Doctor of Philosophy Urmila K. S
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An investigation on the optoelectronic and thermoelectric properties of reactive evaporated degenerate and non degenerate p-type semiconducting compound selenide thin films for photovoltaic and thermoelectric applications Thesis submitted to Cochin University of Science and Technology in partial fulfilment of the requirements for the award of the degree of Doctor of Philosophy By Urmila K. S Solid State Physics Division Department of Physics Cochin University of Science and Technology Kochi – 682022, Kerala, India June 2016 An investigation on the optoelectronic and thermoelectric properties of reactive evaporated degenerate and non degenerate p-type semiconducting compound selenide thin films for photovoltaic and thermoelectric applications Ph.D thesis in the field of Material Science Submitted by: Urmila K. S Solid State Physics Division Department of Physics Cochin University of Science and Technology Kochi – 682022, Kerala, India Email: [email protected] Research Supervisor: Dr. B. Pradeep Professor Solid State Physics Division Department of Physics Cochin University of Science and Technology Kochi – 682022, Kerala, India Email: [email protected] June 2016 Department of Physics Cochin University of Science and Technology Kochi– 682022, Kerala, India Dr. B. Pradeep Professor Certified that the work presented in the thesis entitled “AAn investigation on the optoelectronic and thermoelectric properties of reactive evaporated degenerate and non degenerate p-type semiconducting compound selenide thin films for photovoltaic and thermoelectric applications” is a bonafide record of research done by Ms. Urmila K. S, under my guidance and supervision at Department of Physics, Cochin University of Science and Technology, Kochi, Kerala, India. The work presented in this thesis has not been included in any other dissertation submitted previously for the award of any other degree, diploma, associateship or any other title or recognition from any University/Institution. All the relevant corrections and modifications suggested by the audience during the pre-synopsis seminar and recommended by the doctoral committee of the candidate has been incorporated in the thesis. Kochi - 682022 Prof. B. Pradeep Date: 06.06.2016 (Research Supervisor) Phone: +91 0484 2577404 Fax: +91 0484 2862459 Email: [email protected] DECLARATION I hereby declare that the work presented in the thesis entitled “AAn investigation on the optoelectronic and thermoelectric properties of reactive evaporated degenerate and non degenerate p-type semiconducting compound selenide thin films for photovoltaic and thermoelectric applications” is based on the original research work done by me under the guidance and supervision of Dr. B. Pradeep, Professor, Department of Physics, Cochin University of Science and Technology, Kochi, Kerala, India. The work presented in this thesis has not been included in any other dissertation submitted previously for the award of any other degree, diploma, associateship or any other title or recognition from any University/Institution. Kochi - 682022 Urmila K. S Date: 06.06.2016 Acknowledgement Above all, I thank the Almighty GOD for having been with me throughout as a constant source of motivation and guiding strength and for enabling me to complete my research work successfully. My foremost and utmost gratitude goes to my research supervisor Prof. B. Pradeep, who, in spite of all responsibilities and duties, found time to share his expertise and knowledge with me. It is my proud privilege to express my deep sense of gratitude for his gentle and inspiring guidance, expert advice, good suggestions, patience and understanding nature. I am extremely thankful to him for the encouragement, kindness and moral support extended to me during the tough times of my research work. I extend my sincere thanks to Prof. S. Jayalekshmi, Head of the Department and all the former Heads of the Department for allowing me to use the facilities necessary for the work. I am extremely grateful to all the faculty members of the department for their helpful attitude and constant support. I am thankful to all the office staff, laboratory staff and library staff for their timely help and cooperation. I specially appreciate the sincere support of Dr. Rachel Reena Philip, Assistant Professor, Department of Physics, Union Christian College, Aluva. I am deeply indebted to her for the valuable advice, good comments, encouragement and constant prayers that have helped me a lot during the course of the study. I remember with utmost thanks the help, advice and kind support extended to me by Mrs. Rajani Jacob, Research Scholar, Department of Physics, Union Christian College, Aluva. I am extremely grateful to all the scientists at University Grants Commission-Department of Atomic Energy (UGC-DAE) Consortium for Scientific Research, Indore, for allowing me to use the experimental facilities related to my work. Especially, I would like to thank, Dr. T. Shripathi for helping me with X-ray photoelectron spectroscopy (XPS) measurements, Dr. V. Ganesan for atomic force microscopy (AFM) measurements, Dr. G. S. Okram for thermoelectric power measurements, Dr. R. Rawat for electrical conductivity measurements and Dr. A. M. Awasthi for thermal conductivity measurements. I acknowledge all the scientists at Sophisticated Test and Instrumentation Centre (STIC) at Cochin University of Science and Technology (CUSAT), in particular, Dr. Shibu. M. Eappen for his timely assistance with energy dispersive analysis of X-rays (EDAX) and scanning electron microscopy (SEM) analysis. I acknowledge the financial assistance from CUSAT in the form of research fellowship for the initial two years and UGC for providing research fellowship in science for meritorious students (RFSMS) for the remaining years of my study. I would like to express my sincere and special thanks to my seniors, Mrs. Namitha Asokan T and Mrs. Reena Rajan for the care and concern they have shown towards me and for helping me during the initial phase of my research work. I thank my labmates: Mr. Anuroop R, Mr. Abhilash A, Mr. Sreejith P and Mrs. Hiba Rahman E, for extending all sorts of help whenever necessary during the various stages of my research work. I owe a word of thanks to all the M.Sc and M.Phil students who joined our laboratory from time to time for their kind acts of love. I acknowledge the cooperative and helpful attitude of all my fellow research scholars in the department. Words are not enough to express my love to my parents: My father and My mother. I express my deepest gratitude to them for their constant prayers, love, care, patience, encouragement to pursue my interests and continuing support to complete my research work. I recognize with sincere appreciation all my relatives and friends for the generous and kind support they offered me to make my study a success. Last but not the least, I would like to thank everyone who was important to the successful completion of my research work. Urmila K. S Dedicated to My Parents....... Preface The use of energy in our day to day life has grown exponentially and conserving energy to meet the world’s escalating energy demands is the need of the hour. During the past decade there is a heightened awareness all over the world that the production costs of energy from coal, oil and natural gas is increasingly higher and at the same time the energy technologies involving their use are contributing to a serious rise in the greenhouse gases in the environment and a consequent global warming. As a result, more attention is focused on the utilization of clean energy technologies, especially solar energy which has a great potential to meet a large fraction of world’s energy demands using photovoltaics (PV). The heart of the PV system that efficiently convert sunlight directly into electricity through photovoltaic effect is the solar cell - originally developed for space applications in the 1950s, are now used in consumer products, mounted on roofs of houses or assembled into large power stations. The leading technology in the commercial production of solar cells is based on silicon wafers. However the expensive nature of crystalline silicon is not likely to meet the substantial cost reductions that are necessary for large scale production of solar cells. This scenario has paved way for the entry of thin film solar cell modules into the solar market with the idea of fabricating cheaper solar cells. However, substantial research and technological advancements in thin film PV cells has started with the advent of the chalcogenide compounds – compounds comprising of heavier chalcogens (especially sulphides, selenides and tellurides). In particular, the thin film PV built on the chalcogenide materials such as CdTe, CdS, Cu(In,Ga)(S,Se)2 has become a product of high demand in the past years and its production keeps growing. But extensive research is necessary to further develop these PV materials and to make them competitive with the other state-of-the-art materials. On the other hand, out of the world’s huge primary energy consumption, more than 60% of the installed primary energy is dissipated as waste heat into the environment. This invokes serious environmental hazards such as increase in CO2 emissions and consequently an alarming rise in atmospheric temperature. Therefore the efficient reuse of waste heat is urgently required to save our society and to sustain the world’s enormous energy consumption. The environmental concern over the existing refrigerants is another serious issue. The outcome of widespread research on the reuse of discarded heat and viable alternate refrigerant resulted in the development of thermoelectrics (TE) which uses a thermoelectric module - a device that converts heat into electricity through Seebeck effect or electricity into cooling through Peltier effect. It is interesting to note that, most of the well established and emerging TE materials are based on chalcogenide compounds in the form of crystals, thin films or alloys. The prime candidates of TE technology are based on tellurides such as Bi2Te3, PbTe, SnTe and so on. But Te is scarce and expensive and it becomes necessary to opt for better alternatives that can replace Te based TE devices in the near future.