Density variations in thermoelectrics

G. D. Mahan

Citation: Journal of Applied Physics 87, 7326 (2000); doi: 10.1063/1.372988
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These various electric material whose dimensions are long compared to the authors use different notations. INTRODUCTION Putting in this feature eliminates the violation of Poisson’s equation. These equa. and e is density. which is optimized to give the coefficient of performance 共COP兲. NUMBER 10 15 MAY 2000 Density variations in thermoelectrics G. 共2兲 The T(r). since particles enter the barrier material by thermal excita- tion. Knoxville. We have examined several such books. ␮ ¯ is the electrochemical potential. 共2兲 feature is discussed below. 23 Nov 2014 01:49:58 . Once we started to put in variations in the particle trostatic potential.00 7326 © 2000 American Institute of Physics [This article is copyrighted as indicated in the article. and particle diffusion. Oak Ridge National Laboratory. We consider the II. Tennessee 37831-6032 共Received 8 December 1999. and Solid State Division. 共3兲 The time scale for diffusion of heat or particles.135. heat currents.1–4 Here we wish to dis. We find.1–4 Here we discuss the fundamen. even for the case that the word ‘‘potential’’ is misleading since the ␮ s are actually particle density is the same at both ends. Downloaded to ] IP: 134. The varies along the length of the bar. that the density variation has L 11 1 J/e⫽⫺ ¯ ⫹L 12“ “␮ . This time cuss the new physics which arises from having a nonuniform scale is milliseconds. in terms of macroscopic variables such as temperature This time scale in semiconductors is picoseconds. then the barrier will have different particle densities at the two ends of the barrier. Thermoelectrics are materials with high relative values We are also interested in the transient equations. D. Here the word ‘‘particle’’ denotes scale. surprisingly. The usual neglect of energies. Our interest is only in the third time distribution of particles. 共1兲 no effect upon the efficiency of the device. Mahana) Department of Physics and Astronomy. the con. Oak e2 e 0021-8979/2000/87(10)/7326/7/$17. This time scale in semiconductors is nanoseconds. 关S0021-8979共00兲03510-6兴 I. The particle density always the charge of the particle which is negative for electrons. time scale for particle scattering which provides energy re- tions are well known and well documented for the case that laxation. then macroscopic equations should so their results appear different. JOURNAL OF APPLIED PHYSICS VOLUME 87. The basic formulas for the currents are provided cept of thermionic refrigeration5–8 has led to devices being in books on nonequilibrium statistical mechanics. First. Clearly there will be particle diffusion along the length of the barrier. which are given in the next section.aip. The COP depends upon the temperature difference ⌬T. and the Appendix A. density. and provide such a solution. © 2000 American Institute of Physics.134 On: Sun. The motivation for this work is twofold. heat. Reuse of AIP content is subject to the terms at: http://scitation. Using the standard definitions of the transport variations in particle density is never justified. then a truth emerged. articles. The density equations 关Barnard9兴 the above equations can be written as always varies as long as there is a current flowing in the bar. along with research ticles being excited over a barrier. UNIFORM DENSITY case of the efficiency of a thermoelectric device when there The following equations are obtained for the electrical is a variation in particle density besides the usual variations current J and heat current JQ from Refs. when a solid has electrical currents. If the barrier is a thermo.9–13 constructed and tested which have the cooling due to par. voltage V(r) and particle density n(r). These solutions are used to calculate the efficiency of a thermoelectric refrigerator. the particle density n(r) is uniform. T T 冉冊 The other motivation for this work is that the usual ther- L 21 1 moelectric equations actually violate Poissons equation. ␮ is the chemical potential. 9–14: 冉冊 in temperature and electrostatic potential. ␴T ␴ ST 2 L 11⫽ . In this case we can use the equilibrium formulas for either electrons or holes in a semiconductor. University of Tennessee. Any of the Seebeck coefficient. and decided that they all agree on the basic equa- tions. The resolution of this puzzle is to T T introduce variations in particle density along the length of where ␮ ¯ ⫽ ␮ ⫹eV. ticles.71. Solutions are presented in one dimension for currents down a bar. particle mean free path. for particle scattering which changes particle momentum. This JQ ⫽⫺ “␮ ¯ ⫹L 22“ . Getting the different nota- be used to describe the flow of particles in the barrier. and a variety of symbols. accepted 9 February 2000兲 Equations are solved to give the variations in temperature. V is the elec- the bar. Since tions straight shows they all agree. interacting system has a variety of time scales: 共1兲 The time tal equations for the transport of electricity. 共3兲 a兲 Electronic mail: gmahan@utk. the flow of electrical current J and heat current JQ . L 22⫽T 2 共 K⫹T ␴ S 2 兲 . and par. L 12⫽ . and potential. This topic is discussed in the temperature is different at the two ends of the barrier. but does not depend upon the density difference ⌬n between the two ends of the bar.

