KR20210141064A - Method for manufacturing fillar-type perovskite - Google Patents

Abstract

The present specification relates to a method for manufacturing column-shaped perovskite, column-shaped perovskite manufactured thereby, an optical film including the column-shaped perovskite, a scintillator using the same, and an X-ray detector, wherein the method includes the steps of: coating a substrate with a first solution including an organic halide or an inorganic halide and a metal halide; forming particles by heat-treating the coated substrate at 50 to 150 deg. C; and forming column-shaped perovskite by bringing the formed particles in contact with a second solution including an organic halide, an inorganic halide, or a mixture thereof at 50 to 150 deg. C.

Description

Manufacturing method of columnar perovskite {METHOD FOR MANUFACTURING FILLAR-TYPE PEROVSKITE}

The present specification relates to a method for manufacturing columnar perovskite.

Recently, an X-ray detector such as a Flat Panel X-ray Detector (FPXD) has been developed and is widely used in medical and industrial fields.

The X-ray detector outputs an X-ray image captured by X-rays or an X-ray fluoroscopic image as a digital signal. Such an X-ray detector is divided into a direct method (direct conversion method) and an indirect method (indirect conversion method).

In the direct method, a photoconductor (photoconductor) converts X-rays directly into electric charges, and in the indirect method, a scintillator (scintillator) converts X-rays into visible light, and then converts the converted visible light into photoelectric conversion such as a photodiode. It is a method of converting into electric charge through the device.

Conventional scintillators apply CsI:TI due to their excellent X-ray-visible light conversion efficiency and decay time. have.

Therefore, it is necessary to study materials and processes that can increase production efficiency while having the same X-ray-visible light conversion efficiency and decay time.

Korean Patent Application Publication No. 2017-0051463

The present specification provides a method for manufacturing a columnar perovskite, a columnar perovskite manufactured by the manufacturing method, an optical film including the columnar perovskite, a scintillator including the optical film, and the It provides an X-ray detector comprising.

An exemplary embodiment of the present specification is an organic halide or an inorganic halide on a substrate; and coating a first solution containing a metal halide;

forming particles by heat-treating the coated substrate at 50° C. to 150° C.; and

Columnar perovskite comprising the step of contacting the formed particles with a second solution containing an organic halide, an inorganic halide or a mixture thereof at 50°C to 150°C to form a columnar perovskite It provides a manufacturing method of

Another embodiment of the present specification provides a columnar perovskite manufactured by the above manufacturing method.

Another exemplary embodiment of the present specification provides an optical film comprising the columnar perovskite.

Another embodiment of the present specification is a substrate; And it provides an optical film comprising a plurality of perovskite in the form of a column provided on the substrate.

Another exemplary embodiment of the present specification provides a scintillator including the optical film.

Another exemplary embodiment of the present specification includes an X-ray detector including the scintillator.

The manufacturing method of columnar perovskite according to an exemplary embodiment of the present specification is possible at low temperature and atmospheric pressure. Accordingly, there is an effect that the production efficiency is improved.

The scintillator to which the columnar perovskite manufactured according to an exemplary embodiment of the present specification is applied exhibits high resolution and high sensitivity.

1 is a diagram illustrating scattering characteristics of visible light according to the shape of a material applied to a scintillator.
2 is a view showing the SEM measurement results of the perovskite prepared in Example 1.
3 is a view showing the SEM measurement results of the perovskite of Comparative Example 1.

Hereinafter, the present specification will be described in detail.

In the present specification, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

In the present specification, when a member is said to be located "on" another member, this includes not only a case in which a member is in contact with another member but also a case in which another member exists between the two members.

An exemplary embodiment of the present specification is an organic halide or an inorganic halide on a substrate; and coating a first solution containing a metal halide;

forming particles by heat-treating the coated substrate at 50° C. to 150° C.; and

Columnar perovskite comprising the step of contacting the formed particles with a second solution containing an organic halide, an inorganic halide or a mixture thereof at 50°C to 150°C to form a columnar perovskite It provides a manufacturing method of

Perovskite is attracting attention as a material applied to scintillators because of its fast decay time and high X-ray-visible light conversion efficiency. However, the conventional perovskite has been manufactured in the form of nanoparticles or microparticles, and when this type of perovskite is applied to a scintillator, light transmittance is lowered, so there is a problem in that the X-ray-visible light conversion efficiency is lowered. In this case, the light is visible light emitted after absorbing X-rays.

