The research and development of novel photovoltaic technologies is going through a golden era, thanks to the demonstration of remarkable efficiencies across a broad range of semiconductor classes and device architectures. In parallel with these developments, the opportunities for characterizing the structure of a semiconductor film in situ of a processing step have also increased, to the extent that in situ and in operando experiments are becoming readily accessible to researchers. These combined advances represent the subject matter of this article, wherein studies that improve our understanding of structure formation and evolution in perovskite and organic semiconductor films for innovative solar cells are reviewed. Although focus is placed on the dynamics of semiconductor film formation, the review also highlights recent research on environmental testing, a key component in the development of materials with high intrinsic stability.

In situ and operando measurement techniques combined with nanoscale resolution have proven invaluable in multiple fields of study. We argue that evaluating device performance as well as material behavior by correlative X-ray microscopy with <100 nm resolution can radically change the approach for optimizing absorbers, interfaces and full devices in solar cell research. In this article, we thoroughly discuss the measurement technique of X-ray beam induced current and point out fundamental differences between measurements of wafer-based silicon and thin-film solar cells. Based on reports of the last years, we showcase the potential that X-ray microscopy measurements have in combination with in situ and operando approaches throughout the solar cell lifecycle: from the growth of individual layers to the performance under operating conditions and degradation mechanisms. Enabled by new developments in synchrotron beamlines, the combination of high spatial resolution with high brilliance and a safe working distance allows for the insertion of measurement equipment that can pave the way for a new class of experiments. Applied to photovoltaics research, we highlight today’s opportunities and challenges in the field of nanoscale X-ray microscopy, and give an outlook on future developments.

Recently, in situ characterization methods have attracted increasing attention, especially in organic photovoltaics (OPV) field, since they provide greater insight into the mechanism of film formation, thus help to identify optimized processing conditions used to process the most efficient organic bulk-heterojunction thin films. In combination with various powerful X-ray-based characterization methods, several studies observed the morphological changes under the influence of different processing conditions. In this review, we summarize the fundamentals and implementation of X-ray-based and optical characterization methods, utilized in in situ mode and introduce the reader a better overview of the information acquired from a given technique in terms of microstructure formation in OPV. While we give a chronological development of in situ characterization methods in the field of OPV, we discuss the interplay between thermodynamics of solutions and drying kinetics of different types of organic blends.

Bragg coherent X-ray diffraction imaging has been used to determine the structure of the initial clusters of α-Fe nano crystals which form upon annealing of an iron-based amorphous alloy or metallic glass. The method is able to identify the shapes and strain of these crystallites without any need for cutting the sample, so can visualize them in three dimensions in their intact state. In this way, the delicate dendritic structures on the exterior of the crystallites can be seen and its density versus radius relationship identifies a fractal dimension of the porous region that is consistent with diffusion-limited aggregation models. The crystal sizes were found to be around 60 nm after annealing at 700 °C growing to about 330 nm after annealing at 750 °C. This article introduces the BCDI method and describes its application to characterize previously recrystallized samples of iron-based amorphous alloys. It paves the way for a possible future in situ nucleation/growth investigation of the relationship between kinetics and nanostructure of metallic glass.

Photovoltaics made from organic–inorganic hybrid perovskite semiconductors are attracting significant interest due to their ability to harvest sunlight with remarkable efficiency. The presence of lead in the best performing devices raises concerns regarding their toxicity, a problem that may create barriers to commercialization. Hybrid perovskites with reduced lead content are being investigated to overcome this issue and here we evaluate bismuth as a possible lead substitute. For a series of hybrid perovskite films with the general composition CH3NH3(Pb y Bi1−y )I3−x Cl x , we characterize their optical and structural properties using UV–Vis spectroscopy, scanning electron microscopy and grazing incidence wide angle X-ray scattering. We show that they form crystalline structures with an optical band gap, around 2 eV for CH3NH3BiI3. However, preliminary solar cell tests show low power conversion efficiencies (<0.01%) due to both incomplete precursor conversion and material de-wetting from the substrate. The overall outcome is severely limited photocurrent. With current processing methods the general applicability of hybrid bismuth perovskites in photovoltaics may be limited.

The successful and widely used two-step process of producing the hybrid organic-inorganic perovskite CH3NH3PbI3, consists of converting a solution deposited PbI2 film by reacting it with CH3NH3I. Here, we investigate the solidification of PbI2 films from a DMF solution by performing in situ grazing incidence wide angle X-ray scattering (GIWAXS) measurements. The measurements reveal an elaborate sol–gel process involving three PbI2⋅DMF solvate complexes—including disordered and ordered ones—prior to PbI2 formation. The ordered solvates appear to be metastable as they transform into the PbI2 phase in air within minutes without annealing. Morphological analysis of air-dried and annealed films reveals that the air-dried PbI2 is substantially more porous when the coating process produces one of the intermediate solvates, making this more suitable for subsequent conversion into the perovskite phase. The observation of metastable solvates on the pathway to PbI2 formation open up new opportunities for influencing the two-step conversion of metal halides into efficient light harvesting or emitting perovskite semiconductors.