23 Nov 2014 01:49:58 . 共6兲 ⳵T C ⫽“• 关 K“T 兴 ⫹ ␳ J 2 ⫺TJ•“ On: Sun. No. 共8兲 For systems in which the density n is homogeneous. The last term in the last equation is a variation on the Thomson coefficient ␶ ⫽T ⳵ S/ ⳵ T. a small density of electrons. For example. 共13兲 d ln共 f 兲 ⌳共 y 兲⫽ . d k3 1 冑␲ 0 e x⫺y ⫹1 n⫽2 共 2 ␲ 兲 3 e ␤ ( ⑀ k ⫺ ␮ ) ⫹1 ⬇2e ␤␮ 冕 d 3k e ⫺ ␤⑀ ␬ ⫽ 2 e ␤␮ . 10. the function over the range of ⫺5⬍y⬍5 which covers all so that the correction to the effective Seebeck coefficient is useful materials. 共17兲 共2␲兲 3 ␭T 3 3 2␲ប2 g 共 y 兲 ⫽y⫺ . which in our notation means it is negative. Note that these functions apply to all mate- large. 共10兲 The current has an effective Seebeck coefficient which con- tains the derivative of the chemical potential with respect to temperature. Downloaded to ] IP: 134. D. since our version allows variations with the Seebeck due to changes in the material. Vol. introducing the function f (y) where y⫽ ␮ /(k B T) It is important to note that this correction always lowers 2 the magnitude of the Seebeck coefficient. As discussed by Barnard. The density 冕 冑xdx of particles is then ⬁ 2 f 共 y 兲⫽ 共16兲 冕 . Reuse of AIP content is subject to the terms at: http://scitation. 15 May 2000 G. 共15兲 negative so that S is negative and ␦ S is positive. 共7兲 ⳵t where ␴ ⫽1/␳ is the electrical conductivity. Top curve shows g(y) as a function of y. besides changes in temperature. K is the thermal conductivity at zero current. 共9兲 S̄⫽S⫹ 冉 冊 ⳵␮ e⳵T n ⬅S⫹ ␦ S. ␭ T3 e⬎0. For holes.135. 共19兲 冉 冊 冋 册 dy ⳵␮ kB 3 ⫽ ln共 n␭ T3 /2兲 ⫺ . For electrons. This term is usually neglected but should be included. 共5兲 “•J⫽0.9 the chemical potential ␮ (n. 共4兲 JQ ⫽STJ⫺K“T. 共11兲 冉 冊 ⳵␮ e⳵T n ⫽ kB e g共 y 兲. consider a semiconductor which has FIG. 共18兲 ␭ T2 ⫽ . C is the heat capacity per unit volume. J. rials! It is interesting that g(y) is always negative. The way we have written it is correct. such as doping. then the current equation becomes J⫽⫺ ␴ “V⫺ ␴ S̄“T. 87.aip.T) is a function of particle density n and the tempera- ture T “␮⫽ 冉 冊⳵␮ ⳵n T “n⫹ 冉 冊 ⳵␮ ⳵T n “T. and S is positive and ␦ S is negative. and S is the Seebeck coefficient. Appl.71. lower curves show f (y) and ⌳⫽d ln(f)/dy. 共12兲 2⌳ 共 y 兲 mk B T ␮ ⫽k B T ln共 n␭ T3 /2兲 . 共14兲 e⳵T n e 2 Figure 1 shows a graph of g(y) and ⌳(y) vs y. Phys. e is n⫽ f 共 ␤␮ 兲 . The existence of [This article is copyrighted as indicated in the article.. At large A more general formula for all densities is derived by values of y then g(y) decreases to zero. so that Maxwell–Boltzmann statistics apply. Thermoelec- trics generally operate best when y⬃0 so we have graphed Both terms in brackets are negative in the present example. Mahan 7327 J⫽⫺ ␴ 关 “ 共 ␮ ¯ /e 兲 ⫹S“T 兴 . 1. The chemical potential is below the band edge.

