Spray Pyrolysed Zinc Oxide Thin Films : Effects of Doping and Ion Beam Irradiation

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.

Effect of Substrate Temperature on the Structural and Luminescent Characteristics of RF-Magnetron-Sputtered ZnGa2O4:Dy3+ Thin Films

ZnGa2O4:Dy3+ phosphor thin films were deposited on quartz substrates by radio frequency rf magnetron sputtering and the effect of substrate temperature on its structural and luminescent properties was investigated. Polycrystalline film could be deposited even at room temperature. The crystalline behavior, Zn/Ga ratio, and surface morphology of the films were found to be highly sensitive to substrate temperature. Under UV illumination, the as-deposited films at and above 300°C gave white luminescence even without any postdeposition treatments. The photoluminescent PL emission can be attributed to the combined effect of multicolor emissions from the single luminescence center Dy3+ via host-sensitization. Maximum PL emission intensity was observed for the film deposited at 600°C, and the CIE chromaticity coordinates of the emission were determined to be x,y = 0.34, 0.31 .

Optical and electrical properties of co-sputtered amorphous transparent conducting zinc indium tin oxide thin films

Highly conductive and transparent thin films of amorphous zinc indium tin oxide are prepared at room temperature by co-sputtering of zinc 10 oxide and indium tin oxide. Cationic contents in the films are varied by adjusting the power to the sputtering targets. Optical transmission study of 11 films showed an average transmission greater than 85% across the visible region. Maximum conductivity of 6×102 S cm−1 is obtained for Zn/In/ 12 Sn atomic ratio 0.4/0.4/0.2 in the film. Hall mobility strongly depends on carrier concentration and maximum mobility obtained is 18 cm2 V−1 s−1 13 at a carrier concentration of 2.1×1020 cm−3. Optical band gap of films varied from 3.44 eV to 3 eV with the increase of zinc content in the film 14 while the refractive index of the films at 600 nm is about 2.0.

Photoconductivity studies on some semiconducting thin films for photovoltaic applications

Photoconductivity (PC) processes may be the most suitable technique for obtaining information about the states in the gap. It finds applications in photovoItaics, photo detection and radiation measurements. The main task in the area of photovoltaics, is to increase the efficiency of the device and also to develop new materials with good optoelectronic properties useful for energy conversion, keeping the idea of cost effectiveness. Photoconduction includes generation and recombination of carriers and their transport to the electrodes. So thermal relaxation process, charge carrier statistics, effects of electrodes and several mechanisms of recombination are involved in photoconductivity.A major effect of trapping is to make the experimentally observed decay time of photocurrent, longer than carrier lifetime. If no trapping centers are present, then observed photocurrent will decay in the same way as the density of free carriers and the observed decay time will be equal to carrier lifetime. If the density of free carriers is much less than density of trapped carriers, the entire decay of photocurrent is effectively dominated by the rate of trap emptying rather than by the rate of recombination.In the present study, the decay time of carriers was measured using photoconductive decay (PCD) technique. For the measurements, the film was loaded in a liquid Helium cryostat and the temperature was controlled using Lakshore Auto tuning temperature controller (Model 321). White light was used to illuminate the required area of the sample. Heat radiation from the light source was avoided by passing the light beam through a water filter. The decay current. after switching off the illumination. was measured using a Kiethely 2000 multi meter. Sets of PCD measurements were taken varying sample temperature, sample preparation temperature, thickness of the film, partial pressure of Oxygen and concentration of a particular element in a compound. Decay times were calculated using the rate window technique, which is a decay sampling technique particularly suited to computerized analysis. For PCD curves with two well-defined regions, two windows were chosen, one at the fast decay region and the other at the slow decay region. The curves in a particular window were exponentially fitted using Microsoft Excel 2000 programme. These decay times were plotted against sample temperature and sample preparation temperature to study the effect of various defects in the film. These studies were done in order to optimize conditions of preparation technique so as to get good photosensitive samples. useful for photovoltaic applications.Materials selected for the study were CdS, In2Se3, CuIn2Se3 and CuInS2• Photoconductivity studies done on these samples are organised in six chapters including introduction and conclusion.

Photothermal beam deflection for non-destructive evaluation of semiconductor thin films

