Confocal Raman Microscopy PDF
Preview Confocal Raman Microscopy
SpringerSeriesin OPTICAL SCIENCES 158 foundedbyH.K.V.Lotsch Editor-in-Chief: W.T.Rhodes,Atlanta EditorialBoard:A.Adibi,Atlanta T.Asakura,Sapporo T.W.Hänsch,Garching T.Kamiya,Tokyo F.Krausz,Garching B.Monemar,Linköping H.Venghaus,Berlin H.Weber,Berlin H.Weinfurter,München SpringerSeriesin OPTICAL SCIENCES The Springer Series in Optical Sciences, under the leadership of Editor-in-Chief William T. Rhodes, Georgia Institute of Technology, USA, provides an expanding selection of research monographs in all major areas of optics: lasers and quantum optics, ultrafast phenomena, optical spectroscopy techniques, optoelectronics, quantum information, information optics, applied laser technology, industrialapplications,andothertopicsofcontemporaryinterest. Withthisbroadcoverageoftopics,theseriesisofusetoallresearchscientistsandengineerswhoneed up-to-datereferencebooks. The editors encourage prospective authors to correspond with them in advance of submitting a manuscript.SubmissionofmanuscriptsshouldbemadetotheEditor-in-ChieforoneoftheEditors.See alsowww.springer.com/series/624 Editor-in-Chief WilliamT.Rhodes GeorgiaInstituteofTechnology SchoolofElectricalandComputerEngineering Atlanta,GA30332-0250,USA E-mail:[email protected] EditorialBoard AliAdibi Hans-Kopfermann-Straße1 GeorgiaInstituteofTechnology 85748Garching,Germany SchoolofElectricalandComputerEngineering E-mail:[email protected] Atlanta,GA30332-0250,USA BoMonemar E-mail:[email protected] DepartmentofPhysics ToshimitsuAsakura andMeasurementTechnology Hokkai-GakuenUniversity MaterialsScienceDivision FacultyofEngineering LinköpingUniversity 1-1,Minami-26,Nishi11,Chuo-ku 58183Linköping,Sweden Sapporo,Hokkaido064-0926,Japan E-mail:[email protected] E-mail:[email protected] HerbertVenghaus TheodorW.Hänsch FraunhoferInstitutfürNachrichtentechnik Max-Planck-InstitutfürQuantenoptik Heinrich-Hertz-Institut Hans-Kopfermann-Straße1 Einsteinufer37 85748Garching,Germany 10587Berlin,Germany E-mail:[email protected] E-mail:[email protected] TakeshiKamiya HorstWeber MinistryofEducation,Culture,Sports TechnischeUniversitätBerlin ScienceandTechnology OptischesInstitut NationalInstitutionforAcademicDegrees Straßedes17.Juni135 3-29-1Otsuka,Bunkyo-ku 10623Berlin,Germany Tokyo112-0012,Japan E-mail:[email protected] E-mail:[email protected] HaraldWeinfurter FerencKrausz Ludwig-Maximilians-UniversitätMünchen Ludwig-Maximilians-UniversitätMünchen SektionPhysik LehrstuhlfürExperimentellePhysik Schellingstraße4/III AmCoulombwall1 80799München,Germany 85748Garching,Germanyand E-mail:[email protected] Max-Planck-InstitutfürQuantenoptik Forfurthervolumes: http://www.springer.com/series/624 Thomas Dieing Olaf Hollricher Jan Toporski Editors Confocal Raman Microscopy With155Figures 123 Editors Dr.ThomasDieing Dr.OlafHollricher Applications&Support Research&Development WITecGmbH WITecGmbH Lise-Meitner-Strasse6 Lise-Meitner-Strasse6 89081Ulm,Germany 89081Ulm,Germany [email protected] [email protected] Dr.JanToporski Sales WITecGmbH Lise-Meitner-Strasse6 89081Ulm,Germany [email protected] SpringerSeriesinOpticalSciences ISSN0342-4111 e-ISSN1556-1534 ISBN978-3-642-12521-8 e-ISBN978-3-642-12522-5 DOI10.1007/978-3-642-12522-5 SpringerHeidelbergDordrechtLondonNewYork LibraryofCongressControlNumber:2010932505 (cid:2)c Springer-VerlagBerlinHeidelberg2010 Thisworkissubjecttocopyright.Allrightsarereserved,whetherthewholeorpartofthematerial isconcerned,specificallytherightsoftranslation,reprinting,reuseofillustrations,recitation,broad- casting,reproductiononmicrofilmorinanyotherway,andstorageindatabanks.Duplicationof thispublicationorpartsthereofispermittedonlyundertheprovisionsoftheGermanCopyrightLaw ofSeptember9,1965,initscurrentversion,andpermissionforusemustalwaysbeobtainedfrom Springer.ViolationsareliabletoprosecutionundertheGermanCopyrightLaw. Theuseofgeneraldescriptivenames,registerednames,trademarks,etc.inthispublicationdoesnot imply,evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfromtherelevantpro- tectivelawsandregulationsandthereforefreeforgeneraluse. Coverdesign:IntegraSoftwareServicesPvt.Ltd.,Pondicherry Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) Preface ReadersofthisbookareawarethatthetheoryoftheRamaneffecthasbeenknown forover80years,thoughroutineRamanspectroscopyexperimentswereperformed only after almost another half century of technological development. Since then, theanalyticalpotentialofthisspecificlight-scatteringeffecthasbeenexploredfor