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评述第51卷第20期2006年10月www.scichina.com2347KeithP.Johnston(,100872;DepartmentofChemicalEngineering,CenterforNanoandMolecularScienceandTechnology,UniversityofTexasatAustin,Austin,TX78712,USA.E-mail:zhang_xg@chem.ruc.edu.cn),,,.,.,,,,.,,,.,..,,.,90nm.,,.,,.(supercriticalCO2,SCCO2).SCCO2,,,.25,CO21.5mN/m,,0mN/m,,,,.,CO2.SCCO2.,.CO2,.44,30MPa,CO2,CO2,SCCO2.,3%,,CO2.CO2[1].CO2,SCCO2.CO2,.DeSimone[2]SCCO2PS-b-PFOA,.1994,Johnston[3~6]CO2,10nmCO2.1996,Bright[7]第51卷第20期2006年10月评述2348www.scichina.com67000CO2,SCCO2.[8~10]Dynol-604Ls-,SCCO2,CO2.CO2,CO2.SCCO2.,,(0.2~10μm)..300mml57nm,157nm.,CO2[11],CO2,.CO2.,.SCCO2.SCCO2,,[12].,SCCO2.SCCO2,.,(THPMA)CO2,193nmCO2[13].,THPMASCCO2.SCCO2.CO2,,,.DeSimone[14~16],,SCCO2“”..SCCO2,.CO2,SCCO2.1(low-k),(interconnect)(R)(C).RC.,,(low-k).,,.,,.,(72mN/m),90nm,.,,,,.,,.,,.,Laplace:LV2cosPRγθΔ=,(1)(1).,γLV,R,θ..ΔP0,,.,θ180°,,5nm,13.8MPa;ΔP0,,.,评述第51卷第20期2006年10月www.scichina.com2349,.,.,SCCO2,0mN/m,,.SCCO2,Watkins[17](chemicalfluiddeposition,CFD).,SCCO2.,SCCO2,3.(),.,().,100nm.CFD,,.,CO2,.,SCCO2tethraethylorthosilicate(TEOS)[18].TEOS,,,.,TEOSSCCO2,TEOS1.2nm.,TEOS,TEOS,TEOS.,,.,.,JSRMethylsilsesquioxane(MSQ),MSQ,MSQ2.2~2.5.CO2[19].CO2,,.SCCO2,CO2..[20]MSQ(1):CO2,,SCCO2[19,21].:CO2,CO2MSQ.CO2,,CO2.CO2,.,,.,MSQ,CO2.1MSQ()(η)1atm=1.013105Pa,,MSQ[22~26].,.SCCO2,.CO2,[20](第51卷第20期2006年10月评述2350www.scichina.com2).CO2,CO22[27],3,CO2[20].,,CO2.235,13.79MPa,CO2MSQSEMCO2:5mL/min,:30min335,13.79MPa,CO2MSQSEMCO2:5mL/min,:30minCO2,,:SRRCSCγγγ+,(2),S,R,CCO2.,,,.Calvo[28]CO2.,,,CO2.,,.CO2,,Johnston[4,7]CO2.[20]TMN-3(2,6,8-triethyl-4-nonylether)CO2,(4).,CO2(),,,.CO2TMN-3,[6].,(5)[20].,,,CO2.(1)MSQSEM(45),CO2(),MSQ.435,13.79MPa,CO2MSQSEMCO2:5mL/min,:30min535,13.79MPa,CO2+MSQSEMCO2:5mL/min,:30min评述第51卷第20期2006年10月www.scichina.com23512,.(),().,[29]:4324HdELσ≥,(3),d,H,L,E,σ.(3),.,[30],.(3),.[31],[32].,,.,,,(6).CO2,40,20.68MPa,CO20.2%(),CO2,CO2-,79mN/m,20mN/m,,CO2[33].CO2,CO2,,CO2,..,6,SEM150nm,150nm,4CO2,[33,34].Namatsu[35],SCCO2,CO2,.(fluoroethercarboxylatesurfactant)CO2,CO2,,.Namatsu,,,.[33]TMN,(7).CO2,CO2,CO2.-,,CO2,;,,,,CO2.,.,CO2,CO2,[33].7SCCO2SEM40,20.68MPa.150nm,150nm,43SCCO2.,,,第51卷第20期2006年10月评述2352www.scichina.com.,SCCO2,,,,.,SCCO2,,,.,SCCO2.