EXTENDED ESSAY IN PHYSICS Uy Quoc Nguyen Berg Videreg aende Skole May 2011 Conductivity of graphite for small

temperature intervals

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Extended Essay

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Abstract. In this extended essay I have studied the conductivity of graphites relation to the temperature. The research question for this extended essay is thus: What is the relationship between the conductivity and temperature of graphite for small temperature intervals?. The approach for this research was intended to be purely theoretical and so there are no self-conducting experiments throughout the essay. However, data from an investigation done by L. J. Collier and his colleagues was exploited in order provide an easy way to derive the nal result for the relationship between the conductivity and temperature changes. Furthermore, theories of conductivity in semi-conductors were established by introducing the properties of metallic-conductors in order to provide a solid base for understanding the mechanism of freely moving electrons in graphite. That means it started o by introducing the most basic concepts to Ohms law and then proceeded to study the inuence of the drift velocity of electrons. Moreover, electronic orbital theories were also applied as it is crucial for the understanding of electron and hole interactions. The conclusion that was nally deduced is that the conductivity of graphite are has a linear relationship with the change in temperature and is given by: 0 (T ) = 1 + T where is the temperature coecient of resistivity. However, it is also concluded that this expression is only valid for small temperature changes because it would lead to absurd result for large temperature intervals. That is graphite becomes a superconductor at 0 C and so on.

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Extended Essay Contents

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1. Introduction 1.1. Approach 2. Ohms Law Re-investigated 2.1. The Drift Velocity 2.2. The Current and Potential Dierence 3. Structure of Graphite 3.1. Orbitals and Electron Congurations 3.2. Hybridization of Orbitals 3.3. Delocalization of Electrons and Holes 4. The Conductivity and Temperature Relationship 5. Conclusion and Evaluation Bibliography

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Extended Essay 1. Introduction

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Ohms law is an idealized model, that is the law is not obeyed for every situation. The law states that: for a constant temperature the potential dierence at the ends of an electrical conductor is directly proportional with the current owing through it1. This means that the resistance for the electrical conductor, being the constant of the ratio between the potential dierence and the current, is dependent on temperature. This law was discovered by the German physicist Georg Simon Ohm in 1826 and was published in 1827 as a book Die galvanische Kette, mathematisch bearbeitet (The galvanic circuit, worked mathematically)2. Later years, in 1911 the Dutch physicist Heike Kamerlingh Onnes conducted an experiment in Leiden where he cooled down pure mercury with liqueed helium. His result showed that the electrical resistance in metallic conductors disappeared when the temperature of the conductor were below a critical temperature3. Thus, the metallic conductors became perfect conductors also known as superconductors. 2 years later the Nobel Prize in Physics was awarded to Kamerlingh Onnes for his discovery of this phenomenon4. Today, the application of the superconductivity for research is crucial in physics. One of its most important applications can be found with The Large Hadron Collider (LHC) located at Cern in Geneva, Switzerland. LHC, is a particle accelerator with a circumference of 26.7km. Its goal in high-energy particle physics research is to collide beams of hadrons in order to search for new particles and conrm the hypothesized particle, the Higgs Boson5. In addition, it is also used to collide lead ion beams with energies up to 1150TeV in order to study new states of matter. The requirement for colliding these high-energy beams of particles is to bend the beams to a xed radius. This requirement is met by exploiting high-eld superconducting magnets6.

Oxford Dictionary of Physics: Sixth edition (Oxford University Press, 2009), page 371. 2 Georg Simon Ohm: Die galvanische Kette, mathematisch bearbeitet (Berlin T.H. Riemann 1827). 3 J.R. Waldram: Superconductivity of Metals and Cuprates (IOP Publishing Ltd 1996), page 1-2. 4 The Nobel Prize in Physics 1913. Nobelprize.org. 20 Nov 2010 http://nobelprize.org/nobel prizes/physics/laureates/1913/ 5 Scientic American. Scienticamerican.com. 21 Nov 2010 http://www.scienticamerican.com/article.cfm?id=5-goals-for-the-lhc 6 CERN Document Server. Cdsweb.cern.ch. 21 Nov 2010 http://cdsweb.cern.ch/record/473537/les/lhc-project-report-441.pdf