decadesandresultedinawealthofscientificpublications.Ittookanothermajorstep intechnicaldevelopmenttowardtheendofthesecondmillenniumthatallowedthe three-dimensional chemometric characterization of materials with high sensitivity and diffraction-limited resolution by combining confocal microscopy and Raman spectroscopy. With the inception of the resulting high-resolution confocal Raman microscopy as a novel analytical technique, new realms for the application of this method were defined and new research goals formulated. This has resulted in an expandingpoolofexperienceandexpertise. The motivation to compile this book largely emerged from the observation that among the substantial portfolio of excellent publications of monographs on Raman spectroscopy, there are few dedicated to confocal Raman microscopy or evenhigh-resolutionconfocalRamanimaging.Encouragedadditionallybyconver- sation and discussion with experts in the field of confocal Raman microscopy, we realized the demand for a reference work that condenses background information onphysical,technical,hardware,andsoftwareaspectsthatserveasprerequisitesfor high-end analytical microscopy equipment. Equally important are comprehensive dataevaluationmethodstofurtherandfosterdataprocessing,permittingadvance- ment of research by simply providing tools to obtain novel results and make new discoveries. Thegoalofthisbookthereforeistoprovidethebestpossibleoverviewofthethe- oreticalandpracticalfactsandissuesassociatedwithconfocalRamanmicroscopy. With the incorporation of over a dozen contributions from expert scientists and researchgroupsspanningawiderangeofapplicationsinacademicresearchaswell asindustry-drivenresearchanddevelopment,thisfirsteditionof“confocalRaman microscopy” provides a comprehensive frame of reference for anyone involved in researchemployingconfocalRamanmicroscopy.Aimingtokeeppacewithtechno- logicaladvancement,itisourintentiontokeepthisbookasup-to-dateaspossible v vi Preface inordertoprovideourreadershipwiththecurrentstateoftheartinconfocalRaman microscopy. We therefore welcome any constructive comments or suggestions for allfutureeditions. Ulm,Germany ThomasDieing May2010 OlafHollricher JanToporski Contents 1 High-ResolutionOpticalandConfocalMicroscopy ................ 1 OlafHollricherandWolframIbach 1.1 Introduction .............................................. 1 1.2 IntroductiontoTheoreticalConsiderationsinHigh-Resolution Microscopy .............................................. 3 1.3 IntroductiontoConfocalMicroscopy ......................... 3 1.4 ElectromagneticScatteringinOpticalSystems ................. 4 1.5 3D-IntensityDistributionintheFocus ........................ 5 1.5.1 LargeApertureAngles.............................. 6 1.5.2 TransitiontoSmallApertureAngles .................. 9 1.6 TheoryofImageFormation ................................. 11 1.6.1 Microscope ....................................... 11 1.6.2 ConfocalMicroscope............................... 12 1.6.3 ConfocalRamanMicroscope ........................ 12 1.7 ImageFormationforLightScattering......................... 13 1.7.1 ScatteringPoint ................................... 13 1.7.2 ReflectionataMirror............................... 15 1.8 ImageFormationforRamanScattering ....................... 16 1.8.1 RamanEmittingPoint .............................. 16 1.8.2 RamanEmissionofaLayer ......................... 17 1.9 PinholeSize .............................................. 18 References ..................................................... 20 2 IntroductiontotheFundamentalsofRamanSpectroscopy ......... 21 BenjaminDietzek,DanaCialla,MichaelSchmitt,andJürgenPopp 2.1 Introduction .............................................. 21 2.2 ClassicalPictureofLightScattering .......................... 22 2.2.1 FrequencyDependenceofRamanScattering ........... 22 2.2.2 Classical “Selection Rule” and Comparison to IR Absorption ....................................... 24 2.2.3 ScatteredRamanIntensity........................... 25 2.2.4 ShortfallsoftheClassicalPicture..................... 27 vii viii Contents 2.3 RamanCross-SectionEnhancementMechanisms ............... 27 2.3.1 ResonantRamanScattering.......................... 28 2.3.2 AdvantagesandApplicationsofResonance RamanScattering ................................. 31 2.3.3 Surface-EnhancedRamanScattering.................. 34 References ..................................................... 40 3 RamanInstrumentationforConfocalRamanMicroscopy .......... 43 OlafHollricher 3.1 Introduction .............................................. 