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# PRL 102, 166808 (2009

)

PHYSICAL REVIEW LETTERS

week ending 24 APRIL 2009

**Anomalous Thermoelectric Transport of Dirac Particles in Graphene
**

Peng Wei, Wenzhong Bao, Yong Pu, Chun Ning Lau, and Jing Shi

Department of Physics and Astronomy, University of California, Riverside, California 92521, USA (Received 12 December 2008; published 24 April 2009) We report a thermoelectric study of graphene in both zero and applied magnetic ﬁelds. As a direct consequence of the pﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ dispersion of massless particles, we ﬁnd that the Seebeck coefﬁcient linear Sxx diverges with 1= jn2D j, where n2D is the carrier density. We observe a very large Nernst signal Sxy ($50 "V=K at 8 T) at the Dirac point, and an oscillatory dependence of both Sxx and Sxy on n2D at low temperatures. Our results underscore the anomalous thermoelectric transport in graphene, which may be used as a highly sensitive probe for impurity bands near the Dirac point.

DOI: 10.1103/PhysRevLett.102.166808 PACS numbers: 73.23.Àb, 72.15.Gd, 72.15.Jf, 73.50.Lw

The unusual band structure of graphene gives rise to a host of intriguing phenomena in electrical transport properties that have been under extensive experimental investigations [1–6]. In solids, both charge and heat ﬂows are simultaneously generated when an electrochemical potential or a temperature gradient is present, leading to additional effects. Fundamentally related to the electrical conductivity, other transport coefﬁcients such as thermal conductivity and thermoelectric coefﬁcients are also determined by the band structure and scattering mechanisms. Thermoelectric coefﬁcients, in particular, involve the energy derivatives of the electrical transport counterparts such as the conductivity ' and the Hall angle ÂH . The anomalies in the latter are very often ampliﬁed and cause markedly distinct features in the former near the Dirac point. Furthermore, in the regime where the Mott relation is applicable, the relationship between the measured electrical conductivity and the Seebeck coefﬁcient reveals how the chemical potential depends on the gate voltage or carrier density, which is dictated by the energy dispersion. Therefore, the thermoelectric transport coefﬁcients can offer unique information and are complementary to the electrical transport coefﬁcients. A number of theoretical predictions have been made on transport coefﬁcients other than electrical conductivities in graphene [7–9] which to date remain experimentally unexplored. Single-layer graphene sheets are mechanically exfoliated onto degenerately doped silicon substrates that are covered with 300 nm of silicon dioxide. After locating suitable graphene sheets, we perform standard electronbeam lithography to attach electrodes in Hall-bar geometry. The electrodes consist of 7 nm of Cr and 100 nm of Au, and also serve as local thermometers. A microfabricated heater located on the right of Fig. 1(a) generates nearly parallel constant temperature contours along the graphene sample. The thermal voltage generated is measured across the two parallel Cr=Au electrodes $20 "m apart. These also double as local thermometers whose resistance is measured by the four-point method. A temperature difference of $10 mK between the two Cr=Au wires can be readily measured for temperature T > 10 K. An additional 0031-9007=09=102(16)=166808(4)

pair of Cr=Au leads is used for transverse (Hall or Nernst) voltage measurements. All measurements were carried out in a cryostat with T ranging from 1.5 to 300 K and magnetic ﬁeld B up to 8 T. In this work, the results are from two representative devices (#1 and #2) out of approximately two dozen fabricated devices. They are singlelayer graphene as determined from optical images, and are often corroborated by the well-deﬁned half-integer quantum Hall effect at low temperature. The carrier mobility "c is typically $3000 cm2 =V s.

(a)

(b) 12

Positive Current Negative Current

Vth ( V)

8

4

0 0.0 0.1

39 V/K

0.2 0.3

T (K)

FIG. 1 (color). (a) SEM image and circuit schematic of a graphene device for thermoelectric measurements. (b) ÁT vs thermovoltage change 4Vth for a series of heater power steps at 255 K and zero gate voltage. The linear ﬁt of this curve gives the thermopower of 39 "V=K.