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Extended Essay

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The focused question for this extended essay will be: What is the relationship between the conductivity and temperature of graphite and temperature for small temperature intervals? My main reason for choosing this question is because I wanted to study how Ohms law is dependent on temperature and nd a mathematical expression for the conductivity of a conductor as a function within a temperature interval. This curiosity was developed when I witnessed superconductivity for the rst time, many years ago before I started the IB programme, in the University of Oslo when they demonstrated how the concept of superconductivity could be exploited in maglev transportation. Also my supervisor encouraged me to choose a specic conductor to make my focused question more narrowed. In this case, I chose graphite as my electrical conductor because it is not a metallic conductor and therefore does not conduct electricity in the same manner as metals and may be more interesting to study than any metallic conductors.

1.1. Approach. One problem that occurs when studying this topic is that conductivity is a quantum mechanical phenomenon. Thus, it is only completely understood using the quantum theory. However, the IB Physics HL syllabus only oer a brief introduction to quantum physics, the knowledge required to study conductivity in the context of quantum physics was beyond my limit of understanding. Furthermore, the mathematics required to understand the physics on that level is too advanced for the knowledge acquired in mathematics HL to handle. Even so, the focused question is going to be approached with the attempt of using classical physics to provide arguments to the conclusion. The essay is going to have a theoretical approach using Ohms law as a reference to compare the outcome of a new derived expression for current. This new expression is going to be derived after discussion of mobile electrons and resistivity within a metallic conductor. After the idea have been established for a metallic conductor, the discussion will be carried to the structure of graphite considering hybridized orbitals, delocalization of electrons within the covalent bonds, between the carbon atoms and how graphite conduct electricity through the interaction between electrons and holes. For both cases, the eect of temperature is going to be included. To the end of the essay the relationship between the resistivity of graphite and temperature for small temperature intervals is elaborated and the expression for that is going to be derived. 5

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Extended Essay 2. Ohms Law Re-investigated

Physics

Ohms law states that for a constant temperature there is a linear relationship between the potential dierence V at the ends of a conductor and the current I in the conductor. Hence, (1) V I

The proportionality constant is thus the resistance R throughout the conductor and Ohms law nally becomes: (2) V = RI

However, both the resistance and the current are dependent on the temperature. Thus, the equations can then be written as a function of temperature: (3) V = R(T )I(T )

This case is going to be further investigated. 2.1. The Drift Velocity. Take for instance a metallic conductor of length l. Metallic conductors are basically a composition of metallic elements creating metallic bonds between the atoms with their electrons. These electrons are thus freely to move around with enormous speed due to thermal energy. Because, these free electrons move in random directions there are no net ow of charges through the conductor, consequently there are no current running through the conductor7. If we then apply a constant potential dierence V from a to b on the conductor, the electric eld created in the conductor will do work on the electrons bringing them from point a to point b. Hence, the force that is acting on each individual electron with charge e is given by: (4) F = e E And thus, there will be a net ow of charges in one direction. Therefore, there will be a current in the conductor. The electrons which rst moved with enormous speed is now moving with a tremendous reduction of speed. This is due to the increased number of collisions between the vibrating ions and the moving electrons in the conductor, because it is forced to move in one specic direction. This new net velocity is called the drift velocity denoted . vd If the times between each collision are then the acceleration of one particular electron is given by the equation: = d vd (5) a d
& Zemanskys: University Physics 12th edition with modern physics (Pearson Education, Inc 2008) page 847.
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Thus, solving this dierential equation gives the drift velocity : vd (6) dvd = d a (7) = + c vd a

The constant c is the drift velocity when = 0 thus v0 . Now, if we assume that all the drift velocity is completely destroyed after each collision that is v0 = 0 then equation 7 can be rewritten as: = (8) v a
d

