Banerjee Hrishit, Nazeeruddin Mohammad Khaja, Chakraborty Sudip
School of Science and Engineering, University of Dundee, Nethergate, Dundee, Angus DD1 4HN, UK.
Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, Cambridgeshire CB2 1EW, U.K.
ACS Appl Mater Interfaces. 2025 Apr 2;17(13):19701-19711. doi: 10.1021/acsami.5c00201. Epub 2025 Mar 24.
The 2D/3D or 2D/quasi-2D composite mixed-dimensional construction of hybrid perovskite interfaces is gaining increasing attention due to their enhanced stability toward degradation without compromising the corresponding solar cell efficiency. Much of this is due to the interfacial charge transfer and its consequences on the electronic and optical response of the composite system, which are instrumental in the context of stability and efficiency. In this work, we have considered a case study of an experimentally motivated 2D/quasi-2D interface constructed based on Ruddlesden-Popper phases of (A43)PbI (2D phase) and (A43)MAPbI (quasi-2D phase) hybrid perovskites to envisage the unique tuning of electronic and optical properties through the associated charge transfer using density functional theory calculations based on both generalized gradient approximation as well as hybrid functionals, including corrections for nonlocal exchange obtained from Hartree-Fock. The corresponding tuning of the band gap is observed to be related to a unique charge transfer process between the 2D and quasi-2D counterparts of the interface mediated from the valence to conduction band edges of the composite. We have found that the optical absorption spectra can also be tuned by the construction of such a heterointerface and the emergence of a unique two-peak feature on the absorption edge, which is not present in either the 2D or quasi-2D hybrid perovskites. This feature is observed to be enhanced in the case of hybrid functionals, showing the importance of nonlocal exchange in optical spectra. We also compared the quasi-2D structure with the prototypical 3D structure MAPbI to show the progression of properties with dimensionality. The formation of the composite interface is found to increase the spectroscopic limited maximum efficiency for the use of these materials as solar cells from ≈24% for individual components to ≈32% for the composite heterostructure.
二维/三维或二维/准二维混合钙钛矿界面的复合混合维结构因其在不影响相应太阳能电池效率的情况下对降解具有增强的稳定性而受到越来越多的关注。这在很大程度上归因于界面电荷转移及其对复合系统电子和光学响应的影响，这在稳定性和效率方面起着重要作用。在这项工作中，我们考虑了一个基于（A43）PbI（二维相）和（A43）MAPbI（准二维相）混合钙钛矿的Ruddlesden-Popper相构建的实验驱动的二维/准二维界面的案例研究，以通过基于广义梯度近似以及混合泛函（包括从Hartree-Fock获得的非局部交换校正）的密度泛函理论计算，设想通过相关电荷转移对电子和光学性质进行独特调节。观察到带隙的相应调节与界面二维和准二维对应物之间从复合价带到导带边缘介导的独特电荷转移过程有关。我们发现，这种异质界面的构建以及吸收边缘上独特的双峰特征的出现也可以调节光吸收光谱，这在二维或准二维混合钙钛矿中都不存在。在混合泛函的情况下，观察到这一特征得到增强，表明非局部交换在光谱中的重要性。我们还将准二维结构与典型的三维结构MAPbI进行了比较，以展示性质随维度的变化。发现复合界面的形成将这些材料用作太阳能电池的光谱限制最大效率从单个组件的约24%提高到复合异质结构的约32%。
