I

Basics of luminescence

History of cathodoluminescence

History of Cathodoluminescence
1879 CROOKS Luminescence studies on crystals after bombardment with a cathode ray SIPPEL, LONG & AGRELL First application for thin section petrography SMITH & STENSTROM Cathodoluminescence studies with the microprobe KRINSLEY & HYDE Cathodoluminescence studies with the SEM ZINKERNAGEL First CL microscope in Germany

1965 1965 1971 1978

Germany SLMS = Society for Luminescence Microscopy and Spectroscopy Knoxville. USA .2001 International Conference „Cathodoluminescence in geosciences: New insights from CL in combination with other techniques“ Freiberg.

Basics of luminescence ??? .

Basics of luminescence Luminescence = transformation of diverse kinds of energy into visible light .

molecules or a crystal from an excited electronic state to a ground state with lesser energy. (Marfunin1979) Fluorescence = luminescence emission with a lifetime < 10-8 s Phosphorescence = luminescence emission with a lifetime > 10-8 s .Basics of luminescence Luminescence of inorganic and organic substances results from an emission transition of anions.

Basics of luminescence Main processes of luminescence (1) absorption of excitation energy and stimulation of the system into an excited state (2) (3) transformation and transfer of the excitation energy emission of light and relaxation of the system into an unexcited condition .

Schematic model of luminescence processes UV Excitation by energy thermal excitation biological processes electrons photoluminescence thermoluminescence bioluminescence cathodoluminescence e- Emission of light .

Bioluminescence .

Primary electron beam Back scattered electrons Cathodoluminescence Secondary electrons X-rays Auger electrons Sample Specimen current Scattered electrons Unscattered electrons .

Electron beam interaction with a solid incident electron beam Sample surface secondary electrons back scattered electrons primary X-ray excitation 2-8 µm cathodoluminescence continuum radiation (Bremsstrahlung) .

electron energy ρ .Electron beam interaction with a solid incident electron beam Penetration depth of electrons: sample surface R = 900 · ρ-0.3 R = 450 · ρ-0.8 · E01.7 for for E0 # 10 keV E0 > 10 keV R R .density of the solid .penetration depth E0 .9 · E01.

The band model The band model .

Energy levels in a band scheme for different crystal types E conduction band conduction band band gap band gap conduction band valence band valence band valence band conductor semiconductor insulator .

Electron transitions in a band scheme for different crystal types E conduction ban E (photon energy) E valence band conductor semiconductor insulator .

Positions of ion activator energy levels in a band scheme for different crystal types E Conduction band donor acceptor activator Valence band (a) semiconductor (small interband spacing) (b) insulator (broad interband spacing) .

(a) (b) 1 2 (c) (d) (e) E Conduction band trap luminescence activator Valence band .

Conduction band E radiationless emission excitation luminescence activator Valence band .

The configurational coordinate The configurational coordinate model model .

(modified after Yacobi & Holt 1990) .Basics of luminescence excited state absorption band ground state emission band Configurational coordinate diagram for transitions according to the Franck-Condon principle with related absorption and emission bands. respectively.

Basics of luminescence Stokes shift 2 1 Excitation (1) and emission (2) spectra of Mn2+ in calcite (after Medlin 1964) .

Basics of luminescence The sensitivity of the electronic states of the Mn2+ ion in octahedral coordination to changes in the intensity of the crystal field splitting Dq and representation in a configurational diagram (modified after Marfunin 1979 and Medlin 1968) .

??? How can we use the luminescence signal ?? .

REE2+/3+. vacancies) extrinsic trace elements (Mn2+.Basics of luminescence Visualization of the real structure of solids by CL Pol CL Luminescence centres intrinsic lattice defects (broken bonds.) . etc.

g... Pb2+. Tl+) electron-hole centres (e. Cr3+. etc. clusters.g. S2-.g. Fe3+) rare earth elements (REE2+/3+) actinides (especially uranyl UO22+) heavy metals (e.) .. O2-.Basics of luminescence Types of luminescence centres transition metal ions (e. Mn2+. F-centres) crystallophosphores of the ZnS type (semiconductor) more extended defects (dislocations.

intensity [counts] o 2400 2200 2000 1800 1600 1400 1200 1000 800 300 400 500 Dy3+ Eu2+ Sm3+ Nd3+ 600 700 800 900 1000 1100 wavelength [nm] . zoning and internal structures of solids apatite 2600 (2) CL spectroscopy determination of the real structure detection of trace elements. their valence and structural position Sm3+ rel.Basics of luminescence Detection of the cathodoluminescence emission (1) CL microscopy contrasting of different phases visualization of defects.

