THIN FILM TECHNOLOGY

INTRODUCTION
A thin film may be defined as two-dimensional material born of atomby-atom or molecule-by-molecule or ion-by-ion condensation process. A thin film is geometry of material having one of its dimensions about 1. It should be emphasized here that it is not simply small thickness, which endows thin films with special and distinct properties, but rather the microstructure resulting from the unique way of their coming into progressive addition of the basic building blocks one by one, which is more important. In thin films, deviation from the properties of the corresponding bulk materials arise because of their small thickness, large surface to volume ratio and unique physical structure, which is a direct consequence of the growth process. Some of the phenomenon arising as a natural consequence of small thickness are optical interference, electronic tunneling through an insulating layer, high resistivity and low temperature coefficient of resistance, increase in critical magnetic field and critical temperature of superconductor. The high surface to volume ratio of thin films due to their small thickness and microstructure can influence a number of phenomena such as gas adsorption, diffusion and catalytic activity.

THIN FILM GROWTH PROCESS

Any thin film deposition process involves three main steps: (1) Production of the appropriate atomic, molecular or ionic species (2) Their transport to the substrate through a medium (3) Condensation on the substrate The general picture of step-by-step growth process emerging out of the various experimental and theoretical studies can be presented as follows: 1. The unit species, on impinging the substrate lose their velocity component normal to the substrate and are physically adsorbed on the substrate surface. 2. The adsorbed species are not in thermal equilibrium with the substrate initially and move over the substrate surface. In this process they interact among themselves forming bigger clusters. 3. The cluster or the nuclei as they are called are thermodynamically unstable and tend to desorb in a time depending on the deposition parameters. If the deposition parameters are such that a cluster collides with other adsorbed species before getting desorbed it starts growing in the size. After a certain critical size is reached the cluster becomes thermodynamically stable and nucleation barrier is said to have been overcome. This step involving the formation of stable,

chemisorbed, critical sized nuclei are called the nucleation stage. 4. The critical nuclei grow in number as well as in size until a saturation nucleation density is reached. The nucleation density and the average nucleus size depend on a number of parameters such as the energy of the impinging species, the rate of impingement, the activation energies of adsorption, desorption and thermal diffusion, and the temperature, topography and chemical nature of the substrate. A nucleus can grow both parallel to the substrate by surface diffusion of the adsorbed species as well as perpendicular to it by direct impingement of the incident species. In general, however, the rate of lateral growth at this stage is much higher than the perpendicular growth. The grown nuclei are called islands. 5. The next stage in the process of film formation is the coalescence stage, in which the small islands start coalescing with each other in attempt to reduce the surface area. This tendency to form bigger islands is termed agglomeration and is enhanced by increasing the surface mobility of the adsorbed species, as for example, by increasing the substrate temperature. in some cases formation of new nuclei may occur on the areas freshly exposed as consequence of coalescence. 6. Larger islands grow together leaving channels and holes of uncovered substrate. The structure of the films at this stage changes from discontinuous island type to porous network type. Filling of the channels and holes forms a completely continuous film. The growth process may be summarized as consisting of a statistical process of nucleation surface-diffusion controlled growth of the three dimensional nuclei and formation of an network structure and its subsequent filling to give a continuous film. Depending on the thermodynamic parameters of the deposit and the substrate surface, the initial nucleation and growth stages may be described as of (a) layer type, (b) island type and (c) mixed type called Stranski-Krastanov type. This is illustrated in the figure. In almost all-practical cases, the growth takes place by island fabrication. Island Type

Layer Type

Stranski-Krastanov type

STUDY OF VACUUM TECHNOLOGY

Vacuum the words stands for pressure levels much lower than the atmospheric pressure levels much lower than the atmospheric pressure level. General units of vacuum are TORR, PASCAL. Etc. 1 torr= 1mm of mercury displacement. A true vacuum is a space containing no matter at all. It is impossible however to create a true vacuum. Pumping air out of a container can produce an almost total vacuum, but some air molecules will always remain inside. The open space between the stars is the closest thing we know to a true vacuum. History of Vacuum In ancient times Aristotle stated, Nature abhors a vacuum. It is believed that a vacuum was impossible in the natural world, in the 17 th century the Italian Physicist and Mathematician Evangelist Tirrucelli (1608 47) showed this was not true by producing the first vacuum. Vacuums were not properly studied until 1650. With the invention of the first air extraction pump, by the German engineer Otto Von Guericke (1602 - 86). Having produced a pump that could successfully suck the air out of vessel. The Need for Vacuum All thin film deposition method requires vacuum because it improves the mean free path of atoms of material being deposited. The mean free path is an average distance of travel between subsequent collisions. It is most valuable concept since it gives a measure of how readily particles will travel through gas. Now during the travel from source to substrate, the phenomena of atomic or molecular scattering and randomization occur. This scattering is due to the collision of atoms or molecules of all kinds of vapour species and residual gas molecules in the chamber. The scattering is related to density, pressure of atoms, molecules in the gas phase and it defines the mean free path. From the kinetic theory of gas this mean free path is calculated as: mfp=KT/(P.r2. .2) Where K is Boltzmann constant, T is absolute temperature, r is molecular diameter, P is pressure in Pascal Thus mfp is directly proportional to temperature of gas and inversely proportional to pressure and square of the molecular diameter. At room temperature (300K) for the typical diameter of 3A =1.455/P

The scattering probability is given as fraction N/N o of molecules that are scattered in distance d during their travel through gas. N/No=1-e-d/ Where, No is total number of molecules N is number of molecules that suffers collisions d is distance between source and substrate is mean free path So at pressure of 10-4 Pascal only 0.3% molecules will suffer collisions i.e. during evaporation molecular motion is non-randomized. Here we have seen that to have greater lambda, pressure should be reduced and a high lambda gives a least scattering probability and thus the film deposition rate will be high also because of the less scattering, most molecules get from source to substrate.

