TWI717527B - Composition - Google Patents

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TWI717527B
TWI717527B TW106120710A TW106120710A TWI717527B TW I717527 B TWI717527 B TW I717527B TW 106120710 A TW106120710 A TW 106120710A TW 106120710 A TW106120710 A TW 106120710A TW I717527 B TWI717527 B TW I717527B
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ion
crystal structure
compound
perovskite
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TW201835294A (en
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内藤翔太
酒谷能彰
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日商住友化學股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D17/00—Rubidium, caesium or francium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • 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

Abstract

The present invention relates to a composition wherein a compound having a perovskite-type crystal structure is dispersed in a medium, the compound comprising A ion, B ion, X ion and M ion, wherein the molar ratio [M/(M+B)], which is calculated by dividing the molar number of M ion by the total molar number of M ion and B ion, is 0.7 or less, and wherein A ion is a cesium ion, an organic ammonium ion or an amidinium ion locating at each vertex of a hexahedron the center of which is B ion in the perovskite-type crystal structure; B ion is a lead ion; M ion is a divalent or trivalent metal element cation the 6-coordinated ionic radius of which is 0.9 Å to 1.5 Å; X ion is Cl-, Br-, F-, I- and SCN- locating at each vertex of an octahedron the center of which is B ion in the perovskite-type crystal structure.

Description

組成物 Composition

本發明係關於一種組成物。 The present invention relates to a composition.

本案係主張2016年6月24日在日本申請的特願2016-126046號的優先權，此處援用其內容。 This case claims the priority of Special Application No. 2016-126046 filed in Japan on June 24, 2016, and its content is quoted here.

傳統以來，已知具有由有機物的陽離子、鹵化物離子及2價金屬離子所構成的有機-無機鈣鈦礦(Perovskite)型結晶構造的化合物。近年來，對具有在金屬離子的位置具有14族元素(Ge、Sn及Pb)的離子之鈣鈦礦型結晶構造的化合物之導電性及發光特性的關心日益提高。 Conventionally, compounds having organic-inorganic Perovskite crystal structures composed of organic cations, halide ions, and divalent metal ions have been known. In recent years, there has been increasing interest in the conductivity and luminescence characteristics of compounds having a perovskite-type crystal structure with ions of group 14 elements (Ge, Sn, and Pb) at the positions of metal ions.

特別是前述2價金屬離子為Pb(II)時，在紫外線區域至紅色光譜區域的範圍，觀察到室溫下強烈發光的現象(非專利文獻1)。而且，會依鹵化物離子的種類而可調整發光波長(非專利文獻2)。 In particular, when the aforementioned divalent metal ion is Pb(II), a phenomenon of strong light emission at room temperature is observed in the range from the ultraviolet region to the red spectral region (Non-Patent Document 1). Furthermore, the emission wavelength can be adjusted according to the type of halide ion (Non-Patent Document 2).

[先前技術文獻] [Prior Technical Literature] [非專利文獻] [Non-Patent Literature]

[非專利文獻1]M. Era, A. Shimizu and M. Nagano, Rep. Prog. Polym. Phys. Jpn., 42, 473-474(1999) [Non-Patent Document 1] M. Era, A. Shimizu and M. Nagano, Rep. Prog. Polym. Phys. Jpn., 42, 473-474 (1999)

[非專利文獻2]L. Protesescu, S. Yakunin, M. I. Bodnarchuk, F. Krieg, R. Caputo, C.H. Hendon, R.X. Yang, A. Walsh, And M.V. Kovalenko, Nano Letter. 15, 3692-3696 (2015) [Non-Patent Document 2] L. Protesescu, S. Yakunin, MI Bodnarchuk, F. Krieg, R. Caputo, CH Hendon, RX Yang, A. Walsh, And MV Kovalenko, Nano Letter. 15, 3692-3696 (2015)

但是，為了將如上述非專利文獻1或非專利文獻2記載的具有鈣鈦礦型結晶構造的化合物作為發光材料在產業上應用，要求前述化合物進一步的量子產率的提高。 However, in order to use the compound having a perovskite-type crystal structure as described in Non-Patent Document 1 or Non-Patent Document 2 as a light-emitting material for industrial application, further improvement in quantum yield of the aforementioned compound is required.

本發明，係有鑑於上述課題而成者，其目的係提供一種包含量子產率高且具有鈣鈦礦型結晶構造的化合物的組成物。 The present invention was made in view of the above-mentioned problems, and its object is to provide a composition including a compound having a high quantum yield and a perovskite-type crystal structure.

為了解決上述課題，本發明人等深入研究的結果，達成以下的本發明。 In order to solve the above-mentioned problems, the inventors of the present invention have achieved the following invention as a result of intensive studies.

亦即，本發明的實施態樣，包含下述[1]至[6]的發明。 That is, the embodiments of the present invention include the following inventions [1] to [6].

[1]一種具有鈣鈦礦型結晶構造的化合物分散於介質中之組成物，該化合物係以A、B、X及M為構成成分，M的莫耳數量除以M及B的合計莫耳數量的莫耳比[M/(M+B)]的值為0.7以下；(A為位於在前述鈣鈦礦型結晶構造中以B為中心的六 面體的各頂點之銫離子、有機銨離子或脒鎓(amidinium)離子；B為鉛離子；M為於六配位的離子半徑為0.9Å以上1.5Å以下之2價或3價金屬元素的陽離子，M的至少一部分在前述鈣鈦礦型結晶構造中取代B的一部分；X表示位於在前述鈣鈦礦型結晶構造中以B為中心的八面體的各頂點的成分，其係選自氯化物離子、溴化物離子、氟化物離子、碘化物離子及硫氰酸根離子所成群的1種以上的陰離子)。 [1] A composition in which a compound having a perovskite crystal structure is dispersed in a medium, the compound is composed of A, B, X, and M, and the number of moles of M divided by the total moles of M and B The molar ratio of the quantity [M/(M+B)] is 0.7 or less; (A is the cesium ion and organic ammonium located at each vertex of the hexahedron centered on B in the aforementioned perovskite crystal structure Ion or amidinium ion; B is lead ion; M is a cation of a divalent or trivalent metal element with an ionic radius of 0.9 Å to 1.5 Å in hexacoordination, at least a part of M is in the aforementioned perovskite Part of B in the type crystal structure; X represents the component located at each vertex of the octahedron centered at B in the aforementioned perovskite type crystal structure, which is selected from chloride ion, bromide ion, fluoride ion , Iodide ion and thiocyanate ion group of one or more anions).

[2]如[1]記載的組成物，其中，前述M為鹼土金屬元素的陽離子或稀土元素的陽離子。 [2] The composition according to [1], wherein the aforementioned M is a cation of an alkaline earth metal element or a cation of a rare earth element.

[3]如[1]或[2]記載的組成物，其中，前述M為鈣離子或鈰離子。 [3] The composition according to [1] or [2], wherein the aforementioned M is calcium ion or cerium ion.

[4]如[1]至[3]中任一項記載的組成物，其中，前述A為有機銨離子。 [4] The composition according to any one of [1] to [3], wherein the aforementioned A is an organic ammonium ion.

[5]如[1]至[4]中任一項記載的組成物，其中，前述介質為液體。 [5] The composition according to any one of [1] to [4], wherein the medium is a liquid.

[6]如[1]至[4]中任一項記載的組成物，其中，前述介質為樹脂。 [6] The composition according to any one of [1] to [4], wherein the medium is a resin.

根據本發明，可提供一種包含量子產率高的具有鈣鈦礦型結晶構造的化合物之組成物。 According to the present invention, it is possible to provide a composition containing a compound having a perovskite crystal structure with a high quantum yield.

以下，顯示實施態樣以詳細地說明本發明。 Hereinafter, the embodiments are shown to explain the present invention in detail.

<組成物> <Composition>

本發明係後述之具有鈣鈦礦型結晶構造的化合物分散於介質中之組成物。 The present invention is a composition in which a compound having a perovskite-type crystal structure described later is dispersed in a medium.

作為具有鈣鈦礦型結晶構造的化合物分散於介質中之組成物，可列舉：後述之具有鈣鈦礦型結晶構造的化合物分散於液體中之分散液組成物、及後述之具有鈣鈦礦型結晶構造的化合物分散於樹脂中之樹脂組成物。 As a composition in which a compound having a perovskite-type crystal structure is dispersed in a medium, a dispersion composition in which a compound having a perovskite-type crystal structure is dispersed in a liquid described later, and a composition having a perovskite-type crystal structure described later A resin composition in which a compound with a crystalline structure is dispersed in a resin.

前述組成物，可具有後述的具有鈣鈦礦型結晶構造的化合物以外的其他成分。作為其他成分，可列舉例如：若干雜質、以及以A、B、X及/或M為構成成分的具有非結晶構造的化合物。作為雜質，可列舉例如：包含A、B及/或M的鹵化物；B及/或M的氧化物、複合氧化物；以及包含A、B、X及/或M的其他化合物。 The aforementioned composition may have components other than the compound having a perovskite crystal structure described later. As other components, for example, some impurities and compounds having an amorphous structure with A, B, X, and/or M as constituent components can be cited. Examples of impurities include halides containing A, B, and/or M; oxides and composite oxides of B and/or M; and other compounds containing A, B, X, and/or M.

《化合物》 "Compounds"

本發明之組成物所包含之具有鈣鈦礦型結晶構造的化合物，其係以A、B、X及M為構成成分，M的莫耳數量除以M及B的合計莫耳數量的莫耳比[M/(M+B)]的值為0.7以下的具有鈣鈦礦型結晶構造的化合物。 The compound having a perovskite-type crystal structure contained in the composition of the present invention is composed of A, B, X and M, and the number of moles of M divided by the total number of moles of M and B A compound having a perovskite-type crystal structure having a ratio [M/(M+B)] value of 0.7 or less.

本發明之化合物中，A為位於在前述鈣鈦礦型結晶構造中以B為中心的六面體的各頂點的銫離子、有機銨離子或脒鎓(amidinium)離子。B為鉛離子。M係於六配位的離子半徑為0.9至1.5Å之2價或3價金屬元素的陽離子，M的至少一部分在前述鈣鈦礦型結晶構造中取代B的一部分。X表示位於在前述鈣鈦礦型結晶構造中以B為中心的 八面體的各頂點的成分，係選自氯化物離子、溴化物離子、氟化物離子、碘化物離子及硫氰酸根離子所成群的1種以上的陰離子。 In the compound of the present invention, A is a cesium ion, an organic ammonium ion, or an amidinium ion located at each vertex of a hexahedron centered on B in the aforementioned perovskite-type crystal structure. B is lead ion. M is a cation of a divalent or trivalent metal element with a hexacoordinate ion radius of 0.9 to 1.5 Å, and at least a part of M replaces a part of B in the aforementioned perovskite crystal structure. X represents a component located at each vertex of an octahedron centered at B in the aforementioned perovskite crystal structure, and is selected from chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion. Groups of one or more anions.

又，在此，1Å=0.1nm(以下相同)時，M於六配位的離子半徑為0.09nm以上、0.15nm以下。 Here, when 1Å=0.1nm (the same applies to the following), the ionic radius of the six coordination of M is 0.09nm or more and 0.15nm or less.

作為以A、B、X及M為構成成分的具有鈣鈦礦型結晶構造的化合物方面，並無特別限制，可為具有3維構造、2維構造、擬似2維構造的任意構造的化合物。 The compound having a perovskite-type crystal structure containing A, B, X, and M as constituent components is not particularly limited, and may be a compound having any structure having a three-dimensional structure, a two-dimensional structure, or a pseudo-two-dimensional structure.

於3維構造時，鈣鈦礦型結晶構造係以AB(1-a)MaX(3+δ)表示。 In the case of a three-dimensional structure, the perovskite crystal structure is represented by AB (1-a) M a X (3+ δ ) .

於2維構造時，鈣鈦礦型結晶構造係以A2B(1-a)MaX(4+δ)表示。 In the case of a two-dimensional structure, the perovskite crystal structure is represented by A 2 B (1-a) M a X (4+ δ ) .

a表示M的莫耳數量除以M及B的合計莫耳數量的莫耳比[M/(M+B)]。 a represents the molar ratio of the number of moles of M divided by the total number of moles of M and B [M/(M+B)].

δ為可對應B及M的電荷平衡而適當地改變的數，係0以上0.7以下。例如A為1價陽離子，B為2價陽離子(Pb離子)，M為2價或3價的金屬元素的陽離子以及X為1價陰離子時，可以使前述化合物成為中性(電荷為0)之方式選擇δ。 δ is a number that can be changed appropriately according to the charge balance of B and M, and is 0 or more and 0.7 or less. For example, when A is a monovalent cation, B is a divalent cation (Pb ion), M is a cation of a divalent or trivalent metal element, and X is a monovalent anion, the aforementioned compound can be made neutral (the charge is 0). Choose δ as the method .

通常具有鈣鈦礦型結晶構造的化合物的基本構造為3維構造或2維構造。 Generally, the basic structure of a compound having a perovskite crystal structure is a three-dimensional structure or a two-dimensional structure.

於3維構造時，其組成式係以A’B’X’3表示。此處，A’表示有機陽離子或無機陽離子，B’表示金屬陽離子，X’表示鹵化物離子或硫氰酸根離子。 When the three-dimensional structure in which the composition formula based 'represents 3 to A'B'X. Here, A'represents an organic cation or an inorganic cation, B'represents a metal cation, and X'represents a halide ion or a thiocyanate ion.

於2維構造時，其組成式係以A’2B’X’4表示。在此，A’、B’及X’表示與上述相同的意義。 When the two-dimensional structure in which the composition system to the formula A '2 B'X' 4 Fig. Here, A', B', and X'have the same meaning as described above.

於上述3維構造時，以B’為中心，具有頂點為X’之B’X’6表示的頂點共有八面體的3維網絡。 In the above three-dimensional structure, a three-dimensional network in which the vertices represented by B'X' 6 with vertices X'share an octahedron with B'as the center.

於上述2維構造時，以B’為中心，藉由頂點為X’之B’X’6表示的八面體在相同平面上的4個頂點X’共有，形成2維相連的B’X’6所構成的層與A’所構成的層交錯積層的構造。 In the above-mentioned two-dimensional structure, with B'as the center, the octahedron represented by B'X' 6 with the vertex X'has four vertices X'on the same plane shared by four vertices X'to form a two-dimensional connected B'X The layer formed by ' 6 and the layer formed by A'are staggered and stacked.

B’為可採取X’的八面體配位之金屬陽離子。 B'is a metal cation that can adopt the octahedral coordination of X'.

A’位於以B’為中心的六面體的各頂點。 A'is located at each vertex of a hexahedron centered on B'.

本說明書中，鈣鈦礦構造係可藉由X射線繞射圖形確認。 In this manual, the perovskite structure can be confirmed by X-ray diffraction patterns.

於前述3維構造的具有鈣鈦礦型結晶構造的化合物時，於X射線繞射圖形中，通常在2 θ=12至18°的位置，確認來自(hkl)=(001)的繞射峰或在2 θ=18至25°的位置，確認來自(hkl)=(100)的繞射峰。以在2 θ=13至16°的位置，確認來自(hkl)=(001)的繞射峰或在2 θ=20至23°的位置，確認來自(hkl)=(100)的繞射峰更佳。 For the aforementioned three-dimensional compound with perovskite crystal structure, in the X-ray diffraction pattern, the diffraction peak from (hkl)=(001) is usually located at 2 θ=12 to 18° Or at the position of 2 θ=18-25°, confirm the diffraction peak from (hkl)=(100). To confirm the diffraction peak from (hkl)=(001) at 2 θ=13 to 16° or at 2 θ=20 to 23° to confirm the diffraction peak from (hkl)=(100) Better.

於前述2維構造的具有鈣鈦礦型結晶構造的化合物時，於X射線繞射圖形中，通常在2 θ=1至10°的位置，確認來自(hkl)=(002)的繞射峰，以在2 θ=2至8°的位置，確認來自(hkl)=(002)的繞射峰更佳。 In the case of the compound with the perovskite crystal structure of the aforementioned two-dimensional structure, in the X-ray diffraction pattern, the diffraction peak from (hkl)=(002) is usually located at 2 θ=1 to 10° , To confirm that the diffraction peak from (hkl)=(002) is better at 2 θ=2 to 8°.

本發明人等深入研究的結果，發現藉由於具有鈣鈦礦型結晶構造的化合物中，使A’成分的有機陽離 子或無機陽離子為銫離子、有機銨離子或脒鎓離子(A成分)，B’成分的金屬元素之陽離子為鉛離子(B成分)，複數個A成分及/或B成分的一部分被於六配位的離子半徑為0.9Å以上1.5Å以下之2價或3價金屬元素的陽離子(M成分)取代並作成組成物，即可提高量子產率。 As a result of intensive research, the inventors found that the organic cation or inorganic cation of component A'is cesium ion, organic ammonium ion or amidinium ion (component A) in a compound having a perovskite crystal structure. The cation of the metal element of the component is lead ion (component B), and a part of the plural A component and/or B component is hexacoordinated to a divalent or trivalent metal element with a radius of 0.9 Å to 1.5 Å The cation (component M) is substituted and made into a composition to increase the quantum yield.

本發明之組成物所包含的化合物，係以下述通式(1)所示的具有鈣鈦礦型結晶構造的化合物為佳。 The compound contained in the composition of the present invention is preferably a compound having a perovskite crystal structure represented by the following general formula (1).

