2 Thin Film Fundamenials this book. However, in this chapter only the nature of films, their deposition technology and thickness measure- ment techniques etc. will be discussed in brief. 2. NATURE OF THIN FILM ‘The term “thin film’ has often been loosely used in literatures to imply not only a layer of a solid material but also of a liquid or a gaseous phase. However, all topics on thin films discussed in this book will be limited to solid films only. Further, there is neither any well-defined limit of its thickness to imply the end Of the thin film stage nor one to indicate its transition to the thicker film region. All basic researches on thin films are generally confined (o a limited range of thickness, say between a few A to about 5000 A depending on the properties to be investigated, whereas for technological applications where reliability of performance is the most important criterion, the thickness limit at the lower range is generally higher than 1000 A and can be as high as 5-10 jm or even more. In order to cover this wide range of film thickness both for basic researches and applications, a “‘thin film’ may be arbitrarily defined as a solid layer having a thickness varying from a few A to about 10 yim or so. Since the thickness limitation is rather arbitrary, even somewhat thicker films may also come within the scope of the above definition. Within the connotation of thin film, often a further subdivision of thickness is made under the categories (i) ultra thin, (ii) thin (or very thin) and (iii) comparatively thicker ones, the last one generally being greater than 1000 A. The categorics (i) ranging from a few to about 50-100 A and (ii) from about 100 A to 1000 A or less are all arbitrarily fixed for convenience and the transition regions from one category to the next one are not distinct at all. It may be mentioned here that the above confusion in the nomenclature or definition of film thickness is further complicated by the coinnage of a new term thick films"* which are of great practical impor- tance. This new term indicates an entirely new class of films rather composite film layers obtained by the process of screen printing and subsequently firing a paste composed of a mixture of metalvalloys or oxide powder along with or without glass or ceramic particles suspended in some organic solvent vehicles and these films have thickness of about 10 jum and often more. The nature of these “thick films’* which are used for printed circuits and for other purposes is quite different from the thin films we are going to consider and hence the former will not be discussed in this book. Whatever be the film thickness limit, an ideal film can mathematically be defined as a homogeneous solid material contained between two parallel planes and extended infinitely in two directions (say x.y) but restricted along the third direction (2), which is perpendicular to the x-y planc. The dimension along redirection is known as the film thickness (d or #). Its magnitude may vary from a limit d +0 to any arbitrary value say to 10 jim or more but always remaining much less than those along the other two directions i.e, x and y. A real film, however, deviates considerably from the ideal case since its two surfaces areThin Film 3 never exactly parallel even when formed in the best experimental deposition conditions and also the material contained between the two surfaces are rarely homogencous, neither uniformly distributed nor of the same species. It is also ‘a common experience that a film may also contain many imperfections, impuri- ies, dislocations, grain boundaries and various other defects (cf. Chapter 3) and may also be discontinuous. Further the top surface of a film often develops some topographical features and asperities characteristic of the growth conditions and these features are sometimes so prominent as to be visible even to naked eyes. Some of these features can, no doubt, be minimised by appro- Priate control of the deposition condition but cannot altogether by avoided. ‘The bottom surface of a film in contact with a substrate generally takes up the topographical features of the latter. Some of the factors which determine the physical, electrical, optical and other properties of a film are the following viz. rate of deposition, substrate temperature. environmental conditions. residual gas pressure in the system, purity of the material to be deposited, inclusion of forcign matter in the deposi inhomogeneity of the film, structural and composional variations of the film in localised or wider areas etc. some of which have been actually observed?4, A transition from the bulk to the thin film state may even cause a drastic change in its properties as illustrated by the behaviour of alkali metals and also noble metals. Thus highly conducting sodium. potassium, rubidum, and also gold. platinum etc. having positive temperature coefficient of resistance (TCR) in the bulk form show negative TCR when in thin film states thus behaving as semiconducting films. Bulk bismuth and antimony which are metallic in nature behave as semiconductors in the thin film state’, Buckel and Hilsch® observed that thin bismuth films unlike bulk showed superconducting properties at low temperatures. Highly disordered or amorphous films have electrical or magnetic properties which may differ by several orders from that of the bulk single crystals. All films whether prepared by vacuum deposition or by other techniques are invariably associated with some growth defects or imperfections” "© such as lattice defects, stacking faults, twinning, disorders in atomic arrangement, dislocations, grain boundaries, foreign atom inclusion, etc. Surface states of a film also play a dominant role in modifying electrical and other propenies. In addition because of a high surface 1o volume ratio in a film, a freshly formed film surface becomes highly reactive. Further because of the unbalancing of forces near the surface region, new phenomena such as thermionic emission, adsorption of gases, catalysis, solid state reactions, etc. characteristic of a surface are more often observed in thin films rather than in bulk. It is, therefore, of utmost importance to study thin films not only because of tremendous technological importance but also of our inadequate knowledge about their interactions with the clectrical, magnetic and electromagnetic fields. There is often a considerable deviation from that of the bulk behaviour and sometimes new phenomena are observed in the thin film state. Further from these studies4 Thin Film Fundamentals it may be possible in certain cases to. predict their interactions with bulk materials. In this book thin film properties will be dealt in different chapters. initially by an analogy with the bulk material and then making appropriate modifications of the models taking into consideration various factors likely to be operative in the thin film state. 