PhysRevB_77_094402

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EvolutionofelectronicstatesinRCoO3(R=rareearth):HeatcapacitymeasurementsMakotoTachibana,1TakahiroYoshida,2HitoshiKawaji,2TooruAtake,2andEijiTakayama-Muromachi31ICYS,NationalInstituteforMaterialsScience,Namiki1-1,Tsukuba,Ibaraki305-0044,Japan

2MaterialsandStructuresLaboratory,TokyoInstituteofTechnology,4259Nagatsuta-cho,Midori-ku,Yokohama226-8503,Japan

3AdvancedNanoMaterialsLaboratory,NationalInstituteforMaterialsScience,Namiki1-1,Tsukuba,Ibaraki305-0044,Japan

͑Received22November2007;revisedmanuscriptreceived11January2008;published5March2008͒

TheelectronicphasediagramofRCoO3

͑R=rare-earth͒perovskiteshasbeenmappedoutthroughhigh-

pressuresynthesisandheatcapacity͑Cp

͒measurements.IncontrasttoR=Lawherethespin-statetransition

andinsulator-metaltransitioneachshowsabroadCpanomaly,theseanomaliesmergeintoalargeCppeakforsmallerR.Adetailedstructuralstudyemployingsynchrotronx-raypowderdiffractionshowsthattheonsettemperatureforthespin-statetransitioniscorrelatedwiththe␴*-bondingegbandwidth.ApossiblescenarioonthespinstateisprovidedtoexplaintheCpanomalyandphasediagram.

DOI:10.1103/PhysRevB.77.094402PACSnumber͑s͒:75.30.Wx,65.40.Ba,71.30.ϩh,75.40.Cx

I.INTRODUCTIONThenatureofspin-stateandinsulator-metal͑IM͒transi-tionsinperovskiteRCoO3,whereRisatrivalentrareearth,remainsoneofthemostintriguingproblemsposedbytran-sitionmetaloxides.Inadditiontotheintricateinterplaybe-tweencharge,spin,andorbitaldegreesoffreedom,whichisacharacteristicofstronglycorrelatedoxides,thecobaltatesshowthermalexcitationsofspinstates.Asaresult,interpre-tationoftheelectronicphenomenarequiressomeassump-tionsonthespinstate,whileidentifyingthespinstatere-quiresdetailedandpreciseunderstandingoftheelectronicphenomena.Thispredicamenthasresultedinlong-standingcontroversy,thehistoryofwhichgoesbacktothe1950s͑Ref.1͒andstillcontinuestoday.InRCoO3,thegroundstateofthelocalizedCo3+ionsisthenonmagneticS=0thatcor-respondstothelow-spin͑LS͒t2g6eg0configuration.Asthecrystal-fieldsplitting⌬CFbetweenthet2gandegstatesisonlyslightlylargerthantheHundcouplingenergy,thesystemcanbethermallyexcitedtoeitherahigh-spin͑HS͒͑S=2;t2g4eg2͒oranintermediate-spin͑IS͒͑S=1;t2g5eg1͒con-figuration.ForR=La,whichhasthelargestionicradiusamongtherareearth͑seeFig.1͒,thesignaturefortheonsetofspin-statetransitionatTonsetϳ35Kisseeninthemag-neticsusceptibility,2–4heatcapacity,3,5andthermalexpansion.4Identifyingtheexcitedstateisdifficult,however,sincetheanalysisrequiresvariousassumptionsondegen-eracy,spin-orbitcoupling,andactivationenergy.Within-creasingtemperatureT,themagneticsusceptibilityfirstshowsabroadpeakatϳ100K.2–4Thispeakisnotaccom-paniedbyanomalyinotherthermodynamicmeasurements,3,4implyingthatthespin-statetransitionisassociatedwithther-malexcitationsandnotaphasetransition.Around530K,thephasetransitiontoametallicphaseismarkedbydistinctanomalyinthemagneticsusceptibility,4,6resistivity,7heatcapacity,5andthermalexpansion.6Followingtheresultsofband-structurecalculations,8anumberofstudiessupportedtheISstateasthefirstexcited-spinstate,withtheIMtran-sitionpossiblyaccompaniedbyadditionaltransitiontotheHSstate.6,9However,thisscenarioisnotconsistentwithsomeexperiments,mostnotablytheelectronspinresonance10andheatcapacity.3Aseriesofrecentstudies3,11,12showedthataconsistentpicturecanbeachievedbyexcitationstoatriplydegenerateHSstate,wheretheac-tivationenergyincreaseswithincreasingHSpopulation.Withinthispicture,thesystemisinaninhomogeneousmixed-spinstateatroomtemperature,possiblytransformingtoanISstateabovetheIMtransition.3,13SubstitutionofsmallerRforR=Laincreasesthecoopera-tiverotationsofthecorner-sharingCoO6octahedra,reducing

theCo-O-CobondanglesandthebandwidthofCo͑3d͒-O͑2p͒interactions.Thisfeatureoftheperovskitestructuresuggeststhatbetterunderstandingofthespin-stateandIMtransitionsmaybeachievedthroughsystematicstud-iesasafunctionoftheionicradiusofR͑rR͒.Indeed,an

1.051.11.151.2020040060080010001010.210.410.610.8

T(K)

rR(Å)

LaPrNdSmEuGdTbDyYHoErTmYbLuW-1(arb.units)

Nonmagneticinsulator

Paramagneticinsulator

ParamagneticmetalTIM(Cp)

Tonset(χ)

RCoO3

TIM(ρ)

FIG.1.TheelectronicphasediagramforRCoO3asafunctionoftheionicradiusR͑rR

͒.Thesolidsquaresaretheonsettempera-

turesforthespin-statetransitiondeterminedfrommagneticsuscep-tibility.SourcesareR=La,Pr,andNd͑Ref.2͒,R=Eu͑Ref.14͒,andR=YandLu͑Ref.15͒.TheopensquaresaretheinverseofbandwidthW−1,obtainedfromthestructuralparameters.Theopen

andfilledcirclesrepresenttheinsulator-metaltransitiontempera-turesdeterminedfromheatcapacity͓R=La͑Ref.5͒;others,thisstudy͔andresistivity͑Ref.16͒,respectively.ThelattermaydependonsamplequalityasTIM͑␳͒ϳTIM͑Cp