Thermoelectric efficiency in graded indium-doped PbTe crystals

Z. Dashevsky, S. Shusterman, M. P. Dariel, and I. Drabkin

Citation: Journal of Applied Physics 92, 1425 (2002); doi: 10.1063/1.1490152
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nevertheless. Russia 共Received 25 March 2002. ␴ and k. each containing a different concentration of dopant ele- tration up to N In⬇5 at.00 1425 © 2002 American Institute of Physics [This article is copyrighted as indicated in the article. The resulting functionally graded material. over the 50– 600 °C temperature range. NUMBER 3 1 AUGUST 2002 Thermoelectric efficiency in graded indium-doped PbTe crystals Z. count of diffusion-induced homogenization effects and result 共iii兲 Indium atoms in interstitial positions are neutral and in the degradation of the conversion efficiency. the Fermi level must adjust itself to band gap. The solubility of In in which a gradient of PbI2 has been set up.1063/1. maintain a constant location of the Fermi level. the electron density. based on mined by the impurity level E D . Israel I. consist of wave sition of the Fermi level as a function of temperature was functions that belong to several bands. S. to an optimal value of Z over a wide temperature range. The correspond- ing s orbital is. In order to maintain this optimal Z value. Its location does not depend on the In concen- ers.2 The preparation of PbTe is of the order of 3–5 at. %. which is determined by the dopant concentration. a level that corresponds to a concentration of conversion efficiency and is commensurate with the tempera- only 0. as a function of electron density. based on PbTe crystals. Deep lying In the framework of the abovementioned model. The intrinsic disadvantage of this approach is that at 共ii兲 Each indium atom that occupies one Pb lattice site high temperature. Reuse of AIP content is subject to the terms at: http://scitation. respectively. Their energy levels.9 Recently.aip. the cor- semiconductor materials may be improved by generating an responding s level is viewed as the deep-lying one. %.5 Such a appropriate graded concentration of the dopant. Beer-Sheva 84105. IV–VI compounds a deep-lying impurity level.e. The behavior of indium in IV–VI semicon- ture distribution over the thermoelectric leg. Thus. with respect to the conduction band edge. where S is the Seebeck coefficient. must increase with increasing temperature.1490152兴 I.3 ductors has been subject to several investigations. and may lie within a band as well as within a atoms are introduced.4 Indium generates in pinning of the Fermi level. the preserve charge neutrality: s shell does not participate in bond formation and the In ⫹ a兲 Electronic mail: dariel@bgumail. are not connected to any particular band edge. accepted for publication 7 May 2002兲 High efficiency thermoelectric conversion is achieved by using materials with a maximum figure of merit Z⫽S 2 ␴ /k. Dashevsky. teric level. A maximal value of figure of merit Z. Ben-Gurion University of the Negev. Drabkin Institute of Chemical Problems for Microelectronics. the po- states. in play in PbTe donor-like 共1兲 0021-8979/2002/92(3)/1425/6/$19. E F .. leading to the so-called PbTe crystals doped with indium. P. the ini- contributes one electron on an impurity level and two al- tial dopant concentration gradient may decrease on an ac- lowed states. For an indium impurity on a substitutional site. calculated for a given indium concentration.56. n⫽N D .05 at.bgu. Dariela) Department of Materials Engineering. E C . JOURNAL OF APPLIED PHYSICS VOLUME 92.1 One plays both donor and acceptor properties. usually display an elevated value of Z over a narrow temperature range. Shusterman. of nonbonding nature and is It is well established that the efficiency of thermoelectric strongly localized on the impurity atom. and hence. parallel to level not only releases but also accepts electrons. after extended duration in service. do not contribute to the charge carrier concentration.6 – 8 It was One common approach that has been used for the prepa- established that: ration of such a functionally graded thermoelectric material 共i兲 At low temperature the indium energy level E D is consists of sintering a compacted stack of PbTe powder lay- close to E C . Indium atoms located on substitutional sites dis- moelectric material for the 100– 600 °C temperature range. the Fermi level E F is deter- for the preparation of a FG thermoelectric material. and M. When impurity consequently. it is an ampho- well-known example is that of lead telluride. displays a practically constant value of the Seebeck coefficient. namely. 关DOI: 10. Moscow 109017. based on PbTe具In典. © 2002 American Institute of Physics. INTRODUCTION orbitals hybridize into an excited sp 2 state.198. and it dis- the temperature gradient that prevails along the sample. We present a method for the generation of a dopant 共indium兲 concentration profile in n-type PbTe crystals that gives rise to a constant location of the Fermi level. the electrical and thermal conductivities. an n-type ther. As a result. E C and E V . Downloaded to ] IP: 93. the electron a functionally graded material 共FGM兲 requires determining density reaches a saturation level of n⫽(3 – 5)⫻1018 cm⫺3 the specific carrier concentration profile that leads to optimal at T⫽300 K. we have put forward and described a concept 共iv兲 At low temperature.59 On: Sun. ments. High quality homogeneous thermoelectric materials. in contrast to shallow lying ones. 18 May 2014 16:00:08 . the impurity level is half-filled. %. is attained only for one specific location of the Fermi level.

