Formamidinium Incorporates into Rb-based Non-Perovskite Phases in Solar Cell Formulations.

Organic-inorganic hybrid perovskite materials, such as formamidinium lead iodide (FAPbI), are among the most promising emerging photovoltaic materials. However, the spontaneous phase transition from the photoactive perovskite phase to an inactive non-perovskite phase complicates the application of FAPbI in solar cells. To remedy this, alkali metal cations, most often Cs, Rb or K, are included during perovskite synthesis to stabilize the photoactive phase.

Light-Induced Metallic and Paramagnetic Defects in Halide Perovskites from Magnetic Resonance.

Halide perovskites are promising next-generation solar cell materials, but their commercialization is hampered by their propensity to degrade under operating conditions, particularly under heat, humidity, and light. Identifying degradation products and linking them to the degradation mechanism at the atomic scale is necessary to design more stable perovskite materials. Here we use magnetic resonance methods to identify and characterize the formation of both metallic lead clusters and Pb defects upon light-induced degradation of methylammonium lead halide perovskite using nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) measurements.

Stabilization of highly efficient perovskite solar cells with a tailored supramolecular interface.

The presence of defects at the interface between the perovskite film and the carrier transport layer poses significant challenges to the performance and stability of perovskite solar cells (PSCs). Addressing this issue, we introduce a dual host-guest (DHG) complexation strategy to modulate both the bulk and interfacial properties of FAPbI-rich PSCs. Through NMR spectroscopy, a synergistic effect of the dual treatment is observed.

Hydrogen Diffusion in Hybrid Perovskites from Exchange NMR.

Ion migration is an important phenomenon affecting the performance of hybrid perovskite solar cells. It is particularly challenging, however, to disentangle the contribution of H diffusion from that of other ions, and the atomic-scale mechanism remains unclear. Here, we use H exchange NMR to prove that H ions exchange between MA cations on the time scale of seconds for both MAPbI and FAMAPbI perovskites.

Light-Induced H NMR Hyperpolarization in Solids at 9.4 and 21.1 T.

The inherently low sensitivity of nuclear magnetic resonance (NMR) spectroscopy is the major limiting factor for its application to elucidate structure and dynamics in solids. In the solid state, nuclear spin hyperpolarization methods based on microwave-induced dynamic nuclear polarization (DNP) provide a versatile platform to enhance the bulk NMR signal of many different sample formulations, leading to significant sensitivity improvements. Here we show that H NMR hyperpolarization can also be generated in solids at high magnetic fields by optical irradiation of the sample.

Magic Angle Spinning Solid-State C Photochemically Induced Dynamic Nuclear Polarization by a Synthetic Donor-Chromophore-Acceptor System at 9.4 T.

Solid-state photochemically induced dynamic nuclear polarization (photo-CIDNP) is a nuclear magnetic resonance spectroscopy technique in which nuclear spin hyperpolarization is generated upon optical irradiation of an appropriate donor-acceptor system. Until now, solid-state photo-CIDNP at high magnetic fields has been observed only in photosynthetic reaction centers and flavoproteins. In the present work, we show that the effect is not limited to such biomolecular samples, and solid-state C photo-CIDNP can be observed at 9.

Probing structural and dynamic properties of MAPbCl hybrid perovskite using Mn EPR.

Hybrid methylammonium (MA) lead halide perovskites have emerged as materials exhibiting excellent photovoltaic performance related to their rich structural and dynamic properties. Here, we use multifrequency (X-, Q-, and W-band) electron paramagnetic resonance (EPR) spectroscopy of Mn impurities in MAPbCl to probe the structural and dynamic properties of both the organic and inorganic sublattices of this compound. The temperature dependent continuous-wave (CW) EPR experiments reveal a sudden change of the Mn spin Hamiltonian parameters at the phase transition to the ordered orthorhombic phase indicating its first-order character and significant slowing down of the MA cation reorientation.

Axial-Equatorial Halide Ordering in Layered Hybrid Perovskites from Isotropic-Anisotropic Pb NMR.

