A simplified Cu(In, Ga)(S, Se)2/Zn(O, S)/ZnO:Al stack for chalcopyrite thin-film solar cells is proposed. In this stack the Zn(O, S) layer combines the roles of the traditional CdS buffer and undoped ZnO layers. It will be shown that Zn(O, S) films can be sputtered in argon atmosphere from a single mixed target without substrate heating. The photovoltaic performance of the simplified stack matches that of the conventional approach. Replacing the ZnO target with a ZnO/ZnS target may therefore be sufficient to omit the CdS buffer layer and avoid the associated complexity, safety and recycling issues, and to lower production cost.

Valence band offsets ΔEVBM at ZnSx O1–x/Cu(In,Ga)(Se,S)2 (CIGSSe) heterojunctions have been studied by photoemission spectroscopy (XPS, UPS) as a function of composition x in sputtered ZnSx O1–x films. In the composition range from ZnO to ZnS we found ΔEVBM between –(2.1 ± 0.3) eV and –(0.8 ± 0.4) eV, respectively. Considering the optical band gaps, the conduction band offsets ΔECBM range from –(0.1 ± 0.3) eV to +(1.4 ± 0.4) eV. These results suggest that sputtered ZnSx O1–x is suitable as substitution for the CdS buffer and ZnO window layers in standard chalcopyrite‐based solar cells. Current–voltage characteristics of the solar cells have been investigated as a function of the composition x. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

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 Fermi level close to the CdS conduction band, leading to an inversion at the heterointerface and thus reducing the recombination at interface defects and increasing the open-circuit voltage. A shallow bulk acceptor about 0.15 eV above the valence band edge is observed to increase with increasing Zn concentration in the CuInS2 absorbers and is responsible for a gradual decrease in the short-circuit current and the gain in the open-circuit voltage as the Zn concentration increases.

In an effort to eliminate the CdS buffer layer and its costly preparation process we are considering sputtered buffer layers. In particular, we report in this contribution on the reactive sputtering of wide gap Zn(O,S) compound semiconductors and their application in solar cells with different types of chalcopyrite absorbers. While we were able to freely adjust the composition through the oxygen partial pressure, the structural and optical properties are superior when the composition is close to the ternary endpoints. Open circuit voltage and short circuit current density as a function of Sulphur content in the buffer show opposite trends. Working cells were achieved with low band gap as well as wide band gap absorbers, however, their performance is so far inferior to that of the standard stacks.

The class of half-Heusler compounds opens possibilities to find alternatives for II-VI or III-V compound semiconductors. We aim to find suitable substitutes for the cadmium sulphide buffer layer in chalcopyrite-based thin film solar cells, where the buffer layer is located between the p-type chalcopyrite absorber and an n-type transparent window layer. We report here the preparation of radio-frequency-sputtered lithium copper sulphide "LiCuS" and lithium zinc phosphide "LiZnP" films. The optical analysis of these films revealed band gaps between 1.8 and 2.5 eV, respectively. Chemical properties of the film surface and both interfaces between the film and a Cu(In,Ga)Se-2 layer and between the film and an (Zn,Mg)O layer were investigated by in-situ photoelectron spectroscopy. The valence band offsets to the Cu(In,Ga)Se-2 layer were estimated to be (0.4 +/- 0.1) eV for "LiCuS"/Cu(In,Ga)Se-2 and (0.5 +/- 0.8) eV for "LiZnP"/Cu(In,Ga)Se-2. This leads to positive conduction band offsets of > 1 eV. These rather large offsets are not compatible with efficient solar cell devices. Under atmospheric conditions "LiCuS" and "LiZnP" films show rapid decomposition. (C) 2010 Elsevier B.V. All rights reserved.