3. DEPOSITION TECHNOLOGY Thin films can be prepared from a variety of materials such as metals, semi- conductors, insulators or dielectrics etc. and for this purpose various prepa- tative techniques have also been developed"""?. Newer methods are also being evolved to improve the quality of the deposits with maximum reproducible Properties and minimum variation in their compositions. Techniques involved in general are : (a) Thermal deposition in vacuo by resistive healing, electron beam gun or laser gun evaporation, ete. from suitable sources, (b) Sputtering of cathode materials in presence of inert or active gases either at low or medium Pressures, (c) Chemical vapour deposition (CVD) by pyrolysis, dissociations, reactions in vapour phase, (d) Chemical deposition from solutions including Fig. 1. A sketch of a typical vacuum deposition unit with rotary and cil diffusion pump.Thin Film s electro-deposition, anodic oxidation, electroless plating, chemical displace- ment, chemical reaction, etc. The primary requirement for the methods (a) and (b) is a high vacuum deposition system at a pressure of about 107° torr or even less. In methods (c) and (d) a high vacuum is not an essential condition, though the process (c) is sometimes carried out at a slightly lower or higher than ambient pressure so as to maintain a good flow of gascous species through the system, The choice of a preparative technique is, however, guided by several actors particularly the melting point of the charge, its stability, desired purity and characteristics of deposits, etc. and these can often be achieved by several methods. Fig. 1 shows a sketch of a conventional oil diffusion pump type vacuum deposition unit. 3.1 Therma! Deposition in Vacuo It is the most commonly used technique adopied for the deposition of metals. alloys and also many compounds. This involves the evaporation or sublimation of the material in vacuo by thermal energy and allowing the vapour stream of the charge to condense on a substrate so as to form a continuous and adherent deposit of desired thickness. ‘The quality and the characteristics of the deposit will depend on the rate of deposition, substrate temperature, ambient Pressure, ete. and the uniformity of the film on several factors inter alia the geometry of the evaporant source and its distance from the substrate. 3.2 Kinetic Theory of Gas and Emission Condition" ‘The influence of deposition conditions on the characteristics of films can be better understood from an elementary consideration of the kinetic theory of gases. A solid material, when melted or sublimed in vacuo, forms vapour atoms or molecules which will exert in an enclosed space a pressure known as vapour pressure. At a steady state of evaporation these vapour atoms or molecules will have an equilibrium vapour pressure (p) which is given by the relation pe Mor Ta 9.656 x 10" pT cm~> Ib where WV is the total number of vapour atoms or molecules. V is the volume of the enclosed chamber, T is the absolute temperature of the gascous species and & is Boltzmann's constant, These atoms or molecules in gascous state will, however, collide with one another afier a certain mean free time (t) and the average distance of travel before suffering a collision with another can be expressed by the relations 1 Is (4-0) 2a or 1 = kT pro? V2) 2bThin Film u 4 - and e [14 evap]? 1 where cos® = cos = Wr Thickness distributions for other types of sources have been thoroughly dealt by Holland" and Glang. In the thermal deposition method, vacuurn should be as high as possible ie. the residual vapour pressure should be very low and preferably below 10-* torr or even lower. The evaporant sueam of molecules will then have a large mean free path as defined by Eq. 2b or 2c and strike the substrate without any significant loss of their kinetic energy duc to the collisions of residual gas molecules. The residual but very low air pressure in the vacuum chamber also ensures the non-formation of any oxide layer during the evaporation of metals and alloys. If the vacuum is poor i.e. when the residual air pressure is not low, then the deposits are likely to be contaminated with some oxides formed during the deposition process and often these deposits become blackish and powdery and non-adherent to the substrate. A. high substrate temperature generally improves the physical characteristics of the deposited films by imparting greater mobility to the vapour molecules or atoms condensing over the substrate for migration over its surface. Effects of substrate temperature and other factors will be discussed in Chapter 5. Uniformity of the deposit thickness over the substrate surface is generally achieved by placing the substrate at an appropriate distance from the evaporant source and also rotating it either around its axis or that of the source or both as the case may be. 4, RESISTANCE HEATING 4,1 Thermal Evaporation Refractory metals like tungsten, molybdenum or tantalum are generally used in the form of wire or strip having different shapes. The choice of a particular refractory metal as a heating source depends on the materials to be evaporated. so that the evaporant material does not react with the refractory metal at the high temperature of evaporation. However, the formation of alloy with the source cannot always be avoided. Hence a coating of refractory oxides such as of Al,O,, BeO or other suitable materials is often given over the filament or strip so as to prevent a direct contact between the molten charge and the refractory metal. In any case, when a direct heating of the charge is made, the filament or the strip is precleaned by passing a heavy current through it so as to make it white hot or incandescent for a very short period so that all the surface impurities of the filament or the strip are removed by evaporation and this12 Thin Film Fundamentals Process is called flash cleaning. After the above cleaning of the filament, strip or boat whatever may be the form of the evaporating source a little amount of the charge is then put into it and a current is stawly passed through the source and gradually increased so that the melt forms a bead or a layer over the heating sowne. Usually a shutter is placed in between the heating source and the substrate so that no vapour stream of the charge can reach the substrate. When appropriate deposition conditions are established, ie. vacuo, filament and substrate temperatures, source to substrate distance and inclination ¥ (cf. Fig. 4) etc.. the shutter is then removed out of the line of vapour stream of the charge in vacuo and the deposition on the substrate starts. When the required film thickness is obtained, this is again brought into the