WO2017142089A1 - Composé et matériau luminescent - Google Patents

Composé et matériau luminescent Download PDF

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Publication number
WO2017142089A1
WO2017142089A1 PCT/JP2017/006002 JP2017006002W WO2017142089A1 WO 2017142089 A1 WO2017142089 A1 WO 2017142089A1 JP 2017006002 W JP2017006002 W JP 2017006002W WO 2017142089 A1 WO2017142089 A1 WO 2017142089A1
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Prior art keywords
ion
compound
bromide
solution
perovskite
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PCT/JP2017/006002
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English (en)
Japanese (ja)
Inventor
翔太 内藤
正直 江良
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住友化学株式会社
国立大学法人佐賀大学
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Application filed by 住友化学株式会社, 国立大学法人佐賀大学 filed Critical 住友化学株式会社
Priority to CN201780008752.4A priority Critical patent/CN108602756B/zh
Priority to JP2018500238A priority patent/JP6786582B2/ja
Publication of WO2017142089A1 publication Critical patent/WO2017142089A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C01G21/16—Halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/24—Lead compounds

Definitions

  • the present invention relates to a compound and a light emitting material.
  • This application claims priority based on Japanese Patent Application No. 2016-30201 filed in Japan on February 19, 2016 and Japanese Patent Application No. 2016-122603 filed in Japan on June 24, 2016, and its contents Is hereby incorporated by reference.
  • an organic-inorganic perovskite AMX 3 compound comprising an organic cation (A), a halide ion (X), and a divalent metal ion (M) is known.
  • A organic cation
  • X halide ion
  • M divalent metal ion
  • Non-patent Document 1 when the divalent metal ion is Pb (II), a strong light emission phenomenon at room temperature has been observed in the range from the ultraviolet region to the red spectral region (Non-patent Document 1). Further, the emission wavelength can be adjusted depending on the type of halide ion (X) (Non-patent Document 2).
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a compound having a perovskite structure having high emission intensity when used as a light emitting material, and a light emitting material containing the compound.
  • the embodiments of the present invention include the following [1] to [6].
  • a compound having a structure (A is a monovalent cation located at each vertex of a hexahedron centered on B in the perovskite crystal structure.
  • B is a lead ion.
  • M is a divalent or trivalent metal ion, and is a cation selected from metal ions having an ionic radius in a hexacoordination of 0.9 to 1.5 ⁇ , and at least a part of M is In the perovskite crystal structure, a part of B is substituted.
  • X represents a component located at each vertex of an octahedron centered on B in the perovskite crystal structure, and is selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion, and thiocyanate ion. And at least chloride ion or bromide ion as X.
  • the value of the molar ratio [M / (M + B)] obtained by dividing A amount by the total amount of M and B is 0, with A, B, X, and M as components. It is a compound having a perovskite crystal structure that is 0.7 or less.
  • A is a monovalent cation located at each vertex of a hexahedron centered on B in the perovskite crystal structure.
  • B is Pb ion.
  • M is a divalent or trivalent metal ion, and is a cation selected from metal ions having an ionic radius in a hexacoordination of 0.9 to 1.5 ⁇ , and at least a part of M is In the perovskite crystal structure, a part of B is substituted.
  • X represents a component located at each vertex of an octahedron centered on B in the perovskite crystal structure, and is selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion, and thiocyanate ion. One or more ions. However, X includes at least a chloride ion or a bromide ion.
  • the basic structure of a compound having a perovskite crystal structure is a three-dimensional structure or a two-dimensional structure.
  • A′B′X ′ 3 When the basic structure is a three-dimensional structure, it is represented by A′B′X ′ 3 .
  • a ′ represents an organic cation or an inorganic cation
  • B ′ represents a metal cation
  • X ′ represents a halide ion or a thiocyanate ion.
  • a ′, B ′, and X ′ represent the same meaning as described above.
  • the basic structure When the basic structure is the above-described three-dimensional structure or two-dimensional structure, it has a three-dimensional network of vertex shared octahedrons represented by B′X ′ 6 with B ′ as the center and the vertex as X ′.
  • B ′ is a metal cation capable of taking the octahedral coordination of X ′.
