M. Bär

Cliff-like conduction band offset and KCN-induced recombination barrier enhancement at the CdS/Cu2ZnSnS4 thin-film solar cell heterojunction

The electronic structure of the CdS/Cu2ZnSnS4 (CZTS) heterojunction was investigated by direct and inverse photoemission. The effects of a KCN etch of the CZTS absorber prior to CdS deposition on the band alignment at the respective interface were studied. We find a “cliff”-like conduction band offset at the CdS/CZTS interface independent of absorber pretreatment and a significant etch-induced enhancement of the energetic barrier for charge carrier recombination across the CdS/CZTS interface.

Determination of the band gap depth profile of the penternary Cu(In(1-X)GaX)(SYSe(1-Y))2 chalcopyrite from its composition gradient

A simple model is introduced which determines the optical band-gap energy Eg for penternary Cu(In(1−X)GaX)(SYSe(1−Y))2 (CIGSSe) alloys from its Ga∕(Ga+In) ratio as well as from its S∕(S+Se) ratio. In order to verify the model the depth dependent composition of a CIGSSe sample was revealed by elastic recoil detection analysis. Applying the model, the concentration profiles were transferred in an Eg profile. Finally, these values were compared with optical band-gap energies, which were obtained directly by independent characterization methods.

CdS and Cd(OH)2 formation during Cd treatments of Cu(In,Ga)(S,Se)2 thin-film solar cell absorbers

The surface modifications induced by treating Cu(In,Ga)(S,Se)2 films in an aqueous ammonia hydroxide-based solution of Cd2+ ions—as used in record Cu(In,Ga)(S,Se)2 solar cells without a CdS buffer layer—have been investigated for different Cd2+ concentrations. Employing a combination of x-ray photoelectron spectroscopy, Auger electron spectroscopy, and x-ray emission spectroscopy, it is possible to distinguish two different surface modifications. For Cd2+ concentrations below 4.5 mM in the solution we observe the formation of a CdS monolayer, while higher Cd2+ concentrations lead to the additional deposition of a cadmium hydroxide film on the CdS/Cu(In,Ga)(S,Se)2 surface.

Direct observation of an inhomogeneous chlorine distribution in CH3NH3PbI3−xClx layers: surface depletion and interface enrichment

We have used hard X-ray photoelectron spectroscopy (HAXPES) at different photon energies and fluorescence yield X-ray absorption spectroscopy (FY-XAS) to non-destructively investigate CH3NH3PbI3−xClx perovskite thin films on compact TiO2. This combination of spectroscopic techniques allows the variation of information depth from the perovskite layer surface to the top-most part of the underlying compact TiO2 layer. We have taken advantage of this to understand the distribution of chlorine throughout the perovskite/TiO2 layer stack. No Cl is detected using HAXPES, indicating surface depletion of Cl and allowing us to place an upper limit on the amount of Cl in the perovskite layer: x 0.40) consistent with both enhanced concentrations of Cl deep beneath the perovskite film surface and near the CH3NH3PbI3−xClx perovskite/TiO2 interface. The consequences of this distribution of Cl in the CH3NH3PbI3−xClx perovskite layer on device performance are discussed.

Potassium Postdeposition Treatment-Induced Band Gap Widening at Cu(In,Ga)Se2 Surfaces – Reason for Performance Leap?

Direct and inverse photoemission were used to study the impact of alkali fluoride postdeposition treatments on the chemical and electronic surface structure of Cu(In,Ga)Se2 (CIGSe) thin films used for high-efficiency flexible solar cells. We find a large surface band gap (E(g)(Surf), up to 2.52 eV) for a NaF/KF-postdeposition treated (PDT) absorber significantly increases compared to the CIGSe bulk band gap and to the Eg(Surf) of 1.61 eV found for an absorber treated with NaF only. Both the valence band maximum (VBM) and the conduction band minimum shift away from the Fermi level. Depth-dependent photoemission measurements reveal that the VBM decreases with increasing surface sensitivity for both samples; this effect is more pronounced for the NaF/KF-PDT CIGSe sample. The observed electronic structure changes can be linked to the recent breakthroughs in CIGSe device efficiencies.

