Insight into the Magnetization Reversal and Exchange Bias in - Ceramics et al. - 2021 - Unknown

《Insight into the Magnetization Reversal and Exchange Bias in - Ceramics et al. - 2021 - Unknown》由会员上传分享，免费在线阅读，更多相关内容在学术论文-天天文库。

pubs.acs.org/JPCCArticleInsightintotheMagnetizationReversalandExchangeBiasinRFe0.5Cr0.5O3CeramicsLiHou,LeiShi,*JiyinZhao,RuixueTong,andYangXinCiteThis:J.Phys.Chem.C2021,125,7950−7958ReadOnlineACCESSMetrics&MoreArticleRecommendationsABSTRACT:TheR-dependentstructuralandmagneticproper-tiesofthedisorderedRFe0.5Cr0.5O3(R=Ce,Pr,Nd,Sm)ceramicsaresystemicallyinvestigated.BasedonthemodelcomposedoftheparamagneticRsublatticeandthecantedantiferromagneticFe/Crsublattice,byestimatingthetemperature-dependentmagnet-izationsofthesamples,itisfoundthatthemomentsofpolarizedPr3+andNd3+areantiparalleltothemomentofFe3+/Cr3+inthecompounds,whichleadstothepresenceofmagnetizationreversal(MR)inNdFe0.5Cr0.5O3orsuppressedMRinPrFe0.5Cr0.5O3duetotheweakanisotropy,respectively.Inaddition,agiantpositive(negative)exchangebias(EB)effectisobserveddistinctlyintheR=Nd(Sm)compounds,whichisattributedtothe“pinningeffect”ofRonFe/Crspinsduetotheantiferromagnetic(ferromagnetic)couplingbetweentheRandFe/Crsublattices.ItissuggestedthatanintrinsiccorrelationexistsbetweentheMRandEBeffectsbecauseofthemagneticinteractionbetweentheRandFe/Crsublattices.ThesignoftheEBfieldisdeterminedbythecompetitionbetweentheZeemanenergyoftheR3+spinsandthecouplingenergybetweenFe/CrandRsublattices.TheseresultscontributetothephysicalmechanismoftheMRandEBeffects,whichareusefulforthepracticalapplicationsofRFe0.5Cr0.5O3ceramics.1.INTRODUCTIONcompensationtemperature(Tcomp)inthefield-cooled18mode.ThisbehaviorcanbeappliedinmagneticdataRare-earthorthoferrites(RFeO3)andorthochromites19recording,nonvolatilemagneticmemoryutilizingthetwo(RCrO3)(Risarare-earthelementofthelanthanideseries)20havebeenintensivelystudiedfordecadesduetotheirdistinctstatesofmagnetization,andspin-resolvingdevices21compellingmagneticproperties,1−5whicharemainlyinducedusingthezeromagnetization.Severalmechanismshavebeenbythecomplex3d−4finteractionsbetweentheFe3+/Cr3+andproposedtounderstandtheMRphenomenonobservedinR3+ions.6−10BothRFeOandRCrOfamiliesshowaweaksomeRFe0.5Cr0.5O3ceramics.Maoetal.supposedthattheMR33ferromagnetic(WFM)stateascribedtothecantedanti-observedinYFe0.5Cr0.5O3isresultedfromthecompetitionferromagnetic(AFM)interactionintheFe3+andCr3+betweenthesingle-ionmagneticanisotropy(SIMA)andtheDownloadedviaUNIVOFPRINCEEDWARDISLANDonMay16,2021at07:03:28(UTC).20Seehttps://pubs.acs.org/sharingguidelinesforoptionsonhowtolegitimatelysharepublishedarticles.sublattices,respectively.TheAFMNeeltemperaturéTN1antisymmetricDzyaloshinsky−Moriya(DM)interaction.(620−740K)11,12originatedfromtheFe3+−O2−−Fe3+super-However,Dasarietal.arguedthattheMRinYFeCrO1−xx3exchangeinteractionismuchhigherthanthatforCr3+ionswithx=0.5complieswithamodelcomprisingtheisotropic(110−300K).13ThemomentsofR3+ionsareorderedat22super-exchangeandtheDMinteractions.Besides,Boraand11,13cryogenictemperatureTN2.Recently,severalstrikingRavistudiedtheMRinLaCr1−xFexO3withx≤0.5andfoundpropertieswereobservedinthemixedorthochromite−thattheMRforalowFeconcentrationisduetotheorthoferrite(RFe0.5Cr0.5O3)ceramics,includingthemagneto-paramagnetic(PM)behaviorofthedopedFeionsunderthe1415caloriceffect,negativethermalexpansion,andmagneto-influenceofanegativeinternalfieldarisingfromtheAFM16,17electriceffect,whichcreatedanupsurgeofresearchonorderedCr3+ions,butforx=0.45and0.50,thecompetitionRFe0.5Cr0.5O3ceramics.ItisobviousthatdifferentcationicbetweenSIMAandDMinteractionsisimportant.23Mean-mixturesmayinducenewpropertiesandthusmakecomprehensionoftherelatedmechanismmoredifficult.However,adeepunderstandingoftherelatedmagneticReceived:January21,2021interactionsisimportantforbothphysicaltheoryandpracticalRevised:March16,2021applications.Published:April6,2021Magnetizationreversal(MR),oneofthemostwidelystudiedphenomenainRFeO3andRCrO3,isaphenomenoninwhichthenetmagnetizationchangesitssignata©2021AmericanChemicalSocietyhttps://doi.org/10.1021/acs.jpcc.1c005627950J.Phys.Chem.C2021,125,7950−7958

1TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure1.(a)XRDpatterns(left)andenlargedviewofXRDpatternsintherangeof2θ=32.1−33.5°(right)forRFe0.5Cr0.5O3(R=Ce,Pr,Nd,Sm)ceramics;(b)RietveldrefinedresultsoftheXRDpatternforCeFe0.5Cr0.5O3;(c)Rdependenceofthelatticeconstantsa,b,andc;(d)RamanspectraoftheRFe0.5Cr0.5O3(R=Ce,Pr,Nd,Sm)ceramics.Table1.StructuralParametersObtainedfromtheRietveldRefinementoftheRoom-TemperatureXRDPatternsforRFe0.5Cr0.5O3(R=Ce,Pr,Nd,Sm)CompoundsparametersR=CeR=PrR=NdR=SmcrystalstructureorthogonalorthogonalorthogonalorthogonalspacegroupPbnmPbnmPbnmPbnma(Å)5.4995(2)5.4667(1)5.4364(1)5.3834(1)b(Å)5.5181(1)5.5239(1)5.5329(1)5.5475(1)c(Å)7.7695(2)7.7501(2)7.7284(1)7.6767(1)volume(Å3)235.78(1)234.03(1)232.46(1)229.26(0)R(x,y,z)−0.0061(2),0.0324(1),0.25−0.0063(2),0.0387(1),0.25−0.0092(1),0.0443(1),0.25−0.0125(1),0.0541(1),0.25U(Å2),Occ.0.73(2),0.51.19(2),0.51.22(2),0.51.51(2),0.5isoFe(x,y,z)0.5,0.0,0.00.5,0.0,0.00.5,0.0,0.00.5,0.0,0.0U(Å2),Occ.0.62(2),0.25(0)0.71(2),0.25(0)0.61(2),0.24(0)1.17(2),0.24(0)isoCr(x,y,z)0.5,0.0,0.00.5,0.0,0.00.5,0.0,0.00.5,0.0,0.0U(Å2),Occ.0.62(2),0.25(1)0.71(2),0.25(0)0.61(2),0.26(0)1.17(2),0.26(0)isoO1(x,y,z)0.0877(13),0.4939(11),0.250.0801(16),0.4900(9),0.250.0882(12),0.4872(8),0.250.0952(10),0.4776(8),0.25U(Å2),Occ.0.33(18),0.50.18(11),0.51.28(12),0.51.91(11),0.5isoO2(x,y,z)0.7175(12),0.2908(11),0.7096(9),0.2939(8),0.7094(8),0.2977(7),0.7032(6),0.2955(6),0.0336(6)0.0420(7)0.0401(5)0.0415(4)U(Å2),Occ.0.36(11),1.00.20(7),1.00.44(7),1.00.65(7),1.0isoRp,Rwp,Rexp,RB,RF7.04,9.85,6.45,1.86,1.155.60,7.82,6.26,1.40,1.015.78,7.79,6.34,1.72,1.216.52,8.79,6.46,2.02,1.45χ22.331.561.511.8518,25,29while,Yinetal.foundthattheMRinRFe0.5Cr0.5O3couldbeces.However,theoriginoftheEBeffectinthesesingle-ascribedtothedifferenttemperaturedependencesofthenetphasematerialsisstillanopenissue.momentMofR3+andFe3+ionsintheFe-richclustersandTogetaninsightintothenatureoftheR-dependentR−FetheMofR3+andCr3+intheCr-richclusters.24OnthemagneticbehaviorinRFeCrOceramics,inthismanu-R−Cr0.50.53otherhand,recently,Fitaetal.observedtheexchange-biasscript,aseriesofRFe0.5Cr0.5O3compoundswithR=PMions(EB)effectassociatedwithMRinLuFe0.5Cr0.5O3thatresulted(Ce,Pr,Nd,Sm)weresynthesizedbythesolid-statereactionfromthecompetitionofvariousDMinteractionsbetweenFe3+method,andtheirstructuralandstrikingmagneticproperties,3+25includingtheMRandEBeffects,weresystemicallyandCrions.TheEBeffectistheshiftofthehysteresisloopalongthefieldaxisafterfieldcoolingfromabovetheNeeĺinvestigated.BasedonamodelcomprisingthePMRsublattice26temperature,whichhasbeenobservedinRFeO3andRCrO3andthecantedAFMFe/Crsublattice,byestimatingthe27,28withspontaneousMR.Materialswiththecoexistenceofmagneticbehaviorofallofthesamples,theinternalinteractionMRandEBeffectsofferpotentialapplicationsinmakingisanalyzedindetail.Itisfoundthatthereisanintrinsicthermallyassistedmagneticrandomaccessmemories,correlationbetweentheMRandEBeffects.ThesignoftheEBthermomagneticswitches,andothermultifunctionaldevi-fieldisdeterminedbythecompetitionbetweentheZeeman7951https://doi.org/10.1021/acs.jpcc.1c00562J.Phys.Chem.C2021,125,7950−7958

2TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure2.XPSspectraof(a)R3d;(b)Fe2p;and(c)Cr2pfortheRFe0.5Cr0.5O3(R=Ce,Pr,Nd,Sm)ceramics.energyoftheR3+spinsandthecouplingenergybetweenthewhichisinaccordancewiththeratioofthenominalmaterials.Fe/CrandRsublattices.Noobviousrock-saltorderingofFe3+/Cr3+ionsasthatexistinginanordereddoubleperovskiteisobservedinthe2.EXPERIMENTALSECTIONRFe0.5Cr0.5O3samples,whichisconsistentwiththeresults15,30previouslyreported.Additionally,toillustrateclearlytheThepolycrystallineRFe0.5Cr0.5O3(R=Ce,Pr,Nd,Sm)differenceinthediffractionpatterns,theXRDpatternsintheceramicswerepreparedbythesolid-statereactionmethod.rangeof2θ=32.1−33.5°areenlarged,asshowninFigure1aThestoichiometricamountsofrare-earthoxide(Pr6O11,(right),wherethemainpeaknear32.4°inR=CeissplitintoNd2O3,Sm2O3),ironoxide(Fe2O3),andchromicoxidethreepeaks((020),(112),and(200))inR=Sm,anda(Cr2O3)wererepeatedlygroundandsinteredat900,1000,significantshiftofthepeaksisobserved.Thelatticeconstantsand1100°Cinairfor24h,respectively.Theproductswerea,b,andcobtainedbyRietveldrefinementaresummarizedinpressedintopelletsandfinallysinteredat1200°Cfor24hto3+Figure1c.ItisfoundthatthelatticeconstantbincreaseswithobtainRFe0.5Cr0.5O3(R=Pr,Nd,Sm)ceramics.SinceCedecreaseintheR3+ionicradiusfrom1.01Å(Ce3+ion),0.99ÅionsareeasilyoxidizedintoCe4+ions,thereducediron(Fe)(Pr3+ion),0.983Å(Nd3+ion)to0.958Å(Sm3+ion),31asandchromium(Cr)wereusedasstartingmaterialsforR=Ceindicatedbytheleft-shiftedpeak(020)inthesamplesfromRceramics,besidesceriumoxide(CeO2)andFe2O3andCr2O3=CetoSm.Meanwhile,bothconstantsaandcdecreasepowders,andthentheirmixturewaswellgroundandpressed3+linearlywithdecreaseintheRionicradius,asindicatedbyintopellets.Afterthat,thewell-crystallizedCeFe0.5Cr0.5O3wastheright-shiftedpeaks(112)and(200)inthesamplesfromRobtainedbysinteringat1000°Cfor4daysinanevacuated=CetoSm.Themonotonicdecreaseisrelatedtotheandsealedquartztube,followedbyquenchingtoroom11,32increasedstructuraldistortioninRFe0.5Cr0.5O3.temperature.TheRamanspectraoftheRFe0.5Cr0.5O3(R=Ce,Pr,Nd,Thephasecompositionsandstructuresofthecompounds−1Sm)ceramicsweremeasuredintherangeof50−900cm,aswerecharacterizedusingX-raydiffraction(XRD,RigakushowninFigure1d,toreflectthestructuraldistortionSmartLab)withCuKα(λ=1.54187Å)radiation.Theexplicitly.ItcanbeclearlyseenthatthevibrationmodesatRamanspectrainthebackscatteringgeometryweremeasured−1+200−500cmshifttohigherwavenumbers,indicatingthatonaJYLABRAMHRRamanspectroscopewithanAr(∼532thetiltanglesoftheFe/CrO6octahedronincreasewithnmline)laserastheexcitationlightsource.Thevalencestates3+decreaseintheRionicradius,asobservedintheparentoftheelementswereinvestigatedbyX-rayphotoelectron33,34RFeO3andRCrO3ceramics.Thevibrationmodeatspectroscopy(XPS,ESCALAB25Xi,Thermo).Themagnetic−1around700cminallsampleswasattributedtothein-planemeasurementswereperformedwithaSuperconductingsymmetricoxygenbreathingmode(S)ofFeO6/CrO6QuantumInterferenceDevice(SQUID)(10K≤T≤300octahedra,whichisduetotheorbital-mediatedelectron−K,−5T≤H≤5T).phononcoupling,asthatobservedinotherRCr0.