By combining equation 4 and 8, and solving for the drift velocity vd we get that: = e E (9) vd me where me is the mass of the electrons. 2.2. The Current and Potential Dierence. When a potential dierence V is applied over a conductor with length l an electric eld is created inside that conductor. The electrons being charged particles is experiencing this electric eld and will thus try to make it zero. Therefore, the electrons are moving with a drift velocity vd given by equation 9 and a current I is created. Current is dened as the rate of ow of a charge at a particular cross section8. Thus, (10) I= dQ dt

where Q is the charge. Consider any metallic conductor with a cross sectional area A and length l. A potential dierence V is applied of a length l on that conductor and the electrons will get a drift velocity vd given by equation 9. The number of electrons passing through that cross sectional area per time is n and after a time dt the electrons have travelled dx = vd dt. The amount of charge dQ travelling through the cross sectional area A is consequently: (11) dQ = neAvd dt

When dividing dt on both sides of the equation in order to nd the rate of ow of charges through the cross sectional area A. Hence, we obtain equation 10 which is the denition for current. (12) I = neAvd

If we now substitute for the drift velocity vd given by equation 9 an expression of current with the electric eld created by the potential
8Oxford

Dictionary of Physics: Sixth edition (Oxford University Press, 2009),

page 110

Uy Quoc Nguyen dierence is obtained. (13)

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I=

ne2 AE me

The factor ne e is dependent on the property of the conductor, that is m how many free electrons per ions and the time interval between each collisions. This property is known as the conductivity and is denoted . If we then substitute the term for conductivity we get that the current is given by (14) I = A E Since, the electric eld E created by the potential dierence V is V (15) E = l By substituting equation 15 into equation 14 and solving for V will give us the expression l (16) V = I A Resistivity is dened as a measure of a metals ability to oppose the ow of an electric current9. A conductor with small resistivity is considered to be a good conductor and vice versa. Hence, the resistivity is given by the reciprocal of conductivity: 1 (17) = Substituting this into equation 16 nally gives l (18) V = I A By comparing equation 18 and equation 3 we arrive to the result that the resistance is l (19) R= A Since, the cross sectional area A and the length l of the conductor is constant, the resistivity is the only factor that is dependent on temperature. The ions within the conductors vibrate with amplitude according to the temperature. Thus, an increase in temperature will decrease the time interval between each collisions . Thus, the electrons will experience a higher resistivity and the drift velocity vd becomes smaller and the rate of ow of charges dQ through a cross sectional dt area A will also decrease10.
Dictionary of Physics: Sixth edition (Oxford University Press, 2009), page 472 10Sears & Zemanskys: University Physics 12th edition with modern physics (Pearson Education, Inc 2008), page 852
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Extended Essay 3. Structure of Graphite

Physics

Graphite is a substance which is composed of layers of graphenes held together by an intermolecular force called van der Waals forces. Moreover, graphenes are again composed of carbons. These carbons are bound together by the intramolecular force: covalent bonds to each other creating planars of hexagonal nets of carbons11. Hence, each carbon is bound to 3 other carbons. Carbon has 4 valence electrons which can be exploited for covalent bonding to other elements. Thus, due to this fact, if carbon is then bounded to 3 other carbons then this results to 2 single bonds to 2 of the carbons and 1 double bond to the last one. The double bond is of great interest in the context of conductivity for graphite. When orbital theory is applied to carbon we nd that each carbons in graphene is sp2 hybridized12. This means that all the carbons have a resonance structure in which the electrons are delocalized between the bonds13. Thus, the delocalization of electrons will almost function as free mobile electrons in a metallic conductor and thus graphite will be able to conduct electricity. These things are going to be further discussed. 3.1. Orbitals and Electron Congurations. The atomic model has an interesting history. The most popular model which is greatly used in junior- and senior high schools is the model proposed by the Danish physicist Niels Henrik David Bohr, who was awarded the Nobel Prize in Physics in 1922 for his work14. However, the atomic model introduced in the middle school is somewhat simplied. The electrons orbital around the nucleus is more complex. The atomic model proposes certain energy levels in which electrons can exist in the atom. The rst energy level consists of 2 electrons while the higher energy levels are able to hold onto 8 electrons and even more when moving to even higher energy levels. However, each energy level consists of sublevels which are considered to be orbitals denoted s, p, d and f in which electrons are probable to exist15.