original position in vacuo so as to cut off further deposition on the substrate and the heating of the filament is then gradually stopped. If the charge consists of two or more constituents which have different vapour pressures, then the one having higher vapour pressure will tend to vaporise at a lower temperature than the other and hence at a particular temperature of evaporation the proportion of the higher vapour pressure constituent will be more than the other. This happens in many alloy systems, This means that the composition of vapour stream of the charge will be different from that of the charge itself and when condensed the deposits will have different composition even assuming that the condensation rate is the same for all the constituent species. Further in addition to the vapour pressure the evaporation rate of a species depends on its molecular weight, temperature, etc. (ef. Eq. 3a and b). For a binary alloy partial pressures of the constituent components may be assumed to follow Raoult’s taw for dilute solutions ie. the vapour pressure of cach component is depressed compared to that of the pure state by an amount Proportional to its concentration. Eq. 3b denoting the rate of evaporation of pure clement may also be extended to the binary alloys. Thus for two pure clements A and B the rates of evaporation at a temperature T and with partial vapours pressures P, and P, may be denoted as E, and Ey respectively (cf. Eq, 3b). If My and Mg are the molecular weights of A and B, then the ratio of the rates deposition of the wo will be a3 Ey_ (Pa) (Me z En | Pal | Me Assuming that Raoult’s law of depression of vapour pressure is valid for the binary alloy system AB, then according to Holland!', the ratio of evaporation of two components A and B from the alloy. will be Fas (Pa Me ® Ey Wy’ | Pp My where W, and IW ate the weight concentrations of the two components A and Bin the binary alloy AB If it is assumed that the hing coefficients of the twoThin Film 13 components are the same, then E/E, ratio will also represent the deposit composition of the alloy on the substrate. Ii is thus seen that the composi depends not only on the initial alloy composition but also an the factor under parenthesis in Eq. 8b. Unless the latter is unity which is not usually so, the deposit composition will not follow the bulk alloy composition ie. W, : Wp. Further as the evaporation of the alloy continues the composition of the molten charge also changes becoming richer in one of the two components as observed in many cases. This leads to a further variation of the E,/E, ratio and hence of the deposit composition. It is, therefore, not easy to deposit films of the same composition as that of the alloy charge by the usual thermal deposition process. If the deposition parameters are carefully adjusted by varying the rate of deposition, the substrate temperature etc., it may not altogether be difficult to get deposits of some fixed composition, though not necessarily exactly the same as that of bulk alloy charge. A typical case of the variation of deposit compo- sition is a nichrome alloy say of composiiton 80 : 20 nickel and chromium. A continuous vacuum evaporation of the above melt leads to films initially of composition 70 : 30 and later on to 50: SO, Holland!' observed that metals can be classified into two groups such that when an alloy is made from a combi- nation of two, one from each group, then on evaporation it would give deposits of some fixed composition. Table 1 gives some information regarding the thermal evaporation characteristics of some elements, alloys and compounds ete. It has so far been tacitly assumed that in vacuum-deposition process the solid bulk charge changes 0 the gascous state by thermal energy and on condensation on a substrate the deposit mass retains the same composition as that of the charge. This is, no doubt, an ideal situation and is generally valid for elements only but for alloys and compounds it is not so. In most cases the gaseous phase contains not only the molecules of the original charge but also the dissociated or even associated products of them leading to mixtures of several species. The propertics of the different species depend on the stability of the original matcrial under the thermodynamical conditions of evaporation. Mass spectrometry and other techniques have amply demonstrated their presence not only in the gascous phase but also in the solid deposit mass (cf. Table 1). The deposit layers are hence likely to be inhomogeneous and the distribution of these species in the films will also be non-uniform. Homogencity of films and the uniform distribution of these species can partially be achieved by raising the substrate temperature or by post-deposition anncaling treatment invacuo at an appropriate temperature or by the both methods. However, by a Proper combination of different variants it is sometime possible to obtain films of composition close to that of the charge. For materials which are not reasonably stable at the ambient thermal and vacuum conditions of deposition the composition of the deposit layers may vary widely from one extremity of pure material to other of completely dissociated (or associated) product or products. The latter species are generally treatcd as impuritics in the deposit18 Thin Film Fundamentals layers except for cases where these species are particularly desired and even in these cases the products are not pure. 42 Flash Evaporation This method is generally adopted when a material has a tendency to decompose or dissociate during evaporation as in the case of some alloys, group III-V compounds such as InSb, AlSb, etc., titanates, molybdates, even some oxides of metals, etc. Basically the process is similar to the thermal evaporation techniques with the difference that only a small amount of the charge in powder form is fed at a time to a white hot boat of tungsten, molybdenum or tantalum so that an instantaneous evaporation of the total charge takes place without leaving any residuc. Because of the high tcmpcraturc of the boat as well as the limited amount of the charge fed at a time to the boat, there will be no time for constituents to build up by differential vapour pressure as mentioned in the previous section (cf. Eqs. 8a and b). Hence the composition of the gascous phase will be more or less the same as that of the charge and it is expected that ‘on condensation the deposits will retain the composition of the evaporant. This method of deposition is called ‘flash evaporation’, Since there is no accumulation of the charge on the heated boat before the arrival of the next charge. the question of the enrichment of the residue by one constituent as in the normal process does not arise at all. The charge in powder form is fed from a reservoir or a hopper to the heated boat through a chute and the feeding rate can be made continuous or intermittant by using a vibrator of a suitable cam Fig. 5. A sketch of a flash evaporation arrangement.Thin Film 9 arrangement (Fig. 5). All other requirements for depositions are more or less similar to those of the normal evaporation process. For some oxides or titanates often a part of the molten charge is maintained over the heated boat which is then constantly fed by a small amount of fresh charge depending on the rate of evaporation. By this method a constant composition film can be produced. 