No. with the same electrochemical potential ␮ ¯ ⫽␮. 共21兲 FIG. and ␮ ¯? of ln(f). The left metal m m⌳ k BT has a barrier e ␾ L to the electrons. 共28兲 The function ␩ (J) is maximized with respect to the current. It is not changed by the variations then measuring the induced voltage difference ⌬V a which in the density. in the semiconductor. but the electrochemical potential is consider a bar of length L with a cold (T c ) end (x⫽0) and constant. 87. and there may be less variation in volt. potential V(r). If ⌬T⫽0. and ticles on thermoelectrics. rent flowing. 共27兲 as the applied voltage V a between the two 共20兲 e 2 D⫽ ␴ 冉 冊 ⳵␮ ⳵n T ⫽ ␴ k BT 1 n ⌳共 y 兲 . The slanted line connecting them is the conduc- Maxwell–Boltzmann statistics. then the expression J Q 共 x⫽0 兲 ST c J⫺K⌬T/L⫺ ␳ J 2 L/2 for the current is ␩共 J 兲⫽ ⫽ . leads. 2. there is no change in the then the measurement actually gives e(S⫺S l )⫽⌬V a /⌬T. ␴⫽ . 共b兲 JQ ⫽TSJ⫺K“T. ␮ ¯ has the same value as hot (T h ) end (x⫽L). This feature is shown below. Yet the efficiency is ⌬T 共 1⫹ ␥ 兲 still given by the expression 共25兲. The equations for the electrical current and heat current are J⫽⫺ ␴ 关 “ 共 ␮ ¯ /e 兲 ⫹S“T 兴 ⫽⫺ ␴ 关 “V⫹S̄“T 兴 ⫺eD“n. efficiency of the device. and how it tem. 2共a兲. There are now three active unknown variables: temperature T(r). between the two ends of the bar. T̄⫽ 共 T c ⫹T h 兲 . Since the voltage reading is done by wire nents in ␮ ¯ ⫽ ␮ ⫹eV. which Next consider the situation in Fig. 共7兲 is still Since the system is in equilibrium. Since ␮ ¯ is a constant. there is no electric COP⫽ . Mahan S̄ in the equations has no effect upon the efficiency of a thermoelectric refrigerator or generator. and density n(r). 10. results when J⫽0. chemical potential. 7328 J. JW ⫽ 共 ST⫹ ␮ ¯ /e 兲 J⫺K“T. chemical potential also must depend upon position and is 共4兲 is ⫺⌬ ␮ ¯ /e⫽ ␳ LJ⫹S⌬T. With these definitions. Note that the electrostatic S 2 T̄ 1 potential V(x) in the semiconductor is not the same quantity ␥ 2 ⫽1⫹ . The line E c (x)⫽e 关 V(x)⫹ ␾ L 兴 . These quantities are related by the Einstein expres. 23 Nov 2014 01:49:58 . As an example. There is a voltage difference V a and a in the electrodes.135.71. The density will change the various compo. Phys. Downloaded to ] IP: 134. It is the temperature difference ⌬T⫽T h ⫺T c . ␳K 2 The Seebeck coefficient is usually measured by impos- This expression is the usual COP which is found in all ar. the diffusion coefficient depends on the derivative are ␮ . ␴⫽ D⌳. So in the semiconductor. For the case of Fermi–Dirac tion band minimum E c (x). Any measurement gives the difference of the Seebeck be- [This article is copyrighted as indicated in the article. consider a three layer device as shown in sion Fig. 共22兲 Same device as in 共a兲 with an applied voltage of V a ⫽ ␾ L ⫺ ␾ R to achieve a flatband condition in the semiconductor. what statistics. We find this result surprising. Note that it is not the chemical potential which is con- depends upon the variations in the density. while the right metal has a The Einstein expression has ⌳⫽1 for particles which obey barrier e ␾ R . D. T c ␥ ⫺T h For this one choice of applied voltage. The efficiency is stant. Reuse of AIP content is subject to the terms at: http://scitation. dx and the maximum is the coefficient of performance 共COP兲 The current is driven purely by the diffusion of the particles. It is unchanged by the variations in particle density. 15 May 2000 G. 共24兲 The middle layer is an n-type semiconductor.. 共25兲 J 共 ⫺V a 兲 J ␳ LJ⫹S⌬T dn J⫽⫺eD . age and more in ␮ . with no heat or cur- valid. Appl. Now. ing a small temperature difference ⌬T across a sample. 2共b兲. 共a兲 Semiconductor barrier with two different metal electrodes. 共23兲 In the first equation we have introduced the diffusion coeffi- cient D. The change in the variation of the potential. stant everywhere. On the left and right there are two different metal ne 2 ␶ k BT ␶ e 2n electrodes. Vol. The variation of density is introduced through a chemi- cal potential ␮ (r) and a related function ␮ ¯ ⫽ ␮ ⫹eV. As an example.134 On: Sun.V. then the electrochemical potential ⌬ ␮ ¯ for a given current J from Eq. 共26兲 field and no drift term in the current. the transient Eq. D⫽ . independent of position. It is the change in the electro- ␮ (x)⫽ ␮ ¯ ⫺eV(x).aip. and the leads have their own Seebeck coefficient S l . III. INHOMOGENEOUS SYSTEMS Now consider the case that the density of particles n(r) can vary in the system. where there is an equals the voltage difference eV a ⫽ ␮ ¯ R⫺ ␮ ¯ L supplied by the applied voltage V a ⫽ ␾ L ⫺ ␾ R which makes E c ⫽eV be a con- 9 external battery. However. then ␮ ¯ is the same at all locations in the sys- Now consider the efficiency of a refrigerator.

