MATERIALS AND METHODS This chapter gives the description of materials and methods used for synthesizing light emitting nanomaterials. It also deals with the various techniques and instruments used for characterization of the prepared light emitting nanomaterials. 1. MATERIALS The synthesis of efficient nanophosphors requires host lattice, activators, fuels and some fluxes. The various chemicals used for the synthesis of the nanophosphors discussed in this thesis are listed below: 1) Aluminium nitrate nonahydrate [Al(NO3)3.9H2O] 2) Ammonium dihydrogen orthophosphate [NH4H2PO4] 3) Barium nitrate [Ba(NO3)2] 4) Calcium nitrate tetrahydrate [Ca(NO3)2.4H2O] 5) Citric acid [C6H8O7.H2O] 6) Europium(III) nitrate hexahydrate [Eu(NO3)3.6H2O] 7) Europium(III) nitrate pentahydrate [Eu(NO3)3.5H2O] 8) Gadolinium(III) nitrate hexahydrate [Gd(NO3)3.6H2O] 9) Lanthanum nitrate hexahydrate [La(NO3)3.6H2O] 10) L-tartaric acid [C4H6O6] 11) Magnesium nitrate hexahydrate [Mg(NO3)2.6H2O] 12) Orthoboric acid [H3BO3] 13) Potassium nitrate [KNO3] 14) Strontium nitrate [Sr(NO3)2] 15) Terbium(III) nitrate pentahydrate [Tb(NO3)3.5H2O] 16) Urea [H2NCONH2] 17) Yttrium nítrate tetrahydrate [Y(NO3)3.4H2O] 18) Zinc nítrate hydrate [Zn(NO3)2.xH2O] Keeping in mind that even a small amount of impurity lowers the luminescent intensity of the light emitting nanomaterials, all these chemicals used for the synthesis of the nanophosphors were of high purity i.e. 99.98%. Other chemicals such as acids and solvents used were also of reagent grade/analytical grade. 54 2. Methods for the synthesis of nanophosphors Nanophosphors consist of a crystalline host materials or a matrix in which a small amount of certain impurities called activators are incorporated. Sometimes a little quantity of flux is also required for the synthesis of these luminescent materials. Nanophosphors synthesis generally proceeds via two step reactions. In the first step, activator ions are induced into the existing host materials taken for the synthesis and in the second step, host materials synthesis and activator introduction takes place simultaneously during the process of firing in the furnace. Activators are primarily responsible for the luminescence in light emitting nanomaterials. The starting materials for the synthesis of nanophosphors are blended in a ratio which may deviate considerably from the stoichiometric composition of the phosphor. Very thorough mixing of the raw materials before firing is extremely important for the successful synthesis of the nanophosphors. Some of the best methods used for mixing of raw materials are slurring, wet ball milling, dry ball milling, mortaring etc. The excess components present in the raw materials other than the required amount as per final product of the nanophosphors, either vaporizes during synthesis or is consumed to create by-products. Sometimes these are removed by washing after the completion of the reaction. The final product thus obtained is very close to the stoichiometric composition of the nanophosphors [1]. Extensive trials on the preparation and characterization of nanophosphors of different host materials doped with activators and co-activators become unavoidable before any worthwhile result is obtained. Synthesis techniques of nanophosphors are broadly divided into two categories: physical methods and chemical methods. Physical methods include molecular beam epitaxy, ionized cluster beam, liquid metal ion source, consolidation and gas aggregation of monomers. Chemical methods include colloidal capping, cluster formation, sol gel, electro-chemical, combustion etc. [2]. The author has employed combustion method and sol gel process for the synthesis of nanomaterials mentioned in the thesis. These are described briefly here: A. Combustion method Combustion synthesis is a novel technique that has received great attention in the past few years. This method was discovered in Patil’s laboratory in India in 1988 [3]. It is also known as self-propagating high temperature synthesis. K.C. Patil serendipitously synthesized fine particles of α-alumina and related oxide materials 55 using this method in his laboratory. Since the preparation of α-alumina foam by rapidly heating a solution of aluminium nitrate and urea [4], quite a number of advanced materials have been prepared by means of combustion synthesis [5]. For example, a variety of useful oxides such as yttria [6-7], ceria [7-8], zirconia [7,9-10], zinc oxide [11-12], iron oxide [13], thoria [14], aluminates [15-18], chromites [19-22], ferrites [23-24], manganites [22,25], titanates [26-27] etc. have been obtained using this technique. This method involves a highly exothermic reaction which occurs with the evolution of heat and light, when the mixture of fuel and oxidizer are ignited. The common fuels employed for the combustion process are urea (CH4N2O), carbohydrazide (CH6N4O), oxalyl dihydrazide (C2H6N4O2), glycine (C2H5NO2), diformyl hydrazine (C2H4N2O2) etc. All these fuels contain nitrogen but differ in the reducing power and amounts of gases these generate, which obviously affects the characterization of the reaction products. The nitrate salts are favoured as oxidizer because they serve as water-soluble low temperature nitrogen source for the synthesis. Stoichiometric compositions of metal nitrates and fuels are calculated based upon propellant chemistry. Thus, heat of combustion is maximum for O/F ratio 1 [4]. Based on the concepts used in propellant chemistry [4], the elements C, H, V, B or any other metal are considered as reducing elements with valencies 4+, 1+, 5+, 3+ (or valency of the metal ion in that compound), respectively and oxygen is an oxidizer having the valency of 2-. The valency of nitrogen is taken as zero because of its conversion to molecular nitrogen during combustion. Accordingly, the oxidizing (O) and reducing (F) valencies for M(NO3)3 and urea can be calculated as follows: M(NO3)3 Urea, CH4N2O 1M = 3+ C = 4+ 9O = 18- 4H = 4+ 3N = 0 O =2- 15- 2N = 0 6+ Where M = Y, Gd, La, Al, Tb, Ce. The oxidizing and reducing valencies of metal nitrates and fuels used in the combustion synthesis of oxide nanophosphors are summarized in table 2.2.1. 