18 resultados para ATOMIC-FORCE SPECTROSCOPY

em Cochin University of Science


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In recent years scientists have made rapid and significant advances in the field of semiconductor physics. One of the most important fields of current interest in materials science is the fundamental aspects and applications of conducting transparent oxide thin films (TCO). The characteristic properties of such coatings are low electrical resistivity and high transparency in the visible region. The first semitransparent and electrically conducting CdO film was reported as early as in 1907 [1]. Though early work on these films was performed out of purely scientific interest, substantial technological advances in such films were made after 1940. The technological interest in the study of transparent semiconducting films was generated mainly due to the potential applications of these materials both in industry and research. Such films demonstrated their utility as transparent electrical heaters for windscreens in the aircraft industry. However, during the last decade, these conducting transparent films have been widely used in a variety of other applications such as gas sensors [2], solar cells [3], heat reflectors [4], light emitting devices [5] and laser damage resistant coatings in high power laser technology [6]. Just a few materials dominate the current TCO industry and the two dominant markets for TCO’s are in architectural applications and flat panel displays. The architectural use of TCO is for energy efficient windows. Fluorine doped tin oxide (FTO), deposited using a pyrolysis process is the TCO usually finds maximum application. SnO2 also finds application ad coatings for windows, which are efficient in preventing radiative heat loss, due to low emissivity (0.16). Pyrolitic tin oxide is used in PV modules, touch screens and plasma displays. However indium tin oxide (ITO) is mostly used in the majority of flat panel display (FPD) applications. In FPDs, the basic function of ITO is as transparent electrodes. The volume of FPD’s produced, and hence the volume of ITO coatings produced, continues to grow rapidly. But the current increase in the cost of indium and the scarcity of this material created the difficulty in obtaining low cost TCOs. Hence search for alternative TCO materials has been a topic of active research for the last few decades. This resulted in the development of binary materials like ZnO, SnO2, CdO and ternary materials like II Zn2SnO4, CdSb2O6:Y, ZnSO3, GaInO3 etc. The use of multicomponent oxide materials makes it possible to have TCO films suitable for specialized applications because by altering their chemical compositions, one can control the electrical, optical, chemical and physical properties. But the advantages of using binary materials are the easiness to control the chemical compositions and depositions conditions. Recently, there were reports claiming the deposition of CdO:In films with a resistivity of the order of 10-5 ohm cm for flat panel displays and solar cells. However they find limited use because of Cd-Toxicity. In this regard, ZnO films developed in 1980s, are very useful as these use Zn, an abundant, inexpensive and nontoxic material. Resistivity of this material is still not very low, but can be reduced through doping with group-III elements like In, Al or Ga or with F [6]. Hence there is a great interest in ZnO as an alternative of ITO. In the present study, we prepared and characterized transparent and conducting ZnO thin films, using a cost effective technique viz Chemical Spray Pyrolysis (CSP). This technique is also suitable for large area film deposition. It involves spraying a solution, (usually aqueous) containing soluble salts of the constituents of the desired compound, onto a heated substrate.

