m M n X m+2n

[0040] (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)

[0041] According to the method for manufacturing organic-inorganic hybrid metal halide glass according to an embodiment of the present application, the organic-inorganic hybrid metal halide glass in which the polycrystalline and glassy states are reversibly converted through the distance between adjacent transition metals can be provided.

[0042] According to the organic-inorganic hybrid metal halide glass of the embodiment of the present application, not only can processability be maximized through the conversion from a crystalline state to a glass state, but the problem of being unable to process curved surfaces, i.e., having a substantially non-planar structure, can also be resolved. Furthermore, the organic-inorganic hybrid metal halide glass can enable melt-based 3D printing.

[0043] In addition, according to an embodiment of the present application, the organic-inorganic hybrid metal halide glass can be applied as a color conversion layer of an organic light-emitting diode (LED). Specifically, the organic-inorganic hybrid metal halide glass can be applied to a display by emitting green light using a blue or white backlight as an excitation source.

[0044] In addition, according to an embodiment of the present application, the organic-inorganic hybrid metal halide glass can be printed through a 3D printer to be manufactured into a 3D structure, and due to its green light-emitting properties, it can be applied as an ornament.

[0045]

[0046] FIG. 1 is a drawing illustrating a method for manufacturing organic-inorganic hybrid metal halide glass according to an embodiment of the present application.

[0047] FIG. 2 is a drawing for explaining in more detail a method for manufacturing organic-inorganic hybrid metal halide glass according to an embodiment of the present application.

[0048] FIG. 3 is a diagram illustrating an organic cation material at the A site according to an embodiment of the present application.

[0049] FIG. 4 is a drawing for explaining an organic-inorganic hybrid metal halide according to an embodiment of the present application.

[0050] FIG. 5 is a diagram illustrating the optimization of the distance between anions by an organic cation derived from an organic-inorganic hybrid metal halide according to an embodiment of the present application.

[0051] FIG. 6 is a diagram illustrating the control of the distance between anions by an organic cation derived according to one embodiment of the present application.

[0052] Figure 7 is a diagram illustrating the distance between anions when the size of the organic cation is small or large according to a comparative example.

[0053] FIG. 8 is a diagram illustrating the melting point according to the composition in the experimental example of the present application.

[0054] Figure 9 is a photograph showing whether glass is formed according to the composition in the experimental example of the present application.

[0055] Figure 10 is the result of analyzing the transmittance according to the composition in the experimental example of the present application.

[0056] FIG. 11 is a photograph of an organic-inorganic hybrid metal halide glass manufactured according to an experimental example of the present application.

[0057] Figure 12 shows the results of X-ray diffraction (XRD) analysis of organic-inorganic hybrid metal halide glass prepared according to the experimental example of the present application.

[0058] Figure 13 is the result of ultraviolet-visible spectroscopy (UV-vis spectroscopy) of organic-inorganic hybrid metal halide glass prepared according to the experimental example of the present application.

[0059] Figure 14 shows the photoluminescence (PL) measurement results of organic-inorganic hybrid metal halide glass prepared according to the experimental example of the present application.

[0060] Figure 15 shows the thermogravimetric differential scanning thermal analysis (TG-DSC) measurement results of organic-inorganic hybrid metal halide glass prepared according to the experimental example of the present application.

[0061] FIG. 16 is a diagram illustrating the distance between adjacent Mn and Mn (Mn-Mn), photoluminescence quantum yield (PLQY), photoluminescence spectrum (PL peak), and full width at half maximum (FWHM) of organic-inorganic hybrid metal halide glasses according to Experimental Examples 1-1 to 1-4 of the present application.

[0062] FIG. 17 is a diagram illustrating the distance (Mn-Mn) between adjacent Mn and Mn of organic-inorganic hybrid metal halide glass according to Experimental Examples 1-1 to 1-4 of the present application.

[0063] FIG. 18 is a diagram illustrating the photoluminescence quantum yield (PLQY) of organic-inorganic hybrid metal halide glass according to Experimental Examples 1-3 and 1-4 of the present application.

[0064] FIG. 19 is a diagram illustrating the band gap of organic-inorganic hybrid metal halide glass according to Experimental Examples 2-1 to 2-3 of the present application.

