Controlling the surface and interface properties of halide perovskites (HaPs) materials is key to improve performance and stability of HaP‐based optoelectronic devices such as solar cells. Here, an ...overview is given on the use of different photoemission spectroscopy (PES) techniques as a tool kit to investigate chemical and electronic properties of surfaces and interfaces in research on HaP compounds. The primary focus of the article is X‐ray photoelectron spectroscopy (XPS), hard X‐ray photoemission spectroscopy (HAXPES), ultraviolet photoemission spectroscopy (UPS), and inverse photoemission spectroscopy (IPES), highlighting the importance of good practices during PES measurements. Starting from the working principles of PES, critical measurement conditions are discussed. In particular, the exposure of the HaP surface to vacuum and high energy radiation can cause accelerated ageing, degradation, and also ionic migration in the sample. The impact of these changes on the electronic and chemical properties is discussed, followed by an analysis of the specific challenges encountered when performing PES measurements of HaPs. These include the deviation from pristine surface conditions, determination of “soft” band edges, and assessment of band bending. The review concludes by emphasizing good practices for PES measurements of HaP samples and outlining the scope of operando type measurements to capture the transient behavior of HaPs in the experiment.
The central focus of this review is on the possibilities and intricacies in the use of photoemission spectroscopy (PES) techniques for research on halide perovskite materials. Accurate description of the chemical and electronical properties can thus be obtained, by coupling complementary PES techniques, such as ultraviolet photoemission spectroscopy, inverse photoemission spectroscopy, and X‐ray photoemission spectroscopy.
Organic-inorganic perovskite solar cells have attracted tremendous attention because of their remarkably high power conversion efficiencies. To further improve device performance, it is imperative to ...obtain fundamental understandings on the photo-response and long-term stability down to the microscopic level. Here, we report the quantitative nanoscale photoconductivity imaging on two methylammonium lead triiodide thin films with different efficiencies by light-stimulated microwave impedance microscopy. The microwave signals are largely uniform across grains and grain boundaries, suggesting that microstructures do not lead to strong spatial variations of the intrinsic photo-response. In contrast, the measured photoconductivity and lifetime are strongly affected by bulk properties such as the sample crystallinity. As visualized by the spatial evolution of local photoconductivity, the degradation process begins with the disintegration of grains rather than nucleation and propagation from visible boundaries between grains. Our findings provide insights to improve the electro-optical properties of perovskite thin films towards large-scale commercialization.
Efficient lead (Pb)‐free inverted planar formamidinium tin triiodide (FASnI3) perovskite solar cells (PVSCs) are demonstrated. Our FASnI3 PVSCs achieved average power conversion efficiencies (PCEs) ...of 5.41% ± 0.46% and a maximum PCE of 6.22% under forward voltage scan. The PVSCs exhibit small photocurrent–voltage hysteresis and high reproducibility. The champion cell shows a steady‐state efficiency of ≈6.00% for over 100 s.
Organometallic halide perovskite solar cells (PSCs) have shown great promise as a low-cost, high-efficiency photovoltaic technology. Structural and electro-optical properties of the perovskite ...absorber layer are most critical to device operation characteristics. Here we present a facile fabrication of high-efficiency PSCs based on compact, large-grain, pinhole-free CH3NH3PbI3-xBrx (MAPbI3-xBrx) thin films with high reproducibility. A simple methylammonium bromide (MABr) treatment via spin-coating with a proper MABr concentration converts MAPbI3 thin films with different initial film qualities (for example, grain size and pinholes) to high-quality MAPbI3-xBrx thin films following an Ostwald ripening process, which is strongly affected by MABr concentration and is ineffective when replacing MABr with methylammonium iodide. A higher MABr concentration enhances I-Br anion exchange reaction, yielding poorer device performance. This MABr-selective Ostwald ripening process improves cell efficiency but also enhances device stability and thus represents a simple, promising strategy for further improving PSC performance with higher reproducibility and reliability.
