Document 6535987
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Document 6535987
Chapter III Experimental Techniques and Sample Preparation Chapter III Experimental Techniques and Sample Preparation 3.1 Introduction ZnO thin films are highly attractive in the development of materials area, due to their interesting physical properties as high transparency in the visible and nearultraviolet (UV–Vis) spectral regions, as well as their luminescence. The applications of ZnO have attracted much attention in recent years. Compared to physical coating processes in a vacuum, the sol-gel method can be used with an enormous range of mostly commercially available starting materials. This allows multifunctional layers to be produced. Besides the simple processing of the colloidal solutions (sols), the sol-gel method is compatible with established coating technologies (dip-coating, spraying, centrifugation, blade coating, etc.), has low investment costs and the crystalline quality of the ZnO prepared by the sol–gel process shows hexagonal structure. Notably, the sol–gel processes with an annealing treatment and doping are intimately affect the crystallization and physical properties. 3.2 Sol-gel Process The sol-gel process may be described as: “Formation of an oxide network through polycondensation reactions of a molecular precursor in a liquid”. A sol is a stable dispersion of colloidal particles or polymers in a solvent. The particles may be amorphous or crystalline. An aerosol is particles in a gas phase, while a sol is particles in a liquid. A sol consists of a liquid with colloidal particles which are not dissolved, but do not agglomerate or sediment. The method may provide good control over stoichiometry and reduced sintering temperature. The different sol-gel processing options are given in Fig 3.1 44 Chapter III Experimental Techniques and Sample Preparation Fig 3.1 Sol-Gel Processing options 3.3 Preparation of sol and coating Fig 3.2 common preparation of sol In the sol-gel process, the precursors (starting compounds) for preparation of a colloid consist of a metal or metalloid element surrounded by various ligands [Jeffrey Brinker, 1990]. For example, the common precursors for zinc oxide include inorganic 45 Chapter III Experimental Techniques and Sample Preparation (containing no carbon) salts such as ZnCl2 and organic compounds such as Zinc acetate (Zn (CH3CO2)2). The later material is the most widely used precursor in zinc oxide (ZnO) sol gel research. Metal alkoxides are popular precursors because they react readily with the solvents (water or alcohol). The reaction is called the hydrolysis, which gives the sol. This sol is coated through dip or spin coating technique. The spin coater used in the present work is shown in Fig 3.3 Fig 3.3 Spin coater (HOLMARC) used in this work The sol prepared was deposited on the cleaned glass substrate using the above spin coater rotated at the rate of 3000rpm. After each coating the film is heated and the coating is repeated for few times to get a desired thickness of the film. Finally the film is annealed at suitable temperature. 46 Chapter III Experimental Techniques and Sample Preparation 3.4 Characterization Techniques Thin films are often characterised using a number of different physical characterisation techniques. The techniques used in this thesis are briefly presented in this section. 3.4.1 Structure Determination by X-Ray Diffraction (XRD) X-ray diffraction (XRD) is a versatile, non-destructive technique that reveals detailed information about the chemical composition and crystallographic structure of natural and manufactured materials. Atoms of a pure solid are arranged in a regular periodic pattern called ‘a lattice’. The inter-atomic distance and interaction of atoms in any crystalline lattice is unique and results in a unique X-ray diffraction (XRD) pattern to identify its crystal structure. When X-ray radiation with a wavelength, λ, is incident onto a crystal, a diffraction peak occurs if the Bragg criterion [Bragg W.L., 1913] for constructive interference is satisfied (the sharpness of this peak is a measure of the degree of ordering in the crystal) Nλ = 2d sinθ----------------------------(3.1) Fig 3.4 View of Bragg´s Law: nλ=2dsinθ where d is the inter-plane separation of the lattice, n = 0, 1, 2, ... is the interference order and θ is the angle of incidence as shown in Fig 3.4. In this work, the structure and lattice parameters of ZnO films were analyzed by a X-ray diffractometer (XRD) with Cu (Kα) 47 Chapter III Experimental Techniques and Sample Preparation radiation with = 1.5405 Å (40 kV, 30 mA). XRD can be used to extract information on a number of thin film properties, such as crystalline structure, phase composition, residual stress state, film thickness, grain size, and crystallographic orientation, and is thus a very powerful technique. The values of lattice constants a and c for various layers calculated using equation [Yasemin Caglar et al., 2009] 2 1 4 h2 hk k 2 l 2 (3.2) d2 3 a2 c where ‘d’ is the interplanar spacing and h, k, and l are the Miller indices. The preferential growth orientation was determined using a texture coefficient TC(hkl). This factor is calculated using the following relation [Caglar et al., 2006]: TChkl I ( hkl ) / I 0( hkl ) N 1 n I ( hkl ) / I 0( hkl ) (3.3) where I(hkl) is the measured relative intensity of a plane (hkl),Io(hkl) is the standard intensity of the plane (hkl) taken from the JCPDS data, N is the reflection number and n is the number of diffraction peaks. A sample with randomly oriented crystallite presents TC(hkl) = 1, while the larger this value, the larger abundance of crystallites oriented at the (h k l) direction. From the XRD pattern, the average crystallite size could be calculated using the Debye Scherrer’s formula [Cullity, B.D., 1978] D 0.9 (3.4) cos where D is the grain size, λ is the wavelength of the x-ray radiation used, β is the full width at half maximum (FWHM) of the diffraction peak and θ is the Bragg diffraction angle of the XRD peak. The relative percentage error for the observed and JCPDS standard d –value for all the films is calculated using the formula [Shinde et al., 2008], 48 Chapter III Experimental Techniques and Sample Preparation Relative percentage error, d % ZH Z Z 100 (3.5) where ZH is the observed d-value and Z is the standard d-value from JCPDS data file. 3.4.2 Surface Morphology by Field Emission Scanning Electron Microscopy (FESEM) Figure 3.5 Schematic diagram of a FESEM. Electron microscopes use a beam of highly energetic electrons to probe objects on a very fine scale. In standard electron microscopes, electrons are mostly generated by “heating” a tungsten filament (electron gun). They are also produced by a crystal of LaB6. The use of LaB6 results in a higher electron density in the beam and a better resolution than that with the conventional device. In a field emission (FE) electron microscope (Fig 3.5), on the other hand, no heating but a so-called "cold" source is employed. Field emission is the emission of electrons from the surface of a conductor caused by a strong electric field. An extremely thin and sharp tungsten needle (tip diameter 10–100 nm) works as a cathode. The FE source reasonably combines with scanning electron microscopes (SEMs) whose development has been supported by advances in secondary electron detector technology. The acceleration voltage between cathode and anode is commonly in the order of magnitude of 0.5 to 30 kV, and the 49 Chapter III Experimental Techniques and Sample Preparation apparatus requires an extreme vacuum (~10–6 Pa) in the column of the microscope. Because the electron beam produced by the FE source is about 1000 times smaller than that in a standard microscope with a thermal electron gun, the image quality will be markedly improved; for example, resolution is on the order of ~2 nm at 1 keV and ~1 nm at 15 keV. Therefore, the FE scanning electron microscope (FE-SEM) is a very useful tool for highresolution surface imaging in the fields of nanomaterials science. 3.4.3 Chemical Composition by EDAX and XPS EDAX Energy dispersive X-ray spectroscopy (EDS, EDX or EDXRF) is an analytical technique used for the elemental analysis or chemical characterization of a sample. It is one of the variants of XRF. As a type of spectroscopy, it relies on the investigation of a sample through interactions between electromagnetic radiation and matter, analyzing xrays emitted by the matter in response to being hit with charged particles. Its characterization capabilities are due in large part to the fundamental principle that each element has a unique atomic structure allowing x-rays that are characteristic of an element's atomic structure to be identified uniquely from each other. To stimulate the emission of characteristic X-rays from a specimen, a high energy beam of charged particles such as electrons or protons (see PIXE), or a beam of X-rays, is focused into the sample being studied. At rest, an atom within the sample contains ground state (or unexcited) electrons in discrete energy levels or electron shells bound to the nucleus. The incident beam may excite an electron in an inner shell, ejecting it from the shell while creating an electron hole where the electron was. An electron from an outer, higherenergy shell then fills the hole, and the difference in energy between the higher-energy shell and the lower energy shell may be released in the form of an X-ray (Fig 3.6). The number and energy of the X-rays emitted from a specimen can be measured by an energy dispersive spectrometer. As the energy of the X-rays are characteristic of the difference in energy between the two shells, and of the atomic structure of the element from which they were emitted, this allows the elemental composition of the specimen to be measured. The excess energy of the electron that migrates to an inner shell to fill the newly-created hole can do more than