APb(1-a)MaX(3+δ)(0<a≦0.7，0≦δ≦0.7)…(1)[通式(1)中，A為銫離子、有機銨離子或脒鎓離子，M為於六配位的離子半徑為0.9Å以上1.5Å以下之2價或3價金屬元素的陽離子，X為選自氯化物離子、溴化物離子、氟化物離子、碘化物離子及硫氰酸根離子所成群的1種以上的陰離子。通式(1)中，a為大於0且在0.7以下，δ為0以上且在0.7以下。] APb (1-a) M a X (3+ δ ) (0<a≦0.7, 0≦ δ ≦0.7)…(1) [In the general formula (1), A is cesium ion, organic ammonium ion or amidinium Ion, M is a cation of a divalent or trivalent metal element with an ionic radius of 0.9 Å to 1.5 Å in the six-coordinate, X is selected from chloride ion, bromide ion, fluoride ion, iodide ion and sulfur One or more anions grouped by cyanate ions. In the general formula (1), a is more than 0 and 0.7 or less, and δ is 0 or more and 0.7 or less. ]

一般鈣鈦礦的基本構造形態為ABX3，具有頂點共有BX6八面體的3維網絡。ABX3構造中的B成分為可採取X陰離子的八面體配位的金屬陽離子。ABX3構造中的B成分係可採取X陰離子的八面體配位的金屬陽離子。A陽離子位於以B原子為中心的六面體的各頂點，一般為有機陽離子或無機陽離子。ABX3構造的X成分，通常為鹵化物離子。 Generally, the basic structural form of perovskite is ABX 3 , with a three-dimensional network with vertices sharing BX 6 octahedrons. The B component in the ABX 3 structure is a metal cation that can adopt the octahedral coordination of X anion. The B component in the ABX 3 structure can be a metal cation with an octahedral coordination of the X anion. The A cation is located at each vertex of the hexahedron centered on the B atom, and is generally an organic cation or an inorganic cation. The X component of the ABX 3 structure is usually a halide ion.

本發明人等深入研究的結果，發現於上述ABX3表示的鈣鈦礦型結晶構造的基本構造中，以B成分的金屬陽離子為鉛，藉由前述3維網絡中以其他原子取代複 數鉛離子的一部分並作成組成物，即可提高量子產率。 As a result of intensive research, the inventors found that in the basic structure of the perovskite crystal structure represented by ABX 3 , the metal cation of the B component is lead, and the plural lead ions are replaced by other atoms in the aforementioned three-dimensional network. The quantum yield can be improved by forming a part of it into a composition.

本發明中，通式(1)所示的具有鈣鈦礦型結晶構造的化合物，作為A、B成分係以鉛、M及X為主成分。此處，M係指取代金屬陽離子的鉛離子的一部分的原子。又，M在前述基本構造中取代B成分(鉛離子)存在的位置、或取代A成分存在的位置、或存在於構成前述基本構造的骨架的晶格間隙。但是，M的至少一部分，以在前述鈣鈦礦型結晶構造中取代B的一部分者為佳。 In the present invention, the compound having a perovskite-type crystal structure represented by the general formula (1) has lead, M, and X as the main components as the A and B components. Here, M means an atom that replaces a part of the lead ion of the metal cation. In addition, M substitutes the position where the B component (lead ion) exists in the basic structure, or the position where the A component exists, or exists in the lattice gaps constituting the skeleton of the basic structure. However, it is preferable that at least a part of M is substituted for a part of B in the aforementioned perovskite crystal structure.

以下，對於本發明中以A、B、X及M為構成成分之具有鈣鈦礦型結晶構造的化合物進行說明。 Hereinafter, the compound having a perovskite-type crystal structure that has A, B, X, and M as constituent components in the present invention will be described.

〔A〕 〔A〕

本發明之組成物所包含的具有鈣鈦礦型結晶構造的化合物中，A為銫離子、有機銨離子或脒鎓離子。 In the compound having a perovskite crystal structure contained in the composition of the present invention, A is a cesium ion, an organic ammonium ion, or an amidinium ion.

具有鈣鈦礦型結晶構造的化合物中，於A為銫離子、碳原子數3以下的有機銨離子或碳原子數3以下的脒鎓離子時，一般鈣鈦礦型結晶構造係具有以AB(1-a)MaX3表示之3維構造。 Among the compounds having a perovskite crystal structure, when A is a cesium ion, an organic ammonium ion with carbon atoms of 3 or less, or an amidinium ion with carbon atoms of 3 or less, the perovskite crystal structure generally has AB ( 1-a) Three-dimensional structure represented by M a X 3 .

作為A所示之有機銨離子，可列舉例如下述通式(A1)表示的有機銨離子。 Examples of the organic ammonium ion represented by A include organic ammonium ions represented by the following general formula (A1).

Figure 106120710-A0202-12-0008-1
Figure 106120710-A0202-12-0008-1

通式(A1)中，R1至R4分別獨立表示氫原子、可具有以胺基作為取代基的烷基或可具有以胺基作為取代基的環烷基。但是R1至R4不會全部是氫原子。 In the general formula (A1), R 1 to R 4 each independently represent a hydrogen atom, an alkyl group which may have an amino group as a substituent, or a cycloalkyl group which may have an amino group as a substituent. However, not all R 1 to R 4 are hydrogen atoms.

R1至R4所示的烷基，可為直鏈狀，亦可為分支鏈狀，亦可具有胺基作為取代基。 The alkyl group represented by R 1 to R 4 may be linear or branched, and may have an amino group as a substituent.

R1至R4所示的烷基的碳原子數，通常為1至20，以1至4為佳，以1至3更佳。 The number of carbon atoms of the alkyl group represented by R 1 to R 4 is usually 1 to 20, preferably 1 to 4, and more preferably 1 to 3.

R1至R4所示的環烷基，可具有胺基作為取代基。 The cycloalkyl group represented by R 1 to R 4 may have an amino group as a substituent.

R1至R4所示的環烷基的碳原子數，通常為3至30，以3至11為佳，以3至8更佳。 The number of carbon atoms of the cycloalkyl group represented by R 1 to R 4 is usually 3 to 30, preferably 3 to 11, and more preferably 3 to 8.

R1至R4所示的基方面，係以氫原子或烷基為佳。 The group represented by R 1 to R 4 is preferably a hydrogen atom or an alkyl group.

藉由減少通式(A1)中所含的烷基及環烷基之數以及減少烷基及環烷基的碳原子數，即可得到量子產率高的具有3維構造的鈣鈦礦型結晶構造的化合物。 By reducing the number of alkyl groups and cycloalkyl groups contained in the general formula (A1) and reducing the number of carbon atoms of the alkyl groups and cycloalkyl groups, a perovskite type with a three-dimensional structure with high quantum yield can be obtained Crystal structure compound.

烷基或環烷基的碳原子數為4以上時，可得到一部分或全部具有2維及/或擬似2維(quasi-2D)的鈣鈦礦型結晶構造的化合物。2維的鈣鈦礦型結晶構造無限大地積層時，等同於3維的鈣鈦礦型結晶構造(參考文獻：P.P.Boix et al,J.Phys.Chem.Lett.2015,6,898-907等)。 When the number of carbon atoms of the alkyl group or cycloalkyl group is 4 or more, a part or all of a compound having a two-dimensional and/or quasi-2D (quasi-2D) perovskite crystal structure can be obtained. When a 2-dimensional perovskite crystal structure is infinitely deposited, it is equivalent to a 3-dimensional perovskite crystal structure (reference: P.P.Boix et al, J.Phys.Chem.Lett.2015, 6,898-907, etc.).

R1至R4所示的烷基中所含的碳原子的合計數係以1至4為佳，R1至R4所示的環烷基中所含的碳原子的合計數係以3至4為佳。以R1為碳原子數1至3的烷基，R2至 R4為氫原子者更佳。 The total number of carbon atoms contained in the alkyl group represented by R 1 to R 4 is preferably 1 to 4, and the total number of carbon atoms contained in the cycloalkyl group represented by R 1 to R 4 is 3 Up to 4 is better. It is more preferable that R 1 is an alkyl group having 1 to 3 carbon atoms, and R 2 to R 4 are hydrogen atoms.

以A為CH3NH3 +(亦稱為甲基銨離子)、C2H5NH3 +(亦稱為乙基銨離子)或C3H7NH3 +(亦稱為丙基銨離子)者為佳，以CH3NH3 +或C2H5NH3 +更佳，以CH3NH3 +又更佳。 Let A be CH 3 NH 3 + (also known as methyl ammonium ion), C 2 H 5 NH 3 + (also known as ethyl ammonium ion) or C 3 H 7 NH 3 + (also known as propyl ammonium ion) ) Is preferred, CH 3 NH 3 + or C 2 H 5 NH 3 + is more preferred, and CH 3 NH 3 + is even more preferred.

A表示的脒鎓離子方面，可列舉例如下述通式(A2)表示的脒鎓離子的例。 With regard to the amidinium ion represented by A, examples of the amidinium ion represented by the following general formula (A2) can be cited.

(R5R6N=CH-NR7R8)+…(A2) (R 5 R 6 N=CH-NR 7 R 8 ) + …(A2)

通式(A2)中，R5至R8分別獨立地表示氫原子、可具有胺基作為取代基的烷基或可具有胺基作為取代基的環烷基。 In the general formula (A2), R 5 to R 8 each independently represent a hydrogen atom, an alkyl group which may have an amino group as a substituent, or a cycloalkyl group which may have an amino group as a substituent.

R5至R8所示的烷基，可為直鏈狀，亦可為分支鏈狀，亦可具有胺基作為取代基。 The alkyl group represented by R 5 to R 8 may be linear or branched, and may have an amino group as a substituent.

R5至R8所示的烷基的碳原子數，通常為1至20，以1至4為佳，以1至3更佳。 The number of carbon atoms of the alkyl group represented by R 5 to R 8 is usually 1 to 20, preferably 1 to 4, and more preferably 1 to 3.

R5至R8所示的環烷基，可具有胺基作為取代基。 The cycloalkyl group represented by R 5 to R 8 may have an amino group as a substituent.

R5至R8所示的環烷基的碳原子數，通常為3至20，以3至11為佳，以3至8更佳。 The number of carbon atoms of the cycloalkyl group represented by R 5 to R 8 is usually 3 to 20, preferably 3 to 11, and more preferably 3 to 8.

作為R5至R8所示的基，係以氫原子或烷基為佳。 The group represented by R 5 to R 8 is preferably a hydrogen atom or an alkyl group.

藉由減少通式(A2)中所含的烷基及環烷基的數以及減少烷基及環烷基的碳原子數，可得到量子產率高的具有3維構造的鈣鈦礦型結晶構造的化合物。 By reducing the number of alkyl groups and cycloalkyl groups contained in the general formula (A2) and reducing the number of carbon atoms of alkyl groups and cycloalkyl groups, a perovskite crystal with a three-dimensional structure with high quantum yield can be obtained Structured compound.

烷基或環烷基的碳原子數為4以上時，可得到一部分或全部具有2維及/或擬似2維(quasi-2D)的鈣鈦礦型結晶構造的化合物。而且，R5至R8所示的烷基中所含的碳原子數的合計數係以1至4為佳，R5至R8所示的環烷基中所含的碳原子數的合計數係以3至4為佳。以R5為碳原子數1至3的烷基，R6至R8為氫原子者更佳。 When the number of carbon atoms of the alkyl group or cycloalkyl group is 4 or more, a part or all of a compound having a two-dimensional and/or quasi-2D (quasi-2D) perovskite crystal structure can be obtained. Furthermore, the total number of carbon atoms contained in the alkyl group represented by R 5 to R 8 is preferably 1 to 4, and the total number of carbon atoms contained in the cycloalkyl group represented by R 5 to R 8 The number system is preferably 3 to 4. It is more preferable that R 5 is an alkyl group having 1 to 3 carbon atoms, and R 6 to R 8 are hydrogen atoms.

〔M〕 〔M〕

M意指取代A成分及/或B成分的一部分的成分，在前述具有鈣鈦礦型結晶構造的化合物的基本構造中，可存在於構成基本構造的骨架的晶格間隙。 M means a component that replaces a part of the A component and/or the B component, and in the basic structure of the compound having the perovskite crystal structure described above, it may exist in the lattice gaps constituting the skeleton of the basic structure.

M係於六配位的離子半徑為0.9Å以上1.5Å以下之2價或3價金屬元素的陽離子。前述於六配位的離子半徑，較佳為0.95Å以上1.4Å以下，更佳為0.95Å以上1.3Å以下。 M is a cation of a divalent or trivalent metal element with a six-coordinate ion radius of 0.9Å to 1.5Å. The aforementioned ionic radius at the six-coordinate is preferably 0.95 Å or more and 1.4 Å or less, more preferably 0.95 Å or more and 1.3 Å or less.

從維持具有鈣鈦礦型結晶構造的化合物的鈣鈦礦結晶構造，得到充分的發光強度的觀點來看，作為M，可列舉例如：鋇離子(於六配位的離子半徑：1.35Å)、鈣離子(於六配位的離子半徑：1.00Å)、鈰離子(於六配位的離子半徑：1.01Å)、鏑離子(於六配位的離子半徑：1.07Å)、鑭離子(於六配位的離子半徑：1.03Å)、釤離子(於六配位的離子半徑：1.19Å)、鍶離子(於六配位的離子半徑：1.18Å)、鐿離子(於六配位的離子半徑：1.02Å)等金屬元素的陽離子。 From the viewpoint of maintaining the perovskite crystal structure of the compound having the perovskite crystal structure and obtaining sufficient luminous intensity, as M, for example, barium ions (ion radius at six coordination: 1.35 Å), Calcium ion (ionic radius coordinated in six: 1.00Å), cerium ion (ionic radius coordinated in six: 1.01Å), dysprosium ion (ionic radius coordinated in six: 1.07Å), lanthanum ion (ionic radius in six Coordinated ion radius: 1.03Å), samarium ion (ionic radius in six-coordinated: 1.19Å), strontium ion (ionic radius in six-coordinated: 1.18Å), ytterbium ion (ion in six-coordinated radius : 1.02Å) and other metal cations.

本發明中，「離子半徑」之值可使用Shannon之離子半 徑的文獻值(參照論文：R.D.Shannon,Acta Crystallogr.,Sect.A,32,751(1976))。 In the present invention, the value of "ionic radius" can use the literature value of Shannon's ion radius (refer to the paper: R.D. Shannon, Acta Crystallogr., Sect. A, 32, 751 (1976)).

其中，M係以鹼土金屬元素的陽離子或稀土元素的陽離子為佳，以鈣離子或鈰離子更佳。 Among them, the M series is preferably alkaline earth metal element cations or rare earth element cations, and calcium ion or cerium ion is more preferred.

〔a〕 [A]

a表示M的莫耳數量除以M及B的合計莫耳數量的莫耳比之[M/(B+M)]。 a represents the molar ratio of the number of moles of M divided by the total number of moles of M and B [M/(B+M)].

從維持具有鈣鈦礦型結晶構造的化合物之結晶構造，得到充分的量子產率之觀點來看，a為大於0且在0.7以下。從維持具有鈣鈦礦型結晶構造的化合物之結晶構造，得到充分的量子產率之觀點來看，a係以0.01以上0.7以下為佳，以0.02以上0.5以下更佳，以0.03以上0.3以下又更佳，以0.04以上0.2以下為特佳。 From the viewpoint of maintaining the crystal structure of the compound having the perovskite crystal structure and obtaining a sufficient quantum yield, a is greater than 0 and 0.7 or less. From the standpoint of maintaining the crystal structure of the compound with the perovskite crystal structure and obtaining sufficient quantum yield, a is preferably 0.01 or more and 0.7 or less, more preferably 0.02 or more and 0.5 or less, and 0.03 or more and 0.3 or less. More preferably, it is particularly preferably not less than 0.04 and not more than 0.2.

〔X〕 〔X〕

X為選自氯化物離子、溴化物離子、氟化物離子、碘化物離子及硫氰酸根離子所成群的1種以上的陰離子。其中宜使用氯化物離子、溴化物離子。 X is one or more anions selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion, and thiocyanate ion. Among them, chloride ion and bromide ion are preferably used.

X含有氯化物離子或溴化物離子時，氯化物離子或溴化物離子的含量對X的合計莫耳數量而言係以10至100莫耳%為佳，以30至100莫耳%更佳，以70至100莫耳%又更佳，以80至100莫耳%為特佳。 When X contains chloride ions or bromide ions, the content of chloride ions or bromide ions is preferably 10 to 100 mol%, and more preferably 30 to 100 mol% relative to the total molar amount of X. It is more preferably from 70 to 100 mol%, and particularly preferably from 80 to 100 mol%.

X包含2種以上的鹵化物離子時，氯化物離子或溴化物離子的含有率，對X的合計莫耳數量而言，以10莫耳%以上為佳，以30莫耳%以上更佳，以70莫耳%以上又更佳， 以80莫耳%以上為特佳。 When X contains two or more types of halide ions, the content of chloride ions or bromide ions is preferably 10 mol% or more, and more preferably 30 mol% or more in terms of the total moles of X. More than 70 mol% is more preferable, and more than 80 mol% is particularly preferable.

其中，X以包含溴化物離子為佳。X為2種以上的鹵化物離子時，前述鹵化物離子的含有率，可依據發光波長適當地選擇。 Among them, X preferably contains bromide ions. When X is two or more types of halide ions, the content of the aforementioned halide ions can be appropriately selected depending on the emission wavelength.

