Physical Review Letters 92, 047002 (2004) Gap Structure of the Spin-Triplet Superconductor Sr RuO 2 4 Determined from the Field-Orientation Dependence of Specific Heat K. Deguchi,1,∗ Z. Q. Mao,1,† H. Yaguchi,1 and Y. Maeno1,2 1Department of Physics, Graduate School of Science, Kyoto University, Kyoto 606-8502, Japan 4 2Kyoto University International Innovation Center, Kyoto 606-8501, Japan 0 (Dated: February 2, 2008) 0 2 Wereportthefield-orientationdependentspecificheatofthespin-tripletsuperconductorSr2RuO4 underthemagneticfieldalignedparalleltotheRuO2planeswithhighaccuracy. Belowabout0.3K, n striking4-foldoscillations ofthedensityofstatesreflectingthesuperconductinggap structurehave a been resolved for the first time. Wealso obtained strong evidence of multi-band superconductivity J andconcludedthatthesuperconductinggapintheactiveband,responsibleforthesuperconducting 0 instability, is modulated with a minimum along the[100] direction. 3 PACSnumbers: 74.70.Pq,74.25.Bt,74.25.Op,74.25.Dw ] n o c Sincethediscoveryofitssuperconductivity[1],thelay- ture inthe active bandis currentlyof prime importance. - ered ruthenate Sr RuO has attracted a keen interest The field-orientation dependent specific heat is a direct r 2 4 p in the physics community [2]. The superconductivity of measure of the QP density of states (DOS) and thus a u Sr RuO has pronounced unconventional features such powerfulprobeoftheSCgapstructure[25,26,27,28]. In 2 4 s as: the invariance of the spin susceptibility across its this Letter, we report high precision experiments of the . at superconducting (SC) transition temperature Tc [3, 4], specific heatas a function of the angle betweenthe crys- m appearance of spontaneous internal field [5], evidence tallographic axes and the magnetic field H within the for two-component order parameter [6] and absence of a RuO plane. We reveal that the SC state of Sr RuO - 2 2 4 d Hebel-Slichterpeak[7]. Thesefeaturesarecoherentlyun- has a band-dependent gap and that the gap of its active n derstood in terms of spin-triplet superconductivity with SCbandhasstrongin-planeanisotropywithaminimum o the vector order parameter d(k) = zˆ∆ (k +ik ), rep- along the [100] direction, as illustrated in Fig. 1. c 0 x y [ resenting the spin state Sz = 0 and the orbital wave Single crystals of Sr RuO were grown by a floating- 2 4 3 function with Lz =+1, called a chiral p-wave state. zone method in an infrared image furnace [29]. After v The above vector order parameter leads to the gap specific-heatmeasurementsontwocrystalstoconfirmthe 6 ∆(k) = ∆0(kx2 + ky2)1/2, which is isotropic because of reproducibilityof salientcharacteristicssuchasa double 6 the quasi-two dimensionality of the Fermi surface con- SC transition [30], the sample with T = 1.48 K, close c 3 sisting of three cylindrical sheets [8]. However, a num- to the estimated value for an impurity and defect free 1 ber of experimental results [9, 10, 11, 12, 13] revealed specimen (T = 1.50 K) [31], was chosen for detailed 1 c0 3 the power-law temperature dependence of quasiparticle study. This crystal was cut and cleaved from the sin- 0 (QP) excitations, which suggest lines of nodes or node- / likestructuresintheSCgap. Therehavebeenmanythe- t a oreticalattempts(anisotropicp-waveorf-wavestates)to m resolvethiscontroversy[14,15,16,17,18,19]. Although - all these models suggest a substantial gap anisotropy, d magnetothermalconductivitymeasurementswiththeap- n o plied field rotated within the RuO2 plane down to 0.35 c K revealed little anisotropy [20, 21]. To explain those : experimental facts as well as the mechanism of the spin- v i tripletsuperconductivity,severaltheories[22,23],taking X the orbital dependent superconductivity (ODS) into ac- r count [24], have been proposed. In these models, there a are active and passive bands to the superconductivity: the SC instability originatesfromthe activebandwith a large gap amplitude; pair hopping across active to pas- sive bands leads to a small gap in the passive bands. FIG.1: Left: Electronicspecificheatdividedbytemperature The gap structure with horizontal lines of nodes [22] or Ce/T for H k [100], as a function of field strength and tem- strong in-plane anisotropy [23] in the passive bands was perature. AcontourplotisshownonthebottomH−T plane, proposed. with the same color scale as the 3D plot. Right: Supercon- In order to identify the mechanism of the spin-triplet ductinggapstructurefortheactivebandγ deducedfromthe superconductivity, the determination of the gap struc- presentstudy,correspondingtod(k)=zˆ∆0(sinakx+isinaky). 