原子层沉积技术及其创新运用_施云波

12520149NanotechnologyandPrecisionEngineeringVol．12No．5Sept．2014DOI10.13494/j．npe．20140011112221．1500802．100029本文分析并总结了涉及原子层沉积(atomiclayerdeposition，ALD)技术基本原理的若干问题．介绍了等离子增强原子层沉积(plasmaenhancedatomiclayerdeposition，PEALD)技术的优势及常见运用．相对于传统ALD系统，PEALD最大的特点在于其能够通过等离子体放电来活化前驱体源，提高对前驱体源，尤其是气态源的利用．利用PEALD这一特点可以增加传统ALD技术中可用氮源的种类．同时PEALD原位掺杂作为一种掺杂方法能够用于对光催化材料的掺杂改性，提高其光催化性能．此外，PEALD技术还适用于温度敏感材料和柔性材料上的薄膜沉积，可以获得更低的电阻率和更高的薄膜密度等．本文重点介绍了本课题组提出的PEALD原位掺杂技术及其对TiO2光催化剂的掺杂改性运用．最后对原位掺杂技术的研究方向和发展进行了展望．TiO2－xNxO641A1672-6030201405-0328-062014-03-10．2009ZX02037-003．1966—[e-mail]hnologyandItsInnovativeApplicationsShiYunbo1YuMingyan12ＲaoZhipeng2ZhaoShirui21．TheHigherEducationalKeyLaboratoryforMeasuring＆ControlTechnologyandInstrumentationofHeilongjiangProvinceSchoolofMeasurement-ControlTechnologyandCommunicationsEngineeringHarbinUniversityofScienceandTechnologyHarbin150080China2．KeyLaboratoryofMicroelectronicsDevices＆IntegratedTechnologyInstituteofMicroelectronicsChineseAcademyofSciencesBeijing100029ChinaAbstractSeveralproblemsofatomiclayerdepositionALDtechnologyareanalysedandsummarizedinthispaper．AdditionallytheadvantagesandapplicationsofplasmaenhancedatomiclayerdepositionPEALDtechnologyareintroduced．ComparedtotraditionalALDsystemthegreatestfeatureofPEALDisitsabilitytoactivateprecursorsourcethroughtheplasmadischargetoimprovetheutilizationratiooftheprecursorsourceespeciallythegaseoussource．ThisfeatureofPEALDcanincreasethetypesofavailablenitrogensourcesintraditionalALD．MeanwhilePEALDin-situdopingcanbeusedtoim-provephotocatalyticpropertiesofphotocatalyticmaterials．FurthermorePEALDtechnologyisalsosuit-ableforthinfilmdepositionoftemperature-sensitivematerialsandflexiblematerialstoachievelowerelec-tricalresistivityandhigherdensityofthinfilm．Moreimportantlythemethodofin-situdopingtechnologyofPEALDanditsimpactonTiO2photocatalystareinvestigated．Finallythefuturestudyandthedevel-opmentofin-situdopingtechnologyofPEALDarepresented．Keywordsatomiclayerdepositionplasmaenhancedatomiclayerdepositionin-situdopingTiO2－xNxatomiclayerdepositionALD206020149·329·1-2Suntola3ZnSMnAl2O3、．90ALDALD4-6．plasmaenhancedatom-iclayerdepositionPEALD．、7．1ALD1Fig．1Thethicknessofdepositedfilmde-terminedbyatomicradius1.1ALDALD2．ALD．8-9．ALD0.01～0.20nm/cycle．ALD．①1M1M②MG2“”“”③④．ALDCVD10．2“”“”Fig．2The“shadoweffect”or“stericeffect”causedbylargefunctionalgroups1.2ALDALDALDALDT-ALD．ALDALD．300～500℃150～250℃ALD．ALD、．2PEALD2.1PEALDALD．ALD．photothermalphotolytic．PEALDALD．PEALDALD．microwave、ECＲＲF．3PEALD．