  • a ′ is located at each vertex of a hexahedron centered on B ′.
  • the compound having a perovskite crystal structure containing A, B, X, and M as components is not particularly limited, and the basic structure is any one of a three-dimensional structure, a two-dimensional structure, and a pseudo two-dimensional structure.
  • the compound which has the structure of may be sufficient.
  • the basic structure is a three-dimensional structure
  • the perovskite crystal structure is represented by AB (1-a) M a X (3 + ⁇ ) .
  • the perovskite crystal structure is represented by A 2 B (1-a) M a X (4 + ⁇ ) .
  • the a represents the molar ratio [M / (M + B)].
  • ⁇ is a number that can be appropriately changed according to the charge balance of B and M, and is preferably 0 or more and 0.7 or less.
  • A is a monovalent cation
  • B is a divalent anion (Pb ion)
  • M is a divalent or trivalent anion (metal ion)
  • X is a monovalent anion (chloride ion
  • ⁇ may be selected so that the compound is neutral (charge is 0) when it is one or more ions selected from the group consisting of bromide ion, fluoride ion, iodide ion and thiocyanate ion). it can.
  • the metal cation of the B ′ component is Pb ion (B component), and a part of the plurality of Pb ions (B component) is M component.
  • the luminescence intensity of the compound can be improved by substituting with a cation selected from metal ions that are valence metal ions and have an ionic radius in hexacoordination of 0.9 to 1.5 ⁇ . I found out that I can do it.
  • At least a part of M in the compound having a perovskite crystal structure according to this embodiment means a component that substitutes a part of the lead ion represented by B.
  • M may be present at the position where the B component (lead ion) is present in the basic structure described above, or may be present at the position where the A component is present. It may exist in the lattice gap of the skeleton constituting the structure.
  • a compound having a perovskite crystal structure containing A, B, X, and M as components in the present embodiment will be described later.
  • the perovskite crystal structure is, for example, when a compound is measured by means of X-ray diffraction (XRD, Cu K ⁇ ray, X'pert PRO MPD, made by Spectris),
  • XRD X-ray diffraction
  • Cu K ⁇ ray Cu K ⁇ ray
  • X'pert PRO MPD made by Spectris
  • A is a monovalent cation
  • M is a divalent or trivalent metal ion
  • the six-coordinate ion radius is 0.9 to 1.5
  • X is at least one ion selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion (where X is at least Including a chloride ion or bromide ion), and has a perovskite structure represented by the following general formula (1).
  • A is a monovalent cation
  • B is a divalent anion (Pb ion)
  • M is a divalent or trivalent anion (metal ion)
  • X is a monovalent anion (chloride ion
  • ⁇ may be selected so that the compound is neutral (charge is 0) when it is one or more ions selected from the group consisting of bromide ion, fluoride ion, iodide ion and thiocyanate ion). it can.
  • the basic structural form of the perovskite structure is an A′B′X ′ 3 structure.
  • the basic structural form of the perovskite is an A′B′X ′ 3 structure, and has a three-dimensional network of vertex sharing B′X ′ 6 octahedrons.
  • the B ′ component of the A′B′X ′ 3 structure is a metal cation that can take octahedral coordination of the X ′ anion.
  • the A ′ cation is located at each apex of the hexahedron centered on the B ′ atom, and is an organic cation or an inorganic cation in this embodiment.
  • the X ′ component of the A′B′X ′ 3 structure is usually a halide ion.
  • the metal cation of the B component is lead, and a part of the plurality of lead ions is substituted with other atoms, whereby It has been found that the emission intensity can be improved.
  • the compound having a perovskite structure represented by the general formula (1) (hereinafter sometimes referred to as “compound (1)”) is mainly composed of A, Pb (lead), M, and X. Ingredients.
  • M means an atom that substitutes a part of the Pb ion that is a metal cation.
  • M may replace the position where the B component (lead ion) exists in the basic structure, may replace the position where the A component exists, or the lattice gap of the skeleton constituting the basic structure. May be present.
  • the compound having a perovskite crystal structure having A, B, X, and M as components in the present embodiment will be described.
  • A is a monovalent cation.