(:20576140).1JohnstonKP,PeckDG,KimS.Modelingsupercriticalmixtures——howpredictiveisit?IndEngChemRes,1989,28:1115—1125[DOI]2DeSimoneJM,GuanZ,ElsberndCS.Synthesisoffluoropoly-mersinsupercriticalcarbondioxide.Science,1992,257:945—947[DOI]3HarrisonK,GoveasJ,JohnstonKP,etal,Water-in-carbondioxidemicroemulsionswithafluorocarbon-hydrocarbonhybridsurfactant.Langmuir,1994,10:3536—3541[DOI]4JohnstonKP,ChoD,DaRochaSRP,etal.Waterincarbondiox-idemacroemulsionsandminiemulsionswithahydrocarbonsur-factant.Langmuir,2001,17(23):7191—7193[DOI]5LeeCT,RyooW,SmithPG,etal,Carbondioxide-in-watermi-croemulsions.JAmChemSoc,2003,125:3181—3189[DOI]6RyooW,WebberSE,JohnstonKP.Water-in-carbondioxidemi-croemulsionswithmethylatedbranchedhydrocarbonsurfactants.IndEngChemRes,2003,42(25):6348—6358[DOI]7JohnstonKP,HarrisonKL,ClarkeMJ,etal.Water-in-carbondi-oxidemicroemulsions:anewenvironmentforhydrophilesinclud-ingproteins.Science,1996.271:624—626[DOI]8LiuJ,HanB,LiG,etal.Investigationofnonionicsurfactantdynol-604basedreversemicroemulsionsformedinsupercriticalcarbondioxide.Langmuir,2001,17:8040—8043[DOI]9LiuJ,HanB,WangZ,etal.SolubilityofLs-36andLs-45surfac-tantsinsupercriticalCO2andloadingwaterintheCO2/water/sur-factantsystems.Langmuir,2002,18(8):3086—3089[DOI]10LiuJ,HanB,ZhangJ,etal.Formationofwater-in-CO2microe-mulsionswithnon-fluoroussurfactantLs-54andsolubilizationofbiomacromolecules.ChemEurJ,2002,8(6):1356—1360[DOI]11HogganEN,FlowersD,WangK,etal.Spincoatingofphotoresistsusingliquidcarbondioxide.IndEngChemRes,2004,43:2113—2122[DOI]12CaoC,FadeevAY,McCarthyTJ.Reactionsoforganosilaneswithsilicasurfacesincarbondioxide.Langmuir,2001,17:757—761[DOI]13SundararajanN,YangS,OginoK,etal.SupercriticalCO2proc-essingforsubmicronimagingoffluoropolymers.ChemMater,2000,12:41—48[DOI]14KimJ,NovickB,DeSimoneJM,etal.UltrathinfilmdepositionbyliquidCO2freemeniscuscoating-uniformityandmorphology.Langmuir,2006,22:642—657[DOI]15LiuB,RollandJP,DeSimoneJM,etal.Fabricationofultrami-croelectrodesusinga“teflon-like”coatingmaterial.AnalChem,2005,77(9):3013—3017[DOI]16NovickBJ,DeSimoneJM,CarbonellRG.Depositionofthinpolymericfilmsfromliquidcarbondioxideusingahigh-pressurefree-meniscuscoatingprocess.IndEngChemRes,2004,43(2):515—524[DOI]17BlackburnJM,LongDP,CabañasA,etal.Depositionofconfor-malcopperandnickelfilmsfromsupercriticalcarbondioxide.Science,2001,294:141—145[DOI]18FukushimaY,WakayamaH.Nanoscalecastingusingsupercriticalfluid.JPhysChemB,1999,103:3062—3064[DOI]19SirardSM,ZieglerKJ,SanchezIC,etal.Anomalouspropertiesofpoly(methylmethacrylate)thinfilmsinsupercriticalcarbondi-oxide.Macromolecules,2002,35:1928—1935[DOI]20ZhangX,PhamJQ,GreenPF,etal.Water-in-carbondioxidemicroe-mulsionsforremovingpostetchresiduesfrompatternedporouslow-kdielectric.JVacSciTechnolB,2003,21(6):2569—2598[DOI]21SirardSM,GreenPF,JohnstonKP.Spectroscopicell