4.3 Multi Evaporation Process In this technique several sources are simultaneously used for the evaporation of the constituent species or depositions are made sequentially i.e. one after another from different sources on the substrate to form the desired composite films. The rate and the time of deposition of cach species will generally determine the film composition. These deposits are then heat treated in vacuo for homogenisation, for ensuring a complete reaction between the constituent elements and also removing excess of more volatile components from them. ‘This technique is particularly suitable for film composition especially non-stoichiometric ones which cannot be easily prepared by the conventional _method'’, The simultaneous deposition process from different sources is known as ‘co-evaporation’ technique. 4A RL. or Induction Heating It is also possible to melt the charge by Rf. or induction heating and the evaporation takes place as in the case of thermal heating. In this technique it is possible to avoid contamination of the charge. However, the method is not suitable for general application. 5. ELECTRON BEAM METHOD This is one of the best methods for the deposition of metals, alloys, refractory metals etc. at a high rate and is now routinely used for the production of metal film resistors and others. Multi electron beam sources are also used for special applications. In this technique an electron beam accelerated with a voltage of say 2-10 kV is focussed on the surface of a charge which is normally kept inside a graphite crucible placed on a water cooled copper block. The high energy clectron beam emitting from the cathode impinges on the charge which is at the same potential as the anode is converted into intense heat energy which melts the charge. By suitably focussing the electron beam and controlling its intensity it is possible to keep the top surface of the charge in a molten condition from which evaporation can take place. As a result a fresh surface is exposed every time for further melting and evaporation. Hence a deposit of more or less of a constant composition is obtained. The temperature attained by the charge at the surface can be as high as about 3000°C or more by this method and hence refractory metals such as W, Mo, Ta, etc. can be melted and evaporated by this technique.Thin Film 21 methods are given by severa: workers". It is also possible to have an oscillating electron beam to facilitate the melting of the charge. In all cases necessary Precautions arc taken so thal evaporation is discontinued before the charge is exhausted since the last residue may contain some of the impurities coming out of the container vessel such as graphite or other material. It may be mentioned here that because of the high temperature of working, the electron beam gun assembly is water cooled. 6, CATHODICSPUTTERING ‘The deposition of metal films by sputtering from a cathode by the glow discharge method was first observed by Grove!. Since then numerous investigations have been made on the physics of sputtering and it is only in the recent years that the process is now better understood. The ejection of atoms from the cathode surface by impinging of energetic positive ions of noble gases such as helium, argon, neon, krypton at a reduced pressure under a high de voltage gives rise to the sputtering phenomenon. An increasing interest in the deposition of films of technological importance for devices fabricated from metals, alloys, oxidic and other compounds of refractory nature has led to a detailed study of this process'*!7 and it is now possible to make various resistive, semiconducting, superconducting and magnetic films by this technique in a better way. If the process does not involve any chemical reaction between the bombarding gas ions and the cathode it is known as ‘*physical sputtering‘. If, on the other hand, some reactions are involved then it is termed as “reactive sputtering”. Both these types of sputtering are carried out in a comparatively poor vacuum and are known as high pressure sputtering. ‘The mechanism of the process involves a momentum-transfer between the impinging energetic ions or neutrals and the cathode-surface atoms as a result of which a physical removal of atoms takes place. This momentum transfer theory of Stark'® has been amply verified by various workers especially by Wehner '®?!. Conclusions drawn are that the sputtering yield increases with the energy and the mass of the bombarding ions and also with the decrease of angle of incidence to the target. A minimum energy is required to start the sputtering process. Sputtered atoms have much higher energies than those of the thermally evaporated ones and the former are, however, ejected along the crystallographic directions of the cathode-metal lattices. Sputtering yield also decreases with the large increase of the ion-cnergy because of the decper penetration of ions or neutrals inside the lattice. Sputtering is also accompanied by the emission of secondary electrons (y-clectrons) from the cathode surface, Auger transition (radiation fess) also takes place along with emission of yelectrons. The yield is. however, insensitive to the cathode temperature. According to Pease”? the sputtering yield can be expressed by the equation2 Thin Film Fundamentals in In(E/E,) = Ane = ae Yo Aw cE 16[ In? ° where A is the cross section for imparting an energy E greater than E, which is the energy required for displacing an atom from its place, E is the mean energy of the struck atoms, E, is the sublimation energy and n is the number of target atoms per unit volume. Further the factor A n™ is the number of atoms that each knock hits as it passes through the layer. For normal cases Ewa? > E> 2E, Sputtered atoms are basically neutral i.e. atomic in nature. However, a small percentage say about 15 may be in the ionised state. Part of the sputtered material may form polyatomic species and complexes but their relative abundance will be quite negligible compared to the number of neutral atoms. During sputiering some of the atoms of the cathode i.e. the target are likely to be displaced due to the impact of the energetic positive ions to new positions in the lattice and surface migration of atoms may also occur. If the ions are heavy and have high kinetic energy then the target may also be damaged due to their impact. 