emit an X-ray. Often, instead of X-ray emission, the excess energy 50 Chapter III Experimental Techniques and Sample Preparation is transferred to a third electron from a further outer shell, prompting its ejection. This ejected species is called an Auger electron, and the method for its analysis is known as Auger Electron Spectroscopy (AES). Fig 3.6 Elements in an EDX spectrum are identified based on the energy content of the X-rays emitted by their electrons as these electrons transfer from a higher-energy shell to a lower-energy one. XPS Information on the quantity and kinetic energy of ejected electrons is used to determine the binding energy of these now-liberated electrons, which is element-specific and allows chemical characterization of a sample. X-ray photoelectron spectroscopy (XPS) is a surface sensitive technique, which provides information both about chemical composition and chemical bonding. The phenomenon is based on the photoelectric effect outlined by Einstein in 1905 where the concept of the photon was used to describe the ejection of electrons from a surface when photons impinge upon it. For XPS, Al Kα (1486.6eV) or Mg Kα (1253.6eV) are often the photon energies of choice. Other X-ray lines can also be chosen such as Ti Kα (2040eV). The XPS technique is highly surface specific due to the short range of the photoelectrons that are excited from the solid. The energy of the photoelectrons leaving the sample are determined and this gives a spectrum with a series of photoelectron peaks. The binding energy of the peaks are characteristic of each element. The peak areas can be used (with appropriate sensitivity factors) to determine the composition of the materials surface. The shape of each peak and the 51 Chapter III Experimental Techniques and Sample Preparation binding energy can be slightly altered by the chemical state of the emitting atom. Hence XPS can provide chemical bonding information as well. XPS is not sensitive to hydrogen or helium, but can detect all other elements. XPS must be carried out in ultra high vaccum (UHV). Fig 3.7 Diagram of the Side View of XPS System. The analysis of composition has been widely applied in the thin film research fields. One can obtain the composition of thin films from XPS spectra. The information of all elements in thin film can be gained from the survey scan spectrum of XPS. The detailed information of each element in the thin film can be obtained from the narrow scan spectrum of XPS. 3.4.4 Transmission Electron Microscope TEMs use electrons as “light source” and their much lower wavelength make it possible to get a resolution a thousand times better than with a light microscope. A "light source" at the top of the microscope emits the electrons that travel through vacuum in the column of the microscope. Instead of glass lenses focusing the light in the light microscope, the TEM uses electromagnetic lenses to focus the electrons into a very thin beam. The electron beam then travels through the specimen you want to study. Depending on the density of the material present, some of the electrons are scattered and disappear from the beam. At the bottom of the microscope the unscattered electrons hit a fluorescent screen, which gives rise to a "shadow image" of the specimen with its different parts displayed in varied darkness according to their density. The image can be 52 Chapter III Experimental Techniques and Sample Preparation studied directly by the operator or photographed with a camera. The possibility for high magnifications has made the TEM a valuable tool in both medical, biological and materials research. Fig 3.8 A schematic diagram of the transmission electron microscope 3.4.5 UV-Vis Absorption Spectrophotometer The purpose of this instrument is to determine the amount of light of a specific wavelength absorbed by an analyte in a sample. The samples may be gases or liquids or solid materials, an analyte dissolved in a solvent. The double beam spectrometer consists of multifrequency source, grating, beam splitter, sample and reference holder then optical detector. 53 Chapter III Experimental Techniques and Sample Preparation Fig 3.9 Double beam spectrophotometer. The optical transmittance of all samples was measured by this spectrometer in the range of wavelength 300–1000 nm. Transmittance of the films are connected with the absorption coefficient (α) by the relation [Manifacier et al., 1976] 1 t 1 T (ln ) (3.6) or the absorption coefficient (α) could be evaluated by the relation [Suwanboon et al., 2008) A (3.7) d s' where A is the measured absorbance and d s' is the thickness of sample in UV–Vis cell. The bandgap of semiconductor materials will increase with the decrease in particle size(S C SINGH et al., 2010), which leads to the shift of the absorption edge towards high energy side, which is the so called quantum size effect. Band gap values are obtained by extrapolating the linear portion in the plots of (αhν)2 versus (hν) to cut the