Cu(In,Ga)Se2 films are used as absorber layers in chalcopyrite thin film solar cells. As the gallium concentration in the absorber can be used to control the band gap, there have been many efforts to vary the gallium concentration in depth to gain an optimum balance of light absorption, carrier collection, and recombination at different depths of the absorber film, leading to improved quantum efficiency. In this study, we investigate the effect of the maximum substrate temperature during film growth on the depth dependent gallium concentration. For the in-depth gallium concentration analyses, we use two techniques, covering complementary depth ranges. Angle dependent soft x-ray emission spectroscopy provides access to information depths between 20 and 470 nm, which covers the depth range of the space charge region, where most of the photoexcited carriers are generated. Therefore, this depth range is of particular interest. To complement this investigation we use secondary neutral mass spectrometry, which destructively probes the whole thickness of the absorber (≈2 μm). The two methods show increasingly pronounced gallium and indium gradients with decreasing maximum substrate temperature. The probing of the complementary depth ranges of the absorbers gives a consistent picture of the in-depth gallium distribution, which provides a solid basis for a comprehensive discussion about the effect of a reduced substrate temperature on the formation of gallium gradients in Cu(In,Ga)Se2 and the device performance of the corresponding reference solar cells.

First results are presented for chalcopyrite solar cells with Cd-free dry buffer layers prepared by two different vacuum deposition techniques on sequentially processed Cu(In, Ga)(S,Se) 2 absorbers. The deposition techniques are namely thermal evaporation of In 2 S 3 compound powder and the reactive sputtering of Zn(O,S) layers. Both approaches are suitable for an in-line assembly into an industrial production line. The influence of the variation of process parameters such as buffer layer thickness and annealing time on current-voltage characteristics and quantum efficiency is shown. Best cell results exceed 14% conversion efficiency for the In 2 S 3 approach (>;11% for the Zn(O,S) approach) which is comparable but slightly less than the standard CdS reference cells (>;15%).

The electronic and chemical properties of the (Zn1−x,Mgx)O/CuIn(S,Se)2 interface, prepared by sputtering of thin (Zn,Mg)O layers, were investigated with direct and inverse photoelectron spectroscopy on in situ prepared samples. With the combination of both techniques we have determined the band alignment at this interface as a function of Mg-content in the range 0≤x≤0.30. We find that the band alignment at the interface can be tailored between a “cliff” (downward step) in the conduction band for pure ZnO and a “spike” (upward step) for high Mg-contents. A direct influence of the band alignment modifications on the solar cell parameters is found.

The surface Cu-depletion of chalcopyrite thin films and its influence on the interface properties of related solar cells have been subject of a controversial debate for many years. Although the nature of this Cu-depletion and its extension in depth are crucial for the device physics, there are only a few contradictory experimental results that address this topic. To clarify this issue, we performed depth-dependent compositional analysis by angle dependent soft x-ray emission spectroscopy (AXES) on Cu(In,Ga)Se2 thin films with different integral Cu-contents. By considering depth profiles from literature and by taking the accuracy of AXES into account, our numerical AXES simulations predict a pronounced angle dependence for our samples. However, our experimental data show only a minor angle dependence, which leads to the conclusion that the Cu-depleted surface layer must be restricted to a very thin surface layer, which is not accessible by AXES. This conclusion is consistent with the result from our previous investigation by hard x-ray photoelectron spectroscopy, where we found a Cu-depleted surface layer in the subnanometer regime. Consequently the present study gives further experimental evidence for the surface reconstruction model proposed by first-principles calculations. Supported by secondary neutral mass spectroscopy, we show that the minor angle dependence in our AXES data can be attributed to a Ga-gradient in the chalcopyrite material.

Band offsets at Sb2S3/Cu(In,Ga)Se2 heterojunctions have been studied by x-ray and ultraviolet photoemission spectroscopy. The valence and conduction band offset have been estimated to −(0.6±0.3) eV and (0.2±0.3) eV, respectively. This result suggests Sb2S3 as a potential buffer layer material for chalcopyrite based solar cells. However, Cu(In,Ga)Se2/Sb2S3/ZnO solar cells have been investigated. While the open circuit voltage ranged up to ∼0.4–0.5 V, the short circuit current was limited to ∼1.8–4.9 mA/cm2. A photocurrent of about 30 mA/cm2 was found for negative bias. On the basis of bias dependent quantum efficiency measurements and calculations, limiting mechanisms are discussed.

