Christina Gretener

Potassium-induced surface modification of Cu(In,Ga)Se2 thin films for high-efficiency solar cells

Thin-film photovoltaic devices based on chalcopyrite Cu(In,Ga)Se2 (CIGS) absorber layers show excellent light-to-power conversion efficiencies exceeding 20%. This high performance level requires a small amount of alkaline metals incorporated into the CIGS layer, naturally provided by soda lime glass substrates used for processing of champion devices. The use of flexible substrates requires distinct incorporation of the alkaline metals, and so far mainly Na was believed to be the most favourable element, whereas other alkaline metals have resulted in significantly inferior device performance. Here we present a new sequential post-deposition treatment of the CIGS layer with sodium and potassium fluoride that enables fabrication of flexible photovoltaic devices with a remarkable conversion efficiency due to modified interface properties and mitigation of optical losses in the CdS buffer layer. The described treatment leads to a significant depletion of Cu and Ga concentrations in the CIGS near-surface region and enables a significant thickness reduction of the CdS buffer layer without the commonly observed losses in photovoltaic parameters. Ion exchange processes, well known in other research areas, are proposed as underlying mechanisms responsible for the changes in chemical composition of the deposited CIGS layer and interface properties of the heterojunction.

Highly efficient Cu(In,Ga)Se2 solar cells grown on flexible polymer films

Solar cells based on polycrystalline Cu(In,Ga)Se(2) absorber layers have yielded the highest conversion efficiency among all thin-film technologies, and the use of flexible polymer films as substrates offers several advantages in lowering manufacturing costs. However, given that conversion efficiency is crucial for cost-competitiveness, it is necessary to develop devices on flexible substrates that perform as well as those obtained on rigid substrates. Such comparable performance has not previously been achieved, primarily because polymer films require much lower substrate temperatures during absorber deposition, generally resulting in much lower efficiencies. Here we identify a strong composition gradient in the absorber layer as the main reason for inferior performance and show that, by adjusting it appropriately, very high efficiencies can be obtained. This implies that future manufacturing of highly efficient flexible solar cells could lower the cost of solar electricity and thus become a significant branch of the photovoltaic industry.

Doping of polycrystalline CdTe for high-efficiency solar cells on flexible metal foil

Roll-to-roll manufacturing of CdTe solar cells on flexible metal foil substrates is one of the most attractive options for low-cost photovoltaic module production. However, various efforts to grow CdTe solar cells on metal foil have resulted in low efficiencies. This is caused by the fact that the conventional device structure must be inverted, which imposes severe restrictions on device processing and consequently limits the electronic quality of the CdTe layer. Here we introduce an innovative concept for the controlled doping of the CdTe layer in the inverted device structure by means of evaporation of sub-monolayer amounts of Cu and subsequent annealing, which enables breakthrough efficiencies up to 13.6%. For the first time, CdTe solar cells on metal foil exceed the 10% efficiency threshold for industrialization. The controlled doping of CdTe with Cu leads to increased hole density, enhanced carrier lifetime and improved carrier collection in the solar cell. Our results offer new research directions for solving persistent challenges of CdTe photovoltaics.

Highly transparent and conductive ZnO: Al thin films from a low temperature aqueous solution approach.

A solution deposition approach for high-performance aluminum-doped zinc oxide (AZO) thin films (visible transparency > 90% and sheet resistance down to 25 Ω/sq) with process temperatures not exceeding 85 °C is presented. This allows the non-vacuum deposition of AZO on temperature sensitive substrates such as polymer films for flexible and transparent electronics, or inorganic and organic thin film photovoltaics.

Alkali-templated surface nanopatterning of chalcogenide thin films: a novel approach toward solar cells with enhanced efficiency.

Concepts of localized contacts and junctions through surface passivation layers are already advantageously applied in Si wafer-based photovoltaic technologies. For Cu(In,Ga)Se2 thin film solar cells, such concepts are generally not applied, especially at the heterojunction, because of the lack of a simple method yielding features with the required size and distribution. Here, we show a novel, innovative surface nanopatterning approach to form homogeneously distributed nanostructures (<30 nm) on the faceted, rough surface of polycrystalline chalcogenide thin films. The method, based on selective dissolution of self-assembled and well-defined alkali condensates in water, opens up new research opportunities toward development of thin film solar cells with enhanced efficiency.

