At present, there is a huge development in optoelectronic applications using lead halide perovskites. Considering that device performance is largely governed by the transport of charges across ...interfaces and, therefore, the interfacial electronic structure, fundamental investigations of perovskite interfaces are highly necessary. In this study, we use high-resolution soft X-ray photoelectron spectroscopy based on synchrotron radiation to explore the interfacial energetics for the molecular layer of TIPS-pentacene and lead halide perovskite single crystals. We perform ultrahigh vacuum studies on multiple thicknesses of an in situ formed interface of TIPS-pentacene with four different in situ cleaved perovskite single crystals (MAPbI3, MAPbBr3, FAPbBr3, and Cs x FA1–x PbBr y I3–y ). Our findings reveal a substantial shift of the TIPS-pentacene energy levels toward higher binding energies with increasing thickness, while the perovskite energy levels remain largely unaffected regardless of their composition. These shifts can be interpreted as band bending in the TIPS-pentacene, and such effects should be considered when assessing the energy alignment at perovskite/organic transport material interfaces. Furthermore, we were able to follow a reorganization on the MAPbI3 surface with the transformation of the surface C 1s into bulk C 1s.
The chemical shift of core level binding energies makes electron spectroscopy for chemical analysis (ESCA) a workhorse analytical tool for science and industry. For some elements, close lying and ...overlapping spectral features within the natural life time broadening restrict applications. We establish how the core level binding energy chemical shift can be picked up experimentally by the additional selectivity through Auger electron photoelectron coincidence spectroscopy (APECS). Coincident measurement of Ni 3p photoemission with different MVV Auger regions from specific decay channels, narrows the 3p core-levels to a width of 1.2 eV, resolves the spin-orbit splitting of 1.6 eV and determines the chemical shift of Ni 3p levels of a Ni(111) single crystal and its oxidized surface layer to 0.6 eV.
Abstract The layered dichalcogenide MoS $$_{2}$$ 2 is relevant for electrochemical Li adsorption/intercalation, in the course of which the material undergoes a concomitant structural phase transition ...from semiconducting 2H-MoS $$_{2}$$ 2 to metallic 1T-Li $$_{\mathrm{x}}$$ x MoS $$_{2}$$ 2 . With the core hole clock approach at the S L $$_{1}$$ 1 X-ray absorption edge we quantify the ultrafast directional charge transfer of excited S3p electrons in-plane ( $$\parallel$$ ‖ ) and out-of-plane ( $$\perp$$ ⊥ ) for 2H-MoS $$_{2}$$ 2 as $$\tau _{2H,\parallel } = 0.38 \pm 0.08$$ τ 2 H , ‖ = 0.38 ± 0.08 fs and $$\tau _{2H,\perp } = 0.33 \pm 0.06$$ τ 2 H , ⊥ = 0.33 ± 0.06 fs and for 1T-Li $$_{\mathrm{x}}$$ x MoS $$_{2}$$ 2 as $$\tau _{1T,\parallel } = 0.32 \pm 0.12$$ τ 1 T , ‖ = 0.32 ± 0.12 fs and $$\tau _{1T,\perp } = 0.09 \pm 0.07$$ τ 1 T , ⊥ = 0.09 ± 0.07 fs. The isotropic charge delocalization of S3p electrons in the semiconducting 2H phase within the S-Mo-S sheets is assigned to the specific symmetry of the Mo-S bonding arrangement. Formation of 1T-Li $$_{\mathrm{x}}$$ x MoS $$_{2}$$ 2 by lithiation accelerates the in-plane charge transfer by a factor of $$\sim 1.2$$ ∼ 1.2 due to electron injection to the Mo-S covalent bonds and concomitant structural repositioning of S atoms within the S-Mo-S sheets. For excitation into out-of-plane orbitals, an accelerated charge transfer by a factor of $$\sim 3.7$$ ∼ 3.7 upon lithiation occurs due to S-Li coupling.
Electron spectroscopy with the unprecedented transmission of angle-resolved time-of-flight detection, in combination with pulsed X-ray sources, brings new impetus to functional materials science. We ...showcase recent developments towards chemical sensitivity from electron spectroscopy for chemical analysis and structural information from photoelectron diffraction using the phase transition properties of 1T-TaS
. Our development platform is the
instrument located at the
at BESSY II, where femtosecond and picosecond X-ray pulses can be generated and extracted. The scientific potential is put into perspective to the current rapidly developing pulsed X-ray source capabilities from Lasers and Free-Electron Lasers.
Abstract
For the layered transition metal dichalcogenide 1T-TaS
2
, we establish through a unique experimental approach and density functional theory, how ultrafast charge transfer in 1T-TaS
2
takes ...on isotropic three-dimensional character or anisotropic two-dimensional character, depending on the commensurability of the charge density wave phases of 1T-TaS
2
. The X-ray spectroscopic core-hole-clock method prepares selectively in- and out-of-plane polarized sulfur 3p orbital occupation with respect to the 1T-TaS
2
planes and monitors sub-femtosecond wave packet delocalization. Despite being a prototypical two-dimensional material, isotropic three-dimensional charge transfer is found in the commensurate charge density wave phase (CCDW), indicating strong coupling between layers. In contrast, anisotropic two-dimensional charge transfer occurs for the nearly commensurate phase (NCDW). In direct comparison, theory shows that interlayer interaction in the CCDW phase – not layer stacking variations – causes isotropic three-dimensional charge transfer. This is presumably a general mechanism for phase transitions and tailored properties of dichalcogenides with charge density waves.