56 Table 2.2.1 Oxidizing and reducing valencies of metal nitrates and fuels M(NO3)2 10- M(NO3)3 15- M(NO3)4 20- NH4NO3 2- Urea, CH4N2O 6+ Glycine, C2H5NO2 9+ Carbohydrazide (CH), CH6N4O2 8+ Oxalyl dihydrazide (ODH), C2H6N4O2 10+ 3-Methyl Pyrazole 5-One (3MP5O), C4H6N2O 20+ Diformyl hydrazine (DFH), C2H4N2O2 8+ NH4VO3 3+ Hence, for any combustion synthesis, the mixture of metal nitrates (as an oxidizer) and a proper organic fuel are dissolved in a minimum amount of water in a pyrex vessel and introduced into a muffle furnace maintained at temperature of ~500°C as shown in Fig.2.2.1. Hot plate can also be used for the process. Fig. 2.2.1 Muffle Furnace The combustion reactions are carried out at low temperature initially below the phase transition of the target product. The solution boils, foams and ignites to burn with flame 57 or sometimes only smouldering is noticed, to yield voluminous foamy powder in 3-5 minutes occupying the whole volume of the reaction container as shown in Fig. 2.2.2. Fig. 2.2.2 Showing formation of voluminous combustion product. The chemical energy released during this exothermic process rapidly heat the system to high temperatures (1600°C) without any external heat source, such a high temperature leads to formation and crystallization of nanophosphors. A key feature of this technique is that the heat required to drive the synthesis is provided for the main part by an exothermal reaction occurring among the reagents, thus greatly reducing the amount of heat that has to be supplied by an external source. Actually, metal nitrates can also be decomposed by simple calcination into metal oxides, upon heating to or above their decomposition temperature; afterwards these oxides can further react together giving new substances. But, in this case, a constant external heat supply is necessary to maintain the system at the high temperature required for accomplishing the appropriate reaction. On the contrary, the combination of nitrates with a sacrificial fuel causes the ignition of this mixture of precursors at a rather low temperature as well as advance of an exothermal reaction that provides itself the heat necessary for the synthesis. In this way the system is not forced to stay at high temperature for a long period of time, thus preventing particles sintering. In addition, as the reagents are mixed in an aqueous solution, this method enables a good chemical homogeneity of the system, which leads to a nearly 58 instantaneous reaction. Thus, combustion synthesis provides an interesting alternative to other elaborate techniques because it offers several attractive advantages such as simplicity of experimental set-up, surprisingly short time between the preparation of reactants and the availability of the final product, economic due to energy saving. If on one hand the combustion synthesis is an efficient, quick and straight forward method for the preparation of oxide materials, on the other hand the mechanism of the process in terms of reactions involved is quite complex. Besides, it has been shown that the properties of the resulting oxide powders (crystalline or amorphous structure, crystallite size, purity, surface area, particle clustering and agglomeration, etc.) strongly depend on the processing parameters adopted [28]. Most of the previous investigations reported in the literature dealt with the properties of final products and were aimed at evaluating the influence exerted by the composition of the reactant mixture on both phase composition and microstructure of the oxides obtained. For example, product characteristics were observed to depend on the kind of sacrificial fuel used [15-17] as well as on the adoption as precursors of acetates instead of nitrates [16]; these characteristics were also found to change with both the nitrates/fuel ratio and the concentration of precursors in the water solution [6,8,19]. Despite these extensive investigations, the mechanism of the combustion synthesis is still not well understood, probably owing to the short synthesis times and the great number of parameters that influence the process. At any rate its knowledge entails great importance in order to control the characteristics of the final products. Three main possible mechanisms, which differ in kind and succession of chemical reactions involved in this complex process, were expounded in the literature. Kingsley et al. [4] suggested that during the first step of combustion synthesis the thermal decomposition of urea and aluminium nitrate occur simultaneously. Urea decomposes initially to biuret and ammonia and, at higher temperatures, to cyanic acid (HCNO) trimer, while aluminium nitrate decomposes to amorphous alumina and nitrogen oxide. According to these authors, afterwards, final gas phase reactions between combustible species (like ammonia and cyanic acid) and oxides of nitrogen occur, causing the appearance of a flame. Li et al [15] and Chandramouli et al [14] also supported this