Tailoring Interlayer Charge Transfer Dynamics in 2D Perovskites with Electroactive Spacer Molecules.
Tailoring Interlayer Charge Transfer Dynamics in 2D Perovskites with Electroactive Spacer Molecules.
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DOI：
10.1021/jacs.3c05974
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发表时间：
2023-10-04
影响因子：
15
通讯作者：
Stranks, Samuel D.
中科院分区：
文献类型：
--
作者：
Boeije, Yorrick;Van Gompel, Wouter T. M.;Zhang, Youcheng;Ghosh, Pratyush;Zelewski, Szymon J.;Maufort, Arthur;Roose, Bart;Ooi, Zher Ying;Chowdhury, Rituparno;Devroey, Ilan;Lenaers, Stijn;Tew, Alasdair;Dai, Linjie;Dey, Krishanu;Salway, Hayden;Friend, Richard H.;Sirringhaus, Henning;Lutsen, Laurence;Vanderzande, Dirk;Rao, Akshay;Stranks, Samuel D.
混合有机-无机铅卤化物钙钛矿家族是光电应用的强烈兴趣的主题，从发光二极管到光电子器件到X射线探测器。由于大多数有机分子的惰性性质，无机亚晶格通常主导钙钛矿的电子结构并因此主导其光电性质。在此，我们使用光学和电子活性的咔唑基Cz-Ci分子作为二维（2D）钙钛矿结构中的阳离子，其中Ci表示烷基铵链，i表示链中CH 2单元的数量，从3到5变化。通过研究（Cz-Ci）2 PbI 4的光物理和电荷传输特性，我们证明了无机卤化铅和有机层之间的可调电子耦合。最强的层间电子耦合被发现为（Cz-C3）2 PbI 4，光热偏转光谱结果显着揭示了有机-无机电荷转移状态。超快瞬态吸收光谱测量表明超快空穴从光激发的铅卤化物层的Cz-Ci分子，其效率增加，通过改变链长从i = 5到i = 3。电荷转移导致长寿命的载流子（10-100 ns）和淬灭的发射，与更常规的2D钙钛矿（PEA）2 PbI 4中的结合激子的快速（亚ns）和有效的辐射衰减形成鲜明对比，其中苯基乙基铵（PEA）充当惰性间隔物。电荷传输测量进一步支持增强的层间耦合，显示出从i = 5到i = 3的增加的面外载流子迁移率。这项研究为通过有机物世界中广泛的功能性合理设计具有无机-有机电子特性的2D钙钛矿铺平了道路。
The family of hybrid organic–inorganic lead-halide perovskites are the subject of intense interest for optoelectronic applications, from light-emitting diodes to photovoltaics to X-ray detectors. Due to the inert nature of most organic molecules, the inorganic sublattice generally dominates the electronic structure and therefore the optoelectronic properties of perovskites. Here, we use optically and electronically active carbazole-based Cz-Ci molecules, where Ci indicates an alkylammonium chain and i indicates the number of CH2 units in the chain, varying from 3 to 5, as cations in the two-dimensional (2D) perovskite structure. By investigating the photophysics and charge transport characteristics of (Cz-Ci)2PbI4, we demonstrate a tunable electronic coupling between the inorganic lead-halide and organic layers. The strongest interlayer electronic coupling was found for (Cz-C3)2PbI4, where photothermal deflection spectroscopy results remarkably reveal an organic–inorganic charge transfer state. Ultrafast transient absorption spectroscopy measurements demonstrate ultrafast hole transfer from the photoexcited lead-halide layer to the Cz-Ci molecules, the efficiency of which increases by varying the chain length from i = 5 to i = 3. The charge transfer results in long-lived carriers (10–100 ns) and quenched emission, in stark contrast to the fast (sub-ns) and efficient radiative decay of bound excitons in the more conventional 2D perovskite (PEA)2PbI4, in which phenylethylammonium (PEA) acts as an inert spacer. Electrical charge transport measurements further support enhanced interlayer coupling, showing increased out-of-plane carrier mobility from i = 5 to i = 3. This study paves the way for the rational design of 2D perovskites with combined inorganic–organic electronic properties through the wide range of functionalities available in the world of organics.
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影响因子：
5.7
作者：
Gelvez-Rueda, Maria C.;Van Gompel, Wouter T. M.;Grozema, Ferdinand C.
通讯作者：
Grozema, Ferdinand C.
影响因子：
19
作者：
Dai, Qingqing;Li, Hong;Bredas, Jean-Luc
通讯作者：
Bredas, Jean-Luc
影响因子：
16.6
作者：
Blancon JC;Stier AV;Tsai H;Nie W;Stoumpos CC;Traoré B;Pedesseau L;Kepenekian M;Katsutani F;Noe GT;Kono J;Tretiak S;Crooker SA;Katan C;Kanatzidis MG;Crochet JJ;Even J;Mohite AD
通讯作者：
Mohite AD
影响因子：
21.8
作者：
Gao, Yao;Shi, Enzheng;Dou, Letian
通讯作者：
Dou, Letian
影响因子：
4.6
作者：
Du, Ke-zhao;Tu, Qing;Mitzi, David B.
通讯作者：
Mitzi, David B.