Dion-Jacobson phase

Dion-Jacobson (DJ) phases are a type of perovskite structure represented by the general formula MIA(n-1)B(n)X(3n+1). The structure of a DJ phase consists of two-dimensional ABX3 perovskite-like layers, where A and B are cations, M is a monovalent cation, X is an anion (typically oxygen or a halide) and n represents the number of octahedral BX6 layers stacked in between the M cations. [1]

The first recognized Dion-Jacobson phases were reported by M. Dion in September 1981, in which Dion prepared and characterized a series of n = 3 MICa2Nb3O10 (MI = Li, Na, K, Rb, Cs, NH4, Tl) compounds.[2]

Crystal structure

The general formula for the Dion-Jacobson phase can be written as MIA(n-1)B(n)X(3n+1), where A and B are cations, M is a monovalent cation, and X is an anion. The structure consists of perovskite-like two-dimensional layers, constructed by stacking n corner-shared BX6 octahedra with the A cation in 12-fold cuboctahedral coordination with the anions. The perovskite-like layers are separated by the M cation, which is typically 8-coordinate. Depending on the identity of the monovalent cation, the perovskite-like layers can be displaced by 1/2 of the unit cell parameter, which changes the coordination environment of the M cation to 4-coordinate.[1]

The M and A cations can also be organic cations, such as methylammonium and ethylenediamine.[3] This produces a hybrid organic-inorganic structure that can increase stability through interactions between two organic ligands.[4]

Synthesis

Inorganic Dion-Jacobson perovskites, such as KLaNb2O7, have been synthesized via high temperature solid state reactions between the respective carbonate and oxide precursors.[5] Two-dimensional Dion-Jacobson halide perovskites, such as (3AMPY)(MA)Pb2I7 (3AMPY = 3-(aminomethyl)pyridinium and MA= methylammonium) have been synthesized via precipitation reactions as well.[6]

Applications

Dion-Jacobson oxides have applications as ferroelectrics, piezoelectrics, and photocatalysts. The layering between differently-charged M cations reduces the symmetry of the BO6 octahedra, which breaks inversion symmetry and allows for or enhances these properties. Both n = 2 and n = 3 Dion-Jacobson phases can be used for these applications.[7] Hybrid organic-inorganic Dion-Jacobson phases have additional uses as photovoltaics and photodetectors, having better stability than three-dimensional hybrid perovskites.[8][9]

The stability of hybrid organic-inorganic Dion-Jacobson phases with photovoltaic properties facilitates their use in perovskite solar cells. Hybrid organic-inorganic Dion-Jacobson phases have a divalent organic cation which can bridge adjacent ABX3 layers, eliminating the van der Waals gap with a stable structure formed by hydrogen bonding. The improved structure allows for more efficient interlayer charge transport and environmental stability.[9] Dion-Jacobson phases can be used as the absorbing layer in two-dimensional solar cells or as a layer for passivation on top of 3D perovskites to improve stability and power conversion efficiency. For example, an efficiency of 24.9% was achieved with a two-dimensional Dion-Jacobson solar cell, which retained 97% of its initial power conversion efficiency after 1000 hours in ambient air.[10] When used as a top layer in a three-dimensional solar cell, a power conversion efficiency of 19.5% was achieved with 83% of the original efficiency retained after 1260 hours under continuous illumination.[9]

Through additive manufacturing, the performance of Dion-Jacobson phases can be improved even further. Incorporating chloride salts or thiocyanate salts into the precursor solution can coordinate ions from those compounds with undercoordinated ions often used in perovskite photovoltaics, such as Pb2+ and Sn2+, to reduce trap states and improve the power conversion efficiency of Dion-Jacobson solar cells. Other additives, such as dimethyl sulfoxide, can slow down crystallization to create larger grains and improve the structural properties of Dion-Jacobson phases.[11]

See also

  • Aurivillius phase
  • Ruddlesden-Popper phase

References

  1. ^ a b Cava, Robert. "Perovskite Structure and Derivatives". Cava Lab Solid State Chemistry Research Group. Retrieved 25 April 2025.
  2. ^ Dion, M. (1981). "Nouvelles Familles de Phases MIM2IINb3O10 a Feuillets "Perovskites."". Mater. Res. Bull. 16 (11): 1429–1435. doi:10.1016/0025-5408(81)90063-5.
  3. ^ Zhang, Yuling; Wang, Ruyue; Tan, Zhan'ao (2023). "Crystal growth of two-dimensional organic–inorganic hybrid perovskites and their application in photovoltaics". Journal of Materials Chemistry A. 11 (22): 11607–11636. doi:10.1039/d3ta01496g.
  4. ^ Azmi, Randi; Utomo, Drajad Satrio; Liu, Yanping; Zhumagali, Shynggys; De Wolf, Stefaan (27 October 2025). "Dimensionality engineering of perovskites for stable heterojunction-based photovoltaics". Nature Reviews Materials. doi:10.1038/s41578-025-00847-6.
  5. ^ Sato, M.; Abo, J.; Jin, T.; Ohta, M. (1993). "Structure and Ionic Conductivity of MLaNb2O7 (M = K, Na, Li, H)". J. Alloys Compd. 192 (1–2): 81–83. doi:10.1016/0925-8388(93)90192-p.
  6. ^ Li, X.; Ke, W.; Traoré, B.; Guo, P.; Hadar, I. (2019). "Two-Dimensional Dion–Jacobson Hybrid Lead Iodide Perovskites with Aromatic Diammonium Cations" (PDF). Journal of the American Chemical Society. 141 (32): 12880–12890. Bibcode:2019JAChS.14112880L. doi:10.1021/jacs.9b06398. PMID 31313919.
  7. ^ Evans, Hayden A.; Mao, Lingling; Seshadri, Ram; Cheetham, Anthony K. (26 July 2021). "Layered Double Perovskites". Annual Review of Materials Research. 51 (1): 351–380. doi:10.1146/annurev-matsci-092320-102133.
  8. ^ Yadav, Abhishek; Ahmad, Shahab (21 August 2024). "Single Crystal Ruddlesden–Popper and Dion–Jacobson Metal Halide Perovskites for Visible Light Photodetectors: Present Status and Future Perspectives". ACS Applied Materials & Interfaces. 16 (33): 43134–43155. doi:10.1021/acsami.4c07170.
  9. ^ a b c Wu, Luyan (8 July 2023). "Stabilization of Inorganic Perovskite Solar Cells with a 2D Dion-Jacobson Passivating Layer". Advanced Materials. 35 (42): 2. doi:10.1002/adma.202304150. hdl:11584/371143. Retrieved 18 November 2025.
  10. ^ Yang, Tinghuan (20 March 2019). "Amidino-based Dion-Jacobson 2D perovskite for efficient and stable 2D/3D heterostructure perovskite solar cells". Joule. 7 (3): 1. doi:10.1016/j.joule.2023.02.003. Retrieved 18 November 2025.
  11. ^ Liu, Min; Pauporte, Thierry (24 May 2023). "Additive Engineering for Stable and Efficient Dion–Jacobson Phase Perovskite Solar Cells". Springer Nature. 15: 2–23. doi:10.1007/s40820-023-01110-9. Retrieved 18 November 2025.
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