In addition, since the performance of the scintillator is affected by the crystalline quality of the manufactured perovskite in the prior art, a vacuum deposition method was used to improve the crystalline quality, and thus there is a problem in that the perovskite production efficiency is reduced.

On the other hand, the perovskite manufacturing method according to an exemplary embodiment of the present specification produces a columnar perovskite and has little influence on the crystallinity, so it has excellent performance when applied to a scintillator even in a solution process and an atmospheric pressure process. Perovskite can be prepared. That is, since the columnar perovskite is manufactured under the relaxed process conditions, the process efficiency is improved.

In addition, an exemplary embodiment of the present specification also shows the effect of improving the transmittance of light by manufacturing the perovskite in the form of a column. Specifically, by applying the columnar perovskite to the scintillator, light scattering is reduced and vertical transmittance is improved to ensure high resolution. In this case, the light is visible light emitted after absorbing X-rays.

In addition, the columnar perovskite according to an exemplary embodiment of the present specification is less affected by crystallinity and has a high Z value (eg, Pb) because matching with a photodiode can be adjusted by adjusting the emission spectrum. It is possible to reach the target scintillator efficiency even with a low thickness by applying

1 is a diagram illustrating scattering characteristics of visible light according to the shape of a material applied to a scintillator extracted from Detectors for synchrotron tomography, advanced tomographic methods in materials research and engineering, 66, 277, 2008, 31, 34. Specifically, FIG. 1 shows the scattering characteristics of visible light emitted by the scintillator by absorbing X-rays.

In FIG. 1, (a) shows a case where a powder-type material is applied, (b) shows a case where a film-type material is applied, and (c) shows a case where a columnar material is applied.

Since the scintillator converts X-rays into visible light and enables imaging through the lower photodiode, light transmittance plays a very important role in image resolution.

Referring to FIG. 1 , it can be seen that when a columnar material is applied to the scintillator rather than a powder or film, scattering of transmitted visible light is less. Specifically, when X-rays are irradiated to the film, the X-rays are absorbed from the film and then converted to visible light and scattered or transmitted. can be checked Therefore, when the columnar perovskite is applied to the scintillator, it can be predicted that the X-ray absorption rate is high and the visible light transmittance is improved, so that the X-ray-visible light conversion efficiency is the highest.

In the present specification, visible light has the same definition as used in the art. For example, the visible electromagnetic wave may have a wavelength range of 380 nm to 780 nm.

In the present specification, X-ray is the same as the definition used in the art. For example, the wavelength range may be from 10 ^-8 m to 10 ^-11 m.

In one embodiment of the present specification, the substrate can be used without limitation as long as it is a material used in the art. For example, a silicon photodiode, a glass substrate, a thin glass substrate, or a plastic substrate may be used. The plastic substrate is a flexible film such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether ether ketone and polyimide in the form of a single layer or a multilayer. may be included.

In the present specification, the columnar shape means a shape in which perovskite crystals are formed in a direction perpendicular to the substrate.

In one embodiment of the present specification, the first solution includes an organic halide and a metal halide.

In an exemplary embodiment of the present specification, the first solution includes an inorganic halide and a metal halide.

In one embodiment of the present specification, the particles formed by heat-treating the coated substrate act as a seed of the columnar perovskite produced later. That is, the perovskite is formed in a columnar shape from the particles.

In one embodiment of the present specification, the particles have a diameter of 100 nm or less. In this case, the diameter can be measured through SEM.

In one embodiment of the present specification, it is determined that the particles are formed as seeds when they cover 50% or more of the substrate.

In one embodiment of the present specification, the particles are perovskite particles.

In one embodiment of the present specification, the particles are formed on a substrate.

An exemplary embodiment of the present specification includes forming particles on the substrate by heat-treating the substrate coated with the first solution at 50° C. to 150° C.

In an exemplary embodiment of the present specification, the metal halide is represented by the following formula (1).