本發明的組成物所包含之具有鈣鈦礦型結晶構造的化合物，作為AB(1-a)MaX(3+δ)表示的具有3維構造的鈣鈦礦型結晶構造的化合物的具體例，可列舉：CH3NH3Pb(1-a)CaaBr3(0<a≦0.7)、CH3NH3Pb(1-a)CeaBr(3+δ)(0<a≦0.7、0<δ≦0.7)、CH3NH3Pb(1-a)BaaBr3(0<a≦0.7)、CH3NH3Pb(1-a)SraBr3(0<a≦0.7)、CH3NH3Pb(1-a)LaaBr(3+δ)(0<a≦0.7、0<δ≦0.7)、CsPb(1-a)CaaBr3(0<a≦0.7)、CsPb(1-a)CeaBr(3+δ)(0<a≦0.7、0<δ≦0.7)、CsPb(1-a)BaaBr3(0<a≦0.7)、CsPb(1-a)SraBr3(0<a≦0.7)、CsPb(1-a)LaaBr(3+δ)(0<a≦0.7、0<δ≦0.7)、CH3NH3Pb(1-a)CaaBr(3-y)Iy(0<a≦0.7、0<y<3)、CH3NH3Pb(1-a)CeaBr(3+δ-y)Iy(0<a≦0.7、0<δ≦0.7、0<y<3)、CH3NH3Pb(1-a)BaaBr(3-y)Iy(0<a≦0.7、0<y<3)、CH3NH3Pb(1-a)SraBr(3-y)Iy(0<a≦0.7、0<y<3)、CH3NH3Pb(1-a)LaaBr(3+δ-y)Iy(0<a≦0.7、0<δ≦0.7、0<y<3)、CH3NH3Pb(1-a)CaaBr(3-y)Cly(0<a≦0.7、0<y<3)、CH3NH3Pb(1-a)CeaBr(3+δ-y)Cly(0<a≦0.7、0<δ≦0.7、0<y<3)、CH3NH3Pb(1-a)BaaBr(3-y)Cly(0<a≦0.7、0<y<3)、CH3NH3Pb(1-a)SraBr(3-y)Cly(0<a≦0.7、0<y<3)、CH3NH3Pb(1-a)LaaBr(3+δ-y)Cly(0<a≦0.7、0<δ≦0.7、0<y<3)、(H2N=CH-NH2)CaaBr3(0<a≦0.7)、(H2N=CH-NH2)CeaBr(3+δ)(0<a≦0.7、0<δ≦0.7)、(H2N=CH-NH2)Pb(1-a)CaaBr(3-y)Iy(0<a≦0.7、0<y<3)、(H2N= CH-NH2)Pb(1-a)CeaBr(3-y)Cly(0<a≦0.7、0<y<3)等為佳者。但是，前述(3+δ-y)必須為0以上。 The compound having a perovskite-type crystal structure contained in the composition of the present invention is specific as a compound having a three-dimensional structure represented by AB (1-a) M a X (3+ δ ) having a perovskite-type crystal structure Examples include: CH 3 NH 3 Pb (1-a) Ca a Br 3 (0<a≦0.7), CH 3 NH 3 Pb (1-a) Ce a Br (3+ δ ) (0<a≦ 0.7, 0< δ ≦0.7), CH 3 NH 3 Pb (1-a) Ba a Br 3 (0<a≦0.7), CH 3 NH 3 Pb (1-a) Sr a Br 3 (0<a≦ 0.7), CH 3 NH 3 Pb (1-a) La a Br (3+ δ ) (0<a≦0.7, 0< δ ≦0.7), CsPb (1-a) Ca a Br 3 (0<a≦ 0.7), CsPb (1-a) Ce a Br (3+ δ ) (0<a≦0.7, 0< δ ≦0.7), CsPb (1-a) Ba a Br 3 (0<a≦0.7), CsPb (1-a) Sr a Br 3 (0<a≦0.7), CsPb (1-a) La a Br (3+ δ ) (0<a≦0.7, 0< δ ≦0.7), CH 3 NH 3 Pb (1-a) Ca a Br (3-y) I y (0<a≦0.7, 0<y<3), CH 3 NH 3 Pb (1-a) Ce a Br (3+ δ -y) I y (0<a≦0.7, 0< δ ≦0.7, 0<y<3), CH 3 NH 3 Pb (1-a) Ba a Br (3-y) I y (0<a≦0.7, 0<y<3), CH 3 NH 3 Pb (1-a) Sr a Br (3-y) I y (0<a≦0.7, 0<y<3), CH 3 NH 3 Pb (1-a) La a Br (3+ δ -y) I y (0<a≦0.7, 0< δ ≦0.7, 0<y<3), CH 3 NH 3 Pb (1-a) Ca a Br (3-y) Cl y (0<a≦0.7, 0<y<3), CH 3 NH 3 Pb (1-a) Ce a Br (3+ δ -y) Cl y (0<a≦0.7, 0< δ ≦0.7, 0<y<3), CH 3 NH 3 Pb (1-a) Ba a Br (3-y) Cl y (0<a≦0.7, 0<y<3), CH 3 NH 3 Pb (1-a ) Sr a Br (3-y) Cl y (0<a≦0.7, 0<y<3), CH 3 NH 3 Pb (1-a) La a Br (3+ δ -y) Cl y (0<a≦0.7, 0< δ ≦0.7, 0<y<3), (H 2 N=CH-NH 2 )Ca a Br 3 (0<a≦0.7), (H 2 N=CH-NH 2 )Ce a Br (3+ δ ) (0< a≦0.7, 0< δ ≦0.7), (H 2 N=CH-NH 2 )Pb (1-a) Ca a Br (3-y) I y (0<a≦0.7, 0<y<3) , (H 2 N= CH-NH 2 )Pb (1-a) Ce a Br (3-y) Cl y (0<a≦0.7, 0<y<3), etc. are preferred. However, the aforementioned (3+ δ -y) must be 0 or more.

本發明的組成物所包含之具有鈣鈦礦型結晶構造的化合物，作為A2B(1-a)MaX(4+δ)表示的具有2維構造的鈣鈦礦型結晶構造的化合物的具體例，可列舉：(C4H9NH3)2Pb(1-a)CaaBr4(0<a≦0.7)、(C4H9NH3)2Pb(1-a)CeaBr(4+δ)(0<a≦0.7、0<δ≦0.7)、(C4H9NH3)2Pb(1-a)CoaBr4(0<a≦0.7)、(C4H9NH3)2Pb(1-a)SraBr4(0<a≦0.7)、(C7H15NH3)3Pb(1-a)ZnaBr4(0<a≦0.7)、(C7H15NH3)2Pb(1-a)CaaBr4(0<a≦0.7)、(C7H15NH3)2Pb(1-a)CeaBr(4+δ)(0<a≦0.7、0<δ≦0.7)、(C7H15NH3)2Pb(1-a)SraBr4(0<a≦0.7)、(C4H9NH3)2Pb(1-a)CaaBr(4-y)Iy(0<a≦0.7、0<y<4)、(C4H9NH3)2Pb(1-a)CeaBr(4+δ-y)Iy(0<a≦0.7、0<δ≦0.7、0<y<4)、(C4H9NH3)2Pb(1-a)SraBr(4-y)Iy(0<a≦0.7、0<y<4)、(C4H9NH3)2Pb(1-a)BaaBr(4-y)Iy(0<a≦0.7、0<y<4)、(C4H9NH3)2Pb(1-a)CaaBr(4-y)Cly(0<a≦0.7、0<y<4)、(C4H9NH3)2Pb(1-a)CeaBr(4+δ-y)Cly(0<a≦0.7、0<δ≦0.7、0<y<4)、(C4H9NH3)2Pb(1-a)SraBr(4-y)Cly(0<a≦0.7、0<y<4)、(C4H9NH3)2Pb(1-a)BaaBr(4-y)Cly(0<a≦0.7、0<y<4)等為佳者。但是，前述(4+δ-y)必須為0以上。 The compound having a perovskite crystal structure contained in the composition of the present invention is a compound having a perovskite crystal structure having a two-dimensional structure represented by A 2 B (1-a) M a X (4+ δ ) Specific examples include: (C 4 H 9 NH 3 ) 2 Pb (1-a) Ca a Br 4 (0<a≦0.7), (C 4 H 9 NH 3 ) 2 Pb (1-a) Ce a Br (4+ δ ) (0<a≦0.7, 0< δ ≦0.7), (C 4 H 9 NH 3 ) 2 Pb (1-a) Co a Br 4 (0<a≦0.7), (C 4 H 9 NH 3 ) 2 Pb (1-a) Sr a Br 4 (0<a≦0.7), (C 7 H 15 NH 3 ) 3 Pb (1-a) Zn a Br 4 (0<a≦0.7) ), (C 7 H 15 NH 3 ) 2 Pb (1-a) Ca a Br 4 (0<a≦0.7), (C 7 H 15 NH 3 ) 2 Pb (1-a) Ce a Br (4+ δ ) (0<a≦0.7, 0< δ ≦0.7), (C 7 H 15 NH 3 ) 2 Pb (1-a) Sr a Br 4 (0<a≦0.7), (C 4 H 9 NH 3 ) 2 Pb (1-a) Ca a Br (4-y) I y (0<a≦0.7, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Ce a Br (4+ δ -y) I y (0<a≦0.7, 0< δ ≦0.7, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Sr a Br (4- y) I y (0<a≦0.7, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Ba a Br (4-y) I y (0<a≦0.7, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Ca a Br (4-y) Cl y (0<a≦0.7, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Ce a Br (4+ δ -y) Cl y (0<a≦0.7, 0< δ ≦0.7, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Sr a Br (4-y) Cl y (0<a≦0.7, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Ba a Br (4-y) Cl y (0<a≦0.7, 0<y<4) etc. are better. However, the aforementioned (4+ δ -y) must be 0 or more.

≪發光光譜≫ ≪Luminescence spectrum≫

本發明的組成物所包含之具有鈣鈦礦型結晶構造的化合物，係在可見光波長區域發出螢光的發光體，X為溴化物離子時，發出通常在480nm以上，以500nm以上為佳，以520nm以上更佳，以700nm以下為佳，以600nm以下更佳，以580nm以下又更佳的波長範圍之範圍具有峰值的 螢光者。 The compound having a perovskite-type crystal structure contained in the composition of the present invention is a luminescent body that emits fluorescence in the visible light wavelength region. When X is a bromide ion, the emission is usually above 480 nm, preferably above 500 nm. 520nm or more is more preferable, 700nm or less is more preferable, 600nm or less is more preferable, and 580nm or less is a more preferable wavelength range for the phosphor with peak.

上述的上限值及下限值，可任意組合。 The above upper limit and lower limit can be combined arbitrarily.

作為本發明的又一其他方面，具有鈣鈦礦型結晶構造的化合物中的X為溴化物離子時，發出的螢光的峰值，通常為480至700nm，以500至600nm為佳，以520至580nm更佳。 As yet another aspect of the present invention, when X in the compound having a perovskite crystal structure is a bromide ion, the peak of fluorescence emitted is usually 480 to 700 nm, preferably 500 to 600 nm, and 520 to 580nm is better.

X為碘化物離子時，發出通常在520nm以上，以530nm以上為佳，以540nm以上更佳，又通常在800nm以下，以750nm以下為佳，以730nm以下更佳的波長範圍之範圍具有峰值的螢光者。 When X is an iodide ion, the emission is usually above 520nm, preferably above 530nm, more preferably above 540nm, and usually below 800nm, preferably below 750nm, with a peak in the range of the better wavelength range below 730nm Fluorescent.

上述的上限值及下限值，可任意組合。 The above upper limit and lower limit can be combined arbitrarily.

作為本發明的又一其他方面，具有鈣鈦礦型結晶構造的化合物中的X為碘化物離子時，發出的螢光的峰值，通常為520至800nm，以530至750nm為佳，以540至730nm更佳。 As yet another aspect of the present invention, when X in the compound having a perovskite crystal structure is an iodide ion, the peak of the fluorescence emitted is usually 520 to 800 nm, preferably 530 to 750 nm, and 540 to 730nm is better.

X為氯化物離子時，發出通常在300nm以上，以310nm以上為佳，以330nm以上更佳，又通常在600nm以下為佳，以580nm以下為佳，以550nm以下更佳的波長範圍之範圍具有峰值的螢光者。上述的上限值及下限值，可任意組合。 When X is a chloride ion, the emission is usually above 300nm, preferably above 310nm, more preferably above 330nm, and usually below 600nm, preferably below 580nm, and preferably within a wavelength range below 550nm Peak phosphor. The above upper limit and lower limit can be combined arbitrarily.

作為本發明的又一其他方面，具有鈣鈦礦型結晶構造的化合物中的X為氯化物離子時，發出的螢光的峰值，通常為300至600nm，以310至580nm為佳，以330至550nm更佳。 As yet another aspect of the present invention, when X in the compound having a perovskite crystal structure is a chloride ion, the peak of fluorescence emitted is usually 300 to 600 nm, preferably 310 to 580 nm, and 330 to 550nm is better.

<分散液組成物> <Dispersion liquid composition>

本發明之分散液組成物，係上述組成物中之介質為液體之組成物，且上述具有鈣鈦礦型結晶構造的化合物分散於液體中。藉由將上述具有鈣鈦礦型結晶構造的化合物作成分散液組成物，即可提高量子產率。 The dispersion composition of the present invention is a composition in which the medium in the composition is a liquid, and the compound having a perovskite-type crystal structure is dispersed in the liquid. The quantum yield can be improved by using the above-mentioned compound having a perovskite crystal structure as a dispersion liquid composition.

本說明書中，所謂「液體」，係指1大氣壓、25℃下為液體狀態的物質。 In this specification, the term "liquid" refers to a substance that is in a liquid state at 1 atmosphere of pressure and 25°C.

本說明書中，所謂「分散於液體中」，係指粒子漂浮或懸浮於液體中的狀態。 In this specification, the term "dispersed in liquid" refers to a state where particles are floating or suspended in liquid.

分散液組成物係可包含上述之具有鈣鈦礦型結晶構造的化合物以及液體以外的其他成分。作為前述成分，例如以雜質、A、B、X及/或M作為構成成分的具有非結晶構造的化合物以及封端配位子。 The dispersion composition system may contain the above-mentioned compound having a perovskite crystal structure and other components other than the liquid. As the aforementioned components, for example, a compound having an amorphous structure having impurities, A, B, X, and/or M as constituent components, and a blocking ligand.

作為雜質，例如包含A、B及M的鹵化物；B及M的氧化物、複合氧化物；以及包含A、B、X及M的其他化合物。其他成分，對分散液組成物的總質量而言係以10質量%以下為佳。 Examples of impurities include halides of A, B, and M; oxides and composite oxides of B and M; and other compounds including A, B, X, and M. The other components are preferably 10% by mass or less based on the total mass of the dispersion composition.

分散液組成物中所含的液體(惟樹脂除外)，只要是可分散上述具有鈣鈦礦型結晶構造的化合物的液體，即無特別限制。 The liquid contained in the dispersion composition (except for resin) is not particularly limited as long as it can disperse the above-mentioned compound having a perovskite-type crystal structure.

分散液組成物中所含的液體(惟樹脂除外)，以不易溶解上述具有鈣鈦礦型結晶構造的化合物者為佳。 The liquid contained in the dispersion composition (except for resin) is preferably one that does not easily dissolve the above-mentioned compound having a perovskite crystal structure.

作為分散液組成物中所含的液體(惟樹脂除外)，例如甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸戊酯、乙酸甲酯、 乙酸乙酯、乙酸戊酯等的酯類；γ-丁內酯、N-甲基-2-吡咯啶酮、丙酮、二甲基酮、二異丁基酮、環戊酮、環己酮、甲基環己酮等的酮類；二***、甲基第3丁基醚、二異丙醚、二甲氧基甲烷、二甲氧基乙烷、1,4-二噁烷、1,3-二氧戊環、4-甲基二氧戊環、四氫呋喃、甲基四氫呋喃、苯甲醚、苯***等的醚類；甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、第3丁醇、1-戊醇、2-甲基-2-丁醇、甲氧基丙醇、二丙酮醇、環己醇、2-氟乙醇、2,2,2-三氟乙醇、2,2,3,3-四氟-1-丙醇等的醇類；乙二醇單甲醚、乙二醇單***、乙二醇單丁醚、乙二醇單***乙酸酯、三乙二醇二甲醚等的二醇醚；N,N-二甲基甲醯胺、乙醯胺、N.N-二甲基乙醯胺等的具有醯胺基的有機溶劑；乙腈、異丁腈、丙腈、甲氧基乙腈等的具有腈基的有機溶劑；碳酸伸乙酯、碳酸伸丙酯等的具有烴基的有機溶劑；氯甲烷、二氯甲烷、三氯甲烷等的具有鹵烴基的有機溶劑；正-戊烷、環己烷、正-己烷、苯、甲苯、二甲苯等的具有烴基的有機溶劑；二甲基亞碸等。 As the liquid contained in the dispersion composition (except resin), for example, esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate, etc.; γ -Butyrolactone, N-methyl-2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone and other ketones; diethyl ether, Methyl 3rd butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane Ethers such as ring, tetrahydrofuran, methyltetrahydrofuran, anisole, phenylethyl ether; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, third butanol, 1- Pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3- Alcohols such as tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, etc. Glycol ether; N,N-dimethylformamide, acetamide, NN-dimethylacetamide, and other organic solvents with amide groups; acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile Organic solvents with nitrile groups such as ethylene carbonate and propylene carbonate; organic solvents with hydrocarbon groups such as ethylene carbonate and propylene carbonate; organic solvents with halogenated hydrocarbon groups such as methyl chloride, dichloromethane, and chloroform; n-pentane, Organic solvents with hydrocarbon groups such as cyclohexane, n-hexane, benzene, toluene, and xylene; dimethyl sulfide, etc.

該等有機溶劑之中，以甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸戊酯、乙酸甲酯、乙酸乙酯、乙酸戊酯等的酯類；γ-丁內酯、丙酮、二甲基酮、二異丁基酮、環戊酮、環己酮、甲基環己酮等的酮類；二***、甲基第3丁基醚、二異丙醚、二甲氧基甲烷、二甲氧基乙烷、1,4-二噁烷、1,3-二氧戊環、4-甲基二氧戊環、四氫呋喃、甲基四氫呋喃、苯甲醚、苯***等的醚類；乙腈、異丁腈、丙腈、甲氧基 乙腈等的具有腈基的有機溶劑；碳酸伸乙酯、碳酸伸丙酯等的具有碳酸酯基的有機溶劑；氯甲烷、二氯甲烷、三氯甲烷等的具有鹵烴基的有機溶劑；正-戊烷、環己烷、正-己烷、苯、甲苯、二甲苯等的具有烴基的有機溶劑，由於被認為極性低、不易溶解具有鈣鈦礦型結晶構造的化合物，因而為佳，以氯甲烷、二氯甲烷、三氯甲烷等的具有鹵烴基的有機溶劑；正-戊烷、環己烷、正-己烷、苯、甲苯、二甲苯等的烴基系有機溶劑更佳。 Among these organic solvents, esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate, etc.; γ-butyrolactone, acetone, dimethyl Base ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone and other ketones; diethyl ether, methyl 3 butyl ether, diisopropyl ether, dimethoxymethane, two Ethers such as methoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenylethyl ether, etc.; acetonitrile Organic solvents with nitrile groups such as, isobutyronitrile, propionitrile, and methoxyacetonitrile; organic solvents with carbonate groups such as ethylene carbonate and propylene carbonate; methyl chloride, methylene chloride, chloroform Organic solvents with halogenated hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene and other organic solvents with hydrocarbon groups are considered to be low in polarity and difficult to dissolve. Compounds with crystalline structure are therefore preferred. Organic solvents with halogenated hydrocarbon groups such as methyl chloride, dichloromethane and chloroform; n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene, etc. The hydrocarbon-based organic solvent is better.