Non-destructive testing (NDT) is the use of non-invasive techniques to determine the integrity of a material, component, or structure. Engineers and scientists use NDT in a variety of applications, including medical imaging, materials analysis, and process control.Photothermal beam deflection technique is one of the most promising NDT technologies. Tremendous R&D effort has been made for improving the efficiency and simplicity of this technique. It is a popular technique because it can probe surfaces irrespective of the size of the sample and its surroundings. This technique has been used to characterize several semiconductor materials, because of its non-destructive and non-contact evaluation strategy. Its application further extends to analysis of wide variety of materials. Instrumentation of a NDT technique is very crucial for any material analysis. Chapter two explores the various excitation sources, source modulation techniques, detection and signal processing schemes currently practised. The features of the experimental arrangement including the steps for alignment, automation, data acquisition and data analysis are explained giving due importance to details.Theoretical studies form the backbone of photothermal techniques. The outcome of a theoretical work is the foundation of an application.The reliability of the theoretical model developed and used is proven from the studies done on crystalline.The technique is applied for analysis of transport properties such as thermal diffusivity, mobility, surface recombination velocity and minority carrier life time of the material and thermal imaging of solar cell absorber layer materials like CuInS2, CuInSe2 and SnS thin films.analysis of In2S3 thin films, which are used as buffer layer material in solar cells. The various influences of film composition, chlorine and silver incorporation in this material is brought out from the measurement of transport properties and analysis of sub band gap levels.The application of photothermal deflection technique for characterization of solar cells is a relatively new area that requires considerable attention.The application of photothermal deflection technique for characterization of solar cells is a relatively new area that requires considerable attention. Chapter six thus elucidates the theoretical aspects of application of photothermal techniques for solar cell analysis. The experimental design and method for determination of solar cell efficiency, optimum load resistance and series resistance with results from the analysis of CuInS2/In2S3 based solar cell forms the skeleton of this chapter.

Dynamics of laser produced silver plasma under film deposition conditions studied using optical emission spectroscopy

Laser produced plasma from silver is generated using a Q-switched Nd:YAG laser. Optical emission spectroscopy is used to carry out time of flight (TOF) analysis of atomic particles. An anomalous double peak profile in the TOF distribution is observed at low pressure. A collection of slower species emerge at reduced pressure below 4 X lO-3 mbar and this species has a greater velocity spread. At high pressure the plasma expansion follows the shockwave model with cylindrical symmetry whereas at reduced pressure it shows unsteady adiabatic expansion (UAE). During UAE the species show a parabolic increases in the expansion time with radial distance whereas during shock wave expansion the exponent is less than one. The angular distribution of the ablated species in the plume is obtained from the measurement of optical density of thin films deposited on to glass substrates kept perpendicular to the plume. There is a sharp variation in the film thickness away from the film centre due to asymmetries in the plume.

Two Dimensional Large Amplitude Quasi Solitons in Thin Helium Films

Large amplitude local density fluctuations in a thin superfluid He film is considered. It is shown that these large amplitude fluctuations travel and behave like "quasi-solitons" under collision, even when the full nonlinearity arising from the Van der Waals potential is taken into account.

Effect of self assembly on the nonlinear optical characteristics of ZnO thin films

In the present work, we report the third order nonlinear optical properties of ZnO thin films deposited using self assembly, sol gel process as well as pulsed laser ablation by z scan technique. ZnO thin films clearly exhibit a negative nonlinear index of refraction at 532 nm and the observed nonlinear refraction is attributed to two photon absorption followed by free carrier absorption. Although the absolute nonlinear values for these films are comparable, there is a change in the sign of the absorptive nonlinearity of the films. The films developed by dip coating and pulsed laser ablation exhibit reverse saturable absorption whereas the self assembled film exhibits saturable absorption. These different nonlinear characteristics in the self assembled films can be mainly attributed to the saturation of linear absorption of the ZnO defect states.

Electron energy loss spectroscopy assessment of cationic migration in La2/3Ca1/3MnO3 thin films

Màster en Nanociència i Nanotecnologia curs 2006-2007. Directors: Francesca Peiró i Martínez and Jordi Arbiol i Cobos

Evidence of extended orientational order in amorphous Fe/Sm thin films

Amorphous thin films of Fe/Sm, prepared by evaporation methods, have been magnetically characterized and the results were interpreted in terms of the random magnets theory. The samples behave as 2D and 3D random magnets depending on the total thickness of the film. From our data the existence of orientational order, which greatly influences the magnetic behavior of the films, is also clear.

Formation And Electrical Properties Of Polyacrylonitrile Thin Films Prepared By Plasma - Polymerisation

Due to the great versatility of the properties of polymer thin films, special interest has been taken in recent years on their preparation and electrical properties. The present thesis is entirely devoted to the study of the formation, structure and electrical properties of plasma» polymerised polyacrylonitrile (PAN) thin films. Eventhough the studies are confined to a single polymer film, the results in general are applicable to similar polar polymer films.