E Hall: Solid State Physics (John Wiley & Sons Ltd. 1974), page 42 E Hall: Solid State Physics (John Wiley & Sons Ltd. 1974), page 42 13John Green & Sadru Damji: Chemistry 3rd edition (IBID Press, reprinted 2008), page 119 14The Nobel Prize in Physics 1922. Nobelprize.org. 28 Nov 2010 http://nobelprize.org/nobel prizes/physics/laureates/1922/ 15Sears & Zemanskys: University Physics 12th edition with modern physics (Pearson Education, Inc 2008), page 1406-1407
12H.

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Figure 1. Orbitals of a hydrogen atom of sublevels s to f The gure16 above shows how the orbitals of an hydrogen atom is visualized. Each orbital can only contain a maximum of 2 electrons of opposite spins17. The rst energy level only consist of 1s orbital which is why it is only able to hold on to 2 electrons. The second and the third energy level consist of 1s and 3p (px , py and pz ) orbitals each. Every element has all the orbitals available but only lls the lowest orbitals with electrons. The arrangement of electrons about the nucleus of an atom is called for an electron conguration18. This model is also applicable for other elements as well and in this case the model in Figure 1 is going to be applied to the carbon atom. Carbon is the number 6 element in the periodic table. Thus, a neutral carbon has 2 electrons in the rst s-orbital (1s). Moreover, it also have 2 electrons in the second s-orbital (2s) and then it has 2 more electrons in the rst p-orbital (2p) which is found in the second energy level. Thus, the electron conguration of carbon is written as: 1s2 2s2 2p2 Although it is called the orbitals, it is not for certain that the electrons are orbiting the nucleus in that region. In physics the orbitals are often referred to as the probability density for electrons. 3.2. Hybridization of Orbitals.
Chemwiki chemwiki.ucdavis.edu 28 Nov 2010 http://chemwiki.ucdavis.edu/@api/deki/les/4826/=Single electron orbitals.jpg 17John Green & Sadru Damji: Chemistry 3rd edition (IBID Press, reprinted 2008), page 61 18Oxford Dictionary of Chemistry: Sixth edition (Oxford University Press, 2008), page 139
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Extended Essay

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Carbon is an element which tends to form covalent bonds to other elements. In the case of a carbon to carbon bond, one carbon can either be bound to 4 other carbons due to its 4 valence electrons, or it can be bound to 3 other carbons as in a graphite layer, or to 2 other carbons. Before any element starts to form covalent bonds with other elements its orbitals usually overlap each other to make a hybrid orbital19 or hybrid wave functions20. This process when orbitals overlap to make hybrids is often referred to as hybridization. Carbon can form 3 dierent hybridized orbitals. These three hybridizations are directly related to the amount of covalent bonds a carbon can create with other elements which was mentioned above. When carbon overlaps its orbitals to form an hybridized orbital, it sends one of the electron from its 2s orbital to a higher orbital, the 2p orbital. Hence, get the electron conguration: 1s2 2s1 2p1 2p1 2p1 x y z Now, if carbon wants to create 4 single bonds also known as -bonds, every orbital from the second energy level that is 2s, 2px , 2py and 2pz overlap to form 4 hybrid orbitals with 1 electron in each orbital. Thus, each electron can contribute to form 4-bond to other elements21 and it is sp3 hybridized. However, if carbon wants to form 2 double bonds which means that this involves 2-bonds and 2-bonds, it will only overlap 2s orbital with one of the 2p orbitals to make 2 hybrid orbitals and thus 2-bonds. Moreover, 2 of the 2p orbitals is not hybridized and hence contribute to create 2-bonds22 and becomes sp hybridized. Thus, in the case of carbon bonds in graphene, it overlaps 2s and 2 of the 2p orbitals to form 3-bonds and thus leaving the last 2p orbital to form -bond to one of the other carbons thus becomes sp2 hybridized. 3.3. Delocalization of Electrons and Holes. Since, every electrons are negatively charged, a sp2 hybridized carbon will have a structure which makes all of its -bonds displaced 120 from each other. Thus, makes the graphene into a planar sheet where all the carbons are bound together into a hexagonal net23. Furthermore, due to carbon being sp2 hybridized, there will be a -bond to one of the other carbons. However, since all of the carbons which are bounded
Green & Sadru Damji: Chemistry 3rd edition (IBID 2008), page 114 20Sears & Zemanskys: University Physics 12th edition with (Pearson Education, Inc 2008), page 1435 21John Green & Sadru Damji: Chemistry 3rd edition (IBID 2008), page 116 22John Green & Sadru Damji: Chemistry 3rd edition (IBID 2008), page 116 23John Green & Sadru Damji: Chemistry 3rd edition (IBID 2008), page 116
19John

