Transient metastable behavior caused by magnesium-doped zinc oxide emitters in CdSeTe/CdTe solar cells

Metastable behavior in highly efficient MZO/CdSeTe/CdTe solar cells has been reported previously. Different preconditioning procedures have been studied that are used to recover the performance of the devices. 11 wt% of MgO content in the MZO layer has shown to give optimized photovoltaic parameters in the device compared to other MZO compositions. J – V characteristics before preconditioning of the devices with higher MgO content show an “ S ” shaped behavior, which is removed during preconditioning. However, this recovery remained only for 3 days while the devices were stored under vacuum in the dark. Temperature-dependent J – V and capacitance measurements before and after preconditioning revealed the presence of recombination centers and defect levels at the MZO/absorber interface. Previous studies have shown degradation of MZO occurring if the layer is exposed to ambient atmosphere. Hall effect measurements on the MZO films showed no significant changes after any preconditioning or CdCl 2 treatment. Secondary-ion mass spectrometry images show diffusion of oxygen from the MZO layer into the CdSeTe region after CdCl 2 treatments. This likely enables the MZO to function as a buffer layer since it will increase the carrier concentration due to the formation of oxygen vacancies. As-deposited MZO thin films are insulating. However, the oxygen vacancies in the MZO layer also increase its reactivity and instability. </p

Ga-doping of MZO in CdSeTe/CdTe thin film solar cells

Metastable effects in high efficiency MZO/CdSeTe/CdTe solar cells have been studied in an attempt to recover the device performance. Devices with the MZO buffer layer have shown an 'S' shaped behaviour in the J-V characteristics before any preconditioning. This is removed after light soaking under 1000 Wm-2 at 25 °C. However, this recovery remained only for a short period of time while the devices were stored under vacuum in the dark. Recent studies with Ga doping of the buffer MZO has shown the removal of this metastability in the J-V characteristics of CdTe devices can be achieved without light soaking. A significant improvement in conductivity and Hall signal has been measured with Ga doped MZO layers compared to previously measured MZO films. However, a gradual decrease in the Hall signal has been observed over time after films were light soaked and removed from the desiccator.</p

Large area survey grain size and texture optimization for thin film CdTe solar sells using xenon-plasma focused ion beam (PFIB)

Microstructural analysis of high efficiency thin film CdTe solar cells has been obtained over large areas. Analysis regions are device cross-sections approximately 0.325 mm in length. The samples have been prepared using a xenon-plasma focused ion beam (Xe-PFIB). The detailed images of the microstructure were obtained using backscattered electron imaging and electron backscatter diffraction (EBSD). As deposited devices and those with a low level of cadmium chloride treatment both show strong (111) growth texture. A high density of twins is seen in the columnar grains. Three As doped FTO/CdZnS/CdTe with varying process conditions we devices with 13.1 %, 16.3% and 17% conversion efficiency were investigated. Lowest efficiency device was CdCl2 treated at 420°C for 10 minutes while the 16.3 and 17% devices were both treated at 440°C for 10 minutes. The large area analysis revealed a partial recrystallisation state in the 16.3% efficient device which was induced by an incomplete chloride activation process. The analysis confirms that the efficiency of the devices tends to correlate with grain size. It also showed that a strong correlation exists between device efficiency and the randomization of the texture away from the (111) grain orientation. EBSD can be used to survey large areas and to mark out features for more detailed analysis using transmission electron microscopy (TEM). As an example, we show how using an EBSD scanned cross-sectional area can identify a partially recrystallized region which is then extracted and analyzed in detail using TEM

Measurement of band alignment between ZnO based front emitters and CdCl₂ treated CdSeTe/CdTe absorbers

Thin film CdSeTe/CdTe solar cells have achieved > 22% record efficiency and generated solar electricity at a cost as low as 3 US cents per kW.hr in large scale utilities. In this work, the use of ZnO based n-type emitters is considered with the aim of improving the thin film CdSeTe/CdTe photovoltaic device efficiency still further. The measured conduction band offsets (CBOs) between ZnO and CdSeTe are determined to be in the “cliff” conformation. These CBOs will be optimized to achieve a “spike” conformation by incorporating suitable dopants to achieve high device efficiency. This work identifies new pathways to highly efficient ZnO based n-type emitters for arsenic doped CdTe solar cells. In particular, we have identified Sn, Ce and Cs as suitable dopants to generate the preferred ‘spike’ in the band alignment between the emitter layer and the CdSeTe absorber. Suitably doped emitter layers will be used in device research to reduce the deficit in open circuit voltage.</p