CL emission spectra .

the greater are the Stokes shift and the width of the emission line.The activator-ligand distances in the different excited states and the slope of the energy levels depend on the intensity of the crystal field (expressed as crystal field splitting = 10Dq) .The crystal field theory local environment of the activator ion (Burns. . 1993) .The stronger the interaction of the activator ion with the lattice.

The crystal field theory local environment of the activator ion Factors influencing values of or 10Dq are: .type of the activator ion (size.local symmetry of the ligand environment etc. charge) . .type of the ligands .the interaction distance .

intensity [counts] zircon 12000 Dy3+ zircon scheelite 8000 Dy3+ Dy 3+ anhydrite Sm3+ Dy3+ 4000 calcite fluorite Tm3+ Sm3+ Tb3+ 0 300 400 500 600 700 800 wavelength [nm] apatite 400 500 600 700 [nm] CL spectra of narrow emission lines (e.g. REE3+) CL emission spectra are specific of the activator ion .Influence of the crystal field on CL emission spectra Influence of the crystal field on CL emission spectra (1) influence of the crystal field = weak Dy3+ Dy3+Sm3+Sm3+Dy3+ 16000 rel.

ENERGY LEVELS OF THE REE3+ .

A .Basics of luminescence Energy levels diagram and emission spectrum of Eu3+ in Eu2(SO4)3 * 8H2O (after Marfunin 1979) f .oscillatory strength (effectiveness of excitation).probability of emission transitions .

g. Mn2+.Influence of the crystal field on CL emission spectra Influence of the crystal field on CL emission spectra (2) influence of the crystal field = strong 400 rel. intensity [counts] calcite 300 Mn2+ Mn2+ activated CL of CaCO3: aragonite 200 green (~560 nm) calcite 100 300 400 500 600 700 800 yellow-orange (~610 nm) red (~655 nm) magnesite wavelength [nm] CL spectra of broad emission bands (e. Fe3+) CL emission spectra are specific of the host crystal .

Visual and spectral detection of Mn2+ activated CL in natural carbonates 500 µm sea lily stalk (calcite CaCO3) .

Mn2+-distribution in crystal hetero-structures: CaCO3 and MgCO3-cluster in Mg-Calcite .

Cation positions of common luminescence centres in silicates (Ramseyer & Mullis 2000) .

intensity [counts] plagioclase red IR wavelength [nm] 750 740 730 720 710 700 690 680 0 20 40 60 80 100 lunar plagioclases 600 400 Mn2+ 200 Fe3+ 0 300 400 500 600 700 wavelength [nm] 800 900 An content [mol-%] Position of the Fe3+ activated CL emission band in plagioclases in relation to the anorthite content .Influence of the crystal field on the broad CL emission bands in mixed crystals 800 rel.

Instrumentation Instrumentation .

Scanning Electron Microscope JEOL 6400 with OXFORD Mono-CL detector .

primary electron beam OXFORD Mono CL mirror sample silica-glass fibre guide Cathodoluminescence detector on a scanning electron microscope .

Hot-cathode luminescence microscope HC1-LM (designed by Rolf Neuser. Bochum) .

Cold-cathode luminescence microscope (CITL) (Cambridge Instruments) .

Cold-cathode luminescence microscope with EDX detector (Cambridge Instruments) (Vortisch et al. 2003) .

Instrumentation Instrumentation hot-cathode microscope microscope cold-cathode microscope microscope objective thin section leaded glass viewing point specimen corona points discharge tube curved electrode condenser optic axis light source cathode h hig tage o l le v b ca focus coil .

IR) analytical spot ca. 30 µm true luminescence colours resolution 1-2 µm polarizing microscopy. 1 µm panchromatic CL images (grey levels) resolution << 1 µm SE.1-0. 0.5 mA ionized gas („cold cathode“) glass optics: 380-1200 nm (Vis .5-15 nA mirror optics: 200-800 nm (UV . stationary mode heated filament („hot cathode“) 14 kV.IR) analytical spot ca. scanning mode heated filament 20 kV. 0. EDX/WDX.Cathodoluminescence techniques SEM-CL polished sample surface focused electron beam. cooling stage CL microscopy polished thin (thick) section defocused electron beam. BSE. (EDX) .