[Formula 1]

MX1 _a1

In Formula 1,

a1 is an integer of 1 to 4 as the ionic valence of M,

M is ^{Rb +, Sn +, Cu 2} +, Ni 2 +, Co 2 +, Fe 2 +, Mn 2 +, Cr 2 +, Pd 2 +, Cd 2 +, Ge 2 +, Sn 2 +, Pb 2 ^+, Yb ^2+, Bi ^{+ 3,} Sb ^{+ 3,} Al ^{+ 3,} and Sn ^{4 +} is a metal ion selected from,

X1 is a halogen ion.

In the present specification, the halogen ion is F ^- , Cl ^- , Br ^- or I ^- .

In the present specification, the ionic valence means the charge of the ion. For example, when M is Rb ⁺ , a1 is 1, and when M is Cu ^{2 +} , a1 is 2.

In an exemplary embodiment of the present specification, M is Sn ⁺ , Pb ^{2 +} , Bi ^{3 +} , Sb ^{3 +} or Sn ^{4 +} .

In an exemplary embodiment of the present specification, the metal halide is BiI ₃ , SbI ₃ , SnI ₄ , PbI ₂ , BiBr ₃ , SbBr ₃ , SnBr ₄ , PbBr ₂ , BiCl ₃ , SbCl ₃ , SnCl ₄ and PbCl ₂ more than one of

In one embodiment of the present specification, the concentration of the metal halide in the first solution is 0.1M to 1M. When the metal halide is less than 0.1M, the perovskite is formed only in the form of particles, and when the metal halide is more than 1M, there is a problem in that the perovskite is formed in a direction other than the columnar shape.

In one embodiment of the present specification, the first solution further comprises a halogen acid.

In the present specification, the halogen acid is HBr, HI or HCl.

In an exemplary embodiment of the present specification, the first solution further includes at least one of HBr, HI, and HCl.

In one embodiment of the present specification, the concentration of the halogen acid in the first solution is 0.1M to 2M. Specifically, the concentration of the halogen acid in the first solution is 0.5M to 1.5M. When the concentration of the halogen acid is included in the above range, the crystallinity of the formed perovskite is improved.

In an exemplary embodiment of the present specification, the organic halide or inorganic halide is represented by the following formula (2).

[Formula 2]

RX2

In Formula 2,

R is C _n H _{2n + 1} NH ₃ ⁺ , NH ₄ ⁺ , HC(NH ₂ ) ₂ ⁺ , Cs ⁺ , NF ₄ ⁺ , NCl ₄ ⁺ , PF ₄ ⁺ , PCl ₄ ⁺ , CH ₃ PH ₃ ⁺ , CH ₃ AsH ₃ ⁺ , CH ₃ SbH ₃ ⁺ , PH ₄ ⁺ , AsH ₄ ⁺ , Rb ⁺ and SbH ₄ ⁺ is a monovalent cation selected from,

n is an integer from 1 to 9,

X2 is a halogen ion.

Specifically, the organohalide is CH ₃ NH ₃ I, CH ₃ NH ₃ Br, CH ₃ NH ₃ Cl, HC(NH ₂ ) ₂ I, HC(NH ₂ ) ₂ Br or HC(NH ₂ ) ₂ Cl can

Specifically, the inorganic halide may be CsI, CsBr, CsCl, RbI, RbBr or RbCl.

In one embodiment of the present specification, the concentration of the organic halide or inorganic halide in the first solution is 0.1M to 2M. Specifically, the concentration of the organic halide or inorganic halide in the first solution is 0.1M to 1M.

In an exemplary embodiment of the present specification, an organic halide or an inorganic halide in the first solution; All residues except for the metal halide and the halogen acid are solvents.

In the exemplary embodiment of the present specification, the solvent included in the first solution is not limited as long as it is a solvent capable of dissolving the organic halide, inorganic halide and/or metal halide. For example, in water, dimethylformamide (DMF), octadecene, dimethylsulfoxide (DMSO), N-methylformamide (MNF), dichloromethane (DCM) and isopropylacetate (IPA) It may be one or more, but is not limited thereto.

In an exemplary embodiment of the present specification, the second solution includes an organic halide.

In one embodiment of the present specification, the second solution includes an inorganic halide.

In an exemplary embodiment of the present specification, the second solution includes a mixture of an organic halide and an inorganic halide.