[0065] FIG. 20 is a drawing illustrating the stability over time of organic-inorganic hybrid metal halide glass according to Experimental Examples 2-1 to 2-3 of the present application.

[0066] FIG. 21 is a drawing illustrating the symmetry of organic-inorganic hybrid metal halide glass according to Experimental Example 2-1 and Experimental Example 2-3 of the present application.

[0067] FIG. 22 is a drawing for explaining the degree of disorder of organic-inorganic hybrid metal halide glass according to Experimental Examples 2-1 to 2-3 of the present application.

[0068]

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075]

[0076] FIG. 1 is a drawing for explaining a method for manufacturing organic-inorganic hybrid metal halide glass according to an embodiment of the present application, FIG. 2 is a drawing for explaining a method for manufacturing organic-inorganic hybrid metal halide glass according to an embodiment of the present application in more detail, FIG. 3 is a drawing for explaining an organic cation material at the A site according to an embodiment of the present application, FIG. 4 is a drawing for explaining an organic-inorganic hybrid metal halide according to an embodiment of the present application, FIG. 5 is a drawing for explaining the optimization of the distance between anions by an organic cation derived from an organic-inorganic hybrid metal halide according to an embodiment of the present application, FIG. 6 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, and FIG. 7 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.

[0077] Referring to FIGS. 1, 2, and 3, an organic cationic substance (11) at the A site and a transition metal halide (12) at the M and X sites in the following chemical formula can be crushed to produce a glass source (32) (S110). Specifically, for example, the transition metal halide (12) may be manganese(IV) bromide (MnBr4).

[0078] Chemical formula

[0079] A m M n X m+2n

[0080] 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.

[0081] Alternatively, the organic cation material (11) at the A position in the above chemical formula may be at least one of the materials shown in FIG. 3.

[0082] 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.

[0083] 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.

[0084] Referring to FIGS. 4 and 5, 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.

[0085] According to an embodiment of the present application, the size and stereovolume of the organic cation (11) at the A site can be derived such that the organic-inorganic hybrid metal halide (10) represented by the chemical formula has a maximum value for the photoluminescence spectrum and photoluminescence quantum yield, and a minimum value for the full width at half maximum. Specifically, for example, referring to FIG. 6, 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.

[0086] Accordingly, the organic-inorganic hybrid metal halide (10) represented by the above chemical formula may have a maximum value for the photoluminescence spectrum and photoluminescence quantum yield, and a minimum value for the full width at half maximum.

[0087] Unlike the embodiment of the present application, as shown in FIG. 7(a), if the size of the organic cation (11) at site A is excessively small, the distance between adjacent transition metals is shortened, and a non-radiative energy transfer path can be activated.

[0088] Accordingly, the luminescence characteristics and luminescence efficiency of organic-inorganic hybrid metal halides may be reduced.

[0089] On the other hand, as shown in FIG. 7(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.

[0090] Accordingly, the luminescence characteristics and luminescence efficiency of organic-inorganic hybrid metal halides may be reduced.

[0091] However, according to an embodiment of the present application, the organic cation (11) at the A site can be derived to have a size and stereovolume that control the distance between adjacent transition metals, namely adjacent Mn and Mn, to a range of greater than 9.582 Å and less than 10.447 Å, and as a result, the organic-inorganic hybrid metal halide (10) represented by the chemical formula can have a maximum value for the photoluminescence spectrum and photoluminescence quantum yield, and a minimum value for the full width at half maximum.

[0092] Referring further to FIGS. 1 and FIGS. 2, the glass source (32) is heat-treated above its melting point and then cooled to produce an organic-inorganic hybrid metal halide glass (41) (S120).

[0093] According to one embodiment, the heat treatment of the glass source (32) can be performed in an inert gas atmosphere.

[0094] Accordingly, the influence of oxygen and / or moisture in the atmosphere is minimized during the melting process of the polycrystalline glass source (32), thereby minimizing the oxidation and / or thermal decomposition reactions of the organic-inorganic hybrid metal halide glass (41) being manufactured. In addition, the generation of unnecessary by-products is minimized during the melting process of the polycrystalline glass source (32), so that the organic-inorganic hybrid metal halide glass (41) being manufactured can be formed uniformly and with high purity. Furthermore, the loss of optical performance of the organic-inorganic hybrid metal halide glass (41) in a glass state after heat treatment can be minimized.

