JP3542077B2 - Organic ammonium / inorganic layered perovskite compound and production method thereof - Google Patents
Organic ammonium / inorganic layered perovskite compound and production method thereof Download PDFInfo
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- JP3542077B2 JP3542077B2 JP2000274233A JP2000274233A JP3542077B2 JP 3542077 B2 JP3542077 B2 JP 3542077B2 JP 2000274233 A JP2000274233 A JP 2000274233A JP 2000274233 A JP2000274233 A JP 2000274233A JP 3542077 B2 JP3542077 B2 JP 3542077B2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims description 37
- 150000001875 compounds Chemical class 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000010409 thin film Substances 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000012044 organic layer Substances 0.000 claims description 14
- 229910001502 inorganic halide Inorganic materials 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000010408 film Substances 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 125000003367 polycyclic group Chemical group 0.000 claims description 8
- 238000004528 spin coating Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 229910021480 group 4 element Inorganic materials 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 14
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- -1 rare earth metal cation Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 0 *[n]1c(cccc2)c2c2ccccc12 Chemical compound *[n]1c(cccc2)c2c2ccccc12 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、光機能材料として有用な有機アンモニウム・無機層状ペロブスカイト化合物とその製造方法に関する。
【０００２】
【従来の技術】
層状ペロブスカイト化合物は、有機層と無機層とが交互に積層した超格子構造を形成し、無機ハライドの種類により低次元半導体、磁性体、発光体として興味深い物性を有している。加えて、有機層に機能性発色団を導入することで、有機層と無機層との機能を組み合わせた新しい機能材料としての可能性も示されている。
【０００３】
この層状ペロブスカイト化合物としては、Ａを有機アンモニウム分子、ＭをＩＶ族元素または遷移金属、Ｘをハロゲンとして一般式Ａ２ ＭＸ４ で表され、有機アンモニウム分子Ａ層と無機ハライドＭＸ４ 層が交互に積層した超格子構造（図５にその模式図を示す。）が知られている。また、Ａを有機アンモニウム陽イオン、Ｍを２価の希土類金属の陽イオン、Ｘをハロゲン（Ｃｌ，Ｂｒ，Ｉ）として一般式Ａ２ ＭＸ４ で表され、有機アンモニウム分子Ａ層と無機ハライドＭＸ４ 層が交互に積層した超格子構造も知られている（特開平１０−３１６６８５号公報）。
【０００４】
