TY - JOUR
T1 - On the Mechanism of Solvents Catalyzed Structural Transformation in Metal Halide Perovskites
AU - Xi, Jun
AU - Jiang, Junke
AU - Duim, Herman
AU - Chen, Lijun
AU - You, Jiaxue
AU - Portale, Giuseppe
AU - Liu, Shengzhong
AU - Tao, Shuxia
AU - Loi, Maria Antonietta
N1 - Funding Information:
J.X. and J.J. contributed equally to this work. The authors appreciate the technical support from Arjen Kamp and Teo Zaharia. J.X. and M.A.L. acknowledge the Materials for Sustainability (Mat4Sus) program (739.017.005) of the Netherlands Organization for Scientific Research (NWO). This work is part of the program of the NWO‐focus Group “Next Generation Organic Photovoltaics”, participating in the Dutch Institute for Fundamental Energy Research (DIFFER). M.A.L. and L.C. would like to acknowledge the financial support of the CogniGron research center of the University of Groningen. S.T. and J.J. acknowledge funding by the Computational Sciences for Energy Research (CSER) tenure track program of Shell and NWO (Project number15CST04‐2) and NWO START‐UP, the Netherlands.
Funding Information:
J.X. and J.J. contributed equally to this work. The authors appreciate the technical support from Arjen Kamp and Teo Zaharia. J.X. and M.A.L. acknowledge the Materials for Sustainability (Mat4Sus) program (739.017.005) of the Netherlands Organization for Scientific Research (NWO). This work is part of the program of the NWO-focus Group “Next Generation Organic Photovoltaics”, participating in the Dutch Institute for Fundamental Energy Research (DIFFER). M.A.L. and L.C. would like to acknowledge the financial support of the CogniGron research center of the University of Groningen. S.T. and J.J. acknowledge funding by the Computational Sciences for Energy Research (CSER) tenure track program of Shell and NWO (Project number15CST04-2) and NWO START-UP, the Netherlands.
Publisher Copyright:
© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.
PY - 2023/8/17
Y1 - 2023/8/17
N2 - Metal halide perovskites show the capability of performing structural transformation, allowing the formation of functional heterostructures. Unfortunately, the elusive mechanism governing these transformations limits their technological application. Herein, the mechanism of 2D–3D structural transformation is unraveled as catalyzed by solvents. By combining a spatial-temporal cation interdiffusivity simulation with experimental findings, it is validated that, protic solvents foster the dissociation degree of formadinium iodide (FAI) via dynamic hydrogen bond, then the stronger hydrogen bond of phenylethylamine (PEA) cation with selected solvents compared to dissociated FA cation facilitates 2D–3D transformation from (PEA)2PbI4 to FAPbI3. It is discovered that, the energy barrier of PEA out-diffusion and the lateral transition barrier of inorganic slab are diminished. For 2D films the protic solvents catalyze grain centers (GCs) and grain boundaries (GBs) transforme into 3D phases and quasi-2D phases, respectively. While in the solvent-free case, GCs transform into 3D–2D heterostructures along the direction perpendicular to the substrate, and most GBs evolve into 3D phases. Finally, memristor devices fabricated using the transformed films uncover that, GBs composed of 3D phases are more prone to ion migration. This work elucidates the fundamental mechanism of structural transformation in metal halide perovskites, allowing their use to fabricate complex heterostructures.
AB - Metal halide perovskites show the capability of performing structural transformation, allowing the formation of functional heterostructures. Unfortunately, the elusive mechanism governing these transformations limits their technological application. Herein, the mechanism of 2D–3D structural transformation is unraveled as catalyzed by solvents. By combining a spatial-temporal cation interdiffusivity simulation with experimental findings, it is validated that, protic solvents foster the dissociation degree of formadinium iodide (FAI) via dynamic hydrogen bond, then the stronger hydrogen bond of phenylethylamine (PEA) cation with selected solvents compared to dissociated FA cation facilitates 2D–3D transformation from (PEA)2PbI4 to FAPbI3. It is discovered that, the energy barrier of PEA out-diffusion and the lateral transition barrier of inorganic slab are diminished. For 2D films the protic solvents catalyze grain centers (GCs) and grain boundaries (GBs) transforme into 3D phases and quasi-2D phases, respectively. While in the solvent-free case, GCs transform into 3D–2D heterostructures along the direction perpendicular to the substrate, and most GBs evolve into 3D phases. Finally, memristor devices fabricated using the transformed films uncover that, GBs composed of 3D phases are more prone to ion migration. This work elucidates the fundamental mechanism of structural transformation in metal halide perovskites, allowing their use to fabricate complex heterostructures.
KW - cation interdiffusivity
KW - heterostructures
KW - metal halide perovskites
KW - solvent catalysis
KW - structural transformation
UR - http://www.scopus.com/inward/record.url?scp=85163713338&partnerID=8YFLogxK
U2 - 10.1002/adma.202302896
DO - 10.1002/adma.202302896
M3 - Article
AN - SCOPUS:85163713338
SN - 0935-9648
VL - 35
JO - Advanced materials
JF - Advanced materials
IS - 33
M1 - 2302896
ER -