Bandgap-tuneable mixed-halide 3D perovskites are of interest for multi-junction solar cells, but suffer from photoinduced spatial halide segregation. Mixed-halide 2D perovskites are more resistant to halide segregation and are promising coatings for 3D perovskite solar cells. The properties of mixed-halide compositions depend on the local halide distribution, which is challenging to study at the level of single octahedra.

Optically Enhanced Solid-State H NMR Spectroscopy.

Low sensitivity is the primary limitation to extending nuclear magnetic resonance (NMR) techniques to more advanced chemical and structural studies. Photochemically induced dynamic nuclear polarization (photo-CIDNP) is an NMR hyperpolarization technique where light is used to excite a suitable donor-acceptor system, creating a spin-correlated radical pair whose evolution drives nuclear hyperpolarization. Systems that exhibit photo-CIDNP in solids are not common, and this effect has, up to now, only been observed for C and N nuclei.

Dynamic Nuclear Polarization of Inorganic Halide Perovskites.

The intrinsic low sensitivity of nuclear magnetic resonance (NMR) experiments limits their utility for structure determination of materials. Dynamic nuclear polarization (DNP) under magic angle spinning (MAS) has shown tremendous potential to overcome this key limitation, enabling the acquisition of highly selective and sensitive NMR spectra. However, so far, DNP methods have not been explored in the context of inorganic lead halide perovskites, which are a leading class of semiconductor materials for optoelectronic applications.

Dynamic nuclear polarisation of H in Gd-doped In(OH).

Dynamic nuclear polarisation (DNP) of solids doped with high-spin metal ions, such as Gd, is a useful strategy to enhance the nuclear magnetic resonance (NMR) sensitivity for these samples. Spin diffusion can relay polarisation throughout a sample, which is most effective for dense H networks, while the efficiency of DNP using Gd depends on the symmetry of the metal site. Here, we investigate cubic In(OH) as a high-symmetry, proton-containing material for endogenous Gd DNP.

Light-Induced Halide Segregation in 2D and Quasi-2D Mixed-Halide Perovskites.

Photoinduced halide segregation hinders widespread application of three-dimensional (3D) mixed-halide perovskites. Much less is known about this phenomenon in lower-dimensional systems. Here, we study photoinduced halide segregation in lower-dimensional mixed iodide-bromide perovskites (PEAMA Pb (Br I ), with PEA: phenethylammonium and MA: methylammonium) through time-dependent photoluminescence (PL) spectroscopy.

A Complete Picture of Cation Dynamics in Hybrid Perovskite Materials from Solid-State NMR Spectroscopy.

The organic cations in hybrid organic-inorganic perovskites rotate rapidly inside the cuboctahedral cavities formed by the inorganic lattice, influencing optoelectronic properties. Here, we provide a complete quantitative picture of cation dynamics for formamidinium-based perovskites and mixed-cation compositions, which are the most widely used and promising absorber layers for perovskite solar cells today. We use H and N quadrupolar solid-state NMR relaxometry under magic-angle spinning to determine the activation energy () and correlation time (τ) at room temperature for rotation about each principal axis of a series of organic cations.

Surface differences of oxide nanocrystals determined by geometry and exogenously coordinated water molecules.

Determining the different surfaces of oxide nanocrystals is key in developing structure-property relations. In many cases, only surface geometry is considered while ignoring the influence of surroundings, such as ubiquitous water on the surface. Here we apply O solid-state NMR spectroscopy to explore the facet differences of morphology-controlled ceria nanocrystals considering both geometry and water adsorption.

Dynamic Nuclear Polarization Enables NMR of Surface Passivating Agents on Hybrid Perovskite Thin Films.

Surface and bulk molecular modulators are the key to improving the efficiency and stability of hybrid perovskite solar cells. However, due to their low concentration, heterogeneous environments, and low sample mass, it remains challenging to characterize their structure and dynamics at the atomic level, as required to establish structure-activity relationships. Nuclear magnetic resonance (NMR) spectroscopy has revealed a wealth of information on the atomic-level structure of hybrid perovskites, but the inherent insensitivity of NMR severely limits its utility to characterize thin-film samples.