従来の発色団を有機層に導入した層状ペロブスカイト化合物においては、発色団はナフタレンのような嵩の小さなもの、あるいはアゾベンゼンのような棒状のものに限られていた。また、その化合物薄膜の製造方法としては、発色団を有する有機アミンハロゲン化水素酸塩と無機ハライドＭＸ２ を有機溶媒に溶解し、その溶液からキャスト法あるいはスピンコート法により製膜する方法が知られている（Ｍ．Ｅｒａ， Ｋ．Ｍａｅｄａ， ａｎｄ Ｔ．Ｔｓｕｔｓｕｉ， Ｃｈｅｍｉｓｔｒｙ Ｌｅｔｔｅｒｓ， １２３５−１２３６ （１９９７） 。
【０００５】
本発明者は、先にラングミュア−ブロジェット法により機能性発色団を導入した層状ペロブスカイト有機／無機超格子材料の製造とその発光デバイスへの応用について報告した（「量子効果等の物理現象３回シンポジウム予稿集」、１９５頁、１９９９年１２月２１日、科学技術振興事業団）。
【０００６】
【発明が解決しようとする課題】
従来の技術では、層状ペロブスカイト化合物の有機層に導入できる発色団はナフタレンやアゾベンゼンのような２個以下の有機環からなる嵩の小さなものに限られていた。本発明の目的は、３個以上の有機環からなる嵩高い発色団（以下、「嵩高い発色団」と称する。）を有機層に導入することを可能にし、より多様な発色団を導入した層状ペロブスカイト化合物とその薄膜の製造方法を提供することにある。
【０００７】
【課題を解決するための手段】
本発明は、嵩高い発色団を有する有機アンモニウム分子とアルキルアンモニウム分子との混合物を用いることで、嵩高い発色団を有機アンモニウム・無機層状ペロブスカイト化合物の有機層に導入することを可能にした。
【０００８】
すなわち、本発明は、Ａを有機アンモニウム分子、ＭをＩＶ族元素または遷移金属、Ｘをハロゲン（Ｃｌ，Ｂｒ，またはＩ）として一般式Ａ２ ＭＸ４ で表され、有機アンモニウム分子Ａと無機ハライドＭＸ４ が交互に積層した超格子構造を形成する有機アンモニウム・無機層状ペロブスカイト化合物において、有機アンモニウム分子Ａ層に３個以上の多環系からなる発色団が導入されていることを特徴とする有機アンモニウム・無機層状ペロブスカイト化合物である。
【０００９】
また、本発明は、３個以上の多環系からなる発色団が、芳香環または複素環あるいは両者の複合環からなる発色団であることを特徴とする上記の有機アンモニウム・無機層状ペロブスカイト化合物である。
【００１０】
また、本発明は、３個以上の多環系からなる発色団を導入した有機アンモニウム分子、アルキルアンモニウム分子および無機ハライドを有機溶媒に溶解し、その溶液から製膜することを特徴とする上記の有機アンモニウム・無機層状ペロブスカイト化合物の薄膜の製造方法である。
【００１１】
また、本発明は、３個以上の多環系からなる発色団を導入した有機アンモニウム分子が、発色団Ａｒおよびメチレン鎖（ＣＨ２ ）ｎ からなる有機アミンハロゲン化水素酸塩Ａｒ−（ＣＨ２ ）ｎ −ＮＨ３ Ｘ（Ｘは、Ｃｌ，Ｂｒ，またはＩ）であり、アルキルアンモニウム分子がそのメチレン鎖と同じ長さのアルキル基を有するアルキルアミンハロゲン化水素酸塩Ｃｎ Ｈ２ｎ＋１ＮＨ３ Ｘ（Ｘは、Ｃｌ，Ｂｒ，またはＩ）であることを特徴とする上記の有機アンモニウム・無機層状ペロブスカイト化合物の薄膜の製造方法である。
【００１２】
また、本発明は、製膜法が、スピンコート法であることを特徴とする上記の有機アンモニウム・無機層状ペロブスカイト化合物の薄膜の製造方法である。
【００１３】
また、本発明は、有機溶媒が、ジメチルホルムアミドまたはジメチルスルホオキサイドであることを特徴とする上記の有機アンモニウム・無機層状ペロブスカイト化合物の薄膜の製造方法である。
【００１４】
ここで、ＩＶ族元素は、Ｇｅ，Ｓｎ，またはＰｂ、遷移金属は、Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，またはＣｄである。また、無機ハライドは、これらＩＶ族元素または遷移金属をＭとし、ハロゲン（Ｃｌ，Ｂｒ，またはＩ）をＸとしたときに、化学式ＭＸ２ で表される化合物である。
【００１５】
【発明実施の形態】
以下に、本発明の実施の形態を図を用いて説明する。図１は、本発明の実施例の一形態を示すもので、使用する有機アンモニウム分子の構造および形成される層状ペロブスカイト化合物の薄膜の構造を模式的に示したものである。
【００１６】
従来の１種の有機アンモニウム分子のみを用いた層状ペロブスカイト化合物の薄膜の製造方法では、発色団が導入される有機層の空間が限られてしまうため、導入できる発色団の大きさや形状に制約があった。
【００１７】
しかし、図１の模式図に示すように、発色団（以下、「Ａｒ」で示す。）およびメチレン鎖（ＣＨ２ ）ｎ からなる有機アミンハロゲン化水素酸塩Ａｒ−（ＣＨ２ ）ｎ −ＮＨ３ Ｘとアルキルアミンがメチレン鎖と同じ長さのアルキル基を有するアルキルアミンハロゲン化水素酸塩Ｃｎ Ｈ２ｎ＋１ＮＨ３ Ｘとの２種の有機アンモニウム分子を用いることで、アルキルアンモニウム分子が嵩高い発色団を導入できる空間を作り出し、有機層に嵩高い発色団Ａｒの導入が可能となる。