k ava k ava 冕 ␬ 冕␴ nority charge carriers. electrons from the In level The integration of this expression allows determining the annihilate the minority carriers and exert a twofold beneficial temperature difference on the thermoelectric leg effect by: 共a兲 Maintaining the high value of the Seebeck coefficient Q h L S 共 T h 兲 IT h L ⌬T⫽T h ⫺T c ⫽⫺ ⫹ up to 600 °C. ⫽⫺ ⫹ ⫺ dy able for achieving the maximal value of figure of merit over dx a␬共 T 兲 a␬共 T 兲 a␬共 T 兲 0 a ␴ 共t兲 冕 a wide temperature range. 共5兲. Calculated Fermi level in homogeneous PbTe具In典 as a function of Optimization of the indium profile along the thermoelec- temperature and of the In concentration. 共iii兲 Setting the lowest dopant concentration region to coincide with the low temperature edge of the thermoelectric leg. Reuse of AIP content is subject to the terms at: http://scitation. Fortunately. Phys. where n is the electron density in the conduction band and to x⫽L at T c . L 1 x 1 共b兲 Eliminating the appearance in the heat conduction of ⫺I 2 dx dy an additional term due to bipolar diffusion of electron-hole 0 a 共T兲 0 共 T 兲a 冕 ␬ 冕 pairs. The electron be determined from the heat flux equation under steady state density is given by: conditions:10 n⫽4 ␲ 共 2m de kT/h 2 兲 3/2F 1/2共 ␮ * 兲 . Downloaded to ] IP: 93.56. the temperature distribution along a leg can ⫹ ND . 共9兲 [This article is copyrighted as indicated in the article. 共ii兲 Increasing the In concentration aligned parallel to the increasing temperature along the thermoelectric leg. II. 1 August 2002 Dashevsky et al. the negative influence ⫺ T dy. ⫺I dx T dy. Note that as the temperature increases. 共2兲 d dx 冉 a␬共 T 兲 dT dx ⫽⫺I 2 1 ␴共 T 兲a 冊 ⫹I dS dT T dT dx . the the number of equivalent minima in the conduction band. TEMPERATURE PROFILE SIMULATION FIG. 共4兲 m de is the density-of-state-effective mass for electrons in the where a is the cross section of the material and I is the conduction band. 共5兲 kT dx x⫽0 where N D is the indium concentration and E D is the In im- purity level. For a thermoelectric leg of length L that extends from x⫽0 at T h . at a position which is the most favor. in order to minimize the adverse effect of a large impu- rity concentration on the electron mobility. where k is the Boltzmann constant. and 共6兲. we have adopted a strat. in PbTe m de ⫽(M c ) 2/3 (m l ⫻m 2t ) 1/3 共M c is current.aip.59 On: Sun. 共4兲 is found using the boundary (E F ⫺E C )/kT. This was done in order to maintain a constant position of the Fermi level. the number of ionized donors 共indium兲. 3. where the average thermal conductivity is ciency. and F 1/2( ␮ * ) is the Fermi integral.198. Using Eqs. The solution of Eq. the temperature distribution is the indium concentration has to increase in order for the expressed as 冕 Fermi level to stay close to the impurity level adjacent to the dT Qh S 共 T h 兲 IT h I2 x1 conduction edge E C . 18 May 2014 16:00:08 . L 1 x dS dT On the basis of these premises. 1426 J. 92. the second term for the Thomson effect contribu- the conduction band兲. taking into account the 冋 冊册 2 Peltier effect is given by Eqs. No. The heat ⫹ The number of ionized donors N D . 