ABSTRACT

The main objective of this project is To Study the Performance characteristics of a single Thermo-Electric generator module to compare theoretical and experimental results and also discuss its applications.

Thermoelectric generators are all solid-state devices that convert heat into electricity. Unlike traditional dynamic heat engines, thermoelectric generators contain no moving parts and are completely silent. Such generators have been used reliably for over 30 years of maintenance-free operation in deep space probes such as the Voyager missions of NASA. Compared to large, traditional heat engines, thermoelectric generators have lower efficiency. But for small applications, Thermoelectrics can become competitive because they are compact, simple (inexpensive) and scalable. Thermoelectric systems can be easily designed to operate with small heat sources and small temperature differences. Such small generators could be mass produced for use in automotive waste heat recovery or home co-generation of heat and electricity. Thermoelectrics have even been miniaturized to harvest body heat for powering a wristwatch.

PREFACE

The following report consists in depth description and illustration of Semiconductor Physics The Seebeck effect Materials required Making of a Thermo-electric generator Working of a Thermoelectric generator Performance characteristics of a Thermoelectric generator Application of Thermoelectric generators Necessity of Thermoelectric power Future of Thermoelectric power as an alternate source of energy.

1.1 INTRODUCTION TO SEMICONDUCTORS

A semiconductor is a material which has electrical conductivity between that of

a conductor such as copper and an insulator such as glass. The conductivity of a semiconductor increases with increasing temperature, behaviour opposite to that of a metal. Semiconductors can display a range of useful properties such as passing current more easily in one direction than the other. Because the conductive properties of a semiconductor can be modified by controlled addition of impurities or by the application of electrical fields or light, semiconductors are very useful devices for amplification of signals, switching, and energy conversion. Understanding the properties of semiconductors relies on quantum physics to explain the motions of electrons through a lattice of atoms. Current conduction in a semiconductor occurs via free electrons and "holes", collectively known as charge carriers. Adding impurity atoms to a semiconducting material, known as "doping", greatly increases the number of charge carriers within it. When a doped semiconductor contains excess holes it is called "p-type", and when it contains excess free electrons it is known as "n-type". The semiconductor material used in devices is doped under highly controlled conditions to precisely control the location and concentration of p- and ntype dopants. A single semiconductor crystal can have multiple p- and n-type regions; the p n junctions between these regions have many useful electronic properties and characteristics. Semiconductors are the foundation of modern electronics, including radio, computers, and telephones. Semiconductor-based electronic components include transistors, solar cells, many kinds of diodes including the light-emitting diode (LED), the silicon controlled rectifier, photo-diodes, and digital and analog integrated circuits. Increasing understanding of semiconductor materials and fabrication processes has made possible continuing increases in the complexity and speed of semiconductor devices, an effect known as Moore's law.

1.2 HISTORY OF SEMCONDUCTORS

The history of the understanding of semiconductors begins with experiments on the electrical properties of materials. The properties of negative temperature coefficient of resistance, rectification, and light-sensitivity were observed starting in the early 19th century. In 1833, Michael Faraday reported that the resistance of specimens of silver sulfide decreases when they are heated. This is contrary to the behavior of metallic substances such as copper. In 1839, A. E. Becquerel reported observation of a voltage between a solid and a liquid electrolyte when struck by light, the photovoltaic effect. In 1873 Willoughby Smith observed that selenium resistors exhibit decreasing resistance when light falls on them. In 1874 Karl Ferdinand Braun observed conduction and rectification in metallic sulphides, and Arthur Schuster found that a copper oxide layer on wires has rectification properties that ceases when the wires are cleaned. Adams and Day observed the photovoltaic effect in selenium in 1876. A unified explanation of these phenomena required a theory of solid state physics which developed greatly in the first half of the 20th Century. In 1878 Edwin Herbert Hall demonstrated the deflection of flowing charge carriers by an applied magnetic field, the Hall Effect. The discovery of the electron by J.J. Thomson in 1897 prompted theories of electron-based conduction in solids. Karl Baedeker, by observing a Hall effect with the reverse sign to that in metals, theorized that copper iodide had positive charge carriers. Johan Koenigsberger classified solid materials as metals, insulators and "variable conductors" in 1914. Felix Bloch published a theory of the movement of electrons through atomic lattices in 1928. In 1930, B. Gudden stated that conductivity in semiconductors was due to minor concentrations of impurities. By 1931, the band theory of conduction had been established by Alan Herries Wilson and the concept of band gaps had been developed. Walter H. Schottky and Nevill Francis Mott developed models of the potential barrier and of the characteristics of a metal-semiconductor junction. By 1938, Boris Davydov had developed a theory of the copper-oxide rectifer, identifying the effect of the pn junction and the importance of minority carriers and surface states. Agreement between theoretical predictions (based on developing quantum mechanics) and experimental results was sometimes poor. This was later explained by John Bardeen as due to the extreme "structure sensitive" behavior of semiconductors, whose properties change dramatically based on tiny amounts of impurities. Commercially pure materials of the 1920s