2 gle crystalline rod, to a size of 2.8 × 4.8 mm2 in the ab-plane and 0.50 mm along the c-axis. The side of the crystal was intentionally misaligned from the [110] axis by 16◦. The field-orientation dependence of the specific heat was measured by a relaxation method with a dilu- tionrefrigerator. Sinceaslightfieldmisalignmentcauses 2-fold anisotropy of the specific heat due to the large H anisotropy (H /H ≈20) [30], the rotation of c2 c2kab c2kc the field H within the RuO plane with high accuracy 2 is very important. For this experiment, we built a mea- surementsystemconsistingoftwoorthogonallyarranged SC magnets [32] to control the polar angle of the field H. The twoSCmagnetsareinstalledinadewarseating on a mechanical rotating stage to control the azimuthal angle. Withthedilutionrefrigeratorfixed,wecanrotate FIG.2: (a),(b)FieldandtemperaturedependenceofCe/T of the field H continuously within the RuO plane with a Sr2RuO4 in magnetic fieldsparallel to the[100] (open circle) 2 and [110] (closed circle) directions. misalignment no greater than 0.01◦ from the plane. TheelectronicspecificheatC underthein-planemag- e ponent in the raw data guarantees that the in-plane netic fields was obtainedafter subtractionof the phonon field alignment is accurate during the azimuthal-angle contributionwithaDebyetemperatureof410K.Theleft rotation. Thus C (T,H,φ) can be decomposed into panel of Fig. 1 shows C /T for the [100] field direction, e e φ-independent and 4-fold oscillatory terms, where the asafunctionoffieldandtemperature. Thefigureiscon- in-plane azimuthal field angle φ is defined from the structed fromdata involving13 temperature-sweeps and [100] direction: C (T,H,φ) = C (T,H)+ C (T,H,φ). 11field-sweeps. Atlowtemperaturesinzerofield,power- e 0 4 C (T,H,φ)/C isthenormalizedangularvariationterm, law temperature dependence of C /T ∝T was observed, 4 N e corresponding to the QPs excited from the line nodes or node-like structure in the gap. Now we focus on the field dependence of C /T at low e temperature shown in Fig. 1 and Fig. 2 (a). C /T in- e creases sharply up to about 0.15 T and then gradually for higher fields. This unusual shoulder is naturally ex- plained by the presence of two kinds of gaps [9]. On the basisofthedifferentorbitalcharactersofthethreeFermi surfaces (α,β, and γ) [8], the gap amplitudes ∆ and αβ ∆ are expected to be significantly different [24]. The γ normalized DOS of those bands are Nαβ = 0.43 and Ntotal Nγ = 0.57 [2]. Since the position of the shoulder in Ntotal C /T corresponds well with the partial DOS of the α e and β bands, we conclude that the active band which has a robust SC gap in fields is the γ-band, mainly de- rived from the in-plane d orbital of Ru 4d electrons. xy Figures 2 (a) and (b) show the field and temperature dependence of C /T under the in-plane magnetic fields e H k [100] and H k [110] and indicate the existence of a slight in-plane anisotropy. Inthemixedstate,theQPenergyspectrumisaffected by the Doppler shift δω = ~k·v , where v is the su- s s perfluid velocity around the vortices and ~k is the QP momentum. This energy shift gives rise to a finite DOS at the Fermi level in the case of δω ≥ ∆(k) [34]. Since v ⊥ H, δω = 0 for k k H. Thus the generation of s nodal QPs is suppressed for H k nodal directions and FIG.3: Thein-planefield-orientation dependenceof normal- yields minima in Ce/T [25, 26, 27]. ized4-foldcomponentofthespecificheatatseveralfieldsand Figure 3 shows the field-orientationdependence of the temperatures. Only1.45 Tdata is reduced to1/3. Thesolid specific heat. The absence of a 2-fold oscillatory com- lines are fits with f4(φ) given in thetext. 