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A key challenge for photoelectrochemical water splitting is that high performance semiconductors are not stable in aqueous electrolytes, necessitating corrosion protection layers such as TiO2. In the best case, the protection layer would also serve as the heterojunction partner, minimizing complexity and thereby cost. However, the bands of most high performance semiconductors are poorly aligned with TiO2, limiting the photovoltage. Here, we describe a method to overcome this limitation through the placement of a tunable dipole layer at the interface of the p- and n-type materials, shifting the relative band positions to enable an increased photovoltage. The introduction of a phosphonic acid (PA, H3PO3) layer increases the photovoltage of TiO2-protected Si, Sb2Se3, and Cu2O photocathodes. The dipole effect scales with PA surface coverage, and gives even larger shifts when multilayers are employed. By varying the thickness from submonolayer to multilayer (up to 2 nm), we are able to tune the photovoltage of p-Si/TiO2 over a range of 400 mV.

The application of TiO2 as part of the buffer layer stack in thin film Cu(In,Ga)Se2 (CIGS) solar cells is investigated for the improvement of the photovoltaic device performance. In a standard device configuration a CdS/ZnO/Al:ZnO layer stack is applied onto the CIGS absorber layer. By decreasing the CdS buffer layer thickness a higher photocurrent is expected from a reduced parasitic absorption. When the CdS layer is not fully covering the CIGS surface, losses in VOC and FF are observed in I-V measurements due to the arising unfavorable CIGS/ZnO band alignment and sputter damage on the CIGS surface. Here we present thin TiO2 layers deposited by atomic layer deposition at low temperature as alternative to the unintentionally doped ZnO. With this approach, the photocurrent can be increased without adversely affecting VOC. Comparable device efficiency is achieved for the investigated structure and the reference process with the gain in current density being compensated by increased series resistance. Temperature dependent I-V measurements coupled with 1D-SCAPS simulations suggest a positive conduction band offset at the CdS/TiO2 interface limiting the FF. ALD-TiO2 is suggested as a more suitable intermediate buffer layer than sputtered ZnO when thin CdS buffer layers are applied.

Multi-junction solar cells are known to have a considerably increased efficiency potential over their typical single junction counterparts. In order to produce low cost and lightweight multi-junction devices, the availability of suitable narrow ( In this contribution we report on the RbF post deposition treatment of narrow bandgap CIGS absorbers grown with a single bandgap grading approach. We discuss the necessary deposition conditions and the observed improvements on solar cells performance. A certified record efficiency of 18.0% for an absorber with 1.00 eV optoelectronic bandgap is presented and its suitability for perovskite/CIGS tandem devices is shown.

This review summarizes the current status of Cu(In,Ga)(S,Se)2 (CIGS) thin film solar cell technology with a focus on recent advancements and emerging concepts intended for higher efficiency and novel applications. The recent developments and trends of research in laboratories and industrial achievements communicated within the last years are reviewed, and the major developments linked to alkali post deposition treatment and composition grading in CIGS, surface passivation, buffer, and transparent contact layers are emphasized. Encouraging results have been achieved for CIGS-based tandem solar cells and for improvement in low light device performance. Challenges of technology transfer of lab's record high efficiency cells to average industrial production are obvious from the reported efficiency values. One section is dedicated to development and opportunities offered by flexible and lightweight CIGS modules. Copyright © 2016 John Wiley & Sons, Ltd.

Absorbers for planar perovskite solar cells are often prepared by two-step deposition methods, where a thick compact PbI2 layer is deposited followed by conversion to perovskite using CH3NH3I solution. The surface of the precursor layer quickly reacts with the CH3NH3I solution, which hinders further diffusion of CH3NH3I into the layer, consequently leading to significant amounts of residual PbI2 at room temperature. Here, we report a novel concept that employs a porous nanostructured PbI2 layer consisting of nanoplates to rapidly prepare single phase perovskite layer. The non-compact nanoplate morphology is achieved in a controllable manner by thermal evaporation of PbI2 on TiO2-coated FTO substrate and allows easy penetration of CH3NH3I solution into the whole PbI2 layer, thus facilitating fast and complete conversion. The amount of PbI2 residual can be controlled by varying the CH3NH3I concentration. The growth of the nanoplates is governed by the intrinsic crystallographic structure of the deposited material, crystal characteristics of the underlying substrate, and deposition method. The introduced process enables planar perovskite solar cells with efficiency of 8.6% measured at maximum power point. This work opens a new route for rapid preparation of other three-dimensional organic–inorganic hybrid perovskites by rational tailoring the metal halide morphology.

A promising way to enhance the efficiency of CIGS solar cells is by combining them with perovskite solar cells in tandem devices. However, so far, such tandem devices had limited efficiency due to challenges in developing NIR-transparent perovskite top cells, which allow photons with energy below the perovskite band gap to be transmitted to the bottom cell. Here, a process for the fabrication of NIR-transparent perovskite solar cells is presented, which enables power conversion efficiencies up to 12.1% combined with an average sub-band gap transmission of 71% for photons with wavelength between 800 and 1000 nm. The combination of a NIR-transparent perovskite top cell with a CIGS bottom cell enabled a tandem device with 19.5% efficiency, which is the highest reported efficiency for a polycrystalline thin film tandem solar cell. Future developments of perovskite/CIGS tandem devices are discussed and prospects for devices with efficiency toward and above 27% are given.