VACUUM PUMPS
Vacuum pumps (more correctly called air pumps) create a near vacuum by removing the gas molecules from a vessel. Diffusion pumps allow a substance to diffuse into the pump intake, and then remove it. Modern diffusion pumps can reduce the pressure inside a container to approximately 10-4 Pascal i.e. about 10-9 times normal atmospheric pressure. Vacuum can also be created using ion pumps and turbo pumps. Ion pumps are used for very low pressure gases. They work by ionizing a gas, then absorbing the ions on the surface of a cathode inside the vessel. Turbo pumps use a rotating turbine to extract the gas. Confusingly a high vacuum is one in which the pressure is very low, and a low vacuum is one in which it is not quite so low. The vacuum can be obtained with the help of different types of pumps. Rotary Pump Diffusion Pump Turbo-molecular Pump Getter Pump Cryo Pump

The Rotary Pump is used to obtain rough vacuum. The Diffusion pump is used to obtain high vacuum. The Turbo-molecular, Getter and Cryo Pumps are used to obtain ultra-high vacuum. The Oil Sealed Mechanical Rotary Pump and the Diffusion Pump will be discussed. Oil Sealed Mechanical Rotary Pump Principle: Electric motor drives rotating cylinder having plungers which sweeps the gas from one region (may be a vessel or chamber) to another region which is the atmosphere. There is gas tight seal between both the regions. Here the oil acts both as seal and lubricant. Operation: There are four stages in one revolution of the motor. The revolution cycle is divided into induction, isolation, compression and exhaust phases. During operation gas molecules entering the inlet of the pump pass into the volume created by the eccentric mounting of the rotor in the stator. The crescent shaped gas volume is then compressed, forcing the exhaust valve open and permitting gas discharge. To complete the seal, a thin oil film is continuously maintained between the components by oil drawn from the oil reservoir into the pump interior. If the number of revolutions per minute is n the free air displacement SD is given by SD=2nV liter/min Where V is volume of gas between two blades expressed in liter.

So during one revolution, 2V volume of air coming from the chamber at inlet A is swept out from the chamber outlet valve and finally with the help of oil it will be given out into the atmosphere. Here unlike our expectation the pumping speed is no longer constant. As the pressure at A decreases, there is leakage of air into the pump due to: - small gap between the rotor and stator (typically 0.025mm) - small swept volume of gas between rotor and stator - the vapour pressure of oil - the oil itself tends to decompose into gas at high temperature. Small pumps directly connected to the driving motor have been designed to run at 1450 rpm. So we cant get vacuum greater than 10 -2 torr. If we still want to reduce the pressure we have to make use of the diffusion pumps. The Diffusion Pump Principle: To drive the low velocity molecules of gas in preferred direction it requires a high velocity stream by heating the silicon oil. Operation: The term diffusion pump is normally applied to jet pumps, which utilize the vapour of liquid comparatively low vapour pressure at room temperature. This pump is first itself evacuated up to 10 -2 torr with the help of rotary pump. The water supply is turned on. The Silicon oil now can be heated and within perhaps 15 to 20 minutes begins to boil. The hot oil vapour formed fills and escapes from the jet nozzles. The vapour expands in passing from a region of comparatively high pressure to one of low pressure. An annular vapour jet is created which is moving at a velocity that is supersonic and impinges on the inside of the water cooled outer wall. Here the vapour condenses and the oil flows down the wall and is returned to the boiler for recycling. Gas molecules diffusing into the pump mouth are likely to collide with the much heavier oil vapour molecules and will most probably receive a velocity component directed towards the exhaust side of the pump, where they will be subsequently removed from the diffusion pump by the rotary pump. The cross section of the diffusion pump is shown in the figure. It consists of a cylindrical housing within which the jet assembly and boiler are arranged. The nozzles of the jet are arranged in such a way that the vapour steam from them is directed downward and outward. Typical diffusion jet assembly consists of three or four annular slits and one ejector. A high purity hydrocarbon pump fluid is used in the diffusion pump. The fluid must have high viscosity, chemical stability against temperature and resistance to oxidation.

PRESSURE MEASUREMENT GAUGES

To measure vacuum there are two pressure gauges employed in this system. They are (1) Pirani Gauge and (2) Penning Gauge Pirani Gauge Principle: Heat transfer by the air molecules and the resistance of the filament increases with the temperature. Configuration of the Pirani Gauge is shown in fig. Pirani filament is made up of tungsten or nickel. This filament is placed in a glass tube. This tube is connected to the chamber with air tight seal, where we want to measure the pressure. Pirani filament is placed in one arm of the Wheatstone bridge, as shown in fig. Adjacent arm has compensating head. Both heads are kept in proximity. At constant current the bridge remains in balance at atmospheric pressure and gives zero reading in galvanometer. As pressure reduces, the resistance of filament increases, the bridge becomes unbalanced and galvanometer reads the off balance current, which is then calibrated in terms of pressure in torr. With this gauge we can measure up to 10-3 torr. To measure still low pressure we can use Penning gauge. Penning Gauge Principle: Cold cathode ionization Here electrons pass through gas, they will ionize the gas molecules, thereby producing an ionic current in the gas chamber on the application of high voltage between anode and cathode as shown in figure. Now the number of ion pairs produced will depend on the gas pressure. At the low pressure it is not possible to sustain sufficient ionization of gas unless electron mean free path greatly increases. So to get ionic current even at low pressure Penning had used permanent magnet so that the electrons which are collected directly by anode. With the application of magnetic field the electrons move in a spiral path thereby producing more ion pairs and confirm the discharge. As current reduces these ionic current also reduces, this is then calibrated in terms of pressure in torr.