theory. On the contrary, Segadaes et al. [11,18,26] suggested that the overall combustion reaction could be dismembered into partial reactions of thermodynamic 59 significance, among which a combustion reaction between the fuel and the oxygen produced in the decomposition of the nitrates supplied the heat needed for the synthesis reaction. Suresh et al [13] suggested that a direct reaction between a metal nitrate and a sacrificial fuel occurs during combustion synthesis. This last reaction results in the complete fuel consumption and, being exothermal and autocatalytic once ignited, goes to completion without taking any heat from external sources. Some attempts of investigating, in an indirect way, the progress of combustion synthesis reactions by using calorimetric and thermal-gravimetric techniques are reported in the literature[14,17,23,27] while experimental results about the gases developed during the advancement of the process are not yet available. Actually, the combination of calorimetry and thermal-gravimetry with the simultaneous analysis of gaseous reaction products is a powerful tool, suitable for better understanding the mechanism of combustion synthesis. The combustion synthesis technique proves to be a simple, efficient, quick and straight forward route to synthesize nanophosphors. This method provides high purity, high crystallinity and high homogeneity even at low firing temperature, thus this route proves to be better than the conventional method. Hence in the present study author has adopted combustion synthesis for the preparation of some nanophosphors. B. Sol-Gel Method The sol-gel process is a wet chemical technique widely used in the fields of materials science and ceramic engineering. The sol-gel technology was developed during the past 40 years as an alternative for the preparation of glasses and ceramics at considerably lower temperatures. The initial systems represent a solution where different polymerization and polycondensation processes lead to the gradual formation of the solid phase network. The sol formed is at first subjected to a series of operations: gelling, drying, pressing and casting, which results in various structural and phase transformations. This allows formation of powders, fibers, coatings, bulk monolithic products etc. from the same initial composition. According to Sakka [29] who is one of the pioneers in this new trend of technological development, the sol-gel technology is a typical nanotechnology because all gel products may contain nanoparticles or are nanocomposites. In this sense it plays a principle role in the development of modern nanotechnology for the preparation of 60 new materials. Sol-gel research grew to be so important that in the beginning of 80’s reasonably good number of the papers were published and in 1990’s more than 35,000 papers were published worldwide on the process [30-32]. The successful development of modern nanophosphors technology associated with the synthesis of nanomaterials is, to a large extent, due to the application of different variants of submicron powders. Based on the data concerning the development of sol-gel technologies, in summary one can say that a very important moment is the choice of appropriate precursors. Most often these are alkoxides, soluble metal salts, polymers, colloids, which depending on their nature, may be combined with suitable solvents and the aggregation processes stimulating solid phase formation can be controlled. Fig. 2.2.3 shows schematically the most used variant of the sol-gel process. Fig. 2.2.3 Different routes of the sol-gel processing A general method proposed by Kachichana [33], according to which a chemical process starting from the solutions and leading to a solid phase without precipitate is a sol-gel process even if the system does not represents an infinite solid network. One of the methods involves the combination of chemical reactions which turns a homogeneous solution of reactants into an infinite molecular weight polymer. This polymer is a three dimensional interconnected pores. The polymer is isotropic, homogeneous and uniform and it replicates its mold exactly and miniaturizes all 61 features without distortion. Thus the polymer net works provide nanostructure and nanophase porosity. The non-hydrolytic sol-gel method (without participation of water) is also promising, especially with respect to transition metal oxides. This concerns mainly reactions associated to chloride hydrolysis with metal alkoxides [34, 35]. The process has been available to synthesized oxide of the silicon [36-40], titanium [38-41], aluminum [39-42], aluminosilicates and silicon-titanium [43-47]. Matrix oxide is an important host for rare earths ions due to large application fields such as phosphors, solid –state lasers, non-linear optic and others [48.49]. Another method widely used during the last decade is the Pechini method [50, 51,52]. This method is based on esterification processes between chelate complexes of metal ions (soluble metal salts , nitrates, acetates, etc. combined with a chelate agent , citric acid or EDTA) and ethylene glycol. The resin obtained in this way is transformed, after thermal treatment, into a nanosized powder in which the particles are distributed within very narrow limits (monodispersity) and the reactivity is enhanced. The above examples from various scientific regions also confirm that the sol-gel methods are among the main routes of obtaining hybrid and nanostructured materials. Sol-gel process has also been adopted in the thesis to synthesize nanomaterials