Cathodoluminescence imaging Cathodoluminescence imaging SE Polmi zircon BSE quartz CL CL 10 µm 500 µm .

CL microscope with attached CCD based viedeo camera electronic steerage Computer aided image analysis vacuum pumps Cathodoluminescence microscope HC1-LM .

Hot-cathode luminescence microscope HC1-LM Sample chamber sample holder screen brass clips sample is fixed upside down in the sample holder Electron gun transparency ! Wehnelt cylinder .

Cathodoluminescence microscopy
Polarising microscopy

microscope
sample

electron beam

filament

Light source

Cathodoluminescence microscopy

Sample preparation

Sample preparation
28 mm

1. Polished thin section
48 mm

sample holder (glass) epoxy resin sample (~25 µm)

application for all CL equipments

Sample preparation 2. Polished section Sample holder (plastics) epoxy resin sample piece application for SEM-CL („cold-cathode“ microscopes) .

Sample preparation
28 mm

48 mm

4. Sample holder for fluid inclusion preparates

sample holder (metallic) sample piece glass plate

application for all CL equipments

Sample preparation
3. Polished sample piece

sample piece

application for SEM-CL („cold-cathode“ microscopes)

Sample preparation
5. Pressed tablet (powder samples)
pressed tablet of powder sample

application for SEM-CL („cold-cathode“ microscopes)

coating material: C. Au.Sample preparation Coating with conducting material . Ag. Cu for SEM-CL and „hot-cathode“ CL microscopes .to prevent the built up of electrical charge during electron irradiation . Al.

Documentation .

analysis of minerals with very low CL intensities .Documentation Convetional photos/slides Nikon photo camera Kodak Ektachrome 400 HC Digital micrographs Digital video camera KAPPA 961-1138 CF 20 DXC Advantages of CCD: high spatial resolution high sentsitivity .low accumulation time direct combination with image analysis .

Spectral CL measurements .

4 nm resolution daptation 30µm screen) 14 kV. 600.High-resolution CL spectroscopy 150. 0. 1200 lines/mm Silica-glass fibre guide 0.2 mA data processing .

High-resolution CL spectroscopy Silica-glass fibre guide Triple-grating spectrograph Nitrogen-cooled CCD-detector daptation CL microscope .

Factors influencing CL properties/intensity .

) type of equipment time (especially transient CL) crystalllographic factors luminescence activation sensitizing quenching . thickness) sample coating (quality. material) temperature analytical conditions (acceleration voltage. etc. thickness. vacuum. beam current.Factors influencing the CL intensity analytical factors sample preparation (sample surface.

Basics of luminescence Analytical parameters influencing cathodoluminescence 3 1000 relative intensity 2 relative intensity -120 -100 -80 -60 -40 -20 0 +20 100 10 1 1 0 0.1 1 10 100 temperature [°C] Specimen current at 20 kV [nA] Variation of CL intensity with sample temperature for quartz (modified after Hanusiak & White 1975) Variation of the intensity of quartz CL with beam current (modified after Hanusiak 1975) .

Tl+. Sensitizing of luminescence: (1) emission-reabsorption („cascade“ luminescence) (2) resonance radiationless (3) nonresonance radiationless typical sensitizer ions: Quenching of luminescence: (1) ions with intensive absorption (1) concentration quenching bands in the UV (e.g.) Co2+) charge transfer bands (e.g.Basics of luminescence Sensitizing and quenching Interaction between two or more ions with transfer of ecitation energy from one ion to another resulting in changes of their luminescence. Pb2+) (self quenching) for sensitization of Mn2+ (2) quenching by ions with intense (2) ions of transition metals (e. Cu+.g. Mn2+. Fe 2+ for sensitization of REE3+ (3) quenching due to lattice defects (3) REE2+/3+ for sensitization of REE3+ (4) thermal quenching .

emission excitation radiationless transition excitation activator activator luminescence emission concentration quenching .