The main of electrons. The left-hand side In this case the boundary conditions are that ␦ n(0)⫽ is zero. In this section we derive and solve the equations which gives these varia- tions for the time-independent solution. For example. Therefore. (S⫽240 ␮ V/K. It is The quantity n J appears to be negligibly small. the solution is K ⫽⫺ ␳ J 2 . The disad. which be different at the two ends of the bar: n h at the hot end and are unchanged when variations are allowed in ␦ n(x). n J⫽ 2 ⫽ . No. If n̄ is the average conducting charge due to electrons or holes. The The second derivative of the temperature is given above quantity S̄ cannot be measured directly. one could have n 0 ⫽0. The theory of these space charges was discussed variation in ␦ n(x) is due to ⌬n. It is found choice is undesirable for devices. 共35兲 A bar of length L has variations in temperature ␦ T(x). 87. in Ref. 共37兲 ⑀ k BT constants.. but n J remains small. den. of particles. and taking S̄⫽S.S. Integrate this equation starting at the the barrier.aip. and taking V(0)⫽0 barrier has been doped with donors or acceptors in such a way that the barrier is charge neutral on the average. 5. In that case n(x)⫺n 0 ⬅ ␦ n(x). not S̄. ␬ ⫽10). Even if one postulates that there is dJ no density variation in the solution. in fact there is one. for bismuth telluride. Vol. 共42兲 For currents down a bar the equation is d 2 V/dx 2 2 sinh共 q D L/2兲 ⫽⫺e 关 n(x)⫺n 0 兴 / ⑀ . and Poisson’s the leads which has a small value of S l ⬇0. These are the standard solutions. 共38兲 x ␳J2 cosh共 q D L/2兲 T 共 x 兲 ⫽T c ⫹⌬T ⫹ x 共 L⫺x 兲 . The transport coef- ficients ␴ . 共29兲 dx quantity q D is the screening wave vector. 15 May 2000 G.135.␦ n(L)⫽⌬n/2. which produces its own potential. The second equation gives that the second derivative of the temperature is due to the Joule heating. and 冋 册 of V is given by Poisson’s equation in terms of the density variations cosh关 q D 共 x⫺L/2兲兴 ␦ n 共 x 兲 ⫽n J ⫺1 cosh共 q D L/2兲 e ⵜ 2 V⫽⫺ 关 n 共 r兲 ⫺n 0 兴 . where one wants to control easily from Eq. 共30兲 冋 册 dx 2 cosh关 q D 共 x⫺L/2兲兴 ␦ n⫽n J ⫺1 . if one applies the boundary condition that ␦ n⫽0 at both ends of d 2T the bar. In thermoelectric devices the current densities This potential has a maximum which is a barrier to the flow are typically J⬃MA/m2 .71. 共33兲 ⑀ ⌬n sinh关 q D 共 x⫺L/2兲兴 ⫹ .134 On: Sun. So we derive the equation d 2V d 2T d 2n 0⫽ 2 ⫹S̄ 2 ⫹e ␳ D . Usually wire is selected for choose n 0 ⫽n̄. Reuse of AIP content is subject to the terms at: http://scitation. Phys. There is a variation of density due to the Joule heating. 共40兲 dV dT dn ⫺ ␳ J⫽ ⫹S̄ ⫹e ␳ D . The next decision is to choose n 0 . The ⫽0. Downloaded to ] IP: 134. ⫽17 ␮ ⍀ m. then ⫺V 共 x 兲 ⫽ ␳ Jx⫹S̄ 关 T 共 x 兲 ⫺T c 兴 ⫹e ␳ D ␦ n 共 x 兲 ⫹ 冋 ⌬n 2 册 . D. On the right. and that the same S density. 共34兲 dx dx dx 2 IV. ⑀ K en dx 2 sity ␦ n(x) and electrostatic potential V(x). K⫽1 W/Km. SPATIAL VARIATIONS A physical problem was formulated in the prior section. 共32兲 dx dx dx ␦ n 共 x 兲 ⫽n 共 x 兲 ⫺n̄. goes into the formula for the coefficient of performance. Mahan 7329 tween two different materials.K are assumed to be a constant along the length 冋 d2 dx 2 ⫺q D 2 册 ␦ n⫽ S̄J 2 eDK . and is further discussed in Appendix B. by Joule heating. The third The more general solution is to have the particle density to equation gives T(x). Numerical solutions for the case they are not ne 2 constants show little change from treating them as 2 qD ⫽ ⌳. The main point is equation creates a potential due to the variations in charge that the measurement gives S. The average density is Rewrite the equation for the current as n̄⫽ 12 共 n h ⫹n c 兲 . 