containing varying proportions of trace contaminants produced differing experimental results. This spurred the development of improved material refining techniques, culminating in modern semiconductor refineries producing materials with parts-per-trillion purity. Devices using semiconductors at first were constructed based on empirical knowledge, but semiconductor theory provided a guide to construction of more capable and reliable devices. Alexander Graham Bell used the light-sensitive property of selenium to Photophone transmit sound over a beam of light in 1880. A working solar cell, of low efficiency, was constructed by Charles Fritts in 1883 using a metal plate coated with selenium and a thin layer of gold; the device became commercially useful in photographic light meters in the 1930s.[3] Pointcontact microwave detector rectifiers made of lead sulfide were used by Jagadish Chandra Bose in 1904; the cat's-whisker detector using natural galena or other materials became a common device in the development of radio. However, it was somewhat unpredictable in operation and required manual adjustment for best performance. In 1906 H.J. Round observed light emission when electric current passed through silicon carbide crystals, the principle behind the light emitting diode. Oleg Losev observed similar light emission in 1922 but at the time the effect had no practical use. Power rectifiers, using copper oxide and selenium, were developed in the 1920s and became commercially important as an alternative to vacuum tube rectifiers. In the years preceding World War II, infra-red detection and communications devices prompted research into lead-sulfide and lead-selenide materials. These devices were used for detecting ships and aircraft, for infrared rangefinders, and for voice communication systems. The point-contact crystal detector became vital for microwave radio systems, since available vacuum tube devices could not serve as detectors above about 4000 MHz; advanced radar systems relied on the fast response of crystal detectors. Considerable research and development of silicon materials occurred during the war to develop detectors of consistent quality. Detector and power rectifiers could not amplify a signal. Many efforts were made to develop a solid-state amplifier, but these were unsuccessful because of limited theoretical understanding of semiconductor materials.[3] In 1922 Oleg Losev developed two-

terminal,negative resistance amplifiers for radio; however, he perished in the Siege of Leningrad. In 1926 J.E. Lilenfeld patented a device resembling a modern field-effect transistor, but it was not practical. R. Hilsch and R. W. Pohl in 1938 demonstrated a solid-

state amplifier using a structure resembling the control grid of a vacuum tube; although the device displayed power gain, it had a cut-off frequency of one cycle per second, too low for any practical applications, but an effective application of the available theory.[3] At Bell Labs, William Shockley and A. Holden started investigating solid-state amplifiers in 1938. The first pn junction in silicon was observed by Russell Ohl about 1941, when a specimen was found to be light-sensitive, with a sharp boundary between p-type impurity at one end and n-type at the other. A slice cut from the specimen at the pn boundary developed a voltage when exposed to light. In France, during the war, Herbert Matar had observed amplification between adjacent point contacts on a germanium base. After the war, Matar's group announced their "Transistron" amplifier only shortly after Bell Labs announced the "transistor".

Fig 1. Raw germanium

Fig 2. Silicon

1.3 SEMICONDUCTOR MATERIALS

A large number of elements and compounds have semiconducting properties, including:

Certain pure elements found in Group IV of the periodic table; the most commercially important of these elements are silicon and germanium.

Binary compounds, particularly between elements in Groups III and V, such as gallium arsenide, Groups II and VI, groups IV and VI, and between different group IV elements, e.g. silicon carbide.

Certain ternary compounds, oxides and alloys. A number of organic compounds.

An intrinsic semiconductor is made up of one pure element or pure compound. At room temperature, the conductivity of intrinsic semiconductors is relatively low because there are very few charge carriers available. Conductivity is greatly enhanced by a process called doping, in which very small amounts of other elements are added to the intrinsic crystal to create what is called an extrinsic semiconductor. Most common semiconducting materials are crystalline solids, but amorphous and liquid semiconductors are also known. These include hydrogenated amorphous silicon and mixtures of arsenic, selenium and tellurium in a variety of proportions. These compounds share with better known semiconductors the properties of intermediate conductivity and a rapid variation of conductivity with temperature, as well as occasional negative resistance. Such disordered materials lack the rigid crystalline structure of conventional semiconductors such as silicon. They are generally used in thin film structures, which do not require material of higher electronic quality, being relatively insensitive to impurities and radiation damage.

Fig 3. Periodic table indicating semiconductors

1.4 ENERGY BANDS AND ELECTRICAL CONDUCTION

Semiconductors are defined by their unique electric conductive behaviour. Metals are good conductors because at their Fermi level, there is a large density of energetically available states that each electron can occupy. Electrons can move quite freely between energy levels without a high energy cost. Metal conductivity decreases with temperature increase because thermal vibrations of crystal lattice disrupt the free motion of electrons. Insulators, by contrast, are very poor conductors of electricity because there is a large difference in energies (called a band gap) between electron-occupied energy levels and empty energy levels that allow for electron motion.

Insulator conductivity increases with temperature because heat provides energy to promote electrons across the band gap to the higher electron conduction energy levels (called the conduction band). Semiconductors, on the other hand, have an intermediate level of
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electric conductivity when compared to metals and insulators. Their band gap is small enough that small increase in temperature promotes sufficient number of electrons (to result in measurable currents) from the lowest energy levels (in the valence band) to the conduction band. This creates electron holes, or unoccupied levels, in the valence band, and very loosely held electrons in the conduction band.

Fig 4. A simplified diagram illustrating the energy band levels of an insulator, a semiconductor, and a conductor. Electrons can only exist in certain energy levels.

In the classic crystalline semiconductors, electrons can have energies only within certain bands (ranges). The range of energy runs from the ground state, in which electrons are tightly bound to the atom, up to a level where the electron can escape entirely from the material. Each energy band corresponds to a large number of discrete quantum states of the electrons. Most of the states with low energy (closer to the nucleus) are occupied, up to the valence band.