  • A is preferably a cesium ion or an organic ammonium ion.
  • organic ammonium ion of A examples include a cation represented by the following general formula (A1).
  • R 1 to R 4 are each independently a hydrogen atom or an alkyl group, and one of the hydrogen atoms constituting each alkyl group may be substituted with an amino group.
  • the alkyl group for R 1 to R 4 is preferably a linear or branched alkyl group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and a C 1 to 3 carbon group.
  • a linear or branched alkyl group is more preferable.
  • the total number of carbon atoms in the alkyl group of R 1 ⁇ R 4 is 1-4, among the R 1 ⁇ R 4, R 1 is an alkyl group having 1 to 3 carbon atoms, R 2 It is particularly preferable that R 4 is a hydrogen atom.
  • A is preferably CH 3 NH 3 + , C 2 H 5 NH 3 + or C 3 H 7 NH 3 + , and is CH 3 NH 3 + or C 2 H 5 NH 3 + . More preferably, it is most preferably CH 3 NH 3 + (methylammonium ion).
  • the B component is a metal cation that becomes the center of the crystal structure.
  • the B component is Pb (lead).
  • the Pb ions in this embodiment are divalent Pb ions.
  • the emission intensity of the compound of the present embodiment can be improved by substituting a part of the B component (Pb ion) contained in the plurality of crystal structures constituting the compound with other atoms.
  • M substitutes a part of the Pb ion that is a metal cation. More specifically, M is a divalent or trivalent metal ion, and is a cation selected from metal ions having an ionic radius in a hexacoordinate of 0.9 to 1.5.
  • the ion radius of the metal ion represented by M is preferably 0.95 to 1.4 and more preferably 0.95 to 1.3.
  • M is, for example, a barium ion (six-coordinate ion radius; 1.35 ⁇ ) ), Calcium ions (6-coordinate ion radius; 1.00 ⁇ ), cerium ions (6-coordinate ion radius; 1.01 ⁇ ), dysprosium ions (6-coordinate ion radius; 1.07 ⁇ ), Lanthanum ion (6-coordinate ion radius; 1.03 ⁇ ), samarium ion (6-coordinate ion radius; 1.19 ⁇ ), strontium ion (6-coordinate ion radius; 1.18 ⁇ ), or ytterbium Cations of elements such as ions (6 coordination ionic radii: 1.02 ⁇ ) can be given.
  • M is preferably an alkaline earth metal ion, and more preferably a calcium ion.
  • a is preferably 0.01 or more and 0.7 or less, and more preferably 0.02 or more and 0.6 or less.
  • the value a is a value calculated from the value obtained by measuring the synthesized compound using ICP-MS described in ⁇ Method for calculating a ⁇ below.
  • the value of a that is, the molar ratio [M / (M + B)] can be measured using ICP-MS (ELAN DRCII, manufactured by PerkinElmer). The molar ratio is measured after a compound having a perovskite crystal structure is dissolved using nitric acid or the like.
  • the value of the molar ratio [M / (M + B)] is a value calculated according to the following formula (T).
  • Mmol is the number of moles of M measured by ICP-MS
  • Pbmol is the number of moles of Pb measured by ICP-MS.
  • the value calculated by the above ⁇ calculation method for a ⁇ is preferably “a”.
  • the value of a is a charge ratio adjusted so that a in the compound of the first embodiment and the second embodiment is a desired value when the compound of the present embodiment is synthesized. It can also be calculated from the value.
  • X is at least one ion selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion.
  • X contains a chloride ion or a bromide ion at least.
  • the amount of chloride ion or bromide ion is preferably 10% or more, more preferably 30% or more, further preferably 70% or more, and particularly preferably 80% or more, when expressed in mol% in X.
  • the upper limit value is not particularly limited, but can be arbitrarily selected as long as it is 100% or less.
  • X contains a bromide ion.
  • the content ratio of the anions can be appropriately selected depending on the emission wavelength.
  • ions When two or more ions are selected as X, a combination of bromide ions and chloride ions, or a combination of bromide ions and iodide ions is preferable.
