J. Klaer

Solar hydrogen evolution using metal-free photocatalytic polymeric carbon nitride/CuInS2 composites as photocathodes

Polymeric carbon nitride (g-C3N4) films were synthesized on polycrystalline semiconductor CuInS2 chalcopyrite thin film electrodes by thermal polycondensation and were investigated as photocathodes for the hydrogen evolution reaction (HER) under photoelectrochemical conditions. The composite photocathode materials were compared to g-C3N4 powders and were characterized with grazing incidence X-ray diffraction and X-ray photoemission spectroscopy as well as Fourier transform infrared and Raman spectroscopies. Surface modification of polycrystalline CuInS2 semiconducting thin films with photocatalytically active g-C3N4 films revealed structural and chemical properties corresponding to the properties of g-C3N4 powders. The g-C3N4/CuInS2 composite photocathode material generates a cathodic photocurrent at potentials up to +0.36 V vs. RHE in 0.1 M H2SO4 aqueous solution (pH 1), which corresponds to a +0.15 V higher onset potential of cathodic photocurrent than the unmodified CuInS2 semiconducting thin film photocathodes. The cathodic photocurrent for the modified composite photocathode materials was reduced by almost 60% at the hydrogen redox potential. However, the photocurrent generated from the g-C3N4/CuInS2 composite electrode was stable for 22 h. Therefore, the presence of the polymeric g-C3N4 films composed of a network of nanoporous crystallites strongly protects the CuInS2 semiconducting substrate from degradation and photocorrosion under acidic conditions. Conversion of visible light to hydrogen by photoelectrochemical water splitting can thus be successfully achieved by g-C3N4 films synthesized on polycrystalline CuInS2 chalcopyrite electrodes.

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 ...

Processes for chalcopyrite-based solar cells

Abstract This contribution deals with the investigations of chalcopyrite solar cells. Main attention is paid to absorber materials with band gaps larger than 1.5 eV. Besides the different efforts to modify and optimise stoichiometric CuInS 2 films, novel deposition technologies for CuGaSe 2 films and buffer layers as well as alternative buffer layers were studied and compared. With ZnSe as alternative buffer layer on Cu(InGa)(S,Se) 2 absorbers developed by SSI Camarillo and Siemens Solar, Munich, total area efficiencies up to 13.7% and active area efficiencies up to 15.7% could be reached, respectively. For CuInS 2 two important results were achieved. The efficiency of Cu-poor CuInS 2 cells could be increased to 8.3%. Standard Cu-rich prepared devices led to a new record efficiency of 12.5%.

Nondestructive depth-resolved spectroscopic investigation of the heavily intermixed In2S3/Cu(In,Ga)Se2 interface

The chemical structure of the interface between a nominal In2S3 buffer and a Cu(In,Ga)Se2 (CIGSe) thin-film solar cell absorber was investigated by soft x-ray photoelectron and emission spectroscopy. We find a heavily intermixed, complex interface structure, in which Cu diffuses into (and Na through) the buffer layer, while the CIGSe absorber surface/interface region is partially sulfurized. Based on our spectroscopic analysis, a comprehensive picture of the chemical interface structure is proposed.

Intermixing at the heterointerface between ZnS∕Zn(S,O) bilayer buffer and CuInS2 thin film solar cell absorber

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. After identifying the deposited Zn compound, as ZnS∕Zn(S,O) bilayer buffer in former investigations [M. Bar et al., J. Appl. Phys. 99, 123503 (2006)], this time the focus lies on potential diffusion/intermixing processes at the buffer/absorber interface possibly, clarifying the effect of the heat treatment, which drastically enhances the device performance of respective final solar cells. The interface formation was investigated by x-ray photoelectron and x-ray excited Auger electron spectroscopy. In addition, photoelectron spectroscopy (PES) measurements were also conducted using tunable monochromat...