本發明的分散液組成物，可包含封端配位子(capping ligand)。所謂封端配位子，係指吸附於粒子(具有鈣鈦礦型結晶構造的化合物)的表面，為了使穩定分散於分散溶劑中的化合物，作為封端配位子，例如後述通式(A3)表示的銨鹽及(A4)表示的具有羧基的化合物。本發明的分散液組成物，可包含通式(A3)表示的銨鹽及通式(A4)表示的具有羧基的化合物之任一者，亦可包含兩者。 The dispersion composition of the present invention may include a capping ligand. The so-called blocked ligand refers to a compound adsorbed on the surface of a particle (a compound having a perovskite-type crystal structure) to be stably dispersed in a dispersing solvent. As a blocked ligand, for example, the following general formula (A3 The ammonium salt represented by) and the compound having a carboxyl group represented by (A4). The dispersion liquid composition of the present invention may contain either of the ammonium salt represented by the general formula (A3) and the compound having a carboxyl group represented by the general formula (A4), or both.

分散液組成物，可包含通式(A3)表示的銨鹽。 The dispersion liquid composition may contain an ammonium salt represented by the general formula (A3).

Figure 106120710-A0202-12-0018-2
Figure 106120710-A0202-12-0018-2

通式(A3)中，R9至R12分別獨立地表示氫原子、可具有胺基作為取代基的烷基、可具有1個胺基作為 取代基的不飽和烴基或可具有胺基作為取代基的環烷基。 In the general formula (A3), R 9 to R 12 each independently represent a hydrogen atom, an alkyl group which may have an amino group as a substituent, an unsaturated hydrocarbon group which may have an amino group as a substituent, or an amino group as a substituent Cycloalkyl group.

R9至R12所示的烷基，可為直鏈狀，亦可為分支鏈狀，亦可具有胺基作為取代基。 The alkyl group represented by R 9 to R 12 may be linear or branched, and may have an amino group as a substituent.

R9至R12所示的烷基的碳原子數，通常為1至20，以5至20為佳，以8至20更佳。 The number of carbon atoms of the alkyl group represented by R 9 to R 12 is usually 1 to 20, preferably 5 to 20, and more preferably 8 to 20.

R9至R12所示的不飽和烴基，可為直鏈狀，亦可為分支鏈狀，亦可具有1個胺基作為取代基。R9至R12所示的不飽和烴基的碳原子數，通常為2至20，以5至20為佳，以8至20更佳。 The unsaturated hydrocarbon group represented by R 9 to R 12 may be linear or branched, and may have one amino group as a substituent. The number of carbon atoms of the unsaturated hydrocarbon group represented by R 9 to R 12 is usually from 2 to 20, preferably from 5 to 20, and more preferably from 8 to 20.

R9至R12所示的環烷基，可具有胺基作為取代基。 The cycloalkyl group represented by R 9 to R 12 may have an amino group as a substituent.

R9至R12所示的環烷基的碳原子數，通常為3至30，以3至20為佳，以3至11更佳。 The number of carbon atoms of the cycloalkyl group represented by R 9 to R 12 is usually 3 to 30, preferably 3 to 20, and more preferably 3 to 11.

R9至R12係以氫原子、烷基或不飽和烴基為佳。作為不飽和烴基，係以烯基為佳。 R 9 to R 12 are preferably hydrogen atom, alkyl group or unsaturated hydrocarbon group. As the unsaturated hydrocarbon group, an alkenyl group is preferred.

通式(A3)表示的銨鹽，可吸附於上述具有鈣鈦礦型結晶構造的化合物的表面，亦可分散於溶劑中。作為前述銨鹽的相對陰離子，並無特別限制，例如Br-、Cl-、I-、F-的鹵化物離子。 The ammonium salt represented by the general formula (A3) may be adsorbed on the surface of the above-mentioned compound having a perovskite crystal structure, or may be dispersed in a solvent. As the counter anion of the salt is not particularly limited, for example Br -, Cl -, I - , F - is a halide ion.

作為通式(A3)表示的銨鹽，以正-辛基胺的鹽、油胺的鹽為佳。 As the ammonium salt represented by the general formula (A3), a salt of n-octylamine and a salt of oleylamine are preferred.

分散液組成物，可包含(A4)表示之具有羧基的化合物。 The dispersion composition may contain the compound having a carboxyl group represented by (A4).

R13-CO2H…(A4) R 13 -CO 2 H…(A4)

通式(A4)中，R13表示可具有1個羧基作為取代基的烷基、可具有1個羧基作為取代基的不飽和烴基或可具有1個羧基作為取代基的環烷基。 In the general formula (A4), R 13 represents an alkyl group which may have one carboxy group as a substituent, an unsaturated hydrocarbon group which may have one carboxy group as a substituent, or a cycloalkyl group which may have one carboxy group as a substituent.

R13所示的烷基，可為直鏈狀，亦可為分支鏈狀，亦可具有1個羧基作為取代基。R13所示的烷基的碳原子數，通常為1至20，以5至20為佳，以8至20更佳。 The alkyl group represented by R 13 may be linear or branched, and may have one carboxyl group as a substituent. The number of carbon atoms of the alkyl group represented by R 13 is usually from 1 to 20, preferably from 5 to 20, and more preferably from 8 to 20.

R13所示的不飽和烴基，可為直鏈狀，亦可為分支鏈狀，亦可具有1個羧基作為取代基。R13所示的不飽和烴基的碳原子數，通常為2至20，以5至20為佳，以8至20更佳。 The unsaturated hydrocarbon group represented by R 13 may be linear or branched, and may have one carboxyl group as a substituent. The number of carbon atoms of the unsaturated hydrocarbon group represented by R 13 is usually 2-20, preferably 5-20, more preferably 8-20.

R13所示的環烷基，可具有1個羧基作為取代基。 The cycloalkyl represented by R 13 may have one carboxyl group as a substituent.

R13所示的環烷基的碳原子數，通常為3至30，以3至20為佳，以3至11更佳。 The number of carbon atoms of the cycloalkyl group represented by R 13 is usually 3 to 30, preferably 3 to 20, and more preferably 3 to 11.

R13係以烷基或不飽和烴基為佳。作為不飽和烴基，係以烯基為佳。 R 13 is preferably an alkyl group or an unsaturated hydrocarbon group. As the unsaturated hydrocarbon group, an alkenyl group is preferred.

通式(A4)表示的具有羧基的化合物，可吸附於上述具有鈣鈦礦型結晶構造的化合物的表面，亦可分散於溶劑中。 The compound having a carboxyl group represented by the general formula (A4) may be adsorbed on the surface of the compound having a perovskite-type crystal structure, or may be dispersed in a solvent.

作為通式(A4)表示的具有羧基的化合物，係以油酸為佳。 As the compound having a carboxyl group represented by the general formula (A4), oleic acid is preferred.

分散液組成物中所含的上述具有鈣鈦礦型結晶構造的化合物的含量，並無特別限制，從使具有鈣鈦礦型結晶構造的化合物不易聚集的觀點及防止濃度猝滅的 觀點，對前述分散液組成物的總質量而言，係以50質量%以下為佳，以10質量%以下更佳，又從得到充分的量子產率的觀點，係以1質量ppm以上為佳，以10質量ppm以上更佳。 The content of the compound having the perovskite crystal structure contained in the dispersion composition is not particularly limited. From the viewpoint of preventing the compound having the perovskite crystal structure from being aggregated and the viewpoint of preventing concentration quenching, The total mass of the aforementioned dispersion composition is preferably 50% by mass or less, more preferably 10% by mass or less, and from the viewpoint of obtaining sufficient quantum yield, it is preferably 1 ppm by mass or more, and 10 The mass ppm or more is better.

作為本發明的其他方面，分散液組成物中所含的前述具有鈣鈦礦型結晶構造的化合物的含量，對前述分散液組成物的總質量而言，係以1質量ppm以上50質量%以下為佳，以10質量ppm以上10質量%以下更佳。 As another aspect of the present invention, the content of the compound having a perovskite-type crystal structure contained in the dispersion composition is 1 mass ppm to 50 mass% with respect to the total mass of the dispersion composition Preferably, it is more preferably 10 mass ppm or more and 10 mass% or less.

本說明書中，對分散液組成物的總質量而言，前述具有鈣鈦礦型結晶構造的化合物的含量，例如藉由電感耦合電漿質量分析計(以下亦稱為ICP-MS)、電感耦合電漿發光分光分析法(以下亦稱為ICP-AES)、離子層析法等，可藉由分析構成前述鈣鈦礦型結晶構造的元素而測定，且可通過測定構成前述鈣鈦礦型結晶構造的元素的一部分，並從莫耳比算出而測定。 In this specification, with respect to the total mass of the dispersion composition, the content of the aforementioned compound having a perovskite-type crystal structure is determined by, for example, inductively coupled plasma mass analyzer (hereinafter also referred to as ICP-MS), inductively coupled Plasma luminescence spectrometry (hereinafter also referred to as ICP-AES), ion chromatography, etc. can be determined by analyzing the elements constituting the perovskite crystal structure, and can be determined by measuring the perovskite crystal structure. A part of the element of the structure is calculated and measured from the molar ratio.

分散於分散液組成物中的上述具有鈣鈦礦型結晶構造的化合物的平均粒徑，並無特別限制，從充分維持結晶構造的觀點，平均粒徑係以1nm以上為佳，以2nm以上更佳，以3nm以上又更佳，又從使具有鈣鈦礦型結晶構造的化合物不易沈降的觀點，平均粒徑係以10μm以下為佳，以1μm以下更佳，以500nm以下又更佳。 The average particle size of the compound having a perovskite crystal structure dispersed in the dispersion composition is not particularly limited. From the viewpoint of sufficiently maintaining the crystal structure, the average particle size is preferably 1 nm or more, and more preferably 2 nm or more Preferably, it is more preferably 3 nm or more, and from the viewpoint of making the compound having a perovskite crystal structure less likely to settle, the average particle size is preferably 10 μm or less, more preferably 1 μm or less, and more preferably 500 nm or less.

作為本發明的其他方面，分散於分散液組成物的前述具有鈣鈦礦型結晶構造的化合物的平均粒徑係以1nm至10μm為佳，以2nm至1μm更佳，以3nm至500nm又 更佳。 As another aspect of the present invention, the average particle size of the aforementioned compound having a perovskite crystal structure dispersed in the dispersion composition is preferably 1 nm to 10 μm, more preferably 2 nm to 1 μm, and more preferably 3 nm to 500 nm. .

本說明書中，分散於分散液組成物中的前述具有鈣鈦礦型結晶構造的化合物的平均粒徑，例如可藉由穿透型電子顯微鏡(以下亦稱為TEM)、掃描型電子顯微鏡(以下亦稱為SEM)測定。具體而言，係可藉由TEM或SEM，觀察分散於前述分散液組成物中的20個前述具有鈣鈦礦型結晶構造的化合物的粒徑，藉由計算該等的平均值，可求得前述平均粒徑。 In this specification, the average particle size of the compound having the perovskite crystal structure dispersed in the dispersion composition can be measured by, for example, a transmission electron microscope (hereinafter also referred to as TEM), a scanning electron microscope (hereinafter Also known as SEM) measurement. Specifically, the particle size of the 20 compounds having a perovskite-type crystal structure dispersed in the dispersion composition can be observed by TEM or SEM, and the average value of these can be calculated. The aforementioned average particle size.

分散液組成物中所含的上述具有鈣鈦礦型結晶構造的化合物的粒徑分佈，並無特別限制，從充分維持結晶構造的觀點，中間值粒徑D50係以3nm以上為佳，以4nm以上更佳，以5nm以上又更佳，又從使具有鈣鈦礦型結晶構造的化合物不易沈降的觀點，係以5μm以下為佳，以500nm以下更佳，以100nm以下又更佳。具體而言，藉由TEM或SEM，觀察分散於前述分散液組成物中的20個前述具有鈣鈦礦型結晶構造的化合物的粒徑，從該等的分佈，可求得前述中間值粒徑D50。 The particle size distribution of the compound having a perovskite crystal structure contained in the dispersion composition is not particularly limited. From the viewpoint of adequately maintaining the crystal structure, the median particle size D50 is preferably 3 nm or more, and 4 nm The above is more preferably 5 nm or more, and from the viewpoint of making the compound having a perovskite crystal structure less likely to settle, it is preferably 5 μm or less, more preferably 500 nm or less, and more preferably 100 nm or less. Specifically, the particle size of the 20 compounds having a perovskite crystal structure dispersed in the dispersion composition was observed by TEM or SEM, and the median particle size can be obtained from these distributions D50.

作為本發明的其他方面，分散液組成物中所含的前述具有鈣鈦礦型結晶構造的化合物的粒徑分佈，中間值粒徑D50係以3nm至5μm為佳，以4nm至500nm更佳，以5nm至100nm又更佳。 As another aspect of the present invention, for the particle size distribution of the aforementioned compound having a perovskite crystal structure contained in the dispersion composition, the median particle size D50 is preferably 3 nm to 5 μm, more preferably 4 nm to 500 nm, It is more preferably from 5nm to 100nm.

本說明書中，分散於分散液組成物中的前述具有鈣鈦礦型結晶構造的化合物的粒徑分佈，可藉由TEM或SEM測定。 In this specification, the particle size distribution of the compound having a perovskite crystal structure dispersed in the dispersion composition can be measured by TEM or SEM.

≪a的算出≫ ≪Calculation of a≫

本發明的分散液組成物中，上述M的莫耳數量除以M及B的合計莫耳數量的莫耳比[M/(M+B)]的值，可使用ICP-MS(ELAN DRCII、珀金埃默爾(Perkin Elmer)製造)測定。分散液組成物中具有鈣鈦礦型結晶構造的化合物，可使用N,N-二甲基甲醯胺等溶劑經溶解後進行測定。 In the dispersion composition of the present invention, the molar ratio [M/(M+B)] of the molar number of M divided by the total molar number of M and B can be obtained using ICP-MS (ELAN DRCII, Perkin Elmer (Perkin Elmer) measurement. A compound having a perovskite crystal structure in the dispersion composition can be measured after being dissolved in a solvent such as N,N-dimethylformamide.

具體而言，前述莫耳比[M/(M+B)]的值可為根據下述式(T)算出的值。下述式(T)中，Mmol表示經ICP-MS測定的M的莫耳數，Pbmol表示經ICP-MS測定的Pb的莫耳數。 Specifically, the value of the aforementioned molar ratio [M/(M+B)] may be a value calculated according to the following formula (T). In the following formula (T), Mmol represents the molar number of M measured by ICP-MS, and Pbmol represents the molar number of Pb measured by ICP-MS.

[M/(M+B)]=(Mmol)/(Mmol+Pbmol)…(T) [M/(M+B)]=(Mmol)/(Mmol+Pbmol)…(T)

≪量子產率的測定≫ ≪Measurement of quantum yield≫

本發明的分散液組成物的量子產率，可使用絕對PL量子產率測定裝置(浜松光子學公司製、商品名C9920-02、測定條件：激發光450nm、室溫、大氣下)進行測定。分散液組成物的量子產率，係將具有鈣鈦礦型結晶構造的化合物對前述分散液組成物的總質量而言調整為100至2000ppm(μg/g)的濃度下進行測定。 The quantum yield of the dispersion composition of the present invention can be measured using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., trade name C9920-02, measurement conditions: excitation light 450 nm, room temperature, under the atmosphere). The quantum yield of the dispersion composition is measured by adjusting the compound having a perovskite-type crystal structure to a concentration of 100 to 2000 ppm (μg/g) relative to the total mass of the aforementioned dispersion composition.

本發明的一方面，係包含有機銨離子作為A成分的本發明的組成物，上述方法所測定的量子產率為75%以上的組成物。 One aspect of the present invention is a composition of the present invention containing organic ammonium ions as component A, and a composition having a quantum yield of 75% or more as measured by the above method.

作為前述量子產率，係以75至100%為佳，以80至100%更佳。 As the aforementioned quantum yield, 75 to 100% is preferred, and 80 to 100% is more preferred.

本發明的其他方面，係包含銫離子作為A成分的本發明的組成物，上述方法所測定的量子產率為40%以上的組 成物。 Another aspect of the present invention is a composition of the present invention containing cesium ions as component A, and a composition having a quantum yield of 40% or more as measured by the above method.

作為前述量子產率，係以40至100%為佳，以40至80%更佳。 As the aforementioned quantum yield, 40 to 100% is preferred, and 40 to 80% is more preferred.

<樹脂組成物> <Resin composition>

本發明的樹脂組成物，係上述組成物中之介質為樹脂的組成物，且上述具有鈣鈦礦型結晶構造的化合物分散於樹脂中。藉由使上述具有鈣鈦礦型結晶構造的化合物成為樹脂組成物，可提高量子產率。 The resin composition of the present invention is a composition in which the medium in the composition is a resin, and the compound having a perovskite crystal structure is dispersed in the resin. By making the above-mentioned compound having a perovskite crystal structure into a resin composition, the quantum yield can be improved.

本說明書中，所謂「樹脂」，係指有機高分子化合物。 In this specification, "resin" refers to an organic polymer compound.

本說明書中，所謂「分散於樹脂中」，係指粒子漂浮或懸浮於樹脂中的狀態。 In this specification, the term "dispersed in resin" refers to a state where particles are floating or suspended in resin.

前述粒子的平均粒徑，可列舉例如：1nm至1000nm。 The average particle diameter of the aforementioned particles includes, for example, 1 nm to 1000 nm.