3 where C is the electronic specific heat in the normal matethecontributionof∆C /γ T fromtheactiveband N e N c state: C = γ T with γ = 37.8 mJ/K2mol. There for the gap structures #1 and #2: ∆C /γ T = (1.22 N N N e N c is no discernible angular variation in the normal state to 1.07)× 0.57 = 0.70 to 0.61 with the gap minimum (µ H = 1.7 T > µ H ); possibilities of angular varia- (∆ /∆ = 1/2 to 1/4) [16], while ∆C /γ T = 0 0 c2 min max e N c tionoriginatingfromexperimentalsetuporotherextrin- 0.75×0.57 = 0.42 with the line nodes [17]. From the sic contributions are excluded. experimental result ∆C /γ T = 0.73 in Fig. 1 and the e N c For fields near H (1.2 T ≤ µ H ≤ 1.45 T), a si- estimatedadditionalcontributionfromthepassivebands c2 0 nusoidal 4-fold angular variation is observed : C4(φ) ∝ ∆Ce/γNTc ∼ 0.04 [23], d(k) = zˆ∆0(sinakx + isinaky) f (φ) = −cos4φ. This is consistent with the in-plane si- with the gap minimum is promising for the active band. 4 nusoidalanisotropyofH withthemaximuminthe[110] To facilitate a comparison with theories, although c2 direction [21, 33]: C = Hc2k[110]−Hc2k[100]dCeHcos4φ. they are presently available only for line-node gaps [26, 4 Hc2k[110]+Hc2k[100] dH 27], we decomposed C into two parts: C (T,0) due Since H decreases with increasing T, the oscillation e 0 c2 to the thermally excited QPs and ∆C (T,H) due to amplitude at 1.3 T increases strongly at 0.51 K. For 0 the field induced QPs, consisting of an isotropic com- µ H < 1.2 T, however, a non-sinusoidal 4-fold angular 0 ponent and a 4-fold anisotropic component A (T,H): variation approximated as C (φ) ∝ f (φ) = 2|sin2φ|−1 4 4 4 C (T,H,φ)=C (T,0)+∆C (T,H)[1+A (T,H)f (φ)], is observed. Importantly, a phase inversion in C (φ) oc- e 0 0 4 4 4 A (T,H)f (φ) = C4(T,H,φ), where f was defined pre- curs across about µ0H = 1.2 T: C4(φ) takes minima at 4 4 ∆C0(T,H) 4 φ= πn(φ= π+πn,n: integer)forµ H <1.2T(µ H ≥ viously for low- and high-field ranges. Figures 4 (a) 2 4 2 0 0 1.2 T), and thus the angular variation for µ H < 1.2 T and (b) show the field and temperature dependence of 0 cannot be due to the in-plane Hc2 anisotropy. Therefore A4. The field dependence of A4 with a maximum of 4% we conclude that the non-sinusoidal 4-fold oscillations anisotropy at 0.31 K shows a monotone decrease from originate from the SC gap structure. This result does the delocalized-QP dominant region at low fields to the not contradictthe previous measurementsof the magne- Hc2-anisotropydominantregionathighfields. The tem- tothermal conductivity down to 0.35 K [20, 21], which perature dependence of A4 with 3% anisotropy at 0.9 reported little in-plane anisotropy, because these clear T showsasmoothdecreasewithincreasingtemperature. oscillations emerge only at lower T (T/T ≤0.2). Theseresultsareinsemi-quantitativeagreementwithre- c cent theories [26, 27] which predict 4 to 1.5% anisotropy For the field range 0.15 T < µ H < 1.2 T, where the 0 from gap structures with vertical line nodes. QPs in the active band γ are the dominant source of in- In contrastto the theoretical prediction [27], however, plane anisotropy,we first deduce the existence of a node at combined low fields (µ H ≤ 0.15 T) and low tem- or gap minimum along the [100] direction, because C 0 e peratures (T ≤ 0.3 K) where QPs on both the active takes a minimum. In addition, we found that the 4-fold and passive bands are important for the anisotropy, A oscillationshaveanon-sinusoidal form, approximatedas 4 rapidlydecreases. ThissteepreductionofA isprimarily C (φ) ∝ 2|sin2φ|−1, since cusp-like features are clearly 4 4 seen at the minima (φ = πn). Strong k dependence of attributable to the non-zero gap minima ∆min of the ac- 2 z tiveγ band(#1). Infact,atthelowesttemperaturesthe the gapfunction wouldenhance the QP excitations even if H is parallel to the nodal direction, so that the cusp- 4-fold oscillations