【００１８】
具体的には、発色団Ａｒを有する有機アミンハロゲン化水素酸塩Ａｒ−（ＣＨ２ ）ｎ −ＮＨ３ Ｘとアルキルアミンハロゲン化水素酸塩Ｃｎ Ｈ２ｎ＋１ＮＨ３ Ｘとを所定のモル比、好ましくは２：１で混合し、さらに、混合した有機アンモニウム分子と無機ハライドＭＸ２ とを所定のモル比、好ましくは２：１となるよに無機ハライドＭＸ２ を加えて、有機溶媒に溶解した溶液から通常のスピンコート法やキャスト法によって製膜することにより、嵩高い発色団を導入した層状ペロブスカイト化合物の薄膜が製造できる。成膜に際し、有機アミンハロゲン化水素酸塩および無機ハライドを高い濃度で溶解するために極性の高いジメチルホルムアミドまたはジメチルスルホオキサイドを溶媒として用いた。
【００１９】
本発明は、カルバゾール発色団のみに限られるものでなく、芳香環または複素環（ピロール環、チオフェン環、フラン環、ピリジン環）の何れかまたは両者の環の３個以上の多環系発色団にも適用できる。
【００２０】
【実施例】
実施例１
嵩高い発色団としてカルバゾール発色団を有する下記の式に示す有機アミン臭化水素酸塩を用いて、臭化鉛系層状ペロブスカイト薄膜の製造を試みた結果を、実施例として示す。
【００２１】
【化１】
カルバゾール発色団を有する有機アミン臭化水素酸塩とプロビルアミン臭化水素酸塩をモル比２：１で混合し、これに臭化鉛を合計の有機アミン臭化水素酸塩と臭化鉛とのモル比が２：１となるように加えて、ジメチルホルムアミドに溶解した。この溶液からスピンコート法を用いて製膜した。スピンコートの条件は、溶媒：ジメチルホルムアミド、溶液濃度：濃度２×１０−３ｍｏｌ／ｌ、回転数：２０００回転／分で、溶融石英板上に厚さ２０ｎｍで成膜した。
【００２３】
図２に、製造した薄膜の吸収スペクトルを示す。これによれば、３９０ｎｍ付近に臭化鉛系層状ペロブスカイト化合物に特徴的な強く鋭い励起子吸収が観測されている。加えて３００ｎｍ付近にカルバゾール発色団に起因した吸収も観測されている。さらに、発光スペクトルの測定から、臭化鉛系層状ペロブスカイトの励起子生成に起因した鋭い励起子発光が４００ｎｍ付近に観測されることも確認している。このことより、層状ペロブスカイト化合物の構造が形成されていることが分かる。また、この薄膜のＸ線回折プロファイルを図３に示す。層状ペロブスカイトの層構造に起因した回折ピークが観測され、この結果からも、層状ペロブスカイト化合物の構造が形成されていることが分かる。
【００２４】
比較例１
比較のため、カルバゾール発色団を有する有機アミン臭化水素酸塩のみを用い、実施例１と同様にスピンコート法により薄膜を製造した。その薄膜の吸収スペクトルを図４に示す。この薄膜において、臭化鉛系層状ペロブスカイト化合物に特徴的な３９０ｎｍ付近の鋭い励起子吸収が見られず、層状ペロブスカイト化合物の薄膜が形成されていないことが分かる。
【００２５】
以上のことから、カルバゾール発色団を有する有機アミン臭化水素酸塩とアルキルアミン臭化水素酸塩との混合により、嵩高いカルバゾール発色団を導入した層状ペロブスカイト化合物の薄膜が製造可能であることが確認された。
【００２６】
【発明の効果】
本発明によれば、次のような効果を奏することができる。（１）多様な大きさおよび形態の発色団を有機層に導入することが可能になり、低次元半導体、磁性体、発光体として興味深い物性を有している層状ペロブスカイト化合物の薄膜の材料設計の自由度が大きくなる。（２）様々な機能性を有する発色団を有機層に導入することが可能になり、有機層と無機層との相互作用を利用した新しい機能材料の構築が可能となる。
【図面の簡単な説明】
【図１】図１は、アルキルアンモニウム分子との混合による嵩高い発色団の有機層への導入の説明図。
【図２】図２は、実施例１により製造した薄膜の吸収スペクトルである。
【図３】図３は、実施例１により製造した薄膜のＸ線回折プロファイルである。
【図４】図４は、比較例１により製造した薄膜の吸収スペクトルである。
【図５】図５は、有機アンモニウム分子層と無機ハライド層が交互に積層した層状ペロブスカイト化合物の超格子構造の模式図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an organic ammonium / inorganic layered perovskite compound useful as an optical functional material and a method for producing the same.