樹脂組成物，係可含有上述具有鈣鈦礦型結晶構造的化合物及樹脂以外的其他成分。作為前述成分，可列舉例如：雜質、以A、B、X及/或M作為構成成分的具有非結晶構造的化合物以及封端配位子。作為雜質，可列舉例如：包含A、B及/或M的鹵化物；B及/或M的氧化物、複合氧化物；以及包含A、B、X及/或M的其他化合物。其他成分，係以相對於分散液組成物的總質量為10質量%以下為佳。 The resin composition may contain the above-mentioned compound having a perovskite crystal structure and other components other than the resin. Examples of the aforementioned components include impurities, compounds having an amorphous structure having A, B, X, and/or M as constituent components, and capped ligands. Examples of impurities include halides containing A, B, and/or M; oxides and composite oxides of B and/or M; and other compounds containing A, B, X, and/or M. The other components are preferably 10% by mass or less with respect to the total mass of the dispersion composition.

本發明的樹脂組成物的形態並無特別限制，可依據用途適當地決定。具有鈣鈦礦型結晶構造的化合物分散之樹脂組成物，可為膜狀，亦可成形為板狀。 The form of the resin composition of the present invention is not particularly limited, and can be appropriately determined according to the application. The resin composition in which a compound having a perovskite crystal structure is dispersed may be in the form of a film or formed into a plate.

本發明的樹脂組成物中，具有鈣鈦礦型結 晶構造的化合物分散之樹脂，並無特別限制，惟於製造前述樹脂組成物的溫度中，以對前述具有鈣鈦礦型結晶構造的化合物的溶解度低者為佳。 In the resin composition of the present invention, the resin in which the compound having the perovskite-type crystal structure is dispersed is not particularly limited, but the temperature at which the resin composition is produced is suitable for the compound having the perovskite-type crystal structure. The one with low solubility is better.

作為前述樹脂，例如聚苯乙烯、甲基丙烯酸樹脂等。 As the aforementioned resin, for example, polystyrene, methacrylic resin, and the like.

本發明的樹脂組成物，可包含封端配位子。所謂封端配位子，係指吸附於粒子(具有鈣鈦礦型結晶構造的化合物)的表面，為了使穩定分散於分散介質中的化合物，作為封端配位子，可列舉例如上述通式(A3)表示的銨鹽及(A4)表示的具有羧基的化合物。本發明的樹脂組成物，可包含銨鹽及具有羧基的化合物之任一者，亦可包含兩者。 The resin composition of the present invention may include a blocking ligand. The term “blocking ligand” refers to a compound that is adsorbed on the surface of a particle (a compound having a perovskite type crystal structure) and is used to stabilize the dispersion in a dispersion medium. Examples of the “blocking ligand” include the above general formula The ammonium salt represented by (A3) and the compound having a carboxyl group represented by (A4). The resin composition of the present invention may contain any one of an ammonium salt and a compound having a carboxyl group, or both.

作為本發明的樹脂組成物可包含之通式(A3)表示的銨鹽，以含正-辛基胺的銨鹽、含油胺的銨鹽為佳。(A3)表示的銨鹽，可吸附於具有鈣鈦礦型結晶構造的化合物的表面，亦可分散於樹脂中。作為前述銨鹽的相對陰離子，並無特別限制，可列舉例如：Br-、Cl-、I-、F-的鹵化物離子。 As the ammonium salt represented by the general formula (A3) that can be contained in the resin composition of the present invention, n-octylamine-containing ammonium salt and oleylamine-containing ammonium salt are preferred. The ammonium salt represented by (A3) can be adsorbed on the surface of a compound having a perovskite crystal structure, or can be dispersed in a resin. As the counter anion of the salt is not particularly limited, and include, for example: Br -, Cl -, I -, F - is a halide ion.

作為本發明的樹脂組成物可包含之通式(A4)表示的具有羧基的化合物，以油酸為佳。 As the compound having a carboxyl group represented by the general formula (A4) that can be contained in the resin composition of the present invention, oleic acid is preferred.

通式(A4)表示的具有羧基的化合物，可吸附於具有鈣鈦礦型結晶構造的化合物的表面，亦可分散於樹脂中。 The compound having a carboxyl group represented by the general formula (A4) may be adsorbed on the surface of a compound having a perovskite crystal structure, or may be dispersed in a resin.

樹脂組成物中所含的具有鈣鈦礦型結晶構造的化合物的量，並無特別限制，從使具有鈣鈦礦型結晶構造的化合物不易聚集的觀點及防止濃度猝滅的觀點，對 前述樹脂組成物的總質量而言，係以50質量%以下為佳，以10質量%以下更佳，又從得到充分的量子產率的觀點，係以1質量ppm以上為佳，以10質量ppm以上更佳。 The amount of the compound having the perovskite crystal structure contained in the resin composition is not particularly limited. From the viewpoint of preventing the compound having the perovskite crystal structure from being aggregated and the viewpoint of preventing concentration quenching, the resin composition The total mass of the composition is preferably 50% by mass or less, more preferably 10% by mass or less, and from the viewpoint of obtaining sufficient quantum yield, it is preferably 1 mass ppm or more, and 10 mass ppm or more Better.

作為本發明的其他方面，樹脂組成物中所含的前述具有鈣鈦礦型結晶構造的化合物的含量，對前述樹脂組成物的總質量而言，係以1質量ppm以上50質量%以下為佳，以10質量ppm以上10質量%以下更佳。 As another aspect of the present invention, the content of the compound having a perovskite-type crystal structure contained in the resin composition is preferably 1 mass ppm or more and 50 mass% or less with respect to the total mass of the resin composition , More preferably 10 mass ppm or more and 10 mass% or less.

於本說明書中，相對於樹脂組成物的總質量，前述具有鈣鈦礦型結晶構造的化合物之含量可例如藉由ICP-MS測定。 In this specification, the content of the aforementioned compound having a perovskite crystal structure relative to the total mass of the resin composition can be measured, for example, by ICP-MS.

分散於樹脂組成物的具有鈣鈦礦型結晶構造的化合物的平均粒徑，並無特別限制，惟與分散於前述分散液組成物中的具有鈣鈦礦型結晶構造的化合物的平均粒徑相同。 The average particle size of the compound having a perovskite crystal structure dispersed in the resin composition is not particularly limited, but it is the same as the average particle size of the compound having a perovskite crystal structure dispersed in the aforementioned dispersion composition .

樹脂組成物中所含的具有鈣鈦礦型結晶構造的化合物的粒徑分佈，並無特別限制，惟與分散於前述分散液組成物中之具有鈣鈦礦型結晶構造的化合物的粒徑分佈相同。 The particle size distribution of the compound having the perovskite-type crystal structure contained in the resin composition is not particularly limited, but the particle size distribution of the compound having the perovskite-type crystal structure dispersed in the aforementioned dispersion composition the same.

≪a的算出≫ ≪Calculation of a≫

本發明的樹脂組成物中，上述M的莫耳數量除以M及B的合計莫耳數量的莫耳比[M/(M+B)]的值，係與前述分散液組成物相同，可使用ICP-MS(ELAN DRCII、珀金埃默爾(Perkin Elmer)製造)測定。 In the resin composition of the present invention, the molar ratio [M/(M+B)] of the molar number of M divided by the total molar number of M and B is the same as the aforementioned dispersion composition. It is measured using ICP-MS (ELAN DRCII, manufactured by Perkin Elmer).

≪量子產率的測定≫ ≪Measurement of quantum yield≫

本發明的樹脂組成物的量子產率，係與前述分散液組成物相同，可使用絕對PL量子產率測定裝置(浜松光子學公司製、商品名C9920-02、測定條件：激發光450nm、室溫、大氣下)進行測定。 The quantum yield of the resin composition of the present invention is the same as the aforementioned dispersion composition, and an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., trade name C9920-02, measurement conditions: excitation light 450 nm, chamber Temperature and atmosphere).

<分散液組成物的製造方法> <Method for manufacturing dispersion liquid composition>

本發明的分散液組成物，可參考已知的文獻(Nano Lett.2015,15,3692-3696,ACS Nano,2015,9,4533-4542等)，藉由以下所述的方法製造。 The dispersion composition of the present invention can refer to known documents (Nano Lett. 2015, 15, 3692-3696, ACS Nano, 2015, 9, 4533-4542, etc.), and be manufactured by the method described below.

例如，作為本發明的分散液組成物的製造方法，係例如包含下述步驟之製造方法：將包含B及X的化合物、包含M及X的化合物及包含A的化合物或包含A及X的化合物溶解於溶劑而得到溶液的步驟，以及將所得的溶液，與對具有鈣鈦礦型結晶構造的化合物的溶解度比在得到溶液的步驟中使用的溶劑低的溶劑進行混合的步驟(分散液組成物的製造方法的第1實施態樣)。 For example, as a method of producing the dispersion composition of the present invention, there is, for example, a method of producing a compound containing B and X, a compound containing M and X, and a compound containing A or a compound containing A and X The step of dissolving in a solvent to obtain a solution, and the step of mixing the obtained solution with a solvent that has a lower solubility for a compound having a perovskite crystal structure than the solvent used in the step of obtaining the solution (dispersion composition The first embodiment of the manufacturing method).

而且，例如一種包含下述步驟之製造方法：將包含B及X的化合物、包含M及X的化合物及包含A的化合物或包含A及X的化合物，添加至高溫的溶劑，使其溶解而得到溶液的步驟，以及將所得的溶液進行冷卻的步驟(分散液組成物的製造方法的第2實施態樣)。 And, for example, a manufacturing method including the following steps: a compound including B and X, a compound including M and X, and a compound including A or a compound including A and X are added to a high-temperature solvent and dissolved to obtain The step of the solution, and the step of cooling the obtained solution (the second embodiment of the method for producing a dispersion composition).

<分散液組成物的製造方法的第1實施態樣> <The first embodiment of the manufacturing method of the dispersion composition>

以下，對於以下製造方法進行說明，該製造方法係包含下述步驟：將包含B及X的化合物、包含M及X的化 合物及包含A的化合物或包含A及X的化合物使溶解於溶劑而得到溶液的步驟；以及將所得的溶液，與對具有鈣鈦礦型結晶構造的化合物的溶解度比在得到溶液的步驟中使用的溶劑低的溶劑進行混合的步驟。 Hereinafter, the following manufacturing method will be described. The manufacturing method includes the steps of dissolving a compound containing B and X, a compound containing M and X, and a compound containing A, or a compound containing A and X in a solvent. The step of solution; and the step of mixing the obtained solution with a solvent having a lower solubility for the compound having a perovskite crystal structure than the solvent used in the step of obtaining the solution.

再者，所謂溶解度，係指進行混合步驟的溫度中之溶解度。 Furthermore, the so-called solubility refers to the solubility at the temperature at which the mixing step is performed.

前述製造方法，從可穩定地分散具有鈣鈦礦型結晶構造的化合物的觀點，以包含添加封端配位子的步驟為佳。封端配位子，以在前述混合步驟之前添加為佳，於溶解有A、B、X及M的溶液中添加封端配位子、添加於對具有鈣鈦礦型結晶構造的化合物的溶解度比在得到溶液的步驟中使用的溶劑低的溶劑中添加，或亦可於溶解有A、B、X及M的溶液及對具有鈣鈦礦型結晶構造的化合物的溶解度比在得到溶液的步驟中使用的溶劑低的溶劑兩者中添加。 The aforementioned production method preferably includes a step of adding a blocking ligand from the viewpoint of stably dispersing a compound having a perovskite-type crystal structure. The blocking ligand is preferably added before the aforementioned mixing step. The blocking ligand is added to the solution in which A, B, X, and M are dissolved, and added to the solubility of the compound with the perovskite crystal structure It can be added to a solvent lower than the solvent used in the step of obtaining the solution, or it can also be added to a solution in which A, B, X, and M are dissolved, and the solubility of the compound having a perovskite type crystal structure is higher than that in the step of obtaining the solution. The solvent used in the low solvent is added to both.

前述製造方法，係以在前述混合步驟之後，包含藉由離心、過濾等的方法除去粗顆粒的步驟為佳。藉由前述除去步驟所除去的粗顆粒的大小，係以10μm以上為佳，以1μm以上更佳，以500nm以上又更佳。 The aforementioned manufacturing method preferably includes a step of removing coarse particles by centrifugation, filtration, etc., after the aforementioned mixing step. The size of the coarse particles removed by the aforementioned removal step is preferably 10 μm or more, more preferably 1 μm or more, and more preferably 500 nm or more.

前述溶液與對具有鈣鈦礦型結晶構造的化合物的溶解度比在得到前述溶液的步驟所使用的溶劑低的溶劑進行混合的步驟，可為(a)將前述溶液滴入至對具有鈣鈦礦型結晶構造的化合物的溶解度比在得到溶液的步驟所使用的溶劑低的溶劑中的步驟，亦可為(b)於前述溶液中，滴入對具有鈣鈦礦型結晶構造的化合物的溶解度比在得到 溶液的步驟所使用的溶劑低的溶劑的步驟，從提高分散性的觀點，係以(a)為佳。 The step of mixing the aforementioned solution with a solvent having a lower solubility for the compound having a perovskite type crystal structure than the solvent used in the step of obtaining the aforementioned solution may be (a) dripping the aforementioned solution into a compound having a perovskite The step in which the solubility of the compound with the perovskite-type crystal structure is lower than that of the solvent used in the step of obtaining the solution may also be (b) in the aforementioned solution, the solubility of the compound with the perovskite-type crystal structure is lower than In the step of obtaining a solution using a low-solvent solvent, from the viewpoint of improving dispersibility, (a) is preferred.

滴入時進行攪拌者，從提高分散性的觀點上為佳。 Stirring during dripping is preferred from the viewpoint of improving dispersibility.

於前述溶液與對具有鈣鈦礦型結晶構造的化合物的溶解度比在得到前述溶液的步驟所使用的溶劑低的溶劑進行混合的步驟中，溫度並無特別限制，惟從確保具有鈣鈦礦型結晶構造的化合物的析出容易性的觀點，以0至40℃的範圍為佳，以10至30℃的範圍更佳。 In the step of mixing the aforementioned solution with a solvent having a lower solubility for the compound having a perovskite type crystal structure than the solvent used in the step of obtaining the aforementioned solution, the temperature is not particularly limited, but it must be ensured that it has a perovskite type From the viewpoint of the ease of precipitation of the compound of the crystal structure, the range of 0 to 40°C is preferred, and the range of 10 to 30°C is more preferred.

製造時，可調整上述調配的化合物的種類及其量，使a及δ成為所期望的值。 At the time of production, the kind and amount of the compound to be blended can be adjusted so that a and δ become desired values.

作為前述製造方法所使用的對具有鈣鈦礦型結晶構造的化合物的溶解度不同的2種的溶劑，並無特別限制，例如為選自甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、第3丁醇、1-戊醇、2-甲基-2-丁醇、甲氧基丙醇、二丙酮醇、環己醇、2-氟乙醇、2,2,2-三氟乙醇、2,2,3,3-四氟-1-丙醇等的醇類；乙二醇單甲醚、乙二醇單***、乙二醇單丁醚、乙二醇單***乙酸酯、三乙二醇二甲醚等的二醇醚；N,N-二甲基甲醯胺、乙醯胺、N.N-二甲基乙醯胺等的具有醯胺基的有機溶劑；二甲基亞碸、甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸戊酯、乙酸甲酯、乙酸乙酯、乙酸戊酯等的酯類；γ-丁內酯、N-甲基-2-吡咯啶酮、丙酮、二甲基酮、二異丁基酮、環戊酮、環己酮、甲基環己酮等的酮類；二***、甲基第3丁基醚、二異丙醚、二甲氧基甲烷、二甲氧基乙烷、1,4-二噁烷、1,3-二氧戊環、4-甲基 二氧戊環、四氫呋喃、甲基四氫呋喃、苯甲醚、苯***等的醚類；乙腈、異丁腈、丙腈、甲氧基乙腈等的具有腈基的有機溶劑；碳酸伸乙酯、碳酸伸丙酯等的具有碳酸酯基的有機溶劑；氯甲烷、二氯甲烷、三氯甲烷等的具有鹵化烴基的有機溶劑；正-戊烷、環己烷、正-己烷、苯、甲苯、二甲苯等的具有烴基的有機溶劑所成群的2種溶劑。 There are no particular limitations on the two solvents used in the aforementioned production method that have different solubility for the compound having the perovskite crystal structure, and for example, they are selected from methanol, ethanol, 1-propanol, 2-propanol, and 1 -Butanol, 2-butanol, 3rd butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2, Alcohols such as 2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and ethylene glycol Glycol ethers such as alcohol monoethyl ether acetate and triethylene glycol dimethyl ether; N,N-dimethylformamide, acetamide, NN-dimethylacetamide and other glycol ethers having an amido group Organic solvents; dimethyl sulfide, methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate and other esters; γ-butyrolactone, N-methyl 2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone and other ketones; diethyl ether, methyl 3 butyl ether, Diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, Ethers such as anisole and phenethyl ether; organic solvents with nitrile groups such as acetonitrile, isobutyronitrile, propionitrile, and methoxyacetonitrile; organic solvents with carbonate groups such as ethylene carbonate and propylene carbonate Solvents; organic solvents with halogenated hydrocarbon groups such as methyl chloride, dichloromethane, and chloroform; organic solvents with hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene, etc. Group of 2 solvents.

包含於前述製造方法之得到溶液的步驟所使用的溶劑，以對具有鈣鈦礦型結晶構造的化合物的溶解度高的溶劑為佳，例如於室溫(10℃至30℃)下進行前述步驟時，例如甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、第3丁醇、1-戊醇、2-甲基-2-丁醇、甲氧基丙醇、二丙酮醇、環己醇、2-氟乙醇、2,2,2-三氟乙醇、2,2,3,3-四氟-1-丙醇等的醇類；乙二醇單甲醚、乙二醇單***、乙二醇單丁醚、乙二醇單***乙酸酯、三乙二醇二甲醚等的二醇醚；N,N-二甲基甲醯胺、乙醯胺、N.N-二甲基乙醯胺等的具有醯胺基的有機溶劑；二甲基亞碸。 The solvent used in the step of obtaining the solution included in the aforementioned manufacturing method is preferably a solvent with high solubility for the compound having a perovskite crystal structure, for example, when the aforementioned step is performed at room temperature (10°C to 30°C) , Such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 3rd butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol Alcohol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and other alcohols; ethylene glycol monomethyl Glycol ethers such as ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether; N,N-dimethylformamide, acetamide Organic solvents with amide groups such as amines and NN-dimethylacetamide; dimethylsulfene.