Absorber texture and the efficiency of polycrystalline thin film CdTe solar cells

A range of microstructural changes occur during the deposition and activation of CdTe based thin film solar cells. In particular, the cadmium chloride (CdCl2) activation treatment results in wholesale recrystallisation which transforms the conversion efficiency of the solar cell. One of the noticeable effects is the change of preferred orientation of the CdTe absorber. Highly orientated [111] texture is observed in as deposited or under-treated CdTe based devices. Optimized activation results in a more randomized texture and the [111] preferred texture component is significantly weakened. In this paper we use Electron Backscatter Diffraction to characterise absorber cross-sections. The focus is on how randomization of the absorber texture reflects device performance. We have had access to a range of CdTe devices using a variety of deposition techniques. We have observed a clear pattern that shows that devices with a highly orientated [111] texture have poor efficiency. Devices with a randomized texture have much higher efficiency. Here we illustrate this empirical correlation using devices deposited by Metal Organic Chemical Vapour Deposition with a range of efficiencies from 13.1 % to 17 %. We have also included the analysis of an absorber from a 18.7 % high efficiency CdSeTe/CdTe device to show that texture is similarly important in these advanced devices. We have been able to quantify the effect of texture by using multiples of uniform density or (MUD) values from the inverse pole figures. MUD figures close to 1 correlate with highest efficiency. Although the random texture of the absorber microstructure is only one of several important process factors, it appears to be a necessary feature for highest efficiency CdTe-based polycrystalline solar cells.</p

The effect of remnant CdSe layers on the performance of CdSeTe/CdTe photovoltaic devices

Thin film CdTe-based photovoltaic devices have achieved high efficiency above 22 %. The recent improvement in efficiency is due to Se alloying in the CdTe absorbers to form a CdSeTe/CdTe structure. The subsequent band gap grading increases the short circuit current density. The Se can be introduced by depositing a precursor thin film of either CdSe or a CdSeTe alloy and then diffusing the Se into the CdTe during the high temperature cadmium chloride activation process. Using CdSe is preferred because it is easier to control the Se concentration. However, during fabrication of the CdSeTe/CdTe devices, the CdSe thickness needs to be precisely controlled to prevent the retention of a CdSe remnant layer after the activation treatment. Retention of a remnant CdSe layer causes a dramatic reduction in device efficiency. In this work, we show that the reduction in efficiency is caused by a number of factors. The remnant CdSe layer is n-type which moves the position of the p-n junction. Also, it is widely thought that the CdSe remnants are photo-inactive. In this work, we clarify that the individual CdSe grains are actually highly photo-active. However, the grain sizes in the CdSe remnant and the adjacent CdSeTe layer are very small resulting in a high grain boundary area. Although the grain boundaries are passivated with chlorine, cathodoluminescence imaging and electrical measurements show that this is only partially effective. Also, EQE measurements show that the remnant CdSe causes parasitic absorption. Overall, the remnant CdSe layer causes a reduction in short circuit current density and device efficiency. The thickness of the CdSe precursor layer and the cadmium chloride activation process conditions must be precisely optimised to ensure that all the CdSe is consumed and inter-diffused to form the CdSeTe alloy for highest efficiency devices.</p

Achieving 21.4% efficient CdSeTe/CdTe solar cells using highly resistive intrinsic ZnO buffer layers

In this study, the use of intrinsic and highly insulating ZnO buffer layers to achieve high conversion efficiencies in CdSeTe/CdTe solar cells is reported. The buffer layers are deposited on commercial SnO2:F coated soda‐lime glass substrates and then fabricated into arsenic‐doped CdSeTe/CdTe devices using an absorber and back contact deposited by First Solar. The ZnO thickness is varied from 30 to 200 nm. The devices incorporating a 50 nm ZnO buffer layer achieved an efficiency of 21.23% without an anti‐reflection coating. An improved efficiency of 21.44% is obtained on a substrate with a multilayer anti‐reflection coating deposited prior to device fabrication. The highly efficient ZnO based devices are stable and do not develop anomalous J‐V behavior following environmental tests. High resolution microstructural analysis reveals the formation of a high‐quality ZnO/CdSeTe interface. Unusually, chlorine is not detected as a discrete layer at the interface, these observations point to a high‐quality interface. The extrapolation of Voc to 0 K indicates that interface recombination dominates, suggesting that further improvement is possible. Using device modeling, an attempt is made to understand how this type of device performs so well.</p