6.1 Glow Discharge Sputtering ‘The simprest method of sputtering is the by the glow discharge technique. ‘This can be understood from the behaviour of gases at reduced pressures under a high de voltage source. Conduction through a gas is not generally possible unless a high de voltage is applied between two electrodes with a gas or air in between them. A current (ionisation current) can pass through the gas or air only when a break down of gas or air molecules occurs resulting in their ionisation, The minimum voltage at which breakdown takes place is called breakdown voltage V,. This, however, decreases with the lowering of the gas pressure (Fig. 7a). Conduction through a gas al a reduced pressure under an increasing dc voltage gives rise to several electrical and visual phenomena which are of importance to understand the sputtering process. If the gas pressure is reduced beyond a certain stage ie. when vacuum is very high the break down of gas and its ionisation becomes increasingly difficult. Soon after, V, instead of decreasing, increases with the lowering of gas pressure ie. with the increase of vacuum and at a very high vacuum ionisation of gas may not take place even at a considerable high voltage such as 30 keV or more. Our primary concem is for the region where V, decreases with the reduction of gas pressure. Voltage-current or ionisation characteristics between two electrodes al a reduced gus pressure under a d.c. power are illustrated in Fig. 7b. The graph shows several regions as indicated by numerals 1 to 10 and of these regions 6 and 7 are relevant for sputtering especially the last one for continuous deposition. Further the current increase is negligibly small with the rise ofThin Film 23 @ ) Pig 7 i) Vadaion of Vp wih pe reser: (b) Voltage—current characteristics of a gas at a reduced pressure in a discharge tube with numerals indicating differeet regions of the J—V curve: 1 random burst; 2- photo electric current; 3- Townsend discharge; 4- corona; 5- rebsormal glow, 6 normal glow discharge: 7- abnormal glow discharge: 8- transition region: 9- arc discharge and 10- break down vokare (Vs) coesponding to Townsend discharge. voltage in the initial stage (1 and 2) until a minimum voltage as indicated by the dotted line 10 known as break down voltage (V,) is reached. It is then followed by a large increase in current at a constant voltage continuous with V, in the Townsend region (3). The graph then shows a sharp fall of voltage with the increase of current (regions 4 and 5). It is then followed by a constant voltage region (6) known as the normal cathode glow discharge region where a glow appears on the cathode but covering it only partially. The next region (7) where the large increase in voltage as well as current is called the abnormal glow region. In this case the cathode is fully covered by the glow. A continuous sputtering can take place only in this region. The luminous glows in regions 6 and 7 are self supporting duc to the ejection of secondary (y) electrons from theray Thin Film Fundamentals cathode by the impact of positive ions. Subsequent regions 8 and 9 are of little importance for sputtering. Luminous normal and abnormal glow discharges show some broad visual features namely bright and dark regions the details of which may vary wth factors such as gas pressure, cathode shape etc. (Fig. 8a). These consist of (1) cathode glow, (11) cathode or Crookes dark space, (III) negative glow, (IV) Faraday dark space. (V) positive column etc. as one goes from the cathode to the anode. There may also be some other regions such as Aston dark space near the cathode which may not be visibly distinguished in the normal case. Luminosity of the negative glow (III) is the most intense and the next in order comes the positive column (V). If the inter electrode distance is increased or decreased some of the above regions may increase or decrease and the latter in some case may even merge together. The voltage fall across these gaseous column between the two electrodes is not uniform and maximum occurs at the cathode dark region (II) (Fig. 8b). From various considerations the visual phenomenon and sputtering process have been envisaged in the following way. 0D! — V Voliage Oe Glow Discharge Cohema @) Fig.&. (a) Schematic diagram of different regions in a glow discharge column: (i) cathode tow, oon « dark space, (iti) negative glow, (iv) Paraday dark space, (v) positive colunm, (vi) anode glow; (b) Corresponding voltage drop at different regions along the column. An electron emiued from the cathode under a d.c. high voltage whilst passing through the cathode dark space acquires high energy because of a high voltage fall and moves to the edge of the negative glow region. Different Phenomena appearing in a discharge tube at a reduced pressure can broadly be understood from the following considerations vit. (a) ionisation occurs by collision and (b) only excited atoms or molecules emit light but not moving electrons. The above high energy electrons then make collisions with gas molecules and ionise them releasing an electron from each collision till it losesThin Film 2s its energy to a state which is inadequate for further ionisation. Thus in this region a considerable number of positive ion-electron pairs are generated. These ionised (or excited) molecules emit light giving rise to the negative glow (III). The positive ions resulting from such collisions tend to slow down the clectrons and the later in tum lose thcir power to ionise the gascous molecules and accumulate thus forming a negatively space charged regions beyond the negative glow region (i.e. 111) known as Faraday dark space (IV). Electrons being light, however, move towards the anode under the positive field, acquire suffi- cient energy and begin to ionise gascous molecules in the region corresponding to positive column (V). It may be mentioned here that since the moving electrons by themselves do not emit light, the region they pass through before colliding with molecules will be dark. Positively charged ions formed in the negative glow space region (III) move through it to the cathode dark space (II) by diffusion and are then accelerated to the cathode and strike its surface with a voltage nearly equal to the full voltage drop. This results in the sputtering of the cathode material as well as the emission of secondary electrons which maintain the glow discharge. Because of the heavy mass of the ions (positive) and their high momenta, their impact will cause a displacement of atoms in the cathode and a consequent damage of the target as mentioned carlier, Since the lengths of the dark and the luminous regions are dependent on