包含於前述製造方法之混合步驟中使用的溶劑，以對具有鈣鈦礦型結晶構造的化合物的溶解度低的溶劑為佳，例如於室溫(10℃至30℃)下進行前述步驟時，例如甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸戊酯、乙酸甲酯、乙酸乙酯、乙酸戊酯等的酯類；γ-丁內酯、N-甲基-2-吡咯啶酮、丙酮、二甲基酮、二異丁基酮、環戊酮、環己酮、甲基環己酮等的酮類；二***、甲基第3丁基醚、二異丙醚、二甲氧基甲烷、二甲氧基乙烷、1,4-二噁烷、1,3-二氧戊環、 4-甲基二氧戊環、四氫呋喃、甲基四氫呋喃、苯甲醚、苯***等的醚類；乙腈、異丁腈、丙腈、甲氧基乙腈等的具有腈基的有機溶劑；碳酸伸乙酯、碳酸伸丙酯等的具有碳酸酯基的有機溶劑；氯甲烷、二氯甲烷、三氯甲烷等的具有鹵烴基的有機溶劑；正-戊烷、環己烷、正-己烷、苯、甲苯、二甲苯等的具有烴基的有機溶劑。 The solvent included in the mixing step of the aforementioned manufacturing method is preferably a solvent with low solubility for the compound having a perovskite crystal structure. For example, when the aforementioned step is performed at room temperature (10°C to 30°C), for example, Esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate, etc.; γ-butyrolactone, N-methyl-2-pyrrolidone, acetone , Dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone and other ketones; diethyl ether, methyl 3 butyl ether, diisopropyl ether, dimethoxy Ethers such as methane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenylethyl ether, etc. Classes; organic solvents with nitrile groups such as acetonitrile, isobutyronitrile, propionitrile, and methoxyacetonitrile; organic solvents with carbonate groups such as ethylene carbonate and propylene carbonate; methyl chloride, methylene chloride, Organic solvents with halogenated hydrocarbon groups such as chloroform; organic solvents with hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene, and xylene.

溶解度不同的2種溶劑中，溶解度差以100μg/溶劑100g至90g/溶劑100g為佳，以1mg/溶劑100g至90g/溶劑100g更佳。從溶解度差為100μg/溶劑100g至90g/溶劑100g的觀點，例如於室溫(10℃至30℃)下進行混合步驟時，在得到溶液的步驟所使用的溶劑為N,N-二甲基乙醯胺等的具有醯胺基的有機溶劑或二甲基亞碸，以在混合步驟中使用的溶劑為氯甲烷、二氯甲烷、三氯甲烷等的具有鹵烴基的有機溶劑；正-戊烷、環己烷、正-己烷、苯、甲苯、二甲苯等的具有烴基的有機溶劑為佳。 Among the two solvents with different solubility, the difference in solubility is preferably 100μg/solvent 100g to 90g/solvent 100g, and more preferably 1mg/solvent 100g to 90g/solvent 100g. From the viewpoint that the solubility difference is 100μg/solvent 100g to 90g/solvent 100g, for example, when the mixing step is performed at room temperature (10°C to 30°C), the solvent used in the step of obtaining the solution is N,N-dimethyl An organic solvent having an amide group such as acetamide or dimethyl sulfide, and the solvent used in the mixing step is an organic solvent having a halogenated hydrocarbon group such as methyl chloride, dichloromethane, and chloroform; n-pentyl Organic solvents with hydrocarbon groups such as alkanes, cyclohexane, n-hexane, benzene, toluene, and xylene are preferred.

<分散液組成物的製造方法的第2實施態樣> <The second embodiment of the manufacturing method of the dispersion composition>

對包含下述步驟之製造方法進行說明：將包含B及X的化合物、包含M及X的化合物及包含A的化合物或包含A及X的化合物添加至高溫的溶劑，使其溶解，得到溶液的步驟；以及將所得的溶液進行冷卻的步驟。 The manufacturing method including the following steps is described: a compound containing B and X, a compound containing M and X, and a compound containing A or a compound containing A and X are added to a high-temperature solvent and dissolved to obtain a solution Step; and the step of cooling the resulting solution.

前述製造方法中，藉由因溫度差之溶解度的差，使本發明的具有鈣鈦礦型結晶構造的化合物析出，可製造本發明的具有鈣鈦礦型結晶構造的化合物。 In the aforementioned production method, the compound having the perovskite-type crystal structure of the present invention is precipitated by the difference in solubility due to the temperature difference, so that the compound having the perovskite-type crystal structure of the present invention can be produced.

前述製造方法，從可穩定地分散具有鈣鈦礦型結晶構造的化合物的觀點，以包含添加封端配位子的步驟為佳。 The aforementioned production method preferably includes a step of adding a blocking ligand from the viewpoint of stably dispersing a compound having a perovskite-type crystal structure.

前述製造方法，在冷卻步驟之後，以包含藉由離心、過濾等的方法除去粗顆粒的步驟為佳。藉由前述除去步驟所除去的粗顆粒的大小，以10μm以上為佳，以1μm以上更佳，以500nm以上又更佳。 The aforementioned manufacturing method preferably includes a step of removing coarse particles by centrifugation, filtration, etc., after the cooling step. The size of the coarse particles removed by the aforementioned removal step is preferably 10 μm or more, more preferably 1 μm or more, and more preferably 500 nm or more.

此處，所謂高溫的溶劑，只要是溶解包含B及X的化合物、包含M及X的化合物及包含A的化合物或包含A及X的化合物的溫度的溶劑即可，例如以60至600℃的溶劑為佳，以80至400℃的溶劑更佳。 Here, the so-called high-temperature solvent may be a solvent that dissolves a compound containing B and X, a compound containing M and X, and a compound containing A, or a compound containing A and X, for example, at a temperature of 60 to 600°C. The solvent is preferred, and the solvent at 80 to 400°C is more preferred.

作為冷卻的溫度，以-20至50℃為佳，以-10至30℃更佳。 The cooling temperature is preferably -20 to 50°C, more preferably -10 to 30°C.

作為冷卻速度，以0.1至1500℃/分鐘為佳，以10至150℃/分鐘更佳。 The cooling rate is preferably 0.1 to 1500°C/min, and more preferably 10 to 150°C/min.

作為前述製造方法所使用的溶劑，只要是可溶解包含B及X的化合物、包含M及X的化合物、包含A的化合物或包含A及X的化合物的溶劑即可，並無特別限制，例如與前述的分散液組成物中所含的液體(惟樹脂除外)相同者。 The solvent used in the aforementioned manufacturing method is not particularly limited as long as it can dissolve the compound containing B and X, the compound containing M and X, the compound containing A, or the compound containing A and X, and for example, The liquids (except the resin) contained in the aforementioned dispersion liquid composition are the same.

作為從包含具有鈣鈦礦型結晶構造的化合物的分散液取出具有鈣鈦礦型結晶構造的化合物的方法，例如藉由固液分離只回收具有鈣鈦礦型結晶構造的化合物的方法。 As a method of extracting a compound having a perovskite crystal structure from a dispersion liquid containing a compound having a perovskite crystal structure, for example, a method of recovering only a compound having a perovskite crystal structure by solid-liquid separation.

前述固液分離的方法，例如過濾等的方法、利用溶劑的蒸發的方法等。 The aforementioned method of solid-liquid separation includes, for example, a method such as filtration, a method using evaporation of a solvent, and the like.

<樹脂組成物的製造方法> <Manufacturing method of resin composition>

例如作為本發明的樹脂組成物的製造方法，可列舉包含下述步驟之製造方法：將上述具有鈣鈦礦型結晶構造的化合物或本發明的分散液組成物，與樹脂溶解於溶劑的溶液進行混合的步驟；以及除去溶劑的步驟。 For example, as a manufacturing method of the resin composition of the present invention, a manufacturing method including the following steps: the above-mentioned compound having a perovskite crystal structure or the dispersion composition of the present invention is mixed with a solution in which a resin is dissolved in a solvent. The step of mixing; and the step of removing the solvent.

而且，可列舉包含下述步驟之製造方法：將上述具有鈣鈦礦型結晶構造的化合物或本發明的分散液組成物，與單體進行混合的步驟；以及使單體聚合而得到樹脂組成物的步驟。 Furthermore, a manufacturing method including the following steps: a step of mixing the above-mentioned compound having a perovskite crystal structure or the dispersion composition of the present invention with a monomer; and polymerizing the monomer to obtain a resin composition A step of.

以下，對於包含下述步驟的樹脂組成物之製造方法進行說明：將上述具有鈣鈦礦型結晶構造的化合物或本發明的分散液組成物，與樹脂溶解於溶劑的溶液進行混合的步驟；以及除去溶劑的步驟。 Hereinafter, a method for producing a resin composition including the steps of mixing the above-mentioned compound having a perovskite crystal structure or the dispersion composition of the present invention with a solution in which the resin is dissolved in a solvent will be described; and The step of removing the solvent.

在將上述具有鈣鈦礦型結晶構造的化合物或本發明的分散液組成物與樹脂溶解於溶劑的溶液進行混合之步驟中，可為(a)將上述具有鈣鈦礦型結晶構造的化合物或本發明的分散液組成物滴入樹脂溶解於溶劑中的溶液中，亦可為(b)將樹脂溶解於溶劑的溶液滴入本發明的具有鈣鈦礦型結晶構造的化合物或本發明的分散液組成物中，從提高分散性的觀點上，以(a)為佳。 In the step of mixing the compound having a perovskite crystal structure or the dispersion composition of the present invention with a solution in which a resin is dissolved in a solvent, (a) the compound having a perovskite crystal structure or The dispersion composition of the present invention is dropped into the solution in which the resin is dissolved in the solvent, or (b) the solution in which the resin is dissolved in the solvent is dropped into the compound having a perovskite-type crystal structure of the present invention or the dispersion of the present invention In the liquid composition, (a) is preferable from the viewpoint of improving dispersibility.

混合時進行攪拌者，從提高分散性的觀點上為佳。 Those who stir during mixing are preferred from the viewpoint of improving dispersibility.

上述具有鈣鈦礦型結晶構造的化合物或本發明的分散 液組成物與溶解於溶劑的樹脂進行混合之步驟中，溫度並無特別限制，從均勻混合的觀點，以0至100℃的範圍為佳，以10至80℃的範圍更佳。 In the step of mixing the above-mentioned compound having a perovskite-type crystal structure or the dispersion composition of the present invention with a resin dissolved in a solvent, the temperature is not particularly limited. From the viewpoint of uniform mixing, the range of 0 to 100°C is Preferably, the range of 10 to 80°C is more preferable.

作為除去溶劑的方法，例如可為藉由室溫下靜置的自然乾燥，可為藉由使用真空乾燥機的減壓乾燥、或藉由加熱而使溶劑蒸發的方法等。 As a method of removing the solvent, for example, natural drying by standing at room temperature, reduced-pressure drying by using a vacuum dryer, or a method of evaporating the solvent by heating, etc. may be used.

作為上述溶解樹脂的溶劑，只要是可溶解樹脂的溶劑，即無特別限定，惟以不易溶解上述具有鈣鈦礦型結晶構造的化合物者為佳。 The solvent for dissolving the resin is not particularly limited as long as it can dissolve the resin, but it is preferably one that does not easily dissolve the compound having a perovskite-type crystal structure.

作為上述溶解樹脂的溶劑，例如與前述的分散液組成物中所含的液體(惟樹脂除外)為相同者。 The solvent for dissolving the resin is, for example, the same as the liquid (except for the resin) contained in the aforementioned dispersion liquid composition.

該等之中，以甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸戊酯、乙酸甲酯、乙酸乙酯、乙酸戊酯等的酯類；γ-丁內酯、丙酮、二甲基酮、二異丁基酮、環戊酮、環己酮、甲基環己酮等的酮類；二***、甲基第3丁基醚、二異丙醚、二甲氧基甲烷、二甲氧基乙烷、1,4-二噁烷、1,3-二氧戊環、4-甲基二氧戊環、四氫呋喃、甲基四氫呋喃、苯甲醚、苯***等的醚類；乙腈、異丁腈、丙腈、甲氧基乙腈等的具有腈基的有機溶劑；碳酸伸乙酯、碳酸伸丙酯等的具有碳酸酯系的有機溶劑；氯甲烷、二氯甲烷、三氯甲烷等的具有鹵烴基的有機溶劑；正-戊烷、環己烷、正-己烷、苯、甲苯、二甲苯等的具有烴基的有機溶劑，被認為極性低、不易溶解具有鈣鈦礦型結晶構造的化合物，因而為佳，以氯甲烷、二氯甲烷、三氯甲烷等的具有鹵烴基的有機溶劑； 正-戊烷、環己烷、正-己烷、苯、甲苯、二甲苯等的具有烴基的有機溶劑更佳。 Among these, esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate, etc.; γ-butyrolactone, acetone, dimethyl ketone , Diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone and other ketones; diethyl ether, methyl 3 butyl ether, diisopropyl ether, dimethoxymethane, dimethoxymethane Ethers such as methyl ethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenylethyl ether, etc.; acetonitrile, iso Organic solvents with nitrile groups such as butyronitrile, propionitrile, and methoxyacetonitrile; organic solvents with carbonate series such as ethylene carbonate and propylene carbonate; methyl chloride, dichloromethane, trichloromethane, etc. Organic solvents with halogenated hydrocarbon groups; organic solvents with hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene, etc., which are considered to be low in polarity and difficult to dissolve those with a perovskite crystal structure Compounds, therefore preferably, are organic solvents with halogenated hydrocarbon groups such as methyl chloride, dichloromethane, and chloroform; n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene, etc. have hydrocarbon groups The organic solvent is better.

以下對於包含下述步驟之製造方法進行說明：具有鈣鈦礦型結晶構造的化合物或本發明的分散液組成物，與單體進行混合的步驟；以及使單體聚合而得到樹脂組成物的步驟。 The following describes a manufacturing method including the following steps: a step of mixing a compound having a perovskite crystal structure or a dispersion composition of the present invention with a monomer; and a step of polymerizing the monomer to obtain a resin composition .

具有鈣鈦礦型結晶構造的化合物或本發明的分散液組成物與單體進行混合的步驟，可為(a)將上述具有鈣鈦礦型結晶構造的化合物或本發明的分散液組成物滴入單體中，亦可為(b)將單體滴入上述具有鈣鈦礦型結晶構造的化合物或本發明的分散液組成物中，惟從提高分散性的觀點上，以(a)為佳。 The step of mixing a compound having a perovskite-type crystal structure or the dispersion composition of the present invention with a monomer may be (a) dropping the above-mentioned compound having a perovskite-type crystal structure or the dispersion composition of the present invention Into the monomer, (b) dropping the monomer into the above-mentioned compound having a perovskite crystal structure or the dispersion composition of the present invention, but from the viewpoint of improving the dispersibility, (a) is good.

混合時進行攪拌者，從提高分散性的觀點上為佳。 Those who stir during mixing are preferred from the viewpoint of improving dispersibility.

上述具有鈣鈦礦型結晶構造的化合物或本發明的分散液組成物與單體進行混合的步驟中，溫度並無特別限制，惟從均勻混合的觀點上，係以0至100℃的範圍為佳，以10至80℃的範圍更佳。 In the step of mixing the compound having a perovskite-type crystal structure or the dispersion composition of the present invention with the monomer, the temperature is not particularly limited, but from the viewpoint of uniform mixing, the range is from 0 to 100°C. Preferably, the range of 10 to 80°C is more preferable.

作為前述製造方法所使用的單體，例如苯乙烯、甲基丙烯酸甲酯。 As the monomer used in the aforementioned production method, for example, styrene and methyl methacrylate.

前述製造方法中，作為使單體聚合的方法，可適當地使用自由基聚合等的習知的聚合反應。例如於自由基聚合時，在上述具有鈣鈦礦型結晶構造的化合物或本發明的分散液組成物與單體的混合物中，添加自由基聚合引發劑，藉由產生自由基而使用的聚合反應，以產生 自由基而進行聚合反應。 In the aforementioned production method, as a method of polymerizing monomers, conventional polymerization reactions such as radical polymerization can be suitably used. For example, during radical polymerization, the above-mentioned compound having a perovskite-type crystal structure or the mixture of the dispersion composition of the present invention and monomers is added with a radical polymerization initiator to generate free radicals for polymerization reaction , To generate free radicals for polymerization.

自由基聚合引發劑並無特別限定者，惟例如光自由基聚合引發劑。 The radical polymerization initiator is not particularly limited, but, for example, a photo radical polymerization initiator.

作為上述光自由基聚合引發劑，例如雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物(bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide)。 As the photoradical polymerization initiator, for example, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide).

再者，本發明的技術範圍，不限於上述的實施態樣，在不脫離本發明的要旨的範圍內，可加入各種變更。 In addition, the technical scope of the present invention is not limited to the above-mentioned embodiments, and various modifications can be added without departing from the gist of the present invention.