Germany) (Kempe & Götze 2002) .Influence of excitation energy and delay time on emission spectra of laser-induced time-resolved luminescence (apatite Ehrenfriedersdorf.

ceramics. magnesite feldspar. zircon. kaolinite technical products (synthetic minerals. quartz. glasses !) no luminescence of conductors. halite anhydrite. iron minerals and Fe-rich phases . aragonite. dolomite.Basics of luminescence Mineral groups and minerals showing CL in general all insulators and semiconductors elements sulfides oxides halides sulfates phosphates carbonates silicates diamond sphalerite corundum. alunite apatite calcite. cassiterite. periclase fluorite.

Namibia .300 µm CL of orthopyroxene (with carbonate) from an alkaline complex.

zoning) reconstruction of geological processes characterisation of technical products (also non-crystalline phases !) . mineral distribution and quantification typomorphic properties (CL colour.General applications of CL in geosciences identification of minerals. CL behaviour. spectral characteristics) crystal chemistry (trace elements. internal structures.

Identification of minerals Mineral distribution Quantification of mineral abundance calcite ? quartz feldspar .

Applications of CL Identification of minerals .mineral distribution .texture Pol Plag CL Q Kf 500 µm .

Identification of minerals .mineral distribution Pol F Q C CL 500 µm kaolinite zircon 500 µm 400 µm .

intergrowth.information concerning texture.chemical analysis provides no information concerning phase composition .comparison of optical and CL microscopy possible . limited application for non-crystalline samples . .clear phase contrast by CL and automatization of analysis by computer aided image analysis . porosity.polarizing microscopy is time consuming.Quantification of mineral abundance by combined CL and image analysis Aim: . etc.X-ray diffraction without information concerning texture. grain size.quantification of phases in addition to conventional methods Limits of other methods: .only one thin section necessary . limits for fine-grained samples Advantages of combined CL and image analysis: . phase distribution. etc.

CL microscope with attached CCD based viedeo camera electronic steerage Computer aided image analysis vacuum pumps Cathodoluminescence microscope HC1-LM .

magnification .) (3) definition of the CL colours of the different mineral phases by combining the values of colour and brightness (4) false-colour imaging of the different phases (thresholding) and conversion to binary mode (5) processing of phases in the binary mode (6) definition of options and measuring (7) extraction of data and interpretation the number of fields of view depends on: . etc. brightness.the homogeneity/heterogeneity of the sample .Image processing algorithm: (1) shadow correction by means of low-pass filtering (2) basic image processing (focus. contrast.contents of mineral phases analysed .

3 45 45.3 4.3 C Q Q weight-% vol-% analysed composition vol-% % 30 20 10 5 5.5 1 0.Quantitative CL microscopy of synthetic standard samples Pol CL C F F Q F C 300 µm calibrated composition 60 50 40 45 45.7 46.7 46.54 0.72 quartz alkali feldspar calcite magnetite .

Quantification of mineral abundance by combined CL and image analysis CL image Thresholding Quantification of feldspar content Binary mode .

Mineral composition of Cretaceous sandstones of the Elbe valley. Germany (Magnus & Götze 1997) quartz feldspar carbonate kaolinite pore space .

Typomorphic properties of minerals .

First classification of quartz types according to their CL properties after ZINKERNAGEL (1978) .

Applications of CL Typomorphic CL properties of quartz granite rhyolite schist hydrothermal .

quantification ?? .Crystal chemistry l NaAl A Ti Fe K Ge Li .trace-element distribution .

Intensity [counts] Eu2+ 1200 1 2 Dy3+ Er3+ Dy3+ Dy3+ Sm3+ Dy3+ Crystal chemistry 800 Sm3+ 400 fluorite Chemnitz. Chemnitz (Germany) .Applications of CL 1600 rel. Germany 300 400 500 600 700 800 1 2 o o 0 wavelength [nm] 100 µm fluorite.

Isotope geochemistry 16O 18O .

zoning and alteration features in samples for the analysis of stable isotopes detection of relic cores and internal structures in zircon used for age dating .Application of CL in isotope geochemistry and geochronology detection of internal structures.

zoning) reconstruction of geological processes characterisation of technical products (also non-crystalline phases !) .General applications of CL in geosciences identification of minerals. spectral characteristics) crystal chemistry (trace elements. mineral distribution and quantification typomorphic properties (CL colour. internal structures. CL behaviour.

Characterisation of technical products .

biomaterials etc.waste materials .archeometry . .Technical and industrial applications: .ceramics .glass .building stones and materials .refractory materials .

Applications of CL Glass Al content and cathodoluminescence in silica glass .