共39兲 eDKq D eK⌳ stant. the second derivative ⫺⌬n/2. That The final quantity to be determined is V(x). a current of J vantage of this choice is that the injected electrons or holes ⫽1 A/cm2 gives n J ⬃23/ cm3 which is a very small density form a charged plasma. we assume that the semiconductor cold end (x⫽0). ⑀ ⫽ ␬⑀ 0 . 10. n c at the cold end. ⌬n⫽n h ⫺n c . J. 共43兲 [This article is copyrighted as indicated in the article. 共31兲 L 2K S̄J 2 ⑀ S̄ ␳ J 2 The first equation shows that the current density J is a con. since dJ/dx⫽0. e S̄ ␳ J 2 k B T d 2 ␦ n 0⫽⫺ ␦ n 共 x 兲 ⫺ ⫹ . Appl. 共41兲 Take another derivative of this equation. ␳ In a pure semiconductor. Using values the density of background charge due to donors or 共32兲.15 From the conservation of energy flow 共7兲 one has The above equation is new. 共36兲 of the bar. 23 Nov 2014 01:49:58 .

DISCUSSION University of Tennessee. and is the basic energy currents. This is the voltage suggestion was that ballistic transport is unnecessary: even if change in the barrier layer. A refrigerator based upon thermionic emission depends upon JE ⫽ 兺 p. 共48兲 ␭ 3c ␭ 3h K K This formula depends neither upon the current nor the ap. be thermally excited to get into the barrier. In that Another feature of these expressions is that ⌬n is indepen. The amount of variation depends upon ␳ JL ␰ sinh共 ␰ 兲 the effective Seebeck coefficient S̄. The above equation appears to be a diffusion current ⫺eD“n. 共36兲. 7330 J. Mahan ⫺V 共 L 兲 ⫽⫺⌬V⫽ ␳ JL⫹S̄⌬T⫹e ␳ D⌬n. Phys. flow of heat. Yet the potential V(x) varies between the two end ACKNOWLEDGMENTS points. ␴ ␷p n p. Reuse of AIP content is subject to the terms at: http://scitation. then Fick’s Law 共28兲 has the solution ⌬n⫽ always density variations inside of the bar when a current is ⫺JL/(eD) and the expression for V(x) is given in terms of flowing. There are several definitions of heat or energy current. ␴ .aip. although these formulas are not correct in in density do not alter this standard formula. Research support is acknowledged from the Office of Naval Research Contract No. 2. The original theory had these elec- The second equation provides the most general expression trons traversing the barrier region ballistically. electricity. This contradiction is re- The above solution shows that Fig. Also define ␮¯ ⫽ ␮ ⫹eV where diffusion of particles is more important than drift in an electric field. 共A2兲 [This article is copyrighted as indicated in the article. with respect to variations in the cur. The second derivative of the potential has a constant value plied voltage V a . Since There is no benefit from thermionic phenomena. The present theory is the first to note that Joule heating ⫺V 共 x 兲 ⫽ ␰ L2 ⫺ ␰ 2 ⫹2 ⫺1 2 2Kq D cosh共 ␰ L 兲 must produce variations in the charge density in a wire or bar 冋 册 which carries current. this argument is untrue in the limit that the barrier region is ductor barrier to the other. Here I review the several The final result depends upon ⌬T but not ⌬n. and is not the applied voltage V a . boundary condition has no effect on the device efficiency. case we can rewrite Eq. 15 May 2000 G. We find that this ure 2共a兲 shows a case where V a ⫽0 but ⌬V⫽0. rent. as is the the density of particles. ⫹ ⫺ . while Fig. 10. ⇒ⵜ 2 V⫽⫺S̄ⵜ 2 T. 