[0095] According to one embodiment, the polycrystalline glass source (32) can be rapidly cooled after the heat treatment.

[0096] As a result, there may be insufficient time for atoms in the polycrystalline glass source (32) to form a regular arrangement. Accordingly, the conversion from the polycrystalline, i.e., the crystalline state to the glass state may be easy.

[0097] That is, according to an embodiment of the present application, the polycrystalline glass source (32) can be converted into a liquid state through the heat treatment and into a glass-state organic-inorganic hybrid metal halide glass (41) through the rapid cooling. The glass-state organic-inorganic hybrid metal halide glass (41) is more disordered than the crystalline state but can maintain a solid state.

[0098] As a result, according to an embodiment of the present application, three-dimensional printing based on melting may be possible.

[0099] 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.

[0100] In other words, according to an embodiment of the present application, the above formula A m M n X m+2n In the organic-inorganic hybrid metal halide glass (41) described above, as the distance between adjacent transition metals is optimized by the organic cation material (11), the polycrystalline and glassy states can be reversibly converted through the distance between adjacent transition metals in the substantially manufactured organic-inorganic hybrid metal halide glass (41).

[0101] As a result, according to the embodiments 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 a substantially non-planar structure, i.e., a curved surface, can be resolved, and melt-based 3D printing can be made possible.

[0102]

[0103] According to the method for manufacturing organic-inorganic hybrid metal halide glass designed according to the embodiments of the present application described above, the organic-inorganic hybrid metal halide glass (41) in which the polycrystalline and glassy states are reversibly converted through the distance between adjacent transition metals can be provided.

[0104] According to the organic-inorganic hybrid metal halide glass (41) of the embodiment of the present application, not only can processability be maximized through the conversion from a crystalline state to a glass state, but the problem of being unable to process a curved surface, i.e., a substantially non-planar structure, can also be resolved. Furthermore, the organic-inorganic hybrid metal halide glass (41) can enable melt-based 3D printing.

[0105]

[0106] Specific experimental examples and characteristic evaluation results according to the embodiments of the present application are described below.

[0107]

[0108] Manufacturing of organic-inorganic hybrid metal halide glass according to experimental example

[0109] Using the organic cationic material at site A shown in Fig. 3, an organic-inorganic hybrid metal halide glass according to the experimental example was prepared, the melting point was confirmed for each composition, and an experiment was conducted to determine whether glass is formed upon rapid cooling.

[0110]

[0111] FIG. 8 is a diagram illustrating the melting point according to the composition in an experimental example of the present application, and FIG. 9 is a photograph showing whether glass is formed according to the composition in an experimental example of the present application.

[0112] Referring to FIGS. 8 and 9, when an organic-inorganic hybrid metal halide glass is manufactured using the organic cationic material at the A site shown in FIG. 3 according to the experimental example of the present application, it can be seen that the melting point is around 200°C and the glass is mostly transparent.

[0113]

[0114] Figure 10 is the result of analyzing the transmittance according to the composition in the experimental example of the present application.

[0115] Referring to FIG. 10, it can be seen that an organic-inorganic hybrid metal halide glass prepared using the organic cation material at the A site shown in FIG. 3 according to an experimental example of the present application has an excellent transmittance of at least 85%.

[0116]

[0117] Manufacturing of organic-inorganic hybrid metal halide glass according to experimental example

[0118] The glass source was prepared by mixing and grinding 1 mmol of (CHTP)Br and 1 mmol of MnBr2, which are organic cation-containing substances, in a mortar with an agate pestle for 5 minutes while adding 0.5 mL of anhydrous ethanol.

[0119] The above glass source was heat-treated at 260°C for 10 minutes in a glove box under an argon atmosphere, and then air-cooled to produce an organic-inorganic hybrid metal halide glass according to the experimental example.

[0120]

[0121] FIG. 11 is a photograph of an organic-inorganic hybrid metal halide glass manufactured according to an experimental example of the present application.

[0122] Referring to FIG. 11, it can be seen that the organic-inorganic hybrid metal halide glass prepared according to the experimental example of the present application emits green light when irradiated with ultraviolet light of 365 nm.