  • Specific examples of the compounds of the first embodiment and the second embodiment include CH 3 NH 3 Pb (1-a) Ca a Br (3 + ⁇ ) (0 ⁇ a ⁇ 0.7, 0 ⁇ ⁇ ⁇ 0. 7), CH 3 NH 3 Pb (1-a) Sr a Br (3 + ⁇ ) (0 ⁇ a ⁇ 0.7, 0 ⁇ ⁇ ⁇ 0.7), CH 3 NH 3 Pb (1-a) La a Br (3 + ⁇ ) (0 ⁇ a ⁇ 0.7, 0 ⁇ ⁇ ⁇ 0.7), CH 3 NH 3 Pb (1-a) Ba a Br (3 + ⁇ ) (0 ⁇ a ⁇ 0.7, 0 ⁇ ⁇ ⁇ 0.7), CH 3 NH 3 Pb (1-a) Dy a Br (3 + ⁇ ) (0 ⁇ a ⁇ 0.7, 0 ⁇ ⁇ ⁇ 0.7), CH 3 NH 3 Pb (1-a) Ca a (Br 2 Cl) (3 + ⁇ ) (0 ⁇ a ⁇ 0.7, 0 ⁇
  • the compound having a perovskite structure according to this embodiment can be synthesized by a self-assembly reaction using a solution.
  • a solution obtained by dissolving a compound containing Pb and the above X, a compound containing the above M and the above X, and a compound containing the above A and the above X in a solvent is applied, and the solvent is removed.
  • the compound having the perovskite structure of this embodiment can be synthesized.
  • a coating film is formed by applying a solution obtained by dissolving a compound containing Pb and the above-described X and the above-described compound containing M and the above-described X in a solvent, and removing the solvent.
  • the compound having the perovskite structure of this embodiment can be synthesized by applying a solution obtained by dissolving the compound containing A and X described above in a solvent onto the coating film and removing the solvent.
  • the type and amount of the compound to be blended may be adjusted so that a and ⁇ in the compounds of the first embodiment and the second embodiment have desired values.
  • the compound having a perovskite structure according to the present embodiment is a light emitter that emits fluorescence in the visible light wavelength region.
  • X is a bromide ion
  • it is usually 480 nm or more, preferably 500 nm or more, more preferably 520 nm or more. It emits fluorescence. Further, it emits fluorescence in a wavelength range of usually 700 nm or less, preferably 600 nm or less, more preferably 580 nm or less.
  • the above upper limit value and lower limit value can be arbitrarily combined.
  • the maximum emission intensity of the compound having the perovskite structure of the present embodiment is obtained from the maximum intensity in the visible light wavelength region measured using a fluorometer and the transmittance of excitation light measured using an ultraviolet-visible absorptiometer.
  • a fluorometer for example, a spectrofluorometer (FT-6500) manufactured by JASCO Corporation can be used.
  • FT-6500 spectrofluorometer
  • the ultraviolet-visible absorptiometer for example, an ultraviolet-visible absorptiometer (trade name: V-670) manufactured by JASCO Corporation can be used.
  • the maximum light emission intensity of the compound is a value corrected according to the following formula (S).
  • Pmax is the maximum intensity in the visible light wavelength region
  • Ep indicates the transmittance (%) of excitation light. Pmax / (100 ⁇ Ep) ⁇ 100 (S)
  • the present embodiment provides a light emitting material including the compounds of the first embodiment and the second embodiment.
  • the luminescent material using the compounds of the first embodiment and the second embodiment may have components other than the compounds of the first embodiment and the second embodiment.
  • it may further include a compound having a slight impurity or a perovskite structure and having the same or similar composition as the compounds of the first embodiment and the second embodiment described above.
  • the form of the light emitting material containing the compound having a perovskite structure is not particularly limited, and can be appropriately determined according to the application.
  • a film obtained by forming the compound of the first embodiment and the second embodiment into a film form, or an adsorbent formed into a powder form and adsorbed on a base material may be used.
  • the film or adsorbent of the compound having the perovskite structure of the present embodiment is obtained by dissolving the compound of the first embodiment and the second embodiment in an organic solvent, and then applying the gravure coating method, bar coating method, printing method, spraying method. , And a coating method such as a spin coating method, a dip method, or a die coating method.
