Optimization of Two Stage Process for the Growth of In2S3 , CuInSe2 and CuIn (Sel-xSx)2Thin Films for Solar Cell Application

Two stage processes consisting of precursor preparation by thermal evaporation followed by chalcogenisation in the required atmosphere is found to be a feasible technique for the PV materials such as n-Beta In2S3, p-CulnSe2, p-CulnS2 and p-CuIn(Sel_xSx)2. The growth parameters such as chalcogenisation temperature and duration of chalcogenisation etc have been optimised in the present study.Single phase Beta-In2S3 thin films can be obtained by sulfurising the indium films above 300°C for 45 minutes. Low sulfurisation temperatures required prolonged annealing after the sulfurisation to obtain single phase Beta-1n2S3, which resulted in high material loss. The maximum band gap of 2.58 eV was obtained for the nearly stoichiometric Beta-In2S3 film which was sulfurised at 350°C. This wider band gap, n type Beta-In2S3 can be used as an alternative to toxic CdS as window layer in photovoltaics .The systematic study on the structural optical and electrical properties of CuInSe2 films by varying the process parameters such as the duration of selenization and the selenization temperature led to the conclusion that for the growth of single-phase CuInSe2, the optimum selenization temperature is 350°C and duration is 3 hours. The presence of some binary phases in films for shorter selenization period and lower selenization temperature may be due to the incomplete reaction and indium loss. Optical band gap energy of 1.05 eV obtained for the films under the optimum condition.In order to obtain a closer match to the solar spectrum it is desirable to increase the band gap of the CulnSe2 by a few meV . Further research works were carried out to produce graded band gap CuIn(Se,S)2 absorber films by incorporation of sulfur into CuInSe2. It was observed that when the CulnSe2 prepared by two stage process were post annealed in sulfur atmosphere, the sulfur may be occupying the interstitial positions or forming a CuInS2 phase along with CuInSe2 phase. The sulfur treatment during the selenization process OfCu11 ln9 precursors resulted in Culn (Se,S)2 thin films. A band gap of 1.38 eV was obtained for the CuIn(Se,S)2.The optimised thin films n-beta 1n2S3, p-CulnSe2 and p-Culn(Sel-xSx)2 can be used for fabrication of polycrystalline solar cells.

Antioxidant enzyme activity in Acidithiobacillus ferrooxidans LR maintained in contact with chalcopyrite

The total protein content and activity of the enzymes glutathione reductase (GR), superoxide dismutase (SOD) and thioredoxin reductase (TrxR) were evaluated in Acidithiobacillus ferrooxidans LR cells maintained in contact with the metal sulfide chalcopyrite for 1 and 10 days. A significant decrease in total protein content was observed in cells maintained for 10 days in the presence of chalcopyrite, suggesting proteolytic breakdown clue to exposure to the metal sulfide. Following 10 clays of contact with chalcopyrite, increases in GR, SOD and TrxR activities were detected, suggesting the formation of reactive oxygen species. After ten clays, there was a fivefold increase in GR activity, of which, isoenzyme IV represented approximately 82% of the total. An increase in Fe-SOD activity following ten days exposure to chalcopyrite was also determined, as measured on non-denaturing polyacrylamide gels. Also, after 10 days. an approximately 31-fold increase was observed for TrxR activity. The presence of oxidative stress when A. ferrooxidans is in the presence of chalcopyrite could have a negative impact on bioleaching. (C) 2010 Elsevier Ltd. All rights reserved.

Spectroscopic ellipsometry study of the In1-x Gax Asy P1-y / InP Heterojunctions grown by metalorganic chemical-vapor deposition

The dielectric functions of InP, In0.53Ga0.47As, and In0.75Ga0.25As0.5P0.5 epitaxial layers have been measured using a polarization modulation spectroscopic ellipsometer in the 1.5 to 5.3 eV region. The oxide removal procedure has been carefully checked by comparing spectroscopic ellipsometry and x ray photoelectron spectroscopy measurements. These reference data have been used to investigate the structural nature of metalorganic chemical vapor deposition grown In0.53Ga0.47As/InP and In0.75Ga0.25As0.5P0.5/InP heterojunctions, currently used for photodiodes and laser diodes. The sharpness of the interfaces has been systematically compared for the two types of heterojunctions: In1 xGaxAsy/InP and InP/In1 xGaxAsyP1 y. The sharpest interface is obtained for InP growth on In0.75Ga0.25As0.5P0.5 where the interface region is estimated to be (10±10) Å thick. The importance of performing in situ SE measurements is emphasized.