involving chelating agents (citric acid and L-tartaric acid), which is easier to process, energy saving and cost effective compared to with those of the traditional sol-gel methods [53, 54]. There are carboxylate (-COOH) and hydroxyl (-OH) functional groups existing in the molecular structure of chelating agents which can act as bidentate ligands and establish polynuclear complex with metals [55-58]. Thus these ligands may offer the opportunity for different kinds of ions coming in close proximity and the molecular level mixing leading to high degree of homogeneity with small particle size and high surface area for example, it was demonstrated that the tartaric acid in synthesizing BiFeO3 resided in the formation of hetrometallic polynuclear complexes in the solution, where reacting metal atoms came in close proximity [55]. The nanoparticles were synthesized according to the flow chart presented in Fig. 2.2.4. The high purity starting materials were weighed according to the nominal composition of the required host lattice and dissolved in minimum amount of diluted HNO3 to get a transparent solution. Chelating ligand in different ratios with respect to the total metal ions of the host lattice was then slowly added to the solution. Different molar ratios of metal ions to organic acids (1:1, 1:2, 1:3 and 1:4) were taken to 62 investigate the effect of these acids content on particle size, surface area and photoluminescence properties of the prepared nanoparticles. However, no observable changes were indicated on the size of the particle and surface area with different amount of organic acids. The highest emission intensity was observed when the ratio of metal ion to organic acid was 1:2. It may be due to the reason that high chelating acid concentration brought about a higher carbon impurity left in the samples which is not favorable for luminescence while the lower acid amount accelerated the rate of hydrolysis which yielded in the formation of inhomogeneous nanoparticles. Zhou et al have observed similar behaviour of the carbon contents on the luminescent of YAG prepared by solgel process using citric acid [59]. The observed results indicated that the suitable molar ratio of metal ion to tartaric acid is 1:2 in order to have good emission intensity of the nanoparticles. Fig. 2.2.4 Flow chart for the synthesis of light emitting nanoparticles. The mixture was heated under constant stirring at 80oC for 2 hrs, which made the mixture denser forming the ‘sol’. Then, the sol was heated at 120oC until a gel was formed and dried subsequently to get a grey fluffy powder. Conditions of formation of gel strongly depend on the nature of the chelating ligand employed. In case of tartaric 63 acid precipitates immediately appeared; while solutions of citric acid remained transparent for many hours. This differences in behaviour remained after the gelification process. Tartaric gels were fluffy grey and poorly viscous, while citric acid gel samples were whitish and more viscous, chelating agent geometry may be argued to account for their different behavior. In case of tartaric acid double chelating “claw” geometry may initiate 1D or 2D polymeric structure formation [60, 61] which is likely to quickly develop up to the formation of stable nucleus leading to the observed precipitation phenomenon. In case of citric acid, due to the lack of double opposite chelating “claw” the precipitation process could not occur. The dried gel was collected and subjected to the further heat treatment at various temperatures ranging from 500-1200oC for 3 hrs. The synthesized materials obtained through sol-gel process have been characterized by photoluminescence (PL) spectra, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X- ray analysis (EDAX) and X-ray diffraction (XRD) techniques. The sol-gel approach is a cost effective and low-temperature technique that allows for the fine control of the product’s chemical composition. Even small quantities of dopants, such as rare earth elements, can be introduced in the sol and end up uniformly dispersed in the final product. Sol-gel derived materials have diverse application in optics, electronics, energy, space, sensors, medicine, reactive materials and separation technology. This route is faster than solid state reaction and leads to mixing at molecular level of the constituents as well as formation of a better chemically homogenized product. 3. INSTRUMENTATION In material characterization, basically the synthesized materials are characterized by variety of techniques to assure that the appropriate materials with suitable properties are synthesized. A brief discussion of some of the techniques and instruments utilized for the characterization of nanophosphors is given below: A) LUMINESCENCE SPECTROSCOPY i) Principle The photoluminescent spectrum is obtained by plotting the relationship between the wavelength and the intensity of emitted light from a sample excited by an appropriate excitation source of constant energy. The source of excitation can be UV 64 and visible light such as tungsten lamp, discharge lamp, xenon discharge lamp, mercury discharge lamp, laser [62-63], excimer lamp [64], electron beam excitation etc. The spectrum is obtained using a monochromator equipped with an appropriate light detector. In an excitation spectrum, the relationship is obtained by observing changes in the emitted light intensity at a set wavelength while varying the excitation energy. When the excitation source is light, single-frequency light produced by a monochromator impinges on the sample and the emitted light intensity is recorded as the excitation wavelength is varied. In a spectrum, intensity of light at a particular wavelength is expressed along the ordinate and the wavelength along the abscissa. The units of the ordinate are either irradiance E (W.m-2) or number of photons Ep (photons.m-2). The units of the abscissa are expressed in terms of wavelength  (nm) or wave number v (cm-1). Using these units, the spectrum irradiance is expressed as E ( )  dE (W . m2 . nm1 ) d (1) dE  (W . m2 .