原子层沉积技术的发展现状及应用前景-魏呵呵

　魏呵呵　何　刚＊　邓　彬　李文东　李太申(　　230601)LatestDevelopmentandApplicationProspectsofAtomicLayerDepositionTechnologyWeiHehe,HeGang＊,DengBin,LiWendong,LiTaishen(SchoolofPhysicsandMaterialsScience,RadiationDetectionMaterials&DeviceFabricationLab,AnhuiUniversity,Hefei230601,China)　　Abstract　Thelatestdevelopmentofatomiclayerdeposition(ALD)technologywastentativelyreviewed.ALDhasbeenwidelyusedinfabricationofavarietyofelectronicschips,opticaldevices,sensors,andsolarcellsbecauseALDiscapableofdepositinghighlypurehomogenousfilmswithwell-controlledfilmthicknessandchemicalcontents.Thediscus-sionsfocusedon:i)theprincipleofALDtechnology,itscharacteristics,andtechnicaladvantages;ii)themechanismsofchemicalself-limiting(CS)andresponseself-limiting(RS),andpossiblewaystoachieveALD,suchasthermal-ALD(T-ALD),plasma-enhancedALD(PE-ALD),electrochemicalALD(EC-ALD),andetc.;iii)itsapplicationsinsynthesisofhighkmaterials,interconnectingmaterialsforintegratedcircuit(IC),nanostructuredmaterials,opticalfilmsandcatalysts.ThedevelopmenttrendsofALDtechnologyanditspotentialapplicationswerealsobrieflydiscussed.　　Keywords　Atomiclayerdeposition,Thin-filmdeposition,High-kmaterials,Opticalthinfilms,Catalyst　　　,、,,(ALD),、,,、、、。ALD、、、、ALDALDALD(T-ALD,PE-ALDEC-ALD);ALD(k、IC)、、、。,ALD。　　　k　　:O487　　　:A　　　doi:10.3969/j.issn.1672-7126.2014.04.201　1.1　(AtomicLayerDeposition,ALD),(AtomicLayerEpitaxy,ALE),(AtomicLayerChemicalVaporDeposition,ALCVD),(CVD)。ALD,,(surfacesaturationreactions),。ALD4[1-2](1):2013-05-19＊:Tel:[phone];E-mail:[e-mail]41334　420144　　　　　　　　　　　　　　　CHINESEJOURNALOFVACUUMSCIENCEANDTECHNOLOGY　　　　　　　　　　　;(2);(3),;(4),。,[2-3]。,ALD,,[4-5]:(1)()。。(2)。,,,。(3)。,。(4)。,,。(5)。,。(6),。1.2　ALDALD(self-limiting),ALD。。1ALD、[6-7]。1.3　CS-ALDRS-ALD[8],ALD,(Chemicalself-limiting,CS)(Responseself-limiting,RS)。:1(a),ML2,ML2,,ML2;AN2,1。:ML2+AN2※MA(film)+2LN←。,ML2(),,,LNAN2,MA。,。,ML2,。ML2。1　Fig.1　SchematicillustrationofCS-andRS-ALDsreactions1　ALD、Tab.1　Characteristics,impactonfilmgrowth,andapplicationad-vantagesofALDtechnologyALD,,、;(400℃);。,RS-ALD,CS-ALD:,。1(b),(AN),,(ML2)414　　　　　　　　34:AN+ML2=AML+LN←,AML,,NLML2;(AN2),AML,:AML+AN2=MAN+LN←。,,。,RS-ALD,ALD。2　ALDALD,ALD,。ALD,,ALD,ALDALD、ALD、ALD,ALD。ALDALD。2.1　T-ALD(Thermal-ALD,T-ALD)、ALD。ALD。2.2　PE-ALD:(Plasma-EnhancedALD,PE-ALD)ALD[9]。,,ALD。:,,,。,。:ALD、。(1)ALD,2(2)ALD,3。,ALD。(3),4。　　2　ALD　　　　　　　3　ALD　　　　　　4　ALD　　　　　　　　　Fig.2　SchematicdiagramoftheradicalFig.3　SchematicdiagramofFig.4　Schematicsofaremote　　　enhancementALDreactor　　　directplasmaALDreactor　　　plasmaALDreactor　　T-ALD,PE-ALD:(1)(5)。