共7兲 of minority carriers 共holes兲 on the thermoelectric properties a␬共 T 兲 0 dT dy cannot be neglected. respectively: 冉 冏 ⫹ ND ⫽N D 1⫺ . 共5兲 and 共6兲. Vol. 1. 共3兲 E D ⫺E F dT 1⫹exp Q h ⫽S 共 T h 兲 IT h ⫺a ␬ 共 T h 兲 . 共4兲. 共6兲 purity concentration. k a⫺1 ␯ ⫽ 1 L 冕0 L 1 k共 T 兲 dx. The left-hand side represents heat conduction. tric leg requires determining the temperature profile that is set up in the semiconductor located between the high tem- perature T h and the low temperature T c reservoirs. h is the Planck constant. is given by7 flux at the hot side and cold The strategy consisted of: 共i兲 Setting up an indium concentration profile in an ini- tially p-type PbTe crystal by diffusion from a gaseous source. Appl. Figure 1 shows a plot of the calculated values for different temperatures and different levels of indium im- Q c ⫽S 共 T c 兲 IT c ⫺a ␬ 共 T c 兲 dT dx 冏 x⫽L . m l first term on the right-hand side stands for the Joule heat and m t are the longitudinal and transverse effective mass in generation. conditions at the hot and the cold sides of the leg. as a result of the decreasing effect of the mi. I x dS dT At high temperature T⬎400 °C. ␮ * is the reduced Fermi level equal to tion. 共8兲 egy for designing an indium concentration profile in the 0 a 共T兲 0 dT dy PbTe crystal with the purpose of obtaining optimal effi..

respectively. Under mation for the temperature distribution along the thermoelec.g. perature 共80 K兲.org/termsconditions. 18 May 2014 16:00:08 . 共12兲 cally active and may act as charge carriers that participate in k 共 T h 兲 k 共 T c 兲 ⌬T the electrical conduction process. the temperature distribution T(x) was the crystal. these circumstances the carrier concentration is equal to the tric leg. Phys. EXPERIMENT A. about 1 cm thick. on the cold side and n⫽8⫻1019 cm⫺3 on the hot side兲 are A second group of crystals was grown from a PbTe melt shown in Fig. The results of these calculations for PbTe crystals concentration of the lattice point defects 共metal vacancies兲 with constant electron concentrations 共n⫽5⫻1018 and 8 namely. direct measurement of the carrier concentration. Integration of Eq. low angle grain boundaries or twins. To pre- n 2 ⫽8⫻1019 cm⫺3 . they are electri- c⫽ . A 具100典 oriented seed PbTe crystal was used. Reuse of AIP content is subject to the terms at: http://scitation. 1427 III. ␴. the terms in Eq. as well as a better control of the gradient. 2.12 These defects can be k 共 T h 兲 T h ⫺k 共 T c 兲 T c quenched-in by sufficiently rapid cooling. doped with Na (Pb0. 2: two homogeneous PbTe crystals with electron density n 1 ⫽5⫻1018 and PbTe. 2.198. as compared to crucible confined growth tech- niques. Vol. Deviations from the stoichiometric ⌬k composition of crystalline PbTe in equilibrium at elevated b⫽ . 共7兲 yields a second approxi.01Te).aip.56. respectively. Appl. 92. the crucible and the crystal were rotated in oppo- calculated from Eq. The option for an improved control on the axial temperature gradient is important both for preventing constitutional supercooling ef- fects and also for the prevention of undesirable crystals de- fects. In order to enhance the temperature dependence of thermal conductivity. for I⫽0 is given by difference between the concentration of electrically active 冋冉 冊 excess native defects. as a function of the location. 