[0123]

[0124] Figure 12 shows the results of X-ray diffraction (XRD) analysis of organic-inorganic hybrid metal halide glass prepared according to the experimental example of the present application.

[0125] Referring to FIG. 12, it can be seen that the organic-inorganic hybrid metal halide glass prepared according to the experimental example of the present application is a single phase of a polycrystalline material and has an amorphous structure which is a characteristic of glass material.

[0126]

[0127] Figure 13 shows the results of ultraviolet-visible spectroscopy (UV-vis spectroscopy) of organic-inorganic hybrid metal halide glass prepared according to the experimental example of the present application.

[0128] Referring to FIG. 13, it can be seen that the organic-inorganic hybrid metal halide glass manufactured according to the experimental example of the present application has transmittance in the 200 to 800 nm range.

[0129]

[0130] Figure 14 shows the photoluminescence (PL) measurement results of organic-inorganic hybrid metal halide glass prepared according to the experimental example of the present application.

[0131] Referring to FIG. 14, it can be seen that the organic-inorganic hybrid metal halide glass prepared according to the experimental example of the present application has a higher emission peak than polycrystal in the 500 to 700 nm region.

[0132]

[0133] Figure 15 shows the thermogravimetric differential scanning thermal analysis (TG-DSC) measurement results of organic-inorganic hybrid metal halide glass prepared according to the experimental example of the present application.

[0134] Referring to FIG. 15, it can be seen that the organic-inorganic hybrid metal halide glass prepared according to the experimental example of the present application melts at 206.8 °C.

[0135]

[0136] Preparation of organic-inorganic hybrid metal halide glass (ex1-1) according to Experimental Example 1-1

[0137] In the experimental example described above, 1 mmol of (PPh4)Br and 1 mmol of MnBr2 were mixed as organic cation-containing materials to prepare an organic-inorganic hybrid metal halide glass (ex1-1) according to Experimental Example 1-1.

[0138]

[0139] Preparation of organic-inorganic hybrid metal halide glass (ex1-2) according to Experimental Example 1-2

[0140] In the experimental example described above, 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 glass (ex1-2) according to experimental example 1-2.

[0141]

[0142] Preparation of organic-inorganic hybrid metal halide glass (ex1-3) according to Experimental Example 1-3

[0143] In the same manner as the experimental example described above, an organic-inorganic hybrid metal halide glass (ex1-3) according to experimental example 1-3 was prepared.

[0144]

[0145] Preparation of organic-inorganic hybrid metal halide glass (ex1-4) according to Experimental Example 1-4

[0146] In the experimental example described above, 1 mmol of (4-MBz)Br and 1 mmol of MnBr were mixed with the novel organic cation derived above to prepare an organic-inorganic hybrid metal halide glass (ex1-4) according to experimental example 1-4.

[0147]

[0148] Experimental Examples 1-1 to 1-4 described above can be summarized as shown in Table 1 below.

[0149]

[0150] Classification: Organic Cations

[0151] Experimental Example 1-1 (ex1-1) Tetraphenylphosphonium (PPh4)

[0152] Experimental Example 1-2 (ex1-2) Benzyltriphenylphosphonium (BzTP)

[0153] Experimental Example 1-3 (ex1-3) Cyclohexyltriphenylphosphonium (CHTP)

[0154] Experimental Example 1-4 (ex1-4) 4-methylbenzyltriphenylphosphonium (4-MBz)

[0155]

[0156] FIG. 16 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 halide glass according to Experimental Examples 1-1 to 1-4 of the present application, FIG. 17 is a figure for explaining the distance between adjacent Mn and Mn (Mn-Mn) of organic-inorganic hybrid metal halide glass according to Experimental Examples 1-1 to 1-4 of the present application, and FIG. 18 is a figure for explaining the photoluminescence quantum yield (PLQY) of organic-inorganic hybrid metal halide glass according to Experimental Examples 1-3 and 1-4 of the present application.

[0157] Figures 16 to 18 can be summarized as shown in Table 2 below.

[0158] Table 2

[0159] Classification Experiment Examples 1-1(ex1-1) 1-2(ex1-2) 1-3(ex1-3) 1-4(ex1-4)

[0160] Mn-Mn(Å) 9.528 9.794 9.922 10.447

[0161] PLQY(%) 99.79 99.8 98.2 98.2

[0162] PL peak(λ em ) 511 514 516 515

[0163] FWHM(nm) 41 43 42 45

[0164]

[0165] Referring to FIGS. 16 to 18 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.