The ability to manipulate quantum dot (QD) surfaces is foundational to their technological deployment. Surface manipulation of metal halide perovskite (MHP) QDs has proven particularly challenging in ...comparison to that of more established inorganic materials due to dynamic surface species and low material formation energy; most conventional methods of chemical manipulation targeted at the MHP QD surface will result in transformation or dissolution of the MHP crystal. In previous work, we have demonstrated record-efficiency QD solar cells (QDSCs) based on ligand-exchange procedures that electronically couple MHP QDs yet maintain their nanocrystalline size, which stabilizes the corner-sharing structure of the constituent PbI6 4– octahedra with optoelectronic properties optimal for solar energy conversion. In this work, we employ a variety of spectroscopic techniques to develop a molecular-level understanding of the MHP QD surface chemistry in this system. We individually target both the anionic (oleate) and cationic (oleylammonium) ligands. We find that atmospheric moisture aids the process by hydrolysis of methyl acetate to generate acetic acid and methanol. Acetic acid then replaces native oleate ligands to yield QD surface-bound acetate and free oleic acid. The native oleylammonium ligands remain throughout this film deposition process and are exchanged during a final treatment step employing smaller cationsnamely, formamidinium. This final treatment has a narrow processing window; initial treatment at this stage leads to a more strongly coupled QD regime followed by transformation into a bulk MHP film after longer treatment. These insights provide chemical understanding to the deposition of high-quality, electronically coupled MHP QD films that maintain both quantum confinement and their crystalline phase and attain high photovoltaic performance.
Lead thiocyanate in the perovskite precursor can increase the grain size of a perovskite thin film and reduce the conductivity of the grain boundaries, leading to perovskite solar cells with reduced ...hysteresis and enhanced fill factor. A planar perovskite solar cell with grain boundary and interface passivation achieves a steady‐state efficiency of 18.42%.
A general doping strategy, using a wide range of acids with different pKa values as additive, is demonstrated to enhance the conductivity of spiro‐OMeTAD, the dominant hole transport material in ...perovskite solar cells (PSCs). Hysteresis‐less planar PSCs with ≈19% efficiency and better open‐circuit voltage and fill factor is achieved with acid doped spiro‐OMeTAD.
Photovoltaic applications of perovskite semiconductor material systems have generated considerable interest in part because of predictions that primary defect energy levels reside outside the ...bandgap. We present experimental evidence that this enabling material property is present in the halide-lead perovskite, CH3NH3PbI3 (MAPbI3), consistent with theoretical predictions. By performing X-ray photoemission spectroscopy, we induce and track dynamic chemical and electronic transformations in the perovskite. These data show compositional changes that begin immediately with exposure to X-ray irradiation, whereas the predominant electronic structure of the thin film on compact TiO2 appears tolerant to the formation of compensating defect pairs of VI and VMA and for a large range of I/Pb ratios. Changing film composition is correlated with a shift of the valence-band maximum only as the halide–lead ratio drops below 2.5. This delay is attributed to the invariance of MAPbI3 electronic structure to distributed defects that can significantly transform the electronic density of states only when in high concentrations.
We developed lead halide perovskite quantum dot (QD) films with tuned surface chemistry based on A-site cation halide salt (AX) treatments. QD perovskites offer colloidal synthesis and processing ...using industrially friendly solvents, which decouples grain growth from film deposition, and at present produce larger open-circuit voltages (VOC's) than thin-film perovskites. CsPbI3 QDs, with a tunable bandgap between 1.75 and 2.13 eV, are an ideal top cell candidate for all-perovskite multijunction solar cells because of their demonstrated small VOC deficit. We show that charge carrier mobility within perovskite QD films is dictated by the chemical conditions at the QD-QD junctions. The AX treatments provide a method for tuning the coupling between perovskite QDs, which is exploited for improved charge transport for fabricating high-quality QD films and devices. The AX treatments presented here double the film mobility, enabling increased photocurrent, and lead to a record certified QD solar cell efficiency of 13.43%.
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