In one embodiment of the present specification, the concentration of the organic halide, the inorganic halide, or a mixture thereof in the second solution is 0.1M to 2M. Specifically, the concentration of the organic halide, the inorganic halide, or a mixture thereof in the second solution is 0.1M to 1M. When the concentration of the organic halide, the inorganic halide or a mixture thereof is included in the above range, the crystallinity of the formed perovskite is improved.

In an exemplary embodiment of the present specification, the second solution includes an organic halide. Specifically, the second solution contains 0.1M to 2M of the organohalide.

In one embodiment of the present specification, the second solution includes an inorganic halide. Specifically, the second solution contains 0.1M to 2M of the inorganic halide.

In one embodiment of the present specification, the second solution further comprises a metal halide. In this case, the description of the metal halide included in the first solution is applied equally to the metal halide. For example, the second solution contains the metal halide represented by Formula 1 at a concentration of 0.1M to 1M.

In the exemplary embodiment of the present specification, the solvent included in the second solution is not limited as long as it is a solvent capable of dissolving the organic halide, the inorganic halide, a mixture thereof, and/or the metal halide. For example, it may be one or more of gamma butyrolactone, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), and ethanol, but is not limited thereto.

In one embodiment of the present specification, the second solution further comprises a surfactant. The surfactant is not limited as long as it is a material used in the art. For example, it may be oleylamine, oleic acid, or a mixture thereof, but is not limited thereto.

In one embodiment of the present specification, the contacting may be performed by methods such as supporting, spin coating, dip coating, screen printing, spray coating, doctor blade and brush painting. Specifically, the contacting may be performed by supporting the formed particles in the second solution.

An exemplary embodiment of the present specification, an organic halide or an inorganic halide before coating the first solution on the substrate; and heat-treating the first solution containing the metal halide. At this time, the heat treatment is performed at 50 °C to 200 °C.

Specifically, an exemplary embodiment of the present specification is an organic halide or an inorganic halide; and heat-treating the first solution containing the metal halide at 50° C. to 200° C.;

coating the heat-treated first solution on a substrate;

heat-treating the coated substrate at 50° C. to 150° C. to form particles on the substrate; and

Columnar perovskite comprising the step of contacting the formed particles with a second solution containing an organic halide, an inorganic halide or a mixture thereof at 50°C to 150°C to form a columnar perovskite It provides a manufacturing method of

In one embodiment of the present specification, particles are formed through the heat treatment of the first solution.

In one embodiment of the present specification, the solvent is removed through heat treatment after coating the first solution on the substrate. Accordingly, particles are finally formed on the substrate through the heat treatment.

In one embodiment of the present specification, the manufacturing method of the columnar perovskite is made at atmospheric pressure.

In the present specification, the atmospheric pressure is 0.8 atm to 1.2 atm. Specifically, the atmospheric pressure is 1 atm.

In the present specification, 1 atm = 760 mmHg.

The perovskite manufacturing method according to an exemplary embodiment of the present specification exhibits an effect of improving manufacturing efficiency because it is a solution process and proceeds under normal pressure conditions.

In one embodiment of the present specification, the length of the perovskite is 50 μm to 500 μm. Specifically, the length of the columnar perovskite is 50 μm to 300 μm. When the length of the perovskite satisfies the above range, X-rays can be sufficiently absorbed while the loss of converted visible light is minimized.

In the present specification, the length of the perovskite means the longest length in the vertical direction with respect to the substrate.

In one embodiment of the present specification, the particle diameter of the columnar perovskite is 400 nm to 50 μm. Specifically, the particle diameter of the perovskite is 400 nm to 20 μm.

In the present specification, the particle diameter means the longest length of a plane or cross-section horizontal to the substrate. Specifically, it means the longest length of the surface of the columnar perovskite in contact with the substrate.

In one embodiment of the present specification, the length and particle diameter can be measured through the shape analysis of the cross section and / or surface of the perovskite. For example, it can be analyzed by measuring SEM.

In an exemplary embodiment of the present specification, the perovskite is represented by any one of the following Chemical Formulas 3-1 to 3-6.