  • the organic solvent is not particularly limited as long as it can dissolve the aforementioned A, Pb, M, X, and other components before dissolution into ions.
  • the organic solvent may have various organic compounds and a branched structure or a cyclic structure, and may have a plurality of functional groups such as —O—, —CO—, —COO—, or —OH,
  • the hydrogen atom may be substituted with a halogen atom such as fluorine.
  • organic solvent examples include esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, or pentyl acetate; ⁇ -butyrolactone, N-methyl-2-pyrrolidone, acetone , Ketones such as dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, or methylcyclohexanone; diethyl ether, methyl-tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane , Ethers such as 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole or phenetole; methanol, ethanol, 1-propanol 2-propanol 2-
  • any one or more of pressure reduction, drying, and ventilation is performed as needed, and an organic solvent is volatilized. It is preferable. Drying may be performed at room temperature or by heating. The temperature for heating can be appropriately determined in consideration of the time required for drying and the heat resistance of the substrate, but is preferably 50 to 200 ° C., more preferably 50 to 100 ° C.
  • Example 1 A glass substrate having a size of 2.5 cm ⁇ 2.5 cm was prepared. This glass substrate was treated with ozone UV.
  • Lead bromide (PbBr 2 ) was dissolved in a solvent of N, N-dimethylformamide (hereinafter referred to as “DMF”) at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M.
  • DMF N, N-dimethylformamide
  • CaBr 2 calcium bromide
  • CaBr 2 calcium bromide
  • methylammonium bromide (CH 3 NH 3 Br) was dissolved in DMF solvent at 70 ° C. to prepare a methylammonium bromide solution having a concentration of 0.1M.
  • the above lead bromide solution and calcium bromide solution were mixed so that the molar ratio of Ca / (Ca + Pb) was 0.03 to prepare a solution.
  • the solution was applied to the glass substrate by spin coating at a rotation speed of 1000 rpm, and dried in air at 100 ° C.
  • Example 2 A coating film of a compound having a perovskite structure was obtained in the same manner as in Example 1 except that Ca / (Ca + Pb) was set to 0.05.
  • Example 3 A coating film of a compound having a perovskite structure was obtained in the same manner as in Example 1 except that Ca / (Ca + Pb) was 0.1.
  • Example 4 A coating film of a compound having a perovskite structure was obtained in the same manner as in Example 1 except that Ca / (Ca + Pb) was 0.2.
  • a glass substrate having a size of 2.5 cm ⁇ 2.5 cm was prepared. This glass substrate was treated with ozone UV.
  • Lead bromide (PbBr 2 ) was dissolved in a DMF solvent at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M.
  • methylammonium bromide (CH 3 NH 3 Br) was dissolved in a DMF solvent to prepare a methylammonium bromide solution having a concentration of 0.1M.
  • the solution was applied to the glass substrate by spin coating at a rotation speed of 1000 rpm, and dried at 100 ° C. for 10 minutes to obtain a coating film of a compound having a perovskite structure.
  • a glass substrate having a size of 2.5 cm ⁇ 2.5 cm was prepared. This glass substrate was treated with ozone UV.
  • Lead iodide (PbI 2 ) was dissolved in a DMF solvent at 70 ° C. to prepare a 0.1 M concentration lead iodide solution.
  • Methyl ammonium iodide (CH 3 NH 3 I) was dissolved in a DMF solvent at 70 ° C. to prepare a methyl ammonium iodide solution having a concentration of 0.1M.
  • the solution was applied to the glass substrate by spin coating at a rotation speed of 1000 rpm, and dried at 100 ° C. for 10 minutes to obtain a coating film of a compound having a perovskite structure.
  • a glass substrate having a size of 2.5 cm ⁇ 2.5 cm was prepared. This glass substrate was treated with ozone UV.
  • Lead iodide (PbI 2 ) was dissolved in a DMF solvent at 70 ° C. to prepare a 0.1 M concentration lead iodide solution.
  • calcium iodide (CaI 2 ) was dissolved in a DMF solvent at 70 ° C. to prepare a calcium iodide solution having a concentration of 0.1M.