Semiconductors and insulators are distinguished from metals by the population of electrons in each band. The valence band in any given metal is nearly filled with electrons under usual conditions, and metals have many free electrons with energies in the conduction band. In semiconductors, only a few electrons exist in the conduction band just above the valence band, and an insulator has almost no free electrons.

The ease with which electrons in the semiconductor can be excited from the valence band to the conduction band depends on the band gap. The size of this energy gap (band gap) determines whether a material is semiconductor or an insulator (nominally this dividing line is roughly 4 eV). With covalent bonds, an electron moves by hopping to a neighbouring bond. The Pauli Exclusion Principle requires the electron to be lifted into the higher anti-bonding state of that bond. For delocalized states, for example in one dimension that is in a nanowire, for every energy there is a state with electrons flowing in one direction and another state with the electrons flowing in the other. For a net current to flow, more states for one direction than for the other direction must be occupied. For this to occur, energy is required, as in the semiconductor the next higher states lie above the band gap. Often this is stated as: full bands do not contribute to the electrical conductivity. However, as the temperature of a semiconductor rises above absolute zero, there is more energy in the semiconductor to spend on lattice vibration and on exciting electrons into the conduction band.

Electrons excited to the conduction band also leave behind electron holes, i.e. unoccupied states in the valence band. Both the conduction band electrons and the valence band holes contribute to electrical conductivity. The holes themselves don't move, but a neighbouring electron can move to fill the hole, leaving a hole at the place it has just come from, and in this way the holes appear to move, and the holes behave as if they were actual positively charged particles.

One covalent bond between neighbouring atoms in the solid is ten times stronger than the binding of the single electron to the atom, so freeing the electron does not imply destruction of the crystal structure.

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1.5 DOPING OF SEMICONDUCTORS

The conductivity of semiconductors may easily be modified by introducing impurities into their crystal lattice. The process of adding controlled impurities to a semiconductor is known as doping. The amount of impurity, or dopant, added to an intrinsic (pure) semiconductor varies its level of conductivity. Doped semiconductors are referred to as extrinsic. By adding impurity to pure semiconductors, the electrical conductivity may be varied by factors of thousands or millions.

A 1 cm3 specimen of a metal or semiconductor has of the order of 1022 atoms. In a metal, every atom donates at least one free electron for conduction, thus 1 cm3 of metal contains on the order of 1022 free electrons. Whereas a 1 cm3 of sample pure germanium at 20 C, contains about 4.21022 atoms but only 2.51013 free electrons and 2.51013 holes. The addition of 0.001% of arsenic (an impurity) donates an extra 1017 free electrons in the same volume and the electrical conductivity is increased by a factor of 10,000.

The materials chosen as suitable dopants depend on the atomic properties of both the dopant and the material to be doped. In general, dopants that produce the desired controlled changes are classified as either electron acceptors or donors. Semiconductors doped with

donor impurities are called n-type, while those doped with acceptor impurities are known as p-type. The n and p type designations indicate which charge carrier acts as the material's majority carrier. The opposite carrier is called the minority carrier, which exists due to thermal excitation at a much lower concentration compared to the majority carrier.

For example, the pure semiconductor silicon has four valence electrons which bond each silicon atom to its neighbors. In silicon, the most common dopants are group III and group V elements. Group III elements all contain three valence electrons, causing them to function as acceptors when used to dope silicon. When an acceptor atom replaces a silicon atom in the crystal, a vacant state ( an electron "hole") is created, which can move around the lattice and functions as a charge carrier. Group V elements have five valence electrons, which allows them to act as a donor; substitution of these atoms for silicon creates an extra free electron.

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Therefore, a silicon crystal doped with boron creates a p-type semiconductor whereas one doped with phosphorus results in an n-type material.

Fig 5 Pentavalent & trivalent impurities

1.6 P TYPE SEMICONDUCTORS

A P - type semiconductor is formed when a small amount of trivalent impurity is added to pure Germanium or silicon atom crystal. The addition of trivalent impurity produces a large no. of holes to the host crystals. To explain the formation of P - type semiconductor, let us introduce a trivalent impurity into the lattice of a pure silicon crystal. The trivalent atom has 3 valance electrons and form covalent bonds with neighbouring atoms. The 4th bond is incomplete. The trivalent atom then attracts an electron from an adjacent atom there by completing the 4th bond and forming a hole in the adjacent atom. Since a trivalent impurity atom provides 1 hole, an enormous increase occurs in the number of holes. The impure crystals so obtained are called P - type semiconductors where P represents the positive charge on hole. Thus the majority carrier in a P - type semiconductor is holes. Free electrons are also present in the P - type semiconductor. These are thermally generated and since they relatively few, they are called minority carriers. The trivalent impurity atoms are called acceptors because each accepts an electron when the atom is introduced into the host crystal.

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Fig 6 Trivalent impurity with silicon (p-type)

1.7 N TYPE SEMICONDUCTORS

An N - type semiconductor is formed when a small amount of pentavalent impurity is added to a pure Germanium or Silicon crystal. The addition of pentavalent impurity produces a large no. of free electrons in the host crystal.