共44兲 the extra efficiency due to the fact that only ‘‘hot’’ electrons can surmount the barrier. 共47兲 2 2 ␳J2 S̄ ␳ J 2 n c⫽ e ⫺e ␾ L ␤ c . from the V. The variations free electron gas. since 冋 冉 冊册 the right-hand side is indeed related to variations in the den- S̄ ␳ J 2 cosh共 ␰ 兲 sity.135. The above equation is not too wrong. They have been used to derive the most gen- eral equation for the efficiency of a thermoelectric refrigera- APPENDIX A: HEAT CURRENTS tor. We assume the electrons have to electrochemical potentials between the two electrodes. An alternate for the voltage drop ⌬V across the device. 2共b兲 is for the U. which is not the same as the long enough that it can be treated as a normal thermoelectric applied voltage on the device. Since n J is negligible. if the ends are at different temperatures. Even solved by writing it as Eq. and a den- sity variation. Fig. even when there are no variations due to the bound- ␰ ⫽q D (x⫺L/2). This expression depends upon the current flow. This topic is discussed in my book. 共34兲 in three dimensions as dent of V a or J. 2共b兲 shows the contrary case where V a ⫽0. ⌬V⫽0. ⫺V a ⫽ ␳ JL⫹S⌬T then an alternate expression is One reason for this investigation is to resolve a puzzle ⌬V⫽V a ⫺e ␳ D⌬n⫹ ␦ S⌬T. No. 共A1兲 is actually unchanged by the fact that the electrons have to be thermally excited into the semiconductor barrier region.. The efficiency is optimized. 23 Nov 2014 01:49:58 . and from Oak Ridge National Laboratory managed by Lockheed Martin Energy Research We have derived in one dimension the equations for the Corp. ␴ ␷p n p. the density of par. The equation is actually when ⌬V⫽0 the band is not flat between the ends. which is given by the Joule heating. One result is that the efficiency of the three layer device J⫽e 兺 p. even in the case interacting systems. 87. Department of Energy under Contract No. n h⫽ e ⫺e ␾ R ␤ h . N00014-98-1-0742. have a temperature gradient. Downloaded to ] IP: 134. and particles in materials which DE-AC05-96OR22464. 2 ␰ L sinh共 ␰ L 兲 This expression vanishes at both end points ␰ ⫽⫾ ␰ L so that ⌬V⫽0.S. A nonzero current means the band is not flat. ␰ L ⫽q D L/2 ary conditions. Here we show that There can be a voltage change from one end of the semicon. violation of Poisson’s equation. they still have the benefit These differences were discussed above in relation to Fig.71. There are ⫽0 also. ␴ ⑀ p . D. the electrons scatter in the barrier. 共45兲 regarding the usual equations for thermoelectrics. Appl. which gives the ‘‘coefficient of performance’’ 共COP兲. 共46兲 ⵜ 2 T⫽⫺ . of the energy filter of thermal excitation. In the above example. an applied voltage.134 On: Sun. ⇒ⵜ 2 V⫽ . Vol. The usual equations neglect variations in the particle density. and seems unrelated to ticles n(x) is also effectively independent of V a . then “•J⫽0. If ⌬T related to variations in the quasiparticle density. In each case I give the formulas for a same expression widely used in the literature. The latter is the difference in with boundary conditions.