Press, reprinted modern physics Press, reprinted Press, reprinted Press, reprinted

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together are all sp2 hybridized the -bond can be equally said to be bound to any carbon that particular carbon is -bonded to. Hence, the wave function of the electron in the leftover 2p orbital is extended over the whole graphite layer. Thus, the electron is delocalized24 and can move freely around the whole graphite layer. Accordingly, if a potential dierence is applied on graphene the electron will move in the opposite direction of the electric eld and a current is created and which is how graphite are able to conduct electricity. Suppose all the electrons on graphene are standing still except for one. That one electron is thus bounded to one particular carbon atom and is also forced to stay at rest. This is due to the other electrons because there are no space in the 2p orbital that the electron can jump into. Then a potential dierence is applied over the graphite layer and the electrons starts to drift in one direction. The electron behind can then occupy the empty 2p orbital and wait for another 2p orbital to be available to move to. Now, the space that the electrons are leaving behind are called holes25. When a potential dierence is applied to a graphite layer the electrons will start to move in one direction, and the holes which act as positive charges moves in the opposite directions. Thus, the conductivity of a semiconductor such as graphite are dependent on the mobility of both the electrons and the holes as well. So that the conductivity of a semiconductor is (20) = e + h Where e is given by the term in equation 14 ne2 e pe2 h + me mh where p is the number of holes and mh are their mass. Now, if we dene mobility to be26: vd (22) = E Then the conductivity for a semiconductor in this case graphite is given by27 (21) = (23) = e (ph ne ) This is the intrinsic conductivity which is the conductivity of a pure semiconductor. In the context of conductivity in pure semiconductors has a dierent meaning. In this case, will be the average amount
Green & Sadru Damji: Chemistry 3rd edition (IBID Press, reprinted 2008), page 118 25Sears & Zemanskys: University Physics 12th edition with modern physics (Pearson Education, Inc 2008), page 1455 26H. E Hall: Solid State Physics (John Wiley & Sons Ltd. 1974), page 98 27H. E Hall: Solid State Physics (John Wiley & Sons Ltd. 1974), page 98
24John

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of time the electron spend on travelling to each 2p orbitals. as well as in this case will decrease with increasing temperature due to the electrons undergoes thermal excitations28 and thus become more mobile. The conductivity is also very dependent on how many holes per electrons the conductor has. If there are a large amount of holes in the semi-conductor the electrons can move more freely and thus the semi-conductor is able to conduct electricity better. 4. The Conductivity and Temperature Relationship In 22. August 1938 a report concerning the variation with temperature of the electrical resistance of carbon and graphite between 0 C and 900 C were submitted to the Photometry Division of the National Physical Laboratory in Teddington29. It was an experiment conducted by L. J. Collier and his colleagues in order to investigate how the electrical conductivity of carbon and graphite is related to the temperature. In this experiment they used carbon rods which were heated in vacuum in a nichrome-wound resistor-furnace30. In order to measure the resistance they had a xed current from a battery. After the pre-work they started to measure the resistance and temperatures with an increment of about 50 C. This experiment was conducted upon a total of ve carbon rods and two complete sets of observations were made on each rod except for one. The table below31 shows the data acquired from the experiment. On each rods the ratio between the resistance at temperature T C, RT , and the resistance at temperature 0 C, R0 were calculated. Moreover, a mean ratio was also calculated.

Figure 2. Table taken directly from their work.

& Zemanskys: University Physics 12th edition with modern physics (Pearson Education, Inc 2008), page 852 29L. J. Collier et al 1939 Proc. Phys. Soc. 51 page. 147 30L. J. Collier et al 1939 Proc. Phys. Soc. 51 page. 147 31L. J. Collier et al 1939 Proc. Phys. Soc. 51 page. 150
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Now from this data we can deduce that the ratio for each rod including the mean is decreasing with increasing temperature. This means that RT < R0 for temperatures T > 0 C. In this case the resistivity must be the one factor that is decreasing according to equation 19. Now, through this data they found the relation32 of the form: (24) RT = R0 1 3.17 104 T + 1.73 107 T 2 6.3 1011 T 3 This is probably the equation for a best t polynomial with the order of 3. As we can conclude from equation 24 also is that RT is decreasing for higher temperatures as the leading coecient in this third degree polynomial is negative. When plotted the ratio RT with temperature T they obtained a graph R0 that looks like the one below33.

