High Resolution Surface Mass SpectrometryTOFSIMSCEAC：高分辨率质谱通TOFSIMS的表面

High Resolution Surface Mass Spectrometry by TOF-SIMS The challenge of chemical nanoanalysis Secondary Ion Mass Spectrometry - SIMS Analytical application of TOF-SIMS Perspectives Key questions in nanoanalysis Identification (What?) Localisation (Where?) Quantification (How much?) NanotechnologyDefinition: In at least one dimension 10 000 High mass accuracy (1-10 ppm) High transmission for high masses and at high mass resolution All elements and isotopes Molecular species High sensitivity (ppb, attomole) High lateral (50 nm)and depth (1nm) resolutionStatic SIMSOxidized and contaminated molybdenum surface(1973)I Intact Molecules (m 10 000 High mass accuracy (1-10 ppm) High transmission for high masses and at high mass resolution All elements and isotopes Molecular species High sensitivity (ppb, attomole) High lateral (50 nm)and depth (1nm) resolutionTi30SiH2Omass (u)47.9548.05110210IntensityCrSiC2mass (u)51.9552.05110210310IntensityFeSi2mass (u)55.9556.05110210310410510Intensity63CuSiClmass (u)62.9563.05110210310Intensitymass resolution (FWHM):Ti:13119Cr:12813Fe:12009Cu:13849data taken from 003_r.datcoverage (atoms/cm2):Ti:6.1E10Cr:8.2E09Fe:3.1E09Cu:2.1E10Trace Metal Detection / mass resolution1 Monolayer = 1.5E15 atoms/cm) the error is estimated to be within a factor of 2 to 3. Elementdetection limitsdetection limits(atoms / cm2)(atoms / cm2)7Li1E752Cr1E811B5E755Mn1E9Na1E756Fe2E824Mg2E758Ni1E9Al2E7Co2E839K1E763Cu3E840Ca3E769Ga1E948Ti2E8*As3E951V2E898Mo6E9 TOF-SIMS Detection Limits 051015202510010110210310411B12C30SiIntensitydepth (nm)1017101810191020B-concentration (atoms/cm3)intensityB concentration / atoms/cm3depth / nm051015202510010110210310411B12CNa7Li30Siintensitydepth (nm)depth / nmDepth profilingReconstructed profile (Li, Na)Mg+Ga+Sr+Cr+Fe+Y+Surface20 nmBulk595 nmCrossectionzy View2D Images and Cross Sections(Sample provided by Prof. Martin, RWTH Aachen, Germany)Material ScienceSurface ImagingBlooming Effect on PolymerPolymer (PP)Melt StabiliserAntioxidantPolymer, Stabiliser, AntioxidantField of View: 284 x 284 m2Particle Analysis / UraniumCa+2,6 104Na+1,1 105K+5,2 104Cr+4,5 10269+Ga3,9 106 238xU1,7 105Fe+1,4 103Zn+1,4 1031mAg+Si+Si5,010+5Ag6,410+31moverlayNanoextraction Laser-SNMSTOF-SIMS1m1mSi5,1+105Ag+5,11031mAg+Si+overlayLB-multilayer system: Lipids: DPPC/DPPG (4:1), Protein: 0.4 mol% SP-CAFMtopographyFLM10 mTOF-SIMS+10 mLaser-SNMS110: C5H8N358: C3H8N30: CH4N58: C3H8N ProteinLipidPhase Separationdye-labeled lipidAu2 imaging - Placenta cell complexExample provided by Alain Brunelle,ICSN, CNRS, FranceFesum ofcholesterol ionsMouse Brain Sectionsum ofphospholipid ionsCorrelation Analysis: 3 Colour Overlaycorpus callosumcaudateputammencanteriorcommissurenucleustriangularisseptiField of View: 8 x 8 mm2to be published by A. Brunelle et. al. ICSN, CNRS, FranceField of View: 18 x 18 mm2Rat Brain CrossSection255 Carboxylate 283 C18 Fatty acid771 Phospholipid892 Triclyceridemass (u)1801902002102202302402500 x102.03.04.05.06.0IntensityField of View: 52.7 x 52.7 m2Salbutamol (M+H)+max counts: 20 total counts: 2.12 x 105 one pixel: 100 x 100 nm2Salbutamol only 100 shots applied 20 integral counts Salbutamol 2 x 10-20 mole detected from a 100 nm spot Applications in Life Sciences Fundamental researchTissues, cells, membranes, biopolymers, lipids, .Biomedicine, biology, biochemistry. DiagnosticsBiochips, chromatographies, nanofluidics, marker, molecular pathology, . DrugsDelivery systems (tablets, nanoparticles, polymers,.), localisation in cells and tissues (ADME), contamination, screening, . BiomaterialsArtificial membranes, substrates for cell growth and artificial tissues, protein- and cell-adhesion, biocompatibility, . Directions of future development Fundamental researchUnderstanding the secondary ion formation processExperimental and theoretical model systemsUHV experiments Technical developmentSensitivity: Impact cascade, chemical environment, Laser-SNMS, .Lateral resolution: Spot size, impact cascadeDepth resolution: Impact cascade Instrument developmentNew cluster ions (N,O,He, metals, . )Cluster FIBLaser-SNMS Analytical applicationNanoelectronics and nanomaterialsNanobioanalytics Nanoparticles Transformation probabilities 1l below10nm (control of beam diameter and impact cascade)Moleculare 3D-analysisSelective bonding and yield control Some challenges in molecular nanoanalysis Single Molecule Detection / IdentificationSubattomol-Analytics, sample fixed in a well-defined surface area Individual Cell Analysis Chemical content of a single cell (ML separation) SIMS ChipChip-arrays for selected molecular species (or classes of molecules)Microstructured and -functionalized surfaces (separation, yield optimisation) Selective bonding and yield control Zeptomole Detector TLC, Gelchromatography , Isotachophoresis, . Nanoproteomics Immobilysed enzymes (trypsine) Moleculare Pathology Electron microscopy Imaging TOF-SIMS