various factors viz. gas pressure, anode to cathode distance, voltage, etc. as mentioned before and also their inter-telationship, the study of the basic process is difficult in a simple discharge tube. However, with the insertion of a third electrode and making it more negative with respect to the anode i.e, a second cathode known as the Langmuit’s probe the basic process has been investigated in details by applying different negative voltages at the new cathode. The introduction of an additional electrode does not alter the basic phenomena in a glow discharge of the two electrode sysicm but makes it amenable to study the effect of the individual factor. Thus at equilibrium the ion current density (J) due to the plasma is given by Langmuir space charge equation J (WF) (de f9) 2 efmy® 10a where V is the voltage difference between the target and plasma, 1 is the thickness of the sheath i.e. the dark cathode space, € g is the permittivity of the free space, ¢ is the electronic charge and m is the mass of the ions. For parallel plate electrodes Eq. 10a can be written as!! J 22S 10° ye ample 10» Further the ion current J is related to the density of the ions (n°) in the plasma ic. the number of ions per unit volume in the plasma by the equation J= (Ws) a" Fe ordfe= (14) at "26 Thin Film Fundamentals where ¥ is the average drift velocity of the plasma ions. In a similar way the phenomenon occurring at the anode region can be studied by making the additional electrode more positive with respect to the anode. It may be men- tioned here that the cathode glow is maintained by the emission of y-clectrons from the cathode. The composition of the sputtered film generally conforms to that of the cathode material and the deposition is primarily due to momentum-transfer between the impinging ions and the cathode material as mentioned before. Since process does not depend on temperature and as there is practically no mass transfer, the sputtered material will be of the same composition as that of the target. However, a slight deviation may occur due to the variation of the sticking coefficients of the constituent elements of the cathode material to the substrate surface. In order to have an ion beam under a high voliage (say 1-10 kV) the Pressure of the chamber should be about 10-' to 10-? torr. Under the action of the accelerating potential of electrons the gas inside the chamber gets ionised and depending on the voltage between the two electrodes the positive ions flow towards the cathode. In the normal sputicring method inert gases such as helium, neon, argon, etc. are used for ionisation and subsequent sputtering of the cathode. This is achieved by evacuating the chamber initially to about 10~° to 10~ torr and then passing a purified inert gas through a needle valve al a controlled rate, so that the chamber pressure increases to a range of 107! to 10- torr required for sputtering. The usual pressure is about 0.01 to 0.2 torr. ‘The rate of sputtering depends on several factors as mentioned before. The cathode which is at a high negative voltage is generally water cooled and its shape is usually in the form of a disc. The base plate which is generally at the ground potential forms the anode. Substrates placed over the base plate are also at the ground potential and are sometimes kept at a higher temperature. Sputtering deposition rates are generally lower than the thermal method and often less than 2000 A per minute. Recently efforts have been made to increase the sputtering rate and new equipments have been designed which give high rates as good as those of electron beam methods. Materials used for sputtering usually are metals, alloys, semiconductors or diclectrics. Often a cathode shield kept at the ground potential is placed around the cathode and quite close to it. It has an opening through which the sputiered material can come out and deposit on the substrates. Both the cathode disc and the substrate are placed parallel to each other and the distance between them is a few centimeters only. Since the deposition process is primarily by the momen- tum transfer mechanism and the diffusion of the cathode material to its surface occurs without any appreciable mass transfer or increase in temperature, the deposits normally retain the cathode material composition. This has been achieved in many films deposited from alloy-cathode targets. However. in some cases, a slight deviation has been observed. Thus the sputtering of a 85 : IS nichrome cathode leads to a film of about 80 : 20 compositon. This technique isThin Film 27 particularly suitable for refractory materials which cannot casily be deposited by other methods. The advantage of this system known as high pressure sputtering is its simplicity, possible use of high sputtering rates and also deposition of film of uniform thickness and of uniform physical properties. Its chief disadvantages are occlusions of residual gases in the sputtered films, lower efficiency of sputtering at higher ionisation rate, structural (physical) inconsis- tencies of deposits etc. 6.2 Low Pressure Sputtering ‘Some of the disadvantages mentioned above can be removed by sputtering at lower pressures known as low pressure sputtering normally carried out at or below 10~ torr gas pressure and in some cases as low as 10~*to 10” torr. It has already been mentioned that ionisation of gas molecules generally takes place at low vacuum say 10-' to 10? torr. It is difficult to ionise the residual gas molecules below 10? torr since the rate of collision of gas decreases with the lowering of pressure. The ionisation can, however, be achieved simply by increasing the number of electrons for ionisation by inserting a second cathode in the system (triode system) or by increasing the effective free path length of ionising electrons by the usc of crossed magnetic and electrical fields as in Penning discharge system. In the former case a secondary hot electron gun is introduced to increase the total concentration of ionising electrons and the process is further enhanced by the presence of a magnetic field inclined to the lines force between the cathode and the anode. In such cases the gas pressure is about one order less than for the normal sputtering and the magnetic field is also less. The advantage of this system is that a fine control of sputtering rate can be made by adjusting the magnetic feld. In the latter case ionisation is increased by increasing the number of collisions of the residual gas with ionising electrons by spiraling their paths, instead of straight ones, under a strong magnetic field. With appropriate shapes of cathodes and suitable magnetic fields say in the form of two solenoids in oppasition, a high rate of deposition can be made at pressure of about 10-* torr. In a third method low pressure sputtering is carried out by the use of radio frequency of several order mega hertz. This method is separately discussed in Section 6.4. 