Energy currents and their forces according to different authors ⳵S where ␮ ¯ ⫽ ␮ ⫹eV. He does not give Eq.X Y ) which drive them. generally reduce the size of the intrinsic barrier.135. 共B1兲 different energy currents. and Here we treat the case of a symmetric barrier. 共A9兲 a vacuum. where ␤ ⫽1/k B T. 共7兲. The solution is found easily. This process was described by Langmuir16 for the case that the barrier was JY ⫽L 21X J ⫹L 22X Y .134 On: Sun. 87. His version of the above JH 1 ⫺ 关共ⵜ␮兲T⫹ⵜ共eV兲兴 T ⵜ 冉冊 1 T J⬘q JQ equation is 0⫽“• 共 K“T 兲 ⫹ ␳ J 2 ⫺TJ• 关共 ⳵ S/ ⳵ T 兲 “T⫹ 共 “S 兲 T 兴 共A12兲 which agrees with Haase. We have adopted14 his notation for the currents. ␴ 共 ⑀ p ⫹eV 兲 . 共A5兲 共5兲 de Groot and Mazur13 do not discuss the time depen- dence of thermoelectric phenomena. 共B2兲 F⫽1. ␴ ␷p n p. D. We use J for electrical current. barrier. In each case there are several items which less parameter b⬅e ␾␤ . JH ⫽JE ⫺HJ/e⫽JQ ⫺ 共 S e T/e 兲 J. then the space charge forms a J/e⫽L 11X J ⫹L 12X Y . so that e is negative for electrons. Here we wish to comment on the five references. which has show they all agree on the above formulas. Poisson’s equa- are important: 共1兲 They use different conventions on the sign tion in the barrier region is.. the proper equations are “•J ⫽0 and “•JW ⫽0. JQ 1 JS ⫽ ⫽ T T 兺 p.aip. 共A4兲 0⫽“•JW ⫽J•“ 共 ST⫹ ␮ ¯ /e 兲 ⫺“• 共 K“T 兲 共A13兲 when using ⫺“ ␮ ¯ /e⫽ ␳ J⫹S“T. which changes molar quantities to physics units 冑 冉 冊 Cp ⳵T qD L ⫽“ 共 ␭ ⬁ “T 兲 ⫹ ␳ J 2 ⫺J• 关 ␶ “T⫹T 共 “S 兲 T 兴 .Je JQ* quantity in the last bracket is clearly just 关 T“S 兴 . ␴ 共 ⑀ p ⫺ ␮ 兲 . Reuse of AIP content is subject to the terms at: http://scitation. J.17 The same process occurs in a semiconductor also show the symbol for the energy current used by differ. 共B3兲 V ⳵t 2 2 [This article is copyrighted as indicated in the This choice of energy current is not common. JS ⵜ␮¯ ⵜT Js̄ JS Js.71. If ⳵t the barrier is not doped. The JE e 冋 ⫺ ⵜV⫹ⵜ T 冉 冊册 冉 冊 ␮ T ⵜ 1 T Ju Jq . 共A10兲 s⫽ x⫺ . They all call the particle current J so it is not duce a dielectric constant and effective mass for the semi- listed. subject to the boundary condi- 共2兲 Haase12 in Eq. Downloaded to ] IP: 134. Mahan 7331 TABLE I. We publications. m * /m e ⬍1 factor of charge e.25. These two parameters ␬ ⫽ ⑀ / ⑀ 0 ⬎1. The irreversible production of entropy can be written as VI. and has been discussed in numerous The relevent forces for each case are given in Table I.5. 共2兲 They use d2 2e 2 U 共 x 兲 ⫽⫺ exp关 ⫺ ␤ U 共 x 兲兴 . 15 May 2000 G. The symbol J S is the entropy current. 共7兲.68兲. “S⫽ “T⫹ 共 “S 兲 T .JY ) and the forces (X J . where U(x)⫽eV(x) of the charge e. 共A8兲 plasma which will create an intrinsic barrier. 共A11兲 ⳵T JY XJ XY Barnard Callen de Groot Haase where ␭ ⬁ ⬅K and his * S ⌰ ⫽⫺S as shown in 共4.tot JS and neglects transient phenomena. which gives a dimension- ferent notation. The symbol H⫽ ␮ ⫹TS e denotes enthalpy while S e is the entropy. Here the symbol Y denotes one The semiconductor barrier region will have an average of the energy currents listed above number of charge carriers n̄ injected into it by the metal ⳵Se electrodes. 23 Nov 2014 01:49:58 . 共4-25. 共4兲 Callen10 uses the symbol ␮ to denote ␮ ¯ ⫽ ␮ ⫹eV. which explains the conductor. APPENDIX B: INTRINSIC BARRIER a summation over the currents (J. Their formulas for the currents agree with the others. 共A6兲 All of the above treatments give the same equations. ␴ 共 ⑀ p ⫺ ␮ 兲 . ␴ ␷p n p. 共A7兲 doping of the barrier. Phys.56兲 lists the following equation tion at the ends that U(0)⫽U(L)⫽e ␾ for our Eq. This agrees with the above formulas JW ⫽JE ⫹VJ⫽JQ ⫹ 共 ␮ ¯ /e 兲 J⫽ 兺 p. His ‘‘energy vector W’’ ⫺ ⫺ T T is the energy current we call JW . About the only change in the formalism is to intro- ent authors. He JQ ⫽JE ⫺ ␮ J⫽ 兺 p. and is not used JW ⫺ⵜ 冋 冉 冊册 冉 冊 ␮ ¯ T ⵜ 1 T JW JU here. Vol. Each has a dif. 共3兲 Domenicali11 gives only the steady state equation. The most efficient device will have intentional ⫽J•X J ⫹JY •X Y . Here we take it to be the charge on the particle. Haase uses as his energy current JH which gives a force with the deriva- JQ 1 ⫺ ⵜ␮ T ¯ 冉冊 ⵜ 1 T JQ JQ Jq ⫺ ␮ J tive of the chemical potential at constant T:(“ ␮ ) T . Appl. a work function e ␾ on each end. in order to cancel this space charge. No. dx 2 ⑀ ␭ T3 共1兲 Barnard9 is the easiest to follow. 共A3兲 claims that in steady state. ␴ ␷p n p. We have altered his notation by setting his ␤ U 共 x 兲 ⫽u⫹2 ln关 cos共 se ⫺u/2兲兴 . 10.