VACUUM COATING UNIT OPERATION

The complete coating unit is shown in the figure. The operation is divided into three parts for easier understanding of the working. They are (1) Evacuation Process (2) Evacuation Reverse Process (3) Precaution Evacuation Process 1. Close all the valves tightly. - air admittance to chamber (valve no.7) - air admittance to rotary pump (valve no.9) - roughing valve (valve no.8) - backing valve (valve no.10) - baffle valve (valve no.13) 2. Switch on the rotary pump and check its operation whether it is working properly or not with the help of given pirani gauge which measures the low pressure of the tube between valve 8 and 10 3. Now open valve no.8 (roughing valve) to evacuate the chamber, wait for 20 min up to when the pirani gauge reading is at below 10-2 torr. 4. After the chamber is totally evacuated close valve no.8 and now open valve no.10 to evacuate the diffusion pump. 5. Wait for 15 to 20 min and then switch on the water supply. 6. Again check vacuum in the chamber by performing the setp3. 7. Now switch on the heater and check the vacuum on the meter. After a few minutes open valve no.13 (baffle valve) which evacuates the chamber through diffusion pump and wait for one hour to reach the high vacuum (10-5 torr). 8. Measure the pressure of the chamber with the help of given penning gauge. 9. After required vacuum has been obtained, do evaporation of the material. If necessary give supply to substrate heater, measure the suitable temperature with the help of thermocouple. Evacuation Reverse Process 1. Close the baffle valve first. 2. Switch off the heater supply. 3. Close the valve no.10 (backing valve) after the diffusion pump gets cooled. 4. Open the valve no.9 (air admittance to rotary) and at the same time switch off the rotary pump, to avoid over flowing. Perform both the processes simultaneously. 5. After 20 minutes shut off the water supply. 6. Now slowly open valve no.7 to admit air into chamber and take the film out.

Precautions: 1. Before switching off the rotary pump isolate the chamber and diffusion pump by closing valve no.8 and 10 (roughing and backing valve) 2. When you are not using the unit, diffusion pump should be isolated by valve no.10 and 13 i.e. in rest position the vacuum should be there in the diffusion pump. So never leave valve no.10 and 13 open in the rest position. 3. Before you switch on the diffusion pump check that the chamber is evacuated or not and also check the water flow with proper force is there or not. If both conditions are full filled then switch on the diffusion pump. Precautions On Power Failure 1. Immediately close valve no.10 2. Open valve no.9, close valve no.13 3. All switches must be turned off. 4. Stop the water flow after 15 to 20 minutes till the diffusion pump cools down

STUDY OF THIN FILM TECHNOLOGY

There are basically two types of film deposition. They are 1. Physical Vapour Deposition (PVD) 2. Chemical Vapour Deposition (CVD) Physical Vapour Deposition PVD is one of the vapour deposition techniques. The most important characteristic feature of PVD technique is that the transport of vapours from source to substrate takes place by physical means. This is achieved by carrying out the deposition essentially in a vacuum of such magnitude that the mean free path of the ambient gas molecules is greater than the dimension of the deposition chamber and the source to substrate distance. Under such low-pressure ambient conditions, the transport of the material from source to substrate occurs by one of the PVD methods. The two most commonly used PVD methods and their classification is as under: Evaporation - Thermal Evaporation - Two source Evaporation - Flash Evaporation - RF Induction Heating - Molecular Beam Epitaxy - Electron Beam Evaporation Sputtering - DC Diode Sputtering - RF Sputtering - Magnetron Sputtering - Ion Beam Sputtering Thermal Evaporation, Flash Evaporation, EB Evaporation and DC Diode Sputtering will be discussed here. Thermal Evaporation The evaporation of materials in a vacuum system requires a vapour source to support the evaporant and to supply the heat of vapourization while maintaining the charge at a temperature sufficiently high to produce the desired vapour pressure. The simplest vapour sources are resistance-heated wire and metal foils of various types, as shown if the figure. They are commercially available in a variety of sizes and shapes. Materials of construction are the refractory metals, which have high melting points and low vapour pressure. Mos commonly used are the transition group materials like tungsten (3380 C), Molybdenum (2610C), Tantalum (3000C), Platinum (1770C).

Wire sources are generally made form wire of diameter 0.02 to 0.06 in., and their use is limited to evaporants which wet the surface of wire (i.e. filament) upon melting and then held on by surface tension, it is also possible to use wires of the materials to deposited, provided that the materials will sublime (e.g. Ni, Cr). Metal foil sources are fabricated from 0.005 to 0.015 in. thick sheets of W, Mo, Ta or Pt. Electrical connections to wire and foil sources are made by attaching their ends to heavy copper or stainless steel clams. The latter are usually part of massive metal bars connected rigidity to a pair of electrical feed-throughs. Since the electrical resistance of the wire and foil sources in small, low voltage power supplies rated at 1 to 3KW are required. Typical arrangements consist of a step-down transformer (5V to 20V) whose primary side is connected to a variable 220V transformer [variac]. The secondary current may be as low as 20A for some of the wire sources, or current exceeds 100A, it is advisable to use water cooled feed throughs. The arrangement for a typical thermal evaporation is shown in the figure. Evaporation is accomplished by gradually increasing the current flowing through the wire foil source to first melt the material thereby wetting the filament. Once the filament is wetted, the current through it is increased to accomplish the evaporation. Advantages: Direct evaporation is attractive because it is simple and inexpensive and produces no ionization radiation. Disadvantages: 1. Possible contamination from the filament 2. Because of the small material capacity thickness a film may be limited and small through put. 3. This technique cannot be used to evaporate composite materials or compounds. Flash Evaporation Flash evaporation is technique for the deposition of films whose constituents have different vapour pressure. This method does not require provisions to monitor the vapour density nor is the control of the source temperature particularly critical. The objective of film composition control is accomplished by evaporating to completion small quantities of the constituents in the desired ratio. Only one filament is used at a temperature sufficiently high to evaporate the less volatile material. The basic principle is that a finely divided powder of the material is vibrated onto a very hot source, where it evaporates immediately on contact with the source. In these circumstances the composition of deposited film is the same as the original material powder. Powder dispensers which operate by mechanically or electromagnetically induced vibrations have been