We report on the growth and characterization of molecular mixed thin films of α-sexithiophene (6T), a well-known organic p-type semiconductor with high hole mobility, together with its perfluorinated counterpart, the so far rarely studied tetradecafluoro-α-sexithiophene (PF6T). Pure and blended thin films of these two molecules with different mixing ratios were grown on silicon oxide in ultrahigh vacuum by coevaporation. The effect of perfluorination and mixing on crystal structure, morphology, electronic, and optical properties was examined. The evolution of the PF6T crystal structure was followed in situ in real time by X-ray scattering. We found a new thin film structure different from the reported bulk phase with molecules either standing-up or lying-down depending on the growth temperature. The different morphologies of pure films and blends were investigated with atomic force microscopy. The impact of mixing on the core-levels and on the highest occupied molecular orbitals of 6T and PF6T is discussed.

Morphology can play a critical role in determining function in organic photovoltaic (OPV) systems. Recently molecular acceptors have showed promise to replace fullerene derivatives as acceptor materials in bulk heterojunction solar cells and have achieved >10% efficiencies in single junction devices. The nearly identical mass/electron densities between the donor (polymer) and acceptor (molecule) materials results in poor material contrast compared to fullerene-based OPVs and therefore morphology characterization using techniques that rely on mass/electron density variations poses a challenge. This inhibits a fundamental understanding of the structure–property relationships for non-fullerene acceptor materials. We demonstrate that low angle annular dark field scanning transmission electron microscopy and resonant soft X-ray scattering form a set of complementary tools that can provide quantitative characterization of fullerene as well as non-fullerene based organic photovoltaic systems.

A major obstacle in the organic solar cell field is the inability to predict the relevant microstructural length scales that determine charge transport of the interpenetrating polymer/small molecule network based on the component chemical structures. This has led to a trial-and-error approach, which is extremely labor-intensive. This manuscript is our attempt to move toward forming a link between small molecule chemical structure and the morphological hierarchy of the blend. We focus on geometric motifs of small molecule organic semiconductors which have 2D, nonspherical 3D, and quasispherical 3D molecular orbital extent. We find that phase separation in these blends is a function of the molecular structure, and that the small molecule chemical structure is coupled to the crystallite orientation distribution of the polymer matrix. We further find that the ability of a molecule to form a network with a well-defined length scale of phase separation depends on the polymer persistence length.

In situ and ex situ neutron reflectivity is used to characterize annealed regioregular-P3HT/PCBM bilayers. In situ annealing of a 20 nm PCBM/35 nm P3HT bilayer at 170 °C reveals rapid mixing of PCBM and P3HT to produce a polymer-rich layer that contains around 18–20% PCBM. Samples with three different thicknesses of P3HT layer are ex situ annealed at 140 °C. This again reveals migration of PCBM into the P3HT and vice versa, with the polymer-rich layer in the 20 nm PCBM/35 nm P3HT sample containing 19% PCBM. Complete migration of the entire PCBM layer into the P3HT layer is observed for a 20 nm PCBM/80 nm P3HT bilayer. The robustness of fitted model composition profiles, in comparison with real-space imaging of sample surface morphology and previous work on annealed P3HT/PCBM bilayer compositions, is discussed in detail.

The presence of interfaces and geometrical confinement can have a strong influence on the structure and morphology of thin films of semicrystalline polymers. Using surface-sensitive grazing incidence wide angle X-ray scattering and atomic force microscopy to investigate the vertical structure of thin films of poly(3-hexylthiophene) crystallized from the melt, we show that highly oriented crystallites are induced at the air/polymer interface and not as sometimes assumed at the interface to the substrate. These crystallites are oriented with their crystallographic a-axis perpendicular to the plane of the film. While the corresponding orientation dominates in thinner films, for sufficiently thick films (>60 nm) a layer containing unoriented crystals is present below the surface layer. Due to the anisotropic charge transport properties, the observed effects are expected to be of special relevance for potential applications of semiconductor polymers in the field of organic photovoltaics for which vertical transport in thicker films plays an important role.

Microstructural and morphological features of the layers forming integrated PTB7/PC71BM organic solar cells with Ca/Al cathode are studied. The effects of vacuum treatment on properties and durability were addressed using complementary approaches: time-resolved experiments revealing the structural evolution of the active layers under illumination were conducted combining the in situ energy dispersive X-ray diffraction (EDXD) technique with atomic force microscopy (AFM); space-resolved characterization of the integrated devices was possible via high resolution X-ray diffraction, using a nano-focused synchrotron radiation X-ray beam to discriminate the device components. Active layers surface morphology is stable under illumination and PC71BM structural properties remain unaltered. PTB7 undergoes crystallinity depletion, mainly at the active layer/cathode interface. This effect is actually inhibited in the device submitted to vacuum treatment, proving that this procedure induces stabilization at the cathode’s buried interface, as verified by fourier transform infrared (FTIR) spectroscopy. Importantly, the protective role of the vacuum treatment results in a significant photovoltaic durability enhancement.

Probing the distribution of donor and acceptor molecules in the active layer of polymer solar cells requires high-resolution methods that provide chemical contrast. A combination of the synchrotron-based soft X-ray technique near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and scanning transmission X-ray microscopy (STXM) can map surface composition and local composition in lateral phase-separated domains, as well as identify molecular signatures of degradation. Here we illustrate, by way of selected results, the relevance of these complementary techniques to the field of organic photovoltaics. We demonstrate firstly that the determination of local composition from X-ray absorption spectra requires cautious use of fitting techniques. Furthermore, we show that drop-like clusters of PC70BM formed during the transfer of spin-coated polymer:PC70BM blend films onto Cu-grids lead to an underestimation of PC70BM/polymer concentration ratios. Finally, we show that the selective degradation of one of the components can impair the accurate determination of local blend composition.