(cm1 )1  dv (2) or E (v )  and the spectral photon irradiance is expressed as E p ( )  dE p d ( photons . m2 . nm1 ) (3)  photons m (4) or E p (v )  dE p dv 2 (cm1 )1  Depending upon the type of the experiment, the units are selected. For quantum efficiency, photon irradiance is employed whereas for energy efficiency, irradiance is employed. The luminosity of a phosphor is expressed in terms of irradiance, which is obtained by integrating the spectral data, E(), multiplied by the relative photopic spectral luminous efficiency, V(), divided by the light equivalence value, [65-66] Km = 673 lm.Watt-1 i.e.  L  K m  V ( )E ( )d  , lm.m2 0 65 (5) ii) CIE colorimetric system In the study of color perception, one of the first mathematically defined color spaces was the CIE colorimetric system [67] established by the CIE in 1931. This is the most important concept used these days. The CIE chromaticity diagram is shown in Fig. 2.3.1. This system consists of the RGB and the XYZ colorimetric systems. The XYZ system, which will also be explained below, was laid down as an extension of the RGB system for practical applications. Fig. 2.3.1 CIE Chromaticity Diagram The RGB system was derived from results of psychophysical experiments. In the experiments, the observers viewed a circular field with an angular diameter of 2°. The circular field consisted of two identical half circles adjacently located on the right and left. The color of the two identical half circles adjacently located on the right and left. The color of the two half circles was independently variable. One of the two half circles was used as the reference field and another was used as the test field. Colors of the reference field were called the reference colors and those of the test field of the same intensity at various wavelengths over the entire visible range. The test colors, on the other hand, were composed with a mixture of the three primary colors, red (700 nm), green (546.1 nm), and blue (453.8 nm). The numbers in parentheses show the wavelengths of the respective primary colors. By varying the mixing ratio of the three 66 primary colors, the observers varied the colors of the test field. In this way, the color of the test field was made to match that of the adjacent reference field. During the observations, it was found that in some wavelength ranges mixtures of three primary colors could not match the reference colors. In these wavelength ranges, matches were established if an amount of one of the three primary colors was added to the monochromatic reference colors. This implies that matches can be established by the subtracting one of the primary colors form the mixtures. In other words, there are some wavelength ranges where the stimulus of the primary colors is negative. In this way, the mixture ratio of the primary colors to match all the spectral colors over the entire visible range was obtained. It was assumed, when a match was established, that the reciprocals of the energy ratio of each primary color of the test field corresponded to the relative strength of the stimuli of the respective primary colors at the wavelength of the reference with which the color was matched. Based on the above assumption, three spectral distribution curves of the relative strength of the stimulus for each of the three primary colors (red, green and blue) over the entire visible range were obtained. The curves are called the spectral tristimulus values or the color matching coefficients. They are r(), g(), and b(), respectively.  in the parenthesis is the wavelength. As, the sum of the three tristimulus values at each wavelength is always 100%, the mixture ratio of the three primary colors can be obtained by any two of the three tristimulus values. The RGB color metric system is based on this and all colors are indicated on the r() and g() coordinates. To overcome difficulties associated with the negative stimulus of the primary colors, based on the above mentioned color matching experiments, three imaginary reference color stimuli [X], [Y], and [Z] were introduced. By employing the imaginary reference color stimuli, the original tristimulus values were converted mathematically into positive values and all colors could be composed by mixing (not subtracting) these three stimuli. This is the basis of the XYZ colorimetric system. Y has been chosen to correspond with the lightness stimulus. Based on the similar idea with that of the RGB colorimetric system, all colors are indicated by these coordinates. Test light source colors are specified below. The tristimulus value (X, Y and Z) for a test light source, which has a spectral energy distribution P (), are calculated with the following formulae: 67 780 X K  P (  ) x ( ) d  (6) 380 Y  KP ( ) y ( ) d  (7) 780  P ( ) z ( ) d  ZK (8) 380 K Where 1 P( )Y ( )d  and x( ) , y( ) , and z ( ) are the spectral stimulus values for 2°. These quantities are written as x10 ( ) , y10 ( ) , z10 ( ) for 10. The chromaticity coordinates of the color of the light sources x and y are calculated with the following formulae. x X X Y  Z (9) y Y X Y  Z (10) The colors of light sources on the XYZ colorimetric system are specified with Y calculated with Eq. 7 and x and y calculated with Eq. 9 and 10 respectively. Specification of the nonluminous object colors The tristimulus values [68] (X, Y, and Z) of the object for which the spectral reflectance (or spectral transmittance) is  ( ) and  ( ) are given by 1 X K 780  P (  )  ( ) x ( ) d  (11) 380 780 1 Y  P( )  ( ) y( )d  K 380 Z 1 K (12) 780  P ( )  ( ) z ( ) d  (13) 380 780 Where K   P ( ) y ( ) d  380 P( ) is the spectral power distribution of the light source which illuminates the object, and x( ) , y( ) , and z ( ) are the CIE spectral trichromatic stimuli for fields of 68 2° or 10°. The chromaticity co-ordinates of the color of the objects can then be calculated, as with the light sources, using Eq. 9 and 10. CIE co-ordinates are powerful concept because they facilitate representing an entire luminescent spectrum by two numbers and the simplicity of the visual method for obtaining the color gamut of phosphors is quite attractive. The main drawback of CIE co-ordinate system is that it involves complexity in calculation but the spectrophotometer used by us automatically calculated the CIE co-ordinates. iii) Procedure Photoluminescence (PL) spectra were taken in solid powder form of the nanophosphors. For photoluminescence measurements, 0.05 g powder samples were pressed into pellets (10mm diameter and 1mm thickness), then exposed to a ultraviolet rays of suitable wavelength using xenon arch lamp. All measurements were carried out at room temperature. The emission color was analyzed and confirmed with the help of Commission de I Eclairage (CIE) chromaticity coordinate diagram. iv) Instrument Photoluminescence Spectrophotometer spectra F-7000 (Fig. were 2.3.2) recorded with and Konica Hitachi Flourescence Minolta’s portable spectroradiometer CS-1000 (Fig.2.3.3). The emission color co-ordinates were analyzed by Minolta spectroradiometer. Even PL experiments were performed in backscattering geometry used for exciting a He–Cd laser (325 nm) Q1 with an optical power of 30 mW. The emitted light was analyzed by HR-4000 Ocean Optics USB spectrometer optimized for the UV–vis range. Fig.2.3.2 Hitachi Flourescence Spectrophotometer F-7000 69 Fig.2.3.3 Minolta Spectroradiometer CS-1000 B) X-RAY DIFFRACTION STUDIES In 1895, German Physicist W.C. Roentgen discovered invisible rays which are known as X-rays. These rays affect photographic film similar to that of light but more penetrating than light. It was in 1912, when German Physicist Van Laue established the wave like nature of X-rays. In the same year two English physicists W.H. Bragg and his son W.L. Bragg successfully analysed the same experiment and derived the conditions for diffraction from a 3d-periodic arrangement of atoms. X-rays are electromagnetic radiation of very much shorter wavelength compared to that of light. The X-rays used in diffraction have wavelengths in the range of 0.5-2.5 Ǻ and thus lie in between gamma and ultraviolet rays. X-rays carry energy and the rate of flow of this energy through unit area perpendicular to the direction of motion of the wave is proportional to the square of the amplitude of the wave and known as intensity (I) of the radiation. X-rays are produced when an electrically charged particle (e.g. electrons) of sufficient kinetic energy is rapidly decelerated. When electrons moving at high speeds are directed to a metal target, a very small percentage of their kinetic energy is converted into X-rays. Most of the kinetic energy of the electrons striking the target is converted to heat, less than 1% being transformed into X-rays. The X-rays emitted by the target consist of a continuous range of wavelengths and is called the white or continuous radiation. The minimum wavelength in the continuous spectrum is inversely proportional to the applied voltage which accelerates the electrons towards the target. The intensity is zero upto a certain wavelength, called the short wavelength limit 70 (SWL). It increases rapidly to a maximum and then decreases with no sharp limit on the long wavelength side. The continuous spectrum gets generated due to the emission of energy as a result of declaration of electrons heating the target. Electrons which are stopped in a single impact give rise to maximum energy. The corresponding wavelength, [69] known as short wavelength limit, is given by Eq. 14. SWL = 12.40x 103/V (14) If an electron is not completely stopped in one encounter, it undergoes a glancing impact which only partially decreases its velocity, then only a fraction of its energy is emitted as radiation; the corresponding X-ray has a wavelength longer than SWL. The totality of these wavelengths, ranging upward from SWL constitutes the continuous spectrum. The total X-ray energy emitted per second, i.e. intensity is given by Eq. 15. I continuous spectrum = Ai Z Vm (15) Where A is proportionality constant, m is a constant of about 2, i is the current and Z is the atomic number of the target [70]. The material of the target affects the intensity but not the wavelength distribution of the continuous spectrum. When the applied voltage is sufficiently high, in addition to the white radiation, a characteristic radiation of a specific wavelength and high intensity is also emitted by the target. However, these are narrow and their wavelengths are characteristics of the target metal. These radiations fall into several sets, K, L, M, etc in the order of increasing wavelength. Ordinarily K lines are useful in X-ray diffraction