A comprehensive picture of Cu doping in CdTe solar cells

The importance of Cu for CdTe solar cell absorber doping has been increasingly recognized in recent years. Currently different models are being discussed how to understand the case of CuCd substitutional doping in polycrystalline CdTe solar cells. In this work, an understanding is developed, which is based on a low concentration deep acceptor doped CdTe layer (Na ∼ 5 × 1014 cm−3, Ea ∼ 300 meV above the valence band). Despite their non-shallow nature, CuCd acceptors are fully or at least heavily (>30%) ionized. The low hole concentration in CdTe (∼1 × 1014 cm−3) originates directly from low Cu solubility in CdTe bulk material and is not caused by partial ionization or compensation as proposed by earlier models. The three to four orders of magnitude difference between bulk acceptor concentration and average Cu concentration in polycrystalline CdTe is attributed to grain boundary segregation of Cu. Our model is derived from substrate and superstrate CdTe solar cell measurements, controlled CdTe doping and qu...

Enhanced Carrier Collection from CdS Passivated Grains in Solution-Processed Cu2ZnSn(S,Se)4 Solar Cells

Solution processing of Cu2ZnSn(S,Se)4 (CZTSSe)-kesterite solar cells is attractive because of easy manufacturing using readily available metal salts. The solution-processed CZTSSe absorbers, however, often suffer from poor morphology with a bilayer structure, exhibiting a dense top crust and a porous bottom layer, albeit yielding efficiencies of over 10%. To understand whether the cell performance is limited by this porous layer, a systematic compositional study using (scanning) transmission electron microscopy ((S)TEM) and energy-dispersive X-ray spectroscopy of the dimethyl sulfoxide processed CZTSSe absorbers is presented. TEM investigation revealed a thin layer of CdS that is formed around the small CZTSSe grains in the porous bottom layer during the chemical bath deposition step. This CdS passivation is found to be beneficial for the cell performance as it increases the carrier collection and facilitates the electron transport. Electron-beam-induced current measurements reveal an enhanced carrier collection for this buried region as compared to reference cells with evaporated CdS.

Hydrogenated indium oxide window layers for high-efficiency Cu(In,Ga)Se2 solar cells

High mobility hydrogenated indium oxide is investigated as a transparent contact for thin film Cu(In,Ga)Se2 (CIGS) solar cells. Hydrogen doping of In2O3 thin films is achieved by injection of H2O water vapor or H2 gas during the sputter process. As-deposited amorphous In2O3:H films exhibit a high electron mobility of ∼50 cm2/Vs at room temperature. A bulk hydrogen concentration of ∼4 at. % was measured for both optimized H2O and H2-processed films, although the H2O-derived film exhibits a doping gradient as detected by elastic recoil detection analysis. Amorphous IOH films are implemented as front contacts in CIGS based solar cells, and their performance is compared with the reference ZnO:Al electrodes. The most significant feature of IOH containing devices is an enhanced open circuit voltage (VOC) of ∼20 mV regardless of the doping approach, whereas the short circuit current and fill factor remain the same for the H2O case or slightly decrease for H2. The overall power conversion efficiency is improved f...

CdTe thin films doped by Cu and Ag - a comparison in substrate configuration solar cells

One of the main problems to be solved in order to raise the efficiency of CdTe solar cells is the low acceptor concentration in polycrystalline CdTe layers which is limiting the open circuit voltage. The commonly used acceptor dopant Cu not only forms rather deep acceptor defects but is also likely to limit the net acceptor concentration due to the formation of compensating donor type defects. In this work, Ag is examined as a possible candidate for improving acceptor concentration in CdTe thin films. Hole density in CdTe layers with varying elemental Ag concentration follows a similar trend as previously reported for Cu doping. In finished solar cells efficiencies up to 11.6 % could be reached using Ag as acceptor dopant. Measurements of hole density, barrier height, space charge region width and depth dependent elemental distribution indicate the similarity of the Ag and Cu doping process.

Progress towards 14% efficient CdTe solar cells in substrate configuration

CdTe solar cells are conventionally grown in superstrate configuration. However, the growth in substrate configuration offers more control of junction properties as recrystallization of CdTe and junction formation with CdS can be decoupled. In this paper the influence of various annealing treatment conditions of the CdS layer on its morphology and phase and on the device properties is presented. The presence of CdCl2 during this annealing treatment is important for the phase change of the CdS layer to hexagonal wurtzite and for high efficiencies. A CdCl2 treatment of the CdS at 360 °C improves the efficiency of the device without the adverse effect of pinhole formation in the CdS. CdTe solar cells in substrate configuration with more than 13% efficiency are achieved as a progress towards 14% efficiency.