Development of the low bandgap materials Ge:H and GeSn:H by plasma enhanced chemical vapor deposition

Abstract

The development in solar cells began with wafer based cells, also called the first generation photovoltaic technology. Most of these wafer based cells were made of crystalline silicon. As a crystalline silicon cell must be relatively thick to absorb most of the incoming energy, the second generation (thin film solar cells) was introduced. In the third generation the focus is more on achieving high efficiencies at low production costs. A way to achieve higher efficiencies is by the use of multi-junction devices. In such devices, different sub cells are stacked onto each other and in this way a larger part of the solar spectrum can be utilized. Moreover, the fabrication costs of multi-junction devices can significantly be reduced by using a cheap processing technique, like plasma enhanced chemical vapor deposition (PECVD).

When germanium and germanium-tin are passivated by hydrogen atoms, Ge:H has its theoretical bandgap in the 0.9-1.1eV range and GeSn:H its bandgap in the 0.6-1.0eV range. The use of such low bandgap materials facilitates absorption of photons in the infrared spectrum, what reduces the non-absorption losses. Their low bandgaps make them perfect candidates to act as the absorber material in a bottom cell in a multi-junction device. Both materials can also be processed by PECVD.

In this thesis about 100 Ge(Sn):H films were PECVD processed in the CASCADE reactor located in the Else Kooi Lab. The objective was optimizing the plasma conditions to obtain device quality thin films. A device quality bottom cell material must fulfil some requirements, like having a low bandgap, being intrinsic and having a high photo response. The influence of various deposition parameters was investigated to characterize their effect on the material properties.

It was found that a densification of Ge(Sn):H generally lead to lower bandgap energies. Densification of these materials can be caused by increasing the substrate temperature (in the 250-300°C range). Next to this, a decrease in hydrogen dilution (in the 100-400 range) also leads to lower bandgap energies for the amorphous Ge(Sn):H films. By combining a substrate temperature of 290°C with a hydrogen dilution of 100, promising a-Ge:H films were processed containing refractive indexes above 5.3, optical bandgap energies below 1.1eV, activation energies above 330meV and dark conductivities below 5∙10-4 Ω-1cm-1. The material properties of the processed a-GeSn:H films were even closer to a device quality bottom cell material. Nevertheless, processing device quality GeSn:H layers remains challenging. Adding relatively large amounts of tetramethyltin (TMT) into the plasma chamber led to clusters of tin and significant oxygen and carbon concentrations throughout the layer. Managing the atomic carbon, oxygen, germanium and tin fractions could be crucial in obtaining device quality bottom cell absorber layers based on GeSn:H in the future.