共4兲. 1. Crystal growth PbTe crystals were grown by the Czochralski technique. 3: graded PbTe crystal with n⫽5⫻1018 cm⫺3 at T c and vent decomposition of the melt during crystal growth. No.11 The advantage of the Czochralski technique is that it also enables the application of high axial temperature gradients. When the content of electri- The temperature distribution along the leg as a function cally active foreign impurities is low. respectively. As a the equalization of the heat flux through the lateral surface of first approximation. 共7兲 were calculated tak. The liquid encap- sulant was a molten boron trioxide (B2 O3 ) layer. and 共metal vacancies or nonmetal interstitials兲 form acceptor lev- ⌬k⫽k(T c )⫺k(T h ). knowing K cm⫺1 and 5–10 mm h⫺1. e. as compared to the of coordinate x. all acceptor impurities are ionized. J. 1 August 2002 Dashevsky et al.99Na0. Downloaded to ] IP: 93. polycrystalline PbTe is placed in the crucible and FIG. %兲. where 关 V 兴 and 关I兴 denote the vacancy and interstitial concen- 共15兲 Using this equation for the temperature profile along trations. 3. Calculated temperature profile in an n-type PbTe crystal with ex- the furnace is heated to above the melting temperature of tremities fixed at 50 °C (T c ) and 500 °C (T h ). the hole carrier concentration can be 1 k共 Th兲 x/L expressed as: T共 x 兲⫽ k 共 T c 兲 ⌬T⫺ ␬ 共 T h 兲 T h ⌬␬ k共 Tc兲 册 ⫹␬共 Tc兲Tc . originating from too steep temperature gradients. where b and c are constants The crystals were grown from a PbTe melt with an ex- cess Te 共up to 1 at. The atomic imperfections and k(T h ) and k(T c ) are the thermal conductivity on the hot or lattice point defects associated with excess nonmetal and the cold side of the thermoelectric leg. The crystal orien- perature dependence of the thermal conductivity: tation was determined by the Laue diffraction method. a liq- n⫽8⫻1019 cm⫺3 at T h . vacan- cies. In the crystal growing process. of the order of (1 – 5) ⫻1019 cm⫺3 兲 and for a graded material 共n⫽5⫻1018 cm⫺3 ⫻1018 cm⫺3 .. Na is a shallow acceptor in [This article is copyrighted as indicated in the article. 共11兲 ⌬Tk 共 T h 兲 k 共 T c 兲 temperatures induce the formation of lattice defects. Molten boron trioxide is inert to PbTe at the growth temperature. uid encapsulation method was employed. Back- 1 reflection photographs of an 具100典 oriented PbTe crystal k⫽ .. and possibly interstitials. 共10兲 clearly revealed the fourfold symmetry and the absence of bT⫹c any other reflections. thermoelectric leg. to the excess Te.59 On: Sun. assuming for the tem- site directions at an angular rate of 1 s⫺1. els with zero activation energy. The temperature gradient at the crystallization An analytical solution for temperature along the thermo- front and the crystal pull rate were of the order of 20–25 electric leg T(x) can be determined from Eq. 共14兲 p⫽2 关 V Pb兴 ⫹0 关 I Te兴 . 共4兲. The Hall effect is the most commonly used method for ing into account the known temperature dependence of S. At low tem- and k in PbTe. for I⫽0 and.