2.2PEALD2.2.1低温生长，结构易控PEALD．．、、H、O、N．·330·1253PEALDFig．3StructurediagramofPEALDequipment2.2.2增加了源的种类H2、N2ALD．ALDPEALD．H2N2．2.2.3减少反应时间．4．．4ALDPEALDFig．4SequencediagramofALDandPEALD2.2.4减少杂质，降低电阻率，提高薄膜致密性PEALD．O2OC、H．O、H、．5611PEALD．12PEALD、．5TDMATNH3200℃TiNFig．5TrendofelectricalresistivityofTiNfilmchangedwithplasmapowerwithTDMATandNH3sourcesat200℃6ALDPEALDTiNFig．6DistributionofimpuritycontentinTiNfilmpreparedbyALDandPEALDrespectively2.2.5增加吸附几率，提高反应速率711PEALD20149·331·ALD．PEALD100℃N2NH3．N．PEALD．PEALD．PEALD．PEALD．7N2NH3ALDPEALDTiNFig．7ThegrowthrateofTiNfilmpreparedbyALDandPEALDrespectivelywithN2andNH3sources2.2.6PEALD的原位掺杂PEALDPEALDin-situdopingtech-niquePEALD．PEALD8．①ALD②③④posi-tivesequencePreversesecquenceＲ．PEALDPEALDPEALD．8PEALDFig．8TheschematicprincipleofPEALDin-situdoping3PEALDNTiO2NTiO213．NTiO2NTiO2．NTiO214-15．PEALD．Pore·332·12516ALDTiO2TiNNNH3．ALDNH3ALDTiO2．N1sXXPS9．N50WN396eV．HＲTEM10PLPL11．9300℃450℃NTiO2N1sXPSFig．9N1sXPSspectraofN-dopedTiO2sampleaf-tergrowingat300℃andrapidthermalan-nealingat450℃10300℃、50W450℃NTiO2HＲTEMFig．10HＲTEMcrosssectionimageofN-dopedTiO2sampleaftergrowingat300℃50Wandrapidthermalannealingat450℃MO12NTiO212．11NTiO2PLFig．11PLspectraofN-dopedTiO2filmandpureTiO2film12NTiO2Fig．12PhotocatalyticdegradationofMObyN-dopedandpureTiO2filmsundervisiblelightirradiation4PEALD．1．．．2N．TiO2NN．NN．20149·333·1ShevjakovAMKuznetsovaGNAleskovskiiVB．Inchemistryofhigh-temperaturematerialsC．Proceedingsofthe2ndUSSＲConferenceonHigh-TemperatureChemistryofOxides．LeningradUSSＲ196526-29inＲussian．2PuurunenＲL．SurfacechemistryofatomiclayerdepositionAcasestudyforthetrimethylaluminum/waterprocessJ．JournalofAppliedPhysics20059712121301．3SuntolaT．AtomiclayerepitaxyJ．ThinSolidFilms1992216184-89．4LuJAarikJSundqvistJetal．AnalyticalTEMcharac-terizationoftheinterfaciallayerbetweenALDHfO2filmandsiliconsubstrateJ．JournalofCrystalGrowth20052733510-514．5GuziewiczEGodlewskiMWachnickiLetal．ALDgrownzincoxidewithcontrollableelectricalpropertiesJ．SemiconductorScienceandTechnology2012277074011．6KalkowskiGＲohdeMＲisseSetal．DirectbondingofglasssubstratesJ．ECSTransactions2010334349-355．7．J．2012497483-490．CaoYanqiangLiAidong．PrincipleandapplicationsofplasmaenhancedatomiclayerdepositionJ．Micronano-electronicTechnology2012497483-490inChi-nese．8GronerMDElamJWFabreguetteFHetal．ElectricalcharacterizationofthinAl2O3filmsgrownbyatomiclayerdepositiononsiliconandvariousmetalsubstratesJ．ThinSolidFilms20024131186-197．9ZhangXiangLiuBangwuZhaoYanetal．Influenceofannealingtemperatureonpassivationpe