Journal of Applied Physics
Using the full potential linearized augmented plane wave method based on the spin density functional theory, we investigate the ferromagnetic properties, the electronic structure, and the formation energy of Ga(0.9375)M(0.0625)N (M=vacancy, Ca). The calculations indicate that both cases prefer ferromagnetic ground state. The magnetic moments mainly come from the N atoms surrounding the defect centers, which are different from the conventional diluted magnetic semiconductor. High formation energy for the Ga vacancy Suggests that the defect concentration is too low to result in the ferromagnetic GaN. The formation energy for the two substitutional (Ca(Ga),Ca(N)) and two interstitial sites (tetrahedral T, Ca(i-T) and octahedral O, Ca(i-O)) doped configurations indicates that Ca prefers the substitutional Ga in GaN. The defect concentrations for the Ga(0.9375)Ca(0.0625)N under thermal equilibrium N-rich and N-realistic growth conditions are also discussed, respectively. The calculations show that defect concentration under N-rich condition can readily reach 7%, while under N-realistic growth condition, the maximum defect concentration is as low as 1.71% when the growth temperature increases to 1100 K (melting point of GaN). These results suggest that it would be a little difficult to achieve ferromagnetic state for Ga(0.9375)Ca(0.0625)N using the chemical-equilibrium fabrication method, such as chemical precipitation. Using the same method as that for Cu-doped ZnO [L. H. Ye et al., Phys. Rev. B 73, 033203 (2006)], the transition temperature of Ga(0.9375)Ca(0.0625)N may be close to room temperature. (C) 2008 American Institute of Physics.
关键词:
generalized gradient approximation;doped zno;gan;semiconductors;calcium;systems;origin
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
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null
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null
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null
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null
于红超
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康海笑
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焦正波
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吕功煊
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毕迎普
催化学报
doi:10.1016/S1872-2067(15)60938-X
半导体光催化材料既可以利用太阳能催化分解水制氢和降解各种有机污染物，同时还可以将温室气体CO2还原成有机低碳烷烃燃料，因此光催化是解决当今能源和环境问题最理想的途径之一.然而，目前所报道的可见光光催化材料大多具有较高的光生载流子复合率和较差的可见光吸收，导致其量子效率较低.因此，开发新型高效可见光光催化材料，拓展半导体材料光谱响应范围以及促进光生电子和空穴有效分离，成为目前光催化材料研究领域急需解决的科学问题.2010年Ye等首次报道了Ag3PO4在光催化中的应用，该材料表现出优异的光催化分解水制氧及降解有机污染物性能，在光吸收波长大于420 nm时的量子效率达到90%.然而，作为一种新型光催化材料，其组成、结构和晶面等对光催化性能的影响尚不清楚.因此，我们开展了Ag3PO4半导体纳米材料的表面微观结构调控研究，创制了一系列具有特殊形貌和选择暴露晶面的Ag3PO4基可见光催化材料，其表现出独特的光催化氧化性能.例如，利用金属络合法制备了具有(100)，(110)，(111)，(221)和(332)等晶面的Ag3PO4晶体，发现通过调控其暴露晶面可进一步提高光催化性能.利用Ag纳米材料所具有的独特表面等离子体共振效应以及良好的导电性，构建了Ag/Ag3PO4核壳型纳米线、项链状Ag/Ag3PO4纳米线、项链状及均匀分布的Ag3PO4/PAN纳米复合纤维等异质光催化材料，提高了光生电子-空穴的分离效率，实现了有机污染物的高效催化氧化消除.然而，由于Ag3PO4在光催化反应过程中的稳定性较差以及成本较高，严重限制了其实际应用.因此，设计和制备具有高稳定性、低成本的Ag3PO4光催化材料成为目前急需开展的研究领域.本文以Ba3(PO4)2纳米片为模板和磷酸离子源，通过阳离子置换法一步制备了具有中空结构的Ba离子掺杂Ag3PO4光催化材料. ；光催化结果表明， Ba离子的掺杂不但可以有效提高Ag3PO4光催化活性，并且可改变降解有机污染物甲基橙(MO)和罗丹明B(RhB)的选择性，实现优先降解MO.另外，此法制备的Ag3PO4材料经重复使用多次后仍表现出较高的光催化性能.进一步研究表明， Ba离子掺杂增强了Ag3PO4的表面电负性，因而吸附具有负电性的MO能力增加，使其光催化性能提高，此外，该法还可用于制备Ba3(PO4)2/Ag3PO4复合光催化材料，当Ag3PO4含量为40%时，该复合材料具有与纯相Ag3PO4相同的光催化剂活性.由此可见，通过合理掺杂金属离子及形成复合结构可以有效提高Ag3PO4光催化材料的活性和稳定性，降低Ag3PO4用量，这对Ag3PO4光催化材料的设计与改进具有一定指导意义.
关键词:
光催化
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磷酸银
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中空纳米片
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钡掺杂