13 The determination of the local Seebeck coefficient tributes one electron to the conduction band. as determined by EDS. These results can be accounted for by assuming a model that rests on the C. Thus. 18 May 2014 16:00:08 . as described above. V 1 and V 2 . tion of a Cu–CuNi thermocouple. a kick-out-like mechanism. Doping with In large negative value reflecting the effect of the large In ad- dition. RESULTS AND DISCUSSION The variation of the Seebeck coefficient S. The Seebeck coefficient S of electrical that encounters a Pb vacancy becomes an ‘‘active’’ atom. The S values for all crystals in which In had diffused 共curves 1–3兲 drop at the front end of the crystal to a B. increase 共algebraically兲. The voltage 共e兲 The energy barrier for the dissociative mechanism is values. centration and to negative values of the Seebeck coefficient. on the annealing temperature. A very thin and 共d兲 At In concentrations that exceed the initial V Pb con- sharp probe. of the two thermocouples are measured long as V Pb sites are available. respectively. but due to the presence of Na the diffusion equation for a constant surface source. the diffusing Ini will prefer- simultaneously. 3. The concentration n-type PbTe. as will be described in the Na-doped p-type PbTe crystals that had no excess Te and following. measured in a PbTe with practically zero ionization energy. entially occupy these sites.1– 4 at. The transition from n. Vol. We have made ⫹V Pb⫽InPb⫹e. FIG. The apparatus that has been constructed al. Profile of the Seebeck coefficient in Pb0. The face concentration C S as determined by EDS as a function of penetration profile of In in this crystal also indicates a cross- the annealing temperature is shown in Fig.. Pbi are donors and contribute one couple is in good electric and thermal contact with the p-type conductivity 共p-n Doping was done by indium that diffused from a gaseous junction兲 causes a change of sign of the Seebeck coefficient source (In4 Te3 ). 4.198. % substituting for Pb on the Pb sublattice overcompensates the range and can be varied by changing the diffusion length and V Pb⫹⫹ acceptors and transforms the initial p-type PbTe into the annealing temperature 共600–700 °C兲. 1428 J. IV. 3. initially variations were measured along a direction normal to the reflect the number of In atoms located on Pb lattice sites. Each such ‘‘active’’ In con- crystal.59 On: Sun. The Seebeck coefficient The values of S.01 and Na-doped PbTe crystals after diffusion of indium. lowed a spatial resolution of 10 ␮m. Determination of the In dopant profile in the PbTe following premises: crystal 共a兲 Indium atoms in stoichiometric PbTe diffuse essen- The determination of dopant concentration variations tially by an interstitial mechanism. 92. The presence of In concentration profile of the In dopant lies in the 0. The sur- on the Pb lattice sites had an initial hole concentration. use of a recently developed method for local Seebeck coef. but external free surface on a polished plane of the crystal. hence. The hole con. 共c兲 The Seebeck coefficient is sensitive only to active In ficient measurements along the surface of the doped atoms located on Pb lattice sites. over point of the Seebeck coefficient occurring closer to the In source. Interstitial Pb atoms. heated to temperature T 1 . similar thermo. Phys. Ini ⫹PbPb⫽Pbi its tip with the surface of the isothermal sample maintained ⫹InPb⫹2e. as one proceeds into the crystal. The scanning the local Seebeck coefficient. according to the ‘‘dissociative mechanism’’ reaction: Ini tion and. FIG. Dependence of the In surface concentration. any In interstitial of utmost importance. as one proceeds along the diffusion [This article is copyrighted as indicated in the article. 4. of the dopant distribution. 1 August 2002 Dashevsky et al. Reuse of AIP content is subject to the terms at: http://scitation. allowing to maintain a constant level of and its location can be determined. and of the location of the p-n junction in the doped crystals is 共b兲 In the PbTe crystal with excess Te. direction parallel to the penetration of In by diffusion in a centration in these crystals was p⬇7⫻1019 cm⫺3 . namely at a higher In concentration.12 sample and its junction is at temperature T o . was assumed to be consistent with the solution of hence no structural vacancies.aip. between the Cu–Cu and the CuNi–CuNi significantly lower than for the kickout mechanism. p-type PbTe 共grown from a melt with excess Te兲 crystal is shown in Fig.99Te1. Downloaded to ] IP: 93. No. conducting materials is a measure of the carrier concentra. Similar measurements were carried out in the profile of In within the crystal. 3.8 is carried out by a simple probe technique. by surface In concentration during the diffusion anneal. takes place leading to an increased electron con- at temperature T o . is placed in contact at centrations. The measuring probe is actually the junc. as wires. A second.