5Fe0.5O335,36compounds.ItcanbefoundthattheSmodeshiftstoa3.RESULTSANDDISCUSSIONlowerwavenumber(redshift)withthelanthanidesubstitutionTheXRDpatternsoftheRFe0.5Cr0.5O3(R=Ce,Pr,Nd,Sm)fromCetoSm,whichcanbeattributedtotheaveragebond-ceramicsareshowninFigure1a(left).Meanwhile,toconfirmlengthincreaseofFe/Cr−OinRFe0.5Cr0.5O3duetothe3+37thepurityofthesamples,theXRDpatternsforallofthedecreaseintheRionicradius,indicatingtheincreasedsamplesweresimulatedbytheRietveldmethodandthelatticedistortion.representativeresultforR=CeisshowninFigure1b.TheToconfirmthevalencestateofmagneticions(R,FeandcrystalstructureparametersandreliabilityfactorsobtainedCr),theXPSmeasurementsoftheRFe0.5Cr0.5O3(R=Ce,Pr,fromXRDrefinementforallofthesamplesarelistedinTableNd,Sm)ceramicswerecarriedout.TheR3dcore-level1.FromtheXRDfittingresults,itisconfirmedthatthespectraofallofthesamplesareshowninFigure2a,whichRFe0.5Cr0.5O3(R=Ce,Pr,Nd,Sm)ceramicsarecrystallizedcomprisetwowell-separatedspin-orbitsplitpeaksR3d5/2andwithaGdFeO3-typedistortedperovskitestructureofanR3d3/2ataround1083.1and1110.2eVforR=Sm,982andorthogonalspacegroupPbnmandwithoutanyimpurities.The1004.5eVforR=Nd,933.5and953.5eVforR=Pr,andFeandCratomsarerandomlydistributedinthe4b(0.5,0,0)881.2,885.5,899.5,and903.9eVforR=Ce,respectively,sitewithoccupanciesofapproximately0.25,respectively,correspondingtotheSm3+,38Nd3+,39Pr3+,16andCe3+ions.407952https://doi.org/10.1021/acs.jpcc.1c00562J.Phys.Chem.C2021,125,7950−7958

3TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure3.ZFC,FCC,andFCWmagnetizationsM(T)oftheRFe0.5Cr0.5O3ceramicsunderamagneticfieldof100Oe:(a)R=Ce;(b)R=Pr;(c)R=Nd;and(d)R=Sm.Meanwhile,thespectraoftheFe2p3/2corelevelforallthemagnetizationM(T)appearsatatemperatureofaround150samples(seeinFigure2b)canbefittedwellwithtwoK,accompaniedbyalargethermo-magneticirreversibilitydistinctivepeakscorrespondingtotheFe2+andFe3+ionswithbetweentheFCCandFCWprocesses.Theabruptdropin40bindingenergiesof710.1and711.5eV,respectively.ItisM(T)canbeattributedtoaspin-reorientation(SR)transitionobservedthatthearearatiooftheFe2+/Fe3+peaksisalmostfromΓtoΓ,asobservedintheparentceramicsCeFeO.41413unchangedwithmainlyFe3+ions,indicatingtheprominenceofForR=Prsample(seeinFigure3b),anabnormalnegativeFe3+inallofthesamples.Inaddition,thecore-levelXPSCr2pmagnetizationisobservedintheZFCmode.Thenegativespectra(Figure2c)canbefittedwellwithtwoCr2pcoremagnetizationisalsofoundintheZFCM(T)curveofR=Nd,levels(2p3/2and2p1/2)andonesatellitepeakusingtheasshowninFigure3c,whichissimilartothatobservedintheGaussian−Lorentzianfunctionat576.5,586.2,and587.1eV,FCM(T)oftheNdFe0.5Cr0.5O3ceramicsunderasmall42respectively.Thisdoubletseparationof9.7eVsuggeststhatCrmagneticfield(0.38Oe),indicatingthatthenegativeZFC16ionsexistinthe+3oxidationstate.TheFeandCrionsaremagnetizationpossiblyresultedfromthesmallresidualpredominantlytrivalent,verifyingthatthemajorityoftheFemagnetismintheSQUID,asrevealedbytheexperiments.InandCratomsaredistributedinadisorderedmanner.addition,thereversalofmagnetizationfrompositivetoThemagneticcharacteristicsforallofthesampleswerenegativeunderFCCandFCWmodes,i.e.,MR,isfoundininvestigatedwithasuperconductingquantuminterferencetheR=Ndsample,showingazeromagnetizationatthedevice(SQUID).Thetemperature-dependentzero-field-cool-compensationtemperatureTcomp=18K.Besides,forR=Sm,ing(ZFC),field-cooled-cooling(FCC),andfield-cooled-asshowninFigure3d,themagnetizationexhibitsasharpwarming(FCW)magnetizationsM(T)oftheRFe0.5Cr0.5O3increasebelow50K.