1234 共1997兲. 1998兲. and 17 J. 共B5兲 12 R. 1960兲. edited by H.aip. Note The constant u is the maximum potential. Vol. Vol. but the gains are small. J. Phys. D. Mahan. Many-Particle Physics. ting U⫽e ␾ at the ends 11 C. Sofo. 52. 4406 共1981兲. Phys. 1994兲. 5 G. Woods. Rev. Phys.71.3 are shown in Fig. Callen. Lett. 3. Phys. Phys. 1990兲. 15 G. Appl. Phys. FIG. London. Phys. Modern Thermoelectrics 共Reston. New York. 87. O. 1990兲. 81. New York. 4362 共1994兲. Chap. 8 G. Appl. [This article is copyrighted as indicated in the article. 4551 共1991兲. Shakouri and J. Barnard. 2 冑2 LD 14 G. At L⫽0 the so- lution goes to b since the space charge region shrinks to zero. Mahan. Thermodynamics of Irreversible Processes 共Dover. Domenicali. 23 Nov 2014 01:49:58 . 4. Rev. M. 7332 J. Phys. Downloaded to ] IP: 134. 21. J. It is determined by set. Here u(L)⫽U max /k B T. Vol. M.15 1 H. 1310 共1954兲. 51. New York. B. 17. D. b⫽u⫹2ln关 cos共 s L e ⫺u/2兲兴 . Langmuir. 15 May 2000 G. Haase. Appl. Appl. 51. 4 G. 70. Mahan. 1983兲. No. 4683 2e 2 共1998兲. an input parameter. 2 qD ⫽ . where b is 16 I. Electronic Refrigeration 共 7 G. Appl. Mazur. E. 419 共1923兲. Mahan the results for b⫽2. 1972兲. Non-equilibrium Thermodynamics 共Dover.. R. At large values of L it goes to a value which is independent of b. 4016 共1998兲. 1986兲. J. B. J. 共B4兲 9 R. conductor. 共Plenum. Equation 共B5兲 is a nonlinear equation for u(L). 25. Spaepen 共Academic. Rev. This latter solution was given by us earlier. Thermodynamics 共Wiley. London. J. Phys. and M. Alter- nately. 10. D. Rowe and C. D. Lett. Bhandari. Ehrenreich and where U max is the maximum barrier height in the center of the semi- F. J. The u(L) for two values of b⫽e ␾ /k B T. D. 877 共1953兲. 92. Bartkowiak. D. edited by D. Mahan and L.135. Mahan. Appl. Goldsmid. 10 H. 6 A. q DL L 13 S. 3. Appl. 76. Phys. 71. Chap. p. J.134 On: Sun. and are avoided by doping the semiconductor with donors or accepters with an average density n̄.5 These barriers are detrimental to the performance of the refrigerator. D. topic. 共B6兲 New York. deGroot and P. Bowers. VA. 3 CRC Handbook of Thermoelectrics. 2 D. Thermoelectricity in Metals and Alloys 共Taylor and Fran- ⑀ ␭ T3 k B T cis. Mahan. J. Rowe 共CRC. 1984兲. Scott. 80. one could even vary the density of donors or accep- tors to try to improve the device performance. 83. which is found in the first edition is superior to the second edition for the treatment of this the middle of the barrier at x⫽L/2. D. 2nd ed. Reuse of AIP content is subject to the terms at: http://scitation. Boca Raton. in Solid State Physics.M. s L⫽ ⬅ . M. New York. It is easily solved on the computer.