Colloidal-ALD-Grown Hybrid Shells Nucleate via a Ligand-Precursor Complex.

Colloidal atomic layer deposition (c-ALD) enables the growth of hybrid organic-inorganic oxide shells with tunable thickness at the nanometer scale around ligand-functionalized inorganic nanoparticles (NPs). This recently developed method has demonstrated improved stability of NPs and of their dispersions, a key requirement for their application. Nevertheless, the mechanism by which the inorganic shells form is still unknown, as is the nature of multiple complex interfaces between the NPs, the organic ligands functionalizing the surface, and the shell.

The Role of Alkyl Chain Length and Halide Counter Ion in Layered Dion-Jacobson Perovskites with Aromatic Spacers.

Layered hybrid perovskites based on Dion-Jacobson phases are of interest to various optoelectronic applications. However, the understanding of their structure-property relationships remains limited. Here, we present a systematic study of Dion-Jacobson perovskites based on (S)PbX ( = 1) compositions incorporating phenylene-derived aromatic spacers (S) with different anchoring alkylammonium groups and halides (X = I, Br).

Tetrafluoroborate-Induced Reduction in Defect Density in Hybrid Perovskites through Halide Management.

Hybrid-perovskite-based optoelectronic devices are demonstrating unprecedented growth in performance, and defect passivation approaches are highly promising routes to further improve properties. Here, the effect of the molecular ion BF , introduced via methylammonium tetrafluoroborate (MABF ) in a surface treatment for MAPbI perovskite, is reported. Optical spectroscopy characterization shows that the introduction of tetrafluoroborate leads to reduced non-radiative charge-carrier recombination with a reduction in first-order recombination rate from 6.

Multimodal host-guest complexation for efficient and stable perovskite photovoltaics.

Formamidinium lead iodide perovskites are promising light-harvesting materials, yet stabilizing them under operating conditions without compromising optimal optoelectronic properties remains challenging. We report a multimodal host-guest complexation strategy to overcome this challenge using a crown ether, dibenzo-21-crown-7, which acts as a vehicle that assembles at the interface and delivers Cs ions into the interior while modulating the material. This provides a local gradient of doping at the nanoscale that assists in photoinduced charge separation while passivating surface and bulk defects, stabilizing the perovskite phase through a synergistic effect of the host, guest, and host-guest complex.

Pseudo-halide anion engineering for α-FAPbI perovskite solar cells.

Metal halide perovskites of the general formula ABX-where A is a monovalent cation such as caesium, methylammonium or formamidinium; B is divalent lead, tin or germanium; and X is a halide anion-have shown great potential as light harvesters for thin-film photovoltaics. Among a large number of compositions investigated, the cubic α-phase of formamidinium lead triiodide (FAPbI) has emerged as the most promising semiconductor for highly efficient and stable perovskite solar cells, and maximizing the performance of this material in such devices is of vital importance for the perovskite research community. Here we introduce an anion engineering concept that uses the pseudo-halide anion formate (HCOO) to suppress anion-vacancy defects that are present at grain boundaries and at the surface of the perovskite films and to augment the crystallinity of the films.

Nanoscale Phase Segregation in Supramolecular π-Templating for Hybrid Perovskite Photovoltaics from NMR Crystallography.

The use of layered perovskites is an important strategy to improve the stability of hybrid perovskite materials and their optoelectronic devices. However, tailoring their properties requires accurate structure determination at the atomic scale, which is a challenge for conventional diffraction-based techniques. We demonstrate the use of nuclear magnetic resonance (NMR) crystallography in determining the structure of layered hybrid perovskites for a mixed-spacer model composed of 2-phenylethylammonium (PEA) and 2-(perfluorophenyl)ethylammonium (FEA) moieties, revealing nanoscale phase segregation.