(R=Ce,Pr,Nd,Sm)ceramicsunderafieldof100OeareTheMRphenomenonhasbeenobservedindifferentshowninFigure3.Itcanbefoundthatthemagneticbehaviormagneticmetaloxides,including(a)thepolycrystalline4344oftheRFe0.5Cr0.5O3compoundsishighlydependentontheCo2VO4andCo2TiO4spinels,whichisexplainedbytheR3+cations.AsshownintheinsetofFigure3,theFe3+/Cr3+antiparallelmomentsofFMCo2+attheAsiteandCo2+/V4+atmomentsorderatTN=274,238,252,and242KforR=Ce,theBsite;(b)RFe0.5Cr0.5O3withR=non-magneticions(La,Pr,NdandSmsamples,respectively,indicatingthatthecantedY,andLu),whosemagnetismismainlyoriginatedfromtheAFMorderedtemperaturedecreaseswithdecreaseintheR3+cantedAFMsublatticesofFe/Cr−O−Fe/Cr;theobservedionicradiusduetothestrengthenedstructuraldistortion,asMRisattributedtothecompetitionbetweentheSIMA/revealedbyXRDandRamananalysis,exceptforR=Prisotropicsuper-exchangeandtheDMinteractionofFe/Cr−20,22,23,25sample,whichmaybeattributedtothepresenceofalocallyO−Fe/Cr;(c)perovskiteRFeO3andRCrO3ceramicsorderedFe−O−CrarrangementinthePrFe0.5Cr0.5O3samplewithR=PMions,forwhichtheobservedMRisascribedtoandtheFMinteractionscausedbythesuper-exchangetheantiparallelorderingamongthecantedAFMFe/CrandinteractionofFe3+−O2−−Cr3+(e2−O−e0).16BelowNeeĺPMRsublattices.9,45Besides,someextrinsicreasonshavealsoggtemperature,themagnetizationM(T)increasesgraduallywithbeensuggestedfortheMR,suchasthecore−shellstructure,46,47decreaseinthetemperature,whichiscausedbytheWFMthemagneticimpurities,andsampleinhomogeneities.InmomentduetotheantisymmetricDMinteraction-inducedthiswork,anattempttofittheM(T)dataofthesamplestothespincantingofthedominantlydisorderedFe3+/Cr3+ions.ForcompetitionbetweentheSIMAandtheDMinteraction23wasR=Cesample,asshowninFigure3a,itisclearlyobservedunsuccessful,whichcanbeattributedtotheeffectofthePMthatasthetemperaturedecreases,anabruptdropinmomentsofR3+ionsabovethetemperatureTintheN27953https://doi.org/10.1021/acs.jpcc.1c00562J.Phys.Chem.C2021,125,7950−7958

4TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure4.ModifiedCurie−WeissfittotheFCmagnetizationoftheRFe0.5Cr0.5O3ceramicsfor(a)R=Ce;(b)R=Pr;(c)R=Nd;and(d)R=Sm.RFe0.5Cr0.5O3(R=Ce,Pr,Nd,Sm)samples.Infact,thePMisobserved.Theseresultsindicatethatasecond-orderSRR3+ionsexperienceaneffectivemolecularfieldoriginatedfromtransitionfromΓ4toΓ2possiblyexistedintheR=Pr,NdandtheneighboringorderedcantedAFMFe/Crsublattice.Smsamples.Therefore,skinningtotheferrimagneticRFeO3andRCrO3Inaddition,thevalueoftheCurie−WeisstemperatureΘisceramics,theobservednetmagnetizationoftheRFe0.5Cr0.5O3negativeforallofthesamples,signifyingtheAFMnatureofcompoundscanbeestimatedbythemodifiedCurie−WeisstheR3+ions.ThesmallestvaluesofMandHarefoundinFe/CrI18equationasfollowsR=Ce(1.5emu/moland288Oe,respectively),asshowninFigure4a,whichareclosetozeroduetotheformationoftheM=+MCHHRI()+EcollinearAFMΓ1stateoftheFe3+/Cr3+ionsatlowFe/CrT−Θtemperature.ThemagnitudeofMFe/CrdecreaseswiththedecreasingradiusofR3+ionsfortheremainingsampleswhereMFe/Crisaconstantrelatedtothespontaneous(−123.5,64.5,and19.9emu/molforR=Pr,Nd,andSm,magnetizationoftheFe/Crsublattice(whenastablelong-3+3+respectively),whichisattributedtotheweakenedFe/Cr−rangemagneticorderintheFe/Crsublatticehasbeen2−3+3+3+O−Fe/Crsuper-exchangeinteractionsduetotheformed),CRistheCurieconstantoftheRions,HIanddecreaseoftheFe3+/Cr3+−O2−−Fe3+/Cr3+anglecausedbyHEaretheinternal(duetotheFe/Crsublatticeordering)andthelatticedistortion.Besides,fortheR=CeandSmsamples,externalmagneticfields,respectively,andΘistheCurie−Weisstemperature.bothMFe/CrandHIarepositive(Figure4a,d),indicatingthat3+theinternalfieldoftheFe/CrsublatticeisinthesameToconfirmtheeffectofdifferentPMRionsonthemagneticproperty,themeasuredM(T)dataintheFCWmodedirectionastheWFMmomentMFe/Crthatisparalleltotheappliedmagneticfield.Asaresult,noMRappearsintheR=forallofthesamplesarefittedbytheabove-mentionedequation,asshowninFigure4.ItcanbefoundfromthefigureCeandSmsamples.Onthecontrary,thesignsofMFe/CrandthatexceptfortheR=Cesample,theM(T)dataintheFCWHIfortheR=PrandNdsamplesareopposite(Figure4b,c),modeforalloftheremainingsamplesatlowtemperaturecanwhichrevealstheoppositeinternalfieldoftheFe/Crsublatticebefittedwellwithagoodnessoffit(R2)closeto1.FortheR=totheWFMmomentMFe/Cr.Specifically,forR=Prsample,itCesample,thedeviationoftheR2valuefrom1canbeisclearlyfoundthattheWFMmomentMFe/CrisantiparalleltoattributedtothedominationofthecollinearAFMinteractiontheappliedmagneticfield,whiletheinternalfieldimposedby3+3+theorderedFe3+/Cr3+ionsonthePMPr3+ionsisparalleltoamongtheFe/CrionsduetotheSRtransitionfromtheWFMΓ4toAFMΓ1stateatlowtemperature.Besides,atheappliedmagneticfieldandshowsthelargestvalueofHI.ThepositivemagneticmomentofthepolarizedPr3+ionsbifurcationisclearlyobservedbetweenthefittedandmeasuredcurvesabovethetemperatureTb≈100KforR=Prand50KsurpassesthenegativemomentoftheFe/Crsublattice,leadingforR=Nd,Sm,respectively,indicatingthatanadditionaltotheincreaseofthepositivenetmagnetizationwithdecreasemagnetictransitionmayappearintheFe/CrsublatticeatinthetemperatureintheFCmode.ForR=NdintheFCaboveTb.ItisnoticedthattheM(T)curveisalmostlinearinmode,theWFMmomentMFe/Crisparalleltotheappliedmagneticfield,whilethemomentofthepolarizedNd3+ionsisthetemperaturerangeTb

5TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure5.Field-cooledM−HcurvesoftheRFe0.5Cr0.5O3ceramicsat10Kfor(a)R=Ce;(b)R=Pr;(c)R=Nd;and(d)R=Sm(thecoolingfieldis5kOe).magneticpolarizationoftheNdsublatticeexactlycancelstheNdandSm(seeFigure5c,d),suggestingtheexistenceoftheFMcontributionoftheFe/Crsublattice.Asawhole,theEBeffectintheR=NdandSmcompounds.TheEBfieldisinducedFe/Cr-andR-sublatticemagnetizationscanbeeithercalculatedbytherelationH=(H++H−)/2,42andis1453EBparallelorantiparallelduetothe3d−4finteraction.However,and−21871OefortheR=NdandSmsamples,respectively.althoughtheantiparallelmagnetizationoftheFe/CrandRItisworthnotingthat,differentfromtheEBobservedinthe27,28sublatticeshasbeenobservedinbothR=PrandNdsamples,literature,thegiantEBeffectcanstillbeobservedintheRthephenomenonofMRonlyappearsinR=Nd.Itisnoticed=SmsamplewithoutMR.thattheoppositeWFMmomentMFe/CrtotheexternalfieldisIngeneral,apinnedFMcomponentisveryimportantforonlyobservedintheR=Prsample,indicatingtheexistenceoftheEBorigin,leadingthenecessitytoidentifytheFM50theweakmagneticanisotropy.Fromthesepoints,itcanbecontributioninthematerials.ForthetraditionalEBinFM/inducedthattwobasicconditionsareneededsimultaneouslyAFMinterfacialsystems,theHEBisdeterminedbythe51forthepresenceofMR.Oneisthecoexistenceofatleasttwofollowingformulamagneticsublattices(orclusters)withanantiparallelorderingshowingdifferenttemperaturedependencesofthesiteJINTHEB=≥,withKtAFMAFMJINTmoments.TheotheroneisthemomentsfromdifferentMtFMFMmagneticsublattices(orclusters)coupledunderastrongmagneticanisotropy.Otherwise,thenetmagnetizationoftheHere,theJINTistheinterfacecouplingconstant,MFMisthesamplewillrotatealongtheappliedfieldwithouttheMRmagnetizationofthepinnedFMlayer,tFMisthethicknessofoccurring,asobservedintheR=Prsample.theFMlayer,andtAFMandKAFMarethethicknessandOntheotherhand,theEBeffectisusuallyassociatedwithanisotropyoftheAFMlayer,respectively.TheEBfieldHEBistheexchangecouplingattheinterfacesbetweentheFMandinverselyproportionaltothemagnetizationofthepinnedFMAFMcomponents,whichismanifestedbyashiftinthelayer.Infact,thecollinearAFMinteractionintheFe/CrhysteresisloopalongthefieldaxiswhenthesystemiscooledsublatticeatalowtemperatureintheR=Cesampleviolates26,48,49downunderanexternalmagneticfield.InordertotheconditionfortheEBeffect(needforanFMcomponent).investigatetheEBeffectinRFe0.5Cr0.5O3,thefield-cooledFortheremainingsamples,itcanbefoundthatthefittingisothermalmagnetichysteresisloops(M−Hloops)at10KvalueofWFMmagnetizationfortheFe/Crsublatticeincreasesweremeasuredintherangeof−50and+50kOeaftertheintheorderR=Sm

6TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFortheR=Prsample,thevalueofHI(JINT)istoolargetoFe/CrandRsublattices,thechangesinthesignoftheEBfieldmeetthecondition(JINT≤KAFMtAFM)forEB,leadingtoanwithtemperaturecanalsobeattributedtothecompetitionbetweenthetemperature-dependentZeemanenergyoftheR3+effectivereductioninthemagneticanisotropyofthematerial.ThemomentofthesamplerotatesalongthedirectionofthespinsandthecouplingenergybetweentheFe/CrandRappliedfieldandnoloopshiftcanbeobserved.sublattices.Fromanotherperspective,justasthatintheFromtheseresults,itcanbeconcludedthattheEBeffectintraditionalEBeffectobservedforanFM/AFMmultilayerRFe0.5Cr0.5O3(R=PMions)isascribedtothetwointeractingsystem,anAFMcouplingisnecessarytoshowapositiveEB56magneticsublattices,wheretheWFMmomentinducedbytheeffect.Accordingly,inthematerialsexhibitingapositiveEBcantedAFMFe/CrsublatticeplaystheroleofthepinnedFMeffect,theWFMspinsoftheFe/CrsublatticeareantiparallelcomponentandtheFMorAFMcouplingbetweentheRandtotheinternalfieldHIduetotheAFMcoupling,whichwillFe/CrsublatticesisananalogoftheinterfacialexchangecausethemagnetizationtoreversewhenthecouplingenergydominatestheZeemanenergyoftheFe3+/Cr3+spinsinteraction.Inotherwords,theEBeffectinRFe0.5Cr0.5O3(R=PMions)isoriginatedfromthe“pinningeffect”ofRonthe(HFe/Cr‑Zeeman=HcoolMFe/Cr).Fe/Crsublattice.However,themagnitudeoftheinternalcouplingHI(JINT)shouldbemoderate.Forexample,neither4.CONCLUSIONSMRnorEBbehaviorisshowninPrCrO3ceramics,butbothInsummary,theR-dependentstructuralandmagneticMRandEBcanbeobtainedbyreplacingPr3+ionswith3+3+9,52properties,includingtheMRandEBeffects,inthedisorderednonmagneticrareearthions,suchasLaandYions,RFe0.5Cr0.5O3(R=Ce,Pr,Nd,Sm)ceramicsaresystemicallywhichcanbeattributedtothedecreaseoftheR-ionicmagnetic3+3+investigated.BasedonamodelcomprisingthePMRfunctionontheB-siteCrions(HI).Besides,itisnotedthatsublatticeandthecantedAFMFe/Crsublattice,byestimatingtheEBfieldHEBispositiveinR=Ndwhileitisnegativeinthethetemperature-dependentmagnetizationofallofthesamples,R=Smsample,whichwillbediscussedbelow.3+3+itisfoundthatthemomentsofpolarizedPrandNdionsBasedontheaboveanalysis,itcanbefoundthattheMR3+3+areantiparalleltothemomentofFe/Crinthecompounds,andEBphenomenaonlycoexistinRFe27,280.5Cr0.5O3(andRFeO3whichresultsintheMRintheFCmodeinNdFe0.5Cr0.5O3,orRCrO)withFe3+/Cr3+inthecantedAFMspin3buttheweakanisotropyleadstotheabsenceofMRinconfigurationoftheΓ4orΓ2state,whichindicatesthattherePrFe0.5Cr0.5O3.Inaddition,