[0002]
[Prior art]
The layered perovskite compound forms a superlattice structure in which an organic layer and an inorganic layer are alternately stacked, and has interesting physical properties as a low-dimensional semiconductor, a magnetic material, and a luminescent material depending on the type of inorganic halide. In addition, by introducing a functional chromophore into the organic layer, the possibility of a new functional material combining the functions of the organic layer and the inorganic layer is also shown.
[0003]
As the layered perovskite compound, A an organic ammonium molecules, IV group elements or transition metal M, represented by the general formula A 2 MX 4 X as halogen, organic ammonium molecules A layer and the inorganic halide MX 4 layers alternately A stacked superlattice structure (a schematic diagram of which is shown in FIG. 5) is known. A is an organic ammonium cation, M is a divalent rare earth metal cation, X is a halogen (Cl, Br, I), and is represented by the general formula A 2 MX 4. The organic ammonium molecule A layer and the inorganic halide MX A superlattice structure in which four layers are alternately stacked is also known (Japanese Patent Laid-Open No. Hei 10-316686).
[0004]
In a conventional layered perovskite compound in which a chromophore is introduced into an organic layer, the chromophore is limited to a small one such as naphthalene or a rod-like one such as azobenzene. As the production method of the compound thin film, a method of the organic amine hydrohalides and inorganic halide MX 2 is dissolved in an organic solvent, forming a film by a casting method or a spin coating method from a solution thereof having a chromophore known (M. Era, K. Maeda, and T. Tsutsui, Chemistry Letters, 1235-1236 (1997)).
[0005]
The present inventor has previously reported the production of a layered perovskite organic / inorganic superlattice material into which a functional chromophore was introduced by the Langmuir-Blodgett method and its application to light emitting devices ("Physical phenomena such as quantum effect 3 times"). Proceedings of the Symposium ”, 195 pages, Science and Technology Promotion Agency, December 21, 1999).
[0006]
[Problems to be solved by the invention]
In the prior art, chromophores that can be introduced into the organic layer of the layered perovskite compound are limited to those having a small bulk consisting of two or less organic rings, such as naphthalene and azobenzene. An object of the present invention is to allow a bulky chromophore composed of three or more organic rings (hereinafter, referred to as a "bulky chromophore") to be introduced into an organic layer, and to introduce a more diverse chromophore. It is an object of the present invention to provide a method for producing a layered perovskite compound and a thin film thereof.
[0007]
[Means for Solving the Problems]
The present invention makes it possible to introduce a bulky chromophore into an organic layer of an organic ammonium / inorganic layered perovskite compound by using a mixture of an organic ammonium molecule having a bulky chromophore and an alkylammonium molecule.
[0008]
That is, the present invention is represented by the general formula A 2 MX 4 where A is an organic ammonium molecule, M is a group IV element or transition metal, and X is halogen (Cl, Br, or I). An organic ammonium / inorganic layered perovskite compound that forms a superlattice structure in which MX 4 is alternately stacked, wherein a chromophore composed of three or more polycyclic systems is introduced into the organic ammonium molecule A layer. Ammonium / inorganic layered perovskite compound.
[0009]
Further, the present invention provides the above-mentioned organic ammonium / inorganic layered perovskite compound, wherein the chromophore composed of three or more polycyclic systems is a chromophore composed of an aromatic ring or a heterocyclic ring or a complex ring of both. is there.
[0010]
Further, the present invention is characterized in that an organic ammonium molecule, an alkylammonium molecule and an inorganic halide in which a chromophore composed of three or more polycyclic systems are introduced are dissolved in an organic solvent, and the film is formed from the solution. This is a method for producing a thin film of an organic ammonium / inorganic layered perovskite compound.
[0011]
Further, the present invention provides an organic ammonium hydrohalide Ar- (CH 2 ) comprising a chromophore Ar and a methylene chain (CH 2 ) n in which an organic ammonium molecule into which a chromophore composed of three or more polycyclic systems is introduced. ) n -NH 3 X (X is, Cl, Br or I),, alkylamine hydrohalides alkylammonium molecule has an alkyl group having the same length as the methylene chain C n H 2n + 1 NH 3 X (X is Cl, Br, or I). The method for producing a thin film of an organic ammonium / inorganic layered perovskite compound as described above, wherein X is Cl, Br, or I.
[0012]
Further, the present invention is the method for producing a thin film of the above-mentioned organic ammonium / inorganic layered perovskite compound, wherein the film formation method is a spin coating method.