[0166] 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.

[0167] In addition, referring to FIGS. 16 to 18 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.

[0168] 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.

[0169]

[0170] Preparation of organic-inorganic hybrid metal halide glass (ex2-1) according to Experimental Example 2-1

[0171] 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.

[0172] 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.

[0173] 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.

[0174] The opening of the second vial was sealed, and antisolvent vapor diffusion was performed at room temperature (25 ℃) for 24 hours to produce a glass source.

[0175] The above glass source was filled into a mold prepared according to the above experimental example, and after heat treatment at 260°C for 1 hour in a quartz furnace under a vacuum and argon atmosphere, air-cooled to produce an organic-inorganic hybrid metal halide glass (ex2-1) according to experimental example 2-1.

[0176]

[0177] Preparation of organic-inorganic hybrid metal halide glass (ex2-2) according to Experimental Example 2-2

[0178] In the above-described Experimental Example 2-1, an organic-inorganic hybrid metal halide glass (ex2-2) according to Experimental Example 2-2 was prepared by melting at 400 K.

[0179]

[0180] Preparation of organic-inorganic hybrid metal halide glass (ex2-3) according to Experimental Example 2-3

[0181] In the above-described Experimental Example 2-1, an organic-inorganic hybrid metal halide glass (ex2-3) according to Experimental Example 2-3 was prepared by melting at 700 K.

[0182]

[0183] Experimental Examples 2-1 to 2-3 described above can be summarized as shown in Table 3 below.

[0184] Table 3

[0185] Differential temperature

[0186] Experimental Example 2-1 (ex2-1) 300 K

[0187] Experimental Example 2-2 (ex2-2) 400 K

[0188] Experimental Example 2-3 (ex2-3) 500 K

[0189]

[0190] FIG. 19 is a diagram illustrating the bandgap of organic-inorganic hybrid metal halide glass according to Experimental Examples 2-1 to 2-3 of the present application, FIG. 20 is a diagram illustrating the stability over time of organic-inorganic hybrid metal halide glass according to Experimental Examples 2-1 to 2-3 of the present application, FIG. 21 is a diagram illustrating the symmetry of organic-inorganic hybrid metal halide glass according to Experimental Examples 2-1 and 2-3 of the present application, and FIG. 22 is a diagram illustrating the disorder of organic-inorganic hybrid metal halide glass according to Experimental Examples 2-1 to 2-3 of the present application.

[0191] FIGS. 19 to 22 were derived from the simulation results of the present application.

[0192] Referring to Fig. 19, 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).

[0193] In addition, referring to FIG. 20, 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.

[0194] In addition, referring to Fig. 21, 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).

[0195] Additionally, referring to Fig. 22, it can be seen that the peak increased when the temperature was increased from 300 K to 400 K according to Experimental Example 2-1 (ex2-1) and Experimental Example 2-2 (ex2-2). Furthermore, it can be seen that the peak was highest when the temperature was 400 K according to Experimental Example 2-2 (ex2-2). On the other hand, it can be seen that the peak actually decreased when the temperature was increased to 700 K according to Experimental Example 2-3 (ex2-3), exceeding Experimental Example 2-2 (ex2-2).

[0196] Thus, the critical significance of a temperature of 400 K according to the above experimental example 2-2 (ex2-2) can be proven.

[0197]

[0198] Although the present application has been described in detail using preferred embodiments, the scope of the present application is not limited to specific embodiments and should be interpreted by the appended claims. Furthermore, those skilled in the art will understand that many modifications and variations are possible without departing from the scope of the present application.

Claims

1. A step of preparing a glass source by grinding an organic cation substance at the A site in the following chemical formula and a transition metal halide at the M and X sites in the following chemical formula; and A method for manufacturing organic-inorganic hybrid metal halide glass, comprising the step of heat-treating the glass source above its melting point and then cooling it to produce an organic-inorganic hybrid metal halide glass. 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, The above chemical formula includes A2MnBr4, and The organic cation at site A above is a cyclohexyltriphenylphosphonium cation (CHTP + ) and 4-methylbenzyltriphenylphosphonium cation (4-MBz + It comprises any one selected from the group of organic cations including ), The organic cation at site A above is a manganese bromide anion (MnBr4 2- A method for manufacturing organic-inorganic hybrid metal halide glass, comprising isolating Mn centers located between tetrahedrons.

