材料期刊网

反相微乳液合成单分散的四方形SnO2纳米晶

余长林 , 周晚琴 , 杨凯 , 李立清 , CHAO Fang-Fang , LI Xin

无机材料学报 doi:10.3724/SP.J.1077.2010.10282

通过设计反相微乳液反应体系,在水热条件下缓慢氧化SnF2,合成了单分散的四方形SnO2纳米晶.利用X射线多晶粉末衍射、扫描电镜、高分辩透射电镜对合成样品的形貌和结构进行了表征.实验结果表明,通过控制油胺的添加量调控微乳液水相的pH值,可以对SnO2的形貌进行调控.使用适当量的油胺,可以获得分散性极好、大小为10 nm左右的规则四方SnO2纳米晶.合适的pH值有利于晶核的定向生长,从而在微乳液反应器中形成了规则的SnO2四方纳米晶.

关键词: 反相微乳液 , 四方SnO2纳米晶 , 油胺 , 水热

New criteria of glass forming ability, thermal stability and characteristic temperatures for various bulk metallic glass systems

Materials Science and Engineering a-Structural Materials Properties Microstructure and Processing

Six mathematical criteria used for quantitatively measuring their glass forming ability, thermal stability and characteristic temperatures (temperature of glass transition T-g, crystallization onset T-x and liquidus T-l) of various bulk metallic glasses (BMGs) have been proposed in this article. It is found that the criteria are suitable for evaluating these quantities for BMGs. The estimated results are better than those calculated by Fang et al.'s models and Lu et al.'s gamma criterion, but our analyses indicate that these criteria, defined by the data (Pauling electronegativity xi, atomic radius ri, electron concentration ni and melting temperature T-mi) easily found in literatures, still need to be further refined in future research for shortcomings of the parameters. (C) 2007 Elsevier B.V. All rights reserved.

关键词: bulk metallic glasses;glass forming ability;thermal stability;supercooled liquid regions;mechanical-properties;amorphous-alloys;transition temperature;bond parameters;strength;binary;widths;ag

ATOMIC FORCE MICROSCOPY OBSERVATION OF MAGNETRON SPUTTERED ALUMINUM-SILICON ALLOY FILMS

金属学报(英文版)