[Formula 3-1]

RMX ₃

[Formula 3-2]

R ₂ MX ₃

[Formula 3-3]

RMX ₄

[Formula 3-4]

RM ₂ X ₅

[Formula 3-5]

R ₂ MX ₄

[Formula 3-6]

R ₃ M ₂ X ₉

In Formulas 3-1 to 3-6,

R is C _n H _{2n + 1} NH ₃ ⁺ , NH ₄ ⁺ , HC(NH ₂ ) ₂ ⁺ , Cs ⁺ , NF ₄ ⁺ , NCl ₄ ⁺ , PF ₄ ⁺ , PCl ₄ ⁺ , CH ₃ PH ₃ ⁺ , CH ₃ AsH ₃ ⁺ , CH ₃ SbH ₃ ⁺ , PH ₄ ⁺ , AsH ₄ ⁺ , Rb ⁺ and SbH ₄ ⁺ is a monovalent cation selected from,

M is ^{Rb +, Sn +, Cu 2} +, Ni 2 +, Co 2 +, Fe 2 +, Mn 2 +, Cr 2 +, Pd 2 +, Cd 2 +, Ge 2 +, Sn 2 +, Pb 2 and ^+, Yb ^2+, Bi ^{+ 3,} Sb ^{+ 3,} Al ^{+ 3,} and the metal ion is selected from Sn ^{4 +,}

n is an integer from 1 to 9,

X is a halogen ion.

An exemplary embodiment of the present specification provides a columnar perovskite manufactured according to the manufacturing method.

In one embodiment of the present specification, the columnar perovskite has a crystal density of 4 g/m ³ or more. The upper limit of the density of the crystal is not limited, but may be ^{, for example, 50 g/m 3 .} Specifically, the columnar perovskite may have a crystal density of 4 g/m ³ to 30 g/m ³ .

In one embodiment of the present specification, the density of the crystal can be measured through an X-ray diffraction analyzer.

In one embodiment of the present specification, the columnar perovskite absorbs light of 450 nm or less. Specifically, it absorbs X-rays. More specifically, it absorbs light from ^{10 -8} m to 10 ^{-11 m.}

An exemplary embodiment of the present specification provides an optical film comprising the columnar perovskite.

In one embodiment of the present specification, the thickness of the optical film is 50 μm or less. Specifically, the thickness of the optical film is 400 nm to 50 μm. According to an exemplary embodiment of the present specification, since the thickness of the optical film is very thin, 50 μm or less, as described above, it is possible to bend, and accordingly, it is also applicable to a flexible device.

In one embodiment of the present specification, the thickness of the optical film can be measured through SEM.

In an exemplary embodiment of the present specification, the transmittance of the optical film to visible light is 50% or more. Specifically, the transmittance of the optical film to visible light is 60% or more. More specifically, the transmittance of the optical film with respect to visible light is 60% or more and 100% or less.

In one embodiment of the present specification, the transmittance can be measured through IR.

In one embodiment of the present specification, the optical film includes a plurality of columnar perovskite. For example, the optical film contains 10 ⁵ to 10 ⁹ columnar perovskite. Specifically, the optical film contains 10 ⁶ to 4x10 ⁸ columnar perovskite.

An exemplary embodiment of the present specification provides a scintillator including the optical film.

In one embodiment of the present specification, the scintillator serves to absorb the energy of the incident radiation and emit visible light.

In the exemplary embodiment of the present specification, the incident radiation may be X-rays.

An exemplary embodiment of the present specification provides an X-ray detector including the scintillator.

In the exemplary embodiment of the present specification, the X-ray detector includes a substrate, a scintillator, and a photodetector.

Specifically, the X-ray detector may include a substrate; a TFT array provided on the substrate; a photo detector provided on the TFT array; and a scintillator provided on the photo detector.

In another exemplary embodiment of the present specification, the X-ray detector includes: a photodetector comprising a photodetector-side substrate and a photoelectric conversion layer; and a scintillator panel including a scintillator and a scintillator side substrate.

Specifically, the X-ray detector may include a photodetector-side substrate; a photoelectric conversion layer formed on the photodetector side substrate; a scintillator layer formed on the photoelectric conversion layer; and a scintillator-side substrate formed on the scintillator layer.

In the exemplary embodiment of the present specification, materials used in the art may be used as the photodetector-side substrate and the photoelectric conversion layer. For example, an insulating substrate such as glass, ceramic, or resin may be used as the photodetector-side substrate.

In one embodiment of the present specification, the photodetector may be a photodiode.