Optimization of the use of carbon paste electrodes (CPE) for electrochemical study of the chalcopyrite

The use of carbon paste electrodes (CPE) of mineral sulfides can be useful for electrochemical studies to overcome problems by using massive ones. Using CPE-chalcopyrite some variables were electrochemically evaluated. These variables were: (i) the atmosphere of preparation (air or argon) of CPE and elapsed time till its use; (ii) scan rate for voltammetric measurements and (iii) chalcopyrite concentration in the CPE. Based on cyclic voltammetry, open-circuit potential and electrochemical impedance results the recommendations are: oxygen-free atmosphere to prepare and kept the CPE until around two ours, scan rates from 10 to 40 mV s-1, and chalcopyrite concentrations > 20%.

Investigation of structural, optical and electrical properties and valence band splitting in cu-ln-se compounds

Investigations on thin films that started decades back due to scientific curiosity in the properties of a two-dimensional solid, has developed into a leading research field in recent years due to the ever expanding applications of the thin films in the fann of a variety of active and passive microminiaturized components and devices, solar cells, radiation sowces and detectors, magnetic memory devices, interference filters, refection and antireflection coatings etc. [1]. The recent environment and energy resource concerns have aroused an enonnous interest in the study of materials in thin film form suitable for renewable energy sources such as photovoltaic devices. Recognition of the immense potential applications of the chalcopyrites that can fonn homojunctions or heterojunctions for solar cell fabrication has attracted many researchers to extensive and intense research on them. In this thesis, we have started with studies performed on CuInSe, thin films, a technologically well recognized compound belonging to the l•ill-VI family of semiconductors and have riveted on investigations on the preparation and characterization of compoWlds Culn3Se5. Culn5Seg and CuIn7Se12, an interesting group of compounds related to CuInSe2 called Ordered Vacancy Compounds, having promising applications in photovoltaic devices. A pioneering work attempted on preparing and characterizing the compound Culn7Sel2 is detailed in the chapters on OVC's. Investigation on valence band splitting in avc's have also been attempted for the first time and included as the last chapter in the thesis. Some of the salient features of the chalcopyrite c.ompounds are given in the next section .of this introductory chapter.

Gene expression modulation by chalcopyrite and bornite in Acidithiobacillus ferrooxidans

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Differential proteomic analysis of Acidithiobacillus ferrooxidans cells maintained in contact with bornite or chalcopyrite: Proteins involved with the early bacterial response

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Optimization of the use of carbon paste electrodes (CPE) for electrochemical study of the chalcopyrite

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electrochemical noise analysis of chalcopyrite carbon paste electrodes by Acidithiobacillus ferrooxidans

The electrochemical response of chalcopyrite was studied using electrochemical noise analysis (ENA). The assay was carried out under constant aeration using 30 mL in two electrochemical cells containing iron-free mineral salts solution. These cells were initially monitored for 56 hours, After 72 hours, 7.25x 10(10) cells mL(-1) of A, ferrooxidans strain LR were added in both cells and monitored until 128 h. Subsequent to this period, 0.927 mmol L-1 of silver ions and 400 mmol L-1 of chloride ions were added each one separately. Both conditions were monitored until 168 hours. According to results obtained, it was observed that Cl- ions addition induced an accelerated corrosion process. However, there is a tendency of the system to reach the stationary state due to repassivation of the electrodic surface. In the other side, the Ag+ addition contributed for the maintenance of the oxidant atmosphere, in spite of controversial effect caused by considerable variations in the R-n values, resulting in a instability in the chalcopyrite reactivity.

Oxidative dissolution of chalcopyrite by Acidithiobacillus ferrooxidans analyzed by electrochemical impedance spectroscopy and atomic force microscopy

The microbiological leaching of chalcopyrite (CuFeS2) is of great interest because of its potential application to many CuFeS2-rich ore materials. However, the efficiency of the microbiological process is very limited because this mineral is one of the most refractory to bacterial attack. Knowledge of bacterial role during chalcopyrite oxidation is very important in order to improve the efficiency of bioleaching operation. The oxidative dissolution of a massive chalcopyrite electrode by Acidithiobacillus ferrooxidans was evaluated by electrochemical impedance spectroscopy (EIS) and atomic force microscopy (AFM). A massive chalcopyrite electrode was utilized in a Tait-type electrochemical cell in acid medium for different immersion times in the presence or absence of bacterium. The differences observed in the impedance diagrams were correlated with the adhesion process of bacteria on the mineral surface. (C) 2004 Elsevier B.V. All rights reserved.