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Transparent conducting oxides (TCO’s) have been known and used for technologically important applications for more than 50 years. The oxide materials such as In2O3, SnO2 and impurity doped SnO2: Sb, SnO2: F and In2O3: Sn (indium tin oxide) were primarily used as TCO’s. Indium based oxides had been widely used as TCO’s for the past few decades. But the current increase in the cost of indium and scarcity of this material created the difficulty in obtaining low cost TCO’s. Hence the search for alternative TCO material has been a topic of active research for the last few decades. This resulted in the development of various binary and ternary compounds. But the advantages of using binary oxides are the easiness to control the composition and deposition parameters. ZnO has been identified as the one of the promising candidate for transparent electronic applications owing to its exciting optoelectronic properties. Some optoelectronics applications of ZnO overlap with that of GaN, another wide band gap semiconductor which is widely used for the production of green, blue-violet and white light emitting devices. However ZnO has some advantages over GaN among which are the availability of fairly high quality ZnO bulk single crystals and large excitonic binding energy. ZnO also has much simpler crystal-growth technology, resulting in a potentially lower cost for ZnO based devices. Most of the TCO’s are n-type semiconductors and are utilized as transparent electrodes in variety of commercial applications such as photovoltaics, electrochromic windows, flat panel displays. TCO’s provide a great potential for realizing diverse range of active functions, novel functions can be integrated into the materials according to the requirement. However the application of TCO’s has been restricted to transparent electrodes, ii notwithstanding the fact that TCO’s are n-type semiconductors. The basic reason is the lack of p-type TCO, many of the active functions in semiconductor originate from the nature of pn-junction. In 1997, H. Kawazoe et al reported the CuAlO2 as the first p-type TCO along with the chemical design concept for the exploration of other p-type TCO’s. This has led to the fabrication of all transparent diode and transistors. Fabrication of nanostructures of TCO has been a focus of an ever-increasing number of researchers world wide, mainly due to their unique optical and electronic properties which makes them ideal for a wide spectrum of applications ranging from flexible displays, quantum well lasers to in vivo biological imaging and therapeutic agents. ZnO is a highly multifunctional material system with highly promising application potential for UV light emitting diodes, diode lasers, sensors, etc. ZnO nanocrystals and nanorods doped with transition metal impurities have also attracted great interest, recently, for their spin-electronic applications This thesis summarizes the results on the growth and characterization of ZnO based diodes and nanostructures by pulsed laser ablation. Various ZnO based heterojunction diodes have been fabricated using pulsed laser deposition (PLD) and their electrical characteristics were interpreted using existing models. Pulsed laser ablation has been employed to fabricate ZnO quantum dots, ZnO nanorods and ZnMgO/ZnO multiple quantum well structures with the aim of studying the luminescent properties.

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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.

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Roughness and defects induced on few-layer graphene (FLG) irradiated by Ar+ ions at different energies were investigated using X-ray photoemission spectroscopy (XPS) and atomic force microscopy techniques. The results provide direct experimental evidence of ripple formation, sp2 to sp3 hybridized carbon transformation, electronic damage, Ar+ implantation, unusual defects and edge reconstructions in FLG, which depend on the irradiation energy. In addition, shadowing effects similar to those found in oblique-angle growth of thin films were seen. Reliable quantification of the transition from the sp2-bonding to sp3-hybridized state as a result of Ar+ ion irradiation is achieved from the deconvolution of the XPS C (1s) peak. Although the ion irradiation effect is demonstrated through the shape of the derivative of the Auger transition C KVV spectra, we show that the D parameter values obtained from these spectra which are normally used in the literature fail to account for the sp2 to sp3 hybridization transition. In contrast to what is known, it is revealed that using ion irradiation at large FLG sample tilt angles can lead to edge reconstructions. Furthermore, FLG irradiation by low energy of 0.25 keV can be a plausible way of peeling graphene layers without the need of Joule heating reported previously

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Metglas 2826 MB having a nominal composition of Fe40Ni38Mo4B18 is an excellent soft magnetic material and finds application in sensors and memory heads. However, the thin-film forms of Fe40Ni38Mo4B18 are seldom studied, although they are important in micro-electro-mechanical systems/nano-electromechanical systems devices. The stoichiometry of the film plays a vital role in determining the structural and magnetic properties of Fe40Ni38Mo4B18 thin films: retaining the composition in thin films is a challenge. Thin films of 52 nm thickness were fabricated by RF sputtering technique on silicon substrate from a target of nominal composition of Fe40Ni38Mo4B18. The films were annealed at temperatures of 400 °C and 600 °C. The micro-structural studies of films using glancing x-ray diffractometer (GXRD) and transmission electron microscope (TEM) revealed that pristine films are crystalline with (FeNiMo)23B6 phase. Atomic force microscope (AFM) images were subjected to power spectral density analysis to understand the probable surface evolution mechanism during sputtering and annealing. X-ray photoelectron spectroscopy (XPS) was employed to determine the film composition. The sluggish growth of crystallites with annealing is attributed to the presence of molybdenum in the thin film. The observed changes in magnetic properties were correlated with annealing induced structural, compositional and morphological changes

