 Addition of large organic molecules to halide perovskites => dimensionality reduction and

formation of 2D phases
 Hybrid Organic-Inorganic Halide Perovskites (HOIHP)
 2DHP = 2D layered hybrid perovskites
 2 most commonly formed 2D phases: Ruddlesden–Popper (RP) (Y)2(A)n-1(B)n(X)3n + 1 (double
layers of organic syst. that anchor to and impose a relative offset of adjacent inorganic slabs
consisting of n layers of Pb-I octahedra), or the Dion–Jacobson (DJ) Y(A)n-1(B)n(X)3n + 1 type
(single layer of bifunctional ligands – Y – separates 2 consecutive inorganic frameworks; thinner
organic layer => better orbital overlap => improved transport properties).
 2D materials: longer carrier lifetimes
 Mixed 2D/3D phases formed for higher n
 Increase n => charge mobility increase
 Organic spacer layer: mostly insulating => charge transport in perpendicular to the inorganic
layers through the organic layers - an order of magnitude slower than within the inorganic
sheets
 Efficiencies of 2D systems much lower compared to 3D perovskites, due to shorter diffusion
lengths orthogonal to the inorganic plane and consequently, large band gaps
 But: stability improvements for 2D
 Organic ligands: anchor perovskite material to ETL = electron-transporting layer
 Tunable degree of hydrophobicity (selection of size and type of organic ligands)
 Classical MD simulations: Generalized Amber Force Field (GAFF); LAMMPS suite of codes
 Trial structures optimized: CG (Conjugate Gradient) algorithm
 NPT (isothermal-isobaric ensemble equilibration)
 Electronic properties: GGA (Generalized Gradient Approximation) DFT (PBEsol functional): find
lowest E config of structure obtained from classical MD
 Dispersions corrections: empirical D3 (important for syst w large organic molecules)
 Electronic band gaps: hybrid PBE0 functional with explicit incorporation of spin-orbit coupling
(SOC)
 Lennard Jones potential: model for spherical particle w charge +1 (cation A) (σ: size of particle =
distance where potential is 0; ε: potential energy well depth for vdW dispersion interactions)
 Can use this isotropic model bc at room temp, the anisotropic nature of cations is averaged out
due to free rotation)
 Construct structural map in σ- ε space (different phases stable in different regions)
 Lorentz Berthelot mixing rules: provide the interaction energy between two dissimilar non-
bonded atoms, usually for the part of the potential representing the van der Waals interaction.
 More cubic struct of inorganic layer (octahedral tilting angles approaching 90) => deeper organic
spacer is penetrating perovskite layer (interoctahedral space largest for cubic => allows deeper
penetration)
 More cubic => lower band gap (better orbital overlap of antibonding p on I and s on Pb that form
TVB = top of valence band => destabilization)
 d1 space between 2 perovskite layers (thickness of organic layer): varies linearly with geometric
length of spacer (fully extended)
 Increase thickness inorganic layer => decrease band gap, converging towards band gaps of 3D
 Band gap depends more on n (how thick), not electronic properties of spacers (electronic
properties controlled by inorganic layers)
 Exciton = bound state of electron and hole which are attracted to each other
 Hindered transport through spacer layer: demonstrated by higher hole & electron effective
masses in the out-of-plane direction than in-plane
 Charge carrier tunnelling probabilities through spacer layer: small

1. Thickness of organic layer ~ geometric length of spacer

2. Penetration depth spacer into inorganic layer => octahedral tilting =>
phase & band gap
3. Band gap is fct of n (mainly)
4. Transport properties depend on thickness of inorganic layer mainly