6.3 Reactive Sputtering During sputtering it is also possible that under certain conditions the target material may react with the ionised gascous species in the chamber. In the normal sputtering cases only inert gases are used. If gases like oxygen of nitrogen are used as media, the ionised species derived from them can react with the target to form oxide or nitride!" films. Oxide films such as CuO, CoO, Co.O,, NiO, etc. have been obtained from hot targets", Nitrides, borides and many other films which cannot be easily prepared by other techniques can be made by the reactive sputtering process using nitrogen, borohydride or other suitable media. It appears that the sputtered material during its flight from the28 Thin Film Fundamentals target to the substrate reacts with the ionised nitrogen or boron or other species. These reactions are quite vigorous and films of reacted materials are deposited on the substrate surface. It is also possible to form films of mixed nitrides, borides, ete. If the target is made of some suitable composition and an appropriate gaseous atmosphere is maintained in the sputtering chamber, then different types of films of mixed compositions can be prepared comparatively easily. 6.4 R.F. Sputtering So far we have discussed the sputtering process arising from the application of a d.c. voltage between twa electrodes. Enhanced ionisation can be achieved in the rf, field so that sputtering can be done at pressure lower than that of the ordinary glow discharge. The effect of a.c. voltage for gas discharges requires some discussions to understand the rf. sputtering technique which has been developed quite recently”. With a low frequency a.c. field between two electrodes of a discharge tube. there will not be any ionisation of gases since both the electrodes will have alternate polarities. However, if the two electrodes are placed closer, dark regions will be found around each of them, thus suggesting as if these electrodes work as cathodes as in high d.c. fields. Actually there will always be some dic. discharges which cannot be sustained during the alternation of the polarities of the two electrodes. With increasing frequencies say in the range between 100 kHe. to about a few MHz there will be a sustained glow discharge due to the ionisation of gases by the oscillating clectrons of high frequency field and not by the secondary electrons as in the case of d.c. discharges. The phenomenon of gas discharge at high frequencies has been discussed by Brown™. These electrons gain energy from the field and move in different directions and hence do not require any high ficld, The mechanism of ‘energy absorption by electrons in rf. fields has been discussed by Levitskii”. ‘These plasma electrons also acquire some positive voltage with respect to the electrodes. If these electrodes are of different sizes, a d.c. voltage will develop between them™**"”, In rf. sputtering method an impedance matching between the power supply and the discharge tube is necessary. Several factors which are essential for r.f. sputtering have been discussed by Maissel"”, This technique is particularly useful for the deposition of dielectric materials since in dec. sputicring some positive charge also builds up on the dielectric material target surface as a result of which sputtering efficiency goes down. This can, however, be avoided by using the rf. method i.c. by applying a high frequency potential (MHz range) to the gascous plasma. During the process, neutralisation of positive charges over the dielectric material takes place periodically. At one half of the ac. cycle the surface is biased negative thus repelling the plasma electrons by forming a sheath of ions which are accelerated towards the target and hence an ion current is maintained. The rate of the change of the surface potential with time is given by dV/dr = U/C where J is the ion current and CisThin Film 35 8.3), The mirror like silver deposits from a solution of silver nitrate by using formaldehyde as a reducing agent is an example of the above process. In a similar way copper and many other metal films can also be deposited from appropriate baths, If the substrate is a non-conductor, then sensitisation and activation treatments have to be carried out as used in the case of electroless depositions 8&5 Chemical Displacement ‘This method, though mentioned here, is not suitable for making any good film. This process depends on the difference in the relative electrode potentials of two metals in their aqueous salt solutions. If a lower electrode potential metal is dipped in a salt of a higher electrode potential, then due to the difference in their solution pressures, the later metal gets deposited on the surface of the former as in the case of dipping a zinc rod in a copper sulphate or a siver nitrate solution. A deposition of copper or silver takes place over the zinc rod and an equivalent amount of zinc goes into the solution. This process stops after sometime. These films are generally porous, non-adherent and inhomogeneous. 9, FILM THICKNESS AND ITS CONTROL Thickness plays an important role in the film properties unlike a bulk material and almost all film properties are thickness dependent at least for thin films as will be evident from different chapters of this book. Reproducible properties are achieved only when the film thickness and the deposition parameters are kept constant. In many applications, particularly so in the case of optical devices such as interference filters, anti-reflection coatings, etc. the success of the fabrication depends only on the deposition of specific thickness of the dielectric layers. In other cases even though a specific thickness may not be strictly necessary, a good control of it will still be essential. In all thickness measurements it is generally assured that these films are homogencous and more or less uniformly deposited on the substrate so that these will have a mean thickness (d or 1). However, when films are thin, i.e. their thicknesses are low say less than about 500 A and specially in the cases of ultra-thin films, the deposit layers will be discontinuous and non-uniform and may be interspersed with voids or pinholes. In such cases a mean film thickness may not have any significance at all since d at any specific area may vary from 0 to any value much higher than the so called mean film thickness. It only indicates the likely magnitude of the film thickness if all deposits would have been uniformly deposited ot distributed over the total substrate surface. If the deposition is carried out in a controlled condition then mean d or t will be close to the film thickness at any place over the substrate