  • the above lead iodide solution and calcium iodide solution were mixed so that the molar ratio of Ca / (Ca + Pb) was 0.05 to prepare a solution.
  • the solution was applied to the glass substrate by spin coating at a rotation speed of 1000 rpm, and dried in air at 100 ° C. for 10 minutes to obtain a coating film of a compound having a perovskite structure.
  • the emission spectra of the coating films of the compounds having the perovskite structure obtained in Examples 1 to 4 and Comparative Example 1 were measured with a fluorometer (trade name FT-6500, manufactured by JASCO Corporation, trade name FT-6500, wavelength cut filter, excitation light 430 nm, Sensitivity high). Moreover, the transmittance
  • the emission spectrum of the coating film of the compound having the perovskite structure obtained in Comparative Examples 2 and 3 was measured with a fluorometer (manufactured by JASCO, trade name FT-6500, wavelength cut filter of 600 nm or less, excitation light 550 nm, sensitivity high). It measured using. Further, the transmittance was measured using an ultraviolet-visible absorptiometer of the coating film. In addition, the comparison of the luminescence intensity between the coating films was performed by correcting the maximum luminescence intensity near the wavelength of 750 nm by the following formula (S) -2. [Maximum emission intensity near wavelength 750 nm / (100 ⁇ transmittance at wavelength 550 nm)] ⁇ 100 (S) -2
  • Table 1 shows the composition of the compounds having the perovskite structure of Examples 1 to 4 and Comparative Examples 1 to 3 and the maximum emission intensity.
  • M / (M + Pb) is a value in the charging ratio of “a” in the general formula (1).
  • the light-emitting materials of Examples 1 to 4 including the compound having the perovskite structure according to the present embodiment have excellent emission intensity as compared with the compounds having the perovskite structure of Comparative Examples 1 to 3. It was confirmed that
  • Example 5 A glass substrate having a size of 2.5 cm ⁇ 2.5 cm was prepared. This glass substrate was treated with ozone UV. Lead bromide (PbBr 2 ) was dissolved in a DMF solvent at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M. Similarly, strontium bromide (SrBr 2 ) was dissolved in a DMF solvent at 70 ° C. to prepare a strontium bromide solution having a concentration of 0.1M. Next, methylammonium bromide (CH 3 NH 3 Br) was dissolved in DMF solvent at 70 ° C.
  • a methylammonium bromide solution having a concentration of 0.1M having a concentration of 0.1M.
  • the above lead bromide solution and strontium bromide solution were mixed so that the molar ratio of Sr / (Sr + Pb) was 0.1 to prepare a solution.
  • the solution was applied to the glass substrate by spin coating at a rotation speed of 1000 rpm, and dried in air at 100 ° C. for 10 minutes to obtain a coating film of a compound having a perovskite structure.
  • Example 6 A coating film of a compound having a perovskite structure was obtained in the same manner as in Example 5 except that Sr / (Sr + Pb) was 0.2.
  • Example 7 A coating film of a compound having a perovskite structure was obtained in the same manner as in Example 5 except that Sr / (Sr + Pb) was set to 0.3.
  • Example 8 A coating film of a compound having a perovskite structure was obtained in the same manner as in Example 5 except that Sr / (Sr + Pb) was set to 0.5.
  • Example 9 A glass substrate having a size of 2.5 cm ⁇ 2.5 cm was prepared. This glass substrate was treated with ozone UV.
  • Lead bromide (PbBr 2 ) was dissolved in a DMF solvent at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M.
  • lanthanum bromide (LaBr 3 ) was dissolved in a DMF solvent at 70 ° C. to prepare a lanthanum bromide solution having a concentration of 0.1M.
  • methylammonium bromide CH 3 NH 3 Br
  • the above lead bromide solution and strontium bromide solution were mixed so that La / (La + Pb) was 0.05 by molar ratio to prepare a solution.
  • the solution was applied to the glass substrate by spin coating at a rotation speed of 1000 rpm, and dried in air at 100 ° C. for 10 minutes to obtain a coating film of a compound having a perovskite structure.
  • Example 10 A coating film of a compound having a perovskite structure was obtained in the same manner as in Example 9 except that La / (La + Pb) was set to 0.1.