In the exemplary embodiment of the present specification, the photodiode may be an amorphous silicon photodiode.

In the exemplary embodiment of the present specification, the scintillator layer includes the scintillator described above, and a plurality of scintillators may be provided at regular intervals. For example, a plurality of scintillators may be provided with a partition wall therebetween.

In the exemplary embodiment of the present specification, the scintillator side substrate is preferably a material having high radiation transmittance, and any material used in the art may be used without limitation. For example, plate glass made of glass such as borosilicate glass and chemically strengthened glass; ceramic substrates made of ceramics such as sapphire, silicon nitride, and silicon carbide; semiconductor substrates made of semiconductors such as silicon, germanium, gallium arsenide, gallium phosphorus, and gallium nitrogen; polymer films or plastic films such as cellulose acetate film, polyester film, polyethylene terephthalate film, polyamide film, polyimide film, and polycarbonate film; metal sheets, such as an aluminum sheet, an iron sheet, and a copper sheet; a metal sheet having a coating layer of metal oxide; And a material selected from the group consisting of a carbon substrate may be used. Specifically, a plastic film and a plate glass may be used in terms of flatness and heat resistance.

In one embodiment of the present specification, layers used in the art may be applied to the X-ray detector. For example, a radiation shielding layer or a reflective layer may be applied.

In the case of the radiation shielding layer, a material having a radiation shielding function may be used to prevent radiation from being emitted to the outside of the X-ray detector. Specifically, metal plates such as iron and lead plates; and a glass plate containing a metal such as iron, lead, gold, silver, copper, platinum, tungsten, or molybdenum may be used.

In the exemplary embodiment of the present specification, the radiation shielding layer is provided between the scintillator layer and the scintillator side substrate.

One embodiment of the present specification is a substrate; And it provides an optical film comprising a plurality of perovskite in the form of a column provided on the substrate.

At this time, the description of the plurality of perovskite perovskite manufactured through the above-described manufacturing method is equally applied. For example, the length of each of the plurality of perovskite included in the optical film is 50 μm to 500 μm.

In one embodiment of the present specification, 10 ⁵ to 10 ⁹ columnar perovskite is provided on the substrate. Specifically, 10 ⁶ to 4x10 ⁸ columnar perovskite is provided on the substrate.

An exemplary embodiment of the present specification provides a tillator including the optical film.

An exemplary embodiment of the present specification provides an X-ray detector including the scintillator.

In this case, the description of the scintillator and the X-ray detector is the same as for the scintillator and the X-ray detector.

Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present specification to those of ordinary skill in the art.

Example One.

A first solution was formed by dissolving a mixture of CsI and SnI ₄ in a 2:1 molar ratio in a solution in which HI, octadecene and DMF were mixed in a 1:1:2 ratio at a concentration of 0.3M. The first solution was heat-treated at 150° C. for 30 minutes. The heat-treated first solution was spin-coated on a substrate at 300 rpm to 500 rpm, and heat-treated at 100° C. to form particles.

A solution was prepared in which CsI and SnI ₄ were dissolved in gamma butyrolactone in a molar ratio of 2:1. A mixture of oleylamine and oleic acid was added to the solution. At this time, the volume ratio of the solution and the mixture was 13:1. Then, 0.5 mol of HI was added to prepare a second solution. The formed particles were supported in the second solution at 70° C. to 120° C. to form columnar perovskite.

Figure 2 shows the SEM measurement results of the perovskite prepared in Example 1.

2, it can be confirmed that the perovskite was prepared in the form of a column on the substrate.

comparative example One.

SEM was measured by purchasing commercially available perovskite powder (Finetech, GP-XX, Gd ₂ OS:Td material).

3 shows the SEM measurement results of the perovskite prepared in Comparative Example 1.

3, it can be confirmed that commercially available perovskite is not in the form of a column.