To explain the formation of N - type semiconductor, let us introduce a pentavalent impurity atom into the lattice of pure silicon crystal. The pentavalent atom has 5 valance electrons, but only 4 form covalent bonds with the neighbouring atoms. The 5th electron finds no place in the covalent bonding so becomes free. Since an impurity atom provides one free electron, an enormous increase occurs in the no. of free electrons. The impure semiconductor so obtained is then called as N - type semiconductor where N represents negative charge on an electron. Thus the majority carrier in N - type semiconductor is free electrons. Holes are also present in the N - type semiconductor. These are thermally generated and since they are relatively few, they are called minority carrier.

The pentavalent impurity atom are called donor because each donate a free electron to the host crystal.

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Fig 7 Pentavalent impurity with silicon (n-type)

1.8 P N JUNCTION
A pn junction is a boundary or interface between two types of semiconductor material, ptype and n-type, inside a single crystal of semiconductor. It is created by doping, for example by ion implantation, diffusion of dopants, or by epitaxy(growing a layer of crystal doped with one type of dopant on top of a layer of crystal doped with another type of dopant). If two separate pieces of material were used, this would introduce a grain boundary between the semiconductors that severely inhibits its utility by scattering the electrons and holes

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Fig. 8 P-N junction

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2.1 THE THERMOELECTRIC EFFECT

The thermoelectric effect is the direct conversion of temperature differences to electric voltage and vice-versa. A thermoelectric device creates voltage when there is a different temperature on each side. Conversely, when a voltage is applied to it, it creates a temperature difference. At the atomic scale, an applied temperature gradient causes charge carriers in the material to diffuse from the hot side to the cold side. This effect can be used to generate electricity, measure temperature or change the temperature of objects. Because the direction of heating and cooling is determined by the polarity of the applied voltage, thermoelectric devices can be used as temperature controllers. The term "thermoelectric effect" encompasses three separately identified effects: the Seebeck effect, Peltier effect and Thomson effect. Textbooks may refer to it as the PeltierSeebeck effect. This separation derives from the independent discoveries of French physicist Jean Charles Athanase Peltier and Baltic German physicist Thomas Johann Seebeck. Joule heating, the heat that is generated whenever a voltage is applied across a resistive material, is related though it is not generally termed a thermoelectric effect. The PeltierSeebeck and Thomson effects are thermodynamically reversible,[1] whereas Joule heating is not.

2.2 SEEBECK EFFECT

Fig 9 seebeck effect A thermoelectric circuit composed of materials of different Seebeck coefficient (p-doped and n-doped semiconductors), configured as a thermoelectric generator. If the load is removed then the current stops, and the circuit functions as a temperature-sensing thermocouple.

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The Seebeck effect is the conversion of temperature differences directly into electricity and is named after the Baltic German physicist Thomas Johann Seebeck, who, in 1821 discovered that a compass needle would be deflected by a closed loop formed by two metals joined in two places, with a temperature difference between the junctions. This was because the metals responded differently to the temperature difference, creating a current loop and a magnetic field. Seebeck did not recognize there was an electric current involved, so he called the phenomenon the thermomagnetic effect. Danish physicist Hans Christian rsted rectified the mistake and coined the term "thermoelectricity".

where

is the Seebeck coefficient (also known as thermopower), a property of the is the gradient in temperature .

local material, and

The Seebeck coefficients generally vary as function of temperature, and depend strongly on the composition of the conductor. For ordinary materials at room temperature, the Seebeck coefficient may range in value from -100 V/K to +1000 V/K (see Thermoelectric materials) If the system reaches a steady state where simply by the emf: , then the voltage gradient is given

. This simple relationship, which does not

depend on conductivity, is used in the thermocouple to measure a temperature difference; an absolute temperature may be found by performing the voltage measurement at a known reference temperature. Conversely, a metal of unknown composition can be classified by its thermoelectric effect if a metallic probe of known composition, kept at a constant temperature, is held in contact with it (the unknown material is locally heated to the probe temperature). Industrial quality control instruments use this as thermoelectric alloy sorting to identify metal alloys. Thermocouples in series form a thermopile, sometimes constructed in order to increase the output voltage, since the voltage induced over each individual couple is small. Thermoelectric generators are used for creating power from heat differentials and exploit this effect.

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2.3 THE PELTIER EFFECT

Fig 10 peltier effect The Peltier effect is the presence of heating or cooling at an electrified junction of two different conductors and is named for French physicist Jean Charles Athanase Peltier, who discovered it in 1834. When a current is made to flow through a junction between two conductors A and B, heat may be generated (or removed) at the junction. The Peltier heat generated at the junction per unit time, , is equal to

where

) is the Peltier coefficient of conductor A (B), and

is the electric

current (from A to B). Note that the total heat generated at the junction is not determined by the Peltier effect alone, as it may also be influenced by Joule heating and thermal gradient effects (see below). The Peltier coefficients represent how much heat is carried per unit charge. Since charge current must be continuous across a junction, the associated heat flow will develop a discontinuity if and are different. The Peltier effect can be considered as the

back-action counterpart to the Seebeck effect (analogous to the back-emf in magnetic induction): if a simple thermoelectric circuit is closed then the Seebeck effect will drive a current, which in turn (via the Peltier effect) will always transfer heat from the hot to the cold junction. A typical Peltier heat pump device involves multiple junctions in series, through which a current is driven. Some of the junctions lose heat due to the Peltier effect, while others gain heat. Thermoelectric heat pumps exploit this phenomenon, as do thermoelectric cooling devices found in refrigerators.