166808-1

Ó 2009 The American Physical Society

The qﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ dashed lines are the ﬁts described by jSxx j $ 1= jVg À VD j. for a 2D system with a linear dispersion qﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ pﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ relation. Let us assume ' $ j"j . Away from VD on the hole side. 1(b)] [10]. At zero magnetic ﬁeld. Sxx decreases with decreasing Vg . we can conclude that the dispersion relation is linear rather than quadratic. 1=Vth extrapolates to zero at almost the same Vg for different temperatures. 2(b)]. The 16 K data (red circle) were multiplied by a factor of 5. 2(a)]. This region coincides with the minimum in '. similar to the behavior of the previous device. then we expect " ¼ @vF n2D % / Æ jVg À VD j. (c) 1=jVth j vs Vg plot for the same data in (a). From this diverging behavior of Sxx . Green dashed lines are the best power-law ﬁts with exponent $0:95.0 197K (x 10 Vth 12 -2 0. Sxx stays ﬂat on the electron side.13]. Vth undergoes a sign change at the Dirac point Vg ¼ VD ¼ 10 V. 2 (color).(hole-) doped regime. 2(c). indicating a diverging behavior of Sxx . the Dirac point. Clearly. Green dashed lines are straight lines as guides to the eye. qﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ The fact that jVth j or jSxx j diverges as 1= jVg À VD j is actually a direct manifestation of the linear dispersion of the Dirac particles in graphene.5 V ) -2 Fit 1. Not every device shows the electron-hole symmetry shown in Fig. qﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ scaling approximately with 1= jVg À VD j [dashed line in Fig. indicating the carrier type changes from hole to electron as Vg -VD is swept from negative to positive. The shaded area is for jVg À VD j < 10 V. Fitting a straight line to the ÁVth vs ÁT data.PRL 102. 2 (b) 1=Vth vs Vg plot for the same data shown in (a). ' exhibits the characteristic minimum at Vg $ VD . and the straight lines are drawn 2 in the linear region. FIG. which is sufﬁciently general to include both dirty ( $ 2) and clean ( $ 1) limits [12. Vth crosses zero.5 253K 0. the 1=Vth plot shows a better linear relationship with Vg over the whole range. (a) Vth vs Vg for three different temperatures. as is the case in '. Vth has a ﬁnite slope near VD over a 20 V range in Vg which corresponds to $ Æ 100 meV change in chemical potential " measured from the Dirac point. we have Sxx $ pﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ . and hence Sxx $ À1 Vg ÀVD . The dashed lines are the power-law ﬁts with exponent $0:95 and cross zero in the vicinity of the Dirac point from both sides. the same Vth data are also plotted as 1=jVth j vs Vg in Fig. 166808 (2009) PHYSICAL REVIEW LETTERS week ending 24 APRIL 2009 253K 197K 16K Fit We generate a temperature gradient and measure both the temperature difference ÁT and thermal voltage change ÁVth . where the þðÀÞ sign corresponds to the electron. 2. and the 1= jVg À VD j dependence breaks down. Combining Àsgnð"Þ these relations. This makes the thermoelectric transport uniquely sensitive to the electronic band structure. where charged impurities modify the conductivity [11–14]. In contrast. Figure 2(a) shows Vth as a function of Vg for three temperatures. the magnitude of Vth decreases. Figure 3(a) displays Sxx vs Vg of a different device with VD $ 33 V for several values of T ranging from 11 to 255 K. As Vg is further away from VD on both sides. On the other hand. For comparison. In addi2 tion. we expect the Mott relation Sxx ¼ À 3eB @ ln'ð"Þ @" 1 to hold. This Vg dependence is more noticeable in the 2 linear dependence of 1=Vth on Vg [Fig. indicating a strong electron-hole asymmetry as seen 166808-2 . as expected for Dirac particles. but 1=jVth j does not. Note that near the qﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ Dirac point. as denoted by the hatched region. yielding Sxx $ À " for highly doped regimes. in which " / n2D . and vF is the Fermi velocity. This is in contrast jVg ÀVD j (a) 6 3 Vth ( V) 0 3 (k ) 2 1 0 -60 -30 0 30 60 90 Vg (v) x5 -3 -6 -60 -30 0 30 Vg (V) 60 90 (b) 1.0 -60 -30 0 30 60 90 Vg ( V ) (c) V ) | Vth | (x 10 -1 15 12 9 197K 6 3 -1 5 253K 0 -60 -30 0 30 Vg ( V ) 60 90 to the ordinary 2D electron systems with a quadratic dispersion relation. It is worth noting that the exponent is absorbed in the prefactor of Sxx and does not affect the functional dependence of Sxx . For degenerate electron %2 k2 T systems. we extract the Seebeck coefﬁcient Sxx ¼ À ÁVth from the slope ÁT [Fig.