Pump-probe photoelectron spectroscopy (PES) is a versatile tool to investigate the dynamics of transient states of excited matter. Vacuum space-charge effects can mask these dynamics and complicate ...the interpretation of electron spectra. Here we report on space-charge effects in Au 4f photoemission from a polycrystalline gold surface, excited with moderately intense 90 ps (FWHM) soft x-ray probe pulses, under the influence of the Coulomb forces exerted by a pump electron cloud, which was produced by intense 40 fs laser pulses. The experimentally observed kinetic energy shift and spectral broadening of the Au 4f lines, measured with highly-efficient time-of-flight spectroscopy, are in good agreement with simulations utilizing a mean-field model of the electrostatic pump electron potential. This confirms that the line broadening is predominantly caused by variations in the take-off time of the probe electrons without appreciable influence of local scattering events. Our findings might be of general interest for pump-probe PES with picosecond-pulse-length sources.
The concept of bonding and antibonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding ...interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access. Here we apply time-resolved soft X-ray spectroscopy at a free-electron laser to directly observe the decreased bonding–antibonding splitting following bond-activation using an ultrashort optical laser pulse.
A heterojunction is the key junction for charge extraction in many thin film solar cell technologies. However, the structure and band alignment of the heterojunction in the operating device are often ...difficult to predict from calculations and, due to the complexity and narrow thickness of the interface, are difficult to measure directly. In this study, we demonstrate a technique for direct measurement of the band alignment and interfacial electric field variations of a fully functional lead halide perovskite solar cell structure under operating conditions using hard X-ray photoelectron spectroscopy (HAXPES). We describe the design considerations required in both the solar cell devices and the measurement setup and show results for the perovskite, hole transport, and gold layers at the back contact of the solar cell. For the investigated design, the HAXPES measurements suggest that 70% of the photovoltage was generated at this back contact, distributed rather equally between the hole transport material/gold interface and the perovskite/hole transport material interface. In addition, we were also able to reconstruct the band alignment at the back contact at equilibrium in the dark and at open circuit under illumination.
Development of functional and stable solid polymer electrolytes (SPEs) for battery applications is an important step towards both safer batteries and for the realization of lithium-based or ...anode-less batteries. The interface between the lithium and the solid polymer electrolyte is one of the bottlenecks, where severe degradation is expected. Here, the stability of three different SPEs - poly(ethylene oxide) (PEO), poly( -caprolactone) (PCL) and poly(trimethylene carbonate) (PTMC) - together with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, is investigated after they have been exposed to lithium metal under UHV conditions. Degradation compounds,
e.g.
Li-O-R, LiF and Li
x
S
y
O
z
, are identified for all SPEs using soft X-ray photoelectron spectroscopy. A competing degradation between polymer and salt is identified in the outermost surface region (<7 nm), and is dependent on the polymer host. PTMC:LiTFSI shows the most severe decomposition of both polymer and salt followed by PCL:LiTFSI and PEO:LiTFSI. In addition, the movement of lithium species through the decomposed interface shows large variation depending on the polymer electrolyte system.
The electrode electrolyte interface is essential to our understanding of batteries and how they operate. In this article we examine the interface between three polymer electrolytes and lithium metal using photoelectron spectroscopy.
In heterogeneous catalysis the surface-adsorbate bond strength is critical for the function of the system. Here we study a series consisting of multilayer, bilayer and monolayer N2O on Ni(111) and ...employ Auger-photoelectron coincidence spectroscopy (APECS) to study the interaction between the molecule and the substrate directly. We observe intensity in the nitrogen Auger spectra that arise from the interaction between molecule and surface (not observed in free molecules) whereas the oxygen spectra are thickness-independent. Since the two nitrogen atoms of N2O are chemically inequivalent we can assign the intensity present in the bilayer and monolayer cases to orbitals centered on the terminal nitrogen which is closest to the Ni(111) surface. Using ab initio, molecular dynamics and solid-state density functional theory calculations we infer a Blyholder model of the surface bond as consisting of donation from the terminal nitrogen lone-pair valence orbital with back-donation from the metal into the unoccupied orbitals on that nitrogen. This coincidence technique can readily be used to study substrate–adsorbate interactions directly with chemical and orbital specificity — this opens up prospects to study fundamental steps of molecular adsorption and heterogeneous catalysis with unprecedented detail.
Display omitted
•Direct observation of surface–molecular electron sharing.•Coincidence spectroscopy reveals hidden spectral features.•Blyholder backdonation between N2O and Ni(111).
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