Postfabrication surface treatment strategies have been instrumental to the stability and performance improvements of halide perovskite photovoltaics in recent years. However, a consensus understanding of the complex reconstruction processes occurring at the surface is still lacking. Here, we combined complementary surface-sensitive and depth-resolved techniques to investigate the mechanistic reconstruction of the perovskite surface at the microscale level. We observed a reconstruction toward a more PbI 2 -rich top surface induced by the commonly used solvent isopropyl alcohol (IPA). We discuss several implications of this reconstruction on the surface thermodynamics and energetics. Particularly, our observations suggest that IPA assists in the adsorption process of organic ammonium salts to the surface to enhance their defect passivation effects.

The quasi Fermi level splitting is measured for Cu(In,Ga)Se2 absorber layers with different copper to (indium + gallium) ratios and for different gallium contents in the range of 20%–40%. For absorbers with a [Cu]/[In + Ga] ratio below one, the measured quasi Fermi level splitting is 120 meV higher compared to absorbers grown under copper excess independent of the gallium content, contrary to the ternary CuInSe2 where the splitting is slightly higher for absorber layers grown under copper excess. Possible explanations are the gallium gradient determined by the secondary ion mass spectrometry measurement which is less pronounced towards the surface for stoichiometric absorber layers or a fundamentally different recombination mechanism in the presence of gallium. Comparing the quasi Fermi level splitting of an absorber to the open circuit voltage of the corresponding solar cell, the difference for copper poor cells is much lower (60 meV) than that for copper rich cells (140 meV). The higher loss in V OC in the case of the Cu-rich material is attributed to tunneling enhanced recombination due to higher band bending within the space charge region.

Complex phenomena are prevalent during the formation of materials, which affect their processing-structure-function relationships. Thin films of methylammonium lead iodide (CH3NH3PbI3, MAPI) are processed by spin coating, antisolvent drop, and annealing of colloidal precursors. The structure and properties of transient and stable phases formed during the process are reported, and the mechanistic insights of the underlying transitions are revealed by combining in situ data from grazing-incidence wide-angle X-ray scattering and photoluminescence spectroscopy. Here, we report the detailed insights on the embryonic stages of organic-inorganic perovskite formation. The physicochemical evolution during the conversion proceeds in four steps: i) An instant nucleation of polydisperse MAPI nanocrystals on antisolvent drop, ii) the instantaneous partial conversion of metastable nanocrystals into orthorhombic solvent-complex by cluster coalescence, iii) the thermal decomposition (dissolution) of the stable solvent-complex into plumboiodide fragments upon evaporation of solvent from the complex and iv) the formation (recrystallization) of cubic MAPI crystals in thin film.

Compared with their three-dimensional counterparts, low-dimensional metal halide perovskites with periodic inorganic/organic structures have shown promising stability and hysteresis-free electrical performance, which paves the way for next-generation optoelectronic devices. However, when integrated in devices, they have relatively limited efficiencies because devices usually require carrier transport through the film thickness direction. In conventionally grown single crystals, the carrier transport in the thickness direction is hindered by the insulating organic spacers. In addition, the strong quantum confinement from the organic spacers limits the generation and transport of free carriers. The carrier dynamics is further compromised by the presence of grain boundaries in polycrystals. Here, we report a low-dimensional metal halide perovskite superlattice with efficient carrier transport in three dimensions by epitaxial growth. Epitaxy on a slightly lattice-mismatched substrate compresses the organic spacers in the superlattice, which weakens the quantum confinement and further improves carrier dynamics. The performance of a low-dimensional perovskite superlattice solar cell has been certified under the quasi-steady state for the first time. Moreover, the device shows an unusually high open-circuit voltage, due to a unique intra-band exciton relaxation mechanism.

Bromide inclusion altered the formation dynamics and defect physics of wide-bandgap perovskite compositions.

The electronic defects in any semiconductor play a decisive role for the usability of this material in an optoelectronic device. Electronic defects determine the doping level as well as the recombination centers of a solar cell absorber. Cu(In, Ga)Se 2 is used in thin-film solar cells with high and stable efficiencies. The electronic defects in this class of materials have been studied experimentally by photoluminescence, admittance, and photocurrent spectroscopies for many decades now. The literature results are summarized and compared to new results by photoluminescence of deep defects. These observations are related to other experimental methods that investigate the physicochemical structure of defects. To finally assign the electronic defect signatures to actual physicochemical defects, a comparison with theoretical predictions is necessary. In recent years the accuracy of these calculations has greatly improved by the use of hybrid functionals. A comprehensive model of the electronic defects in Cu(In, Ga)Se 2 is proposed based on experiments and theory. The consequences for solar cell efficiency are discussed.

Halide perovskites have emerged as materials for high-performance optoelectronic devices. Often, progress made to date in terms of higher efficiency and stability is based on increasing material complexity that is, formation of multicomponent halide perovskites with multiple cations and anions. In this review article, the use of in situ optical methods, namely photoluminescence (PL) and UV-Vis, that provide access to the relevant time-and length-scales to ascertain chemistry-property relationships by monitoring evolving properties is discussed. Additionally, because halide perovskites are electron-ion conductors and prone to solid-state ion transport under various external stimuli application of these optical methods in the context of ionic movement, is described to reveal mechanistic insights. Finally, examples of using in situ PL and UV-Vis to study degradation and phase transitions are reviewed to demonstrate the wealth of information that can be obtained regarding many different aspects of ongoing research activities in the field of halide perovskites.

Thin-film solar cells consist of several layers. The interfaces between these layers can provide critical recombination paths and consequently play a vital role in the efficiency of the solar cell. One of the main challenges for polycrystalline semiconductor absorber materials is the absorber-buffer interface. The Cu(In, Ga)Se 2 system is particularly interesting in this context, since Cu-rich absorbers are dominated by recombination at the interface, while Cu-poor ones are not. This paper unveils the root cause of the challenge in the interface of Cu-rich solar cells in terms of a Se-related defect with an activation energy of 200 ± 20 meV. This defect causes interface recombination and is responsible for the deficiency of open-circuit voltage in Cu-rich cells. Moreover, this paper demonstrates that the origin of this defect is due to the etching step necessary to remove secondary phases. Postdeposition surface treatments or modified buffer layers are shown to passivate this defect, to reduce interface recombination, and to increase the efficiency.