. Sxy is directly proportional @" to the energy derivative of the Hall angle ÂH or inversely proportional to the cyclotron mass mÃ . In relating Vg to n2D for above estimations. In classical transport.to hole-doped regimes. As Vg approaches VD from the hole side. which is in good agreement with the values obtained by others [17]. A value of Cg ¼ 103 aF="m2 is determined from our Hall data. resulting in a nonzero transverse voltage Vy . the magnitude of Sxx is close to zero. In the impurity scattering model.16] near the Dirac point. In ferromagnets. In a magnetic ﬁeld. however. vF ranges from 0. The transverse effect or the Nernst effect is y y measured by Sxy ¼ À jrTj ¼ ÁTx . On the electron side. e. 4(a)]. For massless particles. and the red line is a linear ﬁt. we use C V C " n2D ¼ ge g þ n ¼ eg ðVg À VD Þ. In nonmagnetic metals. we only focus on the relatively low-T region on the hole side where the Mott relation apparently holds. Sxx follows different T dependence for different Vg [in Fig. even at Vg ¼ 60 V (or $30 V right of VD ). For graphene. Furthermore. The departure from the linear T dependence is an indication of the potential breakdown of the Mott relation. The Mott relation only holds if kB T ) 1.8~1. Away from VD on the hole side. Here. It is reasonable to expect high-order corrections in the Sommerfeld expansion at relatively high temperature where the condition j"j ) kB T fails.g. the vanishing cyclotron mass can indeed lead to a %2 k2 TB Sxy Peak ( V / K) (a) Sxy ( V / K) 40 20 0 40 8T (c) 20 0 0 2 4 6 B(T) 8 1T 8 4 0 -4 -8 20 -2 -1 0 n 1 2 11 K 8 4 0 -4 8 0 -8 30 15 0 -15 40 20 0 -20 100 K Sxy ( V / K ) -20 Sxx ( V / K ) 0 (b) G ( e / h) 12 10 8 6 4 2 0 -2 -2 20 40 Vg ( V ) n -1 0 1 2 60 0 -20 40 0 200 K 6 Sxx ( V / K) 3 =6 =6 -40 60 0 -60 -2 -1 0 1 2 255 K 0 -3 2 =2 =2 -6 2 -1 0 1 12 -2 n2D ( x 10 cm ) n FIG. (c) Sxx (black triangle) and Sxy (red circle) vs Landau level index n for four different temperatures at B ¼ 8 T. another relevant energy scale is the bandwidth of impurity states [15. and we attribute it to the unique band structure of graphene. The corresponding Landau level index n is shown on the top axis. we attribute the departure from the linear T dependence on the electron @ ( B ð@ÂH Þ" ¼ 3 @" ½mÃ sgnð"Þ. Near VD .7x10 m/s 50 T (K) 100 6 0V 5V 10V 15V 20V 45V 50V 55V 59V 0 side to the asymmetric nature of the band of impurity states.20]: Sxy ¼ À % B Â 3 e 3 -1 -1 E ÁV -40 0 100 200 300 T (K) FIG. Sxy is negligibly small ( $ 10 nV=K per tesla) [18]. at Vg ¼ 0 V or $33 V left of VD . 166808 (2009) (a) Sxx ( V / K) 60 40 20 0 -20 -40 0 20 PHYSICAL REVIEW LETTERS 11 K 20 K 30 K 40 K 50 K 100 K 200 K 255 K week ending 24 APRIL 2009 40 60 V g (V) ( x10 uV K m ) (b) 80 2 1 0 0 Fit Sxx ( V / K) 40 vF= 0. Sxx remains nonlinear in T except at very low temperatures. we observe a broad transition region in Sxx connecting the electron. carriers diffusing under rT experience the Lorentz force. Since Sxx is proportional to T. For this device. the Mott rela2 k2 T tion takes the following form [7. (b) T dependence of Sxx at different gate voltpﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ ages. we plot pﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ Sxx jn2D j (called ) vs T in the inset of Fig. which ensures ' to be a slow-varying function of energy over this band of impurity states [16]. The slope of the linear ﬁt is proportional to =vF . The inset is the T dependence of ¼ Sxx jn2D j at Vg ¼ 0 V for low temperatures. 3(b)]. Inset: B dependence of Sxy at Vg ¼ VD . (b) Two-terminal conductance G and thermopower Sxx vs carrier density n2D at T ¼ 11 K and B ¼ 8 T. 4 (color). in ' by others [12]. where Cg is the capaci" tance per unit area and n is the induced density by charged impurities at the Dirac point. this band can be highly asymmetric due to the ﬁnite scattering potential. 3 (color). Sxx is nearly a straight line for the whole temperature range. we observe an exceedingly large Nernst peak ($50 "V=K at 8 T) at the Dirac point [Fig. 3(b). and pﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ inversely proportional to " or vF jn2D j. spin-orbit coupling can lead to a large spontaneous Nernst signal [19]. (a) Vg dependence of Nernst signal Sxy at 160 K with different magnetic ﬁelds (1–8 T). For this reason. when jVg À VD j ¼ 30 V. (a) Vg dependence of longitudinal Seebeck coefﬁcient Sxx at different temperatures (11–255 K) and zero magnetic ﬁeld. Sxx begins to deviate from the linear T dependence at progressively lower temperatures. Extracted from the slope.8 to 1:7 Â 106 m=s depending on the value of (from 1 to 2). Near VD . j"j is about 160 meV measured from the Dirac point.PRL 102. Here. 166808-3 .