Claims (17)

an organic halide or an inorganic halide on a substrate; and coating a first solution containing a metal halide;
forming particles by heat-treating the coated substrate at 50° C. to 150° C.; and
Columnar perovskite comprising the step of contacting the formed particles with a second solution containing an organic halide, an inorganic halide or a mixture thereof at 50°C to 150°C to form a columnar perovskite manufacturing method. The method according to claim 1,
The metal halide is a method for producing a columnar perovskite that is represented by the following formula (1):
[Formula 1]
MX1 _a1
In Formula 1,
a1 is an integer of 1 to 4 as the ionic valence of M,
M is ^{Rb +, Sn +, Cu 2} +, Ni 2 +, Co 2 +, Fe 2 +, Mn 2 +, Cr 2 +, Pd 2 +, Cd 2 +, Ge 2 +, Sn 2 +, Pb 2 ^+, Yb ^2+, Bi ^{+ 3,} Sb ^{+ 3,} Al ^{+ 3,} and Sn ^{4 +} is a metal ion selected from,
X1 is a halogen ion. The method according to claim 1,
The concentration of the metal halide in the first solution is a method for producing a columnar perovskite of 0.1M to 1M. The method according to claim 1,
The first solution is a method for producing a columnar perovskite further comprising a halogen acid. The method according to claim 1,
The method for producing the columnar perovskite is a method for producing a columnar perovskite that is made at atmospheric pressure. The method according to claim 1,
The method for producing a columnar perovskite wherein the organic halide or inorganic halide is represented by the following Chemical Formula 2:
[Formula 2]
RX2
In Formula 2,
R is C _n H _{2n + 1} NH ₃ ⁺ , NH ₄ ⁺ , HC(NH ₂ ) ₂ ⁺ , Cs ⁺ , NF ₄ ⁺ , NCl ₄ ⁺ , PF ₄ ⁺ , PCl ₄ ⁺ , CH ₃ PH ₃ ⁺ , CH ₃ AsH ₃ ⁺ , CH ₃ SbH ₃ ⁺ , PH ₄ ⁺ , AsH ₄ ⁺ , Rb ⁺ and SbH ₄ ⁺ is a monovalent cation selected from,
n is an integer from 1 to 9,
X2 is a halogen ion. The method according to claim 1,
The second solution is a method for producing a columnar perovskite further comprising a metal halide. The method according to claim 1,
The length of the columnar perovskite is 50 μm to 500 μm of the method for producing a columnar perovskite. The method according to claim 1,
A method for producing a columnar perovskite, the particle diameter of the columnar perovskite is 400nm to 50㎛. The method according to claim 1,
The columnar perovskite is a method for producing a columnar perovskite represented by any one of the following Chemical Formulas 3-1 to 3-6:
[Formula 3-1]
RMX ₃
[Formula 3-2]
R ₂ MX ₃
[Formula 3-3]
RMX ₄
[Formula 3-4]
RM ₂ X ₅
[Formula 3-5]
R ₂ MX ₄
[Formula 3-6]
R ₃ M ₂ X ₉
In Formulas 3-1 to 3-6,
R is C _n H _{2n + 1} NH ₃ ⁺ , NH ₄ ⁺ , HC(NH ₂ ) ₂ ⁺ , Cs ⁺ , NF ₄ ⁺ , NCl ₄ ⁺ , PF ₄ ⁺ , PCl ₄ ⁺ , CH ₃ PH ₃ ⁺ , CH ₃ AsH ₃ ⁺ , CH ₃ SbH ₃ ⁺ , PH ₄ ⁺ , AsH ₄ ⁺ , Rb ⁺ and SbH ₄ ⁺ is a monovalent cation selected from,
M is ^{Rb +, Sn +, Cu 2} +, Ni 2 +, Co 2 +, Fe 2 +, Mn 2 +, Cr 2 +, Pd 2 +, Cd 2 +, Ge 2 +, Sn 2 +, Pb 2 ^+, Yb ^2+, Bi ^{+ 3,} Sb ^{+ 3,} Al ^{+ 3,} and Sn ^{4 +} is a metal ion selected from,
n is an integer from 1 to 9,
X is a halogen ion. A columnar perovskite manufactured according to any one of claims 1 to 10. The columnar perovskite according to claim 11, wherein the columnar perovskite has a crystal density of 4 g/cm ³ or more. The method according to claim 11, The columnar perovskite is a columnar perovskite that absorbs light of 450nm or less, An optical film comprising the columnar perovskite according to claim 11 . Board; and
An optical film comprising a plurality of columnar perovskite provided on the substrate. A scintillator comprising the optical film according to claim 14 . An X-ray detector comprising the scintillator according to claim 16 .

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