  • the light emitting materials of Examples 5 to 10 including the compound having the perovskite structure according to the present embodiment have superior light emission intensity as compared with the compound having the perovskite structure of Comparative Example 1. I was able to confirm.
  • Example 6 As a result of measurement by ICP-MS, the value of [M / (M + Pb)] in Example 6 was 0.20. As a result of measurement by ICP-MS, the value of [M / (M + Pb)] in Example 7 was 0.29. As a result of measurement by ICP-MS, the value of [M / (M + Pb)] in Example 8 was 0.51.
  • Example 11 A glass substrate having a size of 2.5 cm ⁇ 2.5 cm was prepared. This glass substrate was treated with ozone UV.
  • Lead bromide (PbBr 2 ) was dissolved in a solvent of N, N-dimethylformamide (hereinafter referred to as “DMF”) at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M.
  • DMF N, N-dimethylformamide
  • barium bromide (BaBr 2 ) was dissolved in a DMF solvent at 70 ° C. to prepare a barium bromide solution having a concentration of 0.1M.
  • methylammonium bromide (CH 3 NH 3 Br) was dissolved in DMF solvent at 70 ° C.
  • a methylammonium bromide solution having a concentration of 0.1M having a concentration of 0.1M.
  • the above lead bromide solution and barium bromide solution were mixed so that Ba / (Ba + Pb) was 0.03 in molar ratio to prepare a solution.
  • the solution was applied to the glass substrate by spin coating at a rotation speed of 1000 rpm, and dried in air at 100 ° C. for 10 minutes to obtain a coating film of a compound having a perovskite structure.
  • Example 12 A coating film of a compound having a perovskite structure was obtained in the same manner as in Example 11 except that Ba / (Ba + Pb) was set to 0.05.
  • Example 13 A coating film of a compound having a perovskite structure was obtained in the same manner as in Example 11 except that Ba / (Ba + Pb) was 0.1.
  • Example 14 A glass substrate having a size of 2.5 cm ⁇ 2.5 cm was prepared. This glass substrate was treated with ozone UV.
  • Lead bromide (PbBr 2 ) was dissolved in a solvent of N, N-dimethylformamide (hereinafter referred to as “DMF”) at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M.
  • DMF N, N-dimethylformamide
  • DyBr 3 dysprosium bromide
  • was dissolved in a DMF solvent at 70 ° C. to prepare a dysprosium bromide solution having a concentration of 0.1M.
  • methylammonium bromide (CH 3 NH 3 Br) was dissolved in DMF solvent at 70 ° C.
  • a methylammonium bromide solution having a concentration of 0.1M having a concentration of 0.1M.
  • the above lead bromide solution and dysprosium bromide solution were mixed so that the molar ratio Dy / (Dy + Pb) was 0.1 to prepare a solution.
  • the solution was applied to the glass substrate by spin coating at a rotation speed of 1000 rpm, and dried in air at 100 ° C. for 10 minutes to obtain a coating film of a compound having a perovskite structure.
  • Example 15 A glass substrate having a size of 2.5 cm ⁇ 2.5 cm was prepared. This glass substrate was treated with ozone UV.
  • Lead bromide (PbBr 2 ) was dissolved in a solvent of N, N-dimethylformamide (hereinafter referred to as “DMF”) at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M.
  • calcium bromide (CaBr 2 ) was dissolved in a DMF solvent at 70 ° C. to prepare a calcium bromide solution having a concentration of 0.1M.
  • methylammonium chloride (CH 3 NH 3 Cl) was dissolved in a DMF solvent at 70 ° C.
  • the above lead bromide solution and calcium bromide solution were mixed so that the molar ratio of Ca / (Ca + Pb) was 0.1 to prepare a solution.
  • the solution was applied to the glass substrate by spin coating at a rotation speed of 1000 rpm, and dried in air at 100 ° C. for 10 minutes to obtain a coating film of a compound having a perovskite structure.
  • Example 16 A glass substrate having a size of 2.5 cm ⁇ 2.5 cm was prepared. This glass substrate was treated with ozone UV.