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3.1 THERMOELECTIC GENERATOR

Fig 11 thermoelectric generator

Thermoelectric generators (also called Seebeck generators) are devices which convert heat (temperature differences) directly into electrical energy, using a phenomenon called the "Seebeck effect" (or "thermoelectric effect"). A thermoelectric generator is a device made up of p n type semi conductors A thermoelectric module is a array of thermocouples connected electrically in series but thermally in parallel Many couples are used becuause the voltage drop across one couple is only on the order of millivolts. Connecting many in series brings the voltage closer to that found in typical DC power sources. A thermoelectric device creates a voltage when there is a different temperature on each side. temperature difference provides the voltage but it is the heat flow which enables the current.

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Fig 12 .TEG effect A thermoelectric produces electrical power from heat flow across a temperature gradient. As the heat flows from hot to cold, free charge carriers (electrons or holes) in the material are also driven to the cold end (Fig. 1). The resulting voltage (V) is proportional to the temperature difference (T) via the Seebeck coefficient, , (V = T). By connecting an electron conducting (n-type) and hole conducting (p-type) material in series, a net voltage is produced that can be driven through a load. A good thermoelectric material has a Seebeck coefficient between 100 V/K and 300 V/K; thus, in order to achieve a few volts at the load, many thermoelectric couples need to be connected in series to make the thermoelectric device

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3.2 GENERAL CALCULATIONS

21

Many couples are used (in both power generation and cooling) becuause the voltage drop across one couple is only on the order of millivolts. Connecting many in series brings the voltage closer to that found in typical DC power souces. The Seebeck voltage (not including the Ohmic, IR voltage drop) of the couple, S is derived from the Seebeck coefficient of the ntype and p-type elements and the number of couples, n.

The electrical resistance of the device depends not only on the electrical resistance of the thermoelectric materials but also the electrical resistnace of the metal interconnects and the contact resistance between the interconnects and the thermoelectric materials. All of these contributions are temperature dependent making the exact computation of the resistance complex. The device resistance, R, can be approximated

assuming temperature independent properties. Here Rl is the interconnect and contact resistance (loss) per couple, l is the length (height) and A is the cross-sectional area of the thermoelectric elements.

Similar to the electrical resistance, the total thermal conductance of the device can be approximated by

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3.3 POWER OF A TEG

Just as the power in a resistor is V2/R the power produced in a thermoelectric generator depends on the square of the voltage (Seebeck coefficient and temperature difference) divided by the resistivity. Notice also that the power per area can be arbitrarily adjusted with l (length).

3.4 ZT of a thermoelectric (figure of merit)

The efficiency of a thermoelectric material depends on the thermoelectric properties, Seebeck coefficient, electrical resistivity and thermal conductivity These material properties all appear together and thus form a new material property which we call zT, the Thermoelectric Figure of Merit.

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3.5 Efficiency of Thermoelectric generator

A thermoelectric generator converts heat (Q) into electrical power (P) with efficiency .The amount of heat, Q, that can be directed though the thermoelectric materials frequently depends on the size of the heat exchangers used to harvest the heat on the hot side and reject it on the cold side. As the heat exchangers are typically much larger than the thermoelectric generators themselves, when size is a constraint (or high P/V is desired) the design for maximum power P = Q. Small Thermoelectric Generators may take precedence over maximum efficiency. In this case the temperature difference (and therefore thermoelectric efficiency as described below) may be only half that between the heat source and sink.The efficiency of a thermoelectric converter depends heavily on the temperature difference T = Thot Tcold across the device. This is because the thermoelectric generator, like all heat engines, cannot have an efficiency greater than that of a ( Carnot ). The efficiency of a thermoelectric generator is typically defined as

Where the first term is the Carnot efficiency and ZT is the figure of merit for the device. While the calculation ofefficiency Schematic of a thermoelectric generator. Many thermoelectric couples (top) of n-type and p-type thermoelectric semiconductors are connected electrically in series and thermally in parallel to make a thermoelectric generator. The flow of heat drives the free electrons (e-) and holes (h+) producing electrical power from heat. a thermoelectric generator efficiency can be complex, use of the average material figure of merit, zT, can provide an approximation for ZT. Here, Seebeck coefficient (), electrical resistivity (), and thermal conductivity () are temperature (T) dependent materials properties.

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4.1 Materials used

The thermoelectric power factor maximizes somewhere between a metal and semiconductors. Good thermoelectric materials are typically heavily doped semiconductors with carrier concentration of 1019 to 1021 carriers/cm3. To ensure that the net Seebeck effect is large, there should only be a single type of carrier. Mixed n-type and p-type conduction will lead to opposing Seebeck effect and low thermopower (defined here as absolute value of Seebeck coefficient). By having a band gap large enough, n-type and p-type carriers can be separated, and doping will produce only a single carrier type. Thus good thermoelectric materials have band gaps large enough to have only a single carrier type but small enough to sufficiently high doping and high mobility (which leads to high electrical conductivity). A material with a large thermoelectric power factor and therefore zT, needs to have a large Seebeck coefficient (found in low carrier concentration semiconductors or insulators) and a large electrical conductivity (found in high carrier concentration metals)

Graph 1. Material selection

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Using these principles, a variety of high zT materials have been developed. Many materials have an upper temperature limit of operation, above which the material is unstable. Thus no single material is best for all temperature ranges, so different materials should be selected for different applications based on the temperature of operation.