245411 (2006). Phys. I. however.-L. F. 246803 (2007). Proc. 486 (2000). Rev. M. 4(c)]. and T. P. B 76. B 76. N. Clayhold et al. P.. the relatively large magnitude of Sxx between the LL’s may be caused by the broadened LL’s due to disorders. P. Lett. Peres. S. Q. Obloh. Castro Neto. Phys. Xu et al. At low temperatures and B ¼ 8 T. 166808-4 . 4252 (1994). U. The nonvanishing Sxx was previously attributed to the activated behavior in ordinary 2D electron systems. In graphene devices. 1939 (1984). B. these generic anomalies are somewhat masked near the Dirac point. Rev. A 193. The origin of this feature is unknown. Johnson. B 73. 4(a)]. In this regime.. N. Lett. S. 197403 (2007). 146801 (2005). Nature Phys.. Science 306. Nature Phys. 4. Rev. Proc. Castro Neto et al. 035402 (2007). Lett. 101.. Gusynin and S. the observed Sxx peaks at the LL’s are consistent with the calculations in the integer quantum Hall regime [21]. Nature (London) 438. Science 317. Guinea. the oscillations in Sxx and Sxy become weaker. Sondheimer. 226601 (2004).. Phys. Rev. the device conductance exhibits clear quantum Hall plateaus as Vg is varied. 197 (2005).. 102. N. ÂH is directly proportional to B. Phys. accompanied by an additional small dip (peak) on the hole (electron) side. Tan et al. 95. 096807 (2009). Additionally. 98. pﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ In summary. Vivek Aji. Mod.3]. Indeed. Zuev et al. Y. V. with an estimated slope of $5:4 "V=KÃ T at 160 K. Phys. Lett. W. Girvin. B 73. 104. These peaks (dips) correspond to the LL indices n ¼ 1 and n ¼ 2 for holes (electrons). Sci. However.. Rev. 125411 (2006). Lett. However. Lee et al. With disorders. Phys. This is in very good agreement with the experimentally observed peak value ($50 "V=K). M. P. the characteristic width of the Nernst peak is primarily determined by . Phys. Lett. Novoselov et al. and P. Phys. R. A. We expect to see Sxx ! 0 at low temperatures and the predicted activated behavior at high temperatures in cleaner samples. Girvin and M. The Nernst width remains nearly unchanged as a consequence. Phys. yielding Sxy $ 68 "V=K.. K. 18392 (2007).. S. Sci. Nature (London) 438. Shan-Wen Tsai. Z. B. H. Y. Rev. Pu et al. 166808 (2009) PHYSICAL REVIEW LETTERS week ending 24 APRIL 2009 diverging behavior in Sxy . J. Martin et al. K.. In our samples. Rev. Ploog. As discussed earlier. In higher mobility graphene samples. Stauber. [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] K. Acad. G. Gusynin and S. Y. Novoselov et al. Zhang et al. L1147 (1982). 256801 (2003). although the overall magnitude of both Sxx and the central peak in Sxy increases [Fig. Rev. and J. J. Phys. 193401 (2007). K. Dora and P. 532 (2008)..A. B 29. Rev. J. Phys.. 096802 (2008). acknowledge the support of NSF CAREER No. At T ¼ 11 K. V. Rev. the diverging behavior (jSxx j $ 1= jn2D j) of the Seebeck coefﬁcient along with the exceedingly large Nernst peak at the Dirac point is characteristic of the massless particles in graphene.