粒裕希停桑谩。疲希遥茫拧。停桑茫遥希樱茫希校佟。希拢樱牛遥郑粒裕桑希巍。希啤。停粒牵危牛裕遥希巍。樱校眨裕裕牛遥牛摹。粒蹋眨停桑危眨停樱桑蹋桑茫希巍。粒蹋蹋希佟。疲桑蹋停?##2##3##4##5ATOMICFORCEMICROSCOPYOBSERVATIONOFMAGNETRONSPUTTEREDALUMINUM-SILICONALLOYFILMSJ.W.Wu,J.H.FangandZ.H.Lu(NationalLaboratoryofMoleculeandBiomoleculeElectronics,SoutheastUniversity,Nanjing210096,ChinaManuscriptreceived27October1995)Abstrcat:Twodifferentsurfacemorphologycharacteristicsofmagnetronsputteredaluminumsilicon(Al-Si)alloyfilmsdepositedat0and200℃wereobservedbyatomicforcemicroscopy(AFM).Oneisirregularlyshapedgrainsputtogtheronaplane.TheotherisirregularlyshapedgrainsPiledupinspace.Nanometer-sizedparticleswithheightsfrom1.6to2.9nmwerefirstobserved.Onthebasisoftheseobservationsthegrowthmechanismofmagnetronsputteredfilmsisdiscussed.Keywords:magnetronsputtering,Al-Sialloy,surfacemorphology,atomicforcemicroscopy,filmgrowthmechanism1.IntroductionTheuseofaluminumalloys[1,2],inparticularAl-Si,isacommonfeatureinmanysinglelevelandmultilevelinterconnectionschemesadoptedinthemanufactureofmicroelectronicdevicesbecauseofseveraldesirableproperties.TheAl-Sigrainmorphology(size.geometryanddistributionofgrainsisassociatedwithstepcoverage[3],electromigration[4]andinterconnectsresistivity[5]etc..Thus,characterizationofAl-Sialloysurfacemorphologyisveryimportant,especiallywhenintegratedintensityincreasesandlinewidthsof0.3to0.5μmbecomecommon.Inthepasttwentyyears,theAl-Sialloysurfacemorphologywhichaffectsthereliabilityofmicroelectronicdeviceshasbeenwidelyinvestigatedbyscanningelectronmicroscopy(SEM),transmissionelectronmicroscopy(TEM)etc.[5-7].However,SEMandTEMhavetheirlimitationorinconvenience,forexample,theverticalresolutionofSEMisnothighandTEMneedscomplexsamplepreparation.Recently,anewgrainboundaryetchingmethodwasproposed￣[8]whichalsoneedstroublesomechemicaletching.Atomicforcemicroscopy(AFM),sinceitsemerging,hasbecomemoreandmoreusefulinphysics,chemistry,materialsscienceandsurfacescience,becauseofitshighresolution,easeofsamplepreparationandrealsurfacetopography.Recently,discussion[9,10]waspresentedonhowAFMwillplayaroleinsemiconductorindustry.Asaresponsetothisdiscussion,weusedAFMtoinvestigateAl-SialloysurfacemorphologyandhaveobtainedsomeresultswhichcannotberevealedbySEMorTEM.ThisindicatesthatAFMisagoodcharacterizationtoolinsemiconductorindustry.2.SamplePreparationInourexperiments,aluminumwith30ppmsiliconwassputteredonsiliconsubstrateinbatchdepositionmodeAllthreefilmswiththicknessof1.6μmweredepositedusinganargonsputteringpressureof4.2×10￣-3Pa.TheotherdepositionparametersaredescribedinTable1.Thesubstratewascleanedusingstandardpremetallizationcleaningtechniquespriortofilmdeposition.3.ExperimentalResultsandDiscussionTheAFMmeasurementswereperformedonacommercialsystem(NanoscopeIII,DigitalInstruments,SantaBarbara).Thetipismadeofmicrofabricatedsiliconnitride(Si_3N_4)Itisattachedtoa200μmcantileverwithaforceconstantofabout0.12N/m.Beforethesurfaceofsamplewasexamined.agoodtipwithananometer-sizedprotrusionatitsendwasselectedbeforehand,whichcanbeobtainedbyimagingtheatomicstructureofmicasubstrateandagoldgrid.AtypicaloperatingforcebetweenthetipandAl-Sisamplesurfaceisoftheorderof10￣-8Nandallimagesweretakenatroomtemperatureinair.AtypicaltopographicviewoftheAl-SifilmsisshowninFig.1(allimagescansizeis5by5μma,bandcarerespectivelyforsample1,2,and3).FromFig.la,itcanbeseenthatirregularlyshapedgrainstiltinginvaryingdegreespileupinspace,andgroovesamongtheirregularlyshapedgrainsaredifficulttodecideatacertainarea(wedefineitascharacteristicA).Toourknowledge,onreportsonthesurfacemorphologyhavebeenpresentedbefore.InFig1b,however,irregularlyshapedgrainsassembleonaPlaneandgroovesamongtheirregularlyshapedgrainsareeasytodecide(wedefineitascharacteristicB),whichisinagreementwithmanypreviousreports[5-7].InFig.1c,bothcharacteristicA(arrowA)andcharacteristicB(arrowB)wereobserved.IndoingAFMexperiments,weselectedfivedifferentscanareastobeimagedforeachsampleandfoundthatallimagesofeachsamplearerespectivelysimilartoFig.1a,bandc.Also,wenotedthatthesurfaceofinFig.1a.WethinkthatdepositionparameterswillinfluenceAl-Sisurfacemorphology,andthetiltedgrainsmaybesusceptibletomicrocracking.Byreducingthescansizeareato2by2μm(Fig.2aandb).Weobtainedmanyidenticalresultsasdescribedabove,suchasirregularlyshapedgrainsetc.Forthefirsttime,wefoundnanometersizedparticlesonirregularlyshapedgrainsurfacewhichcannotberevealedbySEMbecausethediameterofthesenanoparticlesisabout10nmandtheheightofthesenanoparticlesisintherangeof1.6to2.9nm.Inimaging,wenotedthatrotatingthescandirectionandchangingthescanfrequencydidnotaffectthestructureofthesegrainsasshowninFig.2aandb,rulingoutthepossibilitythatscanninginfluencedtheshapeoftheseparticlesorcausedsomesimilarimagingartifacts.Also,wenotedthatthenanoparticleswerenotobservedontheslopesofthegrooves(Fig.2aandb).Thisphenomenoncanbeexplainedasfollows:thepotentialenergyattheslopeislargerthanthatelsewhere,sotheparticlesseemmorelikelytobedepositedontheseareaswithlowerpotentialenergy.Fig.2c,scansize250by250nm,isazoomtopographicimage(whiteoutlineinb).Itshowsunevendistributionofthenanoparticles.Andtheheightdifferenceofthenanoparticlesindicatesdifferentgrowingspeed.Wethinkbasedonthemorphologyofnanoparticles,thattheheightdifferenceandunevendistributionofthesenanoparticlesshowdifferentgrowingadvantageandindicatethatatomshaveenoughenergytomovetoasuitablegrowingspot.Theenergymaybefromthefollowingsources:surfacetemperaturefluctuation,stressdifferenceorcollisionbetweenhighspeedsputteredatoms.Thesenanoparticlesgoongrowingandformmanyirregularlyshapedgrains.AndtheseirregularlyshapedgrainsfurtherconnecteachotheraccordingtocharacteristicAorB,finallyformingtheAl-Sisurfacemorphology.4.ConclusionWecandrawthefollowingconclusionsfromtheabove.First,theexperimentalresultsshowedthatAFMisapowerfultooltoinvestigatethedetailsofAl-Sisurfacemorphologywhichcangreatlyenrichourknowledgeofthefilmgrowthmechanism.Second,depositionconditionsplayanimportantroleindeterminingtheAl-Sisurfacemorphology.Third,thetwoAl-Sisurfacemorphologycharacteristicsarethatirregularlyshapedgrainsassembleonaplaneandirregularlyshapedgrainstiltinginvaryingdegreespileupinspace.Fourth,forthefirsttime,nanoparticleswereobservedonirregularlyshapedgrainsurfacewhichsuggestedthatthefilmgrowthmechanismwasbyinhomogeneousnucleation.Acknowledgements-BeneficialdiscussionswereheldwithDr.ZhenandMr.Zhu.ThisworkwaspartiallysupportedbytheNationalNaturalScienceFoundationofChina.RFFERENCES｜｜1D.pramanikandA.N.Saxena,SolidStateTechnol.26(1983)127.2D.pramanikandA.N.Saxena,SolidStateTechnol.26(1983)131.3D.pramanikandA.N.Saxena,SolidStateTechnol.33(1990)73.4S.S.IyerandC.Y.Worg,J.Appl.phys.57(1985)4594.5J.F.Smith,SolidStateTechnol.27(1984)135.6D.GerthandD.Katzer,ThinSolidFilm208(1992)67.7R.J.WilsonandB.L.Weiss,ThinSolidFilm207(1991)291.8E.G.Solley,J.H.Linn,R.W.BelcherandM.G.Shlepr,SolidStateTechnol33(1990)409I.SmithandRHowland,SolidStateTechnol.33(1990)53.10L.Peters,SemiconductorInternational16(1993)62.##61D.pramanikandA.N.Saxena,SolidStateTechnol.26(1983)127.2D.pramanikandA.N.Saxena,SolidStateTechnol.26(1983)131.3D.pramanikandA.N.Saxena,SolidStateTechnol.33(1990)73.4S.S.IyerandC.Y.Worg,J.Appl.phys.57(1985)4594.5J.F.Smith,SolidStateTechnol.27(1984)135.6D.GerthandD.Katzer,ThinSolidFilm208(1992)67.7R.J.WilsonandB.L.Weiss,ThinSolidFilm207(1991)291.8E.G.Solley,J.H.Linn,R.W.BelcherandM.G.Shlepr,SolidStateTechnol33(1990)409I.SmithandRHowland,SolidStateTechnol.33(1990)53.10L.Peters,SemiconductorInternational16(1993)62.##A##BATOMIC FORCE MICROSCOPY OBSERVATION OF MAGNETRON SPUTTERED ALUMINUM-SILICON ALLOY FILMS$$$$J.W.Wu,J.H. Fang and Z.H.Lu (National Laboratory of Molecule and Biomolecule Electronics,Southeast University,Nanjing 210096, China Manuscript received 27 October 1995)Abstrcat:Two different surface morphology characteristics of magnetron sputtered aluminumsilicon(Al-Si)alloy films deposited at 0 and 200℃ were observed by atomic force microscopy(AFM).One is irregularly shaped grains put togther on a plane.The other is irregularly shaped grains Piled up in space. Nanometer-sized particles with heights from 1.6 to 2.9 nm were first observed. On the basis of these observations the growth mechanism of magnetron sputtered films is discussed.

关键词: :magnetron sputtering , null , null , null , null