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The chemical and electronic structure of hybrid organometallic (CH₃NH₃PbI₍₃₋ₓ₎Clₓ) and inorganic (CsSnBr₃) perovskite materials on compact TiO₂ (c-TiO₂) is studied using x-ray and electron based spectroscopic techniques. The morphology and local elemental composition of CH₃NH₃PbI₍₃₋ₓ₎Clₓ, used as absorbers in PV devices, defining the film quality and influencing the performance of respective solar cells is studied in detail by using photoemission electron microscopy (PEEM). An incomplete coverage, with holes reaching down to the c-TiO₂ was revealed; three different topological regions with different degrees of coverage and chemical composition were identified. Depending on the degree of coverage a variation in I oxidation and the formation of Pb⁰ in the vicinity of the c-TiO₂ is found. The valence band maxima (VBM) derived from experimental data for the perovskite and c-TiO₂, combined with information from literature on spiro-MeOTAD suggests an energy level alignment resulting in an excellent charge selectivity at the absorber/spiro-MeOTAD and absorber/c-TiO₂ interfaces respectively. Further, the derived energy level alignment indicates a large recombination barrier (~2 eV), preventing shunts due to direct contact between c-TiO₂ and spiro-MeOTAD in the pin-holes.
In-situ ambient pressure hard x-ray photoelectron spectroscopy (AP-HAXPES) studies of 60 and 300 nm CH₃NH₃PbI₍₃₋ₓ₎Clₓ have been performed under varies conditions (i.e. vacuum/water and dark/UV light) to gain insight into the degradation mechanism responsible for the short lifetime of the absorber. The 60 nm perovskite forms Pb⁰ in water vapor (non-defined illumination) in presence of x-rays. The 300 nm perovskite sample shows a complex behavior under illumination/dark. In water vapor/dark the perovskite dissolves into its organic (MAI) and inorganic (PbI₂) components. Under illumination PbI₂ further decomposes to Pb⁰ induced by UV light and x-rays.
For alternative inorganic CsSnBr₃ perovskites, the impact of SnF₂ on the chemical and electronic structure is studied to identify its role for the improved performance of the solar cell. HAXPES and lab-XPS measurements performed on CsSnBr₃ with and without SnF₂ indicate two Sn, Cs, and Br species in all samples, where the second Sn species is attributed to oxidized Sn (Sn⁴⁺). When adding SnF₂ to the precursor solution, the coverage is improved and less Sn⁴⁺ and Cs and Br secondary species can be observed, revealing an oxidation inhibiting effect of SnF₂. Additionally, SnF₂ impacts the electronic structure, enhancing the density of states close to the VBM.
The properties of Si thin films for solar cells, the interaction with different substrates and the influence of dopants are examined with synchrotron based x-ray spectroscopy – primarily x-ray emission spectroscopy (XES) and hard x-ray photoelectron spectroscopy (HAXPES). The films are studied as-deposited (i.e., amorphous, a-Si) and after conversion into polycrystalline (poly-Si) employing solid phase crystallization (SPC). Si L2,3 XES spectra of thin-film Si samples can be described by a superposition of a-Si and monocrystalline Si-wafer (c-Si) reference spectra. According to a quantification based on that superposition principle, none of the investigated samples are completely crystallized – a measurable a-Si component always remains (5-20 %) regardless of deposition and treatment conditions. Based on additional results from electron back scattering diffraction different models are developed which may explain this finding. According to these models, the remnant a-Si component can be attributed to amorphous/disordered material at the grain boundaries. Using one of these models, the thickness of this grain-surrounding material s could be approximated to be (1.5 ± 0.5) nm. Further investigations of the SPC process reveal a faster crystallization for boron-doped samples, and a slower crystallization for phosphorous-doped samples, when compared to the crystallization of undoped a Si:H thin films. The peculiarities of B K XES spectra (and observed changes upon SPC) indicate that boron could act as a nucleation center promoting crystallization. Si L2,3 XES spectra of a-Si:H and P-doped poly-Si exhibit spectral features above the valence band maximum at 100 eV that could be attributed to a-Si defect states and n+-dopant states, respectively. The SPC crystallization velocity of Si thin films on ZnO:Al/glass is found to be faster than that on SiNx/glass substrate. Multiple indications for oxidization at the poly-Si/ZnO:Al interface are found based on our Si L2,3 XES analysis. Spatially resolved x-ray photoelectron spectroscopy data support this and even suggest the formation of sub-oxides or zinc silicate as an interface species. The electronic structure of the buried a-SiOx:H(B)/ZnO:Al and µc-Si:H(B)/ZnO:Al interfaces are unraveled with “depth resolved” hard x-ray photoelectron spectroscopy. A surface band bending limited to the very surface of the silicon layers is found. The valence band maxima for the Si cover layers and the ZnO:Al TCO are determined and interface induced band bending for both interfaces are derived. At the a-SiOx:H(B)/ZnO:Al interface a tunnel barrier of (0.22 ± 0.31) eV and at µc-Si:H(B)/ZnO:Al interface a tunnel barrier of (-0.08 ± 0.31) eV is determined. This explains a previously empirically found solar cell efficiency increase produced by introducing a µc-Si:H(B) buffer layer between an a-Si p-i-n cell and the ZnO:Al/glass substrate.