In an effort to eliminate the standard CdS buffer layer from chalcopyrite‐based thin film solar cells we have investigated sputtered Zn(O,S) films. They were prepared by partially reactive sputtering from a ZnS target in an argon/oxygen mixture. Single phase, polycrystalline films were achieved for substrate temperatures of at least 100 °C. Test devices prepared in a completely dry process showed superior blue response and active area conversion efficiencies up to 13.7%. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

There are still open questions regarding the nature of the positive effect of the presence of Na on the performance of Cu(In,Ga)Se2 based, chalcopyrite thin film solar cells, especially at low processing temperatures. Studying Cu(In,Ga)Se2 thin film devices fabricated from low-temperature coevaporated absorbers on polyimide substrates by admittance and J-V-T measurements, characteristic properties are identified for different amounts of Na present during the growth. A roll-over behavior can be directly correlated with the Na-content. X-ray photoelectron spectroscopy shows the development of a MoSe2 phase at the back contact of the device. Efficiencies of 15.1% with MgF2 antireflection coating are demonstrated.

In a standard chalcopyrite-based thin film solar cell, the formation of the heterojunction is mediated by a thin buffer layer. This buffer is prepared by chemical bath deposition of CdS. The cell is completed by an undoped ZnO film followed by the highly doped transparent front contact. An alternative structure without any buffer layer where the undoped ZnO is replaced by (Zn,Mg)O has been suggested previously by Minemoto et al. [T. Minemoto, Y. Hashimoto, T. Satoh, T. Negami, H. Takakura, Y. Hamakawa, J. Appl. Phys. 89 (2001) 8327]. By adapting and applying this approach to CuInS2 absorbers from industrial pilot production we achieved efficiencies of 8% for small area cells (as compared to 9.4% for a reference cell with CdS buffer) as well as monolithically integrated test structures.

Chalcopyrite thin film solar cells with an In2S3 buffer showed high efficiencies above 15%, but only after annealing at 200 °C. One possible explanation is a Cu interdiffusion at the absorber/buffer interface. We were able to directly measure a Cu interdiffusion with a new tool at the BESSY synchrotron facility: HIKE (high kinetic energy X‐ray photoelectron spectroscopy). Due to its increased information depth of up to 10–20 nm HIKE is able to provide chemical information even through thin closed overlayers. The HIKE endstation also allows in‐situ heating. A layer stack of In2S3/ Cu(In,Ga)Se2 was prepared and heated in‐situ up to a temperature of 300 °C while continuously measuring HIKE spectra. A strong increase of the Cu signal above temperatures around 200 °C was found. With this setup we were able to directly monitor the Cu diffusion from the absorber into the buffer layer. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

The formation of the interface between a magnetron sputtered (Zn1−x,Mgx)O buffer layer and a CuIn(S,Se)2 absorber in thin film solar cells has been investigated by x-ray photoelectron spectroscopy and x-ray induced Auger electron spectroscopy. Detailed analysis of the spectra shows the incorporation of Zn into the absorber surface in the initial stage of the deposition process forming ZnS and/or ZnSe bonds. As a result we find the buffer layer to be Zn-depleted near the interface.

We report the electro deposition of In2S3 buffer layers for CuInS2 solar cells. All materials and deposition conditions were selected taking into account environmental, economic and technological aspects of a potential transfer to large volume industrial production. Different bath compositions and electro deposition parameters were studied. The obtained films exhibited complete substrate coverage, confirmed by SEM and XPS. In/S ratio close to 2/3 was obtained. XPS measurements detected the presence of indium hydroxide, transforming into oxide upon anneal at 200°C. Maximum photoelectric conversion efficiency of 7.1% was obtained, limited mainly by a low fill factor (51%). Further process optimization is expected to lead to efficiencies comparable to CdS buffers. So far, open-circuit voltages as high as 660mV were demonstrated.