employed mostly for the evaporation of compounds. They do not allow the same latitude in feed-rate adjustment as disk device because the trickle of powder tends to become discontinuous or non-uniform under various conditions. Here the supply is stepped down. The current is supplied to the electro magnet through a potentiometer. By varying the potentiometric resistance changes, thus the current supplied to the electro magnet is changed in turn changing the vibration frequency. Figure shows the schematic arrangement for flash evaporation. Advantages: 1. Method is suitable for evaporation of III-V group compound semiconductors such as AlSb, GaSb, GaP etc and some alloys in which one of the elements has very high vapour pressure or is volatile. 2. Film is uniform and homogeneous in composition. Electron Beam Heating Instead of supplying energy by resistance of induction heating, vapourization of material can also be accomplished by electron bombardment. A stream of electron is accelerated through fields of typically 5 to 20KV and focused onto the evaporant source. Upon impingement most of the kinetic particle energy is converted into heat and temperature exceeding 3000C may be obtained. Devices operating on the principle of electron bombardment heating are referred to as electron guns. A wide variety of electron guns has been used and these have been classified into - Work-accelerated guns - Self-accelerated guns - Bent-beam guns A bent beam electron gun is shown in fig. The electron gun consists of a heated tungsten filament, which is used to produce electron beam by thermionic emission. Electron beam is accelerated through a potential of 5 to 20KV and focused on the material. Using a permanent magnet the path of electron beam is bended. The focused bent beam of electron melts the material contained in a hearth, a water-cooled block with a large holding capacity of the material. Only electrons come in contact with the material to be evaporated, so that it can be a low contamination. The hearth is the place where the material to be deposited is kept. The heath is not contaminated as the beam is focused on the material only. The system may consist of more than one hearth for multi film evaporation. Advantages: 1. The temperature at the focused spot is as high as 3000 C. At such a high temperature most of the refractory metals, oxides and compounds having high melting point can be evaporated.

2. Since the temperature is high only at a focused spot, rest of the material remain cool and thus there is reduced contamination. 3. Extremely high rate of evaporation is achieved. 4. Multi-hearth evaporation is possible. Disadvantages: 1. The electron energy is sufficient to ionize residual gas or evaporant molecules encountered along the way. Since ionization causes loss of beam energy and focus, the pressure in the vacuum chamber must be below 10-4 torr. 2. Generation of X-rays by the electron beam. Sputtering When a solid surface is bombarded with energetic particles, the surface is eroded and the surface atoms are removed due to collisions between the surface atoms and the energetic particles. This phenomenon is known as sputter or sputtering. The energetic particles, which cause sputtering, may be ions, neutral atoms, neutrons, electrons or photons. DC Diode Sputtering Several sputtering systems are proposed for thin film deposition. Among these sputtering systems the basic model is the DC sputtering system. The other sputtering systems are improved versions of the DC diode sputtering system. The DC sputtering system is composed of a pair of planar electrodes. One of the electrodes is cold cathode and the other is anode. Top of the cathode is covered with target materials to be deposited and reverse side of the cathode is water-cooled. The substrates are placed on the anode. In the DC sputtering system the sputtered particles collide with gas molecules and then arrive at the substrate. The gas pressure is very high. The mean free path of the sputtered particles may be less than the electrode spacing. Advantages: 1. Sputtering of the material does not require high temperatures. 2. Reactive or chemical sputtering is possible. 3. All the metals can be easily sputtered. Disadvantages: 1. Some what contaminated films, but contamination less than evaporation methods. 2. Deposition rate is lower compared to the evaporation process. 3. Cathode must exhibit high conductance since it serves as an element of the gas-discharge circuit.

DETERMINATION OF OPTICAL BAND GAP

Optical band gap is one of the methods to characterize a thin film. The other method is the electrical method. Before knowing how to find optical band gap we first deal with the working principle of the spectrophotometer. Working Principle Of Spectrophotometer We use the Systronics spectrophotometer - type 105. It is a single beam grating spectrophotometer with a wavelength range of 340nms to 960nms. Over the entire wavelength range it fives a constant spectral bandwidth of 10nms. The cell compartment is designed to accommodate 10mm (1cm) path length test tube holders. The unit can give percentage transmittance or absorbance. The optical diagram is shown in figure. Spectrophotometer measures the ratio of the radiant power of two electromagnetic beams at a particular wavelength. Spectrophotometer consists of - Source - Detector - Grating The light source is a straight filament tungsten iodide lamp. The light energy is condensed onto the entrance slit placed at the focal plane of collimating lens and thus plane parallel beam strikes the grating surface. The dispersed spectrum is refocused onto the exit slit by another de-collimating lens. Thus the exit slit is an image of entrance slit in different colours (wavelength). The grating is coupled to the cam through a lever and the rotation of the cam gives the spectral scan in the exit slit plane. The radiation that passes through the slit is calibrated against standard emission lines Na, Hg, He source. The wavelength is displayed on a dial fixed to cam, which is calibrated from 340 to 960nms at intervals of 5nms, but numbered at every 20nms. The optics of the instrument is set for the first order dispersion of the grating. As the second order spectrum of the grating would invariably overlap with its first order. It is eliminated by the insertion of an order cutoff filter in the light path. For any wavelength settings above 600nms the red filter must be inserted in the light path. The radiation finally passes through sample and falls on the photodetector. To protect the photo-detector from being exposed to constant light, a mechanical shutter is provided in the light path. It is operated by a press to read button. So only when the button is pressed, the light reaches the photo-detector.