theEBeffectisobservedobviouslymaybeanintrinsiccorrelationbetweenthem.Ononehand,intheR=NdandSmcompounds,whichisattributedtothetheEBeffectcanbeobservedinalmostalloftheferrimagnetic27pinningeffectofRontheFe/CrsublatticeduetothematerialsthatexhibitMR,suchasRFeO3(R=Nd,Sm,Er),interactionbetweentheRandFe/Crsublattices.Itis28,53,54RCrO3(R=Ce,Gd,Tm),andRFe0.5Cr0.5O3(R=Ndsuggestedthatthereisanintrinsiccorrelationbetweenthe5525inthiswork,Y,Lu).Inthesematerials,thenegativetwophenomenaofMRandEBthroughthemagneticmagnetizationappearsbelowTcompwiththepositiveEBfieldinteractionbetweentheRandFe/Crsublattices.ThesignofandthepositivemagnetizationaboveTcompisaccompaniedbytheEBfieldisascribedtothecompetitionbetweenthethenegativeEBfield.Ontheotherhand,MRisobservedwithZeemanenergyoftheR3+spinsandthecouplingenergythepositiveEBfieldinRFe0.5Cr0.5O3withR=Nd,butbetweentheFe/CrandRsublattices.TheseresultscontributeunobservedwiththenegativeEBfieldintheR=Smsample.tothepracticalapplicationsandphysicaltheoryofCombiningwiththeobservationoftheEBeffectinother13RFe0.5Cr0.5O3ceramics.similarseries,itissuggestedthattheMRappearsonlyinthematerialsshowingpositiveEB.Theseinterrelatedphenomena■areapprehensibleandreasonable.Asabovementioned,theAUTHORINFORMATIONpresenceofMRneedsanantiparallelorderingoftwoCorrespondingAuthorsublatticeswithdifferentvaluesandtemperaturedependences.LeiShi−HefeiNationalLaboratoryforPhysicalSciencesatAsobservedfortheR=Ndsample,theWFMmomentoftheMicroscale,UniversityofScienceandTechnologyofChina,Fe/CrsublatticeisparalleltotheexternalfieldandtheHefei,Anhui230026,People’sRepublicofChina;interactionbetweentheFe/CrandRsublatticesisorcid.org/0000-0002-0947-6617;Phone:+86551antiferromagnetic.Whenthesamplesarecooledto10K63607924;Email:shil@ustc.edu.cn;Fax:+86551underalargeenoughexternalfieldHcool,thespinsofthePM63602803R3+ionsareparalleltoHduetotheZeemanenergyofthecool3+AuthorsRspins(HR‑Zeeman=HcoolMR)beingbiggerthanthecouplingenergy(HINT=JINTSFa/CrSR)betweentheFe/CrandRLiHou−HefeiNationalLaboratoryforPhysicalSciencesatsublattices.Asaresult,whentheexternalfieldisreversedat10Microscale,UniversityofScienceandTechnologyofChina,K,theWFMspinsoftheFe3+/Cr3+ionswillstarttorotateinaHefei,Anhui230026,People’sRepublicofChinasmallerfield,duetotheAFMinteractionwiththespinsoftheJiyinZhao−HefeiNationalLaboratoryforPhysicalSciencesPMR3+ions,whichexertatorqueinthesamedirectionastheatMicroscale,UniversityofScienceandTechnologyoffield,givingapositiveEBfield(asthatintheR=Ndsample).China,Hefei,Anhui230026,People’sRepublicofChinaHowever,forthematerialswithoutMR,theinteractionRuixueTong−HefeiNationalLaboratoryforPhysicalSciencesatMicroscale,UniversityofScienceandTechnologybetweentheFe/CrandRsublatticesisferromagneticandthespinsofthePMR3+ionsarealsointhesamedirectionasofChina,Hefei,Anhui230026,People’sRepublicofChinaYangXin−HefeiNationalLaboratoryforPhysicalSciencesatHcool.Then,theWFMspinswillstarttorotateunderalargerfield,duetotheFMinteractionwiththespinsofthePMR3+Microscale,UniversityofScienceandTechnologyofChina,Hefei,Anhui230026,People’sRepublicofChinaionsexertingatorqueintheoppositedirectionofthefield,givinganegativeEBfield(asthatintheR=Smsample).InCompletecontactinformationisavailableat:thematerialsshowingMRwiththeAFMcouplingbetweenthehttps://pubs.acs.org/10.1021/acs.jpcc.1c005627956https://doi.org/10.1021/acs.jpcc.1c00562J.Phys.Chem.C2021,125,7950−7958

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