キネティック・イソトープ・エフェクトは,メチラモニウム・リード・トリオイド・ペロフスキットにおけるプロトン・トンネリングの実験的証拠を提供する
Yan-Fang Chen1,2, Yu-Tang Tsai1,2, Lionel Hirsch1,2
1Université Bordeaux, CNRS, UMR 5218, IMS , F-33400 Talence, France.
Journal of the American Chemical Society
|October 26, 2017
まとめ
ハイブリッドペロブスキットのプロトントンネリングは,同位体ラベリングを使用して確認されました. これらの材料の陽子移動メカニズムと エネルギーバリアの洞察を明らかにしました
科学分野:
- 材料科学
- 固体物理学
- 化学物理学
背景:
- MAPbI3のような有機と無機の混合ペロブスキットは,様々な電子アプリケーションのための有望な材料です.
- イオン移動メカニズムを理解することは,デバイスの安定性と性能にとって極めて重要です.
- メチラモニウム (MA) の成分における陽子の移動は,材料の性質に影響を与える.
研究 の 目的:
- MAPbI3ペロブスキートにおけるプロトントンネリングの発生とメカニズムを調査する.
- 陽子移動のダイナミクスにおける同位体置換の役割を解明する.
- 異なるペロブスキート相における陽子移動に関連した活性化エネルギーを決定する.
主な方法:
- メチラモニウム (MA) コンポーネントのデュテリウムによる同位体ラベル付け
- 介電性反応の測定
- 主要および次要の運動同位体効果の分析.
- アクティベーションエネルギーとプレエクスポネンショナル因子の計算
主要な成果:
- アムニウム群のデュテレーションにより,陽子の移動が加速した (逆原発同位体効果).
- メチル群のデュテレーションは正常な二次同位体効果を示した.
- 陽子移動の活性化エネルギーは50 meV (四角形) と27 meV (オルソロンビック) であり,アンモニアのデュテレーションにより減少した.
- 低活性化バリアとA_H/A_D比 (0.3-0.4) は陽子トンネリングを示しています.
結論:
- 陽子トンネリングは,MAPbI3ペロブスキートにおける陽子移動の重要なメカニズムである.
- アイソトープの標識は,トンネルを他の移動メカニズムから区別するための強力なツールを提供します.
- PEDOT:PSS層からの外部イオン移動は,観察されたペロブスキットの行動に影響を与える可能性があります.
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