Specifications Wavelength: 340nms to 960nms Bandwidth: 10nms Transmission: 100% fsd Absorbance: 0.05A Sample holder: 1cm wide slide Detector: High quality Si photo diode of uniform spectral response through the range Grating: 600 lines/nm Source: 50 watts tungsten halogen lamp Experiment Here we are going to determine the optical energy gap of ZnS material. To prepare the film follow thin film fabrication technique. After preparing the film cut the slide so that it can be inserted in to the sample holder of the spectrophotometer. Now measure the transmittance of the film at different wavelength by spectrophotometer. Obtain the absorbance of the film with the help of scale. Find the absorption coefficient () with the help of the relation: = Absorbance/thickness Draw the graph of (h)2 (h). From the graph find out the band gap. Direct Band gap: In the direct band gap material both energy and momentum must be conserved in the order for an electron and hole to recombine and emit a photon. Although the photon can have considerable energy its momentum is h/c and is very small. Therefore, the most simple and probable recombination process will be that in which the electron and hole will have the same value of momentum such as situation may occur in many II-VI, III-V compounds where the conduction band, minima lies at the zero momentum portion as shown in the figure. Direct band gap obey k spectrum rule. i.e. k1=k2 (i.e. VB=CB) GaAs, GaAsP, GaP, etc are direct band gap materials. Indirect Band Gap: In figure an indirect band gap structure is shown. The CB minima and the VB maxima occur at different values of momentum. Here band-to-band recombination involves a third particle to conserve momentum.

Phonon (lattice vibration) serves this purpose. However the probability of electron-hole recombination in this three-particle process is drastically reduced radiatively to simple, two particle direct recombination process. There k scaler rule is not obeyed. Result The optical energy of the thin film ZnS/ZnTe is ________ eV measured from the graph (h)2 (h). Observation Table
Wavelength nm. E = h =1.2410
3

% Transmission T

Absorbance A

= (A/t) 104

(h)2

(m)

SUBSTRATES
Specific applications require different substrate materials, which offer an acceptable compromise for the purpose on hand. Ideally the substrate should provide only mechanical support but not interact with the film except for sufficient adhesion. In practice however the substrate exerts considerable influence on the thin film characteristics. Substrate Requirements 1. Atomically smooth surface. 2. Inertness to chemicals used in processing.

3. High volume and surface resistivity. 4. High thermal conductivity. 5. Coefficient of expansion similar to film. 6. High mechanical strength. 7. High thermal shock resistance. 8. Zero porosity. 9. High re-crystallization temperature. 10.Good dimensional tolerances. 11.Excellent cutting and module-separation properties. 12.Low cost. The common substrate materials used are: - Glasses - Poly- and single-crystalline ceramics - Semiconductors - Metals Substrate Cleaning Substrate cleaning is a very important part of any thin film fabrication process. The various methods used for substrate cleaning are 1. Glow-discharge Cleaning 2. Hot Solvent Cleaning 3. Ultrasonic Cleaning 4. Drying

Glow Discharge Cleaning It is the most widely used technique to clean substrates in situ and immediately prior to film deposition. Here the substrates are exposed to the plasma of a glow discharge. Typically the discharge is established between the two electrodes and is used in the vicinity of the substrates such that the surface of the latter is immersed in the plasma. The discharge voltages may vary from 50V to 5000V. In glow-discharge removal of impurities on the substrate surface are brought about by one or more of the following mechanisms - Straight forward heating due to impingement of charged particles and their recombination. - Impurity desorption through electron bombardment. - Impurity desorption resulting from low-energy ion or neutral particle bombardment. - Anodization of organic residues by chemical reaction with dissociated oxygen. - Modification of glass substrates through the addition of oxygen, enhanced nucleation during subsequent film deposition. Hot solvent Cleaning It is mostly conducted in the form of vapour degassing i.e. the substrate is suspended above the boiling liquid in a closed container. The rising solvent vapour condenses on the object to be cleaned thereby heating it and increasing the rate of dissolution of surface contaminants. As the spent solution drips back into the bath, fresh and clean distillate repeats the process. Ultrasonic Cleaning Here dissolution of residues is enhanced by the intense local stirring action of the shock waves created in the solvent. Thus solvent saturated with impurities is continually carried away from the substrate surface and fresh, less saturated liquid is admitted. Mechanical vibrations induced in the substrate further aid in loosening gross contaminants such as particular matter flakes. The parameters, which affect the efficiency of ultrasonic cleaning, are - The frequency of vibration. - Applied power - Type and temperature of the solvent - Surface tension and viscosity of the solvent - Presence of nucleating particle and dissolved gases

Drying The drying of wet cleaned substrates is also critical because recontamination can occur unless stringent precautions are taken. Drying may be accomplished - in a vapour degreaser - in a clean oven - under electric lamp - with hot filtered air or nitrogen

FABRICATION OF THIN FILM CAPACITOR

Figure shows the structure and configuration of a typical thin film capacitor whose per unit area capacitance is given by C= /d. The dielectric film strongly depends on the technology employed. In monolithic ICs, the capacitors are formed by utilizing the p-n junction capacitance under reverse bias. Although such capacitors are good enough for normal circuit applications due to poor performance with respect to - stability - temperature coefficient of capacitance - voltage dependence - density and parasites They are not suitable for special circuit applications such as RC communication filters and precision oscillators. The thin film capacitor can overcome most of these disadvantages. Basic Requirements Of TFC Materials Some of the important properties of materials used for fabrication of TFCs are as below. 1. The magnitude pf capacitance (C) is a function of electrode area (A), electrodes separation (d) and nature of dielectric. Thus the capacitance density (C/A) is equal to C=A E o/d= (8.85 x 10-12)E/d -12 Where 8.85 x 10 is permitivity of free space. E is dielectric constant of insulator. In order to conserve substrate area the capacitor density should be as high as possible. 2. The high capacitance density can be achieved in two ways. Choose the material of high dielectric constant or reduced the electrode separation (d). 3. However, if the thickness of the dielectric layer between electrodes (d) is reduced, (C/A) increases, resulting in electrical arcing. This is called breakdown strength and is the characteristic of dielectric. 4. For a practical TFC the maximum working voltage (V W) is a more important parameter than the dielectric breakdown strength. V W may

be defined as the level of the voltage stress for which the failure rate of the TFCs is equal to the maximum permissible for a given operation. 5. The maximum permissible electric field (V m -1) for the dielectric, the plate separation d=VW/S and hence the capacitance density (C/A) must be equal to 8.85 x 10-12 (KS/VW). In this expression the product KS is a material characteristic and it is called the area efficiency factor of the dielectric. Obviously higher the value of this factor more suitable the dielectric becomes for use in a TFC.