The development of a novel chemistry for the chemical bath deposition of Zn(O,S) buffer layers for Cu(In,Ga)Se2 (CIGS) solar cells is desired for a higher growth rate, hence reduced deposition time, while reducing simultaneously the required concentration of reactants. State-of-the-art recipes are based on thiourea as sulphide precursor requiring a high molarity of reactants and relatively long deposition times due to the slow decomposition rate of thiourea. In this contribution thioamide based sulphide precursors were investigated for their decomposition and growth behaviour. A co-solvent approach in an ethanolic/aqueous ammonia medium was evaluated omitting the need for additional complexants. By replacing thiourea with the investigated thioamides, homogeneous dense layers of around 30 nm were grown with a greatly decreased deposition time of 8 min compared to 25 min for thiourea. Likewise, the concentration of the sulphide precursor was 40-fold reduced. The photovoltaic performance as characterized by external quantum efficiency and current–voltage measurements, showed conversion efficiencies of 15% comparable to the thiourea based process.

We report on the application of ZnxTiyO deposited by atomic layer deposition (ALD) as buffer layer in thin film Cu(In,Ga)Se2 (CIGS) solar cells to improve the photovoltaic device performance. State-of-the-art CIGS devices employ a CdS/ZnO layer stack sandwiched between the absorber layer and the front contact. Replacing the sputter deposited ZnO with ALD-ZnxTiyO allowed a reduction of the CdS layer thickness without adversely affecting open-circuit voltage (VOC). This leads to an increased photocurrent density with a device efficiency of up to 20.8% by minimizing the parasitic absorption losses commonly observed for CdS. ALD was chosen as method to deposit homogeneous layers of ZnxTiyO with varying Ti content with a [Ti]/([Ti] + [Zn]) atomic fraction up to ∼0.35 at a relatively low temperature of 373 K. The Ti content influenced the absorption behavior of the ZnxTiyO layer by increasing the optical bandgap >3.5 eV in the investigated range. Temperature-dependent current–voltage (I–V) measurements of solar cells were performed to investigate the photocurrent blocking behavior observed for high Ti content. Possible conduction band discontinuities introduced by ZnxTiyO are discussed based on X-ray photoelectron spectroscopy (XPS) measurements.

We report on the use of a high bandgap metal-oxide at the front interface of Cu(In,Ga)Se-2 (CIGS) solar cells in a point contact concept for reduced interface recombination. Highly resistive HfO2 is applied on the CIGS surface by atomic layer deposition (ALD). Aspects of the surface passivating effect of HfO2 on CIGS were investigated by time-resolved photoluminescence (TRPL), electron beam induced current (EBIC) and capacitance-voltage (C-V) measurements. Two structuring methods for point contact formation are compared, a lithographic top-down and a simple bottom-up approach using NaCl as template. The former method employed a plasma etch step which was found to degrade the performance of solar cells when applied on the CIGS surface. The template method omitted sputtering and allowed patterning of HfO2 up to 10 nm thickness without adversely impacting the open-circuit voltage (V-OC). EBIC revealed an improved carrier collection due to the HfO2 coating and a long term stable PL decay was observed. Yet, the point contact concept with HfO2 was not significantly influencing the performance of a CIGS solar cell for the investigated parameter range. The work has received funding from the Swiss Federal Office of Energy under contract No SI/501145-01 and the Swiss State Secretariat for Education, Research and Innovation (SERI) under contract No 15.0158. The work has received support from the European Union's Horizon 2020 research and innovation programme under grant agreement No 641004 (Sharc25).

Time-resolved photoluminescence (TRPL) is applied to determine an effective lifetime of minority charge carriers in semiconductors. Such effective lifetimes include recombination channels in the bulk as well as at the surfaces and interfaces of the device. In the case of Cu(In,Ga)Se2 absorbers used for solar cell applications, trapping of minority carriers has also been reported to impact the effective minority carrier lifetime. Trapping can be indicated by an increased temperature dependence of the experimentally determined photoluminescence decay time when compared to the temperature dependence of Shockley–Read–Hall (SRH) recombination alone and can lead to an overestimation of the minority carrier lifetime. Here, it is shown by technology computer-aided design (TCAD) simulations and by experiment that the intentional double-graded bandgap profile of high efficiency Cu(In,Ga)Se2 absorbers causes a temperature dependence of the PL decay time similar to trapping in case of a recombinative front surface. It is demonstrated that a passivated front surface results in a temperature dependence of the decay time that can be explained without minority carrier trapping and thus enables the assessment of the absorber quality by means of the minority carrier lifetime. Comparison with the absolute PL yield and the quasi-Fermi-level splitting (QFLS) corroborate the conclusion that the measured decay time corresponds to the bulk minority carrier lifetime of 250 ns for the double-graded CIGS absorber under investigation., Graphical Abstract