[0013]
Further, the present invention is the above-mentioned method for producing a thin film of an organic ammonium / inorganic layered perovskite compound, wherein the organic solvent is dimethylformamide or dimethylsulfoxide.
[0014]
Here, the group IV element is Ge, Sn, or Pb, and the transition metal is Cr, Mn, Fe, Co, Ni, Cu, Zn, or Cd. The inorganic halide is these Group IV element or a transition metal and M, halogen (Cl, Br or I,) a when a X, a compound represented by the formula MX 2.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
An embodiment of the present invention will be described below with reference to the drawings. FIG. 1 shows an embodiment of the present invention, and schematically shows the structure of an organic ammonium molecule used and the structure of a thin film of a layered perovskite compound to be formed.
[0016]
In the conventional method for producing a thin film of a layered perovskite compound using only one kind of organic ammonium molecule, the space of the organic layer into which the chromophore is introduced is limited, and thus the size and shape of the chromophore that can be introduced are limited. there were.
[0017]
However, as shown in the schematic diagram of FIG. 1, an organic amine hydrohalide Ar- (CH 2 ) n -NH composed of a chromophore (hereinafter referred to as “Ar”) and a methylene chain (CH 2 ) n . 3 X and alkylamines by using two kinds of organic ammonium molecules with alkylamine hydrohalide C n H 2n + 1 NH 3 X having an alkyl group having the same length as the methylene chain, high bulk alkylammonium molecules A space in which the chromophore can be introduced is created, and the bulky chromophore Ar can be introduced into the organic layer.
[0018]
Specifically, an organic amine hydrohalide having a chromophore Ar Ar- (CH 2) n -NH 3 X with an alkylamine hydrohalide C n H 2n + 1 NH 3 X and the predetermined molar ratio, preferably 2: 1 mixture, further mixed organic ammonium molecules and inorganic halide MX 2 and a predetermined molar ratio, preferably 2: 1 and added to the inorganic halide MX 2 to Yo becomes, dissolved in an organic solvent By forming a film from a solution by a usual spin coating method or casting method, a thin film of a layered perovskite compound into which a bulky chromophore has been introduced can be manufactured. In forming the film, highly polar dimethylformamide or dimethylsulfoxide was used as a solvent in order to dissolve the organic amine hydrohalide and the inorganic halide at a high concentration.
[0019]
The present invention is not limited to carbazole chromophores, but includes three or more polycyclic chromophores of either aromatic rings or heterocyclic rings (pyrrole ring, thiophene ring, furan ring, pyridine ring) or both rings. Also applicable to
[0020]
【Example】
Example 1
The results of an attempt to produce a lead bromide layered perovskite thin film using an organic amine hydrobromide having a carbazole chromophore as a bulky chromophore and represented by the following formula are shown as examples.
[0021]
Embedded image
An organic amine hydrobromide having a carbazole chromophore and a provylamine hydrobromide are mixed at a molar ratio of 2: 1 and lead bromide is added to the total organic amine hydrobromide and lead bromide. And dissolved in dimethylformamide. A film was formed from this solution using a spin coating method. Spin coating conditions were as follows: solvent: dimethylformamide, solution concentration: concentration 2 × 10 −3 mol / l, number of revolutions: 2000 revolutions / minute, and a film was formed on a fused quartz plate with a thickness of 20 nm.
[0023]
FIG. 2 shows an absorption spectrum of the manufactured thin film. According to this, a strong and sharp exciton absorption characteristic of a lead bromide-based layered perovskite compound is observed at around 390 nm. In addition, absorption due to the carbazole chromophore was observed around 300 nm. Further, from the measurement of the emission spectrum, it was confirmed that sharp exciton emission due to exciton generation of the lead bromide-based layered perovskite was observed at around 400 nm. This indicates that the structure of the layered perovskite compound was formed. FIG. 3 shows an X-ray diffraction profile of the thin film. A diffraction peak due to the layer structure of the layered perovskite is observed, and this result also indicates that the structure of the layered perovskite compound is formed.
[0024]
Comparative Example 1
For comparison, a thin film was produced by spin coating in the same manner as in Example 1, using only the organic amine hydrobromide having a carbazole chromophore. FIG. 4 shows the absorption spectrum of the thin film. In this thin film, sharp exciton absorption near 390 nm characteristic of the lead bromide-based layered perovskite compound was not observed, and it was found that a thin film of the layered perovskite compound was not formed.