6. The maximum working voltage times the capacitance density (V W . C/A) is defined as the charge-storage factor. The charge-storage factor is used as a figure of merit for evaluating different dielectric materials as it provides information about the substrate area needed for a given capacitance at a given voltage. 7. The current flowing through a charged capacitor is the leakage current and is determined by applying a DC voltage for a fixed time. The leakage current rapidly increases with increasing voltage. From leakage current at a given test value of voltage, resistance may be determined i.e. Vtest/Vpeak. Then the product gives insulation voltage of the capacitance. The phenomenon of dielectric absorption i.e. the time required to charge the capacitor must be as small as possible. 8. For the good TFC the dependence of capacitance on temperature (TCC) should be least or minimum. 9. Similarly the voltage coefficient of capacitance (VCC) also should be small. Usually capacitance falls with increase in voltage. 10.For TFC, the dissipation factor may be expressed as, 2fCS(R1+R2) where CS is equivalent capacitance at frequency f, R2 is true ohmic resistance of capacitor electrode leads R1 is hypothetical resistance corresponding to dielectric dissipation factor (2fCR1) of capacitor dielectric. The dissipation factor and capacitance will both depend on frequency. Ideally frequency impedance should be the least. If tan is higher, more losses in power. If loss is significant, tan =1. 11.From the above discussion it is clear that the dissipation factor and the capacitance both depend on frequency. Ideally frequency impedance should be least Fabrication Of Thin Film Capacitor By Sputtering Clean chamber and associated elements with acetone so as to make them moisture free and to reach the desire pressure immediately. Also clean the substrate with water and then with acetone. Here substrate is a cover slip. Place it on the anode and cover it with the chamber.

Close the air inlet valve and the switch on the rotary pump. The material to be deposited here is silver placed on the cathode. With 4 to 5 minutes, the pressure reaches to 10 -2 Torr. Then switch on the supply for generating plasma. About 8A current is required for that. After the desired thickness is deposited on the substrate switch off the plasma supply and then remove the vacuum i.e. open-air inlet valve and switch off rotary simultaneously. For fabrication of capacitor, deposit film on both the sides of the substrate. So a film will be form the plates and the substrate as the dielectric. Keep always some vacuum in the chamber by isolating it from the rotary pump, so as to prevent any corrosion.

Observation Table Temperature C Capacitance pF TCC ppm/C

(Cap at T2 Cap at T1) 106 ppm/oC TCC =-----------------------------x-------------Cap at T1 (T2 T1) Materials For TFCs The dielectric materials used in the fabrication of TFCs can be broadly divided into three classes: - Inorganic materials (SiO, SiO2, Si3N4) - Metal Oxide Dielectric (Ta2O5, Ta-N, Ta-Al) - Organic Insulator (i.e. Parylene) One reason for rapid adoption of tantalum based dielectric materials for TFCs is the compatible technique used for making TFCs on one end and TFRs and conductors on the other hand, on one and the same substrate. Ta based TFCs have large capacitance density, low TCC and dissipation factor, low leakage current, high breakdown voltage and good stability. Thus, presently they are the most prospective TFCs used in hybrid circuits. Tantalum oxide films can be deposited by series of methods Anodic oxidation Sputtering Plasma oxidation Thermal oxidation

Advantages of Thin Film Capacitors - The per unit area capacitance of film capacitor can be 10 times as high as that of MOS capacitors and diffuse capacitors. - Maximum capacitance of film capacitor can be a few orders of amplitude higher than those of monolithic capacitor largely because at an increased area, the facts that the area of hybrid IC substrate greatly exceeds the area of the semiconductor IC chip. - Thick film capacitor area almost comparable to thin film capacitor in most of the parameters, the temperature coefficient being probably the exception. - For high frequency, TFC, the optical dielectric is SiO. CuO parameters also resemble those of SiO. Fabrication Of Capacitor By Sputtering Clean the chamber and associated elements with acetone so as to make them all moisture free and to reach the desired pressure immediately. Clean the substrate with water and then with acetone. Here the substrate is microscopic of 24mm diameter cover slip. Place it on the anode and cover with the chamber. Close the air inlet valve and switch on the rotary pump. The material to be deposited here i.e. silver is placed on cathode. Within 4 to 5 minutes pressure will reach around 10 -2 torr. Then switch on the supply for generating the plasma. About 8 amps current is required for that. After the desired thickness is obtained on the substrate, switch off the plasma supply and then remove vacuum i.e. open-air inlet valve and switch off the rotary simultaneously. For fabrication of the capacitor, deposit films on both sides of the substrate. So film will form on both sides and the substrate acts as a dielectric. As a precautionary measure always keep some vacuum in the chamber by isolating it with rotary pump so as to prevent any corrosion.