hence. counterbalances the initial hole concentration. 6兲. Vol. A similar analysis was performed tribute to the Seebeck 92. Thermovoltage as a function of temperature in doped n-type PbTe crystals.. The practically constant value [This article is copyrighted as indicated in the article.99Te1. The measured Seebeck co- centration at 700 °C is high.. measured thermovoltage.198. as determined by EDS measurements. These high temperatures. the overall concentration profiles of In in both instances should be the same. At this temperature for the Seebeck coefficient profiles in Na-doped PbTe. The elec.01 with the relatively high structural vacancy con. V of the graded n-doped PbTe 具In典 ting to the appropriate solution of the diffusion equation. 5兲. The portion that was cut coincided with the region in two holes. thus S⫽S n ⫺S p ␴ n⫹ ␴ p ␴ n⫹ ␴ p indium can become active only via the kickout mechanism. n and p are the concentrations of electrons centration equals the initial hole concentration that is present 共majority carriers兲 and holes 共minority carriers兲. the dominant mechanism b p 冉 冊 冉 冊 is through the reaction Ini ⫹PbPb⫽Pbi ⫹InPb⫹2e. a path. We can estimate the In concentration is sensitive only to active InPb atoms. larger In concentration. 18 May 2014 16:00:08 . b is the ratio of electron and hole mobilities 共b in PbTe is ties of In in Na-doped PbTe are lower by an order of mag. this electron con. small concentration of holes may cause a drastic decrease of ror兲 value of the activation energy as for the PbTe crystals the Seebeck coefficient and. A 4 mm thick slice was cut from the p-type PbTe sample cess Te. via the kickout mechanism. allowed stant (S⬇⫺250 ␮ V/K) over a wide temperature range. electron-hole pairs can undergo thermal results support the initial assumption regarding the interstitial excitation.5⫻10⫺9 cm2 /s. thus at the crossover in N In at a location x at which the Seebeck coefficient reverses the Na doped PbTe crystal.aip. V Pb .. In diffused by an interstitial Pb0. Downloaded to ] IP: 93. a significant 关 Ini 兴 is still present. Phys. the diffu. the temperature of the upper surface increased to 550 °C. it is because the Seebeck coefficient istic of In-free PbTe. Both the electron and the hole components con- diffusivity of In in PbTe. the contribution of reflect the effect of the lack of 关 V Pb兴 on the active In con- the electrons due to the presence of In on Pb lattice sites centration. Appl. This behavior C 共 x. as determined by the See- point corresponds to 2/3 of the initial 关 V Pb兴 concentration. The apparently lower diffusivities of In in Na-doped PbTe tive 共sample doped with In兲. ⫽S n ⫺S p . Reuse of AIP content is subject to the terms at: http://scitation. Diffusivity of In as a function of the reciprocal temperature in both PbTe-based crystals. 5. The sion coefficient of indium in PbTe was approximated by fit. beck coefficient measurements. 3.01 and in Na-doped PbTe crystals. its sign from positive 共sample with V Pb acceptors兲 to nega. Hence at this point 关 InPb兴 equals 0.e.T 兲 ⫽C s erfc共 x/2冑Dt 兲 .5 eV 共Fig. It is noteworthy that the dependence V(⌬T) is linear within a close approximation. No. Since each In that that had been doped with In that originated from the gaseous jumps into a V Pb contributes three electrons versus the initial phase. At estimating the activation energy E a ⬇1. 共17兲 p p tron concentration increases by two electrons for each sub. close to 1兲. due to the ex. at elevated temperature 共Fig. If the crossover in the Na- doped PbTe appears to occur at a lower penetration. mechanism. of the conversion effi- containing structural vacancies.5 where S n and S p are partial terms for electrons and holes 关Na兴. The two end surfaces of the This latter value is known from the prediffusion Hall effect graded crystal were polished and positioned between two flat measurements. we can deduce that the In concentration at that which an In gradient was set up. 1 August 2002 Dashevsky et al. is shown in Fig. i. i.99Te1. even the presence of a nitude but associated with the same 共within experimental er. At the Seebeck coefficient crossover. shown ␴n ␴p in Fig. J. FIG. D⬇4. b⫹ nb b⫹ n n stitution of Pb on a lattice site by an interstitial In atom. 1429 FIG.59 On: Sun. 5. Using this value and that of the surface con. but since the overall 关 NaPb兴 is low. character. Pb lattice vacancies. change sign and revert to the positive value. there are no structural V Pb . consequently.56. Further efficient S⫽V/⌬T in PbTe doped with In is practically con- measurements performed at different temperatures. 6. 共16兲 of V(T) is very different from that in homogeneous n-type The value of the diffusion coefficient of indium in PbTe 共doped only by iodine兲 which reaches a saturation level Pb0.e. At point x. The diffusivi. 共17兲. According to Eq. surfaces. respectively. on account of the presence of the Na dopant. In Na-doped PbTe. Since we assumed that in ciency at a high temperature. The lower surface was kept at constant 50 °C and centration. 6.