x-axis, i.e., at (αhν)2 =0, which is obtained by the Tauc’s relationship [Tauc, 1970]. The optical bandgap, Eg, is determined from the absorbance spectra, where a steep increase in the absorption is observed due to the band–band transition using the general relation h A(h Eg )n (3.8) 54 Chapter III Experimental Techniques and Sample Preparation where A is a constant related to the effective masses of charge carriers associated with valence and conduction bands, Eg the bandgap energy, hν the photon energy, and n = 2 or 1/2, depending on whether the transition is indirect or direct, respectively. h A(h Eg )2 (3.9) h A(h Eg )1/2 (3.10) 3.4.6 Photoluminescence Photoluminescence spectroscopy (PL) is a powerful optical method used for characterizing materials. It can be used to find impurities and defects in semiconductors, and to determine semiconductor band gaps. A material absorbs light, creating an electron hole pair; an electron from the valence band jumps to the conduction band leaving a hole. The photon emitted upon recombination corresponds to the energy difference between the valence and conduction bands, and is hence lower in energy than the excitation photon. Fig 3.10 Photoluminescence Spectrophotometer. 55 Chapter III Experimental Techniques and Sample Preparation Luminescence is light that accompanies the transition from an electronically excited atom or molecule to a lower energy state. The forms of luminescence are distinguished by the method used to produce the electronically excited species. When produced by absorption of incident radiation, the light emission is known as photoluminescence. Photoluminescence that is short-lived (10−8 s or less between excitation and emission) is known as fluorescence. Photoluminescence that is longerlived (from 10−6 s all the way up to seconds) is known as phosphorescence. The reason for the difference in lifetime is that fluorescence involves an allowed, high-probability transition while phosphorescence involves a forbidden, low-probability transition. Photoluminescence excitation spectra are determined by measuring emission intensity at a fixed wavelength while varying the wavelength of the incident light used to produce the electronically excited species responsible for emission. The excitation spectrum is a measure of the efficiency of electronic excitation as a function of excitation wavelength. Photoluminescence emission spectra are determined by exciting at a fixed wavelength and varying the wavelength at which emission is observed. Between excitation and emission, electronically excited molecules normally lose some of their energy because of relaxation processes. As a consequence, the emission spectrum is at longer wavelengths, that is, at lower energy, than the excitation spectrum. 3.4.7 Vibrating Sample Magnetometer (VSM) A vibrating sample magnetometer or VSM is a scientific instrument that measures magnetic properties of material. If a sample of any material is placed in a uniform magnetic field, created between the poles of a electromagnet, a dipole moment will be induced. If the sample vibrates with sinusoidal motion a sinusoidal electrical signal can be induced in suitable placed pick-up coils. The signal has the same frequency of vibration and its amplitude will be proportional to the magnetic moment, amplitude, and relative position with respect to the pick-up coils system. 56 Chapter III Experimental Techniques and Sample Preparation Some of the most common measurements done are: hysteresis loops, susceptibility or saturation magnetization as a function of temperature (thermo magnetic analysis), magnetization curves as a function as a function of angle (anisotropy), and magnetization as a function of time. Fig 3.11 Vibrating Sample Magnetometer (Lakeshore VSM 7410) All the above instrumentations are used in the present work to study the structural, optical, and magnetic properties of the pure and doped zinc oxide films. 57 Chapter III Experimental Techniques and Sample Preparation References Bragg W.L., 1913, The Diffraction of Short Electromagnetic Waves by a Crystal, Proc. Cambridge Phil. Soc., 17, 43-57. Caglar.M, Y. Caglar, S. Ilican, Journal of Optoelectronics and Advanced Materials,8 (4) (2006), 1410 – 1413. Cullity, B.D., “Elements of x-ray diffraction”, 2nd edn.. Addison-Wesley, Reading, MA.1978. Jeffrey Brinker.C, George W. Scherer, “The Physics and Chemistry of Sol-Gel processing”, 1990. Manifacier.J.C, J Gasiot and J P Fillard, J. Phys. E: Sci. Instrum. 9, 1002 (1976). Shinde.S.S, P S Shinde, C H Bhosale and K Y Rajpure, J. Phys. D: Appl. Phys., 41 (2008), P. 105. Singh.S.C, R.K.Swarnkar and R. Gopal, Bull. Mater. Sci., 33 (1) (2010), 21–26. Suwanboon.S, P. Amornpitoksuk, A. Haidoux, J.C. Tedenac , Journal of Alloys and Compounds, 462 (2008), 335–339. Tauc.J, The optical properties of solids,(North-Holland, Amsterdam, 1970. Yasemin Caglar, Seval Aksoy, Saliha Ilican, Mujdat Caglar, Superlattices and Microstructures, 46 (2009), 469-475. 58