FABRICATION OF GAS SENSOR

It has been appreciated for over 30 years that the surface composition of semi-conducting oxides can be influenced by the composition of the gaseous ambient. Gas sensitive resistors based on the principal and employing tin dioxide as the active element have proved to be simple, sensitive and inexpensive. Currently such devices are widely used to give an alarm against hydrocarbon leaks in the air. Tin oxide sensors tend to be nonselective. Although this characteristic is a significant disadvantage for some application, it has led to the additional investigation of the use of similar devices to monitor the presence of a range of toxic gases in air. A variety of materials have been used for sensing gases and vapours. These materials include electronic ceramics, often consisting of a combination of oxide material. Gas sensing generally involves a catalytic

reaction such as oxidation or reduction of the gas of vapour by the surface of the sensor. A number of catalytic materials such as Pt, Pd, Bi 2O3, MoO3 are used as sensors, although a material having high catalytic activity need not necessarily be the best sensor. Materials The various materials used are semiconductor oxides (SnO 2, ZnO, Fe2O3), catalytic oxides (V2O5, CuO, TiO2, Fe2O3), metals deposited on oxide supports (Pt/SnO2, Pt/ZnO, Pd/SnO2) and mixed oxides (LnCoO3, LnNiO3, La2XSrXCuO4). Material Preparation The oxide material is generally used in the form of a wafer (thin pellet) of a film (thick or thin) deposited on a substrate (glass, silica, silicon, alumina). Gas sensors in the form of thin or thick films seem to be more promising detectors over the pellet form because they are potentially of low cost, rugged and have low consumption of electric power. Semi-conducting oxides are prepared by dehydrating ammoniated metal nitrates by decomposing the metal nitrates, carbonates, acetates etc. These powders are pressed into pellets with or without a binder and sintered at an appropriate temperature for a specific period. This sintered pellet is polished and the electrodes are formed on both the sides for sensitive measurements. The sintering temperature is crucial, since the surface as well as bulk properties of the oxides are determined by it. In the case of thin film, metal electrodes (Pt, Au, etc) are first formed on the substrate material and the film of appropriate metal oxide (SnO 2, ZnO, TiO2, Fe2O3, etc) is then formed by RF sputtering, magnetron sputtering, spray pyrolysis or CVD. The film is annealed at an appropriate temperature to attain the required properties. Metal supported on semi-conducting oxides (catalytic materials) are prepared by dipping the pellets or films of the oxides in a solution of the metal salts for Pt, H2PtCl6.H2O; for Pd, PdCl2; for Ag, AgNO3 and are fired at 700-9000K. Reduction in H2 is carried out if necessary. Chemo Sensors Chemical sensors are used to detect chemicals and gases in the environment at low concentrations, the relation between the partial pressure (PO2) and the electrical conduction () can be expressed = [Const. Exp (-E/kT) PO2] 1/N Where E is activation energy for the electrical conduction and N is a constant determined by the dominant type of bulk defect involved in the equilibrium between oxygen and the sensor.

The surface of most metal oxides exhibit a complex structure compromising metals ions, oxygen ions, impurity and imperfections acting as surface ACCEPTORS or surface DONORS. The extraction or injection of electrons by these surface acceptors or donors is connected with the generation or variation of space charge layer. There are two stages, to the gas sensing effect: Atmospheric oxygen gets adsorbed on the surface and carrier from the conduction band of N-type gas sensors, because O and O species. This phenomenon reduces the overall conductance. The reducing agents, such as hydrogen, carbon monoxide and hydrocarbon gases, will react with chemi-adsorbed oxygen, this will reinject the carrier and increase the sensor conductance. Chemical sensors are classified as chemo-resisters, chemo-capacitors and chemo-transistors. Measurement Of Gas Sensing Property The experimental setup generally employed to study the gas sensing properties by a dynamic flow system as well as by a static system is shown in figures below respectively. In a dynamic flow system, the test gas or vapour is mixed with dry air and passed into the chamber with constant flow rate and the temperature of the sensor is mentioned using a temperature controller. A DC voltage is applied by using a constant potential source across the sensor through a standard resistor and the voltage developed across the standard resistor is measured to record the change in conductivity of the sensor in the presence of the test gas. In a static system, the test gas is mixed with dry air and is introduced into the chamber and stirred well with the help of small fan fixed inside the chamber. In the case of humidity measurement, instead of the test gas, humid air (100% RH) is mixed with dry air in appropriate proportion while measuring the sensitivity. Sensitivity The change in resistance of oxide gas sensors arises from the change in concentration near the surface by the reaction with gases or vapours. A reducing molecule or atom adsorbed at the sensor surface, acts as a surface donor injecting electrons into the semiconductor. The adsorption can be associated with decomposition or dissociation of the gas or the vapour. The opposite phenomenon occurs during exposure to oxidizing gases like NO. In case of N type semiconductor the resistance of the pellet or film decreases when the sensor is in contact with the oxidizing gas or vapour in case of P type semiconductor sensor.

The sensitivity S of a sensor is expressed as the ratio of the change in the resistance in the sensor in the presence of the gas or vapour to the original resistance at that temperature and for a specific concentration. S= Rgas/Rair It varies with temperature and concentration of gas or vapour. Another way of expressing sensitivity is in terms of the ratio of the change in conductance / conductivity of the sensor in the presence of the gas or vapour to its conductance / conductivity in air at a particular temperature and for a specific concentration of the gas or vapour. S=Gg Ga/Ga Sensitivity is also expressed as the response ratio of R as R=100 x (Rg Ra/Rg) for p-type sensors R=100 x (Ra Rg/Rg) for n-type sensors Fabrication Of In2O3 Thin Film Sensor The source material is a fine powder of Indium Oxide (In 2O3 Alfa, Johnson-Matthey). The growth of In2O3 thin films was carried out by direct thermal evaporation technique in high vacuum of the order of 10 -5 torr. The In2O3 thin films of thickness of about 150nm were grown on glass substrates of 10nm x 10nm total surface area. The substrate temperature was kept constant at 5730K for the deposition of In 2O3 thin films. The films so obtain were annealed at 6730K for one hour in 80% relative humidity. After annealing, the films show a resistivity about 8.5 x 10 -4 cm. Determination Of Gas Sensitivity In2O3 thin film gas sensors are a type of variable resistances whose resistivity changes in presence of gases. The sensitivity to oxidizing gases is defined as Gair - Ggas SO = --------------------Ggas While the sensitivity to reducing gases is Ggas - Gair SR = -----------------------Gair Where Ggas is the film conductance in presence of test gas and G air is the background conductance in absence of test gas. Heating In2O3 thin film gas sensors on a special fabricated miniature heater carried out the measurements of conductance. The gas sensors were continuously heated

from 3000K to 5250K and the changes in conductance of the In 2O3 films in presence of auto exhaust gases were measured. X-ray Diffraction The crystallinity of the In2O3 film was analyzed by the X-ray diffractometer Xpert manufactured by Philips Holland. The results of the Xray diffraction are shown in the figure along with the parameters. The result confirms that In2O3 film has a cubic structure and peaks similar to those reported by ASTM card for In2O3.