—During the preparation of this manuscript. 4. W. the anomaly in Sxy depends on the carrier mobility as well as . Similar to Sxx whose diverging behavior is greatly modiﬁed by the disorders. 201 (2005).. 142. B 76. and Vicent Ugarte for many helpful discussions. H94003-07-2-0703. Rev. 101. and the slope of the straight line is $6 "V=KÃ T. and C. F. W. Y.-W.. Kim. L. NSF No. Soc. 1530 (2007). M. Rev. Natl. 073412 (2007). Lofwander and M. T. which is greater than kB T.. Sharapov. the anomalies are expected to be more drastically pronounced. This change in ÂH occurs over $ 204 meV as estimated from the width of the conductance minimum.S. Sxy also changes sign at these ﬁllings. 99. Lopes dos Santos. the n ¼ 1 and n ¼ 2 peaks in Sxx on both electron and hole sides are also expected. H. J. we estimate the magnitude of Sxy at the Dirac point both from ÂH outside this region where the Mott relation holds and from . J. the anomaly is diminished by the impurity states near the Dirac point. In conventional 2D electron systems. E. Z. Li et al. Phys. Fogelstrom. and ONR/DMEA Grant No. In graphene samples. DMR/0748910. B 50. 109 (2009). Authors would like to thank Chandra Varma for suggesting the thermopower study on graphene. Phys. acknowledge the support of DOE DE-FG02-07ER46351 and ONR/ DMEA H94003-07-2-0703. Bolotin et al. Phys. H. Rev. K. we became aware of related work with a similar conclusion from Zuev et al. G. Lett. Perez. we observe oscillations in Sxx [Figs. and the side peaks and dips in Sxy that correlate with the oscillatory structures in Sxx . 4(b) and 4(c)] that are reminiscent of the Shubnikov–de Hass oscillations in &xx [2. Phys. von Klitzing. Peres. Since we have ÂH ¼ À"c Bsgnð"Þ ("c : carrier mobility). P. We expect to see more pronounced anomalous behavior in both Sxx and Sxy in cleaner samples. and A. Y. Z. we obtain ÁÂH $ 2:2 with an 8 T magnetic ﬁeld at 255 K. Recall that the Mott relation breaks down in this region. A. M. 81. 91. the linear B dependence of Sxy is observed [Fig. Note added. 236 (1984). Here. Rev. 117208 (2008). 93.PRL 102. Adam et al. Johnson and S. the diverging behavior can be retrieved from those quantities as the chemical potential approaches the Dirac point. R. Phys. we do not observe vanishing Sxx as " is located between the two adjacent LL’s. 144 (2008). Jiang et al. It is also worth noting that Sxx crosses zero at the Dirac point (in the lowest LL). CBET/0756359. M.. R. H.. Thalmeier. Surf. S. M. S. B. Lett. 666 (2004). but it could reveal some peculiarities of the zeroth LL at high magnetic ﬁelds. and K. 484 (1948). Phys. M. Sxx shows peaks (dips) as " is inside the broadened Landau levels (LL) on the hole (electron) side. As the temperature increases. A.. Sharapov. Rev. Nature (London) 406. Small. [22]. Miao et al. and thank Chris Dames. Rev. M. which indicates a linear B-field dependence in Sxy . C 15.