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Although the cadmium chloride treatment is an essential process for high efficiency thin film cadmium telluride photovoltaic devices, the precise mechanisms involved that improve the cadmium telluride layer are not well understood. In this investigation we apply advanced micro-structural characterization techniques to study the effect of varying the time of the cadmium chloride annealing treatment on the micro-structure of cadmium telluride solar cells deposited by close spaced sublimation (CSS) and relate this to cell performance. A range of techniques has been used to observe the morphological changes to the micro-structure as well as the chemical and crystallographic changes as a function of treatment parameters. Electrical tests that link the device performance with the micro-structural properties of the cells have also been undertaken. Techniques used include Transmission Electron Microscopy (TEM) for sub-grain analysis and XPS for composition-depth profiling. The study provides a new insight in to the mechanisms involved in the initiation and the subsequent complete re-crystallization of the cadmium telluride layer.
It is well known that the cadmium chloride annealing treatment is an essential step in the manufacture of efficient thin film cadmium telluride solar cells. It has been recognized that the combination of annealing at ∼4000C together with the addition of cadmium chloride at the surface induces re-crystallisation of the cadmium telluride layer and also affects the n-type cadmium sulfide. We have applied advanced micro-structural characterization techniques to distinguish the effect of the annealing and the cadmium chloride treatments on the properties of the cadmium telluride deposited via close space sublimation (CSS) and relate these observations to device performance. Transmission electron microscopy (TEM) has shown a variation in stacking fault density with annealing temperature and annealing time. Stacking faults observed within the cadmium telluride grains in TEM were partially removed post annealing; these findings show that temperature alone has a role in the reduction of stacking faults. However, since we have previously observed almost complete removal of stacking faults with annealing in combination with cadmium chloride, the cadmium chloride is essential to defect removal and high efficiency cells.
A new magnetron sputtering strategy is introduced that utilizes high plasma density (~5mA.cm-2) to avoid or reduce high temperature processing. The technique uses magnetrons of opposing magnetic polarity to create a “closed field” in which the plasma density is enhanced without the need for high applied Voltages. A batch system has been used which employs a rotating vertical drum as the substrate carrier and a symmetrical array of linear magnetrons. The magnetrons are fitted with target materials for each of the thin films required in the photovoltaic (PV) stack including the CdTe absorber layer, CdS window layer, metal contact using the conventional superstrate configuration. The “closed field” sputtering technology allows scale up not only for larger batch system designs but it is also configurable for “in-line” or “roll to roll” formats for large scale production. The morphology of each of the layers is characterized using a variety of structural and optical techniques including Field Emission Gun SEM and X-ray diffraction (XRD).
ZnSe:Cl epilayers have been grown on (100) GaAs by MBE using a Zn to Se beam flux ratio of 2:1 and substrate temperatures as low as 225 °C. The ZnSe:Cl epilayers are highly conducting and exhibit bright blue-violet edge luminescence at 300 K. A mobility of 2480 cm2 /V-s at 40 K was measured for an n-type ZnSe:CI film that was Cl-doped to ∼2.3×1017 cm−3 and for which a compensation ratio (NA/ND) of ∼3% was calculated. Carrier concentrations as large as 6.7×1018cm−3 were obtained by increasing the temperature of the MBE oven containing the C1 dopant.
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