Figure 3. Graph also taken directly from their work Our main focus on this graph is the slightly curved function and the linear function which the function is corresponding to the table given above, as the curved functions are values that corresponds to another experiment. The function is slightly curved and thus as the range of temperature here is large we can conclude that for a small temperature interval the relationship between RT and T is linear. Hence the ratio RT is proportional to some temperature interval T with an initial R0 value of 1: RT (25) = kT + 1 R0
32L. 33L.

J. Collier et al 1939 Proc. Phys. Soc. 51 page. 150 J. Collier et al 1939 Proc. Phys. Soc. 51 page. 151

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Extended Essay

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Now, k is called the temperature coecient in physics and is most of the time denoted with . Thus equation 25 can be written as: RT (26) = T + 1 R0 So solving for RT which is the R(T ) stated at the beginning of this essay: (27) R(T ) = R0 (1 + T ) We can also express this in terms of resistivity: l l (28) (T ) = 0 (1 + T ) A A (29) (T ) = 0 (1 + T ) Now, the relationship between the conductivity and resistivity is given in equation 17 therefore in terms of the equation becomes 1 1 (30) = (1 + T ) (T ) 0 0 (31) (T ) = 1 + T This temperature coecient of resistivity for graphite is approximately34 = 0.0005( C)1 in room temperature. Thus, for increased temperature the denominator decreases which again causes an increase in the conductivity of graphite. However, when the temperature interval T approaches 2000 C the conductivity (T ) approaches innity. This shows that the equation does not hold for high temperature intervals. Moreover, the temperature coecient of conductivity of graphite might have another value when measured for other temperature intervals. 5. Conclusion and Evaluation The conductivity of graphite does show some other interesting properties than metallic-conductors. One of them is that it is a better conductor at higher temperatures in contrast to the metallic-conductors becomes better conductors at lower temperatures. The relationship between the conductivity of graphite and temperature is thus: 0 (T ) = 1 + T However, as further investigated this relationship does not hold for every temperature intervals. As the temperature interval approaches 2000 C graphite becomes a superconductor. Indeed it becomes a superconductor at high temperatures however, as far as the expression
& Zemanskys: University Physics 12th edition with modern physics (Pearson Education, Inc 2008), page 852
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is concerned it can as well as be superconducting at T = 0. Therefore, this expression is again investigated with the purpose of studying small temperature changes. This expression must then be concerned as classical conductivity study as superconductivity does require far more advanced study of quantum mechanics in order to describe the phenomena. Further study of this topic may be to check how the coecient is varying with dierent temperature intervals. Thus a more general expression may be derived from it in order to expand the limitation of the temperature interval.

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Extended Essay Bibliography

Physics

Sears & Zemanskys: University Physics 12th edition with modern physics (Pearson Education, Inc 2008) H. E. Hall: Solid State Physics (John Wiley & Sons Ltd. 1974) J.R. Waldram: Superconductivity of Metals and Cuprates (IOP Publishing Ltd 1996) L. J. Collier et al 1939 Proc. Phys. Soc. 51: page 147 - 152 (IOPscience) John Green & Sadru Damji: Chemistry 3rd edition (IBID Press, reprinted 2008) Nobelprize.org: The Nobel Prize in Physics 1913 and The Nobel Prize in Physics 1922 (viewed 20. & 28. Nov 2010) Scientic American: Sidebar: 5 goals for the LHC (viewed 21. Nov 2010) CERN Document Server: Superconductivity and Cryogenics For the Large Hadron Collider (viewed 21. Nov 2010) Oxford Dictionary of Physics: Sixth edition (Oxford University Press 2009) Georg Simon Ohm: Die galvanische Kette, mathematish bearbeitet (Berlin T.H. Riemann 1827)

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