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From the early stages of the twentieth century, polyaniline (PANI), a well-known and extensively studied conducting polymer has captured the attention of scientific community owing to its interesting electrical and optical properties. Starting from its structural properties, to the currently pursued optical, electrical and electrochemical properties, extensive investigations on pure PANI and its composites are still much relevant to explore its potentialities to the maximum extent. The synthesis of highly crystalline PANI films with ordered structure and high electrical conductivity has not been pursued in depth yet. Recently, nanostructured PANI and the nanocomposites of PANI have attracted a great deal of research attention owing to the possibilities of applications in optical switching devices, optoelectronics and energy storage devices. The work presented in the thesis is centered around the realization of highly conducting and structurally ordered PANI and its composites for applications mainly in the areas of nonlinear optics and electrochemical energy storage. Out of the vast variety of application fields of PANI, these two areas are specifically selected for the present studies, because of the following observations. The non-linear optical properties and the energy storing properties of PANI depend quite sensitively on the extent of conjugation of the polymer structure, the type and concentration of the dopants added and the type and size of the nano particles selected for making the nanocomposites. The first phase of the work is devoted to the synthesis of highly ordered and conducting films of PANI doped with various dopants and the structural, morphological and electrical characterization followed by the synthesis of metal nanoparticles incorporated PANI samples and the detailed optical characterization in the linear and nonlinear regimes. The second phase of the work comprises the investigations on the prospects of PANI in realizing polymer based rechargeable lithium ion cells with the inherent structural flexibility of polymer systems and environmental safety and stability. Secondary battery systems have become an inevitable part of daily life. They can be found in most of the portable electronic gadgets and recently they have started powering automobiles, although the power generated is low. The efficient storage of electrical energy generated from solar cells is achieved by using suitable secondary battery systems. The development of rechargeable battery systems having excellent charge storage capacity, cyclability, environmental friendliness and flexibility has yet to be realized in practice. Rechargeable Li-ion cells employing cathode active materials like LiCoO2, LiMn2O4, LiFePO4 have got remarkable charge storage capacity with least charge leakage when not in use. However, material toxicity, chance of cell explosion and lack of effective cell recycling mechanism pose significant risk factors which are to be addressed seriously. These cells also lack flexibility in their design due to the structural characteristics of the electrode materials. Global research is directed towards identifying new class of electrode materials with less risk factors and better structural stability and flexibility. Polymer based electrode materials with inherent flexibility, stability and eco-friendliness can be a suitable choice. One of the prime drawbacks of polymer based cathode materials is the low electronic conductivity. Hence the real task with this class of materials is to get better electronic conductivity with good electrical storage capability. Electronic conductivity can be enhanced by using proper dopants. In the designing of rechargeable Li-ion cells with polymer based cathode active materials, the key issue is to identify the optimum lithiation of the polymer cathode which can ensure the highest electronic conductivity and specific charge capacity possible The development of conducting polymer based rechargeable Li-ion