Effect of varying process parameters on CdTe thin film device performance and its relationship to film microstructure

The performance of CdTe thin film photovoltaic devices are sensitive to process parameters. In this study, efforts are made to further understand the effects of process parameters like process temperature and variation in cadmium chloride passivation treatment on CdTe films deposited using a sublimation based deposition system. The effects on film microstructure are studied using advanced microstructural characterization methods like TEM, SEM, EDS and SIMS while electrical performance is studied using various electrical measurements such as current density vs. voltage and electroluminescence. The aim of this study is to provide new insight into the understanding of relationship between fabrication process, device performance and thin film microstructure

Characterization of CdTe photovoltaic devices passivated using hydrogen plasma

Thin-film polycrystalline CdTe photovoltaic devices were studied using electrical and material characterization methods to understand the effects of hydrogen plasma passivation treatment. Devices were fabricated using sublimation and were exposed to hydrogen plasma for 10, 20 and 30 minutes. Current density vs voltage measurements were performed to measure the performance of the devices. Capacitance vs voltage graphs showed that dopants are active and the device behaved like a CdCl2 passivated device. Microscopic characterization was performed using SEM and (S)TEM that showed larger grains and more homogenous film coverage as compared to films without passivation suggesting grain growth during H2 passivation

Effect of the cadmium chloride treatment on RF sputtered Cd0.6Zn0.4Te films for application in multijunction solar cells

Single phase Cd0.6 Zn 0.4Te (CdZnTe) films of 1 μm thickness were deposited by radio frequency planar magnetron sputter deposition on commercial soda lime glass samples coated with fluorine-doped tin oxide and cadmium sulphide (CdS). The stack was then treated with cadmium chloride (CdCl2) at different temperatures using a constant treatment time. The effect of the CdCl2 treatment was studied using optical, materials, and electrical characterization of the samples and compared with the as-deposited CdZnTe film with the same stack configuration. The band gap deduced from Tauc plots on the as-deposited CdZnTe thin film was 1.72 eV. The deposited film had good crystalline quality with a preferred orientation along the {111} plane. After the CdCl2 treatment, the absorption edge shifted toward longer wavelength region and new peaks corresponding to cadmium telluride (CdTe) emerged in the x-ray diffraction pattern. This suggested loss of zinc after the CdCl2 treatment. The cross sectional transmission electron microscope images of the sample treated at 400 °C and the energy dispersive elemental maps revealed the absence of chlorine along the grain boundaries of CdZnTe and residual CdTe. The presence of chlorine in the CdTe devices plays a vital role in drastically improving the device performance which was not observed in CdZnTe samples treated with CdCl2. The loss of zinc from the surface and incomplete recrystallization of the grains together with the presence of high densities of stacking faults were observed. The surface images using scanning electron microscopy showed that the morphology of the grains changed from small spherical shape to large grains formed due to the fusion of small grains with distinct grain boundaries visible at the higher CdCl2 treatment temperatures. The absence of chlorine along the grain boundaries, incomplete recrystallization and distinct grain boundaries is understood to cause the poor performance of the fabricated devices

Activation of thin film CdTe solar cells using a cadmium bromide treatment

The activation of CdTe with a cadmium chloride annealing treatment is a vital step in the fabrication of high efficiency solar cells. Thin film MZO/CdTe cells have been activated using CdBr2 instead of CdCl2 with a lower activation process temperature. Using this method, CdBr2 does activate the cell as revealed by J-V and EQE measurements. TEM and EDX elemental maps from device cross-sections confirm that bromine is present in the grain boundaries. TEM shows that the treatment removes stacking faults at 425 °C. CdBr2 treatment resulted in a relatively modest conversion efficiency of 5.49% when treated at 375 °C. Nevertheless, the experiments shed further light on the mechanisms involved in the activation

The effect of a post-activation annealing treatment on thin film CdTe device performance

The cadmium chloride activation treatment of cadmium telluride solar cells is essential for producing high efficiency devices. The treatment has many effects but the most significant is the complete removal of stacking faults in the cadmium telluride grains and the diffusion of Chlorine along the grain boundaries of the device. Chlorine decorates all cadmium telluride and cadmium sulphide grain boundaries and also builds up along the CdTe/CdS junction. . This paper reveals that by annealing devices to temperatures of 400ºC to 480 ºC for times ranging from 30 to 600 seconds in moderate vacuum results in the re-appearance of stacking faults and the removal of Choline from the grain boundaries. STEM analysis confirms the re-appearance of the stacking faults and SIMS and EDX confirm the removal of chlorine from the grain boundaries. This directly corresponds to a lowering in cell efficiency. The study provides further evidence that CdCl2 diffusion and certain microstructural defects directly affect the performance of cadmium telluride photovoltaic devices