Oxidation of chalcopyrite by Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans in shake flasks

Chalcopyrite oxidation was evaluated with two acidophilic thiobacilli that are important in bioleaching processes. Acidithiobacillus thiooxidans in pure culture did not oxidize CuFeS2 but oxidized externally added S in the presence of CuFeS2. Acidithiobacillus ferrooxidans released Cu2+ and soluble Fe from chalcopyrite, and the time course lead to a gradual passivation of chalcopyrite whereby Cu2+ dissolution leveled off. Fe3+ acted as a chemical oxidant in CuFeS2 leaching and was reduced to Fe2+. Parallel bacterial re-oxidation of Fe2+ contributed to a high Fe3+/Fe2+ ratio and an increase in redox potential. Chemical oxidation of chalcopyrite was slow compared with A. ferrooxidans-initiated solubilization. X-ray analysis revealed new solid phases: (i) jarosite, found in solids from A. ferrooxidans cultures and in chemical controls that initially received Fe2+ or Fe3+, and (ii) S-0, found mostly in iron-amended A. ferrooxidans culture and the corresponding chemical controls. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Oxidative dissolution of chalcopyrite by Thiobacillus ferrooxidans

The oxidative dissolution of research-grade chalcopyrite was characterized in respirometric and growth experiments with Thiobacillus ferrooxidans. In respirometric experiments with chalcopyrite, the pH of mineral salts medium increased to values that inhibited the oxygen uptake activity of T. ferrooxidans. In glycine-H 2SO 4 buffered medium the pH remained stable and oxygen uptake was not inhibited. In cultures growing with chalcopyrite as the sole source of energy, pH changes were only minor during the incubation. The redox potential values increased to about 600 mV during the bacterial oxidation of chalcopyrite in the presence and absence of additional Fe 2+, while they remained at about 350 mV in abiotic control flasks. Iron in chalcopyrite was solubilized and oxidized to Fe 3+ by T. ferrooxidans. In the abiotic controls, by comparison, less iron was solubilized and it remained as Fe 2+. Jarosite was a major solid- phase product in T. ferrooxidans cultures. The solub'flization of copper from chalcopyrite in inoculated flasks was enhanced in the presence of additional Fe 2+.Accumulation of S 0, reflecting partial oxidation of the S-entity of chalcopyrite, was apparent from the x-ray diffraction analysis of solid residues from the inoculated flasks as well the abiotic controls. © 1997 Elsevier B.V. All rights reserved.

Chalcopyrite and bornite differentially affect protein synthesis in planktonic cells of Acidithiobacillus ferrooxidans

Acidithiobacillus ferrooxidans is used in bioleaching industrial operations to recover metal ions from mineral sulfides. Chalcopyrite and bornite are copper sulfides that have the same elemental composition, but differ in their susceptibility to the bioleaching process. Our objective was to identify differentially expressed proteins in A. ferrooxidans LR cells exposed to chalcopyrite or bornite, as a sole energy source, for 24 hours. Compared to the control (without minerals), proteins were induced or repressed in planktonic cells after contact with chalcopyrite or bornite by 24 hours. These results demonstrated that the time of exposure to the copper minerals was enough to trigger distinct responses in the A. ferrooxidans metabolism. © 2007 Trans Tech Publications.

A preliminary differential proteomic analysis of the periplasmic fraction in Acidithiobacillus ferrooxidans planktonic and attached cells exposed to chalcopyrite

The Acidithiobacillus ferrooxidans periplasmic space is known to have proteins involved in the respiratory chains. There are no reports about the expression of the periplasmic proteins in A. ferrooxidans cells attached to chalcopyrite. In this preliminary work, it was compared the periplasmic protein profiles of A. ferrooxidans planktonic and attached cells after exposure to chalcopyrite for 2 hours. The bacterial response to chalcopyrite was investigated by a proteomic approach (two- dimensional gel electrophoresis and mass spectrometry). Four proteins differentially expressed between planktonic and attached cells after exposure to chalcopyrite were identified. Two of these proteins, repressed in chalcopyrite- attached cells, were both identified as superoxide dismutase, whereas the single strand binding protein (SSB) and the PspA/IM30 protein were induced. These results showed that A. ferrooxidans chalcopyrite- attached and planktonic cells show differential expression of the periplasmic proteins and that a proteomic approach can provide a valuable tool to detect proteins related to the A. ferrooxidans response to attachment to the mineral substrates. © (2009) Trans Tech Publications.