cells with high specific capacity and excellent cycling characteristics is a highly competitive area among research and development groups, worldwide. Polymer based rechargeable batteries are specifically attractive due to the environmentally benign nature and the possible constructional flexibility they offer. Among polymers having electrical transport properties suitable for rechargeable battery applications, polyaniline is the most favoured one due to its tunable electrical conducting properties and the availability of cost effective precursor materials for its synthesis. The performance of a battery depends significantly on the characteristics of its integral parts, the cathode, anode and the electrolyte, which in turn depend on the materials used. Many research groups are involved in developing new electrode and electrolyte materials to enhance the overall performance efficiency of the battery. Currently explored electrolytes for Li ion battery applications are in liquid or gel form, which makes well-defined sealing essential. The use of solid electrolytes eliminates the need for containment of liquid electrolytes, which will certainly simplify the cell design and improve the safety and durability. The other advantages of polymer electrolytes include dimensional stability, safety and the ability to prevent lithium dendrite formation. One of the ultimate aims of the present work is to realize all solid state, flexible and environment friendly Li-ion cells with high specific capacity and excellent cycling stability. Part of the present work is hence focused on identifying good polymer based solid electrolytes essential for realizing all solid state polymer based Li ion cells.The present work is an attempt to study the versatile roles of polyaniline in two different fields of technological applications like nonlinear optics and energy storage. Conducting form of doped PANI films with good extent of crystallinity have been realized using a level surface assisted casting method in addition to the generally employed technique of spin coating. Metal nanoparticles embedded PANI offers a rich source for nonlinear optical studies and hence gold and silver nanoparticles have been used for making the nanocomposites in bulk and thin film forms. These PANI nanocomposites are found to exhibit quite dominant third order optical non-linearity. The highlight of these studies is the observation of the interesting phenomenon of the switching between saturable absorption (SA) and reverse saturable absorption (RSA) in the films of Ag/PANI and Au/PANI nanocomposites, which offers prospects of applications in optical switching. The investigations on the energy storage prospects of PANI were carried out on Li enriched PANI which was used as the cathode active material for assembling rechargeable Li-ion cells. For Li enrichment or Li doping of PANI, n-Butyllithium (n-BuLi) in hexanes was used. The Li doping as well as the Li-ion cell assembling were carried out in an argon filled glove box. Coin cells were assembled with Li doped PANI with different doping concentrations, as the cathode, LiPF6 as the electrolyte and Li metal as the anode. These coin cells are found to show reasonably good specific capacity around 22mAh/g and excellent cycling stability and coulombic efficiency around 99%. To improve the specific capacity, composites of Li doped PANI with inorganic cathode active materials like LiFePO4 and LiMn2O4 were synthesized and coin cells were assembled as mentioned earlier to assess the electrochemical capability. The cells assembled using the composite cathodes are found to show significant enhancement in specific capacity to around 40mAh/g. One of the other interesting observations is the complete blocking of the adverse effects of Jahn-Teller distortion, when the composite cathode, PANI-LiMn2O4 is used for assembling the Li-ion cells. This distortion is generally observed, near room temperature, when LiMn2O4 is used as the cathode, which significantly reduces the cycling stability of the cells.