because longer wavelengths lines are being easily absorbed. Several lines are possible in the K set i.e. K1, K2, and K1. Among these K1 is preferred for X-ray diffraction. i) Basic Principles of Diffraction X-ray diffraction can be explained in simple terms by the reflection of an X-ray beam from a stock of parallel equidistant atomic planes. The diffracted beam is thus composed of a large number of scattered rays mutually reinforcing each other. Diffraction essentially is a scattering phenomenon. When X-ray interacts with atom, it 71 gives rise to scattering in all directions; in some of these directions the scattered beams will be completely in phase and so reinforce each other to form diffracted beams. Fig. 2.3.4 Diffraction of X-rays by a crystal Fig. 2.3.4 shows a set of parallel planes in a crystal. A beam of X-rays of wavelength  is directed towards the crystal at an angle  to the atomic planes. The atomic planes are considered to be semi-transparent. i.e. they allow a part of the X-rays to pass through and reflect the other part. Considering rays 1, Ia in the incident beam, they strike the atom at K and P in the first plane of atoms and are scattered in all directions. However, only I and Ia out of all scattered rays are completely in phase and so capable of reinforcing one another. Rays 1 and 2 are scattered by atoms K and L, and the path difference for rays is given in Eq. 16. ML+LN = d sin  + d sin  = 2 d sin  (16) The two scattered rays will be completely in phase if this path difference is equal to an integral multiple of wavelengths, i.e. n=2d sin (17) Eq. 17 is known as Bragg Law and  is known as the Bragg angle [71,72] where maximum intensity occurs and n is the order of diffraction. At other angles, there is little or no diffracted intensity because of destructive interference. Sin = n/2d≤1 ≤2d for n=1 72 Thus, first order Bragg reflection can occur only for wavelengths ≤2d. Since the lattice spacing d is of the order of angstroms, X-rays (wavelength in Ǻ) are well suitable for diffraction studies. This means that spacing d can be easily evaluated from measurements of first order Bragg angle  using Bragg’s law with n=1. If the regular arrangement of atoms in a crystal is considered, stacks of parallel lattice planes are found with different characteristic spacings. Therefore, each crystallographic phase shows a characteristic set of d-spacings which yields a diffraction pattern with intensities at the corresponding Bragg angle  [73]. The average crystalline size in phosphors powders can be estimated using the Scherrer equation based on diffraction peak broadening. This scherrer equation (Eq. 18) has been drawn from Bragg’s Law. Scherrer equation, D=  (18) Where, D is the average crystallite size  is the x-ray wavelength  is the diffraction angle.  is the full width at half maximum(FWHM) in radian. Sample identification can be easy by comparing the experimental diffraction pattern to that in the JCPDS files. Sample preparation is relatively simple; powders can be pressed into a disc, film, or smeared onto a substrate and the experiment does not require vacuum. The particle size and its crystalline behavior were analysed by observing the peak broadening and noise in diffraction pattern. ii) Instrument Rigaku D/Max 2000-Ultima plus (Fig. 2.3.5), Rigaku Mini Flex’ ii and Rigaku Ultima IV diffractometers were used to analyse XRD pattern of the various nanophosphors. 73 Fig. 2.3.5 Rigaku D/Max 2000-Ultima plus Diffractometer C) ENERGY DISPERSIVE X-RAY ANALYSIS Energy dispersive X-ray analysis is an experiment that determines the amount in weight percent of various elements present in a compound. By EDAX technique a quantitative analysis can be made of elements with atomic number of 6 (carbon) or greater. This type of analysis is useful for organic as well as inorganic compounds. Combining the EDAX spectrum with the SEM allows the identification, at micro structural level, of compositional gradients at grain boundaries, second phases, impurities, inclusions, and small amounts of material. In the scanning mode, the SEM/EDS unit can be used to produce maps of element location, concentration, and distribution. i) Principle One of the instruments most commonly used in conjunction with the SEM is the Energy Dispersive X-ray Spectrometer (EDS). The X-ray spectrometer converts a Xray photon into an electrical pulse with specific characteristics of amplitude and width. A multi-channel analyzer measures the pulse and increments a corresponding "energy slot" in a monitor display. The location of the slot is proportional to the energy of the X-ray photon entering the detector. The display is a histogram of the X-ray energy received by the detector, with individual "peaks," the heights of which are proportional to the amount of a particular element in the specimen being analyzed. The locations of the peaks are directly related to the particular X-ray "fingerprint" of the elements present. Consequently, the presence of a peak, its height, and several other factors, 74 allows the analyst to identify elements within a sample, and with the use of appropriate standards and software, a quantitative analysis can be made of elements with atomic number of 6 (carbon) or greater. ii) Instrument The energy dispersive X-ray analyses were performed by JEOL-JSM- 6300 scanning electron microscope. D) SCANNING ELECTRON MICROSCOPY Scanning electron microscopy also known as SEM, can generate impressive physical and structural details. The scanning electron microscope is based on scanning a finely focused electron