4.2 Bismuth Telluride Bi2Te3 ( ZT 0.8 - 1.0 @ room temp)

Bismuth telluride (Bi2Te3) is a gray powder that is a compound of bismuth and tellurium also known as bismuth(III) telluride. It is a semiconductor which, when alloyed with antimony or selenium is an efficient thermoelectric material for refrigeration or portable power generation. Topologically protected surface states have been observed in Bismuth telluride.

Fig 13.structure Bismuth telluride

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Fig 14 .Bismuth telluride band structure can be described as a many-ellipsoidal model with 6 constant-energy ellipsoids that are centred on the reflection planes.[2] Bi2Te3 cleaves easily along the trigonal axis due to Van der Waals bonding between neighbouring tellurium atoms. Due to this, bismuth telluride based material that are used for power generation or cooling applications must be polycrystalline. Furthermore, the Seebeck coefficient of bulk Bi2Te3 becomes compensated around room temperature, forcing the materials used in power generation devices to be an alloy of bismuth, antimony, tellurium, and selenium.[1]

Recently, researchers have attempted to improve the efficiency of Bi 2Te3 based materials by creating structures where one or more dimensions are reduced, such as nanowires or thin films. In one such instance n-type bismuth telluride was shown to have an improved Seebeck coefficient (voltage per unit temperature difference) of 287 V/K at 54 Celsius,[3] However, one must realize that Seebeck Coefficient and electrical conductivity have a trade-off; a higher Seebeck coefficient results in decreased carrier concentration and decreased electrical conductivity.[4] Bismuth telluride is a narrow gap layered semiconductor with a trigonal unit cell. The valence and conduction In another case, researchers report that bismuth telluride has high electrical conductivity of 1.1105 Sm/m2 with its very low lattice thermal conductivity of 1.20 W/(mK), similar to ordinary glass.

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4.3 OCCURENCE

The mineral form of Bi2Te3 is tellurobismuthite which is moderately rare. There are many natural bismuth tellurides of different stoichiometry, as well as compounds of the Bi-Te-S(Se) system, like Bi2Te2S (tetradymite).

Fig 15 .bismuth telluride powder Bismuth Telluride is prepared by sealing a sample of bismuth and tellurium metal in a quartz tube under vacuum (critical, as an unsealed or leaking sample may explode in a furnace) and heating it to 800C in a muffle furnace.

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4.4 Other materials

SKUTTERITE

Fig 16

Crystal Structure of Yb14MnSb11

Fig 17

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5.1 THEORITICAL CALCULATION OF EFFICIENCY

According to theory , the efficiency of a thermo electric generator is given by the formula

For the given specimen ,i.e. commercial thermoelectric generator ,which is made of Bismuth telluride , the value of its figure of merit ZT must be found out by using

Here ,

= Seebeck coefficient of bismuth telluride

T = Operating Temperature

= Resistivity
= thermal conductivity All these properties considered for bismuth telluride,, the average value of ZT of Bismuth telluride over a vast temperature range lies between 0.8 1.0. Let us assume ZT=0.9 for theoretical purpose

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For comparison with the practical model yet to come, the temperatures have been assumed similar to what have been done in the experimental model.

Thot C

Tcold C

T C

ZT

Carnot efficiency
T/ Thot

Efficiency

44.1

23.5

20.6

0.9

46.7

7.005

51.2 58.9 68.7 79.9 93.2

23.6 23.6 23.8 24 24.1

26.6 35.3 44.9 55.9 69.1

0.9 0.9 0.9 0.9 0.9

51.9 59.9 65.3 69.9 72.3

7.78 8.95 9.75 10.4 10.85

Table 1

The theoretical efficiency of the thermoelectric generator ranges between 7-11% within the given temperature range.

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6.1 PERFORMANCE OF THERMOELECTRIC GENERATOR

There are several ways to calculate the power generation performance of a thermoelectric generator, either by averaging the schemes or by using finite element analysis. The advantage of averaging schemes is that an immediate answer is obtained from simplified analytical equations.

6.2 EXPERIMENTAL SETUP

A commercial thermoelectric device was used for the experimental testing and is a model TEC112706 Bismuth Telluride device with a physical size of 40mm x 40mm x 3.5 mm. The device has 127 couples and a photo of the device is shown in Figure 1 below.

Figure 18: Photo of thermoelectric device used for testing (model TEC1-12706).

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A testing assembly was constructed such that a known heat could be added to hot side of the device. By measuring the power output of the thermoelectric device through a load, the efficiency of the thermoelectric device can be calculated as follows:

= P out / Q in
Where, = thermal efficiency

Pout = measured power output of the device (watts) Qin = measured input heat to the device (watts)

The testing assembly consisted of

Sno. 1 2 3 4 5 6 7 8 9 Thermoelectric generator D.C. Power Supply Heating coil Hot water beaker Cold water beaker Thermometers (2) Digital voltmeters

Object
(model TEC1-12706).

External load resistance (variable) Aluminium plates assembly for TEG. Table 2

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6.3 SET UP
For experimentation, the thermoelectric generator was sandwiched between two aluminium plates. One plate was immersed into a hot water beaker. The other was immersed into a cold water beaker. Both were separated from physical contact. A heating coil was immersed into the water of the hot water beaker. The heating coil was connected to a D.C. power supply. The two wires of the thermoelectric generator were connected to an external variable load resistance. Two thermometers were placed each in the hot water and the cold water beakers. A digital voltmeter was connected to the resistance to measure the output voltage of the TEG.