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Stable, OH free zinc oxide (ZnO) nanoparticles were synthesized by hydrothermal method by varying the growth temperature and concentration of the precursors. The formation of ZnO nanoparticles were confirmed by x-ray diffraction (XRD), transmission electron microscopy (TEM) and selected area electron diffraction (SAED) studies. The average particle size have been found to be about 7-24 nm and the compositional analysis is done with inductively coupled plasma atomic emission spectroscopy (ICP-AES). Diffuse reflectance spectroscopy (DRS) results shows that the band gap of ZnO nanoparticles is blue shifted with decrease in particle size. Photoluminescence properties of ZnO nanoparticles at room temperature were studied and the green photoluminescent emission from ZnO nanoparticles can originate from the oxygen vacancy or ZnO interstitial related defects.

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Aim of the present work was to automate CSP process, to deposit and characterize CuInS2/In2S3 layers using this system and to fabricate devices using these films.An automated spray system for the deposition of compound semiconductor thin films was designed and developed so as to eliminate the manual labour involved in spraying and facilitate standardization of the method. The system was designed such that parameters like spray rate, movement of spray head, duration of spray, temperature of substrate, pressure of carrier gas and height of the spray head from the substrate could be varied. Using this system, binary, ternary as well as quaternary films could be successfully deposited.The second part of the work deal with deposition and characterization of CuInS2 and In2S3 layers respectively.In the case of CuInS2 absorbers, the effects of different preparation conditions and post deposition treatments on the optoelectronic, morphological and structural properties were investigated. It was observed that preparation conditions and post deposition treatments played crucial role in controlling the properties of the films. The studies in this direction were useful in understanding how the variation in spray parameters tailored the properties of the absorber layer. These results were subsequently made use of in device fabrication process.Effects of copper incorporation in In2S3 films were investigated to find how the diffusion of Cu from CuInS2 to In2S3 will affect the properties at the junction. It was noticed that there was a regular variation in the opto-electronic properties with increase in copper concentration.Devices were fabricated on ITO coated glass using CuInS2 as absorber and In2S3 as buffer layer with silver as the top electrode. Stable devices could be deposited over an area of 0.25 cm2, even though the efficiency obtained was not high. Using manual spray system, we could achieve devices of area 0.01 cm2 only. Thus automation helped in obtaining repeatable results over larger areas than those obtained while using the manual unit. Silver diffusion on the cells before coating the electrodes resulted in better collection of carriers.From this work it was seen CuInS2/In2S3 junction deposited through automated spray process has potential to achieve high efficiencies.

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The main objective of this thesis work is to optimize the growth conditions for obtaining crystalline and conducting Lao.5Sro.5Co03 (LSCO) and Lao.5Sro.5Coo.5.5Nio.5O3 (LSCNO) thin films at low processing temperatures. The films are prepared by radio frequency magnetron sputtering under various deposition conditions. The thin films were used as electrodes for the fabrication of ferroelectric capacitors using BaO.7SrO.3 Ti03 (BST) and PbZro.52 Tio.4803 (PZT). The structural and transport properties of the La1_xSrxCo03 and Lao.5Sro.5Co1_xNix03 are also investigated. The characterization of the bulk and the thin films were performed using different tools. A powder X-ray diffractometer was used to analyze the crystalline nature of the material. The transport properties were investigated by measuring the temperature dependence of resistivity using a four probe technique. The magnetoresistance and thermoelectric power were also used to investigate the transport properties. Atomic force microscope was used to study the surface morphology and thin film roughness. The ferroelectric properties of the capacitors were investigated using RT66A ferroelectric tester.

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Fe–Ni based amorphous thin films were prepared by thermal evaporation. These films were irradiated by 108 MeV Ag8+ ions at room temperature with fluences ranging from 1 1012 to 3 1013 ions/cm2 using a 15 UD Pelletron accelerator. Glancing angle x-ray diffraction studies showed that the irradiated films retain their amorphous nature. The topographical evolution of the films under swift heavy ion SHI bombardment was probed using atomic force microscope and it was noticed that surface roughening was taking place with ion beam irradiation. Magnetic measurements using a vibrating sample magnetometer showed that the coercivity of the films increases with an increase in the ion fluence. The observed coercivity changes are correlated with topographical evolution of the films under SHI irradiation. The ability to modify the magnetic properties via SHI irradiation could be utilized for applications in thin film magnetism

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Magnetic properties of nano-crystalline soft magnetic alloys have usually been correlated to structural evolution with heat treatment. However, literature reports pertaining to the study of nano-crystalline thin films are less abundant. Thin films of Fe40Ni38B18Mo4 were deposited on glass substrates under a high vacuum of ≈ 10−6 Torr by employing resistive heating. They were annealed at various temperatures ranging from 373 to 773K based on differential scanning calorimetric studies carried out on the ribbons. The magnetic characteristics were investigated using vibrating sample magnetometry. Morphological characterizations were carried out using atomic force microscopy (AFM), and magnetic force microscopy (MFM) imaging is used to study the domain characteristics. The variation of magnetic properties with thermal annealing is also investigated. From AFM and MFM images it can be inferred that the crystallization temperature of the as-prepared films are lower than their bulk counterparts. Also there is a progressive evolution of coercivity up to 573 K, which is an indication of the lowering of nano-crystallization temperature in thin films. The variation of coercivity with the structural evolution of the thin films with annealing is discussed and a plausible explanation is provided using the modified random anisotropy model