surface Film thickness measurement techniques are based on different principles such as the mass difference, light absorption. interference effect, conductivity, capacitance, etc. of the films with increasing thickness. These measurements42 Thin Film Fundamentals It has already been shown that from the above readings of the ellipsometer it is possible to evaluate optical constants (n, k) with the help of the Eqs. 25d and c of Chap. 11. For calculation of film thickness ¢ in the case of transparent film from Y and A Eqs. 30a to 30e are used. However, for absorbing films there will be three unknown quantities n, k and d of the film to be determined from two ellipsometer parameters x and y which is not possible. There are several methods by which the above difficulty can be surmounted. The details of the ellipsometric measurements have been given in Chanter 11. A schematic diagram of an ellipsometer is shown in Fig. 11 9.2.3 Interferometry Film thickness can also be measured accurately from interference fringes using multiple beam interferometry and also from the fringes of equal chromatic order (FECO) techniques. In the former case two reflecting surfaces are brought in close proximity such that a small wedge with a small air gap in between them is formed. If a monochromatic light is now incident on them at normal incidence, then an interference of light due to interactions of multiple reflected beams in air gap will take place resulting in a series of fringes (Fizeau) which can be observed in the back reflected light. The distance between the fringes or lines depends on the air gap as well as one the wave length of the monochromatic light. This principle is adopted and suitably modified for the multiple beam interferometric method of the measurement of film thickness A film, the thickness of which is to be determined, is deposited on a flat surface so as to leave a sharp edge between the film and the uncoated region of the substrate. An optically flat surface is generally preferred as a substrate and often a good microscopic glass slide is good enough for this purpose. The substrate with a coating of the film is then given a heavy and highly reflecting coating of a metal such as silver ot aluminium so as to form a sharp step on the film edge. Another flat (optically) glass stide known as the reference plate, with a partially transparent film of the same metal, is then placed over the specimen with their metal coated surface in contact with each other so as to leave a small air gap at the step. A monochromatic parallel beam of light passing through a beam splitter or a glass plate inclined at 45° is then i assembly and reflected ‘on a photographic plate (Fig. 12a). A set of sharp fringes perpendicular to the step with equal displacements will be observed (Fig. 12b) and the thickness (4) can be determined using the relation 1 = bia 3t where b is the displacement of the fringes at the step and a is the distance between consecutive fringes. These fringe displacements which are in the form of parallel lines, however, occur al the film edge. The sharpness of fringes depends on the reflectivity of the metal coating, the spread of the incident beam. air gap etc. It is also essential that the metal coatings on the two plates viz. substrate and the reference plate should be of the same material since aThin Film 3° phase change occurs when a beam of light is incident on each of the metal coating. This technique is capable of resolution as low as about 10 A and routinely about 20-30 A. This is one of the simplest methods which can be adopted for measurements of thickness varying say from 30-20,000 A. This is the only property-independent method for + measurement. In the FECO method two optical flats with a film of thickness # on one of them are placed parallel to each other (Fig. 13). Both the plates are given a heavy coating of silver as before to have sharp fringes. In this case a white light instead of a monochromatic one is incident normally through a beam splitter and the back reflected (or transmitted) light is then observed by an interference objective or through a spectrometer. Film thickness r is then calculated from the following relation =% te yan 32 microscope beam splitter source condenser collimator \ _—— | (a) Cl» P, Q , PET / 8 o Fig. 12. (2) A schematic arrangement of multiple beam interferomatic vechnique: (h) equal duplacement fringes44 Thin Film Fundamentals where m is the order of reflections and A is the change in the wave length. The accuracy of this method is about 5 A. In this case parallel lines or bands are observed instead of steps at wavelengths so that 1/2 is constant. In the case of the back reflected light the fringes or lines are dark in the white back ground whereas for transmission cases the pattems are reversed that is white lines or bands on the dark back grounds. Thickness down to about 15 A can be measured by this method. Fig. 13. Fringes of equal chromatic order technique (FECO) (after Scot et al) (Reprinted with the permission of American Institute of Physics, New York). 9.3 Other Methods ‘There are several other methods which are less universal and can be used for some specific cases and some of them are eminently suitable for mass or routine productions, In some of them the basic assumption is that the film Properties such as resistance, capacitance, Hall voltage, etc. are dependent only ‘on the film thickness, but not on deposition conditions. Such a criterion may be satisfied only in routine or mass production cases where a standard procedure is adopted. Since film properties are dependent also on the deposition para- meters the methods depending on the above properties are used in specific cases only and for restricted thickness range. Film thickness can also be estimated from its absorption property of radi- ation such as light, x-rays, a-rays, Brrays, electron beam etc, and the absorption is generally an exponential function of the film thickness. The principle of film thickness determination from optical absorption will also be discussed in Chap. 11 and hence not given here. Absorption of x-rays, a and B rays by a material takes place when these are allowed to pass through it. This propery is then used for the determination of the thickness of the material and can be used say between about 100 A to about 1 mm of thickness. High velocity electron beam say between 50 kV to 100 kV can be used for measuring film thickness of about a few thousand A. In the later method electron absorption is measured when the Bragg reflection is absent. The back scattering of ot or B rays by a material, x-rays fluorescence, electron microprobe methods etc, are also used for measuring film thickness, though some of these ate not straight forward and involve the measurements of the mass of the material.