3. In Paragraph 2, The organic cation at the above A site controls the distance between adjacent Mn and Mn depending on its size and stereovolume, and A method for manufacturing organic-inorganic hybrid metal halide glass, comprising controlling the photoluminescence spectrum, full width at half maximum, and photoluminescence quantum yield according to the distance between the above Mn and Mn.

4. In Paragraph 3, The organic cation at the above A site controls the distance between adjacent Mn and Mn to a range greater than 9.582 Å and less than 10.447 Å, and A method for manufacturing organic-inorganic hybrid metal halide glass, comprising having a maximum value for the photoluminescence spectrum and photoluminescence quantum yield, and a minimum value for the full width at half maximum within the above range.

5. In Paragraph 4, A method for manufacturing organic-inorganic hybrid metal halide glass, comprising reversibly converting between polycrystalline and glassy states through the distance between adjacent Mn and Mn.

6. In Paragraph 2, The cyclohexyltriphenylphosphonium cation (CHTP) at the above A site + ) is a tetraphenylphosphonium cation (PPh4 + It includes one phenyl group of which is substituted with cyclohexyl, and The 4-methylbenzyltriphenylphosphonium cation (4-MBz) at the above A site + ) is a benzyltriphenylphosphonium cation (BzTP + A method for manufacturing organic-inorganic hybrid metal halide glass comprising adding a para-methyl group to the benzyl group of ).

7. In Paragraph 1, A method for manufacturing organic-inorganic hybrid metal halide glass, wherein the above-mentioned glass source is rapidly cooled after the above-mentioned heat treatment.

8. In Paragraph 2, A method for manufacturing organic-inorganic hybrid metal halide glass, wherein the above glass source is polycrystalline and rapidly cooled after the above heat treatment, so that the organic-inorganic hybrid metal halide glass is in a glass state.

9. In Paragraph 1, A method for manufacturing organic-inorganic hybrid metal halide glass, wherein the melting point is greater than 200°C and less than 300°C.

10. An organic-inorganic hybrid metal halide glass that reversibly converts between polycrystalline and glassy states and is represented by the following chemical formula. Chemical formula A2MX4 (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, and X is at least one selected from the group of halogens including F, Cl, Br, and I) 11. In Paragraph 10, The above chemical formula includes A2MnBr4, and The organic cation at site A above is a cyclohexyltriphenylphosphonium cation (CHTP + ) and 4-methylbenzyltriphenylphosphonium cation (4-MBz + It comprises any one selected from the group of organic cations including ), The organic cation at site A above is a manganese bromide anion (MnBr4 2- Organic-inorganic hybrid metal halide glass comprising isolating Mn centers located between tetrahedrons.

12. In Paragraph 11, The organic cation at the above A site controls the distance between adjacent Mn and Mn depending on its size and stereovolume, and The photoluminescence spectrum, full width at half maximum, and photoluminescence quantum yield are controlled according to the distance between the above Mn and Mn, wherein The organic cation at the above A site controls the distance between adjacent Mn and Mn to a range greater than 9.582 Å and less than 10.447 Å, and Organic-inorganic hybrid metal halide glass comprising, within the above range, having a maximum value for the photoluminescence spectrum and photoluminescence quantum yield, and a minimum value for the full width at half maximum.

13. In Paragraph 12, Organic-inorganic hybrid metal halide glass comprising a polycrystalline and glassy state that is reversibly converted through the distance between the adjacent Mn and Mn.

14. In Paragraph 11, The cyclohexyltriphenylphosphonium cation (CHTP) at the above A site + ) is a tetraphenylphosphonium cation (PPh4 + It includes one phenyl group of which is substituted with cyclohexyl, and The 4-methylbenzyltriphenylphosphonium cation (4-MBz) at the above A site + ) is a benzyltriphenylphosphonium cation (BzTP + Organic-inorganic hybrid metal halide glass comprising a para-methyl group added to the benzyl group of ).

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