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Superparamagnetic nanocomposites based on g-Fe2O3 and sulphonated polystyrene have been synthesized by ion exchange process and the preparation conditions were optimized. Samples were subjected to cycling to study the effect of cycling on the magnetic properties of these composites. The structural and magnetization studies have been carried out. Magnetization studies show the dependence of magnetization on the number of ion exchange cycles. Doping of cobalt at the range in to the g-Fe2O3 lattice was effected in situ and the doping was varied in the atomic percentage range 1–10. The exact amount of cobalt dopant as well as the iron content was estimated by Atomic Absorption Spectroscopy. The effect of cobalt in modifying the properties of the composites was then studied and the results indicate that the coercivity can be tuned by the amount of cobalt in the composites. The tuning of both the magnetization and the coercivity can be achieved by a combination of cycling of ion exchange and the incorporation of cobalt

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The growth of Fe–Ni based amorphous nanocolumns has been studied using atomic force microscopy. The root mean square roughness of the film surface increased with the deposition time but showed a little change at higher deposition time. It was found that the separation between the nanostructures increased sharply during the initial stages of growth and the change was less pronounced at higher deposition time. During the initial stages of the column growth, a roughening process due to self shadowing is dominant and, as the deposition time increases, a smoothening mechanism takes place due to the surface diffusion of adatoms

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Swift heavy ion induced changes in microstructure and surface morphology of vapor deposited Fe–Ni based metallic glass thin films have been investigated by using atomic force microscopy, X-ray diffraction and transmission electron microscopy. Ion beam irradiation was carried out at room temperature with 103 MeV Au9+ beam with fluences ranging from 3 1011 to 3 1013 ions/cm2. The atomic force microscopy images were subjected to power spectral density analysis and roughness analysis using an image analysis software. Clusters were found in the image of as-deposited samples, which indicates that the film growth is dominated by the island growth mode. As-deposited films were amorphous as evidenced from X-ray diffraction; however, high resolution transmission electron microscopy measurements revealed a short range atomic order in the samples with crystallites of size around 3 nm embedded in an amorphous matrix. X-ray diffraction pattern of the as-deposited films after irradiation does not show any appreciable changes, indicating that the passage of swift heavy ions stabilizes the short range atomic ordering, or even creates further amorphization. The crystallinity of the as-deposited Fe–Ni based films was improved by thermal annealing, and diffraction results indicated that ion beam irradiation on annealed samples results in grain fragmentation. On bombarding annealed films, the surface roughness of the films decreased initially, then, at higher fluences it increased. The observed change in surface morphology of the irradiated films is attributed to the interplay between ion induced sputtering, volume diffusion and surface diffusion

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We have investigated the effects of swift heavy ion irradiation on thermally evaporated 44 nm thick, amorphous Co77Fe23 thin films on silicon substrates using 100 MeV Ag7+ ions fluences of 1 1011 ions/ cm2, 1 1012 ions/cm2, 1 1013 ions/cm2, and 3 1013 ions/cm2. The structural modifications upon swift heavy irradiation were investigated using glancing angle X-ray diffraction. The surface morphological evolution of thin film with irradiation was studied using Atomic Force Microscopy. Power spectral density analysis was used to correlate the roughness variation with structural modifications investigated using X-ray diffraction. Magnetic measurements were carried out using vibrating sample magnetometry and the observed variation in coercivity of the irradiated films is explained on the basis of stress relaxation. Magnetic force microscopy images are subjected to analysis using the scanning probe image processor software. These results are in agreement with the results obtained using vibrating sample magnetometry. The magnetic and structural properties are correlated