FABRICATION OF ELECTOLUMINESENCE CELL

Luminescence is the phenomenon of emission of light from a body as a result of absorption of energy. Luminescence in a material is associated with the presence of certain specific radiative recombination centers. The luminescence centers may be created either by certain impurity atoms called the activator atoms in an interstitial or substitution position of one of the lattice ions or by stoichiometric excess of one of the constituents. Luminescence resulting from the action of an electric field or an electric current through the material is called electro-luminescence. In electro-luminescence, light is emitted by one of the two following processes: - Field effect or impact- ionization electro-luminescence - Injection or recombination electo-luminescence ZnS:Mn is the most promising light emitting device among the Thin Film Electro-luminescence [TFEL] devices. The maximum luminescence level that can be obtained depends on the thickness of ZnS:Mn layer, which also affects the operation voltage. The thickness of ZnS:Mn layer is thus an important parameter when choosing an optimal device structure. The luminescent and relative power efficiency can be measure by using sinusoidal excitation source. Under sinusoidal excitation, the device current with respect to the device voltage can be separated into quadrature current (non-dissipative) and into phase current (dissipative). Below the threshold voltage, for electro-luminescence, the dissipative current, which is due to electrode losses and dielectric losses in the thin ZnS:Mn films, is proportional to the device voltage. Above the threshold voltage additional dissipative current flows and it increases rapidly with device voltage. This excess dissipative current multiplied by device voltage is approximately equal to the electrical power of the ZnS:Mn film. Many attempts have been made to improve the performance of the TFEL device. Presently available devices sand-witched between two insulating layers require a very high driving voltage of more than 200 volts; this is a serious disadvantage of practical applications. ZnS semiconductor with a direct and gap of 3.7eV at room temperature has a potential application for Glow Emitting Diodes. The peak of the initial band is around 470nm. Fabrication of the Electro-luminescence Cell

The structure of the electro-luminescence thin film device fabricated is shown in the figure. The substrate used is an ordinary glass slide. All the layers except the transparent electrode and the aluminium electrode were done by electron beam (EB) evaporation and were done in one vacuum cycle. The transparent conducting electrode of ITO[In 2O3 + 17%SnO2] were prepared by direct evaporation technique wherein the substrate was heated at 3500C.The glass plates thus obtained had 85% transmittance were used as a substrate for fabrication of the device. Patterns of ITO were made by etching it chemically. The Al2O3 film was deposited by the EB evaporation technique. The active layer was prepared by evaporating electro-luminescence ZnS:Mn phosphor prepared in the laboratory by the EB technique. Prior to deposition, the substrates were subjected to ion bombardment cleaning at a pressure of 10-2 torr and the thickness was monitored and controlled with a quartz film thickness monitor. During the deposition the substrate was kept at 350 0C wherein the In2O3 film was deposited with a thickness of around 250nm. The fabrication was effected by the deposition of aluminium oxide of thickness around 200nm at room temperature. A thicker layer of 250nm ZnS:Mn at 2000C followed this. another layer of aluminium oxide of thickness 250nm was deposited. The fabrication was complete by positioning the aluminium rear electrodes of approximately 200nm thickness through proper mica mask such that on a single substrate several cells of emitting area were obtained. The aluminium electrode was deposited by the direct evaporation technique at room temperature. X-ray Diffraction Using a diffractometer manufactured by Philips made the analysis by X-ray of the crystal structure, Holland named Xpert. The conditions are described with peaks in the figure. The results of the measurement are shown in the figure. The data of X-ray analysis was compared with ASTM (American Standard Testing Materials) card for ZnS.

MAINTAINANCE AND REPAIR OF VACUUM SYTEMS

The laboratory consists of one EB unit, one Sputtering unit and two Ordinary vacuum units. During our course of study of thin film deposition technology we faced some problems with the functioning of the units. The units were cleaned daily and checked for any electrical faults before they were started. This helped in maintaining the surrounding of the units clean from dust particles. The troubles faced during our working with the system are discussed. The two ordinary vacuum units faced some problems like not attaining the standard vacuum levels in the line, roughing and the backing position. These problems were due to minor leaks in the o-ring, gauge setting, crystal setting and the meters. Changing the necessary o-rings, tightening the gauges and the tightening crystal settings, rectified this. The meter circuitry was checked and they were rectified after comparison with a standard circuit. The problem if persisted then the valves was tightened (line and baffle). When high vacuum suddenly dropped then it was found that the heater was damaged. So changing the heater rectified this. Some time when temperature was given to the substrate the vacuum would drop but would not recover. Opening the gas ballast for few minutes so that the moisture present in the oil was removed rectified this. When the problem persisted the lubricant (hydrocarbon) oil of the rotary pump was changed. The Sputtering unit is a small unit. The oil of the rotary pump moved into the chamber due to the low pressure in the chamber when there was a power failure. Cleaning the chamber thoroughly with acetone and Petroleum ether rectified this, also the rotary pump was cleaned and new oil was filled in the pump. Even though the pump was functioning the plasma was not obtained, checking the circuits and the required modifications was made rectified this.