  • Lead bromide (PbBr 2 ) was dissolved in a solvent of N, N-dimethylformamide (hereinafter referred to as “DMF”) at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M.
  • calcium bromide (CaBr 2 ) was dissolved in a DMF solvent at 70 ° C. to prepare a calcium bromide solution having a concentration of 0.1M.
  • methylammonium iodide (CH 3 NH 3 I) was dissolved in a DMF solvent at 70 ° C.
  • a methylammonium iodide solution having a concentration of 0.1M having a concentration of 0.1M.
  • the above lead bromide solution and calcium bromide solution were mixed so that the molar ratio of Ca / (Ca + Pb) was 0.1 to prepare a solution.
  • the solution was applied to the glass substrate by spin coating at a rotation speed of 1000 rpm, and dried in air at 100 ° C. for 10 minutes to obtain a coating film of a compound having a perovskite structure.
  • a glass substrate having a size of 2.5 cm ⁇ 2.5 cm was prepared. This glass substrate was treated with ozone UV.
  • Lead bromide (PbBr 2 ) was dissolved in a solvent of N, N-dimethylformamide (hereinafter referred to as “DMF”) at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M.
  • methylammonium chloride (CH 3 NH 3 Cl) was dissolved in a DMF solvent at 70 ° C. to prepare a 0.1M concentration methylammonium chloride solution.
  • the solution was applied to the glass substrate by spin coating at a rotation speed of 1000 rpm, and dried in air at 100 ° C. for 10 minutes to obtain a coating film of a compound having a perovskite structure.
  • a glass substrate having a size of 2.5 cm ⁇ 2.5 cm was prepared. This glass substrate was treated with ozone UV.
  • Lead bromide (PbBr 2 ) was dissolved in a solvent of N, N-dimethylformamide (hereinafter referred to as “DMF”) at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M.
  • methylammonium iodide (CH 3 NH 3 I) was dissolved in a DMF solvent at 70 ° C. to prepare a methylammonium iodide solution having a concentration of 0.1M.
  • the solution was applied to the glass substrate by spin coating at a rotation speed of 1000 rpm, and dried in air at 100 ° C. for 10 minutes to obtain a coating film of a compound having a perovskite structure.
  • Tables 3 and 4 below show the composition of the compounds having the perovskite structure of Examples 11 to 14 and Comparative Examples 4 to 5 and the maximum emission intensity.
  • M / (M + Pb) is a value in the charging ratio of “a” in the general formula (1).
  • this embodiment is applied to Examples 11 to 13 using barium ions as divalent or trivalent metal ions to which this embodiment is applied and Examples 14 using dysprosium ions.
  • the maximum emission intensity was higher than that of Comparative Example 1 that was not used.
  • Example 15 to which the present embodiment was applied using two types of halide ions (Br and Cl) as X had higher maximum emission intensity than Comparative Example 4 to which the present embodiment was not applied.
  • Example 16 to which the present embodiment was applied using two types of halide ions (Br and I) as X had higher maximum emission intensity than Comparative Example 5 to which the present embodiment was not applied.
  • the compound having the perovskite structure of the present embodiment and the light emitting material using the compound can be suitably used in the field of light emission related materials.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Luminescent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un composé ayant une structure perovskite et présentant une intensité de luminescence élevée, et un matériau luminescent comprenant le composé. Le composé qui présente une structure cristalline perovskite comprend A, B, X, et M comme composants, où le rapport molaire obtenu en divisant la quantité de M par la quantité totale de M et B, M/(M+B), est de 0,7 ou moins (A est un cation monovalent localisé à chacun des vortex d'un hexaèdre centré par B dans la structure cristalline perovskite. B est un ion plomb. M est un cation qui est un ion métallique divalent ou trivalent avec lequel certains des sites B dans la structure cristalline perovskite sont substitués, et qui est sélectionné parmi les ions métalliques ayant un rayon d'ion de coordination 6 de 0,9 à 1,5 Å. X indique des composants situés aux vortex d'un octaèdre centré par B dans la structure cristalline perovskite, et est au moins un type d'ion sélectionné parmi le groupe constitué de Cl-, Br-, F-, I-, et SCN-, X comprenant au moins un ion chlorure ou un ion bromure).
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