Appl. D. W. 15. No. and M. approach for preparing thermoelectric materials with im- eration of the thermoelectric generator. Proceedings of the 共iv兲 Local Seebeck coefficient measurements along XV Internernational Conference on Thermoelectrics. It is 1 unlikely. Forum 103-105. L. 18 May 2014 16:00:08 . V. Mahan. Z.56. Sov. 1996. Kaidanov. Pasadena. Semicond. and M. over a concentration commensurate with optimal conversion effi. A. 3兲. V. of S up to 600 °C that was observed can be attributed to the of indium in Pb1⫺x Te1⫹x (E a ⫽1. Proceedings of the XVI International Confer- ence on Thermoelectrics. wide temperature range 共50– 600 °C兲. D. Dmitriev. China. E. 13 E. Phys. Horow- cancies. Khokhlov. A significant In con. A. Mater. Phys. 92. Beijing. I. Growth 234. Dresden. Dariel.1 eV. leg in spite of the downward diffusion flux along the tem. 412. 5 forward and has been confirmed experimentally. I. 103 共1981兲. present in the In-generated level annihilated the latter. Muller. Ravich. material based on PbTe crystals doped with In has been put Soc. thereby. Vol. M. Jarashneli. This high level of In ensures that a sufficient content beck coefficient corresponds to an optimal carrier concentra- of In will be maintained at the T h side of the thermoelectric tion distribution. Dariel. 11 M. is well above that needed to ensure a carrier a practically constant value of the Seebeck coefficient. Phys. 1150 ture will allow any concentration buildup in that region. Muller. 1430 J. D. Jerusalem. Veis. Reuse of AIP content is subject to the terms at: http://scitation. 9 共1993兲. [This article is copyrighted as indicated in the article. 共vi兲 The results demonstrate the validity of the FGM perature gradient. 387 共1993兲. Helmers. however. Proceedings of the 24 International Con- 共ii兲 Doping heavily with indium the T h side of the PbTe ference on Physics of Semiconductors. 1998. and M. CONCLUSIONS 3 Y. Z. the thermoelectric figure of merit. 513 共1999兲. I. 1997. Germany. that the diffusivities of In at low tempera. Yu. 31 共1985兲.D O ⫽(9⫾2) negligible influence of the minority carriers. V. and H. and L. P. 545. generated by the In concentration profile. Phys. Kaidanov and Yu. Bocharova. 共v兲 The graded material displays a linear dependence of The near-surface concentration of In. CA. Shusterman.198. P. proved efficiency for energy conversion. and A. 2001. 28. Th-P186. A. Dashevsky. 364. S. suggesting T h . Proc. Horowitz. not affect adversely the position of the Fermi level and. 1 August 2002 Dashevsky et al. R. V. S.aip. Phys. in the course of extended durations of op. 共1998兲. Z. The electrons ⫻10⫺2 cm2 /s) and to design In concentration Solid State Phys. 3. Onopko and A. A. W. Niino. Dashevsky. Cryst. Heiliger. Usp. Sov. about 3 at.4⫾0. Ryabova. 51. Akimov. Dashevsky. to n type. I. Shiota and I. 9 T. 2 I. Defect Diffus. Shusterman. Status Solidi A 137. A. Palmetshofer. Israel. A. I. Krupitskaya. Downloaded to ] IP: 93. 34. The influx of In transforms the conductivity from p itz. E. crystal allows maintaining an In concentration that ensures 7 V. This value of the See- ciency. p. Appl. Reinshaus. A. Dariel. that diffusion effects in the course of extended operation do 8 B. % at the thermovoltage on the temperature difference. 139 共1984兲. 共i兲 A concept for the preparation of a FG thermoelectric 4 Z. Res. Phys.59 On: Sun. Submann. Proceedings of the XX Internernational Conference on Thermoelectrics. 83.. centration reaching the T c side of the thermoelectric leg may affect negatively the mobility of the charge carriers. and R. 12 L. 81 共1997兲. Symp. A: Solids Surf. J. 6 V. P. Nishida. N. J. 共Fig. Kotelnikov. 共iii兲 Indium diffuses from a gaseous source into a p-type 10 G. Gelbstein. the crystal allowed determining the diffusion parameters p. P. J. Appl. 164 共2002兲. Ryskin. Schilz. Dashevsky. crystal with an excess of Te that generates structural Pb va.