Depth-resolved band gap in Cu(In,Ga)(S,Se)2 thin films

The surface composition of Cu(In,Ga)(S,Se)2 (“CIGSSe”) thin films intrinsically deviates from the corresponding bulk composition, which also modifies the electronic structure and thus the optical properties. We used a combination of photon and electron spectroscopies with different information depths to gain depth-resolved information on the band gap energy (Eg) in CIG(S)Se thin films. We find an increasing Eg with decreasing information depth, indicating the formation of a surface region with significantly higher Eg. This Eg-widened surface region extends further into the bulk of the sulfur-free CIGSe thin film compared to the CIGSSe thin film.

Observation and Mediation of the Presence of Metallic Lead in Organic-Inorganic Perovskite Films.

We have employed soft and hard X-ray photoelectron spectroscopies to study the depth-dependent chemical composition of mixed-halide perovskite thin films used in high-performance solar cells. We detect substantial amounts of metallic lead in the perovskite films, which correlate with significant density of states above the valence band maximum. The metallic lead content is higher in the bulk of the perovskite films than at the surface. Using an optimized postanneal process in air, we can reduce the metallic lead content in the perovskite film. This process reduces the amount of metallic lead and a corresponding increase in the photoluminescence quantum efficiency of the perovskite films can be observed. This correlation indicates that metallic lead impurities are likely a key defect whose concentration can be controlled by simple annealing procedures in order to increase the performance for perovskite solar cells.

Chemical and electronic surface structure of 20%-efficient Cu(In,Ga)Se2 thin film solar cell absorbers

The chemical and electronic surface structure of 20%-efficient Cu(In,Ga)Se2 thin film solar cell absorbers was investigated as a function of deposition process termination (i.e., ending the growth process in absence of either Ga or In). In addition to the expected In (Ga) enrichment, direct and inverse photoemission reveal a decreased Cu surface content and a larger surface band gap for the “In-terminated” absorber.

Formation of a ZnS∕Zn(S,O) bilayer buffer on CuInS2 thin film solar cell absorbers by chemical bath deposition

The application of Zn compounds as buffer layers was recently extended to wide-gap CuInS2 (CIS) based thin film solar cells. Using an alternative chemical deposition route for the buffer preparation aiming at the deposition of a single-layer, nominal ZnS buffer without the need for any toxic reactants such as hydrazine has helped us to achieve a similar efficiency as respective CdS-buffered reference devices. In order to shed light on the differences of other Zn-compound buffers deposited in conventional chemical baths [chemical bath deposition (CBD)] compared to the buffer layers deposited by this alternative CBD process, the composition of the deposited buffers was investigated by x-ray excited Auger electron and x-ray photoelectron spectroscopy to potentially clarify their superiority in terms of device performance. We have found that in the early stages of this alternative CBD process a thin ZnS layer is formed on the CIS, whereas in the second half of the CBD the growth rate is greatly increased and Zn(S,O) with a ZnS∕(ZnS+ZnO) ratio of ∼80% is deposited. Thus, a ZnS∕Zn(S,O) bilayer buffer is deposited on the CIS thin film solar cell absorbers by the alternative chemical deposition route used in this investigation. No major changes of these findings after a postannealing of the buffer/CIS sample series and recharacterization could be identified.The application of Zn compounds as buffer layers was recently extended to wide-gap CuInS2 (CIS) based thin film solar cells. Using an alternative chemical deposition route for the buffer preparation aiming at the deposition of a single-layer, nominal ZnS buffer without the need for any toxic reactants such as hydrazine has helped us to achieve a similar efficiency as respective CdS-buffered reference devices. In order to shed light on the differences of other Zn-compound buffers deposited in conventional chemical baths [chemical bath deposition (CBD)] compared to the buffer layers deposited by this alternative CBD process, the composition of the deposited buffers was investigated by x-ray excited Auger electron and x-ray photoelectron spectroscopy to potentially clarify their superiority in terms of device performance. We have found that in the early stages of this alternative CBD process a thin ZnS layer is formed on the CIS, whereas in the second half of the CBD the growth rate is greatly increased and ...

Impact of KCN etching on the chemical and electronic surface structure of Cu2ZnSnS4 thin-film solar cell absorbers

The chemical and electronic surface structure of Cu2ZnSnS4thin-filmsolar cell absorbers has been investigated by direct and inverse photoemission. Particular emphasis was placed on the impact of KCN etching, which significantly alters the surface composition and is best explained by a preferred etching of Cu and, to a lesser degree, Sn. As a consequence the surfaceband gap increased from (1.53 ± 0.15) eV, which agrees with optically derived bulk band gap values, to (1.91 ± 0.15) eV.