Current transport in Cu(In,Ga)S2 based solar cells with high open circuit voltage-bulk vs. interface

Cu(In,Ga)S 2 thin films prepared by rapid thermal sulfurization of metallic precursors yielded solar cells with efficiencies reaching 12.9% [1]. A good short circuit current density was observed together with open circuit voltages up to 850 mV. However, the fill factor was close to, but typically did not exceed 70%. In this contribution we report on the role of junction formation by chemical bath deposition on these parameters. Concentrations in the bath and deposition times were varied. A comparison is made between CdS and Zn(S,O) buffer layers. The influence of the incorporated gallium on surface properties was investigated by ultraviolet photoelectron spectroscopy (UPS) for the valence band edge and near edge X-ray absorption fine structure (NEXAFS) for the conduction band edge. Even in our best cell (13.1%) the activation energy of the saturation current is found to be still smaller than the band gap. High diode ideality factors and voltage dependent current collection prevent higher fill factors.

Damp heat stability of chalcopyrite mini-modules: evaluation of specific test structures

Damp heat stress (85% relative humidity at 85/spl deg/C) has been used to test long term stability of CIS thin film photovoltaic devices. Two CIS absorber types have been examined, CuInS/sub 2/ and Cu(In,Ga)Se/sub 2/. Module degradation is dominated by an increase of the series resistance R/sub s/. In order to get information about the ZnO sheet resistance R/sub sq/ and the Mo/ZnO contact resistance R/sub c/, which are the most important contributions to R/sub s/, specially designed transmission-line test structures are used. Degradation of R/sub c/ strongly depends on the point of time when the second scribe for integrated series connection, P2, is made, while degradation of R/sub sq/ is strongly affected by the underlying absorber layer. Module-type solar cells without metal grid and complete mini-modules have been exposed to the same damp heat stress and yield additional information about degradation of other electrical parameters.

Combined electron backscatter diffraction and cathodoluminescence measurements on CuInS2/Mo/glass stacks and CuInS2 thin-film solar cells

Electron backscatter diffraction (EBSD) and cathodoluminescence (CL) measurements in a scanning electron microscope were performed on cross sections of CuInS2 thin films and ZnO/CdS/CuInS2/Mo/glass thin-film solar cells. The CuInS2 layers analyzed for the present study were grown by a rapid thermal process. The regions of the CuInS2 layers emitting high CL intensity of band-band luminescence are situated near the top surface (or close to the interface with ZnO/CdS). This can be attributed to an enhanced crystal quality of the thin films in this region. The phenomenon may be related to the recrystallization via solid-state reactions with CuxS phases, which is assumed to run from the top to the bottom of the growing CuInS2 layer. The distribution of CL intensities is independent of the sample temperature, the acceleration voltage of the electron beam, and of whether or not the ZnO/CdS window layers are present. When comparing CL images and EBSD maps on identical sample positions, pronounced intragrain CL co...

CuInS2–CdS heterojunction valence band offset measured with near-UV constant final state yield spectroscopy

The valence band offset of the heterojunction between CuInS2 (CIS) and chemical bath deposited CdS has been determined both by means of combined x-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) and by near-UV constant final state (CFS) yield spectroscopy. The use of the latter shows that this spectroscopic method is indeed suitable for the investigation of chalcopyrite thin films. The higher information depth due to the low excitation energies (7.5–4.0 eV) used in CFS makes it possible to obtain a signal from the valence band of the CIS substrate even after a relatively thick (∼5 nm) CdS layer has been deposited. The number of samples needed to determine the band offset is reduced from three to one and the effects of chemical changes on the CIS surface can be accounted for because the valence band edges of both materials are measured directly. The valence band offsets with the XPS/UPS and CFS methods were determined to be 1.25±0.20 and 1.45±0.20 eV, respectively.

Effect of Zn incorporation into CuInS2 solar cell absorbers on microstructural and electrical properties

Zn incorporation into CuInS2 absorbers is found to increase the open-circuit voltage but decrease the short-circuit current of the corresponding thin-film solar cells. In this article, we study the effect of Zn incorporation into CuInS2 absorbers with a focus on the mechanisms leading to the measured changes in the electrical properties of the solar cells. Solar cells with varying Zn concentrations in their absorbers are characterized via the application of transmission electron microscopy, quantum efficiency, and current-voltage measurements, as well as admittance, x-ray photoelectron and photoluminescence spectroscopy. A Zn accumulation on the absorber side of the CuInS2–CdS interface and a higher structural defect density within the absorber are found after Zn incorporation. Capacitance, quantum efficiency, and current-voltage measurements in combination with device simulations suggest that Zn incorporation induces or enhances a shallow donor at the CuInS2–CdS interface. The interface defect pins the F...