• Energy Research

Making use of previously designed and experimentally tested results of graded bandgap devices, and the comprehensive electrodeposition of semiconducting materials knowledge, a three layer n-n-p device structure was fabricated and tested for their electronic properties and solar cell performance. Glass/FTO/n-CdS/n-CdTe/p-CdTe/Au devices were fabricated and studied as a first step towards development\ud of graded bandgap devices using electroplated materials. Efficiencies up to 15.3% were observed for lab-scale small devices.

All-electrodeposited ZnS, CdS and CdTe thin layers have been incorporated in a graded bandgap solar cell structure of glass/FTO/n-ZnS/n-CdS/n-CdTe/Au have been fabricated and an average conversion efficiency of 14.18% was achieved under AM1.5 illuminated condition. Based on former work in which 10% conversion efficiency was reported, optimisation has been made to the semiconductor layers, precursors, thicknesses and the post-growth treatment. These results demonstrate the advantages of multi-layer graded bandgap device configuration and the inclusion of gallium based post-growth treatment (CdCl2+Ga2(SO4)3) on the CdS/CdTe-based device structure. The fabricated devices were characterised using both current-voltage (I-V) and capacitance-voltage (C-V) techniques. Under dark I-V condition, a rectification factor (R.F.) of 104.8, ideality factor (n) of 1.60 and a barrier height (ϕb) >0.82 eV were observed. Under AM1.5 illuminated I-V condition, short-circuit current density (Jsc) of 34.08 mAcm-2, open-circuit voltage (Voc) of 730 mV, fill-factor (FF) of 0.57 and conversion efficiency of 14.18% were observed. Under dark C-V condition, doping density (ND) of 7.79×1014 cm-3 and a depletion width (W) of 1092 nm were achieved. In addition, the work demonstrates the capability of two-electrode system as a simplification to the conventional three-electrode system in the electrodeposition of semiconductors.

In this study, a two-electrode electrodeposition technique was employed to grow thin films of antimony selenide (Sb2Se3) on glass/fluorine-doped tin oxide (FTO) substrates. The highest quality thin films were consistently obtained within the range of 1600 mV to 1950 mV. Subsequent electrodeposition experiments were conducted at discrete voltages to produce various layers of thin films. Photoelectrochemical cell (PEC) measurements were performed to characterize the semiconductor material layers, leading to the identification of both p-Type and n-Type conductivity types. Optical absorption spectroscopic analysis revealed energy bandgap values ranging from 1.10 eV to 1.90 eV for AD-deposited Sb2Se3 samples and 1.08 eV to 1.68 eV for heat-treated Sb2Se3 samples, confirming the semiconducting nature of the Sb2Se3 material. Additionally, other characterization techniques, including X-ray diffraction analysis, reveal that the AD-deposited layers are almost amorphous, and heat treatment shows that the material is within the orthorhombic crystalline system. Heat-treated layers grown at ~1740 mV showed highly crystalline material with a bandgap nearing the bulk bandgap of Sb2Se3. Raman spectroscopy identified vibrational modes specific to the Sb2Se3 phase, further confirming its crystallinity. To explore the thin-film morphology, Scanning Electron Microscopy (SEM) was employed, revealing uniformly deposited material composed of grains of varying sizes at different voltages. Energy Dispersive X-ray analysis (EDX) confirmed the presence of antimony and selenium in the material layers.

In order to produce high efficiency solar cells based on CdTe, CdCl2 post-growth treatment is an essential processing step. This treatment can be further improved by adding elements such as Fluorine and Gallium into the CdCl2 solution. Through systematic experimentation, it has been found that the pH value of the treatment solution also affect the conversion efficiency of the solar cells. This work therefore focuses on the effect of pH value of CdCl2+Ga2(SO4)3 aqueous solution on the device efficiencies. The graded bandgap device structure, glass/FTO/n-ZnS/n-CdS/n-CdTe/Au was used in this work. The pH values of 1.00, 2.00 and 3.00 for CdCl2+Ga2(SO4)3 solutions were utilised for the activation of glass/FTO/n-ZnS/n-CdS/n-CdTe layers and its effects were explored for both the CdTe material and device properties. It has been found that both CdTe material properties and solar cell device properties are superior when the pH value of 2.00 is used for post-growth treatment. The best conversion efficiency observed in this work for the above graded bandgap device is 12.2%.

A 3-layer graded-bandgap solar cell with glass/FTO/ZnS/CdS/CdTe/Au structure has been fabricated using all-electrodeposited ZnS, CdS and CdTe thin layers. The three semiconductor layers were electrodeposited using a two-electrode system for process simplification. The incorporation of a wide bandgap amorphous ZnS as a buffer/window layer to form glass/FTO/ZnS/CdS/CdTe/Au solar cell resulted in the formation of this 3-layer graded-bandgap device structure. This has yielded corresponding improvement in all the solar cell parameters resulting in a conversion efficiency >10% under AM1.5 illumination conditions at room temperature, compared to the 8.0% efficiency of a 2-layer glass/FTO/CdS/CdTe/Au reference solar cell structure. These results demonstrate the advantages of the multi-layer graded-bandgap device architecture over the conventional 2-layer structure. In addition, they demonstrate the effective application of the two-electrode system as a simplification to the conventional three-electrode system in the electrodeposition of semiconductors with the elimination of the reference electrode as a possible impurity source.

Electrochemical deposition and characterization of nanocrystallite-CdS thin films for thin film solar cell application are reported. The two-electrode system used provides a relatively simple and cost-effective approach for large-scale deposition of semiconductors for solar cell and other optoelectronic device application. Five CdS thin films were deposited for 45 minutes each at different cathodic deposition voltages in order to study their properties. X-ray diffraction study reveals that the as-deposited films contain mixed phases of hexagonal and cubic CdS crystallites with large amounts of internal strain and dislocation density. Postdeposition annealing results in phase transformation which leaves the films with only the hexagonal crystal phase and reduced strain and dislocation density while increasing the crystallite sizes from 21.0–42.0 nm to 31.2–63.0 nm. Photoelectrochemical cell study shows that all the CdS films have n-type electrical conductivity. Optical characterization reveals that all samples show similar transmittance and absorbance responses with the transmittance slightly increasing towards higher growth voltages. All the annealed films show energy bandgap of 2.42 eV. Scanning electron microscopy and energy dispersive X-ray analyses show that grains on the surface of the films tend to get cemented together after annealing with prior CdCl2 treatment while all the films are S-rich.

This review paper summarises the key issues of CdTe and CdS/CdTe solar cells as observed over the past four decades, and focuses on two growth techniques, electrodeposition (ED) and closed space sublimation (CSS), which have successfully passed through the commercialisation process. Comprehensive experience in electrical contacts to CdTe, surfaces & interfaces, electroplated CdTe and solar cell development work led to the design and experimentally test grading of band gap multilayer solar cells, which has been applied to the CdS/CdTe structure. This paper presents the consistent and reproducible results learned through electroplated CdTe and devices, and suggestions are made for achieving or surpassing the record efficiency of 22.1% using the CSS material growth technique.