Hydrogen Bonding and Stability of Hybrid Organic–Inorganic Perovskites

Abstract

In the past few years, the efficiency of solar cells based on hybrid organic-inorganic perovskites has exceeded the level needed for commercialization. However, existing perovskites solar cells (PSCs) suffer from several intrinsic instabilities, which prevent them from reaching industrial maturity, and stabilizing PSCs has become a critically important problem. Here we propose to stabilize PSCs chemically by strengthening the interactions between the organic cation and inorganic anion of the perovskite framework. In particular, we show that replacing the methylammonium cation with alternative protonated cations allows an increase in the stability of the perovskite by forming strong hydrogen bonds with the halide anions. This interaction also provides opportunities for tuning the electronic states near the bandgap. These mechanisms should have a universal character in different hybrid organic-inorganic framework materials that are widely used.

A hybrid organic-inorganic perovskite dataset

“…In these panels, the lowest-energy structure of each HOIP is indicated by a colored symbol while data from the energetically competing structures are shown in gray ( a ) or given within an error bar ( b ). Experimental data of bandgap and dielectric constants of these HOIPs is obtained from refs 8,64,65,66,67 68,69 70,71 72,73 74,75 76,77 78,79 and refs 74–83, respectively. In ( c – f ), the simulated and measured XRD spectra for MAPbBr 3 65 , MAPbI 3 84 , IPAGeI 3 73 , and MASnI 3 5,85 , are shown.…”

Application of Perovskite‐Structured Materials in Field‐Effect Transistors

“…[128,[148][149][150] Furthermore, large organic cations are less mobile in the lattice, leading to more stable crystal structure. [153] Additionally, CH 3 NH 3 PbBr 3 -based FETs exhibited better stability compared to CH 3 NH 3 PbI 3 , [114] which shows a weak hysteresis with hole and electron mobilities of ≈5 and ≈3 cm 2 V −1 s −1 , respectively. The aromatic ammonium (PEA) has a larger molecule size, therefore is less mobile than MA.…”

Solar Cell Materials by Design: Hybrid Pyroxene Corner‐Sharing VO4 Tetrahedral Chains

“…Recently,o ur group hass hown . [40][41][42] In the next section, we will follow this strategy and focus our screening effort on:i )reducing the band gap in this class of materials, ii)allowing ab etter absorption in the visible range,i ii) keeping the 1D VO 4 chain structure, and iv) distorting the tetrahedra. The black,r ed, and blue linesrepresent the conductivity tensors s xx , s yy ,a nd s zz ,respectively.…”

“…In the case of H 3 SVO 3 ,t he stability enhancement is attributed to the hydrogen-bonding effect ( Figures S4-S6). [40][41][42] Finally,t he associated absorption spectra for the screened materials are calculated in the independent particlea pproximation and plotted in Figure 9. [40][41][42] Finally,t he associated absorption spectra for the screened materials are calculated in the independent particlea pproximation and plotted in Figure 9.…”

“…We will use computational design to identify materials with ab and gap that is optimal for photovoltaic applications( 1.0-1.7 eV) [10,11,39] by replacing Cs with ar ange of molecular cations. Certainly,t he incorporation of molecules will generate additional stability [40][41][42] issues that will also be addressed. Adetailed analysis can be found in the Supporting Information.…”