<用途> <Use>

作為本發明的包含具有鈣鈦礦型結晶構造的化合物之組成物的用途，可列舉例如EL顯示器、液晶顯示器用波長轉換材料。具體而言，例如(1)將本發明之包含具有鈣鈦礦型結晶構造的化合物之組成物分散於樹脂並放入玻璃管中後密封，將其沿著導光板的端面(側面)配置於光源的藍色發光二極體與導光板之間，將藍色光轉換為綠色光、紅色光的背光(邊緣型背光)；(2)將本發明的包含具有鈣鈦礦型結晶構造的化合物之組成物分散於樹脂等並成形為薄片狀，將此以2片阻隔膜密封之膜設置在導光板上，從放置於導光板的端面(側面)的藍色發光二極體，通過導光板，照射於前述薄片的藍色光轉換為綠色光、紅色光的背光(表面黏著方式的背光)；(3)使本發明的包含具有鈣鈦礦型結晶構造的化合物之組成物分散於樹脂等，並設置於藍色發光二極體的發光部附近，被照射的藍色光轉換為綠色光、 紅色光的背光(晶片方式的背光)；以及(4)將本發明的具有鈣鈦礦型結晶構造的化合物分散於光阻中。設置於彩色濾光片上，從光源照射的藍色光轉換為綠色光、紅色光的背光。 The use of the composition containing the compound having a perovskite crystal structure of the present invention includes, for example, wavelength conversion materials for EL displays and liquid crystal displays. Specifically, for example, (1) The composition of the present invention containing a compound having a perovskite-type crystal structure is dispersed in a resin and placed in a glass tube, then sealed, and arranged along the end surface (side surface) of the light guide plate Between the blue light-emitting diode of the light source and the light guide plate, a backlight (edge-type backlight) that converts blue light into green light and red light; (2) The compound of the present invention containing a perovskite crystal structure The composition is dispersed in resin and formed into a thin sheet. The film sealed with two barrier films is placed on the light guide plate. The blue light-emitting diode placed on the end surface (side) of the light guide plate passes through the light guide plate. The blue light irradiated on the aforementioned sheet is converted into green light and red light (surface adhesion type backlight); (3) The composition containing the compound with the perovskite type crystal structure of the present invention is dispersed in resin, etc., and It is installed near the light-emitting part of the blue light-emitting diode, and the irradiated blue light is converted into green light and red light (the backlight of the chip method); and (4) the perovskite crystal structure of the present invention The compound is dispersed in the photoresist. Set on the color filter, the blue light irradiated from the light source is converted into green light and red light.

作為本發明的包含具有鈣鈦礦型結晶構造的化合物之組成物的用途，可列舉例如雷射二極體用的波長轉換材料。具體而言，例如使本發明的包含具有鈣鈦礦型結晶構造的化合物之組成物成形，配置於光源的藍色發光二極體的後段，將藍色光轉換為綠色光、紅色光並發出白色光的照明。 The use of the composition containing the compound having a perovskite crystal structure of the present invention includes, for example, a wavelength conversion material for laser diodes. Specifically, for example, a composition containing a compound having a perovskite-type crystal structure of the present invention is molded, and arranged at the back stage of a blue light-emitting diode of a light source to convert blue light into green light and red light and emit white light Lighting of light.

而且，本發明之包含具有鈣鈦礦型結晶構造的化合物之組成物，例如可作為LED的發光層的材料使用。 Furthermore, the composition of the present invention including a compound having a perovskite crystal structure can be used as a material for the light-emitting layer of an LED, for example.

作為本發明的包含具有鈣鈦礦型結晶構造的化合物的LED，例如混合本發明的包含具有鈣鈦礦型結晶構造的化合物之組成物及ZnS等的導電性粒子而積層為膜狀，於單面積層n型傳輸層，另一單面用p型傳輸層積層的構造，流通電流，p型半導體的電洞與n型半導體的電子在接合面的具有鈣鈦礦型結晶構造的化合物中電荷抵消而發光的方式。 As an LED containing a compound having a perovskite-type crystal structure of the present invention, for example, a composition containing a compound having a perovskite-type crystal structure of the present invention and conductive particles such as ZnS are mixed to be laminated in a film shape. The area layer is an n-type transport layer, and the other side is laminated with a p-type transport layer. The current flows, and the holes of the p-type semiconductor and the electrons of the n-type semiconductor are charged in the compound with the perovskite-type crystal structure on the junction surface Offset and shine.

再者，本發明的包含具有鈣鈦礦型結晶構造的化合物之組成物，可利用作為太陽能電池的活性層中所含的電子傳輸材料。 Furthermore, the composition containing a compound having a perovskite-type crystal structure of the present invention can be used as an electron transport material contained in an active layer of a solar cell.

作為前述太陽能電池，其構成並無特別限制，例如依 序具有氟摻雜的氧化錫(FTO)基板、氧化鈦緻密層、多孔性氧化鋁層、由本發明的包含具有鈣鈦礦型結晶構造的化合物之組成物所產生的活性層、2,2’,7,7’-四(N,N’-二-對甲氧基苯基胺)-9,9’-螺雙茀(Spiro-OMeTAD)等的電洞傳輸層及銀(Ag)電極的太陽能電池。 As the aforementioned solar cell, its composition is not particularly limited. For example, a fluorine-doped tin oxide (FTO) substrate, a dense layer of titanium oxide, a porous alumina layer, and the composition of the present invention have a perovskite crystal structure. The active layer produced by the composition of the compound, 2,2',7,7'-tetra(N,N'-di-p-methoxyphenylamine)-9,9'-Spiro-OMeTAD ) And other hole transport layers and silver (Ag) electrode solar cells.

氧化鈦緻密層具有電子傳輸的功能、抑制FTO的粗糙度的效果及抑制反電子移動的功能。 The titanium oxide dense layer has the function of electron transport, the effect of suppressing the roughness of FTO, and the function of suppressing the movement of counterelectrons.

多孔性氧化鋁層具有提高光吸收效率的功能。 The porous alumina layer has a function of improving light absorption efficiency.

由本發明的包含具有鈣鈦礦型結晶構造的化合物之組成物所產生的活性層係發揮電荷分離及電子傳輸的作用。 The active layer produced by the composition containing the compound having the perovskite-type crystal structure of the present invention plays a role of charge separation and electron transport.

〔實施例〕 [Example]

以下，基於實施例及比較例，更具體地說明本發明，惟本發明不限於以下的實施例。 Hereinafter, the present invention will be explained more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.

(包含具有鈣鈦礦型結晶構造的化合物之分散組成物的合成) (Synthesis of dispersion composition containing compound with perovskite crystal structure)

[實施例1] [Example 1]

混合溴化甲基銨(CH3NH3Br)0.32mmol、溴化鉛(PbBr2)0.388mmol、溴化鈣(CaBr2)0.012mmol、正辛基胺40μL、油酸1mL及DMF10mL，製作溶液。 Mix 0.32mmol of methylammonium bromide (CH 3 NH 3 Br), 0.388mmol of lead bromide (PbBr 2 ), 0.012mmol of calcium bromide (CaBr 2 ), 40μL of n-octylamine, 1mL of oleic acid and 10mL of DMF to make a solution .

然後，將20mL的甲苯一邊用磁力攪拌器攪拌，一邊於前述甲苯中添加前述溶液4mL。攪拌1小時後，以10000rpm、10分鐘的離心將沉澱分離，得到上清液的包含具有鈣鈦礦型結晶構造的化合物的分散液組成物。 Then, while stirring 20 mL of toluene with a magnetic stirrer, 4 mL of the aforementioned solution was added to the aforementioned toluene. After stirring for 1 hour, the precipitate was separated by centrifugation at 10,000 rpm for 10 minutes to obtain a supernatant liquid composition containing a compound having a perovskite crystal structure.

[實施例2] [Example 2]

除了溴化鉛(PbBr2)為0.38mmol、溴化鈣(CaBr2)為0.02mmol以外，使用與上述實施例1相同的方法，得到包含具有鈣鈦礦型結晶構造的化合物的分散液組成物。 Except that lead bromide (PbBr 2 ) was 0.38 mmol and calcium bromide (CaBr 2 ) was 0.02 mmol, the same method as in Example 1 was used to obtain a dispersion composition containing a compound having a perovskite-type crystal structure .

[實施例3] [Example 3]

除了溴化鉛(PbBr2)為0.36mmol、溴化鈣(CaBr2)為0.04mmol以外，使用與上述實施例1相同的方法，得到包含具有鈣鈦礦型結晶構造的化合物的分散液組成物。 Except that the lead bromide (PbBr 2 ) was 0.36 mmol and the calcium bromide (CaBr 2 ) was 0.04 mmol, the same method as in Example 1 was used to obtain a dispersion composition containing a compound having a perovskite crystal structure .

[實施例4] [Example 4]

混合溴化甲基銨(CH3NH3Br)0.32mmol、溴化鉛(PbBr2)0.388mmol、溴化鈰(CeBr2)0.012mmol、正辛基胺40μL、油酸1mL及DMF10mL，製作溶液。 Mix 0.32mmol of methylammonium bromide (CH 3 NH 3 Br), 0.388mmol of lead bromide (PbBr 2 ), 0.012mmol of cerium bromide (CeBr 2 ), 40μL of n-octylamine, 1mL of oleic acid and 10mL of DMF to make a solution .

然後，將20mL的甲苯一邊用磁力攪拌器攪拌，一邊於前述甲苯中添加前述溶液4mL。攪拌1小時後，以10000rpm、10分鐘的離心將沉澱分離，得到上清液的包含具有鈣鈦礦型結晶構造的化合物的分散液組成物。 Then, while stirring 20 mL of toluene with a magnetic stirrer, 4 mL of the aforementioned solution was added to the aforementioned toluene. After stirring for 1 hour, the precipitate was separated by centrifugation at 10,000 rpm for 10 minutes to obtain a supernatant liquid composition containing a compound having a perovskite crystal structure.

[實施例5] [Example 5]

除了溴化鉛(PbBr2)為0.38mmol、溴化鈰(CeBr2)為0.02mmol以外，使用與上述實施例4相同的方法，得到包含具有鈣鈦礦型結晶構造的化合物的分散液組成物。 Except that the lead bromide (PbBr 2 ) was 0.38 mmol and the cerium bromide (CeBr 2 ) was 0.02 mmol, the same method as in Example 4 was used to obtain a dispersion composition containing a compound having a perovskite crystal structure .

用X射線繞射測定裝置(XRD、CuK α線、X’pert PRO MPD，Spectris公司製)測定X射線繞射圖形時，在2 θ=14°的位置具有來自(hkl)=(001)的繞射峰，確認具有3維的鈣鈦礦型結晶構造。 When measuring the X-ray diffraction pattern with an X-ray diffraction measuring device (XRD, CuK α line, X'pert PRO MPD, manufactured by Spectris), the X-ray diffraction pattern from (hkl)=(001) at the position of 2θ=14° The diffraction peak was confirmed to have a three-dimensional perovskite crystal structure.

[比較例1] [Comparative Example 1]

混合溴化甲基銨(CH3NH3Br)0.32mmol、溴化鉛(PbBr2)0.4mmol、正辛基胺40μL、油酸1mL及DMF10mL，製作溶液。 0.32 mmol of methylammonium bromide (CH 3 NH 3 Br), 0.4 mmol of lead bromide (PbBr 2 ), 40 μL of n-octylamine, 1 mL of oleic acid, and 10 mL of DMF were mixed to prepare a solution.

然後，將20mL的甲苯一邊用磁力攪拌器攪拌，一邊於甲苯中添加前述溶液4mL。攪拌1小時後，以10000rpm、10分鐘的離心將沉澱分離，得到上清液的包含具有鈣鈦礦型結晶構造的化合物的分散液組成物。 Then, while stirring 20 mL of toluene with a magnetic stirrer, 4 mL of the aforementioned solution was added to the toluene. After stirring for 1 hour, the precipitate was separated by centrifugation at 10,000 rpm for 10 minutes to obtain a supernatant liquid composition containing a compound having a perovskite crystal structure.

用X射線繞射測定裝置(XRD、CuK α線、X’pert PRO MPD，Spectris公司製)測定X射線繞射圖形時，在2 θ=14°的位置具有來自(hkl)=(001)的繞射峰，確認具有3維的鈣鈦礦型結晶構造。 When measuring the X-ray diffraction pattern with an X-ray diffraction measuring device (XRD, CuK α line, X'pert PRO MPD, manufactured by Spectris), the X-ray diffraction pattern from (hkl)=(001) at the position of 2θ=14° The diffraction peak was confirmed to have a three-dimensional perovskite crystal structure.

[比較例2] [Comparative Example 2]

準備2.5cm×2.5cm大小的玻璃基板。將該玻璃基板進行臭氧UV處理。 Prepare a 2.5cm×2.5cm glass substrate. This glass substrate was subjected to ozone UV treatment.

在70℃使溴化鉛(PbBr2)溶解於N,N-二甲基甲醯胺(以下記載為「DMF」)的溶劑中，製作0.1M濃度的溴化鉛溶液。同樣地，在70℃使溴化鈣(CaBr2)溶解於DMF的溶劑中，製作0.1M濃度的溴化鈣溶液。然後，在70℃使溴化甲基銨(CH3NH3Br)溶解於DMF的溶劑中，製作0.1M濃度的溴化甲基銨溶液。上述的溴化鉛溶液與溴化鈣溶液，以莫耳比Ca/(Ca+Pb)成為0.1之方式混合，製作溶液。然後，使莫耳比(溴化甲基銨)/(Ca+Pb)成為1之方式進一步混合溶液。 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 with a concentration of 0.1M. Similarly, calcium bromide (CaBr 2 ) was dissolved in a solvent of DMF at 70°C to prepare a calcium bromide solution with a concentration of 0.1 M. Then, methyl ammonium bromide (CH 3 NH 3 Br) was dissolved in the solvent of DMF at 70° C. to prepare a methyl ammonium bromide solution with a concentration of 0.1 M. The above-mentioned lead bromide solution and calcium bromide solution are mixed so that the molar ratio Ca/(Ca+Pb) becomes 0.1 to prepare a solution. Then, the solution was further mixed so that the molar ratio (methyl ammonium bromide)/(Ca+Pb) became 1.

於上述玻璃基板，藉由旋轉塗佈機，以1000rpm的旋 轉數塗佈前述溶液，在大氣中，以100℃乾燥10分鐘，得到具有鈣鈦礦型結晶構造的化合物的塗佈膜。 The above-mentioned glass substrate was coated with the above-mentioned solution at a rotation speed of 1000 rpm by a spin coater, and dried at 100°C for 10 minutes in the atmosphere to obtain a coating film of a compound having a perovskite-type crystal structure.

用X射線繞射測定裝置(XRD、CuK α線、X’pert PRO MPD，Spectris公司製)測定X射線繞射圖形時，在2 θ=14°的位置具有來自(hkl)=(001)的繞射峰，確認具有3維的鈣鈦礦型結晶構造。 When measuring the X-ray diffraction pattern with an X-ray diffraction measuring device (XRD, CuK α line, X'pert PRO MPD, manufactured by Spectris), the X-ray diffraction pattern from (hkl)=(001) at the position of 2θ=14° The diffraction peak was confirmed to have a three-dimensional perovskite crystal structure.

[比較例3] [Comparative Example 3]

準備2.5cm×2.5cm大小的玻璃基板。將該玻璃基板進行臭氧UV處理。 Prepare a 2.5cm×2.5cm glass substrate. This glass substrate was subjected to ozone UV treatment.

在70℃使溴化鉛(PbBr2)溶解於DMF的溶劑中，製作0.1M濃度的溴化鉛溶液。在70℃使溴化甲基銨(CH3NH3Br)溶解於DMF的溶劑中，製作0.1M濃度的溴化甲基銨溶液。然後，以莫耳比(溴化甲基銨)/(Pb)=1之方式混合溶液。 Lead bromide (PbBr 2 ) was dissolved in a solvent of DMF at 70°C to prepare a lead bromide solution with a concentration of 0.1 M. Methyl ammonium bromide (CH 3 NH 3 Br) was dissolved in a solvent of DMF at 70° C. to prepare a methyl ammonium bromide solution with a concentration of 0.1 M. Then, the solution was mixed so that the molar ratio (methylammonium bromide)/(Pb)=1.

於上述玻璃基板，藉由旋轉塗佈機，以1000rpm的旋轉數塗佈前述溶液，使在100℃乾燥10分鐘，得到具有鈣鈦礦型結晶構造的化合物的塗佈膜。 On the glass substrate, the solution was applied with a spin coater 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 crystal structure.

使用X射線繞射測定裝置(XRD、CuK α線、X’pert PRO MPD，Spectris公司製)測定X射線繞射圖形時，在2 θ=14°的位置具有來自(hkl)=(001)的繞射峰，確認具有3維的鈣鈦礦型結晶構造。 When the X-ray diffraction pattern is measured using an X-ray diffraction measuring device (XRD, CuK α line, X'pert PRO MPD, manufactured by Spectris), the X-ray diffraction pattern is measured at a position of 2θ=14° from (hkl)=(001) The diffraction peak was confirmed to have a three-dimensional perovskite crystal structure.

(M取代量的測定) (Determination of M substitution amount)

對實施例1至5及比較例1、比較例2所得之包含具有鈣鈦礦型結晶構造的化合物的分散液組成物10mL，添加DMF 1mL，使具有鈣鈦礦型結晶構造的化合物溶解。藉 由ICP-MS(ELAN DRCII、珀金埃默爾製)測定溶解後的溶液中之M(Ca或Ce)及B(Pb)的莫耳數量，通過應用「M/(M+Pb)」的式，評估具有鈣鈦礦型結晶構造的化合物中所含的M(Ca或Ce)之量。 To 10 mL of the dispersion liquid composition containing the compound having the perovskite crystal structure obtained in Examples 1 to 5 and Comparative Example 1 and Comparative Example 2, 1 mL of DMF was added to dissolve the compound having the perovskite crystal structure. Measure the number of moles of M (Ca or Ce) and B (Pb) in the dissolved solution by ICP-MS (ELAN DRCII, Perkin Emer), and apply "M/(M+Pb)" To evaluate the amount of M (Ca or Ce) contained in a compound having a perovskite crystal structure.

(量子產率的測定) (Measurement of Quantum Yield)

實施例1至5及比較例1所得之包含具有鈣鈦礦型結晶構造的化合物的分散液組成物的量子產率，使用絕對PL量子產率測定裝置(浜松光子學公司製、商品名C9920-02、測定條件：激發光450nm、室溫、大氣下)進行測定。 The quantum yield of the dispersion liquid composition containing the compound having the perovskite crystal structure obtained in Examples 1 to 5 and Comparative Example 1 was measured using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., trade name C9920- 02. Measurement conditions: Excitation light 450nm, room temperature, atmosphere) for measurement.

相對於前述分散液組成物的總質量，將具有鈣鈦礦型結晶構造的化合物的濃度為1000ppm(μg/g)，進行量子產率。 The concentration of the compound having the perovskite-type crystal structure was 1000 ppm (μg/g) relative to the total mass of the aforementioned dispersion liquid composition, and the quantum yield was performed.