Swift heavy ion induced surface and microstructural evolution in metallic glass thin films

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

On tuning the orientation of grains of spray pyrolysed ZnO thin films

Effect of varying spray rate on the structure and optoelectronic properties of spray pyrolysed ZnO film is analysed. ZnO films were characterised using different techniques such as X-ray diffraction (XRD), photoluminescence, electrical resistivity measurement, and optical absorption. The XRD analysis proved that, with the increase in spray rate, orientation of the grains changed from (1 0 1) plane to (0 0 2) plane. The films exhibited luminescence in two regions—one was the ‘near band-edge’ (NBE) (∼380 nm) emission and the other one was the ‘blue-green emission’ (∼503 nm). Intensity of the blue-green emission decreased after orientation of grains shifted to (0 0 2) plane. Scanning electron microscope (SEM) analysis of the films asserts that spray rate has major role in improving the crystallographic properties of the films. Moreover resistivity of the films could be lowered to 2.4×10−2 cm without any doping or post-deposition annealing

Optimization of the Mechanical and Optical Properties of Tunable Optical Sensor Arrays (TOSA) for a Nanospectrometer in the Visible and Near Infrared Spectral Range

Tunable Optical Sensor Arrays (TOSA) based on Fabry-Pérot (FP) filters, for high quality spectroscopic applications in the visible and near infrared spectral range are investigated within this work. The optical performance of the FP filters is improved by using ion beam sputtered niobium pentoxide (Nb2O5) and silicon dioxide (SiO2) Distributed Bragg Reflectors (DBRs) as mirrors. Due to their high refractive index contrast, only a few alternating pairs of Nb2O5 and SiO2 films can achieve DBRs with high reflectivity in a wide spectral range, while ion beam sputter deposition (IBSD) is utilized due to its ability to produce films with high optical purity. However, IBSD films are highly stressed; resulting in stress induced mirror curvature and suspension bending in the free standing filter suspensions of the MEMS (Micro-Electro-Mechanical Systems) FP filters. Stress induced mirror curvature results in filter transmission line degradation, while suspension bending results in high required filter tuning voltages. Moreover, stress induced suspension bending results in higher order mode filter operation which in turn degrades the optical resolution of the filter. Therefore, the deposition process is optimized to achieve both near zero absorption and low residual stress. High energy ion bombardment during film deposition is utilized to reduce the film density, and hence the film compressive stress. Utilizing this technique, the compressive stress of Nb2O5 is reduced by ~43%, while that for SiO2 is reduced by ~40%. Filters fabricated with stress reduced films show curvatures as low as 100 nm for 70 μm mirrors. To reduce the stress induced bending in the free standing filter suspensions, a stress optimized multi-layer suspension design is presented; with a tensile stressed metal sandwiched between two compressively stressed films. The stress in Physical Vapor Deposited (PVD) metals is therefore characterized for use as filter top-electrode and stress compensating layer. Surface micromachining is used to fabricate tunable FP filters in the visible spectral range using the above mentioned design. The upward bending of the suspensions is reduced from several micrometers to less than 100 nm and 250 nm for two different suspension layer combinations. Mechanical tuning of up to 188 nm is obtained by applying 40 V of actuation voltage. Alternatively, a filter line with transmission of 65.5%, Full Width at Half Maximum (FWHM) of 10.5 nm and a stopband of 170 nm (at an output wavelength of 594 nm) is achieved. Numerical model simulations are also performed to study the validity of the stress optimized suspension design for the near infrared spectral range, wherein membrane displacement and suspension deformation due to material residual stress is studied. Two bandpass filter designs based on quarter-wave and non-quarter-wave layers are presented as integral components of the TOSA. With a filter passband of 135 nm and a broad stopband of over 650 nm, high average filter transmission of 88% is achieved inside the passband, while maximum filter transmission of less than 1.6% outside the passband is achieved.

Optimization in the Technological Steps for the Fabrication of Large Area Micromirror Arrays

Micromirror arrays are a very strong candidate for future energy saving applications. Within this work, the fabrication process for these micromirror arrays has been optimized and some steps for the large area fabrication of micromirror modules were performed. At first the surface roughness of the insulation layer of silicon dioxide (SiO2) was investigated. This SiO2 thin layer was deposited on three different type of substrates i.e. silicon, glass and Polyethylene Naphthalate (PEN) substrates. The deposition techniques which has been used are Plasma Enhanced Chemical Vapor Deposition (PECVD), Physical Vapor Deposition (PVD) and Ion Beam Sputter Deposition (IBSD). The thickness of the SiO2 thin layer was kept constant at 150nm for each deposition process. The surface roughness was measured by Stylus Profilometry and Atomic Force Microscopy (AFM). It was found that the layer which was deposited by IBSD has got the minimum surface roughness value and the layer which was deposited by PECVD process has the highest surface roughness value. During the same investigation, the substrate temperature of PECVD was varied from 80° C to 300° C with the step size of 40° C and it was found that the surface roughness keeps on increasing as the substrate holder temperature increases in the PECVD process. A new insulation layer system was proposed to minimize the dielectric breakdown effect in insulation layer for micromirror arrays. The conventional bilayer system was replaced by five layer system but the total thickness of insulation layer remains the same. It was found that during the actuation of micromirror arrays structure, the dielectric breakdown effect was reduced considerably as compared to the bilayer system. In the second step the fabrication process of the micromirror arrays was successfully adapted and transferred from glass substrates to the flexible PEN substrates by optimizing the conventional process recipe. In the last section, a large module of micromirror arrays was fabricated by electrically interconnecting four 10cm×10cm micromirror modules on a glass pane having dimensions of 21cm×21cm.