beam across the surfaces of a specimen. The latter reflects the beam into two directions X and Y. These reflection signals are collected, and their intensities are displayed on a cathode-ray-tube screen by brightness modulation. As already indicated, the method allows specimen magnifications to more than 100,000 while maintaining a large depth of focus. The ease of sample scanning of a SEM over large distances is quite appealing, in that a large sample scanning-viewing area is first surveyed at generally low magnifications to seek out particular areas of interest, followed by high magnification of those specific areas for subsequent detailed investigations. Hence, specific surfaces irregularities, for example, known to be present or noted at low magnifications can be identified and further investigated at significantly higher magnifications. Such studies can highlight unexpected geometrical configurations, unique shapes of particulates, or the degree of deficiency. The SEM is also extensively employed for the generation of dimensional and spatial relationship details of structure elements. i) Fundamental electron-material interactions SEM tools rely on the generation of electrons accelerated through an electric field to acquire sufficient kinetic energy. These energized electrons are then directed onto the material to be investigated. The electron interaction with the material results in a number of different energy dissipation modes. The particular type of released energy depends on the energized electron interaction with the various orbital electrons of the material. If the ejected orbital electron is weakly bound, it emerges with only a few eVs of energy. These are termed secondary electrons. Secondary electrons generated sufficiently deep within the material are reabsorbed by that material before they can 75 reach the surface, whereas those generated near the surface can escape and therefore are detectable. Secondary electrons created at topographic peak areas in a material will have a greater chance to escape than those generated in topographic troughs. Furthermore, since the greatest density of secondary electrons is created by the primary beam of energized electrons before they spread into the material to undergo other possible energy signals. The ability to capture both the topographic sensitivity and the spatial resolution forms the basis for high-resolution microscopy of the material surfaces as measured by a SEM tool. As long as a material surface exhibits some degree of surface irregularities, it generates a SEM micrographic image. The ultimate spatial resolution of a SEM image is proportional to the tool’s ability to generate an electron current density. The development of the field mission gun Crewe in 1968 greatly advanced the resolution of a SEM. The gun creates extremely high electron current densities by forcibly emitting electrons from a needlepointed metal tip under an intense electric field and ultra-high-vacuum conditions. ii) SEM Analysis SEM photo microscopy tends to be the preferred means to obtain any initial high-resolution data of a particular sample. It is quite useful for the most dimensional and structural shape information, including feature-to feature comparisons to evaluate consistencies or abnormalities. iii) Instrument The morphology of the nanocrystals was studied by using different scanning electron microscopes (SEM) such as JEOL -JSM-6300 scanning electron microscope operating at 10 kV and Philips XL 30 instrument. The Philips XL30,scanning electron microscope is shown in Fig. 2.3.6. Fig. 2.3.6 The Philips XL30, fully computer-controlled scanning electron microscope 76 E) TRANSMISSION ELECTRON MICROSCOPY TEM is a microscopy technique where by a beam of electrons is transmitted through an ultra thin specimen, interacting with the specimen as it passes through. An image is formed from the interaction of the electrons transmitted through the specimen; the image is magnified and focused onto an imaging device, such as a CCD camera. TEMs are capable of imaging at a significantly higher resolution than light microscopes, owing to the small de Broglie wavelength of electrons. This enables the instrument to be able to examine fine detail-even as small as a single column of atoms, which is tens of thousands times smaller than the smallest resolvable object in a light microscope. TEM forms a major analysis method in a range of scientific fields, in both physical and biological sciences. ii) Working principle TEM works like a slide projector. A projector shines a beam of light which transmits through the slide. The patterns painted on the slide only allow certain parts of the light beam to pass through. Thus the transmitted beam replicates the patterns on the slide, forming an enlarged image of the slide when falling on the screen. TEMs work the same way except that they shine a beam of electrons (like the light in a slide projector) through the specimen (like the slide). However, in TEM, the transmission of electron beam is highly dependent on the properties of material being examined. Such properties include density, composition, etc. For example, porous material will allow more electrons to pass through while dense material will allow less. As a result, a specimen with a non-uniform density can be examined by this technique. Whatever part is transmitted is projected onto a phosphor screen for the user to see. For preparation of samples for TEM analysis, the nanophosphors were dispersed well in an appropriate solvent. 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