are suppressed below a threshold field like features would have been strongly suppressed [25]. Most of the proposed gap structures can be classi- fied into four groups as summarized in Table I. #1 and #2 provide the direction of the gap minima con- sistent with our observation. To distinguish between #1 with gap minima and #2 with nodes, we examine the specific heat jump ∆C /γ T at T in zero field. e N c c The jump originates mainly from the active band with large ∆ because of ∆C /γ T ∝ ∂∆2/∂T| . We esti- e N c Tc TABLE I: The classified order parameters with the typical gap structures for Sr2RuO4. # d(k) direction of node or ∆min Ref. 132 zˆzˆ∆∆zˆ0∆0((k0sx2kinx−akkykx(y2k)+x(ki+xsini+kayik)kyy)) [1[[011001]00]]tinnnooyddgeeassp [[[111786]]] uF4-aIfGtoel.dd4af:rnoim(sao)tt,rho(epbyfi)tAtFi4niegilndttoahntehdseptoeecsmcifiiplclearhtaoetaruytr.edTadhteaepipennodiFneitngs.cae3r,eowfevhtaihllee- 4 (cid:26) zˆ∆zˆ∆0(0kkxz+(kxik+y)ickoys)c2kz horizontal nodes [19] tHhekli[n10e0s]firnomFigt.he2.dTiffweoremnceethiondCseyibeledtwcoeennsisHtenkt r[e1s1u0l]tsa.nd 4 of about 0.3 T, which should correspond to δω = ∆ . min However, even at 0.15 T below the threshold, increasing temperature leads to an increase in A only up to about 4 ∗ Electronic address: [email protected] 0.25 K (Fig. 4 (b)). This behavior is at least in part ex- † Presentaddress: PhysicsDepartment,TulaneUniversity, plainedbyincluding contributionsofbothfieldandtem- 2001 Percival Stern,New Orleans, LA 70118, USA. perature in the QP excitations, but a more quantitative [1] Y. Maeno et al.,Nature(London) 372, 532 (1994). theoreticalanalysisis needed to examine this possibility. [2] A.P.MackenzieandY.Maeno,Rev.Mod.Phys.75,657 (2003) and thereferences therein. [3] K. Ishida et al., Nature (London) 396, 658 (1998); K. Let us finally discuss the roles of the passive bands in Ishida et al., Phys.Rev.B 63, 060507(R) (2001). the oscillations in Ce. While the present experimental [4] J.A. Duffyet al.,Phys. Rev.Lett. 85, 5412 (2000). study has resolved the directions of gap minima in the [5] G.M. Luke et al., Nature(London) 394, 558 (1998). γ band, there still remain two types of possibilities for [6] P.G. Kealey et al.,Phys. Rev.Lett. 84, 6094 (2000). the passive bands α and β to account for the power-law [7] K. 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Jpn. 71, 404 For the required nodal structure of the passive bands, (2002); Y. Yanase and M. Ogata, ibid. 72, 673 (2003); the presentresults maycontaindecisive informationand Y. Yanase et al.,Physics Reports 387, 1 (2003). call for a more quantitative theoretical work to enable [24] D.F. Agterberg et al.,Phys. Rev.Lett.78, 3374 (1997). the full assignment of the gap structures in all bands. [25] I. Vekhteret al., Phys.Rev.B 59, R9023 (1999). [26] H.WonandK.Maki,Europhys.Lett.56,729(2001);H. Won and K. Maki, cond-mat/0004105. We thank N. Kikugawa, K. Machida, T. Nomura, H. [27] P. Miranovi´c et al.,Phys. Rev.B 68, 052501 (2003). Ikeda, Kosaku Yamada, T. Ohmi, M. Sigrist, K. Ishida, [28] T. Park et al.,Phys. Rev.Lett.90, 177001 (2003). A.P.Mackenzie,S.A.Grigera,K.Maki,andT.Ishiguro [29] Z.Q. Mao et al., Mat. Res. Bull. 35, 1813 (2000). [30] K.Deguchiet al.,J.Phys.Soc.Jpn.71,2839 (2002); H. for stimulating discussions and comments. This work Yaguchi et al.,Phys. Rev.B 66, 214514 (2002). wasinpartsupportedbytheGrants-in-AidforScientific [31] A.P. Mackenzie et al., Phys. Rev. Lett. 80, 161 (1998); Research from JSPS and MEXT of Japan, by a CREST Z.Q. Mao et al., Phys.Rev.B 60, 610 (1999). grant from JST, and by the 21COE program “Center [32] Cryomagnetics,inc.,“VectorMagnet”allowingahorizon- for Diversity and Universality in Physics” from MEXT talfieldofupto5Tandaverticalfieldofupto3T.The of Japan. K. D. has been supported by JSPS Research details of the apparatus is described in : K. Deguchi, T. Fellowship for Young Scientists. Ishiguro, and Y. Maeno, cond-mat/0311587. 5 [33] Z.Q. Mao et al.,Phys.Rev. Lett.84, 991 (2000). [34] G.E. Volovik, JETP Lett. 58, 469 (1993).