對於具有鈣鈦礦型結晶構造的化合物的濃度的測定方法進行說明。對實施例1至5及比較例1所得之包含具有鈣鈦礦型結晶構造的化合物的分散液組成物10mL，添加DMF 1mL，使具有鈣鈦礦型結晶構造的化合物溶解。所得的溶液中的M(Ca或Ce)及B(Pb)的莫耳數量，藉由ICP-MS(ELAN DRCII、珀金埃默爾製)測定，並從莫耳比通過應用CH3NH3Pb(1-a)MaX(3+δ)(0<a≦0.7,0≦δ≦0.7)或CH3NH3PbBr3的式，測定具有鈣鈦礦型結晶構造的化合物的濃度。 The method for measuring the concentration of a compound having a perovskite crystal structure will be described. To 10 mL of the dispersion liquid composition containing the compound having the perovskite crystal structure obtained in Examples 1 to 5 and Comparative Example 1, 1 mL of DMF was added to dissolve the compound having the perovskite crystal structure. The molar amount of M (Ca or Ce) and B (Pb) in the obtained solution was measured by ICP-MS (ELAN DRCII, Perkin Emmer), and measured from the molar ratio by applying CH 3 NH 3 Pb (1-a) MaX(3+ δ ) (0<a≦0.7, 0≦δ≦0.7) or CH 3 NH 3 PbBr 3 formula to measure the concentration of a compound having a perovskite crystal structure.

(量子產率的測定) (Measurement of Quantum Yield)

將比較例2至3所得之具有鈣鈦礦型結晶構造的化合物的薄膜的量子產率，使用絕對PL量子產率測定裝置(浜松光子學公司製、商品名C9920-02、測定條件：激發光450 nm、室溫、大氣下)進行測定。將比較例2至3所得之具有鈣鈦礦型結晶構造的化合物的薄膜與玻璃基板一起裁切成1cm×1cm的大小，進行量子產率的測定。 The quantum yield of the thin film of the compound having the perovskite crystal structure obtained in Comparative Examples 2 to 3 was measured using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., trade name C9920-02, measurement conditions: excitation light 450 nm, room temperature, atmosphere) for measurement. The thin films of the compounds having the perovskite crystal structure obtained in Comparative Examples 2 to 3 were cut into a size of 1 cm×1 cm together with the glass substrate, and the quantum yield was measured.

以下之表1，表示實施例1至5及比較例1至3的包含具有鈣鈦礦型結晶構造的化合物的分散液組成物的構成及量子產率。表1中，「M/(M+Pb)」表示藉由ICP-MS測定的M的莫耳數量除以M及B(鉛離子)的合計莫耳數量的莫耳比。 Table 1 below shows the composition and quantum yield of the dispersion composition containing the compound having the perovskite crystal structure of Examples 1 to 5 and Comparative Examples 1 to 3. In Table 1, "M/(M+Pb)" represents the molar ratio of the number of moles of M measured by ICP-MS divided by the total number of moles of M and B (lead ions).

Figure 106120710-A0202-12-0043-3
Figure 106120710-A0202-12-0043-3

從上述的結果，確認相較於不使用本發明的比較例1的分散液組成物及比較例2至3的具有鈣鈦礦型結晶構造的化合物之薄膜，使用本發明的實施例1至5的分散液組成物具有良好的量子產率。 From the above results, it was confirmed that the dispersion composition of Comparative Example 1 of the present invention and the thin film of the compound having a perovskite-type crystal structure of Comparative Examples 2 to 3 were used in comparison with Examples 1 to 5 of the present invention. The dispersion composition has good quantum yield.

[實施例6] [Example 6]

以使銫的濃度成為2700ppm(μg/g)之方式於溴化銫(CsBr)中添加混合DMF10mL。將溴化鉛(PbBr2)0.38mmol、溴化鈣(CaBr2)0.02mmol、正辛基胺88μL、油酸1mL與上 述溴化銫溶液混合，製作溶液。 10 mL of DMF was added and mixed to cesium bromide (CsBr) so that the concentration of cesium became 2700 ppm (μg/g). The lead bromide (PbBr 2) 0.38mmol, calcium bromide (CaBr 2) 0.02mmol, 88 l n-octyl amine, oleic acid 1mL cesium bromide solution mixed with the above prepared solution.

然後，將20mL的甲苯一邊用磁力攪拌器攪拌，一邊於前述甲苯中添加前述溶液4mL。攪拌1小時後，以10000rpm、10分鐘的離心將沉澱分離，得到上清液的包含具有鈣鈦礦型結晶構造的化合物的分散液組成物。 Then, while stirring 20 mL of toluene with a magnetic stirrer, 4 mL of the aforementioned solution was added to the aforementioned toluene. After stirring for 1 hour, the precipitate was separated by centrifugation at 10,000 rpm for 10 minutes to obtain a supernatant liquid composition containing a compound having a perovskite crystal structure.

[比較例4] [Comparative Example 4]

以使銫的濃度成為2700ppm(μg/g)之方式於溴化銫(CsBr)中添加混合DMF10mL。將溴化鉛(PbBr2)0.4mmol、正辛基胺88μL、油酸1mL與上述溴化銫溶液混合，製作溶液。 10 mL of DMF was added and mixed to cesium bromide (CsBr) so that the concentration of cesium became 2700 ppm (μg/g). 0.4 mmol of lead bromide (PbBr 2 ), 88 μL of n-octylamine, and 1 mL of oleic acid were mixed with the above cesium bromide solution to prepare a solution.

然後，將20mL的甲苯一邊用磁力攪拌器攪拌，一邊於前述甲苯中添加前述溶液4mL。攪拌1小時後，以10000rpm、10分鐘的離心將沉澱分離，得到上清液的包含具有鈣鈦礦型結晶構造的化合物的分散液組成物。 Then, while stirring 20 mL of toluene with a magnetic stirrer, 4 mL of the aforementioned solution was added to the aforementioned toluene. After stirring for 1 hour, the precipitate was separated by centrifugation at 10,000 rpm for 10 minutes to obtain a supernatant liquid composition containing a compound having a perovskite crystal structure.

(M取代量的測定) (Determination of M substitution amount)

對實施例6所得之包含具有鈣鈦礦型結晶構造的化合物的分散液組成物10mL，添加DMF 1mL，使具有鈣鈦礦型結晶構造的化合物溶解。溶解後的溶液中之M(Ca)及B(Pb)的莫耳數量，藉由ICP-MS(ELAN DRCII、珀金埃默爾製)測定，具有鈣鈦礦型結晶構造的化合物中所含的M(Ca)之莫耳數量通過應用「M/(M+Pb)」的式，進行評估。 To 10 mL of the dispersion liquid composition containing the compound having the perovskite crystal structure obtained in Example 6, 1 mL of DMF was added to dissolve the compound having the perovskite crystal structure. The number of moles of M (Ca) and B (Pb) in the dissolved solution was measured by ICP-MS (ELAN DRCII, manufactured by Perkin Emmel), and contained in the compound having a perovskite crystal structure The number of moles of M(Ca) is evaluated by applying the formula "M/(M+Pb)".

(量子產率的測定) (Measurement of Quantum Yield)

將實施例6及比較例4所得之包含具有鈣鈦礦型結晶構造的化合物的分散液組成物的量子產率，使用絕對PL 量子產率測定裝置(浜松光子學公司製、商品名C9920-02、測定條件：激發光450nm、室溫、大氣下)進行測定。相對於前述分散液組成物的總質量，將具有鈣鈦礦型結晶構造的化合物的濃度調整為900ppm(μg/g)，進行量子產率的測定。 The quantum yield of the dispersion liquid composition containing the compound having the perovskite crystal structure obtained in Example 6 and Comparative Example 4 was measured using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., trade name C9920-02 , Measurement conditions: Excitation light 450nm, room temperature, atmosphere) for measurement. The concentration of the compound having a perovskite crystal structure was adjusted to 900 ppm (μg/g) relative to the total mass of the aforementioned dispersion liquid composition, and the quantum yield was measured.

(具有鈣鈦礦型結晶構造的化合物的測定) (Measurement of compounds with perovskite crystal structure)

實施例及比較例所得之組成物的具有鈣鈦礦型結晶構造的化合物的濃度，分別於包含具有鈣鈦礦型結晶構造的化合物及溶劑的分散液中，藉由添加N,N-二甲基甲醯胺使具有鈣鈦礦型結晶構造的化合物溶解後，使用ICP-MS(ELAN DRCII、珀金埃默爾製)及離子色層分析儀進行測定。 The concentration of the compound having the perovskite-type crystal structure of the composition obtained in the examples and the comparative example is each in a dispersion containing the compound having the perovskite-type crystal structure and a solvent, by adding N,N-dimethyl After dissolving a compound having a perovskite-type crystal structure with methylformamide, it was measured using ICP-MS (ELAN DRCII, manufactured by Perkin Emmer) and an ion chromatography.

以下之表2，記載實施例6及比較例4的包含具有鈣鈦礦型結晶構造的化合物的分散液組成物的構成及量子產率。表2中，[M/(M+Pb)]表示將M的莫耳數量除以M及B(鉛離子)的合計莫耳數量的莫耳比。 Table 2 below describes the composition and quantum yield of the dispersion liquid composition containing the compound having the perovskite crystal structure of Example 6 and Comparative Example 4. In Table 2, [M/(M+Pb)] represents the molar ratio obtained by dividing the number of moles of M by the total number of moles of M and B (lead ion).

Figure 106120710-A0202-12-0045-4
Figure 106120710-A0202-12-0045-4

從上述的結果，確認相較於不使用本發明的比較例4的分散液組成物，使用本發明的實施例6的分散液組成物具有良好的量子產率。 From the above results, it was confirmed that the dispersion composition of Example 6 of the present invention has a good quantum yield compared to the dispersion composition of Comparative Example 4 that did not use the present invention.

[參考例1] [Reference example 1]

實施例1至6記載的本發明的分散液組成物與樹脂混合後，除去液體，可得到本發明的樹脂組成物，放入玻璃管等之中加以密封後，將其配置於光源的藍色發光二極體與導光板之間，製造可將藍色發光二極體的藍色光轉換為綠色光、紅色光的背光。 After the dispersion composition of the present invention described in Examples 1 to 6 is mixed with the resin, the liquid is removed to obtain the resin composition of the present invention, which is placed in a glass tube, etc., sealed, and placed on the blue light source Between the light-emitting diode and the light guide plate, a backlight that can convert the blue light of the blue light-emitting diode into green light and red light is manufactured.

[參考例2] [Reference example 2]

實施例1至6記載的分散液組成物與樹脂混合後，除去液體並製成薄片，可得到本發明的樹脂組成物，將其用2片阻隔膜夾住密封的膜，配置於導光板上，製造從放置於導光板的端面(側面)的藍色發光二極體，通過導光板而照射於前述薄片的藍色光可轉換為綠色光、紅色光的背光。 After mixing the dispersion composition described in Examples 1 to 6 with the resin, removing the liquid and forming a sheet, the resin composition of the present invention can be obtained. The sealing film is sandwiched between two barrier films and arranged on a light guide plate. A blue light emitting diode placed on the end surface (side) of the light guide plate is manufactured, and the blue light irradiated on the aforementioned sheet through the light guide plate can be converted into a backlight that can be converted into green light and red light.

[參考例3] [Reference example 3]

實施例1至6記載的本發明的分散液組成物與樹脂混合後，除去溶劑，可得到本發明的樹脂組成物，藉由設置在藍色發光二極體的發光部附近，製造可將照射的藍色光轉換為綠色光、紅色光的背光。 After the dispersion composition of the present invention described in Examples 1 to 6 is mixed with the resin, the solvent is removed, and the resin composition of the present invention can be obtained. The resin composition of the present invention is provided near the light-emitting part of a blue light-emitting diode to produce The blue light is converted into green and red backlight.

[參考例4] [Reference example 4]

實施例1至6記載的本發明的分散液組成物與光阻混合後，除去溶劑，可得到波長轉換材料。將所得之波長轉換材料，配置於光源的藍色發光二極體與導光板之間、或光源的OLED的後段，製造可將光源的藍色光轉換為綠色光、紅色光的背光。 After mixing the dispersion liquid composition of the present invention described in Examples 1 to 6 and the photoresist, the solvent is removed to obtain a wavelength conversion material. The obtained wavelength conversion material is arranged between the blue light-emitting diode of the light source and the light guide plate, or the back stage of the OLED of the light source, to manufacture a backlight that can convert the blue light of the light source into green light and red light.

[參考例5] [Reference example 5]

將實施例1至6記載的分散液組成物及ZnS等的導電 性粒子混合並成膜，於其單面積層n型傳輸層，並於另一單面積層p型傳輸層而得到LED。藉由使電流通過，p型半導體的電洞與n型半導體的電子在接合面的具有鈣鈦礦型結晶構造的化合物中可使電荷抵消而發光。 The dispersion composition described in Examples 1 to 6 and conductive particles such as ZnS were mixed and formed into a film, and an n-type transmission layer was layered on a single area thereof and a p-type transmission layer was layered on another single area to obtain an LED. By passing an electric current, the holes of the p-type semiconductor and the electrons of the n-type semiconductor can offset the charges in the compound having the perovskite-type crystal structure on the junction surface and emit light.

[參考例6] [Reference example 6]

於摻雜氟的氧化錫(FTO)基板的表面上，積層氧化鈦緻密層，從其上積層多孔性氧化鋁層，再於其上使用實施例1至6記載的分散液組成物積層鈣鈦礦層，又從其上積層2,2’,7,7’-四(N,N’-二-對甲氧基苯基胺)-9,9’-螺雙茀(2,2’,7,7’-tetrakis-(N,N’-di-p-methoxyphenylamine)-9,9’-spirobifluorene)(Spiro-OMeTAD)等的電洞傳輸層，再於其上積層銀(Ag)層，製作太陽能電池。 On the surface of a fluorine-doped tin oxide (FTO) substrate, a dense layer of titanium oxide was laminated, a porous alumina layer was laminated thereon, and then perovskite was laminated using the dispersion composition described in Examples 1 to 6 Ore layer, and layer 2,2',7,7'-tetra(N,N'-bis-p-methoxyphenylamine)-9,9'-spirobifu(2,2',7 ,7'-tetrakis-(N,N'-di-p-methoxyphenylamine)-9,9'-spirobifluorene)(Spiro-OMeTAD) and other hole transport layers, and then a silver (Ag) layer is laminated on it to make Solar battery.

[參考例7] [Reference example 7]

將實施例1至6記載的本發明的包含具有鈣鈦礦型結晶構造的化合物的分散液組成物與樹脂混合後，除去溶劑而成形者，可得到本發明的包含具有鈣鈦礦型結晶構造的化合物的樹脂組成物，將此設置在藍色發光二極體的後段時，製造從藍色發光二極體照射在前述樹脂成形體的藍色光轉換為綠色光、紅色光而發出白色光的雷射二極體照明。 After mixing the dispersion composition of the present invention described in Examples 1 to 6 containing the compound having a perovskite-type crystal structure with a resin, and then removing the solvent and forming a shape, the present invention can be obtained by mixing the composition having a perovskite-type crystal structure. When the resin composition of the compound is placed in the back stage of the blue light-emitting diode, the blue light emitted from the blue light-emitting diode irradiated on the resin molded body is converted into green light and red light to emit white light Laser diode lighting.

[產業上的可利用性] [Industrial availability]

根據本發明，可提供具有高量子產率且於介質中分散具有鈣鈦礦型結晶構造的化合物之組成物。 According to the present invention, a composition having a high quantum yield and a compound having a perovskite crystal structure dispersed in a medium can be provided.

因此，本發明的組成物可適合使用於發光相關的材料領域中。 Therefore, the composition of the present invention can be suitably used in the field of luminescence-related materials.

Claims (6)

一種於介質中分散之具有鈣鈦礦型結晶構造的化合物之組成物，該化合物係以A、B、X及M為構成成分，M的莫耳數量除以M及B的合計莫耳數量的莫耳比[M/(M+B)]的值為0.7以下；A為位於在前述鈣鈦礦型結晶構造中以B為中心的六面體的各頂點之銫離子、有機銨離子或脒鎓離子；B為鉛離子；M為於六配位的離子半徑為0.9Å以上1.5Å以下之3價金屬元素的陽離子，M的至少一部分在前述鈣鈦礦型結晶構造中取代B的一部分；X表示位於在前述鈣鈦礦型結晶構造中以B為中心的八面體的各頂點的成分，其係選自氯化物離子、溴化物離子、氟化物離子、碘化物離子及硫氰酸根離子所成群的1種以上的陰離子。 A composition of a compound with a perovskite crystal structure dispersed in a medium, the compound is composed of A, B, X, and M, and the number of moles of M divided by the total number of moles of M and B The value of the molar ratio [M/(M+B)] is 0.7 or less; A is the cesium ion, organic ammonium ion or amidine located at each vertex of the hexahedron centered on B in the aforementioned perovskite crystal structure Onium ion; B is a lead ion; M is a cation of a trivalent metal element with an ionic radius of 0.9 Å to 1.5 Å in hexacoordination, at least a part of M replaces a part of B in the aforementioned perovskite crystal structure; X represents a component located at each vertex of an octahedron centered at B in the aforementioned perovskite-type crystal structure, which is selected from chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion One or more anions grouped together. 如申請專利範圍第1項所述之組成物，其中，前述M為稀土元素的陽離子。 The composition described in item 1 of the scope of patent application, wherein the aforementioned M is a cation of a rare earth element. 如申請專利範圍第1或2項所述之組成物，其中前述M為鈰離子。 The composition described in item 1 or 2 of the scope of patent application, wherein the aforementioned M is a cerium ion. 如申請專利範圍第1或2項所述之組成物，其中，前述A為有機銨離子。 The composition described in item 1 or 2 of the scope of patent application, wherein the aforementioned A is an organic ammonium ion. 如申請專利範圍第1或2項所述之組成物，其中，前述介質為液體。 The composition described in item 1 or 2 of the scope of patent application, wherein the aforementioned medium is a liquid. 如申請專利範圍第1或2項所述之組成物，其中，前 述介質為樹脂。 Such as the composition described in item 1 or 2 of the scope of patent application, in which the former The medium is resin.
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