[0025]
From the above, by mixing an organic amine hydrobromide having a carbazole chromophore and an alkylamine hydrobromide, a thin film of a layered perovskite compound into which a bulky carbazole chromophore has been introduced can be produced. confirmed.
[0026]
【The invention's effect】
According to the present invention, the following effects can be obtained. (1) It is possible to introduce chromophores of various sizes and forms into an organic layer, and to design a material for a thin film of a layered perovskite compound having interesting physical properties as a low-dimensional semiconductor, a magnetic substance, and a light-emitting substance. The degree of freedom increases. (2) A chromophore having various functions can be introduced into an organic layer, and a new functional material utilizing the interaction between an organic layer and an inorganic layer can be constructed.
[Brief description of the drawings]
FIG. 1 is an explanatory diagram of introduction of a bulky chromophore into an organic layer by mixing with an alkylammonium molecule.
FIG. 2 is an absorption spectrum of a thin film manufactured according to Example 1.
FIG. 3 is an X-ray diffraction profile of a thin film manufactured according to Example 1.
FIG. 4 is an absorption spectrum of a thin film manufactured according to Comparative Example 1.
FIG. 5 is a schematic diagram of a superlattice structure of a layered perovskite compound in which an organic ammonium molecule layer and an inorganic halide layer are alternately stacked.
Claims (5)
Ａを有機アンモニウム分子、ＭをＩＶ族元素または遷移金属、Ｘをハロゲン（Ｃｌ，Ｂｒ，またはＩ）として一般式Ａ ２ ＭＸ ４ で表され、有機アンモニウム分子Ａと無機ハライドＭＸ ４ が交互に積層した超格子構造を形成する有機アンモニウム・無機層状ペロブスカイト化合物において、有機アンモニウム分子Ａ層に３個以上の多環系からなる発色団が導入されている有機アンモニウム・無機層状ペロブスカイト化合物を製造することを特徴とする有機アンモニウム・無機層状ペロブスカイト化合物の薄膜の製造方法。An organic ammonium molecule and an alkyl ammonium molecule into which a chromophore composed of three or more polycyclic systems are introduced are mixed, and an inorganic halide is added to the mixed two types of organic ammonium molecules, and the mixture is dissolved in an organic solvent. By forming a film , an alkyl ammonium molecule creates a space where a bulky chromophore can be introduced, and a bulky chromophore is introduced into the organic layer ,
A is an organic ammonium molecule, M is a group IV element or transition metal, X is a halogen (Cl, Br, or I), and is represented by the general formula A 2 MX 4. The organic ammonium molecule A and the inorganic halide MX 4 are alternately laminated. Producing an organic ammonium / inorganic layered perovskite compound having a superlattice structure, wherein a chromophore composed of three or more polycyclic systems is introduced into the organic ammonium molecule A layer. A method for producing a thin film of an organic ammonium / inorganic layered perovskite compound.
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| US10069025B2 (en) | 2012-09-18 | 2018-09-04 | Oxford University Innovation Limited | Optoelectronic device |
| US10079320B2 (en) | 2012-05-18 | 2018-09-18 | Oxford University Innovation Limited | Optoelectronic device comprising perovskites |
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| JP3529733B2 (en) * | 2000-12-15 | 2004-05-24 | 独立行政法人 科学技術振興機構 | Organic-inorganic layered perovskite-type polymer compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10079320B2 (en) | 2012-05-18 | 2018-09-18 | Oxford University Innovation Limited | Optoelectronic device comprising perovskites |
| US10388897B2 (en) | 2012-05-18 | 2019-08-20 | Oxford University Innovation Limited | Optoelectronic device comprising porous scaffold material and perovskites |
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| US11258024B2 (en) | 2012-05-18 | 2022-02-22 | Oxford University Innovation Limited | Optoelectronic devices with organometal perovskites with mixed anions |
| US11276734B2 (en) | 2012-05-18 | 2022-03-15 | Oxford University Innovation Limited | Optoelectronic device comprising porous scaffold material and perovskites |
| US11302833B2 (en) | 2012-05-18 | 2022-04-12 | Oxford University Innovation Limited | Optoelectronic device comprising perovskites |
| US11908962B2 (en) | 2012-05-18 | 2024-02-20 | Oxford University Innovation Limited | Optoelectronic device comprising perovskites |
| US10069025B2 (en) | 2012-09-18 | 2018-09-04 | Oxford University Innovation Limited | Optoelectronic device |
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