Fig 19 : Experimental setup

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6.4 OPERATION

The required parameters were

Temperature of the hot side of the thermoelectric device (thermometer 1) Temperature of the cold side of the thermoelectric device (Thermometer 2) Internal resistance of D.C. power source

Heater voltage, (D.C. input voltage ) Load voltage, measured across variable resistor Load resistance

6.5 PROCEDURE
The D.C. power source was adjusted such that it gives a constant output of 12 volts, Sufficient time was given for the heater coil to heat according to this voltage The heater coil in turn heats the water in the hot water beaker and thus the aluminium plate and the hot side of the thermoelectric generator A thermometer was kept in the hot water beaker and after a homogeneous temperature was obtained , it was noted down as Thot Similarly ,another thermometer was kept in the cold water and temperature was measured as Tcold The temperature difference was calculated as T. The variable load resistance at the output was adjusted such that maximum power was obtained for the given input and this resistance was noted down The output voltage of the TEG was recorded on a digital voltmeter as Vout The same procedure was repeated for 5 input D.C. voltages 12, 14, 16, 18 ,20 V. All the results and calculations were tabulated.

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7 RESULTS
In order to calculate efficiency using Equation (1), the input heat, Qin, and output power Pout, must be found. The input heat is found using the heater voltage and heater resistance as shown in Equation

Qin = Vin * Vin / Rin

Here Rin stands for the internal resistance of the D.C. power source (heating coil) which was calculated as 12 . The Output is calculated using Pout = Vout * Iout Here Iout is given by Vout/Rout

Vin 12 14 16 18 20 22

Thot C

Tcold C

T C

44.1 51.2 58.9 68.7 79.9 93.2

23.5 23.6 23.6 23.8 24 24.1

20.6 26.6 35.3 44.9 55.9 69.1

Table 3

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All the readings are seen and noted down for each value of input voltage Vin The readings are tablualted as shown

Vin

T C

Input(W)

load resistance

Vout

Output(W)

12 14 16 18 20 22

20.6 26.6 35.3 44.9 55.9 69.1

12 16.33 21.33 27 33.33 40.33

3.01 2.81 3.02 2.76 3.38 2.81

0.54 0.65 0.87 1.22 2.48 2.62

0.10 0.15 0.25 0.54 1.83 2.46

0.83 0.91 1.17 1.99 5.41 6.12

Table 4

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Graph 2:Input voltage vs Temp difference T

80

70

60

Temp. difference

50 input voltage vs temp difference Linear (input voltage vs temp difference)

40

30

20

10

0 0 5 10 voltage 15 20 25

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Graph 3: Temperature difference vs. efficiency

efficiency

4 Temp difference vs efficiency 3 Linear () Linear () Linear (Temp difference vs efficiency)

0 0 20 40 60 Temp difference 80

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Graph 4: Input voltage (Vin) vs efficiency

4 efficiency Series1 Linear (Series1) 2

0 0 -1 5 10 Input Voltage 15 20 25

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7.2Comparison between theoretical model and experimental model:Table 5

Thot C

Tcold C

T C

Efficiency Theoretical % 7.005 7.78 8.95 9.75 10.4 10.85

Efficiency Experimental % 0.83 0.91 1.17 1.99 5.41 6.12

44.1 51.2 58.9 68.7 79.9 93.2

23.5 23.6 23.6 23.8 24 24.1

20.6 26.6 35.3 44.9 55.9 69.1

Graph 5 : Comparison graph (Temp difference T vs Efficiency )

12

10

Efficiency

Theoretical Experimental

0 0 10 20 30 40 Temp difference 50 60 70 80

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7.3 CONCLUSION
Results are presented for a particular Bismuth Telluride thermoelectric device (TEC112706).

The load resistance is variable in the experimental setup and the power generation and efficiency are both plotted versus the voltage produced. The maximum temperature difference tested was 69.1C and this produced an efficiency of 6.12% and an output power of 2.46 watts. While this efficiency might seem low, thermoelectric generators are noted for their relatively low conversion efficiency. Also, the maximum temperature difference tested (69.1C) is fairly modest, higher temperature differences would result in higher efficiency. If the graph plot of input temperature difference vs. Efficiency is extended further, it is observed that the greater the temperature gradient ,the more drastic the increase in efficiency

Typical thermoelectric devices require a temperature difference of approximately 500C to achieve an efficiency of 15-20 % 9,10. The Other factor that influences the efficiency is the internal material property ZT of the material which determines how much of the heat is converted to electricity . The current specimen (bismuth telluride ZT= 0.8-1.0) shows maximum experimental efficiency of 6.12%

Compounds with a ZT value around 5 have been discovered,ZT values of 10 -15 in the future will promise a gigantic increase in the efficieny in the order of 20-30%.

Note: Due to economic considerations, one single TEG module was used for experimentation, A group of modules packed together in series would result in higher efficiencies .