,,ALDALD。(2)。ALD,。,,,ALD,PE-ALD4154:,。,、。(3),。(4),Ti,TaTaN,T-ALD。5　T-ALDPE-ALDFig.5　ComparisonofdepositiontimeofT-ALDandPE-CVDtechniques　　,PE-ALDT-ALD,、、[10-11]。6T-ALDPE-ALD,PE-ALDMOSALD[12]。6　T-ALDPE-ALDFig.6　C-VcharacteristicsofLa2O3/Sigaedielectrics,andelectricalpropertiesofLa2O3grownbyT-ALDandPE-ALD2.3　EC-ALD:ALD,,,。:ALD,,。(Electrochemicalatomiclayerdeposition,EC-ALD)ALD,,EC-ALD[13]:(1)EC-ALE,,;(2);(3)(、),,,;(4),EC-ALE,,,。EC-ALD,,,EC-ALD,II-VI(:CdTe,CdSe,ZnSe)IIIA-VA(:GaAs,InAs,InAs/InSb[14-20])。[21]ALD,ALD,,,,(100℃)。[22]ALD,,,SiALD。,,,416　　　　　　　　3480nm,、。[23]ALD,ALD(verticalshowerheadatomlayerdepositionreactor,VS-ALDR),VS-ALDR,VS-ALD,TMGNH3,MONH3,ALD,GaN,TMGNH3,,ALD。3　ALD　　ALD,[24-25]:3.1　ALD,,ALD、,,:(k),,(),(TFEL),,DRAMMRAM,,,--(MIM)。3.1.1　kALDk。Al2O3,TiO2,HfO2,,HfO2Si、N、AlHfO2[26-29]。[30]ALDp-Si(111)TiO2/Si3N4。(TEM)TiO26.0nm,Si3N40.9nm。X(XPS)C、NTiO2,Si3N4SiO2。IV,TiO2/Si3N4。,ALDTiO2/Si3N4,。3.1.2　ICCu,,CuAl。CuSi,Si,Si,ALDSi。T.Cheon[31]ALD,SiRuAlO,Cu。X(XRD):Cu(10nm)/RuAlO(15nm)/Si650℃30min,RuAlO10nmCu,Cu。3.2　ALDALD,,ALD,,,,,,[32-36]。[37]Si3N420nm,ALDSi3N4Al2O3。Al2O3,250℃,0.1nm。7TEM。,1/3。7(a)Al2O3,30nm,7(b)ALD5TEM,25nm,7(c)ALD7TEM。20nm。ALDSi3N4Al2O3,,。　　[38]S-GaAs、(TMA)、TMA+TDMAHGaAs/Al2O3/HfO2、。,TMA+TDMAHTMA,GaAs,(0.2nm),。4174:7　TEMFig.7　TEMimagesofnano-holesbeforeandaftercoatingwithALDfilms3.3　ALD[39]ALD,、H2、NH3、H2O,Si。ALD,1%,,,;ALD,,;ALD,;ALD,。[40]TMA,ALD250℃300℃K9Al2O3。8,,1%。Al2O3,。91nm,,250℃300℃Al2O30.97。Al2O3。　　[41][Ta(OC2H5)5],ALD250℃300℃K9Ta2O5。、XPS、XRD、SEMAFM、。,ALDTa2O5350℃,250℃,,,,。8　Al2O3　Fig.8　ReflectancespectraofAl2O3filmsonquartzsubstrate9　300℃Al2O3Fig.9　300℃depositionofAl2O3filmtransmissionspectraofwavelengthdrift3.4　ALD[42]ALDAl2O3,,Al2O3、Al2O3,,Al2O3。10,Al2O3,2θ≈37°,TiO2(103)。11TiO2,XRD,Al2O3TiO2。4　ALD、、,ALD,418　　　　　　　　34、、。,ALD,ALDALD。,,,,ALD。　　　10　XRD　　　　　　　　　　　　　　　　　　11　TEM　Fig.10　XRDdiagrambeforeandaftermodification　　　　　　　Fig.11　TEMimagesbeforeandaftermodification　　　[1]　KimH.JournalofVacuumScienceTechnology[J],2003,B21(6):2231-2261[2]　LimBS,RahtuA,GordonRG.NatureMaterials[J],2003,(11):749-754[3]　SchumacherM,BaumannPK,SeidelT.Thin-FilmProcessing[J],2006,12(2-3):99-108[4]　YuanJP,WeiL,GuoWX.SurfaceTechnology[J],2010,39(4):77-82[5]　ShenC,LiuXY,HuangGZ.Vacuun[J],2006,43(4):1-6[6]　QiuHB,LiuBW,XiaY,etal.MicronanoelectronicTechnol-ogy[J],2012,49(11):702-708[7]　EditorialOfficeofEPE.EquipmentforElectronicProductsManufacturing[J],2010,180:1-7[8]　ShenC,LiuXY,HuangGZ.Vacuun[J],2006,43(4):1-6[9]　CaoYQ,LiAD.MeasurementandE