43 3.2 TheDevelopmentofRamanMicroscopes ..................... 44 3.3 Confocality............................................... 45 3.4 ThroughputofaConfocalRamanMicroscope.................. 46 3.4.1 LaserWavelength.................................. 47 3.4.2 ExcitationPower .................................. 47 3.4.3 Objective......................................... 48 3.4.4 MicroscopeThroughput............................. 48 3.4.5 CouplingBetweenMicroscopeandSpectrometer ....... 49 3.4.6 SpectrometerThroughput ........................... 49 3.4.7 Gratings.......................................... 50 3.4.8 CCDDetector..................................... 51 3.5 Conclusion ............................................... 60 References ..................................................... 60 4 Software Requirements and Data Analysis in Confocal RamanMicroscopy ............................................ 61 ThomasDieingandWolframIbach 4.1 Introduction .............................................. 61 4.2 RequirementsforDataAcquisitionSoftware................... 62 4.2.1 DataAcquisition................................... 62 4.2.2 CorrelationofSpatialandSpectralData ............... 63 4.3 Description of the Data Sets Acquired in Confocal RamanMicroscopy........................................ 65 4.4 Pre-processingofRamanSpectra ............................ 66 4.4.1 CosmicRayRemoval............................... 66 4.4.2 Smoothing........................................ 68 4.4.3 Background Substraction and Subtraction ofReferenceSpectra............................... 70 4.5 ImageGeneration ......................................... 72 4.5.1 UnivariateImageGeneration ........................ 72 4.5.2 MultivariateImageGeneration ....................... 75 4.6 ImageMasksandSelectiveAverageCalculation................ 81 4.7 CombinationofSingleSpectrawithMulti-spectralDataSets ..... 82 4.7.1 BasisSpectra...................................... 83 4.7.2 FittingProcedure .................................. 83 Contents ix 4.8 CombinationofVariousImages.............................. 84 4.9 TheLawofNumbers....................................... 85 4.10 MaterialsandMethods ..................................... 88 References ..................................................... 89 5 Nano-spectroscopyofIndividualCarbonNanotubesandIsolated GrapheneSheets .............................................. 91 AlainJungen 5.1 Introduction .............................................. 91 5.2 IndividualCarbonNanotubes................................ 92 5.2.1 Phonons.......................................... 92 5.2.2 Theory ........................................... 95 5.2.3 Experiment ....................................... 96 5.2.4 Microscopy ....................................... 98 5.2.5 Thermography ....................................100 5.3 IsolatedGrapheneSheets ...................................101 5.3.1 Theory ...........................................101 5.3.2 Experiment .......................................102 5.3.3 ChargeDistributions ...............................105 5.4 Conclusion ...............................................107 References .....................................................108 6 RamanSpectroscopyandConfocalRamanImaginginMineralogy andPetrography ...............................................111 MarcFriesandAndrewSteele 6.1 Introduction ..............................................111 6.2 RamanSpectroscopyandImagingasaMineralogy/Petrography Tool..................................................... 112 6.2.1 WorkingwithThinSections .........................114 6.2.2 ControlofLaserPower .............................116 6.3 “RamanMineralogy”UsingImagingRamanTechniques.........119 6.3.1 MineralPhaseImaging .............................120 6.3.2 CrystallographicOrientationImaging .................122 6.3.3 PhaseCompositionImaging .........................123 6.4 Examplesof“RamanPetrography”Applications ...............124 6.4.1 RamanAnalysisofShockedMinerals .................124 6.4.2 ContextualImagingofCarbonaceousMaterials.........126 6.4.3 FluidInclusions ...................................129 6.4.4 AncientTerrestrialCarbonaceousMaterials ............130 6.5 RamanMineralogyinFieldGeologyStudies...................130 6.5.1 ExtraterrestrialExploration..........................132 6.6 Conclusion ...............................................133 References .....................................................133
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