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8.1 APPLICATIONS OF THERMOELECTRIC GENERATORS

WASTE HEAT RECOVERY from Cement plants Petrochemical plants Coal fired power plants Refineries Furnaces & most importantly Automotive exhausts and surfaces

Fig 20. Waste heat

Fig 21. Automotive heat

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Heat plays a major role in global energy consumption. Heat itself may be the final use of energy (e.g. residential heating). Heat is also a waste product in the transformation of energy, for example in electric power generation or transportation.

Thermal energy (heat) is a common link between many forms of energy. This means that improving the net heat to electricity efficiency, or bypassing the thermal energy step altogether (as in fuel cells), will improve energy utilization.

Fig 22. Power plant heat

As shown in the above illustration , out of 100 input units only a mere 33% is coming out as useful electrical energy . Majority of the remaining 67 units dissipates as waste heat contributing to global warming.

By use of thermoelectric generators in plants such as these the waste heat can be harvested back in the form of useful electrical energy to further improve the overall efficiency of the plant and reduce global warming effect.

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8.2 AUTOMOTIVE HEAT RECOVERY

Fig 23 As shown above ,for every 100 units of fuel burnt only 12- 15 % is actually utilized in propelling the vehicle forward.

62% goes dissipates as waste heat.

If this waste heat were recycled in the form of useful electrical energy via thermoelectric generators, the overall efficiency of cars would increase drastically.

By utilizing a portion of the lost thermal energy to charge the battery instead of using an alternator (adds drag on the engine) the overall fuel economy can be increased by about 10%.

The present Zt figure of bismuth telluride offers an increase in efficiency by 5-6%.

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The ZT 1.5 efficiency would translate into a 10 percent increase in the fuel economy of cars if the devices are used to replace alternators in automobiles by generating electricity from the heat in exhaust. The ZT 3.0 materials would be a 15% increase in fuel economy of cars and trucks. The devices could begin selling in 3 to 4 years.

If you get up to ZT 5 or so with a cheap enough system then you can replace most of the moving parts of an engine with thermoelectrics. You would generate heat and then use thermoelectrics with no moving parts to convert the heat directly to electricity with higher efficiency.

Fig 24,25. BMW TEG heat recovery system

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As shown in the above illustrations , thermoelectric generators can be attached at the exhaust of the car where waste heat is dissipated

Fig 26,27 TEG assembly at exhaust

By attaching so, the residual heat coming towards the catalytic convertor from the engine exhaust can be trapped into these thermoelectric generators via heat exchangers.

This would effectively trap almost all the waste heat and convert it into useful electrical energy ,which can be used to charge the battery without a dynamo

It can also be used to power sub-systems relieving their dependency on battery, therefore increasing the overall efficiency of the vehicle.

Fig 28. Heat to power flow

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8.3 Cogeneration of Heat and Electricity

Because most electricity is produced by a heat engine, which is limited by Carnot efficiency, much of the energy is lost in the heat rejected. A typical steam power plant is only 40% efficient. The remaining heat is wasted, unless this rejected heat can be used for heating. The use of this heat then can add to the energy utility.

Conversely, any time a fuel is burned to make low temperature heat (such as in a home) the ability to produce useful work or 48lectricity from that heat is wasted. A small cogeneration plant in the home would produce 48lectricity whenever the heat is needed. The added fuel consumed to produce the electricity has essentially the same energy content as the electricity produced. Thus in terms of energy untilization the efficiency of electricity generation approaches 90% compared to the 40% in a typical power plant.

Fig 29.cogeneration

Thermoeletric systems are ideal for small (e.g. single family home) cogeneration because they could be small and silent. Even with their lower thermal to electric efficiency compared to dynamic heat engines, the electricity would be produced with high efficiency (electric power/extra fuel consumed) because the heat rejected will not be wasted.

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9. REPORT CONCLUSION:
-Detailed description and analysis of the physics behind the making of a thermoelectric generator. -Discussion of material properties suitable for thermoelectric generation -Calculation of theoretical efficiency of TEG using given formulae. -Performance test on single thermoelectric generator (model TEC1-12706) -Comparison of both theoretical and practical models/ -Calculation of efficiency of the given thermoelectric generator (bismuth telluride) -Necessity and applications of thermoelectric generator.

EFFICIENCY OF TEG(Theoretical mean)

8-10%

EFFICIENCY OF TEG( experimental mean)

3-5% Note: -Thermoelectric generators are small portable devices with almost negligible weight and no noise of operation -Since there are no internal moving parts, no mechanical losses due to friction occur and device runs smoothly

-In applications such as home co-generation, the desire for silent, vibration, and maintenance free operation will favour thermoelectrics. Residential co-generation and automotive waste heat recovery are two examples where small systems could have an impact on the global energy consumption if implemented on a large-scale.
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BIBLIOGRAPHY

1.) Zorbas, K.T., E. Hatzikraniotis, and K.M. Paraskevopoulos. Power and Efficiency Calculation in Commercial TEG and Application in Wasted Heat Recovery in Automobile, Proceedings of the 5th European Conference on Thermoelectrics, September 10-12, 2007, Odessa, Ukraine, 2.) Snyder, G. Jeffrey. Small Thermoelectric Generators, The Electrochemical Society Interface, Fall 2008, 3.) Cengel, Y.A. and Boles, M.A., Thermodynamics: An Engineering Approach, 6th Edition, McGraw-Hill, 2008, 4.) The Essential Guide to Semiconductors. Prentice Hall PTR, 5.) History of semiconductors John Wiley and Sons (WIE).

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