Polycrystalline CdSeTe/CdTe absorber cells with 28 mA/cm2 short-circuit current

An 800-nm CdSeTe layer was added to the CdTe absorber used in high-efficiency CdTe cells to increase the current and produce an increase in efficiency. The CdSeTe layer employed had a band gap near 1.41 eV, compared to 1.5 eV for CdTe. This lower band-gap allowed a current increase from approximately 26 to over 28 mA/cm2. Voltage same as earlier demonstrated high efficiency CdTe-only device was maintained. The fill-factor was not significantly affected. Improving the short-circuit current and maintaining the open-circuit voltage lead to device efficiency over 19%. QE implied that the approximately half the current was generated in the CdSeTe layer and half in the CdTe. Cross-section STEM and EDS showed good grain structure throughout and diffusion of Se into the CdTe layer was observed. To the best of authors’ knowledge this is the highest efficiency polycrystalline CdTe photovoltaic device demonstrated amongst universities and national labs

Effect of CdCl2 passivation treatment on microstructure and performance of CdSeTe/CdTe thin-film photovoltaic devices

The effects of the CdCl2passivation treatment on thin-film CdTe photovoltaic films and devices have been extensively studied. Recently, with an addition of CdSeTe layer at the front of the absorber layer, device conversion efficiencies in excess of 19% have been demonstrated. The effects of the CdCl2passivation treatment for devices using CdSeTe has not been studied previously. This is the first reported study of the effect of the treatment on the microstructure of the CdSeTe /CdTe absorber. The device efficiency is < 1% for the as-deposited device but this is dramatically increased by the CdCl2treatment. Using Scanning Transmission Electron Microscopy (STEM), we show that the CdCl2passivation of CdSeTe/CdTe films results in the removal of high densities of stacking faults, increase in grain size and reorientation of grains. The CdCl2treatment leads to grading of the absorber CdSeTe/CdTe films by diffusion of Se between the CdSeTe and CdTe regions. Chlorine decorates the CdSeTe and CdTe grain boundaries leading to their passivation. Direct evidence for these effects is presented using STEM and Energy Dispersive X-ray Analysis (EDX) on device cross-sections prepared using focused ion beam etching. The grading of the Se in the device is quantified using EDX line scans. The comparison of CdSeTe/CdTe device microstructure and composition before and after the CdCl2treatment provides insights into the important effects of the process and points the way to further improvements that can be made

Sputtered aluminum oxide and p+ amorphous silicon back-contact for improved hole extraction in polycrystalline CdSexTe1-x and CdTe photovoltaics

A thin layer of Al2O3 at the back of CdSexTe1-x/CdTe devices is shown to passivate the back interface and drastically improve surface recombination lifetimes and photoluminescent response. Despite this, such devices do not show an improvement in open-circuit voltage (VOC.) Adding a p + amorphous silicon layer behind the Al2O3 bends the conduction band upward, reducing the barrier to hole extraction and improving collection. Further optimization of the Al2O3, amorphous silicon (a-Si), and indiumdoped tin oxide (ITO) layers, as well as their interaction with the CdCl2 passivation process, are necessary to translate these electrooptical improvements into gains in voltag

Local Electronic Structure Changes in Polycrystalline CdTe with CdCl₂ Treatment and Air Exposure

Postdeposition CdCl₂ treatment of polycrystalline CdTe is known to increase the photovoltaic device efficiency. However, the precise chemical, structural, and electronic changes that underpin this improvement are still debated. In this study, spectroscopic photoemission electron microscopy was used to spatially map the vacuum level and ionization energy of CdTe films, enabling the identification of electronic structure variations between grains and grain boundaries (GBs). In vacuo preparation and inert transfer of oxide-free CdTe surfaces isolated the separate effects of CdCl₂ treatment and ambient oxygen exposure. Qualitatively, grain boundaries displayed lower work function and downward band bending relative to grain interiors, but only after air exposure of CdCl₂-treated CdTe. Analysis of numerous space charge regions at grain boundaries showed an average depletion width of 290 nm and an average band bending magnitude of 70 meV, corresponding to a GB trap density of 10¹¹ cm^–2 and a net carrier density of 10¹⁵ cm^–3. These results suggest that both CdCl₂ treatment and oxygen exposure may be independently tuned to enhance the CdTe photovoltaic performance by engineering the interface and bulk electronic structure

Selenium passivates grain boundaries in alloyed CdTe solar cells

Cadmium telluride (CdTe) solar cells have achieved efficiencies of over 22%, despite having absorber layer grain sizes less than 10 μm and hence a very high density of grain boundaries. Recent research has shown that this is possible because of partial passivation of grain boundaries during the widely used cadmium chloride treatment, and passivation of grain interior defects by selenium alloying of the CdTe. Here, state-of-the art TEM-based cathodoluminescence imaging is used to show that, in addition to grain interiors, selenium also passivates grain boundaries in alloyed Cd(Sex,Te1-x) material (CST). Specifically, we find that recombination at CST grain boundaries is up to an order of magnitude lower than at CdTe grain boundaries. This further explains the superior performance of selenium graded CdTe devices and provides potential new routes for further efficiency improvement and solar electricity cost reduction